WO2006081759A1 - N-(2-substituted phenyl)-n-methoxycarbamates and their preparation as well as use - Google Patents

N-(2-substituted phenyl)-n-methoxycarbamates and their preparation as well as use Download PDF

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Publication number
WO2006081759A1
WO2006081759A1 PCT/CN2006/000150 CN2006000150W WO2006081759A1 WO 2006081759 A1 WO2006081759 A1 WO 2006081759A1 CN 2006000150 W CN2006000150 W CN 2006000150W WO 2006081759 A1 WO2006081759 A1 WO 2006081759A1
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Prior art keywords
compound
formula
powdery mildew
substituted phenyl
wheat
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English (en)
French (fr)
Inventor
Chunhe Yang
Liwen Geng
Defeng Zhou
Ling Peng
Hong Zhang
Dongliang Cui
Zhinian Li
Liangqing Wang
Shouguo Zang
Zeyong Zhang
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Shenyang Research Institute of Chemical Industry Co Ltd
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Shenyang Research Institute of Chemical Industry Co Ltd
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Priority to EP06705571.5A priority Critical patent/EP1845086B1/en
Priority to US11/814,023 priority patent/US7666884B2/en
Publication of WO2006081759A1 publication Critical patent/WO2006081759A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals

Definitions

  • the invention belongs to the field of agricultural fungicides and relates to N-(2-substituted phenyl)-N-methoxycarbamic acid methyl ester compounds and their preparation and application. Background technique
  • W0-93/15046 discloses carbamate compounds for crop protection with the following formula:
  • WO-96/01256 discloses amides of 2-[(dihydro)pyrazole-3'-yloxymethylene]aniline for controlling animal pests and harmful fungi, having the general formula:
  • An object of the present invention is to provide a N-(2-substituted phenyl)-N-methoxycarbamic acid methyl ester compound which can control crop harmful fungi at a small dose.
  • the technical solution of the present invention is as follows -
  • the present invention provides a methyl N-(2-substituted phenyl)-N-methoxycarbamate compound, as shown in Formula I:
  • X is selected from 0, S, C00 or NR a , wherein R a is hydrogen, C, C 3 alkyl, C 2 -C 4 alkenyl or C 2 -C alkynyl;
  • n is selected from 1-4; when n is greater than 1, R may be the same or different and are respectively selected from halogen or amino;
  • R fur represents the number of substituents R on the pyridine ring is n ; halogen is fluorine, chlorine, Bromine or iodine.
  • Preferred compounds in the present invention are: In the formula I, X is selected from 0 or NR", wherein R" is hydrogen, C, -C 3 fluorenyl, C 2 -C 4 alkenyl or C 2 _C 4 Alkynyl; R is selected from 1-4 halogen atoms, and the halogen atoms may be the same or different and are respectively selected from fluorine, chlorine or desert.
  • X is selected from 0 and is ortho to the nitrogen atom on the pyridine ring;
  • R is selected from 1-4 halogen atoms, and the halogen atoms may be the same or different and are each selected from fluorine or chlorine.
  • the present invention can be illustrated by the compounds listed in Table 1 below, but does not limit the invention.
  • the present invention also provides a preparation method of the N-(2-substituted phenyl)-N-methoxycarbamic acid methyl ester compound represented by the general formula I.
  • halogen such as fluorine, chlorine, bromine or iodine
  • sulfonate such as methanesulfonate, triflate, besylate or 4-methyl Benzobenzene sulfonate.
  • X, n and R are as defined above.
  • the reaction is usually carried out in an organic solvent in an amount of from 100 to 3,000 ml of the starting material.
  • Suitable solvents are: aromatic hydrocarbons, such as toluene, xylene; generations, such as dichloromethane, chloroform, chlorobenzene; ethers, such as diethyl ether, tert-butyl methyl ether, dioxane, tetrahydrofuran; Acetonitrile, propionitrile; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol; ketones such as acetone, methyl ethyl ketone; and dimethyl sulfoxide, dimethyl ketone Amide, dimethylacetamide.
  • Preferred solvents are: dimethylformamide, dichloromethane, acetone, toluene or tert-butyl methyl ether. Mixtures of the above solvents can also be used.
  • a suitable reaction temperature is from - 20 ° C to the boiling point of the solvent.
  • the reaction temperature is from 0 ° C to 100 ° C.
  • the reaction time is preferably 5- 5-hour.
