CN101808986A - 亚氨酸酯化合物和其用于害虫控制的用途 - Google Patents
亚氨酸酯化合物和其用于害虫控制的用途 Download PDFInfo
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- CN101808986A CN101808986A CN200880108786A CN200880108786A CN101808986A CN 101808986 A CN101808986 A CN 101808986A CN 200880108786 A CN200880108786 A CN 200880108786A CN 200880108786 A CN200880108786 A CN 200880108786A CN 101808986 A CN101808986 A CN 101808986A
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- optionally substituted
- radical
- halogen atom
- phenyl
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- 125000005843 halogen group Chemical group 0.000 claims description 108
- 125000004429 atom Chemical group 0.000 claims description 89
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- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 22
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- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 21
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- 125000004705 ethylthio group Chemical group C(C)S* 0.000 claims description 4
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- 125000004739 (C1-C6) alkylsulfonyl group Chemical group 0.000 claims description 3
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims description 3
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- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 3
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 claims description 3
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 claims description 3
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- 150000004679 hydroxides Chemical class 0.000 description 9
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 9
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- 239000000463 material Substances 0.000 description 9
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- 125000001979 organolithium group Chemical group 0.000 description 9
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- 239000011736 potassium bicarbonate Substances 0.000 description 9
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- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 9
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 9
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
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- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
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- 239000002562 thickening agent Substances 0.000 description 1
- DNVLJEWNNDHELH-UHFFFAOYSA-N thiocyclam Chemical compound CN(C)C1CSSSC1 DNVLJEWNNDHELH-UHFFFAOYSA-N 0.000 description 1
- BAKXBZPQTXCKRR-UHFFFAOYSA-N thiodicarb Chemical compound CSC(C)=NOC(=O)NSNC(=O)ON=C(C)SC BAKXBZPQTXCKRR-UHFFFAOYSA-N 0.000 description 1
- 125000005505 thiomorpholino group Chemical group 0.000 description 1
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- QGHREAKMXXNCOA-UHFFFAOYSA-N thiophanate-methyl Chemical compound COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC QGHREAKMXXNCOA-UHFFFAOYSA-N 0.000 description 1
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- BAZVSMNPJJMILC-UHFFFAOYSA-N triadimenol Chemical compound C1=NC=NN1C(C(O)C(C)(C)C)OC1=CC=C(Cl)C=C1 BAZVSMNPJJMILC-UHFFFAOYSA-N 0.000 description 1
- XOPFESVZMSQIKC-UHFFFAOYSA-N triasulfuron Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)OCCCl)=N1 XOPFESVZMSQIKC-UHFFFAOYSA-N 0.000 description 1
- NKNFWVNSBIXGLL-UHFFFAOYSA-N triazamate Chemical compound CCOC(=O)CSC1=NC(C(C)(C)C)=NN1C(=O)N(C)C NKNFWVNSBIXGLL-UHFFFAOYSA-N 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- AMFGTOFWMRQMEM-UHFFFAOYSA-N triazophos Chemical compound N1=C(OP(=S)(OCC)OCC)N=CN1C1=CC=CC=C1 AMFGTOFWMRQMEM-UHFFFAOYSA-N 0.000 description 1
- YMXOXAPKZDWXLY-QWRGUYRKSA-N tribenuron methyl Chemical group COC(=O)[C@H]1CCCC[C@@H]1S(=O)(=O)NC(=O)N(C)C1=NC(C)=NC(OC)=N1 YMXOXAPKZDWXLY-QWRGUYRKSA-N 0.000 description 1
- ZOKXUAHZSKEQSS-UHFFFAOYSA-N tribufos Chemical compound CCCCSP(=O)(SCCCC)SCCCC ZOKXUAHZSKEQSS-UHFFFAOYSA-N 0.000 description 1
- REEQLXCGVXDJSQ-UHFFFAOYSA-N trichlopyr Chemical compound OC(=O)COC1=NC(Cl)=C(Cl)C=C1Cl REEQLXCGVXDJSQ-UHFFFAOYSA-N 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
- ONCZDRURRATYFI-TVJDWZFNSA-N trifloxystrobin Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1CO\N=C(/C)C1=CC=CC(C(F)(F)F)=C1 ONCZDRURRATYFI-TVJDWZFNSA-N 0.000 description 1
- HSMVPDGQOIQYSR-KGENOOAVSA-N triflumizole Chemical compound C1=CN=CN1C(/COCCC)=N/C1=CC=C(Cl)C=C1C(F)(F)F HSMVPDGQOIQYSR-KGENOOAVSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical compound C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
- 239000002753 trypsin inhibitor Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 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
- YNWVFADWVLCOPU-MAUPQMMJSA-N uniconazole P Chemical compound C1=NC=NN1/C([C@@H](O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1 YNWVFADWVLCOPU-MAUPQMMJSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000010497 wheat germ oil Substances 0.000 description 1
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- 239000002023 wood Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P33/00—Antiparasitic agents
- A61P33/14—Ectoparasiticides, e.g. scabicides
-
- 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
-
- 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
- C07C317/46—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
- C07C323/65—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfone or sulfoxide groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/36—Esters of dithiocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/58—Derivatives of thiocarboxylic acids, the doubly-bound oxygen atoms being replaced by nitrogen atoms, e.g. imino-thio ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
- C07C329/12—Dithiocarbonic acids; Derivatives thereof
- C07C329/14—Esters of dithiocarbonic acids
- C07C329/16—Esters of dithiocarbonic acids having sulfur atoms of dithiocarbonic groups bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
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Abstract
Description
技术领域
本发明涉及亚氨酸酯(imidate)化合物和其用于害虫控制的用途。
背景技术
为控制害虫,已经开发和实际上使用了各类化合物。
进一步,一些亚氨酸酯化合物被公开于Journal De La SocieteChemique De Tunisie,1988,第4卷,第3期,189-195页;Bulletin De LaSociete Chimique De France,1988,第5期,875-872页;和RussianChemical bulletin,1983,第32卷,第3期,610-612页中。
发明内容
本发明目的是提供对害虫具有极好控制效果的新型化合物。
本发明的本发明人已经进行致力研究,且结果,他们已经发现由下式(I-1)表示的亚氨酸酯化合物对害虫具有极好的控制作用。由此,本发明已经完成。
本发明提供:
(1)亚氨酸酯化合物,由式(I-1)表示:
其中,
Z表示任选地被选自如下所述的组A的基团取代的具有3到14个构成环的原子的碳环基团,或任选地被选自如下所述的组A的基团取代的具有3到14个构成环的原子的杂环基团;
G表示-A1-R1基团,-S(=O)2-R2基团或-N(R3)-R1基团;
X表示-A2-R4基团,-S(=O)-R5基团或-S(=O)2-R5基团;
X0表示-A3-R6基团,-S(=O)-R7基团,-S(=O)2-R7基团或卤素原子;或
X和X0任选地合起来形成-A2-T0-A3-基团;
M1表示-R8基团,-A8-R8基团,卤素原子或氢原子;
A1,A2和A3独立地表示氧原子或硫原子;
R1表示任选地被选自如下所述的组D的基团取代的C1-C20链烃基团,-Q基团,-T1-Q基团,-T1-S-Q基团或-T1-O-Q基团;
R2表示任选地被选自如下所述的组E的基团取代的C1-C20链烃基团,或任选地被选自如下所述的组B的基团取代的苯基;
R3表示任选地被选自如下所述的组D的基团取代的C1-C20链烃基团,-Q基团,-T1-Q基团,C1-C6烷氧基,C2-C7烷酰基,单(C1-C7烷基)氨基,二(C1-C7烷基)氨基或(C1-C7烷基)苯基氨基;
R4和R6独立地表示任选地被选自如下所述的组D的基团取代的C1-C6链烃基团,-Q基团,-T1-Q基团,-C(=A4)-R11基团,-C(=A4)-A5-R11基团或-S(=O)2-R11基团;
R5和R7独立地表示任选地被选自如下所述的组E的基团取代的C1-C6链烃基团,-Q1基团或-T2-Q1基团
R8表示任选地被选自如下所述的组E的基团取代的C1-C20链烃基团,-Q基团或-T1-Q基团;
A8表示氧原子或硫原子;
T0表示任选地被卤素原子或苯基取代的C2-C6烷二基且其中该烷二基的碳-碳单键可以由氧原子、硫原子和/或羰基中断,-Q9-基团,-T1-Q9-基团或-T1-Q9-T2-基团;
Q表示任选地被选自如下所述的组A的基团取代的具有3到14个构成环的原子的碳环基团,或任选地被选自如下所述的组A的基团取代的具有3到14个构成环的原子的杂环基团;
Q1表示任选地被选自如下所述的组B的基团取代的具有3到14个构成环的原子的碳环基团,或任选地被选自如下所述的组B的基团取代的具有3到14个构成环的原子的杂环基团;
T1和T2独立地表示任选地被卤素原子取代的C1-C6烷二基,或C2-C6烯二基;
A4和A5独立地表示氧原子或硫原子;
Q9表示邻亚苯基或萘-1,8-二基;
R11表示任选地被选自如下所述的组E的基团取代的C1-C6链烃基团,或任选地被选自如下所述的组B的基团取代的具有3到14个构成环的原子的碳环基团,
组A由以下组成:卤素原子,氰基,硝基,甲酰基,任选地被卤素原子取代的C1-C6链烃基团,-A6-L1基团,-N(L3)-L2基团,-N(L3)-N(L2)-L1基团,-N=C(L3)-L2基团,-S(=O)-L1基团,-S(=O)2-L1基团,-S(=O)2-N(L3)-L2基团,-O-S(=O)2-L1基团,-NL2-S(=O)2-L1基团,-C(=A7)-L1基团,-C(=A7)-O-L1基团,-O-C(=A7)-L1基团,-NL2-C(=A7)-L1基团,-O-C(=O)-O-L1基团,-C(=A7)-T4-A6-L1基团,-C(=A7)-N(L3)-L2基团,-Q2基团,-T3-Q2基团,-A6-Q2基团,-A6-T4-Q2基团,-N(L3)-Q2基团,-N(L3)-N(L2)-Q2基团,-N=C(R12)-Q2基团,-S(=O)-Q2基团,-S(=O)2-Q2基团,-S(=O)2-N(L3)-Q2基团,-O-S(=O)2-Q2基团,-NL2-S(=O)2-Q2基团,-C(=A7)-Q2基团,-C(=A7)-A6-Q2基团,-A6-C(=A7)-Q2基团,-NL2-C(=A7)-Q2基团,-C(=A7)-T4-A6-Q2基团,和-C(=A7)-N(L3)-Q2基团;
组B由以下组成:卤素原子,氰基,硝基,任选地被卤素原子取代的C1-C6烷基,任选地被卤素原子取代的C2-C6烯基,任选地被卤素原子取代的C2-C6炔基,C1-C6烷基硫基,和C1-C6烷氧基;
组D由以下组成:卤素原子,氰基,硝基,任选地被卤素原子取代的C1-C6烷氧基,任选地被卤素原子取代的C1-C6烷基硫基,任选地被卤素原子取代的C1-C6烷基磺酰基,任选地被卤素原子取代的(C1-C6烷基)羰基,任选地被卤素原子取代的(C1-C6烷氧基)羰基,和任选地被卤素原子取代的(C1-C6烷氧基)羰氧基;和
组E由以下组成:卤素原子,氰基,硝基,C1-C6烷基硫基,和C1-C6烷氧基;
其中,A6和A7独立地表示氧原子或硫原子;
L1表示任选地被卤素原子取代的C1-C6链烃基团;
L2和L3独立地表示氢原子,任选地被卤素原子取代的C1-C6烷基;
Q2表示任选地被选自上述组B的基团取代的具有3到14个构成环的原子的碳环基团,或任选地被选自上述组B的基团取代的具有3到14个构成环的原子的杂环基团;
T3和T4独立地表示任选地被卤素原子取代的C1-C6烷二基;和
R12表示任选地被卤素原子取代的C1-C6链烃基团或任选地被卤素原子取代的苯基;
(2)根据上述(1)的亚氨酸酯化合物,其中M1是C1-C6烷基,C1-C6烷氧基,C1-C6烷基硫基,任选地被选自该E组的基团取代的苯基,任选地被选自该E组的基团取代的苯氧基,任选地被选自该E组的基团取代的苯基硫基,任选地被选自该E组的基团取代的单环的不饱和的具有3-8个构成环的原子的杂环基,卤素原子或氢原子;
(3)根据上述(1)的亚氨酸酯化合物,其中M1是甲基,乙基,丙基,丁基,苯基,2-甲基苯基,3-甲基苯基,4-甲基苯基,2-氟苯基,3-氟苯基,4-氟苯基,2-氯苯基,3-氯苯基,4-氯苯基,甲氧基,乙氧基,丙氧基,苯氧基,2-甲基苯氧基,3-甲基苯氧基,4-甲基苯氧基,2-氟苯氧基,3-氟苯氧基,4-氟苯氧基,2-氯苯氧基,3-氯苯氧基,4-氯苯氧基,甲硫基,乙硫基,丙硫基,丁硫基,苯基硫基,2-甲基苯基硫基,3-甲基苯基硫基,4-甲基苯基硫基,2-氟苯基硫基,3-氟苯基硫基,4-氟苯基硫基,2-氯苯基硫基,3-氯苯基硫基,4-氯苯基硫基,2-噻吩基,3-噻吩基,2-呋喃基,3-呋喃基,氟原子,氯原子或氢原子;
(4)根据上述(1)的亚氨酸酯化合物,其中M1是甲基,乙基,丙基,丁基,甲氧基,乙氧基,丙氧基,甲硫基,乙硫基,丙硫基,氟原子,或氢原子;
(5)根据上述(1)的亚氨酸酯化合物,其中M1是氢原子;
(6)根据上述(1)到(5)中任一项的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自如下所述的组A′的基团取代的碳环基团,或具有3到14个构成环的原子的任选地被选自如下所述的组A′的基团取代的杂环基团,和
组A′由以下组成:卤素原子,氰基,硝基,甲酰基,任选地被卤素原子取代的C1-C6链烃基团,-A6-L1基团,-C(=A7)-L1基团,-C(=A7)O-L1基团,-O-C(=A7)-L1基团,-NL2-C(=A7)-L1基团,-C(=A7)-N(L3)-L2基团,-Q2基团,-T3-Q2基团,-A6-Q2基团,-A6-T4-Q2基团,-C(=A7)-Q2基团,-C(=A7)-O-Q2基团,-O-C(=A7)-Q2基团,-NL3-C(=A7)-Q2基团和-C(=A7)-N(L3)-Q2基团;
(7)根据上述(1)到(5)中任一项的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自如下所述的组A2′的基团取代的碳环基团,或具有3到14个构成环的原子的任选地被选自如下所述的组A2′的基团取代的杂环基团,和
组A2′由以下组成:卤素原子,任选地被卤素原子取代的C1-C6烷基,任选地被卤素原子取代的C2-C6烯基,任选地被卤素原子取代的C2-C6炔基,任选地被卤素原子取代的C1-C6烷基硫基,任选地被卤素原子取代的C1-C6烷氧基,和任选地被选自如上述(1)中定义的该B组的基团取代的苯基;
(8)根据上述(7)的亚氨酸酯化合物,其中Z是任选地被选自组A2′的基团取代的具有3到14个构成环的原子的碳环基团;
(9)根据上述(8)的亚氨酸酯化合物,其中Z是任选地被选自该组A2′的基团取代的苯基,5-茚满基,或萘基;
(10)根据上述(1)到(5)中任一项的亚氨酸酯化合物,其中Z是任选地被选自如下所述的组A3′的基团取代的苯基,5-茚满基,或萘基,和
组A3′由以下组成:卤素原子,甲基,乙基,丙基,异丙基,丁基,三氟甲基,甲氧基,乙氧基,丙氧基,异丙氧基,丁氧基,三氟甲氧基,3,4-亚甲基二氧基,甲硫基,乙硫基,丙硫基,异丙硫基,丁硫基,三氟甲硫基,苯基,2-甲基苯基,3-甲基苯基,4-甲基苯基,2-乙基苯基,3-乙基苯基,4-乙基苯基,2-丙基苯基,3-丙基苯基,4-丙基苯基,2-异丙基苯基,3-异丙基苯基,4-异丙基苯基,2-氟苯基,3-氟苯基,4-氟苯基,2-氯苯基,3-氯苯基,4-氯苯基,2-溴苯基,3-溴苯基,和4-溴苯基;
(11)根据上述(1)至(10)中任一项的亚氨酸酯化合物,其中G是-A1-R1基团或-N-(R3)-R1基团;
(12)根据上述(1)至(10)中任一项的亚氨酸酯化合物,其中G是-A1-R1基团;
(13)根据上述(1)到(10)中任一项的亚氨酸酯化合物,其中G是-A1-R1基团,且R1是-Q基团或-T1-Q基团且其中Q是如上述(1)所限定的Q1,或任选地被选自卤素原子,氰基,硝基,C1-C6烷基硫基和C1-C6烷氧基的基团取代的C1-C20链烃基团;
(14)根据上述(1)到(10)中任一项的亚氨酸酯化合物,其中G是-A1-R1基团;A1是S;和R1是-Q基团或-T1-Q基团且其中Q是具有3到14个构成环的原子的任选地被选自如上述(1)限定的组B的基团取代的碳环基团,或任选地被选自卤素原子,氰基,硝基,C1-C6烷基硫基和C1-C6烷氧基的基团取代的C1-C20链烃基团;
(15)根据上述(1)到(10)中任一项的亚氨酸酯化合物,其中G是-A1-R1基团;A1是S;和R1是任选地被选自卤素原子,氰基,硝基,C1-C6烷基硫基和C1-C6烷氧基的基团取代的C1-C20链烃基团,或-Q基团或-T1-Q基团且其中Q是任选被选自如权利要求1中定义的该组B的基团取代的苯基或任选地被选自如上述(1)定义的该组B的基团取代的萘基;
(16)根据上述(1)到(10)中任一项的亚氨酸酯化合物,其中G是-A1-R1基团;A1是O;和R1是-Q基团且其中Q是任选地被选自如权利要求1中所定义的该组B的基团取代的苯基或任选地被选自如上述(1)定义的该组B的基团取代的萘基;
(17)根据上述(1)至(16)中任一项的亚氨酸酯化合物,其中X是-A2-R4基团和X0是-A3-R6基团,或X和X0合起来形成-A2-T0-A3-基团;
(18)根据上述(1)至(16)中任一项的亚氨酸酯化合物,其中X是-A2-R4基团和X0是-A3-R6基团;
(19)根据上述(1)到(16)中任一项的亚氨酸酯化合物,其中X是-A2-R4基团;X0是-A3-R6基团;且R4和R6独立地是-Q基团或-T1-Q基团且其中Q是如上述(1)所限定的Q1,或任选地被选自卤素原子,氰基,硝基,C1-C6烷基硫基和C1-C6烷氧基的基团取代的C1-C6链烃基团;
(20)根据上述(1)至(16)中任一项的亚氨酸酯化合物,其中X是-A2-R4基团;X0是-A3-R6基团;且R4和R6独立地是-Q基团或-T1-Q基团且其中Q是如上述(1)所限定的Q1;
(21)根据上述(1)到(16)中任一项的亚氨酸酯化合物,其中X是-A2-R4基团;X0是-A3-R6基团;且R4和R6独立地是-Q基团且其中Q是任选地被选自如上述(1)定义的该组B的基团取代的苯基;
(22)根据上述(1)到(16)中任一项的亚氨酸酯化合物,其中X是-A2-R4基团;X0是-A3-R6基团;A2和A3各自是S;和R4和R6独立地是-Q基团,其中Q是任选地被选自如上述(1)定义的该组B的基团取代的苯基;
(23)杀虫组合物,包括根据上述(1)至(22)中任一项的化合物作为活性成分;
(24)根据上述(1)至(22)中任一项的化合物用于害虫控制的用途;
(25)根据上述(1)至(22)中任一项的化合物的用于生产杀虫组合物的用途;和
(26)控制害虫的方法,其包括施加根据上述(1)至(22)中任一项的化合物至该害虫或该害虫栖息之地。
本发明的化合物对害虫具有极好的控制作用。
用于执行本发明的最佳方式
本说明书中提到的各种取代基将举例说明。
如本文中使用的“具有3到14个构成环的原子的碳环基团”的实例包括具有3-8个构成环的原子的单环的饱和碳环基团,如环丙基,环丁基,环戊基,环己基,等等;具有5至8个构成环的原子的单环不饱和碳环基团,如环丁烯基,环戊烯基,环己烯基(例如2-环己烯-1-基,3-环己烯-1-基等等),苯基,等等;具有8至14个构成环的原子的缩合多环饱和碳环基团,如双环[3.1.0]己基,双环[4.1.0]庚基,双环[3.2.0]庚基,双环[2.2.1]庚基,双环[4.2.0]辛基,双环[3.3.0]辛基,双环[4.3.0]壬基,双环[4.4.0]癸基(也称为全氢萘基),等等;和具有8至14个构成环的原子的缩合多环不饱和碳环基团,如萘基,蒽基,茚满基,1,2,3,4-四氢萘基,芴基,等等。
如本文中使用的“具有3到14个构成环的原子的杂环基团”的实例包括具有3-8个构成环的原子的单环饱和杂环基,其包括碳原子和至少一个选自氧原子,硫原子和氮原子的杂原子;具有5至8个构成环的原子的单环不饱和杂环基,其包括碳原子和至少一个选自氧原子,硫原子和氮原子的杂原子;和具有8到14个构成环的原子的缩合多环杂环基,其包括碳原子和至少一个选自氧原子,硫原子和氮原子的杂原子。
更具体地说,“具有3-8个构成环的原子的单环饱和杂环基,其包括碳原子和至少一个选自氧原子,硫原子和氮原子的杂原子”的实例包括吡咯烷基,咪唑烷基,哌啶基,哌啶子基,哌嗪基,吗啉基,咪唑酮基,吗啉代基团,噻唑烷基,硫吗啉基,硫代吗啉代基团,硫代吗啉代基团,四氢噻吩基,二噻烷基,四氢呋喃基,四氢吡喃基和二噁烷基。
“具有5至8个构成环的原子的单环不饱和杂环基,其包括碳原子和至少一个选自氧原子,硫原子和氮原子的杂原子”的实例包括吡咯基,吡咯啉基,咪唑基,吡唑基,吡啶基,二氢吡啶基团,嘧啶基,吡嗪基,哒嗪基,三唑基(例如4H-1,2,4-三唑基,1H-1,2,3-三唑基,2H-1,2,3-三唑基等),四唑基(例如1H-四唑基,2H-四唑基等),噁唑基,异噁唑基,噁二唑基(例如1,2,4-噁二唑基,1,3,4-噁二唑基,1,2,5-噁二唑基等),噻吩基,噻唑基,异噻唑基,噻二唑基(例如1,2,3-噻二唑基,1,2,4-噻二唑基,1,3,4-噻二唑基,1,2,5-噻二唑基等),二氢噻嗪基,呋喃基,二嗪吡喃基,二噁英基(dioxynyl)基团和dihydroxathiinyl基团。
“具有8到14个构成环的原子的缩合多环杂环基,其包括碳原子和至少一个选自氧原子,硫原子和氮原子的杂原子”的实例包括吲哚基,异氮茚基,indolynyl基团,indolydinyl基团,苯并咪唑基,喹啉基,异喹啉基,吲唑基,苯并三唑基,咪唑并吡啶基,吡唑并吡啶基,苯并噁唑基,苯并噁二唑基,苯并噻唑基,苯并噻二唑基,咪唑并噻二唑基,氧茚基,苯并二氧戊环基,苯并二氧杂环己烷基,二苯并呋喃基,苯并噻吩基,benzodithiinyl基团,二苯并噻吩基和benzoxathiinyl基团。
如本文中使用的“C1-C20链烃基团”的实例包括C1-C20烷基如甲基,乙基,丙基,异丙基,丁基,异丁基,仲丁基,叔丁基,戊基,仲戊基,异戊基,新戊基,己基,异己基,庚基,辛基,3-甲基-1-丙基丁基,壬基,1-丙基己基,癸基,3,5-二甲基辛基,3,7-二甲基辛基,十一烷基,十二烷基,十三烷基,十四烷基,十六烷基,十七烷基,十八烷基,十九烷基,二十烷基(icosyl)基团,等等;C3-C20烯基如2-丙烯基,异丙烯基,2-丁烯基,3-甲基-2-丁烯基,异丁烯基,1-甲代烯丙基,2-戊烯基,2-己烯基,庚烯基,辛烯基,3,5-二甲基辛烯基,3,7-二甲基辛烯基,等等;和C3-C12炔基如炔丙基,2-丁炔基,3-丁炔基,3-戊炔基,3-己炔基,6-庚炔基,7-辛炔基,3,5-二甲基-7-辛炔基,3,7-二甲基-4-辛炔基,等等。
如本文中使用的“C1-C6烷氧基”的实例包括甲氧基,乙氧基,丙氧基和异丙氧基。
如本文中使用的“C2-C7烷酰基”的实例包括甲酰基,乙酰基,丙酰基,丁酰基,2-甲基丙烷酰基,戊烷酰基,2,2-二甲基丙烷酰基和己酰基团。
如本文中使用的“单(C1-C7烷基)氨基”的实例包括甲基氨基,乙基氨基,丙基氨基和丁氨基。
如本文中使用的“二(C1-C7烷基)氨基”的实例包括二甲基氨基,二乙基氨基,甲基乙基氨基,甲基丙基氨基和乙基丙基氨基。
如本文中使用的“(C1-C7烷基)苯基氨基”的实例包括N-甲基-N-苯基氨基和N-乙基-N-苯基氨基。
如本文中使用的“C1-C6链烃基团”的实例包括C1-C6烷基如甲基,乙基,丙基,异丙基,丁基,异丁基,仲丁基,叔丁基,戊基,仲戊基,异戊基,新戊基,己基,异己基,等等;C3-C6烯基如2-丙烯基,异丙烯基,2-丁烯基,3-甲基-2-丁烯基,异丁烯基,1-甲代烯丙基,2-戊烯基,2-己烯基,等等;和C3-C6炔基如炔丙基,2-丁炔基,3-丁炔基,3-戊炔基,3-己炔基,等等。
“任选地被卤素原子或苯基取代的C2-C6烷二基且其中该烷二基的碳-碳单键可以由氧原子、硫原子和/或羰基中断”的C2-C6烷二基的实例包括乙烷-1,2-二基,丙烷-1,2-二基,丙烷-1,3-二基,丁烷-1,4-二基,戊烷-1,5-二基和己烷-1,6-二基。
如本文中使用的“任选地被卤素原子取代的C1-C6烷二基”的实例,包括亚甲基,乙烷-1,1-二基,2,2,2-三氟乙烷-1,1-二基,乙烷-1,2-二基,丙烷-1,1-二基,丙烷-1,2-二基,丙烷-1,3-二基,丁烷-1,4-二基,戊烷-1,5-二基和己烷-1,6-二基。
如本文中使用的“C2-C6烯二基”的实例包括乙烯-1,1-二基和乙烯-1,2-二基。
如本文中使用的,词组“任选地被取代的基团”意思指所述基团的氢原子是任选地被取代的。
本文,当列举两个或更多个取代基团时(例如,当基团任选地被选自组A,B,D,E等等的取代基团取代时),所述基团的一个或多个氢原子任选地被所述取代基团(一个或更多个)取代。当基团的两个或更多个氢原子被取代时,氢原子任选地被相同的取代基团或不同的取代基团取代。
“卤素原子”的实例包括氟原子,氯原子,溴原子和碘原子。
如本文中使用的“任选地被卤素原子取代的C1-C6链烃基团”的实例包括甲基,氟甲基,二氟甲基,三氟甲基,氯甲基,溴甲基,碘甲基,乙基,五氟乙基,2,2,2-三氟乙基,和2,2,2-三氟-1-(三氟甲基)乙基。
如本文中使用的“任选地被卤素原子取代的C1-C6烷基”的实例包括甲基,氟甲基,二氟甲基,三氟甲基,氯甲基,溴甲基,碘甲基,乙基,五氟乙基,2,2,2-三氟乙基,和2,2,2-三氟-1-(三氟甲基)乙基。
如本文中使用的“任选地被卤素原子取代的C2-C6烯基”的实例,包括乙烯基,2-氟乙烯基,2-丙烯基,和3,3-二氯丙烯基。
如本文中使用的“任选地被卤素原子取代的C2-C6炔基”的实例包括乙炔基,炔丙基,和4,4,4-三氟-2-丁炔基。
如本文中使用的“任选地被卤素原子取代的C1-C6烷氧基”的实例包括甲氧基,三氟甲氧基,乙氧基,和2,2,2-三氟乙基。
如本文中使用的“任选地被卤素原子取代的C1-C6烷基硫基”的实例包括甲硫基,三氟甲硫基,和乙硫基。
如本文中使用的“任选地被卤素原子取代的C1-C6烷基磺酰基”的实例包括甲磺酰基团,三氟甲基磺酰基,和乙磺酰基团。
如本文中使用的“任选地被卤素原子取代的(C1-C6烷基)羰基”的实例包括甲基羰基,和乙基羰基。
如本文中使用的“任选地被卤素原子取代的(C1-C6烷氧基)羰基”的实例包括甲氧羰基,和乙氧羰基。
如本文中使用的“任选地被卤素原子取代的(C1-C6烷氧基)羰氧基”的实例包括甲氧基羰基氧基,和乙氧基羰基氧基。
如本文中使用的,组A包括组B,且组B和组D各自包括组E。如本文中使用的,由″Q″表示的基团包括由″Q1″表示的基团。
本发明的化合物的具体实例包括:
由表示式(I-1)的亚氨酸酯化合物,其中M1是C1-C6烷基,C1-C6烷氧基,C1-C6烷基硫基,任选地被选自组E的基团取代的苯基,任选地被选自组E的基团取代的苯氧基,任选地被选自组E的基团取代的苯基硫基,具有3-8个构成环的原子的任选地被选自组E的基团取代的单环不饱和杂环基,卤素原子,或氢原子;
由式(I-1)表示的亚氨酸酯化合物,其中M1是甲基,乙基,丙基,丁基,苯基,2-甲基苯基,3-甲基苯基,4-甲基苯基,2-氟苯基,3-氟苯基,4-氟苯基,2-氯苯基,3-氯苯基,4-氯苯基,甲氧基,乙氧基,丙氧基,苯氧基,2-甲基苯氧基,3-甲基苯氧基,4-甲基苯氧基,2-氟苯氧基,3-氟苯氧基,4-氟苯氧基,2-氯苯氧基,3-氯苯氧基,4-氯苯氧基,甲硫基,乙硫基,丙硫基,丁硫基,苯基硫基,2-甲基苯基硫基,3-甲基苯基硫基,4-甲基苯基硫基,2-氟苯基硫基,3-氟苯基硫基,4-氟苯基硫基,2-氯苯基硫基,3-氯苯基硫基,4-氯苯基硫基,2-噻吩基,3-噻吩基,2-呋喃基,3-呋喃基,氟原子,氯原子,或氢原子;
由式(I-1)表示的亚氨酸酯化合物,其中M1是甲基,乙基,丙基,丁基,甲氧基,乙氧基,丙氧基,甲硫基,乙硫基,丙硫基,氟原子,或氢原子;
由式(I-1)表示的亚氨酸酯化合物,其中M1是氢原子,即,由式(I-2)表示的亚氨酸酯化合物:
其中Z,G,X和X0如上所定义;
由式(I-1)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自该组A2′的基团取代的碳环基团,或具有3到14个构成环的原子的任选地被选自组A2′的基团取代的杂环基团,和
组A2′由以下组成:卤素原子,任选地被卤素原子取代的C1-C6烷基,任选地被卤素原子取代的C2-C6烯基,任选地被卤素原子取代的C2-C6炔基,任选地被卤素原子取代的C1-C6烷基硫基,任选地被卤素原子取代的C1-C6烷氧基,和任选地被选自B组的基团取代的苯基;
由式(I-1)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自该组A2′的基团取代的碳环基团;
由式(I-1)表示的亚氨酸酯化合物,其中Z是任选地被选自该组A2′的基团取代的苯基,任选地被选自该组A2′的基团取代的5-茚满基或任选地被选自该组A2′的基团取代的萘基;
由式(I-1)表示的亚氨酸酯化合物,其中Z是任选地被选自组A3′的基团取代的苯基,任选地被选自组A3′的基团取代的5-茚满基或任选地被选自组A3′的基团取代的萘基,和
组A3′由以下组成:卤素原子,甲基,乙基,丙基,异丙基,丁基,三氟甲基,甲氧基,乙氧基,丙氧基,异丙氧基,丁氧基,三氟甲氧基,3,4-亚甲基二氧基,甲硫基,乙硫基,丙硫基,异丙硫基,丁硫基,三氟甲硫基,苯基,2-甲基苯基,3-甲基苯基,4-甲基苯基,2-乙基苯基,3-乙基苯基,4-乙基苯基,3-丙基苯基,4-丙基苯基,2-异丙基苯基,3-异丙基苯基,4-异丙基苯基,2-氟苯基,3-氟苯基,4-氟苯基,2-氯苯基,3-氯苯基,4-氯苯基,2-溴苯基,3-溴苯基,和4-溴苯基;
由式(I-1)表示的亚氨酸酯化合物,其中G是-A1-R1基团或-N(R3)-R1基团;
由式(I-1)表示的亚氨酸酯化合物,其中G是-A1-R1基团;
由式(I-1)表示的亚氨酸酯化合物,其中G是-A1-R1基团,和R1是-Q1基团,-T1-Q1基团,或任选地被选自组E的基团取代的C1-C20链烃基团;
