CN1169794C - 4-喹啉酚衍生物及以此为有效组分的农业园艺用杀菌剂 - Google Patents
4-喹啉酚衍生物及以此为有效组分的农业园艺用杀菌剂 Download PDFInfo
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- CN1169794C CN1169794C CNB98805678XA CN98805678A CN1169794C CN 1169794 C CN1169794 C CN 1169794C CN B98805678X A CNB98805678X A CN B98805678XA CN 98805678 A CN98805678 A CN 98805678A CN 1169794 C CN1169794 C CN 1169794C
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- 239000000417 fungicide Substances 0.000 title abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 703
- 150000001875 compounds Chemical class 0.000 claims description 99
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
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- 239000002904 solvent Substances 0.000 description 58
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- -1 quinoline skeleton Quinoline derivatives Chemical class 0.000 description 31
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- 230000003595 spectral effect Effects 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
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- 125000003118 aryl group Chemical group 0.000 description 7
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- DBZAGNVZNFWDEH-UHFFFAOYSA-N [6-butan-2-yl-8-(hydroxymethyl)-2,3-dimethylquinolin-4-yl] acetate Chemical compound N1=C(C)C(C)=C(OC(C)=O)C2=CC(C(C)CC)=CC(CO)=C21 DBZAGNVZNFWDEH-UHFFFAOYSA-N 0.000 description 5
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
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- IHRANGNYTKVTLQ-UHFFFAOYSA-N [6-butan-2-yl-8-(chloromethyl)-2,3-dimethylquinolin-4-yl] acetate Chemical compound N1=C(C)C(C)=C(OC(C)=O)C2=CC(C(C)CC)=CC(CCl)=C21 IHRANGNYTKVTLQ-UHFFFAOYSA-N 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
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- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 3
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- HRDXJKGNWSUIBT-UHFFFAOYSA-N methoxybenzene Chemical group [CH2]OC1=CC=CC=C1 HRDXJKGNWSUIBT-UHFFFAOYSA-N 0.000 description 1
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- 230000001717 pathogenic effect Effects 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
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- 150000003248 quinolines Chemical class 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
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- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- 239000003549 soybean oil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/22—Oxygen atoms attached in position 2 or 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/22—Oxygen atoms attached in position 2 or 4
- C07D215/233—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 4
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract
本发明提供了具有良好防治效果的新颖的农业园艺用杀菌剂，以下式(I)表示的4-喹啉酚衍生物或其可用于农业、农业领域的酸加成盐为有效组分。
Description
技术领域
本发明涉及4-喹啉酚衍生物及以此为有效组分的农业园艺用杀菌剂。
背景技术
本申请前的日本专利公开公报平1-246263号、日本专利公开公报平5-202032号、日本专利公开公报平5-271222号、日本专利公开公报平7-285938号中记载了在喹啉骨架的4位上具有烯丙氧基、烯丙硫代基、氨基、嘧啶氧基、嘧啶硫代基、苯甲酰基等取代基的喹啉衍生物对植物病原菌有效，作为农业园艺用杀菌剂很有用。但未揭示喹啉骨架的4位上具有酰氧基的喹啉衍生物具有良好抗菌活性的事实。
此外，日本专利公开公报平3-128355号记载了与本申请的发明化合物类似的4-酰氧基喹啉衍生物及以此为有效组分的杀虫、杀螨剂，但至今仍不知这些化合物对植物病原菌的有效性。
发明的揭示
目前，发现了许多对各种植物病害显现出防治效果的活性物质，开发了各种以这些活性物质为有效组分的农业园艺用杀菌剂。但是，由于出现了抗异变性菌等问题，需要开发出防治效果更好的杀菌剂。
所以，本发明的课题是提供效果更好的新颖的农业园艺用杀菌剂。
为了解决上述问题，本发明者们进行了认真研究，发现4-喹啉酚衍生物中，在喹啉骨架的2位、3位和5～8位上同时具有特定取代基的4-喹啉酚衍生物及其酸加成盐对包括稻瘟病菌、稻胡麻斑病菌、瓜类白粉病菌、马铃薯炭疽病菌等在内的各种植物病原菌显现出良好的抗菌活性，从而完成了本发明。
即，本发明为通式(I)表示的4-喹啉酚衍生物及其酸加成盐和至少含有1种上述组分的农业园艺用杀菌剂，
其中的R1表示氢原子或碱金属、碱土金属、COR4{R4表示氢原子、可被取代的C1～C18烷基、可被取代的C2～C18链烯基、可被取代的C3～C10环烷基、可被取代的苯基低级烷基、可被取代的苯氧基低级烷基、可被取代的芳基、OR5(R5表示可被取代的低级烷基、可被取代的芳基、可被取代的杂环基、可被的取代的苯基低级烷基、可被取代的苯氧基低级烷基)或NR6N7(R6及R7分别表示氢原子、可被取代的C1～C6烷基、可被取代的苯基或R6及R7与N一起形成包含1个或2个杂原子的4～6元环)}，R2表示可被取代的低级烷基，R3表示可被取代的C1～C18烷基、可被取代的低级链烯基或可被取代的低级烷氧基或R2和R3-起表示-(CH2)m-(m为3或4)，W表示在环上取代的相同或不同的1～4个卤原子、可被取代的C1～C10烷基、可被取代的低级链烯基、可被取代的C1～C10烷氧基、可被取代的C3～C10环烷基、可被取代的芳基、可被取代的芳氧基、NR8R9(R8及R9分别表示氢原子、可被取代的C1～C6烷基、可被取代的苯基或R8及R9与N一起形成包含1个或2个杂原子的4～6元环)、COR10(R10表示氢原子、可被取代的低级烷基或可被取代的低级链烯基)、COOR11(R11表示氢原子、可被取代的低级烷基或低级链烯基)、硝基或氰基。
通式(I)表示的4-喹啉酚衍生物中，R1为氢原子或碱金属，例如，较好为钠、钾等；或碱土金属，例如，镁、钙和钡等，较好为镁和钙；或COR4{R4表示氢原子或可被取代的C1～C18烷基，较好为可被取代的C1～C8烷基，更好为C1～C4烷基(例如，甲基、乙基、丙基、异丙基、丁基、异丁基或叔丁基等)，或可被取代的C2～C18链烯基，较好为可被取代的C2～C8链烯基，更好为C2～C4链烯基(例如，乙烯基CH2＝CH-、烯丙基CH2＝CHCH2-或2-丁烯基CH3CH＝CH＝CH2-等)，或可被取代的C3～C10环烷基，较好为可被取代的C3～C6环烷基，或可被取代的苯基低级烷基，或可被取代的苯氧基低级烷基，或可被取代的芳基，或OR5(R5表示可被取代的低级烷基、可被取代的芳基、可被取代的杂环基、可被取代的苯基低级烷基、可被取代的苯氧基低级烷基)或NR6N7(R6及R7分别表示氢原子、可被取代的C1～C6烷基、可被取代的苯基或R6及R7与N一起形成包含1个或2个杂原子的4～6元环)}。
R2表示可被取代的C1～C4烷基。
R3表示可被取代的C1～C18烷基，较好为C1～C6烷基，更好为C1～C4烷基(例如，甲基、乙基、丙基、异丙基、丁基、异丁基或叔丁基等)，可被取代的低级链烯基或可被取代的低级烷氧基或R2与R3一起表示-(CH2)m-(m为3或4)。
W表示在环上取代的相同或不同的1～4个卤原子、可被取代的C1～C10烷基、可被取代的低级链烯基、可被取代的C1～C10烷氧基、可被取代的C3～C10环烷基、可被取代的芳基、可被取代的芳氧基、NR8R9(R8及R9分别表示氢原子、可被取代的C1～C6烷基、可被取代的苯基或R8及R9与N一起形成包含1个或2个杂原子的4～6元环)、COR10(R10表示氢原子、可被取代的低级烷基或可被取代的低级链烯基)、COO11(R11表示氢原子、可被取代的低级烷基或低级链烯基)、硝基或氰基。
上述通式(I)表示的4-喹啉酚衍生物中的适用于农业园艺领域的酸加成盐是指盐酸盐、硝酸盐、硫酸盐、磷酸盐、乙酸盐等一般农业园艺领域可使用的盐类。
通式(I)表示的4-喹啉酚衍生物可以是水合物或溶剂合物，这些具有水合物和溶剂合物的通式(I)表示的化合物也包括在本发明内。
可取代通式(I)表示的4-喹啉酚衍生物的较好的取代基包括卤原子(例如，氟原子、溴原子、氯原子等)，C1～C4烷基、C1～C4烷氧基、羟基、硝基、甲酰基、氰基等。
本说明书中所用的“低级烷基”是指C1～C4烷基，例如，甲基、乙基、丙基、丁基等。
“低级链烯基”是指C2～C4链烯基，例如，乙烯基、(1-或2-)丙烯基、(1-、2-或3-)丁烯基等。
“低级炔基”是指C2～C4炔基，例如，乙炔基、(1-或2-)丙炔基、(1-、2-或3-)丁炔基等。
“低级烷氧基”是指C1～C4烷氧基，例如，甲氧基、乙氧基、丙氧基、丁氧基等。
