CN101312944A - 有机硫化合物及其作为节肢动物杀灭剂的应用 - Google Patents
有机硫化合物及其作为节肢动物杀灭剂的应用 Download PDFInfo
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- CN101312944A CN101312944A CNA2006800433285A CN200680043328A CN101312944A CN 101312944 A CN101312944 A CN 101312944A CN A2006800433285 A CNA2006800433285 A CN A2006800433285A CN 200680043328 A CN200680043328 A CN 200680043328A CN 101312944 A CN101312944 A CN 101312944A
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- YRRBXJLFCBCKNW-UHFFFAOYSA-N prothiocarb Chemical compound CCSC(=O)NCCCN(C)C YRRBXJLFCBCKNW-UHFFFAOYSA-N 0.000 description 1
- QHMTXANCGGJZRX-WUXMJOGZSA-N pymetrozine Chemical compound C1C(C)=NNC(=O)N1\N=C\C1=CC=CN=C1 QHMTXANCGGJZRX-WUXMJOGZSA-N 0.000 description 1
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- OARRHUQTFTUEOS-UHFFFAOYSA-N safranin Chemical compound [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N)C=C2[N+]=1C1=CC=CC=C1 OARRHUQTFTUEOS-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OUBFUQWWKDQSIV-UHFFFAOYSA-N tert-butyl 5,5,6,6,6-pentafluoro-2-(3,3,3-trifluoropropylsulfonyl)hexanoate Chemical compound FC(F)(F)C(F)(F)CCC(C(=O)OC(C)(C)C)S(=O)(=O)CCC(F)(F)F OUBFUQWWKDQSIV-UHFFFAOYSA-N 0.000 description 1
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- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 229960004546 thiabendazole Drugs 0.000 description 1
- NWWZPOKUUAIXIW-FLIBITNWSA-N thiamethoxam Chemical compound [O-][N+](=O)\N=C/1N(C)COCN\1CC1=CN=C(Cl)S1 NWWZPOKUUAIXIW-FLIBITNWSA-N 0.000 description 1
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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Abstract
式(I)所示的化合物对有害节肢动物具有优异的控制活性。
Description
技术领域
本发明涉及有机硫化物及其在控制有害节肢动物(arthropod)中的应用。
背景技术
已经开发和实际使用了许多节肢动物控制剂。
发明内容
本发明提供了对有害节肢动物具有优异活性的新型化合物。
即,本发明提供了一种下式[I]所示的有机硫化合物(下文中可称为本发明的化合物)、一种包括本发明的化合物和惰性载体的有害节肢动物控制剂、以及一种对有害节肢动物或有害节肢动物栖息地应用有效量的本发明的化合物的有害节肢动物控制方法:
其中
R1代表C3-C6氟烷基,
R2代表氰基、C(=O)R5所示基团、或C(=S)R6所示基团,
R3代表氢原子、卤原子、或C1-C4烷基,
R4代表C1-C5氟烷基,
R5和R6独立地代表C1-C4烷氧基、任选被一或两个C1-C4烷基取代的氨基、或C2-C5环氨基,
n代表0、1或2。
具体实施方式
在本发明中,当提到C1-C4或类似形式时是指包括每个取代基在内的总碳原子数。在本发明中,当提到氟烷基时是指在碳原子上被一个或多个氟原子取代的取代烷基。
式(I)中R1所示的C3-C6氟烷基的例子包括:
C3氟烷基,例如2-氟丙基、2,2-二氟丙基、3-氟丙基、3,3-二氟丙基、3,3,3-三氟丙基、2,2,3,3,3-五氟丙基、2,2,3,3-四氟丙基和2,2,2-三氟-(1-三氟甲基)乙基;
C4氟烷基,例如2-氟丁基、2,2-二氟丁基、3-氟丁基、3,3-二氟丁基、4-氟丁基、4,4-二氟丁基、4,4,4-三氟丁基、3,3,4,4,4-五氟丁基、2,2,3,4,4-五氟丁基和2,2,3,3,4,4,4-七氟丁基;
C5氟烷基,例如2-氟戊基、2,2-二氟戊基、3-氟戊基、3,3-二氟戊基、4-氟戊基、4,4-二氟戊基、5-氟戊基、5,5-二氟戊基、5,5,5-三氟戊基、4,4,5,5,5-五氟戊基、3,3,4,4,5,5,5-七氟戊基、2,2,3,3,4,4,5,5-八氟戊基和2,2,3,3,4,4,5,5,5-九氟戊基;
C6氟烷基,例如2-氟己基、2,2-二氟己基、3-氟己基、3,3-二氟己基、4-氟己基、4,4-二氟己基、5-氟己基、5,5-二氟己基、6-氟己基、6,6-二氟己基、6,6,6-三氟己基、5,5,6,6,6-五氟己基、4,4,5,5,6,6,6-七氟己基、3,3,4,4,5,5,6,6,6-九氟己基和2,2,3,3,4,4,5,5,6,6,6-十一氟己基。
式(I)中的R4所示C1-C5氟烷基的例子包括:
C1-C2氟烷基,例如氟甲基、二氟甲基、三氟甲基、1-氟乙基、2-氟乙基、1,1-二氟乙基、2,2-氟乙基、2,2,2-三氟乙基和1,1,2,2,2-五氟乙基;C3氟烷基,例如1-氟丙基、1,1-二氟丙基、2-氟丙基、2,2-二氟丙基、3-氟丙基、3,3-二氟丙基、3,3,3-三氟丙基、1,1,2,2,3,3,3-七氟丙基、2,2,3,3,3-五氟丙基、2,2,2-三氟-(1-三氟甲基)乙基、1,2,2,2-四氟-(1-三氟甲基)乙基和2,2,3,3-四氟丙基;
C4氟烷基,例如1-氟丁基、1,1-二氟丁基、2-氟丁基、2,2-二氟丁基、3-氟丁基、3,3-二氟丁基、4-氟丁基、4,4-二氟丁基、4,4,4-三氟丁基、3,3,4,4,4-五氟丁基、2,2,3,4,4-五氟丁基和2,2,3,3,4,4,4-七氟丁基;
C5氟烷基,例如1-氟戊基、1,1-二氟戊基、2-氟戊基、2,2-二氟戊基、3-氟戊基、3,3-二氟戊基、4-氟戊基、4,4-二氟戊基、5-氟戊基、5,5-二氟戊基、5,5,5-三氟戊基、4,4,5,5,5-五氟戊基、3,3,4,4,5,5,5-七氟戊基、2,2,3,3,4,4,5,5-八氟戊基和2,2,3,3,4,4,5,5,5-九氟戊基。
式(I)中的R3所代表的C1-C4烷基的例子包括甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基。
式(I)中的R5和R6所代表的C1-C4烷氧基的例子包括甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基和叔丁氧基。
式(I)中的R5和R6所代表的任选被一或两个C1-C4烷基取代的氨基的例子包括氨基、甲氨基、乙氨基、丙氨基、2-丙氨基、丁氨基、异丁氨基、叔丁氨基和二甲氨基。
式(I)中的R5和R6所代表的C2-C5环氨基包括1-吖丙啶子基(aziridino)、1-氮杂环丁烷基、1-吡咯烷嗪基(pyrrolizinyl)和1-哌啶子基。
本发明的化合物的实施方式包括如下例子:
式(I)的有机硫化合物,其中n是2;
式(I)的有机硫化合物,其中R2是氰基或C(=O)R5所示基团;
式(I)的有机硫化合物,其中R2是氰基;
式(I)的有机硫化合物,其中R2是C(=O)R5所示基团,且R5是任选被1或2个C1-C4烷基取代的氨基;
式(I)的有机硫化合物,其中R2是C(=O)R5所示基团,且R5是氨基;
式(I)的有机硫化合物,其中R3是卤原子;
式(I)的有机硫化合物,其中R3是氟原子或氯原子;
式(I)的有机硫化合物,其中R4是C1-C3氟烷基;
式(I)的有机硫化合物,其中R4是三氟甲基;
式(I)的有机硫化合物,其中R4是1,1,2,2,2-五氟乙基;
式(I)的有机硫化合物,其中R4是1,1,2,2,3,3,3-七氟丙基;
式(I)的有机硫化合物,其中n是2,且R4是C1-C3氟烷基;
式(I)的有机硫化合物,其中n是2,且R4是三氟甲基;
式(I)的有机硫化合物,其中n是2,且R4是1,1,2,2,2-五氟乙基;
式(I)的有机硫化合物,其中n是2,且R4是1,1,2,2,3,3,3-七氟丙基;
式(I)的有机硫化合物,其中n是2,且R2是氰基或C(=O)R5所示基团;
式(I)的有机硫化合物,其中n是2,且R2是氰基;
式(I)的有机硫化合物,其中n是2,R2是C(=O)R5所示基团,且R5是任选被1或2个C1-C4烷基取代的氨基;
式(I)的有机硫化合物,其中n是C(=O)R5所示基团,且R5是氨基;
式(I)的有机硫化合物,其中n是2,且R3是卤原子;
式(I)的有机硫化合物,其中n是2,且R3是氟原子或氯原子;
式(I)的有机硫化合物,其中R2是氰基或C(=O)R5所示基团,且R3是卤原子;
式(I)的有机硫化合物,其中R2是氰基,且R3是卤原子;
式(I)的有机硫化合物,其中R2是C(=O)R5所示基团,R5是任选被1或2个C1-C4烷基取代的氨基,且R3是卤原子;
式(I)的有机硫化合物,其中R2是C(=O)R5所示基团,R5是氨基,且R3是卤原子;
式(I)的有机硫化合物,其中R2是氰基或C(=O)R5所示基团,且R3是氟原子或氯原子;
式(I)的有机硫化合物,其中R2是氰基,且R3是氟原子或氯原子;
式(I)的有机硫化合物,其中R2是C(=O)R5所示基团,R5是任选被1或2个C1-C4烷基取代的氨基,且R3是氟原子或氯原子;
式(I)的有机硫化合物,其中R2是C(=O)R5所示基团,R5是氨基,且R3是氟原子或氯原子;
式(I)的有机硫化合物,其中n是2,R2是氰基或C(=O)R5所示基团,且R3是卤原子;
式(I)的有机硫化合物,其中n是2,R2是氰基,且R3是卤原子;
式(I)的有机硫化合物,其中n是2,R2是C(=O)R5所示基团,R5是任选被1或2个C1-C4烷基取代的氨基,且R3是卤原子;
式(I)的有机硫化合物,其中n是2,R2是C(=O)R5所示基团,R5是氨基,且R3是卤原子;
式(I)的有机硫化合物,其中n是2,R2是氰基或C(=O)R5所示基团,且R3是氟原子或氯原子;
式(I)的有机硫化合物,其中n是2,R2是氰基,且R3是氟原子或氯原子;
式(I)的有机硫化合物,其中n是2,R2是C(=O)R5所示基团,R5是任选被1或2个C1-C4烷基取代的氨基,且R3是氟原子或氯原子;
式(I)的有机硫化合物,其中n是2,R2是C(=O)R5,R5是氨基,且R3是氟原子或氯原子;
式(I)的有机硫化合物,其中R3是氢原子或卤原子;
式(I)的有机硫化合物,其中R3是氢原子或C1-C4烷基;
式(I)的有机硫化合物,其中R3是卤原子或C1-C4烷基;
式(I)的有机硫化合物,其中R3是氢原子或卤原子,且R4是C1-C3氟烷基;
式(I)的有机硫化合物,其中R3是氢原子或C1-C4烷基,且R4是C1-C3氟烷基;
式(I)的有机硫化合物,其中R3是卤原子或C1-C4烷基,且R4是C1-C3氟烷基。
接下来,描述本发明的化合物的制备方法。
例如,本发明的化合物可以通过遵循以下(制备方法1)到(制备方法12)来制备。
(制备方法1)
可以例如通过使以下化合物(a)和化合物(I-1)反应来制备化合物(I-2),其中在该化合物中R3是C1-C4烷基。
其中R1、R2、R4和n与上述具有相同含义,R3-1代表C1-C4烷基,X代表离去基团如氯原子、溴原子、碘原子、甲磺酰氧基、对甲苯磺酰氧基和三氟甲磺酰氧基。
该反应通常在溶剂中在碱的存在下进行。
用于该反应的溶剂包括,例如,酰胺类(acid amides),例如N,N-二甲基甲酰胺等;醚,例如二乙醚、四氢呋喃等;有机硫化合物,例如二甲亚砜、环丁砜等;卤代烃,例如氯仿、1,2-二氯乙烷、氯苯等;芳烃,例如甲苯、二甲苯等;水;以及它们的混合物。
用于该反应的碱包括,例如,无机碱,例如氢化钠、氢氧化钠、氢氧化钾、碳酸钾等;碱金属醇盐,例如甲醇钠、叔丁醇钾等;碱土金属氨基化物,例如二异丙基氨基化锂(lithium diisopropylamide)等;以及有机碱,例如三乙胺、1,4-二氮杂二环[2.2.2]辛烷、1,8-二氮杂二环[5.4.0]-7-十一烯等。用于该反应的碱量通常为每1摩尔化合物(I-1)使用1到10摩尔的碱。
用于该反应的化合物(a)的量通常是每1摩尔化合物(I-1)使用1到10摩尔。
反应温度通常是-100到100℃,且反应时间通常是1到24小时。
反应结束后,可以通过后处理将化合物(I-2)分离出来,例如将反应混合物倒入水中,用有机溶剂萃取,然后浓缩有机层。如果必要,分离的化合物(I-2)可以通过色谱、重结晶等提纯。
(制备方法2)
可以例如通过使以下化合物(c)和化合物(d)反应来制备化合物(I-3),其中在该化合物中R3是氢原子或C1-C4烷基。
其中R1、R2、R4、n和X具有与上述相同的含义,R3-2表示氢原子或C1-C4烷基。
该反应通常在溶剂中在碱的存在下进行。
用于该反应的溶剂包括,例如,酰胺,如N,N-二甲基甲酰胺等;醚,例如二乙醚、四氢呋喃等;有机硫,例如二甲亚砜、环丁砜等;卤代烃,例如氯仿、1,2-二氯乙烷、氯苯等;芳烃,例如甲苯、二甲苯等;水;和它们的混合物。
用于该反应的碱包括,例如,无机碱,例如氢化钠、氢氧化钠、氢氧化钾、碳酸钾等;碱金属醇盐,例如甲醇钠、叔丁醇钾等;碱金属氨基化物,例如二异丙基氨基化锂等;和有机碱,例如三乙胺、1,4-二氮杂二环[2.2.2]辛烷、1,8-二氮杂二环[5.4.0]-7-十一碳烯等。用于该反应的碱量通常是每1摩尔化合物(d)使用1到10摩尔的碱。
用于该反应的化合物(c)的量通常是每1摩尔化合物(d)使用1到10摩尔的化合物(c)。
反应温度通常是-100到100℃,且反应时间通常是1到24小时。
反应结束之后,可以通过后处理将化合物(I-3)分离,例如将反应混合物倒入水中,用有机溶剂萃取,然后浓缩有机层。如有必要,分离的化合物(I-3)可以通过色谱、重结晶等进行纯化。
可以例如根据(制备方法3)或(制备方法4)来制备化合物(I-4),其中在该化合物中R3是卤原子。
(制备方法3)
该制备方法通过使化合物(I-1)和卤化剂(e)在碱的存在下反应来实现。
其中R1、R2、R4和n具有与上述相同的含义,R3-3表示卤原子。
该反应通常在溶剂中在碱的存在下进行。
用于该反应的溶剂包括,例如,酰胺,如N,N-二甲基甲酰胺等;醚,例如二乙醚、四氢呋喃等;有机硫,例如二甲亚砜、环丁砜等;卤代烃,例如氯仿、1,2-二氯乙烷、氯苯等;芳烃,例如甲苯、二甲苯等;水;和它们的混合物。
用于该反应的碱包括,例如,无机碱,例如氢化钠、氢氧化钠、氢氧化钾、碳酸钾等;碱金属醇盐,例如甲醇钠、叔丁醇钾等;碱金属氨基化物,例如二异丙基氨基化锂等;和有机碱,例如三乙胺、1,4-二氮杂二环[2.2.2]辛烷、1,8-二氮杂二环[5.4.0]-7-十一碳烯等。用于该反应的碱的量碱通常是每1摩尔化合物(I-1)使用1到10摩尔的碱。
用于该反应的卤化剂(e)包括,例如,卤代烃,如四氯化碳、六氯乙烷等;卤素如氟、氯、溴和碘;卤代琥珀酰亚胺如N-氯琥珀酰亚胺、N-溴琥珀酰亚胺、N-碘琥珀酰亚胺等;N-氟代吡啶鎓盐如1-氟-2,4,6-三甲基吡啶鎓三氟甲磺酸盐、1,1′-二氟-2,2′-二吡啶鎓双四氟硼酸盐等;铜卤化物如氯化铜(II)、溴化铜(II)等。
用于该反应的卤化剂(e)的量通常是每1摩尔化合物(I-1)使用1到10摩尔的卤化剂(e)。
反应温度通常是-100到100℃,且反应时间通常是1到24小时。
反应结束之后,可以通过后处理将化合物(I-4)分离,例如将反应混合物倒入水中,用有机溶剂萃取,然后浓缩有机层。如有必要,分离的化合物(I-4)可以通过色谱、重结晶等进行纯化。
(制备方法4)
该制备方法通过使化合物(I-1)和卤化剂(f)在碱的存在下反应来实现。
其中R1、R2、R4、R3-3和n具有与上述相同的含义。
该反应通常是在有或没有溶剂的情况下进行的。
用于该反应的溶剂包括,例如,卤代烃,例如氯仿、四氯化碳、1,2-二氯乙烷、氯苯等;芳烃,例如甲苯、二甲苯等,脂肪腈,例如乙腈、丙腈等;脂肪族羧酸,例如乙酸;二硫化碳;水;及它们的混合物。用于该反应的卤化剂(f)包括,例如,卤素如氟、氯、溴和碘;卤化氢如氟化氢、氯化氢、溴化氢和碘化氢;卤化的硫化合物如亚硫酰氯、亚硫酰溴、磺酰氯等;卤化的磷化合物如三氯化磷、三溴化磷、五氯化磷、三氯氧化磷等。
用于该反应的卤化剂(f)的量通常是每1摩尔化合物(I-1)使用1到10摩尔的卤化剂(f)。
反应温度通常是-100到200℃,且反应时间通常是1到24小时。
反应结束之后,可以通过后处理将化合物(I-4)分离,例如将反应混合物倒入水中,用有机溶剂萃取,然后浓缩有机层。如有必要,分离的化合物(I-4)可以通过色谱、重结晶等进行纯化。
可以根据例如(制备方法5)或(制备方法6)来制备式(I-5)的化合物,其中在该化合物中R2是C(=O)R5表示的基团,R5是C1-C4烷氧基、任选被1或2个C1-C4烷基取代的氨基、或C2-C5环氨基。
(制备方法5)
其中R1、R3、R4、R5和n具有与上述相同的含义,Z代表卤原子。
(步骤5-1)
化合物(i)可以通过使化合物(g)和卤化剂(h)反应来制备。
该反应是在没有溶剂的情况下或者在溶剂中进行的。
用于该反应的溶剂包括,例如,卤代烃,如氯仿、二氯甲烷、1,2-二氯乙烷、氯苯等;芳香烃如甲苯、二甲苯等。
用于该反应的卤化剂(h)包括,例如,草酰氯、亚硫酰氯、亚硫酰溴、三氯化磷、三溴化磷和五氯化磷。用于该反应的卤化剂(h)的量通常是每1摩尔化合物(g)使用1到过量的卤化剂。
反应温度通常是-20到100℃,且反应时间通常是1到24小时。
反应结束后,化合物(i)可以通过进行例如将该反应混合物浓缩的处理来分离。分离的化合物(i)可以通过蒸馏等纯化。
(步骤5-2)
该反应通常是在溶剂中且在碱的存在下进行的。
用于该反应的溶剂包括,例如,酰胺,如N,N-二甲基甲酰胺等;醚,如二乙醚、四氢呋喃等;有机硫化合物,如二甲亚砜、环丁砜等;卤代烃,如氯仿,1,2-二氯乙烷、氯苯等;芳香烃如甲苯、二甲苯等;水;及其混合物。
用于该反应的碱包括,例如,无机碱如氢化钠、氢氧化钠、氢氧化钾、碳酸钾等;以及有机碱如三乙胺、1,4-二氮杂二环[2.2.2]辛烷、1,8-二氮杂二环[5.4.0]-7-十一碳烯等。用于该反应的碱的量通常是每1摩尔化合物(i)使用1到10摩尔碱。
用于该反应的化合物(j)的量通常是每1摩尔化合物(i)使用1到10摩尔的化合物(j)。
反应温度通常是-20到100℃,且反应时间通常是1到24小时。
反应结束后,化合物(I-5)可以通过进行例如下述的后处理来分离:将反应混合物倒入水中,用有机溶剂萃取,然后将有机层浓缩。如有必要,分离的化合物(I-5)可以通过色谱法、重结晶等来提纯。
(制备方法6)
该制备方法是通过使化合物(g)和化合物(j)反应。
其中R1、R3、R4、R5和n具有与上述相同的含义。
该反应通常是在溶剂中且在缩合剂的存在下进行的。
用于该反应的溶剂包括,例如,醚如二乙醚、四氢呋喃等;有机硫化合物如二甲亚砜、环丁砜等;卤代烃如氯仿、1,2-二氯乙烷、氯苯等;以及芳香烃如甲苯、二甲苯等。
用于该反应的缩合剂包括,例如,二环己基碳二亚胺、N-(3-二甲氨基丙基)-N′-乙基碳二亚胺、羰基二咪唑等。
用于该反应的缩合剂的量通常是每1摩尔化合物(g)使用1到10摩尔缩合剂。
用于该反应的化合物(j)的量通常是每1摩尔化合物(q)使用1到10摩尔的化合物(j)。
反应温度通常是-20到100℃,且反应时间通常是1到24小时。
反应结束后,化合物(I-5)可以通过进行例如下述的处理来分离:将反应混合物倒入水中,用有机溶剂萃取,然后将有机层浓缩。如有必要,分离的化合物(I-5)可以通过色谱法、重结晶等来提纯。
(制备方法7)
可以例如通过使以下化合物(c)和化合物(k)反应来制备化合物(I-1),其中在该化合物中R3是氢原子。
其中R1、R2、R4、X和n具有与上述相同的含义。
该反应通常是在溶剂中且在碱的存在下进行的。
用于该反应的溶剂包括,例如,酰胺如N,N-二甲基甲酰胺等;醚如二乙醚、四氢呋喃等;有机硫化合物如二甲亚砜、环丁砜等;卤代烃如氯仿、1,2-二氯乙烷、氯苯等;芳香烃如甲苯、二甲苯等;水;及其混合物。
用于该反应的碱包括,例如,无机碱如氢化钠、氢氧化钠、氢氧化钾、碳酸钾等;碱金属醇盐如甲醇钠、叔丁醇钾等;碱金属氨基化物如二异丙基氨基化锂等;以及有机碱如三乙胺、1,4二氮杂二环[2.2.2]辛烷、1,8-二氮杂二环[5.4.0]-7-十一碳烯等。用于该反应的碱的量通常是每1摩尔化合物(k)使用1到10摩尔碱。
用于该反应的化合物(c)的量通常是每1摩尔化合物(k)使用1到10摩尔的化合物(c)。
反应温度通常是-100到100℃,且反应时间通常是1到24小时。
反应结束后,化合物(I-1)可以通过进行例如下述的后处理来分离:将反应混合物倒入水中,用有机溶剂萃取,然后浓缩有机层。如有必要,分离的化合物(I-1)可以通过色谱法、重结晶等提纯。
(制备方法8)
也可以通过使化合物(I-7)与化合物(p)反应来制备化合物(I-8),其中在化合物(I-7)中R2是C(=O)R5表示的基团,R5是C1-C4烷氧基,且n是2;且其中在化合物(I-8)中R2是C(=O)R5表示的基团,R5是任选被1或2个C1-C4烷基取代的氨基或C2-C5环氨基,且n是2。
其中R1、R3和R4具有与上述相同的含义,R5-1代表C1-C4烷氧基,R5-2代表任选被1或2个C1-C4烷基取代的氨基或C2-C5环氨基。
该反应通常是在溶剂中进行的。
用于该反应的溶剂包括,例如,醚如二乙醚、四氢呋喃等;有机硫化合物如二甲亚砜、环丁砜等;卤代烃如氯仿、1,2-二氯乙烷、氯苯等;以及芳香烃如甲苯、二甲苯等。
用于该反应的化合物(p)的量通常是每1摩尔化合物(I-7)使用1到10摩尔的化合物(p)。
反应温度通常是-20到100℃,且反应时间通常是1到24小时。
反应结束后,化合物(I-8)可以通过进行例如浓缩反应混合物的处理来分离。如有必要,分离的化合物(I-8)也可以通过色谱法、重结晶等来提纯。
(制备方法9)
也可以通过使化合物(I-5)与硫化剂(q)反应来制备化合物(I-9),其中在化合物(I-9)中R2是C(=S)R5所示的基团,且在化合物(I-5)中R2是C(=O)R5所示基团。
其中R1、R3、R4、R5和n具有与上述相同的含义。
该反应通常是在溶剂中进行的。
用于该反应的溶剂包括,例如,卤代烃,如氯仿、1,2-二氯乙烷、氯苯等;芳香烃如甲苯、二甲苯等。
用于该反应的硫化剂(q)包括,例如,无机硫化合物如硫化氢;有机硫化合物如五硫化二磷等;以及2,4-双(4-甲氧苯基)-1,3-二硫代-2,4-二膦烷(phosphetane)2,4-二硫化物等。
用于该反应的硫化剂(q)的量通常是每1摩尔化合物(I-5)使用0.5到10摩尔的硫化剂(q)。
反应温度通常是0到250℃,且反应时间通常是1到72小时。
反应结束后,化合物(I-9)可以通过进行例如浓缩反应混合物的后处理来分离。如有必要,分离的化合物(I-9)可以通过色谱法、重结晶等来提纯。
可以根据(制备方法10)或(制备方法11)来制备化合物(I-10),其中在该化合物中n是0。
(制备方法10)
该制备方法是通过使化合物(r)和化合物(m)反应。
其中R1、R2、R3-2、R4和X具有与上述相同的含义。
该反应通常是在溶剂中且在碱的存在下进行的。
用于该反应的溶剂包括,例如,酰胺如N,N-二甲基甲酰胺等;醚如二乙醚、四氢呋喃等;有机硫化合物如二甲亚砜、环丁砜等;卤代烃如氯仿、1,2-二氯乙烷、氯苯等;芳香烃如甲苯、二甲苯等;水;及其混合物。
用于该反应的碱包括,例如,无机碱如氢化钠、氢氧化钠、氢氧化钾、碳酸钾等;碱金属醇盐如甲醇钠、叔丁醇钾等;碱金属氨基化物如二异丙基氨基化锂等;以及有机碱如三乙胺、1,4二氮杂二环[2.2.2]辛烷、1,8-二氮杂二环[5.4.0]-7-十一碳烯等。
用于该反应的碱的量通常是每1摩尔化合物(r)使用1到10摩尔碱。
用于该反应的化合物(m)的量通常是每1摩尔化合物(r)使用1到10摩尔的化合物(m)。
反应温度通常是-20到100℃,且反应时间通常是1到24小时。
反应结束后,化合物(I-10)可以通过进行例如下述的后处理来分离:将反应混合物倒入水中,用有机溶剂萃取,然后浓缩有机层。如有必要,分离的化合物(I-10)可以通过色谱法、重结晶等提纯。
(制备方法11)
该制备方法是通过使化合物(s)和化合物(o)反应。
其中R1、R2、R3-2、R4和X具有与上述相同的含义。
该反应通常是在溶剂中且在碱的存在下进行的。
用于该反应的溶剂包括,例如,酰胺如N,N-二甲基甲酰胺等;醚如二乙醚、四氢呋喃等;有机硫化合物如二甲亚砜、环丁砜等;卤代烃如氯仿、1,2-二氯乙烷、氯苯等;芳香烃如甲苯、二甲苯等;水;及其混合物。