由式(I-1)表示的亚氨酸酯化合物,其中G是-S-R1基团,R1是-Q1a基团,-T1-Q1a基团,或任选地被选自组E的基团取代的C1-C20链烃基团,且Q1a是具有3到14个构成环的原子的任选地被选自组B的基团取代的碳环基团;
由式(I-1)表示的亚氨酸酯化合物,其中G是-S-R1基团,R1是任选地被选自组E的基团取代的C1-C20链烃基团,-Q1b基团或-T1-Q1b基团,和Q1b是任选地被选自组B的基团取代的苯基或任选地被选自组B的基团取代的萘基;
由式(I-1)表示的亚氨酸酯化合物,其中G是-O-R1a基团,且R1a是任选地被选自组B的基团取代的苯基或任选地被选自组B的基团取代的萘基;
由式(I-1)表示的亚氨酸酯化合物,其中X是-A2-R4基团和X0是-A3-R6基团,或X和X0合起来形成-A2-T0-A3-基团;
由式(I-1)表示的亚氨酸酯化合物,其中X是-A2-R4基团和X0是-A3-R6基团;
由式(I-1)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,且R4和R6独立地是任选地被选自组E的基团取代的C1-C6链烃基团,-Q1基团或-T1-Q1基团;
由式(I-1)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,且R4和R6独立地是-Q1基团或-T1-Q1基团;
由式(I-1)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,且R4和R6独立地是任选地被选自组B的基团取代的苯基;和
由式(I-1)表示的亚氨酸酯化合物,其中X是-S-R4基团,X0是-S-R6基团,且R4和R6独立地是任选地被选自组B的基团取代的苯基。
本发明化合物的具体实例进一步包括:
由式(I-2)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自组A′的基团取代的碳环基团,或具有3到14个构成环的原子的任选地被选自组A′的基团取代的杂环基团,且组A′由以下组成:卤素原子,氰基,硝基,甲酰基,任选地被卤素原子取代的C1-C6链烃基团,-A6-L1基团,-C(=A7)-L1基团,-C(=A7)-O-L1基团,-O-C(=A7)-L1基团,-NL2-C(=A7)-L1基团,-C(=A7)-N(L3)-L2基团,-Q2基团,-T3-Q2基团,-A6-Q2基团,-A6-T4-Q2基团,-C(=A7)-Q2基团,-C(=A7)-O-Q2基团,-O-C(=A7)-Q2基团,-NL3-C(=A7)-Q2基团和-C(=A7)-N(L3)-Q2基团;
由式(I-2)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自组A″的基团取代的碳环基团,或具有3到14个构成环的原子的任选地被选自组A″的基团取代的杂环基团,和组A″由以下组成:卤素原子,甲酰基,任选地被卤素原子取代的C1-C6烷基,任选地被卤素原子取代的C2-C6烯基,任选地被卤素原子取代的C2-C6炔基,任选地被卤素原子取代的C1-C6烷氧基,任选地被卤素原子取代的C1-C6烷基硫基,任选地被卤素原子取代的(C1-C6烷基)羰基,任选地被卤素原子取代的(C1-C6烷氧基)羰基,任选地被卤素原子取代的(C1-C6烷氧基)羰氧基,和任选地被卤素原子或C1-C6烷基取代的苯基;
由式(I-2)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自组A的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自组A′的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自组A″的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自组A的基团取代的杂环基团;
由式(I-2)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自组A′的基团取代的杂环基团;
由式(I-2)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自组A″的基团取代的杂环基团;
由式(I-2)表示的亚氨酸酯化合物,其中Z是任选地被选自组A的基团取代的苯基,或任选地被选自组A的基团取代的萘基;
由式(I-2)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自组A的基团取代的单环饱和碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中Z是具有8到14个构成环的原子的任选地被选自组A的基团取代的缩合多环饱和碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中Z是任选地被选自组A的基团取代的茚满基;
由式(I-2)表示的亚氨酸酯化合物,其中Z是苯基,4-甲基苯基,4-乙基苯基,4-异丙基苯基,4-(2-吡啶基)苯基,4-苯基苯基,4-氯苯基,4-硝基苯基,3-甲基苯基,3-乙基苯基,3-异丙基苯基,3-苯基苯基,3-氯苯基,3,4-二甲基苯基或5-茚满基;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团或-N(R3)-R1基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1-基团和A1是硫原子;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团和A1表示氧原子;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团和R1表示任选地被选自组D的基团取代的C1-C20链烃基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,A1是硫原子,和R1是任选地被选自组D的基团取代的C1-C20链烃基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,A1是硫原子,和R1是C1-C20链烃基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,A1是硫原子,和R1是任选地被选自组D的基团取代的C1-C20烷基;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,和R1是-Q基团,-T1-Q基团,-T1-S-Q基团或-T1-O-Q基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,A1是硫原子,和R1是-Q基团,-T1-Q基团,-T1-S-Q基团或-T1-O-Q基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,A1是氧原子,和R1是-Q基团,-T1-Q基团,-T1-S-Q基团或-T1-O-Q基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,和R1是-Q基团或-T1-Q基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,A1是硫原子,和R1是-Q基团或-T1-Q基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,R1是-Q基团或-T1-Q基团,和Q是具有3到14个构成环的原子的任选地被选自组A的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,R1是-Q基团或-T1-Q基团,和Q是具有3到14个构成环的原子的任选地被选自组A′的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,R1是-Q基团或-T1-Q基团,和Q是具有3到14个构成环的原子的任选地被选自组A″的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,R1是-Q基团或-T1-Q基团,和Q是任选地被选自组A″的基团取代的苯基或任选地被选自组A″的基团取代的萘基;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,R1是-Q基团或-T1-Q基团,和Q是具有3-8个构成环的原子的任选地被选自组A″的基团取代的单环饱和碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,A1是硫原子,R1是-Q基团或-T1-Q基团,和Q是具有3到14个构成环的原子的任选地被选自组A的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,A1是氧原子,R1是-Q基团或-T1-Q基团,和Q是具有3到14个构成环的原子的任选地被选自组A的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,A1是硫原子,R1是-Q基团或-T1-Q基团,和Q是具有3到14个构成环的原子的任选地被选自组A″的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,A1是氧原子,R1是-Q基团或-T1-Q基团,和Q是具有3到14个构成环的原子的任选地被选自组A″的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,A1是硫原子,R1是-Q基团或-T1-Q基团,和Q是任选地被选自组A″的基团取代的苯基或任选地被选自组A″的基团取代的萘基;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,A1是氧原子,R1是-Q基团或-T1-Q基团,和Q是任选地被选自组A″的基团取代的苯基或任选地被选自组A″的基团取代的萘基;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,A1是硫原子,R1是-Q基团或-T1-Q基团,和Q是具有3-8个构成环的原子的任选地被选自组A″的基团取代的单环饱和碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,A1是氧原子,R1是-Q基团或-T1-Q基团,和Q是具有3-8个构成环的原子的任选地被选自组A″的基团取代的单环饱和碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-N(R3)-R1基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-N(R3)-R1基团,且R1和R3独立地表示任选地被选自组D的基团取代的C1-C20链烃基团,-Q基团或-T1-Q基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是苯基硫基,4-甲基苯基硫基,4-乙基苯基硫基,4-异丙基苯基硫基,4-甲氧基苯基硫基,4-(2-吡啶基)苯基硫基,4-苯基苯基硫基,4-氯苯基硫基,4-硝基苯基硫基,3-甲基苯基硫基,3-乙基苯基硫基,3-异丙基苯基硫基,3-苯基苯基硫基,3-氯苯基硫基,3,4-二甲基苯基硫基,1-萘基硫基,2-萘基硫基,5-茚满基硫基,环丙基硫基,环戊基硫基,环己基硫基,2-全氢萘基硫基,苯甲硫基,苯乙基硫基,α-甲基苄基硫基,环丙基甲基硫基,环戊基甲基硫基,环己基甲基硫基,异丙硫基,仲丁硫基,3-甲基-1-丙基丁基硫基,烯丙基硫基,炔丙基硫基,或N-甲基-N-苯基氨基;
由式(I-2)表示的亚氨酸酯化合物,其中G是苯氧基,4-甲基苯氧基,4-乙基苯氧基,4-异丙基苯氧基,4-甲氧基苯氧基,4-苯基苯基硫基,4-氯苯氧基,3-甲基苯氧基,3-乙基苯基硫基,3-异丙基苯氧基,3-苯基苯氧基,3-氯苯氧基,3,4-二甲基苯氧基,1-萘氧基,2-萘氧基或5-茚满基氧基;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团和X0是-A3-R6基团,或X和X0合起来形成-A2-T0-A3-基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,和X0是-A3-R6基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,且A2和A3是硫原子;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,且R4和R6独立地是任选地被选自组D的基团取代的C1-C6链烃基团,-Q基团,-T1-Q基团或-C(=A4)-R11基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,且R4和R6独立地是任选地被选自组D的基团取代的C1-C6链烃基团,-Q基团或-T1-Q基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,且R4和R6独立地是任选地被选自组D的基团取代的C1-C6链烃基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,且R4和R6独立地是C1-C6链烃基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,且R4和R6独立地是-Q基团或-T1-Q基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,R4和R6独立地是-Q基团或-T1-Q基团,和Q是具有3到14个构成环的原子的任选地被选自组A的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,R4和R6独立地是-Q基团或-T1-Q基团,和Q是具有3到14个构成环的原子的任选地被选自组A″的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,R4和R6独立地是-Q基团或-T1-Q基团,和Q是任选地被选自组A的基团取代的苯基或任选地被选自组A的基团取代的萘基;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,R4和R6独立地是-Q基团或-T1-Q基团,和Q是任选地被选自组A″的基团取代的苯基或任选地被选自组A″的基团取代的萘基;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,R4和R6独立地是-Q基团或-T1-Q基团,和Q是具有3-8个构成环的原子的任选地被选自组A″的基团取代的单环饱和碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,R4和R6独立地是-Q基团或-T1-Q基团,和Q是具有3-8个构成环的原子的任选地被选自组A″的基团取代的单环不饱和杂环基;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,A2和A3是硫原子,且R4和R6独立地是任选地被选自组D的基团取代的C1-C6链烃基团,-Q基团或-T1-Q基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,A2和A3是硫原子,且R4和R6是任选地被选自组D的基团取代的C1-C6链烃基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,A2和A3是硫原子,且R4和R6是C1-C6链烃基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,A2和A3是硫原子,且R4和R6独立地是-Q基团或-T1-Q基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,A2和A3是硫原子,R4和R6独立地是-Q基团或-T1-Q基团,和Q是具有3到14个构成环的原子的任选地被选自组A的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,A2和A3是硫原子,R4和R6独立地是-Q基团或-T1-Q基团,和Q是具有3到14个构成环的原子的任选地被选自组A″的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,A2和A3是硫原子,R4和R6独立地是-Q基团或-T1-Q基团,和Q是任选地被选自组A的基团取代的苯基,或任选地被选自组A的基团取代的萘基;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,A2和A3是硫原子,R4和R6独立地是-Q基团或-T1-Q基团,和Q是任选地被选自组A″的基团取代的苯基,或任选地被选自组A″的基团取代的萘基;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,A2和A3是硫原子,R4和R6独立地是-Q基团或-T1-Q基团,和Q是具有3-8个构成环的原子的任选地被选自组A″的基团取代的单环饱和碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中X是-A2-R4基团,X0是-A3-R6基团,A2和A3是硫原子,R4和R6独立地是-Q基团或-T1-Q基团,和Q是具有3-8个构成环的原子的任选地被选自组A″的基团取代的单环不饱和的杂环基;
由式(I-2)表示的亚氨酸酯化合物,其中X和X0合起来形成-A2-T0-A3-基团;
由式(I-2)表示的亚氨酸酯化合物,其中X和X0合起来形成-A2-T0-A3-基团,且A2和A3是硫原子;
由式(I-2)表示的亚氨酸酯化合物,其中X和X0合起来形成-A2-T0-A3-基团,A2和A3是硫原子,和T0是C2-C6烷二基或邻亚苯基;
由式(I-2)表示的亚氨酸酯化合物,其中X和X0独立地是苯基硫基,4-甲基苯基硫基,4-乙基苯基硫基,4-异丙基苯基硫基,4-甲氧基苯基硫基,4-(2-吡啶基)苯基硫基,4-苯基苯基硫基,4-氯苯基硫基,4-氟苯基硫基,4-硝基苯基硫基,3-甲基苯基硫基,3-乙基苯基硫基,3-异丙基苯基硫基,3-苯基苯基硫基,3-氯苯基硫基,3-氟苯基硫基,3-(三氟甲基)苯基硫基,3,4-二甲基苯基硫基,1-萘基硫基,2-萘基硫基,5-茚满基硫基,环丙基硫基,环戊基硫基,环己基硫基,2-全氢萘基硫基,苯甲硫基,苯乙基硫基,α-甲基苄基硫基,环丙基甲基硫基,环戊基甲基硫基或环己基甲基硫基;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,X是-A2-R4基团,和X0是-A3-R6基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,X是-A2-R4基团,X0是-A3-R6基团,和R1,R4和R6独立地是任选地被选自组D的基团取代的C1-C20链烃基团,-Q基团或-T1-Q基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,X是-A2-R4基团,X0是-A3-R6基团,R1,R4和R6独立地是任选地被选自组D的基团取代的C1-C20链烃基团,-Q基团或-T1-Q基团,和Q是具有3到14个构成环的原子的任选地被选自组A的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,X是-A2-R4基团,X0是-A3-R6基团,R1,R4和R6独立地是任选地被选自组D的基团取代的C1-C20链烃基团,-Q基团或-T1-Q基团,和Q是具有3到14个构成环的原子的任选地被选自组A″的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,X是-A2-R4基团,X0是-A3-R6基团,和A1,A2和A3是硫原子;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,X是-A2-R4基团,X0是-A3-R6基团,A1,A2和A3是硫原子,和R1,R4和R6独立地是任选地被选自组D的基团取代的C1-C20链烃基团,-Q基团或-T1-Q基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,X是-A2-R4基团,X0是-A3-R6基团,A1,A2和A3是硫原子,R1,R4和R6独立地是任选地被选自组D的基团取代的C1-C20链烃基团,-Q基团或-T1-Q基团,且Q是具有3到14个构成环的原子的任选地被选自组A的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团,X是-A2-R4基团,X0是-A3-R6基团,A1,A2和A3是硫原子,R1,R4和R6独立地是任选地被选自组D的基团取代的C1-C20链烃基团,-Q基团或-T1-Q基团,且Q是具有3到14个构成环的原子的任选地被选自组A″的基团取代的碳环基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团或-N-(R3)-R1基团,X是-A2-R4基团,X0是-A3-R6基团,或X和X0合起来形成-A2-T0-A3-基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团或-N-(R3)-R1基团,X是-A2-R4基团,X0是-A3-R6基团,或X和X0合起来形成-A2-T0-A3-基团,且R4和R6独立地是任选地被选自组D的基团取代的C1-C6链烃基团,-Q基团,-T1-Q基团或-C(=A4)-R11基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团或-N-(R3)-R1基团,X是-A2-R4基团,X0是-A3-R6基团,且R4和R6独立地是任选地被选自组D的基团取代的C1-C6链烃基团,-Q基团,-T1-Q基团或-C(=A4)-R11基团;
由式(I-2)表示的亚氨酸酯化合物,其中G是-A1-R1基团或-N-(R3)-R1基团,X是-A2-R4基团,X0是-A3-R6基团,且R4和R6独立地是任选地被选自组D的基团取代的C1-C6链烃基团,-Q基团或-T1-Q基团;
由式(I-2)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自组A′的基团取代的碳环基团或具有3到14个构成环的原子的任选地被选自组A′的基团取代的杂环基团,G是-A1-R1基团或-N-(R3)-R1基团,和X是-A2-R4基团和X0是-A3-R6基团,或X和X0合起来形成-A2-T0-A3-基团;
由式(I-2)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自组A′的基团取代的碳环基团或具有3到14个构成环的原子的任选地被选自组A′的基团取代的杂环基团,G是-A1-R1基团或-N(R3)-R1基团,X是-A2-R4基团和X0是-A3-R6基团,或X和X0合起来形成-A2-T0-A3-基团,且R4和R6独立地是任选地被选自组D的基团取代的C1-C6链烃基团,-Q基团,-T1-Q基团或-C(=A4)-R11基团;
由式(I-2)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自组A′的基团取代的碳环基团或具有3到14个构成环的原子的任选地被选自组A′的基团取代的杂环基团,G是-A1-R1基团或-N(R3)-R1基团,X是-A2-R4基团,X0是-A3-R6基团,且R4和R6独立地是任选地被选自组D的基团取代的C1-C6链烃基团,-Q基团,-T1-Q基团或-C(=A4)-R11基团;和
由式(I-2)表示的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自组A′的基团取代的碳环基团或具有3到14个构成环的原子的任选地被选自组A′的基团取代的杂环基团,G是-A1-R1基团或-N(R3)-R1基团,X是-A2-R4基团,X0是-A3-R6基团,且R4和R6独立地是表示任选地被选自组D的基团取代的C1-C6链烃基团,-Q基团或-T1-Q基团。
然后,解释说明本发明化合物的产生方法。本发明的化合物可通过例如如下所述生产过程而产生。
生产过程1
本发明的化合物中,由式(Ia)表示的化合物:
其中Xa表示-A2-R4基团,X0a表示-A3-R6基团,和G,Z,A2,R4,A3和R6如上所定义(以下简称化合物(Ia)),可通过式(II)表示的化合物和式(III)表示的化合物的反应而产生:
其中Xa,G和Z如上所定义(以下简称化合物(II)),
由式表示的化合物(III):
X0a-H (III)
其中X0a是如上所定义的(以下简称化合物(III))。
尽管该化合物(II)可以与过量的化合物(III)反应,1当量的化合物(II)优选与0.8至5当量,更优选0.8至1.2当量的化合物(III)反应。
反应可以根据需要在存在碱或酸的情况下进行。
碱的实例包括碱金属醇化物如乙醇钠,甲醇钠和叔丁醇钾;含氮有机化合物如三乙胺,二异丙基乙胺,吡啶,4-二甲基氨基吡啶和N,N-二甲苯胺;碳酸盐如碳酸钾,碳酸钠,碳酸氢钠和碳酸氢钾;氢氧化物如氢氧化钠和氢氧化钾;金属氢化物如氢化锂,氢化钠和氢化钾;和有机锂如丁基锂和二异丙基氨基化锂。
碱的用量不受特别限制,只要该碱对该反应没有副作用。优选地0.01至1当量,更优选0.01到0.2当量的碱用于1当量的化合物(II)的反应。
酸的实例包括无机酸如盐酸,硫酸和硝酸;有机酸如甲酸,乙酸,丙酸,三氟乙酸,甲磺酸,苯磺酸和对甲苯磺酸;胺的酸加成盐如盐酸三乙胺和盐酸吡啶;和路易斯酸如氯化铝,氯化锌,碘化锌,四氯化钛,氯化铈,三氟甲基磺酸镱和三氟化硼-醚络合物。
酸的用量不受特别限制,只要酸对反应不施加副作用。优选地0.01至1当量,更优选0.01到0.2当量的酸用于1当量的化合物(II)的反应。
反应可在合适的溶剂中进行。
溶剂的实例包括脂肪族烃如戊烷,己烷,庚烷和石油醚;芳族烃如苯,甲苯和二甲苯;醇如甲醇和乙醇;酯如乙酸甲酯,乙酸乙酯,甲酸乙酯和丙酸乙酯;酮如丙酮和丁酮;醚如二乙醚,二丙醚,二异丙醚,二丁醚,四氢呋喃和二氧杂环己烷;腈如乙腈和丙腈;酰胺如二甲基甲酰胺和二甲基乙酰胺;亚砜如二甲基亚砜;砜如环丁砜;磷酰胺如六甲基磷酰胺;卤代烃如二氯甲烷,氯仿,1,2-二氯乙烷和四氯化碳;和芳香族胺如吡啶,甲基吡啶,二甲基吡啶和喹啉。这些溶剂可以被结合在一起使用,或可以作为与水的混合物使用。
反应温度通常是-50至150℃,优选地-20到120℃,和更优选-10至80℃。反应时间通常是0.1至96小时,和优选地0.1到24小时。
完成反应之后,化合物(Ia)可通过常规的后处理分离,例如浓缩反应混合物,或倾倒反应混合物入水然后用有机溶剂提取,随后浓缩。分离的化合物(Ia)可通过常规方法如蒸馏,再沉淀,重结晶或色谱法纯化。
生产过程2
本发明的化合物中,由式(Ib)表示的化合物:
其中Xb表示-A2-R4基团,或两个Xb任选地合起来形成-A2-T0-A3-基团,和G,Z,A2,A3,R4和T0如上所定义(以下简称化合物(Ib)),可通过反应由式(IV)表示的化合物与由式(IIIb)表示的化合物而产生:
其中G和Z如上所定义(以下简称化合物(IV)),
Xb-H (IIIb)
其中Xb如上所定义(以下简称化合物(IIIb))。
尽管该化合物(IV)可以与过量的化合物(IIIb)反应,1当量的化合物(IV)优选地与1至5当量,更优选1至3当量的化合物(IIIb)反应。
反应可以根据需要在存在碱或酸的情况下进行。
碱的实例包括碱金属醇化物如乙醇钠,甲醇钠和叔丁醇钾;含氮有机化合物如三乙胺,二异丙基乙胺,吡啶,4-二甲基氨基吡啶和N,N-二甲苯胺;碳酸盐如碳酸钾,碳酸钠,碳酸氢钠和碳酸氢钾;氢氧化物如氢氧化钠和氢氧化钾;金属氢化物如氢化锂,氢化钠和氢化钾;和有机锂如丁基锂和二异丙基氨基化锂。
碱的用量不受特别限制,只要该碱对该反应没有副作用。优选地0.01至1当量,更优选0.01到0.2当量的碱用于1当量的化合物(IV)的反应。
酸的实例包括无机酸如盐酸,硫酸和硝酸;有机酸如甲酸,乙酸,丙酸,三氟乙酸,甲磺酸,苯磺酸和对甲苯磺酸;胺的酸加成盐如盐酸三乙胺和盐酸吡啶;和路易斯酸如氯化铝,氯化锌,碘化锌,四氯化钛,氯化铈,三氟甲基磺酸镱和三氟化硼-醚络合物。
酸的用量不受特别限制,只要酸对反应不施加副作用。优选地0.01至1当量,更优选0.01到0.2当量的酸用于1当量的化合物(IV)的反应。
反应可在合适的溶剂中进行。
溶剂的实例包括脂肪族烃如戊烷,己烷,庚烷和石油醚;芳族烃如苯,甲苯和二甲苯;酯如乙酸甲酯,乙酸乙酯,甲酸乙酯和丙酸乙酯;酮如丙酮和丁酮;醚如二乙醚,二丙醚,二异丙醚,二丁醚,四氢呋喃和二氧杂环己烷;腈如乙腈和丙腈;酰胺如二甲基甲酰胺和二甲基乙酰胺;亚砜如二甲基亚砜;砜如环丁砜;磷酰胺如六甲基磷酰胺;卤代烃如二氯甲烷,氯仿,1,2-二氯乙烷和四氯化碳;和芳香族胺如吡啶,甲基吡啶,二甲基吡啶和喹啉。这些溶剂可以被结合在一起使用,或可以作为与水的混合物使用。
反应温度通常是-50至150℃,优选地-20到120℃,和更优选-10至80℃。反应时间通常是0.1至96小时,和优选地0.1到24小时。
完成反应之后,化合物(Ib)可通过常规的后处理分离,例如,浓缩反应混合物,或倾倒反应混合物入水然后用有机溶剂提取,随后浓缩。分离的化合物(Ib)可通过常规方法如蒸馏,再沉淀,重结晶或色谱法纯化。
生产过程3
本发明的化合物中,由式(Ic)表示的化合物:
其中Ga表示-A1-R1基团或-N-(R3)-R1基团,和X,X0,Z,A1,R1和R3如上所定义(以下简称化合物(Ic)),可通过反应由式(V)表示的化合物与由式(VI)表示的化合物而产生:
其中Ja表示卤素原子,和X,X0和Z如上所定义(以下简称化合物(V)),
Ga-H (VI)
其中Ga如上所定义(以下简称化合物(VI))。
尽管该化合物(V)可以与过量的化合物(VI)反应,但是1当量的化合物(V)优选地与0.8至5当量,更优选0.8至1.2当量的化合物(VI)反应。
反应可以在存在碱的情况下根据需要进行。
碱的实例包括碱金属醇化物如乙醇钠,甲醇钠和叔丁醇钾;含氮化合物如三乙胺,二异丙基乙胺,吡啶,4-二甲基氨基吡啶和N,N-二甲苯胺;碳酸盐如碳酸钾,碳酸钠,碳酸氢钠和碳酸氢钾;氢氧化物如氢氧化钠和氢氧化钾;金属氢化物如氢化锂,氢化钠和氢化钾;和有机锂如丁基锂和二异丙基氨基化锂。
碱的用量不受特别限制,只要该碱对该反应没有副作用。优选地0.8至5当量,更优选0.8到1.2当量的碱用于1当量的化合物(V)的反应。
反应可在合适的溶剂中进行。
溶剂的实例包括脂肪族烃如戊烷,己烷,庚烷和石油醚;芳族烃如苯,甲苯和二甲苯;酯如乙酸甲酯,乙酸乙酯,甲酸乙酯和丙酸乙酯;酮如丙酮和丁酮;醚如二乙醚,二丙醚,二异丙醚,二丁醚,四氢呋喃和二氧杂环己烷;腈如乙腈和丙腈;酰胺如二甲基甲酰胺和二甲基乙酰胺;亚砜如二甲基亚砜;砜如环丁砜;磷酰胺如六甲基磷酰胺;卤代烃如二氯甲烷,氯仿,1,2-二氯乙烷和四氯化碳;和芳香族胺如吡啶,甲基吡啶,二甲基吡啶和喹啉。这些溶剂可以被结合在一起使用。
反应温度通常是-50至150℃,优选地-20到120℃,和更优选-10至60℃。反应时间通常是0.1至96小时,和优选地0.1到24小时。
完成反应之后,化合物(Ic)可通过常规的后处理分离,例如,浓缩反应混合物,或倾倒反应混合物入水然后用有机溶剂提取,随后浓缩。分离的化合物(Ic)可通过常规方法如蒸馏,再沉淀,重结晶或色谱法纯化。
生产过程4
本发明的化合物中,由式(Id)表示的化合物:
其中R1a表示任选地被选自组D的基团取代的C1-C20链烃基团,-T1-Q基团或-T1-A1-Q基团,和X,X0,Z,T1,A1和Q如上所定义(以下简称化合物(Id)),可通过反应由式(VII)表示的化合物与由式(VIII)表示的化合物而产生:
其中X,X0和Z如上所定义(以下简称化合物(VII)):
R1a-Jb (VIII)
其中Jb表示卤素原子,或离去基团如O-S(=O)2-Jc基团(其中Jc表示任选地被卤素取代的C1-C3烷基,如甲基或三氟甲基,或任选地被C1-C3烷基取代的苯基),和R1a如上所定义(以下简称化合物(VIII))。
尽管该化合物(VII)可以与过量的化合物(VIII)反应,但是1当量的化合物(VII)优选地与0.8至5当量,更优选0.8至1.2当量的化合物(VIII)反应。
反应可以在存在碱的情况下根据需要进行。
碱的实例包括碱金属醇化物如乙醇钠,甲醇钠和叔丁醇钾;含氮化合物如三乙胺,二异丙基乙胺,吡啶,4-二甲基氨基吡啶和N,N-二甲苯胺;碳酸盐如碳酸钾,碳酸钠,碳酸氢钠和碳酸氢钾;氢氧化物如氢氧化钠和氢氧化钾;金属氢化物如氢化锂,氢化钠和氢化钾;和有机锂如丁基锂和二异丙基氨基化锂。
碱的用量不受特别限制,只要该碱对该反应没有副作用。优选地0.8至5当量,更优选0.8到1.2当量的碱用于1当量的化合物(VII)的反应。
反应可在合适的溶剂中进行。
溶剂的实例包括脂肪族烃如戊烷,己烷,庚烷和石油醚;芳族烃如苯,甲苯和二甲苯;酯如乙酸甲酯,乙酸乙酯,甲酸乙酯和丙酸乙酯;酮如丙酮和丁酮;醚如二乙醚,二丙醚,二异丙醚,二丁醚,四氢呋喃和二氧杂环己烷;腈如乙腈和丙腈;酰胺如二甲基甲酰胺和二甲基乙酰胺;亚砜如二甲基亚砜;砜如环丁砜;磷酰胺如六甲基磷酰胺;卤代烃如二氯甲烷,氯仿,1,2-二氯乙烷和四氯化碳;和芳香族胺如吡啶,甲基吡啶,二甲基吡啶和喹啉。这些溶剂可以被结合在一起使用,或可以作为与水的混合物使用。
反应温度通常是-50至150℃,优选地-20到120℃,和更优选-10至60℃。反应时间通常是0.1至96小时,和优选地0.1到24小时。
完成反应之后,化合物(Id)可通过常规的后处理分离,例如,浓缩反应混合物,或倾倒反应混合物入水然后用有机溶剂提取,随后浓缩。分离的化合物(Id)可通过常规方法如蒸馏,再沉淀,重结晶或色谱法纯化。
生产过程5
本发明的化合物中,由式(Ie)表示的化合物:
其中M1a表示-R8基团,-A8-R8基团,或卤素原子,和Xa,X0a,G,Z,A8和R8如上所定义(以下简称化合物(Ie)),可通过反应由式(II’)表示的化合物与化合物(III))而产生:
其中M1a,Xa,G和Z如上所定义(以下简称化合物(II′))。
尽管该化合物(II’)可以与过量的化合物(III)反应,但是1当量的化合物(II’)优选与0.8至5当量,更优选0.8至1.2当量的化合物(III)反应。
反应可以根据需要在存在碱或酸的情况下进行。
碱的实例包括碱金属醇化物如乙醇钠,甲醇钠和叔丁醇钾;含氮有机化合物如三乙胺,二异丙基乙胺,吡啶,4-二甲基氨基吡啶和N,N-二甲苯胺;碳酸盐如碳酸钾,碳酸钠,碳酸氢钠和碳酸氢钾;氢氧化物如氢氧化钠和氢氧化钾;金属氢化物如氢化锂,氢化钠和氢化钾;和有机锂如丁基锂和二异丙基氨基化锂。
碱的用量不受特别限制,只要该碱对该反应没有副作用。优选地0.01至1当量,更优选从0.01到0.2当量的碱用于1当量的化合物(II’)的反应。
酸的实例包括无机酸如盐酸,硫酸和硝酸;有机酸如甲酸,乙酸,丙酸,三氟乙酸,甲磺酸,苯磺酸和对甲苯磺酸;胺的酸加成盐如盐酸三乙胺和盐酸吡啶;和路易斯酸如氯化铝,氯化锌,碘化锌,四氯化钛,氯化铈,三氟甲基磺酸镱和三氟化硼-醚络合物。
酸的用量不受特别限制,只要酸对反应不施加副作用。优选地0.01至1当量,更优选从0.01到0.2当量的酸用于1当量的化合物(II’)的反应。
反应可在合适的溶剂中进行。
溶剂的实例包括脂肪族烃如戊烷,己烷,庚烷和石油醚;芳族烃如苯,甲苯和二甲苯;醇如甲醇和乙醇;酯如乙酸甲酯,乙酸乙酯,甲酸乙酯和丙酸乙酯;酮如丙酮和丁酮;醚如二乙醚,二丙醚,二异丙醚,二丁醚,四氢呋喃和二氧杂环己烷;腈如乙腈和丙腈;酰胺如二甲基甲酰胺和二甲基乙酰胺;亚砜如二甲基亚砜;砜如环丁砜;磷酰胺如六甲基磷酰胺;卤代烃如二氯甲烷,氯仿,1,2-二氯乙烷和四氯化碳;和芳香族胺如吡啶,甲基吡啶,二甲基吡啶和喹啉。这些溶剂可以被结合在一起使用,或可以作为与水的混合物使用。
反应温度通常是-50至150℃,优选地-20到120℃,和更优选-10至80℃。反应时间通常是0.1至96小时,和优选地0.1到24小时。
完成反应之后,化合物(Ie)可通过常规的后处理分离,例如,浓缩反应混合物,或倾倒反应混合物入水然后用有机溶剂提取,随后浓缩。分离的化合物(Ie)可通过常规方法如蒸馏,再沉淀,重结晶或色谱法纯化。
生产过程6
本发明的化合物中,由式(If)表示的化合物:
其中M1a,Ga,X,X0和Z如上所定义(以下简称化合物(If)),可通过反应由式(V’)表示的化合物与化合物(VI)而产生:
其中M1a,Ja,X,X0和Z如上所定义(以下简称化合物(V’))。
尽管该化合物(V’)可以与过量的化合物(VI)反应,但是1当量的化合物(V’)优选地与0.8至5当量,更优选0.8至1.2当量的化合物(VI)反应。
反应可以在存在碱的情况下根据需要进行。
碱的实例包括碱金属醇化物如乙醇钠,甲醇钠和叔丁醇钾;含氮化合物如三乙胺,二异丙基乙胺,吡啶,4-二甲基氨基吡啶和N,N-二甲苯胺;碳酸盐如碳酸钾,碳酸钠,碳酸氢钠和碳酸氢钾;氢氧化物如氢氧化钠和氢氧化钾;金属氢化物如氢化锂,氢化钠和氢化钾;和有机锂如丁基锂和二异丙基氨基化锂。
碱的用量不受特别限制,只要该碱对该反应没有副作用。优选地0.8至5当量,更优选0.8到1.2当量的碱用于1当量的化合物(V’)的反应。
反应可在合适的溶剂中进行。
溶剂的实例包括脂肪族烃如戊烷,己烷,庚烷和石油醚;芳族烃如苯,甲苯和二甲苯;酯如乙酸甲酯,乙酸乙酯,甲酸乙酯和丙酸乙酯;酮如丙酮和丁酮;醚如二乙醚,二丙醚,二异丙醚,二丁醚,四氢呋喃和二氧杂环己烷;腈如乙腈和丙腈;酰胺如二甲基甲酰胺和二甲基乙酰胺;亚砜如二甲基亚砜;砜如环丁砜;磷酰胺如六甲基磷酰胺;卤代烃如二氯甲烷,氯仿,1,2-二氯乙烷和四氯化碳;和芳香族胺如吡啶,甲基吡啶,二甲基吡啶和喹啉。这些溶剂可以被结合在一起使用。
反应温度通常是-50至150℃,优选地-20到120℃,和更优选-10至60℃。反应时间通常是0.1至96小时,和优选地0.1到24小时。
