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CN1143958A - 具有农药活性的(4，4-二氟丁-3-烯基硫基)-取代的杂环或碳环类化合物 - Google Patents

具有农药活性的(4，4-二氟丁-3-烯基硫基)-取代的杂环或碳环类化合物 Download PDF

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Publication number
CN1143958A
CN1143958A CN95192029A CN95192029A CN1143958A CN 1143958 A CN1143958 A CN 1143958A CN 95192029 A CN95192029 A CN 95192029A CN 95192029 A CN95192029 A CN 95192029A CN 1143958 A CN1143958 A CN 1143958A
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China
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sch2ch2ch
alkyl
compound
group
arbitrarily replaced
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CN95192029A
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English (en)
Inventor
M·D·特恩布尔
H·S·班萨尔
A·M·史密夫
R·莎尔门
S·菲茨约翰
C·R·A·戈德弗雷
M·B·霍森
N·C·西拉斯
A·J·道灵
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Syngenta Ltd
Original Assignee
Zeneca Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from GB9404717A external-priority patent/GB9404717D0/en
Priority claimed from GB9404716A external-priority patent/GB9404716D0/en
Priority claimed from GB9404718A external-priority patent/GB9404718D0/en
Priority claimed from GB9404719A external-priority patent/GB9404719D0/en
Priority claimed from GB9404720A external-priority patent/GB9404720D0/en
Priority claimed from GB9404721A external-priority patent/GB9404721D0/en
Priority claimed from GBGB9500521.1A external-priority patent/GB9500521D0/en
Application filed by Zeneca Ltd filed Critical Zeneca Ltd
Publication of CN1143958A publication Critical patent/CN1143958A/zh
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
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    • A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
    • A01N33/18—Nitro compounds
    • A01N33/20—Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group
    • A01N33/22—Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group having at least one oxygen or sulfur atom and at least one nitro group directly attached to the same aromatic ring system
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
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    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
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Abstract

式(I)化合物或其盐，其中n为0、1或2；和R为式(II)-(XXI)基团，其中：所述S(O)nCH2CH2CH=CF2基团至少是R1(当与碳原子相连时)、R2、R3、R4、R5或R6中的一个；R1(当与碳原子相连时)、R2、R3、R4、R5或R6各自独立地是氢、被任意取代的烷基、被任意取代的链烯基、链炔基、环烷基、烷基环烷基、烷氧基、链烯氧基、链炔氧基、羟基烷基、烷氧基烷基、被任意取代的芳基、被任意取代的芳烷基、被任意取代的杂芳基、被任意取代的杂芳烷基、被任意取代的芳氧基、被任意取代的芳烷氧基、被任意取代的芳氧基烷基、被任意取代的杂芳氧基、被任意取代的杂芳基烷氧基、被任意取代的杂芳氧基烷基、卤代烷基、卤代链烯基、卤代链炔基、卤代烷氧基、卤代链烯氧基、卤代链炔氧基、卤素、羟基、氰基、硝基、-NR7R8、-NR7COR8、-NR7CSR8、-NR7SO2R8、-N(SO2R7)(SO2R8)、-COR7、-CONR7R8、-烷基CONR7R8、CR7NR8、-COOR7、-OCOR7、-SR7、-SOR7、-SO2R7、-烷基SR7、-烷基SOR7、-烷基SO2R7、-OSO2R7、-SO2NR7R8、-CSNR7R8、SiR7R8R9、-OCH2CO2R7、-OCH2CH2CO2R7、-CONR7SO2R8、-烷基CONR7SO2R8、-NHCONR7R8、-NHCSNR7R8或者R1、R2、R3、R4、R5和R6中相邻两个基团一起形成的稠合的5-或6-元碳环或杂环；R1(当与氮原子相连时)为氢、被任意取代的烷基、环烷基、烷基环烷基、羟基烷基、烷氧基烷基、被任意取代的芳基、被任意取代的芳烷基、被任意取代的芳氧基烷基、被任意取代的杂芳基、被任意取代的杂芳基烷基、被任意取代的杂芳氧基烷基、卤代烷基、羟基、氰基、硝基、-NR7R8、-NR7COR8、-NR7CSR8、-NR7COOR8、-NR7SO2R8、-N(SO2R7)(SO2R8)、-COR7、-CONR7R8、-烷基CONR7R8、-CR7NR8、-COOR7、-OCOR7、-SOR7、-SO2R7、-烷基SR7、-烷基SOR7、-烷基SO2R7、-OSO2R7、-SO2NR7NR8、-SR7、-SOR7、-SO2R7、-CSNR7R8、SiR7R8R7、-OCH2CO2R7、-OCH2CH2CO2R7、-CONR7SO2R8、-烷基CONR7SO2R8、-NHCOR7R8或-NHCSR7R8；以及R7、R8和R9各自独立地是氢、被任意取代的烷基、被任意取代的链烯基、链炔基、被任意取代的芳基或被任意取代的芳烷基、卤代烷基、卤代链烯基、卤代链炔基、卤素或羟基。

Description

具有农药活性的(4，4-二氟丁-3-烯基硫基)- 取代的杂环或碳环类化合物
本发明涉及具有杀线虫、杀昆虫和杀螨活性的新的杂环和苯基衍生物、它们的制备方法、含有它们的组合物以及利用它们杀灭或控制线虫、昆虫或螨有害动物的方法。
本发明提供了一种式(I)化合物或其盐，其中n为0、1或2；和R为式(II)-(XXI)基团，其中：
所述S(O)nCH2CH2CH＝CF2基团至少是R1(当与碳原子相连时)、R2、R3、R4、R5或R6中的一个；
R1(当与碳原子相连时)、R2、R3、R4、R5或R6各自独立地是氢、被任意取代的烷基、被任意取代的链烯基、链炔基、环烷基、烷基环烷基、烷氧基、链烯氧基、链炔氧基、羟基烷基、烷氧基烷基、被任意取代的芳基、被任意取代的芳烷基、被任意取代的杂芳基、被任意取代的杂芳烷基、被任意取代的芳氧基、被任意取代的芳烷氧基、被任意取代的芳氧基烷基、被任意取代的杂芳氧基、被任意取代的杂芳基烷氧基、被任意取代的杂芳氧基烷基、卤代烷基、卤代链烯基、卤代链炔基、卤代烷氧基、卤代链烯氧基、卤代链炔氧基、卤素、羟基、氰基、硝基、-NR7R8、-NR7COR8、-NR7CSR8、-NR7SO2R8、-N(SO2R7)(SO2R8)、-COR7、-CONR7R8、-烷基CONR7R8、-CR7NR8、-COOR7、-OCOR7、-SR7、-SOR7、-SO2R7、-烷基SR7、-烷基SOR7、-烷基SO2R7、-OSO2R7、-SO2NR7R8、-CSNR7R8、-SiR7R8R9、-OCH2CO2R7、-OCH2CH2CO2R7、-CONR7SO2R8、-烷基CONR7SO2R8、-NHCONR7R8、-NHCSNR7R8或者R1、R2、R3、R4、R5和R6中相邻两个基团一起形成的稠合的5-或6-元碳环或杂环；
R1(当与氮原子相连时)为氢、被任意取代的烷基、环烷基、烷基环烷基、羟基烷基、烷氧基烷基、被任意取代的芳基、被任意取代的芳烷基、被任意取代的芳氧基烷基、被任意取代的杂芳基、被任意取代的杂芳基烷基、被任意取代的杂芳氧基烷基、卤代烷基、羟基、氰基、硝基、-NR7R8、-NR7COR8、NR7CSR8、-NR7COOR8、-NR7SO2R8、-N(SO2R7)(SO2R8)、-COR7、-CONR7R8、-烷基CONR7R8、-CR7NR8、-COOR7、-OCOR7、-SOR7、-SO2R7、-烷基SR7、-烷基SOR7、-烷基SO2R7、-OSO2R7、-SO2NR7NR8、-SR7、-SOR7、-SO2R7、-CSNR7R8、-SiR7R8R7、-OCH2CO2R7、-OCH2CH2CO2R7、-CONR7SO2R8、-烷基CONR7SO2R8、-NHCOR7R8或-NHCSR7R8；和
R7、R8和R9各自独立地是氢、被任意取代的烷基、被任意取代的链烯基、链炔基、被任意取代的芳基、被任意取代的芳烷基、卤代烷基、卤代链烯基、卤代链炔基、卤素或羟基。
应当说明的是，仅为了便于参考，我们根据它们在所述R基团上的位置将在此R基团上的取代基进行了命名。例如，当R含有式(II)基团时，取代基R2、R3、R4和R5在所述环上的位置分别为2、3、4和5位。为了避免混淆，所述-S(O)nCH2CH2CH＝CF2基团可以在R1(当与碳原子相连时)-R6所示的任何取代位置上。
当R1-R9中的任何一个基团为烷基或者含有烷基基团时，其可以是直链或支链基团并且优选为C1-6烷基，更优选C1-4烷基，例如甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基。当所述烷基基团作为“键连”基团时，即R-烷基-，例如在R-烷基SR7中时，特别优选C1-4烷基或C1-2烷基。
当R1-R8中的任何一个基团为被取代的烷基或者含有被取代的烷基基团时，其可以含有一个或多个选自下列的取代基，所述取代基为卤素、硝基、氰基、-COOR7或其盐、羟基、烷氧基、烷氧亚氨基、烷氧羰基、氨基甲酰基、一-或二-烷氨基甲酰基、氨基、一-或二-烷氨基、酰氨基(优选C1-6酰氨基)、链烷磺酰基和芳基磺酰基，其本身可以被卤素、烷氧基或硝基取代。
当R1-R8中的任何一个基团为链烯基或链炔基基团或者含有链烯基或链炔基基团时，其可以是直链或支链基团并且优选为C2-6链烯基或C2-6链炔基，更优选C2-4链烯基或C2-4链炔基，例如乙烯基、烯丙基、丁-3-烯基、3-甲基-丁-3-烯基、乙炔基或炔丙基。
当R1-R8中的任何一个基团为被取代的链烯基或者含有被取代的链烯基基团时，其可以含有一个或多个选自下列的取代基，所述取代基为卤素、COOR7或其盐、羟基、硝基和氰基。
当R1-R6中的任何一个基团为环烷基或烷基环烷基基团或者含有环烷基或烷基环烷基基团时，其优选为C3-6环烷基或C4-7烷基环烷基，例如环丙基、环戊基、环己基或甲基环丙基。
当R1-R6中的任何一个基团为烷氧基、链烯氧基、链炔氧基或烷氧基烷基基团或者含有此基团时，其优选为C1-6烷氧基，例如甲氧基、乙氧基、正-丙氧基、异-丙氧基、正-丁氧基、异-丁氧基、仲-丁氧基和叔-丁氧基；C2-6链烯氧基，例如乙烯氧基、烯丙基氧基、丁-3-烯基氧基和3-甲基丁-3-烯基氧基；C2-6链炔氧基，例如炔丙基氧基；C2-6一烷氧基烷基，例如甲氧基甲基，甲氧基乙基和乙氧基甲基；或C3-6二烷氧基烷基，例如二甲氧基甲基和二乙氧基甲基。
当R1-R9中的任何一个基团为芳基或者含有芳基基团时，其优选为C6-10芳基，更优选为苯基。当R1-R9中的任何一个基团为芳烷基时，其优选为C6-10芳基-甲基或C6-10芳基-乙基，更优选为苄基或苯乙基。
当R1-R6中的任何一个基团为杂芳基或者含有杂芳基基团时，其优选为含有至少一个O、N或S杂原子的5或6元环，例如吡啶、吡咯、哌嗪、呋喃或噻吩。当R1-R6中的任何一个基团为杂芳基烷基时，其优选为杂芳基-C1-2烷基。
当R1-R9中的任何一个基团为被取代的芳基、芳烷基、杂芳基或杂芳基烷基基团时，其可以含有一个或多个选自下列的取代基，所述取代基为烷基、烷氧基、卤代烷基、卤素、羟基、COOR7(或其盐)、氨基磺酰基、氰基或硝基。这些基团的实例有4-甲基苯基、4-氯苯基、4-氟苯基、4-硝基苯基、3-三氟甲基苯基、4-三氟甲基苯基、4-氨基磺酰基苯基、4-氯苄基、4-氟苄基、3-三氟甲基苄基、4-三氟甲基苄基、4-硝基苄基和4-甲基苄基。
当R1-R6中的任何一个基团为芳氧基或芳基烷氧基基团时，其优选为苯氧基、苄氧基或苯乙氧基。
当R1-R6中的任何一个基团为被取代的芳氧基、芳基烷氧基、杂芳氧基或杂芳基烷氧基基团时，其可以含有一个或多个选自下列的取代基，所述取代基为烷基、烷氧基、卤代烷基、羟基、氰基或硝基。这些基团的实例有4-甲基苯氧基、4-氯苯氧基、4-氟苯氧基、4-硝基苯氧基、3-三氟甲基苯氧基、4-三氟甲基苯氧基、4-氯苄氧基、4-氟苄氧基、3-三氟甲基苄氧基、4-三氟甲基苄氧基、4-硝基苄氧基和4-甲基苄氧基。
当R1-R9中的任何一个基团为卤素或含有卤素基团时，其优选为氟、氯、溴或碘。更优选的是氟、氯或溴。
当R1-R9中的任何一个基团为卤代烷基、卤代链烯基或卤代链炔基基团时，其可以含有一个或多个卤原子，优选氯、氟或溴。这些基团的实例有氟甲基、二氟甲基、三氟甲基、氯甲基、二氯甲基、三氯甲基、2-氟乙基、2，2，2-三氟乙基、五氟乙基、2，2-二氟乙烯基、3，3-二氯丙-2-烯基、2-氯丙-2-烯基、3，4，4-三氟丁-3-烯基、4-氟丁-3-烯基、4，4-二氟丁-3-烯基和3-甲基-4，4-二氟丁-3-烯基。
当R1-R6中的任何一个基团为卤代烷氧基、卤代链烯氧基或卤代链炔氧基基团时，其可以含有一个或多个卤原子，优选氯、氟或溴。优选的C1-6烷氧基、C2-6链烯氧基和C2-6链炔氧基基团的实例有三氯甲氧基、氟甲氧基、二氟甲氧基、三氟甲氧基、2-氟乙氧基、2，2，2-三氟乙氧基、五氟乙氧基、1，1，2，2-四氟乙氧基、2，2-二氟乙烯基氧基、3，4，4-三氟丁-3-烯基氧基、4-氟丁-3-烯基氧基、4，4-二氟丁-3-烯基氧基、3-甲基-4，4-二氟丁-3-烯基氧基、2-氯丙-2-烯基氧基和3，3-二氯丙-2-烯基氧基。
当R1-R6中的任何一个基团为-NR7R8基团时，其优选为-NH2；单-烷氨基基团，例如甲氨基和乙氨基；或者二-烷氨基基团，例如二甲氨基和二乙氨基。
当R1-R6中的任何一个基团为-NR7COR8基团时，其优选为-NHCHO；C2-6酰氨基基团，例如-NHCOCH3、-NHCOC2H5；或者可被一个或多个选自下列的取代基取代的苯甲酰氨基，所述取代基为卤素，例如氯、氟和溴；烷基，例如甲基和乙基；烷氧基，例如甲氧基和乙氧基；卤代烷基，例如氯甲基、氟甲基、三氟甲基和2，2，2-三氟乙基；卤代烷氧基，例如三氟甲氧基和2，2，2-三氟乙氧基；羟基；氰基和硝基。
当R1-R6中的任何一个基团为-NR7CSR8时，R7和R8优选为烷基，例如甲基和乙基。
当R1-R6中的任何一个基团为-NR7SO2R8基团时，其优选为链烷磺酰氨基，例如-NHSO2CH3和-NHSO2C2H5。
当R1-R6中的任何一个基团为-N(SO2R7)(SO2R8)基团时，其优选为二-(链烷磺酰基)氨基，例如-N(SO2CH3)2和-N(SO2C2H5)2。
当R1-R6中的任何一个基团为-COR7基团时，其优选为C1-6酰基或被任意取代的苯甲酰基。所述苯甲酰基可以被一个或多个选自下列的取代基取代，所述取代基为卤素，例如氯、氟和溴；烷基，例如甲基和乙基；烷氧基，例如甲氧基和乙氧基；卤代烷基，例如氯甲基、氟甲基、三氟甲基和2，2，2-三氟乙基；卤代烷氧基，例如三氟甲氧基和2，2，2-三氟乙氧基；羟基；氰基和硝基。优选的-COR7基团的实例有乙酰基、丙酰基、正-丁酰基、4-氯苯甲酰基、4-氟苯甲酰基、4-溴苯甲酰基、4-甲基苯甲酰基和4-三氟甲基苯甲酰基。
当R1-R6中的任何一个基团为-CONR7R8基团时，其优选为-CONH2；N-烷基-氨基甲酰基，例如-CONHCH3、-CONHC2H5和-CONHCH2CH2CH3；或者N，N-二烷基-氨基甲酰基，例如-CON(CH3)2、-CON(CH3)(C2H5)和-CON(C2H5)2。
当R1-R6中的任何一个基团为-烷基CONR7R8基团时，其优选为-C1-4烷基CONR7R8。
当R1-R6中的任何一个基团为-CR7NR8基团时，其优选为-CH＝NOH。
当R1-R6中的任何一个基团为-COOR7基团时，其优选为-COOH；烷氧羰基，例如甲氧羰基和乙氧羰基；或者卤代链烯氧基羰基，例如3，4，4-三氟丁-3-烯氧基羰基、4-氟丁-3-烯氧基羰基、4，4-二氟丁-3-烯氧基羰基和3-甲基-4，4-二氟丁-3-烯氧基羰基。
当R1-R6中的任何一个基团为-OCOR7基团时，其优选为C2-6酰氧基，例如-OCOCH3或和-OCOC2H5；或者被任意取代的苯甲酰氧基。所述苯甲酰氧基可以含有一个或多个选自下列的取代基，所述取代基为卤素，例如氯、氟和溴；烷基，例如甲基和乙基；烷氧基，例如甲氧基和乙氧基；卤代烷基，例如氯甲基、氟甲基、三氟甲基和2，2，2-三氟乙基；卤代烷氧基，例如三氟甲氧基和2，2，2-三氟乙氧基；羟基；氰基和硝基。
当R1-R6中的任何一个基团为-SR7基团时，R7优选为氢、被任意取代的烷基、被任意取代的链烯基、链炔基、卤代烷基、卤代链烯基、卤代链炔基、被任意取代的芳基或被任意取代的芳烷基。优选的C1-6烷硫基(特别优选C1-4烷基)、C2-6链烯硫基或C2-6链炔硫基基团的实例有甲硫基、乙硫基、正-丙硫基、异-丙硫基、正-丁硫基、异-丁硫基、仲-丁硫基、叔-丁硫基、烯丙基硫基、丁-3-烯基硫基、3-甲基丁-3-烯基硫基和炔丙基硫基。优选的C1-6卤代烷硫基(特别优选C1-4烷基)、C2-6卤代链烯硫基或C2-6卤代链炔硫基基团的实例有氟甲硫基、二氟甲硫基、三氟甲硫基、三氯甲硫基、2-氟乙硫基、2，2，2-三氟乙硫基、3-氟-正-丙硫基、五氟乙硫基、2-氯丙-2-烯基硫基、3，3-二氯丙-2-烯基硫基、3，4，4-三氟丁-3-烯基硫基、4-氟丁-3-烯基硫基、4，4-二氟丁-3-烯基硫基和3-甲基-4，4-二氟丁-3-烯基硫基。优选的C6-10芳硫基和C6-10芳基-C1-2烷硫基基团的实例有3-三氟甲基苄硫基。
当R1-R6中的任何一个基团为-SOR7基团时，其优选为链烷基亚磺酰基、链烯基亚磺酰基或链炔基亚磺酰基基团，例如甲基亚磺酰基或乙基亚磺酰基；或者卤代链烷基亚磺酰基、卤代链烯基亚磺酰基或卤代链炔基亚磺酰基，例如三氟甲基亚磺酰基。在另一个优选方案中，-SOR7优选为-SOF、-SOBr或-SOCl。
当R1-R6中的任何一个基团为-SO2R7基团时，其优选为链烷基磺酰基。链烯基磺酰基、链炔基磺酰基、卤代链烷基磺酰基、卤代链烯基磺酰基、卤代链炔基磺酰基基团；或者被任意取代的苯磺酰基基团。所述苯磺酰基可以含有一个或多个选自下列的取代基，所述取代基为卤素，例如氯、氟和溴；烷基，例如甲基和乙基；烷氧基，例如甲氧基和乙氧基；卤代烷基，例如氯甲基、氟甲基、三氟甲基和2，2，2-三氟乙基；卤代烷氧基，例如三氟甲氧基和2，2，2-三氟乙氧基；羟基；氰基和硝基。此类基团的实例有甲磺酰基、乙磺酰基、三氟甲磺酰基和4-甲基苯磺酰基。在另一个优选方案中，-SO2R7优选为-SO2F、-SO2Br或-SO2Cl。
可以理解的是，式(II)-(XXI)中的R基团可以含有多于一个的-S(O)nCH2CH2CH＝CF2基团。优选的是，所述R基团含有一个或两个此基团。
当R1-R6中的任何一个基团为-OSO2R7基团时，其优选为链烷基磺酰氧基或被任意取代的苯磺酰氧基基团。所述苯磺酰基可以含有一个或多个选自下列的取代基，所述取代基为卤素，例如氯、氟和溴；烷基，例如甲基和乙基；烷氧基，例如甲氧基和乙氧基；卤代烷基，例如氯甲基、氟甲基、三氟甲基和2，2，2-三氟乙基；卤代烷氧基，例如三氟甲氧基和2，2，2-三氟乙氧基；羟基；氰基和硝基。
当R1-R6中的任何一个基团为-SO2NR7R8基团时，其优选为-SO2NH2；烷氨基磺酰基，例如-SO2NHCH3和-SO2NHC2H5；或者二烷氨基磺酰基，例如-SO2N(CH3)2和-SO2N(C2H5)2。
当R1-R6中的任何一个基团为-CSNR7R8基团时，其优选为-CSNH2、-CSNHCH3或-CSN(CH3)2。
当R1-R6中的任何一个基团为-SiR7R8R9基团时，其优选为三烷基甲硅烷基，例如三甲基甲硅烷基和三乙基甲硅烷基。
当R1-R6中的任何一个基团为-OCH2CO2R7基团时，其优选为烷氧羰基甲氧基，例如甲氧羰基甲氧基和乙氧羰基甲氧基。
当R1-R6中的任何一个基团为-OCH2CH2CO2R7基团时，其优选为烷氧羰基乙氧基，例如甲氧羰基乙氧基和乙氧羰基乙氧基。
当R1-R6中的任何一个基团为-CONR7SO2R8基团时，其优选为N-烷基磺酰基氨基甲酰基或N-烷基-N-烷基磺酰基氨基甲酰基基团，例如N-(甲磺酰基)-氨基甲酰基和N-甲基-N-(甲磺酰基)氨基甲酰基。
当R1-R6中的任何一个或多个基团为-烷基CONR7SO2R8基团时，R7和R8优选为烷基，例如乙基和甲基。
当R1-R6中的任何一个基团为-NHCONR7R8基团时，R7和R8优选为烷基，例如乙基和甲基。
当R1-R6中的任何一个基团为-NHCSNR7R8基团时，R7和R8优选为烷基，例如乙基和甲基。
当R1、R2、R3、R4、R5和R6中相邻两个基团一起形成稠合的5-或6-元碳环或杂环时，其优选含有两个氧原子，优选的是，两个取代基可一起形成-(CH2)3-、-(CH2)4-、-CH＝CH-CH＝CH-、-O-CH2-O-，其可被一个或多个卤原子或甲基任意取代，例如-O-CHF-O-或-O-CF2-O-、-O-CH(CH3)-O-、-O-C(CH3)2-O-或-O-(CH2)2-O-。
本发明特别优选的方案是，R1(当与碳原子相连时)-R6各自独立地是氢；硝基；卤素；氰基；-CH＝NOH；C1-4烷基；C1-4卤代烷基；C1-4链烯基；C1-4卤代链烯基；环丙基；羟基；C1-4烷氧基；C2-4烷氧基烷基；-COOH；C2-4烷氧羰基；C2-4卤代链烯氧基羰基；-CONH2；一或二-C1-2烷氨基羰基；C2-4链烷羰基；-CONHSO2 C1-4烷基，优选-CONHSO2CH3；被独立地选自卤素、硝基、C1-4烷基、C1-4烷氧基或氨基磺酰基的基团任意一-或二-取代的苯基；被独立地选自卤素、硝基、C1-4烷基或C1-4烷氧基的基团任意一-或二-取代的苄基；被独立地选自卤素、氰基、C1-4烷基或C1-4烷氧基的基团任意一-或二-取代的苯氧基；被C1-4烷基任意一-或二-取代的氨基；-SH；C1-4烷硫基；被独立地选自卤素或C1-4卤代烷基的基团任意一-或二-取代的苄硫基；C1-4链烯基硫基；C2-4卤代链烯基硫基；第二个S(O)nCH2CH2CH＝CF2基团；C1-4链烷基磺酰基；C1-4卤代链烷基磺酰基；氟磺酰基；一-或二-C1-4烷基氨基磺酰基；5或6元杂芳基，例如呋喃基、吡嗪基、哌啶基或噻吩基，其可被卤素任意取代；或者任意两个相邻基团形成稠合的5-或6-碳环或杂环；和
R1(当与氮原子相连时)为氢；硝基；氰基；-CH＝NOH；C1-4烷基；C1-4卤代烷基；环丙基；羟基；-COOH；C2-4烷氧羰基；C2-4卤代链烯氧基羰基；-CONH2；一或二-C1-2烷氨基羰基；C2-4链烷羰基；-CONHSO2 C1-4烷基，优选-CONHSO2CH3；被独立地选自卤素、硝基、C1-4烷基、C1-4烷氧基或氨基磺酰基的基团任意一-或二-取代的苯基；被独立地选自卤素、硝基、C1-4烷基或C1-4烷氧基的基团任意一-或二-取代的苄基；被独立地选自卤素、氰基、C1-4烷基或C1-4烷氧基的基团任意一-或二-取代的苯氧基；被C1-4烷基任意一-或二-取代的氨基；-SH；C1-4烷硫基；被独立地选自卤素或C1-4卤代烷基的基团任意一-或二-取代的苄硫基；C1-4链烯基硫基；C2-4卤代链烯基硫基；第二个S(O)nCH2CH2CH＝CF2基团；C1-4链烷基磺酰基；C1-4卤代链烷基磺酰基；氟磺酰基；一-或二-C1-4烷基氨基磺酰基；5或6元杂芳基，例如呋喃基、吡嗪基、哌啶基或噻吩基，其可被卤素任意取代。
下列各表给出了本发明化合物的实例。
本发明式(II)化合物的实例如表II所示。
Figure A9519202900171
                     表IINo.    R2                   R3                   R4         R5II.1   2-SCH2CH2CH＝CF2     3-H                  4-H        5-HII.2   2-SOCH2CH2CH＝CF2    3-H                  4-H        5-HII.3   2-SO2CH2CH2CH＝CF2   3-H                  4-H        5-HII.4   2-SCH2CH2CH＝CF2     3-H                  4-H        5-CH3II.5   2-SOCH2CH2CH＝CF2    3-H                  4-H        5-CH3II.6   2-SO2CH2CH2CH＝CF2   3-H                  4-H        5-CH3II.7   2-CH3                3-SCH2CH2CH＝CF2     4-H        5-HII.8   2-CH3                3-SOCH2CH2CH＝CF2    4-H        5-HII.9   2-CH3                3-SO2CH2CH2CH＝CF2   4-H        5-H本发明式(III)化合物的实例如表III所示。
Figure A9519202900181
                        表IIINo.    R2                    R3         R4            R5III.1  2-SCH2CH2CH＝CF2      3-H        4-H           5-HIII.2  2-SOCH2CH2CH＝CF2     3-H        4-H           5-HIII.3  2-SO2CH2CH2CH＝CF2    3-H        4-H           5-HIII.4  2-SCH2CH2CH＝CF2      3-H        4-H           5-CHOIII.5  2-SCH2CH2CH＝CF2      3-H        4-H           5-CH2OHIII.6  2-SCH2CH2CH＝CF2      3-H        4-H           (E)5-CH＝NOHIII.7  2-SCH2CH2CH＝CF2      3-H        4-H           (Z)5-CH＝NOHIII.8  2-SCH2CH2CH＝CF2      3-H        4-H            5-CNIII.9  2-SCH2CH2CH＝CF2      3-H        4-H            5-COCH3III.10 2-SCH2CH2HC＝CF2      3-H        -CH＝CH-CH＝CH-III.11 2-SOCH2CH2CH＝CF2     3-H        -CH＝CH-CH＝CH-III.12 2-SO2CH2CH2CH＝CF2    3-H        -CH＝CH-CH＝CH-
本发明式(IV)化合物的实例如表IV所示。
Figure A9519202900182
                        表IVNo.        R3                  R4                 R5IV.1       3-C6H5              4-H                5-SCH2CH2CH＝CF2IV.2       3-C6H5              4-H                5-SOCH2CH2CH＝CF2IV.3       3-C6H5              4-H                5-SO2CH2CH2CH＝CF2IV.4       3-CN                4-H                5-SCH2CH2CH＝CF2IV.5       3-Cl                4-H                5-SCH2CH2CH＝CF2IV.6       3-CF3               4-H                5-SCH2CH2CH＝CF2IV.7       3-CH3               4-CONH2            5-SCH2CH2CH＝CF2IV.8       3-CH3               4-COOCH2CH3        5-SCH2CH2CH＝CF2IV.9     3-CH3              4-COOH              5-SCH2CH2CH＝CF2IV.10    3-CH3              4-H                 5-SCH2CH2CH＝CF2IV.11    3-H                4-Cl                5-SCH2CH2CH＝CF2IV.12    3-H                4-CN                5-SCH2CH2CH＝CF2IV.13    3-H                4-CN                5-SOCH2CHCH＝CF2IV.14    3-H                4-CN                5-SO2CH2CH2CH＝CF2IV.15    3-H                4-CF3               5-SCH2CH2CH＝CF2IV.16    3-H                4-H                 5-SCH2CH2CH＝CF2IV.17    3-H                4-NO2               5-SCH2CH2CH＝CF2IV.18    3-H                4-SCH2CH2CH＝CF2    5-CNIV.19    3-H                4-SCH2CH2CH＝CF2    5-CF3IV.20    3-SCH2CH2CH＝CF2   4-H                 5-ClIV.21    3-SCH2CH2CH＝CF2   4-Cl                5-HIV.22    3-SO2CH2CH2CH＝CF2 4-CN                5-SO2CH2CH2CH＝CF2IV.23    3-(5-Cl-呋喃-2-基) 4-H                 5-SCH2CH2CH＝CF2IV.24    3-(5-Cl-呋喃-2-基) 4-H                 5-SO2CH2CH2CH＝CF2IV.25    3-(噻吩-2-基)      4-H                 5-SCH2CH2CH＝CF2IV.26    3-(噻吩-2-基)      4-H                 5-SO2CH2CH2CH＝CF2本发明式(V)化合物的实例如表V所示。
Figure A9519202900191
                  表VNo.        R3                  R4                  R5V. 1       3-CF3               4-H                 5-SCH2CH2CH＝CF2V.2        3-Cl                4-CN                5-SCH2CH2CH＝CF2V.3        3-Cl                4-H                 5-SCH2CH2CH＝CF2V.4        3-Cl                4-H                 5-SO2CH2CH2CH＝CF2V.5        3-H                 4-CN                5-SCH2CH2CH＝CF2V.6        3-H                 4-CN                5-SO2CH2CH2CH＝CF2V.7        3-H                 4-SCH2CH2CH＝CF2    5-CF3V.8        3-H                 4-SOCH2CH2CH＝CF2   5-CF3V.9                3-H                    4-SCH2CH2CH＝CF2   5-CNV.10               3-NO2                  4-H                5-SCH2CH2CH＝CF2V.11               3-SCH2CH2CH＝CF2       4-Cl               5-HV.12               3-SCH2CH2CH＝CF2       4-CN               5-SCH2CH2CH＝CF2V.13               3-SO2CH2CH2CH＝CF2     4-CN               5-SOCH2CH2CH＝CF2V.14               3-SOCH2CH2CH＝CF2      4-CN               5-SO2CH2CH＝CF2V.15               3-SO2CH2CH2CH＝CF2     4-CN               5-SO2CH2CH2CH＝CF2V.16               3-SCH2CH2CH＝CF2       4-H                5-Cl本发明式(VI)化合物的实例如表VI所示。
                        表VINo.    R2                    R4                   R5VI.1   2-SCH2CH2CH＝CF2      4-H                  5-HVI.2   2-SOCH2CH2CH＝CF2     4-H                  5-HVI.3   2-SO2CH2CH2CH＝CF2    4-H                  5-HVI.4   2-SCH2CH2CH＝CF2      4-CF3                5-HVI.5   2-SO2CH2CH2CH＝CF2    4-CF3                5-HVI.6   2-SCH2CH2CH＝CF2      4-CH3                5-HVI.7   2-SCH2CH2CH＝CF2      4-CN                 5-HVI.8   2-SCH2CH2CH＝CF2      4-CONH2              5-HVI.9   2-SCH2CH2CH＝CF2      4-COOCH2CH3          5-HVI.10  2-SO2CH2CH2CH＝CF2    4-COOCH2CH3          5-HVI.11  2-SCH2CH2CH＝CF2      4-COOH               5-HVI.12  2-SO2CH2CH2CH＝CF2    4-H                  5-BrVI.13  2-SCH2CH2CH＝CF2      4-H                  5-ClVI.14  2-SO2CH2CH2CH＝CF2    4-H                  5-ClVI.15  2-SCH2CH2CH＝CF2      4-CH3                5-ClVI.16  2-SO2CH2CH2CH＝CF2    4-CH3                5-ClVI.17  2-SCH2CH2CH＝CF2      4-H                  5-FVI.18  2-SCH2CH2CH＝CF2      4-H                  5-C6H5VI.19     2-SCCH2CH2CH＝CF2          4-H                                     5-C6H5VI.20     2-SO2CH2CH2CH＝CF2         4-H                                     5-C6H5VI.21     2-SCH2CH2CH＝CF2           4-H                                     5-CF3VI.22     2-SCH2CH2CH＝CF2           4-H                                     5-CNVI.23     2-SOCH2CH2CH＝CF2          4-H                                     5-CNVI.24     2-SO2CH2CH2CH＝CF2         4-H                                     5-CNVI.25     2-SCH2CH2CH＝CF2           4-CH3                                   5-CNVI.26     2-SOCH2CH2CH＝CF2          4-CH3                                   5-CNVI.27     2-SO2CH2CH2CH＝CF2         4-CH3                                   5-CNVI.28     2-SCH2CH2CH＝CF2           4-H                                     5-COOCH2CH3VI.29     2-SOCH2CH2CH＝CF2          4-H                                     5-COOCH2CH3VI.30     2-SO2CH2CH2CH＝CF2         4-H                                     5-COOCH2CH3VI.31     2-SCH2CH2CH＝CF2           4-CF3                                   5-COOCH2CH3VI.32     2-SCH2CH2CH＝CF2           4-CH3                                   5-COOCH3VI.33     2-SOCH2CH2CH＝CF2          4-CH3                                   5-COOCH3VI.34     2-SO2CH2CH2CH＝CF2         4-CH3                                   5-COOCH3VI.35     2-SCH2CH2CH＝CF2           4-H                                     5-COOHVI.36     2-SCH2CH2CH＝CF2           4-CF3                                   5-COOHVI.37     2-SCH2CH2CH＝CF2           4-CH3                                   5-COOHVI.38     2-SCH2CH2CH＝CF2           4-CH3                                   5-CONHSO2CH3VI.39     2-SCH2CH2CH＝CF2           4-H                                     5-CONH2VI.40     2-SCH2CH2CH＝CF2           4-CH3                                   5-CONF2VI.41     2-SOCH2CH2CH＝CF2          4-CH3                                   5-CONH2VI.42     2-SCH2CH2CH＝CF2           4-H                                     5-NO2VI.43     2-SOCH2CH2CH＝CF2          4-H                                     5-NO2VI.44     2-SO2CH2CH2CH＝CF2         4-H                                     5-NO2VI.45     2-SCH2CH2CH＝CF2           4-H                                     5-SO2FVI.46     2-SOCH2CH2CH＝CF2          4-H                                     5-SO2FVI.47     2-SCH2CH2CH＝CF2           4-H                                     5-SO2NH2VI.48     2-SO2CH2CH2CH＝CF2         4-H                                     5-SO2NH2VI.49     2-H                        4-SCH2CH2CH＝CF2                        5-BrVI.50     2-H                        4-SCH2CH2CH＝CF2                        5-C6H5VI.51     2-H                        4-SOCH2CH2CH＝CF2                       5-C6H5VI.52  2-H                4-SCH2CH2CH＝CF2    5-CF3VI.53  2-H                4-SOCH2CH2CH＝CF2   5-CF3VI.54  2-H                4-SCH2CH2CH＝CF2    5-ClVI.55  2-H                4-SOCH2CH2CH＝CF2   5-ClVI.56  2-H                4-SO2CH2CH2CH＝CF2  5-ClVI.57  2-H                4-SCH2CH2CH＝CF2    5-CNVI.58  2-CH3              4-SCH2CH2CH＝CF2    5-CNVI.59  2-CH3              4-SOCH2CH2CH＝CF2   5-CNVI.60  2-CH3              4-SO2CH2CH2CH＝CF2  5-CNVI.61  2-H                4-SCH2CH2CH＝CF2    5-CONH2VI.62  2-CH3              4-SCH2CH2CH＝CF2    5-CONH2VI.63  2-H                4-SCH2CH2CH＝CF2    5-COOCH2CH3VI.64  2-CH3              4-SCH2CH2CH＝CF2    5-COOCH3VI.65  2-CH3              4-SO2CH2CH2CH＝CF2  5-COOCH3VI.66  2-H                4-SCH2CH2CH＝CF2    5-COOHVI.67  2-H                4-SCH2CH2CH＝CF     5-FVI.68  2-H                4-SCH2CH2CH＝CF2    5-HVI.69  2-H                4-SOCH2CH2CH＝CF2   5-HVI.70  2-H                4-SO2CH2CH2CH＝CF2  5-HVI.71  2-H                4-SCH2CH2CH＝CF2    5-NO2VI.72  2-H                4-SCH2CH2CH＝CF2    5-SO2FVI.73  2-H                4-SCH2CF2CH＝CF2    5-SO2NH2VI.74  2-H                4-Br                5-SCH2CH2CH＝CF2VI.75  2-H                4-C6H5              5-SCH2CH2CH＝CF2VI.76  2-H                4-CF3               5-SCH2CH2CH＝CF2VI.77  2-H                4-CF3               5-SO2CH2CH2CH＝CF2VI.78  2-H                4-Cl                5-SCH2CH2CH＝CF2VI.79  2-H                4-CN                5-SCH2CH2CH＝CF2VI.80  2-H                4-CN                5-SOCH2CH2CH＝CF2VI.81  2-H                4-CN                5-SO2CH2CH2CH＝CF2VI.82  2-CH3              4-CN                5-SCH2CH2CH＝CF2VI.83  2-H                4-CONH2             5-SCH2CH2CH＝CF2VI.84  2-H                4-CONH2             5-SOCH2CH2CH＝CF2VI.85  2-H                4-CONH2           5-SO2CH2CH2CH＝CF2VI.86  2-CH3              4-CONH2           5-SCH2CH2CH＝CF2VI.87  2-H                4-COOCH2CH3       5-SCH2CH2CH＝CF2VI.88  2-H                4-COOCH2CH3       5-SOCH2CH2CH＝CF2VI.89  2-H                4-COOCH2CH3       5-SO2CH2CH2CH＝CF2VI.90  2-CH3              4-COOCH3          5-SCH2CH2CH＝CF2VI.91  2-H                4-COOH            5-SCH2CH2CH＝CF2VI.92  2-H                4-F               5-SCH2CH2CH＝CF2VI.93  2-H                4-H               5-SCH2CH2CH＝CF2VI.94  2-H                4-H               5-SOCH2CH2CH＝CF2VI.95  2-H                4-H               5-SO2CH2CH2CH＝CF2VI.96  2-H                4-NO2             5-SCH2CH2CH＝CF2VI.97  2-H                4-NO2             5-SOCH2CH2CH＝CF2VI.98  2-H                4-SO2F            5-SCH2CH2CH＝CF2VI.99  2-H                4-SO2NH2          5-SCH2CH2CH＝CF2VI.100 2-Br               4-H               5-SCH2CH2CH＝CF2VI.101 2-C6H5             4-H               5-SCH2CH2CH＝CF2VI.102 2-C6H5             4-H               5-SOCH2CH2CH＝CF2VI.103 2-C6H5             4-H               5-SO2CH2CH2CH＝CF2VI.104 2-CF3              4-H               5-SCH2CH2CH＝CF2VI.105 2-CF3              4-H               5-SO2CH2CH2CH＝CF2VI.106 2-Cl               4-H               5-SCH2CH2CH＝CF2VI.107 2-CN               4-H               5-SCH2CH2CH＝CF2VI.108 2-CN               4-CH3             5-SCH2CH2CH＝CF2VI.1O9 2-CONH2            4-H               5-SCH2CH2CH＝CF2VI.110 2-CONH2            4-H               5-SOCH2CH2CH＝CF2VI.111 2-CONH2            4-H               5-SO2CH2CH2CH＝CF2VI.112 2-CONH2            4-CH3             5-SO2CH2CH2CH＝CF2VI.113 2-COOCH2CH3        4-H               5-SCH2CH2CH＝CF2VI.114 2-COOCH3           4-CH3             5-SCH2CH2CH＝CF2VI.115 2-COOH             4-H               5-SCH2CH2CH＝CF2VI.116 2-F                4-H               5-SCH2CH2CH＝CF2VI.117 2-F                4-H               5-SOCH2CH2CH＝CF2VI.115    2-NO2                          4-H                          5-SCH2CH2CH＝CF2VI.119    2-SO2F                         4-H                          5-SCH2CH2CH＝CF2VI.120    2-SO2NF2                       4-H                          5-SCH2CH2CH＝CF2
本发明式(VII)化合物的实例如表VII所示。
Figure A9519202900241
                            表VIINo.     R2                   R4                  R5VII.1   2-SCH2CH2CH＝CF2     4-H                 5-HVII.2   2-SOCH2CH2CH＝CF2    4-H                 5-HVII.3   2-SO2CH2CH2CH＝CF2   4-H                 5-HVII.4   2-SCH2CH2CH＝CF2     4-CF3               5-HVII.5   2-SO2CH2CH2CH＝CF2   4-CF3               5-HVII.6   2-SCH2CH2CH＝CF2     4-CN                5-HVII.7   2-SCH2CH2CH＝CF2     4-CONH2             5-HVII.8   2-SCH2CH2CH＝CF2     4-COOCH2CH3         5-HVII.9   2-SO2CH2CH2CH＝CF2   4-COOCH2CH3         5-HVII.10  2-SCH2CH2CH＝CF2     4-COOH              5-HVII.11  2-SCH2CH2CH＝CF2     4-COOCH2CH3         5-BrVII.12  2-SO2CH2CH2CH＝CF2   4-COOCH2CH3         5-BrVII.13  2-SCH2CH2CH＝CF2     4-COOH              5-BrVII.14  2-SCH2CH2CH＝CF2     4-H                 5-BrVII.15  2-SOCH2CH2CH＝CF2    4-H                 5-BrVII.16  2-SO2CH2CH2CH＝CF2   4-H                 5-BrVII.17  2-SCH2CH2CH＝CF2     4-H                 5-C6H5VII.18  2-SOCH2CH2CH＝CF2    4-H                 5-C6H5VII.19  2-SO2CH2CH2CH＝CF2   4-H                 5-C6H5VII.20  2-SCH2CH2CH＝CF2     4-H                 5-CF3VII.21  2-SCH2CH2CH＝CF2     4-H                 5-CH3VII.22  2-SOCH2CH2CH＝CF2    4-H                 5-CH3VII.23  2-SO2CH2CH2CH＝CF2   4-H                 5-CH3VII.24    2-SCH2CH2CH＝CF2         4-H                                  5-ClVII.25    2-SOCH2CH2CH＝CF2        4-H                                  5-ClVII.26    2-SO2CH2CH2CH＝CF2       4-H                                  5-ClVII.27    2-SCH2CH2CH＝CF2         4-CH3                                5-ClVII.28    2-SO2CH2CH2CH＝CF2       4-CH3                                5-ClVII.29    2-SCH2CH2CH＝CF2         4-H                                  5-CNVII.30    2-SOCH2CH2CH＝CF2        4-H                                  5-CNVII.31    2-SO2CH2CH2CH＝CF2       4-H                                  5-CNVII.32    2-SCH2CH2CH＝CF2         4-CH3                                5-CNVII.33    2-SOCH2CH2CH＝CF2        4-CH3                                5-CNVII.34    2-SO2CH2CH2CH＝CF2       4-CH3                                5-CNVII.35    2-SCH2CH2CH＝CF2         4-H                                  5-CONH2VII.36    2-SCH2CH2CH＝CF2         4-CH3                                5-CONH2VII.37    2-SOCH2CH2CH＝CF2        4-CH3                                5-CONH2VII.38    2-SCH2CH2CH＝CF2         4-H                                  5-COOCH2CH3VII.39    2-SOCH2CH2CH＝CF2        4-H                                  5-COOCH2CH3VII.40    2-SO2CH2CH2CH＝CF2       4-H                                  5-COOCH2CH3VII.41    2-SCH2CH2CH＝CF2         4-CH3                                5-COOCH3VII.42    2-SOCH2CH2CH＝CF2        4-CH3                                5-COOCH3VII.43    2-SO2CH2CH2CH＝CF2       4-CH3                                5-COOCH3VII.44    2-SCH2CH2CH＝CF2         4-H                                  5-COOHVII.45    2-SCH2CH2CH＝CF2         4-CH3                                5-COOHVII.46    2-SCH2CH2CH＝CF2         4-H                                  5-FVII.47    2-SCH2CH2CH＝CF2         4-H                                  5-NO2VII.48    2-SOCH2CH2CH＝CF2        4-H                                  5-NO2VII.49    2-SO2CH2CH2CH＝CF2       4-H                                  5-NO2VII.50    2-SCH2CH2CH＝CF2         4-H                                  5-SO2FVII.51    2-SOCH2CH2CH＝CF2        4-H                                  5-SO2FVII.52    2-SCH2CH2CH＝CF2         4-CH3                                5-SO2FVII.53    2-SO2CH2CH2CH＝CF2       4-CH3                                5-SO2FVII.54    2-SCH2CH2CH＝CF2         4-H                                  5-SO2NH2VII.55    2-SO2CH2CH2CH＝CF2       4-H                                  5-SO2NH2VII.56    2-SCH2CH2CH＝CF2         4-CH3                                5-SO2N(CH2CH3)2VII.57  2-H                 4-SCH2CH2CH＝CF2    5-HVII.58  2-H                 4-SOCH2CH2CH＝CF2   5-HVII.59  2-H                 4-SO2CH2CH2CH＝CF2  5-HVII.60  2-H                 4-SCH2CH2CH＝CF2    5-BrVII.61  2-H                 4-SCH2CH2CH＝CF2    5-C6H5VII.62  2-H                 4-SOCH2CH2CH＝CF2   5-C6H5VII.63  2-H                 4-SCH2CH2CH＝CF2    5-CF3VII.64  2-H                 4-SOCH2CH2CH＝CF2   5-CF3VII.65  2-H                 4-SCH2CH2CH＝CF2    5-ClVII.66  2-H                 4-SOCH2CH2CH＝CF2   5-ClVII.67  2-H                 4-SO2CH2CH2CH＝CF2  5-ClVII.68  2-H                 4-SCH2CH2CH＝CF2    5-CNVII.69  2-CH3               4-SCH2CH2CH＝CF2    5-CNVII.70  2-CH3               4-SOCH2CH2CH＝CF2   5-CNVII.71  2-CH3               4-SO2CH2CH2CH＝CF2  5-CNVII.72  2-H                 4-SCH2CH2CH＝CF2    5-CONH2VII.73  2-CH3               4-SCH2CH2CH＝CF2    5-CONH2VII.74  2-H                 4-SCH2CH2CH＝CF2    5-COOCH2CH3VII.75  2-CH3               4-SCH2CH2CH＝CF2    5-COOCH3VII.76  2-CH3               4-SO2CH2CH2CH＝CF2  5-COOCH3VII.77  2-H                 4-SCH2CH2CH＝CF2    5-COOHVII.78  2-H                 4-SCH2CH2CH＝CF2    5-FVII.79  2-H                 4-SCH2CH2CH＝CF2    5-NO2VII.80  2-H                 4-SCH2CH2CH＝CF2    5-SO2FVII.81  2-H                 4-SCH2CH2CH＝CF2    5-SO2NH2VII.82  2-H                 4-H                 5-SCH2CH2CH＝CF2VII.83  2-H                 4-H                 5-SOCH2CH2CH＝CF2VII.84  2-H                 4-H                 5-SO2CH2CH2CH＝CF2VII.85  2-H                 4-Br                5-SCH2CH2CH＝CF2VII.86  2-H                 4-C6H5              5-SCH2CH2CH＝CF2VII.87  2-H                 4-CF3               5-SCH2CH2CH＝CF2VII.88  2-H                 4-CF3               5-SO2CH2CH2CH＝CF2VII.89  2-H                 4-Cl                5-SCH2CH2CH＝CF2VII.90    2-H                                 4-CN                                 5-SCH2CH2CH＝CF2VII.91    2-H                                 4-CN                                 5-SOCH2CH2CH＝CF2VII.92    2-H                                 4-CN                                 5-SO2CH2CH2CH＝CF2VII.93    2-CH3                               4-CN                                 5-SCH2CH2CH＝CF2VII.94    2-H                                 4-CONH2                              5-SCH2CH2CH＝CF2VII.95    2-H                                 4-CONH2                              5-SOCH2CH2CH＝CF2VII.96    2-H                                 4-CONH2                              5-SO2CH2CH2CH＝CF2VII.97    2-CH3                               4-CONH2                              5-SCH2CH2CH＝CF2VII.98    2-H                                 4-COOCH2CH3                          5-SCH2CH2CH＝CF2VII.99    2-H                                 4-COOCH2CH3                          5-SOCH2CH2CH＝CF2VII.100   2-H                                 4-COOCH2CH3                          5-SO2CH2CH2CH＝CF2VII.101   2-CH3                               4-COOCH3                             5-SCH2CH2CH＝CF2VII.102   2-H                                 4-COOH                               5-SCH2CH2CH＝CF2VII.103   2-H                                 4-F                                  5-SCH2CH2CH＝CF2VII.104   2-H                                 4-NO2                                5-SCH2CH2CH＝CF2VII.105   2-H                                 4-NO2                                5-SOCH2CH2CH＝CF2VII.106   2-H                                 4-SO2F                               5-SCH2CH2CH＝CF2VII.107   2-H                                 4-SO2NH2                             5-SCH2CH2CH＝CF2VII.108   2-Br                                4-H                                  5-SCH2CH2CH＝CF2VII.109   2-C6H5                              4-H                                  5-SCH2CH2CH＝CF2VII.110   2-C6H5                              4-H                                  5-SOCH2CH2CH＝CF2VII.111   2-C6H5                              4-H                                  5-SO2CH2CH2CH＝CF2VII.112   2-CF3                               4-H                                  5-SCH2CH2CH＝CF2VII.113   2-CF3                               4-H                                  5-SO2CH2CH2CH＝CF2VII.114   2-Cl                                4-H                                  5-SCH2CH2CH＝CF2VII.115   2-Cl                                4-H                                  5-SOCH2CH2CH＝CF2VII.116   2-C1                                4-H                                  5-SO2CH2CH2CH＝CF2VII.117   2-CN                                4-H                                  5-SCH2CH2CH＝CF2VII.118   2-CN                                4-CH3                                5-SCH2CH2CH＝CF2VII.119   2-CONH2                             4-H                                  5-SCH2CH2CH＝CF2VII.120   2-CONH2                             4-H                                  5-SOCH2CH2CH＝CF2VII.121   2-CONH2                             4-H                                  5-SO2CH2CH2CH＝CF2VII.122   2-CONH2                             4-CH3                                5-SO2CH2CH2CH＝CF2VII.123 2-COOCH2CH3         4-H    5-SCH2CH2CH＝CF2VII.124 2-COOCH3            4-CH3  5-SCH2CH2CH＝CF2VII.125 2-COOH              4-H    5-SCH2CH2CH＝CF2VII.126 2-F                 4-H    5-SCH2CH2CH＝CF2VII.127 2-F                 4-H    5-SOCH2CH2CH＝CF2VII.128 2-NH2               4-H    5-SCH2CH2CH＝CF2VII.129 2-NO2               4-H    5-SCH2CH2CH＝CF2VII.130 2-O(4-CN-C6H4)      4-H    5-SCH2CH2CH＝CF2VII.131 2-SO2F              4-H    5-SCH2CH2CH＝CF2VII.132 2-SO2NH2            4-H    5-SCH2CH2CH＝CF2VII.133 2-S-(2)-(5-Cl噻唑)  4-H    5-SCH2CH2CH＝CF2VII.134 2-SCH2CH2CH＝CF2    4-二氢 5-二氢本发明式(VIII)化合物的实例如表VIII所示。