用于该反应的碱包括,例如,无机碱如氢化钠、氢氧化钠、氢氧化钾、碳酸钾等;碱金属醇盐如甲醇钠、叔丁醇钾等;碱金属氨基化物如二异丙基氨基化锂等;以及有机碱如三乙胺、1,4二氮杂二环[2.2.2]辛烷、1,8-二氮杂二环[5.4.0]-7-十一碳烯等。用于该反应的碱的量通常是每1摩尔化合物(o)使用1到10摩尔碱。
用于该反应的化合物(s)的量通常是每1摩尔化合物(o)使用1到10摩尔的化合物(s)。
反应温度通常是-20到100℃,且反应时间通常是1到24小时。
反应结束后,化合物(I-10)可以通过进行例如下述的后处理来分离:将反应混合物倒入水中,用有机溶剂萃取,然后浓缩有机层。如有必要,分离的化合物(I-10)可以通过色谱法、重结晶等提纯。
(制备方法12)
以通过使化合物(I-10)氧化来制备化合物(I-11),其中在该化合物中n是1或2。
其中R1、R2、R3-2和R4具有与上述相同的含义,n′代表1或2。
该反应通常是在溶剂中且在氧化剂的存在下进行的。
用于该反应的溶剂包括,例如,醇如甲醇、乙醇等;卤代烃如二氯甲烷、氯仿等;芳香烃如甲苯、二甲苯等;脂肪族羧酸如乙酸、三氟乙酸等;水;及其混合物。
用于该反应的氧化剂包括,例如,过酸如过乙酸、三氟过乙酸、间氯过苯甲酸等;卤素分子如氯和溴;卤代琥珀酰亚胺如N-氯代琥珀酰亚胺;高卤化化合物如高氯酸或其盐、高碘酸或其盐等;高锰酸盐如高锰酸钾等;铬酸盐如铬酸钾等;以及过氧化氢。用于该反应的氧化剂的量通常是每1摩尔化合物(I-10)使用1到10摩尔氧化剂。
反应温度通常是-50到200℃,且反应时间通常是1到72小时。
反应结束后,化合物(I-11)可以通过进行例如下述的后处理来分离:将反应混合物倒入水中,用有机溶剂萃取,然后将有机层浓缩。如有必要,分离的化合物(I-11)可以通过色谱法、重结晶等来提纯。
接下来,说明本发明的化合物的中间体化合物的制备方法作为参考制备方法。
(参考制备方法1-1)
化合物(g)可以通过使化合物(I-6)在酸的存在下水解来制备。
其中R1、R3、R4和n具有与上述相同的含义,R5-3代表甲氧基或乙氧基。
反应通常在水的存在下并通常在有机溶剂中进行。
用于该反应的有机溶剂包括,例如,醇如甲醇、乙醇等;醚如二乙醚、四氢呋喃等;有机硫化合物如二甲亚砜、环丁砜等;卤代烃如氯仿、1,2-二氯乙烷、氯苯等;芳香烃如甲苯、二甲苯等;脂肪族羧酸如甲酸、乙酸等;水;及其混合物。
用于该反应的酸包括,例如,无机酸如盐酸、硫酸等。
用于该反应的酸的量通常是每1摩尔化合物(I-6)使用1到10摩尔酸。
反应温度通常是-20到100℃,且反应时间通常是1到24小时。
反应结束后,化合物(g)可以通过进行例如下述的后处理来分离:将水倒入反应混合物中,用有机溶剂萃取,然后浓缩有机层。如有必要,分离的化合物(g)可以通过色谱法、重结晶等来提纯。
(参考制备方法1-2)
化合物(g)可以通过使化合物(I-6)在碱的存在下水解来制备。
反应通常在水的存在下并通常在有机溶剂中进行。
用于该反应的有机溶剂包括,例如,醇如甲醇、乙醇等;醚如二乙醚、四氢呋喃等;有机硫化合物如二甲亚砜、环丁砜等;芳香烃如甲苯、二甲苯等;及其混合物。
用于该反应的碱包括,例如,无机碱如氢氧化钠、氢氧化钾等。
用于该反应的碱的量通常是每1摩尔化合物(I-6)使用1到10摩尔碱。
反应温度通常是-20到100℃,且反应时间通常是1到24小时。
反应结束后,化合物(g)可以通过进行例如下述的后处理来分离:将水和酸倒入反应混合物中,用有机溶剂萃取,然后浓缩有机层。如有必要,分离的化合物(g)可以通过色谱法、重结晶等来提纯。
(参考制备方法2)
可以例如通过使以下化合物(a)和化合物(k)反应来制备化合物(d-1),其中在化合物(d)中R3-2是C1-C4烷基。
其中R2、R4、R3-1、n和X具有与上述相同的含义。
该反应通常是在溶剂中且在碱的存在下进行的。
用于该反应的溶剂包括,例如,酰胺如N,N-二甲基甲酰胺等;醚如二乙醚、四氢呋喃等;有机硫化合物如二甲亚砜、环丁砜等;卤代烃如氯仿、1,2-二氯乙烷、氯苯等;芳香烃如甲苯、二甲苯等;水;及其混合物。
用于该反应的碱包括,例如,无机碱如氢化钠、氢氧化钠、氢氧化钾、碳酸钾等;碱金属醇盐如甲醇钠、叔丁醇钾等;碱金属氨基化物如二异丙基氨基化锂等;以及有机碱如三乙胺、1,4二氮杂二环[2.2.2]辛烷、1,8-二氮杂二环[5.4.0]-7-十一碳烯等。用于该反应的碱的量通常是每1摩尔化合物(k)使用1到10摩尔碱。
用于该反应的化合物(a)的量通常是每1摩尔化合物(k)使用1到10摩尔的化合物(a)。
反应温度通常是-20到100℃,且反应时间通常是1到24小时。
反应结束后,化合物(d-1)可以通过进行例如下述的后处理来分离:将反应混合物倒入水中,用有机溶剂萃取,然后浓缩有机层。如有必要,分离的化合物(d-1)可以通过色谱法、重结晶等提纯。
(参考制备方法3)
可以根据以下方案来制备化合物(k-1)(其中n是0)和化合物(k-2)(其中n是1或2)。
其中R2、R4、X和n′具有与上述相同的含义。
(步骤III-1-a)
化合物(k-1)可以通过使化合物(1)和化合物(m)反应来制备。
该反应通常是在溶剂中且在碱的存在下进行的。
用于该反应的溶剂包括,例如,酰胺如N,N-二甲基甲酰胺等;醚如二乙醚、四氢呋喃等;有机硫化合物如二甲亚砜、环丁砜等;卤代烃如氯仿、1,2-二氯乙烷、氯苯等;芳香烃如甲苯、二甲苯等;水;及其混合物。
用于该反应的碱包括,例如,无机碱如氢化钠、氢氧化钠、氢氧化钾、碳酸钾等;碱金属醇盐如甲醇钠、叔丁醇钾等;碱金属氨基化物如二异丙基氨基化锂等;以及有机碱如三乙胺、1,4二氮杂二环[2.2.2]辛烷、1,8-二氮杂二环[5.4.0]-7-十一碳烯等。
用于该反应的碱的量通常是每1摩尔化合物(1)使用1到10摩尔碱。
用于该反应的化合物(m)的量通常是每1摩尔化合物(1)使用1到10摩尔的化合物(m)。
反应温度通常是-20到100℃,且反应时间通常是1到24小时。
反应结束后,化合物(k-1)可以通过进行例如下述的后处理来分离:将反应混合物倒入水中,用有机溶剂萃取,然后将有机层浓缩。如有必要,分离的化合物(k-1)可以通过色谱法、重结晶等来提纯。
(步骤III-1-b)
化合物(k-1)还可以通过使化合物(n)和化合物(o)反应来制备。
该反应通常是在溶剂中且在碱的存在下进行的。用于该反应的溶剂包括,例如,酰胺如N,N-二甲基甲酰胺等;醚如二乙醚、四氢呋喃等;有机硫化合物如二甲亚砜、环丁砜等;卤代烃如氯仿、1,2-二氯乙烷、氯苯等;芳香烃如甲苯、二甲苯等;水;及其混合物。
用于该反应的碱包括,例如,无机碱如氢化钠、氢氧化钠、氢氧化钾、碳酸钾等;碱金属醇盐如甲醇钠、叔丁醇钾等;碱金属氨基化物如二异丙基氨基化锂等;以及有机碱如三乙胺、1,4二氮杂二环[2.2.2]辛烷、1,8-二氮杂二环[5.4.0]-7-十一碳烯等。用于该反应的碱的量通常是每1摩尔化合物(o)使用1到10摩尔碱。
用于该反应的化合物(n)的量通常是每1摩尔化合物(o)使用1到10摩尔的化合物(n)。
反应温度通常是-20到100℃,且反应时间通常是1到24小时。
反应结束后,化合物(k-1)可以通过进行例如下述的后处理来分离:将反应混合物倒入水中,用有机溶剂萃取,然后将有机层浓缩。如有必要,分离的化合物(k-1)可以通过色谱法、重结晶等来提纯。
(步骤III-2)
化合物(k-2)可以例如通过使化合物(k-1)氧化来制备。
该反应通常是在溶剂的存在下且在氧化剂的存在下进行的。
用于该反应的溶剂包括,例如,醇如甲醇、乙醇等;卤代烃如二氯甲烷、氯仿等;芳香烃如甲苯、二甲苯等;脂肪族羧酸如乙酸、三氟乙酸等;水;及其混合物。
用于该反应的氧化剂包括,例如,过酸如过乙酸、三氟过乙酸、间氯过苯甲酸等;卤素分子如氯和溴;卤代琥珀酰亚胺如N-氯代琥珀酰亚胺;高卤化化合物如高氯酸或其盐、高碘酸或其盐等;高锰酸盐如高锰酸钾等;铬酸盐如铬酸钾等;以及过氧化氢。用于该反应的氧化剂的量通常是每1摩尔化合物(k-1)使用1到10摩尔氧化剂。
反应温度通常是-50到200℃,且反应时间通常是1到72小时。
反应结束后,化合物(k-2)可以通过进行例如下述的处理来分离:将反应混合物倒入水中,用有机溶剂萃取,然后将有机层浓缩。如有必要,分离的化合物(k-2)可以通过色谱法、重结晶等来提纯。
上述化合物(o)和(s)均可以通过例如The Journal of OrganicChemistry,27(1),93-95页(1962)和HETEROCYCLES,24(5),1331-1346页(1986)中所述的相同方法制备。
上述化合物(t)可以通过例如The Journal of Organic Chemistry,18,1112-1116页(1953)中所述的相同方法制备。
本发明的化合物对其具有控制活性的有害节肢动物可以包括昆虫害虫、螨虫害虫等。具体例子如下所列:
半翅目:
飞虱科(delphacidae),如灰飞虱(laodelphax striatellus)、褐飞虱(nilaparvata lugens)、白背稻虱(sogatella furcifera)等,
浮尘子科(Deltocephalidae),如黑尾叶蝉,二点黑尾叶蝉等,
蚜科,如棉蚜、烟蚜、甘蓝蚜、大戟长管蚜、茄沟无网蚜、禾谷缢管蚜、桔蚜等,
蝽科,如稻绿椿象、点蜂缘椿象、Eysarcoris lewisi、白星蝽、小珀蝽象、Halyomorpha mista、赤条纤盲蝽、赤须盲蝽等,
粉虱科,如温室粉虱、银叶粉虱等,
蜡蚧科,如红圆蹄盾蚧、梨圆蚧、桔矢尖盾蚧、红蜡蚧、吹绵蚧等,
网蝽科,
臭虫科,如温带臭虫,
木虱科等;
鳞翅目:
螟蛾科,如二化螟、稻纵卷叶野螟、棉大卷叶螟、印度谷螟、豆荚野螟、菜心野螟、Pediasia teterrellus等、
夜蛾科,如斜纹夜蛾、粘虫、粉纹夜蛾、棉花实夜蛾、棉铃虫蛾等,
粉蝶科,如菜青虫等,
卷蛾科,如茶小卷叶蛾、梨小食心虫、苹果小卷蛾等,
果蛀蛾科,如桃蛀果蛾等,
潜蛾科如Lyonetia spp等,
毒蛾科,如舞毒蛾、黄毒蛾等,
巢蛾科,如菜蛾等,
细蛾科,如茶细蛾、Phyllonorycter ringoneella等,
麦蛾科,如棉红铃虫等,
灯蛾科,如美国白蛾等,
谷蛾科,如衣蛾、幕谷蛾等;
双翅目:
库蚊科,如淡色库蚊、三带喙库蚊、致倦库蚊等,
伊蚊科,如埃及伊蚊、白纹伊蚊等,
疟蚊科,如中华按蚊等,
摇蚊科,
蝇科,如家蝇、厩腐蝇等,
丽蝇科,
麻蝇科,
厕蝇科,
花蝇科,如灰地种蝇、葱地种蝇等,
潜蝇科,如三叶斑潜蝇,
实蝇科,
果蝇科,
蚤蝇科,如东亚异蚤蝇,
毛蠓科,如毛蠓,
虻科,
蚋科,
螫蝇科等;
鞘翅目:
甲虫(Diabrotica)科,如玉米根萤叶甲、黄瓜十一星叶甲等,
金龟科,如铜色丽金龟、红铜丽金龟等,
象虫科,如玉米象、稻水象甲、裸露绿豆象等,
拟步行虫科比如面粉甲虫、赤拟谷盗等,
叶甲科,如水稻负泥虫,黄守瓜、黄曲条菜跳甲、马铃薯甲虫等,
皮蠹科,如白腹皮蠹,
窃蠹科,
豆甲科,如酸浆瓢虫等,
粉蠹科,
长蠹科,
天牛科,
天牛科,
毒隐翅虫等;
蟑螂目:德国小蠊、黑胸大蠊、美洲大蠊、褐斑大蠊、东方蠊等;
缨翅目:棕榈蓟马、烟蓟马、西花蓟马、花蓟马、茶黄蓟马等;
膜翅目:
蚁科,如Monomorium pharaosis、丝光褐林蚁、无毛凹臭蚁、坚硬双针家蚁、宽结大头蚁、阿根廷蚁等,
胡蜂科,
肿腿蜂科,
叶蜂科,如日本芜菁叶蜂等;
直翅目:蝼蛄科、蝗科、蟋蟀科等;
蚤目:猫蚤、犬栉首蚤、人蚤、印鼠客蚤等;
虱目:体虱、阴虱、阔胸血虱、Dalmalinia ovis、Haemaopinus suis等;
等翅目:黄胸散白蚁,家白蚁,犀白蚁科如黄肢散白蚁、Reticulitermes hesperus、南方散白蚁、Reticulitermes tibialis、Heterotermesaureus等,木白蚁科如小楹白蚁;草白蚁如内华达动白蚁等;
蜱螨目:
叶螨科,如二斑叶螨,神泽氏叶螨、柑桔全爪螨、苹果全爪螨、Oligonychus spp.等,
瘿螨科,如Aculops lycopers、Aculops pelekassi、Aculus schlechtendali等,
跗绒螨科,如侧多食跗线螨等,
细须螨科,
杜克螨科,
蜱科,如长角血蜱,
褐黄血蜱、变异革蜱、褐黄血蜱、Dermacentor taiwanicus、卵形硬蜱、全沟硬蜱、有胛硬蜱、微小牛蜱、美洲花蜱、血红扇头蜱等,
粉螨科,如腐食酪螨等,
尘螨科,如粉尘螨、屋尘螨等,
肉食螨科,如普通肉食螨、马六甲肉食螨、Cheyletus moorei等,
柏氏禽刺螨,Ornithonyssus sylvairum,
皮刺螨科,如鸡皮刺螨;
恙螨,如红纤沙螨,
蜘蛛目:日本红螯蛛、红色寡妇蜘蛛等;
唇足纲:Thereuonema hilgendorfi、模棘蜈蚣等;
倍足亚纲:雅丽酸马陆(oxidue gracilis)、Nedyopus tambanus等;
等足目:鼠妇等;
腹足纲:Limax marginatus、黄蛞蝓等。
本发明的有害节肢动物控制剂包括本发明的化合物和惰性载体。通常,本发明的化合物与固体载体、液体载体和/或气体载体混合,并且如有必要,加入表面活性剂及其他配制助剂以配制成可乳化浓缩物、油溶液、香波制剂、流动剂、粉尘、可润湿性粉剂、颗粒、糊状制剂、微胶囊、泡沫、气溶胶、二氧化碳气制剂、片剂和树脂制剂。这些制剂可以转化为用于毒饵、蚊香、电蚊香片、烟雾剂、薰剂或薰片。
在本发明的有害节肢动物控制剂中,通常含有0.1-95重量%的本发明的化合物。
用于制剂的固体载体包括,例如,粘土的细粉和颗粒(例如,高岭粘土、硅藻土、皂土、Fubasami粘土、酸性粘土等)、合成水合二氧化硅、滑石、陶瓷、其它无机矿物(例如,绢云母、石英、硫、活性碳、碳酸钙、水合氧化硅)或化学肥料(例如,硫酸铵、磷酸铵、硝酸铵、氯化铵、尿素)。
用于制剂的液体载体包括,例如,芳香烃或脂肪烃(例如,二甲苯、甲苯、烷基萘、苯基二甲苯基乙烷、煤油、轻油、己烷、环己烷)、卤代烃(例如,氯苯、二氯甲烷、二氯乙烷、三氯乙烷)、醇(例如,甲醇、乙醇、异丙醇、丁醇、己醇、乙二醇)、醚(例如,二乙醚、乙二醇二甲醚、二甘醇一甲醚、二甘醇一乙醚、丙二醇单甲醚、四氢呋喃、二氧杂环乙烷)、酯(例如,乙酸乙酯、醋酸丁酯)、酮(例如,丙酮、甲基乙基酮、甲基异丁基酮、环己酮)、腈(例如,乙腈、异丁腈)、亚砜(例如,二甲亚砜)、酰胺(例如,N,N-二甲基甲酰胺、N,N-二甲基乙酰胺)、植物油(例如,大豆油、棉子油)、植物精油(例如,橙油、海索油、柠檬油)和水。
用于制剂的气体载体包括,例如,丁烷气、氟冷气、液化石油气(LPG)、二甲醚、二氧化碳等。
表面活性剂包括例如烷基硫酸盐、烷基磺酸酸盐、烷基芳基磺酸盐、烷基芳基醚及其聚氧乙烯衍生物、聚乙二醇醚、多元醇酯和糖醇衍生物。
用于制剂的其它助剂包括粘合剂、分散剂、稳定剂等,具体地说,例如酪蛋白、凝胶、多糖(例如,淀粉、阿拉伯树胶、纤维素衍生物、藻酸)、木质素衍生物、皂土、糖、合成水溶性聚合物(例如,聚乙烯醇、聚乙烯基吡咯烷酮、聚丙烯酸)、PAP(酸式磷酸异丙酯)、BHT(2,6-二叔丁基-4-甲酚)、BHA(2-叔丁基-4-甲氧基苯酚和3-叔丁基-4-甲氧基苯酚的混合物)、植物油、矿物油、脂肪酸和脂肪酸酯。
用于树脂制剂的基质包括,例如,聚氯乙烯基共聚物、聚氨酯等。如有必要,可以向这些基质中加入增塑剂如邻苯二甲酸酯(例如,邻苯二甲酸二甲酯、邻苯二甲酸二辛酯)、己二酸酯和硬脂酸。树脂制剂可以通过下述方法获得:使用已知的捏和机,将化合物捏和到基质中,然后通过注模法、挤塑法、压模法等配制,而且,如有必要,通过铸模法、切割法等,可以将具有一定形状的树脂制剂转变为例如板、膜、带、网、线等的树脂制剂。这些树脂制剂可以转变为例如动物颈圈、动物耳标、片状制剂、吸力线(attraction string)、花插。
用于毒饵的基质包括例如谷物粉末、植物油、糖和结晶纤维素,而且,如有必要,可以向基质中加入抗氧化剂如二丁基羟基甲苯和去甲二氢愈创木酸、防腐剂如脱氢乙酸、防止儿童和宠物误食的药剂如辣椒末、以及吸引害虫的香料如干酪味香料、洋葱味香料和花生油。
本发明的有害节肢动物控制剂通过,例如,直接施用于有害节肢动物和/或施用于有害节肢动物栖息地如植物、动物土壤等来使用。
当本发明的有害节肢动物控制剂用于控制农林害虫时,施用量以活性成分计通常是1到10,000g/ha,优选10到500g/ha。可乳化浓缩物、可湿性粉剂、流动剂和微胶囊制剂通常在用水稀释到活性成分浓度为1到1,000ppm之后施用,而粉尘和颗粒通常直接施用。这些制剂可以直接喷洒到植物上以保护其不受有害节肢动物侵害。生活在土壤中的有害节肢动物可以通过用这些制剂处理土壤来控制,且该制剂还可以在栽植植物之前施用于苗床、或用于处理栽植穴、或者在栽植中施用于植物底部。而且,片状制剂的本发明的有害节肢动物控制剂可以通过下述方法使用:例如环绕植物、在植物附近延伸、以及敷设在植物底部的土表上。
当本发明的有害节肢动物控制剂用于控制流行病时,施用量通常为:在开放空间的情况下,以活性成分计为0.001-10mg/m3,且在用于平面的情况下,以活性成分计为0.001-100mg/m2。可乳化浓缩物、可湿性粉剂和流动剂通常在用水稀释到活性成分浓度为0.01到10,000ppm之后施用,而油性溶液、气溶胶、烟雾剂和毒饵通常直接施用。
当本发明的有害节肢动物控制剂用于控制生活在家畜(如牛、马、猪、绵羊、山羊和鸡)、以及小动物(如狗、猫、大鼠和小鼠)体外的寄生虫时,本发明的有害节肢动物控制剂可以通过兽医已知的方法来施用于所述动物。具体地说,对于全身控制,本发明的有害节肢动物控制剂通过例如片剂、与饲料的混合物、栓剂或注射剂(例如,肌内、皮下、静脉内、腹膜内注射)的方式给药,而对于非全身控制,其通过例如下述的方法给药:喷洒油溶液或水性液体制剂、进行倾注处理或点涂处理、用香波制剂冲洗所述动物、将树脂制剂作为颈圈或耳标附着在所述动物上等。当其给药于动物时,本发明的化合物的量通常是0.1-1,000mg/kg动物体重。
本发明的有害节肢动物控制剂还可以以与其他杀虫剂、杀线虫剂、杀螨剂、杀真菌剂、除草剂、植物生长调节剂、增效剂、肥料、土壤调节剂、动物饲料等的混合物或组合的形式施用。
这种其它杀虫剂和杀螨剂的活性成分包括,例如,拟除虫菊酯化合物,如丙烯除虫菊酯、胺菊酯、炔丙菊酯、苯醚菊酯、苄呋菊酯、苯醚氰菊酯、氯菊酯、氯氰菊酯、α-氯氰菊酯、ξ-氯氰菊酯、溴氰菊酯、四溴菊酯、氟氯氰菊酯、β-氟氯氰菊酯、三氟氯氰菊酯、微升-三氟氯氰菊酯、氟氯苯菊酯、炔咪菊酯、醚菊酯、氰戊菊酯、亚尔发菊酯、杀螨菊酯、氟硅菊酯、联苯菊酯、四氟苯菊酯、氟氰菊酯、τ-氟胺氰菊酯、氟丙菊酯、七氟菊酯、稻虫菊酯、烯炔菊酯、3-(2-甲基-1-丙烯基)-2,2-二甲基环丙烷甲酸2,3,5,6-四氟-4-甲氧基甲基苄酯、3-(1-丙烯基)-2,2-二甲基环丙烷甲酸2,3,5,6-四氟-4-甲氧基甲基苄酯和3-(1-丙烯基)-2,2-二甲基环丙烷甲酸2,3,5,6-四氟-4-甲基苄酯;有机磷酸酯化合物,如敌敌畏、杀螟松、杀螟腈、丙溴磷、虫螨消、稻丰散、异噁唑磷、杀虫畏、倍硫磷、毒死蜱、二嗪农、乙酰甲胺磷、特丁甲拌磷、甲拌磷、氯氧磷、噻唑磷、灭克磷、硫线磷和杀扑磷;氨基甲酸酯化合物,如残杀威、西维因、噁虫酮、仲丁威、灭多虫、硫双灭多威、棉铃成、丙硫威、草氨酰、涕灭威和灭虫威;苯甲酰基苯基脲化合物,如八氟脲、定虫隆、六伏隆、除虫脲、杀铃脲、伏虫脲、氟虫脲、氟啶蜱脲、双苯氟脲杀虫剂和triazuron;保幼激素样物质,如吡丙醚、烯虫酯、烯虫乙酯和苯氧威;新烟碱化合物,如啶虫脒、烯啶虫胺、噻虫啉、噻虫嗪、呋虫胺和可尼丁;N-苯基吡唑化合物,如乙酰虫腈和乙虫清;苯甲酰基肼化合物,如虫酰肼、环虫酰肼、甲氧虫酰肼和卤虫酰肼;杀螨隆;吡蚜酮;氟啶虫酰胺;唑蚜威;稻虱净;多杀菌素;甲氨基阿维菌素苯甲酸盐;虫螨腈;茚虫威;啶虫丙醚;灭蝇胺;唑螨酯;吡螨胺;唑虫酰胺;达螨酮;嘧螨醚;嘧螨酯;乙螨唑;喹螨醚;灭螨醌;噻螨酮;四螨嗪;六苯丁锡氧;三氯杀螨醇、克螨特;伊维菌素;密灭汀;阿米曲拉;巴丹;杀虫磺;噻环氨;硫丹;季酮螨酯;螺甲螨酯;氟虫酰胺;和印苦楝子素。
其它杀真菌剂包括,例如,strobilurin化合物,如嘧菌酯;有机磷酸酯化合物,如灭菌磷;吡咯化合物,如氟菌唑、稻瘟酯和苯醚甲环唑;苯酞;氟酰胺;有效霉素;噻菌灵;哒菌酮;纹枯脲;棉隆;春日霉素;IBP;咯喹酮;恶喹酸;三环唑;嘧菌腙;担菌宁;EDDP;稻瘟灵;carproparnid;双氯氰菌胺;羟基福拉比;咯菌腈;二甲菌核利;和乙霉威。
通过制备例、配方例、实验例等来更详细地构筑本发明。
首先,说明本发明的化合物的制备例。
制备例1
将0.6克1-碘-3,3,3-三氟丙烷和0.5克(3,3,3-三氟丙磺酰基)乙腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.1克氢化钠(60%,在油中),混合物在相同温度下搅拌24小时。然后,向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。用氯化钠的饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到1.44克5,5,5-三氟-2-(3,3,3-三氟丙磺酰基)戊腈(以下称为本发明的化合物(1))。
本发明的化合物(1)
1H-NMR(CDCl3,TMS):δ(ppm)4.00-4.07(m,1H),3.44-3.62(m,2H),2.72-2.87(m,2H),2.36-2.64(m,4H)
制备例2
将0.7克2,2,3,3,3-五氟丙基三氟甲磺酸酯和0.5克(3,3,3-三氟丙磺酰基)乙腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.3克碳酸钾,混合物在相同温度下搅拌40小时。然后,向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。用氯化钠的饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.40克4,4,5,5,5-五氟-2-(3,3,3-五氟丙磺酰基)戊腈(以下称为本发明的化合物(2))。
本发明的化合物(2)
1H-NMR(CDCl3,TMS):δ(ppm)4.22(dd,1H),3.54-3.72(m,2H),2.76-3.06(m,4H)
制备例3
将0.6克1-碘-3,3,4,4,4-五氟丁烷和0.4克(3,3,3-三氟丙磺酰基)乙腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.09克氢化钠(60%,在油中),混合物在相同温度下搅拌20小时。然后,向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。用氯化钠的饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到1.44克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己腈(以下称为本发明的化合物(3))。
本发明的化合物(3)
1H-NMR(CDCl3,TMS):δ(ppm)4.01-4.08(m,1H),3.44-3.62(m,2H),2.73-2.88(m,2H),2.28-2.62(m,4H)
制备例4
将0.9克2,2,3,3,4,4,4-七氟丁基三氟甲磺酸酯和0.5克(3,3,3-三氟丙磺酰基)乙腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.3克碳酸钾,混合物在相同温度下搅拌28小时。然后,向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。用氯化钠的饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.40克4,4,5,5,6,6,6七氟2(3,3,3三氟丙磺酰基)己腈(以下称为本发明的化合物(4))。
本发明的化合物(4)
1H-NMR(CDCl3,TMS):δ(ppm)4.22(dd,1H),3.55-3.72(m,2H),2.78-3.10(m,4H)
制备例5
将0.8克1-碘-3,3,4,4,5,5,5-七氟戊烷和0.5克(3,3,3-三氟丙磺酰基)乙腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.1克氢化钠(60%,在油中),混合物在相同温度下搅拌24小时。然后,向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。用氯化钠的饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.45克5,5,6,6,7,7,7-七氟-2-(3,3,3-三氟丙磺酰基)庚腈(以下称为本发明的化合物(5))。
本发明的化合物(5)
1H-NMR(CDCl3,TMS):δ(ppm)4.04-4.08(m,1H),3.46-3.63(m,2H),2.73-2.88(m,2H),2.34-2.64(m,4H)
制备例6
将1.3克三氟甲磺酸2,2,3,3,4,4,5,5-八氟戊基酯和0.7克(3,3,3-三氟丙磺酰基)乙腈溶解到30毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.5克碳酸钾,混合物在相同温度下搅拌20小时。然后,向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。用氯化钠的饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.32克4,4,5,5,6,6,7,7-八氟-2-(3,3,3-三氟丙磺酰基)庚腈(以下称为本发明的化合物(6))。
本发明的化合物(6)
1H-NMR(CDCl3,TMS):δ(ppm)6.05(tt,1H),4.21(dd,1H),3.50-3.71(m,2H),2.70-3.09(m,4H)
制备例7