完成反应之后,化合物(If)可通过常规的后处理分离,例如,浓缩反应混合物,或倾倒反应混合物入水然后用有机溶剂提取,随后浓缩。分离的化合物(If)可通过常规方法如蒸馏,再沉淀,重结晶或色谱法纯化。
生产过程7
本发明的化合物中,由式(Ig)表示的化合物:
其中M1a,R1a,X,X0和Z如上所定义(以下简称化合物(Ig)),可通过由式(VII′)表示的化合物与化合物(VIII)的反应而产生:
其中M1a,X,X0和Z如上所定义(以下简称化合物(VII′))。
尽管该化合物(VII′)可以与过量的化合物(VIII)反应,但是1当量的化合物(VII′)优选地与0.8至5当量,更优选0.8至1.2当量的化合物(VIII)反应。
反应可以在存在碱的情况下根据需要进行。
碱的实例包括碱金属醇化物如乙醇钠,甲醇钠和叔丁醇钾;含氮化合物如三乙胺,二异丙基乙胺,吡啶,4-二甲基氨基吡啶和N,N-二甲苯胺;碳酸盐如碳酸钾,碳酸钠,碳酸氢钠和碳酸氢钾;氢氧化物如氢氧化钠和氢氧化钾;金属氢化物如氢化锂,氢化钠和氢化钾;和有机锂如丁基锂和二异丙基氨基化锂。
碱的用量不受特别限制,只要该碱对该反应没有副作用。优选地0.8至5当量,更优选0.8到1.2当量的碱用于1当量的化合物(VII’)的反应。
反应可在合适的溶剂中进行。
溶剂的实例包括脂肪族烃如戊烷,己烷,庚烷和石油醚;芳族烃如苯,甲苯和二甲苯;酯如乙酸甲酯,乙酸乙酯,甲酸乙酯和丙酸乙酯;酮如丙酮和丁酮;醚如二乙醚,二丙醚,二异丙醚,二丁醚,四氢呋喃和二氧杂环己烷;腈如乙腈和丙腈;酰胺如二甲基甲酰胺和二甲基乙酰胺;亚砜如二甲基亚砜;砜如环丁砜;磷酰胺如六甲基磷酰胺;卤代烃如二氯甲烷,氯仿,1,2-二氯乙烷和四氯化碳;和芳香族胺如吡啶,甲基吡啶,二甲基吡啶和喹啉。这些溶剂可以被结合在一起使用,或可以作为与水的混合物使用。
反应温度通常是-50至150℃,优选地-20到120℃,和更优选-10至60℃。反应时间通常是0.1至96小时,和优选地0.1到24小时。
完成反应之后,化合物(Ig)可通过常规的后处理分离,例如,浓缩反应混合物,或倾倒反应混合物入水然后用有机溶剂提取,随后浓缩。分离的化合物(Ig)可通过常规方法如蒸馏,再沉淀,重结晶或色谱法纯化。
接下来,显示用于生产本发明的化合物的原料化合物的生产方法。
化合物(II)是已知化合物,或可通过已知的方法(例如描述于WO2007/063702中的方法)而产生。
化合物(III)是已知化合物,或可通过已知的方法而产生。
化合物(IV)是已知化合物,或可从由式(IVa)表示的化合物:
其中G和Z如上所定义,通过已知的方法(例如描述于Synthesis(1),p100,1999,Chem.Lett.P 1261,1989,或WO2007/063702中的方法)产生。
化合物(V)可通过由式(IX)表示的化合物:
其中X,X0和Z如上所定义(以下简称化合物(IX))与卤化剂反应而产生。
用于反应的卤化剂的实例包括亚硫酰氯,硫酰氯,氯氧化磷,五氯化磷,三溴化磷,四氯化碳和四溴化碳。
卤化剂的用量不受特别限制,过量的卤化剂可以作为溶剂使用。优选地,1当量的化合物(IX)与0.8至3当量的卤化剂反应。
反应可以在存在碱的情况下根据需要进行。
碱的实例包括碱金属醇化物如乙醇钠,甲醇钠和叔丁醇钾;含氮化合物如三乙胺,二异丙基乙胺,吡啶,4-二甲基氨基吡啶和N,N-二甲苯胺;碳酸盐如碳酸钾,碳酸钠,碳酸氢钠和碳酸氢钾;氢氧化物如氢氧化钠和氢氧化钾;金属氢化物如氢化锂,氢化钠和氢化钾;有机锂如丁基锂和二异丙基氨基化锂;和磷化合物如三苯膦。
碱的用量不受特别限制,只要该碱对该反应没有副作用。优选地0.8至3当量,更优选0.8到1.2当量的碱用于1当量的化合物(IX)的反应。
反应可在合适的溶剂中进行。
溶剂的实例包括脂肪族烃如戊烷,己烷,庚烷和石油醚;芳族烃如苯,甲苯和二甲苯;酯如乙酸甲酯,乙酸乙酯,甲酸乙酯和丙酸乙酯;酮如丙酮和丁酮;醚如二乙醚,二丙醚,二异丙醚,二丁醚,四氢呋喃和二氧杂环己烷;腈如乙腈和丙腈;酰胺如二甲基甲酰胺和二甲基乙酰胺;亚砜如二甲基亚砜;砜如环丁砜;磷酰胺如六甲基磷酰胺;和卤代烃如二氯甲烷,氯仿,1,2-二氯乙烷和四氯化碳。这些溶剂可以被结合在一起使用。
反应温度通常是-50至150℃,优选地-20到120℃,和更优选-10至80℃。反应时间通常是0.1至96小时,和优选地0.1到24小时。
完成反应之后,尽管该化合物(V)可从反应混合物通过常规方法如蒸馏,再沉淀,重结晶或色谱法纯化,但是该反应混合物可以按照原样用于下一步中。
化合物(VI)是已知化合物,或可通过已知的方法而产生。
化合物(VII)可通过化合物(IX)与硫化剂的反应而产生。
用于反应的硫化剂实例包括五硫化二磷,Lawesson′s反应剂和(Et2Al)2。
硫化剂的用量不受特别限制,可以使用过量的硫化剂。优选地,1当量的化合物(IX)与约0.8至3当量的硫化剂反应。
反应可在合适的溶剂中进行。
溶剂的实例包括脂肪族烃如戊烷,己烷,庚烷和石油醚;芳族烃如苯,甲苯和二甲苯;酯如乙酸甲酯,乙酸乙酯,甲酸乙酯和丙酸乙酯;醚如二乙醚,二丙醚,二异丙醚,二丁醚,四氢呋喃和二氧杂环己烷;腈如乙腈和丙腈;亚砜如二甲基亚砜;砜如环丁砜;和卤代烃如二氯甲烷,氯仿,1,2-二氯乙烷和四氯化碳。这些溶剂可以被结合在一起使用。
反应温度通常是-50至150℃,优选地-20到120℃,和更优选10至100℃。反应时间通常是0.1至96小时,和优选地0.1到24小时。
完成反应之后,尽管该化合物(VII)可从反应混合物通过常规方法如蒸馏,再沉淀,重结晶或色谱法而纯化,但是该反应混合物可以按照原样用于下一步中。
化合物(VIII)是已知化合物,或可通过已知的方法而产生。
化合物(IX)中,由式(IXa)表示的化合物:
其中Xa,X0a和Z如上所定义(以下简称化合物(IXa)),可通过由式(X)表示的化合物与化合物(III)的反应而产生:
其中Xa和Z如上所定义(以下简称化合物(X))。
尽管该化合物(X)可以与过量的化合物(III)反应,但是1当量的化合物(X)优选地与0.8至5当量,更优选0.8至1.2当量的化合物(III)反应。
反应可以根据需要在存在碱或酸的情况下进行。
碱的实例包括碱金属醇化物如乙醇钠,甲醇钠和叔丁醇钾;含氮化合物如三乙胺,二异丙基乙胺,吡啶,4-二甲基氨基吡啶和N,N-二甲苯胺;碳酸盐如碳酸钾,碳酸钠,碳酸氢钠和碳酸氢钾;氢氧化物如氢氧化钠和氢氧化钾;金属氢化物如氢化锂,氢化钠和氢化钾;和有机锂如丁基锂和二异丙基氨基化锂。
碱的用量不受特别限制,只要该碱对该反应没有副作用。优选地0.01至1当量,更优选0.01到0.2当量的碱用于1当量的化合物(X)的反应。
酸的实例包括无机酸如盐酸,硫酸和硝酸;有机酸如甲酸,乙酸,丙酸,三氟乙酸,甲磺酸,苯磺酸和对甲苯磺酸;胺的酸加成盐如盐酸三乙胺和盐酸吡啶;和路易斯酸如氯化铝,氯化锌,碘化锌,四氯化钛,氯化铈,三氟甲基磺酸镱和三氟化硼-醚络合物。
酸的用量不受特别限制,只要酸对反应不施加副作用。优选地0.01至1当量,更优选0.01到0.2当量的酸用于1当量的化合物(X)的反应。
反应可在合适的溶剂中进行。
溶剂的实例包括脂肪族烃如戊烷,己烷,庚烷和石油醚;芳族烃如苯,甲苯和二甲苯;醇如甲醇和乙醇;酯如乙酸甲酯,乙酸乙酯,甲酸乙酯和丙酸乙酯;酮如丙酮和丁酮;醚如二乙醚,二丙醚,二异丙醚,二丁醚,四氢呋喃和二氧杂环己烷;腈如乙腈和丙腈;酰胺如二甲基甲酰胺和二甲基乙酰胺;亚砜如二甲基亚砜;砜如环丁砜;磷酰胺如六甲基磷酰胺;卤代烃如二氯甲烷,氯仿,1,2-二氯乙烷和四氯化碳;和芳香族胺如吡啶,甲基吡啶,二甲基吡啶和喹啉。这些溶剂可以被结合在一起使用,或可以作为与水的混合物使用。
反应温度通常是-50至150℃,优选地-20到120℃,和更优选-10至80℃。反应时间通常是0.1至96小时,和优选地0.1到24小时。
完成反应之后,化合物(IX)可通过常规的后处理分离,例如,浓缩反应混合物,或倾倒反应混合物入水然后用有机溶剂提取,随后浓缩。分离的化合物(IX)可通过常规方法如蒸馏,再沉淀,重结晶或色谱法纯化。
化合物(II’)中,由式(IIe)表示的化合物:
其中M1a,R1a,Xa和Z如上所定义,可通过由式(XI)表示的化合物:
其中M1a,Xa和Z如上所定义,与化合物(VIII)反应而产生。
通过上述的生产过程1至7产生的本发明的化合物可进一步进行本身已知的程序如取代反应,消除反应,氧化反应或还原反应以用所需取代基替代该化合物上的取代基。
本发明的化合物可作为包括几何异构体和立体异构体的各种异构体存在。本发明的化合物的所有异构体和异构体的混合物包括在本发明的范围中。
本发明的化合物对害虫包括卫生学害虫,动物寄生害虫和植物寄生害虫具有极好的控制作用,由此其有效用于害虫控制。当本发明的化合物直接施加至害虫或至害虫栖息之地时,其发挥极好的害虫控制作用。
当本发明的化合物用作组合物用于害虫控制,即,杀虫组合物时,本发明的化合物可以按照原样使用。然而,本发明的化合物通常是配制成通常的农用化学品或动物药物可采取的形式,然后使用。换言之,本发明的杀虫组合物可以是本发明的化合物本身,和然而,其通常包括本发明的化合物和添加剂以采取针对通常的农用化学品或动物药物的合适形式。具体地,本发明的化合物溶解或分散在合适的液体载体中,与合适的固体载体和/或合适的气体载体混合,或吸附到合适的固体载体上以制备可乳化的浓缩物形式,液体制剂,微乳剂,可流动剂,油溶液,可湿性粉剂,粉尘,颗粒,微颗粒,种子-包覆剂,种子-浸渍溶液,发烟杀虫剂,片剂,微胶囊,喷雾剂,气雾剂,二氧化碳气体制剂,加热熏蒸剂如蚊香盘,电子蚊香垫或电子蚊香液,EW制剂,软膏,毒饵,胶囊,丸粒,膜,可注射剂,搽剂,树脂制剂,香波制剂等等形式的本发明的杀虫组合物。本发明的杀虫组合物可进一步包含乳化剂,悬浮剂,分散剂,渗透剂,润湿剂,增稠剂,稳定剂,分散剂等等。本发明的杀虫组合物可通过已知的方法来制备。
液体载体的实例包括水,醇(例如甲醇,乙醇,正丙醇,异丙醇,丁醇,己醇,苯甲醇,乙二醇,丙二醇,苯氧乙醇等),酮(例如丙酮,丁酮,甲基异丁基酮,环己酮等等),醚(例如二异丙醚,1,4-二氧杂环己烷,四氢呋喃,乙二醇单甲醚,乙二醇二甲醚,二甘醇一甲基醚,二甘醇单乙醚,丙二醇单甲醚,二丙二醇单甲醚,3-甲氧基-3-甲基-1-丁醇等),脂肪族烃(例如己烷,环己烷,煤油,燃料油,机械油等),芳族烃(例如甲苯,二甲苯,乙苯,dodesylbenzene,苯基二甲苯基乙烷,溶剂石脑油,甲基萘等),卤代烃(例如二氯甲烷,三氯乙烷,氯仿,四氯化碳等),酰胺(例如N,N-二甲基甲酰胺,N,N-二甲基乙酰胺,N-甲基吡咯烷酮,N-辛基吡咯烷酮等),酯(例如乳酸丁酯,乙酸乙酯,乙酸丁酯,豆蔻酸异丙酯,油酸乙酯,己二酸二异丙基酯,己二酸二异丁酯,丙二醇单甲醚乙酸酯,脂肪酸甘油酯,γ-丁内酯等),腈(例如乙腈,异丁腈,丙腈等),碳酸酯(例如碳酸异丙烯酯等),和植物油(例如豆油,橄榄油,亚麻子油,椰子油,棕榈油,花生油,麦芽油,杏仁油,芝麻油,矿物油,迷迭香油,香茅油,菜籽油,棉子油,玉米油,红花油,橙油等)。这些液体载体可以单独使用,或这些液体载体的两种或更多种,优选地1-3种可以合适的比例混合然后使用。
固体载体(例如稀释剂或填料)的实例包括蔬菜粉(例如大豆粉,烟草粉,面粉,木材粉等),矿物粉(例如高岭土,Fubasami,膨润土,粘土如酸性粘土,滑石如滑石粉或叶蜡石粉,硅藻土,硅石例如云母粉等),合成的水合氧化硅,滑石,陶瓷,其它无机矿物质(例如绢云母,石英,水合硅石等),化学肥料(例如硫酸铵,磷酸铵,硝酸铵,氯化铵,脲等),氧化铝,硫粉末,活性炭,碳酸钙,氯化钾,碳酸氢钠,和乳糖。这些固体载体可以单独使用,或这些固体载体的两种或更多种,优选地1-3种可以合适的比例混合然后使用。
气体载体的实例包括氟烃,丁烷气,LPG(液化石油气),二甲醚,和二氧化碳气。这些气体载体可以单独使用,或这些气体载体的两种或更多种可以合适的比例混合然后使用。或者,一种或多种的这些气体载体可以与合适的液体载体结合在一起使用。
在本发明的化合物配制为软膏的情况下,用于软膏的基础材料实例包括聚乙二醇,果胶,高级脂肪酸和多元醇的酯如单硬脂酸甘油酯,纤维素衍生物如甲基纤维素,海藻酸钠,膨润土,高级醇,多元醇如甘油,矿脂,白凡士林,液状石蜡,猪油,植物油,羊毛脂,无水羊毛脂,氢化油,和树脂。这些基础材料可以单独使用,或这些基础材料的两种或更多种,优选地1-3种可以被结合在一起使用。进一步,如下所列的表面活性剂可以加入基础材料。
在本发明杀虫组合物的制备中表面活性剂可以用作乳化剂,铺展剂,渗透剂,分散剂等等。表面活性剂的实例包括皂;和非离子和阴离子表面活性剂例如聚氧乙烯烷基芳基醚[NOIGEN(商标名),E A142(商标名),生产商为DAI-ICHI KOGYO SEIYAKU CO.,LTD.;NONAL(商标名),生产商为TOHO CHEMICAL INDUSTRY CO.,LTD.],烷基硫酸盐[例如EMAL 10(商标名)和EMAL 40(商标名),生产商为KAOCORPORATION],烷基苯磺酸盐[例如NEOGEN(商标名)和NEOGEN T(商标名),生产商为DAI-ICHI KOGYOU SEIYAKU CO.,LTD.;NEIPELEX(商标名),生产商为KAO CORPORATION],聚乙二醇醚[例如NONIPOL 85(商标名),NONIPOL 100(商标名),和NONIPOL 160(商标名),生产商为SANYO KASEI],聚氧乙烯烷基醚[例如NOIGENET-135(商标名),生产商为DAI-ICHI KOGYO SEIYAKU CO.,LTD.],聚氧乙烯聚氧丙烯嵌段聚合物[例如NEWPOLE PE-64(商标名),生产商为SANYO CHEMICAL INDUSTRIES LTD.],聚醇酯[例如TWEEN 20(商标名)和TWEEN 80(商标名),生产商为KAO CORPORATION],烷基磺基琥珀酸盐[例如SANMOLIN OT20(商标名),生产商为SANYOCHEMICAL INDUSTRIESLTD.;NEWKALGEN EX70(商标名),生产商为TAKEMOTO OIL & FAT CO.,LTD.],烷基萘磺酸盐[NEWKALGENWG-1(商标名),生产商为TAKEMOTO OIL & FAT CO.,LTD.],和烯基萘磺酸盐[SORPOL 5115(商标名),生产商为TOHO CHEMICALINDUSTRY CO.,LTD.]。这些表面活性剂可以单独使用,或这些表面活性剂的两种或更多种,优选地1-3种可以合适的比例混合然后使用。
用于树脂制剂的基础材料的实例包括氯乙烯聚合物,和聚氨酯。如果必要的话,可以向基础材料添加增塑剂如酞酸盐(例如邻苯二甲酸二甲酯,邻苯二甲酸二辛酯等),己二酸酯,硬脂酸等等。树脂制剂的制备是通过使用常规的捏和机捏合本发明的化合物入基础材料,随后进行模塑如注塑,挤出模塑,压模等等。所得的树脂制剂可以通过进一步的模塑、切割等步骤成形为板,膜,带,网,线等等形状,如果必要的话。这些树脂制剂可以使用,例如,动物颈圈,动物耳标,片材,导管(lead),或园艺用桩(horticultural post)的形式。
毒饵的基础材料的实例包括谷类粉,植物油,糖,和结晶纤维素。如果必要的话,可以向基础材料添加抗氧化剂如二丁基羟基甲苯或去甲二氢愈创木酸,防腐剂如脱氢乙酸,防止儿童或宠物误食的试剂如辣椒粉,吸引害虫的香料如乳酪香料,洋葱香料或花生油等等。
另外,粘合剂,分散剂,着色剂,稳定剂等等,具体地,酪蛋白,明胶,糖(例如淀粉,阿拉伯树胶,纤维素衍生物,海藻酸等),木质素衍生物,膨润土,合成的水可溶性聚合物(例如聚乙烯醇,聚乙烯基吡咯烷酮,聚丙烯酸等),PAP(酸性异丙基磷酸酯),BHT(2,6-二叔丁基-4-甲基苯酚),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),描述于Code of Federal Regulation Title 40 p180,USA中的其他物质可用作用于制备本发明杀虫组合物的药物助剂。
本发明的杀虫组合物可以包括本发明的化合物并结合另一杀虫活性成分,如杀昆虫剂(insecticide)(例如拟除虫菊酯杀昆虫剂,有机磷杀昆虫剂,氨基甲酸酯杀昆虫剂,neonicotinoid杀昆虫剂,神经钠通道阻断剂,杀昆虫剂大环内酯,γ-氨基丁酸(GABA)antagonisy,钙通道激活剂,脲杀昆虫剂,昆虫激素模仿剂,天然杀昆虫剂等),杀螨剂,机械油,杀线虫剂,除草剂,植物激素试剂,植物生长调节剂,杀真菌剂(例如含铜杀菌剂,有机氯杀真菌剂,有机硫杀真菌剂,苯酚杀真菌剂等),增效剂,引诱剂,排斥剂,农作物损害减少剂,颜料,肥料,动物饲料(例如兽用如奶牛,猪和小鸡的饲料,玩赏动物如狗和猫的饲料,培养鱼如尾鲽带黄色的幼鱼和sebream的饲料等),动物药物(例如治疗或预防家畜,玩赏动物和培养鱼的疾病的药物),动物营养增补剂,等等。
本发明的杀虫组合物通常包含0.1至80%重量,优选地1至20%重量的本发明的化合物。具体地,本发明的杀虫组合物形式为可乳化的浓缩物,液体制剂或可湿性粉剂(例如可湿性颗粒)时,其通常包含1至80%重量,优选地1至20%重量的本发明的化合物。当本发明的杀虫组合物形式为可乳化的浓缩物或粉尘时,其通常包含0.1至50重量%,优选地0.1至20%重量的本发明的化合物。当本发明的杀虫组合物形式为颗粒时,其通常包含1至50重量%,优选地1至20%重量的本发明的化合物。
另一种杀虫活性成分(例如杀昆虫剂,除草剂,杀螨剂,杀真菌剂等)可以通常0.1至80%重量,优选地1至20%重量存在于本发明的杀虫组合物中。
本发明的杀虫组合物中除上述杀虫活性成分之外的添加剂的含量通常是0.001至99.9%重量,优选地1至99%重量,尽管其取决于杀虫活性成分的种类和含量,杀虫组合物形式等等而变化。具体地,本发明的杀虫组合物中表面活性剂的含量通常是1至20%重量,优选地1至15%重量。在本发明的杀虫组合物中流化助剂的含量通常是1至20%重量。本发明的杀虫组合物中的载体含量通常是1至90%重量,优选地1至70%重量。
当本发明的杀虫组合物为可乳化的浓缩物或可湿性粉剂(例如可湿性颗粒)形式时,优选视情况而定用水等等稀释(例如100至5,000倍)然后喷雾。
本发明的化合物可被用作农作物地如耕地,水田,草地和果园,或非农作物地的杀昆虫剂。本发明的化合物可以控制其中培养下列″农作物植物″的农作物地等等中的害虫,而在一些情况下没有引起对″农作物植物″的副作用。
“农作物植物”的具体实例列举如下:
农作物:玉米、稻、小麦、大麦、黑麦、燕麦、高粱、棉花、大豆、花生、sarrazin(生长在北美东部的一种草本作物)、甜菜、油菜籽、向日葵、甘蔗、烟草等;
蔬菜:茄科植物(茄子、番茄、青椒、辣椒、马铃薯等)、葫芦科植物(黄瓜、南瓜、西葫芦、西瓜、甜瓜等)、狮子花科植物(日本萝卜、芜菁、山葵、大头菜、中国甘蓝、甘蓝、黑芥子、椰菜、花椰菜等)、菊科植物(牛蒡、茼蒿、朝鲜蓟、莴苣等)、百合科植物(大葱、洋葱、大蒜、芦笋等)、伞形科植物(胡萝卜、欧芹、旱芹、欧洲防风草等)、藜科植物(菠菜、瑞士甜菜等)、唇形科植物(日本罗勒、薄荷、罗勒等)、草莓、红薯、山药、芋头等;
果树:苹果类水果树(苹果树、普通梨树、日本梨树、中国木瓜树、木瓜树等)、核果类树(stone fleshy fruit)(桃树、李子树、油桃树、日本李子树、樱桃树、杏树、洋李树等)、柑橘类植物(无核蜜橘树、柑树、柠檬树、酸橙树、柚子树等)、坚果(栗子树、胡桃树、榛子树、杏仁树、阿月浑子树、腰果树、澳大利亚坚果树等)、浆果树(越橘树、橘子树、黑莓树、悬钩子树等)、葡萄树、柿子树、橄榄树、枇杷树、香蕉树、咖啡树、枣椰树、椰子树、油椰子树等;
非果树的树:茶树、桑树、人行道树(白蜡树、桦树、山茱萸、桉树、银杏树、丁香、枫树、橡树、白杨、紫荆、枫树、法国梧桐树、光叶榉树、日本崖柏属树、杉树、日本毒芹、针状刺柏、松树、云杉、紫杉、榆树、七叶树等)、甜荚蒾、罗汉松、日本柳杉、日本扁柏、巴豆树、桃叶卫矛、Chainese howthorn等。
草坪:zoysi(日本草坪草,马斯克林草等),Bermuda grass(Cynodondactylon等),翦股颖(红顶草,Agrostis stolonifera,Agrostis tenuis等),早熟禾属(草地早熟禾,普通早熟禾等),羊茅属(牛尾草,紫羊茅,蔓延羊茅属等),黑麦草(毒麦,黑麦草等),鸭茅,猫尾草,等等;
油料农作物:油椰,巴巴多斯坚果,等等;
其它:花(玫瑰,康乃馨,菊花,Eustoma grandiflorum Shinners(牧场龙胆根),丝石竹,大丁草,金盏花,鼠尾草,矮牵牛,马鞭草属,郁金香,紫菀,龙胆根,百合,三色堇,仙客来属,兰花,铃兰,熏衣草,紫罗兰,装饰性的羽衣甘蓝,樱草属,poinsttia,唐菖蒲,洋兰,雏菊,马鞭草属,cymbidium,秋海棠等),观叶植物;等等。
上述农作物植物包括通过经典育种方法或遗传工程技术赋予了对HPPD抑制剂例如异噁氟草(isoxaflutole)、ALS抑制剂例如咪草烟(imazethapyr)或噻磺隆(thifensulfuron-methyl)、EPSP合成酶抑制剂例如草甘膦、谷氨酰胺合成酶抑制剂例如草铵膦、乙酰辅酶A羧化酶抑制剂例如稀禾定、PPO抑制剂如flumioxazin、或除草剂例如溴苯腈(bromoxynil)、麦草畏或2,4-D具有抗性的农作物植物。
通过经典育种方法赋予抗性的农作物植物的实例包括对咪唑啉酮除草剂例如imazethapyr具有抗性的油菜、小麦(whieat)、向日葵、水稻和玉米,其可以商标名Clearfield(注册商标)商购;和对磺酰脲类ALS抑制剂除草剂例如噻磺隆有抗性的大豆,其可以STS大豆的商标名商购;以及对乙酰辅酶A羧化酶抑制剂(例如trione oxime除草剂和芳氧基苯氧基丙酸除草剂)具有抗性的农作物植物,其实例为SR玉米。例如,赋予乙酰辅酶A羧化酶抑制剂抗性的农作物植物参见Proc.Natl.Acad.Sci.USA 1990,卷87,第7175-7179页。另外,抗乙酰辅酶A羧化酶抑制剂的突变型乙酰辅酶A羧化酶描述于Weed Science卷53:第728-746页,2005。当通过遗传工程技术将编码突变型乙酰辅酶A羧化酶的基因导入农作物植物中时,或者当将与赋予乙酰辅酶A羧化酶抗性有关的突变导入编码农作物植物的乙酰辅酶A羧化酶的基因中时,便可生产出抗乙酰辅酶A羧化酶抑制剂的农作物植物。此外,可通过嵌合法(chimeraplasty)(参见Gura T.1999,Repairing the Genome′s SpellingMistakes(修复基因组的拼写错误),Science 285:316-318),可将引入碱基置换突变的核酸导入农作物植物细胞,以诱导农作物植物的乙酰辅酶A羧化酶抑制剂或除草剂所靶定基因的定点氨基酸置换突变,从而可产生抗乙酰辅酶A羧化酶抑制剂或除草剂的农作物植物。
通过遗传工程技术赋予抗性的农作物植物的实例包括玉米,大豆,棉,油菜和糖用甜菜栽培品种(对草甘膦具有抗性),其是以商标名的RoundupReady TM(注册商标),AgrisureGT等市售可得的。已经通过遗传工程技术赋予抗性的其他农作物植物实例包括玉米,大豆,棉和油菜栽培品种(对草铵膦具有抗性),其是以商标名LibertyLinkTM等等市售可得的。另外,对溴苯腈具有抗性的遗传加工的棉栽培品种可以商品名BXN市售可得。
上述农作物植物包括通过遗传工程技术赋予产生杀虫毒素的能力的农作物植物,例如已知由芽孢杆菌属(Bacillus)产生的选择性毒素。
通过这类经遗传工程改造的植物产生的杀虫毒素的实例包括由蜡样芽孢杆菌(Bacillus cereus)和日本甲虫芽孢杆菌(Bacillus popilliae)得到的杀虫蛋白;由苏云金芽孢杆菌(Bacillus thuringiensis)得到的δ-内毒素,例如Cry1Ab、Cry1Ac、Cry1F、Cry1Fa2、Cry2Ab、Cry3A、Cry3Bb1和Cry9C;由苏云金芽孢杆菌得到的杀虫蛋白,例如VIP 1、VIP 2、VIP 3和VIP 3A;由线虫类得到的杀虫蛋白;由动物产生的毒素,例如蝎毒素、蜘蛛毒素、蜜蜂毒素和昆虫特异性神经毒素;真菌毒素;植物凝集素;凝集素;蛋白酶抑制剂,例如胰蛋白酶抑制剂、丝氨酸蛋白酶抑制剂、patatin、半胱氨酸蛋白酶抑制剂和木瓜蛋白酶抑制剂;核糖体失活蛋白(RIP),例如蓖麻毒蛋白、玉米RIP、相思豆毒蛋白、肥皂草蛋白和briodin;类固醇代谢酶,例如3-羟基类固醇氧化酶、脱皮甾类-UDP-葡糖基转移酶和胆固醇氧化酶;脱皮激素抑制剂;HMG辅酶A还原酶;离子通道抑制剂,例如钠通道抑制剂和钙通道抑制剂;保幼激素酯酶;利尿激素受体;茋合酶;联苄合酶;几丁质酶;以及葡聚糖酶。
通过这类经遗传工程改造的植物产生的杀虫毒素还包括不同杀虫蛋白的杂合毒素,例如杀昆虫蛋白质例如δ-内毒素例如Cry1Ab、Cry1Ac、Cry1F、Cry1Fa2、Cry2Ab、Cry3A、Cry3Bb1和Cry9C、VIP 1、VIP 2、VIP 3和VIP 3A等以及其中构成杀虫蛋白的部分氨基酸缺失或经修饰的毒素。杂合毒素通过遗传工程技术将杀虫蛋白的不同结构域结合来制备。其中构成杀虫蛋白的部分氨基酸缺失的毒素的实例包括其中部分氨基酸缺失的Cry1Ab。其中构成杀虫蛋白的部分氨基酸经修饰的毒素的实例包括其中天然存在的毒素的一个或多个氨基酸被取代的毒素。
杀虫毒素和经遗传工程改造的具有产生杀虫毒素能力的农作物植物参见例如EP-A-0374753、WO 93/07278、WO 95/34656、EP-A-0427529、EP-A-451878、WO 03/052073等。
经遗传工程改造的具有产生杀虫毒素能力的农作物植物特别对鞘翅目害虫、双翅目害虫或鳞翅目害虫的攻击具有抵抗力。
经遗传工程改造的具有一个或多个抗害虫基因从而产生一种或多种杀虫毒素的植物也是已知的,其中一些是市售的。这类经遗传工程改造的植物的实例包括YieldGardTM(表达Cry1Ab毒素的玉米栽培品种)、YieldGard RootwormTM(表达Cry3Bb1毒素的玉米栽培品种)、YieldGardPlusTM(表达Cry1Ab和Cry3Bb1毒素的玉米栽培品种)、Herculex ITM(表达Cry1Fa2毒素的玉米栽培品种和用于赋予草铵膦抗性的膦丝菌素N-乙酰转移酶(PAT))、NuCOTN33BTM(表达Cry1Ac毒素的棉花栽培品种)、Bollgard ITM(表达Cry1Ac毒素的棉花栽培品种)、Bollgard IITM(表达Cry1Ac和Cry2Ab毒素的棉花栽培品种)、VIPCOT TM(表达VIP毒素的棉花栽培品种)、NewLeafTM(表达Cry3A毒素的马铃薯栽培品种)、NatureGard Agrisure GT AdvantageTM(GA21草甘膦抗性特征)、AgrisureCB AdvantageTM(Bt11玉米螟(CB)特征)、ProtectaTM等。
上述农作物植物包括通过遗传工程技术赋予了产生抗病原物质能力的农作物植物。
抗病原物质的实例包括PR蛋白(参见EP-A-0392225中的PRP);离子通道抑制剂,例如钠通道抑制剂和钙通道抑制剂(例如由病毒产生的KP1、KP4、KP6毒素等);茋合酶;联苄合酶;几丁质酶;葡聚糖酶;由微生物产生的物质,例如肽抗生素、含杂环的抗生素;以及参与植物抗病性的蛋白质因子(参见WO 03/000906)等。这类抗病原物质和经遗传工程改造的产生抗病原物质的植物参见EP-A-0392225、WO 05/33818、EP-A-0353191等。
以上所述的作物植物包括已经通过遗传工程技术赋予有益的特征如改性油组分或增强氨基酸含量的那些。该农作物植物的实例包括VISTIVE TM(低亚麻酸大豆,其具有减少的亚麻酸含量),和高赖氨酸(高油)玉米(具有增加的赖氨酸或油含量的玉米)。
此外,以上所述的农作物植物包括组套(stacked)植物,其具有两种或更多种有益的特征如以上所述的传统的抗除草剂(harbicide)的特征,或抗除草剂基因,抗害虫基因,产生抗病原体物质的基因,改性油组分,和增强氨基酸含量的组合。
当本发明的化合物用于如上所述的抗除草剂的农作物植物时,该植物顺序地处理或用本发明的化合物和植物对其具有抗性的除草剂(例如草甘膦或其盐,草铵膦或其盐,其麦草畏盐,咪草烟或其盐,isoxaflutole等)的混合物处理,由此可实现广泛的除草。
可用于与本发明化合物组合的杀昆虫剂,杀螨剂,杀线虫剂,杀真菌剂,除草剂,植物激素试剂,植物生长调节剂,增效剂和农作物损害减少剂(以下,称为″活性成分组X″)的活性成分的实例列举如下。
杀昆虫剂的活性成分的实例包括:
(1)有机磷化合物:
高灭磷、磷化铝、特嘧硫磷、硫线磷、壤虫氯磷、毒虫畏、毒死蜱、甲基毒死蜱、杀螟腈(CYAP)、二嗪农、DCIP(二氯二异丙醚)、除线磷(ECP)、敌敌畏(DDVP)、乐果、甲基毒虫畏、乙拌磷、EPN、乙硫磷、灭克磷、氧嘧啶磷、倍硫磷(MPP)、杀螟松(MEP)、噻唑酮磷、安果、磷化氢、丙胺磷、异噁唑磷、马拉硫磷、甲亚砜磷、杀扑磷(DMTP)、久效磷、二溴磷(BRP)、异砜磷(ESP)、对硫磷、伏杀磷、亚胺硫磷(PMP)、虫螨磷、打杀磷、喹噁磷、稻丰散(PAP)、丙溴磷、丙虫磷、丙硫磷、吡唑硫磷(pyraclorfos)、蔬果磷、乙丙硫磷、嘧丙磷、双硫磷、杀虫威、特丁磷、甲基乙拌磷、敌百虫(DEP)、蚜灭多、甲拌磷、硫线磷,等;
(2)氨基甲酸酯化合物:
棉铃威、噁虫威、丙硫克百威、BPMC、甲萘威、克百威、丁硫克百威、除线威、苯虫威、丁苯威、苯硫威、双氧威、呋线威、异丙威(MIPC)、速灭威、灭多虫、灭虫威、NAC、甲氨叉威、抗蚜威、残杀威(PHC)、XMC、硫双灭多威、灭杀威、涕灭威等;
(3)合成除虫菊酯化合物:
氟酯菊酯、丙烯除虫菊酯、β-氟氯氰菊酯、氟氯菊酯、乙氰菊酯、氟氯氰菊酯、三氟氯氰菊酯、氯氰菊酯、烯炔菊酯、溴氰菊酯、高氰戊菊酯、醚菊酯、甲氰菊酯、杀灭菊酯、氟氰戊菊酯、三氟醚菊酯(flufenoprox)、氟氯苯菊酯、氟胺氰菊酯、卤醚菊酯、咪炔菊酯、苄氯菊酯、右旋丙炔菊酯、除虫菊酯、灭虫菊、σ-氯氰菊酯、灭虫硅醚、七氟菊酯、四溴菊酯、四氟菊酯、胺菊酯、苯醚菊酯、苯醚氰菊酯、α-氯氰菊酯、ζ-氯氰菊酯、λ-三氟氯氰菊酯、γ-三氟氯氰菊酯、消虫菊、τ-氟胺氰菊酯、metofluthrin、2,2-二甲基-3-(1-丙烯基)环丙烷甲酸2,3,5,6-四氟-4-甲基苄酯、2,2-二甲基-3-(2-甲基-1-丙烯基)环丙烷甲酸2,3,5,6-四氟-4-(甲氧基甲基)苄酯、2,2-二甲基-3-(2-氰基-1-丙烯基)环丙烷甲酸2,3,5,6-四氟-4-(甲氧基甲基)苄酯、2,2,3,3-四甲基环丙烷甲酸2,3,5,6-四氟-4-(甲氧基甲基)苄酯,等;
(4)沙蚕毒素化合物:
巴丹、杀虫磺、硫环杀、杀虫单、杀虫双,等;
(5)新烟碱类化合物:
吡虫啉、硝胺烯啶、吡虫清、噻虫嗪(thiamethoxam)、噻虫啉(thiacloprid)、dinotefuran、噻虫胺(clothianidin),等;
(6)苯甲酰脲化合物:
定虫隆、bistrifluron、杀螨硫隆、伏虫脲、氟啶蜱脲、氟螨脲、氟虫脲、氟铃脲、八氟脲、双苯氟脲、noviflumuron、伏虫隆、杀虫隆、triazuron,等;
(7)苯基吡唑化合物:
乙酰虫肼(acetoprole)、乙虫清(ethiprole)、锐特劲、氟吡唑虫、pyriprole、pyrafluprole,等;
(8)Bt毒素杀虫药:
由苏云金芽孢杆菌所获得的活孢子和由苏云金芽孢杆菌所产生的晶体毒素及其混合物;
(9)肼化合物:
环虫酰肼(chromafenozide)、特丁苯酰肼、甲氧苯酰肼、双苯酰肼,等;
(10)有机氯化合物:
艾氏剂、狄氏剂、除螨灵、硫丹、甲氧滴滴涕,等;
(11)天然杀虫药:
机油、硫酸烟碱,等;
(12)其他杀虫药:
齐墩螨素、溴螨酯、噻嗪酮、溴虫清(chlorphenapyr)、环丙三氨三嗪、D-D(1,3-二氯丙烯)、苯甲酸埃玛霉素(emamectin-benzoate)、喹螨醚、吡氟硫磷(flupyrazofos)、蒙512、蒙515(methoprene)、噁二唑虫(indoxacarb)、恶虫酮、milbemycin-A、拒嗪酮、啶虫丙醚(pyridalyl)、蚊蝇醚、艾克敌、氟虫胺、唑虫酰胺(tolfenpyrad)、唑蚜威、氟虫酰胺(flubendiamide)、lepimectin、砷酸、benclothiaz、氰氨钙、石硫合剂、氯丹、DDT、DSP、flufenerim、氟啶虫酰胺(flonicamid)、flurimfen、伐虫脒、metham-ammonium、威百亩、甲基溴、油酸钾、protrifenbute、螺甲满酯(spiromesifen)、硫、氰氟虫腙(metaflumizone)、spirotetramat、pyrifluquinazone、spinetoram、chlorantraniliprole、tralopyril、由下式(A)表示的化合物:
其中Xa1代表甲基、氯原子、溴原子或氟原子,Xa2代表氟原子、氯原子、溴原子、C1-C4卤代烷基或C1-C4卤代烷氧基,Xa3代表氟原子、氯原子或溴原子,Xa4代表任选取代的C1-C4烷基、任选取代的C3-C4烯基、任选取代的C3-C4炔基、任选取代的C3-C5环烷基或氢原子,Xa5代表氢原子或甲基,Xa6代表氢原子、氟原子或氯原子,和Xa7代表氢原子、氟原子或氯原子;
由下式(B)代表的化合物:
其中Xb1代表Xb2-NH-C(=O)基团、Xb2-C(=O)-NH-CH2基团、Xb3-S(O)基团、任选取代的吡咯-1-基、任选取代的咪唑-1-基、任选取代的吡唑-1-基或任选取代的1,2,4-三唑-1-基,Xb2代表任选取代的C1-C4卤代烷基如2,2,2-三氟乙基或任选取代的C3-C6环烷基如环丙基,Xb3代表任选取代的C1-C4烷基如甲基,和Xb4代表氢原子、氰基或甲基;
由下式(C)代表的化合物:
其中Xc1代表任选取代的C1-C4烷基如3,3,3-三氟丙基、任选取代的C1-C4烷氧基如2,2,2-三氯乙氧基或任选取代的苯基如4-氰基苯基或任选取代的吡啶基例如2-氯-3-吡啶基,Xc2代表甲基或三氟甲硫基,和Xc3代表甲基或卤素原子;等。
杀螨剂的活性成分的实例包括灭螨醌、虫螨脒、苯螨特(benzoximate)、联苯肼酯、溴螨酯、灭螨猛、乙酯杀虫螨、CPCBS(杀螨酯)、四螨嗪、丁氟螨酯(cyflumetofen)、开乐散(三氯杀螨醇)、特苯噁唑、杀螨锡、苯硫威、唑螨酯、嘧螨酯(fluacrypyrim)、苄螨醚(fluproxyfen)、噻螨酮、克螨特(BPPS)、杀螨霉素、哒螨酮、嘧胺苯醚、吡螨胺、三氯杀螨砜、螺满酯(spirodiclofen)、螺甲满酯(spiromesifen)、spirotetramat、amidoflumet、cyenopyrafen,等。
杀线虫剂的活性成分的实例包括DCIP、噻唑酮磷、盐酸保松噻(levamisol)、氰土灵、酒石酸莫仑太尔、imicyafos,等。
杀真菌剂的活性成分的实例包括吡咯杀真菌化合物如丙环唑,丙硫菌唑,三唑醇,咪鲜胺,戊菌唑,戊唑醇,氟硅唑,烯唑醇,糠菌唑,氟环唑,噁醚唑,环唑醇,叶菌唑,氟菌唑,氟醚唑,腈菌唑,腈苯唑,己唑醇,氟喹唑,灭菌唑,联苯三唑醇,抑霉唑,和粉唑醇;
环胺杀真菌化合物如芬普福,克啉菌,和苯锈啶;
苯并咪唑杀真菌化合物如carbendezim,苯菌灵,噻苯达唑,和甲基硫菌灵;
腐霉利,嘧菌环胺,嘧霉胺,乙霉威,秋兰姆,氟啶胺,代森锰锌,异菌脲,乙烯菌核利,百菌清,克菌丹,嘧菌胺,拌种咯,咯菌腈,抑菌灵,灭菌丹,醚菌酯,嘧菌酯,肟菌酯,氟嘧菌酯,啶氧菌酯,吡唑醚菌酯,醚菌胺,螺环菌胺,喹氧灵,环酰菌胺,恶唑菌酮,咪唑菌酮,苯酰菌胺,噻唑菌胺,吲唑磺菌胺,丙森锌,苯噻菌胺,赛座灭,双炔酰菌胺,啶酰菌胺,苯菌酮,苯噻菌胺,bixafen,环氟菌胺,和丙氧喹啉。
除草剂和植物激素试剂的活性成分的实例包括:
(1)苯氧基脂肪酸除草化合物如2,4-PA,MCP,MCPB,酚硫杀,甲氯丙酸,氟草烟,绿草定,稗草胺,和萘丙胺;
(2)苯甲酸除草化合物如2,3,6-TBA,麦草畏,二氯吡啶酸,毒莠定,氯氨吡啶酸,二氯喹啉酸,和喹草酸;
(3)尿素除草化合物如敌草隆,利谷隆,绿麦隆,异丙隆,伏草隆,异恶隆,丁唑隆,噻唑隆,苄草隆,杀草隆,和甲基-杀草隆;
(4)三嗪除草化合物如莠去津,ametoryn,氰草津,西玛三嗪,扑灭津,西草净,异戊乙净,扑草净,嗪草酮,和三嗪氟草胺;
(5)联吡啶鎓除草化合物如对草快,和杀草快;
(6)羟基苯基氰除草化合物如溴苯腈和碘苯腈;
(7)二硝基苯胺除草化合物如二甲戊乐灵,氨基氟乐灵,和氟乐灵;
(8)有机磷除草化合物如甲基胺草磷,克蔓磷,地散磷,派草磷,莎稗磷,草甘膦,草铵膦,和双丙氨膦;
(9)氨基甲酸酯除草化合物如燕麦敌,野麦畏,EPTC,苏达灭,杀草丹,禾草畏,草达灭,哌草丹,灭草灵,氯普芬,苯敌草,棉胺宁,稗草丹,和黄草灵;
(10)酰胺除草化合物如敌稗,拿草特,溴丁酰草胺,和乙氧苯草胺;
(11)乙酰氯苯胺除草化合物如乙草胺,草不绿,去草胺,二甲噻草胺,毒草安,吡草胺,异丙甲草胺,丙草胺,噻吩草胺,和烯草胺;
(12)二苯基醚除草化合物如三氟羧草醚-钠,治草醚,乙氧氟草醚,乳氟禾草,氟磺胺草醚,氯硝醚,和苯草醚;
(13)环状酰亚胺除草化合物如恶草灵,吲哚酮草酯,唑草酮,surfentrazone,氟烯草酸,丙炔氟草胺,吡草醚,炔恶草酮,环戊恶草酮,哒草氟,氟丙嘧草酯,和双苯嘧草酮;
(14)吡唑除草化合物如吡草酮,吡唑特,苄草唑,topramezone,和pyrasulfotole;
(15)三酮除草化合物如异恶唑草酮,苯并双环酮,磺草酮,甲基磺草酮,tembotrione,和tefuryltrione;
(16)芳基氧基苯氧基丙酸除草化合物如炔草酯,氰氟草酯,禾草灵,恶唑禾草灵,丁基吡氟禾草灵,氟吡甲禾灵,和精喹禾灵;
(17)三酮肟(trioneoxime)除草化合物如禾草灭,稀禾定,丁氧环酮,烯草酮,cloproxydim,噻草酮,醌肟草,肟草酮,和环苯草酮;
(18)磺酰基脲除草化合物如绿黄隆,甲嘧磺隆,甲磺隆,氯嘧磺隆,苯磺隆,醚苯磺隆,苄嘧磺隆,噻吩磺隆,吡嘧磺隆,氟嘧磺隆,烟嘧磺隆,酰嘧磺隆,醚磺隆,唑吡嘧磺隆,砜嘧磺隆,氯吡嘧磺隆,氟磺隆,胺苯磺隆,氟胺磺隆,啶嘧磺隆,环磺隆,氟啶嘧磺隆,酰磺隆,四唑嘧磺隆,乙氧嘧磺隆,环氧嘧磺隆,甲基碘磺隆钠盐,酰胺磺隆,甲磺胺磺隆,三氟啶黄隆,三氟甲磺隆,嘧苯胺磺隆,氟吡磺隆,和1-(2-氯-6-丙基咪唑[1,2-a]哒嗪-3-基磺酰基)-3-(4,6-二甲氧基嘧啶-2-基)脲;
(19)咪唑啉酮除草化合物如咪草酸,imazamethapyr,甲氧咪,灭草烟,灭草喹,和咪草烟;
(20)磺酰胺除草化合物如氟唑嘧磺草胺,磺草唑胺,双氯磺草胺,双氟磺草胺,氯酯磺草胺,嘧啶并三唑类磺胺,和甲氧磺草胺;