Figure A9519202900291
                        表VIIINo.        R1                   R2                           R4                                           R5VIII.1     1-H                  2-SCH2CH2CH＝CF2             4-H                                          5-HVIII.2     1-H                  2-SO2CH2CH2CH＝CF2           4-H                                          5-HVIII.3     1-C6H5               2-SCH2CH2CH＝CF2             4-H                                          5-HVIII.4     1-C6H5               2-SO2CH2CH2CH＝CF2           4-H                                          5-HVIII.5     1-CH3                2-SCH2CH2CH＝CF2             4-H                                          5-HVIII.6     1-CH3                2-SOCH2CH2CH＝CF2            4-H                                          5-HVIII.7     1-CH3                2-SO2CH2CH2CH＝CF2           4-H                                          5-HVIII.8     1-CH2CH2CH ＝CF2     2-SCH2CH2CH＝CF2             4-H                                          5-HVIII.9     1-CH2CH2CH＝CF2      2-SO2CH2CH2CH＝CF2           4-H                                          5-HVIII.10    1-CH2CH3             2-SCH2CH2CH＝CF2             4-H                                          5-HVIII.11    1-CH2CH3             2-SO2CH2CH2CH＝CF2           4-H                                          5-HVIII.12    1-CH2CH2CH3          2-SCH2CH2CH＝CF2             4-H                                          5-HVIII.13    1-CH2CH2CH3          2-SO2CH2CH2CH＝CF2           4-H                                          5-HVIII.14    1-CH(CH3)2           2-SCH2CH2CH＝CF2             4-H                                          5-HVIII.15    1-CH(CH3)2           2-SO2CH2CH2CH＝CF2           4-H                                          5-HVIII.16    1-C(CH3)3            2-SCH2CH2CH＝CF2             4-H                                          5-HVIII.17    1-C(CH3)3            2-SO2CH2CH2CH＝CF2           4-H                                          5-HVIII.18  1-SO2CH3          2-SCH2CH2CH＝CF2           4-H                    5-HVIII.19  1-H               2-SCH2CH2CH＝CF2           4-C6H5                 5-HVIII.20  1-H               2-SOCH2CH2CH＝CF2          4-C6H5                 5-HVIII.21  1-H               2-SO2CH2CH2CH＝CF2         4-C6H5                 5-HVIII.22  1-CH3             2-SCH2CH2CH＝CF2           4-C6H5                 5-HVIII.23  1-CH3             2-SOCH2CH2CH＝CF2          4-C6H5                 5-HVIII.24  1-CH3             2-SO2CH2CIH2CH＝CF2        4-C6H5                 5-HVIII.25  1-CH3             2-SO2CH2CH2CH＝CF2         4-H                    5-BrVIII.26  1-CH3             2-SCH2CH2CH＝CF2           4-H                    5-CF3VIII.27  1-H               2-SCH2CH2CH＝CF2           4-CH2CH3               5-CH3VIII.28  1-H               2-SO2CH2CH2CH＝CF2         4-CH2CH3               5-CH3VIII.29  1-H               2-SCH2CH2CH＝CF2           4-CH3                  5-CH3VIII.30  1-H               2-SO2CH2CH2CH＝CF2         4-CH3                  5-CH3VIII.31  1-CH3             2-SCH2CH2CH＝CF2           4-CH3                  5-CH3VIII.32  1-CH3             2-SO2CH2CH2CH＝CF2         4-CH3                  5-CH3VIII.33  I-CH2CH3          2-SCH2CH2CH＝CF2           4-CH3                  5-CH3VIII.34  1-CH2CH3          2-SO2CH2CH2CH＝CF2         4-CH3                  5-CH3VIII.35  1-CH3             2-SCH2CH2CH＝CF2           4-H                    5-CH3VIII.36  1-CH3             2-SO2CH2CH2CH＝CF2         4-H                    5-CH3VIII.37  1-CH(CH3)2        2-SCH2CH2CH＝CF2           4-H                    5-CH3VIII.38  1-CH(CH3)2        2-SO2CH2CH2CH＝CF2         4-H                    5-CH3VIII.39  1-CH3             2-SCH2CH2CH＝CF2           4-H                    5-ClVIII.40  1-CH3              2-SO2CH2CH2CH＝CF2         4-H                     5-ClVIII.41  1-CH3              2-SCH2CH2CH＝CF2           4-H                     5-CNVIII.42  1-CH3              2-SOCH2CH2CH＝CF2          4-H                     5-CNVIII.43  1-CH3              2-SO2CH2CH2CH＝CF2         4-H                     5-CNVIII.44  1-CH3              2-SCH2CH2CH＝CF2           4-CH3                   5-CNVIII.45  1-CH3              2-SOCH2CH2CH＝CF2          4-CH3                   5-CNVIII.46  1-CH3              2-SO2CH2CH2CH＝CF2         4-CH3                   5-CNVIII.47  1-CH3              2-SCH2CH2CH＝CF2           4-H                     5-CONH2VIII.48  1-CH3              2-SCH2CH2CH＝CF2           4-CH3                   5-CONH2VIII.49  1-CH3              2-SOCH2CH2CH＝CF2          4-CH3                   5-CONH2VIII.50  1-H                2-SOCH2CH2CH＝CF2          4-H                     5-COOCH2CH3VIII.51  1-H                2-SO2CH2CH2CH＝CF2         4-H                     5-COOCH2CH3VIII.52  1-CH3              2-SCH2CH2CH＝CF2           4-H                     5-COOCH2CH3VIII.53  1-CH3              2-SO2CH2CH2CH＝CF2         4-H                     5-COOCH2CH3VIII.54  1-CH3              2-SCH2CH2CH＝CF2           4-H                     5-COOHVIII.55  1-CH3              2-SCH2CH2CH＝CF2           4-CH2CH 3               5-COOCH3VIII.56  1-CH3              2-SO2CH2CH2CH＝CF2         4-CH2CH3                5-COOCH3VIII.57  1-CH3              2-SCH2CH2CH＝CF2           4-H                     5-FVIII.58  1-H                2-SCH2CH2CH＝CF2           4-CH3                   5-HVIII.59  1-H                2-SO2CH2CH2CH＝CF2         4-CH3                   5-HVIII.60  1-CH3              2-SCH2CH2CH＝CF2           4-CH3                   5-HVIII.61  1-CH3              2-SO2CH2CH2CH＝CF2         4-CH3                   5-HVIII.62  1-CH(CH3)2         2-SCH2CH2CH＝CF2             4-CH3                     5-HVIII.63  1-CH(CH3)2         2-SO2CH2CH2CH＝CF2           4-CH3                     5-HVIII.64  1-H                2-SCH2CH2CH＝CF2             4-COOCH2CH3               5-HVIII.65  1-CH3              2-SCH2CH2CH＝CF2             4-COOCH2CH3               5-HVIII.66  1-CH3              2-SOCH2CH2CH＝CF2            4-COOCH2CH3               5-HVIII.67  1-CH3              2-SO2CH2CH2CH＝CF2           4-COOCH2CH3               5-HVIII.68  1-CH3              2-SCH2CH2CH＝CF2             4-COOCH3                  5-CH2CH3VIII.69  1-CH3              2-SCH2CH2CH＝CF2             4-H                       5-NO2VIII.70  1-CH3              2-SOCH2CH2CH＝CF2            4-H                       5-NO2VIII.71  1-CH3              2-SO2CH2CH2CH＝CF2           4-H                       5-NO2VIII.72  1-CH3              2-SCH2CH2CH＝CF2             4-H                       5-SO2FVIII.73  1-CH3              2-SOCH2CH2CH＝CF2            4-H                       5-SO2FVIII.74  1-CH3              2-SCH2CH2CH＝CF2             4-H                       5-SO2NH2VIII.75  1-CH3              2-SO2CH2CH2CH＝CF2           4-H                       5-SO2NH2VIII.76  1-CH3              2-H                          4-SCH2CH2CH ＝CF2         5-HVIII.77  1-CH3              2-H                          4-SOCH2CH2CH＝CF2         5-HVIII.78  1-CH3              2-H                          4-SO2CH2CH2CH＝CF2        5-HVIII.79  1-CH3              2-H                          4-SCH2CH2CH＝CF2          5-CNVIII.80  1-CH3              2-CH3                        4-SCH2CH2CH＝C2           5-CNVIII.81  1-CH3              2-CH3                        4-SOCH2CH2CH＝CF2         5-CNVIII.82  1-CH3              2-CH3                        4-SO2CH2CH2CH＝CF2        5-CNVIII.83  1-CH3              2-H                          4-SCH2CH2CH＝CF2          5-C6H5VIII.84  1-CH3               2-H                            4-SOCH2CH2CH＝CF2       5-C6H5VIII.85  1-CH3               2-H                            4-SCH2CH2CH＝CF2        5-COOCH2CH3VIII.86  1-CH3               2-CH3                          4-SCH2CH2CH＝CF2        5-COOCH3VIII.87  1-CH3               2-CH3                          4-SO2CH2CH2CH＝CF2      5-COOCH3VIII.88  1-CH3               2-H                            4-SCH2CH2CH＝CF2        5-COOHVIII.89  1-CH3               2-H                            4-SCH2CH2CH＝CF2        5-CONH2VIII.90  1-CH3               2-CH3                          4-SCH2CH2CH＝CF2        5-CONH2VIII.91  1-CH3               2-H                            4-SCH2CH2CH＝CF2        5-ClVIII.92  1-CH3               2-H                            4-SOCH2CH2CH＝CF2       5-ClVIII.93  1-CH3               2-H                            4-SO2CH2CH2CH＝CF2      5-ClVIII.94  1-CH3               2-H                            4-SCH2CH2CH＝CF2        5-FVIII.95  1-CH3               2-H                            4-SCH2CH2CH＝CF2        5-BrVIII.96  1-CH3               2-H                            4-SCH2CH2CH＝CF2        5-SO2NH2VIII.97  1-CH3               2-H                            4-SCH2CH2CH＝CF2        5-SO2FVIII.98  1-CH3               2-H                            4-SCH2CH2CH＝CF2        5-NO2VIII.99  1-CH3               2-H                            4-SCH2CH2CH＝CF2        5-CF3VIII.100 1-CH3               2-H                            4-SOCH2CH2CH＝CF2       5-CF3VIII.101 1-CH3               2-H                            4-H                     5-SCH2CH2CH＝CF2VIII.102 1-CH3               2-H                            4-H                     5-SOCH2CH2CH＝CF2VIII.103 1-CH3               2-H                            4-H                     5-SO2CH2CH2CH＝CF2VIII.104 1-CH3               2-H                            4-CN                    5-SCH2CH2CH＝CF2VIII.105 1-CH3               2-H                            4-CN                    5-SOCH2CH2CH＝CF2VIII.106 1-CH3                 2-H                    4-CN                       5-SO2CH2CH2CH＝CF2VIII.107 1-CH3                 2-CH3                  4-CN                       5-SCH2CH2CH＝CF2VIII.108 1-CH3                 2-H                    4-C6H5                     5-SCH2CH2CH＝CF2VIII.109 1-CH3                 2-H                    4-COOC H2CH 3              5-SCH2CH2CH＝CF2VIII.110 1-CH3                 2-H                    4-COOCH2CH3                5-SOCH2CH2CH＝CF2VIII.111 1-CH3                 2-H                    4-COOCH2CH3                5-SO2CH2CH2CH＝CF2VIII.112 1-CH3                 2-CH3                  4-COOCH3                   5-SCH2CH2CH＝CF2VIII.113 1-CH3                 2-H                    4-COOH                     5-SCH2CH2CH＝CF2VIII.114 1-CH3                 2-H                    4-CONH2                    5-SCH2CH2CH＝CF2VIII.115 1-CH3                 2-H                    4-CONH2                    5-SOCH2CH2CH＝CF2VIII.116 1-CH3                 2-H                    4-CONH 2                   5-SO2CH2CH2CH＝CF2VIII.117 1-CH3                 2-CH3                  4-CONH2                    5-SCH2CH2CH＝CF2VIII.118 1-CH3                 2-H                    4-Cl                       5-SCH2CH2CH＝CF2VIII.119 1-CH3                 2-H                    4-F                        5-SCH2CH2CH＝CF2VIII.120 1-CH3                 2-H                    4-Br                       5-SCH2CH2CH＝CF2VIII.121 1-CH3                 2-H                    4-SO2NH2                   5-SCH2CH2CH＝CF2VIII.122 1-CH3                 2-H                    4-SO2F                     5-SCH2CH2CH＝CF2VIII.123 1-CH3                 2-H                    4-NO2                      5-SCH2CH2CH＝CF2VIII.124 1-CH3                 2-H                    4-NO2                      5-SOCH2CH2CH＝CF2VIII.125 I-CH3                 2-H                    4-CF3                      5-SCH2CH2CH＝CF2VIII.126 1-CH3                 2-H                    4-CF3                      5-SO2CH2CH2CH＝CF2VIII.127 1-CH3                 2-H                    4-H                        5-SCH2CH2CH＝CF2VIII.128 1-CH3            2-H                         4-H                  5-SOCH2CH2CH＝CF2VIII.129 1-CH3            2-H                         4-H                  5-SO2CH2CH2CH＝CF2VIII.130 1-CH3            2-CN                        4-H                  5-SCH2CH2CH＝CF2VIII.131 1-CH3            2-CN                        4-CH3                5-SCH2CH2CH＝CF2VIII.132 1-CH3            2-C6H5                      4-H                  5-SCH2CH2CH＝CF2VIII.133 1-CH3            2-C6H5                      4-H                  5-SOCH2CH2CH＝CF2VIII.134 1-CH3            2-C6H5                      4-H                  5-SO2CH2CH2CH＝CF2VIII.135 1-CH3            2-COOCH2CH3                 4-H                  5-SCH2CH2CH＝CF2VIII.136 1-CH3            2-COOCH3                    4-CH3                5-SCH2CH2CH＝CF2VIII.137 1-CH3            2-COOH                      4-H                  5-SCH2CH2CH＝CF2VIII.138 1-CH3            2-CONH2                     4-H                  5-SCH2CH2CH＝CF2VIII.139 1-CH3            2-CONH2                     4-H                  5-SOCH2CH2CH＝CF2VIII.140 1-CH3            2-CONH2                     4-H                  5-SO2CH2CH2CH＝CF2VIII.141 1-CH3            2-CONH2                     4-CH3                5-SO2CH2CH2CH＝CF2VIII.142 1-CH3            2-Cl                        4-H                  5-SCH2CH2CH＝CF2VIII.143 1-CH3            2-F                         4-H                  5-SCH2CH2CH＝CF2VIII.144 1-CH3            2-F                         4-H                  5-SOCH2CH2CH＝CF2VIII.145 1-CH3            2-Br                        4-H                  5-SCH2CH2CH＝CF2VIII.146 1-CH3            2-SO2NH2                    4-H                  5-SCH2CH2CH＝CF2VIII.147 1-CH3            2-SO2F                      4-H                  5-SCH2CH2CH＝CF2VIII.148 1-CH3            2-NO2                       4-H                  5-SCH2CH2CH＝CF2VIII.149 1-CH3            2-CF3                       4-H                  5-SCH2CH2CH＝CF2VIII.150 1-CH3              2-CF3                       4-H                        5-SO2CH2CH2CH＝CF2VIII.151 1-5键连            2-SCH2CH2CH＝CF2            4-H                        -CH＝CH-CH＝CH-VIII.152 1-5键连            2-SO2CH2CH2CH＝CF2          4-H                        -CH＝CH-CH＝CH-本发明式(IX)化合物的实例如表IX所示。
Figure A9519202900371
                         表IXNo.     R1               R3                       R4                   R5IX.1    1-CH3            3-H                      4-H                  5-SCH2CH2CH＝CF2IX.2    1-CH3            3-H                      4-H                  5-SOCH2CH2CH＝CF2IX.3    1-CH3            3-H                      4-H                  5-SO2CH2CH2CH＝CF2IX.4    1-CH3            3-Cl                     4-H                  5-SCH2CH2CH＝CF2IX.5    1-CH3            3-Cl                     4-H                  5-SOCH2CH2CH＝CF2IX.6    1-CH3            3-Cl                     4-H                  5-SO2CH2CH2CH＝CF2IX.7    1-CH3            3-COOC2H5                4-H                  5-SCH2CH2CH＝CF2IX.8    1-CH3            3-COOC2H5                4-H                  5-SOCH2CH2CH＝CF2IX.9    1-CH3            3-COOC2H5                4-H                  5-SO2CH2CH2CH＝CF2IX.10   1-CH3            3-COOH                   4-H                  5-SCH2CH2CH＝CF2IX.11   1-CH3            3-COOH                   4-H                  5-SOCH2CH2CH＝CF2IX.12   1-CH3            3-COOH                   4-H                  5-SO2CH2CH2CH＝CF2IX.13   1-CH3            3-CONH2                  4-H                  5-SCH2CH2CH＝CF2IX.14    1-CH3                3-CONH2                         4-H                        5-SOCH2CH2CH＝CF2IX.15    1-CH3                3-CONH2                         4-H                        5-SO2CH2CH2CH＝CF2IX 16    1-CH3                3-CN                            4-H                        5-SCH2CH2CH＝CF2IX.17    1-CH3                3-CN                            4-H                        5-SOCH2CH2CH＝CF2IX.18    1-CH3                3-CN                            4-H                        5-SO2CH2CH2CH-CF2IX.19    1-CH3                3-SO2F                          4-H                        5-SCH2CH2CH＝CF2IX.20    1-CH3                3-SO2F                          4-H                        5-SOCH2CH2CH-CF2IX.21    1-CH3                3-SO2F                          4-H                        5-SO2CH2CH2CH＝CF2IX.22    1-CH3                3-SO2NH2                        4-H                        5-SCH2CH2CH＝CF2IX.23    1-CH3                3-SO2NH2                        4-H                        5-SOCH2CH2CH＝CF2IX.24    1-CH3                3-SO2NH2                        4-H                        5-SO2CH2CH2CH＝CF2IX.25    1-CH3                3-H                             4-H                        5-SCH2CH2CH＝CF2IX.26    1-CH3                3-H                             4-H                        5-SOCH2CH2CH＝CF2IX.27    1-CH3                3-H                             4-H                        5-SO2CH2CH＝CF2IX.28    1-CH3                3-H                             4-Cl                       5-SCH2CH2CH＝CF2IX.29    1-CH3                3-H                             4-Cl                       5-SOCH2CH2CH＝CF2IX.30    1-CH3                3-H                             4-Cl                       5-SO2CH2CH2CH＝CF2IX.31    1-CH3                3-H                             4-Br                       5-SCH2CH2CH＝CF2IX.32    1-CH3                3-H                             4-Br                       5-SOCH2CH2CH＝CF2IX.33    1-CH3                3-H                             4-Br                       5-SO2CH2CH2CH＝CF2IX.34    1-CH3                3-H                             4-COOC2H5                  5-SCH2CH2CH＝CF2IX.35    1-CH3                3-H                             4-COOC2H5                  5-SOCH2CH2CH＝CF2IX.36    1-CH3            3-H                     4-COOC2H5                 5-SO2CH2CH2CH＝CF2IX.37    1-CH3            3-H                     4-COOCH(CH3)2             5-SCH2CH2CH＝CF2IX.38    1-CH3            3-H                     4-COOCH(CH3)2             5-SOCH2CH2CH＝CF2IX.39    1-CH3            3-H                     4-COOCH(CH3)2             5-SO2CH2CH2CH＝CF2IX.40    1-CH3            3-H                     4-COOH                    5-SCH2CH2CH＝CF2IX.41    1-CH3            3-H                     4-COOH                    5-SOCH2CH2CH＝CF2IX.42    1-CH3            3-H                     4-COOH                    5-SO2CH2CH2CH＝CF2IX.43    1-CH3            3-H                     4-CONH2                   5-SCH2CH2CH＝CF2IX.44    1-CH3            3-H                     4-CONH2                   5-SOCH2CH2CH＝CF2IX.45    1-CH3            3-H                     4-CONH2                   5-SO2CH2CH2CH＝CF2IX.46    1-CH3            3-H                     4-CN                      5-SCH2CH2CH＝CF2IX.47    1-CH3            3-H                     4-CN                      5-SOCH2CH2CH＝CF2IX.48    1-CH3            3-H                     4-CN                      5-SO2CH2CH2CH＝CF2IX.49    1-CH3            3-H                     4-SO2F                    5-SCH2CH2CH＝CF2IX.50    1-CH3            3-H                     4-SO2F                    5-SOCH2CH2CH＝CF2IX.51    1-CH3            3-H                     4-SO2F                    5-SO2CH2CH2CH＝CF2IX.52    1-CH3            3-H                     4-SO2NH2                  5-SCH2CH2CH＝CF2IX.53    1-CH3            3-H                     4-SO2NH 2                 5-SOCH2CH2CH＝CF2IX.54    1-CH3            3-H                     4-SO2NH2                  5-SO2CH2CH2CH＝CF2IX.55    1-CH3            3-CH3                   4-H                       5-SCH2CH2CH＝CF2IX.56    1-CH3            3-CH3                   4-H                       5-SOCH2CH2CH＝CF2IX.57    1-CH3            3-CH3                   4-H                       5-SO2CH2CH2CH＝CF2IX.58   1-CH3              3-CH3                       4-Cl                   5-SCH2CH2CH＝CF2IX.59   1-CH3              3-CH3                       4-Cl                   5-SOCH2CH2CH＝CF2IX.60   1-CH3              3-CH3                       4-Cl                   5-SO2CH2CH2CH＝CF2IX.61   1-CH3              3-CH3                       4-I                    5-SCH2CH2CH＝CF2IX.62   1-CH3              3-CH3                       4-I                    5-SOCH2CH2CH＝CF2IX.63   1-CH3              3-CH3                       4-I                    5-SO2CH2CH2CH＝CF2IX.64   1-CH3              3-CH3                       4-COOC2H5              5-SCH2CH2CH＝CF2IX.65   1-CH3              3-CH3                       4-COOC2H5              5-SOCH2CH2CH＝CF2IX.66   1-CH3              3-CH3                       4-COOC2H5              5-SO2CH2CH2CH＝CF2IX.67   1-CH3              3-CH3                       4-COOH                 5-SCH2CH2CH＝CF2IX.68   1-CH3              3-CH3                       4-COOH                 5-SOCH2CH2CH＝CF2IX.69   1-CH3              3-CH3                       4-COOH                 5-SO2CH2CH2CH＝CF2IX.70   1-CH3              3-CH3                       4-CONH2                5-SCH2CH2CH＝CF2IX.71   1-CH3              3-CH3                       4-CONH2                5-SOCH2CH2CH＝CF2IX.72   1-CH3              3-CH3                       4-CONH2                5-SO2CH2CH2CH＝CF2IX.73   1-CH3              3-CH3                       4-CN                   5-SCH2CH2CH＝CF2IX.74   1-CH3              3-CH3                       4-CN                   5-SOCH2CH2CH＝CF2IX.75   1-CH3              3-CH3                       4-CN                   5-SO2CH2CH2CH＝CF2IX.76   1-CH3              3-CH3                       4-SO2F                 5-SCH2CH2CH＝CF2IX.77   1-CH3              3-CH3                       4-SO2F                 5-SOCH2CH2CH＝CF2IX.78   1-CH3              3-CH3                       4-SO2F                 5-SO2CH2CH2CH＝CF2IX.79   1-CH3              3-CH3                       4-SO2NH2               5-SCH2CH2CH＝CF2IX.80   1-CH3              3-CH3                       4-SO2NH2                   5-SOCH2CH2CH＝CF2IX.81   1-CH3              3-CH3                       4-SO2NH2                   5-SO2CH2CH2CH＝CF2IX.82   1-CH3              3-CH3                       4-NO2                      5-SCH2CH2CH＝CF2IX.83   1-CH3              3-CH3                       4-NO2                      5-SOCH2CH2CH＝CF2IX.84   1-CH3              3-CH3                       4-NO2                      5-SO2CH2CH2CH＝CF2IX.85   1-CH3              3-CF3                       4-H                        5-SCH2CH2CH＝CF2IX.86   1-CH3              3-CF3                       4-H                        5-SOCH2CH2CH＝CF2IX.87   1-CH3              3-CF3                       4-H                        5-SO2CH2CH2CH＝CF2IX.88   1-CH3              3-C6H5                      4-H                        5-SCH2CH2CH＝CF2IX.89   1-CH3              3-C6H5                      4-H                        5-SOCH2CH2CH＝CF2IX.90   1-CH3              3-C6H5                      4-H                        5-SO2CH2CH2CH＝CF2IX.91   1-CH3              3-C6H5                      4-CN                       5-SCH2CH2CH＝CF2IX.92   1-CH3              3-C6H5                      4-CN                       5-SOCH2CH2CH＝CF2IX.93   1-CH3              3-C6H5                      4-CN                       5-SO2CH2CH2CH＝CF2IX.94   1-CH3              3-SCH2CH2CH＝CF2            4-CN                       5-HIX.95   1-CH3              3-SOCH2CH2CH＝CF2           4-CN                       5-HIX.96   1-CH3              3-SO2CH2CH2CH＝CF2          4-CN                       5-HIX.97   1-CH3              3-SCH2CH2CH＝CF2            4-H                        5-ClIX.98   1-CH3              3-SOCH2CH2CH＝CF2           4-H                        5-ClIX.99   1-CH3              3-SO2CH2CH2CH＝CF2          4-H                        5-ClIX.100  1-CH3              3-SCH2CH2CH＝CF2            4-H                        5-CNIX.101  1-CH3              3-SOCH2CH2CH＝CF2           4-H                        5-CNIX.102  1-CH3           3-SO2CH2CH2CH＝CF2     4-H                     5-CNIX.103  1-CH3           3-SCH2CH2CH＝CF2       4-H                     5-COOC2H5IX.104  1-CH3           3-SOCH2CH2CH＝CF2      4-H                     5-COOC2H5IX.105  1-CH3           3-SO2CH2CH2CH＝CF2     4-H                     5-COOC2H5IX.106  1-CH3           3-SCH2CH2CH＝CF2       4-H                     5-CF3IX.107  1-CH3           3-SOCH2CH2CH＝CF2      4-H                     5-CF3IX.108  1-CH3           3-SO2CH2CH2CH＝CF2     4-H                     5-CF3IX.109  1-CH2COOH       3-SCH2CH2CH＝CF2       4-H                     5-CH3IX.110  1-CH2COOH       3-SOCH2CH2CH＝CF2      4-H                     5-CH3IX 111  1-CH2COOH       3-SO2CH2CH2CH＝CF2     4-H                     5-CH3IX.112  1-CH2COOC2H5    3-SCH2CH2CH＝CF2       4-H                     5-C6H5IX.113  1-CH2COOC2H5    3-SOCH2CH2CH＝CF2      4-H                     5-C6H5IX.114  1-CH2COOC2H5    3-SO2CH2CH2CH＝CF2     4-H                     5-C6H5IX.115  1-CH2CN         3-SCH2CH2CH＝CF2       4-H                     5-(2-Thienyl)IX.116  1-CH2CN         3-SOCH2CH2CH＝CF2      4-H                     5-(2-Thienyl)IX.117  1-CH2CN         3-SO2CH2CH2C＝CF2      4-H                     5-(2-Thienyl)IX.118  1-C6H5          3-H                    4-H                     5-SCH2CH2CH＝CF2IX.119  1-C6H5          3-H                    4-H                     5-SOCH2CH2CH＝CF2IX.120  1-C6H5          3-H                    4-H                     5-SO2CH2CH2CH＝CF2IX.121  1-C6H5          3-H                    4-CN                    5-SCH2CH2CH＝CF2IX.122  1-C6H5          3-H                    4-CN                    5-SOCH2CH2CH＝CF2IX.123  1-C6H5          3-H                    4-CN                    5-SO2CH2CH2CH＝CF2IX.124  1-C6H5             3-H                     4-COOC2H5                5-SCH2CH2CH＝CF2IX.125  1-C6H5             3-H                     4-COOC2H5                5-SOCH2CH2CH＝CF2IX.126  1-C6H5             3-H                     4-COOC2H5                5-SO2CH2CH2CH＝CF2IX.127  1-C6H5             3-H                     4-COOH                   5-SCH2CH2CH＝CF2IX.128  1-C6H5             3-H                     4-COOH                   5-SOCH2CH2CH＝CF2IX.129  1 C6H5             3-H                     4-COOH                   5-SO2CH2CH2CH＝CF2IX.130  1-C6H5             3-H                     4-Cl                     5-SCH2CH2CH＝CF2IX.131  1-C6H5             3-H                     4-Cl                     5-SOCH2CH2CH＝CF2IX.132  1-C6H5             3-H                     4-Cl                     5-SO2CH2CH2CH＝CF2IX.133  1-C6H5             3-H                     4-SO2F                   5-SCH2CH2CH＝CF2IX.134  1-C6H5             3-H                     4-SO2F                   5-SOCH2CH2CH＝CF2IX.135  1-C6H5             3-H                     4-SO2F                   5-SO2CH2CH2CH＝CF2IX.136  1-C6H5             3-CH3                   4-H                      5-SCH2CH2CH＝CF2IX.137  1-C6H5             3-CH3                   4-H                      5-SOCH2CH2CH＝CF2IX.138  1-C6H5             3-CH3                   4-H                      5-SO2CH2CH2CH＝CF2IX.139  1-C6H5             3-CH3                   4-CN                     5-SCH2CH2CH＝CF2IX.140  1-C6H5             3-CH3                   4-CN                     5-SOCH2CH2CH＝CF2IX.141  1-C6H5             3-CH3                   4-CN                     5-SO2CH2CH2CH＝CF2IX.142  1-C6H5             3-CH3                   4-COOC2H5                5-SCH2CH2CH＝CF2IX.143  1-C6H5             3-CH3                   4-COOC2H5                5-SOCH2CH2CH＝CF2IX.144  1-C6H5             3-CH3                   4-COOC2H5                5-SO2CH2CH2CH＝CF2IX.145  1-C6H5             3-CH3                   4-COOH                   5-SCH2CH2CH＝CF2IX.146   1-C6H5               3-CH3                           4-COOH                   5-SOCH2CH2CH＝CF2IX.147   1-C6H5               3-CH3                           4-COOH                   5-SO2CH2CH2CH＝CF2IX.148   1-C6H5               3-CH3                           4-Cl                     5-SCH2CH2CH＝CF2IX.149   1-C6H5               3-CH3                           4-Cl                     5-SOCH2CH2CH＝CF2IX.150   1-C6H5               3-CH3                           4-Cl                     5-SO2CH2CH2CH＝CF2IX.151   1-C6H5               3-CH3                           4-SO2F                   5-SCH2CH2CH＝CF2IX.152   1-C6H5               3-CH3                           4-SO2F                   5-SOCH2CH2CH＝CF2IX.153   1-C6H5               3-CH3                           4-SO2F                   5-SO2CH2CH2CH＝CF2IX.154   1-C6H5               3-Cl                            4-H                      5-SCH2CH2CH＝CF2IX.155   1-C6H5               3-Cl                            4-H                      5-SOCH2CH2CH＝CF2IX.156   1-C6H5               3-Cl                            4-H                      5-SO2CH2CH2CH＝CF2IX.157   1-C6H5               3-COOC2H5                       4-H                      5-SCH2CH2CH＝CF2IX.158   1-C6H5               3-COOC2H5                       4-H                      5-SOCH2CHC2CH＝CF2IX.159   1-C6H5               3-COOC2H5                       4-H                      5-SO2CH2CH2CH＝CF2IX.160   1-C6H5               3-COOH                          4-H                      5-SCH2CH2CH＝CF2IX.161   1-C6H5               3-COOH                          4-H                      5-SOCH2CH2CH＝CF2IX.162   1-C6H5               3-COOH                          4-H                      5-SO2CH2CH2CH＝CF2IX.163   1-C6H5               3-CONH2                         4-H                      5-SCH2CH2CH＝CF2IX.164   1-C6H5               3-CONH2                         4-H                      5-SOCH2CH2CH＝CF2IX.165   1-C6H5               3-CONH2                         4-H                      5-SO2CH2CH2CH＝CF2IX.166   1-C6H5               3-CN                            4-H                      5-SCH2CH2CH＝CF2IX.167   1-C6H5               3-CN                            4-H                      5-SOCH2CH2CH＝CF2IX.168     1-C6H5                          3-CN                       4-H                     5-SO2CH2CH2CH＝CF2IX.169     1-C6H5                          3-SO2F                     4-H                     5-SCH2CH2CH＝CF2IX.170     1-C6H5                          3-SO2F                     4-H                     5-SOCH2CH2CH＝CF2IX.171     1-C6H5                          3-SO2F                     4-H                     5-SO2CH2CH2CH＝CF2IX.172     1-C6H5                          3-SO2NH2                   4-H                     5-SCH2CH2CH＝CF2IX.173     1-C6H5                          3-SO2NH2                   4-H                     5-SOCH2CH2CH＝CF2IX.174     1-C6H5                          3-SO2NH2                   4-H                     5-SO2CH2CH2CH＝CF2IX.175     1-CH3                           3-H                        4-SCH2CH2CH＝CF2        5-CNIX.176     1-CH3                           3-H                        4-SOCH2CH2CH＝CF2       5-CNIX.177     1-CH3                           3-H                        4-SO2CH2CH2C＝CF2       5-CNIX.178     1-CH3                           3-H                        4-SCH2CH2CH＝CF2        5-COOC2H5IX.179     1-CH3                           3-H                        4-SOCH2CH2CH＝CF2       5-COOC2H5IX.180     1-CH3                           3-H                        4-SO2CH2CH2C＝CF2       5-COOC2H5IX.181     1-CH3                           3-H                        4-SCH2CH2CH＝CF2        5-CF3IX.182     1-CH3                           3-H                        4-SOCH2CH2CH＝CF2       5-CF3IX.183     1-CH3                           3-H                        4-SO2CH2CH2CH＝CF2      5-CF3IX.184     1-CH3                           3-CN                       4-SCH2CH2CH＝CF2        5-HIX.185     1-CH3                           3-CN                       4-SOCH2CH2CH＝CF2       5-HIX.186     1-CH3                           3-CN                       4-SO2CH2CH2CH＝CF2      5-HIX.187     1-CH3                           3-COOC2H5                  4-SCH2CH2CH＝CF2        5-HIX.188     1-CH3                           3-COOC2H5                  4-SOCH2CH2CH＝CF2       5-HIX.189     1-CH3                           3-COOC2H5                  4-SO2CH2CH2CH＝CF2      5-HIX.190   1-CH3                3-CF3                           4-SCH2CH2CH＝CF2       5-HIX.191   1-CH3                3-CF3                           4-SOCH2CH2CH＝CF2      5-HIX.192   1-CH3                3-CF3                           4-SO2CH2CH2CH＝CF2     5-H本发明式(X)化合物的实例如表X所示。    