  • Suitable bases are selected from the group consisting of: alkali metal or alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide; alkali or alkaline earth metal oxides such as lithium oxide, sodium oxide, oxidation Calcium or magnesium oxide; alkali metal or alkaline earth metal hydride such as lithium hydride, sodium hydride, potassium hydride or calcium hydride; alkali metal amide such as lithium amide, sodium amide or potassium amide; alkali metal or alkaline earth metal carbonate a salt such as lithium carbonate, sodium carbonate, potassium carbonate or calcium carbonate; an alkali metal hydrogencarbonate such as sodium hydrogencarbonate; an alkali metal alkylate such as methyl lithium, butyl lithium or phenyl lithium; Such as methyl magnesium chloride; alkali metal or alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium t-butoxid
  • Preferred bases are: sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
  • the base is usually used in an equimolar amount or in excess of the starting materials. Some of the above suitable bases can also be used as a solvent.
  • reaction of converting the compound ruthenium into the corresponding metal compound with a base and then reacting with the compound m is more advantageous for the reaction to proceed smoothly.
  • the compound oxime can be prepared by known methods (see WO9315046, WO0246142, US5824705).
  • the compound II moiety is commercially available or can be prepared by a known method such as hydrolysis of the corresponding halopyridine or aminolysis (see J. Chem. Soc.l 971, 167, JP 58154561).
  • Compound I can also be prepared according to the following reaction formula:
  • Hal is a halogen atom, and the other substituents are as defined above.
  • the present invention includes a salt of a methyl N-(2-substituted phenyl)-N-methoxycarbamate compound represented by the formula I.
  • the acids which can be used in the preparation of the above salts are mainly inorganic acids, for example, hydrohalic acids such as hydrochloric acid or hydrobromic acid, phosphoric acid, sulfuric acid, nitric acid; organic acids such as formic acid, acetic acid, oxalic acid, malonic acid, lactic acid. , malic acid, succinic acid, tartaric acid, citric acid, salicylic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid.
  • hydrohalic acids such as hydrochloric acid or hydrobromic acid, phosphoric acid, sulfuric acid, nitric acid
  • organic acids such as formic acid, acetic acid, oxalic acid, malonic acid, lactic acid.
  • malic acid, succinic acid, tartaric acid, citric acid, salicylic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid are
  • the N-(2-substituted phenyl)-N-methoxycarbamic acid methyl ester compound of the invention and the salt thereof have good bactericidal activity and can be used for controlling algal fungi and ascomycetes on various crops Diseases caused by pathogenic bacteria in the subphylum, basidiomycete and deuteromycetes.
  • the present invention also provides a bactericidal composition, wherein the active component of the composition is a N-(2-substituted phenyl)-N-methoxycarbamic acid methyl ester compound of the formula I;
  • the active ingredient is present in an amount of from 0.1 to 99% by weight, the balance being an agriculturally acceptable carrier.
  • the above active component may be a single compound of the formula I or a mixture of several compounds.
  • the carrier contained in the composition of the present invention is one which satisfies the following conditions: It is formulated with the active ingredient to facilitate application to a subject to be treated, such as plants, seeds or soil; or to facilitate storage, transportation or handling.
  • the carrier can be any solid or liquid, such as those employed in formulating bactericidal compositions.
  • Suitable solid carriers include natural or synthetic silicates such as diatomaceous earth, talc, aluminum silicate (kaolin), montmorillonite or mica; calcium carbonate, calcium sulphate, ammonium sulphate; synthetic calcium silicate or silicon Aluminum acid; elements such as carbon or sulfur; natural or synthetic resins such as benzofuran resins, polyvinyl chloride, styrene polymers or copolymers; solid polychlorinated phenols; waxes such as beeswax, paraffin.
  • natural or synthetic silicates such as diatomaceous earth, talc, aluminum silicate (kaolin), montmorillonite or mica
  • calcium carbonate, calcium sulphate, ammonium sulphate synthetic calcium silicate or silicon Aluminum acid
  • elements such as carbon or sulfur
  • natural or synthetic resins such as benzofuran resins, polyvinyl chloride, styrene polymers or copolymers
  • solid polychlorinated phenols waxes such as be
  • Suitable liquid carriers include water; alcohols such as isopropanol, ethanol, n-butanol, glycerol or ethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, pyrrolidone, phenylethyl Ketone or cyclohexanone; ether; aromatic hydrocarbon such as toluene, xylene or mineral spirit; petroleum fraction such as kerosene or mineral oil; vegetable oil; dimethylformamide and the like. Usually, mixtures of these liquids are also suitable.
  • compositions of the present invention typically comprise at least one surfactant.
  • the surfactant may be an emulsifier, a dispersing agent, a penetrating agent, a spreading agent or a wetting agent: it may be an ionic surfactant or a nonionic surfactant.
  • composition of the present invention can be formulated into various preparations according to methods known to those skilled in the art, such as aqueous preparations, wettable powders, powders, granules, concentrated emulsions, emulsifiable concentrates, water-dispersible granules, suspensions, aerosols.