“C1～C18烷基”是指甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基和十八烷基等。
“C2～C18链烯基”是指乙烯基、(1-或2-)丙烯基、(1-、2-或3-)丁烯基、(1-、2-、3-或4-)戊烯基、(1-、2-、3-、4-或5-)己烯基、(1-、2-、3-、4-、5-或6-)庚烯基、(1-、2-、3-、4-、5-、6-或7-)辛烯基、(1-、2-、3-、4-、5-、6-、7-或8-)壬烯基、(1-、2-、3-、4-、5-、6-、7-、8-或9-)癸烯基、(1-、2-、3-、4-、5-、6-、7-、8-、9-或10-)十一碳烯基、(1-、2-、3-、4-、5-、6-、7-、8-、9-、10-或11-)十二碳烯基、(1-、2-、3-、4-、5-、6-、7-、8-、9-、10-、11-或12-)十三碳烯基、(1-、2-、3-、4-、5-、6-、7-、8-、9-、10-、11-、12-或13-)十四碳烯基、(1-、2-、3-、4-、5-、6-、7-、8-、9-、10-、11-、12-、13-或14-)十五碳烯基、(1-、2-、3-、4-、5-、6-、7-、8-、9-、10-、11-、12-、13-、14-或15-)十六碳烯基、(1-、2-、3-、4-、5-、6-、7-、8-、9-、10-、11-、12-、13-、14-、15-或16-)十七碳烯基、(1-、2-、3-、4-、5-、6-、7-、8-、9-、10-、11-、12-、13-、14-、15-、16-或17-)十八碳烯基等。
“C3～C10环烷基”是指环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环壬基和环癸基。
“C1～C10烷氧基”是指甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基和癸氧基。
“苯基低级烷基”是指苄基、(1-或2-)苯乙基、(1-、2-或3-)苯丙基、(1-、2-、3-或4-)苯丁基等具有C1～C4烷基部分的苯烷基。
“苯氧基低级烷基”是指苯氧甲基、(1-或2-)苯氧乙基、(1-、2-或3-)苯氧丙基、(1-、2-、3-或4-)苯氧丁基等具有C1～C4烷基部分的苯氧烷基。
以下表1所示的是通式(I)表示的本发明化合物4-羟基喹啉衍生物的具体例子。
以下表1和实施例中所用的省略符号具有以下含义：
iso-C3H7 异丙基
t-C4H9 叔丁基
s-C4H9 仲丁基
c-C5H9 环戊基
c-C6H11 环己基
n-戊基 正戊基
表1
| 化合物编号 | R1 | R2 | R3 | W |
| 1 | H | CH3 | CH3 | 6-CH3 |
| 2 | CH3CO | CH3 | CH3 | 6-CH3 |
| 3 | C6H5CO | CH3 | CH3 | 6-CH3 |
| 4 | CH3OCO | CH3 | CH3 | 6-CH3 |
| 5 | H | CH3 | CH3 | 6-CH3O |
| 6 | CH3CO | CH3 | CH3 | 6-CH3O |
| 7 | C6H5CO | CH3 | CH3 | 6-CH3O |
| 8 | CH3OCO | CH3 | CH3 | 6-CH3O |
| 9 | H | CH3 | CH3 | 6-C2H5 |
| 10 | CH3CO | CH3 | CH3 | 6-C2H5 |
| 11 | C6H5CO | CH3 | CH3 | 6-C2H5 |
| 12 | CH3OCO | CH3 | CH3 | 6-C2H5 |
| 13 | H | CH3 | CH3 | 6-C3H7 |
| 14 | CH3CO | CH3 | CH3 | 6-C3H7 |
| 15 | C6H5CO | CH3 | CH3 | 6-C3H7 |
| 16 | CH3OCO | CH3 | CH3 | 6-C3H7 |
| 17 | (C2H5)2NCO | CH3 | CH3 | 6-C3H7 |
| 18 | H | CH3 | CH3 | 6-iso-C3H7 |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 19 | CH3CO | CH3 | CH3 | 6-iso-C3H7 |
| 20 | C6H5CO | CH3 | CH3 | 6-iso-C3H7 |
| 21 | CH3OCO | CH3 | CH3 | 6-iso-C3H7 |
| 22 | (C2H5)2NCO | CH3 | CH3 | 6-iso-C3H7 |
| 23 | H | CH3 | CH3 | 6-i5o-C3H7O |
| 24 | CH3CO | CH3 | CH3 | 6-iso-C3H7O |
| 25 | C6H5CO | CH3 | CH3 | 6-iso-C3H7O |
| 26 | CH3OCO | CH3 | CH3 | 6-iso-C3H7O |
| 27 | C6H5OCO | CH3 | CH3 | 6-iso-C3H7O |
| 28 | H | CH3 | CH3 | 6-C4H9 |
| 29 | CH3CO | CH3 | CH3 | 6-C4H9 |
| 30 | C2H5CO | CH3 | CH3 | 6-C4H9 |
| 31 | c-C3H5CO | CH3 | CH3 | 6-C4H9 |
| 32 | t-C4H9CO | CH3 | CH3 | 6-C4H9 |
| 33 | C6H5CO | CH3 | CH3 | 6-C4H9 |
| 34 | 4-CH3O-C6H4CO | CH3 | CH3 | 6-C4H9 |
| 35 | 4-Cl-C6H4CO | CH3 | CH3 | 6-C4H9 |
| 36 | CH3OCO | CH3 | CH3 | 6-C4H9 |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 37 | C2H5OCO | CH3 | CH3 | 6-C4H9 |
| 38 | C8H17OCO | CH3 | CH3 | 6-C4H9 |
| 39 | C6H5OCO | CH3 | CH3 | 6-C4H9 |
| 40 | 4-CH3O-C6H4CO | CH3 | CH3 | 6-C4H9 |
| 41 | 4-Cl-C6H4OCO | CH3 | CH3 | 6-C4H9 |
| 42 | (C2H6)2NCO | CH3 | CH3 | 6-C4H9 |
| 43 | (C6H5)2NCO | CH3 | CH3 | 6-C4H9 |
| 44 | CH3CO | C2H5 | CH3 | 6-C4H9 |
| 45 | CH3CO | C3H7 | CH3 | 6-C4H9 |
| 46 | CH3CO | C4H9 | CH3 | 6-C4H9 |
| 47 | CH3CO | CH3 | C2H5 | 6-C4H9 |
| 48 | CH3CO | CH3 | C3H7 | 6-C4H9 |
| 49 | CH3CO | CH3 | C4H9 | 6-C4H9 |
| 50 | H | -(CH2)4- | 6-C4H9 | |
| 51 | CH3CO | -(CH2)4- | 6-C4H9 | |
| 52 | C2H5CO | -(CH2)4- | 6-C4H9 | |
| 53 | C6H5CO | -(CH2)4- | 6-C4H9 | |
| 54 | H | CH3 | CH3 | 6-s-C4H9 |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 55 | CH3CO | CH3 | CH3 | 6-s-C4H9 - |
| 56 | C2H5CO | CH3 | CH3 | 6-s-C4H9 |
| 57 | c-C3H5CO | CH3 | CH3 | 6-s-C4H9 |
| 58 | 1-C4H9CO | CH3 | CH3 | 6-s-C4H9 |
| 59 | 1-C4H9CH2CO | CH3 | CH3 | 6-s-C4H9 |
| 60 | C8H17CO | CH3 | CH3 | 6-s-C4H9 |
| 61 | C6H5CO | CH3 | CH3 | 6-s-C4H9 |
| 62 | 4-CH3O-C6H4CO | CH3 | CH3 | 6-s-C4H9 |
| 63 | 4-Cl-C6H4CO | CH3 | CH3 | 6-s-C4H9 |
| 64 | 2，6-di-CH3O-C6H3CO | CH3 | CH3 | 6-s-C4H9 |
| 65 | CH3OCO | CH3 | CH3 | 6-s-C4H9 |
| 66 | C2H5OCO | CH3 | CH3 | 6-s-C4H9 |
| 67 | C8H17OCO | CH3 | CH3 | 6-s-C4H9 |
| 68 | C6H5OCO | CH3 | CH3 | 6-s-C4H9 |
| 69 | 4-CH3O-C6H4OCO | CH3 | CH3 | 6-s-C4H9 |
| 70 | 4-Cl-C6H4OCO | CH3 | CH3 | 6-s-C4H9 |
| 71 | (CH3)2NCO | CH3 | CH3 | 6-s-C4H9 |
| 72 | (C2H5)2NCO | CH3 | CH3 | 6-s-C4H9 |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 73 | CH3(C6H5)NCO | CH3 | CH3 | 6-s-C4H9 |
| 74 | (C6H5)2NCO | CH3 | CH3 | 6-s-C4H9 |
| 75 | H | CH3 | CH3O | 6-t-C4H9 |
| 76 | CH3CO | CH3 | CH3O | 6-t-C4H9 |
| 77 | H | CH3 | CH3O | 6-s-C4H9 |
| 78 | CH3CO | CH3 | CH3O | 6-s-C4H9 |
| 79 | CH3CO | CH3 | CF3 | 6-s-C4H9 |
| 80 | H | CH3 | CF3 | 6-s-C4H9 |
| 81 | CH3CO | CH3 | CF3 | 6-t-C4H9 |
| 82 | H | CH3 | CF3 | 6-t-C4H9 |
| 83 | H | CH3 | CH3 | 6-t-C4H9 |
| 84 | CH3CO | CH3 | CH3 | 6-t-C4H9 |
| 85 | C2H5CO | CH3 | CH3 | 6-t-C4H9 |
| 86 | c-C3H5CO | CH3 | CH3 | 6-t-C4H9 |
| 87 | C6H5CO | CH3 | CH3 | 6-t-C4H9 |
| 88 | CH3OCO | CH3 | CH3 | 6-t-C4H9 |
| 89 | C2H5OCO | CH3 | CH3 | 6-t-C4H9 |
| 90 | C6H5OCO | CH3 | CH3 | 6-t-C4H9 |
表1(续)
| 化合物编号 | R1 | R3 | R3 | W |
| 91 | (C2H5)2NCO | CH3 | CH3 | 6-t-C4H9 |
| 92 | H | CH3 | CH3 | 6-iso-C4H9 |
| 93 | CH3CO | CH3 | CH3 | 6-iso-C4H9 |
| 94 | C6H5CO | CH3 | CH3 | 6-iso-C4H9 |
| 95 | CH3OCO | CH3 | CH3 | 6-i5o-C4H9 |
| 96 | C6H5OCO | CH3 | CH3 | 6-iso-C4H9 |
| 97 | H | CH3 | CH3 | 6-C5H11 |
| 98 | CH3CO | CH3 | CH3 | 6-C5H11 |
| 99 | C6H5CO | CH3 | CH3 | 6-C5H11 |
| 100 | CH3OCO | CH3 | CH3 | 6-C5H11 |
| 101 | C6H5OCO | CH3 | CH3 | 6-C5H11 |