ention are set 表XNo.                R3                 R5X.1                3-c-C3H5           5-SCH2CH2CH＝CF2X.2                3-C≡CH            5-SCH2CH2CH＝CF2X.3                3-C6H5             5-SCH2CH2CH＝CF2X.4                3-C6H5             5-SOCH2CH2CH＝CF2X.5                3-C6H5             5-SO2CH2CH2CH＝CF2X.6                3-CF2H             5-SCH2CH2CH＝CF2X.7                3-CF3              5-SCH2CH2CH＝CF2X.8                3-CH(CH3)2         5-SCH2CH2CH＝CF2X.9                3-CH＝CH2          5-SCH2CH2CH＝CF2X.10               3-CH2Br            5-SCH2CH2CH＝CF2X.11               3-CF2C6H5          5-SCH2CH2CH＝CF2X.12               3-CH2C6H5          5-SOCH2CH2CH＝CF2X.13               3-CH2CF3           5-SCH2CH2CH＝CF2X.14               3-CH2CF3           5-SOCH2CH2CH＝CF2X.15               3-CH2CF3           5-SO2CH2CH2CH＝CF2X.16               3-CH2CH＝CH2       5-SCH2CH2CH＝CF2X.17               3-CH2CH2F          5-SCH2CH2CH＝CF2X.18               3-CH2CH3           5-SCH2CH2CH＝CF2X.19               3-CH2CN            5-SCH2CH2CH＝CF2X.20               3-CH2CN            5-SOCH2CH2CH＝CF2X.21               3-CH2CONH2         5-SCH2CH2CH＝CF2X.22               3-CH2COOCH2CH3     5-SCH2CH2CH＝CF2X.23               3-CH2N(CH3)2       5-SCH2CH2CH＝CF2X.24               3-CH2NHCOCH3       5-SCH2CH2CH＝CF2X.25               3-CH2NHCOOCH3      5-SCH2CH2CH＝CF2X.26               3-CH2OCH3          5-SCH2CH2CH＝CF2X.27               3-CH2OCH3          5-SO2CH2CH2CH＝CF2X.28               3-CH2OH                                  5-SCH2CH2CH＝CF2X.29               3-CH2OH                                  5-SOCH2CH2CH＝CF2X.30               3-CH2SO2C6H5                             5-SCH2CH2CH＝CF2X.31               3-CH2SO2C6H5                             5-SO2CH2CH2CH＝CF2X.32               3-CH3                                    5-SCH2CH2CH＝CF2X.33               3-CH3                                    5-SOCH2CH2CH＝CF2X.34               3-CH3                                    5-SO2CH2CH2CH＝CF2X.35               3-COC6H5                                 5-SCH2CH2CH＝CF2X.36               3-COCH3                                  5-SCH2CH2CH＝CF2X.37               3-CON(CH3)2                              5-SCH2CH2CH＝CF2X.38               3-CONH2                                  5-SCH2CH2CH＝CF2X.39               3-CONHCH2C6H5                            5-SCH2CH2CH＝CF2X.40               3-CONHCH2C6H5                            5-SOCH2CH2CH＝CF2X.41               3-CONHCH2CH2CH＝CF2                      5-SCH2CH2CH＝CF2X.42               3-CONHCH3                                5-SCH2CH2CH＝CF2X.43               3-CONHSO2CH3                             5-SCH2CH2CH＝CF2X.44               3-COOC6H5                                5-SCH2CH2CH＝CF2X.45               3-COOC6H5                                5-SOCH2CH2CH＝CF2X.46               3-COOC6H5                                5-SO2CH2CH2CH＝CF2X.47               3-COOCH2CH2CH＝CF2                       5-SCH2CH2CH＝CF2X.48               3-COOCH2CH2CH＝CF2                       5-SOCH2CH2CH＝CF2X.49               3-COOCH2CH2CH＝CF2                       5-SO2CH2CH2CH＝CF2X.50               3-COOCH2CH2F                             5-SCH2CH2CH＝CF2X.51               3-COOCH3                                 5-SCH2CH2CH＝CF2X.52               3-COOH                                   5-SCH2CH2CH＝CF2X.53               3-COSCH2CH2CH＝CF2                       5-SCH2CH2CH＝CF2X.54               3-CSNH2                                  5-SCH2CH2CH＝CF2X.55               3-H                                      5-SCH2CH2CH＝CF2X.56               3-H                                      5-OCH2CH2CH＝CF2X.57               3-H                                      5-SO2CH2CH2CH＝CF2X.58               3-N(SO2CH3)2                             5-SCH2CH2CH＝CF2X.59               3-NHCH2CH3                               5-SCH2CH2CH＝CF2X.60               3-NHCHO                                  5-SCH2CH2CH＝CF2X.61       3-NHCOOCH3              5-SCH2CH2CH＝CF2X.62       3-NHCOCF3               5-SCH2CH2CH＝CF2X.63       3-NHCOCF3               5-SOCH2CH2CH＝CF2X.64       3-NHCOCH3               5-SCH2CH2CH＝CF2X.65       3-NHCOCH3               5-SO2CH2CH2CH＝CF2X.66       3-NHCSCH2CH3            5-SCH2CH2CH＝CF2X.67       3-NHCSNHCH2CH3          5-SCH2CH2CH＝CF2X.68       3-NHSO2CH3              5-SCH2CH2CH＝CF2X.69       3-OCF2CF2H              5-SCH2CH2CH＝CF2X.70       3-OF3                   5-SCH2CH2CH＝CF2X.71       3-OCF3                  5-SOCH2CH2CH＝CF2X.72       3-OCH2C6H5              5-SCH2CH2CH＝CF2X.73       3-OCH2C6H5              5-SO2CH2CH2CH＝CF2X.74       3-OCH2CF3               5-SCH2CH2CH＝CF2X.75       3-OCH2CF3               5-SOCH2CH2CH＝CF2X.76       3-OCH2CF3               5-SO2CH2CH2CH＝CF2X.77       3-OCH2CH＝CC12          5-SCH2CH2CH＝CF2X.78       3-OCH2CH2CH＝CF2        5-SCH2CH2CH＝CF2X.79       3-OCH2CH2CH＝CF2        5-SOCH2CH2CH＝CF2X.80       3-OCH2CH2CH＝CF2        5-SO2CH2CH2CH＝CF2X.81       3-OCH2CH2F              5-SCH2CH2CH＝CF2X.82       3-OCH2COOH              5-SCH2CH2CH＝CF2X.83       3-OCH3                  5-SCH2CH2CH＝CF2X.84       3-OCOC6H5               5-SCH2CH2CH＝CF2X.85       3-OCOCH3                5-SCH2CH2CH＝CF2X.86       3-OC6H5                 5-SCH2CH2CH＝CF2X.87       3-OC6H5                 5-SOCH2CH2CH＝CF2X.88       3-OC6H5                 5-SO2CH2CH2CH＝CF2X.89       3-OSO2CH3               5-SCH2CH2CH＝CF2X.90       3-OSO2CH3               5-SOCH2CH2CH＝CF2X.91       3-SCF3                  5-SCH2CH2CH＝CF2X.92       3-SCH2CH2CH＝CF2        5-C6H5X.93       3-SOCH2CH2CH＝CF2       5-C6H5X.94       3-SO2CH2CH2CH＝CF2               5-C6H5X.95       3-SCH2CH2CH＝CF2                 5-CF2HX.96       3-SCH2CH2CH＝CF2                 5-CF3X.97       3-SCH2CH2CH＝CF2                 5-CH2C6H5X.98       3-SOCH2CH2CH＝CF2                5-CH2C6H5X.99       3-SCH2CH2CH＝CF2                 5-CH2CF3X.100      3-SCH2CH2CH＝CF2                 5-CH2CH2FX.101      3-SCH2CH2CH＝CF2                 5-CH2ClX.102      3-SCH2CH2CH＝CF2                 5-CH2CNX.103      3-SCH2CH2CH＝CF2                 5-CH2OCH3X.104      3-SCH2CH2CH＝CF2                 5-CH2OHX.105      3-SCH2CH2CH＝CF2                 5-CH3X.106      3-SO2CH2CH2CH＝CF2               5-CH3X.107      3-SCH2CH2CH＝CF2                 5-ClX.108      3-SCH2CH2CH＝CF2                 5-CNX.109      3-SCH2CH2CH＝CF2                 5-CON(CH3)2X.110      3-SCH2CH2CH＝CF2                 5-COOCH2CH2CH＝CF2X 111      3-SCH2CH2CH＝CF2                 5-COOCH2CH2FX.112      3-SCH2CH2CH＝CF2                 5-COOCH3X.113      3-SCH2CH2CH＝CF2                 5-FX.114      3-SCH2CH2CH＝CF2                 5-HX.115      3-SCH2CH2CH＝CF2                 5-N(SO2CH3)2X.116      3-SCH2CH2CH＝CF2                 5-NHCHOX.117      3-SCH2CH2CH＝CF2                 5-NHCOCF3X.118      3-SCH2CH2CH＝CF2                 5-NHCOOCH3X.119      3-SCH2CH2CH＝CF2                 5-NHSO2CH3X.120      3-SCH2CH2CH＝CF2                 5-NO2X.121      3-SCH2CH2CH＝CF2                 5-OC6H5X.122      3-SCH2CH2CH＝CF2                 5-OCF2HX.123      3-SCH2CH2CH＝CF2                 5-OCF3X 124      3-SCH2CH2CH＝CF2                 5-OCH2CF3X.125      3-SOCH2CH2CH＝CF2                5-OCH2CF3X.126      3-SO2CH2CH2CH＝CF2               5-OCH2CF3X.127    3-SCH2CH2CH＝CF2      5-OCOCH3X.128    3-SCH2CH2CH＝CF2      5-OSO2CH3X.129    3-SCH2CH2CH＝CF2      5-SCH2CH2CH＝CF2X.130    3-SOCH2CH2CH＝CF2     5-SCH2CH2CH＝CF2X.131    3-SO2CH2CH2CH＝CF2    5-SCH2CH2CH＝CF2X.132    3-SCH2CH2CH＝CF2      5-SCH3X.133    3-SCH2CH2CH＝CF2      5-SO2CF3X.134    3-SOCH2CH2CH＝CF2     5-SO2CH2CH2CH＝CF2X.135    3-SO2CH2CH2CH＝CF2    5-SO2CH2CH2CH＝CF2X.136    3-SCH2CH2CH＝CF2      5-SO2CH3X.137    3-SO2CH2CH2CH＝CF2    5-SO2CH3X.138    3-SCH2CH2CH＝CF2      5-SO2N(CH3)2X.139    3-SCH2CH2CH＝CF2      5-SOCF3X.140    3-SOCH2CH2CH＝CF2     5-SOCH2CH2CH＝CF2X.141    3-SCH3                5-SCH2CH2CH＝CF2X.142    3-SO2CF3              5-SCH2CH2CH＝CF2X.143    3-SO2CF3              5-SO2CH2CH2CH＝CF2X.144    3-SO2CH3              5-SCH2CH2CH＝CF2X.145    3-SO2N(CH3)2          5-SCH2CH2CH＝CF2X.146    3-SO2NH2              5-SCH2CH2CH＝CF2X.147    3-SO2NHCH3            5-SCH2CH2CH＝CF2X.148    3-SO2NHCH3            5-SO2CH2CH2CH＝CF2X.149    3-SOCF3               5-SCH2CH2CH＝CF2X.150    3-SOCF3               5-SOCH2CH2CH＝CF2X.151    3-SOCH3               5-SCH2CH2CH＝CF2X.152    3-SOCH3               5-SO2CH2CH2CH＝CF2X.153    3-(4-CF3-C6H4)        5-SCH2CH2CH＝CF2X.154    3-(4-CF3-C6H4)        5-SO2CH2CH2CH＝CF2X.155    3-(4-CH3-C6H4)        5-SCH2CH2CH＝CF2X.156    3-(4-CN-C6H4)         5-SCH2CH2CH＝CF2X.157    3-(4-CONH2-C6H4)      5-SCH2CH2CH＝CF2X.158    3-(4-CONH2-C6H4)      5-SO2CH2CH2CH＝CF2X.159    3-(4-NO2-C6H4)        5-SCH2CH2CH＝CF2X.160    3-(4-OCH3-C6H4)    5-SCH2CH2CH＝CF2本发明式(XI)化合物的实例如表XI所示。
                  表XINo.                R3                                         R5XI.1               3-Br                                       5-SCH2CH2CH＝CF2XI.2               3-c-C5H9                                   5-SCH2CH2CH＝CF2XI.3               3-c-C5H9                                   5-SOCH2CH2CH＝CF2XI.4               3-C≡CH                                    5-SCH2CH2CH＝CF2XI.5               3-C6H5                                     5-SCH2CH2CH＝CF2XI.6               3-C6H5                                     5-SOCH2CH2CH＝CF2XI.7               3-C6H5                                     5-SO2CH2CH2CH＝CF2XI.8               3-CF2H                                     5-SCH2CH2CH＝CF2XI.9               3-CF3                                      5-SCH2CH2CH＝CF2XI.10              3-CH＝CH2                                  5-SCH2CH2CH＝CF2XI.11              3-CH＝CHCH3                                5-SCH2CH2CH＝CF2XI.12              3-CH＝CHCN                                 5-SCH2CH2CH＝CF2XI.13              3-CH＝CHNO2                                5-SCH2CH2CH＝CF2XI.14              3-CH＝NOCH3                                5-SCH2CH2CH＝CF2XI.15              3-CH2(3-CF3-C6H4)                          5-SCH2CH2CH＝CF2XI.16              3-CH2(3-CF3-C6H4)                          5-SCH2CH2CH＝CF2XI.17              3-CH2C6H5                                  5-SCH2CH2CH＝CF2XI.18              3-CH2C6H5                                  5-SOCH2CH2CH＝CF2XI.19              3-CH2C6H5                                  5-SO2CH2CH2CH＝CF2XI.20              3-CH2CF3                                   5-SCH2CH2CH＝CF2XI.21              3-CH2CF3                                   5-SOCH2CH2CH＝CF2XI.22              3-CH2CH＝CH2                               5-SCH2CH2CH＝CF2XI.23              3-CH2CH3                                   5-SCH2CH2CH＝CF2XI.24              3-CH2CH3                                   5-SO2CH2CH2CH＝CF2XI.25              3-CH2Cl                                    5-SCH2CH2CH＝CF2XI.26              3-CH2CN                 5-SCH2CH2CH＝CF2XI.27              3-CH2CONH2              5-SCH2CH2CH＝CF2XI.28              3-CH2N(CH3)2            5-SCH2CH2CH＝CF2XI.29              3-CH2NHCOCH3            5-SCH2CH2CH＝CF2XI.30              3-CH2OCH2CH2CH2CH3      5-SCH2CH2CH＝CF2XI.31              3-CH2OCH2CH2CH3         5-SCH2CH2CH＝CF2XI.32              3-CH2OCH2CH3            5-SCH2CH2CH＝CF2XI.33              3-CH2OCH2CH3            5-SOCH2CH2CH＝CF2XI.34              3-CH2OCH3               5-SCH2CH2CH＝CF2XI.35              3-CH2OCH3               5-SOCH2CH2CH＝CF2XI.36              3-CH2OCH3               5-SO2CH2CH2CH＝CF2XI.37              3-CH2OH                 5-SCH2CH2CH＝CF2XI.38              3-CH2SCH2CH2CH＝CF2     5-SCH2CH2CH＝CF2XI.39              3-CH2SO2C6H5            5-SCH2CH2CH＝CF2XI.40              3-CH3                   5-SCH2CH2CH＝CF2XI.41              3-CH3                   5-SOCH2CH2CH＝CF2XI.42              3-CH3                   5-SO2CH2CH2CH＝CF2XI.43              3-Cl                    5-SCH2CH2CH＝CF2XI.44              3-Cl                    5-SO2CH2CH2CH＝CF2XI.45              3-CN                    5-SCH2CH2CH＝CF2XI.46              3-COC6H5                5-SCH2CH2CH＝CF2XI.47              3-COCH3                 5-SCH2CH2CH＝CF2XI.48              3-CON(CH3)2             5-SCH2CH2CH＝CF2XI.49              3-CON(CH3)C2H5          5-SCH2CH2CH＝CF2XI.50              3-CONH2                 5-SCH2CH2CH＝CF2XI.51              3-CONHCH2C6H5           5-SCH2CH2CH＝CF2XI.52              3-CONHCH2CH2CH＝CF2     5-SCH2CH2CH＝CF2XI.53              3-CONHCH2CH2CH3         5-SCH2CH2CH＝CF2XI.54              3-CONHCH3               5-SCH2CH2CH＝CF2XI.55              3-CONHCH3               5-SOCH2CH2CH＝CF2XI.56              3-CONHCH3               5-SO2CH2CH2CH＝CF2XI.57              3-CONHSO2CH3            5-SCH2CH2CH＝CF2XI.58              3-COOC6H5               5-SCH2CH2CH＝CF2XI.59              3-COOCH2CH2CH＝CF2       5-SCH2CH2CH＝CF2XI.60              3-COOCH2CH2F             5-SCH2CH2CH＝CF2XI.61              3-COOCH2CH3              5-SCH2CH2CH＝CF2XI.62              3-COOCH3                 5-SCH2CH2CH＝CF2XI.63              3-COOH                   5-SCH2CH2CH＝CF2XI.64              3-COSCH2CH2CH＝CF2       5-SCH2CH2CH＝CF2XI.65              3-CSNH2                  5-SCH2CH2CH＝CF2XI.66              3-F                      5-SCH2CH2CH＝CF2XI.67              3-H                      5-SCH2CH2CH＝CF2XI.68              3-H                      5-SOCH2CH2CH＝CF2XI.69              3-H                      5-SO2CH2CH2CH＝CF2XI.70              3-N(SO2CH3)2             5-SCH2CH2CH＝CF2XI.71              3-NHCHO                  5-SCH2CH2CH＝CF2XI.72              3-NHCOC2H5               5-SCH2CH2CH＝CF2XI.73              3-NHCOCF3                5-SCH2CH2CH＝CF2XI.74              3-NHCOCH3                5-SCH2CH2CH＝CF2XI.75              3-NHCSCH2CH3             5-SCH2CH2CH＝CF2XI.76              3-NHCSNHCH2CH3           5-SCH2CH2CH＝CF2XI.77              3-NHSO2CH3               5-SCH2CH2CH＝CF2XI.78              3-NO2                    5-SCH2CH2CH＝CF2XI.79              3-OC6H5                  5-SCH2CH2CH＝CF2XI.80              3-OCF2CF2H               5-SCH2CH2CH＝CF2XI.81              3-OCF2H                  5-SCH2CH2CH＝CF2XI.82              3-OCF3                   5-SCH2CH2CH＝CF2XI.83              3-OCH2CF3                5-SCH2CH2CH＝CF2XI.84              3-OCH2CF3                5-SOCH2CH2CH＝CF2XI.85              3-OCH2CF3                5-SO2CH2CH2CH＝CF2XI.86              3-OCH2CH＝CC12           5-SCH2CH2CH＝CF2XI.87              3-OCH3                   5-SCH2CH2CH＝CF2XI.88              3-OCOC2H5                5-SCH2CH2CH＝CF2XI.89              3-OCOC6H5                5-SCH2CH2CH＝CF2XI.90              3-OCOCH3                 5-SCH2CH2CH＝CF2XI.91              3-OSO2CH3                5-SCH2CH2CH＝CF2XI.92              3-SCF3                           5-SCH2CH2CH＝CF2XI.93              3-SCH2CH2CH＝CF2                 5-CF3XI.94              3-SCH2CH2CH＝CF2                 5-CH2C6H5XI.95              3-SCH2CH2CH＝CF2                 5-CH2CF3XI.96              3-SCH2CH2CH＝CF2                 5-CH2CH＝CH2XI.97              3-SCH2CH2CH＝CF2                 5-CH2CNXI.98              3-SCH2CH2CH＝CF2                 5-CH2CONH2XI.99              3-SCH2CH2CH＝CF2                 5-CH2NHCOCH3XI.100             3-SCH2CH2CH＝CF2                 5-CH2OCH3XI.101             3-SCH2CH2CH＝CF2                 5-CH3XI.102             3-SCH2CH2CH＝CF2                 5-ClXI.103             3-SCH2CH2CH＝CF2                 5-CNXI.104             3-SCH2CH2CH＝CF2                 5-COOCH3XI.105             3-SCH2CH2CH＝CF2                 5-NHCHOXI.106             3-SCH2CH2CH＝CF2                 5-OC6H5XI.107             3-SCH2CH2CH＝CF2                 5-OCH2CF3XI.108             3-SCH2CH2CH＝CF2                 5-OCH3XI.109             3-SCH2CH2CH＝CF2                 5-SCH2CH2CH＝CF2XI.110             3-SCH3                           5-SCH2CH2CH＝CF2XI.111             3-SO2C2H5                        5-SCH2CH2CH＝CF2XI.112             3-SO2CF3                         5-SCH2CH2CH＝CF2XI.113             3-SO2CH2CH2CH＝CF2               5-OCH2CF3XI.114             3-SO2CH2CH2CH＝CF2               5-SCH2CH2CH＝CF2XI.115             3-SO2CH2CH2CH＝CF2               5-SOCH2CH2CH＝CF2XI.116             3-SO2F                           5-SCH2CH2CH＝CF2XI.117             3-SO2N(CH3)2                     5-SCH2CH2CH＝CF2XI.118             3-SO2NH2                         5-SCH2CH2CH＝CF2XI.119             3-SO2NHCH3                       5-SCH2CH2CH＝CF2XI.120             3-SOCF3                          5-SCH2CH2CH＝CF2XI.121             3-SOCH2CH2CH＝CF2                5-CH2CNXI.122             3-SOCH2CH2CH＝CF2                5-OCH2CF3XI.123             3-SOCH2CH2CH＝CF2                5-SCH2CH2CH＝CF2XI.124             3-SOCH3                          5-SCH2CH2CH＝CF2XI.125           3-(2-Pyrazinyl)                          5-SCH2CH2CH＝CF2XI.126           3-(3-F-C6H4)                             5-SCH2CH2CH＝CF2XI.127           3-(3-NO2-C6H4)                           5-SCH2CH2CH＝CF2XI.128           3-(3-NO2-C6H4)                           5-SOCH2CH2CH＝CF2XI.129           3-(3-NO2-C6H4)                           5-SO2CH2CH2CH＝CF2XI.130           3-(4-F-C6H4)                             5-SCH2CH2CH＝CF2XI.131           3-(4-F-C6H4)                             5-SOCH2CH2CH＝CF2XI.132           3-(4-F-C6H4)                             5-SO2CH2CH2CH＝CF2
本发明式(XII)化合物的实例如表XII所示。
Figure A9519202900561
                表XIINo.         R2                       R5XII.1       2-SCH2CH2CH＝CF2         5-c-C3H5XII.2       2-SCH2CH2CH＝CF2         5-C≡CHXII.3       2-SCH2CH2CH＝CF2         5-C6H5XII.4       2-SOCH2CH2CH＝CF2        5-C6H5XII.5       2-SO2CH2CH2CH＝CF2       5-C6H5XII.6       2-SCH2CH2CH＝CF2         5-CF2HXII.7       2-SCH2CH2CH＝CF2         5-CF3XII.8       2-SCH2CH2CH＝CF2         5-CH(CH3)2XII.9       2-SO2CH2CH2CH＝CF2       5-CH(CH3)2XII.10      2-SCH2CH2CH＝CF2         5-CH＝CH2XII.11      2-SCH2CH2CH＝CF2         5-CH2(2，6-di F -C6H3)XII.12      2-SCH2CH2CH＝CF2         5-CH2(4-NO2-C6H4)XII.13      2-SO2CH2CH2CH＝CF2       5-CH2(4-NO2-C6H4)XII.14      2-SOCH2CH2CH＝CF2        5-CH2(4-OCH3-C6H4)XII.15      2-SO2CH2CH2CH＝CF2       5-CH2(4-OCH3-C6H4)XII.16      2-SCH2CH2CH＝CF2         5-CH2BrXII.17      2-SCH2CH2CH＝CF2         5-CH2C6H5XII.18      2-SOCH2CH2CH＝CF2        5-CH2C6H5XII.19    2-SO2CH2CH2CH＝CF2              5-CH2C6H5XII.20    2-SCH2CH2CH＝CF2                5-CH2CF3XII.21    2-SOCH2CH2CH＝CF2               5-CH2CF3XII.22    2-SO2CH2CH2CH＝CF2              5-CH2CF3XII.23    2-SCH2CH2CH＝CF2                5-CH2CH(CH3)2XII.24    2-SCH2CH2CH＝CF2                5-CH2CH＝CH2XII.25    2-SCH2CH2CH＝CF2                5-CH2CH2CH2CH2CH3XII.26    2-SOCH2CH2CH＝CF2               5-CH2CH2CH2CH2CH3XII.27    2-SO2CH2CH2CH＝CF2              5-CH2CH2CH2CH2CH3XII.28    2-SCH2CH2CH＝CF2                5-CH2CH2CH2CH3XII.29    2-SOCH2CH2CH＝F2                5-CH2CH2CH2CH3XII.30    2-SO2CH2CH2CH＝CF2              5-CH2CH2CH3XII.31    2-SCH2CH2CH＝CF2                5-CH2CH2CH3XII.32    2-SOCH2CH2CH＝CF2               5-CH2CH2CH3XII.33    2-SO2CH2CH2CH＝CF2              5-CH2CH2CH3XII.34    2-SCH2CH2CH＝CF2                5-CH2CH2FXII.35    2-SCH2CH2CH＝CF2                5-CH2CH3XII.36    2-SCH2CH2CH＝CF2                5-CH2CNXII.37    2-SOCH2CH2CH＝CF2               5-CH2CNXII.38    2-SCH2CH2CH＝CF2                5-CH2CONH2XII.39    2-SCH2CH2CH＝CF2                5-CH2COOCH2CH3XII.40    2-SCH2CH2CH＝CF2                5-CH2N(CH3)2XII.41    2-SCH2CH2CH＝CF2                5-CH2NHCOCH3XII.42    2-SCH2CH2CH＝CF2                5-CH2NHCOOCH3XII.43    2-SCH2CH2CH＝CF2                5-CH2OCH3XII.44    2-SO2CH2CH2CH＝CF2              5-CH2OCH3XII.45    2-SCH2CH2CH＝CF2                5-CH2OHXII.46    2-SOCH2CH2CH＝CF2               5-CH2OHXII.47    2-SCH2CH2CH＝CF2                5-CH2SO2C6H5XII.48    2-SO2CH2CH2CH＝CF2              5-CH2SO2C6H5XII.49    2-SCH2CH2CH＝CF2                5-CH3XII.50    2-SOCH2CH2CH＝CF2               5-CH3XII.51    2-SO2CH2CH2CH＝CF2              5-CH3XII.52            2-SCH2CH2CH＝CF2         5-COC6H5XII.53            2-SCH2CH2CH＝CF2         5-COCH3XII.54            2-SCH2CH2CH＝CF2         5-CON(CH3)2XII.55            2-SCH2CH2CH＝CF2         5-CONH2XII.56            2-SCH2CH2CH＝CF2         5-CONHCH2C6H5XII.57            2-SOCH2CH2CH＝CF2        5-CONHCH2C6H5XII.58            2-SCH2CH2CH＝CF2         5-CONHCH2CH2CH＝CF2XII.59            2-SCH2CH2CH＝CF2         5-CONHCH3XII.60            2-SCH2CH2CH＝CF2         5-CONHSO2CH3XII.61            2-SCH2CH2CH＝CF2         5-COOC6H5XII.62            2-SOCH2CH2CH＝CF2        5-COOC6H5XII.63            2-SO2CH2CH2CH＝CF2       5-COOC6H5XII.64            2-SCH2CH2CH＝CF2         5-COOCH2CH2CH＝CF2XII.65            2-SOCH2CH2CH＝CF2        5-COOCH2CH2CH＝CF2XII.66            2-SO2CH2CH2CH＝CF2       5-COOCH2CH2CH＝CF2XII.67            2-SCH2CH2CH＝CF2         5-COOCH2CH2FXII.68            2-SCH2CH2CH＝CF2         5-COOCH2CH3XII.69            2-SCH2CH2CH＝CF2         5-COOCH3XII.70            2-SCH2CH2CH＝CF2         5-COOHXII.71            2-SCH2CH2CH＝CF2         5-COSCH2CH2CH＝CF2XII.72            2-SCH2CH2CH＝CF2         5-CSNH2XII.73            2-SCH2CH2CH＝CF2         5-HXII.74            2-SOCH2CH2CH＝CF2        5-HXII.75            2-SO2CH2CH2CH＝CF2       5-HXII.76            2-SCH2CH2CH＝CF2         5-N(SO2CH3)2XII.77            2-SCH2CH2CH＝CF2         5-NHCH2CH3XII.78            2-SCH2CH2CH＝CF2         5-NHCHOXII.79            2-SCH2CH2CH＝CF2         5-NHCOOCH3XII.80            2-SCH2CH2CH＝CF2         5-NHCOCF3XII.81            2-SOCH2CH2CH＝CF2        5-NHCOCF3XII.82            2-SCH2CH2CH＝CF2         5-NHCOCH3XII.83            2-SO2CH2CH2CH＝CF2       5-NHCOCH3XII.84            2-SCH2CH2CH＝CF2         5-NHCSCH2CH3XII.85            2-SCH2CH2CH＝CF2                   5-NHCSNHCH2CH3XII.86            2-SCH2CH2CH＝CF2                   5-NHSO2CH3XII.87            2-SCH2CH2CH＝CF2                   5-OCF2CF2HXII.88            2-SCH2CH2CH＝CF2                   5-OCF3XII.89            2-SOCH2CH2CH＝CF2                  5-OCF3XII.90            2-SCH2CH2CH＝CF2                   5-OCH2C6H5XII.91            2-SO2CH2CH2CH＝CF2                 5-OCH2C6H5XII.92            2-SCH2CH2CH＝CF2                   5-OCH2CF3XII.93            2-SOCH2CH2CH＝CF2                  5-OCH2CF3XII.94            2-SO2CH2CH2CH＝CF2                 5-OCH2CF3XII.95            2-SCH2CH2CH＝CF2                   5-OCH2CH＝CCl2XII.96            2-SCH2CH2CH＝CF2                   5-OCH2CH2CH＝CF2XII.97            2-SOCH2CH2CH＝CF2                  5-OCH2CH2CH＝CF2XII.98            2-SO2CH2CH2CH＝CF2                 5-OCH2CH2CH＝CF2XII.99            2-SCH2CH2CH＝CF2                   5-OCH2CH2FXII.100           2-SCH2CH2CH＝CF2                   5-OCH2COOHXII.101           2-SCH2CH2CH＝CF2                   5-OCH3XII.102           2-SCH2CH2CH＝CF2                   5-OCOC6H5XII.103           2-SCH2CH2CH＝CF2                   5-OCOCH3XII.104           2-SCH2CH2CH＝CF2                   5-OC6H5XII.105           2-SOCH2CH2CH＝CF2                  5-OC6H5XII.106           2-SO2CH2CH2CH＝CF2                 5-OC6H5XII.107           2-SCH2CH2CH＝CF2                   5-OSO2CH3XII.108           2-SOCH2CH2CH＝CF2                  5-OSO2CH3XII.109           2-SCH2CH2CH＝CF2                   5-SCF3XII.110           2-SCH2CH2CH＝CF2                   5-SCH2CH2CH＝CF2XII.111           2-SCH2CH2CH＝CF2                   5-SCH3XII.112           2-SCH2CH2CH＝CF2                   5-SO2CF3XII.113           2-SO2CH2CH2CH＝CF2                 5-SO2CF3XII.114           2-SCH2CH2CH＝CF2                   5-SO2CH2CH2CH＝CF2XII.115           2-SO2CH2CH2CH＝CF2                 5-SO2CH2CH2CH＝CF2XII.116           2-SCH2CH2CH＝CF2                   5-SO2CH3XII.117           2-SCH2CH2CH＝CF2                   5-SO2N(CH3)2XII.118           2-SCH2CH2CH＝CF2                  5-SO2NH2XII.119           2-SCH2CH2CH＝CF2                  5-SO2NHCH3XII.120           2-SO2CH2CH2CH＝CF2                5-SO2NHCH3XII.121           2-SCH2CH2CH＝CF2                  5-SOCF3XII.122           2-SOCH2CH2CH＝CF2                 5-SOCF3XII.123           2-SCH2CH2CH＝CF2                  5-SOCH2CH2CH＝CF2XII.124           2-SOCH2CH2CH＝CF2                 5-SOCH2CH2CH＝CF2XII.125           2-SO2CH2CH2CH＝CF2                5-SOCH2CH2CH＝CF2XII.126           2-SCH2CH2CH＝CF2                  5-SOCH3XII.127           2-SO2CH2CH2CH＝CF2                5-SOCH3XII.128           2-SCH2CH2CH＝CF2                  5-(2-CH3-C6H4)XII.129           2-SOCH2CH2CH＝CF2                 5-(2-CH3-C6H4)XII.130           2-SO2CH2CH2CH＝CF2                5-(2-CH3-C6H4)XII.131           2-SCH2CH2CH＝CF2                  5-(2-Furyl)XII.132           2-SCH2CH2CH＝CF2                  5-(2-OCH3-C6H4)XII.133           2-SCH2CH2CH＝CF2                  5-(2-Thiophenyl)XII.134           2-SCH2CH2CH＝CF2                  5-(3-Furyl)XII.135           2-SCH2CH2CH＝CF2                  5-(4-CF3-C6H4)XII.136           2-SO2CH2CH2CH＝CF2                5-(4-CF3-C6H4)XII.137           2-SCH2CH2CH＝CF2                  5-(4-CH3-C6H4)XII.138           2-SCH2CH2CH＝CF2                  5-(4-CN-C6H4)XII.139           2-SCH2CH2CH＝CF2                  5-(4-CONH2-C6H4)XII.140           2-SO2CH2CH2CH＝CF2                5-(4-CONH2-C6H4)XII.141           2-SCH2CH2CH＝CF2                  5-(4-NO2-C6H4)XII.142           2-SOCH2CH2CH＝CF2                 5-(4-NO2-C6H4)XII.143           2-SO2CH2CH2CH＝CF2                5-(4-NO2-C6H4)XII.144           2-SCH2CH2CH＝CF2                  5-(4-OCH3-C6H4)XII.145           2-SOCH2CH2CH＝CF2                 5-(4-OCH3-C6H4)XII.146           2-SO2CH2CH2CH＝CF2                5-(4-OCH3-C6H4)XII.147           2-SCH2CH2CH＝CF2                  5-(4-OH-C6H4)XII.148           2-SCH2CH2CH＝CF2                  5-(4-Pyridinyl)
本发明式(XIII)化合物的实例如表XIII所示。
Figure A9519202900611