  • aqueous preparations such as wettable powders, powders, granules, concentrated emulsions, emulsifiable concentrates, water-dispersible granules, suspensions, aerosols.
  • dosage forms such as agents or aerosols.
  • compositions of the present invention can be carried out by foliar spray, seed treatment or soil treatment.
  • one or more other bactericides may be added to the compositions of the present invention, thereby creating additional advantages and benefits.
  • composition of the present invention may be used alone or in combination with other known insecticides, herbicides, plant growth regulators or fertilizers.
  • the compound of the present invention and the composition thereof have good bactericidal activity and can be used for controlling diseases caused by pathogenic bacteria in the genus Algin, Ascomycete, Basidiomycetes and Deuteromycetes on various crops. Including but not limited to the prevention and control of the following plant diseases: wheat powdery mildew, melon powdery mildew, apple powdery mildew, grape powdery mildew, strawberry powdery mildew; wheat rust, soybean rust, wheat rot fungus root rot, cucumber black star disease, rice evil Mulberry disease, rice sheath blight, cucumber blight, cucumber anthracnose, rice blast, rice blast, rice leaf blight.
  • the compounds of the present invention and compositions thereof can be used as agricultural fungicides for controlling plant fungal diseases on wheat, cucumber, watermelon, apple, grape, strawberry, soybean, rice, and corn.
  • Example 1 Preparation of methyl N-methoxy-N-[2-[[(3,5,6 trichloropyridine-2-yl)oxy]methyl]phenyl]carbamate ( Compound 13 ) .
  • Example 4 50% water dispersible granules
  • the above components are uniformly mixed and ground, and a small amount of water is kneaded, granulated, and dried to obtain a water-dispersible granule containing 50% of an active ingredient.
  • Compound 13 was dissolved in pyrrolidone and solvent oil, and then emulsifier A and emulsifier B were added and mixed uniformly to obtain a transparent homogeneous solution, i.e., an active ingredient of 15% emulsifiable concentrate.
  • Example 6 35% emulsifiable concentrate
  • Emulsifier OP-10 (emulsifier A ) 7%
  • Compound 49 was dissolved in cyclohexanone and solvent oil, and then emulsifier A and emulsifier B were added to be uniformly mixed to obtain a transparent homogeneous solution, that is, an active ingredient of 35 % of emulsifiable concentrate.
  • Biological activity assay example
  • Example 7 Determination of bactericidal activity of wheat powdery mildew
  • the compound to be tested was weighed quantitatively and dissolved with an appropriate amount of acetone (acetone accounted for 10% of the total volume of the solution). Then, water containing 0.1% by volume of Tween 80 was added and diluted to 200 mg/L. Using a rotary crop sprayer, the spray pressure is 1. 5 kg/cm 2 , and the spray volume is about 1000 L/hm 2 .
  • the spray-treated one-leaf and one-hearted wheat seedlings are naturally air-dried after treatment, and the wheat powdery mildew is inoculated 24 hours later. Spores, continue to be cultured directly in the greenhouse after inoculation. After 7 days of treatment, the control effect of wheat powdery mildew was investigated visually. The results of the bactericidal activity test of some of the compounds of formula I are shown in Table 3.
  • test compound 7, 10, 13 had better protection against wheat powdery mildew than the control agent.
  • Compound 13 (content 95%) was weighed and dissolved in an appropriate amount of acetone (acetone accounted for 10% of the total volume of the solution), and water containing 0.1% Tween 80 was added and diluted to the desired concentration.
  • the water was sprayed on the one-leaf and one-hearted wheat seedlings by a sprayer until the leaves were wetted, and then the powdery mildew which had been cultured for 7 days was shaken off on the wheat leaves, and cultivation was continued for 4 days in the greenhouse.
  • the rotary crop sprayer was used, the spray pressure was 1.5 kg/cm 2 , and the spray volume was about 1000 L/hm 2 . After the spray treatment, it was naturally air-dried and placed in a greenhouse for normal management. After 7 days, the reference control of the blank control was visually investigated for control effect.
  • the control drug epidifenate (BAS490F, prepared according to US5354883, content 95%) was prepared using the same method and dosage. The test results are shown in Table 5.
  • the test uses a toxic medium method. Quantitatively weigh compound 13 (content 95%), dissolve it with appropriate amount of acetone (acetone accounts for 10% of the whole solution volume), then add water containing 0.1% Tween 80, dilute to the desired concentration of the drug solution, and use the same The water is diluted in a series of concentrations for testing.