(21)嘧啶基氧基苯甲酸除草化合物如嘧草硫醚,双草醚,嘧草醚,嘧啶肟草醚,和环酯草醚;和
(22)其它除草化合物如噻草平,除草定,特草定,草克乐,异恶草胺,地乐酚,杀草强,环庚草醚,灭草环,dalapon,二氟吡隆-钠,氟硫草定,噻草定,氟酮磺隆-钠,丙苯磺隆-钠,苯噻草胺,氟噻草胺,四唑草胺,唑草胺,茚草酮,氯恶嗪草,呋草黄,ACN,哒草特,杀草敏,达草灭,呋草酮,吡氟草胺,氟吡草胺,氟丁酰草胺,异恶草松,氨唑草酮,唑啉草酯,和甲基噻烯卡巴腙。
植物生长调节剂的活性成分的实例包括恶霉灵,多效唑,烯效唑-P,抗倒胺,调环酸-钙,艾维激素,1-萘基乙酰胺,脱落酸,吲哚丁酸,乙基吲熟酯,乙烯利,座果酸,矮壮素阳离子,2-4滴丙酸,赤霉素,茉莉酮,苯甲酸嘌呤,调吡脲,顺丁烯二酰肼,过氧化钙,缩节胺)和4-CPA(4-氯苯氧基乙酸)。
增效剂的活性成分的实例包括胡椒基丁醚,增效菊,亚砜,N-(2-乙基己基)-8,9,10-三降冰片-5-烯-2,3-二甲酰亚胺(MGK 264),N-declyimidazole,WARF-抗耐药性剂,TBPT,TPP,IBP,PSCP,甲基碘(CH3I),叔苯基丁烯酮,马来酸二乙基酯,DMC,FDMC,ETP,和ETN。
农作物损害-减少剂的活性成分的实例包括解草嗪,解毒喹,解草胺腈,杀草隆,二氯丙烯胺,解草唑,解草啶,解草安,肟草安,解草恶唑,吡唑解草酯,MG191,解草腈,烯草胺,双苯恶唑酸,cyprosulfamide,肟草安,和1,8-萘二甲酸酐。
本发明的化合物显示出控制效果的害虫实例包括节肢害虫例如有害昆虫和有害螨类,更具体地说,包括以下害虫。
半翅目:
飞虱科(Delphacidae)如灰飞虱(Laodelphax striatellus)、褐飞虱(Nilaparvata lugens)和白背飞虱(Sogatella furcifera);叶蝉科(Deltocephalidae)如黑尾叶蝉(Nephotettix cincticeps)、二点黑尾叶蝉(Nephotettix virescens)和绿茶叶蝉(Empoasca onukii);蚜科(Aphididae)如棉蚜(Aphis gossypii)、烟蚜(Myzus persicae)、甘蓝蚜(Brevicorynebrassicae)、绣线菊蚜(Aphis spiraecola)、马铃薯长管蚜(Macrosiphumeuphorbiae)、土豆沟无网蚜(Aulacorthum solani)、禾谷缢管蚜(Rhopalosiphum padi)、褐橘声蚜(Toxoptera citricidus)和梅大尾蚜(Hyalopterus pruni);蝽科(Pentatomidae)如花角绿蝽(Nezara antennata)、豆蜂缘蝽(Riptortus clavetus)、中稻缘蝽(Leptocorisa chinensis)、尖角二星蝽(Eysarcoris parvus)和茶翅蝽(Halyomorpha mista);粉虱科(Aleyrodidae)如温室粉虱(Trialeurodes vaporariorum)、甘薯粉虱(Bemisiatabaci)、白粉虱(Bemisia argentifolii)、柑橘粉虱(Dialeurodes citri)和黄刺粉虱(Aleurocanthus spiniferus);蚧科(Coccidae)如红肾圆盾蚧(Aonidiellaaurantii)、圣琼斯康盾蚧(Comstockaspis perniciosa)、柑橘尖盾蚧(Unaspiscitri)、红龟蜡蚧(Ceroplastes rubens)、澳洲吹绵蚧(Icerya purchasi)、紫藤臀纹粉蚧(Planococcus kraunhiae)、长尾粉蚧(Pseudococcus longispinis)和桑白盾蚧(Pseudaulacaspis pentagona);网蝽科(Tingidae);叶蜂(cimices)如柳黄毛叶蜂(Cimex lectularius);木虱科(Psyllidae);等。
鳞翅目:
螟蛾科(Pyralidae)如二化螟(Chilo suppressalis)、三化螟(Tryporyzaincertulas)、稻纵卷叶野螟(Cnaphalocrocis medinalis)、棉卷叶野螟(Notarcha derogata)、印度谷斑螟(Plodia interpunctella)、亚洲玉米螟(Ostrinia furnacalis)、菜心野螟(Hellula undalis)和蓝草螟蛾(Pediasiateterrellus);夜蛾科(Noctuidae)如棉贪夜蛾(Spodoptera litura)、贪夜蛾(Spodoptera exigua)、粘虫(Pseudaletia separata)、甘蓝夜蛾(Mamestrabrassicae)、小地老虎(Agrotis ipsilon)、黑点孤独翅夜蛾(Plusia nigrisigna)、Thoricoplusia spp.、阳苔蛾属物种(Heliothis spp.)和夜蛾属物种(Helicoverpa spp.);粉蝶科(Pieridae)如菜粉蝶(Pieris rapae);卷蛾科(Tortricidae)如褐带卷蛾属物种(Adoxophyes spp.)、梨小食心虫(Grapholita molesta)、大豆食心虫(Leguminivora glycinivorella)、日豆小卷蛾(Matsumuraeses azukivora)、棉褐带卷蛾(Adoxophyes orana fasciata)、褐带卷蛾属(Adoxophyes honmai.)、茶长卷蛾(Homona magnanima)、苹果黄卷蛾(Archips fuscocupreanus)和苹果皮小卷蛾(Cydia pomonella);细蛾科(Gracillariidae)如茶细蛾(Caloptilia theivora)和金纹小潜细蛾(Phyllonorycter ringoneella));蛀果蛾科(Carposinidae)如桃蛀果蛾(Carposina niponensis));潜蛾科(Lyonetiidae)如潜蛾属物种(Lyonetiaspp.);毒蛾科(Lymantriidae)如毒蛾属物种(Lymantria spp.)和黄毒蛾属物种(Euproctis spp.);巢蛾科(Yponomeutidae)如小菜蛾(Plutella xylostella);麦蛾科(Gelechiidae)如红铃麦蛾(Pectinophora gossypiella)和马铃薯麦蛾(Phthorimaea operculella));灯蛾科(Arctiidae)如美国白蛾(Hyphantriacunea);谷蛾科(Tineidae)如袋谷蛾(Tinea translucens)、幕谷蛾(Tineolabisselliella);等。
缨翅目:
牧草虫(Thripidae)例如西花蓟马(Frankliniella occidentalis)、棕黄蓟马(Thrips parmi)、茶黄硬蓟马(Scirtothrips dorsalis)、烟蓟马(Thripstabaci)、丽花蓟马(Frankliniella intonsa)等。
双翅目:
库蚊属如淡色库蚊(Culex pipiens pallens)、三带喙(Cluextritaeniorhynchus)和致乏库蚁(Cluex quinquefasciatus);伊蚊属物种(Aedesspp.)如埃及伊蚊(Aedes aegypti)和白纹伊蚊(Aedes albopictus);按蚊属物种(Anopheles spp.)如中华按蚊(Anopheles sinensis);摇蚊科(Chironomidae);蝇科(Muscidae)如家蝇(Musca domestica)和厩腐蝇(Muscina stabulans);丽蝇科(Calliphoridae);麻蝇科(Sarcophagidae);厕蝇科(Fanniidae);花蝇科(Anthomyiidae)如灰地种蝇(Delia platura)和葱地种蝇(Delia antiqua);潜蝇科(Agromyzidae)如日本稻潜苍蝇(Agromyzaoryzae)、小米斑潜蝇(Hydrellia griseola)、蔬菜斑潜蝇(Liriomyza sativae)、三叶草斑潜蝇(Liriomyza trifolii)、豌豆彩潜蝇(Chromatomyia horticola);杆蝇科(Chloropidae)如稻杆蝇(Chlorops oryzae);实蝇科(Tephritidae)如瓜寡鬃实蝇(Dacus cucurbitae)和地中海实蝇(Ceratitis capitata);果蝇科(Drosophilidae);蚤蝇科(Phoridae)如东亚异蚤蝇(Megaselia spiracularis);毛蠓科(Psychodidae)如毛蠓(Clogmia albipunctata);蚋科(Simuliidae);虻科(Tabanidae)如三角虻(Tabanus trigonus);厩螯蝇等;
鞘翅目(Coleoptera):
叶甲属物种(Diabrotica spp.)如玉米根萤叶甲(Diabrotica virgiferavirgifera)和黄瓜十一星叶甲(Diabrotica undecimpunctata howardi);金龟科(Scarabaeidae)如古铜异丽金龟(Anomala cuprea)、古铜异丽金龟(Anomala rufocuprea)和日本金龟子(Popillia japonica);象虫科如玉米象(Sitophilus zeamais)、稻水象(Lissorhoptrus oryzophilus)、绿豆象(Callosobruchus chinensis)、稻象(Echinocnemus squameus)、棉铃象(Anthonomus grandis)和猎长喙象(Sphenophorus venatus);拟步甲科(Tenebrionidae)如黄粉甲(Tenebrio molitor)和赤拟谷稻(Triboliumcastaneum);叶甲科(Chrysomelidae)如水稻负泥虫(Oulema oryzae)、黄守瓜(Aulacophora femoralis)、黄曲条菜跳甲(Phyllotreta striolata)和马铃薯叶甲(Leptinotarsa decemlineata);皮蠹科(Dermestidae)如小圆皮蠢(Anthrenus verbasci)和白腹皮蠹(Dermestes maculates);窃蠹科(Anobiidae)如烟草窃蠢(Lasioderma serricorne);瓢虫科(Epilachna)如马铃薯瓢虫(Epilachna vigintioctopunctata);小蠹科(Scolytidae)如褐粉蠹(Lyctusbrunneus)和纵坑切梢小蠢(Tomicus piniperda);长蠹科(Bostrychidae);蛛甲科(Ptinidae);天牛科(Cerambycidae)如白斑星天牛(Anoplophoramalasiaca);叩甲属物种(Agriotes spp);毒隐翅虫(Paederus fuscipens)等。
直翅目(orthoptera):
亚洲飞蝗(Locusta migratoria)、东方蝼蛄(Gryllotalpa africana)、短翅稻蝗(Oxya yezoensis)、日本稻蝗(Oxya japonica)、蟋蟀等。
蚤目(Siphonaptera):
猫蚤(Ctenocephalides felis)、犬栉首蚤(Ctenocephalides canis)、人蚤(Pulex irritans)、印鼠客蚤(Xenopsylla cheopis)等。
虱目(Anoplura):
人体虱(Pediculus humanus corporis)、阴虱(Phthirus pubis)、牛血虱(Haematopinus eurysternus)、羊虱(Dalmalinia ovis)、猪血虱(Haematopinussuis)等。
膜翅目(Hymenoptera):
蚁科(Formicidae)如小黄家蚁(Monomorium pharaonis)、黑蚁(丝光褐林蚁,Formica fusca japonica)、无毛凹臭蚁(Ochetellus glaber)、双针蚁(Pristomyrmex pungens)、宽结大头蚁(Pheidole noda)、切叶蚁属物种(Acromyrmex spp.)和火蚁属物种(Solenopsis spp.);胡蜂科(Vespidae);bethylid wasps(Betylidae);叶蜂科(Tenthredinidae)如菜叶蜂(Athalia rosae)和日本菜叶蜂(Athalia japonica)等。
蜚蠊科(Blattodea):
德国小蠊(Blattella germanica)、黑胸大蠊(Periplaneta fuliginosa)、美洲大蠊(Periplaneta Americana)、褐斑大蠊(Periplaneta brunnea)、东方蜚蠊(Blatta orientalis)等;
等翅目:
白蚁科如黄胸散白蚁(Reticulitermes speratus)、台湾乳白蚁(Coptotermes formosanus)、小楹白蚁(Incisitermes minor)、单瘤砂白蚁(Cryptotermes domesticus)、黑翅土白蚁(Odontotermes formosanus)、恒春新白蚁(Neotermes koshunensis)、赤树白蚁(Glyptotermes satsumensis)、Glyptotermes nakajimai、黑树白蚁(Glyptotermes fuscus)、Glyptotermeskodamai、Glyptotermes kushimensis、尖叉原白蚁(Hodotermopsisjaponica)、广州乳白蚁(Coptotermes guangzhoensis)、奄美散白蚁(Reticulitermes miyatakei)、东方地下白蚁(欧美散白蚁,Reticulitermesflavipes amamianus)、散白蚁属物种(Reticulitermes sp.)、高山象白蚁(Nasutitermes takasagoesis)、近扭白蚁(Pericapritermes nitobei)、台华歪白蚁(Sinocapritermes mushae)、Reticuliterumes flavipes,鼻白蚁(Reticulitermes hesperus),散白蚁(Reticulitermes virginicus),Reticulitermes tibialis,Heterotermes aureus,和内华达古白蚁(Zootermopsis nevadensis)等。
蜱螨目(Acarina):
叶螨科(Tetranychidae)如二斑叶螨(Tetranychus urticae)、神泽氏叶螨(Tetranychus kanzawai)、柑桔全爪螨(Panonychus citri)、苹果全爪螨(Panonychus ulmi)和小爪螨属物种(Oligonychus spp.);瘿螨科(Eriophyidae)如橘刺皮瘿螨(Aculops pelekassi)、Phyllocoptruta citri、番茄刺皮瘿螨(Aculops lycopersici)、龙首丽瘿螨(Calacarus carinatus)、茶尖叶瘿螨(Acaphylla theavagran)和中国瘿螨(Eriophyes chibaensis)和斯氏刺瘿螨(Aculus schlechtendali);跗线螨科(Tarsonemidae)如侧多食跗线螨(Polyphagotarsonemus latus);细须螨科(Tenuipalpi dae)如紫红短须螨(Brevipalpus phoenicis);杜克螨科(Tuckerellidae);蜱科(Ixodidae)如长角血蜱(Haemaphysalis longicornis)、褐黄血卑(Haemaphysalis flava)、台湾革蜱(Dermacentor taiwanicus)、变异革蜱(Dermacentor variabilis)、卵形硬蜱(Ixodes ovatus)、全沟硬蜱(Ixodes persulcatus)、黑腿蜱(Ixodesscapularis)、美洲花蜱(Amblyomma americanum)、微小牛蜱(Boophilusmicroplus)和血红扇头蜱(Rhipicephalus sanguineus);蚤螨科(Psoroptidae)如狗耳螨(Otodectes cynotis);疥螨科(Sarcoptidae)如人疥螨(Sarcoptesscabiei);蠕形螨科(Demodicidae)如犬蠕形螨(Demodex canis);粉螨科(Acaridae)如腐食酪螨(Tyrophagus putrescentiae)和拟食酪螨(Tyrophagussimilis);麦食螨科(Pyroglyphidae)如粉尘螨(Dermatophagoides farinae)和屋尘螨(Dermatophagoides ptrenyssnus);肉食螨科(Cheyletidae)如普通肉食螨(Cheyletus eruditus)、马六甲肉食螨(Cheyletus malaccensis)和马六甲肉食螨(Cheyletus moorei);皮刺螨科(Dermanyssidae)如柏氏禽刺螨(ornithonyssus bacoti)、林禽刺螨(ornithonyssus sylviarum)和鸡皮刺螨(Dermanyssus gallinae);恙螨科(Trombiculidae)如红维恙螨(Leptotrombidium akamushi);蜘蛛目(Araneae)如日本红螯蛛(Chiracanthium japonicum)、赤背蜘蛛(Latrodectus hasseltii)等。
唇足纲(Chilopoda):蚰蜒(Thereuonema hilgendorfi)、越南巨人蜈蚣(Scolopendra subspinipes)等;
倍足纲(Diplopoda):雅丽酸带马陆(Oxidus gracilis)、胖枝带马陆(Nedyopus tambanus)等;
等足目(Isopoda):平甲虫(Armadillidium vulgare)等;
腹足纲(Gastropoda):Limax marginatus、黄蛞蝓(Limax flavus)等。
线虫纲:
稻白色-尖线虫(Aphelenchoides besseyi),草莓芽线虫(Nothotylenchusacris),南方大豆根结线虫(Meloidogyne incognita),北方大豆根结线虫(Meloidogyne hapla),爪哇大豆根结线虫(Meloidogyne javanica),大豆异皮线虫(Heterodera glycines),马铃薯囊肿线虫(Globodera rostochiensis),咖啡根-损伤线虫(Pratylenchus coffeae),Californiroot-损伤线虫(Pratylenchus neglectus),等等
包括本发明化合物或其盐的杀虫组合物可被用于家畜疾病疗法和畜牧业领域,也可以用于根绝栖息在脊椎动物如人类,母牛,绵羊,山羊,猪,poulty,狗,猫和鱼的身体内部和/或外部的生物体和寄生虫以维持公众健康。该生物体和寄生虫的实例包括扁虱(Ixodes物种)(例如Ixodes scapularis),方头蜱属物种(例如Boophilus microplus),钝眼蜱属物种,璃眼蜱属物种,扇头蜱属物种(例如血红扇头蜱),血蜱属物种(例如Haemaphysalis longicornis),矩头蝉属物种,钝缘蜱属物种(例如Ornithodoros moubata),寄生物样的螨类(Dermahyssus gallinae),林禽刺满(Ornithonyssus sylviarum),疥螨(Sarcoptes spp.)(例如Sarcoptesscabiei),痒螨属物种,皮螨物种,毛囊螨类(Demodex spp.),恙螨(Eutrombicul spp.),Aedes物种(例如亚洲虎蚊子(白纹伊蚊)),按蚊物种,库蚊属物种,库蠓物种,Musca物种,Hypoderma物种,胃蝇属物种,黑角蝇属物种,虻虫物种,蚋属物种,锥蝽属物种,虱(虱目)(例如Damalinia物种,长颚虱属物种,血虱属物种),跳蚤(栉头蚤属物种)(例如猫跳蚤(猫蚤),Xenosylla物种),厨蚁(Monomorium pharaonis),和线虫纲[例如,毛圆线虫(例如巴西钩虫,Trichostrongylus axei,和Trichostrongylus colubriformis),旋毛虫(例如Trichinellspiralis),捻转血矛线虫,细颈线虫属(例如Nematodirus battus),Ostertagiacircumcincta,古柏线虫属物种,短膜壳绦虫等。
对于本发明的害虫控制方法,本发明的化合物或其盐可以按照原样使用,然而,本发明的化合物通常配制成如上所述的本发明的杀虫组合物形式然后使用。本发明的害虫控制方法的包括,例如,通过针对常规的杀虫剂一样的施加方法施加本发明的化合物或其盐或本发明的杀虫组合物至害虫或害虫栖息之地,以允许害虫接触或摄取本发明的化合物或其盐或本发明的杀虫组合物。
害虫栖息之地的实例包括水田,干燥田野,耕地,茶园,果园,非耕地,房子,上升式插秧盘,苗圃箱,苗床土壤,苗圃垫,水耕农场中的水培养介质等。
该施加方法的实例包括喷雾处理,土壤处理,种子处理和水培养介质处理。在本发明中,喷雾处理包括叶面喷洒和卡车喷雾,具体地包括用活性成分(本发明的化合物或其盐)处理植物表面或害虫本身,以发挥对害虫的控制影响。土壤处理包括,例如,用活性成分处理待保护以免受例如害虫进食的损伤的植物根区土壤以直接控制害虫,或使得活性成分从植物根部等等渗透到植物内部以控制害虫。土壤处理的具体实例包括栽植穴处理(栽植穴喷雾,栽植穴处理之后土壤掺入),植物底部处理(植物底部喷雾,在植物底部土壤掺入,植物底部湿透,在稍后的播种提升阶段的植物底部处理),栽植沟处理(栽植沟喷雾,栽植沟处理之后土壤掺入),种植行处理(种植行喷雾,种植行处理之后土壤掺入,在生长期种植行喷雾),在播种时种植行处理(在播种的时候种植行喷雾,在播种的时候种植行处理之后土壤掺入),撒施处理(全面土表喷雾,在撒施处理以后土壤掺入),其它土壤喷涂处理(在成长期叶面喷洒颗粒,在树干下或在主茎周围喷雾,土表喷雾,土表掺入,播种孔喷雾,沟表面喷雾,和在植物之间喷雾),其它湿透处理(土壤湿透,在上升育苗阶段湿透,化学灌浆处理,植物底部湿透,化学滴灌,施化灌溉),苗圃箱处理(苗圃箱表面喷雾,苗圃箱湿透),人工孵化托盘处理(人工孵化托盘喷雾,人工孵化托盘灌溉),苗床处理(苗床表面喷雾,苗床湿透,低地苗床表面喷雾,秧苗浸入),床土掺入处理(床土掺入,播种前的床土掺入),和其它处理(脊掺入,开槽并施肥,表土掺入,在顶盖(canopy)边缘下土壤掺入,种植位置处理,用颗粒的花簇处理,糊剂施肥)。种子处理包括,例如,用活性成分处理待保护免受如害虫进食的损伤的种子,种用马铃薯或农作物植物鳞茎,或其附近以发挥对害虫的控制影响。种子处理的具体实施包括喷雾,涂抹,浸入,浸渍,施涂,薄膜涂层和丸粒涂层。水培养介质处理包括,例如,添加活性成分到水培养介质等等以便允许活性成分从待保护免受例如害虫进食的损伤的农作物植物根部等等渗透到植物内部,由此保护植物免受害虫损伤。水培养介质处理的具体实例包括水培养介质掺入,和水培养介质混合。
上述施加方法的本发明的杀虫组合物施加量可以适当地根据施加定时,施加地点,制剂形式等等改变,其通常是0.3至3,000g,优选地50至3,000g的活性成分(本发明的化合物或其盐)/1公顷的植物生长土壤。当本发明的杀虫组合物为可湿性粉剂形式时,优选将其用水稀释至0.1到1,000ppm,优选地10到500ppm的活性成分然后施加。
本发明的杀虫组合物或其水稀释物可以直接到施加害虫或待被保护免受害虫的植物如农作物植物。或者,耕地土壤可以用本发明的杀虫组合物或其水稀释物处理以控制栖息在该土壤的害虫。
当本发明的杀虫组合物为树脂制剂形式时,其可加工成片材或线形式,然后通过将其缠绕在农作物植物周围,布置在农作物植物附近,敷设在植物底部的土表上的等等方式来施加。
当本发明的杀虫组合物用于传染病控制时,对于施用于空间,施用量通常为0.001-10mg作为活性成分的本发明化合物/m3,对于施用于平面,施用量通常为0.001-100mg作为活性成分的本发明化合物/m2。可乳化浓缩物、可湿性粉末或可流动制剂形式的杀虫组合物通常在用水稀释后施用,这样使得其通常含有0.001-10,000ppm的活性成分。以油溶液、气雾剂、发烟杀虫剂或毒饵形式的杀虫组合物通常以原样使用。
当本发明杀虫组合物被用于控制家畜(如牛、马、猪、绵羊、山羊和小鸡)或小动物(如狗、猫、大鼠和小鼠)的体外寄生虫时,其可通过兽医领域已知的方法应用于所述动物。特别是,当意欲全身控制时,本发明杀虫组合物以例如片剂、与饲料的混合物、栓剂或注射剂(例如,肌内、皮下、静脉内、腹膜内等)给予。当意欲非全身控制时,使用本发明的杀虫组合物的方法包括以油溶液或水性液体的形式用杀虫组合物喷洒、浇泼处理或点滴处理,以香波制剂形式的杀虫组合物洗涤动物,以树脂制剂的形式将由杀虫组合物制备的项圈或耳标与动物附着。当给予动物时,本发明化合物的量通常的范围为每1kg动物体重0.1-1,000mg。
接下来,显示本发明的化合物的实例。如下显示的由式(Iα),式(Iβ)和式(Iγ)表示的化合物是本发明的化合物的具体实例。
由式(Iα)表示的化合物:
其中Ru,Au,Rv,Av,Rw,Aw和Zy是下表1中显示的组合1至487之任一。
[表1]
由式(Iβ)表示的化合物:
其中U,Y,Z,A,X,B,W和R是下表2所示组合1至88之任一。
[表2]
由式(Iγ)表示的化合物:
其中XU,RW,AW和ZY是下表3所示组合1-10之任一。
[表3]
实施例
以下,本发明通过引用生产实施例,参考生产实施例,制剂实施例和测试实施例(本发明不局限于)更详细地描述。
在生产实施例和参考生产实施例中,柱色谱法的反应与操作通过使用TLC(薄层色谱法)等等的分析复核。TLC通过使用MERCK & CO.,LTD.制备的Kieselgel 60F254(70-230目)来进行,采用UV检测器。柱色谱法使用KANTO CHEMICAL CO.,LTD.制备的硅胶60(球形,粒度63至210nm),WAKO PURE CHEMICAL INDUSTRIES LTD制备的Florisil(100至200目)等等来进行。作为中等压力制备性液相色谱,使用YAMAZEN CO.制备的Ultrapack(填料:硅胶)。NMR光谱用JEOL A1-400(400兆赫)型,Bruker AVANCE 400(400兆赫)型光谱仪等等测量,使用四甲基硅烷作为内标(测量温度是25℃,除非另作说明)。
在生产实施例和参考生产实施例中,缩写和术语具有如下所述含义。
s:单峰,br;宽的,brs:宽的单峰,d:双峰,t:三重峰,q:四重峰,Me:甲基,Et:乙基,nPr:丙基,iPr:异丙基,cPr:环丙基,Bu:丁基,iBu:异丁基,sBu:仲丁基,tBu:叔丁基,Hex:己基,cHx:环己基,Ay:烯丙基,Pg:炔丙基,Vn:乙烯基,Ey:乙炔基,Ph:苯基,Bn:苄基;Py:吡啶基,Fu:呋喃基,Th:噻吩基,THF:四氢呋喃,DMF:二甲基甲酰胺,室温:约15至25℃;冰冷:0至5℃。
然后,显示本发明的化合物的生产实施例。
生产实施例1
合成N-(4-甲基苯基)-3,3-双(苯基硫基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物1)
硫代苯酚(1.61克)和叔丁氧基钾(88.9毫克)被添加到在室温的N-(4-甲基苯基)-3-(苯基硫基)硫代丙烯基亚氨酸苯基酯(2.19克)在THF中(45毫升)的溶液,且在室温搅拌该混合物10小时。饱和氯化钠水溶液(50ml)被添加到反应溶液,其然后用乙酸乙酯(100ml)提取。有机层用饱和氯化钠水溶液(50ml)洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=30∶1至己烷∶乙酸乙酯=10∶1),获得本发明的化合物1(2.42克),为黄色油。
1H-NMR(CDCl3)δ(ppm):2.34(3H,s),2.79(2H,dJ=7.2Hz),5.01(1H,t,J=7.2Hz),6.82-6.84(2H,m),7.16-7.42(17H,m)。
生产实施例2
N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物2)以与生产实施例1-(1)同样的方法合成。
1H-NMR(CDCl3)δ(ppm):2.80(2H,d,J=7.2Hz),5.02(1H,t,J=7.2Hz),7.11-7.40(20H,m)。
生产实施例3
合成N-(4-乙基苯基)-3,3-双(苯基硫基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物3)
亚硫酰氯(0.693克),三乙胺(0.563克)和DMF(催化量)被添加到在室温的N-(4-乙基苯基)-3-(苯基硫基)丙烯酰胺(1.06克)在甲苯中(5ml)的溶液,在60℃搅拌该混合物3小时。反应混合物留待冷却之后,不溶物质被滤出和在减压下浓缩该滤液。THF(5ml)被添加到残余物,和在冰冷条件下向其中滴加苯硫酚钠盐(1.36克)在THF(6毫升)中的溶液。在室温搅拌该混合物2小时。然后,向其中添加饱和氯化钠水溶液(50ml)。混合物溶液被用100ml的乙酸乙酯提取两次。有机层被合并,用无水硫酸镁干燥,和在减压下浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=30∶1),获得本发明的化合物3(0.356克),为黄色油。
1H-NMR(CDCl3)δppm:0.88(3H,t,J=6.8Hz),2.65(2H,q,J=6.8Hz),2.79(2H,d,J=7.2Hz),5.01(1H,t,J=7.2Hz),6.86(2H,d,J=8.6Hz),7.13-7.56(17H,m)。
生产实施例4至7
以下化合物以与生产实施例3中同样的方式合成。
N-(4-联苯基)-3,3-双(苯基硫基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物4)
1H-NMR(CDCl3)δppm:2.83(2H,d,J=7.2Hz),5.06(1H,t,J=7.2Hz),7.01-7.63(24H,m)。
N-(4-氯苯基)-3,3-双(苯基硫基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物5)
1H-NMR(CDCl3)δppm:2.78(2H,d,J=7.5Hz),4.97(1H,t,J=7.5Hz),6.84(2H,d,J=8.9Hz),7.21-7.61(17H,m)。
N-(3-甲基苯基)-3,3-双(苯基硫基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物6)
1H-NMR(CDCl3)δppm:2.37(3H,s),2.79(2H,d,J=7.1Hz),5.02(1H,t,J=7.1Hz),6.69-6.75(2H,m),6.92-7.00(1H,m),7.21-7.53(16H,m)。
N-[4-(1-甲基乙基)苯基]-3,3-双(苯基硫基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物7)
1H-NMR(CDCl3)δppm:1.25(6H,d,J=7.0Hz),2.79(2H,d,J=7.2Hz),2.88-2.91(1H,m),5.03(1H,t,J=7.2Hz),6.86-7.43(19H,m)。
生产实施例8
合成N-[2-(甲硫基)噻唑-5-基]-3,3-双(苯基硫基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物8)
四溴化碳(1.6克)和三苯膦(1.3克)被添加到在室温的N-[(2-甲硫基)噻唑-5-基)-3-(苯基硫基)丙烯酰胺(0.74克)在乙腈(30ml)中的溶液,和在其被加热到回流的时候搅拌该混合物5小时。反应混合物留待冷却之后,不溶物质滤出和在减压下浓缩该滤液。DMF(20ml)被添加到残余物,和在冰冷条件下向其中添加苯硫酚钠盐(0.38克)。在相同温度搅拌该混合物0.5小时,然后在室温搅拌2小时。向该反应混合物添加100ml的叔丁基甲基醚,随后用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤。有机层用无水硫酸镁干燥,和在减压下浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=10∶1),获得本发明的化合物8(0.11克),为棕红的油。
1H-NMR(CDCl3)δppm:2.69(3H,s),2.84(2H,d,J=7.2Hz),4.93(1H,t,J=7.2Hz),7.24-7.27(6H,m),7.32-7.43(9H,m),7.63(1H,s)。
生产实施例9和10
以下化合物以与生产实施例1中同样的方式合成。
3,3-双(苯基硫基)-N-[4-(2-吡啶基)苯基]硫代丙亚氨酸苯基酯(此后称为本发明的化合物9)
1H-NMR(CDCl3)δppm:2.81(2H,d,J=7.9Hz),5.03(1H,t,J=7.9Hz),7.02(2H,d,J=8.0Hz),7.18-7.41(16H,m),7.72-7.74(2H,m),2.81(2H,d,J=8.2Hz),8.67-8.69(1H,m)。
N-(5-茚满基)-3,3-双(苯基硫基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物10)。
1H-NMR(CDCl3)δppm:2.05-2.13(2H,m),2.87-2.94(4H,m),2.78(2H,d,J=7.2Hz),5.02(1H,t,J=7.2Hz),6.69-7.40(18H,m)。
生产实施例11
合成3-苄硫基-N-苯基-3-(苯基硫基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物11)
硫代苯酚(0.13毫升)在冰冷条件下滴加至3-苄硫基-N-(苯基)硫代丙烯基亚氨酸苯基酯(0.42克)在THF(10ml)中的溶液,和在相同温度搅拌该混合物1小时。向该反应混合物添加80毫升的叔丁基甲基醚,随后用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤。有机层用无水硫酸镁干燥,和在减压下浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=20∶1),获得本发明的化合物11(0.53克),为黄色油。
1H-NMR(CDCl3)δppm:2.66-2.87(2H,m),3.80-3.99(2H,m),4.46(1H,t,J=7.4Hz),6.87(2H,d,J=7.5Hz),7.10-7.14(1H,m),7.23-7.37(17H,m)。
生产实施例12
3-环己基硫基-N-苯基-3-(苯基硫基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物12)以与生产实施例11中同样的方式合成。
1H-NMR(CDCl3)δppm:1.22-2.10(10H,m),2.65-2.84(2H,m),2.87-2.94(1H,m),4.77(1H,t,J=7.2Hz),6.91(2H,d,J=7.5Hz),7.11-7.15(1H,m),7.26-7.44(12H,m)。
生产实施例13
3-甲硫基-N-苯基-3-(苯基硫基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物13)以与生产实施例3中同样的方式合成。
1H-NMR(CDCl3)δppm:2.14(3H,s),2.72-2.88(2H,m),4.59(1H,t,J=7.4Hz),6.93(2H,d,J=7.7Hz),7.11-7.15(1H,m),7.26-7.45(12H,m)。
生产实施例14
3-乙硫基-N-苯基-3-(苯基硫基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物14)以与生产实施例3中同样的方式合成。
1H-NMR(CDCl3)δppm:1.23(3H,t,J=7.5Hz),2.59-2.87(4H,m),4.67(1H,t,J=7.2Hz),6.92(2H,d,J=7.2Hz),7.11-7.15(1H,m),7.25-7.46(12H,m)。
生产实施例15
合成2-(苯并[1,3]二硫酚-2-基)-N-(苯基)硫代乙亚氨酸苯基酯(此后称为本发明的化合物15)
五氯化磷(0.44克)被添加到在室温的2-(苯并[1,3]二硫酚-2-基)-N-(苯基)乙酰胺(0.60克)在甲苯中(3ml)的溶液,且在室温搅拌该混合物2小时。反应溶液在减压下浓缩之后,DMF(20ml)被添加到残余物,然后在冰冷条件下向其中添加苯硫酚钠盐(0.56克)。在相同温度搅拌该混合物3小时。然后,叔丁基甲基醚(100ml)被添加到该反应混合物,随后用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤。有机层用无水硫酸镁干燥,和在减压下浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=20∶1),获得本发明的化合物15(0.46克),为浅黄色晶体。
1H-NMR(CDCl3)δppm:2.88(2H,d,J=7.2Hz),5.35(1H,t,J=7.2Hz),6.94-7.01(4H,m),7.14-7.16(3H,m),7.27-7.44(7H,m)。
生产实施例16
3,3-双(4-甲基苯基硫基)-N-(苯基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物16)以与生产实施例11中同样的方式合成。