                    表XIIINo.         R2                                 R5XIII.1      2-SCH2CH2CH＝CF2                   5-BrXIII.2      2-SO2CH2CH2CH＝CF2                 5-BrXIII.3      2-SCH2CH2CH＝CF2                   5-C(CH3)3XIII.4      2-SO2CH2CH2CH＝CF2                 5-C(CH3)3XIII.5      2-SCH2CH2CH＝CF2                   5-C(O)C6H5XIII.6      2-SCH2CH2CH＝CF2                   5-c-C3H5XIII.7      2-SO2CH2CH2CH＝CF2                 5-c-C3H5XIII.8      2-SCH2CH2CH＝CF2                   5-C≡CHXIII.9      2-SCH2CH2CH＝CF2                   5-C6H5XIII.10     2-SOCH2CH2CH＝CF2                  5-C6H5XIII.11     2-SO2CH2CH2CH＝CF2                 5-C6H5XIII.12     2-SCH2CH2CH＝CF2                   5-CF2HXIII.13     2-SOCH2CH2CH＝CF2                  5-CF2HXIII.14     2-SCH2CH2CH＝CF2                   5-CF3XIII.15     2-SO2CH2CH2CH＝CF2                 5-CF3XIII.16     2-SCH2CH2CH＝CF2                   5-CH(CH3)2XIII.17     2-SO2CH2CH2CH＝CF2                 5-CH(CH3)2XIII.18     2-SCH2CH2CH＝CF2                   5-CH＝CH2XIII.19     2-SCH2CH2CH＝CF2                   5-CH2BrXIII.20     2-SCH2CH2CH＝CF2                   5-CH2C6H5XIII.21     2-SOCH2CH2CH＝CF2                  5-CH2C6H5XIII.22     2-SO2CH2CH2CH＝CF2                 5-CH2C6H5XIII.23     2-SCH2CH2CH＝CF2                   5-CH2CF3XIII.24     2-SCH2CH2CH＝CF2                   5-CH2CH2FXIII.25     2-SOCH2CH2CH＝CF2                  5-CH2CH2FXIII.26     2-SO2CH2CH2CH＝CF2                 5-CH2CH2FXIII.27     2-SCH2CH2CH＝CF2                   5-CH2CH3XIII.28           2-SOCH2CH2CH＝CF2                  5-CH2CH3XIII.29           2-SO2CH2CH2CH＝CF2                 5-CH2CH3XIII.30           2-SCH2CH2CH＝CF2                   5-CH2CHCH2XIII.31           2-SCH2CH2CH＝CF2                   5-CH2CNXIII.32           2-SCH2CH2CH＝CF2                   5-CH2CONH2XIII.33           2-SCH2CH2CH＝CF2                   5-CH2COOCH2CH3XIII.34           2-SCH2CH2CH＝CF2                   5-CH2N(CH3)2XIII.35           2-SCH2CH2CH＝CF2                   5-CH2OCH3XIII.36           2-SOCH2CH2CH＝CF2                  5-CH2OCH3XIII.37           2-SO2CH2CH2CH＝CF2                 5-CH2OCH3XIII.38           2-SCH2CH2CH＝CF2                   5-CH2OHXIII.39           2-SCH2CH2CH＝CF2                   5-CH2SO2C6H5XIII.40           2-SCH2CH2CH＝CF2                   5-CH3XIII.41           2-SOCH2CH2CH＝CF2                  5-CH3XIII.42           2-SO2CH2CH2CH＝CF2                 5-CH3XIII.43           2-SCH2CH2CH＝CF2                   5-COCH3XIII.44           2-SCH2CH2CH＝CF2                   5-CON(CH3)2XIII.45           2-SCH2CH2CH＝CF2                   5-CONH2XIII.46           2-SCH2CH2CH＝CF2                   5-CONHCH2C6H5XIII.47           2-SCH2CH2CH＝CF2                   5-CONHCH2CH2CH＝CF2XIII.48           2-SOCH2CH2CH＝CF2                  5-CONHCH2CH2CH＝CF2XIII.49           2-SO2CH2CH2CH＝CF2                 5-CONHCH2CH2CH＝CF2XIII.50           2-SCH2CH2CH＝CF2                   5-CONHCH3XIII.51           2-SCH2CH2CH＝CF2                   5-CONHSO2CH3XIII.52           2-SO2CH2CH2CH＝CF2                 5-CONHSO2CH3XIII.53           2-SCH2CH2CH＝CF2                   5-COOC6H5XIII.54           2-SOCH2CH2CH＝CF2                  5-COOC6H5XIII.55           2-SCH2CH2CH＝CF2                   5-COOCH2CH2CH＝CF2XIII.56           2-SOCH2CH2CH＝CF2                  5-COOCH2CH2CH＝CF2XIII.57           2-SO2CH2CH2CH＝CF2                 5-COOCH2CH2CH＝CF2XIII.58           2-SCH2CH2CH＝CF2                   5-COOCH2CH2FXIII.59           2-SCH2CH2CH＝CF2                   5-COOCH3XIII.60           2-SCH2CH2CH＝CF2                   5-COOHXIII.61           2-SCH2CH2CH＝CF2         5-COSCH2CH2CH＝CF2XIII.62           2-SCH2CH2CH＝CF2         5-CSNH2XIII.63           2-SCH2CH2CH＝CF2         5-HXIII.64           2-SOCH2CH2CH＝CF2        5-HXIII.65           2-SO2CH2CH2CH＝CF2       5-HXIII.66           2-SCH2CH2CH＝CF2         5-N(CH3)2XIII.67           2-SCH2CH2CH＝CF2         5-N(SO2CH3)2XIII.68           2-SO2CH2CH2CH＝CF2       5-N(SO2CH3)2XIII.69           2-SCH2CH2CH＝CF2         5-NH2XIII.70           2-SCH2CH2CH＝CF2         5-NHCH3XIII.71           2-SOCH2CH2CH＝CF2        5-NHCH3XIII.72           2-SO2CH2CH2CH＝CF2       5-NHCH3XIII.73           2-SCH2CH2CH＝CF2         5-NHCHOXIII.74           2-SOCH2CH2CH＝CF2        5-NHCHOXIII.75           2-SCH2CH2CH＝CF2         5-NHCOCF3XIII.76           2-SO2CH2CH2CH＝CF2       5-NHCOCF3XIII.77           2-SCH2CH2CH＝CF2         5-NHCOCH3XIII.78           2-SCH2CH2CH＝CF2         5-NHCOOCH3XIII.79           2-SOCH2CH2CH＝CF2        5-NHCOOCH3XIII.80           2-SCH2CH2CH＝F2          5-NHCSCH2CH3XIII.81           2-SCH2CH2CH＝CF2         5-NHCSNHCH2CH3XII1.82           2-SCH2CH2CH＝CF2         5-NHSO2CH3XIIII.83          2-SO2CH2CH2CH＝CF2       5-NHSO2CH3XIII.84           2-SCH2CH2CH＝CF2         5-OC6H5XIII.85           2-SOCH2CH2CH＝CF2        5-OC6H5XIII.86           2-SO2CH2CH2CH＝CF2       5-OC6H5XIII.87           2-SCH2CH2CH＝CF2         5-OCF2CF2HXIII.88           2-SCH2CH2CH＝CF2         5-OCF3XIII.89           2-SOCH2CH2CH＝CF2        5-OCF3XIII.90           2-SO2CH2CH2CH＝CF2       5-OCF3XIII.91           2-SCH2CH2CH＝CF2         5-OCH2C6H5XIII.92           2-SCH2CH2CH＝CF2         5-OCH2CF3XIII.93           2-SOCH2CH2CH＝CF2        5-OCH2CF3XIII.94          2-SO2CH2CH2CH＝CF2               5-OCH2CF3XIII.95          2-SCH2CH2CH＝CF2                 5-OCH2CH＝CC12XIII.96          2-SCH2CH2CH＝CF2                 5-OCH2CH2CH＝CF2XIII.97          2-SOCH2CH2CH＝CF2                5-OCH2CH2CH＝CF2XIII.98          2-SO2CH2CH2CH＝CF2               5-OCH2CH2CH＝CF2XIII.99          2-SCH2CH2CH＝CF2                 5-OCH2CH2FXIII.100         2-SCH2CH2CH＝CF2                 5-OCH2COOCH3XIII.101         2-SCH2CH2CH＝CF2                 5-OCH3XIII.102         2-SOCH2CH2CH＝CF2                5-OCH3XIII.103         2-SO2CH2CH2CH＝CF2               5-OCH3XIII.104         2-SCH2CH2CH＝CF2                 5-OCOC6H5XIII.105         2-SCH2CH2CH＝CF2                 5-OCOCH3XIII.106         2-SCH2CH2CH＝CF2                 5-OSO2CH3XIII.107         2-SOCH2CH2CH＝CF2                5-OSO2CH3XIII.108         2-SO2CH2CH2CH＝CF2               5-OSO2CH3XIII.109         2-SCH2CH2CH＝CF2                 5-SCF3XIII.110         2-SCH2CH2CH＝CF2                 5-SCH2(3-CF3C6H4)XIII.111         2-SOCH2CH2CH＝CF2                5-SCH2(3-CF3C6H4)XIII.112         2-SO2CH2CH2CH＝CF2               5-SCH2(3-CF3C6H4)XIII.113         2-SCH2CH2CH＝CF2                 5-SCH2(4-CF3-C6H4)XIII.114         2-SCH2CH2CH＝CF2                 5-SCH2(c-C3H5)XIII.115         2-SCH2CH2CH＝CF2                 5-SCH2C≡CHXIII.116         2-SCH2CH2CH＝CF2                 5-SCH2CH2CH＝CF2XIII.117         2-SCH2CH2CH＝CF2                 5-SCH2CH2CH＝CF2XIII.118         2-SOCH2CH2CH＝CF2                5-SCH2CH2CH＝CF2XIII.119         2-SCH2CH2CH＝CF2                 5-SCH3XIII.120         2-SOCH2CH2CH＝CF2                5-SCH3XIII.121         2-SO2CH2CH2CH＝CF2               5-SCH3XIII.122         2-SCH2CH2CH＝CF2                 5-SHXIII.123         2-SCH2CH2CH＝CF2                 5-SO2CH2CH2CH＝CF2XIII.124         2-SO2CH2CH2CH＝CF2               5-SO2CH2CH2CH＝CF2XIII.125         2-SCH2CH2CH＝CF2                 5-SO2CH3XIII.126         2-SO2CH2CH2CH＝CF2               5-SO2CH3XIII.127         2-SCH2CH2CH＝CF2                5-SO2N(CH3)2XIII.128         2-SCH2CH2CH＝CF2                5-SO2NH2XIII.129         2-SCH2CH2CH＝CF2                5-SO2NHCH3XIII.130         2-SCH2CH2CH＝CF2                5-SOCF3XIII.131         2-SOCH2CH2CH＝CF2               5-SOCF3XIII.132         2-SCH2CH2CH＝CF2                5-SOCH2CH2CH＝CF2XIII.133         2-SOCH2CH2CH＝CF2               5-SOCH2CH2CH＝CF2XIII.134         2-SO2CH2CH2CH＝CF2              5-SOCH2CH2CH＝CF2XIII.135         2-SCH2CH2CH＝CF2                5-SOCH3XIII.136         2-SCH2CH2CH＝CF2                5-(4-CF3-C6H4)XIII.137         2-SO2CH2CH2CH＝CF2              5-(4-CF3-C6H4)XIII.138         2-SCH2CH2CH＝CF2                5-(4-CH3-C6H4)XIII.139         2-SO2CH2CH2CH＝CF2              5-(4-CH3-C6H4)XIII.140         2-SCH2CH2CH＝CF2                5-(4-CN-C6H4)XIII.141         2-SOCH2CH2CH＝CF2               5-(4-CN-C6H4)XIII.142         2-SCH2CH2CH＝CF2                5-(4-CONH2-C6H4)XIII.143         2-SCH2CH2CH＝CF2                5-(4-H2NSO2-C6H4)XIII.144         2-SCH2CH2CH＝CF2                5-(4-NO2-C6H4)XIII.145         2-SCH2CH2CH＝CF2                5-(4-OCH3-C6H4)XIII.146         2-SOCH2CH2CH＝CF2               5-(4-OCH3-C6H4)XIII.147         2-SO2CH2CH2CH＝CF2              5-(4-OCH3-C6H4)本发明式(XIV)化合物的实例如表XIV所示。
             表XIVNo.     R1       R5XIV.1   1-CH3    5-SCH2CH2CH＝CF2本发明式(XV)化合物的实例如表XV所示。
                  表XVNo.         R1                    R2         R3         R4XV.1        1-SCH2CH2CH＝CF2      2-H        3-H        4-NO2本发明式(XVI)化合物的实例如表XVI所示。
Figure A9519202900671
                                       表XVINo.    R2                  R3                      R4                        R5                 R6XVI.1  2-Cl                3-H                     4-SCH2CH2CH＝CF2          5-H                6-HXVI.2  2-F                 3-F                     4-SCH2CH2CH＝CF2          5-F                6-FXVI.3  2-F                 3-F                     4-SOCH2CH2CH＝CF2         5-F                6-FXVI.4  2-F                 3-F                     4-SO2CH2CH2CH＝CF2        5-F                6-FXVI.5  2-H                 3-H                     4-SCH2CH2CH＝CF2          5-H                6-HXVI.6  2-H                 3-H                     4-SO2CH2CH2CH＝CF2        5-H                6-HXVI.7  2-SCH2CH2CH＝CF2    3-CF3                   4-H                       5-H                6-HXVI.8  2-SCH2CH2CH＝CF2    3-CN                    4-H                       5-H                6-HXVI.9  2-SCH2CH2CH＝CF2    3-CONH2                 4-H                       5-H                6-HXVI.10 2-SCH2CH2CH＝CF2    3-COOCH2CH2CH＝CF2      4-H                       5-H                6-HXVI.11 2-SCH2CH2CH＝CF2    3-H                     4-H                       5-CF3              6-HXVI.12 2-SO2CH2CH2CH＝CF2  3-H                     4-H                       5-CF3              6-HXVI.13 2-SCH2CH2CH＝CF2    3-H                     4-H                       5-Cl               6-HXVI.14 2-SO2CH2CH2CH＝CF2  3-H                     4-H                       5-Cl               6-HXVI.15 2-SCH2CH2CH＝CF2    3-H                     4-H                       5-CN               6-HXVI.16 2-SO2CH2CH2CH＝CF2  3-H                     4-H                       5-CN               6-HXVI.17 2-SCH2CH2CH＝CF2     3-H                 4-H                 5-CONH2              6-HXVI.18 2-SCH2CH2CH＝CF2     3-H                 4-H                 5-COOH               6-HXVI.19 2-SCH2CH2CH＝CF2     3-H                 4-H                 5-H                  6-HXVI.20 2-SO2CH2CH2CH＝CF2   3-H                 4-H                 5-H                  6-HXVI.21 2-SCH2CH2CH＝CF2     3-H                 4-H                 5-NO2                6-HXVI.22 2-SCH2CH2CH＝CF2     3-H                 4-H                 5-SCH2CH2CH＝CF2     6-HXVI.23 2-SCH2CH2CH＝CF2     3-H                 4-H                 5-H                  6-FXVI.24 2-SCH2CH2CH＝CF2     3-NO2               4-H                 5-H                  6-H本发明式(XVII)化合物的实例如表XVII所示。
              表XVIINo.      R3                  R4           R5               R6XVII.1   3-SCH2CH2CH=CF2     4-H          5-H              6-CH3XVII.2   3-SCH2CH2CH=CF2     4-H          5-H              6-ClXVII.3   3-SCH2CH2CH=CF2     4-H          5-H              6-OCH3XVII.4   3-SCH2CH2CH=CF2     4-H          5-H              6-C6H5XVII.5   3-SOCH2CH2CH=CF2    4-H          5-H              6-C6H5XVII.6   3-SO2CH2CH2CH=CF2   4-H          5-H              6-C6H5XVII.7   3-SCH2CH2CH=CF2     -CH=CH-CH=CH-                 6-H本发明式(XVIII)化合物的实例如表XVIII所示。
Figure A9519202900692
                   表XVIIINo.        R2                 R3                               R5                R6XVIII.1    2-SCH2CH2CH=CF2    3-H                              -CH＝CH-CH＝CH-XVIII.2    2-SOCH2CH2CH=CF2   3-H                              -CH＝CH-CH＝CH-XVIII.3    2-SO2CH2CH2CH=CF2  3-H                              -CH＝CH-CH＝CH-XVIII.4    2-SCH2CH2CH=CF2    3-H                              -CH＝CH-CH＝CH-XVIII.5    2-SOCH2CH2CH=CF2   3-H                              -CH＝C(Cl)CH＝CH-XVIII.6    2-SO2CH2CH2CH=CF2  3-H                              -CH＝C(Cl)CH＝CH-XVIII.7    2-SCH2CH2CH=CF2    3-H                              5-H               6-HXVIII.8    2-SOCH2CH2CH=CF2   3-H                              5-H               6-HXVIII.9    2-SO2CH2CH2CH=CF2  3-H                              5-H               6-HXVIII.10   2-SCH2CH2CH=CF2    3-Cl                             5-H               6-HXVIII.11   2-SOCH2CH2CH=CF2   3-Cl                             5-H               6-HXVIII.12   2-SO2CH2CH2CH=CF2  3-Cl                             5-H               6-HXVIII.13   2-SCH2CH2CH=CF2    3-SCH2CH2CH=CF2                  5-H               6-HXVIII.14   2-SCH2CH2CH＝CF2   3-H                             5-H               6-ClXVIII.15   2-SOCH2CH2CH＝CF2  3-H                             5-H               6-ClXVIII.16   2-SO2CH2CH2CH＝CF2 3-H                             5-H               6-Cl本发明式(XIX)化合物的实例如表XIX所示。
Figure A9519202900701
               表XIXNo.      R4                  R5         R6XIX.1    4-SCH2CH2CH＝CF2   -CH＝CH-CH＝CH-本发明式(XX)化合物的实例如表XX所示。
              表XXNo.     R3                 R5                  R6XX.1    3-SCH2CH2CH＝CF2   5-Br                6-HXX.2    3-SCH2CH2CH＝CF2   5-c-C3H5            6-HXX.3    3-SOCH2CH2CH＝CF2  5-c-C3H5            6-HXX.4    3-SCH2CH2CH＝CF2   5-C6H5              6-CH3XX.5    3-SOCH2CH2CH＝CF2  5-C6H5              6-CH3XX.6    3-SO2CH2CH2CH＝CF2 5-C6H5              6-CH3XX.7    3-SOCH2CH2CH＝CF2  5-C6H5              6-CNXX.8    3-SCH2CH2CH＝CF2   5-C6H5              6-HXX.9    3-SO2CH2CH2CH＝CF2 5-C6H5              6-HXX.10   3-SCH2CH2CH＝CF2   5-(4-F-C6H4)        6-HXX.11   3-SOCH2CH2CH＝CF2  5-(4-F-C6H4)        6-HXX.12   3-SCH2CH2CH＝CF2   5-CF2H              6-CH3XX.13   3-SCH2CH2CH＝CF2   5-CF3               6-HXX.14   3-SOCH2CH2CH＝CF2  5-CF3               6-OC6H5XX.15   3-SCH2CH2CH＝CF2   5-CH(CH3)2          6-HXX.16       3-SCH2CH2CH＝CF2      5-CH＝CH2       6-HXX.17       3-SCH2CH2CH＝CF2      5-CH＝CHCN      6-HXX.18       3-SCH2CH2CH＝CF2      5-CH＝CHNO2     6-HXX.19       3-SCH2CH2CH＝CF2      5-CH＝NOCH3     6-CH3XX.20       3-SCH2CH2CH＝CF2      5-CH2C≡CH      6-HXX.21       3-SCH2CH2CH＝CF2      5-CH2C6H5       6-HXX.22       3-SOCH2CH2CH＝CF2     5-CH2C6H5       6-HXX.23       3-SCH2CH2CH＝CF2      5-CH2CF3        6-HXX.24       3-SCH2CH2CH＝CF2      5-CH2CH＝CH2    6-HXX.25       3-SCH2CH2CH＝CF2      5-CH2CS2CH2CH3  6-HXX.26       3-SO2CH2CH2CH＝CF2    5-CH2CH2CH2CH3  6-HXX.27       3-SCH2CH2CH＝CF2      5-CH2CH2CH3     6-HXX.28       3-SO2CH2CH2CH＝CF2    5-CH2CH2CH3     6-HXX.29       3-SCH2CH2CH＝CF2      5-CH2CH2F       6-HXX.30       3-SCH2CH2CH＝CF2      5-CH2CH3        6-HXX.31       3-SCH2CH2CH＝CF2      5-CH2CN         6-CH3XX.32       3-SCH2CH2CH＝CF2      5-CH2CONH2      6-HXX.33       3-SCH2CH2CH＝CF2      5-CH2N(CH3)2    6-CH3XX.34       3-SCH2CH2CH＝CF2      5-CH2NHCOCH3    6-HXX.35       3-SCH2CH2CH＝CF2      5-CH2OCH2CH3    6-HXX.36       3-SOCH2CH2CH＝CF2     5-CH2OCH2CH3    6-HXX.37       3-SCH2CH2CH＝CF2      5-CH2OCH3       6-CH3XX.38       3-SCH2CH2CH＝CF2      5-CH2OH         6-HXX.39       3-SCH2CH2CH＝CF2      5-CH2SO2C6H5    6-HXX.40       3-SCH2CH2CH＝CF2      5-CH3           6-CF2HXX.41       3-SCH2CH2CH＝CF2      5-CH3           6-CH＝CH2XX.42       3-SCH2CH2CH＝CF2      5-CH3           6-CH2CH2FXX.43       3-SCH2CH2CH＝CF2      5-CH3           6-CH2CNXX.44       3-SCH2CH2CH＝CF2      5-CH3           6-CH2N(CH3)2XX.45       3-SCH2CH2CH＝CF2      5-CH3           6-CH2OHXX.46       3-SCH2CH2CH＝CF2      5-CH3           6-CH3XX.47       3-SCH2CH2CH＝CF2      5-CH3           6-CONH2XX.48       3-SCH2CH2CH＝CF2      5-CH3           6-CONHCH3XX.49      3-SCH2CH2CH＝CF2      5-CH3                                6-CONHSO2CH3XX.50      3-SCH2CH2CH＝CF2      5-CH3                                6-COOCH2CH3XX.51      3-SCH2CH2CH＝CF2      5-CH3                                6-COOCH3XX.52      3-SCH2CH2CH＝CF2      5-CH3                                6-HXX.53      3-SOCH2CH2CH＝CF2     5-CH3                                6-HXX.54      3-SO2CH2CH2CH＝CF2    5-CH3                                6-HXX.55      3-SCH2CH2CH＝CF2      5-CH3                                6-NHCHOXX.56      3-SCH2CH2CH＝CF2      5-CH3                                6-NHCOCH3XX.57      3-SCH2CH2CH＝CF2      5-CH3                                6-NHCONH2XX.58      3-SCH2CH2CH＝CF2      5-CH3                                6-OCF2HXX.59      3-SCH2CH2CH＝CF2      5-CH3                                6-OCH2CF3XX.60      3-SCH2CH2CH＝CF2      5-CH3                                6-OCH2CH2FXX.61      3-SCH2CH2CH＝CF2      5-CH3                                6-OCOCH3XX.62      3-SCH2CH2CH＝CF2      5-CH3                                6-OSO2CH3XX.63      3-SCH2CH2CH＝CF2      5-CH3                                6-SO2NH2XX.64      3-SCH2CH2CH＝CF2      5-CH3                                6-SOCH3XX.65      3-SCH2CH2CH＝CF2      5-CHC12                              6-HXX.66      3-SCH2CH2CH＝CF2      5-CHO                                6-CH3XX.67      3-SCH2CH2CH＝CF2      5-Cl                                 6-HXX.68      3-SO2CH2CH2CH＝CF2    5-Cl                                 6-HXX.69      3-SCH2CH2CH＝CF2      5-CN                                 6-HXX.70      3-SOCH2CH2CH＝CF2     5-CN                                 6-HXX.71      3-SCH2CH2CH＝CF2      5-COCH3                              6-HXX.72      3-SCH2CH2CH＝CF2      5-CON(CH3)2                          6-HXX.73      3-SCH2CH2CH＝CF2      5-CONH2                              6-HXX.74      3-SCH2CH2CH＝CF2      5-CONHCH2C6H5                        6-HXX.75      3-SOCH2CH2CH＝CF2     5-CONHCH2CH2CH＝CF2                  6-HXX.76      3-SCH2CH2CH＝CF2      5-CONHCH3                            6-HXX.77      3-SCH2CH2CH＝CF2      5-CONHSO2CH3                         6-CH3XX.78      3-SO2CH2CH2CH＝CF2    5-COOCH2CH2CH＝CF2                   6-HXX.79      3-SCH2CH2CH＝CF2      5-COOCH2CH2F                         6-HXX.80      3-SCH2CH2CH＝CF2      5-COOCH2CH3                          6-HXX.81      3-SCH2CH2CH＝CF2      5-COOCH3                             6-CH3XX.82   3-SOCH2CH2CH＝CF2  5-COOCH3           6-HXX.83   3-SCH2CH2CH＝CF2   5-COOH             6-HXX.84   3-SOCH2CH2CH＝CF2  5-COOH             6-HXX.85   3-SCH2CH2CH＝CF2   5-F                6-HXX.86   3-SCH2CH2CH＝CF2   5-H                6-(1-CH3-cC3H4)XX.87   3-SCH2CH2CH＝CF2   5-H                6-(4-F-C6H4)XX.88   3-SO2CH2CH2CH＝CF2 5-H                6-(4-F-C6H4)XX.89   3-SCH2CH2CH＝CF2   5-H                6-BrXX.90   3-SCH2CH2CH＝CF2   5-H                6-C(CH3)3XX.91   3-SCH2CH2CH＝CF2   5-H                6-c-C3H5XX.92   3-SCH2CH2CH＝CF2   5-H                6-c-C3H9XX.93   3-SCH2CH2CH＝CF2   5-H                6-C≡CHXX.94   3-SCH2CH2CH＝CF2   5-H                6-C6H5XX.95   3-SOCH2CH2CH＝CF2  5-H                6-C6H5XX.96   3-SCH2CH2CH＝CF2   5-H                6-CF3XX.97   3-SO2CH2CH2CH＝CF2 5-H                6-CF3XX.98   3-SCH2CH2CH＝CF2   5-H                6-CH(CH3)2XX.99   3-SCH2CH2CH＝CF2   5-H                6-CH＝CHCNXX.100  3-SCH2CH2CH＝CF2   5-H                6-CH＝CHNO2XX.101  3-SCH2CH2CH＝CF2   5-H                6-CH＝NOCH3XX.102  3-SOCH2CH2CH＝CF2  5-H                6-CH2(4-CF3-C6H4)XX.103  3-SCH2CH2CH＝CF2   5-H                6-CH2C≡CHXX.104  3-SCH2CH2CH＝CF2   5-H                6-CH2C6H5XX.105  3-SOCH2CH2CH＝CF2  5-H                6-CH2C6H5XX.106  3-SCH2CH2CH＝CF2   5-H                6-CH2C6H5XX.107  3-SCH2CH2CH＝CF2   5-H                6-CH2CH＝CH2XX.108  3-SCH2CH2CH＝CF2   5-H                6-CH2CH2CH2CH3XX.109  3-SCH2CH2CH＝CF2   5-H                6-CH2CH2CH3XX.110  3-SCH2CH2CH＝CF2   5-H                6-CH2CH3XX.111  3-SCH2CH2CH＝CF2   5-H                6-CH2CONH2XX.112  3-SCH2CH2CH＝CF2   5-H                6-CH2NHCOCH3XX.113  3-SCH2CH2CH＝CF2   5-H                6-CH2OCH2CH3XX.114  3-SCH2CH2CH＝CF2   5-H                6-CH2OCH3XX.115     3-SCH2CH2CH＝CF2      5-H                                    6-CH2SO2C6H5XX.116     3-SCH2CH2CH＝CF2      5-H                                    6-CH3XX.117     3-SOCH2CH2CH＝CF2     5-H                                    6-CH3XX.118     3-SO2CH2CH2CH＝CF2    5-H                                    6-CH3XX.119     3-SCH2CH2CH＝CF2      5-H                                    6-CHOXX.120     3-SCH2CH2CH＝CF2      5-H                                    6-ClXX.121     3-SOCH2CH2CH＝CF2     5-H                                    6-ClXX.122     3-SCH2CH2CH＝CF2      5-H                                    6-CNXX.123     3-SCH2CH2CH＝CF2      5-H                                    6-COCH3XX.124     3-SCH2CH2CH＝CF2      5-H                                    6-CON(CH3)2XX.125     3-SO2CH2CH2CH＝CF2    5-H                                    6-CON(CH3)C2H5XX.126     3-SCH2CH2CH＝CF2      5-H                                    6-CONHCH2C6H5XX.127     3-SCH2CH2CH＝CF2      5-H                                    6-CONHCH2CH2CH＝CF2XX.128     3-SCH2CH2CH＝CF2      5-H                                    6-CONHCH2CH2CH3XX.129     3-SCH2CH2CH＝CF2      5-H                                    6-COOC6H5XX.130     3-SCH2CH2CH＝CF2      5-H                                    6-COOCH2CH2CH＝CF2XX.131     3-SCH2CH2CH＝CF2      5-H                                    6-COOCH2CH2FXX.132     3-SCH2CH2CH＝CF2      5-H                                    6-COOCH3XX.133     3-SOCH2CH2CH＝CF2     5-H                                    6-COOCH3XX.134     3-SCH2CH2CH＝CF2      5-H                                    6-COOHXX.135     3-SO2CH2CH2CH＝CF2    5-H                                    6-COOHXX.136     3-SCH2CH2CH＝CF2      5-H                                    6-FXX.137     3-SCH2CH2CH＝CF2      5-H                                    6-HXX.138     3-SCH2CH2CH＝CF2      5-H                                    6-NHCH2CH3XX.139     3-SOCH2CH2CH＝CF2     5-H                                    6-NHCH2CH3XX.140     3-SCH2CH2CH＝CF2      5-H                                    6-NHCOC2H5XX.141     3-SCH2CH2CH＝CF2      5-H                                    6-NHCOC6H5XX.142     3-SCH2CH2CH＝CF2      5-H                                    6-NHCOCF3XX.143     3-SCH2CH2CH＝CF2      5-H                                    6-NHCOCH3XX.144     3-SCH2CH2CH＝CF2      5-H                                    6-NHCOOCH3XX.145     3-SCH2CH2CH＝CF2      5-H                                    6-NHCSCH2CH3XX.146     3-SCH2CH2CH＝CF2      5-H                                    6-NHCSNHCH2CH3XX.147     3-SCH2CH2CH＝CF2      5-H                                    6-NHSO2CH3XX.148     3-SCH2CH2CH＝CF2      5-H                                    6-NO2XX.149     3-SCH2CH2CH＝CF2      5-H                                    6-OC4H9XX.150     3-SOCH2CH2CH＝CF2     5-H                                    6-OC5H11XX.151     3-SCH2CH2CH＝CF2      5-H                                    6-OC6H5XX.152     3-SOCH2CH2CH＝CF2     5-H                                    6-OC6H5XX.153     3-SCH2CH2CH＝CF2      5-H                                    6-OCF2CF2HXX.154     3-SCH2CH2CH＝CF2      5-H                                    6-OCF3XX.155     3-SOCH2CH2CH＝CF2     5-H                                    6-OCF3XX.156     3-SO2CH2CH2CH＝CF2    5-H                                    6-OCH(CH3)C2H5XX.157     3-SCH2CH2CH＝CF2      5-H                                    6-OCH2(4-Cl-C6H4)XX.158     3-SO2CH2CH2CH＝CF2    5-H                                    6-OCH2(4-Cl-C6H4)XX.159     3-SCH2CH2CH＝CF2      5-H                                    6-OCH2C6H5XX.160     3-SCH2CH2CH＝CF2      5-H                                    6-OCH2CCl＝CH2XX.161     3-SCH2CH2CH＝CF2      5-H                                    6-CH2CH＝CCl2XX.162     3-SCH2CH2CH＝CF2      5-H                                    6-OCH2CH＝CH2XX.163     3-SO2CH2CH2CH＝CF2    5-H                                    6-OCH2CH＝CH2XX.164     3-SCH2CH2CH＝CF2      5-H                                    6-OCH2CH2CH3XX.165     3-SCH2CH2CH＝CF2      5-H                                    6-OCH2CH2COOCH3XX.166     3-SOCH2CH2CH＝CF2     5-H                                    6-OCH2CH2COOCH3XX.167     3-SCH2CH2CH＝CF2      5-H                                    6-OCH2CH2CH＝CF2XX.168     3-SCH2CH2CH＝CF2      5-H                                    6-OCH2CH3XX.169     3-SCH2CH2CH＝CF2      5-H                                    6-OCH2COOHXX.170     3-SCH2CH2CH＝CF2      5-H                                    6-OCH3XX.171     3-SOCH2CH2CH＝CF2     5-H                                    6-OCH3XX.172     3-SCH2CH2CH＝CF2      5-H                                    6-OCOC2H5XX.173     3-SCH2CH2CH＝CF2      5-H                                    6-OCOC6H5XX.174     3-SCH2CH2CH＝CF2      5-H                                    6-OHXX.175     3-SOCH2CH2CH＝CF2     5-H                                    6-OHXX.176     3-SCH2CH2CH＝CF2      5-H                                    6-SCF3XX.177     3-SOCH2CH2CH＝CF2     5-H                                    6-SCF3XX.178     3-SCH2CH2CH＝CF2      5-H                                    6-SCH2CH2CH3XX.179     3-SCH2CH2CH＝CF2      5-H                                    6-SCH2CH2CH＝CF2XX.180     3-SCH2CH2CH＝CF2      5-H                                    6-SCH3XX.181     3-SOCH2CH2CH＝CF2     5-H                  6-SCH3XX.182     3-SCH2CH2CH＝CF2      5-H                  6-SO2NHCH3XX.183     3-SCH2CH2CH＝CF2      5-H                  6-SOCF3XX.184     3-SCH2CH2CH＝CF2      5-H                  6-SOCH2CH2CH＝CF2XX.185     3-SCH2CH2CH＝CF2      5-NH2                6-CH3XX.186     3-SO2CH2CH2CH＝CF2    5-NHCH2CH3           6-C6H5XX.187     3-SCH2CH2CH＝CF2      5-NHCH2CH3           6-HXX.188     3-SCH2CH2CH＝CF2      5-NHCHO              6-HXX.189     3-SCH2CH2CH＝CF2      5-NHCOCF3            6-CH3XX.190     3-SOCH2CH2CH＝CF2     5-NHCOCH3            6-C6H5XX.191     3-SCH2CH2CH＝CF2      5-NHCOCH3            6-HXX.192     3-SCH2CH2CH＝CF2      5-NHCONH2            6-CH3XX.193     3-SCH2CH2CH＝CF2      5-NHCOOCH3           6-HXX.194     3-SCH2CH2CH＝CF2      5-NHSO2CH3           6-CH3XX.195     3-SCH2CH2CH＝CF2      5-NMe2               6-HXX.196     3-SOCH2CH2CH＝CF2     5-NO2                6-C6H5XX.197     3-SCH2CH2CH＝CF2      5-NO2                6-HXX.198     3-SCH2CH2CH＝CF2      5-OC6H5              6-HXX.199     3-SOCH2CH2CH＝CF2     5-OC6H5              6-HXX.200     3-SOCH2CH2CH＝CF2     5-OC6H5              6-NHCOCH3XX.201     3-SCH2CH2CH＝CF2      5-OCF2CF2H           6-CH3XX.202     3-SCH2CH2CH＝CF2      5-OCF2H              6-HXX.203     3-SCH2CH2CH＝CF2      5-OCF3               6-HXX.204     3-SOCH2CH2CH＝CF2     5-OCF3               6-HXX.205     3-SCH2CH2CH＝CF2      5-OCH(CH3)2          6-HXX.206     3-SOCH2CH2CH＝CF2     5-OCH(CH3)C2H5       6-HXX.207     3-SCH2CH2CH＝CF2      5-OCH2(4-Cl-C6H4)    6-HXX.208     3-SO2CH2CH2CH＝CF2    5-OCH2(4-Cl-C6H4)    6-HXX.209     3-SCH2CH2CH＝CF2      5-OCH2C6H5           6-HXX.210     3-SCH2CH2CH＝CF2      5-OCH2CCl＝CH2       6-HXX.211     3-SCH2CH2CH＝CF2      5-OCH2CF3            6-HXX.212     3-SCH2CH2CH＝CF2      5-OCH2CH＝CH2        6-HXX.213     3-SO2CH2CH2CH＝CF2    5-OCH2CH2COOCH3      6-CH3XX.214     3-SCH2CH2CH＝CF2   5-OCH2CH2COOCH3    6-HXX.215     3-SO2CH2CH2CH＝CF2 5-OCH2CH2COOCH3    6-HXX.216     3-SCH2CH2CH＝CF2   5-OCH2CH2CH＝CF2   6-HXX.217     3-SCH2CH2CH＝CF2   5-OCH2CH2F         6-CH3XX.218     3-SCH2CH2CH＝CF2   5-OCH2CH3          6-HXX.219     3-SCH2CH2CH＝CF2   5-OCH2COOCH3       6-HXX.220     3-SCH2CH2CH＝CF2   5-OCH2COOH         6-HXX.221     3-SCH2CH2CH＝CF2   5-OCH3             6-HXX 222     3-SCH2CH2CH＝CF2   5-OCOC2H5          6-HXX.223     3-SOCH2CH2CH＝CF2  5-OCOC6H5          6-HXX.224     3-SCH2CH2CH＝CF2   5-OCOCH3           6-CH3XX.225     3-SOCH2CH2CH＝CF2  5-OH               6-C6H5XX.226     3-SCH2CH2CH＝CF2   5-OH               6-CH3XX.227     3-SCH2CH2CH＝CF2   5-OH               6-HXX.228     3-SCH2CH2CH＝CF2   5-OSO2CH3          6-HXX.229     3-SCH2CH2CH＝CF2   5-SCF3             6-HXX.230     3-SOCH2CH2CH＝CF2  5-SCF3             6-HXX.231     3-SCH2CH2CH＝CF2   5-SCH2CH2CH＝CF2   6-HXX.232     3-SCH2CH2CH＝CF2   5-SCH2CH2CH3       6-HXX.233     3-SCH2CH2CH＝CF2   5-SCH2CH2CH＝CF2   6-HXX.234     3-SCH2CH2CH＝CF2   5-SCH3             6-HXX.235     3-SOCH2CH2CH＝CF2  5-SCH3             6-HXX.236     3-SCH2CH2CH＝CF2   5-SO2NH2           6-CH3XX.237     3-SCH2CH2CH＝CF2   5-SO2NHCH3         6-HXX.238     3-SCH2CH2CH＝CF2   5-SOCF3            6-HXX.239     3-SCH2CH2CH＝CF2   5-SOCH3            6-CH3XX.240     3-CH3              5-CH3              6-SCH2CH2CH＝CF2XX.241     3-CH3              5-H                6-SCH2CH2CH＝CF2XX.242     3-CH3              5-OC4H9            6-SO2CH2CH2CH＝CF2XX.243     3-CH3              5-SCH2CH2CH＝CF2   6-CH3XX.244     3-CH3              5-SCH2CH2CH＝CF2   6-HXX.245     3-H                5-CH3              6-SCH2CH2CH＝CF2XX.246     3-H                5-H                6-SCH2CH2CH＝CF2XX.247     3-H                                 5-SCH2CH2CH＝CF2         6-CH3XX.248     3-H                                 5-SCH2CH2CH＝CF2         6-HXX.249     3-H                                 5-SOCH2CH2CH＝CF2        6-CH3XX.250     3-H                                 5-SO2CH2CH2CH＝CF2       6-CH3XX.251     3-SCH2CH2CH＝CF2                        -(CH2CH2CH2CH2)-XX.252     3-SOCH2CH2CH＝CF2                       -(CH2CH2CH2CH2)-XX.253     3-SO2CH2CH2CH＝CF2                      -(CH2CH2CH2CH2)-本发明式(XXI)化合物的实例如表XXI所示。
Figure A9519202900781
表XXINo.      R2                    R4        R6XXI.1    2-SCH2CH2CH＝CF2      4-H       6-H
其中n为0的式(I)化合物可以通过各种不同的方法制得。
例如，它们可以通过将相应的式(XXIII)硫醇化合物与适宜的式(XXIV)二氟丁-1-烯(其中L为易离去基团)烷基化剂反应制得。此反应优选在0℃-200℃，惰性溶剂中，在弱碱如碱金属碳酸盐例如碳酸钠或碳酸钾存在下进行。通常，所述反应可以在其沸点在所述范围内的适宜的惰性溶剂如丙酮的回流温度下进行。
式(XXIV)中，所述离去基团L优选为卤素或具有式OSO2Rb的磺酸酯，如式(XXV)所示，其中Rb为C1-4烷基或被C1-4烷基任意取代的苯基。更优选的是，如式(XXVI)所示L为溴。
所述式(XXV)磺酸酯可以通过将1，4-二溴-1，1，2-三氟丁烷与所选择的磺酸的银盐反应并将所得中间体4-甲苯磺酸酯脱溴氟而制得。
在待批国际专利申请PCT/GB94/01570中，我们公开了一种式(XXVI)化合物即4-溴-1，1-二氟丁-1-烯的制备方法，其中将溴化氢与市售4-溴-1，1，2-三氟丁-1-烯在惰性溶剂中进行反应，制得1，4-二溴-1，1，2-三氟丁烷。然后，此中间体可以在适宜溶剂如丙酮或水中用脱溴氟试剂处理，制得所述式(XXVI)化合物。
本领域技术人员可以理解的是，式(XXIII)化合物在等同的巯基和硫酮形式之间存在着互变异构平衡。为了简明起见，除非另有说明，本文中化合物均指它们的巯基形式。
式(XXIII)化合物可以由市售获得或者可以由市售的前体化合物经本领域公知的常规方法制得。
另外，所述式(I)化合物可以通过在本领域公知的此类置换反应条件下，将相应的式(XXVII)化合物(其中L也是易离去基团)与式(XXVIII)巯基化合物反应制得。优选的是，L为卤素或硝基。通常，所述反应是在室温氮气氛下，在相转移催化剂例如溴化四-正-丁基铵存在下，用两相溶剂系统如水/二氯甲烷进行。
所述式(XXVIII)巯基化合物通常以其S-乙酰基或其异硫脲(isothiouronium)氢溴酸盐的形式进行反应，此类化合物易于水解成所述式(XXVIII)巯基化合物。
所述式(I)化合物还可以由相应的式(XXIX)氨基化合物制得，例如，在适宜溶剂如二氯甲烷或乙腈中，在式(XXX)二硫化物存在下，用亚硝酸烷基酯如亚硝酸叔丁基酯可将其进行重氮化。
其中n为1或2的式(I)化合物可以用常规方法，例如在惰性有机溶剂中用适宜的氧化剂处理，将其中n为0的被相应取代的式(I)化合物进行氧化制得。通常，用一当量的适宜氧化剂将式(I)化合物进行氧化，可得到其中n为1的相应的式(I)化合物，而用二当量所述氧化剂进行氧化反应，可得到其中n为2的相应化合物。适宜的氧化剂包括有机和无机过氧化物例如过羧酸或其盐，如间氯过苯甲酸、过苯甲酸、单过氧邻苯二甲酸镁或过一硫酸钾。
这样，本发明另一方面还提供了一种制备其中n为1或2的式(I)化合物的方法，所述方法包括氧化其中n为0的被相应取代的式(I)化合物。
可以理解的是，除了由式(XXIII)、(XXVII)或(XXIX)相应取代的化合物制备式(I)化合物以外，可以用公知的化学方法进行随后的功能基转换以实现对所需环的取代。此类功能基转换的实例包括将硝基还原成氨基，卤化如氯化，将酯水解成酸，将醇氧化成酸，成盐。