  • the test agent diluted with water was added to the heated whole nutrient medium, and a series of concentrations of the drug-containing medium were prepared, poured into a 9 cm culture dish, and cooled to inoculate the test pathogen bacteria cake in vitro. Diameter 0.5 cm), repeated 3 times per treatment.
  • compound 13 has antibacterial activity against a variety of plant pathogenic bacteria, especially for rice sheath blight, Pythium fuliginea, cucumber scab, cucumber anthracnose, rice blast, rice smut, corn leaf blight, etc. The effect is more prominent.
  • the test agent was 15% breast sleeve of compound 13, the treatment dose was 50, 75, 100g ai/lim 2 , and the control agent was 50% dry suspension of ether oxystrobin (BASF), the treatment dose was 75 g ai/hm 2
  • BASF ether oxystrobin
  • the application device is a "worker-nong 16" manual sprayer, applied 4 times, at intervals of 7 days, and the amount of sprayed liquid is 1000 L hm 2 .
  • the control effect was investigated 6 days after the fourth application.
  • the survey method, disease classification and control effect calculation were all implemented in the National Standard of the People's Republic of China.

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Description

- (2-取代苯基) -N-甲氧基氨基甲酸酯类化合物及其制备与应用 技术领域
本发明属于农用杀菌剂领域，涉及 N- (2-取代苯基) - N-甲氧基氨基甲酸甲酯类化合物及其 制备与应用。 背景技术
W0- 93/15046公布了用于作物保护的氨基甲酸酯类化合物， 通式如下:
Figure imgf000003_0001
WO - 96/01256公布了用于防治动物害虫和有害真菌的 2- [ (二氢)吡唑- 3' -基氧亚甲基]苯 胺的酰胺， 通式如下：
R3—
Figure imgf000003_0002
但如本发明所示的 N- (2-取代苯基) -N-甲氧基氨基甲酸甲酯类化合物未见报道。 发明内容
本发明的目的在于提供一种在较小的剂量下就可以控制作物有害真菌的 N- (2-取代苯 基) -N-甲氧基氨基甲酸甲酯类化合物。
本发明的技术方案如下- 本发明提供一种 N- (2-取代苯基) -N-甲氧基氨基甲酸甲酯类化合物， 如通式 I所示：
Figure imgf000003_0003
式中：
X选自 0、 S、 C00或 NRa, 其中 Ra为氢、 C, C3烷基、 C2-C4链烯基或 C2- C 炔基；