| 102 | H | CH3 | CH3 | 6-c-C5H9 |
| 103 | CH3CO | CH3 | CH3 | 6-c-C5H9 |
| 104 | C6H5CO | CH3 | CH3 | 6-c-C5H9 |
| 105 | CH3OCO | CH3 | CH3 | 6-c-C5H9 |
| 106 | (C2H5)2NCO | CH3 | CH3 | 6-c-C5H9 |
| 107 | H | CH3 | CH3 | 6-C6H13 |
| 108 | CH3CO | CH3 | CH3 | 6-C6H13 |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 109 | C6H5CO | CH3 | CH3 | 6-C6H13 |
| 110 | CH3OCO | CH3 | CH3 | 6-C6H13 |
| 111 | H | CH3 | CH3 | 6-c-C6H11 |
| 112 | CH3CO | CH3 | CH3 | 6-c-C6H11 |
| 113 | C2H5CO | CH3 | CH3 | 6-c-C6H11 |
| 114 | C6H5CO | CH3 | CH3 | 6-c-C6H11 |
| 115 | 4-CH3O-C6H4CO | CH3 | CH3 | 6-c-C6H11 |
| 116 | 4-Cl-C6H4CO | CH3 | CH3 | 6-c-C6H11 |
| 117 | CH3OCO | CH3 | CH3 | 6-c-C6H11 |
| 118 | C6H5CO | CH3 | CH3 | 6-c-C6H11 |
| 119 | (C2H5)2NCO | CH3 | CH3 | 6-c-C6H11 |
| 120 | H | CH3 | CH3 | 6-C7H15 |
| 121 | CH3CO | CH3 | CH3 | 6-C7H15 |
| 122 | C6H5CO | CH3 | CH3 | 6-C7H15 |
| 123 | CH3OCO | CH3 | CH3 | 6-C7H15 |
| 124 | C6H5OCO | CH3 | CH3 | 6-C7H15 |
| 125 | H | CH3 | CH3 | 6-C8H17 |
| 126 | CH3CO | CH3 | CH3 | 6-C8H17 |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 127 | C6H5CO | CH3 | CH3 | 6-C8H17 |
| 128 | CH3OCO | CH3 | CH3 | 6-C8H17 |
| 129 | C2H5OCO | CH3 | CH3 | 6-C8H17 |
| 130 | C6H5OCO | CH3 | CH3 | 6-C8H17 |
| 131 | H | CH3 | CH3 | 6-CF3 |
| 132 | CH3CO | CH3 | CH3 | 6-CF3 |
| 133 | C6H5CO | CH3 | CH3 | 6-CF3 |
| 134 | CH3OCO | CH3 | CH3 | 6-CF3 |
| 135 | H | CH3 | CH3 | 6-C6H5O |
| 136 | CH3CO | CH3 | CH3 | 6-C6H5O |
| 137 | C6H5CO | CH3 | CH3 | 6-C6H5O |
| 138 | H | CH3 | CH3 | 5-C2H5 |
| 139 | H | CH3 | CH3 | 5-C3H7 |
| 140 | H | CH3 | CH3 | 7-C2H5 |
| 141 | H | CH3 | CH3 | 7-C3H7 |
| 142 | H | CH3 | CH3 | 8-C2H5 |
| 143 | H | CH3 | CH3 | 8-C3H7 |
| 144 | H | CH3 | CH3 | 6-C4H9，8-CH3 |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 145 | CH3CO | CH3 | CH3 | 6-C4H9，8-CH3 |
| 146 | H | CH3 | CH3 | 6-C4H9，8-F |
| 147 | CH3CO | CH3 | CH3 | 6-C4H9，8-F |
| 148 | H | CH3 | CH3 | 6-C4H9，7-CH3 |
| 149 | CH3CO | CH3 | CH3 | 6-C4H9，7-CH3 |
| 150 | H | CH3 | CH3 | 6-C4H9，7-F |
| 151 | CH3CO | CH3 | CH3 | 6-C4H9，7-F |
| 152 | H | -(CH2)3- | 6-5-C4H9 | |
| 153 | CH3CO | -(CH2)3- | 6-s-C4H9 | |
| 154 | H | CH3 | CH3 | 6-N(CH2CH3)2 |
| 155 | CH3CO | CH3 | CH3 | 6-N(CH2CH3)2 |
| 156 | H | CH3 | CH3 | 6-吗啉代 |
| 157 | CH3CO | CH3 | CH3 | 6-吗啉代 |
| 158 | H | -(CH2)4- | 6-iso-C4H9 | |
| 159 | CH3CO | -(CH2)4- | 6-iso-C4H9 | |
| 160 | C2H5CO | -(CH2)4- | 6-iso-C4H9 | |
| 161 | C6H5CO | -(CH2)4- | 6-iso-C4H9 | |
| 162 | H | -(CH2)4- | 6-s-C4H9 | |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 163 | CH3CO | -(CH2)4- | 6-s-C4H9 | |
| 164 | C2H5CO | -(CH2)4- | 6-s-C4H9 | |
| 165 | C6H5CO | -(CH2)4- | 6-s-C4H9 | |
| 166 | H | -(CH2)4- | 6-N(CH3)2 | |
| 167 | CH3CO | -(CH2)4- | 6-N(CH3)2 | |
| 168 | C2H5CO | -(CH2)4- | 6-N(CH3)2 | |
| 169 | C6H5CO | -(CH2)4- | 6-N(CH3)2 | |
| 170 | c-C6H11CO | CH3 | CH3 | 6-s-C4H9 |
| 171 | 4-NO2-C6H4CO | CH3 | CH3 | 6-s-C4H9 |
| 172 | C6H5CH2CO | CH3 | CH3 | 6-s-C4H9 |
| 173 | C5H11CO | CH3 | CH3 | 6-s-C4H9 |
| 174 | C6H13CO | CH3 | CH3 | 6-s-C4H9 |
| 175 | CH2＝CHCH2CO | CH3 | CH3 | 6-s-C4H9 |
| 176 | iso-C4H9CO | CH3 | CH3 | 6-s-C4H9 |
| 177 | 2，6-diCl-C6H3CO | CH3 | CH3 | 6-s-C4H9 |
| 178 | H | CH3 | CH3 | 6-(1-环戊烯基) |
| 179 | C4H9OCO | CH3 | CH3 | 6-s-C4H9 |
| 180 | C7H15CO | CH3 | CH3 | 6-s-C4H9 |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 181 | H | CH3 | CH3 | 6-Br |
| 182 | CH3CO | CH3 | CH3 | 5-C2H5 |
| 183 | CH3CO | CH3 | CH3 | 7-C2H5 |
| 184 | CH3CO | CH3 | CH3 | 8-C2H5 |
| 185 | CH3CO | CH3 | CH3 | 6-Br |
| 186 | H | CH3 | CH3 | 6-C4H9，8-Br |
| 187 | CH3CO | CH3 | CH3 | 6-C4H9，8-Br |
| 188 | H | CH3 | C8H17 | 6-s-C4H9 |
| 189 | CH3CO | CH3 | C8H17 | 6-s-C4H9 |
| 190 | H | CH3 | CH3 | 6-Br，8-CH3 |
| 191 | H | CH3 | CH3 | 5-CH3，6-Br |
| 192 | H | CH3 | CH3 | 6-Br，7-CH3 |
| 193 | H | CH3 | CH3 | 6-Br，8-F |
| 194 | H | CH3 | CH3 | 6-F，8-CH3 |
| 195 | CH3CO | CH3 | CH3 | 6-Br，8-CH3 |
| 196 | CH3CO | CH3 | CH3 | 6-Br，7-CH3 |
| 197 | CH3CO | CH3 | CH3 | 5-CH3，6-Br |
| 198 | CH3CO | CH3 | CH3 | 6-F，8-CH3 |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 199 | H | CH3 | CH3 | 6-CH3CH＝C(CH3) |
| 200 | CH3CO | CH3 | CH3 | 6-CH3CH＝C(CH3) |
| 201 | H | CH3 | CH3 | 5-CH3，6-s-C4H9 |
| 202 | CH3CO | CH3 | CH3 | 5-CH3，6-s-C4H9 |
| 203 | H | CH3 | CH3 | 6-s-C4H9，7-CH3 |
| 204 | CH3CO | CH3 | CH3 | 6-s-C4H9，7-CH3 |
| 205 | H | CH3 | CH3 | 6-s-C4H9，8-CH3 |
| 206 | CH3CO | CH3 | CH3 | 6-s-C4H9，8-CH3 |
| 207 | H | CH3 | CH3 | 5-F，6-s-C4H9 |
| 208 | CH3CO | CH3 | CH3 | 5-F，6-s-C4H9 |
| 209 | H | CH3 | CH3 | 6-s-C4H9，7-F |
| 210 | CH3CO | CH3 | CH3 | 6-s-C4H9，7-F |
| 211 | H | CH3 | CH3 | 6-s-C4H9，8-F |
| 212 | CH3CO | CH3 | CH3 | 6-s-C4H9，8-F |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 213 | H | CH3 | CH3 | 6-s-C4H9，8-Cl |
| 214 | CH3CO | CH3 | CH3 | 6-s-C4H9，8-Cl |
| 215 | H | CH3 | CH3 | 6-n-C4H9，8-Cl |
| 216 | CH3CO | CH3 | CH3 | 6-n-C4H9，8-Cl |
| 217 | H | CH3 | CH3 | 6-t-C4H9，8-Cl |
| 218 | CH3CO | CH3 | CH3 | 6-t-C4H9，8-Cl |
| 219 | H | CH3 | CH3 | 6-s-C4H9，8-CH3O |
| 220 | CH3CO | CH3 | CH3 | 6-s-C4H9，8-CH3O |
| 221 | H | CH3 | CH3 | 6-n-C4H9，8-CH3O |
| 222 | CH3CO | CH3 | CH3 | 6-n-C4H9，8-CH3O |
| 223 | H | CH3 | CH3 | 6-t-C4H9，8-CH3O |
| 224 | CH3CO | CH3 | CH3 | 6-t-C4H9，8-CH3O |
| 225 | H | CH3 | CH3 | 6-s-C4H9，5-Cl |