本发明各种进一步优选的特征和实施方案将由下列说明性实施例更详细地说明，其中百分比为重量比并且使用下列缩写：mp＝熔点；bp＝沸点；g＝克；gc＝气相色谱；NMR＝核磁共振；s＝单峰；d＝双重峰；dd＝双重双峰；t＝三重峰；q＝四重峰；m＝多重峰；br＝宽峰；M＝摩尔；mM＝毫摩尔；CDCl3＝氘代氯仿。化学位移(δ)从四甲基硅烷测得，以ppm表示。除非另有说明，CDCl3用作NMR谱的溶剂。M+＝由质谱测定的分子离子峰；FAB＝快原子轰击法；tlc＝薄层色谱。
下面给出了用于制备本发明化合物的大量中间体化合物的合成方法，这些化合物中的某些化合物是本领域公知的化合物。
                     制备例1
此实施例阐明了经3-步法制备4-溴-4，4-二氟丁基甲磺酸酯的方法。
步骤1：4-溴-4，4-二氟丁酸
向搅拌下的丙烯酸(1.44g)和乙腈(80cm3)溶液中加入连二亚硫酸钠(4.18g)、碳酸氢钠(2.01g)、水(20cm3)并最后加入二溴二氟甲烷(5cm3)。将此两相混合物于室温下进行搅拌，无机盐逐渐溶解。4小时后GC分析表明丙烯酸已消耗完全。水相用固体氯化钠饱和，分出有机相，用硫酸镁干燥，过滤并减压蒸发，得到含有少量白色固体的浅黄色油状物。将此混合物溶于乙酸乙酯，过滤并减压蒸除溶剂，得到浅黄色油状物(2.54g)。1H NMR(DMSO-d6)：δ2.45(2H，t)；2.65(2H，m)。
步骤2：4-溴-4，4-二氟丁醇
于氮气氛下，将氢化锂铝的乙醚(5cm3，5mM)溶液冷至0℃。保持此温度，搅拌下滴加溶于无水乙醚(5cm3)中的4-溴-4，4-二氟丁酸(1g)。0℃1小时后，通过加入2M盐酸小心地使反应混合物骤冷。分出有机相，用饱和碳酸氢钠溶液洗涤，硫酸镁干燥，过滤并减压蒸发，得到一无色油状物(0.57g)。1H NMR：δ1.82-1.96(2H，m)；2.40-2.60(2H，m)；3.74(2H，t)。
步骤3：甲磺酸4-溴-4，4-二氟丁基酯
搅拌下将4-溴-4，4-二氟丁醇(0.57g)的无水乙醚(5cm3)溶液冷至0℃，保持此温度，加入三乙胺(1.7cm3)。10分钟后，加入甲磺酰氯(0.3cm3)并将混合物于0℃下再搅拌1小时。将反应混合物倾入2M盐酸(2cm3)和乙醚(20cm3)中，分出有机相，用饱和盐水洗涤，然后经过一硅胶柱，进一步用乙醚洗脱。将乙醚级份减压蒸发，得到淡黄色油状物(0.705g)。1H NMR：δ2.04-2.18(2H，m)；2.46-2.64(2H，m)；3.04(3H，s)；4.32(2H，t)。
                   制备例2
此实施例阐明了由市售4-溴-1，1，2-三氟丁-1-烯经3-步法制备4-甲基-苯磺酸4，4-二氟丁-3-烯基酯的方法。
步骤1：1，4-二溴-1，1，2-三氟丁烷的制备
将4-溴-1，1，2-三氟丁-1-烯(Fluorochem Ltd.)(240g)用水(300cm3)洗涤，然后用盐水(300cm3)洗涤并于使用前干燥(MgSO4)。一次加入过氧化苯甲酰(约0.7g)并以使反应温度保持在30-40℃的速度向混合物中通入溴化氢气。2小时后，反应混合物样品gc分析表明，仍有少量原料。将反应混合物用水(300cm3)，然后用饱和碳酸氢钠溶液并再用水(300cm3)洗涤，干燥(MgSO4)并过滤，得到浅黄色油状物(296.7g)，经鉴定为1，4-二溴-1，1，2-三氟丁烷。gc分析表明，此产物的纯度大于98％。1H NMR：δ2.38(2H，m)；3.57(2H，m)；4.90(1H，m)。
步骤2：4-甲基-苯磺酸4-溴-3，4，4-三氟丁基酯的制备
于室温避光下，将步骤1所得产物(1g)滴加到搅拌下的甲苯磺酸银(1.03g)的乙腈(10cm3)悬浮液中。然后将反应于回流下加热24小时，此后gc分析表明原料已消耗完全。将反应混合物冷却至室温，滤除沉淀并用乙酸乙酯洗涤。将滤液和乙酸乙酯洗涤液合并并用水洗涤，水层用乙酸乙酯萃取。合并的乙酸乙酯层用水和盐水洗涤，硫酸镁干燥并减压蒸发，得到褐色油状物(1.21g)。GC分析表明，此产物的纯度＞99％。1H NMR：δ2.20(2H，m)；2.46(3H，s)；4.19(2H，m)；4.74(1H，m)；7.38(2H，d)；7.80(2H，d)。
步骤3：4-甲基-苯磺酸4，4-二氟丁-3-烯基酯的制备
向搅拌下的锌粉(1.41g)和碘(1格令，催化剂)的甲醇(3cm3)悬浮液中加入对甲苯磺酸4-溴-3，4，4-三氟丁基酯(0.71g)的甲醇(2cm3)溶液。将反应混合物于回流下加热2.5小时，此后gc分析表明原料已消耗完全。于锌悬浮液中吸出有机相并将锌用3份乙酸乙酯洗涤。合并的乙酸乙酯部分用2M盐酸洗涤，硫酸镁干燥并减压蒸发，得到褐色液体(0.47g)。GC分析表明，此产物的纯度＞99％。1H NMR：δ2.35(2H，m)；2.46(3H，s)；4.01(2H，m)；4.15(1H，m)；7.38(2H，d)；7.79(2H，d)。
                    制备例3
此实施例阐明了由1，4-二溴-1，1，2-三氟丁烷制备4-溴-1，1-二氟丁-1-烯的方法。
于氮气氛下，将锌粉(0.88g)加入到搅拌下的1，4-二溴-1，1，2-三氟丁烷(1.38g)的含水(1滴)丙酮(6cm3)溶液中。45分钟后，gc分析表明大量原料已经被消耗。然后将此混合物加入到预加热至55℃含有痕量水的丙酮中的更多锌粉(3g)中，在此温度下20分钟后，gc分析表明所述原料已被全部消耗，说明脱溴氟反应业已开始。于75分钟内向所述反应中加入更多的原料(12.34g)，同时使反应混合物保持在55℃。然后继续加热95分钟，样品的GC分析表明约有3％的二溴起始化合物仍未被转化。再加入锌粉(0.16g)并继续加热，直至gc分析表明所有原料均已被消耗。由锌残余物中滗析出丙酮溶液，得到适用于进一步化学反应中的4-溴-1，1-二氟丁-1-烯溶液。
                     制备例4
此实施例阐明了4，4-二氟丁-3-烯基硫代乙酸酯的制备方法。
于室温氮气氛下，将硫代乙酸钾(1.98g)、4-溴-1，1-二氟丁-1-烯(3.0g)和溴化四正丁基铵(0.3g，催化剂)搅拌5小时并静置18小时。所述混合物用Kugelrohr仪进行蒸馏，得到无色液体状4，4-二氟丁-3-烯基硫代乙酸酯(1.12g)；1H NMR：δ2.25(2H，m)；2.30(3H，s)；2.90(2H，t)；4.20(1H，m)；(bp 115℃，120mmHg)。
                      制备例5
此实施例阐明了4，4-二氟丁-3-烯基异硫脲4-甲基-苯磺酸盐的制备方法。
将硫脲(0.29g)和4-甲基-苯磺酸4，4-二氟丁-3-烯基酯(1g)于乙醇(20cm3)中回流下一起加热24小时。将反应混合物冷却并减压蒸除溶剂，得到一油状物，令其缓慢析晶。用己烷研制，得到以其4-甲基-苯磺酸盐形式存在的(4，4-二氟丁-3-烯基)-硫脲(1.14g)。MH+(FAB)＝167；1H NMR(DMSO-d6)：δ2.48(3H，s)；2.46-2.58(2H，m)；3.42(2H，t)；4.66-4.84(1H，m)；7.32(2H，d)；7.68(2H，d)；9.10-9.40(3H，br)。
                      制备例6
此实施例阐明了4，4-二氟丁-3-烯基异硫脲氢溴酸盐的制备方法。
将硫脲(18.5g)加入到4-溴-1，1-二氟丁-1-烯(41.5g)的乙醇(150cm3)溶液中并于搅拌下加热回流18小时。将反应混合物冷却至室温并减压蒸发。所得蜡状固体用乙醚洗涤，过滤，再用乙醚洗涤并吸滤干燥，得到无色固体状所需产物(57g)。MH+＝167；1HNMR(DMSO-d6)：δ2.20(2H，m)；3.20(2H，t)；4.50(1H，m)；8.95(4H，宽单峰)。
用N-甲基硫脲代替硫脲，用上述方法可制得上述中间体的N-甲基衍生物。MH+＝181；1H NMR(DMSO-d6)：δ2.45-2.55(2H，m)；3.0-3.05(3H，d)；3.4-3.5(2H，t)；4.30-4.45(1H，m)；(m.p.74-77.2℃)。
                      制备例7
此实施例阐明了二-(4，4-二氟丁-3-烯基)二硫化物的制备方法。
将二硫化钠(预先由硫化钠一水合物(53g)和硫(7.0g)于乙醇(250cm3)中制得)加入到1-溴-4，4-二氟丁-3-烯(50g)的乙醇(100cm3)溶液中。将反应混合物逐渐加热并于回流下搅拌2小时，然后冷却并减压蒸发。残余物用乙醚萃取，将有机相过滤以除去溴化钠并减压蒸除乙醚，得到一液体，将其于16mmHg，bp120℃下进行蒸馏，得到无色液体状二-(4，4-二氟丁-3-烯基)二硫化物(24g)。
                      实施例II.1
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)呋喃(化合物II.1)的制备方法。
于搅拌下，将丁基锂(6.5cm3，2.5M乙醚溶液)滴加到呋喃(1g)的乙醚(40cm3)溶液中。90分钟后，将反应混合物加热回流30分钟，然后冷至室温。搅拌下分批加入硫粉(0.48g)，2小时后，加入4-溴-1，1-二氟丁-1-烯(3.0g)并于室温下继续搅拌18小时。反应用水中止，产物用乙醚萃取。将合并的有机萃取液干燥，过滤并蒸发，得到深褐色液体。于硅胶上进行色谱分离(用己烷-乙醚混合液洗脱)，得到化合物II.1(0.965g)。1H NMR：δ2.2-2.3(2H，m)；2.7-2.8(2H，t)；4.15-4.35(1H，m)；6.4(1H，dd)；6.53(1H，d)；7.5(1H，d)；(油状物)。
                      实施例II.2
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)-5-甲基呋喃(化合物II.4)的制备方法。
于搅拌下，将丁基锂(5.4cm3，2.5M乙醚溶液)滴加到呋喃(1g)的乙醚(40cm3)溶液中。90分钟后，将反应混合物回流加热30分钟，然后冷至室温。搅拌下分批加入硫粉(0.38g)，2小时后，加入4-溴-1，1-二氟丁-1-烯(2.05g)并继续搅拌18小时。反应用水中止，产物用乙醚萃取。将合并的有机萃取液干燥，过滤并蒸发。于硅胶上进行色谱分离(用己烷-乙醚混合液洗脱)，得到化合物II.4(1.25g)。1H NMR：δ2.2-2.3(2H，m)；2.3(3H，s)；2.7-2.77(2H，t)；           4.16-4.34(1H，m)；5.97(1H，m)；6.43(1H，d)；(油状物)。
                      实施例II.3
此实施例阐明了3-(4，4-二氟丁-3-烯基硫基)-2-甲基呋喃(化合物II.7)的制备方法。
含有2-甲基-3-呋喃硫醇(2.0g)、4-溴-1，1-二氟丁-1-烯(3.24g)和碳酸钾(2.48g)的丙酮(50cm3)溶液回流下加热2小时，然后令其静置18小时。反应用水中止，产物用乙醚萃取。将合并的有机相干燥，过滤并蒸发。于硅胶上进行色谱分离(用10％乙醚的己烷溶液洗脱)，得到化合物II.7(2.338g)；M+＝204；1H NMR：δ2.1-2.25(2H，m)；2.35(3H，s)：2.65(2H，t)；4.1-4.3(1H，m)；6.3(1H，d)；7.3(1H，d)；(油状物)。
                     实施例II.4
此实施例阐明了2-(4，4-二氟丁-3-烯基亚磺酰基)呋喃(化合物II.2)的制备方法。
在冰浴冷却下将3-氯过苯甲酸(0.54g 50％固体重量比，1.58mM)分批加入到化合物II.1(0.30g)的二氯甲烷(5cm3)溶液中。搅拌4小时后，反应于乙酸乙酯和2M NaOH溶液之间配分。分出有机层，再用2MNaOH溶液洗涤，硫酸镁干燥，过滤并蒸发，得到化合物II.2(0.210g)。1H NMR：δ2.3-2.5(2H，m)；3.1-3.4(2H，m)；4.15-4.35(1H，m)；6.5(1H，dd)；7.0(1H，d)；7.7(1H，d)；(油状物)。
用上述方法可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基磺酰基)呋喃(化合物II.3)；1H NMR：δ2.44-
2.55(2H，m)；3.25-3.3(2H，t)；4.1-4.3(1H，m)；6.6(1H，dd)；7.23(1H，d)；
7.67(1H，d)(油状物)，用2.1当量氧化剂由化合物II.1制得。(ii)2-(4，4-二氟丁-3-烯基亚磺酰基)-5-甲基呋喃(化合物II.5)；1H NMR：δ
2.3-2.45(5H，m)；3.0-3.15和3.3-3.4(共2H，m)；4.2-4.3(1H，m)；6.1(1H，
d)；6.85(1H，d)；(油状物)，用1当量氧化剂由化合物II.4制得。(iii)2-(4，4-二氟丁-3-烯基磺酰基)-5-甲基呋喃(化合物II.6)；1H NMR：δ
2.4-2.55(5H，m)；3.2-3.28(2H，t)；4.15-4.3(1H，m)；6.2(1H，d)；7.1(1H，
d)；(油状物)，用2.1当量氧化剂由化合物II.4制得。(iv)3-(4，4-二氟丁-3-烯基亚磺酰基)-2-甲基呋喃(化合物II.8)；1H NMR：
δ2.3-2.45(5H，m)；2.8-2.9和3.1-3.2(共2H，m)；4.2-4.35(1H，m)；
6.66(1H，d)；7.4(1H，d)，用1当量氧化剂由化合物II.4制得。(v)3-(4，4-二氟丁-3-烯基磺酰基)-2-甲基呋喃(化合物II.9)；1H NMR：δ
2.42-2.52(2H，m)；2.6(3H，s)；3.2-3.28(2H，t)；4.1-4.23(1H，m)；6.6(1H，
d)；7.36(1H，d)，用2.1当量氧化剂由化合物II.4制得。
                  实施例III.1
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)噻吩(化合物III.1)的制备方法。
将含有2-巯基噻吩(10g)、4-溴-1，1-二氟丁-1-烯(15.47g)和碳酸钾(11.87g)的丙酮(250cm3)溶液回流加热2小时，然后令其静置18小时。反应用水中止并用乙醚萃取数次。合并的有机萃取液用硫酸镁干燥，过滤并蒸发，得到一琥珀色油状物。于硅胶上进行色谱分离(用5％乙醚的己烷溶液洗脱)，得到化合物III.1(9.5g)；M+＝206；1H NMR：δ2.2-2.4(2H，m)；2.8(2H，t)；4.1-4.3(1H，m)；6.95-7.0(1H，dd)；7.15(1H，d)；7.35(1H，d)；(油状物)。
用上述方法可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基硫基)苯并[b]噻吩(化合物III.10)；1H NMR：δ
2.2-2.3(2H，m)；2.7-2.8(2H，t)；4.15-4.35(1H，m)；6.4(1H，dd)；6.53(1H，
d)；7.5(1H，d)，由苯并噻吩制得。
                   实施例III.2
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)-5-甲酰基噻吩(化合物III.4)的制备方法。
将化合物III.1(1.0g)缓慢地加入到含有二甲基甲酰胺(0.48cm3)和磷酰氯(0.56cm3)的溶液中，反应混合物于100℃下加热2小时，于冰浴中冷却，然后用2M NaOH溶液中和。水溶液用乙醚萃取两次并将合并的有机层用水和NaHCO3溶液洗涤。将有机萃取液用硫酸镁干燥，过滤并蒸发，得到黑色液体。经硅胶过滤(用20％乙醚的己烷溶液洗脱)，得到化合物III.4(0.91g)。M+＝234；1H NMR：δ2.4(2H，m)；3.0(2H，t)；4.2-4.4(1H，m)；7.1(1H，d)；7.7(1H，d)；9.8(1H，s)；(油状物)。
                      实施例III.3
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)-5-羟甲基噻吩(化合物III.5)的制备方法。
将硼氢化钠(0.065g)加入到化合物III.4(0.75g)的乙醇(21cm3)和水(9cm3)溶液中。将反应混合物于室温下搅拌2小时，用2M盐酸使反应中止，然后于水和乙醚之间配分。有机相用硫酸镁干燥，过滤并蒸发，得到绿色液体。于硅胶上进行色谱分离(用20％乙酸乙酯的己烷溶液洗脱)，得到化合物III.5(0.44g)。M+＝236；1H NMR：δ1.8-2.0(1H，br s)；2.3(2H，m)；2.8(2H，t)；4.1-4.3(1H，m)；4.8(2H，s)；6.8(1H，d)；7.0(1H，d)；(油状物)。
                     实施例III.4
此实施例阐明了(E)-和(Z)-2-(4，4-二氟丁-3-烯基硫基)-5-羟基亚氨基噻吩(化合物III.6和III.7)的制备方法。
于乙醇(15cm3)和水(15cm3)中将羟胺盐酸盐(0.9g)和碳酸氢钠(1.09g)一起搅拌5分钟，加入化合物III.4(3g)并将反应混合物于室温下搅拌2小时，然后令其静置18小时。反应混合物于水和乙醚之间配分，有机相用硫酸镁干燥，过滤并蒸发，得到琥珀色液体(3.4g)。于硅胶上进行色谱分离(用20％乙酸乙酯的己烷溶液洗脱)，得到化合物III.6(1.5g)和III.7(1.3g)。M+＝249；1H NMR：δ2.25-2.35(2H，m)；2.85(2H，t)；4.14-4.35(1H，m)；7.05(2H，m)；7.52(1H，br s)；8.18(1H，s)；(油状物)和M+＝249；δ2.25-2.38(2H，m)；2.85-2.95(2H，t)；4.18-4.35(1H，m)；7.08(1H，d)；7.25(1H，d)；7.64(1H，s)；(油状物)。
                    实施例III.5
此实施例阐明了5-氰基-2-(4，4-二氟丁-3-烯基硫基)噻吩(化合物III.8)的制备方法。
将1，1′-羰基-二咪唑(0.326g)加入到化合物III.6(0.5g)的溶液中并将反应混合物于室温下搅拌10分钟，然后回流下加热2小时，令其静置18小时。再加入一当量的1，1′-羰基-二咪唑并将反应混合物回流加热1小时。反应混合物经硅藻土过滤，然后蒸发，得到化合物III.8(0.28g)。1H NMR：δ2.27-2.38(2H，m)；2.94(2H，t)；4.15-4.33(1H，m)；7.05(1H，d)；7.5(1H，d)；(油状物)。
                  实施例III.6
此实施例阐明了5-乙酰基-2-(4，4-二氟丁-3-烯基硫基)噻吩(化合物III.9)的制备方法。
将甲基溴化镁溶液(1.3cm3，3M乙醚溶液，3当量)缓慢加入到化合物III.8(0.3g)的四氢呋喃(10cm3)溶液中。将反应混合物于室温下搅拌3小时，然后蒸除溶剂。残余物于氢氧化铵溶液和氯仿之间配分，有机层用水洗涤，Na2SO4干燥并蒸发。残余物于硅胶上进行色谱分离(用10％乙酸乙酯的己烷溶液洗脱)，得到化合物III.9(0.16g)。1H NMR：δ2.30-2.40(2H，m)；2.50(3H，s)；2.97(2H，t)；4.15-4.33(1H，m)；7.04(1H，d)；7.55(1H，d)；(油状物)。
                    实施例III.7
此实施例阐明了2-(4，4-二氟丁-3-烯基亚磺酰基)噻吩(化合物III.2)的制备方法
室温下将化合物III.1(0.50g)于二氯甲烷(5cm3)中进行搅拌并加入3-氯过苯甲酸(0.834g，50％固体重量比，1当量)。tlc显示原料消耗完全后，通过加入饱和碳酸氢钠水溶液使反应中止，产物用二氯甲烷萃取。分出有机相，用饱和盐水洗涤并用硫酸镁干燥。过滤后，减压蒸发浓缩，得到一液体(0.584g)，将其于硅胶上进行色谱纯化，用20％乙酸乙酯的己烷溶液作洗脱剂，然后用乙醚洗脱得到化合物III.2(0.29g)。1H NMR：δ2.3-2.55(2H，m)；2.9-3.2(2H，m)；4.2-4.5(1H，m)；7.15(1H，m)；7.5(1H，m)；7.7(1H，m)；(油状物)。
用上述方法可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基磺酰基)噻吩(化合物III.3)；1H NMR：δ2.4-
2.6(2H，m)；3.2-3.4(2H，t)；4.1-4.3(1H，m)；7.15(1H，dd)；7.7-7.8(1H，m)；
(油状物)，用2当量氧化剂由化合物III.1制得。(ii)2-(4，4-二氟丁-3-烯基亚磺酰基)苯并[b]噻吩(化合物III.11)；1H NMR：
δ2.3-2.4(2H，m)；3.0-3.2(2H，m)；4.2-4.4(1H，m)；7.45(2H，m)；7.9
(2H，m)；7.75(1H，s)，用1当量氧化剂由化合物III.10制得。(iii)2-(4，4-二氟丁-3-烯基磺酰基)苯并[b]噻吩(化合物III.12)；1H NMR：
δ2.5(2H，m)；3.3(2H，t)；4.2-4.35(1H，m)；7.5(2H，m)；7.9(3H，m)，用2
当量氧化剂由化合物III.10制得。
                   实施例IV.1
此实施例阐明了5-(4，4-二氟丁-3-烯基硫基)-3-甲基异噁唑-4-羧酸乙酯(化合物IV.8)的制备方法。
将4，4-二氟丁-3-烯基硫代乙酸酯(2g)的50％氢氧化钠溶液(6.7cm3)剧烈搅拌30分钟，加入5-氯-4-甲基异噁唑乙酯(2.2g)的二氯甲烷(12cm3)溶液，随后加入溴化四正丁基铵(催化剂)，将反应于室温氮气氛下进行搅拌。3小时后分层，有机相用盐水洗涤，干燥(MgSO4)，过滤并减压蒸发。残余物与880氨一起搅拌以生成结晶。过滤分离出结晶，得到化合物IV.8(2.87g)。1H NMR：δ1.35(3H，t)；2.45(3H，s)；2.50(2H，m)；3.20(2H，t)；4.25(1H，m)；4.30(2H，q)；(mp 41-42℃)。
                    实施例IV.2
此实施例阐明了5-(4，4-二氟丁-3-烯基硫基)-3-甲基异噁唑-4-羧酸(化合物IV.9)的制备方法。
将化合物IV.8(0.5g)的异丙醇(5cm3)和2M NaOH(1cm3)溶液搅拌3小时，然后将混合物倾入水中并用乙酸乙酯洗涤。水层用2M HCl酸化，产物用乙酸乙酯萃取。将萃取液干燥(MgSO4)，过滤并减压蒸发，得到化合物IV.9(0.16g)。M+＝249；1H NMR：δ2.45(3H，s)；2.50(2H，m)；3.20(2H，t)；4.20-4.40(1H，m)；(mp 132-133℃)。
                      实施例IV.3
此实施例阐明了5-(4，4-二氟丁-3-烯基硫基)-3-甲基异噁唑-4-甲酰胺(化合物IV.7)的制备方法。
于0℃下将三乙胺(0.33cm3)和氯代甲酸乙酯(0.24cm3)加入到化合物IV.9(0.56g)的二氯甲烷(15cm3)溶液中。令反应温热至室温并搅拌2小时。向所述溶液中通入氨气直至饱和，然后再将反应搅拌1小时。加入氨水并将产物用二氯甲烷萃取，有机相用水洗涤，干燥(MgSO4)，过滤并减压蒸发。于kugelrohr仪中经蒸馏纯化，得到化合物IV.7(0.069g)。1H NMR：δ2.45(2H.m)；2.50(3H，s)；3.25(2H，t)；4.25(1H，m)；(mp 87℃)。
                   实施例IV.4
此实施例阐明了3-(5-氯呋喃-2-基)-5-(4，4-二氟丁-3-烯基硫基)异噁唑(化合物IV.23)的制备方法
在丙酮/冰浴冷却下，将硫化氢气通入搅拌下的甲醇钾(1.9g)的乙醇(10cm3)溶液中。加入5-氯-3-(5-氯呋喃-2-基)异噁唑(2.2g)并将反应于回流下加热1小时，其间蒸发掉溶剂。加入丙酮(10cm3)和4-溴-1，1-二氟丁-1-烯(2g)并将混合物于回流下再加热2小时。将所得溶液冷却，倾入乙醚和盐水中并分层。水层用乙醚萃取，将合并的有机相用盐水洗涤，干燥(MgSO4)，过滤并减压蒸发，得到黑色固体。于硅胶上经柱色谱法纯化，用10％乙醚的己烷溶液作洗脱剂，得到化合物IV.23(2g)。M+＝291；1H NMR δ2.35-2.50(2H，m)；3.10(2H，t)；4.30(1H，m)；6.30(1H，d)；6.43(1H，s)；6.90(1H，d)；(mp 80-82℃)。
用上述方法可制得下列本发明化合物：
(i)5-(4，4-二氟丁-3-烯基硫基)-3-苯基异噁唑(化合物IV.1)，M+＝267；1H NMR：δ2.43(2H，m)；3.10(2H，t)；4.28(1H，m)；6.50(1H，s)；7.45(3H，m)；7.78(2H，m)；(油状物)，由5-氯-3-苯基异噁唑制得。
                      实施例IV.5
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)-3-甲基异噁唑(化合物IV.10)的制备方法。
于0℃氮气氛下，向搅拌下的丙酮肟(0.365g)的无水四氢呋喃(20cm3)溶液中加入正丁基锂(4.6cm3，2.5M己烷溶液)，结果生成浅黄色沉淀。于0℃搅拌30分钟后，加入二硫化碳(0.3cm3)，生成淡黄色溶液。再过10分钟后，加入3M HCl(20cm3)并将反应于回流下加热3小时，然后冷却。分层，水层用氯仿萃取。将合并的有机层干燥(MgSO4)，过滤并减压蒸发，得到一褐色油状物。然后将此油状物溶于丙酮(11cm3)并加入1-溴-4，4-二氟丁-3-烯(0.77g)和碳酸钾(0.87g)，将反应回流下加热3.5小时，然后冷却。将混合物倾入乙酸乙酯和2M HCl中并分层。水层用乙酸乙酯萃取，将合并的有机相干燥(MgSO4)，过滤并减压蒸发，得到一褐色油状物。于硅胶上经柱色谱法纯化，用1∶9乙酸乙酯∶己烷作洗脱剂，得到2-(4，4-二氟丁-3-烯基硫基)-3-甲基异噁唑(0.105g)。M+＝205；1H NMR：δ2.30(3H，s)；2.40(2H，m)；3.05(2H，t)；4.25(1H，m)；6.00(1H，s)；(油状物)。
                    实施例IV.6
此实施例阐明了3-(5-氯呋喃-2-基)-5-(4，4-二氟丁-3-烯基磺酰基)异噁唑(化合物IV.24)的制备方法。
向搅拌下于冰/丙酮浴中冷却的化合物IV.23(2g)的甲醇(40cm3)溶液中加入单过氧邻苯二甲酸镁(9.4g)。搅拌30分钟后，除去冷却浴并将反应温热至室温，搅拌1小时。将混合物倾入乙醚和盐水中并分层。将合并的有机相用2M NaOH、水和盐水洗涤，干燥(MgSO4)，过滤并减压蒸发，得到化合物IV.24(1.9g)。M+＝323；1H NMR：δ2.50-2.60(2H，m)；3.40(2H，t)；4.25(1H，m)；6.38(1H，d)；7.05(1H，d)；7.20(1H，s)；(mp 86.5-88.5℃)。
用上述方法可制得下列本发明化合物：(i)5-(4，4-二氟丁-3-烯基亚磺酰基)-3-苯基异噁唑(化合物IV.2)，
M+＝283；1H NMR：δ2.53(2H，m)；3.25(2H，t)；4.29(1H，m)；
7.18(1H，s)；7.50(3H，m)；7.80(2H，m)；(油状物)，由化合物IV.1和1
当量氧化剂制得。(ii)5-(4，4-二氟丁-3-烯基磺酰基)-3-苯基异噁唑(化合物IV.3)，
M+＝299；1H NMR：δ2.57(2H，m)；3.43(2H，t)；4.27(1H，m)；
7.2(1H，s)；7.51(3H，m)；7.80(2H，m)；(mp57-58.5℃)，由化合物IV.1
和2当量氧化剂制得。(iii)3-(噻吩-2-基)-5-(4，4-二氟丁-3-烯基磺酰基)异噁唑(化合物IV.26)，
M+＝305；1H NMR：δ2.50-2.63(2H，m)；3.41(2H，t)；4.27(1H，m)；
7.20(1H，s)；7.14-7.23(1H，m)；7.52(2H，m)；(mp55-57℃)，由3-(噻
吩-2-基)-5-(4，4-二氟丁-3-烯基硫基)异噁唑，化合物IV.25制得，
化合物IV.25本身由5-氯-3-(噻吩-2-基)异噁唑经实施例IV.4的方
法制得。
                  实施例V.1
此实施例阐明了3-氯-4-氰基-5-(4，4-二氟丁-3-烯基硫基)异噻唑(化合物V.2)的制备方法。
于15分钟内，将4-氰基-3，5-二氯异噻唑(1g)的甲醇(10cm3)溶液加到加热至50℃的硫化钠一水合物(1.3g)的水(2.6cm3)和甲醇(25cm3)溶液中。将反应搅拌1小时，然后减压蒸除溶剂，得到一黄色固体。将此残余物溶于丙酮(20cm3)，加入4-溴-1，1-二氟丁-1-烯(0.68g)并将反应搅拌12小时。将所得混合物倾入水中并分层，水层用乙酸乙酯萃取。将合并的有机相干燥(MgSO4)，过滤并减压蒸发。于硅胶上经柱色谱法纯化，用1∶1乙酸乙酯∶己烷作洗脱剂，得到化合物V.2(0.88g)。M+＝266；1H NMR：δ2.50(2H，m)；3.20(2H，t)；4.20-4.40(1H，m)；(油状物)。
用上述方法可制得下列本发明化合物：(i)3，5-二-(4，4-二氟丁-3-烯基硫基)-4-氰基异噻唑(化合物V.12)。1H
NMR δ 2.40-2.60(4H，m)；3.20(2H，t)；3.30(2H，t)；4.20-4.40(2H，m)；(油
状物)。
                     实施例V.2
此实施例阐明了5-(4，4-二氟丁-3-烯基磺酰基)-4-氰基异噻唑(化合物V.6)和3，5-二-(4，4-二氟丁-3-烯基磺酰基)-4-氰基异噻唑(化合物V.15)的制备方法。
向化合物V.12(0.1g)的二氯甲烷(5cm3)溶液中加入3-氯过苯甲酸(0.42g)并搅拌反应混合物直至原料消失。将反应混合物倾入乙酸乙酯和水中并分层，水层用乙酸乙酯萃取。合并的乙酸乙酯相用碳酸氢钠洗涤，干燥(MgSO4)，过滤并减压蒸发。将残余物溶于乙醚并加入三乙胺使溶液变浑浊。然后将乙醚溶液用水洗涤，干燥(MgSO4)，过滤并蒸发。残余物于硅胶上经柱色谱法进行纯化，用1∶1乙酸乙酯∶己烷作洗脱剂，得到化合物V.15(0.01g)；M+＝418；1H NMRδ2.60-2.70(4H，m)；3.60(4H，t)；4.30(2H，m)；(油状物)和化合物V.6(0.08g)；M+＝264；1HNMRδ2.60(2H，m)；3.60(2H，t)；4.30(1H，m)；9.40(1H，s)；(油状物)。
                     实施例VI.1
在2、4或5-位上被4，4-二氟丁-3-烯基硫基取代的噁唑类化合物可以由相应取代的巯基-噁唑和适宜的二氟丁-1烯烷基化剂制得。这可通过下列2-(4，4-二氟丁-3-烯基硫基)-5-苯基噁唑(化合物VI.18)的制备得以说明。
向2-巯基-5-苯基噁唑(0.44g)的丙酮(15cm3)溶液中加入4-甲基-苯磺酸4，4-二氟-3-丁烯基酯(0.7g)和碳酸钾(0.369g)并将反应回流加热共8小时，此后仍残有部分对甲苯磺酸酯原料。再加入2-巯基-5-苯基噁唑(0.05g)并继续加热5小时，将反应混合物冷却，倾入乙醚和水中并分层。水层用乙醚萃取并将合并的有机相干燥(MgSO4)，减压蒸发，得到一黄色液体。用5％叔丁基二甲基醚的己烷溶液于硅胶上进行色谱纯化，得到化合物VI.18；M+＝267；1H NMR(CDCl3)δ2.51(2H，m)；3.23(2H，t)；4.3O(1H，m)；7.23-7.47(4H，m)；7.58(2H，d)；(油状物)。
用上述方法可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基硫基)-噁唑(化合物VI.1)，1H NMR(CDCl3)δ
2.45(2H，m)；3.20(2H，t)；4.25(1H，m)；7.10(1H，s)；7.66(1H，s)；(油状
物)，由噁唑-2-硫酮制得。(ii)2-(4，4-二氟丁-3-烯基硫基)-4-甲基噁唑(化合物VI.6)，M+205；1H
NMRδ：2.04(3H，s)；2.45(2H，m)；3.18(2H，t)；4.25(1H，m)；7.38
(1H，q)；(油状物)，由2-巯基-4-甲基噁唑制得。
                    实施例VI.2
此实施例阐明了3-步法制备2-(4，4-二氟丁-3-烯基硫基)4-甲基噁唑-5-羧酸甲酯(化合物VI.32)的方法。
步骤1：2-氨基-4-甲基噁唑-5-羧酸甲酯
于甲醇(200cm3)中将3-氯代乙酰乙酸甲酯(75g)和尿素(90g)进行搅拌并加热回流24小时。将反应混合物冷却至室温并从溶液中滤出沉淀，用冷甲醇洗涤并吸滤干燥。将此固体用2M氢氧化钠水溶液处理并将产物用乙酸乙酯萃取(数次)。减压下蒸除溶剂，得到一无色固体(14.5g)，将其于乙腈中重结晶，mp 225℃(分解)1H NMR(DMSO-d6)：δ2.15(3H，s)；3.75(3H，s)；7.4(2H，br)。
步骤2：2-氯-4-甲基噁唑-5-羧酸甲酯
将步骤1中所得产物(1.56g)分批溶于无水乙腈(40cm3)中并于8℃氮气氛下分批加入到搅拌下的氯化铜(II)(1.61g)和亚硝酸叔丁基酯于乙腈(无水，20cm3)中的混合物中，将所得褐色溶液于20℃下搅拌2小时并减压蒸发。残余物用2M盐酸水溶液处理，产物用乙醚萃取。将有机相干燥(MgSO4)，然后经过一短硅胶柱用乙醚洗涤。将滤液减压蒸发，得到所需黄色固体状中间体(0.9g)。M+＝175。
步骤3：2-(4，4-二氟丁-3-烯基硫基)4-甲基噁唑-5-羧酸甲酯
将步骤2中所得产物(0.176g)和硫脲(0.084g)于乙醇(5cm3)中进行搅拌并于氮气氛下回流加热5小时。将反应冷却并减压蒸除溶剂，得到一黄色胶状物，将其溶于含有4-溴-1，1-二氟丁-1-烯(0.17g)和碳酸钾(0.2g)的丙酮中，将混合物于室温氮气氛下搅拌1小时并静置18小时。减压蒸除溶剂，残余物用水和乙醚处理。分出有机相，干燥(MgSO4)并蒸发，得到化合物VI.32(0.095g)；M+＝175。1H NMR：δ2.45(5H，m)；3.22(2H，t)；3.90(3H，s)；4.25(1H，m)；(油状物)。
                      实施例VI.3
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)-4-甲基噁唑-5-羧酸(化合物VI.37)的制备方法。
将化合物VI.32(0.4g)溶于含有氢氧化钠水溶液(2cm3，2M溶液)的丙-2-醇(10cm3)中并于室温下搅拌5小时。将混合物减压蒸发并将残余物溶于水，用乙酸乙酯萃取，用稀盐酸酸化并用乙酸乙酯(3×100cm3)再萃取。将后一萃取液合并，用饱和盐水洗涤，干燥(MgSO4)并减压蒸发，得到无色固体状所需产物(0.3g)。M+＝249；1H NMR：δ2.5(5H，m)；3.27(2H，t)；4.27(1H，m)；6.5(1H，br s)；(mp 66-68℃)。于室温下，用甲醇钠的无水甲醇溶液(将0.061g钠金属溶于甲醇(10cm3))处理样品(0.7g)以制得此化合物的钠盐，减压蒸除溶剂，得到无色固体状化合物VI.37的钠盐；M+(FAB)＝271；(mp 211-212℃).
用上述方法可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基硫基)-4-三氟甲基噁唑-5-羧酸(化合物VI.36)，
M+＝303；1H NMR：δ2.54(2H，m)；3.32(2H，t)；4.28(1H，m)；7.65(1H，br
s)，由化合物VI.31制得。
                     实施例VI.4
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)-4-三氟甲基噁唑(化合物VI.4)的制备方法。
于0℃下将含有二-(4，4-二氟丁-3-烯基)二硫化物(2.71g)的2-氨基-4-三氟甲基噁唑(0.84g)的二氯甲烷(25cm3)溶液进行搅拌并于氮气氛下滴加亚硝酸叔丁基酯(0.62g)进行处理。将反应溶液减压蒸发，残余物经色谱法(硅胶，己烷洗脱)进行分离，得到化合物VI.4(0.35g)。M+＝259；1H NMR：δ2.50(2H，m)；3.26(3H，t)；4.28(1H，m)；7.95(1H，q)；(油状物)。
用上述方法由相应的氨基噁唑化合物可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基硫基)-4-三氟甲基噁唑-5-羧酸乙酯(化合物
VI.31)，MH+＝322；1H NMR：δ1.40(3H，t)；2.52(2H，m)；3.30(2H，m)；
4.28(1H，m)；4.43(2H，q)；(油状物)，由2-氨基-4-三氟甲基噁唑-5-羧
酸乙酯(以实施例VI.2相似的方法由1，1，1-三氟甲基乙酰乙酸乙酯
和尿素制得)制得。
                    实施例VI.5
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)-5-氯噁唑(化合物VI.13)的制备方法。
将化合物VI.1(2.0g)溶于含有N-氯代琥珀酰亚胺(1.50g)的乙腈(50cm3)中并于室温下搅拌24小时。将混合物减压蒸发，用己烷(50cm3)萃取，过滤并将滤液减压蒸发。残余物经色谱法(硅胶；20％乙醚的己烷溶液洗脱)进行分离，得到化合物VI.13(0.75g)。M+＝225；1H NMR：δ2.46(2H，m)；3.16(2H，t)；4.28(1H，m)；6.86(1H，s)；(油状物)。
用上述方法由化合物VI.6可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基硫基)-4-甲基-5-氯噁唑(化合物VI.15)，
M+＝239；1H NMR：δ2.05(3H，s)；2.45(2H，m)；3.15(2H，t)；
4.25(1H，m)；(油状物)。
                  实施例VI.6
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)-4-甲基噁唑-5-甲酰胺(化合物VI.40)的制备方法。
将化合物VI.32(1.5g)溶于甲醇(10cm3)并于室温下用氨水(35cm3，密度为0.88)处理。将混合物搅拌5小时，用盐水稀释并将产物用乙酸乙酯(2×100cm3)萃取。将合并的有机相用盐水(4×50cm3)洗涤，干燥(MgSO4)并减压蒸发；残余物用己烷洗涤，得到化合物VI.40(1g)。M+＝248；1H NMR(DMSO-d6)：δ2.50(5H，m)；3.26(2H，t)；3.85(3H，s)；4.28(1H，m)；5.6，6.0(2H，br s)；(mp 72-73℃)。
                    实施例VI.7
此实施例阐明了5-氰基-2-(4，4-二氟丁-3-烯基硫基)-4-甲基噁唑(化合物VI.25)的制备方法。
于室温下将化合物VI.40(0.64g)溶于含有无水吡啶(1cm3)的二氯甲烷(10cm3)中并用甲磺酰氯(0.5cm3)处理。将溶液搅拌5小时，静置72小时，再加入甲磺酰氯(0.25cm3)和吡啶(0.5cm3)，搅拌8小时并静置48小时。将混合物用稀盐酸处理，产物用乙酸乙酯萃取。将合并的有机相用盐水洗涤并干燥(MgSO4)。过滤后，减压蒸除溶剂并将残余物经色谱法(硅胶；10％乙酸乙酯的己烷溶液洗脱)进行分离，得到化合物VI.25(0.46g)。M+＝230；1H NMR：δ2.32(3H，s)；2.50(2H，m)；2.58(3H，s)；3.25(2H，t)；3.85(3H，s)；4.28(1H，m)；(油状物)。
                    实施例VI.8
此实施例阐明了N-甲磺酰基2-(4，4-二氟丁-3-烯基硫基)-4-甲基-噁唑甲酰胺(化合物VI.38)的制备方法。
于室温下将化合物VI.37的钠盐(0.52g)于己烷(6.5cm3)中进行搅拌并用草酰氯(0.275g)处理。将混合物搅拌6小时，静置18小时并减压蒸发。将含有噁唑甲酰氯衍生物的残余物用甲磺酰胺(0.20g)的无水丁-2-酮(5cm3)溶液处理，搅拌下回流加热8小时，冷却至室温并静置18小时。将混合物减压蒸发，残余物溶于水，用2M盐酸酸化并将产物用乙醚(2×150cm3)萃取。将乙醚萃取液合并，用饱和氯化钠水溶液洗涤，干燥(MgSO4)，减压蒸发并将残余物经色谱法(硅胶；乙腈洗脱)纯化，得到化合物VI.38(0.20g)。M+＝326；1H NMR：δ2.50(5H，m)；3.27(2H，t)；3.40(3H，s)；4.28(1H，m)；(mp 60-62℃)。
                      实施例VI.9
此实施例阐明了2-(4，4-二氟丁-3-烯基亚磺酰基)-5-苯基噁唑(化合物VI.19)的制备方法。
向化合物VI.18(1g)的二氯甲烷(40cm3)溶液中加入3-氯过苯甲酸(1.3g，50％固体重量比，(1当量))并将反应于室温下搅拌5小时。将反应混合物倾入乙醚和碳酸氢钠水溶液的混合物中，分层。将有机层干燥(MgSO4)并减压蒸发，得到一白色固体，将其于硅胶上经色谱法纯化，用1∶4乙酸乙酯∶己烷洗脱，得到化合物VI.19(0.567g)。M+＝283；1HNMR：δ2.50(2H，m)；3.41(2H，t)；4.29(1H，m)；7.27(1H，s)；7.38-7.55(3H，m)；7.71(2H，d)；(油状物)。
用上述一般方法，只是使用2当量的3-氯过苯甲酸，由相应的硫醚类化合物可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基磺酰基)-4-三氟甲基噁唑(化合物VI.5).1H
NMR：δ2.65(2H，m)；3.58(2H，t)；4.28(1H，m)；8.24(1H，q)；(油状
物)。(ii)5-氯-2-(4，4-二氟丁-3-烯基磺酰基)噁唑(化合物VI.14).MNH4 +＝275；
1H NMR：δ2.60(2H，m)；3.47(2H，t)；4.26(1H，m)；7.18(1H，s)；(油状
物)。(iii)5-氯-2-(4，4-二氟丁-3-烯基磺酰基)-4-甲基噁唑(化合物VI.16).1H
NMR：δ2.25(3H，s)；2.60(2H，m)；3.45(2H，t)；4.26(1H，m)；(油状物)。(iV)2-(4，4-二氟丁-3-烯基磺酰基)-5-苯基噁唑(化合物VI.20).M+＝299；1H
NMR：δ2.62(2H，m)；3.51(2H，t)；4.27(1H，m)；7.26(1H，s)；7.42-7.55
(3H，m)；7.69-7.79(2H，d)；(mp 55-59℃)。
               实施例VII.1
此实施例阐明了由相应取代的巯基噻唑和适宜的二氟丁-3-烯烷基化剂开始制备在2、4或5-位上被4，4-二氟丁-3-烯基硫基基团取代的噻唑类化合物的一般方法。此方法可通过下列2-(4，4-二氟丁-3-烯基硫基)-5-苯基噻唑(化合物VII.17)的制备得以说明。
向2-巯基-5-苯基噻唑(0.483g)的丙酮(15cm3)溶液中加入4-甲基-苯磺酸4，4-二氟-3-丁烯基酯(0.7g)和碳酸钾(0.369g)并将反应回流加热共8小时，此后仍残有部分对甲苯磺酸酯原料。再加入2-巯基-5-苯基噻唑(0.05g)并继续加热5小时，将反应混合物冷却，倾入乙醚和水中并分层。水层用乙醚萃取并将合并的有机相干燥(MgSO4)，减压蒸发，得到一黄色液体。用5％叔丁基二甲基醚的己烷溶液于硅胶上进行色谱纯化，得到化合物VII.17(0.582g)；M+＝283；1H NMR：δ2.51(2H，m)；3.31(2H，t)；4.32(1H，m)；7.26(1H，s)；7.30-7.48(3H，m)；7.89(2H，d)；(油状物)。
用上述方法可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基硫基)-噻唑(化合物VII.1)，M+＝207；1H NMR：
δ2.47(2H，m)；3.26(2H，t)；4.27(1H，m)；7.22(1H，d)；7.68(1H，d)；(油状
物)，由2-巯基噻唑制得。(ii)2-(4，4-二氟丁-3-烯基硫基)-噻唑啉(化合物VII.134)，M+＝209；1H
NMR：δ2.40(2H，m)；3.15(2H，t)；3.4(2H，t)；4.18-4.31(1H，m)；4.2(2H，t)；
(油状物)，由2-巯基噻唑啉制得。
                   实施例VII.2
此实施例阐明了两步法制备2-(4，4-二氟丁-3-烯基硫基)-4-三氟甲基噻唑(化合物VII.4)的方法。
步骤1：2-巯基-4-三氟甲基噻唑的制备
将1-溴-3，3，3-三氟丙-2-酮(5.0g)的叔丁醇(20cm3)溶液用二硫代氨基甲酸铵(2.9g)处理，混合物于室温下搅拌18小时，倾入水中，用乙酸乙酯萃取并将有机相干燥(MgSO4)。减压蒸除溶剂，残余物经色谱法(硅胶；己烷∶乙酸乙酯17∶3-7∶3体积比洗脱)进行分离，得到所需巯基噻唑的水合物(2.16g)。将此产物的一部分(1.0g)加入到含有对甲苯磺酸(0.005g，催化剂)的甲苯(20cm3)并回流加热4小时。用迪安-斯达克装置除去反应中生成的水，将溶液冷却至室温，用水洗涤，干燥(MgSO4)并减压蒸发，得到所需中间体产物(0.37g)；1H NMR：δ7.10(1H，s)；7.80(1H，s)。
步骤2：化合物VII.4的制备
将于含有无水碳酸钾(0.3g)和4-溴-1，1-二氟丁-1-烯(0.34g)的丙酮(15cm3)中的步骤1中所得产物(0.37g)进行搅拌并回流加热4小时。将混合物冷却，倾入水中，用乙酸乙酯萃取，干燥(MgSO4)并减压蒸发，得到化合物VII.4(0.30g)。M+＝275；1H NMR：δ2.50(2H，m)；3.32(2H，t)；4.28(1H，m)；7.60(1H，s)；(油状物)。
用上述步骤2中的方法由相应的巯基噻唑化合物可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基硫基)噻唑-4-羧酸乙酯(化合物VII.8)。1H NMR：
δ 1.40(3H，t)；2.48(2H，m)；3.32(2H，t)；4.28(1H，m)；4.40(2H，q)；
8.03(1H，s)；(油状物)，由2-巯基噻唑-4-羧酸乙酯制得。(ii)2-(4，4-二氟丁-3-烯基硫基)-4-甲基噻唑-5-羧酸甲酯(化合物VII.41)。
1H NMR：δ2.48(2H，m)；2.68(3H，s)；3.26(2H，t)；3.85(3H，s)；
4.28(1H，m)；(油状物)，由2-巯基-4-甲基噻唑-5-羧酸甲酯制得。(iii)2-(4，4-二氟丁-3-烯基硫基)-5-硝基噻唑(化合物VII.47)。M+＝252；1H
NMR：δ2.52(2H，m)；3.35(2H，m)；4.27(1H，m)；8.35(1H，s)；(油状
物)，由2-巯基-5-硝基噻唑(由2-溴-5-硝基噻唑和硫脲制得)制得。
                    实施例VII.3
此实施例阐明了3-步法制备5-氯-2-(4，4-二氟丁-3-烯基硫基)噻唑(化合物VII.24)的方法。
步骤1：2-(4-溴-3，4，4-三氟丁硫基)噻唑
氮气氛下，将含有1，4-二溴-1，1，2-三氟丁烷(27.0g)的丙酮(30cm3)中的2-巯基噻唑(11.7g)分批用无水碳酸钾(13.8g)处理。将反应搅拌1.5小时，过滤并将不溶物用丙酮(4×25cm3)洗涤。将滤液减压蒸发，残余物经色谱法(硅胶，用10％乙酸乙酯的己烷溶液洗脱)进行分离，得到2-(4-溴-3，4，4-三氟丁硫基)噻唑(29.5g)。1H NMR：δ2.2-2.5(2H，m)；3.2-3.6(2H，m)；4.7-5.0(1H，m)；7.23(1H，d)；7.68(1H，d)。
步骤2：2-(4-溴-3，4，4-三氟丁硫基)-5-氯噻唑
于室温氮气氛下，搅拌下，将步骤1中所得化合物(30.6g)的二氯甲烷(130cm3)溶液用硫酰氯(9.6cm3)的二氯甲烷(30cm3)溶液处理1个多小时。将反应再搅拌1小时，缓慢倾入水(250cm3)中并搅拌0.25小时。分出有机相，水相用二氯甲烷(2×75cm3)萃取，合并的有机相用碳酸氢钠水溶液、盐水洗涤并干燥(MgSO4)。减压蒸除溶剂，残余物经色谱法(硅胶；用5％乙醚的己烷溶液洗脱)进行分离，得到2-(4-溴-3，4，4-三氟丁硫基)-5-氯噻唑(28.0g)；1H NMR：δ2.20-2.45(2H，m)；3.25-3.50(2H，m)；4.70-5.0(1H，m)；7.45(1H，s)；(油状物)。
步骤3：化合物VII.24
于氮气氛下水(600cm3)中，将锌粉(33g)与碘(0.17g，催化剂)一起搅拌，加热至80℃并加入浓盐酸(0.5cm3)，随后于1.5小时内分批加入步骤2中所得化合物(125g)。在4小时内，再分批加入锌粉(16.6g)、碘(0.1g)和盐酸(0.6cm3)，以使反应完全。将混合物冷至室温，用二氯甲烷作溶剂经硅藻土过滤并将滤液用二氯甲烷(5×250cm3)萃取。将合并的有机相干燥(MgSO4)，减压蒸发，残余物于硅胶上经色谱法进行分离，用己烷洗脱，得到化合物VII.24(140g)，M+＝241；1H NMR：δ2.42(2H，m)；3.20(2H，t)；4.25(1H，m)；7.45(1H，s)；(油状物)。
                    实施例VII.4
此实施例阐明了5-溴-2-(4，4-二氟丁-3-烯基硫基)噻唑(化合物VII.14)的制备方法。
将2-氨基-5-溴噻唑氢溴酸盐(11g)用碳酸氢钠水溶液处理，二氯甲烷(2×250cm3)萃取并干燥(MgSO4)。将混合物过滤并将滤液加入到二-(4，4-二氟丁-3-烯基)二硫化物(20g)中，于室温氮气氛下，向搅拌下的此溶液中滴加亚硝酸叔丁基酯(9.6cm3)的二氯甲烷(40cm3)溶液。将反应搅拌18小时，在硅胶上蒸发，残余物加到短硅胶柱上，用(1)己烷和(2)己烷∶乙醚，20∶1(体积比)洗脱，得到化合物VII.14(6.4g)。M+＝285；1H NMR：δ2.46(2H，m)；3.24(3H，t)；4.27(1H，m)；7.54(1H，s)；(油状物)。
                     实施例VII.5
此实施例阐明了用不同于实施例VII.4的重氮化法制备2-(4，4-二氟丁-3-烯基硫基)-4-甲基噻唑-5-磺酰氟(化合物VII.52)的方法。
于60℃氮气氛下，将2-氨基-4-甲基噻唑磺酰氟(1.5g)的乙腈(10cm3)溶液滴加到搅拌下的亚硝酸叔丁基酯(1.65cm3)和二-(4，4-二氟丁-3-烯基)二硫化物(2.25g)于乙腈(50cm3)中的混合物中。将混合物加热1小时，减压蒸发并将残余物经色谱法(硅胶；用己烷∶乙酸乙酯4∶1(体积比)洗脱)进行分离，得到化合物VII.52(1.84g)。M+＝303；1H NMR：δ2.50(2H，m)；2.68(3H，s)；3.32(2H，t)；4.28(1H，m)；(油状物)。
用上述方法由相应的氨基噻唑类化合物可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基硫基)-5-甲基噻唑(化合物VII.21)。M+＝221；1H
NMR：δ2.45(5H，m)；3.22(2H，t)；4.26(1H，m)；7.30(1H，s)；(油状物)，由
2-氨基-5-甲基噻唑制得。(ii)5-氯-2-(4，4-二氟丁-3-烯基硫基)噻唑(化合物VII.24).M+＝241；1H
NMR：δ2.45(2H，m)；3.22(2H，t)；4.26(1H，m)；7.45(1H，s)；(油状物)，用
与上述实施例VII.3中不同的方法由2-氨基-5-氯噻唑制得。(iii)5-氯-2-(4，4-二氟丁-3-烯基硫基)-4-甲基噻唑(化合物
VII.27).M+＝255；1H NMR：δ2.35(3H，s)；2.42(2H，m)；3.18(2H，t)；4.26
(1H，m)；(油状物)，由2-氨基-5-氯-4-甲基噻唑制得。
                    实施例VII.6
此实施例阐明了经两步法制备5-溴-2-(4，4-二氟丁-3-烯基硫基)噻唑-4-羧酸乙酯(化合物VII.11)的方法。
步骤1：2-氨基-5-溴噻唑-4-羧酸乙酯的制备
室温下将于浓盐酸(9cm3)中的2-氨基噻唑-4-羧酸乙酯(5.0g)(按照J.Med.Chem.，1971，14，1075中所述相应噁唑化合物的制备方法，由溴代丙酮酸乙酯和硫脲制得)进行搅拌并滴加溴(3.2g)进行处理，然后加热至60℃2小时，用碳酸钠中和并将产物用乙酸乙酯萃取。将有机相干燥(MgSO4)并减压蒸发，得到2-氨基-5-溴噻唑-4-羧酸乙酯(1.54g)。MH+＝251；1H NMR：δ1.40(3H，t)；4.40(2H，t)；5.6(2H，br s)。
步骤2：化合物VII.11的制备
如上述实施例VII.5中所述，在重氮化反应中处理步骤1中所得产物并得到化合物VII.11；M+＝357；1H NMR：δ1.40(3H，t)；2.50(2H，m)；3.30(2H，t)；4.30(1H，m)；4.45(2H，q)；(油状物)。
                    实施例VII.7
此实施例阐明了3-步法制备N，N-二乙基2-(4，4-二氟丁-3-烯基硫基)-4-甲基噻唑-5-磺酰胺(化合物VII.56)的方法。
步骤1：N，N-二乙基2-乙酰氨基-4-甲基噻唑-5-磺酰胺
于室温下将2-乙酰氨基-4-甲基噻唑-5-磺酰氯(5.2g)的四氢呋喃(100cm3)进行搅拌并滴加二乙胺(4.5cm3)处理。将混合物搅拌4小时，减压蒸发并将残余物用乙酸乙酯(200cm3)萃取，用水(2×100cm3)洗涤，干燥(MgSO4)并再减压蒸发，得到N，N-二乙基2-乙酰氨基-4-甲基噻唑-5-磺酰胺(4.9g)。1H NMR：δ1.20(6H，t)；2.28(3H，s)；2.57(3H，s)；3.32(4H，q)；9.7(1H，br s)；(固体)。
步骤2：N，N-二乙基2-氨基-4-甲基噻唑-5-磺酰胺
将步骤1中所得产物(2.5g)溶于甲醇(25cm3)并于氮气氛搅拌下冷却至5℃。滴加甲醇钠的甲醇溶液(2cm3，25％wt/vol溶液)并令混合物温热至室温18小时。将反应回流下加热1小时，冷却，用水(250cm3)稀释，用乙醚(2×100cm3)萃取，干燥(MgSO4)并减压蒸发，得到N，N-二乙基2-氨基-4-甲基噻唑-5-磺酰胺(0.48g)。M+249；1H NMR：δ1.20(6H，t)；2.48(3H，s)；3.28(4H，q)；5.25(2H，br s)；(固体)。
步骤3：化合物VII.56的制备
如上述实施例VII.5中所述，在重氮化反应中处理步骤2中所得产物并得到化合物VII.56；M+＝356；1H NMR：δ1.15(6H，t)；2.45(2H，m)；2.60(3H，s)；3.25(2H，t)；3.26(4H，q)；4.25(1H，m)；(油状物)。
                   实施例VII.8
此实施例阐明了2-氨基-5-(4，4-二氟丁-3-烯基硫基)噻唑(化合物VII.128)的制备方法。
室温下将4，4-二氟丁-3-烯基异硫脲氢溴酸盐(16.87g)加入到氢氧化钾(18.0g)的乙醇(150cm3)溶液中并于氮气氛下搅拌0.2小时。分批加入2-氨基-5-溴噻唑氢溴酸盐(17.76g)的乙醇(150cm3)溶液，将混合物加热至40℃2小时，用盐酸中和并减压蒸发。残余物溶于2M盐酸中，用乙醚萃取，2M氢氧化钠碱化并用乙醚再萃取。将后一乙醚萃取液合并，干燥(MgSO4)并减压蒸发，得到化合物VII.128(8.0g)。M+＝222；1HNMR：δ2.28(2H，m)；2.67(2H，t)；4.24(1H，m)；5.3(2H，两个br s)；7.08(1H，s)；(mp 34.6-35.4℃)。
                      实施例VII.9
此实施例阐明了5-(4，4-二氟丁-3-烯基硫基)噻唑(化合物VII.82)的制备方法。
将化合物VII.128(0.30g)溶于无水四氢呋喃(14cm3)中并于氮气氛下回流加热。在0.25小时内滴加亚硝酸叔丁基酯(0.52cm3)的四氢呋喃(8cm3)溶液，将混合物加热2小时，再加入亚硝酸叔丁基酯(0.52cm3)并继续加热2小时。将溶液冷却，减压蒸发并将残余物经色谱法(硅胶；用己烷∶乙酸乙酯1∶1(体积比)洗脱)进行分离，得到化合物VII.128(0.10g)。1H NMR：δ2.28(2H，m)；2.82(2H，t)；4.24(1H，m)；7.86(1H，s)；8.86(1H，s)；(油状物)。
                   实施例VII.10
此实施例阐明了2-氯-5-(4，4-二氟丁-3-烯基硫基)噻唑(化合物VII.114)的制备方法。
于0℃将化合物VII.128(4.0g)的乙腈(50cm3)溶液加入到搅拌下的于乙腈(50cm3)中的氯化铜(II)(5.38g)和亚硝酸叔丁基酯(3.71g)混合物中并于18小时内令其缓慢地温热至室温。减压蒸除溶剂，将产物溶于乙醚，过滤并将滤液再次蒸发，得到黄褐色液体，将其经色谱法(硅胶；用己烷∶乙醚4∶1(体积比)洗脱)进行分离，得到化合物VII.114(2.43g)。M+＝241；1H NMR：δ2.28(2H，m)；2.68(2H，t)；4.22(1H，m)；7.52(1H，s)(油状物)。
                     实施例VII.11
此实施例阐明了2-(4-氰基苯氧基)-5-(4，4-二氟丁-3-烯基硫基)噻唑(化合物VIII.130)的制备方法
于氮气氛下，将于N-甲基吡咯烷-2-酮(3cm3)中的化合物VII.114(0.483g)、4-氰基苯酚(0.238g)、无水碳酸钾(0.276g)和氟化铯(0.304g)一起进行搅拌并加热至90℃36小时。反应混合物用水稀释，产物用乙醚萃取，干燥(MgSO4)，减压蒸发并将残余物经薄层色谱法(硅胶；用己烷∶乙醚4∶1(体积比)展开)分离，得到化合物VII.130(0.125g)。M+＝324；1H NMR：δ2.28(2H，m)；2.80(2H，t)；4.20(1H，m)；7.40(2H，m)；7.75(2H，m)；(油状物)。
                     实施例VII.12
此实施例阐明了5-(4，4-二氟丁-3-烯基硫基)-噻唑-4-羧酸乙酯(化合物VII.98)的制备方法。
于-40℃氮气氛下，将异氰基乙酸乙酯(2.3g)的无水四氢呋喃(15cm3)溶液加入到搅拌下的叔丁醇钾(2.24g)中。10分钟后，将反应冷却至-78℃并缓慢加入二硫化碳(1.52g)的四氢呋喃(20cm3)溶液。加完后令反应温度升至-10℃并加入4-甲基-苯磺酸4，4-二氟丁-3-烯基酯(5.24g)的四氢呋喃(10cm3)溶液。令混合物温热至室温并搅拌24小时，加热回流3小时并冷却至室温。将反应混合物倾入2M盐酸水溶液中，产物用乙酸乙酯。将有机相干燥(MgSO4)并减压蒸除溶剂。残余物于硅胶上进行柱色谱分离，用1∶1己烷∶乙酸乙酯洗脱，得到化合物VII.98(3.15g)。1H NMR：δ1.45(3H，t)；2.50(2H，m)；3.10(2H，t)；4.3-4.4(1H，m)；4.50(2H，q)；8.65(1H，s)；(油状物)。
                     实施例VII.13
此实施例阐明了5-(4，4-二氟丁-3-烯基硫基)-噻唑-4-甲酰胺(化合物VII.94)的制备方法。
将化合物VII.98(0.5g)的甲醇(8cm3)溶液与氨水(35cm3；密度为0.88)一起搅拌4小时。将溶液过滤并吸滤至干，得到固体状化合物VII.94(0.27g)。1H NMR：δ2.50(2H，m)；3.00(2H，t)；4.30-4.41(1H，m)；5.5和7.0(2H，宽峰)；8.55(1H，s)；(固体mp 140-141℃)。
用上述方法由相应的酯化合物可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基硫基)噻唑-4-甲酰胺(化合物VII.7)，M+＝250；1H
NMR：δ2.50(2H，m)；3.27(2H，t)；4.28(1H，m)；5.9和7.1(2H，br s)；8.03
(1H，s)；(mp 57-58℃)，由化合物VII.8制得。(ii)2-(4，4-二氟丁-3-烯基硫基)-4-甲基噻唑-5-甲酰胺(化合物VII.36)，1H
NMR：δ2.48(2H，m)；2.66(3H，s)；3.26(2H，t)；3.85(3H，s)；4.28(1H，m)；
5.7(2H，br s)；(mp 99-100℃)，由化合物VII.41制得。
                    实施例VII.14
此实施例阐明了4-氰基-5-(4，4-二氟丁-3-烯基硫基)噻唑(化合物VII.90)的制备方法。
将化合物VII.94(0.27g)的无水二氯甲烷(13cm3)溶液用吡啶(1cm3)和甲磺酰氯(0.26cm3)处理。将混合物搅拌5天，再加入甲磺酰氯(0.2cm3)并再搅拌2小时。将反应倾入2M盐酸水溶液中，产物用乙酸乙酯萃取。将有机相干燥(MgSO4)并减压蒸发。残余物于硅胶上进行色谱分离，得到化合物VII.90(0.142g)。1H NMR：δ2.40(2H，m)；3.20(2H，t)；4.30(1H，m)；8.80(1H，s)。
用上述方法由相应的甲酰胺类化合物可制得下列本发明化合物：(i)4-氰基-2-(4，4-二氟丁-3-烯基硫基)噻唑(化合物VII.6)，1H NMR：δ
2.50(2H，m)；3.32(2H，t)；4.26(1H，m)；7.86(1H，s)；(油状物)，由化合物
VII.7制得。(ii)5-氰基-2-(4，4-二氟丁-3-烯基硫基)-4-甲基噻唑(化合物VII.32)，1HNMR：δ2.48(2H，m)；2.58(3H，s)；3.30(2H，t)；3.85(3H，s)；4.28(1H，m)；(油状物)，由化合物VII.36制得。
                   实施例VII.15
此实施例阐明了5-溴-2-(4，4-二氟丁-3-烯基硫基)噻唑-4-羧酸(化合物VII.13)的制备方法。
将化合物VII.11(0.30g)的含有氢氧化钠水溶液(1.2cm3，2M溶液)的甲醇(5cm3)溶液于室温下搅拌18小时，倾入水中并用2M盐酸酸化。产物用乙酸乙酯萃取，干燥(MgSO4)并减压蒸发，得到化合物VII.13(0.18g)。M+＝329；1H NMR：δ2.48(2H，m)；3.30(2H，t)；4.28(1H，m)；7.0(1H，宽单峰)；(mp 86.5-87.5℃)。
用上述方法由相应的酯类化合物可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基硫基)噻唑-4-羧酸(化合物VII.10)，M+＝251；1H
NMR：δ2.50(2H，m)；3.35(2H，t)；4.28(1H，m)；8.18(1H，s)；(mp 114-115
℃)，由化合物VII.8制得。(ii)2-(4，4-二氟丁-3-烯基硫基)-4-甲基噻唑-5-羧酸(化合物VII.45)，
M+＝265；1H NMR：δ2.50(2H，m)；2.70(3H，s)；3.27(2H，t)；
4.28(1H，m)；9.8(1H，宽单峰)；(mp 52.0-53.5℃)，由化合物VII.41制
得。(iii)5-(4，4-二氟丁-3-烯基硫基)噻唑-4-羧酸(化合物VII.102)，M+＝251；
1H NMR：δ2.50(2H，m)；3.10(2H，t)；4.28(1H，m)；8.70(1H，s)；(mp
128.5℃)，由化合物VII.98制得。
                   实施例VII.16
此实施例阐明了适宜制备本发明化合物的方法，其中所述相应未被氧化的化合物中4，4-二氟丁-3-烯基硫基取代基中的硫原子被氧化成亚砜(亚磺酰基)或砜(磺酰基)。
方法A：用过一硫酸钾作氧化剂
5-氯-2-(4，4-二氟丁-3-烯基磺酰基)噻唑(化合物VII.26)的制备
于8℃冷却下0.25小时内，向搅拌下的化合物VII.24(4.83g)的甲醇(50cm3)溶液中滴加过一硫酸钾(27.0g)的水(100cm3)溶液进行处理，并再加入甲醇(50cm3)。将反应于室温下搅拌18小时，由溶液中滤出不溶物，滤液用二氯甲烷(4×50cm3)萃取并干燥(MgSO4)。减压蒸除溶剂并将残余物经色谱法(硅胶；用己烷∶乙酸乙酯4∶1(体积比)洗脱)进行分离，得到化合物VII.26(3.91g)。M(NH4)+＝291；1H NMR：δ2.60(2H，m)；3.50(2H，t)；4.25(1H，m)；7.85(1H，s)；(油状物)。
方法B：利用过氧邻苯二甲酸一镁
5-溴-2-(4，4-二氟丁-3-烯基亚磺酰基)噻唑(化合物VII.15)的制备
将化合物VII.14(1.50g)溶于二氯甲烷(10cm3)并用单过氧邻苯二甲酸镁六水合物(1.6g，80％过酸)和水(15cm3)处理。将混合物于室温下搅拌1小时，用二氯甲烷(90cm3)稀释并将有机相用碳酸氢钠水溶液和水洗涤。将有机相干燥(MgSO4)，减压蒸发并将残余物经色谱法(硅胶；用己烷∶乙酸乙酯10∶1(体积比)洗脱)进行分离，得到化合物VII.15(1.0g).M(NH4)+＝321；1H NMR：δ2.38(1H，m)；2.60(1H，m)；3.20(2H，m)；4.20(1H，m)；7.85(1H，s)；(油状物)。
用上述方法B由相应的硫醚类化合物可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基亚磺酰基)噻唑(化合物VII.2)，MH+＝224；1HNMR：δ2.36(1H，m)；2.50-2.70(1H，m)；3.20(2H，m)；4.22(1H，m)；7.67(1H，d)；7.98(1H，d)；(油状物)，由化合物VII.1和1当量氧化剂制得。(ii)2-(4，4-二氟丁-3-烯基磺酰基)噻唑(化合物VII.3)，MH+＝240；1H
NMR：δ2.55(2H，m)；3.45(2H，t)；4.24(1H，m)；7.78(1H，d)；
8.08(1H，d)；(油状物)，由化合物VII.1和2当量氧化剂制得。(iii)5-溴-2-(4，4-二氟丁-3-烯基磺酰基)噻唑(化合物VII.16)，
M(NH4)+＝335；1H NMR：δ2.58(2H，m)；3.46(2H，t)；4.25(1H，m)；
7.96(1H，s)；(油状物)，由化合物VII.14和2当量氧化剂制得。(iv)2-(4，4-二氟丁-3-烯基亚磺酰基)-5-甲基噻唑(化合物VII.22)，1H
NMR：δ2.38(1H，m)；2.50-2.65(4H，m)；3.15(1H，m)；4.23(1H，m)；7.60
(1H，q)；(油状物)，由化合物VII.21和1当量氧化剂制得。(v)2-(4，4-二氟丁-3-烯基磺酰基)-5-甲基噻唑(化合物VII.23)，1H NMR：
δ2.55(2H，m)；2.60(3H，s)；3.45(2H，t)；4.25(1H，m)；7.73(1H，q)；(油
状物)，由化合物VII.21和2当量氧化剂制得。(vi)5-氯-2-(4，4-二氟丁-3-烯基亚磺酰基)噻唑(化合物VII.25)，
M(NH4)+＝275；1H NMR：δ2.38(1H，m)；2.60(1H，m)；3.18(2H，m)；
4.25(1H，m)；7.74(1H，s)；(油状物)，由化合物VII.24和1当量氧化剂
制得。(Vii)5-(4，4-二氟丁-3-烯基亚磺酰基)噻唑(化合物VII.83)，1H NMR：δ
2.50(2H，m)；3.05(1H，m)；3.20(1H，m)；4.28(1H，m)；8.20(1H，s)；9.12
(1H，s)；(油状物)，由化合物VII.82和1当量氧化剂制得。(Viii)5-(4，4-二氟丁-3-烯基磺酰基)噻唑(化合物VII.84)，1H NMR：δ
2.50(2H，m)；3.30(2H，m)；4.25(1H，m)；8.20(1H，s)；9.12(1H，s)；(油状
物)，由化合物VII.82和2当量氧化剂制得。(ix)2-氯-5-(4，4-二氟丁-3-烯基亚磺酰基)噻唑(化合物VII.115)，1H NMR：
δ2.50(2H，m)；3.05(1H，m)；3.20(1H，m)；4.28(1H，m)；7.85(1H，s)；(油
状物)，由化合物VII.114和1当量氧化剂制得。(x)2-氯-5-(4，4-二氟丁-3-烯基磺酰基)噻唑(化合物VII.116)，1H NMR：
δ2.52(2H，m)；3.30(2H，m)；4.28(1H，m)；8.08(1H，s)；(油状物)，由化
合物VII.114和2当量氧化剂制得。
方法C：利用3-氯过苯甲酸
用上述方法B，只是用3-氯过苯甲酸代替过氧邻苯二甲酸一镁六水合物，由相应的硫醚类化合物可制得下列本发明化合物：(xi)2-(4，4-二氟丁-3-烯基磺酰基)噻唑-4-羧酸乙酯(化合物VII.9)，
M+＝311；1H NMR：δ1.43(3H，t)；2.60(2H，m)；3.56(2H，t)；4.28(1H，m)；
4.48(2H，q)；8.50(1H，s)；(mp 64-65℃)，由化合物VII.8和2当量氧化剂
制得。(xii)5-溴-2-(4，4-二氟丁-3-烯基磺酰基)噻唑-4-羧酸乙酯(化合物
VII.12)，M+＝389，1H NMR：δ1.43(3H，t)；2.60(2H，m)；3.56(2H，t)；
4.28(1H，m)；4.48(2H，q)；(mP 72-73℃)，由化合物VII.11和2当量氧
化剂制得。(xiii)5-氯-2-(4，4-二氟丁-3-烯基磺酰基)-4-甲基噻唑(化合物VII.28)，1H
NMR：δ2.55(2H，m)；2.45(3H，s)；3.40(2H，t)；4.25(1H，m)；(油状物)，
由化合物VII.27和2当量氧化剂制得。(xiv)2-(4，4-二氟丁-3-烯基磺酰基)-4-甲基噻唑-5-羧酸甲酯(化合物
VII.43)，1H NMR：δ2.60(2H，m)；2.85(3H，s)；3.50(1H，t)；3.95(3H，s)；
