CN100455561C - Compound of 1-phenyl-1-methylcyclopropane and application thereof - Google Patents
Compound of 1-phenyl-1-methylcyclopropane and application thereof Download PDFInfo
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- CN100455561C CN100455561C CNB2005100471566A CN200510047156A CN100455561C CN 100455561 C CN100455561 C CN 100455561C CN B2005100471566 A CNB2005100471566 A CN B2005100471566A CN 200510047156 A CN200510047156 A CN 200510047156A CN 100455561 C CN100455561 C CN 100455561C
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- phenyl
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 37
- OGUNTYRKFMVMLS-UHFFFAOYSA-N (1-methylcyclopropyl)benzene Chemical compound C=1C=CC=CC=1C1(C)CC1 OGUNTYRKFMVMLS-UHFFFAOYSA-N 0.000 title claims description 7
- 201000010099 disease Diseases 0.000 claims abstract description 10
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims abstract description 10
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 230000001954 sterilising effect Effects 0.000 claims description 13
- 238000004659 sterilization and disinfection Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 241000238631 Hexapoda Species 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- -1 cyclopropane compound Chemical class 0.000 abstract description 10
- 230000002070 germicidal effect Effects 0.000 abstract 1
- 230000000361 pesticidal effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000749 insecticidal effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 235000014347 soups Nutrition 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 238000003810 ethyl acetate extraction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000855 fungicidal effect Effects 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- 241000221785 Erysiphales Species 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000008062 acetophenones Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- IOCYQQQCJYMWDT-UHFFFAOYSA-N (3-ethyl-2-methoxyquinolin-6-yl)-(4-methoxycyclohexyl)methanone Chemical compound C=1C=C2N=C(OC)C(CC)=CC2=CC=1C(=O)C1CCC(OC)CC1 IOCYQQQCJYMWDT-UHFFFAOYSA-N 0.000 description 1
- SMSVMBMJEYTUOZ-UHFFFAOYSA-N 1-(4-fluoro-3-methylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(F)C(C)=C1 SMSVMBMJEYTUOZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- 241000272639 Brachycaudus mimeuri Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 241000256059 Culex pipiens Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- 241000409991 Mythimna separata Species 0.000 description 1
- 241000896238 Oidium Species 0.000 description 1
- 241000233679 Peronosporaceae Species 0.000 description 1
- 241000500437 Plutella xylostella Species 0.000 description 1
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002521 alkyl halide group Chemical group 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- BFAKENXZKHGIGE-UHFFFAOYSA-N bis(2,3,5,6-tetrafluoro-4-iodophenyl)diazene Chemical compound FC1=C(C(=C(C(=C1F)I)F)F)N=NC1=C(C(=C(C(=C1F)F)I)F)F BFAKENXZKHGIGE-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 230000001418 larval effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005537 sulfoxonium group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses one kind of 1-phenyl-1-mehtyl cyclopropane compound with the general expression as shown. The compound of the present invention has excellent germicidal and pesticidal activity and may be used in preventing and controlling plant diseases and pests.
Description
Technical field
The invention belongs to sterilization, field of pesticides.Relate to a kind of 1-phenyl-1-methyl cyclopropane compounds and application thereof.
Background technology
Because sterilant or sterilant are in use for some time, disease or insect can produce resistance to it, therefore, need constantly invention novel with compound and composition improved tool sterilization or insecticidal activity.
Some has the existing report of preparation (WO01/87826A1) of 1-(4-replacement) phenyl-1-methyl cyclopropane compounds of fungicidal activity.But as the preparation of 1-shown in the present (3-replaces or 4, and 5-two replaces or 3,4, and 5-three replaces) phenyl-1-methyl cyclopropane compounds and sterilization thereof, insecticidal activity are not seen open.