| 226 | CH3CO | CH3 | CH3 | 6-s-C4H9，5-Cl |
| 227 | H | CH3 | CH3 | 6-t-C4H9，5-Cl |
| 228 | CH3CO | CH3 | CH3 | 6-t-C4H9，5-Cl |
| 229 | H | CH3 | CH3 | 6-n-C4H9，5-Cl |
| 230 | CH3CO | CH3 | CH3 | 6-n-C4H9，5-Cl |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 231 | H | CH3 | CH3 | 6-s-C4H9，5-CH3O |
| 232 | CH3CO | CH3 | CH3 | 6-s-C4H9，5-CH3O |
| 233 | H | CH3 | CH3 | 6-n-C4H9，5-CH3O |
| 234 | CH3CO | CH3 | CH3 | 6-n-C4H9，5-CH3O |
| 235 | H | CH3 | CH3 | 6-t-C4H9，5-OCH3 |
| 236 | CH3CO | CH3 | CH3 | 6-t-C4H9，5-OCH3 |
| 237 | H | CH3 | CH3 | 6-s-C4H9，7-Cl |
| 238 | CH3CO | CH3 | CH3 | 6-s-C4H9，7-Cl |
| 239 | H | CH3 | CH3 | 6-t-C4H9，7-Cl |
| 240 | CH3CO | CH3 | CH3 | 6-t-C4H9，7-Cl |
| 241 | H | CH3 | CH3 | 6-n-C4H9，7-Cl |
| 242 | CH3CO | CH3 | CH3 | 6-n-C4H9，7-Cl |
| 243 | H | CH3 | CH3 | 6-s-C4H9，7-CH3O |
| 244 | CH3CO | CH3 | CH3 | 6-s-C4H9，7-CH3O |
| 245 | H | CH3 | CH3 | 6-n-C4H9，7-CH3O |
| 246 | CH3CO | CH3 | CH3 | 6-n-C4H9，7-CH3O |
| 247 | H | CH3 | CH3 | 6-t-C4H9，7-CH3O |
| 248 | CH3CO | CH3 | CH3 | 6-t-C4H9，7-CH3O |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 249 | H | CH3 | CH3 | 6-t-C4H9，8-CH3 |
| 250 | CH3CO | CH3 | CH3 | 6-t-C4H9，8-CH3 |
| 251 | H | CH3 | CH3 | 6-t-C4H9，8-F |
| 252 | CH3CO | CH3 | CH3 | 6-t-C4H9，8-F |
| 253 | H | CH3 | CH3 | 6-t-C4H9，5-CH3 |
| 254 | CH3CO | CH3 | CH3 | 6-t-C4H9，5-CH3 |
| 255 | H | CH3 | CH3 | 6-t-C4H9，5-F |
| 256 | CH3CO | CH3 | CH3 | 6-t-C4H9，5-F |
| 257 | H | CH3 | CH3 | 6-t-C4H9，7-CH3 |
| 258 | CH3CO | CH3 | CH3 | 6-t-C4H9，7-CH3 |
| 259 | H | CH3 | CH3 | 6-t-C4H9，7-F |
| 260 | CH3CO | CH3 | CH3 | 6-t-C4H9，7-F |
| 261 | H | CH3 | CH3 | 6-CH3，8-CH3 |
| 262 | CH3CO | CH3 | CH3 | 6-CH3，8-CH3 |
| 263 | H | CH3 | CH3 | 5-CH3，6-CH3 |
| 264 | CH3CO | CH3 | CH3 | 5-CH3，6-CH3 |
| 265 | H | CH3 | CH3 | 6-CH3，7-CH3 |
| 266 | CH3CO | CH3 | CH3 | 6-CH3，7-CH3 |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 267 | H | CH3 | CH3 | 6-C2H5，8-C2H5 |
| 268 | CH3CO | CH3 | CH3 | 6-C2H5，8-C2H5 |
| 269 | H | CH3 | CH3 | 5-C2H5，6-C2H5 |
| 270 | CH3CO | CH3 | CH3 | 5-C2H5，6-C2H5 |
| 271 | H | CH3 | CH3 | 6-C2H5，7-C2H5 |
| 272 | CH3CO | CH3 | CH3 | 6-C2H5，7-C2H5 |
| 273 | H | CH3 | CH3 | 6-iso-C3H7，8-iso-C3H7 |
| 274 | CH3CO | CH3 | CH3 | 6-iso-C3H7，8-iso-C3H7 |
| 275 | H | CH3 | CH3 | 5-iso-C3H7，6-iso-C3H7 |
| 276 | CH3CO | CH3 | CH3 | 5-iso-C3H7，6-iso-C3H7 |
| 277 | H | CH3 | CH3 | 6-iso-C3H7，7-iso-C3H7 |
| 278 | CH3CO | CH3 | CH3 | 6-iso-C3H7，7-iso-C3H7 |
| 279 | H | CH3 | CH3 | 6-s-C4H9，8-s-C4H9 |
| 280 | CH3CO | CH3 | CH3 | 6-s-C4H9，8-s-C4H9 |
| 281 | H | CH3 | CH3 | 5-s-C4H9，6-s-C4H9 |
| 282 | CH3CO | CH3 | CH3 | 5-s-C4H9，6-s-C4H9 |
| 283 | H | CH3 | CH3 | 6-s-C4H9，7-s-C4H9 |
| 284 | CH3CO | CH3 | CH3 | 6-s-C4H9，7-s-C4H9 |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 285 | H | CH3 | CH3 | 6-t-C4H9，8-t-C4H9 |
| 286 | CH3CO | CH3 | CH3 | 6-t-C4H9，8-t-C4H9 |
| 287 | H | CH3 | CH3 | 5-t-C4H9，6-t-C4H9 |
| 288 | CH3CO | CH3 | CH3 | 5-t-C4H9，6-t-C4H9 |
| 289 | H | CH3 | CH3 | 6-t-C4H9，7-t-C4H9 |
| 290 | CH3CO | CH3 | CH3 | 6-t-C4H9，7-t-C4H9 |
| 291 | H | CH3 | CH3 | 6-c-C3H4(CH3) |
| 292 | CH3CO | CH3 | CH3 | 6-c-C3H4(CH3) |
| 293 | H | CH3 | CH3 | 6-c-C3H4(CH3)，8-CH3 |
| 294 | CH3CO | CH3 | CH3 | 6-c-C3H4(CH3)，8-CH3 |
| 295 | H | CH3 | CH3 | 6-c-C3H4(CH3)，8-Cl |
| 296 | CH3CO | CH3 | CH3 | 6-c-C3H4(CH3)，8-Cl |
| 297 | H | CH3 | CH3 | 6-c-C3H5-CH2 |
| 298 | CH3CO | CH3 | CH3 | 6-c-C3H5-CH2 |
| 299 | H | CH3 | CH3 | 6-c-C3H5-CH2，8-CH3 |
| 300 | CH3CO | CH3 | CH3 | 6-c-C3H5-CH2，8-CH3 |
| 301 | H | CH3 | CH3 | 6-c-C3H5-CH2，8-Cl |
| 302 | CH3CO | CH3 | CH3 | 6-c-C3H5-CH2，8-Cl |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 303 | H | CH3 | CH3 | 6-C6H5 |
| 304 | CH3CO | CH3 | CH3 | 6-C6H5 |
| 305 | H | CH3 | CH3 | 6-C6H5，8-CH3 |
| 306 | CH3CO | CH3 | CH3 | 6-C6H5，8-CH3 |
| 307 | H | CH3 | CH3 | 6-C6H5，8-Cl |
| 308 | CH3CO | CH3 | CH3 | 6-C6H5，8-Cl |
| 309 | H | CH3 | CH3 | 6-(p-Cl)-C6H4 |
| 310 | CH3CO | CH3 | CH3 | 6-(p-Cl)-C6H4 |
| 311 | H | CH3 | CH3 | 6-(p-Cl)-C6H4，8-CH3 |
| 312 | CH3CO | CH3 | CH3 | 6-(p-Cl)-C6H4，8-CH3 |
| 313 | H | CH3 | CH3 | 6-(p-Cl)-C6H4，8-Cl |
| 314 | CH3CO | CH3 | CH3 | 6-(p-Cl)-C6H4，8-Cl |
| 315 | H | CH3 | CH3 | 6-(p-CH3)-C6H4 |
| 316 | CH3CO | CH3 | CH3 | 6-(p-CH3)-C6H4 |
| 317 | H | CH3 | CH3 | 6-(p-CH3)-C6H4，8-CH3 |
| 318 | CH3CO | CH3 | CH3 | 6-(p-CH3)-C6H4，8-CH3 |
| 319 | H | CH3 | CH3 | 6-(p-CH3)-C6H4，8-Cl |
| 320 | CH3CO | CH3 | CH3 | 6-(p-CH3)-C6H4，8-Cl |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 321 | H | CH3 | CH3 | 6-C6H5-CH2 |
| 322 | CH3CO | CH3 | CH3 | 6-C6H5CH2 |
| 323 | H | CH3 | CH3 | 6-C6H5-CH2，8-CH3 |
| 324 | CH3CO | CH3 | CH3 | 6-C6H5-CH2，8-CH3 |
| 325 | H | CH3 | CH3 | 6-C6H5-CH2，8-Cl |
| 326 | CH3CO | CH3 | CH3 | 6-C6H5-CH2，8-Cl |
| 327 | H | CH3 | CH3 | 6-C6H5-C(CH3)2 |
| 328 | CH3CO | CH3 | CH3 | 6-C6H5-C(CH3)2 |
| 329 | H | CH3 | CH3 | 6-C6H5-C(CH3)2，8-CH3 |
| 330 | CH3CO | CH3 | CH3 | 6-C6H5-C(CH3)2，8-CH3 |
| 331 | H | CH3 | CH3 | 6-C6H5C(CH3)2，8-Cl |
| 332 | CH3CO | CH3 | CH3 | 6-C6H5-C(CH3)2，8-Cl |
| 333 | H | CH3 | CH3 | 6-t-C4H9-CH2 |
| 334 | CH3CO | CH3 | CH3 | 6-t-C4H9-CH2 |
| 335 | H | CH3 | CH3 | 6-t-C4H9-CH2，8-CH3 |
| 336 | CH3CO | CH3 | CH3 | 6-t-C4H9-CH2，8-CH3 |
| 337 | H | CH3 | CH3 | 6-t-C4H9-CH2，8-Cl |