1H-NMR(CDCl3)δppm:2.34(6H,s),2.75(2H,d,J=7.2Hz),4.88(1H,t,J=7.2Hz),6.92(2H,dJ=7.5Hz),7.07(4H,d,J=7.7Hz),7.13(1H,t,J=7.5Hz),7.30(6H,d,J=8.0Hz),7.36(5H,t,J=7.4Hz)。
生产实施例17
合成N-(4-甲基苯基)-3,3-双(3-甲基苯基硫基)硫代丙亚氨酸3-甲基苯基酯(此后称为本发明的化合物17)
向N-(4-甲基苯基)-3-(3-甲基苯基硫基)硫代丙烯基亚氨酸3-甲基苯基酯(0.16g)添加3-甲基苯基硫醇(0.51克),和在80℃搅拌该混合物6小时。向该反应混合物添加乙酸乙酯(50ml),随后用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤。有机层用无水硫酸镁干燥,和在减压下浓缩。残余物通过中等压力制备液相色谱体系(YAMAZEN SI-40B;己烷∶乙酸乙酯=9∶1)分离和纯化,获得本发明的化合物17(0.21克),为黄色油。
1H-NMR(CDCl3)δppm:2.29(6H,s),2.31(3H,s),2.35(3H,s),2.80(2H,d,J=7.1Hz),5.01(1H,t,J=7.1Hz),6.82-7.21(16H,m)。
生产实施例18至21
以下化合物以与生产实施例17中同样的方式合成。
3,3-双(4-甲氧基苯基硫基)-N-(4-甲基苯基)硫代丙亚氨酸4-甲氧苯基酯(此后称为本发明的化合物18)
1H-NMR(CDCl3)δppm:2.35(3H,s),2.68(2H,d,J=7.5Hz),3.81(6H,s),3.83(3H,s),4.68(1H,t,J=7.5Hz),6.78-7.38(16H,m)。
N-(3,4-二甲基苯基)-3,3-双(4-甲基苯基硫基)硫代丙亚氨酸4-甲基苯基酯(此后称为本发明的化合物19)
1H-NMR(CDCl3)δppm:2.24(3H,s),2.26(3H,s),2.33(6H,s),2.36(3H,s),2.74(2H,d,J=7.2Hz),4.90(1H,t,J=7.2Hz),6.46-7.34(15H,m)。
3,3-双(2-萘基硫基)-N-(苯基)硫代丙亚氨酸2-萘基酯(此后称为本发明的化合物20)
1H-NMR(CDCl3)δppm:2.93(2H,d,J=7.3Hz),5.24(1H,t,J=7.3Hz),6.99-7.85(26H,m)。
N-(4-甲基苯基)-3,3-双(1-萘基硫基)硫代丙亚氨酸1-萘基酯(此后称为本发明的化合物21)
1H-NMR(CDCl3)δppm:2.36(3H,s),2.72(2H,d,J=7.2Hz),4.90(1H,t,J=7.2Hz),6.98-8.13(25H,m)。
生产实施例22
合成3,3-双(4-氟苯基硫基)-N-(3,4-二甲基苯基)硫代丙亚氨酸十氢萘-2-基酯(此后称为本发明的化合物22)
正丁基锂在己烷中的1.57M溶液(3.4毫升)在氮气气氛下在-70℃被添加到乙炔基三甲基硅烷(0.70毫升)在的THF中(10毫升)的溶液。混合物在搅拌下温热至0℃,和向其中滴加异硫氰酸3,4-二甲基苯基酯(0.82克)在THF(3ml)中的溶液。混合物进一步温热至室温,和向其中添加甲烷磺酸十氢萘-2-基酯(1.3克)在THF(2ml)中的溶液。在其被加热到回流的时候搅拌该混合物7小时。饱和氯化钠水溶液(25毫升)被添加到该反应混合物,其然后用叔丁基甲基醚(20ml)提取两次。有机层被合并,用饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,和在减压下浓缩。残余物置于Florisil柱(乙酸乙酯∶己烷=1∶30),然后在减压下浓缩。甲醇(10毫升)和碳酸钾(催化量)在室温被添加到所得残余物,且在室温搅拌该混合物2小时。然后,向其中添加4-氟硫代苯酚(0.19毫升),混合物进一步搅拌2小时。反应溶液在减压下浓缩,残余物置于硅胶柱色谱法(乙酸乙酯∶己烷=1∶99),获得本发明的化合物22(0.14克)。
1H-NMR(CDCl3)δ(ppm):1.18-1.92(16H,m),2.18-2.25(6H,m),2.84(1.4H,d,J=8.0Hz),3.04(0.6H,d,J=6.5Hz),3.66(0.7H,br),4.27(0.4H,t,J=6.5Hz),4.40(0.6H,t,J=8.0Hz),4.97(0.3H,br),6.39-6.45(1H,m),6.58-6.65(1H,m),6.92-7.10(6H,m),7.24-7.30(2H,m),7.53(1H,br)。
生产实施例23
3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸十氢萘-2-基酯(此后称为本发明的化合物23)以与生产实施例22中同样的方式合成。
1H-NMR(CDCl3)δ(ppm):1.26-1.90(16H,m),2.82-2.84(1.5H,m),3.03(0.5H,br),3.68(0.8H,br),4.41(1H,br),4.97(0.2H,br),6.66-6.70(1H,m),6.81(1H,br),6.94-7.04(5H,m),7.22-7.34(5H,m),7.53(1H,br)。
生产实施例24
合成3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸环己基酯(此后称为本发明的化合物24)
硫代苯酚(0.74毫升)和三乙胺(催化量)在室温被添加到N-苯基-硫代丙亚氨酸环己基酯(0.56克)在氯仿(50ml)中的溶液,和在相同温度搅拌该混合物6小时。向该反应混合物添加100ml的氯仿,随后用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤。有机层用无水硫酸镁干燥,和在减压下浓缩。残余物置于硅胶柱色谱法(己烷∶乙酸乙酯=30∶1),获得本发明的化合物24(0.69克),为黄色油。
1H-NMR(CDCl3)δppm:0.92-1.78(10H,m),2.60(2H,d,J=7.7Hz),3.47-3.52(1H,m),4.17(1H,t,J=7.7Hz),6.42-7.28(13H,m)。
生产实施例25至28
以下化合物以与生产实施例24中同样的方式合成。
3,3-双(4-氯苯基硫基)-N-(苯基)硫代丙亚氨酸环己基酯(此后称为本发明的化合物25)
1H-NMR(CDCl3)δppm:1.10-1.80(10H,m),2.04-2.10(1H,m),2.77-2.89(1.5H,m),3.06(0.5H,brs),3.76(0.5H,brs),4.51(0.5H,t,J=7.6Hz),6.67-6.79(2H,m),7.06-7.45(11H,m)。
N-苯基-3,3-双(3-三氟甲基苯基硫基)硫代丙亚氨酸环己基酯(此后称为本发明的化合物26)
1H-NMR(CDCl3)δppm:1.10-1.81(10H,m),2.04-2.11(1H,m),2.90-2.97(1.5H,m),3.15(0.5H,brs),3.78(0.5H,brs),4.60(0.5H,t,J=7.7Hz),6.67-6.80(2H,m),7.04-7.71(11H,m)。
3,3-双(4-甲基苯基硫基)-N-(苯基)硫代丙亚氨酸环己基酯(此后称为本发明的化合物27)
1H-NMR(CDCl3)δppm:1.10-1.74(10H,m),2.04-2.10(1H,m),2.33(6H,s),2.73-2.85(1.5H,m),3.05(0.5H,brs),3.75(0.5H,brs),4.52(0.5H,t,J=7.2Hz),6.66-6.82(2H,m),7.01-7.49(11H,m)。
N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸环己基酯(此后称为本发明的化合物28)
1H-NMR(CDCl3)δppm:1.05-1.80(8H,m),2.00-2.12(2H,m),2.80-2.93(2H,m),3.68-3.82(1H,brs),4.55-4.67(1H,brs),6.63-7.60(15H,m)。
生产实施例29
合成3,3-双(乙酰基硫代)-N-(苯基)硫代丙亚氨酸环己基酯(此后称为本发明的化合物29)
硫代乙酸(0.29毫升)在室温被添加到N-(苯基)硫代丙亚氨酸环己基酯(1.0克)在乙酸酐(15毫升)中的溶液,和在相同温度搅拌该混合物1.5小时。反应溶液用饱和碳酸氢钠含水溶液中和,随后用80毫升的叔丁基甲基醚提取两次。有机层被合并,用水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=20∶1),获得本发明的化合物29(0.17克),为黄色油。
1H-NMR(CDCl3)δppm:1.15-2.04(10H,m),2.27(3H,brs),2.34(3H,brs),3.02(1H,brs),3.21(0.5H,brs),3.39(1H,brs),3.75(0.5H,brs),5.20(0.5H,brs),5.76(0.5H,brs),6.71-6.82(2H,m),7.08(1H,brs),7.29-7.33(2H,m)。
生产实施例30至41
以下化合物以与生产实施例24中同样的方式合成。
N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物30)
1H-NMR(CDCl3)δppm:0.81-1.84(11H,m),2.52(0.6H,brs),2.92-2.97(3.4H,m),4.96(0.7H,brs),5.15(0.3H,brs),6.67-7.54(15H,m)。
3,3-双(3-氟苯基硫基)-N-(苯基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物31)
1H-NMR(CDCl3)δppm:0.84-1.84(11H,m),2.56(0.4H,brs),2.94(1.6H,d,J=7.8Hz),2.99(1.6H,d,J=5.8Hz),3.09(0.4H,brs),4.63(0.8H,t,J=7.8Hz),5.23(0.2H,m),6.66-7.36(13H,m)。
3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物32)
1H-NMR(CDCl3)δppm:1.00-1.84(11H,m),2.51(0.47H,brs),2.87(1.53H,d,J=7.5Hz),2.97(2H,brs),4.41(0.77H,t,J=7.5Hz),4.95(0.23H,brs),6.67-7.52(13H,m)。
3,3-双(3-氯苯基硫基)-N-(苯基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物33)
1H-NMR(CDCl3)δppm:0.85-1.88(11H,m),2.57(0.4H,brs),2.94(1.6H,d,J=7.8Hz),2.99(1.6H,d,J=5.8Hz),3.09(0.4H,brs),4.58(0.8H,t,J=7.8Hz),5.21(0.2H,m),6.66-7.49(13H,m)。
3,3-双(4-氯苯基硫基)-N-(苯基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物34)
1H-NMR(CDCl3)δppm:1.01-1.87(11H,m),2.52(0.47H,brs),2.76(1.53H,d,J=7.5Hz),2.83-3.05(2H,m),4.51(0.77H,t,J=7.5Hz),5.09(0.23H,brs),6.65-7.45(13H,m)。
3,3-双(3-溴苯基硫基)-N-(苯基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物35)
1H-NMR(CDCl3)δppm:0.85-1.85(11H,m),2.57(0.4H,brs),2.95(1.6H,d,J=7.3Hz),2.99(1.6H,d,J=6.3Hz),3.09(0.4H,brs),4.55(0.8H,t,J=7.3Hz),5.20(0.2H,m),6.68-7.63(13H,m)。
3,3-双(4-溴苯基硫基)-N-(苯基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物36)
1H-NMR(CDCl3)δppm:0.83-1.84(11H,m),2.52(0.25H,brs),2.90(1.75H,d,J=6.8Hz),2.98(1.75H,d,J=5.3Hz),3.03(0.25H,brs),4.53(0.87H,t,J=6.8Hz),5.10(0.13H,m),6.65-7.44(13H,m)。
3,3-双(3-甲基苯基硫基)-N-(苯基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物37)
1H-NMR(CDCl3)δppm:0.81-1.88(11H,m),2.30(6H,s),2.53(0.44H,brs),2.93(1.56H,d,J=6.8Hz),2.98(1.56H,d,J=5.8Hz),3.07(0.44H,brs),4.62(0.78H,t,J=6.8Hz),5.14(0.22H,m),6.66-7.51(13H,m)。
3,3-双(4-甲基苯基硫基)-N-(苯基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物38)
1H-NMR(CDCl3)δppm:0.98-1.87(11H,m),2.30(6H,s),2.49(0.6H,brs),2.87(1.4H,d,J=8.0Hz),2.85-3.04(2H,m),4.52(0.7H,t,J=7.5Hz),4.98(0.3H,brs),6.68-7.44(13H,m)。
3,3-双(3-甲氧基苯基硫基)-N-(苯基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物39)
1H-NMR(CDCl3)δppm:0.82-1.87(11H,m),2.54(0.4H,brs),2.95(1.6H,d,J=7.1Hz),2.98(1.6H,d,J=6.6Hz),3.10(0.4H,brs),3.77(4.8H,s),3.78(1.2H,s),4.68(0.8H,t,J=7.1Hz),5.20(0.2H,m),6.67-7.52(13H,m)。
3,3-双(4-甲氧基苯基硫基)-N-(苯基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物40)
1H-NMR(CDCl3)δppm:0.78-1.88(11H,m),2.47(0.5H,brs),2.84(1.5H,d,J=5.8Hz),2.98(2H,brs),3.80(6H,s),4.34(0.75H,t,J=5.8Hz),4.80(0.25H,m),6.66-7.51(13H,m)。
3,3-双(4-硝基苯基硫基)-N-(苯基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物41)
1H-NMR(CDCl3)δppm:0.86-1.86(11H,m),2.62(0.5H,brs),3.02(1.5H,d,J=5.3Hz),3.05(1.5H,d,J=6.6Hz),3.20(0.5H,brs),4.92(0.75H,t,J=6.6Hz),5.61(0.25H,m),6.70-8.21(13H,m)。
生产实施例42
合成N-(4-苯基氟)-3,3-双(4-氟苯基硫基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物42)
碳酸钾(0.10克)在室温被添加到N-(4-氟苯基)-3-(三甲硅烷基)硫代丙亚氨酸环己基甲基酯(0.70克)在甲醇(5ml)中的溶液,和在相同温度搅拌该混合物10分钟。然后,在室温向其中添加硫代苯酚(0.38克)在乙酸乙酯(4ml)中的溶液和三乙胺(催化量)。在室温搅拌该混合物1小时,然后在减压下浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=30∶1),获得本发明的化合物42(0.23克),为黄色油。
1H-NMR(CDCl3)δppm:0.78-1.30(6H,m),1.59-1.90(5H,m),2.54(0.6H,brs),2.85(1.4H,d,J=7.8Hz),2.97(1.4H,d,J=6.6Hz),2.96-3.03(0.6H,m),4.39(0.7H,t,J=7.8Hz),4.93(0.3H,brs),6.57-6.78(2H,m),6.90-7.01(6H,m),7.30-7.34(3H,m),7.51(1H,brs)。
生产实施例43至46
以下化合物以与生产实施例42中同样的方式合成。
N-(氯苯基)-3,3-双(4-氟苯基硫基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物43)
1H-NMR(CDCl3)δppm:0.77-1.32(6H,m),1.52-1.86(5H,m),2.47-2.68(0.66H,m),2.85(1.34H,brs),2.95(2H,brs),4.35(0.66H,brs),4.73-4.95(0.34H,m),6.52-7.54(12H,m)。
3,3-双(4-氟苯基硫基)-N-(4-甲基苯基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物44)
1H-NMR(CDCl3)δppm:0.76-1.28(6H,m),1.60-1.87(5H,m),2.33(3H,s),2.52(0.7H,brs),2.87(1.3H,d,J=7.6Hz),2.96-3.03(2H,m),4.40(0.7H,t,J=7.6Hz),4.95(0.3H,brs),6.54-6.72(2H,m),6.93-7.12(6H,m),7.27-7.36(3H,m),7.52(1H,brs)。
3,3-双(4-氟苯基硫基)-N-(3-甲基苯基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物45)
1H-NMR(CDCl3)δppm:0.75-1.28(6H,m),1.58-1.87(5H,m),2.27(2.4H,s),2.30(0.6H,s),2.52(0.4H,brs),2.87(1.6H,d,J=7.1Hz),2.95-3.00(2H,m),4.41(0.8H,t,J=7.1Hz),4.96(0.2H,brs),6.43-6.64(2H,m),6.84-7.28(9H,m),7.52(1H,brs)。
3,3-双(4-氟苯基硫基)-N-(4-硝基苯基)硫代丙亚氨酸环己基甲基酯(此后称为本发明的化合物46)
1H-NMR(CDCl3)δppm:0.96-1.28(6H,m),1.54-1.81(5H,m),2.82-2.89(4H,m),4.52(1H,brs),6.79(2H,d,J=8.8Hz),6.98-7.02(4H,m),7.31-7.41(4H,m),8.15(2H,d,J=8.8Hz)。
生产实施例47
3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸环丙基甲基酯(此后称为本发明的化合物47)以与生产实施例1中同样的方式合成。
1H-NMR(CDCl3)δppm:0.33(2H,br),0.58(2H,br),1.13(1H,br),2.87(2H,d,J=7.6Hz),3.02(2H,d,J=6.8Hz),4.41(1H,br),6.66-6.67(2H,m),6.96-7.05(5H,m),7.24-7.30(6H,m)。
生产实施例48
3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸环戊基甲基酯(此后称为本发明的化合物48)以与生产实施例24中同样的方式合成。
1H-NMR(CDCl3)δppm:1.20-1.88(9H,m),2.82-2.90(2H,m),3.05-3.12(2H,m),4.41(1H,brs),6.62-6.71(2H,m),6.79-7.35(11H,m)。
生产实施例49
3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸3-甲基-1-丙基丁基酯(此后称为本发明的化合物49)以与生产实施例11中同样的方式合成。
1H-NMR(CDCl3)δppm:0.91(9H,s),1.24-1.63(6H,m),1.85(1H,br.s),2.85(2H,d,J=7.1Hz),3.96(1H,brs),4.42(1H,brs),6.65(2H,d,J=6.8Hz),6.92-7.36(11H,m)。
生产实施例50至55
以下化合物以与生产实施例24中同样的方式合成。
N-(4-甲基苯基)-3,3-双(苯基硫基)硫代丙亚氨酸1-甲基丙基酯(此后称为本发明的化合物50)
1H-NMR(CDCl3)δppm:1.01(3H,t,J=7.3Hz),1.37(3H,d,J=6.8Hz),1.57-1.67(2H,m),2.32(3H,s),2.91(2H,d,J=7.5Hz),3.76(1H,brs),4.03(1H,t,J=7.5Hz),6.57-7.54(14H,m)。
N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸烯丙基酯(此后称为本发明的化合物51)
1H-NMR(CDCl3)δppm:2.93(2H,br),3.72(2H,br),4.60(1H,brs),5.12(1H,br),5.28(1H,br),5.95(1H,brs),6.67(2H,br),6.97-7.60(13H,m)。
N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸炔丙基酯(此后称为本发明的化合物52)
1H-NMR(CDCl3)δppm:2.19(1H,brs),2.95(2H,brs),3.83(2H,brs),4.55(1H,brs),6.60-7.60(15H,m)。
3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸苄基酯(此后称为本发明的化合物53)
1H-NMR(CDCl3)δppm:2.80-2.95(2H,m),4.27-4.39(3H,m),6.63-6.74(2H,m),6.98-7.09(4H,m),7.17-7.45(12H,m)。
N-(4-甲基苯基)-3,3-双(苯基硫基)硫代丙亚氨酸4-氯苄基酯(此后称为本发明的化合物54)
1H-NMR(CDCl3)δppm:2.33(3H,s),2.92(2H,d,J=7.8Hz),4.23(2H,s),4.55(1H,t,J=7.8Hz),6.55(2H,d,J=7.8Hz),7.05(2H,d,J=7.8Hz),7.24-7.32(14H,m)。
N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸1-乙氧苯基酯(此后称为本发明的化合物55)
1H-NMR(CDCl3)δppm:1.65-1.80(3H,brs),2.80-2.96(2H,brs),4.50-4.61(1H,brs),4.92-5.07(1H,brs),6.60-6.72(2H,brs),7.00-7.50(18H,m)。
生产实施例56
合成N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸苯基酯(此后称为本发明的化合物56)
硫代苯酚(0.068毫升)在冰冷条件下滴加至N-苯基-3-(苯基硫基)丙烯亚氨酸苯基酯(0.20克)在THF(4ml)中的溶液,和在相同温度搅拌该混合物3小时。向该反应混合物添加50毫升的1N氢氧化钠水溶液,随后用50毫升的乙酸乙酯提取。有机层用水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,和在减压下浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=100∶1至50∶1),获得本发明的化合物56(0.096克),为黄色油。
1H-NMR(CDCl3)δppm:2.97(2H,d,J=8.0Hz),4.94(1H,t,J=8.0Hz),6.72-7.40(20H,m)。
生产实施例57至63
以下化合物以与生产实施例56中同样的方式合成。
3,3-双(4-氟苯基硫基)-N-(4-甲基苯基)丙亚氨酸3-甲基苯基酯(此后称为本发明的化合物57)
1H-NMR(CDCl3)δ(ppm):2.30(3H,s),2.35(3H,s),2.89(2H,d,J=8.0Hz),4.70(1H,t,J=8.0Hz),6.60-6.62(1H,m),6.81-6.83(1H,m),6.94-7.03(8H,m),7.17-7.19(1H,m),7.24-7.28(1H,m),7.33-7.41(4H,m)。
N-(3,4-二甲基苯基)-3,3-双(苯基硫基)丙亚氨酸3-甲基苯基酯(此后称为本发明的化合物58)
1H-NMR(CDCl3)δppm:2.17(2.7H,s),2.18(0.3H,s),2.20(2.7H,s),2.24(0.3H,s),2.26(0.3H,s),2.34(2.7H,s),2.78(0.2H,d,J=7.2Hz),2.97(1.8H,d,J=8.0Hz),4.92(0.9H,t,J=8.0Hz),5.02(0.1H,t,J=7.2Hz),6.46-7.43(17H,m)。
3,3-双(4-氟苯基硫基)-N-(3,4-二甲基苯基)丙亚氨酸3-甲基苯基酯(此后称为本发明的化合物59)
1H-NMR(CDCl3)δppm:2.16(3H,s),2.20(3H,s),2.35(3H,s),2.91(2H,d,J=8.0Hz),4.70(1H,t,J=8.0Hz),6.44-7.44(15H,m)。
N-(3,4-二甲基苯基)-3,3-双(4-甲基苯基硫基)丙亚氨酸3-甲基苯基酯(此后称为本发明的化合物60)
1H-NMR(CDCl3)δppm:2.17(3H,s),2.20(3H,s),2.33(6H,s),2.34(3H,s),2.92(2H,d,J=8.0Hz),4.80(1H,t,J=8.0Hz),6.46-7.32(15H,m)。
N-(3,4-二甲基苯基)-3,3-双(4-硝基苯基硫基)丙亚氨酸3-甲基苯基酯(此后称为本发明的化合物61)
1H-NMR(CDCl3)δppm:2.18(3H,s),2.23(3H,s),2.35(3H,s),3.11(2H,d,J=7.9Hz),5.22(1H,t,J=7.9Hz),6.45-8.20(15H,m)。
3,3-双(苯甲硫基)-N-(3,4-二甲基苯基)丙亚氨酸3-甲基苯基酯(此后称为本发明的化合物62)
1H-NMR(CDCl3)δppm:2.16(6H,s),2.32(3H,s),2.83(2H,d,J=7.9Hz),3.63(2H,d,J=13.3Hz),3.77(2H,d,J=13.3Hz),4.10(1H,t,J=7.9Hz),6.39-7.29(17H,m)。
N-(3,4-二甲基苯基)-3,3-双(2-噻吩基硫基)丙亚氨酸3-甲基苯基酯(此后称为本发明的化合物63)
1H-NMR(CDCl3)δppm:2.16(3H,s),2.18(3H,s),2.35(3H,s),2.93(2H,d,J=7.9Hz),4.51(1H,t,J=7.9Hz),6.45-7.44(13H,m)。
生产实施例64
合成3,3-双(环己基硫基)-N-(3,4-二甲基苯基)丙亚氨酸3-甲基苯基酯(此后称为本发明的化合物64)
环己硫醇(0.46克)和催化量的甲醇钠在甲醇中的28%溶液被添加到3-环己基硫基-N-(3,4-二甲基苯基)丙烯亚氨酸3-甲基苯基酯(0.15克),和在60℃搅拌该混合物6小时,然后在80℃搅拌4小时。向该反应混合物添加乙酸乙酯(100ml),其然后用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤,用无水硫酸钠干燥,然后在减压下浓缩。所得残余物进行中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=19∶1),获得本发明的化合物64(0.14克),为黄色油。
1H-NMR(CDCl3)δppm:1.22-1.98(20H,m),2.17(3H,s),2.18(3H,s),2.35(3H,s),2.78-2.80(2H,m),2.92(2H,d,J=8.0Hz),4.33(1H,t,J=8.0Hz),6.50-7.26(7H,m)。
生产实施例65
合成N-甲基-3,3-双(4-甲基苯基硫基)-N,N′-(二苯基)丙脒(此后称为本发明的化合物65)
4-甲基硫基苯酚(0.12克)在氯仿(5ml)中的溶液在冰冷条件下滴加至N-甲基-N,N′-(二苯基)丙脒(propynamidine)(0.23克)在氯仿(5ml)中的溶液。使混合物在室温静置过夜。反应溶液在减压下浓缩之后,残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=5∶1),获得本发明的化合物65(0.30克),为油状。
1H-NMR(CDCl3)δppm:2.32(6H,s),2.89(2H,d,J=8.2Hz),3.33(3H,s),4.05(1H,t,J=8.2Hz),6.55-7.40(18H,m)。
生产实施例66
合成2-甲基-N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸苯基酯(以下简称本发明的化合物66)
硫代苯酚(0.85毫升)和催化量的28%甲醇钠(甲醇中)在室温滴加至2-甲基-N-苯基-3-(苯基硫基)硫代丙烯基亚氨酸苯基酯(0.30克)在甲醇(5ml)中的溶液,且混合物被加热到回流9小时。向该混合物添加叔丁基甲基醚,其用1N氢氧化钠水溶液,净化水然后饱和氯化钠水溶液洗涤,用无水硫酸钠干燥,然后在减压下浓缩。残余物通过中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=20∶1)分离和纯化,获得本发明的化合物66(0.30克),为黄色油。
1H-NMR(CDCl3)δppm:1.42(3H,d,J=6.8Hz),2.88~2.98(1H,m),4.81(1H,d,J=9.4Hz),6.89(2H,d,J=7.7Hz),7.08~7.42(18H,m)。
生产实施例67
2-乙基-N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸苯基酯(以下简称本发明的化合物67)以与生产实施例66中同样的方式合成。
1H-NMR(CDCl3)δppm:0.950(3H,t,J=7.1Hz),1.82~1.96(1H,m),2.08~2.20(1H,m),2.80~2.88(1H,m),4.74(1H,d,J=8.9Hz),6.85(2H,d,J=7.9Hz),7.08~7.42(18H,m)
生产实施例68
合成2-(双(苯基硫基)甲基)-N-苯基-硫代戊亚氨酸苯基酯(以下简称本发明的化合物68)
硫代苯酚(4.7毫升)和三乙胺(0.32毫升)在室温被添加到2-丙基-N-苯基-3-(苯基硫基)硫代丙烯基亚氨酸苯基酯(0.89克)在甲醇(5ml)中的溶液(5ml),和混合物被加热到回流7小时。向该混合物添加叔丁基甲基醚,其用1N氢氧化钠水溶液,净化水然后饱和氯化钠水溶液洗涤,用无水硫酸钠干燥,然后在减压下浓缩。残余物通过中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=30∶1)分离和纯化,获得本发明的化合物68(0.64克),为黄色油。
1H-NMR(CDCl3)δppm:0.840~0.909(3H,m),1.21~1.50(2H,m),1.82~1.95(1H,m),2.02~2.13(1H,m),2.89~3.00(1H,m),4.70~4.80(1H,m),6.84~7.47(20H,m)。
生产实施例69至72
以下化合物以与生产实施例68中同样的方式合成。
N-苯基-2-双(苯基硫基)甲基)硫代己亚氨酸苯基酯(以下简称本发明的化合物69)
1H-NMR(CDCl3)δppm:0.890(3H,t,J=7.0Hz),1.19~1.42(4H,m),1.83~1.95(1H,m),2.02~2.13(1H,m),2.87~2.94(1H,m),4.74(1H,d,J=8.5Hz),6.88(2H,d,J=7.2Hz),7.08~7.42(18H,m)。
2-甲硫基-N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸苯基酯(以下简称本发明的化合物70)
1H-NMR(CDCl3)δppm:2.11(3H,s),3.49(1H,d,J=10.6Hz),5.04(1H,d,J=10.6Hz),6.87(2H,d,J=7.7Hz),7.11~7.51(18H,m)。
N-苯基-3,3-双(苯基硫基)-2-(3-噻吩基)硫代丙亚氨酸苯基酯(以下简称本发明的化合物71)
1H-NMR(CDCl3)δppm:4.07~4.14(1H,m),5.10~5.17(1H,m),6.78~7.49(23H,m)。
2-氟-N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸苯基酯(以下简称本发明的化合物72)
1H-NMR(CDCl3)δppm:4.82~5.00(2H,m),6.84(2H,d,J=7.5Hz),7.10~7.43(18H,m)。
生产实施例73和74
以下化合物以与生产实施例17中同样的方式合成。
N-(4-甲基苯基)-3,3-双(3-三氟甲基苯基硫基)硫代丙亚氨酸3-三氟甲基苯基酯(以下简称本发明的化合物73)
1H-NMR(CDCl3)δppm:2.34(3H,s),2.79(2H,d,J=7.0Hz),5.11(1H,t,J=7.0Hz),6.30~7.66(16H,m)。
N-(4-甲基苯基)-3,3-双(2-噻吩基硫基)硫代丙亚氨酸2-噻吩基酯(以下简称本发明的化合物74)
1H-NMR(CDCl3)δppm:2.34(3H,s),2.82(2H,d,J=7.1Hz),4.61(1H,t,J=7.1Hz),6.85~7.46(13H,m)。
生产实施例75
3,3-双(苯甲酰基硫基)-N-(苯基)硫代丙亚氨酸环己基酯(以下简称本发明的化合物75)以与生产实施例29中同样的方式合成。
1H-NMR(CDCl3)δppm:1.32~2.34(10H,m),3.26~3.77(3H,m),5.47~6.37(1H,m),6.77~8.17(15H,m)。
生产实施例76
合成2-(苯并[1,3]氧代硫醇-2-基)-N-(苯基)硫代乙亚氨酸环己基甲基酯(以下简称本发明的化合物76)
催化量的碳酸钾被添加到在室温的N-苯基-3-(三甲硅烷基)硫代丙亚氨酸环己基甲基酯(1.0克)在甲醇(20ml)中的溶液,和在相同温度搅拌该混合物30分钟。在减压下浓缩该混合物。残余物在硅胶上过滤(己烷∶乙酸乙酯=10∶1)。在减压下浓缩该滤液。向该残余物在室温添加THF(20ml),然后,向其中添加2-羟基硫基苯酚(0.38克)和三乙胺(0.51毫升)。在室温搅拌该混合物3小时。在叔丁基甲基醚(150ml)被添加到混合物以后,其用1N氢氧化钠水溶液,净化水然后饱和氯化钠水溶液洗涤,用无水硫酸钠干燥,然后在减压下浓缩。残余物通过中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=20∶1)分离和纯化,获得本发明的化合物76(0.18克),为黄色油。
1H-NMR(CDCl3)δppm:0.90~1.85(11H,m),2.73~3.47(4H,m),6.26~7.33(10H,m)。
生产实施例77和78
以下化合物以与生产实施例76中同样的方式合成。
2-([1,3]二硫戊环-2-基)-N-(苯基)硫代乙亚氨酸环己基甲基酯(以下简称本发明的化合物77)
1H-NMR(CDCl3)δppm:0.87~1.84(11H,m),2.74~3.24(8H,m),4.79(0.66H,brs),5.08(0.34H,brs),6.76~7.29(5H,m)。
2-(1,5-二氢-苯并[1,3]二硫杂庚环(dithiepin)-3-基)-N-(苯基)硫代乙亚氨酸环己基甲基酯(以下简称本发明的化合物78)
1H-NMR(CDCl3)δppm:0.86~1.86(11H,m),2.66~3.00(4H,m),3.61~4.14(4.3H,m),4.49(0.7H,brs),6.70~7.29(9H,m)。
生产实施例79
合成2-(2-氧代-1,2,3,5-四氢-2λ4-苯并[e][1,3]二硫杂庚环(dithiepin)-3-基)-N-(苯基)硫代乙亚氨酸环己基甲基酯(以下简称本发明的化合物79)
间氯苯甲酸(0.32克)在氯仿(10毫升)中的溶液在冰冷条件下滴加至2-(1,5-二氢-苯并[1,3]dithepin-3-基)-N-(苯基)硫代乙亚氨酸环己基甲基酯(0.62克)在氯仿(15毫升)中的溶液,和在相同温度搅拌该混合物1小时。向该反应混合物添加氯仿(50ml),其用饱和含水碳酸氢钠溶液,净化水然后饱和氯化钠水溶液洗涤,用无水硫酸钠干燥,然后在减压下浓缩。残余物通过中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=5∶1)分离和纯化,获得本发明的化合物79(0.42克),为浅黄色油。
1H-NMR(CDCl3)δppm:1.01~1.88(11H,m),2.66~3.00(4H,m),3.82~4.30(5H,m),6.68~7.34(9H,m)。
生产实施例80
合成3-(4-氟苯基硫基)-3-甲氧基-N-(苯基)硫代乙亚氨酸环己基甲基酯(以下简称本发明的化合物80)