Summary of the invention
The invention provides a kind of 1-(5-three replaces for 3-replacement or 3,4-two replacements or 3,4) phenyl-1-methyl cyclopropane compounds of novel structure, shown in general formula (I):
Wherein:
R
1Be halogen, C
1-C
4Alkyl, C
1-C
3Alkylhalide group or C
1-C
3Alkoxyl group;
R
2Be H, halogen, C
1-C
3Alkyl;
R
3Be H, halogen, C
1-C
3Alkyl;
W is O or NH;
And steric isomer.
Described steric isomer comprises that the B1 key and the phenyl ring of vicinity are trans or cis; B2 key and B1 key are trans or cis; The B3 key is trans or cis with the phenyl ring of vicinity.
Comparatively preferred compound is in the general formula (I) among the present invention:
R
1Be halogen, C
1-C
4Alkyl or C
1-C
3Alkylhalide group;
R
2Be H, halogen, C
1-C
3Alkyl;
R
3Be H, halogen, C
1-C
3Alkyl;
W is O or NH;
The B1 key is trans with the phenyl ring of vicinity;
B2 key and B1 key are trans;
The B3 key is a cis with the phenyl ring of vicinity.
The alkyl of indication comprises the straight or branched alkyl in the general formula.Alkylhalide group is meant the group that alkyl is replaced by one or more halogen atoms.Alkoxyl group is meant the straight or branched form, and end is connected with the group of Sauerstoffatom, for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy etc.Halogen is meant fluorine, chlorine, bromine, iodine.
General formula compound of the present invention (I) can be prepared by following method:
Raw material substituted acetophenone (II) (can be bought by market) (prepares with reference to following document: Smissman E.E.et al.J.Org.Chem.1964 with III, 29,3161), in the presence of alkali as sodium hydroxide, sodium methylate, potassium tert.-butoxide, sodium tert-butoxide etc., be dissolved in The suitable solvent such as chloroform, methylene dichloride, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, DMF, THF, dimethyl sulfoxide (DMSO) or dioxane etc., temperature made compound (IV) for-10 ℃ in 0.5-48 hour to the following reaction of boiling point.
Compound (IV) and trimethylammonium sulfoxonium halogenide (can by buying on the market), in the presence of alkali as sodium hydroxide, sodium methylate, potassium tert.-butoxide, sodium tert-butoxide etc., be dissolved in The suitable solvent such as chloroform, methylene dichloride, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, DMF, THF, dimethyl sulfoxide (DMSO) or dioxane etc., temperature made compound (V) for-10 ℃ in 0.5-48 hour to the following reaction of boiling point.
Compound (V) is in The suitable solvent, and (N-methoxyl group and phenyl ring can be cis or trans, or the mixture of the two, prepare with reference to following document: US5194662) with (VI).Temperature made compound (I-1) for-10 ℃ in 0.5-48 hour to the following reaction of boiling point.Solvent can be chloroform, methylene dichloride, tetracol phenixin, methyl alcohol, ethanol, hexane, benzene, toluene, ethyl acetate, DMF, THF or dioxane etc.Add acid, as sulfuric acid, hydrochloric acid or acetic acid etc. to reacting favourable.
Compound (I-1) is in The suitable solvent, and with aqueous methylamine solution, temperature made compound (I-2) for-10 ℃ in 0.5-48 hour to the following reaction of boiling point.Solvent can be chloroform, methylene dichloride, tetracol phenixin, methyl alcohol, ethanol, hexane, benzene, toluene, ethyl acetate, DMF, THF or dioxane etc.
According to the difference of reaction conditions or the difference of starting raw material, all might there be steric isomerism in compound (IV), compound (V), compound (I-1) and compound (I-2).For example the B1 key can be trans or cis with the phenyl ring of vicinity; B2 key and B1 key can be trans or cis; The B3 key can be trans or cis with the phenyl ring of vicinity.By selecting suitable starting raw material or control reaction conditions, can obtain excessive product of a kind of isomer or individual isomer.Also can for example, obtain individual isomer by crude product is carried out the separation of conventional means by methods such as column chromatography, recrystallizations.