| 338 | CH3CO | CH3 | CH3 | 6-t-C4H9-CH2，8-Cl |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 339 | H | CH3 | CH3 | 6-s-C4H9，8-CH2OH |
| 340 | CH3CO | CH3 | CH3 | 6-s-C4H9，8-CH2OH |
| 341 | H | CH3 | CH3 | 6-t-C4H9，8-CH2OH |
| 342 | CH3CO | CH3 | CH3 | 6-t-C4H9，8-CH2OH |
| 343 | H | CH3 | CH3 | 6-s-C4H9，8-CH2Cl |
| 344 | CH3CO | CH3 | CH3 | 6-s-C4H9，8-CH2Cl |
| 345 | H | CH3 | CH3 | 6-t-C4H9，8-CH2Cl |
| 346 | CH3CO | CH3 | CH3 | 6-t-C4H9，8-CH2Cl |
| 347 | H | CH3 | CH3 | 6-s-C4H9，8-C2H5 |
| 348 | CH3CO | CH3 | CH3 | 6-s-C4H9，8-C2H5 |
| 349 | H | CH3 | CH3 | 6-t-C4H9，8-C2H5 |
| 350 | CH3CO | CH3 | CH3 | 6-t-C4H9，8-C2H5 |
| 351 | H | CH3 | CH3 | 6-c-C5H9，8-CH3 |
| 352 | CH3CO | CH3 | CH3 | 6-c-C5H9，8-CH3 |
| 353 | H | CH3 | CH3 | 6-C-C5H9，8-Cl |
| 354 | CH3CO | CH3 | CH3 | 6-c-C5H9，8-Cl |
| 355 | H | CH3 | CH3 | 6-s-C4H9，8-CHO |
| 356 | CH3CO | CH3 | CH3 | 6-s-C4H9，8-CHO |
表1(续)
| 化合物编号 | R1 | R2 | R3 | W |
| 357 | H | CH3 | CH3 | 6-t-C4H9，8-CHO |
| 358 | CH3CO | CH3 | CH3 | 6-t-C4H9，8-CHO |
| 359 | H | CH3 | CH3 | 6-CH3CH＝C(CH3)，8-CH3 |
| 360 | CH3CO | CH3 | CH3 | 6-CH3CH＝C(CH3)，8-CH3 |
| 361 | H | CH3 | CH3 | 6-CH3CH＝C(CH3)，8-F |
| 362 | CH3CO | CH3 | CH3 | 6-CH3CH＝C(CH3)，8-F |
| 363 | H | CH3 | CH3 | 6-5-C4H9，8-CN |
| 364 | CH3CO | CH3 | CH3 | 6-s-C4H9，8-CN |
| 365 | H | CH3 | CH3 | 6-t-C4H9，8-CN |
| 366 | CH3CO | CH3 | CH3 | 6-t-C4H9，8-CN |
| 367 | H | CH3 | CH3 | 6-s-C4H9，8-NO2 |
| 368 | CH3CO | CH3 | CH3 | 6-s-C4H9，8-NO2 |
| 369 | H | CH3 | CH3 | 6-t-C4H9，8-NO2 |
| 370 | CH3CO | CH3 | CH3 | 6-t-C4H9，8-NO2 |
| 371 | H | CH3 | CH3 | 6-s-C4H9，8-CH3OCO |
| 372 | CH3CO | CH3 | CH3 | 6-s-C4H9，8-CH3OCO |
| 373 | H | CH3 | CH3 | 6-t-C4H9，8-CH3OCO |
| 374 | CH3CO | CH3 | CH3 | 6-t-C4H9，8-CH3OCO |
通式(I)表示的4-喹啉酚衍生物的部分化合物由通式(I)’表示，可以日本专利公开公报平3-128355号记载的公知方法制得，其反应式如下。
即，在碱存在下或无碱的条件下使通式(II)表示的化合物与通式(III)或通式(IV)表示的试剂反应，根据需要变换取代基进行合成。式中的R1～R4和W的含义如前所述。这里的碱包括三乙胺、吡啶等有机胺，碳酸钠、碳酸钾、氢化钠等无机碱。作为原料的通式(II)表示的化合物可以公知方法，即J.Am.Chem.Soc.70，2402(1948)和Tetrahedron Lett.27，5323(1986)为基准，以市售或通过已知方法获得的取代苯胺为原料合成。所用的通式(III)或通式(IV)表示的试剂对应于通式(II)表示的化合物为1～50当量，较好为1～10当量。反应可在不参与反应的有机溶剂，例如，二甲基甲酰胺或二甲亚砜中，在0℃～140℃的温度范围内进行。
上述通式(I)表示的化合物对稻瘟病、稻胡麻斑病、瓜类白粉病、马铃薯炭疽病等具有良好的抗菌活性。
前述通式(I)表示的本发明化合物作为农业园艺用杀菌剂的有效组分使用时，可直接使用，但通常与适当的固体载体、液体载体、气体载体、表面活性剂、分散剂、其他制剂用助剂混合，制成乳剂、溶液剂、水合剂、粉剂、颗粒剂、油剂、烟雾剂、流动剂等剂型后再使用。
固体载体包括滑石粉、膨润土、粘土、白陶土、硅藻土、蛭石、白炭黑、碳酸钙等。液体载体包括甲醇、正己醇、乙二醇等醇类，丙酮、甲基乙基甲酮、环己酮等酮类，正己烷、煤油、石蜡油等脂肪族烃类，甲苯、二甲苯、甲基萘等芳香族烃类，乙醚、二噁烷、四氢呋喃等醚类，乙酸乙酯等酯类，乙腈、异丁腈等腈类，N，N-二甲基甲酰胺、N，N-二甲基乙酰胺等酰胺类，大豆油、棉籽油等植物油类，二甲亚砜和水等。此外，气体载体包括液化丙烷气(LPG)、空气、氮气、二氧化碳、二甲醚等。
用于乳化、分散和展开等的表面活性剂和分散剂包括烷基硫酸酯类、烷基(芳基)磺酸酯类、聚氧烯烃烷基(芳基)醚、多元醇酯类和木质磺酸盐等。
用于改善制剂性状的助剂包括羧甲基纤维素、阿拉伯胶、聚乙二醇、硬脂酸钙等。
上述载体、表面活性剂、分散剂及助剂根据需要可单独使用，也可组合使用。
如果是乳剂，则上述制剂中的有效组分的含量一般为1～75重量％；如是粉剂，则一般为0.3-25重量％；如是水合剂，则一般为1～90重量％；如是颗粒剂，则一般为0.5-10重量％。此外，这些制剂还可与其他杀菌剂、杀虫剂、杀螨剂、除草剂、植物生长调节剂、肥料等混合使用。
本发明的农业园艺用杀菌剂的施用方法包括茎叶散布、水面施用、土壤处理、育苗箱施用、种子消毒等，本领域普通技术人员利用其他方法也能够发挥效果。
实施例
通式(I)表示的4-喹啉酚衍生物的具体制造例如下所述，但本发明并不仅限于此。
实施例1
4-羟基-2，3-二甲基-6-正戊基-喹啉(化合物97)的合成
在路易斯酸催化剂存在下，使4-正戊基苯胺1.63g和乙基-2-乙酰乙酸甲酯1.44g在苯中回流3小时，所得反应混合物用饱和碳酸氢钠溶液和饱和食盐水洗涤后，用无水硫酸钠干燥，蒸去溶剂。然后，使所得中间体在二苯醚中回流30分钟，放冷后减压滤取析出物，获得1.01g的4-羟基-2，3-二甲基-6-正戊基喹啉(收率为42％)。NMR光谱数据如以下表2所示。
实施例2～9
利用与实施例1同样的方法，合成以下化合物。所得化合物的NMR光谱数据如以下表2所示。
实施例2 化合物107(收率为64％)
实施例3 化合物111(收率为56％)
实施例4 化合物125(收率为22％)
实施例5 化合物131(收率为25％)
实施例6 化合物135(收率为24％)
实施例7 化合物152(收率为34％)
实施例8 化合物154(收率为52％)
实施例9 化合物156(收率为52％)
实施例10
4-乙酰氧基-2，3-二甲基-6-正戊基-喹啉(化合物98)的合成
在120℃的温度下，在2ml乙酸酐中搅拌4-羟基-2，3-二甲基-6-正戊基-喹啉(化合物97)100mg，历时4小时。蒸去溶剂后，添加20ml乙酸乙酯，用饱和碳酸氢钠水溶液及饱和食盐水洗涤，并用无水硫酸钠干燥。然后，减压蒸去溶剂，所得粗品用硅胶柱色谱法(和光硅胶C-100，溶剂为正己烷-乙酸乙酯(5∶1))精制，获得4-乙酰氧基-2，3-二甲基-6-正己基-喹啉87.4mg(收率为74％)。NMR光谱数据如以下表2所示。
实施例11～18
利用与实施例10同样的方法，合成以下化合物。所得化合物的NMR光谱数据如表2所示。
实施例11 化合物108(收率为62％)
实施例12 化合物112(收率为68％)
实施例13 化合物126(收率为74％)
实施例14 化合物132(收率为8％)
实施例15 化合物136(收率为76％)
实施例16 化合物153(收率为59％)
实施例17 化合物155(收率为94％)
实施例18 化合物157(收率为87％)
实施例19
4-乙酰氧基-6-(2-丁烯-2-基)-2，3，8-三甲基喹啉(化合物360)的合成
将利用与实施例1同样的方法合成的6-溴-4-羟基-2，3，8-三甲基喹啉26.6g悬浮于70ml N，N-二甲基甲酰胺中，在冰冷条件下添加60％的氢化钠，室温搅拌30分钟。然后，同样在冰冷条件下滴加19g苄基溴，在室温下使其反应一晚。在反应液中加入50ml水，用乙酸乙酯萃取，再用饱和食盐水洗净有机层后，用无水硫酸钠干燥一晚。减压蒸去溶剂，所得粗品用硅胶柱色谱法(和光硅胶C-200，溶剂为正己烷-乙酸乙酯(6∶1))精制，获得4-苄氧基-6-溴-2，3，8-三甲基喹啉24.3g。
将4g所得4-苄氧基-6-溴-2，3，8-三甲基喹啉溶于40ml无水四氢呋喃中，冷却至-78℃，再滴加2.5M正丁基锂的正己烷溶液5ml，搅拌10分钟。将2-丁烷1.2g溶于4ml无水四氢呋喃，然后，滴加到反应液中，于0℃搅拌20分钟。在反应液中加入30ml水，用乙酸乙酯萃取，再用饱和食盐水洗涤有机层后，用无水硫酸钠干燥一晚。减压蒸去溶剂，残留物用硅胶柱色谱法(和光硅胶C-200，溶剂为正己烷-乙酸乙酯(7∶1)精制，获得4-苄氧基-6-(2-羟基丁基-2-基)-2，3，8-三甲基喹啉3.5g。
在2.8g所得4-苄氧基-6-(2-羟基丁基-2-基)-2，3，8-三甲基喹啉中加入20％硫酸10ml，于100℃搅拌80分钟。冷却至室温后，用饱和碳酸钠水溶液中和，用水及正己烷洗净沉淀后减压干燥，获得2.3g粗品。使2.0g粗品悬浮于10ml N，N-二甲基甲酰胺，在冰冷条件下添加60％氢化钠0.37g，室温搅拌30分钟后，在冰冷条件下滴加0.72g乙酰氯，室温搅拌20分钟。在反应液中加入15ml水并搅拌后，用乙酸乙酯萃取，再用饱和食盐水洗净有机层后，用无水硫酸钠干燥一晚。减压蒸去溶剂，粗品用硅胶柱色谱法(和光硅胶C-200，溶剂为正己烷-乙酸乙酯(9∶1)精制，获得4-乙酰氧基-6-(2-丁烯-2-基)-2，3，8-三甲基喹啉1.6g(收率为42％)。NMR光谱数据如以下表2所示。
实施例20
4-乙酰氧基-6-(2-丁烯-2-基)-8-氟-2，3-二甲基喹啉(化合物362)的合成
以6-溴-4-羟基-8-氟-2，3-二甲基喹啉为合成原料，利用与实施例19同样的方法，获得4-乙酰氧基-6-(2-丁烯-2-基)-8-氟-2，3-二甲基喹啉(收率为17％)。NMR光谱数据如以下表2所示。
实施例21
4-乙酰氧基-6-仲丁基-2，3，8-三甲基喹啉(化合物206)的合成
在6ml甲醇中加入用实施例19的方法制得的4-乙酰氧基-6-(2-丁烯-2-基)-2，3，8-三甲基喹啉0.41g和10％钯-碳0.06g，室温搅拌的同时导入氢气，使其反应16小时。过滤反应液，残渣用2ml甲醇洗涤2次。减压蒸去溶剂，获得4-乙酰氧基-6-仲丁基-2，3，8-三甲基喹啉0.37g(收率为90％)。NMR光谱数据如以下表2所示。
实施例22
4-乙酰氧基-6-仲丁基-8-氟-2，3-二甲基喹啉(化合物212)的合成
利用与实施例21同样的方法，以0.37g实施例20获得的4-乙酰氧基-6-(2-丁烯-2-基)-8-氟-2，3-二甲基喹啉为原料，制得4-乙酰氧基-6-仲丁基-8-氟-2，3-二甲基喹啉0.27g(收率为72％)。NMR光谱数据如以下表2所示。
实施例23
4-乙酰氧基-6-环戊基-8-甲基-2，3-二甲基喹啉(化合物352)的合成
利用与实施例21同样的方法，获得4-乙酰氧基-6-环戊基-8-甲基-2，3-二甲基喹啉(收率为37％)。
实施例24