将1.3克1-碘-3,3,4,4,5,5,6,6,6-九氟己烷和0.7克(3,3,3-三氟丙磺酰基)乙腈溶解到30毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.1克碳酸钾,混合物在相同温度下搅拌6小时。然后,向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。用氯化钠的饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.59克5,5,6,6,7,7,8,8,8-九氟-2-(3,3,3-三氟丙磺酰基)辛腈(以下称为本发明的化合物(7))。
本发明的化合物(7)
1H-NMR(CDCl3,TMS):δ(ppm)4.02-4.08(m,1H),3.45-3.63(m,2H),2.73-2.86(m,2H),2.34-2.63(m,4H)
制备例8
将0.6克1-碘-3,3,4,4,4-五氟丁烷和0.4克(3,3,4,4,4-五氟丁磺酰基)乙腈溶解到50毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.5克氢化钠(60%,在油中),混合物在相同温度下搅拌4天。然后,向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。用氯化钠的饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到2.66克5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己腈(以下称为本发明的化合物(8))。
本发明的化合物(8)
1H-NMR(CDCl3,TMS):δ(ppm)4.04-4.09(m,1H),3.48-3.68(m,2H),2.67-2.82(m,2H),2.31-2.61(m,4H)
制备例9
将0.7克三氟甲磺酸2,2,3,3,4,4,4-七氟丁基酯和0.5克(3,3,4,4,4-五氟丁磺酰基)乙腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.3克碳酸钾,混合物在相同温度下搅拌40小时。然后,向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。用氯化钠的饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.38克4,4,5,5,6,6,6-七氟-2-(3,3,4,4,4-五氟丁磺酰基)己腈(以下称为本发明的化合物(9))。
本发明的化合物(9)
1H-NMR(CDCl3,TMS):δ(ppm)4.22(dd,1H),3.56-3.76(m,2H),2.68-3.10(m,4H)
制备例10
将1.8克1-碘-3,3,4,4,4-五氟丁烷和2.0克(3,3,4,4,5,5,5-七氟戊磺酰基)乙腈溶解到50毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.3克氢化钠(60%,在油中),混合物在相同温度下搅拌20小时。然后,向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。用氯化钠的饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到1.43克2-(3,3,4,4,5,5,5-七氟戊磺酰基)-5,5,6,6,6-五氟己腈(以下称为本发明的化合物(10))。
本发明的化合物(10)
1H-NMR(CDCl3,TMS):δ(ppm)4.07(dd,1H),3.48-3.67(m,2H),2.32-2.85(m,6H)
制备例11
将0.2克碘代甲烷和0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.06克氢化钠(60%,在油中),混合物在相同温度下搅拌20小时。然后,向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。用氯化钠的饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.35克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己腈(以下称为本发明的化合物(11))。
本发明的化合物(11)
1H-NMR(CDCl3,TMS):δ(ppm)3.40-3.58(m,2H),2.73-2.88(m,2H),2.16-2.58(m,4H),1.83(s,3H)
制备例12
将0.3克碘代甲烷和0.7克4,4,5,5,6,6,6-七氟-2-(3,3,3-三氟丙磺酰基)己腈溶解到30毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.07克氢化钠(60%,在油中),混合物在相同温度下搅拌24小时。然后,向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。用氯化钠的饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.32克4,4,5,5,6,6,6-七氟-2-甲基-2-(3,3,3-三氟丙磺酰基)己腈(以下称为本发明的化合物(12))。
本发明的化合物(12)
1H-NMR(CDCl3,TMS):δ(ppm)3.48-3.65(m,2H),2.61-3.13(m,4H),2.00(d,3H)
制备例13
将0.2克碘甲烷和0.5克5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.05克氢化钠(在油中,60%),混合物在相同温度下搅拌20小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.49克2-甲基-5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己腈(以下称为本发明的化合物(13))。
本发明的化合物(13)
1H-NMR(CDCl3,TMS):δ(ppm)3.42-3.61(m,2H),2.68-2.82(m,2H),2.18-2.58(m,4H),1.84(s,3H)
制备例14
将0.2克碘甲烷和0.5克5,5,6,6,6-五氟-2-(3,3,4,4,5,5,5-七氟戊磺酰基)己腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.05克氢化钠(在油中,60%),混合物在相同温度下搅拌2天。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.49克2-(3,3,4,4,5,5,5-七氟戊磺酰基)-2-甲基-5,5,6,6,6-五氟己腈(以下称为本发明的化合物(14))。
本发明的化合物(14)
1H-NMR(CDCl3,TMS):δ(ppm)3.42-3.61(m,2H),2.68-2.82(m,2H),2.18-2.58(m,4H),1.84(s,3H)
制备例15
将0.2克碘乙烷和0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.06克氢化钠(在油中,60%),混合物在相同温度下搅拌10小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.37克2-乙基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己腈(以下称为本发明的化合物(15))。
本发明的化合物(15)
1H-NMR(CDCl3,TMS):δ(ppm)3.39-3.58(m,2H),2.72-2.84(m,2H),2.32-2.56(m,4H),2.06-2.26(m,2H),1.28(t,3H)
制备例16
将0.2克1-碘丙烷和0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.06克氢化钠(在油中,60%),混合物在相同温度下搅拌24小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.38克5,5,6,6,6-五氟-2-丙基-2-(3,3,3-三氟丙磺酰基)己腈(以下称为本发明的化合物(16))。
本发明的化合物(16)
1H-NMR(CDCl3,TMS):δ(ppm)3.38-3.58(m,2H),2.72-2.86(m,2H),2.32-2.58(m,4H),1.95-2.11(m,2H),1.58-1.72(m,2H),1.10(t,3H)
制备例17
将0.2克2-碘丙烷和0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.06克氢化钠(在油中,60%),混合物在相同温度下搅拌6小时,在60℃下搅拌2小时,并且在90℃下搅拌6小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.13克5,5,6,6,6-五氟-2-(2-丙基)-2-(3,3,3-三氟丙磺酰基)己腈(以下称为本发明的化合物(17))。
本发明的化合物(17)
1H-NMR(CDCl3,TMS):δ(ppm)3.39-3.60(m,2H),2.70-2.87(m,2H),2.26-2.62(m,5H),1.35(d,3H),1.27(d,3H)
制备例18
将0.3克1-碘丁烷和0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.06克氢化钠(在油中,60%),混合物在相同温度下搅拌8小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.28克2-丁基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己腈(以下称为本发明的化合物(18))。
本发明的化合物(18)
1H-NMR(CDCl3,TMS):δ(ppm)3.38-3.58(m,2H),2.72-2.86(m,2H),2.32-2.58(m,4H),1.94-2.11(m,2H),1.38-1.65(m,4H),1.00(t,3H)
制备例19
将0.3克1-碘戊烷和0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.06克氢化钠(在油中,60%),混合物在相同温度下搅拌20小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.28克2-(3,3,4,4,4-五氟丁基)-2-(3,3,3-三氟丙磺酰基)庚腈(以下称为本发明的化合物(19))。
本发明的化合物(19)
1H-NMR(CDCl3,TMS):δ(ppm)3.38-3.58(m,2H),2.72-2.86(m,2H),2.32-2.58(m,4H),1.94-2.11(m,2H),1.38-1.65(m,6H),1.00(t,3H)
制备例20
将0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己腈溶解到20毫升四氢呋喃中。在0℃下向其中加入0.06克氢化钠(在油中,60%),混合物在相同温度下搅拌0.5小时。然后在相同温度下向混合物中加入0.4克1-氟-2,4,6-三甲基吡啶鎓三氟甲磺酸盐,混合物搅拌0.5小时。而且,混合物在在室温下搅拌10小时。然后,向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.37克2,5,5,6,6,6-六氟-2-(3,3,3-三氟丙磺酰基)己腈(以下称为本发明的化合物(20))。
本发明的化合物(20)
1H-NMR(CDCl3,TMS):δ(ppm)3.54-3.67(m,2H),2.39-2.88(m,6H)
制备例21
将0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己腈溶解到20毫升四氢呋喃中。在0℃下向其中加入0.06克氢化钠(在油中,60%),混合物在相同温度下搅拌0.5小时。然后在相同温度下向混合物中加入0.2克N-氯代琥珀酰亚胺,混合物搅拌0.5小时。进一步地,混合物在室温下搅拌3天。然后,向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.15克2-氯-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己腈(以下称为本发明的化合物(21))。
本发明的化合物(21)
1H-NMR(CDCl3,TMS):δ(ppm)3.66-3.84(m,2H),2.42-2.92(m,6H)
制备例22
将2.0克1-碘-4,4,4-三氟丁烷和2.0克(3,3,3-三氟丙磺酰基)乙酸甲酯溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入1.2克碳酸钾,混合物在相同温度下搅拌20小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.80克6,6,6-三氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯(以下称为本发明的化合物(22))。
本发明的化合物(22)
1H-NMR(CDCl3,TMS):δ(ppm)3.89(s,3H),3.82-3.88(m ,1H),3.30-3.50(m,2H),2.62-2.77(m,2H),2.10-2.24(m,4H),1.64-1.75(m,2H)
制备例23
将1.2克1-碘-3,3,4,4,4-五氟丁烷和1.0克(3,3,3-三氟丙磺酰基)乙酸甲酯溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.6克碳酸钾,其在相同温度下搅拌30小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到1.20克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯(以下称为本发明的化合物(23))。
本发明的化合物(23)
1H-NMR(CDCl3,TMS):δ(ppm)3.90(s,3H),3.86-3.94(m,1H),3.38-3.51(m,2H),2.63-2.78(m,2H),2.38-2.53(m,2H),2.18-2.34(m,2H)
制备例24
将4.8克1-碘-3,3,4,4,4-五氟丁烷和5.0克(3,3,4,4,4-五氟丁磺酰基)乙酸甲酯溶解到50毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.7克氢化钠(在油中,60%),混合物在相同温度下搅拌2天。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到4.69克5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸甲酯(以下称为本发明的化合物(24))。
本发明的化合物(24)
1H-NMR(CDCl3,TMS):δ(ppm)3.91(3,3H),3.89-3.97(m,1H),3.44-3.51(m,2H),2.58-2.73(m,2H),2.39-2.53(m,2H),2.20-2.34(m,2H)
制备例25
将0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸溶解到10毫升二氯甲烷中。随后在室温下逐滴加入2滴N,N-二甲基甲酰胺和0.2毫升草酰氯,然后在相同温度下将混合物搅拌2小时。然后将反应混合物减压浓缩。得到的残渣溶解到20毫升四氢呋喃中,在室温下逐滴加入0.1克叔丁醇和0.2毫升三乙胺。混合物在相同温度下搅拌1小时。向反应混合物中加入氯化铵饱和水溶液,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到0.42克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸叔丁酯(以下称为本发明的化合物(25))。
本发明的化合物(25)
1H-NMR(CDCl3,TMS):δ(ppm)3.75-3.82(m,1H),3.38-3.52(m,2H),2.63-2.78(m,2H),2.18-2.46(m,4H),1.53(s,9H)
制备例26
将0.4克碘甲烷和1.0克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.1克氢化钠(在油中,60%),混合物在相同温度下搅拌3小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.73克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯(以下称为本发明的化合物(26))。
本发明的化合物(26)
1H-NMR(CDCl3,TMS):δ(ppm)3.88(s,3H),3.43-3.52(m,2H),2.63-2.78(m,2H),2.08-2.54(m,4H),1.70(s,3H)
制备例27
将0.4克碘乙烷和1.0克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.1克氢化钠(在油中,60%),混合物在相同温度下搅拌20小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.45克2-乙基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯(以下称为本发明的化合物(27))。
本发明的化合物(27)
1H-NMR(CDCl3,TMS):δ(ppm)3.88(3,3H),3.33-3.65(m,2H),2.06-2.77(m,8H),1.04(t,3H)
制备例28
将0.4克1-碘丙烷和1.0克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.1克氢化钠(在油中,60%),混合物在相同温度下搅拌20小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.89克5,5,6,6,6-五氟-2-丙基-2-(3,3,3-三氟丙磺酰基)己酸甲酯(以下称为本发明的化合物(28))。
本发明的化合物(28)
1H-NMR(CDCl3,TMS):δ(ppm)3.87(s,3H),3.32-3.66(m,2H),1.96-2.76(m,8H),1.16-1.58(m,2H),1.01(t,3H)
制备例29
在0℃下将0.05克氢化钠(在油中,60%)加入到0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯在20毫升四氢呋喃中的溶液中,混合物在相同温度下搅拌0.5小时。然后向其中加入0.4克1-氟-2,4,6-三甲基吡啶鎓三氟甲磺酸盐,并将混合物搅拌0.5小时。进一步地,混合物在在室温下搅拌10小时。向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.39克2,5,5,6,6,6-六氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯(以下称为本发明的化合物(29))。
本发明的化合物(29)
1H-NMR(CDCl3,TMS):δ(ppm)4.00(s,3H),3.26-3.56(m,2H),2.09-2.80(m,6H)
制备例30
将0.7克碘甲烷和2.0克5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丙磺酰基)己酸甲酯溶解到50毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.2克氢化钠(在油中,60%),混合物在相同温度下搅拌4小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到1.20克2-甲基-5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸甲酯(以下称为本发明的化合物(30))。
本发明的化合物(30)
1H-NMR(CDCl3,TMS):δ(ppm)3.90(s,3H),3.46-3.53(m,2H),2.45-2.72(m,3H),2.09-2.34(m,3H),1.71(s,3H)
制备例31
将0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸溶解到10毫升二氯甲烷中。随后在室温下逐滴加入2滴N,N-二甲基甲酰胺和0.2毫升草酰氯,然后在相同温度下将混合物搅拌2小时。然后将反应混合物减压浓缩。将得到的残渣溶解到20毫升四氢呋喃中,并在室温下逐滴加入0.2克氨(30%(w/w)的水溶液)。混合物在相同温度下搅拌2小时。向反应混合物中加入氯化铵饱和水溶液,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到0.24克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(31))。
本发明的化合物(31)
1H-NMR(CDCl3,TMS):δ(ppm)6.34(bs,1H),5.73(bs,1H),3.73(dd,1H),3.21-3.42(m,2H),2.64-2.73(m,2H),2.12-2.48(m,4H)
制备例32
将0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸溶解到10毫升二氯甲烷中。随后在室温下逐滴加入2滴N,N-二甲基甲酰胺和0.2毫升草酰氯,然后在相同温度下将混合物搅拌1小时。然后将反应混合物减压浓缩。将得到的残渣溶解到20毫升四氢呋喃中,并在室温下逐滴加入0.3克甲胺(40%(w/w)的水溶液)。混合物在相同温度下搅拌2小时。向反应混合物中加入氯化铵饱和水溶液,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到0.26克N-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(32))。
本发明的化合物(32)
1H-NMR(CDCl3,TMS):δ(ppm)6.22(bs,1H),3.63(dd,1H),3.18-3.39(m,2H),2.94(d,3H),2.60-2.73(m,2H),2.08-2.50(m,4H)
制备例33
将0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸溶解到10毫升二氯甲烷中。随后在室温下逐滴加入2滴N,N-二甲基甲酰胺和0.2毫升草酰氯,然后在相同温度下将混合物搅拌1小时。然后将反应混合物减压浓缩。将得到的残渣溶解到20毫升四氢呋喃中,并在室温下逐滴加入0.5克二甲胺(40%(w/w)的水溶液)。混合物在相同温度下搅拌2小时。向反应混合物中加入氯化铵饱和水溶液,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到0.30克N,N-二甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(33))。
本发明的化合物(33)
1H-NMR(CDCl3,TMS):δ(ppm)4.31(dd,1H),3.19-3.53(m,2H),3.21(s,3H),3.09(s,3H),2.57-2.70(m,2H),1.98-2.54(m,4H)
制备例34
将1.1克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸溶解到20毫升二氯甲烷中。随后在室温下逐滴加入2滴N,N-二甲基甲酰胺和0.5毫升草酰氯,然后在相同温度下将混合物搅拌2小时。然后将反应混合物减压浓缩。将得到的残渣溶解到20毫升四氢呋喃中,并在室温下逐滴加入0.5克氨(30%(w/w)的水溶液)。混合物在相同温度下搅拌2小时。向反应混合物中加入氯化铵饱和水溶液,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到0.76克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(34))。
本发明的化合物(34)
1H-NMR(CDCl3,TMS):δ(ppm)6.62(bs,1H),5.74(bs,1H),3.20-3.41(m,2H),2.64-2.78(m,2H),2.08-2.54(m,4H),1.68(s,3H)
制备例35
将1.1克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸溶解到20毫升二氯甲烷中。随后在室温下逐滴加入2滴N,N-二甲基甲酰胺和0.5毫升草酰氯,然后在相同温度下将混合物搅拌2小时。然后将反应混合物减压浓缩。将得到的残渣溶解到20毫升四氢呋喃中,并在室温下逐滴加入0.7克甲胺(30%(w/w)的水溶液)。混合物在相同温度下搅拌2小时。向反应混合物中加入氯化铵饱和水溶液,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到0.70克N-甲基-2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(35))。