n选自 1-4; 当 n大于 1时， R可以相同或不同， 分别选自卤素或氨基；
及其盐。
以上给出的通式 I化合物的定义中， R„ 表示吡啶环上取代基 R的个数为 n; 卤素为氟、氯、 溴或碘。
本发明中较为优选的化合物为： 通式 I中， X选自 0或 NR"， 其中的 R"为氢、 C,- C3垸基、 C2 - C4链烯基或 C2_C4炔基； R选自 1-4个卤原子， 卤原子可以相同或不同， 分别选自氟、 氯或 漠。
本发明中进一步优选的化合物为： 通式 I中， X选自 0; R选自 1-4个卤原子， 卤原子可 以相同或不同， 分别选自氟或氯。
本发明中更进一步优选的化合物为： 通式 I中， X选自 0且位于吡啶环上氮原子的邻位；
R选自 1-4个卤原子， 卤原子可以相同或不同， 分别选自氟或氯。
可以用下面表 1所列化合物来说明本发明， 但并不限定本发明。
Figure imgf000004_0001
表 1 :
化合物编号 X (X与吡啶环相连的位 S) Rn 熔点 °c
1 0(2-) 3-C1
2 0(2-) 4-C1
3 0(2-) 5-C1
4 0(2-) 6-C1
5 0(2-) 3,4-C12
6 0(2-) 3,5-C12 油状物
7 0(2-) 3,6-C12 86-87 °C
8 0(2-) 4,5-C12
9 0(2-) 4，6-C12
10 0(2-) 5,6- C12 66-68 °C
11 0(2-) 3,4,5- CB
12 0(2-) 3,4,6- C13
13 0(2-) 3,5，6-C13 94-95 °C
14 0(2-) 4,5,6-C13
15 0(2-) 3,4,5,6-C14 87-88 "C
16 0(2-) 3-Cl,4-F
17 0(2-) 5- CI, 3- F 油状物
18 0(2-) 3-Cl,6-F
19 0(2-) 4-C1 ,3- F
20 0(2-) 4-Cl,5-F 21 0(2-) 4-Cl,6-F
22 0(2-) 5-Cl,3-F
23 0(2-) 5-C1, 4-F
24 0(2-) 5-Cl，6-F
25 0(2-) 5-C1, 3,4-F2
26 0(2-) 6-C1, 3-F
27 0(2-) 6-C1, 4-F
28 0(2-) 6-C1, 5-F
29 0(2-) 6-C1, 3,4-F2
30 0(2-) 6-C1, 3,5-F2
31 0(2-) 6-C1, 4,5-F2
32 0(2-) 3,5-C12,6-F,4-NH2 120-121 °C
33 0(2-) 3-F
34 0(2-) 4-F
35 0(2-) 5-F
36 0(2-) 6-F
37 0(2-) 3,4-F2
38 0(2-) 3,5-F2
39 0(2-) 3,6-F2
40 0(2-) 4,5-F2
41 0(2- ) 4,6- F2
42 0(2- ) 5,6-F2
43 0(2-) 3,4,5-F3
44 0(2-) 3,4,6-F3
45 0(2-) 4，5,6-F3
46 0(2- ) 3,5,6- F3
47 0(2-) 3,4,5,6-F4
48 0(3-) 6-C1 油状物
49 NH(4-) 3,5-C12,2,6-F2
50 NH(2-) 5-1 油状物
51 丽 (3-) ' 6-C1 油状物
52 C00(3- ) 2- CI 油状物
53 C00(3-) 6- CI 油状物 本发明还提供了通式 I所示的 N- (2-取代苯基) - N-甲氧基氨基甲酸甲酯类化合物的制备方 法： 在碱存在下化合物 m与化合物 π反应生成化合物 I， 反应式如下:
Figure imgf000006_0001
式中：
选自可被亲核置换的基团： 例如卤素， 如氟、 氯、 溴或碘； 磺酸酯， 如甲基磺酸酯、 三氟甲基磺酸酯、 苯磺酸酯或 4-甲基苯磺酸酯。
X、 n及 R的定义同前。
反应通常在有机溶剂中进行， 溶剂用量以初始原料计为 100— 3000毫升 I摩尔。
适宜的溶剂为： 芳香烃， 如甲苯、 二甲苯； 代经， 如二氯甲垸、 氯仿、 氯苯； 醚， 如 二乙基醚、 叔丁基甲基醚、 二噁烷、 四氢呋喃； 腈， 如乙腈、 丙腈； 醇， 如甲醇、 乙醇、 正丙 醇、 异丙醇、 正丁醇、 叔丁醇； 酮， 如丙酮、 甲基乙基酮； 以及二甲基亚砜、 二甲基甲酰胺、 二甲基乙酰胺。 优选的溶剂为： 二甲基甲酰胺、 二氯甲烷、 丙酮、 甲苯或叔丁基甲基醚。 还可 使用上述溶剂的混合物。