4-乙酰氧基-6-仲丁基-8-氯-2，3-二甲基喹啉(化合物214)的合成
将4-仲丁基苯胺4.9g溶于N，N-二甲基甲酰胺，室温下在其中滴加溶有4g N-氯-琥珀酰亚胺的20ml N，N-二甲基甲酰胺，搅拌一晚。然后，将反应液倾入100ml水中，用正己烷萃取，所得有机层用饱和食盐水洗涤，再用无水硫酸钠干燥后，减压蒸去溶剂。与实施例1同样，利用所得的4-仲丁基-2-氯苯胺粗品，获得4-羟基-6-仲丁基-8-氯-2，3-二甲基喹啉，以此为原料，与实施例10同样，获得4-乙酰氧基-6-仲丁基-8-氯-2，3-二甲基喹啉287.5mg(收率为17％)。NMR光谱数据如以下表2所示。
实施例25，26
利用与实施例23同样的方法，合成以下化合物。所得化合物的NMR光谱数据如以下表2所示。
实施例25 化合物216(收率为31％)
实施例26 化合物218(收率为8％)
实施例27
4-乙酰氧基-6-仲丁基-8-甲氧基-2，3-二甲基喹啉(化合物220)的合成
以3-甲氧基乙酰苯为合成原料，通过已知的各种反应，获得4-仲丁基-2-甲氧基苯胺。利用530mg所得的4-仲丁基-2-甲氧基苯胺，通过与实施例1和10同样的方法，获得4-乙酰氧基-6-仲丁基-8-甲氧基-2，3-二甲基喹啉264mg(收率为40％)。NMR光谱数据如以下表2所示。
实施例28～32
利用与实施例26同样的方法，合成以下化合物。所得化合物的NMR光谱数据如以下表2所示。
实施例28 化合物262(收率为53％)
实施例29 化合物268(收率为42％)
实施例30 化合物274(收率为49％)
实施例31 化合物280(收率为39％)
实施例32 化合物348(收率为40％)
实施例33
4-乙酰氧基-6-仲丁基-8-甲酰基-2，3-二甲基喹啉(化合物356)的合成
将5g利用与实施例1同样的方法合成的4-羟基-6-仲丁基-8-溴-2，3-二甲基喹啉悬浮于20ml N，N-二甲基甲酰胺，在冰冷条件下添加60％的氢化钠700mg，室温搅拌30分钟。冰冷条件下在反应液中滴加3g苄基溴，室温反应一晚。然后，在反应液中加入50ml水，用乙酸乙酯萃取，再用饱和食盐水洗净有机层后，用无水硫酸钠干燥一晚。减压蒸去溶剂，用硅胶柱色谱法(和光硅胶C-200，溶剂为正己烷)精制所得粗品，获得4-苄氧基-6-仲丁基-8-溴-2，3-二甲基喹啉2.5g。将2.5g所得4-苄氧基-6-仲丁基-8-溴-2，3-二甲基喹啉溶于25ml无水四氢呋喃，冷却至-78℃，在其中滴加2.5M正丁基锂的正己烷溶液2.8ml，搅拌10分钟。接着，将甲酸甲酯1ml溶于2ml无水四氢呋喃中，然后滴加到反应液中，于0℃搅拌30分钟。在反应液中加水50ml，用乙酸乙酯萃取，再用饱和氯化铵水溶液和饱和食盐水洗净有机层后，用无水硫酸钠干燥，减压蒸去溶剂。残留物用硅胶柱色谱法(和光硅胶C-200，溶剂为正己烷-乙酰乙酯(20∶1))精制，获得4-苄氧基-6-仲丁基-8-甲酰基-2，3-二甲基喹啉800mg。
将800mg所得4-苄氧基-6-仲丁基-8-甲酰基-2，3-二甲基喹啉溶于20％硫酸2.5ml，于100℃搅拌1小时。冷却至室温后，用饱和碳酸氢钠水溶液中和反应液，用水及正己烷洗净生成的沉淀后，减压干燥，获得4-羟基-6-仲丁基-8-甲酰基-2，3-二甲基喹啉490mg。将440mg4-羟基-6-仲丁基-8-甲酰基-2，3-二甲基喹啉悬浮于3ml乙酸酐和0.5ml吡啶的混合溶液中，于120℃搅拌1.5小时。然后，用饱和碳酸氢钠中和冷却至室温的反应液，再用乙酸乙酯萃取，并用饱和食盐水洗净所得有机层，用无水硫酸钠干燥后，减压蒸去溶剂。所得粗品用硅胶柱色谱法(和光硅胶C-200，溶剂为正己烷-乙酰乙酯(10∶1))精制后，获得4-乙酰氧基-6-仲丁基-8-甲酰基-2，3-二甲基喹啉220mg(收率为13％)。NMR光谱数据如以下表2所示。
实施例34
4-乙酰氧基-6-仲丁基-8-羟甲基-2，3-二甲基喹啉(化合物340)的合成
将210mg实施例33制得的4-乙酰氧基-6-仲丁基-8-甲酰基-2，3-二甲基喹啉溶于4ml甲醇，然后滴加溶有7mg硼氢化钠的甲醇溶液4ml，室温搅拌1分钟。接着，在反应液中加水20ml，用乙酸乙酯萃取，再用饱和食盐水洗净所得有机层后，用无水硫酸钠干燥，减压蒸去溶剂。所得粗品用硅胶柱色谱法(和光硅胶C-200，溶剂为正己烷-乙酸乙酯(10∶1))精制，获得4-乙酰氧基-6-仲丁基-8-羟甲基-2，3-二甲基喹啉186mg(收率为84％)。NMR光谱数据如以下表2所示。
实施例35
4-乙酰氧基-6-仲丁基-8-氯甲基-2，3-二甲基喹啉(化合物344)的合成
将50mg实施例34制得的4-乙酰氧基-6-仲丁基-8-羟甲基-2，3-二甲基喹啉溶于0.3ml亚硫酰氯中，室温搅拌4.5小时。减压蒸去亚硫酰氯后，在所得粗品中加入0.5ml乙酸酐，于120℃搅拌2小时。减压蒸去乙酸酐，所得残留物用硅胶柱色谱法(和光硅胶C-200，溶剂为正己烷-乙酸乙酯(20∶1))精制，获得4-乙酰氧基-6-仲丁基-8-氯甲基-2，3-二甲基喹啉5mg(收率为23.5％)。NMR光谱数据如以下表2所示。
表2
| 化合物编号 | NMR光谱数据 |
| 97 | 11.37(1H，s)，7.83(1H，s)，7.42(1H，dd，J1＝8.6，J2＝1.6)，7.39(1H，d，J＝8.6)，2.65(2H，t，J＝7.4)，2.36(3H，s)，1.96(3H，s)，1.59(2H，m)，1.29(4H，m)，0.85(3H，t，J＝6.8)溶剂：DMSO-d6 |
| 98 | 7.94(1H，d，J＝8.7)，7.49(1H，dd，J1＝8.7，J2＝1.7)，7.42(1H，s)，2.75(2H，m)，2.71(3H，s)，2.52(3H，s)，2.25(3H，s)，1.68(2H，m)，1.34(4H，m)，0.90(3H，t，J＝6.7)溶剂：CDCl3 |
| 107 | 11.36(1H，s)，7.83(1H，br.s)，7.39(2H，m)，2.65(2H，m)，2.35(3H，s)，1.95(3H，s)，1.58(2H，m)，1.27(6H，m)，0.85(3H，t，J＝6.9) 溶剂：DMSO-d6 |
| 108 | 7.92(1H，d，J＝8.6)，7.49(1H，d，J＝8.6)，7.42(1H，s)，2.75(2H，t，J＝7.8)，2.71(3H，s)，2.52(3H，s)，2.24(3H，s)，1.67(2H，m)，1.39～1.28(6H，m)，0.88(3H，t，J＝7.6)溶剂：CDCl3 |
表2(续)
| 化合物编号 | NMR光谱数据 |
| 111 | 11.32(1H，s)，7.85(1H，d，J＝2.0)，7.44(1H，dd，J1＝8.5，J2＝2.2)，7.38(1H，d，J＝8.6)，2.60(1H，m)，2.34(3H，s)，1.95(3H，s)，1.81(4H，m)，1.70(1H，m)，1.39(4H，m)，1.25(1H，m) 溶剂：DMSO-d6 |
| 112 | 8.18(1H，d，J＝2.0)，7.93(1H，d，J＝8.8)，7.53(1H，dd，J1＝8.8，J2＝2.0)，2.86(3H，s)，2.72(1H，m)，2.70(3H，s)，2.52(3H，s)，1.80(4H，m)，1.77(1H，m)，1.46(4H，m)，1.31(1H，m) 溶剂：CDCl3 |
| 125 | 11.35(1H，s)，7.83(1H，br.s)，7.40(2H，m)，2.65(2H，m)，2.35(3H，s)，1.95(3H，s)，1.58(2H，m)，1.27～1.23(10H，m)，0.84(3H，t，J＝6.6) 溶剂：DMSO-d6 |
| 126 | 7.93(1H，d，J＝8.8)，7.49(1H，dd，J1＝8.8，J2＝1.9)，7.42(1H，d，J＝1.2)，2.75(2H，t，J＝7.8)，2.71(3H，s)，2.52(3H，s)，2.24(3H，s)，1.71～1.25(10H，m)，0.87(3H，t，J＝6.9) 溶剂：CDCl3 |
表2(续)
| 化合物编号 | NMR光谱数据 |
| 131 | 11.78(1H，s)，8.33(1H，br.s)，7.86(1H，dd，J1＝8.8，J2＝2.0)，7.66(1H，d，J＝8.8)，2.40(3H，s)，1.98(3H，s)溶剂：DMSO-d6 |
| 132 | 8.12(1H，d，J＝9.0)，8.00(1H，br.s)，7.82(1H，dd，J1＝9.0，J2＝2.0)，2.54(3H，s)，2.30(3H，s)，2.28(3H，s)溶剂：CDCl3 |
| 135 | 11.53(1H，s)，7.54(1H，d，J＝9.0)，7.47(1H，d，J＝3.1)，7.41(2H，dd，J1＝8.6，J2＝7.5)，7.37(2H，dd，J1＝9.0，J2＝3.1)，7.16(1H，t，J＝7.5)，7.04(2H，dd，J1＝8.6，J2＝1.0)，2.37(3H，s)，1.94(3H，s) 溶剂：DMSO-d6 |
| 136 | 7.98(1H，d，J＝9.4)，7.38(2H，br.d，J＝8.6)，7.35(1H，d，J＝2.7)，7.18(1H，d，J＝2.7)，7.14(1H，br.d，J＝6.7)，7.06(2H，br.dd，J1＝8.6，J2＝0.8)，2.71(3H，s)，2.40(3H，s)溶剂：CDCl3 |
表2(续)
| 化合物编号 | NMR光谱数据 |
| 152 | 11.83(1H，s)，7.90(1H，s)，7.43(2H，s)，2.97(1H，t)，2.68(3H，m)，2.04(2H，t)，1.60(2H，t)，1.23(3H，d)，0.77(3H，t) 溶剂：DMSO-d6 |
| 153 | 7.97(1H，d，J＝8.8)，7.54(1H，d，J＝1.9)，7.51(1H，dd，J1＝8.8，J2＝1.9)，3.19(2H，t，J＝7.7)，2.95(2H，t，J＝7.4)，2.76(1H，m)，2.49(3H，s)，2.20(2H，quint，J＝7.4)，1.67(2H，quint，J＝7.4)，1.31(3H，d，J＝6.9)，0.84(3H，t，J＝7.3) 溶剂：CDCl3 |
| 154 | 11.20(1H，s)，7.36(1H，d，J＝8.7)，7.21(1H，d，J＝2.0)，7.10(1H，dd，J1＝8.7，J2＝2.0)，3.38(4H，q，J＝6.9)，2.34(3H，s)，1.97(3H，s)，1.11(6H，t，J＝6.9)溶剂：DMSO-d6 |
| 155 | 8.56(1H，d，J＝2.8)，7.85(1H，d，J＝9.3)，7.20(1H，dd，J1＝9.3，J2＝2.8)，3.44(4H，q，J＝7.0)，2.64(3H，s)，2.48(3H，s)，2.21(3H，s)，1.21(6H，t，J＝7.0) 溶剂：CDCl3 |
表2(续)
| 化合物编号 | NMR光谱数据 |
| 156 | 11.23(1H，s)，7.40(3H，s)，3.86(4H，m)，3.11(4H，m)，2.35(3H，s)，2.06(3H，s) 溶剂：DMSO-d6 |
| 157 | 8.85(1H，d，J＝2.7)，7.90(1H，d，J＝9.2)，7.39(1H，dd，J1＝9.2，J2＝2.7)，3.90(4H，m)，3.26(4H，m)，2.67(3H，s)，2.50(3H，s)，2.23(3H，s) 溶剂：CDCl3 |
| 206 | 7.31(1H，s)，7.24(1H，s)，2.74(3H，s)，2.69(3H，s)，2.67(1H，m)2.48(3H，s)，2.21(3H，s)，1.63(2H，m)，1.27(3H，d，J＝7.0)0.81(3H，t，J＝7.0) 溶剂：CDCl3 |
| 212 | 7.21(1H，m)，7.19(1H，m)，2.74(1H，m)，2.73(3H，s)，2.50(3H，s)2.24(3H，s)，1.62(2H，m)，1.27(3H，d，J＝7.0)，0.82(3H，t，J＝7.0)溶剂：CDCl3 |