本发明的化合物(35)
1H-NMR(CDCl3,TMS):δ(ppm)6.56(bs,1H),3.14-3.39(m,2H),2.91(d,3H),2.60-2.74(m,2H),2.03-2.53(m,4H),1.67(s,3H)
制备例36
将0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸溶解到10毫升二氯甲烷中。随后在室温下逐滴加入2滴N,N-二甲基甲酰胺和0.2毫升草酰氯,然后在相同温度下将混合物搅拌1小时。然后将反应混合物减压浓缩。将得到的残渣溶解到20毫升四氢呋喃中,并在室温下逐滴加入1.0克二甲胺(40%(w/w)的水溶液)。混合物在相同温度下搅拌4小时。向反应混合物中加入氯化铵饱和水溶液,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到0.97克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)-N,N-2-二甲基-2-甲基己酰胺(以下称为本发明的化合物(36))。
本发明的化合物(36)
1H-NMR(CDCl3,TMS):δ(ppm)3.37(dd,2H),3.16(bs,6H),1.98-2.88(m,6H),1.82(s,3H)
制备例37
将0.5克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸溶解到20毫升二氯甲烷中。随后在室温下逐滴加入1滴N,N-二甲基甲酰胺和0.2毫升草酰氯,然后在相同温度下将混合物搅拌2小时。然后将反应混合物减压浓缩。将得到的残渣溶解到20毫升四氢呋喃中,并在室温下逐滴加入0.2克乙胺(70%(w/w)的水溶液)。混合物在相同温度下搅拌8小时。向反应混合物中加入氯化铵饱和水溶液,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到0.41克N-乙基-2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(37))。
本发明的化合物(37)
1H-NMR(CDCl3,TMS):δ(ppm)6.57(bs,1H),3.13-3.44(m,4H),2.61-2.74(m,2H),2.01-2.52(m,4H),1.66(s,3H),1.18(t,3H)
制备例38
将0.5克2-乙基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸溶解到20毫升二氯甲烷中。随后在室温下逐滴加入1滴N,N-二甲基甲酰胺和0.2毫升草酰氯,然后在相同温度下将混合物搅拌2小时。然后将反应混合物减压浓缩。将得到的残渣溶解到20毫升四氢呋喃中,并在室温下逐滴加入0.2克氨(30%(w/w)的水溶液)。混合物在相同温度下搅拌1小时。向反应混合物中加入氯化铵饱和水溶液,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到0.37克2-乙基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(38))。
本发明的化合物(38)
1H-NMR(CDCl3,TMS):δ(ppm)6.59(bs,1H),5.82(bs,1H),3.19-3.48(m,2H),2.62-2.76(m,2H),2.11-2.52(m,6H),1.10(t,3H)
制备例39
将0.6克1-碘-4,4,4-三氟丁烷和0.5克(3,3,3-三氟丙磺酰基)乙腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.1克氢化钠(在油中,60%),混合物在相同温度下搅拌10小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.57克6,6,6-三氟-2-(3,3,3-三氟丙磺酰基)己腈(以下称为本发明的化合物(39))。
本发明的化合物(39)
1H-NMR(CDCl3,TMS):δ(ppm)3.90-3.97(m,1H),3.41-3.59(m,2H),2.68-2.88(m,2H),1.78-2.36(m,6H)
制备例40
将0.5克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸溶解到20毫升二氯甲烷中。随后在室温下逐滴加入2滴N,N-二甲基甲酰胺和0.2毫升草酰氯,然后在相同温度下将混合物搅拌2小时。然后将反应混合物减压浓缩。得到的残渣溶解到20毫升四氢呋喃中,向其中逐滴加入0.2毫升丙胺。混合物在相同温度下搅拌14小时。向反应混合物中加入氯化铵饱和水溶液,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到0.26克2-甲基-N-丙基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(40))。
本发明的化合物(40)
1H-NMR(CDCl3,TMS):δ(ppm)6.62(bs,1H),3.11-3.38(m,4H),2.00-2.74(m,6H),1.66(s,3H),1.45-1.70(m,2H),0.94(t,3H)
制备例41
将0.5克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸溶解到20毫升二氯甲烷中。随后在室温下逐滴加入2滴N,N-二甲基甲酰胺和0.2毫升草酰氯,然后在相同温度下将混合物搅拌2小时。然后将反应混合物减压浓缩。将得到的残渣溶解到20毫升四氢呋喃中,在室温下向其中逐滴加入0.2克异丙胺。混合物在相同温度下搅拌14小时。向反应混合物中加入氯化铵饱和水溶液,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到0.25克N-异丙基-2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(41))。
本发明的化合物(41)
1H-NMR(CDCl3,TMS):δ(ppm)6.40(bs,1H),4.05-4.18(m,1H),3.10-3.39(m,2H),2.60-2.78(m,2H),1.98-2.52(m,4H),1.65(s,3H),1.19(dd,6H)
制备例42
将0.9克1-碘-3,3,4,4,4-五氟丁烷和1.1克(3,3,4,4,4-七氟戊磺酰基)乙酸甲酯溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.1克氢化钠(在油中,60%),混合物在相同温度下搅拌3天。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到1.12克2-(3,3,4,4,5,5,5-七氟戊磺酰基)-5,5,6,6,6-五氟己酸甲酯(以下称为本发明的化合物(42))。
本发明的化合物(42)
1H-NMR(CDCl3,TMS):δ(ppm)3.91-3.95(m,1H),3.91(s,3H),3.41-3.53(m,2H),2.62-2.77(m,2H),2.38-2.54(m,2H),2.19-2.34(m,2H)
制备例43
将0.2克碘甲烷和0.6克2-(3,3,4,4,5,5,5-七氟戊磺酰基)-5,5,6,6,6-五氟己酸甲酯溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.1克氢化钠(在油中,60%),混合物在相同温度下搅拌10小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.41克2-(3,3,4,4,5,5,5-七氟戊磺酰基)-2-甲基-5,5,6,6,6-五氟己酸甲酯(以下称为本发明的化合物(43))。
本发明的化合物(43)
1H-NMR(CDCl3,TMS):δ(ppm)3.89(s,3H),3.47-3.56(m,2H),2.61-2.78(m,2H),1.95-2.56(m,4H),1.71(s,3H)
制备例44
将0.4克碘甲烷和1.0克6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.1克氢化钠(在油中,60%),混合物在相同温度下搅拌10小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.85克2-甲基-6,6,6-三氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯(以下称为本发明的化合物(44))。
本发明的化合物(44)
1H-NMR(CDCl3,TMS):δ(ppm)3.86(s,3H),3.31-3.55(m,2H),2.62-2.75(m,2H),1.95-2.33(m,4H),1.67(s,3H),1.43-1.80(m,2H)
制备例45
将0.2克碘甲烷和0.5克6,6,6-三氟-2-(3,3,3-三氟丙磺酰基)己腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向其中加入0.06克氢化钠(在油中,60%),混合物在相同温度下搅拌10小时。然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.37克2-甲基-6,6,6-三氟-2-(3,3,3-三氟丙磺酰基)己腈(以下称为本发明的化合物(45))。
本发明的化合物(45)
1H-NMR(CDCl3,TMS):δ(ppm)3.40-3.55(m,2H),2.73-2.88(m,2H),1.85-2.34(m,6H),1.80(s,3H)
制备例46
将1.0克1-碘-3,3,4,4,4-五氟丁烷和1.0克2-(3,3,3-三氟丙磺酰基)丙酸乙酯溶解到20毫升二甲亚砜中。在室温下向其中加入0.2克氢化钠(在油中,60%),混合物在相同温度下搅拌10小时,在60℃下搅拌4小时,然后在90℃下搅拌4小时。然后,将反应混合物冷却到室温,然后向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.47克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸乙酯(以下称为本发明的化合物(46))。
本发明的化合物(46)
1H-NMR(CDCl3,TMS):δ(ppm)4.33(q,2H),3.46-3.53(m,2H),2.63-2.78(m,2H),2.08-2.54(m,4H),1.69(s,3H),1.34(t,3H)
制备例47
将1.8克S-(3,3,3-三氟丙基)硫代苯甲酸酯(benzenethioate)溶解到100毫升四氢呋喃中,然后在冰冷却条件下向该溶液中加入1.5毫升甲醇钠(28%(w/w)的甲醇溶液);然后在相同温度下逐滴加入2.0克2-溴-5,5,6,6,6-五氟己腈,然后在室温下搅拌0.5小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。随后,有机层用10%盐酸和氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到1.6克5,5,6,6,6-五氟-2-(3,3,3-三氟丙硫基)己腈(以下称为本发明的化合物(47))。
本发明的化合物(47)
1H-NMR(CDCl3,TMS):δ(ppm)3.67(t,1H),2.89-3.04(m,2H),2.10-2.58(m,6H)
制备例48
将0.5克S-(3,3,3-三氟丙基)硫代苯甲酸酯(benzenethioate)溶解到20毫升四氢呋喃中,然后在冰冷却条件下向该溶液中加入0.4毫升甲醇钠(28%(w/w)的甲醇溶液);然后在相同温度下逐滴加入0.6克2-溴-5,5,6,6,6-五氟己腈,然后在室温下搅拌1小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。随后,有机层用10%盐酸和氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣溶解到20毫升氯仿中,在冰冷却条件下加入0.5克过乙酸(32%(w/w)乙酸溶液),然后在相同温度下搅拌4小时。反应混合物升高到室温,倒入水中,然后用乙酸乙酯萃取混合物。随后,有机层用碳酸氢钠饱和水溶液和氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.4克5,5,6,6,6-五氟-2-(3,3,3-三氟丙基亚磺酰基)己腈(以下称为本发明的化合物(48))。
本发明的化合物(48)
1H-NMR(CDCl3,TMS):δ(ppm)3.62-3.69(m,1H),2.98-3.38(m,2H),2.25-2.82(m,6H)
制备例49
将1.1克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸溶解到20毫升二氯甲烷中。然后在室温下向该溶液中逐滴加入2滴N,N-二甲基甲酰胺和0.5毫升草酰氯,然后在相同温度下搅拌2小时。反应混合物减压浓缩。得到的残渣溶解到20毫升四氢呋喃中,然后在室温下逐滴加入0.5克氨(30%(w/w)水溶液),然后在相同温度搅拌10小时。向反应混合物中加入氯化铵饱和水溶液,然后用乙酸乙酯萃取。有机层减压浓缩。向得到的残渣中加入1.2克2,4-双(4-甲氧苯基)-1,3-二硫杂-2,4-二膦烷(diphosphetane)2,4-二硫化物和20毫升甲苯的混合物,然后回流加热10小时。反应混合物下降到室温,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.47克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己硫酰胺(以下称为本发明的化合物(49))。
本发明的化合物(49)
1H-NMR(CDCl3,TMS):δ(ppm)8.03(bs,1H),7.80(bs,1H),3.19-3.44(m,2H),2.08-2.78(m,6H),1.85(s,3H)
制备例50
将0.5克5,5,6,6,6-五氟-2-(3,3,3-三氟丙硫基-)己腈和0.2克碘甲烷用20毫升四氢呋喃溶解后,在-78℃下向该溶液中加入1.6毫升双(三甲基甲硅烷基)氨基化钠(1M四氢呋喃溶液)。混合物在相同温度下搅拌0.5小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。随后,有机层用10%盐酸和氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.4克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙硫基)己腈(以下称为本发明的化合物(50))。
本发明的化合物(50)
1H-NMR(CDCl3,TMS):δ(ppm)2.98(t,2H),2.08-2.58(m,6H),1.71(s,3H)
制备例51
将5.7克1-碘-3,3,4,4,5,5,5-七氟戊烷和5.0克(3,3,4,4,4-五氟丁磺酰基)乙酸甲酯溶解到50毫升N,N-二甲基甲酰胺中。在室温下向该溶液中加入0.7克氢化钠(在油中,60%),然后在相同温度下搅拌3天。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到1.80克5,5,6,6,7,7,7-七氟-2-(3,3,4,4,4-五氟丁磺酰基)庚酸甲酯(以下称为本发明的化合物(51))。
本发明的化合物(51)
1H-NMR(CDCl3,TMS):δ(ppm)3.91(s,3H),3.90-3.97(m,1H),3.41-3.54(m,2H),2.20-2.73(m,6H)
制备例52
将0.4克碘甲烷和1.3克5,5,6,6,7,7,7-七氟-2-(3,3,4,4,4-五氟丁磺酰基)庚酸甲酯溶解到50毫升N,N-二甲基甲酰胺中。在室温下向该溶液中加入0.1克氢化钠(在油中,60%),然后在相同温度下搅拌3小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到1.30克5,5,6,6,7,7,7-七氟-2-甲基-2-(3,3,4,4,4-五氟丁磺酰基)庚酸甲酯(以下称为本发明的化合物(52))。
本发明的化合物(52)
1H-NMR(CDCl3,TMS):δ(ppm)3.88(s,3H),3.47-3.54(m,2H),2.08-2.73(m,6H),1.71(s,3H)
制备例53
将0.4克1-碘-3,3,3-三氟丙烷和0.5克(3,3,4,4,4-五氟丁磺酰基)乙腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向该溶液中加入0.08克氢化钠(在油中,60%),然后在相同温度下搅拌20小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.26克2-(3,3,4,4,4-五氟丁磺酰基)-5,5,5-三氟戊腈(以下称为本发明的化合物(53))。
本发明的化合物(53)
1H-NMR(CDCl3,TMS):δ(ppm)4.04-4.08(m,1H),3.47-3.66(m,2H),2.35-2.81(m,6H)
制备例54
将0.6克1-碘-3,3,4,4,5,5,5-七氟戊烷和0.5克(3,3,4,4,4-五氟丁磺酰基)乙腈溶解到20毫升N,N-二甲基甲酰胺中。在室温下向该溶液中加入0.08克氢化钠(在油中,60%),然后在相同温度下搅拌24小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.30克5,5,6,6,7,7,7-七氟-2-(3,3,4,4,4-五氟丁磺酰基)庚腈(以下称为本发明的化合物(54))。
本发明的化合物(54)
1H-NMR(CDCl3,TMS):δ(ppm)4.16-4.22(m,1H),3.50-3.68(m,2H),2.33-2.88(m,6H)
制备例55
将0.5克5,5,6,6,7,7,7-七氟-2-(3,3,4,4,4-五氟丁磺酰基)庚酸溶解到20毫升二氯甲烷中。然后在室温下向该溶液中逐滴加入2滴N,N-二甲基甲酰胺和0.1毫升草酰氯,然后在相同温度下搅拌2小时。反应混合物减压浓缩。得到的残渣溶解到20毫升四氢呋喃中,然后在室温下逐滴加入0.2克氨(30%(w/w)水溶液),然后在相同温度搅拌2小时。向反应混合物中加入氯化铵饱和水溶液,然后用乙酸乙酯萃取。有机层减压浓缩。得到的残渣经过硅胶色谱,得到0.31克5,5,6,6,7,7,7-七氟-2-(3,3,4,4,4-五氟丁磺酰基)庚酰胺(以下称为本发明的化合物(55))。
本发明的化合物(55)
1H-NMR(CDCl3,TMS):δ(ppm)6.31(bs,1H),5.73(bs,1H),3.72-3.78(m,1H),3.24-3.45(m,2H),2.12-2.74(m,6H
制备例56
将1.1克5,5,6,6,7,7,7-七氟-2-甲基-2-(3,3,4,4,4-五氟丁磺酰基)庚酸溶解到20毫升二氯甲烷中。然后在室温下向该溶液中逐滴加入2滴N,N-二甲基甲酰胺和0.4毫升草酰氯,然后在相同温度下搅拌2小时。反应混合物减压浓缩。得到的残渣溶解到50毫升四氢呋喃中,然后在室温下逐滴加入0.4克氨(30%(w/w)水溶液),然后在相同温度搅拌2小时。向反应混合物中加入氯化铵饱和水溶液,然后用乙酸乙酯萃取。有机层减压浓缩。得到的残渣经过硅胶色谱,得到0.60克5,5,6,6,7,7,7-七氟-2-甲基-2-(3,3,4,4,4-五氟丁磺酰基)庚酰胺(以下称为本发明的化合物(56))。
本发明的化合物(56)
1H-NMR(CDCl3,TMS):δ(ppm)6.63(bs,1H),5.76(bs,1H),3.20-3.45(m,2H),2.08-2.73(m,6H),1.70(s,3H)
制备例57
将0.6克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙硫基)己腈用30毫升氯仿溶解,然后在冰冷却条件下向该溶液中加入0.4g过乙酸(32%(w/w)的乙酸溶液);然后在相同温度下搅拌2小时,然后在室温下进一步搅拌10小时。将反应混合物倒入水中,然后用乙酸乙酯萃取。随后,有机层用碳酸氢钠饱和水溶液和氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.25克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙基亚磺酰基)己腈(以下称为本发明的化合物(57))。
本发明的化合物(57)
1H-NMR(CDCl3,TMS):δ(ppm)2.98-3.21(m,2H),2.60-2.82(m,2H),2.04-2.54(m,4H),1.68(s,2H),1.59(s,1H)
制备例58
将0.8克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯溶解到50毫升四氢呋喃中。在室温下向该溶液中加入0.08克氢化钠(在油中,60%),然后在相同温度下搅拌0.5小时;然后在相同温度下加入0.3克N-氯代琥珀酰亚胺,然后搅拌4小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.60克2-氯-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯(以下称为本发明的化合物(58))。
本发明的化合物(58)
1H-NMR(CDCl3,TMS):δ(ppm)3.97(s,3H),3.52-3.92(m,2H),2.18-2.91(m,6H)
制备例59
将0.5克2-氯-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯溶解到50毫升甲醇中。在室温下向该溶液中加入0.5毫升氨(7M甲醇溶液),然后在相同温度下搅拌2小时。反应混合物减压浓缩。得到的残渣经过硅胶色谱,得到0.15克2-氯-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(59))。
本发明的化合物(59)
1H-NMR(CDCl3,TMS):δ(ppm)6.88(bs,1H),6.02(bs,1H),3.38-3.74(m,2H),2.13-2.95(m,6H)
制备例60
将0.5克5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸溶解到20毫升二氯甲烷中。然后在室温下向该溶液中逐滴加入2滴N,N-二甲基甲酰胺和0.2毫升草酰氯,然后在相同温度下搅拌4小时。反应混合物减压浓缩。得到的残渣溶解到20毫升四氢呋喃中,然后在室温下逐滴加入0.2克氨(30%(w/w)水溶液),然后在相同温度搅拌2天。向反应混合物中加入氯化铵饱和水溶液,然后用乙酸乙酯萃取。有机层减压浓缩。得到的残渣经过硅胶色谱,得到0.20克5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酰胺(以下称为本发明的化合物(60))。
本发明的化合物(60)
1H-NMR(CDCl3,TMS):δ(ppm)6.41(bs,1H),5.73(bs,1H),3.74-3.79(m,1H),3.20-3.45(m,2H),2.08-2.74(m,6H)
制备例61
将0.8克2-甲基-5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸溶解到20毫升二氯甲烷中。然后在室温下向该溶液中逐滴加入2滴N,N-二甲基甲酰胺和0.3毫升草酰氯,然后在相同温度下搅拌4小时。反应混合物减压浓缩。得到的残渣溶解到20毫升四氢呋喃中,然后在室温下逐滴加入0.3克氨(30%(w/w)水溶液),然后在相同温度搅拌2天。向反应混合物中加入氯化铵饱和水溶液,然后用乙酸乙酯萃取。有机层减压浓缩。得到的残渣经过硅胶色谱,得到0.60克2-甲基-5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酰胺(以下称为本发明的化合物(61))。
本发明的化合物(61)
1H-NMR(CDCl3,TMS):δ(ppm)6.69(bs,1H),6.01(bs,1H),3.22-3.46(m,2H),2.08-2.73(m,6H),1.69(s,3H)
制备例62
在将2.0克5,5,6,6,6-五氟-2-(3,3,3-三氟丙硫基)己腈用50毫升甲醇溶解之后,在室温下向该溶液中加入12.5毫升甲醇钠(28%(w/w)甲醇溶液),然后在相同温度下搅拌15小时。向该反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。随后,有机层用10%盐酸和氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.8克5,5,6,6,6-五氟--2-(3,3,3-三氟丙硫基)己酸甲酯(以下称为本发明的化合物(62))。
本发明的化合物(62)
1H-NMR(CDCl3,TMS):δ(ppm)3.79(s,3H),3.31(t,1H),2.72-2.90(m,2H),1.93-2.48(m,6H)
制备例63
在将0.3克5,5,6,6,6-五氟-2-(3,3,3-三氟丙硫基)己酸甲酯用20毫升氯仿溶解之后,在冰冷却条件下向该溶液中加入0.2克过乙酸(32%(w/w)乙酸溶液),然后在相同温度下搅拌6小时。将反应混合物倒入水中,然后用乙酸乙酯萃取。随后,有机层用碳酸氢钠饱和水溶液和氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.18克5,5,6,6,6-五氟-2-(3,3,3-三氟丙基亚磺酰基)己酸甲酯(以下称为本发明的化合物(63))。