适宜的反应温度为- 20°C至溶剂的沸点。 优选反应温度为 0°C- 100°C。
反应时间以 0. 5-48小时为宜。
适宜的碱选自： 碱金属或碱土金属的氢氧化物，如氢氧化锂、 氢氧化钠、 氢氧化钾、 氢氧 化钙； 碱金属或碱土金属的氧化物，如氧化锂、 氧化钠、 氧化钙或氧化镁； 碱金属或碱土金属 的氢化物，如氢化锂、 氢化钠、 氢化钾或氢化钙； 碱金属氨化物，如氨基锂、 氨基钠或氨基钾； 碱金属或碱土金属的碳酸盐，如碳酸锂、碳酸钠、碳酸钾或碳酸钙； 碱金属的碳酸氢盐，如碳酸 氫钠； 碱金属烷基化物，如甲基锂、丁基锂或苯基锂； 卤化烷基镁,如氯化甲基镁； 碱金属或碱 土金属的醇盐， 如甲醇钠、 乙醇钠、 乙醇钾、 叔丁醇钾、 二甲氧基镁； 有机碱， 如三甲胺、 三 乙胺、 三异丙基乙胺， N-甲基哌啶、 吡啶， 取代吡啶。
优选的碱为： 氢氧化钠、 氢氧化钾、 碳酸钠或碳酸钾。
碱通常以原料的等摩尔量或者过量使用。 上述某些适宜的碱也可以作为溶剂使用。
釆取先用碱将化合物 Π转化成相应的金属化合物， 再与化合物 m反应的方式更利于反应 顺利进行。
化合物 ΠΙ可以采用已知方法制备 （参见 WO9315046, WO0246142, US5824705 )。 化合物 II部分有市售，也可釆用已知方法例如由相应的卤代吡啶水解或氨解等方法制备 (参见 J.Chem.Soc.l971,167， JP 58154561 )。 化合物 I还可按以下反应式制备:
Figure imgf000007_0001
式中 Hal为卤原子， 其他各取代基定义同前。 本发明包括通式 I所示的 N- (2-取代苯基) - N-甲氧基氨基甲酸甲酯类化合物的盐。
可用于制备上述盐的酸主要有无机酸,例如， 氢卤酸如氢氯酸或氢溴酸、 磷酸、 硫酸、 硝 酸； 也可以是有机酸， 例如甲酸、 乙酸、 草酸、 丙二酸、 乳酸、 苹果酸、 琥珀酸、 酒石酸、 柠 檬酸、 水杨酸、 对甲苯磺酸、 十二烷基苯磺酸。
本发明的 N- (2-取代苯基) - N-甲氧基氨基甲酸甲酯类化合物及其盐具有很好的杀菌活性， 可用于防治在多种作物上由藻菌亚门、子囊菌亚门、担子菌亚门和半知菌类中的病原菌引起的 病害。 本发明还提供了一种杀菌组合物， 该组合物中活性组分为通式 I 所示的 N-(2-取代苯 基) -N-甲氧基氨基甲酸甲酯类化合物； 组合物中的活性组分的重量百分含量为 0.1-99%， 余量 为农业上可接受的载体。
上述活性组分可以是通式 I的单一化合物或几种化合物的混合物。
本发明的组合物中所含有的载体系满足下述条件的物质： 它与活性成分配制后便于施用 于待处理的对象， 例如植物、种子或土壤； 或者有利于贮存、运输或操作。载体可以是固体或 液体等任何通常在配制杀菌组合物中所采用的物质。
合适的固体载体包括天然或合成的硅酸盐、 例如硅藻土、 滑石、 硅酸铝 （高岭土）、 蒙脱 石或云母； 碳酸钙、 硫酸钙、 硫酸铵； 合成的氧化硅酸钙或硅酸铝； 元素如碳或硫； 天然的或 合成的树脂如苯并呋喃树脂， 聚氯乙烯、 苯乙烯聚合物或共聚物； 固体多氯苯酚； 蜡如蜂蜡、 石蜡。
合适的液体载体包括水； 醇如异丙醇、 乙醇、 正丁醇、 丙三醇或乙二醇； 酮如丙酮、 甲 基乙基酮、 甲基异丁基酮、 吡咯垸酮、 苯乙酮或环己酮； 醚； 芳烃如甲苯、 二甲苯或溶剂油； 石油馏分如煤油或矿物油； 植物油； 二甲基甲酰胺等。 通常， 这些液体的混合物也是合适的。
杀菌组合物通常加工成制剂的形式以便于运输和施用，在施用之前由使用者将其稀释。少 量的表面活性剂的存在有助于稀释过程。因此， 本发明的组合物中， 通常含有至少一种表面活 性剂。