4.25(1H，m)；(油状物)，由化合物VII.41和2当量氧化剂制得。(xv)2-(4，4-二氟丁-3-烯基磺酰基)-4-甲基噻唑-5-磺酰氟(化合物
VII.53)，1H NMR：δ 2.60(2H，m)；2.85(3H，s)；3.55(2H，t)；4.28(1H，m)；
(mp 67℃)，由化合物VII.52和2当量氧化剂制得。
                      实施例VIII.1
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)-1-甲基咪唑(化合物VIII.5)的制备方法。
向2-巯基-1-甲基咪唑(9.78g)的丙酮(300cm3)溶液中加入碳酸钾(14.2g)和4-溴-1，1-二氟丁-1-烯(16.12g)的丙酮(100cm3)溶液。将混合物回流下加热18小时并冷却，过滤除去固体无机物，反应混合物通过sorbsil-C30硅胶柱，用乙酸乙酯洗涤。将滤液减压蒸发，得到化合物VIII.5粗品(17.8g)，其适于进行进一步反应(参见实施例VIII.7)。
将部分产物(1g)于sorbsil-C30硅胶上进行色谱纯化，用乙酸乙酯∶己烷3∶7洗脱，得到纯化合物VIII.5(0.776g)。1H NMR：δ2.3-2.4(2H，m)；3.05-3.15(2H，t)；3.60(3H，s)；4.15-4.35(1H，m)；6.95(1H，s)；7.05(1H，s)；(油状物)。
用上述方法利用适宜的巯基咪唑化合物可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基硫基)-1-苯基咪唑(化合物VIII.3)，M+＝266；1H
NMR：δ2.3-2.4(2H，m)；3.1-3.15(2H，t)；4.1-4.25(1H，m)；7.1-7.2
(2H，m)；7.3-7.55(5H，m)；(油状物)。(ii)2-(4，4-二氟丁-3-烯基硫基)-1-乙基咪唑(化合物VIII.10)，M+＝218；1H
NMR：δ1.4(3H，t)；2.3-2.4(2H，m)；3.15(2H，t)；4.0(2H，q)；4.2-
4.35(1H，m)；6.95(1H，s)；7.1(1H，s)；(油状物)。(iii)2-(4，4-二氟丁-3-烯基硫基)-4-乙基-5-甲基咪唑(化合物VIII.27)，
M+＝232；1H NMR：δ1.15(3H，t)；2.15(3H，s)；2.35-2.45(2H，m)；2.5-
2.6(2H，q)；2.95(2H，t)；4.1-4.3(1H，m)；(mp 54-56℃)。(iv)2-(4，4-二氟丁-3-烯基硫基)-4-甲基咪唑(化合物VIII.58)，M+＝204；
1H NMR：δ2.25-.35(5H，m)；3.0(2H，t)；4.15-4.3(1H，m)；6.75(1H，s)；
(油状物)。(v)2-(4，4-二氟丁-3-烯基硫基)-4-乙氧羰基咪唑(化合物VIII.64)，
M+＝262，1H NMR：δ1.3-1.35(3H，t)；2.25-2.35(2H，m)；3.05-3.15
(2H，t)；4.1-4.25(1H，m)；4.3-4.4(2H，q)；7.8(1H，br s)；(mp 57.8-61
℃)。(vi)3-(4，4-二氟丁-3-烯基硫基)咪唑并-[1，5a]-吡啶(化合物VIII.151)，1H
NMR：δ2.30(2H，m)；3.00(2H，t)；4.20(1H，m)；6.65(1H，m)；7.45(1H，dt)；
7.55(1H，s)；8.15(1H，dd)；(油状物)，由2，3-二氢咪唑并-[1，5a]-吡啶-3-
硫酮制得。
                  实施例VIII.2
此实施例阐明了由可经色谱法分离的所述产物混合物制备2-(4，4-二氟丁-3-烯基硫基)-咪唑(化合物VIII.1)和1-(4，4-二氟丁-3-烯基)-2-(4，4-二氟丁-3-烯基硫基)咪唑(化合物VIII.8)的方法。
向2-巯基-咪唑(10.01g)的丙酮(400cm3)溶液中加入碳酸钾(20.73g)和4-溴-1，1-二氟丁-1-烯(18.79g)。将混合物回流下加热18小时并冷却，过滤除去固体无机物，反应混合物通过sorbsil-C30硅胶柱，用乙酸乙酯洗涤。将滤液减压蒸发，得到浅褐色油状物(19.2g)，将其于硅胶上进行色谱分离，用15％乙酸乙酯的己烷溶液，进而用50％乙酸乙酯的己烷溶液洗脱，得到两个主要级份，tlc表明第一个级份(7.4g)含有两种产物。所得白色固体状的第二个级份(10.75g)表明是纯化合物VIII.1。将第一个级份如上所述进一步进行色谱分离，得到化合物VIII.8(1.61g)；M+＝280；1H NMR：δ2.3-2.45(4H，m)；3.1-3.15(2H，t)；3.9-4.0(2H，t)；4.05-4.3(2H，m)；6.95(1H，s)；7.05(1H，s)；(油状物)和化合物VIII.1(5.31g)。将化合物VII.1的样品于乙酸乙酯和己烷中重结晶，得到4.2g产物，M+＝190；1H NMR：δ2.3-2.4(2H，m)；3.0-3.1(2H，t)；4.15-4.3(1H，m)；7.0-7.1(2H，br s)；9.2(1H，br s)；(mp 58.6-59.6℃)。
                      实施例VIII.3
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)-4-苯基咪唑(化合物VIII.19)的制备方法。
将苯甲酰甲基溴(1.611g)的氯仿(7cm3)溶液加入到4，4-二氟丁-3-烯基硫脲氢溴酸盐(2g)的84％乙醇/水溶液(20cm3)中并于搅拌下缓慢地加入碳酸氢钠(2.72g)。将所得黄色悬浮液回流加热3小时，将混合物冷却并减压蒸除溶剂。残余物用温水(2×20cm3)洗涤两次，滗析除去无机物。所得粗产物于硅胶上经色谱法纯化，用20％乙酸乙酯的己烷溶液洗脱，将含有产物的级份用5％乙酸乙酯的己烷溶液再次进行柱色谱分离，如此得到不含有相应的N-苯甲酰甲基衍生物副产物的化合物VIII.19(0.78g)；M+＝266；1H NMR：δ2.3-2.4(2H，m)；3.05-3.1(2H，t)；4.15-4.3(1H，m)；7.2-7.4(4H，m)；7.6-7.75(2H，br s)。
用上述方法可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基硫基)-1-甲基-4-苯基咪唑(化合物VIII.22)，
M+＝280；1H NMR：δ2.35-2.45(2H，m)；3.10-3.18(2H，t)；3.65(3H，s)；
4.19-4.35(1H，m)；7.2-7.25(2H，m)；7.33-7.38(2H，t)；7.72-7.78(2H，d)
(油状物)，由N-甲基4，4-二氟丁-3-烯基异硫脲氢溴酸盐制得。(ii)2-(4，4-二氟丁-3-烯基硫基)-5-乙基-4-甲氧羰基-1-甲基咪唑(化合物
VIII.68)，M+＝290；1H NMR：δ1.2-1.25(3H，t)；2.35-2.45(2H，m)；2.8-
2.9(2H，q)；3.2-3.25(2H，t)；3.78(3H，s)；3.85(3H，s)；4.16-4.32(1H，m)；
(油状物)，由N-甲基4，4-二氟丁-3-烯基异硫脲氢溴酸盐和2-溴-3-氧
代戊酮酸(3-oxopentanoate)甲酯制得。
                      实施例VIII.4
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)-4，5-二甲基咪唑(化合物VIII.29)的制备方法。
将碳酸钾(18.9g)和4，4-二氟丁-3-烯基异硫脲氢溴酸盐(16.9g)加入到3-溴丁-2-酮(10.32g)的二甲基甲酰胺(100cm3)溶液中并将混合物于60℃下搅拌90分钟，然后于80℃下搅拌30分钟。将所得混合物冷却，加入水(100cm3)并将产物用乙醚萃取。将合并的有机相用水和盐水洗涤并干燥(MgSO4)。减压蒸发浓缩，得到浅黄色液体(12.2g)，将其于sorbsil C30硅胶上进行色谱纯化，用30％乙酸乙酯的己烷溶液洗脱，得到三个组份。首先洗脱得到的经鉴定是3-(4，4-二氟丁-3-烯基硫基)丁-2-酮(0.68g)；M+＝194；1H NMR：δ1.4(3H，d)；2.15-2.3(5H，m)；2.45(2H，t)；3.3-3.4(1H，q)；4.1-4.35(1H，m)。第二个被洗脱的化合物是所需化合物VIII.29(4.1g)；M+＝218；1H NMR：δ2.15(6H，s)；2.25-2.35(2H，m)；2.9-3.0(2H，t)；4.15-4.3(1H，m)；(mp 81.4-84.4℃)。第三个被洗脱的化合物经鉴定是化合物VIII.29被3-溴丁-2-酮进一步N-烷基化的产物，即N-(1-甲基丙-2-酮)2-(4，4-二氟丁-3-烯基硫基)-4，5-二甲基咪唑(1.11g)；M+＝217；1H NMR：δ1.55(3H，s)；2.0(3H，s)；2.05(3H，s)；2.15(3H，s)；2.3-2.4(2H，m)；3.0-3.05(2H，t)；4.15-4.35(1H，m)；5.0-5.1(1H，m)；(油状物)。
                    实施例VIII.5
此实施例阐明了由相应的N-H咪唑，经化合物VIII.1碘丙烷烷基化制备2-(4，4-二氟丁-3-烯基硫基)-1-丙基咪唑(化合物VIII.12)的方法。
于氮气氛下将化合物VIII.1(2g)分批加入到(泡腾)氢化钠(0.736g，60％固体油分散体)的二甲基甲酰胺(20cm3)悬浮液中。将混合物搅拌30分钟后，加入碘正丙烷(2.68g)并将反应混合物于室温下搅拌18小时。然后加入水和乙醚并用乙醚萃取产物。将合并的有机相用水和饱和盐水洗涤并干燥(MgSO4)。过滤后，减压蒸除溶剂，得到粗产物(2.7g)，将其于sorbsil C-30硅胶上进行色谱纯化，用乙酸乙酯∶己烷3∶7洗脱，得到化合物VIII.12(2.15g)；M+＝232；1H NMR：δ0.9-0.95(3H，t)；1.75-1.85(2H，m)；2.3-2.45(2H，m)；3.1-3.15(2H，t)3.85-3.95(2H，t)；4.15-4.35(1H，m)；6.9(1H，s)；7.1(1H，s)；(油状物)。
用上述方法，利用适宜的烷基化剂和N-H咪唑原料可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基硫基)-1-(1-甲基乙基)-咪唑(化合物VIII.14)，
M+＝232；1H NMR：δ1.4(6H，d)；2.3-2.4(2H，m)；3.1-3.15(2H，t)；
4.15-4.3(1H，m)；4.5-4.6(1H，m)；7.0(1H，s)；7.1(1H，s)；(油状物)，由化
合物VIII.1制得。(ii)2-(4，4-二氟丁-3-烯基硫基)-1，4，5-三甲基咪唑(化合物VIII.31)，1H
NMR：δ2.15(6H，两个s)；2.25-2.35(2H，m)；2.95(2H，t)；3.5(3H，s)；
4.15-4.3(1H，m)；(油状物)，由化合物VIII.29制得。(iii)1-乙基-2-(4，4-二氟丁-3-烯基硫基)-4，5-二甲基咪唑(化合物
VIII.33)，1H NMR：δ1.25(3H，t)；2.15(6H，brs)；2.3-2.4(2H，m)；3.0
(2H，t)；3.9-3.95(2H，q)；4.15-4.3(1H，m)；(油状物)，由化合物VIII.29
制得。(iV)2-(4，4-二氟丁-3-烯基硫基)-1，5-二甲基咪唑(化合物VIII.35)和2-(4，4-
二氟丁-3-烯基硫基)-1，4-二甲基咪唑(化合物VIII.60)的混合物；1H
NMR：δ2.15(3H，s)；2.3-2.4(2H，m)；3.0-3.05(2H，t)；3.5和3.55(3H，两
个s)；4.15-4.3(1H，m)；6.65和6.80(1H，两个s)，由化合物VIII.58制
得。(V)2-(4，4-二氟丁-3-烯基硫基)-5-甲基-1-(1-甲基乙基)-咪唑(化合物
VIII.37)和2-(4，4-二氟丁-3-烯基硫基)-4-甲基-1-(1-甲基乙基)-咪唑
(化合物VIII.62)的混合物；主要含有第二种异构体，1H NMR：δ
1.35(6H，d)；2.2(3H，s)；2.3-2.4(2H，m)；3.05(2H，t)；4.15-4.3(1H，m)；
4.5-4.6(1H，m)；6.70(1H，s)，由化合物VIII.58制得。(Vi)2-(4，4-二氟丁-3-烯基硫基)-5-乙氧羰基-1-甲基咪唑(化合物
VIII.52)，M+＝276；1H NMR：δ1.32-1.40(3H，t)；2.37-2.47(2H，m)；
3.2-3.3(2H，t)；3.82(3H，s)；4.17-4.32(1H，m)；4.25-4.35(2H，q)；7.7
(1H，s)；(油状物)，由化合物VIII.64制得，此反应生成可经色谱法分
离的化合物VIII.52和VIII.65的混合物，首先洗脱得到上述化合
物。(vii)2-(4，4-二氟丁-3-烯基硫基)-4-乙氧羰基-1-甲基咪唑(化合物
VIII.65)，M+＝276；1H NMR：δ1.35-1.40(3H，t)；2.35-2.42(2H，m)；
3.20-3.27(2H，t)；3.63(3H，s)；4.15-4.30(1H，m)；4.3-4.4(2H，q)；7.60
(1H，s)；(油状物)，由化合物VIII.64制得。
                        实施例VIII.6
此实施例阐明了2-(4，4-二氟丁基-3-烯基硫基)-N-(甲磺酰基)咪唑(化合物VIII.18)的制备方法。
将化合物VIII.1(0.49g)的无水四氢呋喃(3cm3)溶液滴加到冰水冷却下的氢化钠(55％油分散体，0.12g，使用前用己烷洗涤)的无水四氢呋喃(5cm3)悬浮液中。将反应混合物于室温下搅拌2小时，然后加入甲磺酰氯(0.3g)并将反应再搅拌16小时。将反应混合物倾入到乙酸乙酯/水中并分层。水层用乙酸乙酯萃取并将合并的有机相干燥(MgSO4)，过滤并减压蒸发，得到一黄色油状物。于硅胶上进行柱色谱纯化，用3∶7乙酸乙酯∶己烷洗脱，得到化合物VIII.18(0.31g)。1H NMR：δ2.40-2.50(2H，m)；3.30(2H，t)；3.30(3H，s)；4.25(1H，m)；7.05(1H，d)；7.35(1H，d)；(油状物)。
                     实施例VIII.7
此实施例阐明了适宜制备本发明化合物的方法，其中所述相应未被氧化的化合物中4，4-二氟丁-3-烯基硫基取代基中的硫原子被氧化成亚砜(亚磺酰基)或砜(磺酰基)。
由化合物VIII.5制备化合物VIII.7的方法
于二氯甲烷(400cm3)中将化合物VIII.5(18.1g)冷却至0℃并加入3-氯过苯甲酸(61.2g含水固体，2当量)。将混合物于室温下搅拌18小时，然后倾入饱和碳酸氢钠水溶液中。产物用二氯甲烷萃取，有机相用水和饱和盐水洗涤并干燥(MgSO4)。减压蒸除溶剂，得到化合物VIII.7粗品，将其于硅胶上进行色谱分离，用15％乙酸乙酯的己烷溶液，进而用50％乙酸乙酯的己烷溶液洗脱，得到纯化合物VIII1.7。1H NMR：δ2.55-2.6(2H，m)；3.5-3.55(2H，t)；4.0(3H，s)；4.15-4.3(1H，m)；7.0(1H，s)；7.15(1H，s)；(油状物)。
用上述实施例VIII所述方法，除非另有说明，利用2当量氧化剂和适宜的硫醚原料可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基磺酰基)-咪唑(化合物VIII.2)，MH+＝223；1H
NMR：δ2.4-2.6(2H，m)；3.4-3.45(2H，t)；4.1-4.3(1H，m)；7.3-7.4(3H，br
s)；(白色固体，mp.113-114℃)。(ii)2-(4，4-二氟丁-3-烯基磺酰基)-1-苯基咪唑(化合物VIII.4)，
M+＝298；1H NMR：δ2.45-2.55(2H，m)；3.45-3.55(2H，t)；4.15-
4.3(1H，m)；7.2(1H，d)；7.25(1H，d)；7.45-7.55(5H，m)；(油状物)。(iii)1-(4，4-二氟丁基-3-烯基)-2-(4，4-二氟丁-3-烯基磺酰基)咪唑(化合物
VIII.9)，M+＝312；1H NMR：δ2.5-2.65(4H，m)；3.5-3.6(2H，t)；4.1-4.35
(2H，m)；4.4-4.45(2H，t)；7.05(1H，s)；7.15(1H，s)；(油状物)。(iv)2-(4，4-二氟丁-3-烯基磺酰基)-1-乙基咪唑(化合物VIII.11)，
M+＝250；1H NMR：δ1.5(3H，t)；2.5-2.65(2H，m)；3.5-3.6(2H，t)；4.15-
4.35(1H，m)；4.4-4.45(2H，q)；7.05(1H，s)；7.15(1H，s)；(油状物)。(v)2-(4，4-二氟丁-3-烯基磺酰基)-1-丙基咪唑(化合物VIII.13)，
MH+＝265；1H NMR：δ0.9-1.0(3H，t)；1.8-2.0(2H，m)；2.5-2.6(2H，m)；
3.5-3.6(2H，t)；4.15-4.35(3H，m)；7.05(1H，s)；7.15(1H，s)；(油状物)。(vi)2-(4，4-二氟丁-3-烯基磺酰基)-1-(1-甲基乙基)-咪唑(化合物
VIII.15)，M+＝264；1H NMR：δ1.5(6H，d)；2.55-2.65(2H，m)；3.5-3.6
(2H，m)；4.15-4.35(1H，m)；5.15-5.35(1H，m)；7.15(2H，br)；(油状物)。(vii)2-(4，4-二氟丁-3-烯基亚磺酰基)-4-苯基咪唑(化合物VIII.20)，
M+＝282；1H NMR：δ2.35-2.65(2H，m)；3.25-3.4(2H，t)；4.15-4.3
(1H，m)；7.25-7.5(4H，m)；7.6-7.8(2H，m)；(油状物)，用1.5当量氧化剂
制得。(viii)2-(4，4-二氟丁-3-烯基磺酰基)-4-苯基咪唑(化合物VIII.21)，
M+＝298；1H NMR：δ2.45-2.6(2H，m)；3.4-3.5(2H，t)；4.1-4.28(1H，m)；
7.3-7.55(4H，m)；7.7-7.75(2H，d)；(mp.109.6-110.4℃)，用1.5当量氧化
剂制得。(ix)2-(4，4-二氟丁-3-烯基亚磺酰基)-1-甲基-4-苯基咪唑(化合物
VIII.23)，M+＝296；1H NMR：δ2.5-2.65(2H，m)；3.4-3.65(2H，m)；4.0
(3H，s)；4.25-4.4(1H，m)；7.25-7.45(4H，m)；7.7-7.75(2H，dd)；(mp.
106-106.6℃)，用1.5当量氧化剂制得。(x)2-(4，4-二氟丁-3-烯基磺酰基)-1-甲基-4-苯基咪唑(化合物VIII.24)，
M+＝312；1H NMR：δ2.6-2.7(2H，m)；3.58-3.65(2H，t)；4.02(3H，s)；4.2-
4.35(1H，m)；7.25-7.42(4H，m)；7.7-7.75(2H，dd)；(mp.78.6-79.6℃)，用
1.5当量氧化剂制得。(xi)2-(4，4-二氟丁-3-烯基磺酰基)-4-乙基-5-甲基咪唑(化合物VIII.28)，
M+＝264；1H NMR：δ1.15-1.3(3H，q)；2.25(3H，两个s(互变异构体))；
2.45-2.7(4H，m)；3.35-3.45(2H，t)；4.1-4.3(1H，m)；11.3(1H，br s)；(油状
物)。(xii)2-(4，4-二氟丁-3-烯基磺酰基)-4，5-二甲基咪唑(化合物VIII.30)，
M+＝250；1H NMR：δ2.25(6H，两个s)；2.45-2.55(2H，m)；3.35(2H，t)；
4.1-4.25(1H，m)；10.3-10.6(1H，br s)；(mp 113.4-114.6℃)。(xiii)2-(4，4-二氟丁-3-烯基磺酰基)-1，4，5-三甲基咪唑(化合物VIII.32)，
M+＝264；1H NMR：δ2.2(6H，br s)；2.5-2.6(2H，m)；3.4-3.5(2H，t)；3.85
(3H，s)；4.15-4.3(1H，m)；(油状物)。(xiv)1-乙基-2-(4，4-二氟丁-3-烯基磺酰基)-4，5-二甲基咪唑(化合物
VIII.34)，M+＝278；1H NMR：δ1.4(3H，t)；2.15(6H，br s)；2.5-2.6
(2H，m)；3.5(2H，t)；4.15-4.3(1H，m)；(油状物)。(xv)2-(4，4-二氟丁-3-烯基磺酰基)-1，5-二甲基咪唑(化合物VIII.36)和2-
(4，4-二氟丁-3-烯基磺酰基)-1，4-二甲基咪唑(化合物VIII.61)的混合
物，1H NMR：δ2.20(3H，s)；2.25(3H，s)；2.5-2.6(4H，m)；3.45-
3.55(4H，m)；3.85(3H，s)；3.95(3H，s)；4.15-4.3(2H，m)；6.75(1H，s)；
6.95(1H，s)，由上述实施例VIII.5(iv)中制备的化合物VIII.35和
VIII.60的混合物制得。(xvi)2-(4，4-二氟丁-3-烯基磺酰基)-5-甲基-1-(1-甲基乙基)-咪唑(化合物
VIII.38)；1H NMR：δ1.55(6H，d)；2.4(3H，s)；2.55-2.65(2H，m)；3.6(2H，
t)；4.15-4.35(1H，m)；5.15-5.30(1H，m)；6.85(1H，s)和2-(4，4-二氟丁-3-
烯基磺酰基)-4-甲基-1-(1-甲基乙基)-咪唑(化合物VIII.63)；1H
NMR：δ1.45(6H，d)；2.25(3H，s)；2.55-2.65(2H，m)；3.55(2H，t)；4.15-
4.35(1H，m)；5.15-5.30(1H，m)；6.90(1H，s)的18∶82的混合物，由上述
实施例VIII.5(V)中制备的化合物VIII.37和VIII.62的混合物制得。(xvii)2-(4，4-二氟丁-3-烯基磺酰基)-5-乙氧基羰基-1-甲基咪唑(化合物
VIII.53)，M+＝308；1H NMR：δ1.37-1.42(3H，t)；2.55-2.67(2H，m)；
3.6-3.65(2H，t)；4.2-4.35(1H，m)；4.25(3H，s)；4.32-4.4(2H，q)；7.7(1H，
s)；(油状物)。(xviii)2-(4，4-二氟丁-3-烯基磺酰基)-4-甲基咪唑(化合物VIII.59)，
M+＝236；1H NMR：δ2.3-2.4(3H，br)；2.45-2.55(2H，m)；3.4(2H，t)；4.2-
4.4(1H，m)；7.0(1H，br)；(油状物)。(xix)2-(4，4-二氟丁-3-烯基亚磺酰基)-4-乙氧基羰基-1-甲基咪唑(化合物
VIII.66)，M+＝292；1H NMR：δ1.35-1.4(3H，t)；2.49-2.7(2H，m)；3.35-
3.6(2H，m)；4.02(3H，s)；4.2-4.38(1H，m)；4.35-4.42(2H，q)；7.67(1H，s)；
(油状物)，用1.5当量氧化剂制得。(xx)2-(4，4-二氟丁-3-烯基磺酰基)-4-乙氧羰基-1-甲基咪唑(化合物
VIII.67)，M+＝308；1H NMR：δ 1.35-1.4(3H，t)；2.55-2.65(2H，m)；
3.65-3.70(2H，t)；4.02(3H，s)；4.2-4.38(1H，m)；4.35-4.42(2H，q)；7.65
(1H，s)；(油状物)，用1.5当量氧化剂制得。(xxi)3-(4，4-二氟丁-3-烯基磺酰基)咪唑并-[1，5a]-吡啶(化合物
VIII.152)，M+＝272；1H NMR：δ2.50(2H，m)；3.50(2H，t)；4.15(1H，m)；
6.90(1H，m)；7.10(1H，m)；7.20(1H，s)；7.65(1H，m)；8.95(1H，dd)；(油状
物)。
                   实施例IX.1
此实施例阐明了5-(4，4-二氟丁-3-烯基硫基)-1，3-二甲基-4-硝基吡唑(化合物XI.82)的制备方法。
室温下将4，4-二氟丁-3-烯基异硫脲氢溴酸盐(2.46g)和氢氧化钠水溶液(1.2g于12cm3水中)一起搅拌0.3小时。于室温下加入含有溴化四正丁基铵(0.01g，催化剂)的5-氯-1，3-二甲基-4-硝基吡唑(1.76g)的二氯甲烷(12cm3)溶液并将反应混合物于氮气氛下搅拌18小时。反应用水(100cm3)稀释并将产物用二氯甲烷(100cm3)萃取。合并有机相，用水洗涤，干燥(MgSO4)并减压蒸发，得到一浅黄色液体(2.6g)。将样品(0.9g)用色谱法(硅胶；己烷∶乙酸乙酯10∶1(体积比))进行分离，得到化合物IX.82(0.78g)。M+＝263；1H NM R：δ2.25(2H，m)；2.55(3H，s)；3.08(2H，t)；3.94(3H，s)；4.20(1H，m)；(油状物)。
                    实施例IX.2
此实施例阐明了5-(4，4-二氟丁-3-烯基磺酰基)-1，3-二甲基-4-硝基吡唑(化合物IX.84)的制备方法。
将3-氯过苯甲酸(1.74g 50％固体重量比)加入到化合物IX.82(0.526g)的二氯甲烷(10cm3)溶液中并将反应于室温下搅拌3天。反应用二氯甲烷(100cm3)稀释，用饱和碳酸氢钠水溶液，然后用水洗涤。干燥(MgSO4)并减压蒸发，得到一含油固体。粗产物用色谱法进行分离，得到化合物IX.84(0.15g)。1H NMR：δ2.52(3H，m)；2.60(2H，m)；3.74(2H，t)；4.20(3H，s)；4.25(1H，m)；(胶状物)。
                  实施例IX.3
此实施例阐明了3-步法制备5-(4，4-二氟丁-3-烯基硫基)-1，3-二甲基-4-碘吡唑(化合物IX.61)的方法。
步骤1：4-氨基-5-(4，4-二氟丁-3-烯基硫基)-1，3-二甲基吡唑的制备
将化合物IX.82(1.0g)溶于含有水(2cm3)和浓盐酸(催化剂，0.1cm3)的丙-2-醇(10cm3)中并用还原铁粉(1.0g)处理。将化合物进行搅拌并回流下加热3小时，冷却，用固体碳酸氢钠中和并经keiselgel过滤。不溶物用丙-2-醇洗涤，并将滤液减压蒸发，得到红褐色油状所述氨基吡唑中间体(1.0g)。M+＝233。
步骤2：
将步骤1所得产物(4.6g)溶于无水二氯甲烷(25cm3)中并于-15℃下加入到搅拌下的三氟化硼合乙醚(4.26g)的无水二氯甲烷(25cm3)溶液中。向混合物中滴加亚硝酸叔丁基酯的二氯甲烷(10cm3)溶液，令反应温热至5℃0.3小时，用己烷稀释，将溶液过滤，得到褐色固体状所需四氟硼酸重氮盐(6.7g)。
步骤3：化合物IX.61
于35℃将步骤1所得产物(1.33g)分批加入到搅拌下的碘化钾(1.7g)水(5cm3)溶液中，在此过程中反应混合物放出气体并得到一红褐色油状物。于35℃1小时后，将混合物冷却，用水稀释，乙醚(100cm3)萃取，有机相用偏亚硫酸氢钠水溶液，然后用水充分洗涤并干燥(MgSO4)。减压蒸除溶剂，残余油状物经色谱法(硅胶；己烷∶乙酸乙酯10∶1(体积比))进行分离，得到褐色油状化合物IX.61(0.2g)。M+＝344。
                  实施例IX.4
此实施例阐明了5-(4，4-二氟丁-3-烯基硫基)-1，3-二甲基-吡唑(化合物IX.55)的制备方法。
于0℃甲醇(20cm3)中将实施例IX.3步骤2中所得重氮盐(2.0g)进行搅拌并分批加入硼氢化钠(粉末，0.25g)，放出气体，溶液由无色变为黄褐色。令混合物温热至15℃0.5小时，室温下静置18小时，用水稀释，乙醚萃取，干燥(MgSO4)并减压蒸发，得到一红褐色液体。将此液体用色谱法(硅胶；己烷∶乙醚1∶1(体积比))进行分离，得到化合物IX.55(0.42g)。M+＝218；1H NMR：δ2.20-2.30(5H，m)；2.74(2H，m)；3.75(3H，s)；4.23(2H，m)；6.12(1H，s)；(油状物)。
                    实施例IX.5
此实施例阐明了5-(4，4-二氟丁-3-烯基硫基)-1-甲基吡唑-4-基羧酸乙酯(化合物IX.34)的制备方法。
于氮气氛下将二-(4，4-二氟丁-3-烯基)二硫化物(2.90g)和亚硝酸叔丁基酯(1.22g)的乙腈(40cm3)溶液加热至60℃，向搅拌下的溶液中滴加5-氨基-1-甲基吡唑-4-羧酸乙酯(1.00g)的乙腈(10cm3)溶液。加完后，将反应溶液于60℃下加热2小时，减压蒸发并经色谱法(硅胶；己烷∶乙醚5∶1(体积比))进行分离，得到化合物IX.34(产率42％)。M+＝276；1HNMR：δ1.38(3H，t)；2.20(2H，m)；3.05(2H，t)；3.97(3H，s)；4.25(1H，m)；4.34(2H，q)；7.98(1H，s)；(油状物)。
用上述方法和适宜的氨基-吡唑可制得下列本发明化合物：(ii)4-氰基-5-(4，4-二氟丁-3-烯基硫基)-1，3-二甲基吡唑(化合物IX.73)。
1H NMR：δ1.38(3H，t)；2.20(2H，m)；2.38(3H，s)；3.02(2H，t)；3.97(3H，s)；
4.25(1H，m)；(油状物)。(iii)5-(4，4-二氟丁-3-烯基硫基)-1-苯基吡唑-4-基羧酸乙酯(化合物
IX.124)。M+＝338；1H NMR：δ 1.40(3H，t)；2.05(2H，m)；2.88(2H，t)；
3.97(1H，m)；4.37(2H，q)；7.50(5H，m)；8.16(1H，s)；(油状物)。
                 实施例IX.6
此实施例阐明了4-氰基-5-(4，4-二氟丁-3-烯基磺酰基)-1，3-二甲基吡唑(化合物IX.75)的制备方法。
室温下将化合物IX.73(1.32g)的二氯甲烷(120cm3)溶液用3-氯过苯甲酸(3.94g，含50％过酸)处理。将混合物搅拌18小时，再用二氯甲烷稀释并用碳酸钠水溶液、偏亚硫酸氢钠充分洗涤。在将有机相干燥(MgSO4)之前，再用水、碳酸钠和水洗涤。减压蒸除溶剂，残余物经色谱法(硅胶；己烷∶乙醚1∶1(体积比))进行分离，得到化合物IX.75(0.47g)。M+＝275；1H NMR：δ2.42(3H，s)；2.30(2H，m)；2.58(3H，s)；3.38(2H，t)；4.14(3H，s)；4.36(1H，m)；(mp 78-81℃)。
用上述方法和适宜的吡唑化合物可制得下列本发明化合物：(i)4-溴5-(4，4-二氟丁-3-烯基磺酰基)-1-甲基吡唑(化合物IX.33)。1H
NMR：δ2.54(2H，m)；3.35(2H，t)；4.00(3H，s)；4.27(1H，m)；7.55(1H，s)；
(mp 42.6-43.6℃)，由化合物IX.31制得。(ii)5-(4，4-二氟丁-3-烯基磺酰基)-1-甲基吡唑-4-羧酸乙酯(化合物
IX.36)。1H NMR：δ1.38(3H，t)；2.50(2H，m)；3.78(2H，t)；4.15-4.30
(1H，m)；4.36(2H，q)；7.95(1H，s)；(油状物)，由化合物IX.34制得。(iii)5-(4，4-二氟丁-3-烯基磺酰基)-1-苯基吡唑-4-羧酸乙酯(化合物
IX.126)。1H NMR：δ1.42(3H，t)；2.45(2H，m)；3.72(2H，t)；4.18(1H，m)；
4.40(2H，q)；7.35-7.55(5H，m)；8.13(1H，s)；(mp 62.5-63.0℃)，由化合
物IX.124制得。
                    实施例IX.7
此实施例阐明了5-(4，4-二氟丁-3-烯基硫基)-1-甲基吡唑-4-羧酸(化合物IX.40)和5-(4，4-二氟丁-3-烯基硫基)-1-甲基吡唑-4-羧酸丙-2-基酯(化合物IX.37)的制备方法。
将化合物IX.34(1.5g)溶于丙-2-醇(40cm3)并用2M氢氧化钠水溶液(8cm3)处理，于室温下搅拌18小时。混合物用水(100cm3)稀释，用2M盐酸水溶液酸化并用乙酸乙酯(3×50cm3)萃取。将合并的有机相干燥(MgSO4)并减压蒸发，得到一黄色油状物，将其用己烷/乙醚处理固化。由溶液中过滤出固体，用己烷洗涤并吸滤干燥，得到化合物IX.40(0.76g)。1H NMR：δ2.24(2H，m)；3.06(2H，t)；4.00(3H，s)；4.20(1H，m)；8.08(1H，s)；(mp 59.4-60.0℃)。
将己烷/乙醚滤液减压蒸发并将油状物(含有带有约10％步骤1所得起始原料的乙基酯的化合物IX.37)用含有甲醇钠(酯基转移催化剂，10mg)的丙-2-醇(20cm3)处理，将混合物回流下加热5小时。将反应冷却，用水稀释，产物用乙醚萃取。将有机相干燥(MgSO4)并减压蒸发，得到化合物IX.37(0.1g)。M+＝291；1H NMR：δ1.35(6H，d)；2.22(2H，m)；3.05(2H，t)；3.97(3H，s)；4.20(1H，m)；5.20(1H，七重峰(septuplet))；7.95(1H，s)；(油状物)。
                    实施例IX.8
此实施例阐明了5-(4，4-二氟丁-3-烯基磺酰基)-1-甲基吡唑-4-羧酸(化合物IX.42)的制备方法。
将化合物IX.36(0.83g)溶于乙醇(35cm3)并于室温下用氢氧化锂一水合物(0.34g)的水(7cm3)溶液处理。将反应混合物搅拌18小时，减压蒸除乙醇，水相用2M盐酸酸化，产物用乙酸乙酯萃取。将有机相干燥(MgSO4)并减压蒸除溶剂，得到一胶状物，将其用乙醚/己烷研制，得到化合物IX.42(0.43g)。M(NH4)+＝298；1H NMR：δ2.52(2H，m)；3.72(2H，t)；4.10-4.30(3H，m)；8.05(1H，s)；(mp 118.4-122.0℃)。
                   实施例X.1
此实施例说明了用于制备本发明化合物所需中间体巯基-1，2，4-噁二唑类化合物的两种有关的合成方法。5-巯基-1，2，4-噁二唑化合物的一般合成方法是将偕胺肟与活化的硫代羰基化合物例如硫光气或1，1-硫代羰基二咪唑环合。下面利用第一种试剂来说明5-巯基-3-苯基-1，2，4-噁二唑的制备方法。
将苄腈(15g)、羟胺盐酸盐(10g)、碳酸钾(10g)、乙醇(150cm3)和水(15cm3)一起于回流下加热6小时，然后令其冷却过夜。将反应混合物过滤，固体残余物用乙醇洗涤。将滤液和洗液合并并蒸发，所得褐色残余物于乙酸乙酯和水之间配分。分出有机相，用盐水洗涤并干燥(MgSO4)。蒸发，得到一褐色油状物，通过加入乙酸乙酯和己烷使其析晶，得到灰色固体(10.3g)。将所述固体(4.4g)于乙醚(50cm3)中进行搅拌并加入硫光气(0.55cm3)，使得生成粘稠的白色沉淀。将反应物回流加热1小时，然后令其冷却。加入氢氧化钠水溶液(50cm3)并将反应再加热4小时，然后令其冷却，得到一黄色两相反应混合物。分出有机相，水层用乙醚萃取两次。将水层酸化至pH1，使得生成黄色沉淀。水层用乙酸乙酯萃取，将合并的乙酸乙酯层干燥(MgSO4)并蒸发，得到黄褐色固体状5-巯基-3-苯基-1，2，4-噁二唑(0.554g)，无需进一步纯化就将其使用。1H NMR：δ7.45-7.63(3H，m)；7.70-7.90(2H，m)。
下面利用另一种试剂1，1-硫代羰基二咪唑来说明5-巯基-3-甲氧基甲基-1，2，4-噁二唑的制备方法。
将甲氧基乙腈(7.1g)、羟胺盐酸盐(7g)、碳酸钾(13.8g)、乙醇(90cm3)和水(9cm3)一起于50℃下加热9小时，然后令其冷却。将反应混合物过滤，白色固体残余物用乙酸乙酯洗涤。将滤液和洗液合并并蒸发，将所得残余物溶于二氯甲烷。过滤除去不溶物并将滤液蒸发，得到粘稠油状物(9.2g)。将所述油状物加入到含有1，1-硫代羰基二咪唑(5.655g)的甲苯(60cm3)和无水二甲基甲酰胺(4cm3)中并将混合物于室温下搅拌2小时。再静置60小时后，过滤回收所形成的大量固体(得到5.2g)，NMR表明是所述偕胺肟的羟基与硫代羰基基团未发生环合反应的产物。将部分固体(2g)加入到氢化钠(0.33g)的无水二甲基甲酰胺(30cm3)悬浮液中(起沫)，将混合物于室温下搅拌5小时并静置18小时。将反应产物倾入水中，产物用乙酸乙酯萃取。分出合并的有机相，干燥(MgSO4)并减压蒸发，最后于高真空下除去痕量的二甲基甲酰胺，得到5-巯基-3-甲氧基甲基-1，2，4-噁二唑粗品，1H NMR：δ3.2(3H，s)；4.10(2H，s)；6.92-6.98(1H，br s)，无需进一步纯化就将其使用。
                   实施例X.2
此实施例说明了利用上述实施例制备的相应的5-巯基中间体化合物制备5-(4，4-二氟丁-3-烯基硫基)-3-取代的-1，2，4-噁二唑化合物的一般方法。这通过下列5-(4，4-二氟丁-3-烯基硫基)-3-甲氧基甲基-1，2，4-噁二唑，化合物X.26的制备方法得以说明。
向5-巯基-3-甲氧基甲基-1，2，4-噁二唑(2.78g)的丙酮(150cm3)溶液中加入4-溴-1，1-二氟丁-1-烯(4.87g)和碳酸钾(3.15g)并将混合物回流加热18小时。Gc分析表明反应已经完成。过滤除去固体无机物，反应混合物经过一sorbsil-C30硅胶柱，用丙酮洗脱。将滤液减压蒸发，黄色油状残余物于sorbsil-C30上进行色谱分离，用5％乙酸乙酯的己烷溶液洗脱，得到化合物X.26(1.6g)，1H NMR：δ2.47-2.58(2H，m)；3.28-3.35(2H，t)；3.49(3H，s)；4.18-4.36(1H，m)；4.54(2H，s)；(油状物)。
用上述方法和所述适宜的中间体可制得下列本发明化合物：(i)5-(4，4-二氟丁-3-烯基硫基)-3-甲氧基甲基-1，2，4-噁二唑(化合物
X.32)，1H NMR：δ2.37(3H，s)；2.45-2.55(2H，m)；3.22-3.30(2H，t)；
4.16-4.35(1H，m)；(油状物)，由5-巯基-3-甲基-1，2，4-噁二唑制得。(ii)5-(4，4-二氟丁-3-烯基硫基)-3-苯基-1，2，4-噁二唑(化合物X.1)，M+
＝268；1H NMR：δ2.58(2H，m)；3.35(2H，t)；4.31(1H，m)；7.45-7.56
(3H，m)；8.07(2H，d)；(油状物)，由5-巯基-3-苯基-1，2，4-噁二唑制得。
                  实施例X.3
此实施例阐明了由化合物X.26制备5-(4，4-二氟丁-3-烯基硫基)-3-甲氧基甲基-1，2，4-噁二唑(化合物X.27)的方法。
于二氯甲烷(50cm3)中将化合物X.26(0.6g)冷却至0℃并于5分钟内加入3-氯过苯甲酸。将反应混合物倾入饱和碳酸氢钠水溶液中，产物用二氯甲烷萃取。有机层用饱和碳酸氢钠水溶液、水和饱和盐水洗涤并干燥(MgSO4)。减压蒸除溶剂，得到一淡褐色固体，将其于硅胶上进行色谱分离，用10％乙酸乙酯的己烷溶液，进而用20％乙酸乙酯的己烷溶液洗脱，得到化合物X.27，1H NMR：δ2.6-2.71(2H，m)；3.51(3H，s)；3.58-3.65(2H，t)；4.21-4.37(1H，m)；4.69(2H，s)；(油状物)。此产物发现不稳定并且在室温下静置60小时后被明显水解。
                  实施例XI.1A
此实施例通过下列由氯代乙脒盐酸盐制备5-氯-3-氯甲基-1，2，4-噻二唑的方法说明了制备5-氯-3-取代的-1，2，4-噻二唑化合物的一般方法。
将氯代乙脒盐酸盐(12.9g)的二氯甲烷(.100cm3)悬浮液冷却至-5℃并加入全氯甲硫醇(20.44g)。滴加氢氧化钠水溶液(20g，30cm3)(放热)，保持反应混合物的温度低于5℃。加完后，令反应温热至室温并搅拌过夜。混合物用水和二氯甲烷稀释并全部通过一层硅藻土以除去不溶物。分出有机相，用饱和盐水洗涤并用硫酸镁干燥。将产物溶液过滤并减压蒸发，得到褐色油状物(9.72g)，将其无需进一步纯化使用。M+＝168；1H NMR：δ4.75(s)。
按照实施例XI.1A中所述方法可制得下列中间体化合物。所述原料为公知化合物。
(i)5-氯-3-三氟甲基-1，2，4-噻二唑。M+＝188(bp50℃，12mmHg)。
(ii)5-氯-3-甲硫基-1，2，4-噻二唑。M+＝166。
(iii)5-氯-3-甲氧基-1，2，4-噻二唑。M+＝150。
(iv)5-氯-3-(2-吡嗪基)-1，2，4-噻二唑。M+＝198。
如下所述，利用有关方法可制得本发明化合物XI.102。
5-氯-3-(4，4-二氟丁-3-烯基硫基)-1，2，4-噻二唑的制备
将含有十二烷基硫酸钠(0.1g，催化剂)和全氯甲硫醇(7.17g)的4，4-二氟丁-3-烯基异硫脲氢溴酸盐(8.68g)的水(200cm3)悬浮液冷却至0℃并滴加氢氧化钠水溶液(5.6g，200cm3)，保持反应混合物的温度低于5℃。加完后，令反应温热至室温并搅拌过夜。混合物用乙酸乙酯萃取两次，分出有机相，用饱和盐水洗涤并干燥(MgSO4)。将含有产物的溶液过滤并减压蒸发，得到一褐色油状物(8.2g)，将其于硅胶(Sorbsil C30)上进行色谱分离，用乙酸乙酯的己烷溶液作洗脱剂，得到化合物XI.102(2.82g)。M+＝242；1H NMR：δ2.4-2.6(2H，m)；3.2-3.3(3H，t)；4.2-4.4(1H，m)；(油状物)。
                    实施例XI.1B
制备5-[(4-甲苯基)-磺酰基]-3-取代的-1，2，4-噻二唑的一般方法可通过下述由甲氧基乙酰胺经2-步法制备3-甲氧基甲基-5-[(4-甲苯基)-磺酰基]-1，2，4-噻二唑的方法得以说明。
步骤1：5-甲氧基甲基-1，3，4-噁二唑-2-酮的制备
将氯代羰基亚磺酰氯(Chlorocarbonylsulfenyl chloride)(7.35g)加入到甲氧基乙酰胺(5g)的甲苯(30cm3)悬浮液中。搅拌反应混合物并于90-100℃下加热5小时，然后冷却。减压蒸除溶剂，得到一褐色胶状物(6.6g)，M+＝147；1H NMR(DMSO-d6)：δ3.30(3H，s)；4.30(2H，s)；无需进一步纯化将其用于下一步反应。
步骤2：3-甲氧基甲基-5-[(4-甲苯基)-磺酰基]-1，2，4-噻二唑的制备
将4-甲基苯磺酰基氰化物(16.26g)加入到5-甲氧基甲基-1，3，4-噁二唑-2-酮(6.6g)的十二烷(60cm3)乳化液中。搅拌反应混合物并于150℃下加热18小时，然后冷却。加入水并用乙酸乙酯萃取产物。将合并的有机相干燥(MgSO4)并减压蒸除乙酸乙酯，残余物分成褐色液体和澄清十二烷层，除去十二烷层并滗析。将褐色液体于硅胶(Sorbsil C30)上进行色谱分离，用3∶7乙酸乙酯∶己烷作洗脱剂，得到浅橙色油状物，将其静置固化(6.94g)。M+＝284；1H NMR：δ2.40(3H，s)；3.45(3H，s)；4.7(2H，d)；7.4(2H，d)；8.0(2H，d)；(mp 43.4-45.4℃)。
按照实施例XI.1B中所述2-步法可制得下列中间体化合物。所述原料为公知化合物。(i)3-乙基-5-[(4-甲苯基)-磺酰基]-1，2，4-噻二唑，M+＝268；1H NMR：δ
1.3-1.4(3H，t)；2.45(3H，s)；2.95-3.05(2H，q)；7.4(2H，m)；8.0(2H，m)，由丙
酰胺制得。(ii)3-(E-丙-1-烯基)-5-[(4-甲苯基)-磺酰基]-1，2，4-噻二唑，M+＝280；1H
NMR：δ1.95(2H，dd)；2.45(3H，s)；6.5-6.6(1H，m)；7.0-7.1(1H，m)；7.4
(2H，m)；8.0(2H，m)，由丁酰胺制得。
                   实施例XI.2
此实施例通过下列所述制备5-(4，4-二氟丁-3-烯基硫基)-3-甲氧基甲基-1，2，4-噻二唑(化合物XI.34)的方法，说明利用相应的5-氯-或5-[(4-甲苯基)-磺酰基]-1，2，4-噻二唑中间体，制备5-(4，4-二氟丁-3-烯基硫基)-3-取代的-1，2，4-噻二唑类化合物的方法。
将氢氧化钠水溶液(0.848g，10cm3)加入到4，4-二氟丁-3-烯基异硫脲氢溴酸盐(1.75g)中并将混合物于室温下搅拌20分钟。加入3-甲氧基甲基-5-[(4-甲苯基)-磺酰基]-1，2，4-噻二唑(2.01g)的二氯甲烷(10cm3)溶液和溴化四正丁基铵(0.1g，催化剂)并将混合物搅拌20分钟。Tlc分析表明产物已经生成。将混合物再用二氯甲烷(10cm3)稀释并分出有机相，用饱和盐水洗涤，干燥(MgSO4)，过滤并减压蒸发，得到一橙黄色液体。将所述粗产物于硅胶(Sorbsil C30)上进行色谱分离，用1∶4乙酸乙酯∶己烷作洗脱剂，得到化合物XI.34(1.67g)。M+＝252；1H NMR：δ2.45-2.55(2H，m)；3.25-3.35(2H，t)；3.5(3H，s)；4.15-4.35(1H，m)；4.65(2H，s)；(油状物)。
用上述方法，但使用适宜的中间体可制得下列本发明化合物：(i)5-(4，4-二氟丁-3-烯基硫基)-3-三氟甲基-1，2，4-噻二唑(化合物XI.9)。
M+＝276；1H NMR：δ2.5-2.6(2H，m)；3.3-3.4(2H，t)；4.2-4.4(1H，m)；(油
状物)。(ii)5-(4，4-二氟丁-3-烯基硫基)-3-(E-丙-1-烯基)-1，2，4-噻二唑(化合物
XI.11)。M+＝248；1H NMR：δ1.95(3H，dd)：2.5-2.6(2H，m)；3.3(2H，t)；
4.2-4.4(1H，m)；6.45-6.55(1H，m)；(油状物)。(iii)3-乙基-5-(4，4-二氟丁-3-烯基硫基)-1，2，4-噻二唑(化合物XI.23)。
M+＝236；1H NMR：δ1.3-1.4(3H，t)；2.45-2.55(2H，m)；2.9-3.0(2H，q)；
3.3(2H，t)；4.2-4.4(1H，m)；(油状物)。(iv)3-氯甲基-5-(4，4-二氟丁-3-烯基硫基)-1，2，4-噻二唑(化合物XI.25)。
M+＝256；1H NMR：δ2.45-2.55(2H，m)；3.35(2H，t)；4.2-4.35(1H，m)；4.7
(2H，s)；(油状物)。在此反应中可制得另外两种产物，将其进行色谱
分离并进行定性分析。这两种产物是3-(4，4-二氟丁-3-烯基硫甲
基)-5-(4，4-二氟丁-3-烯基硫基)-1，2，4-噻二唑(化合物XI.38)。
M+＝344；1H NMR：δ2.25-2.35(2H，m)；2.45-2.55(2H，m)；2.65(2H，t)；
3.3(2H，t)；3.9(2H，s)；4.15-4.35(2H，m)；(油状物)和5-氯-3-(4，4-二氟
丁-3-烯基硫甲基)-1，2，4-噻二唑。M+＝256；1H NMR：δ2.2-
2.3(2H，m)；2.65(2H，t)；3.9(2H，s)；4.1-4.3(1H，m)；(油状物)。(v)5-(4，4-二氟丁-3-烯基硫基)-3-甲氧基-1，2，4-噻二唑(化合物XI.87)。
M+＝238；1H NMR：δ2.45-2.55(2H，m)；3.3(2H，t)；4.1(3H，s)；4.2-4.35
(1H，m)；(油状物)。(vi)3，5-二-(4，4-二氟丁-3-烯基硫基)-1，2，4-噻二唑(化合物XI.109)，
M+＝330；1H NMR：δ2.45-2.6(4H，m)；3.2-3.35(4H，m)；4.2-4.4(2H，m)；
(油状物)，由化合物XI.102制得。(vii)5-(4，4-二氟丁-3-烯基硫基)-3-(2-吡嗪基)-1，2，4-噻二唑(化合物
XI.125)。M+＝286；1H NMR：δ2.55-2.65(2H，m)；3.35-3.45(2H，t)；
4.25-4.40(1H，m)；8.65(1H，d)；8.75(1H，dd)；9.55(1H，d)；(油状物)。
                实施例XI.3
此实施例阐明了3-丁氧基甲基-5-(4，4-二氟丁-3-烯基硫基)-1，2，4-噻二唑(化合物XI.30)的制备方法。
将碳酸钾(0.444g)和正丁醇(0.397g)加入到化合物XI.25(0.275g)的二甲基甲酰胺(2cm3)溶液中并将混合物于室温下搅拌18小时。Tlc分析表明在混合物中仍含有化合物XI.25，此时加入氢化钠(0.1g)和正丁醇(0.4g)并继续搅拌24小时。加入水，产物用乙醚萃取。将有机相干燥(MgSO4)，过滤并减压蒸发，得到一油状物(0.422g)，将其于硅胶(SorbsilC30)上进行色谱纯化，用10％乙酸乙酯的己烷溶液作洗脱剂，得到化合物XI.30(0.131g)。M+＝294；1H NMR：δ0.95-1.0(3H，t)；1.4-1.55(2H，m)；1.75-1.9(2H，m)；2.25-2.45(2H，m)；2.6-2.7(2H，t)；3.75(2H，s)；4.15-4.3(1H，m)；4.4-4.5(2H，t)；(油状物)。
用正丙醇代替正丁醇，用上述方法可制得下列本发明化合物：(i)5-(4，4-二氟丁-3-烯基硫基)-3-丙氧基甲基-1，2，4-噻二唑(化合物
XI.31)。M+＝280；1H NMR：δ1.0-1.1(3H，t)；1.8-1.95(2H，m)；2.25-2.35
(2H，m)；2.6-2.7(2H，t)；3.75(2H，s)；4.15-4.4(1H，m)；4.4-4.45(2H，t)；(油
状物)。
                   实施例XI.4
此实施例阐明了2-步法制备5-(4，4-二氟丁-3-烯基硫基)-3-甲基-1，2，4-噻二唑(化合物XI.40)的方法。
步骤1：3-甲基-1，2，4-噻二唑-5(4H)-硫酮的制备
向乙脒(5g)的甲醇(100cm3)溶液中加入二硫化碳(4g)、硫(1.7g)和甲醇钠(5.7g)并将混合物回流下加热6小时。将混合物冷却，经高流动性助滤剂(hi-flo filter aid)过滤以除去过量的硫，将滤液于水和乙酸乙酯之间配分。将乙酸乙酯蒸发，得到一褐色油状物，将水层酸化，生成红色固体并过滤。由所述滤液中所得两种固体显然是3-甲基-1，2，4-噻二唑-5(4H)-硫酮和硫的混合物。将这两种固体合并并用于下一步骤。
步骤2：化合物XI.40的制备
向3-甲基-1，2，4-噻二唑-5(4H)-硫酮(1.2g)的丙酮(100cm3)溶液中加入4-甲基苯磺酸4，4-二氟丁-3-烯基酯(2.4g)和碳酸钾(1.2g)并将混合物回流4小时，此后，tlc分析表明原料已消耗完全。将反应物倾入乙酸乙酯和水中并分层。水层用乙酸乙酯萃取并将合并的有机相干燥(MgSO4)，然后将含有产物的溶液过滤并减压蒸发，得到一褐色油状物，将其进行闪式色谱纯化(硅胶，7％乙酸乙酯的己烷溶液)，得到褐色油状5-(4，4-二氟丁-3-烯基硫基)-3-甲基-1，2，4-噻二唑(0.645g)。M+＝222；1H NMR：δ2.56(2H，br q)；2.63(3H，s)；3.30(2H，t)；4.30(1H，m)。
用3-苯基-1，2，4-噻二唑-5(4H)-硫酮作原料，用上述方法可制得下列本发明化合物：(i)5-(4，4-二氟丁-3-烯基硫基)-3-苯基-1，2，4-噻二唑(化合物XI.5)。1H
NMR：δ2.53(2H，q)；3.30(2H，t)；4.24(1H，m)；7.38(3H，m)；8.2(2H，
m)。
                   实施例XI.5
此实施例阐明了3-(4，4-二氟丁-3-烯基硫基)-5-甲氧基-1，2，4-噻二唑(化合物XI.108)的制备方法。
将氢氧化钠(0.182g)加入到化合物XI.102(1g)的甲醇(5cm3)溶液中并将混合物于室温下搅拌45分钟，此时tlc分析表明原料已消耗完全。向所述混合物中加入水和乙醚并将产物用乙醚萃取。将有机相干燥(MgSO4)，过滤并减压蒸发，得到一黄色油状物(0.9g)。经闪式色谱法(硅胶，55乙酸乙酯的己烷溶液)纯化，得到化合物XI.108(0.78g)。M+＝238；1H NMR：δ2.4-2.5(2H，m)；3.2(2H，t)；4.15(3H，s)；4.2-4.35(1H，m)；(油状物)。
                   实施例XI.6
此实施例阐明了5-(4，4-二氟丁-3-烯基硫基)-3-甲硫基-1，2，4-噻二唑(化合物XI.110)的制备方法。
将硫化钠一水合物(0.555g)加入到5-氯-3-甲硫基-1，2，4-噻二唑(1.5g)的乙醇(10cm3)溶液中并将混合物回流下搅拌18小时。将反应混合物冷却并减压蒸除溶剂，得到一黄色固体(1.76g)，将其溶于丙酮(30cm3)，加入碳酸钾(2.22g)和4-溴-1，1-二氟丁-1-烯(1.83g)并将混合物进行搅拌并回流加热18小时。将反应混合物冷却，经高流动性助滤剂过滤以除去无机物，用乙酸乙酯洗涤并减压蒸除溶剂，得到一褐色胶状物，将其于硅胶(Sorbsil C30)上进行色谱纯化，用5％乙酸乙酯的己烷溶液作洗脱剂，得到化合物XI.110(0.392g)。M+＝254；1H NMR：δ2.45-2.55(2H，m)；2.65(3H，s)；3.25-3.35(2H，t)；4.2-4.4(1H，m)；(油状物)。
                  实施例XI.7
此实施例阐明了5-(4，4-二氟丁-3-烯基硫基)-3-(3-硝基苯基)-1，2，4-噻二唑(化合物XI.127)的制备方法。
向冷却至～-10℃搅拌下的甲醇钾(2，2g)和无水乙醇(25cm3)的混合物中通入硫化氢气40分钟。由冷却浴中移出烧瓶，加入5-氯-3-(3-硝基苯基)-1，2，4-噻二唑(3g)并将混合物回流下加热1小时。将反应冷却并倾入乙醚中，过滤生成的沉淀。将含有5-巯基-3-(3-硝基苯基)-1，2，4-噻二唑的滤液放入烧瓶中，加入4-甲基苯磺酸4，4-二氟丁-3-烯基酯(1.5g)和～1g碳酸钾并将混合物回流加热3小时，此后gc分析表明甲苯磺酸酯已基本消耗完全。将反应物倾入乙酸乙酯和水中并分层。水层用乙酸乙酯萃取并将合并的有机相干燥(MgSO4)。减压蒸发，得到一褐色液体，将其经闪式色谱法(硅胶；用5％乙酸乙酯的己烷溶液洗脱)进行纯化，得到化合物XI.127(0.901g)。M+＝329；1H NMR：δ2.60(2H，brq)；3.44(2H，t)；4.34(1H，m)；7.65(1H，t)；8.32(1H，dd)；8.6(1H，d)；9.1(1H，d)；(油状物)。
                    实施例XI.8
此实施例阐明了适宜制备本发明化合物的方法，其中所述相应未被氧化的化合物(按照上述实施例中所述方法制得)中4，4-二氟丁-3-烯基硫基取代基中的硫原子被氧化成亚砜(亚磺酰基)或砜(磺酰基)。
由化合物XI.34制备化合物XI.35和XI.36
于二氯甲烷(10cm3)中将化合物XI.34(0.85g)室温下进行搅拌并加入3-氯过苯甲酸(0.814g，1.4当量)。3.5小时后，tlc分析表明原料已消耗完全，有两种产物生成。通过加入饱和碳酸氢钠水溶液使反应中止并将产物用二氯甲烷萃取。分出有机相，用饱和盐水洗涤并用硫酸镁干燥。过滤后，减压蒸发浓缩，得到一白色固体(1.2g)，将其于硅胶上进行色谱纯化，用3∶7乙酸乙酯∶己烷作洗脱剂，首先得到5-[(4，4-二氟丁-3-烯基)磺酰基]-3-甲氧基甲基-1，2，4-噻二唑(化合物XI.36)(0.298g)。M+＝284；1H NMR：δ2.55-2.65(2H，m)；3.55(3H，s)；3.5-3.6(2H，t)；4.2-4.35(1H，m)；4.80(2H，s)；(油状物)。另外洗脱得到5-[(4，4-二氟丁-3-烯基)亚磺酰基]-3-甲氧基甲基-1，2，4-噻二唑(化合物XI.35)(0.402g)。M+＝268；1H NMR：δ2.3-2.75(2H，m)；3.15-3.4(2H，m)；3.55(3H，s)；4.15-4.35(1H，m)；4.75(2H，s)；(油状物)。
用2当量的氧化剂，用上述方法可制得下列本发明化合物：(i)5-[(4，4-二氟丁-3-烯基)磺酰基]-3-乙基-1，2，4-噻二唑(化合物XI.24)。
M+＝268；1H NMR：δ1.4-1.5(3H，t)；2.55-2.65(2H，m)；3.05-
3.15(2H，q)；3.5-3.55(2H，t)；4.2-4.4(1H，m)；(油状物)。
                   实施例XII.1
在制备本发明化合物中用作中间体化合物的巯基1，3，4-噁二唑类化合物的合成方法是本领域公知的方法。下面将分别阐明两种合成方法。
方法A 2-巯基-5-甲基-1，3，4-噁二唑的制备
向乙酰肼(5g)的乙醇(10cm3)溶液中加入二硫化碳(7.7g)，随后加入氢氧化钾的乙醇溶液(5.7g，20cm3)，生成白色沉淀。然后将反应于室温下搅拌2小时并静置过夜。将反应过滤，得到一白色固体(11g)。将此盐(5g)溶于吡啶(10cm3)并将混合物回流加热共14小时，冷却后，将反应酸化并用乙醚萃取两次。乙醚层用硫酸镁干燥，过滤并减压蒸发，得到一桔黄色固体。将其于乙酸乙酯中重结晶，得到2-巯基-5-甲基-1，3，4-噁二唑(0.655g)。M+＝116；1H NMR：δ2.43(3H，s)；10.9(1H，br s)。
方法B 5-(4-甲氧基苄基)-1，3，4-噁二唑-2(3H)-硫酮的制备
步骤1：(4-甲氧基苯基)乙酰肼的制备
将水合肼(4.7cm3)滴加到(4-甲氧基苯基)乙酸乙酯(3.73g)中，然后加入甲醇(20cm3)以形成均相反应混合物。将此混合物于室温下搅拌18小时，其间有白色沉淀生成。过滤分离出沉淀并用甲醇和水洗涤，空气干燥，得到(4-甲氧基苯基)乙酰肼(2g)。M+＝180；1H NMR：δ3.50(2H，s)；3.80(3H，s)；3.85(2H，br s)；6.70(1H，br s)；6.90(2H，d)；7.20(2H，d)；(固体)。
用上述方法可制得下列中间体化合物：
(i)2-甲基丙酰肼。M+＝102；(固体)。
(ii)环丙基乙酰肼。M+＝100；(固体)。(iii)丁酰肼。1H NMR：δ0.95(3H，t)；1.60-1.75(2H，m)；2.15(2H，t)；3.90
(2H，br s)；6.95(1H，br s)；(固体)。
(iv)丙酰肼。M+＝88；(固体)。(v)戊酰肼。1H NMR：δ0.90(3H，t)；1.30-1.40(2H，m)；1.60-1.70(2H，m)；
2.20(2H，t)；3.90(2H，br s)；6.80(1H，br s)；(固体)。(vi)己酰肼。1H NMR：δ0.90(3H，t)；1.20-1.35(4H，m)；1.60-1.70(2H，m)；
2.15(2H，t)；3.90(2H，br s)；6.70(1H，br s)；(固体)。(vii)(4-硝基苯基)乙酰肼。1H NMR(DMSO-d6)：δ3.50(2H，s)；7.50(2H，d)；
 8.10(2H，d)；(固体)。(viii)(2，6-二氟苯基)乙酰肼。M+＝186；1H NMR：δ 3.60(2H，s)；6.90-
 7.00(2H，m)；7.20-7.30(1H，m)；(固体)。(ix)2-甲基苯甲酰肼。M+＝150；1H NMR：δ2.45(3H，s)；4.10(2H，br s)；
7.00(1H，br s)；7.20-7.40(4H，m)；(固体)。
步骤2：5-(4-甲氧基苄基)-1，3，4-噁二唑-2(3H)-硫酮的制备
将氢氧化钾(0.7g)的水(2cm3)溶液加入到搅拌下的(4-甲氧基苯基)乙酰肼(1.99g)的乙醇(30cm3)溶液中，加入二硫化碳(0.7cm3)并将反应回流加热6小时，然后静置冷却。减压下将反应混合物蒸发至干并将固体残余物溶于水。用浓盐酸调节pH至1，结果生成白色沉淀。过滤分离出沉淀，用水和乙醚洗涤并空气干燥，得到5-(4-甲氧基苄基)-1，3，4-噁二唑-2(3H)-硫酮(1.96g)。M+＝222；1H NMR：δ3.80(3H，s)；3.95(2H，s)；6.90(2H，d)；7.20(2H，d)；(固体)。
用适宜的中间体化合物(已知化合物或如步骤1中所制备)，用上述方法可制得下列化合物：
(i)1，3，4-噁二唑-2(3H)-硫酮。M+＝145；(固体)。
(ii)5-噻吩基-1，3，4-噁二唑-2(3H)-硫酮-5-甲酰胺。M+＝184；(固体).
(iii)5-异丙基-1，3，4-噁二唑-2(3H)-硫酮。M+＝144；(胶状物)。
(iv)5-环丙基-1，3，4-噁二唑-2(3H)-硫酮。M+＝142；(胶状物)。
(v)5-丙基-1，3，4-噁二唑-2(3H)-硫酮。M+＝144；(油状物)。
(vi)5-乙基-1，3，4-噁二唑-2(3H)-硫酮。M+＝130；(油状物)。(vii)5-(4-吡啶基)-1，3，4-噁二唑-2(3H)-硫酮。M+＝179；1H NMR：δ
7.75(2H，d)；8.75(2H，d)；(固体)。(viii)5-丁基-1，3，4-噁二唑-2(3H)-硫酮。1H NMR：δ0.95(3H，t)；1.35-
1.50(2H，m)；1.65-1.75(2H，m)；2.70(2H，t)；2.90(1H，br s)；(油状物)。(ix)5-苯基-1，3，4-噁二唑-2(3H)-硫酮。1H NMR：δ0.90(3H，t)；1.25-
1.45(4H，m)；1.75(2H，m)；2.70(2H，m)；(油状物)。(x)5-(4-硝基苄基)-1，3，4-噁二唑-2(3H)-硫酮。M+＝237；1H NMR：δ
4.20(2H，S)；7.50(2H，d)；8.25(2H，d)；(固体)。(xi)5-(2，6-二氟苄基)-1，3，4-噁二唑-2(3H)-硫酮。1H NMR：δ
4.10(2H，s)；6.90-7.00(2H，m)；7.25-7.40(1H，m)；(固体)。(xii)5-(4-甲氧基苯基)-1，3，4-噁二唑-2(3H)-硫酮。1H NMR：δ
3.80(3H，s)；7.10(2H，d)；7.75(2H，d)；(固体)。(xiii)5-(2-甲基苯基)-1，3，4-噁二唑-2(3H)-硫酮。1H NMR(DMSO-d6)：δ
2.50(3H，s)；7.30-7.40(2H，m)；7.40-7.50(1H，m)；7.55(1H，br d)；(固体)。(xiv)5-(2-甲氧基苯基)-1，3，4-噁二唑-2(3H)-硫酮。M+＝208；(固体)。(xv)5-(4-硝基苯基)-1，3，4-噁二唑-2(3H)-硫酮。M+＝223；1H NMR：δ
8.05(2H，d)；8.30(2H，d)；(固体)。(xvi)5-苄基-1，3，4-噁二唑-2(3H)-硫酮。1H NMR：δ4.00(2H，s)；7.25-
7.40(5H，m)；(固体)。
                 实施例XII.2
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)-5-苯基-1，3，4-噁二唑(化合物XII.3)的制备方法。
向2-巯基-5-苯基-1，3，4-噁二唑(0.499g)的丙酮(15cm3)溶液中加入碳酸钾(0.387g)和4-甲基苯磺酸4，4-二氟丁-3-烯基酯(0.7g)并将混合物回流下加热1.5小时，此后所有原料均已消耗完全。将反应物倾入乙醚和水中并分层。水层用乙醚萃取，将合并的有机层用水洗涤并干燥(MgSO4)。减压蒸发溶剂，得到一浅黄色液体，将其经闪式色谱法纯化，静置固化，得到无色油状化合物XII.3(0.293g)。M+＝268；1H NMR：δ2.58(2H，m)；3.32(2H，t)；4.31(1H，m)；7.45-7.57(3H，m)；8.01(2H，d)；(mp 38-40℃)。
用上述方法，由适宜的中间体化合物(已知化合物或如实施例XII.1中所制备)，只是用4-溴-1，1-二氟丁-1-烯作为烷基化剂代替4-甲基-苯磺酸4，4-二氟丁-3-烯基酯，可制得下列本发明化合物：(i)5-环丙基-2-(4，4-二氟丁-3-烯基硫基)-1，3，4-噁二唑(化合物XII.1)。1H
NMR：δ1.10-1.15(4H，m)；2.10-2.20(1H，m)；2.45-2.55(2H，m)；3.20
(2H，t)；4.30(1H，m)；(油状物)。(ii)2-(4，4-二氟丁-3-烯基硫基)-5-异丙基-1，3，4-噁二唑(化合物XII.8)。
M+＝234；1H NMR：δ1.19(6H，d)；2.50-2.60(2H，m)；3.15(1H，七重
峰)；3.30(2H，t)；4.30(1H，m)；(油状物)。(iii)5-(2，6-二氟苄基)-2-(4，4-二氟丁-3-烯基硫基)-1，3，4-噁二唑(化合物
XII.11)。1H NMR：δ2.45-2.55(2H，m)；3.25(2H，t)；4.20(2H，s)；4.25
(1H，m)；6.90-7.00(2H，m)；7.25-7.35(1H，m)；(油状物)。(iv)2-(4，4-二氟丁-3-烯基硫基)-5-(4-硝基苄基)-1，3，4-噁二唑(化合物
XII.12)。1H NMR：δ2.50-2.60(2H，m)；3.30(2H，t)；4.20(1H，m)；4.30
(2H，s)；7.50(2H，d)；8.20(2H，d)；(油状物)。(v)2-(4，4-二氟丁-3-烯基硫基)-5-异丁基-1，3，4-噁二唑(化合物XII.23)。
1H NMR：δ1.00(6H，d)；2.10-2.20(1H，m)；2.50-2.60(2H，m)；2.70
(2H，d)；3.25(2H，t)；4.30(1H，m)；(油状物)。(vi)2-(4，4-二氟丁-3-烯基硫基)-5-戊基-1，3，4-噁二唑(化合物XII.25)。1H
NMR：δ1.30-1.40(4H，m)；1.70-1.80(2H，m)；2.50-2.55(2H，m)；2.80
(2H，t)；3.25(2H，t)；4.30(1H，m)；(油状物)。(vii)5-丁基-2-(4，4-二氟丁-3-烯基硫基)-1，3，4-噁二唑(化合物XII.28)。1H
NMR：δ0.95(3H，t)；1.35-1.50(2H，m)；1.70-1.80(2H，m)；2.50-2.60(2H，
m)；2.80(2H，t)；3.25(2H，t)；4.30(1H，m)；(油状物)。(viii)2-(4，4-二氟丁-3-烯基硫基)-5-丙基-1，3，4-噁二唑(化合物XII.31)。
1H NMR：δ1.00(3H，t)；1.75-1.90(2H，m)；2.50-2.60(2H，m)；2.80(2H，t)；
3.25(2H，t)；4.30(1H，m)；(油状物)。(ix)2-(4，4-二氟丁-3-烯基硫基)-5-乙基-1，3，4-噁二唑(化合物XII.35)。1H
NMR：δ1.40(3H，t)；2.50-2.60(2H，m)；2.85(2H，t)；3.25(2H，t)；4.30
(1H，m)；(油状物)。(x)2-(4，4-二氟丁-3-烯基硫基)-5-甲基-1，3，4-噁二唑(化合物XII.49)。
M+＝206；1H NMR：δ2.51(2H，m)；2.73(3H，s)；3.27(2H，t)；4.25
(1H，m)；(油状物)。(xi)2-(4，4-二氟丁-3-烯基硫基)-1，3，4-噁二唑-5-甲酰胺(化合物XII.55)。
M+＝235；1H NMR：δ2.50-2.60(2H，m)；3.35(2H，t)；4.30(1H，m)；(mp
113℃)。(xii)2-(4，4-二氟丁-3-烯基硫基)-5-(2-甲基苯基)-1，3，4-噁二唑(化合物
XII.128)。1H NMR：δ2.55-2.65(2H，m)；2.70(3H，s)；3.35(2H，t)；4.30
(1H，m)；7.30-7.45(3H，m)；7.90(1H，d)；(油状物)。(xiii)2-(4，4-二氟丁-3-烯基硫基)-5-(2-呋喃基)-1，3，4-噁二唑(化合物
XII.131)。M+＝258：1H NMR：δ 2.50-2.60(2H，m)；3.35(2H，t)；
4.30(1H，m)；6.60(1H，m)；7.10(1H，d)；7.60(1H，d)；(油状物)。(xiv)2-(4，4-二氟丁-3-烯基硫基)-5-(2-甲氧基苯基)-1，3，4-噁二唑(化合物
XII.132)。1H NMR：δ2.50-2.60(2H，m)；3.30(2H，t)；3.95(3H，s)；4.30
(1H，m)；7.10(2H，m)；7.50(1H，dt)；7.90(1H，dd)；(mp 35-37℃)。(xv)2-(4，4-二氟丁-3-烯基硫基)-5-(2-噻吩基)-1，3，4-噁二唑(化合物
XII.133)。M+＝274：1H NMR：δ2.50-2.60(2H，m)；3.30(2H，t)；
4.30(1H，m)；7.10-7.20(1H，m)；7.55(1H，d)；7.70(1H，d)；(油状物)。(xvi)2-(4，4-二氟丁-3-烯基硫基)-5-(3-呋喃基)-1，3，4-噁二唑(化合物
XII.134)。1H NMR：δ2.50-2.60(2H，m)；3.30(2H，t)；4.30(1H，m)；6.90
(1H，m)；7.50-7.55(1H，m)；8.05(1H，br s)；(油状物)。(xvii)2-(4，4-二氟丁-3-烯基硫基)-5-(4-甲氧基苯基)-1，3，4-噁二唑(化合
物XII.144)。1H NMR：δ2.50-2.60(2H，m)；3.30(2H，t)；3.90(3H，s)；4.30
(1H，m)；7.00(2H，d)；8.00(2H，d)；(油状物)。(xviii)2-(4，4-二氟丁-3-烯基硫基)-5-(4-吡啶基)-1，3，4-噁二唑(化合物
XII.148)。M+＝269：1H NMR：δ2.50-2.65(2H，m)；3.40(2H，t)；4.30
(1H，m)；7.90(2H，d)；8.80(2H，d)；(油状物)。
                   实施例XII，3
此实施例阐明了2-(4，4-二氟丁-3-烯基亚磺酰基)-5-苯基-1，3，4-噁二唑(化合物XII.4)的制备方法。
于0℃搅拌下向化合物XII.3(1g)的无水二氯甲烷溶液中加入3-氯过苯甲酸(1.3g，50％固体重量比，1当量)。令反应温热至室温，搅拌3小时并静置过夜，Tlc分析表明原料已消耗完全。将反应混合物过滤并将滤液于二氯甲烷和碳酸氢钠溶液之间配分，水层用二氯甲烷萃取并将合并的有机相用硫酸镁干燥。减压蒸除溶剂，得到一黄色油状物，将其于硅胶上进行闪式色谱纯化，用25％乙酸乙酯的己烷溶液洗脱，得到化合物XII.4(0.474g)。M+＝284；1H NMR：δ2.67(2H，m)；3.52(2H，m)；4.32(1H，m)；7.50(3H，m)；8.12(2H，d)；(油状物)。