本发明的化合物(63)
1H-NMR(CDCl3,TMS):δ(ppm)3.86(s,1.2H),3.84(s,1.8H),3.57-3.69(m,1H),2.13-3.14(m,8H)
制备例64
将0.5克2,5,5,6,6,6-六氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯溶解到20毫升甲醇中。在室温下向该溶液中加入0.5毫升氨(7M甲醇溶液),然后在相同温度下搅拌0.5小时;然后再加入5毫升氨(7M甲醇溶液),然后在相同温度下搅拌2小时。反应混合物减压浓缩。得到的残渣经过硅胶色谱,得到0.37克2,5,5,6,6,6-六氟-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(64))。
本发明的化合物(64)
1H-NMR(CDCl3,TMS):δ(ppm)6.54(bs,1H),5.88(bs,1H),3.30-3.58(m,2H),2.14-2.83(m,6H)
制备例65
将2.0克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯溶解到50毫升四氢呋喃中。在冰冷却条件下向该溶液中加入0.21克氢化钠(在油中,60%),然后在相同温度下搅拌0.5小时;然后加入0.9克N-溴代琥珀酰亚胺,然后在室温下搅拌12小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.30克2-溴-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯(以下称为本发明的化合物(65))。
本发明的化合物(65)
1H-NMR(CDCl3,TMS):δ(ppm)3.96(s,3H),3.75-4.01(m,2H),2.35-2.92(m,6H)
制备例66
将1.0克2-(3,3,4,4,5,5,5-七氟戊磺酰基)-5,5,6,6,6-五氟己酸甲酯溶解到50毫升四氢呋喃中。在0℃下向该溶液中加入0.08克氢化钠(在油中,60%),然后在相同温度下搅拌0.5小时;随后在相同温度下加入0.6克1-氟-2,4,6-三甲基吡啶鎓三氟甲磺酸盐,然后搅拌1小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.75克2-(3,3,4,4,5,5,5-七氟戊磺酰基)-2,5,5,6,6,6-六氟己酸甲酯(以下称为本发明的化合物(66))。
本发明的化合物(66)
1H-NMR(CDCl3,TMS):δ(ppm)4.00(s,3H),3.34-3.61(m,2H),2.09-2.81(m,6H)
制备例67
将1.5克2-(3,3,4,4,5,5,5-七氟戊磺酰基)-2,5,5,6,6,6-六氟己酸甲酯溶解在30毫升甲醇。在室温下向该溶液中加入1.3毫升氨(7M甲醇溶液),然后在相同温度下搅拌24小时。反应混合物减压浓缩。得到的残渣经过硅胶色谱,得到1.10克2-(3,3,4,4,5,5,5-七氟戊磺酰基)-2,5,5,6,6,6-六氟己酰胺(以下称为本发明的化合物(67))。
本发明的化合物(67)
1H-NMR(CDCl3,TMS):δ(ppm)6.54(bs,1H),5.89(bs,1H),3.34-3.62(m,2H),2.10-2.82(m,6H)
制备例68
将0.3克5,5,6,6,6-五氟-2-(3,3,3-三氟丙硫基)己酸甲酯和0.12克碘甲烷用20毫升四氢呋喃溶解后,在0℃下向该混合物中加入0.9毫升双(三甲基甲硅烷基)氨基化钠(1M四氢呋喃溶液)。混合物在相同温度下搅拌1小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。随后,有机层用10%盐酸和氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.3克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙硫基)己酸甲酯(以下称为本发明的化合物(68))。
本发明的化合物(68)
1H-NMR(CDCl3,TMS):δ(ppm)3.78(s,3H),2.73-2.79(m,2H),1.96-2.41(m,6H),1.50(s,3H)
制备例69
将1.0克2,5,5,6,6,6-六氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯溶解到30毫升甲醇中。在室温下向该溶液中加入3.8毫升甲胺(2M甲醇溶液),然后在相同温度下搅拌2小时。反应混合物减压浓缩。得到的残渣经过硅胶色谱,得到0.92克2,5,5,6,6,6-六氟-N-甲基-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(69))。
本发明的化合物(69)
1H-NMR(CDCl3,TMS):δ(ppm)6.58(bs,1H),3.26-3.58(m,2H),2.99(d,3H),2.04-2.82(m,6H)
制备例70
将1.0克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙硫基)己酸甲酯用50毫升甲醇溶解,然后在室温下向该溶液中加入氢氧化钾水溶液(0.9克氢氧化钾和5毫升水的混合溶液),然后在相同温度下搅拌1天。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩。得到的残渣溶解到20毫升二氯甲烷中;然后在室温下逐滴加入2滴N,N-二甲基甲酰胺和0.4毫升草酰氯,然后在相同温度下搅拌1小时。反应混合物减压浓缩。得到的残渣溶解到20毫升四氢呋喃中,然后在室温下逐滴加入0.4克氨(30%(w/w)水溶液),然后在相同温度下搅拌1小时。向反应混合物中加入氯化铵饱和水溶液,然后用乙酸乙酯萃取。有机层减压浓缩。得到的残渣经过硅胶色谱,得到0.25克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙硫基)己酰胺(以下称为本发明的化合物(70))。
本发明的化合物(70)
1H-NMR(CDCl3,TMS):δ(ppm)6.60(bs,1H),5.49(bs,1H),2.73(t,2H),1.96-2.44(m,6H),1.51(s,3H)
制备例71
将4.4克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙硫基)己酸甲酯用30毫升氯仿溶解,然后在冰冷却条件下向该溶液中加入2.9克过乙酸(32%(w/w)乙酸溶液),然后在相同温度下搅拌4小时。将反应混合物倒入水中,然后用乙酸乙酯萃取。随后用碳酸氢钠饱和水溶液和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到1.10克2-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙基亚磺酰基)己酸甲酯(以下称为本发明的化合物(71))。
本发明的化合物(71)
1H-NMR(CDCl3,TMS):δ(ppm)3.84(s,1.2H),3.82(s,1.8H),2.06-2.84(m,8H),1.53(s,1.2H),1.52(s,1.8H)
制备例72
将1.0克2-(3,3,4,4,4-五氟丁磺酰基)-5,5,6,6,6-五氟己酸甲酯溶解到50毫升四氢呋喃中。在室温下向该溶液中加入0.09克氢化钠(在油中,60%),然后在相同温度下搅拌0.5小时;随后在相同温度下加入0.7克1-氟-2,4,6-三甲基吡啶鎓三氟甲磺酸盐,然后搅拌3小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。
用氯化钠的饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.78克2,5,5,6,6,6-六氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸甲酯(以下称为本发明的化合物(72))。
本发明的化合物(72)
1H-NMR(CDCl3,TMS):δ(ppm)4.00(s,3H),3.33-3.60(m,2H),2.08-2.81(m,6H)
制备例73
将0.6克2,5,5,6,6,6-六氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸甲酯溶解到20毫升甲醇中。在室温下向该溶液中加入0.6毫升氨(7M甲醇溶液),然后在相同温度下搅拌12小时。反应混合物减压浓缩。得到的残渣经过硅胶色谱,得到0.45克2,5,5,6,6,6-六氟-2-(3,3,4,4,4-五氟丁磺酰基)己酰胺(以下称为本发明的化合物(73))。
本发明的化合物(73)
1H-NMR(CDCl3,TMS):δ(ppm)6.55(bs,1H),5.91(bs,1H),3.33-3.61(m,2H),2.04-2.83(m,6H)
制备例74
将0.5克2,5,5,6,6,6-六氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯用30毫升甲醇溶解后,在室温下向该溶液中加入氢氧化钾水溶液(0.4克氢氧化钾和5毫升水的混合溶液),然后在相同温度下搅拌12小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。用氯化钠的饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。将残渣溶解到20毫升二氯甲烷中;然后在室温下逐滴加入2滴N,N-二甲基甲酰胺和0.2毫升草酰氯,然后在相同温度下搅拌2小时。反应混合物减压浓缩。得到的残渣溶解到30毫升四氢呋喃中,然后在室温下逐滴加入0.4克二甲胺(40%(w/w)水溶液);然后在相同温度下搅拌2小时。向反应混合物中加入氯化铵饱和水溶液,然后用乙酸乙酯萃取。有机层减压浓缩。得到的残渣经过硅胶色谱,得到0.26克N,N-二甲基-2,5,5,6,6,6-六氟-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(74))。
本发明的化合物(74)
1H-NMR(CDCl3,TMS):δ(ppm)3.32-3.55(m,2H),3.29(d,3H),3.10(s,3H),2.14-2.97(m,6H)
制备例75
将1.0g 2-氯-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯溶解到30毫升甲醇中。在室温下向该溶液中加入3.6毫升甲胺(2M甲醇溶液),然后在相同温度下搅拌16小时。反应混合物减压浓缩。得到的残渣经过硅胶色谱,得到0.15克2-氯-N-甲基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(75))。
本发明的化合物(75)
1H-NMR(CDCl3,TMS):δ(ppm)6.95(bs,1H),3.35-3.75(m,2H),2.96(d,3H),2.05-2.98(m,6H)
制备例76
将1.0克1-碘-3,3,3-三氟丙烷和1.0克(3,3,3-三氟丙磺酰基)醋酸甲酯溶解到20毫升二甲亚砜中。在室温下向该溶液中加入0.6克碳酸钾,然后在相同温度下搅拌16小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。用氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.42克5,5,5-三氟-2-(3,3,3-三氟丙磺酰基)戊酸甲酯(以下称为本发明的化合物(76))。本发明的化合物(76)
1H-NMR(CDCl3,TMS):δ(ppm)3.90(s,3H),3.88-3.94(m,1H),3.36-3.52(m,2H),2.62-2.78(m,2H),2.38-2.53(m,2H),2.24-2.48(m,2H)
制备例77
将1.0克5,5,5-三氟-2-(3,3,3-三氟丙磺酰基)戊酸甲酯溶解到30毫升四氢呋喃中。在室温下向该溶液中加入0.12克氢化钠(在油中,60%),然后在相同温度下搅拌0.5小时;随后在相同温度下加入0.4克N-氯代琥珀酰亚胺,然后搅拌2小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。用氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.65克2-氯-5,5,5-三氟-2-(3,3,3-三氟丙磺酰基)戊酸甲酯(以下称为本发明的化合物(77))。
本发明的化合物(77)
1H-NMR(CDCl3,TMS):δ(ppm)3.97(s,3H),3.58-3.88(m,2H),2.35-2.88(m,6H)
制备例78
将2.0克甲基1-碘-4,4,4-三氟丁烷和2.0克(3,3,3-三氟丙磺酰基)醋酸酯溶解到30毫升二甲亚砜中。在室温下向该溶液中加入1.2克碳酸钾,然后在相同温度下搅拌3天。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。用氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到1.50克6,6,6-三氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯(以下称为本发明的化合物(78))。
本发明的化合物(78)
1H-NMR(CDCl3,TMS):δ(ppm)3.89(s,3H),3.80-3.90(m,1H),3.28-3.50(m,2H),2.60-2.78(m,2H),2.09-2.27(m,4H),1.62-1.75(m,2H)
制备例79
将1.0克6,6,6-三氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯溶解到30毫升四氢呋喃中。在室温下向该溶液中加入0.12克氢化钠(在油中,60%),然后在相同温度下搅拌0.5小时;随后在相同温度下加入0.4克N-氯代琥珀酰亚胺,然后搅拌4小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。用氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.96克2-氯-6,6,6-三氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯(以下称为本发明的化合物(79))。
本发明的化合物(79)
1H-NMR(CDCl3,TMS):δ(ppm)3.96(s,3H),3.53-3.84(m,2H),2.12-2.79(m,6H),1.72-2.02(m,2H)
制备例80
将0.8克2-氯-6,6,6-三氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯溶解到20毫升甲醇中。在室温下向该溶液中加入0.9毫升氨(7M甲醇溶液),然后在相同温度下搅拌10小时。反应混合物减压浓缩。得到的残渣经过硅胶色谱,得到0.51克2-氯-6,6,6-三氟-2-(3,3,3-三氟丙磺酰基)己酰胺(以下称为本发明的化合物(80))。
本发明的化合物(80)
1H-NMR(CDCl3,TMS):δ(ppm)6.93(bs,1H),6.20(bs,1H),3.36-3.74(m,2H),2.13-2.81(m,6H),1.61-2.01(m,2H)
制备例81
将1.0克2-氯-5,5,5-三氟-2-(3,3,3-三氟丙磺酰基)戊酸甲酯溶解到30毫升甲醇中。在室温下向该溶液中加入1.2毫升氨(7M甲醇溶液),然后在相同温度下搅拌14小时。反应混合物减压浓缩。得到的残渣经过硅胶色谱,得到0.62克2-氯-5,5,5-三氟-2-(3,3,3-三氟丙磺酰基)戊酰胺(以下称为本发明的化合物(81))。
本发明的化合物(81)
1H-NMR(CDCl3,TMS):δ(ppm)6.93(bs,1H),6.36(bs,1H),3.38-3.73(m,2H),2.21-2.92(m,6H)
制备例82
将2.8克1-碘-3,3,4,4,5,5,5-七氟戊烷和2.0克(3,3,3-三氟丙磺酰基)醋酸甲酯溶解到30毫升二甲亚砜中。在室温下向该溶液中加入0.34克氢化钠(60%,在油中),然后在相同温度下搅拌14小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。用氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到2.30克5,5,6,6,7,7,7-七氟-2-(3,3,3-三氟丙磺酰基)庚酸甲酯(以下称为本发明的化合物(82))。
本发明的化合物(82)
1H-NMR(CDCl3,TMS):δ(ppm)3.91(s,3H),3.87-3.95(m,1H),3.36-3.52(m,2H),2.21-2.78(m,6H)
制备例83
将1.0克5,5,6,6,7,7,7-七氟-2-(3,3,3-三氟丙磺酰基)庚酸甲酯溶解到30毫升四氢呋喃中。在室温下向该溶液中加入0.09克氢化钠(在油中,60%),然后在相同温度下搅拌0.5小时;随后在相同温度下加入0.3克N-氯代琥珀酰亚胺,然后搅拌1小时,然后向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。用氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.93克2-氯-5,5,6,6,7,7,7-七氟-2-(3,3,3-三氟丙磺酰基)庚酸甲酯(以下称为本发明的化合物(83))。
本发明的化合物(83)
1H-NMR(CDCl3,TMS):δ(ppm)3.97(s,3H),3.53-3.90(m,2H),2.30-2.91(m,6H)
制备例84
将0.7克2-氯-5,5,6,6,7,7,7-七氟-2-(3,3,3-三氟丙磺酰基)庚酸甲酯溶解到30毫升甲醇中。在室温下向该溶液中加入0.6毫升氨(7M甲醇溶液),然后在相同温度下搅拌10小时。反应混合物减压浓缩。得到的残渣经过硅胶色谱,得到0.50克2-氯-5,5,6,6,7,7,7-七氟-2-(3,3,3-三氟丙磺酰基)庚酸甲酯(以下称为本发明的化合物(84))。
本发明的化合物(84)
1H-NMR(CDCl3,TMS):δ(ppm)6.88(bs,1H),5.94(bs,1H),3.37-3.73(m,2H),2.14-2.96(m,6H)
制备例85
将7.0克1-碘-3,3,4,4,5,5,6,6,6-九氟己烷和4.4克(3,3,3-三氟丙磺酰基)醋酸甲酯溶解到50毫升二甲亚砜中。在室温下向该溶液中加入2.59克碳酸钾。该混合物在60℃下搅拌2天。反应混合物下降到大约室温。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。用氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到1.50克5,5,6,6,7,7,8,8,8-九氟-2-(3,3,3-三氟丙磺酰基)辛酸甲酯(以下称为本发明的化合物(85))。
本发明的化合物(85)
1H-NMR(CDCl3,TMS):δ(ppm)3.92(s,3H),3.87-3.95(m,1H),3.38-3.52(m,2H),2.20-2.78(m,6H)
制备例86
将1.0克5,5,6,6,7,7,8,8,8-九氟-2-(3,3,3-三氟丙磺酰基)辛酸甲酯溶解到30毫升四氢呋喃中。在室温下向该溶液中加入0.08克氢化钠(在油中,60%),然后在相同温度下搅拌0.5小时;随后在相同温度下加入0.3克N-氯代琥珀酰亚胺,然后搅拌16小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。用氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到0.89克2-氯-5,5,6,6,7,7,8,8,8-九氟-2-(3,3,3-三氟丙磺酰基)辛酸甲酯(以下称为本发明的化合物(86))。
本发明的化合物(86)
1H-NMR(CDCl3,TMS):δ(ppm)3.97(s,3H),3.58-3.92(m,2H),2.33-2.94(m,6H)
制备例87
将0.8克2-氯-5,5,6,6,7,7,8,8,8-九氟-2-(3-三氟丙磺酰基)辛酸甲酯溶解到20毫升甲醇中。在室温下向该溶液中加入1.1毫升氨(7M甲醇溶液),然后在相同温度下搅拌12小时。反应混合物减压浓缩。得到的残渣经过硅胶色谱,得到0.45克2-氯-5,5,6,6,7,7,8,8,8-九氟-2-(3,3,3-三氟丙磺酰基)辛酸甲酯(以下称为本发明的化合物(87))。
本发明的化合物(87)
1H-NMR(CDCl3,TMS):δ(ppm)6.88(bs,1H),5.93(bs,1H),3.38-3.77(m,2H),2.15-2.98(m,6H)
制备例88
将2.0克5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸甲酯溶解到30毫升二甲亚砜中。在室温下向该溶液中加入0.19克氢化钠(在油中,60%),然后在相同温度下搅拌0.5小时;随后在相同温度下加入1.9克氯化铜(II),然后搅拌12小时。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。用氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到1.70克2-氯-5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸甲酯(以下称为本发明的化合物(88))。
本发明的化合物(88)
1H-NMR(CDCl3,TMS):δ(ppm)3.98(s,3H),3.63-3.93(m,2H),2.29-2.92(m,6H)
制备例89
将1.5克2-氯-5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸甲酯溶解到30毫升甲醇中。在室温下向该溶液中加入1.4毫升氨(7M甲醇溶液),然后在相同温度下搅拌16小时。反应混合物减压浓缩。得到的残渣经过硅胶色谱,得到1.10克2-氯-5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酰胺(以下称为本发明的化合物(89))。
本发明的化合物(89)
1H-NMR(CDCl3,TMS):δ(ppm)6.96(bs,1H),5.93(bs,1H),3.40-3.78(m,2H),2.13-2.95(m,6H)
如下所示的本发明的化合物(90)到(103)是通过与上述类似的方法制备的。
本发明的化合物(90)
1H-NMR(CDCl3,TMS):δ(ppm)4.00(s,3H),3.26-3.58(m,2H),2.12-2.80(m,6H)
本发明的化合物(91)
1H-NMR(CDCl3,TMS):δ(ppm)6.58(bs,1H),5.92(bs,1H),3.26-3.58(m,2H),2.19-2.83(m,6H)
本发明的化合物(92)
1H-NMR(CDCl3,TMS):δ(ppm)3.90(s,3H),3.88-3.96(m,1H),3.38-3.55(m,2H),2.54-2.73(m,2H),2.23-2.50(m,4H)
本发明的化合物(93)
1H-NMR(CDCl3,TMS):δ(ppm)3.97(s,3H),3.62-3.91(m,2H),2.37-2.88(m,6H)
本发明的化合物(94)
1H-NMR(CDCl3,TMS):δ(ppm)6.87(bs,1H),6.01(bs,1H),3.35-3.80(m,2H),2.19-2.92(m,6H)
本发明的化合物(95)
1H-NMR(CDCl3,TMS):δ(ppm)3.93-3.97(m,1H),3.91(s,3H),3.41-3.55(m,2H),2.21-2.73(m,6H)
本发明的化合物(96)
1H-NMR(CDCl3,TMS):δ(ppm)3.98(s,3H),3.62-3.92(m,2H),2.19-2.94(m,6H)
本发明的化合物(97)
1H-NMR(CDCl3,TMS):δ(ppm)6.88(bs,1H),5.95(bs,1H),3.39-3.78(m,2H),2.14-2.96(m,6H)
本发明的化合物(98)
1H-NMR(CDCl3,TMS):δ(ppm)3.87(s,3H),3.80-3.88(m,1H),3.26-3.50(m,2H),2.59-2.78(m,2H),2.03-2.18(m,4H),1.44-1.72(m,4H)
本发明的化合物(99)
1H-NMR(CDCl3,TMS):δ(ppm)3.94(s,3H),3.50-3.81(m,2H),2.55-2.80(m,3H),2.05-2.32(m,3H),1.50-1.80(m,4H)
本发明的化合物(100)
1H-NMR(CDCl3,TMS):δ(ppm)6.88(bs,1H),5.98(bs,1H),3.34-3.78(m,2H),2.58-2.81(m,3H),2.01-2.28(m,3H),1.40-1.82(m,4H)
本发明的化合物(101)