表面活性剂可以是乳化剂、 分散剂、 渗透剂、 展着剂或润湿剂： 它可以是离子表面活性 剂或非离子表面活性剂。如： 高级脂肪酸盐中含至少 8个碳原子的脂肪酸， 脂肪酸盐； 磺酸盐 中的烷基苯磺酸盐， 垸基磺酸盐， 脂肪酸乙酯磺酸盐， 仲醇聚氧乙烯醚琥珀酸酯磺酸盐， 丁基 萘磺酸盐， 脂肪酰胺磺酸钠； 硫酸酯盐中的脂肪醇硫酸盐， 脂肪醇聚氧乙烯醚硫酸钠； 脂肪 酸酰氯与蛋白质水解物缩合物中的油酰氨基酸钠， 月桂酰肌氨酸钠； 磷酸酯盐； 胺盐型阳离子 表面活性剂中的垸基胺盐型阳离子表面活性剂，氨基醇脂肪酸衍生物阳离子表面活性剂；氨基 酸型两性表面活性剂中的甘氨酸型表面活性剂；咪唑啉型两性表面活性剂，聚乙二醇型非离子 表面活性剂中的长链脂肪醇聚氧乙烯醚，烷基酸聚氧乙烯醚， 聚氧乙烯烷基醇酰胺； 多元醇型 非离子表面活性剂中的甘油脂肪酸和季戊四醇脂肪酸酯， 山梨醇脂肪酸酯，失水山梨醇脂肪酸 和聚氧乙烯失水山梨醇脂肪酸酯;烷基硫醇聚氧乙烯醚;高分子表面活性剂中的丙烯酸共聚物； 硅表面活性剂等。
本发明的组合物可以按照本领域的技术人员所公知的方法制成各种制剂， 例如水剂、 可湿性粉剂、 粉 剂、 颗粒剂、 浓乳剂、 乳油、 水分散粒剂、 悬浮剂、 气雾剂或烟雾剂等多种剂型。
根据不同的作物及病害施用有效量的本发明的组合物， 可釆用叶面喷雾、种子处理或土壤 处理的方法实施。 对于某些应用，可在本发明的组合物中加入一种或多种其它杀菌剂， 由此可产生附加的优 点和效果。
本发明的组合物既可以单独使用也可以和其它已知的杀虫剂、除草剂、植物生长调节剂或 肥料等一起混合使用。
本发明的化合物及其组合物具有很好的杀菌活性， 可用于防治在多种作物上由藻菌亚门、 子囊菌亚门、担子菌亚门和半知菌类中的病原菌引起的病害,包括但不限于防治下列植物病害： 小麦白粉病、 瓜类白粉病、 苹果白粉病、 葡萄白粉病、 草莓白粉病； 小麦锈病、 大豆锈病、 麦 腐霉根腐病、黄瓜黑星病、水稻恶苗病、水稻紋枯病、黄瓜枯萎病、黄瓜炭疽病、水稻稻瘟病、 水稻稻曲病、 玉米小斑病。
因此本发明的化合物及其组合物可作为农用杀菌剂应用于小麦、黄瓜、西瓜、苹果、葡萄、 草莓、 大豆、 水稻、 玉米上防治植物真菌病害。
应明确的是， 在本发明的权利要求所限定的范围内， 可进行各种变换和改动。 具体实施方式
以下为本发明的有代表性的具体实施例， 但它们不应解释为对本发明范围的限制。
合成实施例 ，，
实施例 1 : 制备 N-甲氧基 -N- [2- [ [ (3, 5, 6 三氯吡啶- 2-基)氧]甲基]苯基]氨基甲酸甲酯 (化合物 13 ) .
反应式:
Figure imgf000009_0001
将 0. 4克（2毫摩） 3, 5, 6-三氯吡啶醇（市购）和 0. 6克（2. 2毫摩) N-2-溴甲基苯基- N -甲氧 基氨基甲酸甲酯 (参照 W002/46142制备)溶入 5毫升二甲基甲酰胺中，加入 0. 45克碳酸钾，在 室温下搅拌反应 6个小时。
反应液经乙酸乙酯吸收， 水洗， 再经饱和食盐水洗涤和无水硫酸钠千燥后， 减压脱溶。经 硅胶柱分离得 0. 55克淡黄色固体， 为化合物 13。 含量： 95%， 熔点： 94- 95°C。 实施例 2: 制备 N-甲氧基 -N- [2- [ [ (2， 6-二氟 -3, 5-二氯吡啶- 4-基)氨基]甲基]苯基]氨基 甲酸甲酯 （化合物 49 )
反应式：
Figure imgf000009_0002
将 0. 43克（2.5毫摩） 4-氨基- 2, 6-二氟- 3, 5-二氯吡啶和 0. 77克（2.8毫摩) N- 2-溴甲基苯 基 甲氧基氨基甲酸甲酯溶入 5毫升二甲基甲酰胺中，加入 1. 0克碳酸钾,在 30-35°C下搅拌 反应 4个小时。
反应液经乙酸乙酯吸收， 水洗， 再经饱和食盐水洗涤和无水硫酸钠千燥后， 减压脱溶。 经 硅胶柱分离得 0. 6克淡黄色固体， 为化合物 49。 含量： 95%， 熔点： 82-83°C。 按照上述方法， 适当改变起始化合物， 可得到通式 I中的其它化合物。 部分化合物的核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)见表 2。 表 2: 化合物
结构式 iHNMR
编号
CH30、 ,COOCH3
N
3.77(s,3H),3.81(s,3H),5.20(s,2H),7.29-7.35(m,2H)
6
7.38-7.40(m,3H),7.53-7.54(m, 1 H).