用上述方法由适宜的硫醚可制得下列本发明化合物：(i)2-(4，4-二氟丁-3-烯基亚磺酰基)-5-(4-甲氧基苄基)-1，3，4-噁二唑(化合
物XII.14)。1H NMR：δ2.45-2.70(2H，m)；3.30-3.50(2H，m)；3.80
(3H，s)；4.25(1H，m)；4.25(2H，s)；6.90(2H，d)；7.25(2H，d)；(油状物)。(ii)2-(4，4-二氟丁-3-烯基亚磺酰基)-5-戊基-1，3，4-噁二唑(化合物
XII.26)。1H NMR：δ0.95(3H，t)；1.30-1.40(4H，m)；1.80-1.90(2H，m)；
2.50-2.75(2H，m)；2.95(2H，t)；3.35-3.55(2H，m)；4.30(1H，m)；(油状
物)。(iii)5-丁基2-(4，4-二氟丁-3-烯基亚磺酰基)-1，3，4-噁二唑(化合物
XII.29)。1H NMR：δ1.00(3H，t)；1.40-1.50(2H，m)；1.80-1.90(2H，m)；
2.50-2.75(2H，m)；3.00(2H，t)；3.35-3.55(2H，m)；4.30(1H，m)；(油状
物)。(iv)2-(4，4-二氟丁-3-烯基亚磺酰基)-5-丙基-1，3，4-噁二唑(化合物
XII.32)。1H NMR：δ1.05(3H，t)；1.89-1.95(2H，m)；2.50-2.75(2H，m)；
2.95(2H，t)；3.35-3.55(2H，m)；4.30(1H，m)；(油状物)。(v)2-(4，4-二氟丁-3-烯基亚磺酰基)-5-(2-甲基苯基)-1，3，4-噁二唑(化合
物XII.129)。1H NMR：δ2.55-2.80(2H，m)；2.70(3H，s)；3.40-
3.60(2H，m)；4.30(1H，m)；7.30-7.40(1H，m)；7.45-7.50(1H，m)；8.00
(1H，d)；(油状物)。(vi)2-(4，4-二氟丁-3-烯基亚磺酰基)-5-(4-硝基苯基)-1，3，4-噁二唑(化合
物XII.142)。1H NMR：δ2.55-2.80(2H，m)；3.45-3.70(2H，m)；4.35
(1H，m)；8.35(2H，d)；8.45(2H，d)；(油状物)。(vii)2-(4，4-二氟丁-3-烯基亚磺酰基)-5-(4-甲氧基苯基)-1，3，4-噁二唑(化
合物XII.145)。1H NMR：δ2.50-2.80(2H，m)；3.40-3.60(2H，m)；3.90
(3H，s)；4.30(1H，m)；7.05(2H，d)；8.05(2H，d)；(油状物)。
用上述一般方法，只是用2当量3-氯过苯甲酸作氧化剂由适宜的硫醚可制得下列本发明化合物：(viii)2-(4，4-二氟丁-3-烯基磺酰基)-5-苯基-1，3，4-噁二唑(化合物XII.5)。
M+＝300；1H NMR：δ2.71(2H，m)；3.67(2H，m)；4.33(1H，m)；7.52-7.70
(3H，m)；8.25(2H，d)；(mp 104-106℃)。(ix)2-(4，4-二氟丁-3-烯基磺酰基)-5-异丙基-1，3，4-噁二唑(化合物
XII.9)。1H NMR：δ1.50(6H，d)；2.60-2.70(2H，m)；3.20-3.40(1H，m)；
3.60(2H，t)；4.30(1H，m)；(胶状物)。(x)2-(4，4-二氟丁-3-烯基磺酰基)-5-(4-硝基苄基)-1，3，4-噁二唑(化合物
XII.13)。1H NMR：δ2.60-2.70(2H，m)；3.60(2H，t)；4.30(1H，m)；4.40
(2H，s)；7.55(2H，d)；8.25(2H，d)；(油状物)。(xi)2-(4，4-二氟丁-3-烯基磺酰基)-5-(4-甲氧基苄基)-1，3，4-噁二唑(化合
物XII.15)。1H NMR：δ2.60-2.70(2H，m)；3.65(2H，t)；3.80(3H，s)；4.20
(1H，m)；4.25(2H，s)；6.90(2H，d)；7.25(2H，d)；(mp 60-63℃)。(xii)5-苄基-2-(4，4-二氟丁-3-烯基磺酰基)-1，3，4-噁二唑(化合物
XII.19)。1H NMR：δ2.60(2H，m)；3.60(2H，t)；4.25(1H，m)；4.30(2H，s)；
7.25-7.40(5H，m)；(油状物)。(xiii)2-(4，4-二氟丁-3-烯基磺酰基)-5-戊基-1，3，4-噁二唑(化合物
XII.27)。1H NMR：δ0.95(3H，t)；1.30-1.45(4H，m)；1.80-1.90(2H，m)；
2.60-2.70(2H，m)；3.00(2H，t)；3.60(2H，t)；4.30(1H，m)；(油状物)。(xiv)5-丁基-2-(4，4-二氟丁-3-烯基磺酰基)-1，3，4-噁二唑(化合物
XII.30)。1H NMR：δ1.00(3H，t)；1.40-1.50(2H，m)；1.80-1.90(2H，m)；
2.60-2.70(2H，m)；3.00(2H，t)；3.60(2H，t)；4.30(1H，m)；(油状物)。(xv)2-(4，4-二氟丁-3-烯基磺酰基)-5-丙基-1，3，4-噁二唑(化合物XII.33)。
1H NMR：δ1.10(3H，t)；1.85-2.00(2H，m)；2.60-2.70(2H，m)；2.95(2H，t)；
3.60(2H，t)；4.30(1H，m)；(油状物)。(xvi)2-(4，4-二氟丁-3-烯基磺酰基)-5-甲基-1，3，4-噁二唑(化合物
XII.51)。1H NMR：δ2.20-2.30(2H，m)；2.30(3H，s)；3.60(2H，t)；4.30
(1H，m)；(油状物)。(xvii)2-(4，4-二氟丁-3-烯基磺酰基)-5-(2-甲基苯基)-1，3，4-噁二唑(化合
物XII.130)。1H NMR：δ2.70-2.80(2H，m)；2.75(3H，s)；3.70(2H，t)；
4.30(1H，m)；7.40(1H，d)；7.50(1H，d)；8.00(1H，d)；(mp 90-93℃)。(xviii)2-(4，4-二氟丁-3-烯基磺酰基)-5-(4-硝基苯基)-1，3，4-噁二唑(化合
物XII.143)。M+＝345；1H NMR：δ2.70-2.80(2H，m)；3.70(2H，t)；4.35
(1H，m)；8.35(2H，d)；8.45(2H，d)；(油状物)。(xix)2-(4，4-二氟丁-3-烯基磺酰基)-5-(4-甲氧基苯基)-1，3，4-噁二唑(化合
物XII.146)。1H NMR：δ2.70-2.80(2H，m)；3.65(2H，t)；3.90(3H，s)；
4.30(1H，m)；7.05(2H，d)；8.10(2H，d)；(mp 60℃)。
                    实施例XIII.1
此实施例说明了由本领域公知的相应的噻二唑-2(3H)-硫酮化合物制备2-(4，4-二氟丁-3-烯基硫基)-5-取代的-1，3，4-噻二唑类化合物的一般方法。此方法通过由相应的硫酮和4-甲基-苯磺酸4，4-二氟丁-3-烯基酯制备2-(4，4-二氟丁-3-烯基硫基)-5-甲氨基-1，3，4-噻二唑(化合物XIII.70)得以说明，其中也可使用其他烷基化剂例如4-溴-1，1-二氟丁-1-烯。化合物XIII.70的制备
向5-甲氨基-1，3，4-噻二唑-2(3H)-硫酮(0.393g)的丙酮(10cm3)溶液中加入碳酸钾(0.369g)和4-甲基-苯磺酸4，4-二氟丁-3-烯基酯(0.7g)并将混合物回流加热3小时，此后gc分析表明原料已消耗完全。将反应混合物经高流动性助滤剂过滤并用乙醚充分洗涤。将滤液倾入乙醚和水中并分层。水层用乙醚萃取两次并将合并的有机相干燥。减压蒸除溶剂，得到一褐色油状物，将其于硅胶上进行闪式色谱纯化，用1∶1乙酸乙酯∶己烷洗脱，得到化合物XIII.70(0.273g)。M+＝237；1H NMR：δ2.43(2H，m)；3.04(3H，s)；3.15(2H，t)；4.29(1H，m)；5.36(1H.br s)；(mp52.5-53.5℃)。
利用适宜的巯基噻二唑类化合物并且在某些情况下用4-溴-1，1-二氟丁-1-烯作烷基化剂，用上述一般方法可制得下列本发明化合物。(i)5-环丙基-2-(4，4-二氟丁-3-烯基硫基)-1，3，4-噻二唑(化合物XIII.6)。
M+＝248；1H NMR：δ1.10-1.30(4H，m)；2.30-2.40(1H，m)；2.45-2.55
(2H，m)；3.30(2H，t)；4.30(1H，m)；(油状物)。(ii)2-(4，4-二氟丁-3-烯基硫基)-5-苯基-1，3，4-噻二唑(化合物XIII.9)。
M+＝284；1H NMR：δ2.50-2.60(2H，m)；3.40(2H，t)；4.50(1H，m)；7.40-
7.50(3H，m)；7.85-7.95(2H，m)；(mp 39℃)。(iii)2-(4，4-二氟丁-3-烯基硫基)-5-异丙基-1，3，4-噻二唑(化合物
XIII.16)。M+＝250；1H NMR：δ1.40(3H，s)；1.45(3H，s)；2.45-2.60
(2H，m)；3.35(2H，t)；3.35-3.50(1H，m)；4.30(1H，m)；(油状物)。(iv)5-苄基-2-(4，4-二氟丁-3-烯基硫基)-1，3，4-噻二唑(化合物XIII.20)。
M+＝298；1H NMR：δ2.45-2.55(2H，m)；3.30(2H，t)；4.30(1H，m)；4.40
(2H，s)；7.25-7.40(5H，m)；(油状物)。(v)2-(4，4-二氟丁-3-烯基硫基)-5-甲基-1，3，4-噻二唑(化合物XIII.40)。
M+＝222；1H NMR：δ2.50(2H，m)；2.73(3H，s)；3.35(2H，t)；4.29
(1H，m)；(油状物)。(vi)2-(4，4-二氟丁-3-烯基硫基)-1，3，4-噻二唑-5-甲酰胺(化合物
XIII.45)。M+＝151；1H NMR：δ2.50-2.60(2H，m)；3.45(2H，t)；4.30
(1H，m)；6.80(1H，br s)；7.15(1H，br s)；(mp 168℃)。(vii)2-(4，4-二氟丁-3-烯基硫基)-1，3，4-噻二唑(化合物XIII.63)。
M+＝208；1H NMR：δ2.54(2H，m)；3.43(2H，t)；4.30(1H，m)；9.03
(1H，s)；(油状物)。(viii)5-氨基-2-(4，4-二氟丁-3-烯基硫基)-1，3，4-噻二唑(化合物XIII.69)。
M+＝223；1H NMR：δ2.45(2H，m)；3.20(2H，t)；4.30(1H，m)；5.20(2H，br
s)；(mp 138℃)。(ix)2-(4，4-二氟丁-3-烯基硫基)-5-(3-三氟甲基苄硫基)-1，3，4-噻二唑(化
合物XIII.110)。M+＝304；1H NMR：δ2.51(2H，m)；3.31(2H，t)；4.27
(1H，m)；4.56(2H，s)；7.42-7.70(4H，m)；(油状物)。(x)5-环丙基甲硫基-2-(4，4-二氟丁-3-烯基硫基)-1，3，4-噻二唑(化合物
XIII.114)。M+＝294；1H NMR：δ0.35(2H，m)；0.65(2H，m)；1.25(1H，m)；
2.50(2H，m)；3.25(2H，d)；3.30(2H，t)；4.25(1H，m)；(油状物)。(xi)2，5-二-(4，4-二氟丁-3-烯基硫基)-1，3，4-噻二唑(化合物XIII.117)。
M+＝330；1H NMR：δ2.51(4H，m)；3.32(4H，t)；4.29(2H，m)；(油状物)。(xii)2-(4，4-二氟丁-3-烯基硫基)-5-甲硫基-1，3，4-噻二唑(化合物
XIII.119)。M+＝254；1H NMR：δ2.51(4H，m)；2.77(3H，s)；3.31(2H，t)；
4.20(1H，m)；(油状物)。
(xiii)2-(4，4-二氟丁-3-烯基硫基)-5-(磺酰氨基苯基)-1，3，4-噻二唑(化合物XIII.1 43)。M+＝363；1H NMR：δ2.55-2.65(2H，m)；3.50(2H，t)；4.30(1H，m)；4.95(2H，br s)；8.05(4H，m)；(油状物)。
                    实施例XIII.2
此实施例阐明了由2-氨基-5-取代的噻二唑类化合物制备2-(4，4-二氟丁-3-烯基硫基)-5-取代的-1，3，4-噻二唑类化合物的一般方法。此方法通过下述由2-氨基-5-乙基-1，3，4-噻二唑制备2-(4，4-二氟丁-3-烯基硫基)-5-乙基-1，3，4-噻二唑(化合物XIII.27)的方法得以说明。
化合物XIII.27的制备。
将2-氨基-5-乙基-1，3，4-噻二唑(0.786g)和二-4，4-二氟丁-3-烯基二硫化物(1.5g)的二氯甲烷(25cm3)溶液进行搅拌并于冰-水浴中冷却。加入亚硝酸叔丁基酯(1.2g)，除去冷却浴并将反应回流加热1.3小时。然后将混合物倾入乙醚/水中并分层。水层用乙醚萃取并将合并的有机相干燥(MgSO4)，过滤并减压蒸发，得到一褐色油状物。于硅胶上进行柱色谱纯化，用1∶9和2∶8乙酸乙酯∶己烷作洗脱剂，得到化合物XIII.27(0.959g)。M+＝236；1H NMR：δ1.40(3H，t)；2.45-2.60(2H，m)；3.10(2H，q)；3.35(2H，t)；4.30(1Hm)；(油状物)。
利用适宜的中间体化合物，用上述方法可制得下列本发明化合物：(i)5-溴-2-(4，4-二氟丁-3-烯基硫基)-1，3，4-噻二唑(化合物XIII.1)。
M+＝286；1H NMR：δ2.45-2.60(2H，m)；3.40(2H，t)；4.30(1H，m)；(油状
物)。(ii)2-(4，4-二氟丁-3-烯基硫基)-5-叔丁基-1，3，4-噻二唑(化合物XIII.3)。
M+＝264；1H NMR：δ1.48(9H，s)；2.45-2.60(2H，m)；3.35(2H，t)；4.30
(1H，m)；(油状物)。(iii)2-(4，4-二氟丁-3-烯基硫基)-5-三氟甲基-1，3，4-噻二唑(化合物
XIII.14)。M+＝276；1H NMR：δ2.50-2.60(2H，m)；3.45(2H，t)；4.30
(1H，m)；(油状物)。
                  实施例XIII.3
此实施例阐明了用3-氯过苯甲酸作氧化剂制备2，5-二-(4，4-二氟丁-3-烯基亚磺酰基)-1，3，4-噻二唑(化合物XIII.133)的方法。
于甲醇冰浴中将化合物XIII.117(0.49g)的二氯甲烷(30cm3)溶液冷却至～-10℃，加入3-氯过苯甲酸(1g，50％固体重量比，2当量)，将反应进行搅拌并逐渐温热至室温，然后搅拌7小时并静置18小时。将混合物倾入碳酸氢钠溶液中，产物用乙醚萃取。合并的有机相用碳酸氢钠溶液洗涤并干燥(MgSO4)，减压蒸除溶剂，得到一浅黄色液体，将其于硅胶上进行闪式色谱纯化，用30％乙酸乙酯的己烷溶液洗脱，得到化合物XIII.133(0.168g)。M+＝362；1H NMR：δ2.58(4H，m)；3.36(4H，m)；4.26(2H，m)；(mp 46-48℃)。
用适宜当量数的3-氯过苯甲酸作氧化剂，用上述方法可制得下列本发明化合物。(i)2-(4，4-二氟丁-3-烯基亚磺酰基)-5-苯基-1，3，4-噻二唑(化合物
XIII.10)。M+＝300；1H NMR：δ2.40-2.80(2H，m)；3.30-3.40(2H，m)；
4.30(1H，m)；7.45-7.60(3H，m)；7.95-8.00(2H，m)；(mp 67℃)。(ii)2-(4，4-二氟丁-3-烯基磺酰基)-5-苯基-1，3，4-噻二唑(化合物XIII.11)。
M+＝316；1H NMR：δ2.60-2.75(2H，m)；3.65(2H，t)；4.30(1H，m)；7.45-
7.65(3H，m)；7.95-8.05(2H，m)；(mp 80℃)。(iii)2-(4，4-二氟丁-3-烯基亚磺酰基)-5-甲基-1，3，4-噻二唑(化合物
XIII.41)。M+＝238；1H NMR：δ2.35-2.55(1H，m)；2.55-2.75(1H，m)；
2.90(3H，s)；3.20-3.40(2H，m)；4.30(1H，m)；(油状物)。(iv)2-(4，4-二氟丁-3-烯基磺酰基)-5-甲基-1，3，4-噻二唑(化合物
XIII.42)。M+＝255；1H NMR：δ2.55-2.70(2H，m)；2.95(3H，s)；
3.60(2H，t)；4.30(1H，m)；(油状物)。(v)2-(4，4-二氟丁-3-烯基亚磺酰基)-1，3，4-噻二唑(化合物XIII.64)。
M+＝225；1H NMR：δ2.35-2.50(1H，m)；2.60-2.75(1H，m)；3.25-3.45
(2H，m)；4.30(1H，m)；9.35(1H，s)；(油状物)。(vi)2-(4，4-二氟丁-3-烯基磺酰基)-1，3，4-噻二唑(化合物XIII.65)。
MH+＝241；1H NMR：δ2.60-2.70(2H，m)；3.70(2H，t)；4.30(1H，m)；9.40
(1H，s)；(油状物)。(vii)2，5-二-(4，4-二氟丁-3-烯基磺酰基)-1，3，4-噻二唑(化合物XIII.124)。
M+＝394；1H NMR：δ2.69(4H，m)；3.70(4H，t)；4.30(2H，m)；(mp 88-91
℃)。(viii)2-(4，4-二氟丁-3-烯基磺酰基)-5-(4，4-二氟丁-3-烯基亚磺酰基)-
1，3，4-噻二唑(化合物XIII.134)。M+＝378；1H NMR：δ2.38-
2.55(1H，m)；2.60-2.79(3H，m)；3.38(2H，m)；3.62-3.74(2H，m)；4.19-
4.39(2H，m)；(mp 45-47℃)。
用适宜当量数的单过氧邻苯二甲酸镁作氧化剂，用上述方法可制得下列本发明化合物。(ix)5-溴-2-(4，4-二氟丁-3-烯基磺酰基)-1，3，4-噻二唑(化合物XIII.2)。
M+＝319；1H NMR：δ2.60-2.70(2H，m)；3.65(2H，t)；4.30(1H，m)；(油状
物)。(x)2-(4，4-二氟丁-3-烯基磺酰基)-5-叔丁基-1，3，4-噻二唑(化合物
XIII.4)。M+＝297；1H NMR：δ1.55(9H，s)；2.60-2.70(2H，m)；3.65(2H，t)；
4.30(1H，m)；(mp 37℃)。(xi)5-环丙基-2-(4，4-二氟丁-3-烯基磺酰基)-1，3，4-噻二唑(化合物
XIII.7)。 M+＝281；1H NMR：δ1.25-1.45(4H，m)；2.40-
2.55(1H，m)；2.55-2.65(2H，m)；3.60(2H，t)；4.30(1H，m)；(胶状物)。(xii)2-(4，4-二氟丁-3-烯基磺酰基)-5-三氟甲基-1，3，4-噻二唑(化合物
XIII.15)。M-SO2H+＝243；1H NMR：δ2.60-2.75(2H，m)；3.75(2H，t)；
4.20-4.40(1H，m)；(胶状物)。(xiii)2-(4，4-二氟丁-3-烯基磺酰基)-5-异丙基-1，3，4-噻二唑(化合物
XIII.17)。 M+＝283；1H NMR：δ1.50(3H，s)；1.55(3H，s)；2.60-
2.70(2H，m)；3.50-3.70(3H，m)；4.30(1H，m)；(mp 43℃)。(xiv)2-(4，4-二氟丁-3-烯基亚磺酰基)-5-乙基-1，3，4-噻二唑(化合物
XIII.28)。1H NMR：δ1.50(3H，t)；2.40-2.50(1H，m)；2.60-2.70(1H，m)；
3.20(2H，q)；3.25-3.35(2H，m)；4.25(2H，m)；(胶状物)。(xv)2-(4，4-二氟丁-3-烯基磺酰基)-5-乙基-1，3，4-噻二唑(化合物
XIII.29)。M+＝269；1H NMR：δ1.50(3H，t)；2.60-2.70(2H，m)；
3.20(2H，q)；3.65(2H，t)；4.30(1H，m)；(胶状物)。
                  实施例XIII.4
此实施例说明由化合物XIII.1制备2-(4，4-二氟丁-3-烯基硫基)-5-甲氧基-1，3，4-噻二唑(化合物XIII.101)的方法。
向搅拌下的氢化钠(0.030g)的甲苯(3cm3)悬浮液中加入甲醇(0.022g)，结果泡腾。搅拌10分钟后，加入化合物XIII.1(0.20g)并将反应于室温下搅拌18小时。反应用gc进行分析并再加入部分氢化钠和甲醇，直至观测到原料消耗完全。将反应物倾入水中并分层，产物用乙醚萃取并将合并的有机相干燥(MgSO4)，过滤并减压蒸发，得到一浅黄色油状物。于硅胶上进行柱色谱纯化，用3∶17乙醚∶己烷作洗脱剂，得到化合物XIII.101(0.069g)。M+＝238；1H NMR：δ2.40-2.55(2H，m)；3.25(2H，t)；4.20(3H，s)；4.30(1H，m)；(油状物)。
                   实施例XIV.1
此实施例阐明了5-(4，4-二氟丁-3-烯基硫基)-1-甲基四唑(化合物XIV.1)的制备方法。
用实施例XIII.1所述方法，用4-溴-1，1-二氟丁-1-烯将5-巯基-1-甲基四唑的钠盐烷基化，得到化合物XIV.1。M+＝206；1H NMR：δ2.53(2H，m)；3.38(2H，t)；3.92(3H，s)；4.28(1H，m)；(油状物)。
                    实施例XV.1
此实施例阐明了1-(4，4-二氟丁-3-烯基硫基)-4-硝基苯(化合物XV.1)的制备方法。
将4-硝基-苯硫酚(0.5g)、碳酸钾(0.448g)、4-甲基-苯磺酸4，4-二氟丁-3-烯基酯(0.846g)和碘化钾(0.388g)于丙酮(15cm3)中搅拌并回流加热共6小时，此后tlc未检测到甲苯磺酸酯原料。将反应混合物倾入水中并用3份乙酸乙酯萃取，合并的有机相用2M NaOH洗涤3次，并用饱和盐水洗涤，然后干燥(MgSO4)。减压蒸除溶剂，得到深黄色油状物，将其于硅胶上进行闪式色谱纯化，用5％乙酸乙酯的己烷溶液作洗脱剂，得到化合物XV.1(0.474g)。M+＝245；1H NMR：δ2.42(2H，m)；3.09(2H，t)；4.30(1H，m)；7.35(2H，d)；8.14(2H，d)；(油状物)。
                   实施例XVI.1
此实施例阐明了2-氯-4-(4，4-二氟丁-3-烯基硫基)-吡啶(化合物XVI.1)的制备方法。
将亚硝酸叔丁基酯(0.442g)的二氯甲烷(20cm3)溶液滴加到4-氨基-2-氯吡啶和二-(4，4-二氟丁-3-烯基)二硫化物(1.9g)的二氯甲烷(20cm3)溶液中，同时于0℃下搅拌混合物。将反应混合物搅拌4小时，然后令其于室温下静置18小时。加入水，产物用乙酸乙酯萃取。合并的有机相用饱和盐水洗涤，干燥(MgSO4)，过滤并减压蒸发，得到黄褐色胶状物。于sorbsil-C30上进行色谱分离，用4％乙酸乙酯的己烷溶液作洗脱剂，得到化合物XVI.1(0.134g)。M+＝235；1H NMR：δ2.35-2.46(2H，m)；2.98-3.7(2H，t)；4.18(1H，m)；7.02(1H，d)；7.11(1H，d)；8.14-8.21(1H，d)；(油状物)。
                  实施例XVI.2
此实施例阐明了2-步法制备4-(4，4-二氟丁-3-烯基硫基)-2，3，5，6-四氟吡啶(化合物XVI.2)的方法。
步骤1：2，3，5，6-四氟吡啶-4-硫醇钠盐的制备
将4-氯-2，3，5，6-四氟吡啶(2g)和硫氢化钠二水合物于异丙醇(40cm3)中进行搅拌并回流加热3小时。然后将混合物于室温下搅拌18小时，过滤除去沉淀出的固体，用乙醚洗涤并滗析。将合并的有机溶液减压蒸发，得到以钠盐形式存在的2，3，5，6-四氟吡啶-4-硫醇(2.21g)，无需进一步纯化将其用于第二步反应。
步骤2：(化合物XVI.2)的制备
将步骤1所得中间体(1.7g)、4-溴-1，1-二氟丁-1-烯(1.99g)和碳酸钾(1.53g)于丙酮(30cm3)中进行搅拌并回流加热18小时。过滤除去沉淀的无机物并将滤液减压蒸发，得到深褐色油状物。于sorbsil-C30上进行色谱分离，用己烷作洗脱剂，得到化合物XVI.2(1.82g)。M+＝273；1HNMR：δ2.3-2.42(2H，m)；3.15-3.25(2H，t)；4.15-4.34(1H，m)；(油状物)。
用上述步骤2所述方法可制得下列本发明化合物。所述烷基化剂为4-溴-1，1-二氟丁-1-烯或4-甲基-苯磺酸4，4-二氟丁-3-烯基酯。(i)4-(4，4-二氟丁-3-烯基硫基)-吡啶(化合物XVI.5)，M+＝201；1H NMR：
δ2.40(2H，m)；3.04(2H，t)；4.30(1H，m)；7.11(2H，d)；8.41(2H，d)；(油状
物)，由4-巯基吡啶制得。(ii)2-(4，4-二氟丁-3-烯基硫基)吡啶-3-羧酸4，4-二氟丁-3-烯基酯(化合物
XVI.10)，M+＝335；1H NMR：δ2.43(4H，m)；3.22(2H，t)；4.29(2H，m)；
4.36(2H，t)；7.09(1H，dd)；8.20(1H，dd)；8.57(1H，dd)；(油状物)，由2-
巯基吡啶-3-羧酸制得。在此反应中用碘化钾就地将2当量4-甲基-
苯磺酸4，4-二氟丁-3-烯基酯转变为更具活性的4-碘-1，1-二氟丁-1-
烯(iii)2-(4，4-二氟丁-3-烯基硫基)-5-三氟甲基吡啶(化合物XVI.11)，
1H NMR：δ2.40(2H，m)；3.25(2H，t)；4.25(1H，m)；7.25(1H，dd)；7.45
(1H，dd)；8.40(1H，d)；(油状物)，由2-巯基-5-三氟甲基吡啶制得。(iV)2-(4，4-二氟丁-3-烯基硫基)吡啶(化合物XVI.19)，M+＝201；1H NMR：
δ2.40(2H，m)；3.20(2H，t)；4.30(1H，m)；6.90(1H，dd)；7.20(1H，dd)；
8.40(1H，dd)；(油状物)。(V)4-(4，4-二氟丁-3-烯基硫基)-5-硝基吡啶(化合物XVI.21)，M+＝246；1H
NMR：δ2.45(2H，m)；3.30(2H，t)；4.28(1H，m)；7.30(1H，d)；8.23(1H，dd)；
9.25(1H，d)；(油状物)，由2-巯基-5-硝基吡啶制得。
                   实施例XVI.3
此实施例给出了由2-氯-5-取代的-吡啶类化合物制备2-(4，4-二氟丁-3-烯基硫基)-5-取代的-吡啶类化合物的一般方法。此方法通过由2，5-二氯吡啶制备5-氯-2-(4，4-二氟丁-3-烯基硫基)吡啶(化合物XVI.13)得以说明。
将硫氢化钠二水合物(0.672g)加入到2，5-二氯吡啶(1.48g)的二甲基甲酰胺(20cm3)溶液中，混合物变为蓝色，然后加热至100℃变为绿色。将反应加热7小时，然后加入4-溴-1，1-二氟丁-1-烯(1.71g)和碳酸钾(1.38g)。将反应加热2小时，然后令其冷却。将反应混合物倾入乙醚和2M HCl中并分层。水层用乙醚萃取，合并的有机相用2M HCl、水和盐水洗涤(分别各洗涤3次)，干燥(MgSO4)，过滤并减压蒸发，得到一褐色油状物。于硅胶上进行柱色谱分离，用2％乙醚的己烷溶液作洗脱剂，得到化合物XVI.13(0.805g)。M+＝235；1H NMR：δ2.40(2H，m)；3.20(2H，t)；4.25(1H，m)；7.15(1H，dd)；7.45(1H，dd0；8.40(1H，d)；(油状物)。
用上述方法可制得下列本发明化合物：(i)5-氰基-2-(4，4-二氟丁-3-烯基硫基)吡啶(化合物XVI.15)。1H NMR：
δ2.40(2H，m)；3.25(2H，t)；4.25(1H，m)；7.25(1H，dd)；7.70(1H，dd)；
8.65(1H，d)；(mp 34℃)。
                 实施例XVI.4
此实施例阐明了由2-氯-3-取代的-吡啶类化合物和4，4-二氟丁-3-烯基异硫脲氢溴酸盐制备2-(4，4-二氟丁-3-烯基硫基)-3-取代的-吡啶类化合物的一般方法。此方法通过由2-氯-3-硝基吡啶制备2-(4，4-二氟丁-3-烯基硫基)-3-硝基吡啶(化合物XVI.24)得以说明。
将4，4-二氟丁-3-烯基异硫脲氢溴酸盐(1.24g)加入到氢氧化钠(0.6g)水(10cm3)溶液中并将反应于室温下剧烈搅拌20分钟。向反应中加入2-氯-3-硝基吡啶(0.795g)的二氯甲烷(10cm3)溶液，随后加入溴化四正丁基铵(催化剂)。将反应剧烈搅拌3小时，混合物用二氯甲烷稀释并分层。有机相用盐水洗涤，干燥(MgSO4)，过滤并减压蒸发，得到一黄色油状物。将其于硅胶上进行柱色谱分离，用15％乙醚的己烷溶液作洗脱剂，得到化合物XVI.24(0.847g)。M+＝246；1H NMR：δ2.40(2H，m)；3.25(2H，t)；4.30(1H，m)；7.20(1H，dd)；8.50(1H，dd)；8.70(1H，dd)；(油状物)。
用上述方法可制得下列本发明化合物：(i)3-氰基-2-(4，4-二氟丁-3-烯基硫基)吡啶(化合物XVI.8)。M+＝226；1H
NMR：δ2.40(2H，m)；3.30(2H，t)；4.25(1H，m)；7.10(1H，dd)；7.80
(1H，dd)；8.55(1H，dd)；(油状物)。
                  实施例XVI.5
此实施例阐明了一种适于制备本发明化合物的方法，其中相应未被氧化的化合物(按上述实施例所述方法制得)中4，4-二氟丁-3-烯基硫基取代基的硫原子被氧化成亚砜(亚磺酰基)或砜(磺酰基)。
用1当量氧化剂，由化合物XVI.2制备化合物XVI.3
于二氯甲烷(30cm3)中将化合物XVI.2(0.818g)冷却至0℃并于5分钟内加入3-氯过苯甲酸(0.99g)。混合物于室温下搅拌6小时并静置40小时。将反应混合物倾入饱和碳酸氢钠水溶液中，产物用二氯甲烷萃取。有机层用水洗涤并干燥(MgSO4)。减压蒸除溶剂，得到一黄色油状物，将其于sorbsil-C30上进行色谱分离，用15％乙酸乙酯的己烷溶液洗脱，得到4-(4，4-二氟丁-3-烯基亚磺酰基)-2，3，5，6-四氟吡啶(0.711g)。1HNMR：δ2.45-2.8(2H，m)；3.15-3.3(1H，m)；3.5-3.65(1H，m)；4.2-4.4(1H，m)；(油状物)。
用2当量氧化剂，由化合物XVI.15制备5-氰基-2-(4，4-二氟丁-3-烯基磺酰基)吡啶(化合物XVI.16)
于0℃将3-氯过苯甲酸(3.14g，50％固体)分批加入到搅拌下的化合物XVI.15(1.03g)的二氯甲烷(30cm3)溶液中，然后令反应温热至室温并搅拌4小时。将混合物倾入2M氢氧化钠水溶液中并分层，水层用二氯甲烷萃取，合并的有机层用硫酸镁干燥，过滤并减压蒸发，得到一黄色油状物，将其静置析晶。于硅胶上进行柱色谱分离，用3∶7乙酸乙酯∶己烷作洗脱剂，得到化合物XVI.16(0.785g)。1H NMR：δ2.40(2H，m)；3.25(2H，t)；4.25(1H，m)；7.25(1H，dd)；7.70(1H，dd)；8.65(1H，d)；(mp 34℃)。
用上述方法可制得下列本发明化合物：(i)4-(4，4-二氟丁-3-烯基磺酰基)吡啶(化合物XVI.6)。1H NMR：δ
2.50(2H，m)；3.20(2H，t)；4.25(1H，m)；7.80(2H，d)；8.95(2H，d)；(油状
物)。(ii)2-(4，4-二氟丁-3-烯基磺酰基)-5-三氟甲基吡啶(化合物XVI.12)。1H
NMR：δ2.50(2H，m)；3.50(2H，t)；4.25(1H，m)；8.25(2H，d)；9.00(1H，br
s)；(mp 60℃)。(iii)2-(4，4-二氟丁-3-烯基磺酰基)吡啶(化合物XVI.20)。IH NMR：δ
2.50(2H，m)；3.50(2H，t)；4.25(1H，m)；7.55-7.50(1H，m)；8.00(1H，dt)；
8.10(1H，d)；8.75(1H，d)；(油状物)。
                  实施例XVII.1
此实施例说明用2-步法制备3-(4，4-二氟丁-3-烯基硫基)-6-甲基哒嗪(化合物XVII.1)的方法。
步骤1：3-巯基-6-甲基哒嗪的制备
将3-氯-6-甲基哒嗪(5g)和硫脲(2.96g)一起进行搅拌并于乙醇(50cm3)中回流加热7.5小时。将反应冷却并令其静置18小时。滤除生成的固体沉淀物并用乙醚洗涤，得到3-巯基-6-甲基哒嗪(2.3g)，无需进一步纯化将其用于下一步反应。1H NMR：δ2.40(3H，s)；7.30(1H，d)；7.63(1H，d)；14.5-14.7(1H，br s)。
步骤2：化合物XVII.1的制备
将步骤1所得产物(0.337g)、4-甲基苯磺酸4，4-二氟丁-3-烯基酯(0.70g)、碘化钾(0.444g)和碳酸钾(0.369g)一起进行搅拌并于丙酮(20cm3)中回流加热11小时。过滤除去固体无机物并将滤液减压蒸发，得到一褐色油状物。于硅胶上进行色谱分离，用1∶4乙酸乙酯∶己烷作洗脱剂，得到化合物XVII.1(0.15g)。M+＝216；1H NMR：δ2.48(2H，m)；2.62(3H，s)；3.36(2H，t)；4.20-4.40(1H，m)；7.10(1H，d)；7.21(1H，d)；(油状物)。
用上述步骤1和2所述方法可制得下列本发明化合物和相应的中间体。(i)3-(4，4-二氟丁-3-烯基硫基)-6-氯哒嗪(化合物XVII.2)，M+＝236；1H
NMR：δ2.50(2H，m)；3.39(2H，t)；4.20-4.40(1H，m)；7.27(2H，s)；(油状
物)，由3，6-二氯哒嗪制得。(ii)3-(4，4-二氟丁-3-烯基硫基)-6-甲氧基哒嗪(化合物XVII.3)，
M+＝232；1H NMR：δ2.47(2H，m)；3.31(2H，t)；4.09(3H，s)：4.20-
4.40(1H，m)；6.83(1H，d)；7.20(1H，d)；(固体mp39.3-40.1℃)，由3-氯
-6-甲氧基哒嗪制得。(iii)3-(4，4-二氟丁-3-烯基硫基)-6-苯基哒嗪(化合物XVII.4)，M+＝278；1H
NMR：δ2.54(2H，m)；3.46(2H，t)；4.25-4.42(1H，m)；7.39(1H，d)；7.51
(3H，m)；7.69(1H，d)；8.05(2H，m)；(固体mp91.7-92.1℃)，由3-氯-6-
苯基哒嗪制得。(iv)1-(4，4-二氟丁-3-烯基硫基)-2，3-二氮杂萘(化合物XVII.7)，
M+＝252；1H NMR(CDCl3)：δ2.59(2H，m)；3.55(2H，t)；4.28-
4.45(1H，m)；7.89(3H，m)；8.12(1H，m)；9.25(1H，s)；(油状物)，用上述方
法步骤2由1(2H)-2，3-二氮杂萘硫酮制得。
                  实施例XVII.2
此实施例阐明了由化合物XVII.4制备化合物XVII.5和XVII.6的方法。
室温下将化合物XVII.4(0.5g)于异丙醇(20cm3)进行搅拌并加入单过氧邻苯二甲酸镁六水合物(0.89g于10cm3水中)。将混合物于室温下搅拌20小时，过滤沉淀出的固体并用水洗涤。将滤液倾入饱和碳酸氢钠水溶液中，产物用乙酸乙酯萃取。将合并的有机层用饱和盐水洗涤并干燥(MgSO4)。减压蒸除溶剂，得到一灰白色固体，将其与首次沉淀出的产物合并并于硅胶上进行色谱分离，用30％乙酸乙酯的己烷溶液洗脱。首先回收得到的产物为3-(4，4-二氟丁-3-烯基磺酰基)-6-苯基哒嗪(化合物XVII.6)(0.2g)。M+＝310；1H NMR：δ2.60(2H，m)；3.75(2H，t)；4.20-4.40(1H，m)；7.60(3H，m)；8.11(1H，d)；8.15(2H，m)；8.22(1H，d)；(固体mp141.7-144.3℃)。进一步洗脱得到3-(4，4-二氟丁-3-烯基亚磺酰基)-6-苯基哒嗪(化合物XVII.5)(0.25g)。M+＝294；1H NMR：δ2.40和2.65(2H，m)；3.20-3.40(2H，m)；4.18-4.32(1H，m)；7.59(3H，m)；8.11(1H，d)；8.15(2H，m)；8.21(1H，d)；(mp 133-134℃)。
                  实施例XVIII.1
此实施例阐明了3-步法制备2-(4，4-二氟丁-3-烯基硫基)-喹喔啉(化合物XVIII.1)的方法。
步骤1：喹喔啉-2-硫酮的制备
将2-喹喔啉醇(10g)、五硫化二磷(16.72g)和吡啶(200cm3)一起进行搅拌并回流加热7小时。将反应混合物冷却并减压蒸除大部分吡啶。残余物于乙酸乙酯和水之间配分并分出有机层。水层用进一步用三份乙酸乙酯萃取，合并的有机相用饱和盐水洗涤，干燥(MgSO4)并减压蒸发，得到一褐色含油固体，将其用热乙酸乙酯∶己烷(1∶1)研制，使产物溶解并残留不溶残余物。减压蒸除溶剂，得到桔黄色固体，无需进一步醇化将其一部分用于步骤2中。
步骤2：2-(4-溴-4，4-二氟丁基硫基)-喹喔啉的制备
室温下将步骤1所得产物(1g)、甲磺酸4-溴-4，4-二氟丁基酯(1.65g)和碳酸钾(0.852g)的混合物于丙酮(30cm3)中一起进行搅拌7小时。过滤除去固体无机物并将滤液减压蒸发，得到一褐色油状物。于硅胶上进行色谱分离，用1∶4乙酸乙酯∶己烷作洗脱剂，得到2-(4-溴-4，4-二氟丁基硫基)-喹喔啉(1.375g)。M+＝332；1H NMR：δ2.19(2H，m)；2.50-2.70(2H，m)；3.43(2H，t)；                                    7.60-7.73(2H，m)；7.93(1H，dd)；8.03(1H，dd)；8.60(1H，s)；(油状物)。
步骤3：化合物XVIII.1的制备
将1，8-二氮杂双环[5.4.0]十一-7-烯(DBU)(1.14cm3)和步骤2所得产物(1.275g)于甲苯(30cm3)中一起进行搅拌并回流加热5小时。将混合物冷却，加入过量的乙酸乙酯和2M盐酸水溶液并分出有机相。水相用乙酸乙酯萃取并将合并的有机相用饱和盐水洗涤，干燥(MgSO4)，过滤并减压蒸发，得到一褐色油状物。于硅胶上进行色谱分离，用1∶4乙酸乙酯∶己烷作洗脱剂，得到化合物XVIII.1(0.65g)。M+＝252；1H NMR：δ2.51(2H，m)；3.39(2H，t)；4.30-4.40(1H，m)；7.60-7.75(2H，m)；7.90(1H，dd)；8.03(1H，dd)；8，60(1H，s)；(油状物)。
用上述步骤2和3所述方法可制得下列本发明化合物和相应的中间体：(i)6-氯-2-(4，4-二氟丁-3-烯基硫基)-喹喔啉(化合物XVIII.4)，
M+＝286；1H NMR：δ2.50(2H，m)；3.35(2H，t)；4.20-4.40(1H，m)；
7.65(1H，dd)；7.86(1H，d)；8.01(1H，d)；8.59(1H，s)；(油状物)，由6-氯喹
喔啉-2-硫酮经2-(4-溴-4，4-二氟丁基硫基)-6-氯喹喔啉[1H NMR：δ
2.08-2.21(2H，m)；2.48-2.68(2H，m)；3.40(2H，t)；7.65(1H，dd)；
7.88(1H，d)；8.00(1H，d)；8.60(1H，s)；(油状物)]制得。
                  实施例XVIII.2
此实施例阐明2-步法制备2-(4，4-二氟丁-3-烯基硫基)-吡嗪(化合物XVIII.7)的方法。
步骤1：2-巯基吡嗪的制备
将2-氯吡嗪(5g)和硫脲(3.32g)于乙醇(50cm3)中回流下加热8小时。将反应混合物冷却并减压蒸除乙醇，得到一褐色胶状物(8.31g)，将其与2M氢氧化钠水溶液(50cm3)一起搅拌16小时。过滤沉淀出的固体，用水和丙酮洗涤并真空干燥，得到一黄色固体(0.72g)；1HNMR(DMSO-d6)：δ7.69(1H，d)；7.89(1H，d)；8.6(1H，s)，无需进一步纯化将其用于第二步反应中。
步骤2：化合物XVIII.7的制备
将步骤1所得产物(0.213g)、4-甲基-苯磺酸4，4-二氟丁-3-烯基酯(0.5g)、碳酸钾(0.263g)和碘化钾(0.317g)于丙酮(10cm3)中进行混合并回流下加热9小时，然后令其冷却一个周末。滤除生成的沉淀并将滤液减压蒸发，得到一褐色油状物。于硅胶上进行色谱分离，用1∶4乙酸乙酯∶己烷作洗脱剂，得到化合物XVIII.7(0.3g)。M+＝202；1H NMR：δ2.40(2H，m)；3.21(2H，t)；4.20-4.40(1H，m)；8.20(1H，d)；8.38(1H，t)；8.48(1H，s)；(油状物)。
                  实施例XVIII.3
此实施例阐明了2-步法制备3-氯-2-(4，4-二氟丁-3-烯基硫基)-吡嗪(化合物XVIII.10)的方法。
步骤1：2-氯-3-巯基吡嗪和2，3-二巯基吡嗪的制备
将2，3-二氯吡嗪(1g)和硫氢化钠二水合物(2.5g)于异丙醇(20cm3)中进行混合并将混合物回流下加热1小时。将反应冷却并令其静置36小时。过滤回收所沉淀出的黄色固体，用乙醚洗涤并真空干燥。滗析滤液，将固体溶于热乙醇中，冷却，有少量硫氢化钠沉淀出并滤除。剩余的乙醇溶液用乙醚稀释，马上沉淀出黄色固体(0.3g)，经鉴定为2，3-二巯基吡嗪的二钠盐，MH+(FAB)＝188；1H NMR(DMSO-d6)：δ7.35(1H，d)；7.50(1H，d)。将母液蒸发，得到一黄色固体(0.8g)，经鉴定为2-氯-3-巯基吡嗪的钠盐，M+(FAB)＝145；1H NMR(DMSO-d6)：δ7.35(1H，d)；7.80(1H，d)。
步骤2：3-氯-2-(4，4-二氟丁-3-烯基硫基)-吡嗪的制备
将步骤1所得一硫醇盐(0.8g)、4-甲基-苯磺酸4，4-二氟丁-3-烯基酯(1.24g)和碳酸钾(0.655g)于含有二甲基甲酰胺(5cm3)的丙酮(25cm3)中进行混合并回流下加热15小时，然后令其冷却。滤除沉淀并将滤液减压蒸发，得到一褐色油状物。于硅胶上进行色谱分离，用95∶5己烷∶乙酸乙酯的混合物作洗脱剂，得到化合物XVIII.10(0.45g)。M+＝236；1HNMR：δ2.41(2H，m)；3.20(2H，t)；4.20-4.40(1H，m)；8.05(1H，d)；8.30(1H，d)；(油状物)。其含有(gc)5％化合物XVIII.13杂质。
在此实施例步骤2所述相同条件下，只是用2当量4-甲基-苯磺酸4，4-二氟丁-3-烯基酯处理上述实施例步骤1中所得二-硫醇盐，可得到纯化合物XVIII.13。于硅胶上进行色谱分离，用4∶1己烷∶乙酸乙酯的混合物作洗脱剂，得到2，3-二-(4，4-二氟丁-3-烯基硫基)-吡嗪。M+＝324；1HNMR：δ2.40(4H，m)；3.22(4H，t)；4.20-4.40(2H，m)；8.07(2H，s)；(油状物)。
用上述方法可制得下列本发明化合物：(i)6-氯-2-(4，4-二氟丁-3-烯基硫基)-吡嗪(化合物XVIII.14)，M+＝236；1H
NMR：δ2.42(2H，m)；3.21(2H，t)；4.20-4.40(1H，m)；8.20(1H，s)；8.35
(1H，s)(油状物)，由2，6-二氯吡嗪制得。
                  实施例XVIII.4
此实施例阐明由化合物XVIII.1制备化合物XVIII.2和XVIII.3的方法。
室温下将化合物XVIII.1(0.25g)于乙醇(10cm3)中进行搅拌并于5分钟内加入单过氧邻苯二甲酸镁二水合物(0.589g于5cm3水中)。30分钟后，将混合物加热至70℃1小时。将反应混合物冷却，倾入饱和碳酸氢钠水溶液中，产物用乙酸乙酯萃取。有机层用水洗涤并干燥(MgSO4)。减压蒸除溶剂，得到一灰白色固体(0.15g)，将其于硅胶上进行色谱分离，用10％乙酸乙酯的己烷溶液洗脱。回收得到的主要产物为2-(4，4-二氟丁-3-烯基磺酰基)-喹喔啉(化合物XVIII.3)(0.1g)mp86.5-87.5℃。M+＝284；1H NMR：δ2.61(2H，m)；3.62(2H，t)；4.20-4.40(1H，m)；8.00(2H，m)：8.25(2H，m)；9.51(1H，s)。Tlc分析表明在粗反应产物中存在具有较低比移值(rf)的产物，但并未分离出纯品，此产物为2-(4，4-二氟丁-3-烯基亚磺酰基)-喹喔啉(化合物XVIII.2)。
用上述方法可制得下列本发明化合物：(i)6-氯-2-(4，4-二氟丁-3-烯基亚磺酰基)-吡嗪(化合物XVIII.15)，
M+＝253；1H NMR：δ2.30-2.70(2H，m)；3.00-3.30(2H，m)；4.19-4.35
(1H，m)；8.70(1H，s)；9.10(1H，s)(油状物)，由化合物XVIII.14制得。(ii)6-氯-2-(4，4-二氟丁-3-烯基磺酰基)-吡嗪(化合物XVIII.16)，
M+＝268；1H NMR：δ2.55(2H，m)；3.50(2H，t)；4.20-4.35(1H，m)；8.90
(1H，s)；9.19(1H，s)(油状物)，由化合物XVIII.14制得。
                  实施例VIII.1
此实施例阐明3-步法制备4-(4，4-二氟丁-3-烯基硫基)-1，2，3-苯并三唑(化合物XIX.1)的方法。
步骤1：4-巯基-1，2，3-苯并三唑的制备
将2-氨基苄腈(5g)于吡啶(30cm3)中进行搅拌，加入三乙胺(6cm3)并向反应中通入硫化氢气4小时。然后将混合物倾入水(20cm3)中，将振摇分离出的油状物除去，并与乙醇和甲苯共沸干燥。于0℃2M盐酸(30cm3)中进行搅拌，得到一黄色固体(2-氨基硫代苯甲酰胺，3g)。滴加亚硝酸钠(1.65g)的水(10cm3)溶液并将反应混合物冷却下搅拌1小时，然后令其温热至室温并再搅拌1小时。滤出生成的固体，用水洗涤并用乙醚洗涤干燥，得到一褐色固体(2.15g)。
步骤2：4-(4，4-二氟丁-3-烯基硫基)-1，2，3-苯并三唑的制备
室温下将步骤1所得产物(1g)、甲磺酸4-溴-4，4-二氟丁基酯(1.65g)和碳酸钾(0.852g)于丙酮(30cm3)中进行搅拌36小时。过滤除去固体无机物并将滤液减压蒸发，得到一褐色油状物。于硅胶上进行色谱分离，用1∶4乙酸乙酯∶己烷作洗脱剂，得到两个黄色油状物(分别为0.5g)。首先洗脱得到的油状物经鉴定为N-烷基化产物，而第二个产物是所需要的S-烷基化中间体4-(4-溴-4，4-二氟丁基硫基)-1，2，3-苯并三唑。1H NMR：δ2.18-2.31(2H，m)；2.58-2.71(2H，m)；3.63(2H，t)；7.95(1H，t)；8.09(2H，m)；8.40(1H，d)。
步骤3：化合物XIX.1的制备
将1，8-二氮杂双环[5.4.0]十一-7-烯(DBU)(0.45cm3)和步骤2所得产物(0.5g)于甲苯(15cm3)中进行搅拌并回流加热6小时。将混合物冷却，然后加入过量的乙酸乙酯和2M盐酸水溶液，分出有机相。水相用乙酸乙酯萃取并将合并的有机相用饱和盐水洗涤，硫酸镁干燥，过滤并减压蒸发，得到一黄色油状物。于硅胶上进行色谱分离，用1∶4乙酸乙酯∶己烷作洗脱剂，得到化合物XIX.1(0.25g)。M+＝254；1H NMR：δ2.60(2H，m)；3.60(2H，t)；4.30-4.40(1H，m)；7.93(1H，t)；8.09(2H，m)；8.39(1H，d)；(油状物)。
                    实施例XX.1
下文描述了两种作为制备本发明化合物中间体的巯基-1，2，4-三嗪类化合物的制备方法(方法A和B)。
方法A
一种通过将氨基硫脲与1.2二-羰基化合物反应合成3-巯基-1，2，4-三嗪类化合物的一般方法。此方法通过制备3-巯基-5-甲基-1，2，4-三嗪得以说明。
将碳酸氢钠(8g)水(100cm3)溶液加入到氨基硫脲(8g)的水(100cm3)溶液中。将溶液于5℃下保持18小时，然后用氯仿(10×50cm3)洗涤。用浓盐酸将水层的pH调至2，滤出生成的沉淀，用大量水洗涤并干燥，得到一桔黄色固体(4.036g)。无需进一步纯化将3-巯基-5-甲基-1，2，4-三嗪直接用于下一步骤。
按照上述方法可制得下列巯基三嗪类中间体化合物。在某些情况下，用乙醇代替水作溶剂，原料为市售原料。
(i)3-巯基-1，2，4-三嗪，由乙二醛制得。(ii)3-巯基-5-丙基-6-甲基-1，2，4-三嗪，由己-2，3-二酮制得。1H NMR：
δ0.98(3H，t)；1.54-1.68(2H，m)；2.08(3H，s)；3.04(2H，t)；8.2(1H，br s)。(iii)3-巯基-5-苯基-6-甲基-1，2，4-三嗪，由1-苯基丙-1，2-二酮制得。方法B
另一种制备巯基-1，2，4-三嗪类化合物的方法包括用硫醇盐化试剂例如五硫化二磷处理相应的羟基三嗪(其可以以各种互变异构体形式存在)。此方法通过由1，2，4-三嗪-3，5(2H，4H)-二酮(6-氮杂尿嘧啶)制备1，2，4-三嗪-3，5(2H，4H)-二硫酮得以说明。
6-氮杂尿嘧啶(2g)、五硫化二磷(15.72g)和50cm3吡啶一起进行搅拌并回流加热56小时。将反应混合物冷却并减压蒸除大部分吡啶，残余物用乙醚和水研制，分出有机层。水层用三份乙醚进一步萃取并将合并的有机相用饱和盐水洗涤，干燥(MgSO4)并减压蒸发，得到一褐色油状物，将其于硅胶上进行色谱分离，用5∶1乙酸乙酯∶己烷作洗脱剂，得到桔黄色固体(1g)，无需进一步纯化使用。1H NMR(DMSO-d6)：δ7.95(1H，s)；13.8-14.1(1H，br s)；14.3-14.6(1H，br s)。
基本上按照上述方法，由3-羟基-1，2，4-苯并三嗪制得3-巯基-1，2，4-苯并三嗪；由6-甲基1，2，4-三嗪-5(4H)-酮制得6-甲基-1，2，4-三嗪-5(4H)-硫酮。
                实施例XX.2
此实施例阐明了由相应的被取代的巯基三嗪和适宜的二氟丁-1-烯烷基化剂开始，制备在3、5或6-位上被4，4-二氟丁-3-烯基硫基取代的1，2，4-三嗪的方法。此实施例通过下文中由6-氮杂-2-尿嘧啶和4-甲基-苯磺酸4，4-二氟丁-3-烯基酯制备3-(4，4-二氟丁-3-烯基硫基)-5-羟基-1，2，4-三嗪(化合物XX.227)得以说明。
将4-甲基-苯磺酸4，4-二氟丁-3-烯基酯(1.5g)和碘化钾(0.95g)于乙醇(5cm3)中进行搅拌并回流加热3小时，然后冷却。在此过程中，所述原料转变成更具化学活性和硫-选择性烷基化剂，4-碘-1，1-二氟丁-1-烯。以1M氢氧化钠水溶液(5.73cm3)的形式加入6-氮杂-2-尿嘧啶(0.744g)并将反应混合物于室温下搅拌70小时。反应通过加入过量1M氢氧化钠水溶液和乙酸乙酯进行处理，分出乙酸乙酯层并将水层用更多的乙酸乙酯洗涤，滗析萃取物。然后用2M盐酸水溶液将水层pH调至4，产物用乙酸乙酯(3份)萃取并将合并的有机层用水和饱和盐水洗涤，干燥(MgSO4)。经减压蒸发由溶液中回收产物，得到乳白色固体(0.659)将部分产物再溶于热乙酸乙酯中并过滤除去不溶物。经减压蒸发由溶液中回收得到化合物XX.227，mp 102-103℃；M+＝209；1HNMR(DMSO-d6)：δ2.41(2H，m)；3.25(2H，t)；4.55-4.75(1H，m)；7.69和7.79(共1H，分别为单峰，互变异构质子)。
如下所述，用相关方法可制得化合物XX.247。
室温下将6-甲基-1，2，3-三嗪-5(4H)-硫酮(0.5g)、4-溴-1，1-二氟丁-1-烯(0.673g)和碳酸钾(0.543g)于丙酮(5cm3)中一起搅拌60小时，然后滤除无机物并用丙酮洗涤。经减压蒸发由合并的丙酮溶液中回收溶剂，残余的褐色胶状物于硅胶上进行色谱分离，用20％乙酸乙酯的己烷溶液洗脱，得到5-(4，4-二氟丁-3-烯基硫基)-6-甲基-1，2，4-三嗪(化合物XX.247)(0.075g)。M+＝217；1H NMR：δ2.45(2H，m)；2.60(3H，s)；3.29(2H，t)；4.20-4.40(1H，m)；9.11(1H，s)；(油状物)。
                  实施例XX.3
当巯基三嗪化合物可完全溶于丙酮并且对亲核基团没有其他潜在干扰时，也可使用不同于实施例XX.2的另一种方法。
此方法通过下文中由1，2，4-三嗪-3，5(2H，4H)-二硫酮和4-甲基-苯磺酸4，4-二氟丁-3-烯基酯制备3，5-二-(4，4-二氟丁-3-烯基硫基)-1，2，4-三嗪(化合物XX.231)得以说明。
将1，2，4-三嗪-3，5(2H，4H)-二硫酮(1g)、4-甲基-苯磺酸4，4-二氟丁-3-烯基酯(3.6g)、碘化钾(1.14g)和碳酸钾(0.952g)于丙酮(20cm3)中进行搅拌并回流下加热7小时。将溶液冷却并过滤除去固体。将滤液和洗涤所述固体的丙酮洗液合并并减压蒸发，得到一褐色油状物。于硅胶上进行色谱分离，用15∶85乙酸乙酯∶己烷作洗脱剂，得到桔黄色油状化合物XX.231(1g)。M+＝325；1H NMR：δ2.40-2.55(4H，m)；3.25(4H，m)；4.15-4.40(2H，m)；8.70(1H，s)。
                  实施例XX.4
此实施例阐明了2-步法制备本发明化合物的一般方法，其包括将巯基-取代的1，2，4-三嗪与甲磺酸4-溴-4，4-二氟丁基酯反应，随后将所得中间体进行脱溴化氢作用，此方法通过下文中制备3-(4，4-二氟丁-3-烯基硫基)-5-苯基-6-甲基-1，2，4-三嗪(化合物XX.4)得以说明。
步骤1：3-(4-溴-4，4-二氟丁基硫基)-5-苯基-6-甲基-1，2，4-三嗪
将甲磺酸4-溴-4，4-二氟丁基酯(0.7g)、3-巯基-5-苯基-6-甲基-1，2，4-三嗪(0.5g)和碳酸钾(0.7g)的混合物一起进行搅拌并于丙酮(40cm3)中回流加热14小时。滤除固体无机物并将滤液减压蒸发，得到一褐色油状物(1.058g)。于硅胶上进行色谱分离，用1∶4乙酸乙酯∶己烷作洗脱剂，得到一桔黄色油状物(0.576g)。将其于三氟乙酸(3cm3)中进行搅拌并回流加热6小时以使某些发生了部分水解和开环的产物再环合。经减压蒸除溶剂回收产物并于硅胶上进行色谱分离，得到3-(4-溴-4，4-二氟丁基硫基)-5-苯基-6-甲基-1，2，4-三嗪(0.509g)。1H NMR：δ2.12-2.24(2H，m)；2.48-2.68(2H，m)；2.78(3H，s)；3.36(2H，t)；7.50-7.58(3H，m)；7.68-7.74(2H，m)；(油状物)。
步骤2：3-(4，4-二氟丁-3-烯基硫基)-5-苯基-6-甲基-1，2，4-三嗪
将1，8-二氮杂双环[5.4.0]十一-7-烯(DBU)(1cm3)滴加到搅拌下的步骤1所得产物(0.5g)的甲苯(10cm3)溶液中。混合物于室温下保持20小时，然后加入过量的乙酸乙酯和饱和氯化铵水溶液并分出有机相。水相用乙酸乙酯萃取，合并的有机相用饱和氯化铵水溶液洗涤，干燥(MgSO4)，过滤并减压蒸发，得到一桔黄色油状物(0.43g)。于硅胶上进行色谱分离，用1∶4乙酸乙酯∶己烷作洗脱剂，得到化合物XX.4(0.281g)。M+＝293；1H NMR：δ2.48-2.58(2H，m)；2.76(3H，s)；3.32(2H，t)；4.22-4.40(1H，m)；7.48-7.58(3H，m)；7.68-7.76(2H，m)；(油状物)。
                  实施例XX.5
此实施例阐明了适宜由在3-和5-位上同时带有链烯基硫基基团的化合物制备在5-位上带有烷氧基或被取代的烷氧基基团的本发明化合物的方法，此方法通过由化合物XX.231制备3-(4，4-二氟丁-3-烯基硫基)-5-甲氧基-1，2，4-三嗪(化合物XX.221)得以说明。
于室温下甲醇(15cm3)中将化合物XX.231(0.5g)与甲醇钠(0.083g)一起搅拌1小时。减压蒸除溶剂并将残余物于硅胶上进行色谱分离，用15∶85乙酸乙酯∶己烷洗脱，得到0.12g单一异构体形式的化合物XX.221。M+＝233；1H NMR：δ2.50(2H，m)；3.29(2H，t)；4.02(3H，s)；4.22-4.42(1H，m)；8.55(1H，s)，经nmr证实为5-甲氧基化合物。
在相应的醇溶剂中，利用适宜的醇盐，用上述方法可制得下列本发明化合物：(i)3-(4，4-二氟丁-3-烯基硫基)-5-(1-甲基-乙氧基)-1，2，4-三嗪(化合物
XX.205)。M+＝261；1H NMR：δ1.4(6H，d)；2.5(2H，m)；3.25(2H，t)；4.2-
4.4(1H，m)；5.4(1H，m)；8.45(1H，s)。(ii)3-(4，4-二氟丁-3-烯基硫基)-5-乙氧基-1，2，4-三嗪(化合物XX.218)。
M+＝247；1H NMR：δ1.43(3H，t)；2.50(2H，m)；3.26(2H，t)；4.2-4.4
(1H，m)；4.46(1H，m)；8.5(1H，s)。
                 实施例XX.6
此实施例阐明2-步法用于制备化合物XX.52和XX.116的1∶1混合物的方法。
步骤1：3-(4-溴-4，4-二氟丁基硫基)-5-甲基-1，2，4-三嗪和3-(4-溴-4，4-二氟丁基硫基)-6-甲基-1，2，4-三嗪
将甲磺酸4-溴-4，4-二氟丁基酯(1g)和氨基硫脲(0.475g)于乙醇(20cm3)中一起进行搅拌并回流加热5小时。GC分析表明缩影甲磺酸酯已消耗完全。令混合物冷却并加入水(3cm3)和碳酸氢钠(1g)(泡腾)。然后加入40％重量比的丙酮醛溶液(1cm3)并将混合物于室温下搅拌4小时。TLC分析表明产物已经生成。产物用乙酸乙酯萃取并将有机层干燥，过滤并蒸发，得到一油状物(1.209g)。此中间体产物于硅胶上进行色谱纯化，用1∶4乙酸乙酯∶己烷洗脱，得到黄色油状物(0.464g)，1HNMR：δ2.08-2.20(2H，m)；2.48-2.62(2H，m)；2.52和2.66(共3H，分别为单峰)；3.28-3.38(2H，m)；8.28和8.84(共1H，分别为单峰)；其为5-和6-甲基异构体的约1∶1混合物。
步骤2：3-(4，4-二氟丁-3-烯基硫基)-5-甲基-1，2，4-三嗪和3-(4，4-二氟丁-3-烯基硫基)-6-甲基-1，2，4-三嗪
用实施例XX.4步骤2中所述相似方法，用DBU将步骤1所得混合物进行脱溴化氢作用，产物(0.253g)于硅胶上经色谱法进行纯化，用二氯甲烷洗脱。在此条件下无法分离出5-和6-甲基异构体并且得到0.232g黄色油状物。M+＝217；1H NMR：δ2.44-2.54(2H，m)；2.50和2.66(共3H，分别为单峰)；3.26-3.34(2H，m)；4.22-4.40(2H，m)；8.28和8.82(共1H，分别为单峰)；其为化合物XX.52和化合物XX.116的1∶1混合物。
用上述方法，只是在步骤1中用环己-1，2-二硫酮代替丙酮醛，可制得本发明化合物XX.251。1H NMR：δ1.86-1.98(4H，m)；2.42-2.54(2H，m)；2.84-2.92(2H，m)；3.04-3.12(2H，m)；3.28(2H，t)；4.22-4.38(1H，m)；(油状物)。
                实施例XX.7
此实施例阐明了用于制备可经色谱法分离的化合物XX.52和XX.116的混合物的方法。
将4-甲基-苯磺酸4，4-二氟丁-3-烯基酯(1g)和氨基硫脲(0.4g)于乙醇(20cm3)一起进行搅拌并回流加热6小时。将混合物冷却过夜，此后出现S-烷基化化合物的黄色结晶沉淀。不经分离，只是减压蒸除溶剂，残余物用碳酸氢钠(0.928g)、水(3cm3)和乙醇(20cm3)处理。然后加入40％重量比的丙酮醛溶液(0.9cm3)(轻微泡腾)，将混合物于室温下搅拌1小时。将反应物倾入水中，产物用乙酸乙酯(3份)萃取。将合并有机相干燥，过滤并蒸发，得到一褐色胶状物(0.85g)。于硅胶上进行色谱分离，用10％乙酸乙酯的己烷溶液洗脱，得到含有化合物XX.116(0.05g)的级份(NMR分析，含有10％化合物XX.52)。继续洗脱，得到含有化合物XX.52和XX.116的约1∶1混合物(0.16g)的混合级份。然后得到含有化合物XX.52(0.1g)的级份(NMR分析，含有15％化合物XX.116)。
                  实施例XX.8
此实施例阐明了2-步法制备本发明化合物的一般方法，该方法包括将氨基硫脲与4-溴-1，1-二氟丁-1-烯进行反应，然后用1，2-二羰基化合物将中间体化合物进行环合，此方法通过下文中制备3-(4，4-二氟丁-3-烯基硫基)-1，2，4-三嗪(化合物XX.137)得以说明。
于乙醇(75cm3)中将氨基硫脲(2.6g)与4-溴-1，1-二氟丁-1-烯一起进行搅拌并将混合物回流加热7小时，令其冷却至室温。加入乙二醛(4.2g，40％水溶液)和碳酸氢钠(7.37g)并将所得混合物于室温下搅拌18小时。加入水，产物用3份乙酸乙酯萃取。合并的有机相用饱和盐水洗涤，干燥(MgSO4)，过滤并减压蒸发，得到一褐色胶状物。于硅胶上进行色谱分离，用20％乙酸乙酯的己烷溶液洗脱，得到化合物XX.137。M+＝203；1H NMR：δ2.50(2H，m)；3.30(2H，t)；4.20-4.40(1H，m)；8.39(1H，d)；8.95(1H，d)(油状物)。
用适宜的1，2-二羰基化合物代替乙二醛，用上述方法可制得下列本发明化合物：(i)3-(4，4-二氟丁-3-烯基硫基)-5-丙基-1，2，4-三嗪(化合物XX.27)，由2-
氧代-戊醛制得。M+＝245；1H NMR：δ1.0(3H，t)；1.7-1.85(2H，m)；
2.45-2.55(2H，m)；2.6(2H，t)；3.3(2H，t)；4.2-4.4(1H，m)；8.8(1H，s)(油状
物)。由此制备方法也可得到异构体化合物XX.109；M+＝245；1H
NMR：δ1.0(3H，t)；1.75-1.9(2H，m)；2.45-2.55(2H，m)；2.9(2H，t)；
3.3(2H，t)；4.2-4.4(1H，m)；8.25(1H，s)(油状物)，在色谱法中比较快洗
脱得到的异构体稍后得到的产物占所制备产物混合物的约8％。(ii)3-(4，4-二氟丁-3-烯基硫基)-5-乙基-1，2，4-三嗪(化合物XX.30)，由2-
氧代-丁醛制得。M+＝231；1H NMR：δ1.3-1.4(3H，t)；2.45-2.55(2H，m)；
2.75-2.85(2H，q)；3.25-3.35(2H，t)；4.2-4.4(1H，m)；8.85(1H，s)(油状
物)。在所述反应混合物中可以检测到异构体化合物XX.110，但没
有分离出来。然而，当用1，1-二乙氧基-丁-2-酮代替2-氧代-丁醛时，
此异构体化合物是环合反应中的主要产物。最初，在水中形成亚
胺，随后在含水丙酮中用甲苯磺酸吡啶翁催化环合，得到化合物
XX.110。M+＝231；1H NMR：δ1.4(3H，t)；2.50(2H，m)；2.95(2H，q)；3.3
(2H，t)；4.2-4.4(1H，m)；8.29(1H，s)(油状物)。(iii)3-(4，4-二氟丁-3-烯基硫基)-6-甲基-1，2，4-三嗪-5(4H)-酮(化合物
XX.226)，由丙酮酸制得。M+＝233；1H NMR(DMSO-d6)：δ2.05
(3H，s)；2.30(2H，m)；3.12(2H，t)；4.4-4.6(1H，m)(胶状物)。
用2，2-二氯乙醛代替乙二醛，用上述方法可制得下列本发明化合物：(iv)3-(4，4-二氟丁-3-烯基硫基)-5-(1-甲基-乙基)-1，2，4-三嗪(化合物
XX.15)。M+＝245；1H NMR：δ1.32(6H，d)；2.50(2H，m)；3.0(1H，m)；
3.3(2H，t)；4.20-4.40(1H，m)；8.82(1H，s)(油状物)以及经色谱法较快洗
脱得到的异构体3-(4，4-二氟丁-3-烯基硫基)-6-(1-甲基-乙基)-1，2，4-
三嗪(化合物XX.98)。M+＝245；1H NMR：δ1.4(6H，d)；2.50(2H，m)；
3.18-3.35(3H，m)；4.20-4.40(1H，m)；8.30(1H，s)(油状物)，由2，2-二氯
-3-甲基-丁醛制得。
                  实施例XX.9
此实施例阐明了由化合物XX.52制备5-二氯甲基-3-(4，4-二氟丁-3-烯基硫基)-1，2，4-三嗪(化合物XX.65)的方法。
于四氯化碳(40cm3)中将化合物XX.52(3.1g)和N-氯代琥珀酰亚胺(2g)一起进行搅拌并回流加热1小时。将混合物冷却并于室温下搅拌4小时。减压蒸除溶剂，将黑色焦油状残余物悬浮于乙醚(40cm3)中并经过一高流动性助滤剂滤床。不溶物再用乙醚洗涤并将合并的溶液减压蒸发。残余物于硅胶上进行色谱分离，用乙醚∶己烷1∶1洗脱并将含有产物的级份减压蒸发，经制备薄层色谱进一步纯化，用30％乙醚的己烷溶液展开，得到化合物XX.65(0.2g)。1H NMR：δ2.50(3H，m)；3.3(2H，t)；4.20-4.40(1H，m)；6.50(1H，s)；9.37(1H，s)(油状物)。
                  实施例XX.10
此实施例阐明了由化合物XX.27制备3-(4，4-二氟丁-3-烯基磺酰基)-5-丙基-1，2，4-三嗪(化合物XX.28)的方法。
于5℃下将化合物XX.27(0.2g)于二氯甲烷(5cm3)中进行搅拌并加入3-氯过苯甲酸(0.282g，2当量)，于室温下继续搅拌18小时。加入饱和碳酸氢钠水溶液使反应中止，产物用二氯甲烷萃取。分出有机相，用饱和盐水洗涤并干燥(MgSO4)。过滤后，减压蒸发浓缩，得到一油状物，将其于硅胶上进行色谱分离，用3∶7乙酸乙酯∶己烷作洗脱剂，得到化合物XX.28(0.187g)。M+＝277；1H NMR：δ1.0-1.1(3H，t)；1.8-1.95(2H，m)；2.6-2.7(2H，m)；2.9-3.0(2H，t)；3.7-3.8(2H，t)；4.2-4.4(1H，m)；9.3(1H，s)：(油状物)。
用1.75当量的氧化剂，用上述方法可制得下列本发明化合物：(i)3-(4，4-二氟丁-3-烯基亚磺酰基)-5-甲基-1，2，4-三嗪(化合物
XX.53)；M+＝233；1H NMR：δ2.35-2.7(2H，m)；2.75(3H，s)；3.2-3.4
(2H，m)；4.2-4.35(1H，m)；9.25(1H，s)；(油状物)和3-(4，4-二氟丁-3-烯基
磺酰基)-5-甲基-1，2，4-三嗪(化合物XX.54)；MH+＝250；1H NMR：δ
2.6-2.7(2H，m)；2.8(3H，s)；3.7-3.8(2H，t)；4.25-4.35(1H，m)；9.35(1H，
s)；(油状物)，由化合物XX.52制得。(ii)3-(4，4-二氟丁-3-烯基亚磺酰基)-6-甲基-1，2，4-三嗪(化合物XX.117)；
M+＝234；1H NMR：δ 2.3-2.75(2H，m)；2.85(3H，s)；3.2-3.4(2H，m)；
4.15-4.3(1H，m)；8.7(1H，s)；(油状物)和3-(4，4-二氟丁-3-烯基磺酰
基)-6-甲基-1，2，4-三嗪(化合物XX.118)；MH+＝250；1H NMR：δ2.6-
2.7(2H，m)；2.9(3H，s)；3.65-3.75(2H，t)；4.2-4.4(1H，m)；8.75(1H，s)；
(油状物)，由化合物XX.116制得。
                    实施例XXI.1
此实施例阐明了2-(4，4-二氟丁-3-烯基硫基)-1，3，5-三嗪(化合物XXI.1)的制备方法。
将(4，4-二氟丁-3-烯基)-硫脲(以其4-甲基-苯磺酸盐形式存在)(0.9g)和1，3，5-三嗪(0.216g)于乙醇(20cm3)中一起回流加热4小时。将反应混合物冷却并减压蒸除溶剂，得到一固体，将其用己烷研制。减压蒸发回收溶于己烷的产物，得到化合物XXI.1(0.4g)。M+＝203；1HNMR：δ2.45(2H，m)；3.20(2H，t)；4.20-4.40(1H，m)；8.82(2H，s)；(油状物)。
式(I)化合物为杀线虫剂并可用于控制作物中的线虫，因此，本发明另一方面提供了一种杀灭或控制线虫的方法，该方法包括给线虫施用式(I)化合物。
术语“控制”意指无致死作用，亦即可防止对寄主作物造成损害并可限制线虫数量的增加。这些作用可使得用化学方法引起定向力障碍、固定化、阻碍或诱导孵化。所述化学处理也可对线虫的发育和繁殖产生有害作用。
本发明化合物可用于抗植物性寄生线虫和生活在土壤中的线虫。
植物性寄生线虫的实例有：外寄生物，例如Xiphinema app.、Longidorus spp.和Trichodorus spp.；半寄生物，例如Tylenchulus spp.；移动性内寄生物，例如Pratylenchus spp.、Radopholus spp.和Scutellonema spp.；静止寄生物(sedentary parasites)，例如Heteroderaspp.、Globodera app.和Meloidogyne spp.；以及茎和叶内寄生物，例如Ditylenchus spp.、Aphelenchoides spp.和Hirshmaniella spp.。
式(I)化合物还具有抗不同类型的线虫包括大豆线虫的活性。
本发明化合物还具有抗生长和寄居在农作物、林木、温室作物、omamentals、受保护作物、贮藏食品和纤维制品中的有害动物的活性。这些有害动物包括：
异翅亚目/同翅亚目包括桃蚜(Myzus persicae)、棉蚜(Aphisgossypii)、甜菜蚜(Aphis fabae)、小米蚜(Rhopalosiphum padi)、圆蚧属(Aonidiella spp.)、粉虱属(Trialeurodes spp.)、甘薯粉虱(Bemisia tabaci)、稻褐飞虱(Nilaparyvata lugens)、黑尾叶蝉(Nephotettix cincticepa)、稻绿蝽象(Nezara viridula)、棉黑翅红蝽(Dysdercus suturellus)、棉带纹红蝽(Dysdercus fasciatus)和牧草盲蝽(Lygus lineoralis)。
双翅目包括地中海实蝇(Ceratitis capitata)、大蚊属(Tipula spp)、瑞典麦秆蝇(Oscinella firt)、潜蝇属(Liriomyza spp.)、实蝇属(Liriomyzaspp.)和Peromya spp.