Part general formula of the present invention (I) compound is as shown in table 1:
Table 1:
| Compound | W | R 1 | R 2 | R 3 | B1 (with respect to phenyl ring) | B2 (with respect to B1) | B3 (with respect to phenyl ring) |
| 1 | O | Cl | H | H | Trans | Trans | Cis |
| 2 | O | F | H | H | Trans | Trans | Cis |
| 3 | O | Br | H | H | Trans | Trans | Cis |
| 4 | O | CH 3 | H | H | Trans | Trans | Cis |
| 5 | O | CF 3 | H | H | Trans | Trans | Cis |
| 6A | O | CH 3 | F | H | Trans | Trans | Cis |
| 6B | O | CH 3 | F | H | Trans | Cis | Cis |
| 7 | O | CH 3 | F | CH 3 | Trans | Trans | Cis |
| 8 | NH | Cl | H | H | Trans | Trans | Cis |
| 9 | NH | F | H | H | Trans | Trans | Cis |
| 10 | NH | CH 3 | H | H | Trans | Trans | Cis |
| 11 | NH | CF 3 | H | H | Trans | Trans | Cis |
| 12 | NH | CH 3 | F | H | Trans | Trans | Cis |
| 13 | NH | CH 3 | F | CH 3 | Trans | Trans | Cis |
Compound in the table 1
1H NMR (300MHz, CDCl
3) data are as follows:
| Compound | 1H?NMR(CDCl 3)ppm |
| 1 | 7.445-7.356(m，3H)，7.239-7.108(m，5H)，4.983(s，2H)，4.09(s， 3H)，3.874(s，3H)，1.964(s，3H)，1.718-1.689(t，1H)，1.383-1.346 (t，1H)，1.204(s，3H)，1.176-1.148(m，1H) |
| 2 | 7.469-7.337(m，3H)，7.284-7.163(m，2H)，7.032-6.854(m，3H)， 4.984(s，2H)，4.050(s，3H)，3.860(s，3H)，1.958(s，3H)， 1.744-1.694(t，1H)，1.391-1.353(t，1H)，1.212(s，3H)， 1.183-1.139(m，1H) |
| 3 | 7.445-7.298(m，3H)，7.190-7.152(m，5H)，4.978(s，2H)，4.50(s， 3H)，3.861(s，3H)，1.962(s，3H)，1.714-1.686(t，1H)，1.379-1.341 (t，1H)，1.198(s，3H)，1.170-1.126(m，1H) |
| 4 | 7.455-7.365(m，3H)，7.193-7.168(m，2H)，7.080-6.986(m，3H)， 4.988(s，2H)，4.052(s，3H)，3.863(s，3H)，2.342(s，3H)，1.979(s， 3H)，1.745-1.716(t，1H)，1.375-1.336(t，1H)，1.212(s，3H)， 1.202-1.155(m，1H) |
| 5 | 7.485-7.375(m，6H)，7.215-7.189(m，2H)，7.987(s，2H)，4.056(s， 3H)，3.868(s，3H)，1.977(s，3H)，1.775-1.747(t，1H)，1.418-1.389 (t，1H)，1.233(s，3H)，1.213-1.185(m.1H) |
| 6A | 7.441-7.353-(m，3H)，7.189-6.863(m，4H)，4.986(s，2H)，4.049 (s，3H)，3.860(s，3H)，2.257-2.250(d，3H)，1.977(s，3H)， 1.704-1.678(t，1H)，1.353-1.324(t，1H)，1.181(s，3H)， 1.163-1.130(m，1H) |
| 6B | 7.533-7.472(m，1H)，7.407-7.377(m，2H)，7.210-7.032(m，3H)， 6.783-6.750(t，1H)，5.025(s，2H)，3.948(s，3H)，3.707(s，3H)， 2.104-2.101(m，1H)，2.081(s，3H)，1.849(a，3H)，1.196-1.168 (m，1H)，1.184(s，3H)，0.955-0.933(t，1H) |
| 7 | 7.475-7.336(m，3H)，7.208-7.185(d，1H)，6.892-6.869(d，2H)， 4.985(s，2H)，4.050(s，3H)，3.861(s，3H)，2.235-2.229(d，6H)， 1.981(s，3H)，1.709(t，1H)，1.315-1.287(t，1H)，1.170(s，3H)， 1.123-1.095(m，1H) |
| 8 | 7.545-7.324(m，3H)，7.249-7.112(m，5H)，6.731(s，1H)，4.982(s， 2H)，3.962(s，3H)，2.924-2.909(d，3H)，1.965(s，3H)， 1.738-1.689(t，1H)，1.379-1.324(m，1H)，1.192(s，3H)， 1.156-1.128(m，1H) |