| 214 | 7.63(1H，d，J＝2.0)，7.34(1H，d，J＝2.0)，2.77(3H，s)，2.73(1H，m)，2.51(3H，s)，2.25(3H，s)，1.65(2H，m)，1.30(3H，d，J＝6.9)，0.84(3H，t，J＝7.3) 溶剂：CDCl3 |
| 216 | 7.62(1H，d，J＝1.9)，7.35(1H，dJ＝1.7)，2.77(3H，s)，2.73(2H，t，J＝7.8)2.51(3H，s)，2.25(3H，s)，1.66(2H，m)，1.39(2H，m)，0.95(3H，t，J＝7.3)溶剂：CDCl3 |
| 218 | 7.83(1H，d，J＝2.0)，7.51(1H，d，J＝1.9)，2.77(3H，s)，2.51(3H，s)2.25(3H，s)，1.39(9H，s) 溶剂：CDCl3 |
表2(续)
| 化合物编号 | NMR光谱数据 |
| 220 | 7.01(1H，d，J＝1.5)，6.84(1H，d，J＝1.5)，4.06(3H，s)，2.75(3H，s)2.71(1H，m)，2.50(3H，s)，2.24(3H，s)，1.66(2H，m)，1.30(3H，d，J＝6.8)，0.85(3H，t，J＝7.5) 溶剂：CDCl3 |
| 262 | 7.31(1H，s)，7.27(1H，s)，2.74(3H，s)，2.70(3H，s)，2.50(3H，s)，2.46(3H，s)，2.23(3H，s) 溶剂：CDCl3 |
| 268 | 7.34(1H，s)，7.28(1H，s)，3.25(2H，q，J＝7.5)，2.77(2H，q，J＝7.5)2.70(3H，s)，2.23(3H，s)，1.35(3H，t，J＝7.5)，1.30(3H，t，J＝7.6)溶剂：CDCl3 |
| 274 | 7.40(1H，d，J＝2.0)，7.28(1H，d，J＝1.9)，4.31(1H，m)，3.04(1H，m)2.69(3H，s)，2.50(3H，s)，2.23(3H，s)，1.36(6H，d，J＝6.8)，1.31(6H，d，J＝7.0) 溶剂：CDCl3 |
| 280 | 7.30(1H，d，J＝1.7)，7.24(1H，d，J＝1.7)，4.13(1H，m)，2.73(1H，m)，2.69(3H，s)，2.51(3H，s)，2.22(3H，s)，1.61～1.84(4H，m)1.31(3H，d，J＝7.0)，1.30(3H，d，J＝7.3)，0.87(3H，t，J＝7.3)，0.83(3H，t，J＝7.0) 溶剂：CDCl3 |
| 334 | 7.90(1H，d J＝8.5)，7.44(1H，dd J1＝8.5，J2＝2.0)，7.37(1H，d J＝2.0)，2.71(3H，s)，2.65(2H，s)，2.51(3H，s)，2.56(3H，s)，0.93(9H，s)溶剂：CDCl3 |
| 338 | 7.58(1H，d J＝1.7)，7.31(1H，d J＝1.7)，2.78(3H，s)，2.63(2H，s)，2.51(3H，s)，2.27(3H，s)，0.95(9H，s) 溶剂：CDCl3 |
表2(续)
| 化合物编号 | NMR光谱数据 |
| 340 | 7.34(1H，d，J＝1.7)，7.33(1H，d，J＝1.7)，5.64(1H，br.s)，5.12(2H，s)2.75(1H，m)，2.70(3H，m)，2.51(3H，s)，2.25(3H，s)，1.65(2H，m)1.29(3H，d，J＝6.8)，0.83(3H，t，J＝7.3) 溶剂：CDCl3 |
| 344 | 7.64(1H，d，J＝2.0)，7.39(1H，d，J＝1.9)，5.32(2H，s)，2.75(1H，n)，2.71(3H，s)，2.51(3H，s)，2.24(3H，s)，1.66(2H，m)，1.31(3H，d＝，J＝6.8)，0.84(3H，t，J＝7.3) 溶剂：CDCl3 |
| 348 | 7.33(1H，d，J＝2.0)，7.25(1H，d，J＝2.0)，3.25(2H，q，J＝7.4)，2.73(1H，m)，2.70(3H，s)，2.50(3H，s)，2.23(3H，s)，1.65(2H，m)，1.36(3H，t，J＝7.6)，1.29(3H，d，J＝7.0)，0.84(3H，t，J＝7.4)溶剂：CDCl3 |
| 352 | 7.37(1H，s)，7.29(1H，s)，3.08(1H，m)，2.73(3H，s)，2.69(3H，s)，2.48(3H，s)，2.09(3H，s)，1.7～2.2(8H，m) 溶剂：CDCl3 |
| 356 | 11.43(1H，s)，8.12(1H，d，J＝2.2)，7.69(1H，d，J＝2.0)，2.82(1H，m)，2.76(3H，s)，2.54(3H，s)，2.28(3H，s)，1.69(2H，m)，1.32(3H，d，J＝6.8)，0.83(3H，t，J＝7.3) 溶剂：CDCl3 |
| 360 | 7.53(1H，s)，7.40(1H，s)，5.95(1H，m)，2.74(3H，s)，2.69(3H，s)，2.50(3H，s)，2.22(3H，s)，2.07(3H，s)，1.82(3H，d，J＝6.8)溶剂：CDCl3 |
| 362 | 7.39-7.47(2H，m)，5.98(1H，m)，2.73(3H，s)，2.49(3H，s)，2.24(3H，s)，2.06(3H，s)，1.83(3H，d，J＝7.1) 溶剂：CDCl3 |
表中，s表示单峰，d表示双重峰，t表示三重峰，q表示四重峰，quiht表示五重峰，m表示多重峰。
此外，CDCl3表示氘代氯仿，DMSO-d6表示氘代二甲亚砜。
制剂例1(水合剂)
本发明化合物(化合物29) 25重量％
粘土 30重量％
硅藻土 35重量％
木质磺酸钙 3重量％
聚氧乙烯烷芳基醚 7重量％
均匀混合上述组分，并粉碎，就可制得水合剂。
制剂例2(粉剂)
本发明化合物(化合物29) 2重量％
粘土 60重量％
滑石粉 37重量％
硬脂酸钙 1重量％
均匀混合上述组分就可制得粉剂。
制剂例3(乳剂)
本发明化合物(化合物29) 20重量％
N，N-二甲基甲酰胺 20重量％
二甲苯 50重量％
聚氧乙烯烷芳基醚 10重量％
均匀混合上述组分，并溶解，就可制得乳剂。
制剂例4(颗粒剂)
本发明化合物(化合物29) 5重量％
膨润土 40重量％
滑石粉 53重量％
木质磺酸钙 2重量％
均匀粉碎混合上述组分，加水使其粘合在一起后，造粒干燥，制得颗粒剂。
试验例1(稻瘟病的防治效果试验)
利用喷雾器向栽培于直径为5cm的聚乙烯盆中的4叶期的水稻(品种名：十石)喷洒用水稀释过的浓度为100ppm的供试化合物，在喷洒当天风干后，接种稻瘟病菌的分生孢子悬浮液。接种后在加湿条件下感染40小时。然后，放置在人工气象室内使其发育成长。在接种后第6天计数4片叶子上的病斑数，与未处理区比较，算出防治值，根据以下基准作出评估。
A：防治值在80％以上
B：防治值在50～79％之间
C：防治值不足50％
其结果如表3所示。
表3
| 化合物编号 | 评估 | 化合物编号 | 评估 | 化合物编号 | 评估 | 化合物编号 | 评估 | 化合物编号 | 评估 |
| 2 | B | 54 | A | 92 | B | 173 | A | 206 | A |
| 9 | A | 55 | A | 93 | A | 179 | A | 212 | A |
| 10 | A | 56 | A | 97 | B | 180 | A | 214 | A |
| 13 | A | 57 | A | 98 | A | 182 | B | 216 | A |
| 14 | A | 61 | A | 107 | A | 183 | B | 218 | A |
| 23 | B | 62 | A | 108 | A | 185 | B | 220 | A |
| 24 | B | 63 | A | 111 | B | 186 | B | 262 | B |
| 28 | A | 65 | A | 112 | A | 190 | B | 268 | A |
| 29 | A | 66 | A | 125 | B | 191 | A | 274 | A |
| 31 | A | 67 | A | 126 | A | 192 | A | 340 | A |
| 44 | A | 68 | A | 131 | B | 193 | A | 344 | A |
| 45 | A | 69 | A | 136 | A | 195 | A | 348 | A |
| 46 | A | 70 | A | 153 | B | 197 | A | 352 | A |
| 47 | A | 72 | B | 170 | A | 198 | B | 356 | A |
| 48 | A | 83 | A | 171 | B | 199 | A | 360 | A |
| 49 | A | 84 | A | 172 | A | 200 | A | 362 | A |
试验例2(瓜类白粉病的防治效果试验)
在培植于直径3cm的聚乙烯盆中的黄瓜的第一片叶子展开后，向其喷洒用水稀释过的浓度为200ppm的供试化合物，风干后接种白粉病菌的孢子悬浮液，然后，移入人工气象室，在接种后第十天观察发病程度，与未处理区的发病程度相比，算出防治值，根据以下基准作出评估。
A：防治值在80％以上
B：防治值在50～79％之间
C：防治值不足50％
其结果如表4所示。
表4
| 化合物编号 | 评估 | 化合物编号 | 评估 | 化合物编号 | 评估 |
| 24 | A | 71 | A | 196 | A |
| 29 | B | 72 | A | 197 | A |
| 45 | B | 93 | A | 214 | A |
| 55 | A | 112 | A | 216 | B |
| 56 | A | 136 | A | 218 | A |
| 61 | B | 153 | A | 268 | B |
| 65 | A | 175 | A | 340 | A |
| 66 | A | 176 | A | 344 | A |
| 67 | A | 185 | A | 348 | A |
| 68 | A | 195 | A | 356 | A |
试验例3(抗菌试验)
将马铃薯葡萄糖培养基(日水制药株式会社制)与经丙酮溶解的供试化合物混合，使其最终浓度为100ppm，然后分注入培养皿。待琼脂完全固化后，将经过软木穿孔器打眼的在其他培养皿中培养的各种植物病原菌的菌落的圆筒形切片移植到上述培养皿中，在28或22℃培养。测定48小时后的菌落直径，相对于未处理区求出抑制率，根据以下基准作出评估。
A：抑制率在80％以上
B：抑制率在50～79％之间
C：抑制率不足50％
其结果如表5所示。
表5
| 菌种 | 化合物编号 | |||
| 10 | 28 | 29 | 31 | |
| 稻瘟病菌(Pyricularia oryzae) | A | B | A | A |
| 棉立枯病菌(Rhizoctonia solani) | C | C | C | C |
| 稻胡麻斑病菌(Cochlioborus miyabeanus) | B | C | B | A |
| 稻恶苗病菌(Gibberella fujikuroi) | C | C | B | A |
| 蚕豆花腐病菌(Botrytis cinerea) | C | C | B | A |
| 黄瓜萎蔫病菌(Fusarium oxysporumf.sp.lycopersici) | C | C | B | A |
| 葡萄炭疽病菌(Glomerella cingalata) | B | B | A | A |
| 莴苣小菌核病菌(Sclerotinia minor) | C | C | C | B |
| 茄炭疽病菌(Colletotrichum atramentarium) | B | B | B | A |
| 梨黑斑病菌(Alternaria alternata Japanese pearpathotype) | C | C | C | A |
| 棉黄萎病菌(Verticillium aibo-atrum) | C | A | A | A |
发明效果
通式(I)表示的本发明的新颖的4-喹啉酚衍生物作为农业园艺用杀菌剂具有很有效的作用。
Claims (2)