1H-NMR(CDCl3,TMS):δ(ppm)3.89(s,3H),3.80-3.88(m,1H),3.26-3.54(m,2H),2.59-2.80(m,3H),2.00-2.26(m,3H)1.65-1.78(m,2H)
本发明的化合物(102)
1H-NMR(CDCl3,TMS):δ(ppm)3.96(s,3H),3.50-3.85(m,2H),2.61-2.78(m,3H),1.75-2.40(m,5H)
本发明的化合物(103)
1H-NMR(CDCl3,TMS):δ(ppm)6.95(bs,1H),6.30(bs,1H),3.35-3.78(m,2H),2.61-2.80(m,3H),1.62-2.32(m,5H)
接下来,描述本发明的化合物的例子。
式(I-A)所示的化合物:
其中R1、R2、R3和R4是表1到表83中所述的组合。
[表1]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3 | CNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCN | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH(CH3)2CH(CH3)2CH(CH3)2CH2CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH2CH3CH2CH2CH2CH2CH3CH2CH2CH2CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表2]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3 | CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3 | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3FFFClClClHHHCH3CH3CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表3]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3 | CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3) | ClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表4]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3 | CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2 | FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表5]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3 | CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCO2CH3CO2CH3CO2CH3 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表6]
R1 | R2 | R3 | R4 |
CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3 | CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH(CH3)CONH(CH3)CONH(CH3) | CH3CH3CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表7]
R1 | R2 | R3 | R4 |
CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3 | CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2 | CH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表8]
R1 | R2 | R3 | R4 |
CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3 | CNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3 | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表9]
R1 | R2 | R3 | R4 |
CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3 | CNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3 | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表10]
R1 | R2 | R3 | R4 |
CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3 | CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3) | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表11]
R1 | R2 | R3 | R4 |
CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3 | CONH(CH3)CONH(CH3)CONH(CH3)CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CNCNCNCNCNCNCNCNCN | ClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表12]
R1 | R2 | R3 | R4 |
CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3 | CNCNCNCNCNCNCO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CNCNCNCNCNCNCNCNCN | FFFClClClHHHCH3CH3CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表13]
R1 | R2 | R3 | R4 |
CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3 | CNCNCNCNCNCNCO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2 | FFFClClClHHHCH3CH3CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表14]
R1 | R2 | R3 | R4 |
CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3 | CONH2CONH2CONH2CONH2CONH2CONH2CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2 | FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表15]
R1 | R2 | R3 | R4 |
CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3 | CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCO2CH3CO2CH3CO2CH3 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表16]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3 | CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCO2CH3CO2CH3CO2CH3 | CH3CH3CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表17]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3 | CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH(CH3)CONH(CH3)CONH(CH3) | CH3CH3CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表18]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3 | CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2 | CH3CH3CH3CH2CH3CH2CH3CH2CH3FFFFFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表19]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2H | CON(CH3)2CON(CH3)2CON(CH3)2CNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3 | ClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表20]
R1 | R2 | R3 | R4 |
CH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2H | CO2CH3CO2CH3CO2CH3CNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3 | ClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表21]
R1 | R2 | R3 | R4 |
CH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2H | CO2CH3CO2CH3CO2CH3CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3) | ClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表22]
R1 | R2 | R3 | R4 |
CH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3 | CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CNCNCNCNCNCN | FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表23]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3 | CNCNCNCNCNCNCNCNCNCO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CNCNCNCNCNCN | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表24]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3 | CNCNCNCNCNCNCNCNCNCO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CONH2CONH2CONH2CONH2CONH2CONH2 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表25]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3 | CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CON(CH3)2CON(CH3)2CON(CH3)2 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表26]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3 | CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)NH2C(S)NH2C(S)NH2 | CH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表27]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3 | C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3) | CH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表28]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3 | C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3 | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表29]
R1 | R2 | R3 | R4 |
CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3 | C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3) | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表30]
R1 | R2 | R3 | R4 |
CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CH2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3 | C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3 | ClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表31]
R1 | R2 | R3 | R4 |
CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3 | C(S)OCH3C(S)OCH3C(S)OCH3C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3) | ClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表32]
R1 | R2 | R3 | R4 |
CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3 | C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3 | FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表33]
R1 | R2 | R3 | R4 |
CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3 | C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3) | FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表34]
R1 | R2 | R3 | R4 |
CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3 | C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)OCH3C(S)OCH3C(S)OCH3 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表35]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3 | C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3) | CH3CH3CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表36]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3 | C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | CH3CH3CH3CH2CH3CH2CH3CH2CH3FFFFFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表37]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CH2CF2CF2CF3CH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2H | C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2 | ClClClHHHCH3CH3CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表38]
R1 | R2 | R3 | R4 |
CH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2H | C(S)NH2C(S)NH2C(S)NH2C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | ClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表39]
R1 | R2 | R3 | R4 |
CH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CF2CF2CF2CF2HCH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3 | C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2 | FFFClClClHHHCH3CH3CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表40]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3 | C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表41]
R1 | R2 | R3 | R4 |
CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3CH2CH2CF2CF2CF2CF3 | C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | CH2CH3CH2CH3CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表42]
R1 | R2 | R3 | R4 |
CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3 | CNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCN | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH(CH3)2CH(CH3)2CH(CH3)2CH2CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH2CH3CH2CH2CH2CH2CH3CH2CH2CH2CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表43]
R1 | R2 | R3 | R4 |
CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3 | CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3 | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3FFFClClClHHHCH3CH3CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表44]
R1 | R2 | R3 | R4 |
CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3 | CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3) | ClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表45]
R1 | R2 | R3 | R4 |
CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3 | CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2 | FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表46]
R1 | R2 | R3 | R4 |
CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3 | CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表47]
R1 | R2 | R3 | R4 |
CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3 | C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表48]
R1 | R2 | R3 | R4 |
CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3 | C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | CH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表49]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3 | CNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCN | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH(CH3)2CH(CH3)2CH(CH3)2CH2CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH2CH3CH2CH2CH2CH2CH3CH2CH2CH2CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表50]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3 | CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3 | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3FFFClClClHHHCH3CH3CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF2CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表51]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3 | CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3) | ClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表52]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3 | CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2 | FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表53]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3 | CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表54]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3 | C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表55]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3CF2CF2CF2CF3 | C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | CH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表56]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3 | CNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCN | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH(CH3)2CH(CH3)2CH(CH3)2CH2CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH2CH3CH2CH2CH2CH2CH3CH2CH2CH2CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表57]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3 | CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3 | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3FFFClClClHHHCH3CH3CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表58]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3 | CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3) | ClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表59]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3 | CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2 | FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表60]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3 | CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表61]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3 | C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表62]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3CF2CF2CF2CF2CF3 | C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | CH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表63]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3 | CNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCN | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH(CH3)2CH(CH3)2CH(CH3)2CH2CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH2CH3CH2CH2CH2CH2CH3CH2CH2CH2CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表64]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3 | CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3 | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3FFFClClClHHHCH3CH3CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表65]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3 | CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3) | ClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表66]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3 | CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2 | FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表67]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3 | CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表68]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3 | C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表69]
R1 | R2 | R3 | R4 |
CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3CF2CF2CF2CF2CF2CF3 | C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | CH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表70]
R1 | R2 | R3 | R4 |
CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3 | CNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCN | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH(CH3)2CH(CH3)2CH(CH3)2CH2CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH2CH3CH2CH2CH2CH2CH3CH2CH2CH2CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表71]
R1 | R2 | R3 | R4 |
CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3 | CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3 | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3FFFClClClHHHCH3CH3CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表72]
R1 | R2 | R3 | R4 |
CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3 | CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3) | ClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表73]
R1 | R2 | R3 | R4 |
CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3 | CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2 | FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表74]
R1 | R2 | R3 | R4 |
CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3 | CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表75]
R1 | R2 | R3 | R4 |
CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3 | C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表76]
R1 | R2 | R3 | R4 |
CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3CH2CH2CH2CH2CF3 | C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | CH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表77]
R1 | R2 | R3 | R4 |
CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3 | CNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCNCN | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3CH(CH3)2CH(CH3)2CH(CH3)2CH2CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH2CH3CH2CH2CH2CH2CH3CH2CH2CH2CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表78]
R1 | R2 | R3 | R4 |
CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3 | CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2CH3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3 | HHHCH3CH3CH3CH2CH3CH2CH3CH2CH3CH2CH2CH3CH2CH2CH3CH2CH2CH3FFFClClClHHHCH3CH3CH3FFF | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表79]
R1 | R2 | R3 | R4 |
CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3 | CO2C(CH3)3CO2C(CH3)3CO2C(CH3)3CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH2CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3) | ClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表80]
R1 | R2 | R3 | R4 |
CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3 | CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CONH(CH2CH3)CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2 | FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表81]
R1 | R2 | R3 | R4 |
CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3 | CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2CON(CH3)2C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)OCH3C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH02C(S)NH2 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3FFFClClClHHHCH3CH3CH3 | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表82]
R1 | R2 | R3 | R4 |
CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3 | C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH2C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)NH(CH3)C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | CH2CH3CH2CH3CH2CH3FFFClClClHHHCH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClClHHH | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
[表83]
R1 | R2 | R3 | R4 |
CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3CH2CH2CH2CF2CF3 | C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2C(S)N(CH3)2 | CH3CH3CH3CH2CH3CH2CH3CH2CH3FFFClClCl | CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3CF3CF2CF3CF2CF2CF3 |
式(I-B)所示的化合物:
其中R1、R2、R3和R4是表1到表83中所述的组合。
式(I-C)所示的化合物:
其中R1、R2、R3和R4是表1到表83中所述的组合。
接下来,将通过参考制备例来说明本发明的化合物的中间体的制备。
参考制备例1
将9.6克1-溴-3,3,3-三氟丙烷和5克硫代苯甲酸溶解到30毫升N,N-二甲基甲酰胺中,并且在冰冷却条件下向其中加入1.45克氢化钠(在油中,60%)。混合物在室温下搅拌12小时。向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。分别用10%盐酸和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩。残渣经过硅胶色谱,得到6.90克S-(3,3,3-三氟丙基)硫代苯甲酸酯,其如下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)7.97(d,2H),7.58-7.62(m,1H),7.47(dd,2H),3.24(t,2H),2.44-2.56(m,2H)
参考制备例2
将9.9克1-碘-3,3,4,4,4-五氟丁烷和5克硫代苯甲酸溶解到30毫升N,N-二甲基甲酰胺中,并在冰冷却条件下向其中加入5.0克碳酸钾。混合物在室温下搅拌20小时。向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。分别用10%盐酸和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。残渣经过硅胶色谱,得到7.90克S-(3,3,4,4,4-五氟丁基)硫代苯甲酸酯,其如下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)7.95(d,2H),7.58-7.65(m,1H),7.47(dd,2H),3.27(t,2H),2.38-2.53(m,2H)
参考制备例3
将2.0克1-碘-3,3,4,4,4,5,5,5-七氟戊烷和0.9克硫代苯甲酸溶解到20毫升N,N-二甲基甲酰胺中,并在冰冷却条件下向其中加入0.9克碳酸钾。混合物在室温下搅拌20小时。向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。分别用10%盐酸和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。残渣经过硅胶色谱,得到1.75克S-(3,3,4,4,5,5,5-七氟戊基)硫代苯甲酸酯,其如下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)7.95(d,2H),7.58-7.64(m,1H),7.47(dd,2H),3.29(t,2H),2.40-2.56(m,2H)
参考制备例4
将10克S-(3,3,3-三氟丙基)硫代苯甲酸酯溶解到50毫升四氢呋喃中,并且在冰冷却条件下向其中加入8.4毫升甲醇钠(28%(w/w)甲醇溶液)。进一步地,向其中逐滴加入5.1克溴乙腈,并将混合物在室温下搅拌2小时。向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。分别用10%盐酸和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。将残渣溶解到40毫升乙酸中,并在冰冷却条件下向其中加入20毫升过乙酸(32%(w/w)乙酸溶液)。然后,混合物在60℃下搅拌10小时。反应混合物下降到室温并倒入水中,然后用乙酸乙酯萃取。分别用碳酸氢钠饱和水溶液和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到7.04克(3,3,3-三氟丙磺酰基)乙腈,其由下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)4.06(s,2H),3.48-3.55(m,2H),2.72-2.84(m,2H)
参考制备例5
将7.1克S-(3,3,4,4,4-五氟丁基)硫代苯甲酸酯溶解到50毫升四氢呋喃中,并且在冰冷却条件下向其中加入4.9毫升甲醇钠(28%(w/w)甲醇溶液)。进一步地,向其中逐滴加入3.0克溴乙腈,并将混合物在室温下搅拌20小时。向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。分别用10%盐酸和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩。将残渣溶解到40毫升乙酸中,并在冰冷却条件下向其中加入20毫升过乙酸(32%(w/w)乙酸溶液)。然后,混合物在60℃下搅拌8小时。反应混合物下降到室温并倒入水中,然后用乙酸乙酯萃取。分别用碳酸氢钠饱和水溶液和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到5.47克(3,3,4,4,4-五氟丁磺酰基)乙腈,其如下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)4.07(s,2H),3.51-3.58(m,2H),2.65-2.78(m,2H)
参考制备例6
将9.7克S-(3,3,4,4,5,5,5-七氟戊基)硫代苯甲酸酯溶解到30毫升四氢呋喃中,并且在冰冷却条件下向其中加入5.7毫升甲醇钠(28%(w/w)甲醇溶液)。而且,向其中逐滴加入3.5克溴乙腈,并将混合物在室温下搅拌10小时。向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。分别用10%盐酸和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩。将残渣溶解到40毫升乙酸中,并在冰冷却条件下向其中加入20毫升过乙酸(32%(w/w)乙酸溶液)。然后,混合物在60℃下搅拌6小时。反应混合物下降到室温并倒入水中,然后用乙酸乙酯萃取。分别用碳酸氢钠饱和水溶液和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,然后减压浓缩。得到的残渣经过硅胶色谱,得到6.54克S-(3,3,4,4,5,5,5-七氟戊磺酰基)乙腈,其如下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)4.09(s,2H),3.54-3.59(m,2H),2.69-2.84(m,2H)
参考制备例7
将10克硫代羟乙酸甲酯和21克1-碘-3,3,3-三氟丙烷溶解到200毫升N,N-二甲基甲酰胺中,并在冰冷却条件下向其中加入13克碳酸钾。混合物在室温下搅拌20小时。向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。分别用10%盐酸和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩。将残渣溶解到100毫升乙酸中,并在冰冷却条件下向其中加入50毫升过乙酸(32%(w/w)乙酸溶液)。然后,混合物在60℃下搅拌16小时。反应混合物冷却到室温并倒入水中,然后用乙酸乙酯萃取。分别用碳酸氢钠饱和水溶液和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到14.1克(3,3,3-三氟丙磺酰基)醋酸甲酯,其由下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)4.05(s,2H),3.84(s,3H),3.49-3.57(m,2H),2.66-2.79(m,2H)
参考制备例8
将10克硫代羟乙酸甲酯和26克1-碘-3,3,4,4,4-五氟丁烷溶解到100毫升N,N-二甲基甲酰胺中,并在冰冷却条件下向其中加入13克碳酸钾。混合物在室温下搅拌20小时。向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。分别用10%盐酸和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩。将残渣溶解到100毫升乙酸中,并在冰冷却条件下向其中加入50毫升过乙酸(32%(w/w)乙酸溶液)。然后,混合物在60℃下搅拌16小时。反应混合物冷却到室温并倒入水中,然后用乙酸乙酯萃取。分别用碳酸氢钠饱和水溶液和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到23.1克(3,3,4,4,4-五氟丁磺酰基)醋酸甲酯,其由下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)4.05(s,2H),3.86(s,3H),3.52-3.59(m,2H),2.59-2.75(m,2H)
参考制备例9