| 9 | 7.465-7.346(m，3H)，7.236-7.168(m，2H)，7.031-6.879(m，3H)， 6.736(s，1H)，4.982(s，2H)，3.960(s，3H)，2.923-2.906(d，3H)， 1.958(s，3H)，1.748-1.693(t，1H)，1.386-1.320(m，1H)，1.202(s， 3H)，1.180-1.135(m，1H) |
| 10 | 7.471-7.342(m，3H)，7.193-6.992(m，5H)，6.734(s，1H)，4.980(s， 2H)，3.962(s，3H)，2.921-2.904(d，3H)，2.338(s，3H)，1.977(s， 3H)，1.725-1.697(t，1H)，1.339-1.302(m，1H)，1.201(s，3H)， 1.170-1.144(m，1H) |
| 11 | 7.466-7.342(m，7H)，7.195-7.165(m，1H)，6.750(s，1H)，4.989(s， 2H)，3.963(s，3H)，2.925-2.909(d，3H)，1.976(s，3H)， 1.762-1.713(t，1H)，1.432-1.396(m，1H)，1.219(s，3H)， 1.202-1.156(m，1H) |
| 12 | 7.501-7.325(m，3H)，7.203-7.143(m，2H)，7.085-6.839(m，2H)， 6.725(s，1H)，4.983(s，2H)，3.959(s，3H)，2.921-2.903(d，3H)， 2.247(s，3H)，1.977(s，3H)，1.703-1.635(m，1H)，1.345-1.258(m， 1H)，1.170(s，3H)，1.118-1.063(m，1H) |
| 13 | 7.482-7.452(m，1H)，7.421-7.324(m，2H)，7.198-7.169(m，1H)， 6.892-6.870(d，2H)，6.752-6.735(d，1H)，4.991(s，2H)，3.962(s， 3H)，2.922-2.906(d，3H)，2.236-2.228(d，6H)，1.984(s，3H)， 1.701-1.653(m，1H)，1.319-1.262(m，2H)，1.158(s，3H)， 1.118-1.074(m，1H) |
General formula of the present invention (I) compound has sterilization and insecticidal activity simultaneously.Have now found that general formula (I) compound has the better prevention effect to oidium, Powdery Mildew etc.; Mythimna separata, small cabbage moth, black peach aphid, carmine spider mite and culex pipiens pollens also there is excellent control effect.Therefore, the present invention comprises that also general formula (I) compound is used for the purposes and the purposes that is used to control insect pest of controlling plant disease.
The present invention comprises that also with general formula (I) compound be sterilization, the insect-killing composition of active ingredient.The weight percentage of active ingredient is between 1-99% in this sterilization, the insect-killing composition.Comprise also in this sterilization, the insect-killing composition that agricultural goes up acceptable carrier.
Other embodiments of the present invention are the method for preventing and treating disease, and this method comprises sterilization of the present invention, insect-killing composition are imposed on the described disease growth medium, as imposes on the plant that needs the control disease.Usually the comparatively suitable significant quantity of selecting is that per hectare 5 restrains 5000 grams, and preferred significant quantity is that per hectare 10 restrains 1000 grams.