1. 4-喹啉酚衍生物及其可用于农业园艺领域的酸加成盐，由通式(I)表示，
式中，
R1表示氢原子或C1-C4烷基羰基，
R2表示C1-C4烷基，
R3表示C1-C4烷基，
或R2和R3一起表示-(CH2)m-，其中，m为3或4，
W表示在环上取代的相同或不同的1-4个卤原子、可被卤原子、C1-C4烷基或羟基取代的C1-C10烷基、可被C1-C4烷基取代的C2-C4链烯基、C1-C4烷氧基、C3-C10环烷基、苯氧基和NR8R9，其中，R8及R9分别表示C1-C6烷基，或R8及R9与N一起形成6-吗啉代；COR10，其中，R10表示氢原子；
但是，R1为氢原子，R2为甲基或乙基，R3为甲基，W为在环上取代的相同或不同的1-4个卤原子、C1-C10烷基、卤代C1-C4烷基或C1-C4烷氧基的化合物，以及R1为C1-C4烷基羰基，R2和R3独立地表示C1-C4烷基，或者R2和R3一起表示-(CH2)m-，其中，m为3或4，W为在环上取代的相同或不同的1-4个卤原子、C1-C10烷基或C1-C4烷氧基的化合物除外。
2.农业园艺用杀菌组合物，其特征在于，含有权利要求1所述的4-喹啉酚衍生物及其可用于农业园艺领域的酸加成盐中的至少1种。
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| TW521072B (en) * | 1997-06-02 | 2003-02-21 | Meiji Seika Kaisha | 4-quinolinol derivatives and fungicides containing the same as an active ingredient used for agriculture and horticulture |
| US6787557B2 (en) | 2000-05-30 | 2004-09-07 | Meiji Seika Kaisha, Ltd. | Rice blast control agents |
| BR0208759A (pt) * | 2001-04-12 | 2004-09-14 | Meiji Seika Kaisha | Composto, agente de controle da ectoparasita para mamìferos e aves, uso do composto, e, método para controlar uma ectoparasita |
| TW200304772A (en) * | 2002-03-08 | 2003-10-16 | Meiji Seika Kaisha | Fungicidal composition for control of rice plant disease |
| WO2004007460A1 (ja) * | 2002-07-11 | 2004-01-22 | Meiji Seika Kaisha, Ltd. | ２，３，６−トリアルキル−８−フルオロ−４−キノリン誘導体の製造法 |
| TWI320305B (en) * | 2002-10-30 | 2010-02-11 | Meiji Seika Kaisha | Fungicidal composition for controlling diseases of paddy rice |
| KR100613690B1 (ko) * | 2004-07-30 | 2006-08-21 | 한국화학연구원 | 4-퀴놀린온 유도체 및 이를 포함하는 농원예용 살균제조성물 |
| JP4319223B2 (ja) | 2004-08-04 | 2009-08-26 | 明治製菓株式会社 | キノリン誘導体およびそれを有効成分として含んでなる殺虫剤 |
| MX2008001033A (es) | 2005-07-27 | 2008-03-19 | Hoffmann La Roche | Derivados de 4-ariloxi quinolina como moduladores de 5-ht6. |
| JP5112083B2 (ja) * | 2006-02-03 | 2013-01-09 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | 新規キノリン誘導体およびこれを有効成分として含有する農園芸用殺菌剤 |
| CN103636636B (zh) | 2008-07-03 | 2016-08-17 | 石原产业株式会社 | 防治植物病害的杀真菌组合物和方法 |
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| CN104628639B (zh) * | 2013-11-13 | 2018-08-07 | 浙江省化工研究院有限公司 | 一类含七氟异丙基喹啉类化合物、其制备方法及应用 |
| CN104803913B (zh) * | 2014-01-24 | 2019-02-12 | 浙江省化工研究院有限公司 | 一种碳酸苄基喹啉基酯类化合物、其制备方法及应用 |
| CN104904731B (zh) * | 2014-03-11 | 2017-05-10 | 浙江省化工研究院有限公司 | 一种含碳酸苄酯‑2，3，8‑三甲基‑6‑七氟异丙基‑4‑喹啉酯的杀菌组合物 |
| CN104904732B (zh) * | 2014-03-11 | 2017-05-10 | 浙江省化工研究院有限公司 | 一种含zj5337和三唑类杀菌剂的杀菌组合物 |
| CN104904730B (zh) * | 2014-03-11 | 2017-05-10 | 浙江省化工研究院有限公司 | 一种含碳酸苄酯‑2，3，8‑三甲基‑6‑七氟异丙基‑4‑喹啉酯和三唑类杀菌剂的杀菌组合物 |
| US20200037611A1 (en) * | 2017-03-17 | 2020-02-06 | Meiji Seika Pharma Co., Ltd. | Mesostigmata mite control agent |
| CN108690043B (zh) * | 2017-04-11 | 2019-10-18 | 东莞东阳光科研发有限公司 | 喹啉类衍生物及其制备方法和用途 |
| CN109320452B (zh) * | 2017-07-31 | 2019-10-18 | 东莞东阳光科研发有限公司 | 喹啉类衍生物及其制备方法和用途 |
| CN109776410B (zh) * | 2017-11-15 | 2021-02-05 | 浙江省化工研究院有限公司 | 一类含七氟异丙基喹啉醚类化合物、其制备方法及应用 |
| WO2019117179A1 (ja) | 2017-12-12 | 2019-06-20 | 日本化薬株式会社 | キノリン‐４（１ｈ）－オン誘導体の製造方法 |
| CN110938034B (zh) * | 2018-09-21 | 2021-05-11 | 东莞市东阳光农药研发有限公司 | 喹啉衍生物及其在农业中的应用 |
| CN113880840A (zh) * | 2020-07-01 | 2022-01-04 | 海利尔药业集团股份有限公司 | 一种喹啉酚类衍生物或其作为农药可接受的盐、组合物及其用途 |
| CA3204318A1 (en) | 2020-12-17 | 2022-06-23 | Astrazeneca Ab | N-(2-(4-cyanothiazolidin-3-yl)-2-oxoethyl)-quinoline-4-carboxamides |
| CN112608277B (zh) * | 2020-12-29 | 2022-08-05 | 浙江工业大学 | 一种含氟喹啉酯类化合物及其制备方法和应用 |
| CN114957116A (zh) * | 2022-07-01 | 2022-08-30 | 浙江工业大学 | 2,3-二甲基-8-氟喹啉-4-酯类化合物及其制备方法和应用 |
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| DE2361438C3 (de) * | 1973-12-10 | 1979-12-13 | Hoechst Ag, 6000 Frankfurt | 4-Hydroxychinoün- und 4-Hydroxytetrahydrochinolin-N^N-dimethylcarbamate, Verfahren zu ihrer Herstellung und diese enthaltende insektizide Mittel |
| NZ223875A (en) * | 1987-03-17 | 1991-01-29 | Hoechst Roussel Pharma | 9-aminotetrahydroacridines and related homologues and pharmaceutical compositions |
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1998
- 1998-06-01 TW TW087108526A patent/TW521072B/zh not_active IP Right Cessation
- 1998-06-02 ID IDW991617A patent/ID25582A/id unknown
- 1998-06-02 EP EP98923085A patent/EP0990648B1/en not_active Expired - Lifetime
- 1998-06-02 CN CNB98805678XA patent/CN1169794C/zh not_active Expired - Fee Related
- 1998-06-02 WO PCT/JP1998/002434 patent/WO1998055460A1/ja active IP Right Grant
- 1998-06-02 DE DE69832171T patent/DE69832171T2/de not_active Expired - Lifetime
- 1998-06-02 KR KR1019997011248A patent/KR100362029B1/ko not_active IP Right Cessation
- 1998-06-02 JP JP50205199A patent/JP3934164B2/ja not_active Expired - Lifetime
- 1998-06-02 US US09/424,257 patent/US6680282B2/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| DE69832171D1 (de) | 2005-12-08 |
| EP0990648A4 (en) | 2001-11-21 |
| DE69832171T2 (de) | 2006-07-20 |
| US20040152728A1 (en) | 2004-08-05 |
| KR20010013256A (ko) | 2001-02-26 |
| JP3934164B2 (ja) | 2007-06-20 |
| CN1259124A (zh) | 2000-07-05 |
| EP0990648A1 (en) | 2000-04-05 |
| US7067668B2 (en) | 2006-06-27 |
| KR100362029B1 (ko) | 2002-11-23 |
| ID25582A (id) | 2000-10-19 |
| WO1998055460A1 (fr) | 1998-12-10 |
| US6680282B2 (en) | 2004-01-20 |
| TW521072B (en) | 2003-02-21 |
| EP0990648B1 (en) | 2005-11-02 |
| US20030119863A1 (en) | 2003-06-26 |
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