催化量的碳酸钾被添加到在室温的N-苯基-3-(三甲硅烷基)丙亚氨酸环己基甲基酯(1.0克)在甲醇(20ml)中的溶液,和在相同温度搅拌该混合物30分钟。在减压下浓缩该混合物。残余物在硅胶上过滤(己烷∶乙酸乙酯=10∶1)。在减压下浓缩该滤液。在室温向该残余物添加THF(15毫升),然后,向其中添加甲醇(0.13毫升)和三正丁基膦(0.37毫升)。在室温搅拌该混合物3小时。残余物通过中等压力制备液相色谱(YamazenSI-40B,己烷∶乙酸乙酯=20∶1)分离和纯化,获得主要产品(0.14克)。在室温向该产物添加THF(5ml),然后向其中添加4-氟硫代苯酚。在室温搅拌该混合物3小时,然后在减压下浓缩。残余物通过中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=20∶1)分离和纯化,获得本发明的化合物80(0.12克),为浅黄色油。
1H-NMR(CDCl3)δppm:0.87~1.81(11H,m),2.49~2.93(4H,m),3.42(3H,s),4.76(1H,s),6.61~7.51(9H,m)。
生产实施例81
合成3-(4-氟苯基硫基)-3-糠基氧基-N-(苯基)硫代乙亚氨酸环己基甲基酯(以下简称本发明的化合物81)
催化量的碳酸钾被添加到在室温的N-苯基-3-(三甲硅烷基)硫代丙亚氨酸环己基甲基酯(1.0克)在甲醇(20ml)中的溶液,和在相同温度搅拌该混合物30分钟。在减压下浓缩该混合物。残余物在硅胶上过滤(己烷∶乙酸乙酯=10∶1)。在减压下浓缩该滤液。向该残余物在室温添加THF(15毫升),然后,向其中添加呋喃甲醇(0.26毫升)和三正丁基膦(0.37毫升)。在室温搅拌该混合物3小时。残余物通过中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=20∶1)分离和纯化,获得主要产品(0.30克)。向该产物添加THF(10毫升),然后在冰冷条件下向其中添加4-氟硫代苯酚(0.092毫升)。在相同温度搅拌该混合物2小时,和在室温搅拌8小时,然后在减压下浓缩,获得本发明的化合物81(0.44克),为红色油。
1H-NMR(CDCl3)δppm:0.74~1.85(11H,m),2.47~2.93(4H,m),4.34~5.32(3H,m),6.25~7.58(12H,m)。
生产实施例82
3-双(4-氟苯基硫基)-N-(4-甲氧苯基)硫代丙亚氨酸环己基甲基酯(以下简称本发明的化合物82)以与生产实施例42中同样的方式合成。
1H-NMR(CDCl3)δppm:0.87~1.87(11H,m),2.52(0.6H,d,J=6.8Hz),2.88(1.4H,d,J=8.0Hz),2.97~3.02(2H,m),3.80(3H,s),4.41(0.7H,t,J=8.0Hz),4.95(0.3H,t,J=6.8Hz),6.57~7.51(12H,m)。
生产实施例83
合成N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸丁基酯(以下简称本发明的化合物83)
碘代丁烷(44mg)被添加到N-苯基-3,3-双(苯基硫基)丙硫羧酰胺(76毫克)在无水DMF(2ml)中的溶液。在室温搅拌该混合物5分钟。在碳酸钾(30毫克)添加以后,在室温搅拌该混合物2.5小时。向该混合物添加叔丁基甲基醚(50ml),其用饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,和在减压下浓缩。残余物通过中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=30∶1)分离和纯化,获得本发明的化合物83(51毫克),为无色的油。
1H-NMR(CDCl3)δppm:0.84~1.69(7H,m),2.63(0.4H,brs),2.92(1.6H,d,J=7.5Hz),3.05(2H,m),4.62(0.8H,t,J=7.5Hz),5.16(0.2H,brs),6.76~7.54(15H,m)。
生产实施例84至95
以下化合物以与生产实施例83同样的方法合成。
N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸1-甲基丙基酯(以下简称本发明的化合物84)
1H-NMR(CDCl3)δppm:1.02(3H,t,J=6.8Hz),1.37(3H,d,J=5.8Hz),1.66~1.73(2H,m),2.91(1.6H,d,J=7.3Hz),3.12(0.4H,brs),3.73~3.82(1H,m),4.63(0.8H,t,J=7.3Hz),5.13(0.2H,brs),6.68~7.54(15H,m)。
N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸2-甲基丙基酯(以下简称本发明的化合物85)
1H-NMR(CDCl3)δppm:0.86(1.2H,brs),1.01(2.4H,s),1.02(2.4H,s),1.61(0.2H,brs),1.88~2.03(0.8H,brs),2.50(0.4H,brs),2.94(1.6H,d,J=7.5Hz),2.98(1.6H,d,J=6.5Hz),3.07(0.4H,brs),4.64(0.8H,t,J=7.5Hz),5.16(0.2H,brs),6.66~7.54(15H,m)。
N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸1-甲基戊基酯(以下简称本发明的化合物86)
1H-NMR(CDCl3)δppm:0.87~1.83(12H,m),2.90(1.44H,d,J=7.5Hz),3.12(0.56H,brs),3.80~3.86(1H,m),4.63(0.72H,t,J=7.5Hz),5.14(0.28H,brs),6.68~7.54(15H,m)。
3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸1-甲基戊基酯(以下简称本发明的化合物87)
1H-NMR(CDCl3)δppm:0.88~1.69(12H,m),2.84(1.62H,d,J=7.5Hz),3.05(0.38H,brs),3.81~3.84(1H,m),4.41(0.81H,t,J=7.5Hz),4.95(0.19H,brs),6.66~7.52(13H,m)。
N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸己基酯(以下简称本发明的化合物88)
1H-NMR(CDCl3)δppm:0.83~1.68(11H,m),2.62(0.46H,brs),2.92(1.54H,d,J=7.3Hz),3.04(2H,t,J=6.5Hz),4.62(0.77H,t,J=7.3Hz),5.15(0.23H,brs),6.67~7.54(15H,m)。
3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸己基酯(以下简称本发明的化合物89)
1H-NMR(CDCl3)δppm:0.85~1.68(11H,m),2.62(0.44H,brs),2.87(1.56H,d,J=7.2Hz),3.03~3.07(2H,m),4.40(0.78H,t,J=7.2Hz),4.97(0.22H,brs),6.65~7.52(13H,m)。
N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸环戊基酯(以下简称本发明的化合物90)
1H-NMR(CDCl3)δppm:1.45~2.15(8H,m),2.90(1.28H,d,J=6.8Hz),3.14(0.72H,brs),3.25(0.36H,brs),3.93(0.64H,brs),4.62(0.64H,t,J=6.8Hz),5.18(0.36H,brs),6.68~7.54(15H,m)。
3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸环戊基酯(以下简称本发明的化合物91)
1H-NMR(CDCl3)δppm:1.48~2.20(8H,m),2.84(1.34H,d,J=7.5Hz),3.08(0.66H,brs),3.27(0.33H,brs),3.92~3.96(0.67H,m),4.39(0.67H,t,J=7.5Hz),4.99(0.33H,brs),6.68~7.54(13H,m)。
N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸环戊基甲基酯(以下简称本发明的化合物92)
1H-NMR(CDCl3)δppm:1.06~1.82(8H,m),2.15~2.22(1H,m),2.61(0.40H,brs),2.93(1.6H,d,J=7.5Hz),3.07~3.10(2H,m),4.63(0.80H,t,J=7.5Hz),5.15(0.20H,brs),6.66~7.54(15H,m)。
3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸(四氢呋喃-3-基)甲基酯(以下简称本发明的化合物93)
1H-NMR(CDCl3)δppm:1.71~1.74(1H,m),2.06~2.13(1H,m),2.59~2.67(1H,m),2.87(1.78H,d,J=7.5Hz),3.02(0.22H,brs),3.07~3.21(2H,m),3.35~3.58(1H,m),3.71~3.80(1H,m),3.86~3.93(2H,m),4.38(0.89H,t,J=7.5Hz),4.95(0.11H,brs),6.65~7.52(13H,m)。
3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸3,3,3-三氟丙基酯(以下简称本发明的化合物94)
1H-NMR(CDCl3)δppm:2.26(2H,m),2.88(2H,d,J=8.0Hz),3.20(2H,t,J=7.6Hz),4.34(1H,t,J=8.0Hz),6.65~7.48(13H,m)。
3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸(三甲硅烷基)甲基酯(以下简称本发明的化合物95)
1H-NMR(CDCl3)δppm:0.01(1.62H,brs),0.14(7.38H,s),2.26(2H,s),2.90(1.62H,d,J=7.6Hz),3.07(0.38H,brs),4.38(0.81H,t,J=7.6Hz),4.95(0.19H,brs),6.65~7.50(13H,m)。
生产实施例96
合成N-苯基-3,3-双(苯基硫基)硫代丙亚氨酸三氟甲基酯(以下简称本发明的化合物96)
S-三氟甲基-3,7-二硝基苯并噻吩鎓三氟甲烷磺酸盐(MEC-12)(0.13克)在氮气气氛下在冰冷条件下被添加到N-苯基-3,3-双(苯基硫基)丙硫羧酰胺(0.10克)在无水DMF(2毫升)中的溶液。在氮气气氛下在冰冷条件下搅拌该混合物10分钟。向该混合物添加碳酸钾(36毫克)。在其慢慢地温热至室温的时候在氮气气氛下搅拌该混合物6.5小时。向该反应混合物添加叔丁基甲基醚(50ml),其用饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物通过中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=30∶1)分离和纯化,获得本发明的化合物96(10毫克),为黄色油。
1H-NMR(CDCl3)δppm:3.33(2H,d,J=5.4Hz),5.12(1H,t,J=5.4Hz),6.76~7.52(15H,m)。
生产实施例97
合成3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸(2-氯噻唑-5-基)甲基酯(以下简称本发明的化合物97)
2-氯-5-(氯甲基)噻唑(0.24克)被添加到3,3-双(4-氟苯基硫基)-N-(苯基)丙硫羧酰胺(0.30克)在无水DMF(1毫升)中的溶液。在室温搅拌该混合物5分钟。向该混合物添加碳酸钾(99毫克)。在室温搅拌该混合物2.5小时。向该反应混合物添加叔丁基甲基醚(50ml),其用饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物通过中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=88∶12)分离和纯化,获得本发明的化合物97(0.25克),为黄色油。
1H-NMR(CDCl3)δppm:2.88(1.86H,d,J=8.0Hz),3.15(0.14H,d,J=7.2Hz),4.34(1.86H,s),4.55(0.14H,s),4.29(0.93H,t,J=8.0Hz),5.09(0.07H,t,J=7.2Hz),6.71~8.38(14H,m)。
生产实施例98
3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸(2-噻吩基)甲基酯(以下简称本发明的化合物98)以和生产实施例97同样的方法合成。
1H-NMR(CDCl3)δppm:2.87(1.78H,d,J=7.7Hz),3.02(0.22H,brs),4.34(0.89H,t,J=7.7Hz),4.51(1.78H,s),4.70(0.22H,s),4.93(0.11H,brs),6.72~7.50(16H,m)。
生产实施例99
合成3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸(3-噻吩基)甲基酯(以下简称本发明的化合物99)
亚硫酰氯(0.29毫升)被添加到(3-噻吩基)甲醇(0.23克)在无水THF(2毫升)中的溶液。在50℃搅拌该混合物2小时。在减压下浓缩反应混合物。向该残余物添加无水DMF(3ml)。然后,在室温向其中添加3,3-双(4-氟苯基硫基)-N-(苯基)丙硫羧酰胺(0.84克)在无水DMF(1毫升)中的溶液,碘化钠(0.30克)和碳酸钾(0.28克),且在室温搅拌该混合物3小时。向该反应混合物添加叔丁基甲基醚(50ml),其用饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物通过中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=92∶8)分离和纯化,获得本发明的化合物99(0.46克),为黄色油。
1H-NMR(CDCl3)δppm:2.86(1.62H,d,J=7.8Hz),2.99(0.38H,brs),4.35(0.81H,t,J=7.8Hz),4.29(1.62H,s),4.51(0.38H,s),4.94(0.19H,brs),6.66~7.46(16H,m)。
生产实施例100
3,3-双(4-氟苯基硫基)-N-(苯基)硫代丙亚氨酸(2-氯吡啶-5-基)甲基酯(以下简称本发明的化合物100)以和生产实施例99同样的方法合成。
1H-NMR(CDCl3)δppm:2.86(2H,d,J=8.0Hz),4.22(2H,s),4.28(1H,t,J=8.0Hz),6.61~8.43(16H,m)。
生产实施例101至112
以下化合物以与生产实施例56中同样的方式合成。
N-(5-茚满基)-3,3-双(苯基硫基)丙亚氨酸苯基酯(以下简称本发明的化合物101)
1H-NMR(CDCl3)δppm:2.01~2.08(2H,m),2.79~2.86(4H,m),3.00(2H,d,J=8.0Hz),4.94(1H,t,J=8.0Hz),6.50~7.40(18H,m)。
3,3-双(4-氟苯基硫基)-N-(5-茚满基)丙亚氨酸苯基酯(以下简称本发明的化合物102)
1H-NMR(CDCl3)δppm:2.02~2.09(2H,m),2.79~2.87(4H,m),2.93(2H,d,J=8.0Hz),4.72(1H,t,J=8.0Hz),6.46~7.41(16H,m)。
N-(5-茚满基)-3,3-双(3-甲基苯基硫基)丙亚氨酸苯基酯(以下简称本发明的化合物103)
1H-NMR(CDCl3)δppm:2.00~2.07(2H,m),2.27(6H,m),2.79~2.85(4H,m),3.01(2H,d,J=8.0Hz),4.95(1H,t,J=8.0Hz),6.49~7.36(16H,m)。
N-(5-茚满基)-3,3-双(4-甲氧基苯基硫基)丙亚氨酸苯基酯(以下简称本发明的化合物104)
1H-NMR(CDCl3)δppm:2.01~2.08(2H,m),2.79~2.86(4H,m),2.91(2H,d,J=8.0Hz),3.78(6H,m),4.64(1H,t,J=8.0Hz),6.48~7.38(16H,m)。
N-(5-茚满基)-3,3-双(3-三氟甲基苯基硫基)丙亚氨酸苯基酯(以下简称本发明的化合物105)
1H-NMR(CDCl3)δppm:2.01~2.09(2H,m),2.79~2.86(4H,m),3.05(2H,d,J=7.9Hz),5.02(1H,t,J=7.9Hz),6.48~7.64(16H,m)。
N-(5-茚满基)-3,3-双(2-噻吩基硫基)丙亚氨酸苯基酯(以下简称本发明的化合物106)
1H-NMR(CDCl3)δppm:1.99~2.06(2H,m),2.78~2.83(4H,m),2.95(2H,d,J=7.7Hz),4.53(1H,t,J=7.7Hz),6.47~7.38(14H,m)。
N-(5-茚满基)-3,3-双(2-萘基硫基)丙亚氨酸苯基酯(以下简称本发明的化合物107)
1H-NMR(CDCl3)δppm:1.97~2.04(2H,m),2.72~2.82(4H,m),3.10(2H,d,J=7.9Hz),5.15(1H,t,J=7.9Hz),6.50~7.88(22H,m)。
N-(4-联苯基)-3,3-双(苯基硫基)丙亚氨酸苯基酯(以下简称本发明的化合物108)
1H-NMR(CDCl3)δppm:3.02(2H,d,J=7.8Hz),4.96(1H,t,J=7.8Hz),6.79~7.61(24H,m)。
3,3-双(3-甲基苯基硫基)-N-(4-联苯基)丙亚氨酸苯基酯(以下简称本发明的化合物109)
1H-NMR(CDCl3)δppm:2.27(6H,s),3.03(2H,d,J=8.0Hz),4.97(1H,t,J=8.0Hz),6.80~7.61(22H,m)。
3,3-双(4-氟苯基硫基)-N-(4-联苯基)丙亚氨酸苯基酯(以下简称本发明的化合物110)
1H-NMR(CDCl3)δppm:2.96(2H,d,J=8.0Hz),4.74(1H,t,J=8.0Hz),6.78~7.61(22H,m)。
N-(4-联苯基)-3,3-双(3-三氟甲基苯基硫基)丙亚氨酸苯基酯(以下简称本发明的化合物111)
1H-NMR(CDCl3)δppm:3.07(2H,d,J=7.8Hz),5.04(1H,t,J=7.8Hz),6.73~8.07(22H,m)。
N-(4-联苯基)-3,3-双(2-噻吩基硫基)丙亚氨酸苯基酯(以下简称本发明的化合物112)
1H-NMR(CDCl3)δppm:2.98(2H,d,J=8.0Hz),4.55(1H,t,J=8.0Hz),6.78~7.61(20H,m)。
生产实施例113
合成N-(3,4-二甲基苯基)-3-苯磺酰基-3-苯基硫基-丙亚氨酸3-甲基苯基酯(以下简称本发明的化合物113)
硫代苯酚(0.062毫升)在冰冷条件下被添加到N-(3,4-二甲基苯基)-3-苯磺酰基-丙烯亚氨酸3-甲基苯基酯(0.30克)在THF(10毫升)中的溶液,和搅拌该混合物1小时。在减压下浓缩该混合物。残余物通过硅胶柱色谱法(己烷∶乙酸乙酯=10∶1)分离和纯化,获得本发明的化合物113(0.10克),为黄色油。
1H-NMR(CDCl3)δppm:2.18(3H,s),2.20(3H,s),2.32(3H,s),2.99~3.06(1H,m),3.30~3.34(1H,m),4.84~4.88(1H,m),6.45~6.50(2H,m),6.89~7.58(13H,m),7.80~7.82(2H,m)。
生产实施例114
合成3,3-双(苄氧基)-N-(3,4-二甲基苯基)丙亚氨酸3-甲基苯基酯(以下简称本发明的化合物114)
3-苄氧基-N-(3,4-二甲基苯基)丙烯亚氨酸3-甲基苯基酯(0.72克)在冰冷条件下在氮气气氛下被添加到10%披钯碳(0.20克)在乙酸乙酯(50ml)中的溶液。在氢气氛下搅拌该混合物1.5小时。不溶物质滤出,和在减压下浓缩该滤液。残余物通过硅胶柱色谱法(己烷∶乙酸乙酯=20∶1)分离和纯化,获得本发明的化合物114(0.12克),为浅黄色油。
1H-NMR(CDCl3)δppm:2.13(3H,s),2.17(3H,s),2.32(3H,s),2.89(2H,d,J=6.0Hz),4.53~4.66(4H,m),5.30(1H,t,J=6.0Hz),6.47~6.51(2H,m),6.89~6.96(4H,m),7.19~7.34(11H,m)。
生产实施例115
合成N-(4-联苯基)-3,3-双(3-三氟甲基苯基硫基)丙亚氨酸乙基酯(以下简称本发明的化合物115)
3-三氟甲基苯基硫醇(0.10毫克)在THF(0.5毫升)中的溶液在冰冷条件下被添加到N-(4-联苯基)-3-(3-三氟甲基苯基硫基)丙烯亚氨酸苯基酯和N-(4-联苯基)-3-(3-三氟甲基苯基硫基)丙烯亚氨酸乙基酯的混合物(PhO形式∶EtO形式=79∶21)(0.27毫升)在THF(3ml)中的溶液。搅拌该混合物10.5小时,同时其慢慢地温热至室温。使混合物静置过夜。向该反应混合物添加乙酸乙酯(50ml),其用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物通过中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=40∶1至30∶1)分离和纯化,获得N-(4-联苯基)-3,3-二(3-三氟甲基苯基硫基)丙亚氨酸苯基酯(0.12克)和本发明的化合物115(36毫克),为黄色油。
1H-NMR(CDCl3)δppm:1.34(3H,d,J=7.0Hz),2.86(2H,d,J=7.8Hz),4.27(2H,t,J=7.0Hz),4.84(1H,t,J=7.8Hz),6.59~7.71(17H,m)。
本发明的化合物1至115的结构式显示如下:
其中Y0,Z,X,X0,和E是下表4所示组合的任一种。
[表4]
以下参考生产实施例显示用于产生本发明的化合物的原料化合物的生产。
参考生产实施例1
生产N-(5-茚满基)-3-(苯基硫基)硫代丙烯基亚氨酸苯基酯
亚硫酰氯(0.75毫升)和DMF(催化量)在室温被添加到N-(5-茚满基)-3(苯基硫基)丙烯酰胺(1.21克)在甲苯(50ml)中的溶液,和在70℃搅拌该混合物2小时。在减压下浓缩反应混合物。向该残余物添加THF(40ml),然后在冰冷条件下向其中添加苯硫酚钠盐在THF中的溶液(0.62摩尔/升,10毫升)。在室温搅拌该混合物2小时,然后通过添加1N氢氧化钠水溶液碱化,随后用乙酸乙酯(250ml)提取。有机层用水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,和在减压下浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=100∶1至50∶1),获得N-(5-茚满基)-3-(苯基硫基)硫代丙烯基亚氨酸苯基酯(Z-异构体:0.27克,E-异构体:0.94克)。
Z-异构体:
1H-NMR(CDCl3)δppm:2.03-2.06(2H,m),2.85-2.92(4H,m),5.79(1H,d,J=10.1Hz),6.72-7.53(14H,m)
E-异构体:
1H-NMR(CDCl3)δppm:1.93-2.03(2H,m),2.72-2.90(4H,m),5.70(1H,d,J=14.7Hz),6.70-7.40(13H,m),7.53(1H,d,J=14.7Hz)。
参考生产实施例2-(1)
生产N-(4-甲基苯基)-3-(3-甲基苯基硫基)硫代丙烯基亚氨酸3-甲基苯基酯
亚硫酰氯(0.54毫升)和DMF(催化量)被添加到3-(3-甲基苯基)-N-(4-甲基苯基)丙烯酰胺(E/Z=4/1)(0.84克)在甲苯(15毫升)中的溶液,和在70℃搅拌该混合物1小时。在减压下浓缩该混合物。向该残余物添加无水THF(15毫升)。氢化钠(60%)(0.21克)在氮气气氛下在冰冷条件下被添加到3-甲硫醇(0.44克)在无水THF(5ml)中的溶液(5ml),和在氮气气氛下在室温搅拌该混合物30分钟。反应混合物在冰冷条件下被添加到以上所述的反应混合物,且在室温搅拌该混合物2小时。向该反应混合物添加乙酸乙酯(150ml),其用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物通过中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=30∶1)分离和纯化,获得N-(4-甲基苯基)-3-(3-甲基苯基硫基)硫代丙烯基亚氨酸3-甲基苯基酯(0.75克),为黄色油。
1H-NMR(CDCl3)δppm:2.29(4.2H,s),2.31(0.9H,s),2.32(2.1H,s),2.34(0.9H,s),2.36(0.9H,s),5.67(0.7H,d,J=14.7Hz),5.81(0.3H,d,J=10.1Hz),6.58-7.47(12.3H,m),7.53(0.7H,d,J=14.7Hz)。
参考生产实施例2-(2)至(5)
以下化合物以和参考生产实施例2-(1)同样的方法合成。
N-(4-甲基苯基)-3-(4-甲氧基苯基硫基)硫代丙烯基亚氨酸4-甲氧基苯基酯
1H-NMR(CDCl3)δppm:2.33(2.5H,s),2.36(0.5H,s),3.79(0.5H,s),3.82(0.5H,s),3.82(2.5H,s),3.84(2.5H,s),5.39(0.83H,d,J=14.5Hz),5.74(0.17H,d,J=10.1Hz),6.52-7.43(12.17H,m),7.48(0.83H,d,J=14.5Hz)。
N-(4-甲基苯基)-3-(1-萘基硫基)硫代丙烯基亚氨酸1-萘基酯
1H-NMR(CDCl3)δppm:2.34(2.4H,s),2.41(0.6H,s),5.01(0.79H,d,J=14.5Hz),5.56(0.21H,d,J=10.1Hz),6.22-8.38(19H,m)。
N-(4-甲基苯基)-3-(3-三氟甲基苯基硫基)硫代丙烯基亚氨酸3-三氟甲基苯基酯
1H-NMR(CDCl3)δppm:2.28(0.42H,s),2.32(1.20H,s),2.36(1.38H,s),5.59(0.46H,d,J=14.7Hz),5.83(0.54H,d,J=10.1Hz),6.56~7.83(13H,m)。
N-(4-甲基苯基)-3-(2-噻吩基硫基)硫代丙烯基亚氨酸2-噻吩基酯
1H-NMR(CDCl3)δppm:2.32(1.71H,s),2.34(1.29H,s),5.59(0.43H,d,J=14.5Hz),5.83(0.57H,d,J=9.9Hz),6.74~7.47(11H,m)。
参考生产实施例3-(1)
生产2-甲基-N-苯基-3-(苯基硫基)硫代丙烯基亚氨酸苯基酯
甲苯(4ml)被添加到2-甲基-N-苯基-3-(苯基硫基)丙烯酰胺(0.80克)和五氯化磷(0.62克)的混合物,且在室温搅拌该混合物4小时。在减压下浓缩该混合物。向浓缩物添加DMF(35mL),然后,向其中滴加苯硫酚钠盐(793毫克)。在室温搅拌该混合物2小时。向该反应混合物添加叔丁基甲基醚,然后添加1N氢氧化钠水溶液,由此该溶液被分离。有机层用水洗涤三次,干燥然后浓缩。残余物进行硅胶柱色谱法(己烷/乙酸乙酯=20/1),获得2-甲基-N-苯基-3-(苯基硫基)硫代丙烯基亚氨酸苯基酯(0.4克)。
1H-NMR(CDCl3)δppm:1.56(3H,s),6.79(1H,s),6.81(1H,s),7.00~7.39(15H,m)。
参考生产实施例3-(2)至(4)
以下化合物以和参考生产实施例3-(1)中同样的方式合成。
2-甲硫基-N-苯基-3-(苯基硫基)硫代丙烯基亚氨酸苯基酯
1H-NMR(CDCl3)δppm:2.25(0.7H,s),2.45(2.3H,s),6.76~7.71(16H,m)。
N-苯基-3-(苯基硫基)-2-(3-噻吩基)硫代丙烯基亚氨酸苯基酯
1H-NMR(CDCl3)δppm:6.87~7.62(19H,m)。
2-氟-N-苯基-3-(苯基硫基)硫代丙烯基亚氨酸苯基酯
1H-NMR(CDCl3)δppm:6.84(2H,d,J=7.5Hz),6.91(1H,d,J=32.4Hz),7.08(1H,t,J=7.5Hz),7.16~7.32(12H,m)。
参考生产实施例4-(1)
生产2-乙基-N-苯基-3-(苯基硫基)硫代丙烯基亚氨酸苯基酯
甲苯(20ml)被添加到2-乙基-N-苯基-3-(苯基硫基)丙烯酰胺(3.68克),然后向其中添加亚硫酰氯(1.9毫升)和DMF(10毫克)。回流加热搅拌该混合物1小时。在减压下浓缩该混合物。向浓缩物添加DMF(35mL),然后,在冰冷条件下向其中滴加苯硫酚钠盐(2.0克)。在室温搅拌该混合物1小时。向该反应混合物添加叔丁基甲基醚,然后添加1N氢氧化钠水溶液,由此该溶液被分离。有机层用水洗涤三次,干燥然后浓缩。残余物进行硅胶柱色谱法(己烷/乙酸乙酯=20/1),获得2-乙基-N-苯基-3-(苯基硫基)硫代丙烯基亚氨酸苯基酯(2.03克)。
1H-NMR(CDCl3)δppm:1.17(3H,t,J=7.1Hz),2.51~2.67(2H,br),6.80(2H,d,J=7.3Hz),7.00~7.33(14H,m)。
参考生产实施例4-(2)和(3)
以下化合物以和参考生产实施例4-(1)中同样的方式合成。
2-丙基-N-苯基-3-(苯基硫基)硫代丙烯基亚氨酸苯基酯
1H-NMR(CDCl3)δppm:0.99(3H,t,J=7.2Hz),1.57~1.70(2H,br),2.49-2.61(2H,br),6.76~6.84(2H,br),7.00-7.38(14H,br)。
2-丁基-N-苯基-3-(苯基硫基)硫代丙烯基亚氨酸苯基酯
1H-NMR(CDCl3)δppm:0.96(3H,t,J=7.2Hz),1.32~1.45(2H,m),1.51~1.63(2H,m),2.49-2.63(2H,m),6.76~6.83(2H,m),7.01-7.35(14H,m)。
参考生产实施例5
生产N-(5-茚满基)-3-(苯基硫基)丙烯亚氨酸苯基酯
亚硫酰氯(1.53毫升)和DMF(催化量)被添加到N-(5-茚满基)-3-(苯基硫基)丙烯酰胺(2.47克)在甲苯(80ml)中的溶液,和在70℃搅拌该混合物1小时。在减压下浓缩反应混合物。向该残余物添加无水THF(40ml)。在氮气气氛下在冰冷条件下向苯酚(1.18克)在无水THF(20ml)中的溶液添加氢化钠(60%)(0.769克),然后在氮气气氛下在室温搅拌30分钟。反应混合物在冰冷条件下被添加到以上所述的反应混合物,且在室温搅拌该混合物2.5小时。向该反应混合物添加乙酸乙酯(200ml),其用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物通过硅胶柱色谱法(己烷∶乙酸乙酯=5∶1)分离和纯化,获得N-(5-茚满基)-3-(苯基硫基)丙烯亚氨酸苯基酯(2.56克),为橙色油。
1H-NMR(CDCl3)δppm:2.00~2.08(2H,m),2.80~2.85(4H,m),5.90(0.43H,d,J=10.9Hz),5.99(0.57H,d,J=15.2Hz),6.49~7.50(13.43H,m),7.67(0.57H,d,J=15.2Hz)。
参考生产实施例6
生产N-(4-联苯基)-3-(苯基硫基)丙烯亚氨酸苯基酯
亚硫酰氯(5.85毫升)和DMF(催化量)被添加到N-(4-联苯基)-3-(苯基硫基)丙烯酰胺(10.64克)在甲苯(400毫升)中的溶液,和在70℃搅拌该混合物3小时。在减压下浓缩反应混合物。向该残余物添加无水THF(320毫升)。在氮气气氛下在冰冷条件下向苯酚(4.53克)在无水THF(80ml)中的溶液中添加氢化钠(60%)(2.95克),然后在室温在氮气气氛下搅拌30分钟。反应混合物在冰冷条件下被添加到以上所述的反应混合物,且在室温搅拌该混合物2小时。向该反应混合物添加1N氢氧化钠水溶液和饱和氯化钠水溶液,随后用乙酸乙酯(500ml)提取三次。在减压下浓缩提取物。向该残余物添加乙酸乙酯(200ml),其用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物通过硅胶柱色谱法(己烷∶乙酸乙酯=5∶1)分离和纯化,获得N-(4-联苯基)-3-(苯基硫基)丙烯亚氨酸苯基酯(5.91克),为黄色油。
1H-NMR(CDCl3)δppm:5.93(1H,d,J=15.1Hz),6.78~7.57(19H,m),7.72(1H,d,J=15.1Hz)。
参考生产实施例7
生产N-(3,4-二甲基苯基)-3-(4-硝基苯基硫基)丙烯亚氨酸3-甲基苯基酯
向N-硝基硫苯酚(0.31克)在DMF(10毫升)中的溶液添加60%氢化钠(0.12克),且在室温搅拌该混合物30分钟。反应混合物在冰冷条件下滴加至N-(3,4-二甲基苯基)-3-(苯磺酰基)丙烯亚氨酸3-甲基苯基酯(0.81克)在无水DMF(10毫升)中的溶液。在室温搅拌该混合物1.5小时。向该反应混合物添加叔丁基甲基醚(150ml),其用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤。有机层用无水硫酸镁干燥,然后在减压下浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=87∶13),获得N-(3,4-二甲基苯基)-3-(4-硝基苯基硫基)丙烯亚氨酸3-甲基苯基酯(0.52克),为黄色油。
1H-NMR(CDCl3)δppm:2.20(3H,s),2.36(6H,s),6.21(1H,d,J=15.2Hz),6.50~7.50(9H,m),7.65(1H,d,J=15.2Hz),8.17(2H,m)。
参考生产实施例8-(1)
生产3-(4-氟苯基硫基)-N-(5-茚满基)丙烯亚氨酸苯基酯
向4-氟硫代苯酚(0.22克)在DMF(6毫升)中的溶液添加60%氢化钠(84毫克),且在室温在氮气气氛下搅拌该混合物30分钟。反应混合物在冰冷条件下被添加到N-(5-茚满基)-3-(苯磺酰基)丙烯亚氨酸苯基酯(0.65克)在无水DMF(3ml)中的溶液。在室温搅拌该混合物2小时。向该反应混合物添加叔丁基甲基醚(50ml),其用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物通过中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=19∶1)分离和纯化,获得3-(4-氟苯基硫基)-N-(5-茚满基)丙烯亚氨酸苯基酯(0.16g)。
1H-NMR(CDCl3)δppm:1.95~2.21(2H,m),2.79~2.89(4H,m),5.81(1H,m),6.46~8.18(13H,m)。
参考生产实施例8-(2)至(6)
以下化合物以和参考生产实施例8-(1)同样的方式合成。
N-(5-茚满基)-3-(3-甲基苯基硫基)丙烯亚氨酸苯基酯
1H-NMR(CDCl3)δppm:2.01~2.09(2H,m),2.32(3H,s),2.81~2.85(4H,m),5.97(1H,d,J=15.2Hz),6.49~7.44(12H,m),7.67(1H,d,J=15.2Hz)。
N-(5-茚满基)-3-(4-甲氧基苯基硫基)丙烯亚氨酸苯基酯
1H-NMR(CDCl3)δppm:2.00~2.08(2H,m),2.79~2.84(4H,m),3.78(3H,m),5.80(1H,d,J=15.1Hz),6.46~7.40(12H,m),7.59(1H,d,J=15.1Hz)。
N-(5-茚满基)-3-(3-三氟甲基苯基硫基)丙烯亚氨酸苯基酯
1H-NMR(CDCl3)δppm:2.01~2.08(2H,m),2.80~2.85(4H,m),5.80(0.20H,d,J=15.0Hz),6.02(0.75H,d,J=15.2Hz),6.13(0.05H,d,J=9.9Hz),6.48~7.80(12.80H,m),8.00(0.20H,d,J=15.0Hz)。
N-(5-茚满基)-3-(2-噻吩基硫基)丙烯亚氨酸苯基酯
1H-NMR(CDCl3)δppm:1.96~2.10(2H,m),2.77~2.91(4H,m),5.84(0.74H,d,J=15.0Hz),5.99(0.13H,d,J=15.2Hz),6.09(0.13H,d,J=9.9Hz),6.47~8.04(11.13H,m),7.67(0.74H,d,J=15.2Hz),8.00(0.13H,d,J=15.0Hz)。
N-(5-茚满基)-3-(2-萘基硫基)丙烯亚氨酸苯基酯
1H-NMR(CDCl3)δppm:1.96~2.19(2H,m),2.57~3.05(4H,m),5.65~5.82(0.50H,m),5.99(0.50H,d,J=15.1Hz),6.47~8.26(16H,m)。
参考生产实施例9-(1)
生产N-(4-联苯基)-3-(3-甲基苯基硫基)丙烯亚氨酸苯基酯
在氮气气氛下在冰冷条件下向3-甲基苯基硫醇(0.11克)在无水DMF(10毫升)中的溶液添加60%氢化钠(44mg),且在室温搅拌该混合物30分钟。反应混合物在冰冷条件下被添加到N-(4-联苯基)-3-(苯磺酰基)丙烯亚氨酸苯基酯(0.40克)在无水DMF(10毫升)中的溶液。在室温搅拌该混合物2小时。向该反应混合物添加叔丁基甲基醚(150ml),其用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物通过中等压力制备液相色谱(Yamazen SI-40B,己烷∶乙酸乙酯=19∶1)分离和纯化,获得N-(4-联苯基)-3-(3-甲基苯基硫基)丙烯亚氨酸苯基酯(0.18克)。