Other embodiments of the present invention are the method for pest control, and this method comprises sterilization of the present invention, insect-killing composition are imposed on described insect or its growth medium, as imposes on the plant that needs the control insect pest.Usually the comparatively suitable significant quantity of selecting is that per hectare 50 restrains 5000 grams, and preferred significant quantity is that per hectare 100 restrains 1000 grams.
Compound of the present invention can preparation form use on the blade face.General formula (I) compound is as solubilization of active ingredient or be scattered in the carrier or be mixed with preparation so that be easier to disperse when using as sterilization or sterilant.For example: these chemicals can be made into wettable powder or missible oil.In these compositions, add a kind of liquid or solid carrier at least, and when needing, can add suitable tensio-active agent.
Use for some, can in sterilization of the present invention, insect-killing composition, add one or more other sterilant or sterilant, can produce additional advantage and effect thus.
Compound of the present invention both can use separately also can be mixed together use with other known weedicide, plant-growth regulator or fertilizer etc.
Should be clear and definite be in claim of the present invention institute restricted portion, can carry out various conversion and change.
Embodiment
Following synthetic example, living test are tested the result and be can be used to further specify the present invention, but do not mean that restriction the present invention.
Synthetic example
Compound 6A, 6B and 12 synthetic:
In 3000 milliliters reaction flask, add 3-methyl-4 fluoro acetophenone (109.4 grams, 0.72 mole), ketenes? 2-oxyethyl group butenoic acid ethyl (115 grams, 0.72 mole) and 500 milliliters of anhydrous dimethyl formamides stir.The mixed solution that adds potassium tert.-butoxide (89 grams, 0.79 mole) and 250 milliliters of dimethyl formamides then.Reaction is spent the night under the room temperature.Reaction solution is poured in 1000 ml waters, removed unreacted raw material with 3 * 200 milliliters of ethyl acetate extractions, water is neutralized to pH2 with the hydrochloric acid of 6N, generates yellow solid, filters, and obtains intermediate acid after water and hexanaphthene washing.In the reaction flask with 1000 milliliters of solid inputs, add the hydrochloric acid of 500 milliliters of 1N, be warming up to 50 ℃ of decarboxylations, do not emit to there being gas.Reaction solution is chilled in room temperature impouring 500 ml waters, and with 3 * 200 milliliters of ethyl acetate extractions, organic phase is used anhydrous magnesium sulfate drying after water, saturated common salt water washing, obtains 100 gram brown oil after concentrating, yield 69% (content is in 95%).Warp
1H NMR analyzes and is trans phenyl ketenes (being carbonyl and the phenyl ring heteropleural at two keys).
In 1000 milliliters reaction flask, add trimethylammonium sulfoxonium iodide (101.5 grams, 0.461 potassium tert.-butoxide (51.8 grams mole),, 0.461 mole) and 400 milliliters of dimethyl formamides, stirred 1 hour under the room temperature, add trans phenyl ketenes (88.5 grams then fast, 0.461 mole) and the mixed solution of 100 milliliters of dimethyl formamides, room temperature reaction spends the night.Reaction solution poured in 200 milliliters the frozen water, with 3 * 200 milliliters of ethyl acetate extractions, merge organic phase, after water, saturated common salt water washing, use anhydrous magnesium sulfate drying, obtain 105 gram dark-brown oily matter after concentrating, through column chromatography purify 50 gram light brown oily things, yield is 50% (content is in 95%).
1H NMR analyzes and is trans benzyl ring propyl ketone (being carbonyl and the phenyl ring heteropleural at the cyclopropane face).
In 1000 milliliters reaction flask, add trans benzyl ring propyl ketone (26.8 grams, 0.130 mole), cis oxygen amine (N-methoxyl group and phenyl ring are cis, 34 grams, 0.143 mole), 500 milliliters of anhydrous methanols and 10 Glacial acetic acid, reaction is spent the night under the room temperature.In reaction solution impouring 500 ml waters, with 3 * 200 milliliters of ethyl acetate extractions, organic phase is after water, 1N hydrochloric acid and saturated common salt water washing, use anhydrous magnesium sulfate drying, get light yellow oil 47 grams after the filtering and concentrating, purify to such an extent that 27 gram 6A and 3 restrain 6B (content is all in 95%), yield 54% through column chromatography.