鳞翅目包括大菜粉蝶(Pieris brassicae)、小菜蛾(Plutella xylostella)、埃及棉卷虫(Spodoptera littoralis)和其他粘虫属(Spodoptera spp.)、烟蚜夜蛾(Heliothis virescens)和其他夜蛾属(Heliothis spp.)及Helicoverpaspp.以及印度草螟(Chilo partellus)。
鞘翅目包括辣根猿叶虫(Phaedon cochleariae)、叶甲属(Diabroticaspp.)、地老虎属(Agrotis spp.)和马铃薯甲虫(Leptinotarsadecemlineata)。
蜚蠊亚目包括德国蜚蠊(Blattella germanica)、美洲大蠊(Periplanetaamericana)和东方蜚蠊(Blatta orientalis)。
直翅目包括Chortiocetes terminifera、蝗虫属(Schistocerca spp.)、飞蝗属(Locusta spp.)和蝼蛄属(Scapteriscus spp.)。
螨目包括苹果全爪螨(Panonychus ulmi)、柑桔全爪螨(Panoychuscitri)、棉红蜘蛛(Tetranychus urticae)、朱砂叶螨(Tetranychuscinnabarinus)、柑桔锈螨(Phyllocoptruta oleivora)和短须螨属(Brevipalpus spp.)。
所述化合物还可用于抗对家畜、家庭、公众和动物健康有害的动物，所述有害动物例如：
蚤目包括猫栉头蚤(Ctenocephalides felis)、犬栉头蚤(Ctenocephalidescanis)、印鼠客蚤(Xenopsylla cheopis)和人蚤(Pulex irritans)。
食毛目包括鸡蚤(Menopon gallinae)和雏鸡头羽虱(Cuclotogasterheterographus)。
虱目包括人头虱(Pediculus humanus capitis)、人体虱(Pediculushumanus humanus)和阴虱(Phthirus pubis)。
双翅目包括家蝇(Musca domestica)、埃及伊蚊(Aedes aegypti)、冈比亚按蚊(Anopheles gambiae)、致乏库蚊(Culex quinquefasciatus)、中室斑虻(Chrysops discalis)和全黑虻(Tabanus nigrovittanus)。
麻蝇科包括赤尾麻蝇(Sarcophaga haemorrhoidalis)和黑须污蝇(Wohlfahrtia magnifica)。
丽蝇科包括铜绿蝇(Lucilia cuprina)和嗜人瘤蝇(Cordylobiaanthropophaga)。
狂蝇科包括羊鼻蝇(Oestrus ovis)。
通常，所述化合物可用于抵预或控制有害动物对人和动物的伤害和/或对人和动物疾病的传播。可用本发明化合物抵预和控制的有害动物包括哺乳动物寄生线虫，它们可以是发现于胃肠道、呼吸道的气管或血管以及心脏和有关血管中的寄生线虫。
式(I)化合物可用于对脊椎动物的治疗。所述脊椎动物例如哺乳动物(如人、猪、羊、牛、马、猫和狗)，鸟类(如鸡、鸭、火鸡、鹅、金丝雀和澳洲长尾小鹦鹉)和鱼类(如鲑鱼、鳟鱼和omamental fish)。
向有有害动物的环境中、向需要保护的地域以及直接向所述有害动物的身上施用有效量的本发明化合物可杀灭/控制所述线虫和其他有害动物。
为了便于向线虫、昆虫或螨有害动物所在地或向易被线虫、昆虫或螨有害动物侵害的植物上施用所述化合物，通常将所述化合物配制成组合物，该组合物除了含有式(I)化合物以外，还包含有适宜的惰性稀释剂或载体材料和/或表面活性剂。因此，本发明的另一方面提供了一种杀线虫、杀虫或杀螨组合物，该组合物含有有效量的如本文所定义的式(I)化合物和惰性稀释剂或载体材料以及可任意选择的表面活性剂。
通常，用于控制线虫类有害动物所施用的组合物的量为每公顷0.01-10kg，优选为每公顷0.1-6kg活性成分。
所述组合物可以以粉剂、可湿性粉剂、颗粒剂(缓释或快速释放)、乳油或胶悬剂、液剂、乳剂、种衣剂、烟雾剂或控释组合物例如微胶囊颗粒剂或悬浮剂的形式施用到土壤、植物或其他被保护区域、有害动物所在地或有害动物栖息地。
粉剂可通过将活性成分与一种或多种精细固体载体和/或稀释剂进行混合配制而成，所述载体和稀释剂例如天然粘土、高岭土、叶腊石、皂粘土、氧化铝、蒙脱土、硅藻土(kieselguhr)、白垩、硅藻土(diatomaceous earths)、磷酸钙、碳酸钙和碳酸镁、硫黄、石灰、面粉、滑石和其他有机和无机固体载体。
颗粒剂可以通过将活性成分吸附在多孔颗粒材料上或者吸附在硬芯材上制得，所述多孔颗粒材料例如浮石、美国活性白土、漂白土、硅藻土(kieselguhr)、硅藻土(diatomaceous earths)、粉碎的玉米穗轴芯等；所述硬芯材例如沙子、硅酸盐、无机碳酸盐、硫酸盐、磷酸盐等。通常所用辅助所述活性成分浸渍、粘结和包覆所述固体载体的试剂包括脂族和芳族石油溶剂、醇、聚乙酸乙烯酯、聚乙烯醇、醚、酮、酯、糊精、糖和植物油。其他添加剂还可包括例如乳化剂、润湿剂和分散剂。
微胶囊剂(微胶囊悬浮剂CS)或其他控释制剂还可用于特别是在一段时期内的缓慢释放以及用于种子处理。
另外，所述组合物可以是以浸渍、灌溉或喷雾形式使用的液体制剂形式，它们通常为含有一种或多种已知润湿剂、分散剂或乳化剂(表面活性剂)的所述活性成分的水分散剂或乳剂。以水分散剂或乳剂形式使用的所述组合物通常以含有高比例的一种或多种活性成分的乳油(EC)或胶悬剂(SC)形式施用。EC为均相液体组合物，通常含有基本上溶于不挥发有机溶剂的活性成分。SC为固体活性成分以精细颗粒分散于水中。当使用浓缩剂时，它们将用水稀释并通常以喷雾的方式施用到所需处理的区域。对于农业或园艺业来讲，特别实用的液体制剂含有0.0001％-0.1％重量比的活性成分(约合5-2000g/ha)。
适用于EC的液体溶剂包括甲基酮、甲基异丁基酮、环己酮、二甲苯、甲苯、氯代苯、石蜡、煤油、轻油、醇(例如丁醇)、甲基萘、三甲基苯、三氯乙烯、N-甲基-2-吡咯烷酮和四氢糠醇(THFA)。
润湿剂、分散剂和乳化剂可以是阳离子型、阴离子型或非离子型。适宜的阳离子型试剂包括例如季铵盐化合物，例如十六烷基三甲基溴化铵。适宜的阴离子型试剂包括例如肥皂、硫酸脂族单酯盐、例如十二烷基硫酸钠，磺化芳族化合物的盐，例如十二烷基苯磺酸钠、木素磺酸或丁基萘磺酸钠、钙或铵盐，以及二异丙基-和三异丙基萘磺酸酯的钠盐混合物。适宜的非离子型试剂包括例如高级醇如油醇或十六烷醇环氧乙烷加成物或烷基酚如辛基苯酚、壬基苯酚和辛基甲苯酚环氧乙烷加成物。其他非离子型试剂有由长链脂肪酸与己糖醇酐衍生的偏酯、所述偏酯与环氧乙烷的加成物以及卵磷脂。
这些浓缩剂通常需要贮存较长一段时间并且在贮存后能够用水稀释成含水制剂，此含水制剂仍可保持均相，保持均相的时间足以使其用常规喷雾设备施用。所述浓缩剂可含有1-80％重量比的一种或多种活性成分。当稀释成含水制剂时，根据它们的使用目的，此制剂可以含有不同量的活性成分。
式(I)化合物还可配制成用于种子处理的粉剂(拌种剂DS或水分散性粉剂WS)或液体制剂(浓缩流动剂FS、种子处理用液剂LS)或微胶囊悬浮剂CS。所述制剂可通过常规设备以及通过常规种子处理器施用到种子上。用施用杀虫组合物的公知方法例如喷粉、喷雾或撒粒可将所用组合物施用到所述线虫上、所述线虫所在地、所述线虫栖息地、易被线虫侵害的生长植物上。
本发明化合物可以是所述组合物中的唯一一种活性成分或者可以将它们与一种或多种适宜的其他活性成分例如杀线虫剂或可调节线虫行为的试剂例如孵化剂、杀虫剂、增效剂、除草剂、杀真菌剂或植物生长调节剂进行混合。
与本发明化合物相混合的其他适宜的活性成分可以是可拓宽本发明化合物活性谱或者提高它们在有害动物所在地的残留时间的化合物。例如通过提高作用速度或克服相斥性，可增强本发明化合物的活性或补充其活性。另外，此类多组份混合物有助于克服或防止对个别组份产生耐药性。
所述混合物中包括哪些特定的其他活性成分，将取决于所述混合物的使用目的和所需补充的活性类型。适宜的杀虫剂的实例包括：
a)合成除虫菊酯类例如permethrin、esfenvalerate、deltamethrin、cyhalothrin特别是lambda_cyhalothrin、bifenthrin、分扑菊酯、cyfluthrin、tefluthrin，fish safe pyrethroids例如ethofenprox，天然除虫菊酯、似虫菊、s-反丙烯除虫菊、fenfluthrin、prallethrin和5-苄基-3-呋喃基甲基-(E)-(1R，3S)-2，2-二甲基-3-(2-oxothiolan-3-亚基甲基)环丙烷甲酸酯；
b)有机磷酸酯类例如溴丙磷、乙丙硫磷、甲基一六0五、谷硫磷、甲基一0五九、庚虫磷、甲基乙拌磷、克线磷、久效磷、三唑磷、甲胺磷、乐果、磷胺、马拉松、chloropyrifos、伏杀磷、特丁磷、丰索磷、地虫磷、甲拌磷、腈肟磷、甲基虫螨磷、乙基虫螨磷、杀螟松或二嗪农；
c)氨基甲酸酯类(包括芳基氨基甲酸酯类)例如抗蚜成、cloethocarb、虫螨威、furathiocarb、苯虫威、涕灭成、thiofurox、carbosulfan、噁虫威、fenobucarb、残杀威或oxamyl；
d)苯甲酰脲类例如triflumuron或chlorofluazuron；
e)有机锡化合物类例如三环锡、杀螨锡、唑环锡；
f)大环内酯类例如avermectins或milbemycins，例如abamectin、ivermectin和milbemycin；
g)激素和信息素类；
h)有机氯化合物类例如六氯化苯、DDT、硫丹、氯丹或狄氏剂；
i)脒类例如杀虫脒或杀螨脒；
j)熏蒸剂；
k)硝基亚甲基类例如imidacloprid。
除了上述所列举的几类化学杀虫剂外，如果与所述混合物的使用目的相适合，在所述混合物中还可使用具有特定目的的其他杀虫剂。例如对特定作物具有选择性的杀虫剂，例如可以使用适用于水稻的钻心虫特异性杀虫剂如cartap或buprofezin。另外，在所述组合物中还可以使用对特定昆虫属/时期的杀虫剂例如杀卵剂(ovo-larvicides)如clofentezine、flubenzimine、hexythiazox和三氯杀螨砜，motilicides如开乐散或克螨特，一般杀螨剂例如溴螨酯、乙酯杀螨醇，或生长调节剂例如hydramethylnon、cyromazine、蒙五一五、chlorfluazuron和氟脲杀。
用于所述组合物中的适宜的增效剂的实例包括胡椒基丁醚、增效菊(sesamax)、增效散和十二烷基咪唑。
组合物中所含的适宜的除草剂、杀真菌剂和植物生长调节剂取决于施用目的和所需效果。
可含有的对水稻具有选择性的除草剂的实例有敌稗，用于棉花的植物生长调节剂的实例有″Pix″，而用于水稻的杀真菌剂的实例包括灭瘟素类例如灭瘟素。组合物中本发明化合物与其他活性成分之间的比例取决于多种因素，这些因素包括靶标的类型、需要混合物所产生的效果等。但是，通常，在所施用组合物中其他活性成分一般是按照它们通常施用的比例施用或者在能够产生增效作用的情况下以略低的比例施用。
                  实施例1
用各种有害动物对本发明式(I)化合物的活性进行试验。除非另有说明，所用有害动物用含有百万分之(ppm)500(重量比)的所述化合物的液体组合物进行处理。所述组合物经下列步骤制备：将化合物溶于丙酮∶乙醇(50∶50)的混合物中，溶液用含有0.05％(重量比)商品名为“Synperonic”NP8润湿剂的水稀释，直至液体组合物含有所需浓度的化合物。“Synperonic”为注册商标。
对于每一种有害动物试验方法基本一致，并且该方法包括在介质上载有大量有害动物，所述介质通常为有害动物侵蚀的寄主植物或食物，并且用所述组合物分别或同时处理所述介质及有害动物，然后，通常在处理后一至三天内测定有害动物的死亡率。
每一种化合物的试验结果如表A所示。所述结果用死亡率A、B和C三级表示，其中A表示死亡率低于40％，B表示死亡率为40-70％，而C表示死亡率为80-100％；-表示未对所述化合物进行试验或者表示未获得有意义的试验结果。
有关所述试验有害动物的种类、支持介质或食物以及试验类型及时间如表B中所示。有害动物的种类用字母代码表示。
     表A化合物号    种类(见表B)
    TU  MPa   MD   HV   SE   DBII.1    B    A    A    A    A    -II.2    C    C    A    A    A    -II.3    A    A    A    A    A    -II.4    A    A    A    A    A    -II.5    A    C    A    A    A    -II.6    C    A    A    A    A    -II.7    A    A    A    B    A    -II.8    C    C    A    C    B    -II.9    B    C    A    A    A    -III.1   A    C    A    A    A    BIII.2   C    C    A    C    A    -III.3   A    C    A    A    A    -III.4   A    A    A    A    A    -III.5   A    A    A    A    A    -III.6   A    A    A    C    A    -III.7   A    A    A    B    A    -III.8   A    A    A    A    A    -III.9   B    C    A    A    A    -III.10  A    C    A    B    A    -III.11  A    A    A    A    A    -III.12  B    A    A    A    A    -IV.1    C    C    A    C    B    CIV.2    C    C    A    C    B    CIV.3    C    C    A    B    A    BIV.7    C    C    A    C    A    -IV.8    C    C    A    C    A    -IV.9    C    C    A    C    A    -IV.10   C    C    -    B    A    -IV.23   C    C    A    C    B    -IV.24   C    C    A    A    A    -IV.26   C    C    A    A    A    -V.2     C    C    A    C    C    -V.12    C    C    A    C    A    -V.15    C    C    A    A    A    -VI.1    A    C    A    A    A    -VI.4    A    A    A    A    A    -VI.5    C    C    A    A    A    -VI.6    C    A    A    A    A    -VI.13   B    C    -    A    A    -VI.14   C    C    -    A    A    -VI.15   A    C    -    A    A    -VI.16   C    C    -    B    A    -VI.18   C    C    A    B    A    CVI.19   C    C    B    B    A    AVI.20     C    C    A    A    A    CVI.25     C    C    A    B    A    -VI.31     C    C    A    A    A    -VI.32     C    C    A    A    A    -VI.36     C    A    A    A    A    -VI.37     C    C    A    A    A    -VI.38     C    C    A    A    A    -VII.40    C    C    A    C    A    -VII.1     C    C    B    A    A    BVII.2     C    C    A    C    B    -VII.3     C    A    A    B    A    -VII.4     A    B    A    A    A    -VII.6     C    C    A    B    A    -VII.7     C    C    A    C    A    -VII.8     C    C    A    A    A    -VII.9     C    C    A    B    A    -VII.10    C    B    A    B    A    -VII.11    C    C    A    B    A    -VII.13    C    C    A    B    A    -VII.14    C    C    A    A    A    -VII.15    C    C    A    B    A    -VII.16    C    C    A    A    A    -VII.17    C    C    A    A    A    CVII.21    B    C    A    A    A    -VII.23    A    B    A    A    A    -VII.24    A    C    A    A    A    -VII.25    C    C    A    C    A    -VII.26    C    C    A    B    A    -VII.27    C    C    -    A    A    -VII.28    C    C    -    A    A    -VII.32    C    C    A    C    A    -VII.36    C    C    A    B    A    -VII.41    C    C    A    C    A    -VII.43    C    C    A    B    A    -VII.45    C    C    A    C    A    -VII.47    C    C    A    C    A    -VII.52    C    C    A    A    B    -VII.53    C    C    A    A    A    -VII.56    C    C    A    C    A    -VII.82    C    C    A    B    A    -VII.83    A    C    -    C    A    -VII.84    A    C    -    A    A    -VII.90    C    C    A    B    A    -VII.94    C    C    A    C    A    -VII.98    C    C    A    C    A    -VII.102   A    A    A    A    A    -VII.114   C    A    A    A    A    -VII.115   A    C    A    A    A    -VII.116   B    A    A    A    A    -VII.128   C    C    A    A    A    -VII.130   C    C    -    A    A    -VII.134   A    A    A    C    A    AVIII.1    C    C    A    B    A    -VIII.2    A    C    A    A    A    -VIII.3    C    C    A    B    A    -VIII.4    A    A    A    A    C    -VIII.5    C    C    A    C    A    CVIII.7    C    C    A    A    A    -VIII.8    C    A    A    A    A    -VIII.9    A    A    A    A    A    -VIII.10   C    C    A    A    A    -VIII.11   C    C    A    B    A    -VIII.12   C    C    A    B    A    -VIII.13   A    C    A    A    A    -VIII.14   C    C    A    A    A    -VIII.15   C    B    A    A    A    -VIII.18    C    C    A    A    A    -VIII.19    C    C    A    A    A    -VIII.20    C    C    A    A    A    -VIII.21    A    A    A    A    A    -VIII.22    C    C    A    A    A    -VIII.23    C    C    A    A    C    -VIII.24    C    C    A    A    B    -VIII.27    C    C    A    B    A    -VIII.28    A    C    A    A    A    -VIII.29    C    C    A    C    A    -VIII.30    A    C    A    A    A    -VIII.31    C    C    A    A    A    -VIII.32    B    C    A    A    A    -VIII.33    C    C    A    A    A    -VIII.34    B    B    A    A    A    -VIII.36    C    C    A    A    A    -VIII.52    A    C    -    A    A    -VIII.53    A    C    A    A    A    -VIII.58    C    C    A    C    A    -VIII.59    C    C    A    A    A    -VIII.61    C    C    A    A    A    -VIII.63    A    A    A    A    C    -VIII.64    C    C    A    A    A    -VIII.65    A    B    -    A    A    -VIII.66    A    A    A    A    A    -VIII.67    A    A    A    A    A    -VIII.68    C    C    A    A    A    -VIII.151   C    C    A    B    A    -VIII.152   C    C    -    A    A    -IX.31      C    C    A    A    A    -IX.33      A    A    A    A    A    -IX.34      B    C    A    A    A    -IX.36      A    C    A    A    A    -IX.37     C    C    A    A    B    -IX.40     A    A    A    A    A    -IX.42     A    A    A    A    A    -IX.55     C    A    A    A    A    -IX.61     A    C    A    A    A    -IX.73     C    C    A    A    C    -IX.75     C    C    A    A    A    -IX.82     C    C    A    C    B    -IX.84     C    A    A    C    A    -IX.124    C    A    A    A    A    -IX.126    A    A    A    A    A    -X.3       C    C    A    C    C    -X.26      C    C    A    C    A    -X.32      C    A    A    A    A    -XI.5      C    C    A    C    C    CXI.9      A    A    A    A    A    -XI.11     C    C    A    C    A    -XI.23     C    C    A    C    A    -XI.24     A    C    A    A    A    -XI.25     C    C    A    B    A    -XI.30     A    C    A    A    A    -XI.31     A    C    A    A    A    -XI.34     C    C    A    B    A    -XI.35     C    C    A    C    A    -XI.36     C    C    A    C    A    -XI.38     C    C    A    C    A    -XI.40     C    C    A    A    A    CXI.87     C    C    A    C    A    -XI.102    B    C    A    A    A    -XI.108    B    C    A    B    A    -XI.109    C    A    A    C    B    -XI.110    C    C    A    B    A    -XI.125    C    C    A    C    A    -XI.127   C    C    A    B    B    BXII.1    C    C    A    C    B    -XII.3    C    C    A    C    C    BXII.4    C    C    A    B    A    CXII.5    C    C    A    A    A    BXII.8    C    C    A    A    A    -XII.9    A    B    A    B    A    -XII.11   C    C    A    B    A    -XII.12   C    C    A    B    A    -XII.13   C    C    A    B    A    -XII.14   C    C    A    C    A    -XII.15   C    C    A    A    A    -XII.19   C    C    A    A    B    -XII.23   C    C    A    C    A    -XII.25   C    C    A    C    A    -XII.26   C    C    A    B    A    -XII.27   C    C    A    A    A    -XII.28   C    C    A    C    A    -XII.29   C    C    A    C    A    -XII.30   C    C    A    B    A    -XII.31   C    C    A    A    A    -XII.32   C    C    A    C    A    -XII.33   C    C    A    C    A    -XII.35   C    C    A    A    A    -XII.49   C    C    A    C    A    -XII.51   C    C    A    C    A    -XII.54   C    C    A    C    A    -XII.55   C    A    A    C    A    -XII.68   C    A    A    A    A    -XII.128  C    C    A    B    C    -XII.129  C    C    A    C    A    -XII.130  B    C    A    A    A    -XII.131  C    C    A    C    A    -XII.132    C    C    A    B    C    -XII.133    C    C    A    A    A    -XII.134    C    C    A    C    B    -XII.142    C    C    A    C    A    -XII.143    C    B    A    A    A    -XII.144    C    C    A    B    A    -XII.145    C    C    A    C    A    -XII.146    B    C    A    A    A    -XII.147    C    C    A    A    A    -XII.148    C    C    A    C    A    -XIII.1     C    A    A    B    A    -XIII.2     C    C    A    C    A    -XIII.3     C    C    A    B    A    -XIII.4     C    C    A    A    A    -XIII.6     C    A    A    C    A    -XIII.7     C    C    A    C    A    -XIII.9     C    C    A    C    A    -XIII.10    C    C    A    B    A    -XIII.11    C    C    A    A    A    -XIII.14    A    A    A    A    A    -XIII.15    C    C    A    A    A    -XIII.16    C    A    A    B    A    -XIII.17    C    C    A    C    A    -XIII.18    C    C    A    B    A    -XIII.20    C    C    A    B    A    -XIII.24    C    C    A    B    A    -XIII.27    C    A    A    C    A    -XIII.28    C    C    A    B    A    -XIII.29    C    C    A    B    A    -XIII.40    C    C    A    C    A    BXIII.41    C    C    A    C    A    -XIII.42    C    C    A    C    A    -XIII.45    C    C    A    A    A    -XIII.63   A    A    A    A    A    BXIII.64   C    C    A    C    A    -XIII.65   C    C    A    C    A    -XIII.66   C    C    A    B    A    -XIII.69   C    B    A    B    A    -XIII.70   A    C    A    B    A    AXIII.101  C    C    A    A    A    -XIII.110  C    C    A    C    A    CXIII.114  C    C    A    C    A    -XIII.115  C    C    A    C    A    -XIII.116  A    C    A    C    A    -XIII.117  C    C    B    A    B    BXIII.119  B    C    C    C    A    CXIII.122  C    C    A    A    A    -XIII.124  C    C    B    B    A    BXIII.133  C    C    A    C    A    CXIII.134  C    C    A    B    A    BXIII.143  C    A    A    C    A    -XIV.1     C    C    A    C    A    CXV.1      C    C    A    C    C    CXVI.1     A    C    A    C    B    -XVI.2     A    A    A    A    A    -XVI.3     C    A    A    C    A    -XVI.5     C    C    A    C    B    -XVI.6     C    C    A    C    A    -XVI.7     A    A    A    A    A    -XVI.8     C    C    A    C    A    -XVI.9     C    B    A    A    A    -XVI.10    C    C    A    C    B    CXVI.11    A    B    A    A    A    AXVI.12    C    C    A    A    C    -XVI.13    A    A    A    A    A    -XVI.14    A    A    A    A    A    -XVI.15    B    C    A    A    A    -XVI.16    C    C    A    A    A    -XVI.17    C    C    A    A    A    -XVI.18    C    C    A    A    A    -XVI.19    C    A    A    A    A    BXVI.20    A    A    A    A    A    -XVI.21    C    C    A    C    A    -XVI.22    C    A    A    B    A    -XVI.23    A    A    A    B    A    -XVI.24    C    C    A    B    A    -XVII.1    C    C    A    A    A    CXVII.2    C    C    A    A    A    CXVII.3    B    B    C    C    C    CXVII.4    C    C    A    A    A    BXVII.5    C    C    A    A    A    BXVII.6    A    A    A    A    A    AXVII.7    C    C    A    A    A    CXVIII.1   C    C    A    C    A    CXVIII.3   A    C    B    A    A    CXVIII.4   C    C    A    A    C    CXVIII.7   A    A    A    A    A    CXVIII.10  C    C    A    B    A    -XVIII.13  C    C    A    C    C    -XVIII.14  C    C    A    A    A    -XVIII.15  C    C    A    B    A    -XVIII.16  C    C    A    B    B    -XIX.1     C    C    B    C    A    CXX.4      C    B    A    C    A    CXX.15     C    A    A    A    A    -XX.27     C    C    A    B    A    -XX.28     C    C    A    A    B    -XX.30     C    C    A    A    A    -XX.52     C    C    A    B    A    -XX.53     C    C    A    C    A    -XX.54     C    C    A    B    A    -XX.65     C    C    A    A    A    -XX.98     C    C    A    A    A    -XX.109    C    C    A    C    A    -XX.110    C    C    A    A    A    -XX.116    C    C    A    B    A    -XX.117    C    C    A    C    A    -XX.118    C    C    A    C    A    -XX.137    C    C    A    B    A    -XX.205    C    C    A    C    A    -XX.218    C    C    A    C    A    -XX.221    C    C    A    C    A    -XX.226    C    A    A    C    C    -XX.227    C    C    B    A    A    AXX.231    C    C    A    C    A    -XX.247    C    C    A    C    A    -XX.251    C    C    A    A    A    BXXI.1     C    C    B    A    A    A
                                     表B
字母代码     试验种类   支持介质/食物 试验类型  时间(天)
    TU     棉红蜘蛛(Tetranychus urticae)     法国大豆叶 接触     3
    MPa     桃蚜(Myzus persicae)     小白菜叶 接触     3
    MD     家蝇(Musca domestica)     棉毛/糖 接触     2
    HV     烟蚜夜蛾(Heliothis virescens)     大豆叶 残留     5
    SE     甜菜夜蛾(Spodoptera exigua)     棉花叶 残留     5
    DB     黄瓜条叶甲(Diabrotica balteata) 滤纸/玉米种子 残留     2
“接触”试验是指同时处理有害动物和介质，而“残留”试验是指在有害动物侵害之前对介质进行处理。
                  实施例2
此实施例进一步说明了本发明式(I)化合物的杀害虫活性。
表C中进一步给出了在以不同的比例使用下所试验化合物抗四种有害动物的活性。对TU(棉红蜘蛛，接触试验)、MPa(桃蚜，接触试验)和DB(黄瓜条叶甲，接触试验)进行试验中所用试验方法和详细情况如实施例1和表B中所述，所施用比例如表头中试验类型中所述。对MPb(桃蚜，系统试验)进行试验的方法如下所述：
通过以10ppm和2.5ppm浸湿有2-3周龄的萝卜作物(cv.Cherrybelle)的土壤测定所试验化合物抗桃蚜(peach potatoaphid，Myzus persicae)的活性。使用具有第一个真叶约为2×1cm的作物，除去子叶、生长点和真叶。土壤用一透明盖盖住，在处理的前一天，向每一作物上加入12-18只成熟的蚜虫。处理当天，将每一盆植株置于250cm3的塑料桶中，用聚四氟乙烯胶带粘结以防止蚜虫跑掉。每盆植株用10cm3的水溶液(于1％乙醇和丙酮(1∶1)和0.01％SyneronicNP8(ICI CHemicals and Polymers)中制得)进行化学处理，每一处理过程重复3次。将处理过的作物转移到室温为20℃、相对湿度为60％以及光照期为16小时的恒定环境中。在处理后的第3和5天测定死亡率。
通过以浸渍溶液的形式向2周龄的黄瓜作物(cultivar Telegraph)施用所述杀线虫剂并用线虫侵害土壤，对抗根瘤线虫，黄麻根瘤线虫(Meloidogyne incognita)(MI)的活性进行评估。将10cm3所述试验化合物的水溶液(于1％乙醇和丙酮(1∶1)和0.01％Syneronic NP8(ICI CHemicalsand Polymers)中制得)加入到每一株作物上，以使土壤中最终浓度达到2ppm。每一处理过程重复2次。以每cm3350只线虫的浓度用2cm3新孵化的幼虫悬浮液进行处理后48小时，将黄瓜作物进行栽培。所述试验于25℃光照期为16小时下进行6天，以与未经处理的被侵害的对照组相比根瘤减少的百分比对每株作物的根进行测定。试验结果以与对照组相比根瘤减少的百分比记录于表C中。
除MI以外，表C中四种有害动物的试验结果均以所测定的对照百分比形式表示。-表示未对所述化合物进行试验或者表示未得到有意义的试验结果。
                表C化合物号 TU      MPa    MPa   MPb   MPb   DB    MINo.     100ppm  100ppm 27ppm 10ppm 25ppm 25ppm 2ppmII.1     -       -       -     -     1    -     95II.2     88      -       -     -    100   -    100II.3     -       -       -     -     -    -      0II.4     -       -       -     -     4    -     96II.5     -       -       -     -     -    -     96II.6    39       -       -     -     -    -     88II.7     -       -       -     -     4    -     98II.8     74      -       24    -    100   -     97II.9     -       -       58    -    100   -     98III.1    -       -        5    -     -    -     98III.2    60      -       58    -     97   -     93III.3    -       -        8    -     41   -     83III.4    -       -        -    -     -    -      0III.5    -       -        -    -     -    -     30III.6    -       -        -    -     -    -     47III.7    -       -        -    -     -    -     48III.8    -       -        -    -     -    -      0III.9    -       7        -    -     -    -     88III.10   -       8        -    -     -    -     51III.11   -       -        -    -     -    -      0III.12   -       -        -    -     -    -      0IV.1    100      -        66   92    -    80     0IV.2     94      -        82   84    -    17     0IV.3     60      -         8  100    -    -     96IV.7    100     100       -    -    100   -    100IV.8     92      -        81   -     73   -     0IV.9     93      -        81   -     50   -     0IV.10    -       -        -    -     -    -    11IV.23    -       -        -    97    -    -    99IV.24    -       -        -    -     -    -    88V.2      100    -    84   -    55   -     0V.6       -     -    -    -    -    -    72V.12     100    -   100   -    10   -     0V.15      49    -    50   -   100   -    92VI.1      -     -    2    -    -    -    99VI.4      -     -    -    -    5    -    98VI.5      84    95   -    -   100   -   100VI.6      -     -    -    97   -    -    77VI.13     -     -    -    -    -    -    22VI.14     -     -    -    -    -    -     0VI.15     -     -    -    -    -    -    72VI.16     -     -    -    -    -    -    55VI.18     73    -    65   60   -   100   95VI.19     74    -   100   99   -    -   100VI.20     97    -   100   95   97   53   98VI.25     77    -    15    -   46   -    88VI.32     28    -    12    -   28   -   100VI.36     -     -    -    79   -    -    17VI.37     93    -   100   -    86   -    97VI.40     92    -    98   -   100   -    92VII.1     38    -    0    -    51   -    99VII.2     36    -    39   -   100   -    99VII.3     45    -    -    -    -    -     0VII.4     -     -    7    -    -    -     0VII.6    100    -    98   -    65   -    95VII.7     99    -   100   -    45   -    98VII.8     46    -    16   -    4    -    86VII.9     90    6    -    -    -    -     0VII.10    37    7    -    -    -    -     0VII.12    -     -    -    96   -    -     0VII.14    -     -    -    -    -    -    91VII.15    -     -    -    -    -    -   100VII.16    88   100   -    -    96   -   100VII.17    90   -    9    -    -    60    0VII.22    -    -    -    -    -    -    76VII.23    -    -    -    -    -    -    68VII.24    -    -    17   -    50   -    98VII.25    -    -    -    -    98   -    99VII.26    95   -    30   -    96   -   100VII.27    -    -    -    -    -    -    83VII.28    -    -    -    -    -    -    66VII.32    99   -    79   -    49   -    97VII.36   100   -   100   -    90   -    92VII.41   100   -   100   -    49   -    96VII.43    85  100   -    -    -    -    86VII.45   100   99   -    -    -    -    95VII.47    -    -    -    -    -    -    94VII.52    -    -    -    41   -    -    94VII.53    -    -    -    67   -    -    99VII.56    -    -    -    56   -    -    -VII.83    -    -    -    -    -    -    66VII.84    -    -    -    -    -    -    0VII.90    97   -    92   -    93   -    95VII.94    72   -    5    -    -    -    0VII.98    56   -    11   -    -    -    0VII.102   -    -    -    -    -    -    0VII.114   -    -    -    28   -    -    50VII.115   -    -    -    -    -    -    50VII.116   -    -    -    -    -    -    33VII.128   -    -    -    44   -    -    66VII.130   -    -    -    -    -    -    28VII.134   -    -    -    -    -    -   100VIII.1   100  100   -    -   100   -    98VIII.2    -    93   -    -    98   -    99VIII.3    -    -    -    -    -    -    88VIII.4    -    -    -    18   -    -    39VIII.5     45   -    26   -     96   87   98VIII.7     43   90   -    -     90   -   100VIII.8     -    -    -    -     -    -    59VIII.9     -    -    -    -     -    -    65VIII.10    -    -    -    42    -    -    39VIII.12    -    -    -    -     -    -    48VIII.13    -    4    -    -     -    -    86VIII.14    -    -    -    -     -    -    90VIII.15    -    -    -    -     -    -    97VIII.18    97  100   -    -     -    -    94VIII.19    -    -    -    -     -    -    66VIII.20    -    -    -    4     -    -     0VIII.21    -    -    -    -     -    -     0VIII.22    -    -    -    -     -    -    72VIII.23    -    -    -    76    -    -    44VIII.24    -    -    -    0     -    -    50VIII.27    -    -    -    0     -    -     0VIII.29    -    -    -    -     -    -    11VIII.30    -    -    -    29    -    -    44VIII.31    -    -    -    -     -    -    49VIII.32    -    -    -    -     -    -    99VIII.33    -    -    -    -     -    -     0VIII.34    -    -    -    -     -    -    22VIII.36    -    -    -    -     -    -    66VIII.52    -    -    -    -     -    -    22VIII.59    -    -    -    -     -    -    65VIII.61    -    -    -    -     -    -    66VIII.63    -    -    -    -     -    -    99VIII.64    -    -    -    29    -    -     0VIII.65    -    -    -    48    -    -    72VIII.66    -    -    -    16    -    -    -VIII.67    -    -    -    -     -    -     0VIII.151  100  100   -    -     30   -    99VIII.152 -     -    -    -    -     -    33IX.33    -     -    -    0    -     -    44IX.34    -     -    -    0    -     -    94IX.36    -     -    -    2    -     -     0IX.37    -     -    -    -    -     -    61IX.40    -     -    -    30   -     -    50IX.42    -     -    -     9   -     -    72IX.55    -     -    -    -    -     -    83IX.61    -     -    -    86   -     -    61IX.73    -     -    -   100   -     -    72IX.75    -     -    -    -    -     -    99IX.82    91   100   -    -    -     -     3IX.84    97    -    -    -   100    -    97IX.124   -     -    -    -    -     -    65IX.126   -     -    -    -    -     -    94IX.127   -     -    -    -    -     -    50X.3     100    -   100   52   -     -    94X.26     -     -    -    82   -     -    88X.32     54    -    -    -    -     -    96XI.5    100    -   100   30   -     13  100XI.9     -     -    -    -    26    -    99XI.11    84   100   -    -   100    -    95XI.23    40    14   -    -    48    -    98XI.24    -     -    -    -    95    -    86XI.25    41   100   -    -    -     -    97XI.30    -     81   -    -    -     -     4XI.31    -     29   -    -    -     -    14XI.34   100   100   -    -    99    -    100XI.35    97   100   -    -    98    -     98XI.36   100   100   -    -   100    -     92XI.38   100   100   -    -    52    -     93XI.40    36    -   100  100   95    77   100XI.87    82   100   -    -    92    -    100XI.102    -     -     2     -    -     -     0XI.108    -    100    -     -    93    -    92XI.109   100    -     -     -    35    -    93XI.110    70    -     96    -    59    -    90XI.125   100   100    -     -    80    -    97XI.127   100    -    100   26    -     -     0XII.1     86    -      9    -   100    -    95XII.3    100    -     46    9    65    -    88XII.4    100    -     93   49    -     67   98XII.5     37    -      0   72    -     -    89XII.8     59    -      4   -    100    -    96XII.9     -     42    -    -     -     -    68XII.11    81   100    -    -     50    -   100XII.12    73   100    -    -     -     -    97XII.13    43    20    -    -     -     -    76XII.14    93   100    -    -     95    -    93XII.15    47    11    -    -     -     -    94XII.19    50    30    -    -     -     -    69XII.23    95   100    -    -     97    -    97XII.25   100   100    -    -     56    -    99XII.26    73   100    -    -     77    -    99XII.27    -     98    -    -     -     -    -XII.28   100   100    -    -     -     -    84XII.29    -    100    -    -    100    -    99XII.30    15   100    -    -     -     -    94XII.31    73    -     22   -    100    -    95XII.32   100   100    -    -     98    -    99XII.33    45    37    -    -     -     -    -XII.35   100    87    -    -     95    -    98XII.49    38    -     18   -     97    -    95XII.51    40     8    -    -     51    -    91XII.54   100    80    -    -    100    -    98XII.55    96    -     -    -    100    -    90XII.68      53    -     -     -    -     -      0XII.128    100   100    -     -    26    -     61XII.129    100   100    -     -    86    -     89XII.130     -     77    -     -     5    -     87XII.131     87    -     26    -    54    -     86XII.132     98   100    -     -    -     -     31XII.133     99    -     85    -     6    -      0XII.134     75    -     88    -    97    -      0XII.142     54   100    -     -    92    -     95XII.143     48    39    -     -    65    -     94XII.144    100   100    -     -    -     -     53XII.145     -    100    -     -    32    -     97XII.146     -     45    -     -    -     -     69XII.147     39    56    -     -    -     -     37XII.148     97    97    -     -    -     -     84XIII.1      35    -     -     -    -     -     89XIII.2      95   100    -     -   100    -     98XIII.3      79    84    -     -    88    -     99XIII.4     100   100    -     -   100    -     96XIII.6      79    -     -     -    96    -    100XIII.7      88   100    -     -   100    -     99XIII.9      91    -    100    -    18    -     93XIII.10     94    -    100    -    32    -     96XIII.11     94    -     83    -    96    -     92XIII.14     -     -     -     -     7    -     95XIII.15     43    77    -     -    -     -     94XIII.16     89    -     -     -    89    -     96XIII.17     74   100    -     -   100    -     97XIII.18     85   100    -     -    96    -     99XIII.20     94    -     90    -    48    -      0XIII.24     89   100    -     -    45    -    100XIII.27     69    -     -     -    77    -     99XIII.28    100   100    -     -   100    -     96XIII.29     95    100    -    -   100    -     97XIII.40    100     -      5  100  100    -    100XIII.41    100     -     95   -   100    -     96XIII.42     98     -     35   -   100    -     95XIII.45     81     -     44   -    91    -     97XIII.63     -      -     -    98   -     -    100XIII.64     85     -     97   -    98    -     97XIII.65     73     -     42   -   100    -     98XIII.66    100     93    -    -    -     -     31XIII.69     84     18    -    -    -     -     63XIII.70     -      -     22   -    -     -      0XIII.101    79     98    -    -    99    -    100XIII.110   100     -     64   27   -     79    94XIII.114    96    100    -    -    18    -     97XIII.115    97    100    -    -    45    -     91XIII.116    -     100    -    -    19    -    100XIII.117   100     -    100   77   -     -    100XIII.119    -      -     13   29   82    53    91XIII.122    95    100    -    -    35    -    100XIII.124    78     -     12   -    -     -      0XIII.133   100     -    100  100   -     50   100XIII.134    97     -    100  100   -     -    100XIII.143    -      -     -    -    -     -     41XIV.1       45     -     15  100   -     33     0XV.1        82     -     18   80   -     70    91XVI.1       -      34    -    -    -     -     50XVI.2       -      -     -    -     7    -     82XVI.3       59     -     -    -    97    -     94XVI.5       56     -     39   -    62    -    100XVI.6       88     97    -    -    96    -    100XVI.7       -      -     -    -    -     -      0XVI.8       42    100    -    -    -     -     89XVI.9       68     29    -    -    -     -     12XVI.10     100   -    65  100   -    53   100XVI.11      -    -    2    -    -    -      0XVI.12      20   18   -    -    -    -     81XVI.13      -    -    -    -    -    -     32XVI.14      -    -    -    -    -    -      0XVI.15      -    -    53   -    48   -     94XVI.16     100  100   -    -    -    -     94XVI.17      46   45   -    -    -    -     24XVI.18      25   48   -    -    -    -     43XVI.19      26   -    -    -    -    -      0XVI.20      -    -    -    -    -    -     42XVI.21      82   -   100   -    8    -    100XVI.22      44   -    -    -    -    -     41XVI.23      -    -    -    -    -    -     38XVI.24      81  100   -    -    85   -     97XVII.1      30   -    7    74   -    50     0XVII.2      24   -    1    -    -    27     0XVII.3      -    -    0    -    -    87     0XVII.4      11   -    0    -    -    -      0XVII.5      32   -    7    -    -    -      0XVII.6      -    -    -    -    -    -      0XVII.7      49   -    7    -    -    30     0XVIII.1     95   -   100   35   -    80    92XVIII.3     -    -    45  100   -    23    98XVIII.4     96   -   100   15   -    93    94XVIII.7     -    -    -    -    -    83     0XVIII.10    49   -    65   -    29   -    100XVIII.13   100   -    74   -    53   -      0XVIII.14    56   -     7   -    -    -      0XVIII.15    62   -    38   -    89   -    100XVIII.16    55   -     5   -    94   -    100XIX1       100   -    15   30   -   100    82XX4         91   -    71    8   -    97     0XX.15     100   -     -      -     94    -    100XX.27     69    96    -      -     91    -    100XX.28     31    85    -      -     -     -    73XX.30     69    100   -      -     91    -    99XX.52     63    -     100    -     93    -    96XX.53     97    100   -      -     92    -    100XX.54     43    3     -      -     -     -    61XX.65     52    34    -      -     -     -    47XX.98     85    -     -      -     95    -    100XX.109    50    100   -      -     100   -    99XX.110    77    100   -      -     95    -    99XX.116    68    -     71     -     98    -    96XX.117    100   98    -      -     96    -    100XX.118    34    7     -      -     -     -    21XX.137    47    -     100    -     94    -    95XX.205    79    100   -      -     -     -    94XX.218    81    100   -      -     -     -    97XX.221    42    -     79     -     92    -    99XX.226    94    -     -      -     100   -    97XX.227    86    -     51     100   -     -    100XX.231    88    -     100    -     52    -    100XX.247    90    100   -      -     100   -    94XX.251    18    -     79     26    -     -    0XXI.1     28    -     0      -     -     -    0
              实施例3
在有土壤和寄主植物存在下用接触试验测定本发明化合物的杀线虫活性谱。结果观测到对黄麻根瘤线虫(Meloidogyne incognita)、Globodera rostochiensis、Pratylenchus brachyurus、Tylenchorhynchusclaytoni、Hoplolaimus columbus和毕肖穿孔线虫(Radopholus similis)的活性最强，抗Rotykenchulus reniformis和Belonolaimus 1ongicaudatus的活性适中。
下列实施例阐明了本发明化合物适宜使用的剂型。各组份的量以重量份表示或者以g/升表示，*表示商品名。
              实施例4
此实施例阐明了适于向土壤施用的颗粒剂。所述颗粒剂可用常规方法例如浸渍、包覆、挤压或附聚制得。
                                 ％w/w浸渍颗粒剂：      活性成分               5
              木松香               2.5
              石膏颗粒            92.5
              (20-40目)包覆颗粒剂：      活性成分             0.5
              ‘Solvesso’*200   0.4
              碳酸钙颗粒          99.1
              (30-60目)缓释颗粒剂：      活性成分              10
              聚乙酸乙烯酯/聚氯乙烯  5
              共聚物胶乳
              美国活性白土颗粒      85
              (Attapulgus granules)
              实施例5
此实施例阐明了供喷雾形式使用的剂型。所述化合物可配制成供加水稀释使用的可湿性粉剂、分散性粒剂、胶悬剂、乳剂、悬浮乳剂或微胶囊悬浮剂。
                                    g/l乳油：            活性成分              250
              十二烷基苯磺酸钠       50
              壬基酚乙氧基化物       50
              烷基苯溶剂           至1升
                                   ％w/w可湿性粉剂：      液态活性成分             40
              磺化油分散剂            5
              氧化硅                 25
              十二烷基苯磺酸钠        3
              陶土(高岭土)           27微胶囊悬浮剂：    液态活性成分           250
              二异氰酸甲苯酯         10
              聚亚甲基聚苯基异氰酸   20
              酯
              壬基酚乙氧基化物        6
              磺化油分散剂           15
              苍耳烷胶                1
              膨润土                 10
              杀生物剂‘Proxel’*  0.1
              碳酸钠                  5
              水                    至1升
所述微胶囊悬浮剂可以以喷洒、浸湿土壤或者作为制备适用于土壤的缓释颗粒剂的中间体形式使用。
                           g/l胶悬剂：    固体活性成分        400
        磺化油分散剂        50
        十二烷基硫酸钠      30
        苍耳烷胶             1
        杀生物‘Proxel’* 0.1
        皂粘土              10
        水                至1升
              实施例6
此实施例阐明了以常规机械施用的拌种剂剂型。
                    ％w/w拌种剂：    活性成分       20
        十二烷基苯      3
        品红(染料)    2.7
        滑石         53.3
        氧化硅       至100％
实施例5所述胶悬剂和微胶囊悬浮剂可以以种子处理用浓缩流动剂形式使用。
              实施例7
此实施例阐明了用于静电喷雾的化合物制剂。
                  g/l
活性成分          200
N-甲基吡咯烷酮     50
豆油              120
Solvesso’200     至1升
              实施例8此实施例阐明了适于以毒饵形式使用的剂型。
               ％w/w
活性成分       0.25
冰糖          99.65
丁基化羟基甲苯 0.10
实施例9此实施例阐明了适于以团剂使用的剂型。
                mg
活性成分       1300
淀粉羟乙酸钠    300
微晶纤维素     1200
乳糖           2920
吡咯烷酮        250
硬脂酸镁         30
              实施例10此实施例阐明了适于以可注射悬浮剂形式使用的剂型。
                 mg
活性成分         40
偏亚硫酸氢钠      1
吐温80            1
甲基羟基苯甲酸钠  2
水              至1ml
              实施例11此实施例阐明了适于以注射液形式使用的剂型。
                  mg
活性成分          20
枸橼酸钠           6
橼枸酸            1
氯化钠            7
氯甲酚            1
水              至1ml
              实施例12此实施例阐明了适于以口服悬浮剂形式使用的剂型。
                     g
活性成分          100.0
吐温80              2.0
苍耳烷胶            5.0
二氧化硅胶体       10.0
甲基羟基苯甲酸盐    1.5
橼枸酸一水合物     10.0
橼枸酸钠           10.0
纯水           至1000.0ml
         说明书中所用化学式
R-S(O)nCH2CH2CH＝CF2    (1)
Figure A9519202902021
            说明书中所用化学式
Figure A9519202902031
           说明书中所用化学式R-SH     (XXIII)CF2=CHCH2CH2L    (XXIV)CF2=CHCH2CH2OSO2Rb    (XXV)CF2=CHCH2CH2Br  (XXVI)R-L    (XXVII)CF2=CHCH2CH2SH    (XXVIII)R-NH2   {XXIX)(CF2=CHCH2CH2S)2  (XXX)

Claims (13)

1.下列式(I)化合物或其盐，
R-S(O)nCH2CH2CH＝CF2其中n为0、1或2；和R为下列式(II)-(XXI)基团，
Figure A9519202900031
其中：
所述S(O)nCH2CH2CH＝CF2基团至少是R1(当与碳原子相连时)、R2、R3、R4、R5或R6中的一个；
R1(当与碳原子相连时)、R2、R3、R4、R5或R6各自独立地是氢、被任意取代的烷基、被任意取代的链烯基、链炔基、环烷基、烷基环烷基、烷氧基、链烯氧基、链炔氧基、羟基烷基、烷氧基烷基、被任意取代的芳基、被任意取代的芳烷基、被任意取代的杂芳基、被任意取代的杂芳烷基、被任意取代的芳氧基、被任意取代的芳烷氧基、被任意取代的芳氧基烷基、被任意取代的杂芳氧基、被任意取代的杂芳基烷氧基、被任意取代的杂芳氧基烷基、卤代烷基、卤代链烯基、卤代链炔基、卤代烷氧基、卤代链烯氧基、卤代链炔氧基、卤素、羟基、氰基、硝基、-NR7R8、-NR7COR8、-NR7CSR8、-NR7SO2R8、-N(SO2R7)(SO2R8)、-COR7、-CONR7R8、-烷基CONR7R8、-CR7NR8、-COOR7、-OCOR7、-SR7、-SOR7、-SO2R7、-烷基SR7、-烷基SOR7、-烷基SO2R7、-OSO2R7、-SO2NR7R8、-CSNR7R8、-SiR7R8R9、-OCH2CO2R7、-OCH2CH2CO2R7、-CONR7SO2R8、-烷基CONR7SO2R8、-NHCONR7R8、-NHCSNR7R8或者R1、R2、R3、R4、R5和R6中相邻两个基团一起形成的稠合的5-或6-元碳环或杂环；
R1(当与氮原子相连时)为氢、被任意取代的烷基、环烷基、烷基环烷基、羟基烷基、烷氧基烷基、被任意取代的芳基、被任意取代的芳烷基、被任意取代的芳氧基烷基、被任意取代的杂芳基、被任意取代的杂芳基烷基、被任意取代的杂芳氧基烷基、卤代烷基、羟基、氰基、硝基、-NR7R8、-NR7COR8、NR7CSR8、-NR7COOR8、-NR7SO2R8、-N(SO2R7)(SO2R8)、-COR7、-CONR7R8、-烷基CONR7R8、-CR7NR8、-COOR7、-OCOR7、-SOR7、-SO2R7、-烷基SR7、-烷基SOR7、-烷基SO2R7、-OSO2R7、-SO2NR7NR8、-SR7、-SOR7、-SO2R7、-CSNR7R8、-SiR7R8R7、-OCH2CO2R7、-OCH2CH2CO2R7、-CONR7SO2R8、-烷基CONR7SO2R8、-NHCOR7R8或-NHCSR7R8；和
R7、R8和R9各自独立地是氢、被任意取代的烷基、被任意取代的链烯基、链炔基、被任意取代的芳基或被任意取代的芳烷基、卤代烷基、卤代链烯基、卤代链炔基、卤素或羟基。
2.根据权利要求1的化合物，其中：
所述S(O)nCH2CH2CH＝CF2基团至少是R1(当与碳原子相连时)、R2、R3、R4、R5或R6中的一个；
R1(当与碳原子相连时)、R2、R3、R4、R5或R6各自独立地是氢、被任意取代的C1-6烷基、被任意取代的C2-6链烯基、被任意取代的C2-6链炔基、C3-6环烷基、C4-7烷基环烷基、C1-6烷氧基、C2-6链烯氧基、C2-6链炔氧基、C1-6羟基烷基、C2-6一烷氧基烷基、C3-6二烷氧基烷基、被任意取代的C6-10芳基、被任意取代的C6-10芳基-C1-2烷基、被任意取代的5或6元杂芳基、被任意取代的5或6元杂芳基-C1-6烷基、被任意取代的C6-10芳氧基、被任意取代的C6-10芳基-C1-2烷氧基、C6-10芳氧基-C1-6烷基、被任意取代的5或6元杂芳氧基、被任意取代的5或6元杂芳基-C1-6烷氧基、5或6元杂芳氧基-C1-2烷基、C1-6卤代烷基、C2-6卤代链烯基、C2-6卤代链炔基、C1-6卤代烷氧基、C2-6卤代链烯氧基、C2-6卤代链炔氧基、卤素、羟基、氰基、硝基、-NR7R8、-NR7COR8、-NR7CSR8、-NR7SO2R8、-N(SO2-R7)(SO2-R8)、-COR7、-CONR7R8、-C1-6烷基CONR7R8、-CR7NR8、-COOR7、-OCOR7、-SR7、-SOR7、-SO2R7、-C1-6烷基SR7、-C1-6烷基SOR7、-C1-6烷基SO2R7-OSO2R7、-SO2NR7R8、-CSNR7R8、-SiR7R8R9、-OCH2CO2R7、-OCH2CH2CO2R7、-CONR7SO2R8、-C1-6烷基CONR7SO2R8、-NHCONR7R8、-NHCSNR7R8或者R1、R2、R3和R4中相邻两个基团一起形成的稠合的5-或6-元碳环或杂环；
R1(当与氮原子相连时)为氢、被任意取代的C1-6烷基、C3-6环烷基、C4-6烷基环烷基、C1-6羟基烷基、C2-6一烷氧基烷基、C3-6二烷氧基烷基、被任意取代的C6-10芳基、被任意取代的C6-1O芳基-C1-2烷基、被任意取代的C6-10芳氧基-C1-6烷基、被任意取代的5或6元杂芳基、被任意取代的5或6元杂芳基-C1-2烷基、被任意取代的5或6元杂芳氧基-C1-2烷基、C1-6卤代烷基、羟基、氰基、硝基、-CONR7R8、-C1-6烷基CONR7R8、-NHCOR7R8、-NHCSR7R8、-NR7R8、-NR7COR8、NR7CSR8、-NR7COOR8、-NR7SO2R8、-N(SO2R7)(SO2R8)、-COR7、-COOR7、-OCOR7、-OSO2R7、-SO2NR7N6、-SO2R7、-SOR7、-CSNR7R8、-SiR7R8R7、-OCH2CO2R7、-OCH2CH2CO2R7、-CONR7SO2R8或-C1-6烷基CONR7SO2R8；和
R7、R8和R9各自独立地是氢、被任意取代的C1-6烷基、被任意取代的C2-6链烯基、C2-6链炔基、C1-6卤代烷基、C2-6卤代链烯基、C2-6卤代链炔基、被任意取代的C4-6芳基或被任意取代的C4-6芳基-C1-6烷基、卤素或羟基。
3.根据权利要求2的化合物，其中当R1-R6中的任何一个基团为：
-被取代的烷基或者含有被取代的烷基基团时，其含有一个或多个选自下列的取代基，所述取代基为卤素、硝基、氰基、-COOR7或其盐、羟基、烷氧基、烷氧亚氨基、烷氧羰基、氨基甲酰基、一-或二-烷氨基甲酰基、氨基、一-或二-烷氨基、酰氨基、链烷磺酰基和芳基磺酰基；
-被取代的链烯基或者含有被取代的链烯基基团时，其含有一个或多个选自下列的取代基，所述取代基为卤素、COOR7或其盐、羟基、硝基和氰基；
-被取代的芳基或杂芳基或者含有被取代的芳基或杂芳基基团，其含有一个或多个选自下列的取代基，所述取代基为烷基、烷氧基、卤代烷基、卤素、羟基、ROOR7或其盐、氨基磺酰基、氰基和硝基。
4.根据权利要求2和3中任一权利要求的化合物，其中当R1-R6的中任何一个基团为-SR7时，其优选为被任意取代的C1-6烷硫基、C2-6链烯基硫基、C2-6链炔基硫基、C1-6卤代烷基、C2-6卤代链烯基硫基、C2-6卤代链炔基硫基或C6-10芳硫基。
5.根据权利要求1的化合物，其中：
至少一个R1(当与碳原子相连时)是-S(O)nCH2CH2CH＝CF2基团；
R1(当与碳原子相连时)-R6各自独立地是氢；硝基；卤素；氰基；-CH＝NOH；C1-4烷基；C1-4卤代烷基；C1-4链烯基；C1-4卤代链烯基；环丙基；羟基；C1-4烷氧基；C2-4烷氧基烷基；-COOH；C2-4烷氧羰基；C2-4卤代链烯氧基羰基；-CONH2；一或二-C1-2烷氨基羰基；C2-4链烷羰基；被独立地选自卤素、硝基、C1-4烷基、C1-4烷氧基或氨基磺酰基的基团任意一-或二-取代的苯基；-CONHSO2-C1-4烷基；被独立地选自卤素、硝基、C1-4烷基或C1-4烷氧基的基团任意一-或二-取代的苄基；被独立地选自卤素、氰基、C1-4烷基或C1-4烷氧基的基团任意一-或二-取代的苯氧基；被C1-4烷基任意一-或二-取代的氨基；-SH；C1-4烷硫基；被独立地选自卤素或C1-4卤代烷基的基团任意一-或二-取代的苄硫基；C1-4链烯基硫基；C2-4卤代链烯基硫基；第二个S(O)nCH2CH2CH＝CF2基团；C1-4链烷磺酰基；C1-4卤代链烷磺酰基；氟磺酰基；一-或二-C1-4烷基氨基磺酰基；被卤素任意取代的5或6元杂芳基；或者任意两个相邻基团形成稠合的5-或6-碳环或杂环；和
R1(当与氮原子相连时)为氢；硝基；氰基；-CH＝NOH；C1-4烷基；C1-4卤代烷基；环丙基；羟基；-COOH；C2-4烷氧羰基；C2-4卤代链烯氧基羰基；-CONH2；一或二-C1-2烷氨基羰基；C2-4链烷羰基；被独立地选自卤素、硝基、C1-4烷基、C1-4烷氧基或氨基磺酰基的基团任意一-或二-取代的苯基；-CONHSO2-C1-4烷基；被独立地选自卤素、硝基、C1-4烷基或C1-4烷氧基的基团任意一-或二-取代的苄基；被独立地选自卤素、氰基、C1-4烷基或C1-4烷氧基的基团任意一-或二-取代的苯氧基；被C1-4烷基任意一-或二-取代的氨基；-SH；C1-4烷硫基；被独立地选自卤素或C1-4卤代烷基的基团任意一-或二-取代的苄硫基；C1-4链烯基硫基；C2-4卤代链烯基硫基；C1-4链烷磺酰基；C1-4卤代链烷磺酰基；氟磺酰基；一-或二-C1-4烷基氨基磺酰基；被卤素任意取代的5或6元杂芳基。
6.一种权利要求1-3中任一项中n为0的化合物的制备方法，该方法包括将式(XXIII)化合物与式(XXIV)化合物进行反应，
         R-SH(XXIII)
         CF2＝CHCH2CH2L(XXIV)
其中R如权利要求1-3中任一项所定义，并且L为易离去基团。
7.一种权利要求1-3中任一项中n为0的化合物的制备方法，该方法包括将式(XXVII)化合物与式(XXVIII)化合物进行反应，
         R-L(XXVII)
         CF2＝CHCH2CH2SH(XXVIII)
其中R如权利要求1-3中任一项所定义，并且L为易离去基团。
8.一种权利要求1-3中任一项中n为1或2的化合物的制备方法，该方法包括将式(I)中n为0的相应取代的化合物氧化。
9.一种农用组合物，该组合物包括作为活性成分的权利要求1-3中任一项的化合物和农业上可接受的稀释剂或载体。
10.根据权利要求9的农用组合物，该组合物进一步含有表面活性物质。
11.根据权利要求9和10中任一项的农用组合物，该组合物进一步含有至少一种其他活性成分，所述活性成分为杀虫剂、杀真菌剂、杀菌剂、杀螨剂或其他生物活性化合物。
12.一种权利要求9-11中任一项的农用组合物的制备方法，该方法包括将权利要求1-3中任一项的化合物与农业上可接受的稀释剂或载体进行混合。
13.一种杀灭或控制线虫、昆虫或螨有害动物的方法，该方法包括向所述有害动物、它们的生活环境或所述有害动物易侵袭的作物上施用权利要求1-3中任一项的化合物或权利要求9-11中任一项的组合物。
CN95192029A 1994-03-10 1995-02-27 具有农药活性的(4，4-二氟丁-3-烯基硫基)-取代的杂环或碳环类化合物 Pending CN1143958A (zh)

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CN102686573B (zh) * 2009-11-17 2015-03-11 梅里亚有限公司 用于抵御无脊椎动物害虫的氟化的氧杂或硫杂杂芳基烷基硫化物衍生物
CN102686573A (zh) * 2009-11-17 2012-09-19 梅里亚有限公司 用于抵御无脊椎动物害虫的氟化的氧杂或硫杂杂芳基烷基硫化物衍生物
CN102696609A (zh) * 2012-01-10 2012-10-03 山东中农联合生物科技有限公司 一种含吡啶的三氟丁烯类杀虫剂
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WO2017054524A1 (zh) * 2015-09-30 2017-04-06 山东省联合农药工业有限公司 一种反式结构的含内酯环的杀线虫剂及其制备方法和用途
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LV11686B (en) 1997-06-20
DE69530681D1 (de) 2003-06-12
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