1H-NMR(CDCl3)δppm:2.28(3H,s),5.92(1H,d,J=15.0Hz),6.79~7.74(18H,m),7.72(1H,d,J=15.0Hz)。
参考生产实施例9-(2)至(5)
以下化合物以和参考生产实施例9-(1)同样的方式合成。
3-(4-氟苯基硫基)-N-(4-联苯基)丙烯亚氨酸苯基酯
1H-NMR(CDCl3)δppm:5.84(1H,d,J=15.1Hz),6.76~7.58(18H,m),7.63(1H,d,J=15.1Hz)。
N-(4-联苯基)-3-(3-三氟甲基苯基硫基)丙烯亚氨酸苯基酯
1H-NMR(CDCl3)δppm:5.87(0.29H,d,J=15.1Hz),5.96(0.66H,d,J=15.1Hz),6.19(0.05H,d,J=9.8Hz),6.73~7.97(19H,m)。
N-(4-联苯基)-3-(2-噻吩基)丙烯亚氨酸苯基酯
1H-NMR(CDCl3)δppm:5.78(1H,d,J=15.0Hz),6.76~7.64(17H,m),7.85(1H,d,J=15.0Hz)。
N-(4-联苯基)-3-(3-甲基苯基硫基)丙烯亚氨酸乙基酯
1H-NMR(CDCl3)δppm:1.37(3H,t,J=7.1Hz),4.30(2H,q,J=7.1Hz),5.87(1H,t,J=15.1Hz),6.57~8.19(14H,m)。
参考生产实施例10
生产3-苄氧基-N-(3,4-二甲基苯基)丙烯亚氨酸3-甲基苯基酯
在氮气气氛下在冰冷条件下向苯甲醇(0.78克)在THF(15毫升)中的溶液添加60%氢化钠(90毫克),和在相同温度搅拌该混合物30分钟。反应混合物在冰冷条件下滴加到N-(3,4-二甲基苯基)-3-(苯磺酰基)丙烯亚氨酸3-甲基苯基酯(0.78克)在无水THF(15毫升)中的溶液。在相同温度搅拌该混合物3小时。向该反应混合物添加叔丁基甲基醚(80ml),其用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤。有机层用无水硫酸镁干燥,然后在减压下浓缩,获得3-苄氧基-N-(3,4-二甲基苯基)丙烯亚氨酸3-甲基苯基酯(0.82克)。
1H-NMR(CDCl3)δppm:2.19(6H,s),2.35(3H,s),4.81(2H,s),5.41(1H,d,J=12.6Hz),6.49~6.54(2H,m),6.95~7.00(4H,m),7.22~7.38(6H,m),7.62(1H,d,J=12.6Hz)。
参考生产实施例11-(1)
生产2-甲基-N-苯基-3-(苯基硫基)丙烯酰胺
向2-甲基-3-(苯基硫基)丙烯酸(2.5克)添加甲苯(25毫升),然后添加亚硫酰氯(3.5克)和DMF(10毫克),在其被加热到回流的时候搅拌该混合物1小时。反应混合物被浓缩。向该残余物添加乙酸乙酯(25毫升),然后在冰冷条件下滴加苯胺(2.9克)。在室温搅拌该混合物30分钟。反应混合物顺序地用1N盐酸,饱和含水碳酸氢钠溶液然后饱和氯化钠水溶液洗涤。干燥有机层,然后浓缩获得2-甲基-N-苯基-3-(苯基硫基)丙烯酰胺(3.0克)。
1H-NMR(CDCl3)δppm:2.11(3H,s),7.08~7.59(11H,m)。
参考生产实施例11-(2)至(7)
以下化合物以和参考生产实施例11-(1)同样的方式合成。
2-乙基-N-苯基-3-(苯基硫基)丙烯酰胺
1H-NMR(CDCl3)δppm:1.20(3H,t,J=7.6Hz),2.56(2H,q,,J=7.6Hz),7.11(1H,t,J=7.4Hz),7.28~7.41(7H,m),7.44~7.49(2H,m),7.54(2H,d,J=7.7Hz)。
N-苯基-3-苯基硫基-2-(丙基)丙烯酰胺
1H-NMR(CDCl3)δppm:1.03(3H,t,J=7.4Hz),1.55~1.68(2H,m),2.53(2H,t,J=7.7Hz),7.10(1H,t,J=7.4Hz),7.28~7.41(7H,m),7.43~7.48(2H,m),7.53(2H,d,J=7.6Hz)。
2-丁基-N-苯基-3-(苯基硫基)丙烯酰胺
1H-NMR(CDCl3)δppm:0.98(3H,t,J=7.2Hz),1.36~1.62(4H,m),2.55(2H,t,J=7.6Hz),7.11(1H,t,J=7.5Hz),7.28~7.41(7H,m),7.43~7.48(2H,m),7.51~7.57(2H,m)。
2-(甲硫基)-N-苯基-3-(苯基硫基)丙烯酰胺
1H-NMR(CDCl3)δppm:2.38(3H,s),7.13(1H,t,J=7.5Hz),7.32~7.42(5H,m),7.50~7.55(2H,m),7.63(2H,d,J=7.5Hz),8.43(1H,s),9.12(1H,brs)。
N-苯基-3-苯基硫基-2-(2-噻吩基)丙烯酰胺
1H-NMR(CDCl3)δppm:7.10(1H,t,J=7.4Hz),7.19~7.24(2H,m),7.27~7.40(5H,m),7.44~7.52(5H,m),7.56(1H,dd,J=4.3,1.9Hz),8.14(1H,s)。
2-氟-N-苯基-3-(苯基硫基)丙烯酰胺
1H-NMR(CDCl3)δppm:7.16(1H,t,J=7.5Hz),7.17(1H,d,J=35.2Hz),7.31~7.41(5H,m),7.48(2H,d,J=7.5Hz),7.58(2H,d,J=8.5Hz),7.80(1H,brs)。
参考生产实施例12
生产N-(4-联苯基)-3-(苯基硫基)丙烯酰胺
在室温向N-(4-溴苯基)-3-(苯基硫基)丙烯基氯(2.1克)在N-甲基吡咯烷酮(36毫升)/离子交换水(18毫升)的混合物中的溶液添加苯基硼酸(1.1克),四(三苯基膦)钯(0.14克)和碳酸氢钠(1.0克),和在80℃搅拌该混合物8小时。反应混合物用乙酸乙酯(400毫升)提取。有机层用水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=4∶1至2∶1),获得N-(4-联苯基)-3-(苯基硫基)丙烯酰胺(1.5克),为浅黄色晶体。
1H-NMR(DMSO)δppm:6.06(0.8H,d,J=14.7Hz),6.28(0.2H,d,J=9.9Hz),7.19~7.80(15H,m),10.05(1H,brs)。
参考生产实施例13-(1)
生产N-[2-(甲硫基)噻唑-5-基]-3-(苯基硫基)丙烯酰胺
向3-(苯基硫基)丙烯酸(3.69克)在乙腈(50ml)中的溶液在冰冷条件下添加5-氨基-2-(甲硫基)噻唑(3.00克)在乙腈(10毫升)和三乙胺(2.80毫升)中的溶液。在相同温度搅拌该混合物2小时然后在室温搅拌3小时,然后在减压下浓缩。向该残余物添加1N盐酸(50ml),其用乙酸乙酯(100ml)提取两次。有机层被合并,用水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=1∶1),获得N-[2-(甲硫基)噻唑-5-基]-3-(苯基硫基)丙烯酰胺(1.90克),为暗黄色晶体。
1H-NMR(CDCl3)δppm:2.61(3H,s),5.81(1H,d,J=14.6Hz),7.25~7.46(6H,m),7.89(1H,d,J=14.6Hz),9.12(1H,brs)。
参考生产实施例13-(2)
以下化合物以和参考生产实施例13-(1)同样的方式合成。
N-(5-茚满基)-3-(苯基硫基)丙烯酰胺
1H-NMR(CDCl3)δppm:1.99~2.07(2H,m),2.81~2.85(4H,m),5.84(0.8H,d,J=14.5Hz),5.99(0.2H,d,J=9.9Hz),7.09~7.71(9.2H,m),7.78(0.8H,d,J=14.5Hz)。
参考生产实施例14
生产N-(4-甲基苯基)-3-(3-甲基苯基硫基)丙烯酰胺
在氮气气氛下在冰冷条件下向3-甲基硫基苯酚(0.85克)在DMF(10毫升)中的溶液添加60%氢化钠(81毫克)。在氮气气氛下在室温搅拌该混合物30分钟,然后在冰冷条件下滴加到N-(4-甲基苯基)-3-(苯磺酰基)丙烯酰胺(0.85克)在DMF(10毫升)中的溶液。在室温搅拌该混合物2小时,通过添加1N氢氧化钠水溶液碱化,然后用叔丁基甲基醚(100ml)提取。有机层用水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=3∶1),获得N-(4-甲基苯基)-3-(3-甲基苯基硫基)丙烯酰胺(0.45克),为白色晶体。
1H-NMR(CDCl3)δppm:2.25(4.5H,s),2.31(0.75H,s),2.36(0.75H,s),5.97(0.25H,d,J=9.9Hz),6.01(0.75H,d,J=14.7Hz),7.00~7.51(8.5H,m),7.71(0.75H,d,J=14.7Hz),8.68(0.75H,brs)。
参考生产实施例14-(2)至(5)
以下化合物以和参考生产实施例14-(1)同样的方式合成。
N-(4-甲基苯基)-3-(4-甲氧基苯基硫基)丙烯酰胺
E-异构体:
1H-NMR(CDCl3)δppm:2.30(3H,s),3.85(3H,s),5.56(1H,d,J=14.5Hz),6.80~7.45(9H,m),7.77(1H,d,J=14.5Hz)。
Z-异构体:
1H-NMR(CDCl3)δppm:2.32(3H,s),3.82(3H,s),5.93(1H,d,J=9.7Hz),6.88~7.52(10H,m)。
N-(4-甲基苯基)-3-(1-萘基硫基)丙烯酰胺
E-异构体:
1H-NMR(CDCl3)δppm:2.27(3H,s),5.39(1H,d,J=14.4Hz),6.83(1H,brs),7.01~8.30(11H,m),7.80(1H,d,J=14.4Hz)。
Z-异构体:
1H-NMR(CDCl3)δppm:2.33(3H,s),5.97(1H,d,J=9.7Hz),6.70(1H,brs),7.07(1H,d,J=9.7Hz),7.14~8.44(11H,m)。
N-(4-甲基苯基)-3-(2-噻吩基)丙烯酰胺
1H-NMR(CDCl3)δppm:2.30(3H,s),5.66(1H,d,J=14.4Hz),6.99~7.56(8H,m),7.65(1H,d,J=14.4Hz)。
N-(4-甲基苯基)-3-(3-三氟甲基苯基硫基)丙烯酰胺
1H-NMR(CDCl3)δppm:2.31(3H,s),5.88(1H,d,J=14.6Hz),6.97~7.75(9H,m),7.80(1H,d,J=14.6Hz)。
参考生产实施例15
生产N-(4-甲基苯基)-3-(苯磺酰基)丙烯酰胺
在冰冷条件下向N-(4-甲基苯基)-3-(苯基硫基)丙烯酰胺(0.20克)在氯仿(15毫升)中的溶液添加间氯过苯甲酸(65%)(0.27克),和在相同温度搅拌该混合物3.5小时。向该反应混合物添加氯仿(50ml),其用饱和碳酸氢钠水溶液,水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=2∶1),获得N-(4-甲基苯基)-3-(苯磺酰基)丙烯酰胺(0.16g),为白色晶体。
1H-NMR(CDCl3)δppm:2.31(3H,s),7.12(0.64H,d,J=8.5Hz),7.19(0.36H,d,J=14.7Hz),7.42~7.96(11H,m)。
参考生产实施例16
生产N-(5-茚满基)-3-(苯磺酰基)丙烯亚氨酸苯基酯
在冰冷条件下向N-(5-茚满基)-3-(苯基硫基)丙烯亚氨酸苯基酯(1.96克)在氯仿(50ml)中的溶液添加间氯过苯甲酸(65%)(3.50克),在其慢慢地温热至室温的时候搅拌该混合物4.5小时。反应混合物用饱和含水碳酸氢钠溶液,水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物通过中等压力制备液相色谱(YAMAZEN SI-40C,己烷∶乙酸乙酯=3∶1)分离和纯化,获得N-(5-茚满基)-3-(苯磺酰基)丙烯亚氨酸苯基酯(0.650克),为带黑色的棕色油。
1H-NMR(CDCl3)δppm:2.00~2.15(2H,m),2.80~2.94(4H,m),6.48~8.35(15H,m)。
参考生产实施例17
生产N-(4-联苯基)-3-(苯磺酰基)丙烯亚氨酸乙基酯和N-(4-联苯基)-3-(苯磺酰基)丙烯亚氨酸苯基酯
向N-(4-联苯基)-3-(苯基硫基)丙烯亚氨酸苯基酯(5.70克)添加包含1%乙醇的氯仿(300毫升),然后在冰冷条件下添加间氯过苯甲酸(65%)(8.08克)。在其慢慢地温热至室温的时候搅拌该混合物6小时。反应混合物用饱和含水碳酸氢钠溶液,水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物通过硅胶柱色谱法(己烷∶乙酸乙酯=3∶1)分离和纯化,获得为棕色油的N-(4-联苯基)-3-(苯磺酰基)丙烯亚氨酸乙基酯(0.410克)和为棕色油的N-(4-联苯基)-3-(苯磺酰基)丙烯亚氨酸苯基酯(4.23克)。
N-(4-联苯基)-3-(苯磺酰基)丙烯亚氨酸乙基酯:
1H-NMR(CDCl3)δppm:1.35(3H,t,J=7.1Hz),4.30(2H,q,J=7.1Hz),6.81~8.07(16H,m)。
N-(4-联苯基)-3-(苯磺酰基)丙烯亚氨酸苯基酯:
1H-NMR(CDCl3)δppm:6.81~8.07(21H,m)。
参考生产实施例18
生产3-(乙硫基)-N-(苯基)丙烯酰胺
在室温向3-(乙硫基)丙烯酸(5.67克)在甲苯(50ml)中的溶液添加亚硫酰氯(3.48毫升)和DMF(催化量),和在80℃搅拌该混合物2小时。在减压下浓缩反应混合物。向该残余物添加乙腈(50ml),然后在冰冷条件下滴加苯胺(8.78克)在乙腈(10毫升)中的溶液。在相同温度搅拌该混合物1小时然后在室温搅拌3小时,然后在减压下浓缩。向该残余物添加1N盐酸(50ml),且在室温搅拌该混合物0.5小时。形成的晶体通过过滤收集,用水洗涤,过滤,然后干燥获得3-(乙硫基)-N-(苯基)丙烯酰胺(8.03克),为白色晶体。
1H-NMR(CDCl3)δppm:1.32~1.36(3H,m),2.75~2.81(2H,m),5.91(0.8H,d,J=14.6Hz),5.95(0.2H,d,J=10.0Hz),7.00(0.2H,d,J=10.0Hz),7.07~7.56(6H,m),7.72(0.8H,d,J=14.6Hz)。
参考生产实施例19
生产2-(苯并[1,3]二硫酚-2-基)-N-(苯基)乙酰胺
向2-(苯并[1,3]二硫酚-2-基)乙酸(1.35克)在甲苯(30ml)中的溶液在室温添加亚硫酰氯(0.600毫升)和DMF(催化量),和在80℃搅拌该混合物2小时。在减压下浓缩反应混合物。向该残余物添加乙腈(30ml),然后在冰冷条件下滴加苯胺(1.54克)在乙腈(10毫升)中的溶液。在相同温度搅拌该混合物1小时然后在室温搅拌3小时,然后在减压下浓缩。向该残余物添加1N盐酸(50ml),且在室温搅拌该混合物0.5小时。形成的晶体通过过滤收集,用水洗涤,过滤,然后干燥,获得2-(苯并[1,3]二硫酚-2-基)-N-(苯基)乙酰胺(1.83克),为白色晶体。
1H-NMR(CDCl3)δppm:2.98(2H,d,J=7.4Hz),5.26(1H,t,J=7.4Hz),7.06~7.15(4H,m),7.25~7.35(4H,m),7.48~7.50(2H,m)。
参考生产实施例20-(1)
生产N-苯基-3,3-双(苯基硫基)硫代丙酰胺
向N-苯基-3,3-双(苯基硫基)丙酰胺(0.90克)添加Lawesson’s反应剂(2.0克)和1,4-二氧杂环己烷(20ml),混合物被加热到回流1.5小时。反应混合物留待冷却至室温,然后在减压下浓缩。残余物通过中等压力制备液相色谱(YAMAZEN SI-40B,己烷∶乙酸乙酯=3∶1)分离和纯化,获得N-苯基-3,3-双(苯基硫基)硫代丙酰胺(0.69克),为橙色油。
1H-NMR(CDCl3)δppm:3.04(0.34H,d,J=7.4Hz),3.20(1.66H,d,J=7.1Hz),5.21(0.83H,t,J=7.1Hz),5.44(0.17H,t,J=7.4Hz),7.13~7.67(15H,m),8.97(0.83H,brs),9.50(0.17H,brs)。
参考生产实施例20-(2)
以下化合物以和参考生产实施例20-(1)同样的方式合成。
3,3-双(4-氟苯基硫基)-N-苯基丙酰胺
1H-NMR(CDCl3)δppm:2.97(0.4H,d,J=7.5Hz),3.14(1.6H,d,J=7.2Hz),5.06(0.8H,t,J=7.2Hz),5.23(0.2H,t,J=7.5Hz),6.93~7.67(13H,m),8.94(0.8H,brs),9.53(0.2H,brs)。
参考生产实施例21-(1)
生产N-苯基-3,3-双(苯基硫基)丙酰胺
向N-苯基-3,3-双(苯基硫基)丙烯酰胺(2.04克)添加硫代苯酚(8.21毫升)和三乙胺(1.12毫升),且在室温搅拌该混合物11小时。向该反应混合物添加乙酸乙酯(50ml),其用1N氢氧化钠水溶液,水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后在减压下浓缩。残余物通过中等压力制备液相色谱(YAMAZEN SI-40C,己烷∶乙酸乙酯=85∶15)分离和纯化,获得N-苯基-3,3-双(苯基硫基)丙酰胺(3.00克),为橙色油。
1H-NMR(CDCl3)δppm:2.82(2H,d,J=7.1Hz),4.96(1H,t,J=7.1Hz),7.11~7.53(16H,m)。
参考生产实施例21-(2)
以下化合物以和参考生产实施例21-(1)同样的方式合成。
3,3-双(4-氟苯基硫基)-N-苯基丙酰胺
1H-NMR(CDCl3)δppm:2.78(2H,d,J=7.1Hz),4.79(1H,t,J=7.1Hz),6.97~7.50(14H,m)。
参考生产实施例22-(1)
生产2-乙基-3-(苯基硫基)丙烯酸
向2-乙基-3-(苯基硫基)丙烯酸甲基酯(4.39克)添加乙醇(40ml),然后添加2N氢氧化钠水溶液(20ml),和混合物在室温回流2小时。反应混合物冷却至室温之后,向其中添加水(100ml),添加进一步的叔丁基甲基醚,由此分离各层。含水层通过添加浓盐酸调节到pH 2,然后用叔丁基甲基醚提取。有机层用饱和氯化钠水溶液洗涤,干燥,然后浓缩获得2-乙基-3-(苯基硫基)丙烯酸(4.07克)。
1H-NMR(CDCl3)δppm:1.12(3H,t,J=7.5Hz),2.43(2H,q,J=7.5Hz),7.30~7.41(3H,m),7.44~7.49(2H,m),7.79(1H,s)。
参考生产实施例22-(2)-(6)
以下化合物以和参考生产实施例22-(1)同样的方式合成。
2-甲基-3-(苯基硫基)丙烯酸
1H-NMR(CDCl3)δppm:1.96(3H,d,J=1.1Hz),7.31~7.40(3H,m),7.43~7.50(2H,m),7.82(1H,d,J=1.1Hz)。
3-(苯基硫基)-2-丙基丙烯酸
1H-NMR(CDCl3)δppm:0.98(3H,t,J=7.4Hz),1.50~1.65(2H,m),2.39(2H,t,J=7.6Hz),7.29~7.40(3H,m),7.42~7.50(2H,m),7.83(1H,s)。
2-丁基-3-(苯基硫基)丙烯酸
1H-NMR(CDCl3)δppm:0.95(3H,t,J=7.2Hz),1.34~1.57(4H,m),2.41(2H,t,J=7.6Hz),7.29~7.40(3H,m),7.43~7.48(2H,m),7.81(1H,s)。
2-(甲硫基)-3-(苯基硫基)丙烯酸
1H-NMR(CDCl3)δppm:2.40(3H,s),7.35~7.44(3H,m),7.46-7.54(2H,m),8.31(1H,s)。
3-(苯基硫基)-2-(3-噻吩基)丙烯酸
1H-NMR(CDCl3)δppm:7.31(1H,dd,J=5.1,1.2Hz),7.34~7.42(4H,m),7.46~7.50(2H,m),7.53(1H,dd,J=2.9,1.2Hz),8.13(1H,s)。
2-氟-3-(苯基硫基)丙烯酸
1H-NMR(CDCl3)δppm:7.25(1H,d,J=31.2Hz),7.35~7.43(3H,m),7.46~7.53(2H,m),10.39(1H,brs)。
参考生产实施例23-(1)
生产2-甲基-3-(苯基硫基)丙烯酸甲基酯
向氯仿(100ml)添加2-甲基-3-(对甲苯磺酰氧基)丙烯酸甲基酯(11.0克)和硫代苯酚(6.3克),然后滴加三乙胺(33毫升),和在50℃搅拌该混合物9小时。向该反应混合物添加叔丁基甲基醚,然后添加1N氢氧化钠水溶液,由此分离各层。有机层用饱和氯化钠水溶液洗涤,干燥,然后浓缩。残余物进行硅胶柱色谱法(己烷/乙酸乙酯=10/1),获得2-甲基-3-(苯基硫基)丙烯酸甲基酯(6.5克)。
1H-NMR(CDCl3)δppm:1.97(3H,s),3.74(3H,s),7.27~7.50(5H,m),7.65(1H,s)。
参考生产实施例23-(2)至(4)
以下化合物以和参考生产实施例23-(1)同样的方式合成。
2-乙基-3-(苯基硫基)丙烯酸甲基酯
1H-NMR(CDCl3)δppm:1.11(3H,t,J=7.5Hz),2.44(2H,q,J=7.5Hz),3.74(3H,s),7.30~7.40(3H,m),7.44~7.49(2H,m),7.62(1H,s)。
2-丙基-3-(苯基硫基)丙烯酸甲基酯
1H-NMR(CDCl3)δppm:0.98(3H,t,J=7.3Hz),1.49~1.61(2H,m),2.40(2H,t,J=7.7Hz),3.73(3H,s),7.29~7.40(3H,m),7.43~7.48(2H,m),7.65(1H,s)。
2-丁基-3-(苯基硫基)丙烯酸甲基酯
1H-NMR(CDCl3)δppm:0.95(3H,t,J=7.2Hz),1.34~1.54(4H,m),2.42(2H,t,J=7.6Hz),3.73(3H,s),7.29~7.40(3H,m),7.43~7.48(2H,m),7.63(1H,s)。
参考生产实施例24-(1)
生产2-甲硫基-3-(苯基硫基)丙烯酸甲基酯
向2-甲硫基-3-(对甲苯磺酰氧基)丙烯酸甲基酯(3.05克),三乙胺(2毫升)和氯仿(20ml)的混合物在冰冷条件下慢慢地添加硫代苯酚(1.28g),且在室温搅拌该混合物1小时。向该反应混合物添加叔丁基甲基醚,然后添加1N氢氧化钠水溶液,由此分离各层。有机层用饱和氯化钠水溶液洗涤,干燥,然后浓缩。残余物进行硅胶柱色谱法(己烷/乙酸乙酯=10/1),获得2-甲硫基-3-(苯基硫基)丙烯酸甲基酯(1.64克)。
1H-NMR(CDCl3)δppm:2.39(3H,s),3.79(3H,s),7.35~7.42(3H,m),7.46~7.54(2H,m),8.12(1H,s)。
参考生产实施例24-(2)和(3)
以下化合物以和参考生产实施例24-(1)同样的方式合成。
2-(3-噻吩基)-3-(苯基硫基)丙烯酸甲基酯
1H-NMR(CDCl3)δppm:3.78(3H,s),7.28(1H,dd,J=5.1,1.2Hz),7.34~7.41(4H,m),7.46~7.51(3H,m),7.96(1H,s)。
2-氟-3-(苯基硫基)丙烯酸甲基酯
1H-NMR(CDCl3)δppm:1.33(3H,t,J=7.2Hz),4.29(2H,q,J=7.2Hz),7.05(1H,d,J=31.5Hz),7.32~7.42(3H,m),7.45~7.51(2H,m)。
参考生产实施例25-(1)
生产2-甲基-3-(对甲苯磺酰氧基)丙烯酸甲基酯
向丙酸甲酯(17.6克),甲酸甲酯(24.0克)和DMF(200ml)的混合物在冰冷条件下逐份添加60%氢化钠(17.6克),和在室温搅拌该混合物过夜。反应混合物倾倒入冰冻水,和向其中添加叔丁基甲基醚,由此分离各层。含水层通过添加浓盐酸调节到pH 2,然后用叔丁基甲基醚提取。有机层用饱和氯化钠水溶液洗涤,干燥,然后浓缩,获得残余物(7.6克)。向该残余物添加乙酸乙酯(40ml),三乙胺(8.0克)然后对甲苯磺酰氯(13.7克),和在室温搅拌该混合物过夜。反应混合物用水洗涤,干燥然后浓缩。残余物进行硅胶柱色谱法(己烷/乙酸乙酯=5/1),获得2-甲基-3-(对甲苯磺酰氧基)丙烯酸甲基酯(11.0克)。
1H-NMR(CDCl3)δppm:1.73(3H,s),2.47(3H,s),3.73(3H,s),7.38(2H,d,J=8.2Hz),7.60(1H,s),7.82(2H,d,J=8.2Hz)。
参考生产实施例25-(2)至(5)
以下化合物以和参考生产实施例25-(1)同样的方式合成。
2-乙基-3-(对甲苯磺酰氧基)丙烯酸甲基酯
1H-NMR(CDCl3)δppm:0.87(3H,t,J=7.5Hz),2.22(2H,q,J=7.5Hz),2.47(3H,s),3.73(3H,s),7.26(1H,s),7.38(2H,d,J=8.2Hz),7.82(2H,d,J=8.2Hz)。
2-丙基-3-(对甲苯磺酰氧基)丙烯酸甲基酯
1H-NMR(CDCl3)δppm:0.77(3H,t,J=7.4Hz),1.23~1.34(2H,m),2.18(2H,dd,J=8.7,6.3Hz),2.47(3H,s),3.72(3H,s),7.38(2H,d,J=8.4Hz),7.62(1H,s),7.82(2H,d,J=8.4Hz)。
2-丁基-3-(对甲苯磺酰氧基)丙烯酸甲基酯
1H-NMR(CDCl3)δppm:0.80(3H,t,J=7.0Hz),1.09-1.24(4H,m),2.19(2H,t,J=7.0Hz),2.47(3H,s),3.72(3H,s),7.38(2H,d,J=8.4Hz),7.60(1H,s),7.82(2H,d,J=8.4Hz)。
2-(3-噻吩基)-3-(对甲苯磺酰氧基)丙烯酸甲基酯
1H-NMR(CDCl3)δppm:2.45(3H,s),3.80(3H,s),7.18(1H,dd,J=5.1,1.2Hz),7.25(1H,dd,J=5.1,2.9Hz),7.36(2H,d,J=8.3Hz),7.47(1H,dd,J=2.9,1.2Hz),7.79(2H,d,J=8.3Hz),7.81(1H,s)。
参考生产实施例26
生产2-(甲硫基)-3-(对甲苯磺酰氧基)丙烯酸甲基酯
向2-(甲硫基)-2-丙烯酸甲基酯(25.8克),甲酸甲酯(24.0克)和DMF(200ml)的混合物在冰冷条件下逐份添加60%氢化钠(21.4克),和在室温搅拌该混合物过夜。反应混合物倾倒入冰冻水,和向其中添加叔丁基甲基醚,由此分离各层。含水层通过添加浓硫酸调节到pH 2,然后用叔丁基甲基醚提取。有机层用饱和氯化钠水溶液洗涤,干燥,然后浓缩,获得残余物(21.7克)。向该残余物添加乙酸乙酯(200ml),三乙胺(30ml)然后对甲苯磺酰氯(27.0克),和在室温搅拌该混合物过夜。反应混合物用水洗涤,干燥然后浓缩。残余物进行硅胶柱色谱法(己烷/乙酸乙酯=5/1),获得2-(甲硫基)-3-(对甲苯磺酰氧基)丙烯酸甲基酯(9.72克)。
1H-NMR(CDCl3)δppm:2.23(3H,s),2.47(3H,s),3.79(3H,s),7.39(2H,d,J=8.3Hz),7.85(2H,d,J=8.3Hz),7.93(1H,s)。
参考生产实施例27
生产2-(苯并[1,3]二硫酚-2-基)乙酸
向丙酸甲基酯(0.75毫升)在THF(10毫升)中的溶液在冰冷条件下添加苯-1,2-二硫酚(1.2克)在THF(10毫升)和叔丁氧基钾(催化量)中的溶液,和在相同温度搅拌该混合物3小时然后在室温搅拌3小时。在减压下浓缩反应混合物。向该残余物在室温添加甲醇(5ml),然后添加氢氧化钠(0.45克)的含水溶液(10毫升)。混合物在80℃被搅拌2小时。向该反应混合物添加离子交换水(20ml),其用乙酸乙酯洗涤。含水层通过添加1N盐酸调节到pH 2,然后用乙酸乙酯(70毫升)提取两次。有机层被合并,用水然后饱和氯化钠水溶液洗涤,用无水硫酸镁干燥,然后减压浓缩,获得2-(苯并[1,3]二硫酚-2-基)乙酸(1.35克),为黄色晶体。
1H-NMR(CDCl3)δppm:3.05(2H,d,J=7.5Hz),5.06(1H,t,J=7.5Hz),7.05~7.07(2H,m),7.23~7.26(2H,m)。
参考生产实施例28-(1)
生产N-(4-氟苯基)-3-(三甲硅烷基)硫代丙烯亚氨酸环己基甲基酯
向乙炔基三甲基硅烷(0.89克)在THF(15毫升)中的溶液在-78℃在氮气气氛下添加正丁基锂在己烷中的1.57M溶液(5.0毫升),和在相同温度搅拌该混合物0.5小时。反应混合物温热至0℃之后,在-78℃向其中滴加在THF中(5ml)的异硫氰酸4-氟苯基酯(1.30克)。然后,反应混合物慢慢地温热至0℃。在相同温度,向其中滴加环己基甲基溴(1.52克)在THF(5ml)中的溶液,在50℃搅拌该混合物7小时。溶剂在减压被蒸馏出。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=20∶1),获得N-(4-氟苯基)-3-(三甲硅烷基)硫代丙亚氨酸环己基甲基酯(0.38克),为棕色油。
1H-NMR(CDCl3)δppm:0.12(6H,s),0.29(3H,s),0.89~1.28(5H,m),1.59~1.88(6H,m),3.00~3.03(2H,m),6.86~7.05(4H,m)。
参考生产实施例28-(2)至(5)
以下化合物以和参考生产实施例28-(1)同样的方式合成。
N-(4-氯苯基)-3-(三甲硅烷基)硫代丙烯亚氨酸环己基甲基酯
1H-NMR(CDCl3)δppm:0.12(6H,s),0.29(3H、s),0.91~1.07(5H,m),1.60~1.88(6H,m),3.00~3.03(2H,m),6.85(0.6H,d,J=8.5Hz),6.98(1.4H,d,J=8.7Hz),7.26(1.2H,d,J=8.7Hz),7.30(0.8H,d,J=8.5Hz)。
N-(3-甲基苯基)-3-(三甲硅烷基)硫代丙烯亚氨酸环己基甲基酯
1H-NMR(CDCl3)δppm:0.11(6H,s),0.29(3H,s),0.86~1.32(5H,m),1.57~1.91(6H,m),2.33(2H,s),2.34(1H,s),2.99(0.7H,d,J=7.0Hz),3.03(1.3H,d,J=7.0Hz),6.71(0.7H,d,J=6.8Hz),6.82~6.89(1.3H,m),6.90~6.96(1H,m),7.15~7.25(1H,m)。
N-(4-甲氧苯基)-3-(三甲硅烷基)硫代丙亚氨酸环己基甲基酯
1H-NMR(CDCl3)δppm:0.15(6H,s),0.29(3H、s),0.91~1.28(5H,m),1.64~1.88(6H,m),3.28(2H,d,J=6.5Hz),3.80(3H,s),6.83~7.13(4H,m)。
N-(4-硝基苯基)-3-(三甲硅烷基)硫代丙亚氨酸环己基甲基酯
1H-NMR(CDCl3)δppm:0.10(6H,s),0.31(3H,s),0.93~1.28(5H,m),1.62~1.88(6H,m),3.04(2H,d,J=6.6Hz),6.95~7.08(2H,m),8.16~8.21(2H,m)。
参考生产实施例29
生产N-甲基-N,N′-(二苯基)丙脒
在室温向N-甲基-N,N′-(二苯基)脲(2.0克)在甲苯(15毫升)中的悬浮体添加五氯化磷(1.84克),且在其被加热到回流的时候搅拌该混合物3小时。在减压下浓缩反应混合物。向该残余物添加THF(15毫升),然后在冰冷条件下滴加乙炔基溴化镁在THF中的0.5M溶液(35mL)。在室温搅拌该混合物1小时。然后,水(200ml)被添加到该反应混合物,随后用乙酸乙酯(200ml)提取。有机层用水洗涤,用无水硫酸镁干燥,然后在减压浓缩。残余物进行硅胶柱色谱法(己烷∶乙酸乙酯=5∶1),获得N-甲基-N,N′-(二苯基)丙脒(1.50克),为晶体。
1H-NMR(CDCl3)δppm:2.28(1H,s),3.47(3H,s),6.93~7.07(3H,m),7.22(7H,m)。
接下来,描述制剂实施例。本文,术语“份”是指“重量份”。
制剂实施例1
10份的本发明的化合物1至115中的任一种溶解于35份的二甲苯和35份的N,N-二甲基甲酰胺的混合物。向其中添加14份聚氧化乙烯苯乙烯基苯基醚和6份十二烷基苯磺酸钙,且通过充分搅拌而混合,获得10%可乳化的浓缩物。
制剂实施例2
20份本发明的化合物1至115中的任一种被添加到4份月桂基硫酸钠,2份木素磺酸钙,20份合成的水合氧化硅细粉和54份硅藻土的混合物,且通过充分搅拌而混合,获得20%可湿性粉剂。
制剂实施例3
1份合成的水合氧化硅细粉,2份木素磺酸钙,30份膨润土和65份高岭土粘土被添加到2份本发明的化合物1至115中的任一种,且通过充分搅拌而混合。向该混合物添加适当量的水。混合物被进一步搅拌,用制粒机粒化,然后空气干燥以获得2%颗粒。
制剂实施例4
1份本发明的化合物1至115中的任一种溶解于适当量的丙酮。向其中添加5份合成的水合氧化硅细粉,0.3份PAP(酸式磷酸异丙基酯)和93.7份叶蜡石粘土,且通过充分搅拌而混合。丙酮被蒸发,获得1%粉尘。
制剂实施例5
10份本发明的化合物1至115中的任一种,30份的环己酮与二甲基亚砜(重量比90/10)的混合物,35份的白碳与聚氧化乙烯烷基醚硫酸铵盐(重量比50/50)的混合物,和25份水被混合然后通过湿磨方法细碎获得10%可流动制剂。
制剂实施例6
0.1份本发明的化合物1至115中的任一种溶解于5份二甲苯和5份三氯乙烷的混合物。该溶液与89.9份脱臭汽油混合,获得0.1%油溶液。
制剂实施例7
10毫克本发明的化合物1至115中的任一种溶解于0.5毫升的丙酮。该溶液与5g的粉状体动物饲料(用于饲养的粉状体饲料,通过CleaJapan Inc.制备的CE-2)混合均匀。丙酮被蒸发以获得毒饵。
制剂实施例8
10份本发明的化合物1至115中的任一种,35份的白碳与聚氧化乙烯烷基醚硫酸铵(重量比50/50)的混合物,和55份水被混合然后通过湿磨方法细碎,获得10%可流动制剂。
制剂实施例9
10份本发明的化合物(37)和10份列在如下所述第I组中的杀昆虫剂,杀螨剂,杀线虫剂,杀真菌剂,除草剂,植物激素试剂,植物生长调节剂,增效剂和农作物损害减少剂的任一种添加到4份月桂基硫酸钠,2份木素磺酸钙,20份合成的水合氧化硅细粉和54份硅藻土的混合物,且通过充分搅拌而混合,获得混合的可湿性粉剂。
制剂实施例10
10份本发明的化合物(41)和10份列在如下所述第I组中的任一种杀昆虫剂,杀螨剂,杀线虫剂,杀真菌剂,除草剂,植物激素试剂,植物生长调节剂,增效剂和农作物损害减少剂添加到4份月桂基硫酸钠,2份木素磺酸钙,20份合成的水合氧化硅细粉和54份硅藻土的混合物,且通过充分搅拌而混合,获得混合的可湿性粉剂。
制剂实施例11
10份本发明的化合物(64)和10份列在如下所述第I组中的任一种杀昆虫剂,杀螨剂,杀线虫剂,杀真菌剂,除草剂,植物激素试剂,植物生长调节剂,增效剂和农作物损害减少剂添加到4份月桂基硫酸钠,2份木素磺酸钙,20份合成的水合氧化硅细粉和54份硅藻土的混合物,且通过充分搅拌而混合,获得混合的可湿性粉剂。
制剂实施例12
10份本发明的化合物(67)和10份列在如下所述第I组中的任一种杀昆虫剂,杀螨剂,杀线虫剂,杀真菌剂,除草剂,植物激素试剂,植物生长调节剂,增效剂和农作物损害减少剂添加到4份月桂基硫酸钠,2份木素磺酸钙,20份合成的水合氧化硅细粉和54份硅藻土的混合物,且通过充分搅拌而混合,获得混合的可湿性粉剂。
制剂实施例13
10份本发明的化合物(76)和10份列在如下所述第I组中的任一种杀昆虫剂,杀螨剂,杀线虫剂,杀真菌剂,除草剂,植物激素试剂,植物生长调节剂,增效剂和农作物损害减少剂添加到4份月桂基硫酸钠,2份木素磺酸钙,20份合成的水合氧化硅细粉和54份硅藻土的混合物,且通过充分搅拌而混合,获得混合的可湿性粉剂。
制剂实施例14
10份本发明的化合物(80)和10份列在如下所述第I组中的任一种杀昆虫剂,杀螨剂,杀线虫剂,杀真菌剂,除草剂,植物激素试剂,植物生长调节剂,增效剂和农作物损害减少剂添加到4份月桂基硫酸钠,2份木素磺酸钙,20份合成的水合氧化硅细粉和54份硅藻土的混合物,且通过充分搅拌而混合,获得混合的可湿性粉剂。
制剂实施例15
10份本发明的化合物(95)和10份列在如下所述第I组中的任一种杀昆虫剂,杀螨剂,杀线虫剂,杀真菌剂,除草剂,植物激素试剂,植物生长调节剂,增效剂和农作物损害减少剂添加到4份月桂基硫酸钠,2份木素磺酸钙,20份合成的水合氧化硅细粉和54份硅藻土的混合物,且通过充分搅拌而混合,获得混合的可湿性粉剂。
第I组由以下组成:
任何以下杀昆虫剂:
(1)有机磷化合物:
高灭磷、磷化铝、特嘧硫磷、硫线磷、壤虫氯磷、毒虫畏、毒死蜱、甲基毒死蜱、杀螟腈(CYAP)、二嗪农、DCIP(二氯二异丙醚)、除线磷(ECP)、敌敌畏(DDVP)、乐果、甲基毒虫畏、乙拌磷、EPN、乙硫磷、灭克磷、氧嘧啶磷、倍硫磷(MPP)、杀螟松(MEP)、噻唑酮磷、安果、磷化氢、丙胺磷、异噁唑磷、马拉硫磷、甲亚砜磷、杀扑磷(DMTP)、久效磷、二溴磷(BRP)、异砜磷(ESP)、对硫磷、伏杀磷、亚胺硫磷(PMP)、虫螨磷、打杀磷、喹噁磷、稻丰散(PAP)、丙溴磷、丙虫磷、丙硫磷、吡唑硫磷(pyraclorfos)、蔬果磷、乙丙硫磷、嘧丙磷、双硫磷、杀虫威、特丁磷、甲基乙拌磷、敌百虫(DEP)、蚜灭多、甲拌磷、和硫线磷;
(2)氨基甲酸酯化合物:
棉铃威、噁虫威、丙硫克百威、BPMC、甲萘威、克百威、丁硫克百威、除线威、苯虫威、丁苯威、苯硫威、双氧威、呋线威、异丙威(MIPC)、速灭威、灭多虫、灭虫威、NAC、甲氨叉威、抗蚜威、残杀威(PHC)、XMC、硫双灭多威、灭杀威和涕灭威;
(3)合成除虫菊酯化合物:
氟酯菊酯、丙烯除虫菊酯、四氟苯菊酯、β-氟氯氰菊酯、氟氯菊酯、乙氰菊酯、氟氯氰菊酯、三氟氯氰菊酯、氯氰菊酯、烯炔菊酯、溴氰菊酯、高氰戊菊酯、醚菊酯、甲氰菊酯、杀灭菊酯、氟氰戊菊酯、三氟醚菊酯(flufenoprox)、氟氯苯菊酯、氟胺氰菊酯、卤醚菊酯、咪炔菊酯、苄氯菊酯、右旋丙炔菊酯、除虫菊酯、灭虫菊、σ-氯氰菊酯、灭虫硅醚、七氟菊酯、四溴菊酯、四氟菊酯、胺菊酯、苯醚菊酯、苯醚氰菊酯、α-氯氰菊酯、ζ-氯氰菊酯、λ-三氟氯氰菊酯、γ-三氟氯氰菊酯、消虫菊、τ-氟胺氰菊酯、metofluthrin、2,2-二甲基-3-(1-丙烯基)环丙烷甲酸2,3,5,6-四氟-4-甲基苄酯、2,2-二甲基-3-(2-甲基-1-丙烯基)环丙烷甲酸2,3,5,6-四氟-4-(甲氧基甲基)苄酯、2,2-二甲基-3-(2-氰基-1-丙烯基)环丙烷甲酸2,3,5,6-四氟-4-(甲氧基甲基)苄酯、和2,2,3,3-四甲基环丙烷甲酸2,3,5,6-四氟-4-(甲氧基甲基)苄酯;
(4)沙蚕毒素化合物:
巴丹、杀虫磺、硫环杀、杀虫单、和杀虫双;
(5)新烟碱类化合物:
吡虫啉、硝胺烯啶、吡虫清、噻虫嗪(thiamethoxam)、噻虫啉(thiacloprid)、和噻虫胺(clothianidin);
(6)苯甲酰脲化合物:
定虫隆、bistrifluron、杀螨硫隆、伏虫脲、氟啶蜱脲、氟螨脲、氟虫脲、氟铃脲、八氟脲、双苯氟脲、noviflumuron、伏虫隆、杀虫隆和triazuron;
(7)苯基吡唑化合物:
乙酰虫肼(acetoprole)、乙虫清(ethiprole)、锐特劲、氟吡唑虫、pyriprole和pyrafluprole;
(8)Bt毒素杀虫药:
由苏云金芽孢杆菌所获得的活孢子和由苏云金芽孢杆菌所产生的晶体毒素及其混合物;
(9)肼化合物:
环虫酰肼(chromafenozide)、特丁苯酰肼、甲氧苯酰肼和双苯酰肼;
(10)有机氯化合物:
艾氏剂、狄氏剂、除螨灵、硫丹、和甲氧滴滴涕;
(11)天然杀虫药:
机油、和硫酸烟碱;
(12)其他杀虫药:
齐墩螨素-B、溴螨酯、噻嗪酮、溴虫清(chlorphenapyr)、环丙三氨三嗪、D-D(1,3-二氯丙烯)、苯甲酸埃玛霉素(emamectin-benzoate)、喹螨醚、吡氟硫磷(flupyrazofos)、蒙512、蒙515(methoprene)、噁二唑虫(indoxacarb)、恶虫酮、milbemycin-A、拒嗪酮、啶虫丙醚(pyridalyl)、蚊蝇醚、艾克敌、氟虫胺、唑虫酰胺(tolfenpyrad)、唑蚜威、氟虫酰胺(flubendiamide)、lepimectin、砷酸、benclothiaz、氰氨钙、石硫合剂、氯丹、DDT、DSP、flufenerim、氟啶虫酰胺(flonicamid)、flurimfen、伐虫脒、metham-ammonium、威百亩、甲基溴、油酸钾、protrifenbute、螺甲满酯(spiromesifen)、硫、氰氟虫腙(metaflumizone)、spirotetramat、pyrifluquinazone、spinetoram、chlorantraniliprol e、tralopyril、由下式(A)表示的化合物:
其中Xa1代表甲基、氯原子、溴原子或氟原子,Xa2代表氟原子、氯原子、溴原子、C1-C4卤代烷基或C1-C4卤代烷氧基,Xa3代表氟原子、氯原子或溴原子,Xa4代表任选取代的C1-C4烷基、任选取代的C3-C4链烯基、任选取代的C3-C4炔基、任选取代的C3-C5环烷基或氢原子,Xa5代表氢原子或甲基,Xa6代表氢原子、氟原子或氯原子,和Xa7代表氢原子、氟原子或氯原子;
由下式(B)代表的化合物:
其中Xb1代表Xb2-NH-C(=O)、Xb2-C(=O)-NH-CH2、Xb3-S(O)、任选取代的吡咯-1-基、任选取代的咪唑-1-基、任选取代的吡唑-1-基或任选取代的1,2,4-三唑-1-基,Xb2代表任选取代的C1-C4卤代烷基如2,2,2-三氟乙基或任选取代的C3-C6环烷基如环丙基,Xb3代表任选取代的C1-C4烷基如甲基,和Xb4代表氢原子、氰基或甲基;
由下式(C)代表的化合物:
其中Xc1代表任选取代的C1-C4烷基如3,3,3-三氟丙基、任选取代的C1-C4烷氧基如2,2,2-三氯乙氧基或任选取代的苯基如4-氰基苯基或任选取代的吡啶基例如2-氯-3-吡啶基,Xc2代表甲基或三氟甲硫基,和Xc3代表甲基和卤素原子;
以下的任何杀螨剂:灭螨醌、虫螨脒、苯螨特(benzoximate)、联苯肼酯、溴螨酯、灭螨猛、乙酯杀虫螨、CPCBS(杀螨酯)、四螨嗪、丁氟螨酯(cyflumetofen)、开乐散(三氯杀螨醇)、特苯噁唑、杀螨锡、苯硫威、唑螨酯、嘧螨酯(fluacrypyrim)、苄螨醚(fluproxyfen)、噻螨酮、克螨特(BPPS)、杀螨霉素、哒螨酮、嘧胺苯醚、吡螨胺、三氯杀螨砜、螺满酯(spirodiclofen)、螺甲满酯(spiromesifen)、spirotetramat、amidoflumet和cyenopyrafen。
以下的任何杀线虫剂:DCIP、噻唑酮磷、盐酸保松噻(levamisol)、氰土灵、酒石酸莫仑太尔和imicyafos。
以下的任何杀真菌剂:吡咯杀真菌化合物如丙环唑,丙硫菌唑,三唑醇,咪鲜胺,戊菌唑,戊唑醇,氟硅唑,烯唑醇,糠菌唑,氟环唑,噁醚唑,环唑醇,叶菌唑,氟菌唑,氟醚唑,腈菌唑,腈苯唑,己唑醇,氟喹唑,灭菌唑,联苯三唑醇,抑霉唑,和粉唑醇;
环胺杀真菌化合物如芬普福,克啉菌,和苯锈啶;
苯并咪唑杀真菌化合物如carbendezim,苯菌灵,噻苯达唑,和甲基硫菌灵;
腐霉利,嘧菌环胺,嘧霉胺,乙霉威,秋兰姆,氟啶胺,代森锰锌,异菌脲,乙烯菌核利,百菌清,克菌丹,嘧菌胺,拌种咯,咯菌腈,抑菌灵,灭菌丹,醚菌酯,嘧菌酯,肟菌酯,氟嘧菌酯,啶氧菌酯,吡唑醚菌酯,醚菌胺,螺环菌胺,喹氧灵,环酰菌胺,恶唑菌酮,咪唑菌酮,苯酰菌胺,噻唑菌胺,吲唑磺菌胺,丙森锌,苯噻菌胺,赛座灭,双炔酰菌胺,啶酰菌胺,苯菌酮,苯噻菌胺,bixafen,环氟菌胺,和丙氧喹啉。
以下的任何除草剂和任何植物激素试剂:
(1)苯氧基脂肪酸除草化合物如2,4-PA,MCP,MCPB,酚硫杀,甲氯丙酸,氟草烟,绿草定,稗草胺,和萘丙胺;
(2)苯甲酸除草化合物如2,3,6-TBA,麦草畏,二氯吡啶酸,毒莠定,氯氨吡啶酸,二氯喹啉酸,和喹草酸;
(3)尿素除草化合物如敌草隆,利谷隆,绿麦隆,异丙隆,伏草隆,异恶隆,丁唑隆,噻唑隆,苄草隆,杀草隆,和甲基-杀草隆;
(4)三嗪除草化合物如莠去津,ametoryn,氰草津,西玛三嗪,扑灭津,西草净,异戊乙净,扑草净,嗪草酮,和三嗪氟草胺;
(5)联吡啶鎓除草化合物如对草快,和杀草快;
(6)羟基苯基氰除草化合物如溴苯腈和碘苯腈;
(7)二硝基苯胺除草化合物如二甲戊乐灵,氨基氟乐灵,和氟乐灵;
(8)有机磷除草化合物如甲基胺草磷,克蔓磷,地散磷,派草磷,莎稗磷,草甘膦,草铵膦,和双丙氨膦;
(9)氨基甲酸酯除草化合物如燕麦敌,野麦畏,EPTC,苏达灭,杀草丹,禾草畏,草达灭,哌草丹,灭草灵,氯普芬,苯敌草,棉胺宁,稗草丹,和黄草灵;
(10)酰胺除草化合物如敌稗,拿草特,溴丁酰草胺,和乙氧苯草胺;
(11)乙酰氯苯胺除草化合物如乙草胺,草不绿,去草胺,二甲噻草胺,毒草安,吡草胺,异丙甲草胺,丙草胺,噻吩草胺,和烯草胺;
(12)二苯基醚除草化合物如三氟羧草醚-钠,治草醚,乙氧氟草醚,乳氟禾草,氟磺胺草醚,氯硝醚,和苯草醚;
(13)环状酰亚胺除草化合物如恶草灵,吲哚酮草酯,唑草酮,surfentrazone,氟烯草酸,丙炔氟草胺,吡草醚,炔恶草酮,环戊恶草酮,哒草氟,氟丙嘧草酯,和双苯嘧草酮;
(14)吡唑除草化合物如吡草酮,吡唑特,苄草唑,topramezone,和pyrasulfotole;
(15)三酮除草化合物如异恶唑草酮,苯并双环酮,磺草酮,甲基磺草酮,tembotrione,和tefuryltrione;
(16)芳基氧基苯氧基丙酸除草化合物如炔草酯,氰氟草酯,禾草灵,恶唑禾草灵,丁基吡氟禾草灵,氟吡甲禾灵,和精喹禾灵;
(17)三酮肟(trioneoxime)除草化合物如禾草灭,稀禾定,丁氧环酮,烯草酮,cloproxydim,噻草酮,醌肟草,肟草酮,和环苯草酮;
(18)磺酰基脲除草化合物如绿黄隆,甲嘧磺隆,甲磺隆,氯嘧磺隆,苯磺隆,醚苯磺隆,苄嘧磺隆,噻吩磺隆,吡嘧磺隆,氟嘧磺隆,烟嘧磺隆,酰嘧磺隆,醚磺隆,唑吡嘧磺隆,砜嘧磺隆,氯吡嘧磺隆,氟磺隆,胺苯磺隆,氟胺磺隆,啶嘧磺隆,环磺隆,氟啶嘧磺隆,酰磺隆,四唑嘧磺隆,乙氧嘧磺隆,环氧嘧磺隆,甲基碘磺隆钠盐,酰胺磺隆,甲磺胺磺隆,三氟啶黄隆,三氟甲磺隆,嘧苯胺磺隆,氟吡磺隆,和1-(2-氯-6-丙基咪唑[1,2-a]哒嗪-3-基磺酰基)-3-(4,6-二甲氧基嘧啶-2-基)脲;
(19)咪唑啉酮除草化合物如咪草酸,imazamethapyr,甲氧咪,灭草烟,灭草喹,和咪草烟;
(20)磺酰胺除草化合物如氟唑嘧磺草胺,磺草唑胺,双氯磺草胺,双氟磺草胺,氯酯磺草胺,嘧啶并三唑类磺胺,和甲氧磺草胺;
(21)嘧啶基氧基苯甲酸除草化合物如嘧草硫醚,双草醚,嘧草醚,嘧啶肟草醚,和环酯草醚;和
(22)其它除草化合物如噻草平,除草定,特草定,草克乐,异恶草胺,地乐酚,杀草强,环庚草醚,灭草环,dalapon,二氟吡隆-钠,氟硫草定,噻草定,氟酮磺隆-钠,丙苯磺隆-钠,苯噻草胺,氟噻草胺,四唑草胺,唑草胺,茚草酮,氯恶嗪草,呋草黄,ACN,哒草特,杀草敏,达草灭,呋草酮,吡氟草胺,氟吡草胺,氟丁酰草胺,异恶草松,氨唑草酮,唑啉草酯,和甲基噻烯卡巴腙;
以下的任何植物生长调节剂:恶霉灵,多效唑,烯效唑-P,抗倒胺,调环酸-钙,艾维激素,1-萘基乙酰胺,脱落酸,吲哚丁酸,乙基吲熟酯,乙烯利,座果酸,矮壮素阳离子,2-4滴丙酸,赤霉素,茉莉酮,苯甲酸嘌呤,调吡脲,顺丁烯二酰肼,过氧化钙,缩节胺)和4-CPA(4-氯苯氧基乙酸);
以下的任何增效剂:胡椒基丁醚,增效菊,亚砜,N-(2-乙基己基)-8,9,10-三降冰片-5烯-2,3-二甲酰亚胺(MGK 264),N-declyimidazole,WARF-抗耐药性剂,TBPT,TPP,IBP,PSCP,甲基碘(CH3I),叔苯基丁烯酮,马来酸二乙基酯,DMC,FDMC,ETP,和ETN;和
以下的任何农作物损害-减少剂:解草嗪,解毒喹,解草胺腈,杀草隆,二氯丙烯胺,解草唑,解草啶,解草安,肟草安,解草恶唑,吡唑解草酯,MG191,解草腈,烯草胺,双苯恶唑酸,cyprosulfamide,肟草安,和1,8-萘二甲酸酐。
以下测试实施例表明本发明的化合物针对害虫控制是有效的。
在测试实施例1至9中,在制剂实施例5中获得的制剂用离子交换水稀释以致活性成分的浓度可以是500ppm以制备测试溶液。
测试实施例1(Spodoptera litura)
具有直径5.5厘米的滤纸铺展到具有直径5.5厘米的聚乙烯杯底,并且人工饵料Insecta LF(Nosan Kogyo Corp.)被切成6mm厚度的碎片并进一步切成两半,被放置到滤纸上。然后,2毫升的测试溶液倾倒到滤纸之上。滤纸被风干之后,5只4龄幼虫的Spodoptera litura被释放入聚乙烯杯,并用盖密封杯子。在6天以后,计算死亡昆虫数目。
死亡率通过以下公式计算。
死亡率(%)=(死亡昆虫的数目/测试昆虫的数目)×100
测试化合物的效果用如下指标评估:4:100%,3:80-99%,2:60-79%,1:30-59%和0:0-29%,按照死亡率计。
结果,本发明的化合物1,2,4,5,6,7,11,12,13,14,16,17,18,21,22,23,24,25,26,27,29,30,31,32,33,34,38,47,48,49,50,51,52,53,54,55,57,58,59,60,61,63,65,66,67,72,73,76,80,83,84,85,88,89,90,91,92,95,96,98,99,101,102,103,106,108,109,110,111和115被评价为3或更高。
测试实施例2(Adoxophyes orana)
具有直径5.5厘米的滤纸铺展到具有直径5.5厘米的聚乙烯杯底,且人工饵料,Silkmate 2S(Nosan Kogyo Corp.)被切成2mm厚度的碎片,放置于滤纸上。然后,1毫升的测试溶液倾倒到滤纸之上。滤纸被风干之后,立即将具有直径5.5厘米的滤纸放置在其上。然后,30只1龄的Adoxophyes orana幼虫释放入聚乙烯杯,和用盖密封杯子。在7天以后,计算存活的昆虫数目。
死亡率通过以下公式计算。
死亡率(%)=(死亡昆虫的数目/测试昆虫的数目)×100
测试化合物的效果用如下指标评估:4:100%,3:80-99%,2:60-79%,1:30-59%和0:0-29%,按照死亡率计。
结果,本发明的化合物1,2,4,5,6,7,9,11,12,13,14,16,17,18,20,21,22,23,24,25,26,27,28,30,31,32,33,34,38,47,48,49,50,51,52,53,54,55,57,58,59,60,61,62,73,76,80,83,84,85,88,89,90,91,92,94,95,96,98,99,101,102,103,106,108,110,111和115被评价为指标3或更高。
测试实施例3(Aphis gossypii)
1盎司杯中生长的1叶发育阶段的黄瓜叶上,释放30只Aphisgossypii(包括成虫和幼虫)。次日,20毫升的测试溶液喷雾到叶子上。在6天以后,计算存活的昆虫数目。
基于未处理的杯中提供的昆虫数目的测试昆虫存活率通过以下公式计算。
存活率(%)=(在测试杯中存活昆虫的数目/未处理的杯中昆虫的数目)×100
测试化合物的效果用如下指标评估:4:0%,3:1-10%,2:11-40%,1:41-70%,和0:>70%,按照存活率计。
作为结果,本发明的化合物1,2,6,14,16,17,18,22,23,24,25,27,28,30,32,34,38,48,49,50,57,72,73,83,88,89,90,91和92被评价为指标3或更高。
测试实施例4(Nilaparvata lugens)
稻植物在90毫升塑料杯中生长,和在二或三叶发育阶段,从底部的5厘米处切除茎。然后,20毫升/壶(pot)的测试溶液被喷雾到植物上。在风干以后,30只1龄Nilaparvata lugens幼虫释放入杯,和用盖密封杯子。在6天以后,计算存活的昆虫数目。
基于未处理的杯中提供的昆虫数目的测试昆虫存活率通过以下公式计算。
存活率(%)=(在测试杯中存活昆虫的数目/未处理的杯中昆虫的数目)×100
测试化合物的效果用如下指标评估:4:0%,3:1-10%,2:11-40%,1:41-70%,和0:>70%,按照存活率计。
作为结果,本发明的化合物1,2,13,17,22,23,24,25,27,28,30,31,32,33,34,47,48,49,50,51,52,57,84,85,88,89,90,91,92和95被评价为指标3或更高。
测试实施例5(Musca domestica)
具有直径5.5厘米的滤纸铺展到具有直径5.5厘米的聚乙烯杯底,0.7毫升的测试溶液滴加到滤纸之上。作为饵的30毫克蔗糖匀称放置在滤纸上。10只Musca domestica雌性成虫释放入聚乙烯杯和用盖密封杯子。在24小时以后,计算死亡昆虫数目。
死亡率通过以下公式计算。
死亡率(%)=(死亡昆虫的数目/测试昆虫的数目)×100
测试化合物的效果用如下指标评估:4:100%,3:70-99%,2:40-69%,1:10-39%和0:0-9%,按照死亡率计。
结果,本发明的化合物1,2,5,6,16,24,25,26,28,32,47,48,50,51,57,83,85,88,89,90,91,92和95被评价为指标3或更高。
测试实施例6(Blattalla germanica)
具有直径5.5厘米的滤纸铺展到具有直径5.5厘米的聚乙烯杯底,0.7毫升的测试溶液滴加到滤纸之上。作为饵的30毫克蔗糖匀称放置在滤纸上。2只Blattalla germanica雄性成虫释放入聚乙烯杯和用盖密封杯子。在6天以后,计算死亡昆虫数目。
死亡率通过以下公式计算。
死亡率(%)=(死亡昆虫的数目/测试昆虫的数目)×100
测试化合物的效果用如下指标评估:4:100%,2:50%,和0:0%,按照死亡率计。
结果,本发明的化合物1,4,6,13,16,23,24,25,27,28,
32,34,47,48,49,50,51,53,57,59,60,83,84,85,88,89,
90,91,92和95评价为指标4。
测试实施例7(Culex pipiens pallens)
向100ml的离子交换水添加0.7毫升的测试溶液(活性成分浓度:3.5ppm)。20只末龄Culex pipiens pallens幼虫释放入该溶液。1天后,计算死亡昆虫数目。
死亡率通过以下公式计算。
死亡率(%)=(死亡昆虫的数目/测试昆虫的数目)×100
测试化合物的效果用如下指标评估:4:91-100%,2:11-90%,和0:0-10%,按照死亡率计。
结果,本发明的化合物1,2,5,13,14,16,23,24,25,26,28,50,51,53,57,83,85,90,96,99,110和112评价为指标4。
测试实施例8(Tetranychus urticae)
具有许多只Tetranychus urticae寄生在其上的豆植物的叶子被切掉,然后放置于在3盎司杯中播种后生长一周(a week)的豆植物的叶子上。其被放置一天以致昆虫可以从被切割的叶子移动到该杯子中种植的豆植物的叶子。次日,使用一对镊子除去用于接种的叶子,将20毫升的测试溶液喷雾到植物上。在8天以后,计算该杯子中的豆植物的初生叶上存活的雌性成虫数目。
测试化合物的效果用5阶指标评估:指标4:0至3;指标3:4至10;指标2:11至20;指标1:21至30,和指标0:31或更多,按照存活数目计算。
结果,本发明的化合物1,3,6和10被评价为指标3或更高。
测试实施例9(Plutella xylostella)
在4-叶发育阶段的卷心菜(Brassicae oleacea)上喷雾20毫升的测试溶液。干燥测试溶液后,切断卷心菜的地面上的部分,然后与5只2龄Plutella xylostella幼虫一起放入聚乙烯杯(体积:100毫升)中。杯保持在25℃。在5天以后,计算死亡昆虫数目。
死亡率通过以下公式计算。
死亡率(%)=(死亡昆虫的数目/测试昆虫的数目)×100
测试化合物的效果用如下指标评估:4:100%,3:80-99%,2:60-79%,1:30-59%和0:0-29%,按照死亡率计。
结果,本发明的化合物1,2,4,5,7,13,14,16,17,18,20,22,23,24,25,26,27,28,30,31,32,33,34,38,47,48,49,50,51,53,54,55,57,58,62,63,68,72,73,76,80,83,84,85,86,88,89,90,91,92,95,96,99,101,102,103,108和110被评价为指标3或更高。
测试实施例10(Bemisia tabaci)
在0.1毫升的有机溶剂(二甲苯∶DMF=1∶1)和0.04毫升的二甲苯与Sorpol 3005X(商标;Toho Chemical Industry Co.,Ltd.制备)(体积混合比率;二甲苯∶Sorpol 3005X=1∶9)混合物溶液的混合物中,40毫克的任一种本发明的化合物被溶解,然后用80毫升的离子交换水稀释以制备500ppm溶液。然后,30毫升的500ppm溶液用45毫升的离子交换水稀释制备200ppm溶液。然后,20毫升的200ppm溶液用60毫升的离子交换水稀释以制备50ppm溶液。进一步,20毫升的50ppm溶液用60毫升的离子交换水稀释以制备12.5ppm溶液。向各溶液添加Dyne(商标;Takeda pharmaceutical Co.,Ltd.制备),其量为dyne可被稀释3,000倍以制备测试溶液。
卷心菜在三盎司杯中生长约3周,然后,除第二真叶之外,除去全部叶子。卷心菜上,释放Bemisia tabaci成虫且允许孵蛋3天。然后,除去成虫。杯贮存在温室中8天以培养蛋。然后,20毫升的测试溶液被喷雾到植物上。在7天以后,计算死亡昆虫数目。
测试化合物的效果用5阶指标评估:指标4:死亡率100%,指标3:死亡率90-99%(幼虫的附着面积是未处理情况的1-10%),指标2:死亡率60-89%(幼虫的附着面积是未处理情况的11-40%),指标1:死亡率30-59%(幼虫的附着面积是未处理情况的41-70%),和指标0:死亡率0-29%(幼虫的附着面积是未处理情况的71%或更高)。
结果,本发明的化合物1,2和55在500ppm被评价为指标3或更高。本发明的化合物14,16,17,18,22,30,34,37,42,44,49,50,51,60,70,73,74,86,87,88,89,90,91,92,105,111,112和115在200ppm被评价为指标3或更高。本发明的化合物5,19,24和28在50ppm被评价为指标3或更高。本发明的化合物23,25,57和59在12.5ppm被评价为指标3或更高。
测试实施例11(Haemaphysalis longicornis)
0.5毫克中的任一种本发明的化合物被溶解在1毫升的丙酮中,该溶液均匀地铺展到滤纸(TOYO No.2;5×10厘米)的一侧上。在干燥以后,滤纸对折,且夹住侧面以制备袋。测试扁虱(Haemaphysalislongicornis,非吸血的蛹扁虱,10只扁虱一组)放置入袋。袋被夹住和密封。在2天以后,计算死亡扁虱数目。
结果,本发明的化合物1,24,26,28,42,47,48,49,50,51,83,90和91给出的死亡率为90%或更多。
测试实施例12(Spodoptera litura)
在0.1毫升的有机溶剂(二甲苯∶DMF=1∶1)和0.04毫升的二甲苯与Sorpol 3005X(商标;Toho Chemical Industry Co.,Ltd.制备)(混合比率;二甲苯∶Sorpol 3005X=1∶9)混合物溶液的混合物中,16毫克的任一种本发明的化合物被溶解,然后用80毫升的离子交换水稀释以制备200ppm溶液。然后,20毫升的200ppm溶液用60毫升的离子交换水稀释以制备50ppm溶液。向各溶液添加Dyne(商标;Takeda pharmaceutical Co.,Ltd.制备),其量为dyne可被稀释3,000倍以制备测试溶液。
3盎司杯中生长的在5-叶发育阶段的卷心菜上,喷雾20毫升的测试溶液。在风干以后,10只4龄Spodoptera litura幼虫释放在植物上。在4天以后,计算死亡昆虫数目。
死亡率通过以下公式计算。
死亡率(%)=(死亡昆虫的数目/测试昆虫的数目)×100
测试化合物的效果用如下指标评估:4:100%,3:80-99%,2:60-79%,1:30-59%和0:0-29%,按照死亡率计。
结果,本发明的化合物3,10,19,74,86和87在50ppm被评价为指标3或更高。本发明的化合物104,105,112和113在200ppm被评价为指标3或更高。
测试实施例13(Adoxophyes orana)
在0.1毫升的有机溶剂(二甲苯∶DMF=1∶1)和0.04毫升的二甲苯与Sorpol 3005X(商标;Toho Chemical Industry Co.,Ltd.制备)(体积混合比率;二甲苯∶Sorpol 3005X=1∶9)混合物溶液的混合物中,16毫克的任一种本发明的化合物被溶解,然后用80毫升的离子交换水稀释以制备200ppm溶液。然后,20毫升的200ppm溶液用60毫升的离子交换水稀释以制备50ppm溶液。然后,20毫升的50ppm溶液用60毫升的离子交换水稀释以制备12.5ppm溶液。向各溶液添加Dyne(商标;Takedapharmaceutical Co.,Ltd.制备),其量为dyne可被稀释3,000倍以制备测试溶液。
在3盎司杯中种植的具有约12-15厘米高的苹果秧苗上,喷雾20毫升的测试溶液。在风干以后,约60只1龄Adoxophyes orana幼虫被释放在植物上。
在7天以后,计算存活的昆虫数目。死亡率通过以下公式计算。
死亡率(%)={[(测试昆虫的数目)-(存活昆虫的数目)]/(测试昆虫的数目)}×100
测试化合物的效果用如下指标评估:4:100%,3:80-99%,2:60-79%,1:30-59%和0:0-29%,按照死亡率计。
结果,本发明的化合物10,19,74,86,87,93,104,105,112和113在50ppm被评价为指标3或更高。本发明的化合物3在12.5ppm被评价为指标3或更高。
工业实用性
本发明的化合物具有极好的害虫控制作用,由此其适用作杀虫组合物的活性成分。
Claims (26)
1.亚氨酸酯化合物,由式(I-1)表示:
其中,
Z表示任选地被选自如下所述的组A的基团取代的具有3到14个构成环的原子的碳环基团,或任选地被选自如下所述的组A的基团取代的具有3到14个构成环的原子的杂环基团;
G表示-A1-R1基团,-S(=O)2-R2基团或-N(R3)-R1基团;
X表示-A2-R4基团,-S(=O)-R5基团或-S(=O)2-R5基团;
X0表示-A3-R6基团,-S(=O)-R7基团,-S(=O)2-R7基团或卤素原子;或
X和X0任选地合起来形成-A2-T0-A3-基团;
M1表示-R8基团,-A8-R8基团,卤素原子或氢原子;
A1,A2和A3独立地表示氧原子或硫原子;
R1表示任选地被选自如下所述的组D的基团取代的C1-C20链烃基团,-Q基团,-T1-Q基团,-T1-S-Q基团或-T1-O-Q基团;
R2表示任选地被选自如下所述的组E的基团取代的C1-C20链烃基团,或任选地被选自如下所述的组B的基团取代的苯基;
R3表示任选地被选自如下所述的组D的基团取代的C1-C20链烃基团,-Q基团,-T1-Q基团,C1-C6烷氧基,C2-C7烷酰基,单(C1-C7烷基)氨基,二(C1-C7烷基)氨基或(C1-C7烷基)苯基氨基;
R4和R6独立地表示任选地被选自如下所述的组D的基团取代的C1-C6链烃基团,-Q基团,-T1-Q基团,-C(=A4)-R11基团,-C(=A4)-A5-R11基团或-S(=O)2-R11基团;
R5和R7独立地表示任选地被选自如下所述的组E的基团取代的C1-C6链烃基团,-Q1基团或-T2-Q1基团
R8表示任选地被选自如下所述的组E的基团取代的C1-C20链烃基团,-Q基团或-T1-Q基团;
A8表示氧原子或硫原子;
T0表示任选地被卤素原子或苯基取代的C2-C6烷二基且其中该烷二基的碳-碳单键可以由氧原子、硫原子和/或羰基中断,-Q9基团,-T1-Q9-基团或-T1-Q9-T2-基团;
Q表示任选地被选自如下所述的组A的基团取代的具有3到14个构成环的原子的碳环基团,或任选地被选自如下所述的组A的基团取代的具有3到14个构成环的原子的杂环基团;
Q1表示任选地被选自如下所述的组B的基团取代的具有3到14个构成环的原子的碳环基团,或任选地被选自如下所述的组B的基团取代的具有3到14个构成环的原子的杂环基团;
T1和T2独立地表示任选地被卤素原子取代的C1-C6烷二基,或C2-C6烯二基;
A4和A5独立地表示氧原子或硫原子;
Q9表示邻亚苯基或萘-1,8-二基;
R11表示任选地被选自如下所述的组E的基团取代的C1-C6链烃基团,或任选地被选自如下所述的组B的基团取代的具有3到14个构成环的原子的碳环基团,
组A由以下组成:卤素原子,氰基,硝基,甲酰基,任选地被卤素原子取代的C1-C6链烃基团,-A6-L1基团,-N(L3)-L2基团,-N(L3)-N(L2)-L1基团,-N=C(L3)-L2基团,-S(=O)-L1基团,-S(=O)2-L1基团,-S(=O)2-N(L3)-L2基团,-O-S(=O)2-L1基团,-NL2-S(=O)2-L1基团,-C(=A7)-L1基团,-C(=A7)-O-L1基团,-O-C(=A7)-L1基团,-NL2-C(=A7)-L1基团,-O-C(=O)-O-L1基团,-C(=A7)-T4-A6-L1基团,-C(=A7)-N(L3)-L2基团,-Q2基团,-T3-Q2基团,-A6-Q2基团,-A6-T4-Q2基团,-N(L3)-Q2基团,-N(L3)-N(L2)-Q2基团,-N=C(R12)-Q2基团,-S(=O)-Q2基团,-S(=O)2-Q2基团,-S(=O)2-N(L3)-Q2基团,-O-S(=O)2-Q2基团,-NL2-S(=O)2-Q2基团,-C(=A7)-Q2基团,-C(=A7)-A6-Q2基团,-A6-C(=A7)-Q2基团,-NL2-C(=A7)-Q2基团,-C(=A7)-T4-A6-Q2基团,和-C(=A7)-N(L3)-Q2基团;
组B由以下组成:卤素原子,氰基,硝基,任选地被卤素原子取代的C1-C6烷基,任选地被卤素原子取代的C2-C6烯基,任选地被卤素原子取代的C2-C6炔基,C1-C6烷基硫基,和C1-C6烷氧基;
组D由以下组成:卤素原子,氰基,硝基,任选地被卤素原子取代的C1-C6烷氧基,任选地被卤素原子取代的C1-C6烷基硫基,任选地被卤素原子取代的C1-C6烷基磺酰基,任选地被卤素原子取代的(C1-C6烷基)羰基,任选地被卤素原子取代的(C1-C6烷氧基)羰基,和任选地被卤素原子取代的(C1-C6烷氧基)羰氧基;和
组E由以下组成:卤素原子,氰基,硝基,C1-C6烷基硫基,和C1-C6烷氧基;
其中,A6和A7独立地表示氧原子或硫原子;
L1表示任选地被卤素原子取代的C1-C6链烃基团;
L2和L3独立地表示氢原子,任选地被卤素原子取代的C1-C6烷基;
Q2表示任选地被选自上述组B的基团取代的具有3到14个构成环的原子的碳环基团,或任选地被选自上述组B的基团取代的具有3到14个构成环的原子的杂环基团;
T3和T4独立地表示任选地被卤素原子取代的C1-C6烷二基;和
R12表示任选地被卤素原子取代的C1-C6链烃基团或任选地被卤素原子取代的苯基。
2.根据权利要求1的亚氨酸酯化合物,其中M1是C1-C6烷基,C1-C6烷氧基,C1-C6烷基硫基,任选地被选自该E组的基团取代的苯基,任选地被选自该E组的基团取代的苯氧基,任选地被选自该E组的基团取代的苯基硫基,任选地被选自该E组的基团取代的单环的不饱和的具有3-8个构成环的原子的杂环基,卤素原子或氢原子。
3.根据权利要求1的亚氨酸酯化合物,其中M1是甲基,乙基,丙基,丁基,苯基,2-甲基苯基,3-甲基苯基,4-甲基苯基,2-氟苯基,3-氟苯基,4-氟苯基,2-氯苯基,3-氯苯基,4-氯苯基,甲氧基,乙氧基,丙氧基,苯氧基,2-甲基苯氧基,3-甲基苯氧基,4-甲基苯氧基,2-氟苯氧基,3-氟苯氧基,4-氟苯氧基,2-氯苯氧基,3-氯苯氧基,4-氯苯氧基,甲硫基,乙硫基,丙硫基,丁硫基,苯基硫基,2-甲基苯基硫基,3-甲基苯基硫基,4-甲基苯基硫基,2-氟苯基硫基,3-氟苯基硫基,4-氟苯基硫基,2-氯苯基硫基,3-氯苯基硫基,4-氯苯基硫基,2-噻吩基,3-噻吩基,2-呋喃基,3-呋喃基,氟原子,氯原子或氢原子。
4.根据权利要求1的亚氨酸酯化合物,其中M1是甲基,乙基,丙基,丁基,甲氧基,乙氧基,丙氧基,甲硫基,乙硫基,丙硫基,氟原子,或氢原子。
5.根据权利要求1的亚氨酸酯化合物,其中M1是氢原子。
6.根据权利要求1到5中任一项的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自如下所述的组A′的基团取代的碳环基团,或具有3到14个构成环的原子的任选地被选自如下所述的组A′的基团取代的杂环基团,和
组A′由以下组成:卤素原子,氰基,硝基,甲酰基,任选地被卤素原子取代的C1-C6链烃基团,-A6-L1基团,-C(=A7)-L1基团,-C(=A7)-O-L1基团,-O-C(=A7)-L1基团,-NL2-C(=A7)-L1基团,-C(=A7)-N(L3)-L2基团,-Q2基团,-T3-Q2基团,-A6-Q2基团,-A6-T4-Q2基团,-C(=A7)-Q2基团,-C(=A7)-O-Q2基团,-O-C(=A7)-Q2基团,-NL3-C(=A7)-Q2基团和-C(=A7)-N(L3)-Q2基团。
7.根据权利要求1到5中任一项的亚氨酸酯化合物,其中Z是具有3到14个构成环的原子的任选地被选自如下所述的组A2′的基团取代的碳环基团,或具有3到14个构成环的原子的任选地被选自如下所述的组A2′的基团取代的杂环基团,和
组A2′由以下组成:卤素原子,任选地被卤素原子取代的C1-C6烷基,任选地被卤素原子取代的C2-C6烯基,任选地被卤素原子取代的C2-C6炔基,任选地被卤素原子取代的C1-C6烷基硫基,任选地被卤素原子取代的C1-C6烷氧基,和任选地被选自如权利要求1中定义的该B组的基团取代的苯基。
8.根据权利要求7的亚氨酸酯化合物,其中Z是任选地被选自组A2′的基团取代的具有3到14个构成环的原子的碳环基团。
9.根据权利要求8的亚氨酸酯化合物,其中Z是任选地被选自该组A2′的基团取代的苯基,5-茚满基,或萘基。
10.根据权利要求1到5中任一项的亚氨酸酯化合物,其中Z是任选地被选自如下所述的组A3′的基团取代的苯基,5-茚满基,或萘基,和
组A3′由以下组成:卤素原子,甲基,乙基,丙基,异丙基,丁基,三氟甲基,甲氧基,乙氧基,丙氧基,异丙氧基,丁氧基,三氟甲氧基,3,4-亚甲基二氧基,甲硫基,乙硫基,丙硫基,异丙硫基,丁硫基,三氟甲硫基,苯基,2-甲基苯基,3-甲基苯基,4-甲基苯基,2-乙基苯基,3-乙基苯基,4-乙基苯基,2-丙基苯基,3-丙基苯基,4-丙基苯基,2-异丙基苯基,3-异丙基苯基,4-异丙基苯基,2-氟苯基,3-氟苯基,4-氟苯基,2-氯苯基,3-氯苯基,4-氯苯基,2-溴苯基,3-溴苯基,和4-溴苯基。
11.根据权利要求1至10中任一项的亚氨酸酯化合物,其中G是-A1-R1基团或-N-(R3)-R1基团。
12.根据权利要求1至10中任一项的亚氨酸酯化合物,其中G是-A1-R1基团。
13.根据权利要求1到10中任一项的亚氨酸酯化合物,其中G是-A1-R1基团,且R1是-Q基团或-T1-Q基团且其中Q是如权利要求1所限定的Q1,或任选地被选自卤素原子,氰基,硝基,C1-C6烷基硫基和C1-C6烷氧基的基团取代的C1-C20链烃基团。
14.根据权利要求1到10中任一项的亚氨酸酯化合物,其中G是-A1-R1基团;A1是S;和R1是-Q基团或-T1-Q基团且其中Q是具有3到14个构成环的原子的任选地被选自如权利要求1限定的组B的基团取代的碳环基团,或任选地被选自卤素原子,氰基,硝基,C1-C6烷基硫基和C1-C6烷氧基的基团取代的C1-C20链烃基团。
15.根据权利要求1到10中任一项的亚氨酸酯化合物,其中G是-A1-R1基团;A1是S;和R1是任选地被选自卤素原子,氰基,硝基,C1-C6烷基硫基和C1-C6烷氧基的基团取代的C1-C20链烃基团,或-Q基团或-T1-Q基团且其中Q是任选被选自如权利要求1中定义的该组B的基团取代的苯基或任选地被选自如权利要求1定义的该组B的基团取代的萘基。
16.根据权利要求1到10中任一项的亚氨酸酯化合物,其中G是-A1-R1基团;A1是O;和R1是-Q基团且其中Q是任选地被选自如权利要求1中所定义的该组B的基团取代的苯基或任选地被选自如权利要求1定义的该组B的基团取代的萘基。
17.根据权利要求1至16中任一项的亚氨酸酯化合物,其中X是-A2-R4基团和X0是-A3-R6基团,或X和X0合起来形成-A2-T0-A3-基团。
18.根据权利要求1至16中任一项的亚氨酸酯化合物,其中X是-A2-R4基团和X0是-A3-R6基团。
19.根据权利要求1到16中任一项的亚氨酸酯化合物,其中X是-A2-R4基团;X0是-A3-R6基团;且R4和R6独立地是-Q基团或-T1-Q基团且其中Q是如权利要求1所限定的Q1,或任选地被选自卤素原子,氰基,硝基,C1-C6烷基硫基和C1-C6烷氧基的基团取代的C1-C6链烃基团。
20.根据权利要求1至16中任一项的亚氨酸酯化合物,其中X是-A2-R4基团;X0是-A3-R6基团;且R4和R6独立地是-Q基团或-T1-Q基团且其中Q是如权利要求1所限定的Q1。
21.根据权利要求1到16中任一项的亚氨酸酯化合物,其中X是-A2-R4基团;X0是-A3-R6基团;且R4和R6独立地是-Q基团且其中Q是任选地被选自如权利要求1定义的该组B的基团取代的苯基。
22.根据权利要求1到16中任一项的亚氨酸酯化合物,其中X是-A2-R4基团;X0是-A3-R6基团;A2和A3各自是S;且R4和R6独立地是-Q基团,其中Q是任选地被选自如权利要求1定义的该组B的基团取代的苯基。
23.杀虫组合物,包括根据权利要求1至22中任一项的化合物作为活性成分。
24.根据权利要求1至22中任一项的化合物用于害虫控制的用途。
25.根据权利要求1至22中任一项的化合物的用于生产杀虫组合物的用途。
26.控制害虫的方法,其包括施加根据权利要求1至22中任一项的化合物至该害虫或该害虫栖息之地。
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US9598654B1 (en) * | 2006-10-12 | 2017-03-21 | Stonewick, Llc | Fuel compositions for catalytic burners |
JP2009227655A (ja) * | 2007-11-16 | 2009-10-08 | Sumitomo Chemical Co Ltd | α,β−不飽和イミダート化合物およびそれを含有する有害生物防除剤 |
KR20130121904A (ko) | 2010-11-29 | 2013-11-06 | 바이엘 인텔렉쳐 프로퍼티 게엠베하 | 알파,베타-불포화 이민 |
KR101151383B1 (ko) * | 2012-01-10 | 2012-05-31 | 늘푸른(주) | 공간살포 방역소독유용 친환경 식물성 기유 및 그 제조방법 |
US20160242422A1 (en) * | 2015-02-19 | 2016-08-25 | Mark C. Elizer | Agricultural composition containing chitin and chitinase-producing bacteria for treating soil and plants |
GB201805083D0 (en) * | 2018-03-28 | 2018-05-09 | Croda Int Plc | Agrochemical polymer dispersants |
WO2022008283A1 (en) | 2020-07-07 | 2022-01-13 | Universitat Rovira I Virgili | Reagents for the polyfluoroalkylthiolation of organic compounds and method for production thereof |
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