1It is trans (cyclopropane groups and adjacent N-O key are trans) that H NMR analyzes 6A; 6B is cis (cyclopropane groups and adjacent N-O key are cis).
Add 6A (46 grams, 0.108 mole) in 1000 milliliters reaction flask, 300 ml methanol and 50 milliliter of 40% aqueous methylamine solution at room temperature stir and spend the night.In reaction solution impouring 500 ml waters, with 3 * 200 milliliters of ethyl acetate extractions, organic phase is used anhydrous magnesium sulfate drying after water, 0.1N hydrochloric acid and saturated common salt water washing, get light yellow oil 40 after the filtering and concentrating and digest compound 12, yield 87% (content is in 95%).
Other compounds in the table 1 can make by above similar method.
Give birth to and survey example:
1. test method
The mensuration of fungicidal activity:
Take by weighing test sample and be dissolved in the acetone (acetone: soup=9: 1), add the water that contains 0.1% tween 80, be mixed with 10 milliliters of the soups of desired concn.Manual sprayer is sprayed onto above-mentioned soup on the crop seedling, and spouting liquid is 2 milliliters/processing.Test materials after the processing dries naturally, after 24 hours with inoculator with 5 * 10
5The sporangia suspension of the test disease of individual/milliliter sparges on the crop seedling, is water soaking mode to blade and ends.Place then and cultivate (temperature is 24 ℃, RH=100%, illumination in 12 hours), the bacteriostatic activity of 4 days " Invest, Then Investigate " compounds in the moist chamber.
Investigation result is represented with 100,99,95,90,95,80,70,50,0 nine grades, the anosis and the most serious occurring degree of " 0 " level representative with the representative of " 100 " level:
The mensuration of insecticidal activity:
Take by weighing test sample and be dissolved in the acetone (acetone: soup=9: 1), add the water that contains 0.1% tween 80, be mixed with 10 milliliters of the soups of desired concn.Manual sprayer is sprayed onto above-mentioned soup on the examination material of various worms, and spouting liquid is 2 milliliters/processing.Day by day observe the death condition of larva after the processing, calculate larval mortality.
2. test-results
The sterilization of general formula of the present invention (I) compound, insecticidal activity test result see Table 2, table 3 and table 4.
Table 2: part general formula (I) compound is to the fungicidal activity of cucumber downy mildew
*: the space is represented not survey, down together.
Table 3: part general formula (I) compound is to the fungicidal activity of wheat powdery mildew
Table 4: the insecticidal activity of part general formula (I) compound
Claims (6)
1, a kind of 1-phenyl-1-methyl cyclopropane compounds, shown in general formula (1):
Wherein:
R
1Be methyl;
R
2Be fluorine;
R
3Be H or methyl;
W is O or NH;
The B1 key is trans with the phenyl ring of vicinity;
B2 key and B1 key are trans;
The B3 key is a cis with the phenyl ring of vicinity.
2, the described compound of claim 1 is used for the purposes of controlling plant disease.
3, the described compound of claim 1 is used to control the purposes of insect pest.
4, a kind of sterilization, insect-killing composition, the active ingredient and the agricultural that contain general formula as claimed in claim 1 (I) compound go up acceptable carrier, and the weight percentage of active ingredient is 1-99% in the composition.
5, a kind of method of controlling plant disease is characterized in that: the described composition of claim 4 is imposed on the plant of needs control disease with the effective dose that per hectare 10 restrains 1000 grams.
6, a kind of method of controlling insect pest is characterized in that: the effective doses that the described composition of claim 4 is restrained 1000 grams with per hectare 100 impose on the medium of insect that needs control or its growth.
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| CN1383424A (en) * | 2000-05-15 | 2002-12-04 | 美国陶氏益农公司 | Aryl and heteroacrylcyclopropyl oxime ethers and their use as fungicides |
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