将5克硫代羟乙酸甲酯和15克1-碘-3,3,4,4,5,5,5-七氟戊烷溶解到50毫升N,N-二甲基甲酰胺中,并在冰冷却条件下向其中加入6.5克碳酸钾。混合物在室温下搅拌10小时。向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。分别用10%盐酸和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩。将残渣溶解到50毫升乙酸中,并在冰冷却条件下向其中加入20毫升过乙酸(32%(w/w)乙酸溶液)。然后,混合物在60℃下搅拌4小时。反应混合物冷却到室温并倒入水中,然后用乙酸乙酯萃取。分别用碳酸氢钠饱和水溶液和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到12.6克(3,3,4,4,5,5,5-七氟戊磺酰基)醋酸甲酯,其由下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)4.06(s,2H),3.86(s,3H),3.52-3.59(m,2H),2.63-2.78(m,2H)
参考制备例10
将0.3克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯溶解到30毫升甲醇中。在室温下向其中加入氢氧化钾水溶液(0.3克氢氧化钾和5毫升水的混合溶液),混合物在相同温度下搅拌24小时。向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并减压浓缩,得到0.28克5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸,其如下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)3.91-3.98(m,1H),3.48-3.56(m,2H),2.64-2.78(m,2H),2.23-2.54(m,4H)
参考制备例11
将0.5克2-甲基-5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸甲酯溶解到30毫升甲醇中。在室温下向其中加入氢氧化钾水溶液(0.3克氢氧化钾和5毫升水的混合溶液),混合物在相同温度下搅拌6小时。向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并减压浓缩,得到0.48克2-甲基-5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸,其如下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)3.48-3.54(m,2H),2.67-2.78(m,2H),2.18-2.56(m,4H),1.73(s,3H)
参考制备例12
将0.5克2-乙基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸甲酯溶解到30毫升甲醇中。在室温下向其中加入氢氧化钾水溶液(0.3克氢氧化钾和5毫升水的混合溶液),混合物在相同温度下搅拌10小时。向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并减压浓缩,得到0.48克2-乙基-5,5,6,6,6-五氟-2-(3,3,3-三氟丙磺酰基)己酸,其如下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)3.35-3.71(m,2H),2.08-2.78(m,8H),1.10(t,3H)
参考制备例13
将20克2-巯基丙酸乙酯和33克1-碘-3,3,3-三氟丙烷溶解到200毫升N,N-二甲基甲酰胺中,并在冰冷却条件下向其中加入21克碳酸钾。混合物在室温下搅拌4小时。向反应混合物中加入10%盐酸,并用乙酸乙酯萃取混合物。分别用10%盐酸和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩。将残渣溶解到100毫升乙酸中,并在冰冷却条件下向其中加入30毫升过乙酸(30%(w/w)乙酸溶液)。然后,混合物在60℃下搅拌4小时。反应混合物下降到室温并倒入水中,然后用乙酸乙酯萃取。分别用碳酸氢钠饱和水溶液和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到36.3克2-(3,3,3-三氟丙磺酰基)丙酸乙酯,其由下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)4.24-4.38(m,2H),3.94(q,1H),3.37-3.55(m,2H),2.62-2.78(m,2H),1.69(d,3H),1.34(t,3H)
参考制备例14
在室温下向40克5,5,6,6,6-五氟己腈中逐滴加入11毫升溴和2毫升三溴化磷,然后在90℃下搅拌6小时。反应混合物下降到室温。将反应混合物倒入水中,然后用乙酸乙酯萃取。随后用硫代硫酸钠饱和水溶液和氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩。得到的残渣经过硅胶色谱,得到17.5克2-溴-5,5,6,6,6-五氟己腈,其由下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)3.95-4.04(m,1H),3.49-3.57(m,2H),2.06-2.78(m,6H)
参考制备例15
将0.5克5,5,6,6,7,7,7-七氟-2-(3,3,4,4,4-五氟丁磺酰基)庚酸甲酯溶解到30毫升甲醇中,在室温下加入氢氧化钾水溶液(0.3克氢氧化钾和5毫升水的混合溶液),然后在相同温度下搅拌2天。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并随后减压浓缩,得到0.48克5,5,6,6,7,7,7-七氟-2-(3,3,4,4,4-五氟丁磺酰基)庚酸,其由下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)3.95-4.04(m,1H),3.49-3.57(m,2H),2.06-2.78(m,6H)
参考制备例16
将1.2克5,5,6,6,7,7,7-七氟-2-甲基-2-(3,3,4,4,4-五氟丁磺酰基)庚酸甲酯溶解到30毫升甲醇中,在室温下加入氢氧化钾水溶液(0.8克氢氧化钾和10毫升水的混合溶液),然后在相同温度下搅拌2天。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并随后减压浓缩,得到1.10克5,5,6,6,7,7,7-七氟-2-甲基-2-(3,3,4,4,4-五氟丁磺酰基)庚酸,其由下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)3.50-3.58(m,2H),2.14-2.77(m,6H),1.75(s,3H)
参考制备例17
将0.5克5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸甲酯溶解到50毫升甲醇中,在室温下加入氢氧化钾水溶液(0.4克氢氧化钾和5毫升水的混合溶液),然后在相同温度下搅拌1天。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。用氯化钠饱和水溶液洗涤有机层,用无水硫酸镁干燥,并减压浓缩,得到0.48克5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸,其由下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)3.95-4.01(m,1H),3.50-3.56(m,2H),2.22-2.75(m,6H)
参考制备例18
将0.9克2-甲基-5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸甲酯溶解到50毫升甲醇中,在室温下加入氢氧化钾水溶液(0.7克氢氧化钾和5毫升水的混合溶液),然后在相同温度下搅拌1天。向反应混合物中加入10%盐酸,然后用乙酸乙酯萃取。有机层用氯化钠饱和水溶液洗涤,用无水硫酸镁干燥,并随后减压浓缩,得到0.78克2-甲基-5,5,6,6,6-五氟-2-(3,3,4,4,4-五氟丁磺酰基)己酸,其由下式所示:
1H-NMR(CDCl3,TMS):δ(ppm)3.50-3.59(m,2H),2.16-2.75(m,6H),1.75(s,3H)
以下举例说明配方例。另外,“份”表示重量份。
配方例1
将本发明的化合物(1)到(103)中的每一种取9份,将其溶于37.5份二甲苯和37.5份N,N-二甲基甲酰胺中,并向其中加入10份聚氧乙烯苯乙烯基苯基醚和6份十二烷基苯磺酸钙,然后搅拌并良好混合,得到各种化合物的可乳化浓缩物。
配方例2
将本发明的化合物(1)到(103)中的每一种取40份,向其加入5份SORPOL 5060(TOHO KAGAKU KOGYO的注册商品名),然后良好混合。向混合物中加入32份CARPLEX#80(SHIONOGI&Co.的注册商品名,合成的水合硅酮氧化物(silicone oxide)细粉)和23份300目硅藻土,然后用果汁机(juice mixer)混合,得到每种化合物的可湿性粉剂。
配方例3
将本发明的化合物(1)到(103)中的每一种取3份,向其中加入5份合成水合二氧化硅细粉、5份十二烷基苯磺酸钠、30份膨润土和57份粘土,然后搅拌并良好混合。然后,向该混合物中加入合适量的水,然后进一步搅拌、用成粒器粒化、并风干,得到每种化合物的颗粒。
配方例4
将本发明的化合物(1)到(103)中的每一种取4.5份,使用研钵将其与1份合成水合二氧化硅细粉、1份作为絮凝剂的Doriresu B(Sankyo Co.,Ltd.)和7份粘土良好混合,然后用果汁机搅拌混合。向得到的混合物中加入86.5份切削粘土,然后搅拌并良好混合,得到各种化合物的粉尘。
配方例5
将本发明的化合物(1)到(103)中的每一种取10份,将其与含有50份聚氧乙烯烷基醚硫酸铵盐的35份白碳(white carbon)和55份水混合并通过湿磨法粉碎,得到各种化合物的配方。
配方例6
将本发明的化合物(1)到(103)中的每一种取0.5份,将其溶解在10份二氯甲烷中,得到的溶液与89.5份Iso-Par M(异链烷烃:EXXONCHEMICAL LTD的注册商品名),得到油溶液。
配方例7
将本发明的化合物(1)到(103)中的每一种取0.1份,将其与49.9份NEO-CHIOZOL(CHUO KASEI Co.,LTD)装入气溶胶罐,并将气溶胶阀固定到罐上。然后,用25份二甲醚和25份LPG填充该罐,然后在其上安装促动器,得到油气溶胶。
配方例8
将本发明的化合物(1)到(103)中的每一种取0.6份,将其与0.01份BHT、5份二甲苯、3.39份脱臭煤油和1份乳化剂[Atmos 300(ATMOSCHEMICAL LTD.的注册商品名)]混合并溶解。将得到的溶液与50份蒸馏水装入气溶胶容器,并在该容器上固定阀。在压力下通过该阀充入40份推进剂(LPG),得到水性气溶胶。
以下试验例将证明本发明的化合物可用作有害节肢动物控制剂的活性成分。
试验例1
配方例5中所得配制剂-分别用本发明化合物(1),(2),(3),(4),(5),(6),(8),(9),(11),(12),(13),(14),(15),(16),(17),(18),(20),(21),(22),(23),(24),(25),(26),(27),(29),(30),(31),(32),(33),(34),(35),(36),(37),(38),(39),(40),(41),(44),(45),(46),(47),(48),(49),(50),(52),(53),(55),(56),(57),(58),(59),(60),(61),(63),(64),(65),(67),(68),(71),(72),(73),(74),(75),(78),(79),(80),(81),(82),(83),(84),(86),(87),(88),(89),(90),(91),(93)、(94)、(96)、(97)、(100)、(101)、(102)和(103),将上述配制剂用水稀释,使得活性成分浓度达到55.6ppm,从而制备试验溶液。
将50克molding Bonsoru 2(得自Sumitomo Chemical Co.,Ltd.)置于具有5个直径为5毫米的孔的聚乙烯杯中,在聚乙烯杯中栽植10到15颗稻种。稻植株生长,直到第二片植物叶发芽,然后用如上所述制备的试验溶液处理,该试验溶液被从杯子的底部吸收45毫升的体积。将稻植株在25℃下在温室中放置6天,然后切割成5厘米的相同高度。褐色飞虱(褐飞虱)的三十一龄幼虫被放到稻植株上,然后将其放在25℃的温室中。在释放稻褐飞虱之后的第六天,检查稻植株上寄生的褐色飞虱。结果,在用本发明的化合物(1),(2),(3),(4),(5),(6),(8),(9),(11),(12),(13),(14),(15),(16),(17),(18),(20),(21),(22),(23),(24),(25),(26),(27),(29),(30),(31),(32),(33),(34),(35),(36),(37),(38),(39),(40),(41),(44),(45),(46),(47),(48),(49),(50),(52),(53),(55),(56),(57),(58),(59),(60),(61),(63),(64),(65),(67),(68),(71),(72),(73),(74),(75),(78),(79),(80),(81),(82),(83),(84),(86),(87),(88),(89),(90),(91),(93),(94),(96),(97),(100),(101),(102)和(103)中的每一种进行的处理中,处理后第六天的寄生害虫数目不大于3。
试验例2
根据配方例5所得配制剂分别使用本发明的化合物(1),(2),(3),(4),(5),(6),(8),(9),(10),(11),(12),(13),(14),(15),(16),(17),(18),(19),(20),(21),(22),(23),(25),(26),(28),(29),(30),(31),(32),(33),(34),(35),(36),(37),(38),(39),(40),(41),(43),(44),(45),(46),(47),(48),(49),(50),(52),(53),(55),(56),(57),(58),(59),(60),(61),(63),(64),(65),(66),(67),(68),(69),(70),(71),(72),(73),(74),(75),(78),(79),(80),(81),(82),(84),(86),(87),(88),(89),(90),(91),(93),(94),(95),(96),(97),(99),(100),(101),(102)和(103),将其用水稀释到活性成分浓度达到500ppm,从而制备试验溶液。
在直径为5.5厘米的聚乙烯杯的底部,放置具有相同直径的滤纸,在滤纸上滴加0.7毫升上述试验溶液,然后在其上均匀地加上30毫克蔗糖作为诱饵。将十只雌性家蝇成虫释放到该聚乙烯杯中,并用盖子将其覆盖。24小时之后,检查存活和死亡的家蝇数目,并计算害虫死亡率。
结果,在用本发明的化合物(1),(2),(3),(4),(5),(6),(8),(9),(10),(11),(12),(13),(14),(15),(16),(17),(18),(19),(20),(21),(22),(23),(25),(26),(28),(29),(30),(31),(32),(33),(34),(35),(36),(37),(38),(39),(40),(41),(43),(44),(45),(46),(47),(48),(49),(50),(52),(53),(55),(56),(57),(58),(59),(60),(61),(63),(64),(65),(66),(67),(68),(69),(70),(71),(72),(73),(74),(75),(78),(79),(80),(81),(82),(84),(86),(87),(88),(89),(90),(91),(93),(94),(95),(96),(97),(99),(100),(101),(102)和(103)中的每一个进行的处理中,害虫死亡率均为70%以上。
试验例3
根据配方例5所得配制剂分别使用本发明的化合物(1),(2),(3),(4),(5),(6),(7),(8),(9),(10),(11),(12),(13),(14),(15),(16),(17),(20),(21),(23),(26),(29),(30),(31),(32),(33),(34),(35),(36),(37),(38),(39),(40),(41),(44),(45),(46),(47),(49),(50),(52),(53),(55),(56),(57),(58),(59),(60),(61),(63),(64),(65),(67),(68),(69),(70),(71),(72),(73),(74),(75),(78),(79),(80),(81),(84),(86),(87),(88),(89),(90),(91),(93),(94),(96),(97),(100),(101),(102)和(103),将其用水稀释到活性成分浓度达到500ppm,从而得到试验溶液。
在直径为5.5厘米的聚乙烯杯的底部,铺放具有相同直径的滤纸,并且在滤纸上滴加0.7毫升上述试验溶液,然后在其上均匀放置30毫克蔗糖作为诱饵。将二只德国小蠊成虫释放到该聚乙烯杯中,并用盖子将其覆盖。6天之后,检查存活和死亡的德国小蠊数目,并计算害虫死亡率。
结果,在用本发明的化合物(1),(2),(3),(4),(5),(7),(8),(9),(10),(11),(12),(13),(14),(15),(16),(17),(20),(21),(23),(26),(29),(30),(31),(32),(33),(34),(35),(36),(37),(38),(39),(40),(41),(44),(45),(46),(47),(49),(50),(52),(53),(55),(56),(57),(58),(59),(60),(61),(63),(64),(65),(67),(68),(69),(70),(71),(72),(73),(74),(75),(78),(79),(80),(81),(84),(86),(87),(88),(89),(90),(91),(93),(94),(96),(97),(100),(101),(102)和(103)中的每一种进行的处理中,害虫死亡率均为100%。
试验例4
根据配方例5所得配制剂分别使用本发明的化合物(1),(2),(3),(4),(5),(6),(7),(8),(9),(10),(11),(12),(13),(14),(15),(16),(17),(18),(19),(20),(21),(22),(23),(24),(25),(26),(29),(30),(31),(32),(33),(34),(35),(36),(37),(38),(39),(40),(41),(42)(45),(46),(47),(49),(50),(51),(52),(53),(56),(57),(58),(59),(60),(61),(63),(65),(67),(68),(69),(70),(71),(72),(73),(74),(75),(76),(78),(79),(80),(81),(82),(83),(84),、(86),(87),(88),(89),(90),(91),(92),(93),(94),(95),(96),(97),(100),(102)和(103),将其用水稀释到活性成分浓度达到500ppm,从而制备试验溶液。
将0.7毫升上述试验溶液加到100毫升离子交换水中(活性成分浓度:3.5ppm)。将二十只淡色库蚊的的末龄幼虫释放到该溶液中。一天之后,检查存活和死亡的淡色库蚊数目,并计算害虫死亡率。
结果,在用本发明的化合物(1),(2),(3),(4),(5),(5),(7),(8),(9),(10),(11),(12),(13),(14),(15),(16),(17),(18),(19),(20),(21),(22),(23),(24),(25),(26),(29),(30),(31),(32),(33),(34),(35),(36),(37),(38),(39),(40),(41),(42),(45),(46),(47),(49),(50),(51),(52),(53),(56),(57),(58),(59),(60),(61),(63),(65),(67),(68),(69),(70),(71),(72),(73),(74),(75),(76),(78),(79),(80),(81),(82),(83),(84),(86),(87),(88),(89),(90),(91),(92),(93),(94),(95),(96),(97),(100),(102)和(103)中的每一种进行的处理中,害虫的死亡率不低于90%。
工业实用性
本发明的化合物可用作有害节肢动物剂的活性成分。
Claims (10)
2.根据权利要求1所述的有机硫化合物,其中n是2。
3.根据权利要求1所述的有机硫化合物,其中R2是氰基或C(=O)R5所示基团。
4.根据权利要求1所述的有机硫化合物,其中R2是氰基。
5.根据权利要求1所述的有机硫化合物,其中R2是C(=O)R5所示基团,且R5是任选被1或2个C1-C4烷基取代的氨基。
6.根据权利要求1所述的有机硫化合物,其中R2是C(=O)R5所示基团,且R5是氨基。
7.根据权利要求1所述的有机硫化合物,其中R3是卤原子。
8.一种有害节肢动物控制剂,其包括根据权利要求1所述的有机硫化合物和惰性载体。
9.控制有害节肢动物的方法,该方法包括将有效量的根据权利要求1所述的有机硫化合物应用到有害节肢动物或有害节肢动物栖息地。
10.根据权利要求1所述的化合物在有害节肢动物控制中的应用。
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2006
- 2006-11-01 BR BRPI0618755-2A patent/BRPI0618755A2/pt not_active IP Right Cessation
- 2006-11-01 WO PCT/JP2006/322322 patent/WO2007060839A1/en active Application Filing
- 2006-11-01 EP EP06832438A patent/EP1951664A1/en not_active Withdrawn
- 2006-11-01 KR KR1020087015170A patent/KR20080069268A/ko not_active Application Discontinuation
- 2006-11-01 AU AU2006317486A patent/AU2006317486B9/en not_active Ceased
- 2006-11-01 US US12/094,255 patent/US8017656B2/en not_active Expired - Fee Related
- 2006-11-01 CN CN201210585868.3A patent/CN103121962B/zh not_active Expired - Fee Related
- 2006-11-01 CN CN2006800433285A patent/CN101312944B/zh not_active Expired - Fee Related
- 2006-11-16 TW TW095142376A patent/TWI373462B/zh not_active IP Right Cessation
- 2006-11-20 AR ARP060105073A patent/AR057914A1/es not_active Application Discontinuation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102264696A (zh) * | 2008-12-24 | 2011-11-30 | 住友化学株式会社 | 含硫化合物及其用途 |
CN104557759A (zh) * | 2013-10-17 | 2015-04-29 | 中国科学院大连化学物理研究所 | 一种制备5-磺酰甲基噁唑衍生物的方法 |
Also Published As
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TW200730486A (en) | 2007-08-16 |
AR057914A1 (es) | 2007-12-26 |
CN103121962B (zh) | 2014-11-12 |
EP1951664A1 (en) | 2008-08-06 |
US20090186941A1 (en) | 2009-07-23 |
BRPI0618755A2 (pt) | 2011-09-13 |
WO2007060839A1 (en) | 2007-05-31 |
KR20080069268A (ko) | 2008-07-25 |
AU2006317486B2 (en) | 2011-05-19 |
AU2006317486B9 (en) | 2011-08-04 |
AU2006317486A1 (en) | 2007-05-31 |
TWI373462B (en) | 2012-10-01 |
CN103121962A (zh) | 2013-05-29 |
US8017656B2 (en) | 2011-09-13 |
CN101312944B (zh) | 2013-03-06 |
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