Figure imgf000010_0001
000/900ZN3/X3d 6S.T80/900Z OAV
Figure imgf000011_0001
制剂实施例 以下各组分均以重量百分含量计， 活性组分折百后计量加入。
实施例 3 60%可湿性粉剂
化合物 13 60%
十二烷基苯磺酸钠 1%
木质素磺酸钠 6%
扩散剂 ΝΟ 5%
补足至 100%
各组分 （均为固体） 混合在一起， 在粉碎机中粉碎， 直到细度达到标准 （ 44μπι)， 得 到有效成分为 60%的可湿性粉剂。
实施例 4 50%水分散粒剂
化合物 13 50%
失水山梨醇硫酸酯 1%
聚乙烯吡咯烷酮 3% 木质素磺酸钠 ιο%
硅藻土 补足至 100%
将以上各组分混合均匀后研磨， 加少量水捏合、 造粒、 烘干， 得到含有效成分为 50 %的 水分散粒剂。
实施例 5 15 %乳油
化合物 13 15%
吡咯烷酮 10%
苯乙烯基苯酚聚氧乙烯醚 （乳化剂 A ) 7%
十二烷基苯磺酸钙 （乳化剂 B) 5%
溶剂油 补足至 100%
将化合物 13溶解在吡咯烷酮及溶剂油中，然后加入乳化剂 A和乳化剂 B混合均匀， 得到 透明的均相溶液， 即为有效成分 15 %的乳油。
实施例 6 35 %乳油
化合物 49 35 %
环已酮 20%
乳化剂 OP-10 (乳化剂 A ) 7%
十二烷基苯磺酸钠 （乳化剂 B ) 5 %
溶剂油 补足至 100 %
将化合物 49溶解在环已酮及溶剂油中， 然后加入乳化剂 A和乳化剂 B混合均匀， 得到 透明的均相溶液， 即为有效成分 35 %的乳油。 生物活性测定实施例
实施例 7 对小麦白粉病杀菌活性普筛测定
定量称取待测化合物， 用适量丙酮溶解（丙酮占整个溶液体积的 10%)， ·然后加入含 0. 1% (体积百分比， 下同） 吐温 80的水， 稀释至 200 mg/L。 采用转台式作物喷雾机， 喷雾压力为 1. 5 kg/cm2, 喷液量约为 1000 L/hm2， 喷雾处理生长一叶一心小麦苗， 处理后自然风干， 24 小 时后接种小麦白粉病菌孢子，接种后直接在温室内继续培养。处理 7天后目测调査小麦白粉病 的防效。 部分通式 I化合物的杀菌活性测试结果见表 3。
表 3:
化合物编号 防效 （％)
6 60
7 100
10 100
13 100 15 100
32 60
49 85
实施例 8 对小麦白粉病保护活性测定
定量称取待测化合物， 用适量丙酮溶解（丙酮占整个溶液体积的 10°/。）， 加入含 0. 1 %吐温 80 的水， 稀释至所需浓度的药液， 并用相同的水稀释一系列浓度供试。 采用转台式作物喷雾 机， 喷雾压力为 1. 5 kg/cm2, 喷液量约为 1000 L/hm2, 喷雾处理一叶一心期小麦苗， 处理后 自然风干， 24 小时后接种。 首先用喷雾器将清水喷雾于小麦苗上， 至叶片湿润止。 然后将白' 粉病菌孢子抖落在小麦叶片上， 在温室内继续培养。 7天后参比空白对照发病情况目测调査防 效。 对照药剂醚菌酯 （BAS490F, 参照 US5354883制备， 含量 95%) 釆用相同的方法和浓度设 置。 测试结果见表 4。
Figure imgf000013_0001
Figure imgf000013_0002
结果表明， 测试化合物 7， 10， 13对小麦白粉病的保护防效明显优于对照药剂。
实施例 9 对小麦白粉病治疗活性测定
定量称取化合物 13 (含量 95%)， 用适量丙酮溶解（丙酮占整个溶液体积的 10%)， 加入含 0. 1 %吐温 80的水，稀释至所需浓度的药液。用喷雾器将清水喷雾于一叶一心期小麦苗上， 至 叶片湿润止， 然后将已培养 7天的白粉病菌抖落在小麦叶片上， 并在温室内继续培养 4天。 采用转台式作物喷雾机， 喷雾压力为 1. 5 kg/cm2, 喷液量约为 1000 L/hm2, 喷雾处理后自然 风干， 置于温室内正常管理。 7 天后参比空白对照发病情况目测调查防效。 对照药剂醚菌酯 (BAS490F, 参照 US5354883制备， 含量 95%) 釆用相同的方法和剂量设置。 测试结果见表 5。
表 5 :
Figure imgf000013_0003
结果表明， 化合物 13对小麦白粉病具有优异的治疗效果， 在 3. 125 mg/L下的治疗效果仍 达到 70%, 优于对照药剂。
实施例 10离体杀菌谱测定
试验采用含毒介质法。 定量称取化合物 13 (含量 95%)， 用适量丙酮溶解 （丙酮占整个 溶液体积的 10%), 然后加入含 0. 1 %吐温 80的水， 稀释至所需浓度的药液， 并用相同的水 稀释一系列浓度供试。 在加热的全营养培养基中加入定量以水稀释的供试药剂， 制成一系 列浓度的含药培养基， 倒入 9 cm培养皿中， 冷却后接种离体培养的供试病原菌菌饼 （直径 0. 5 cm), 每处理 3次重复。 处理后置于 27°C培养箱， 3- 4日观察空白对照菌落生长情况， 调查、 测量菌落直径， 计算校正抑菌率。 测试结果见表 6。 表 6:
Figure imgf000014_0002
结果表明， 化合物 13对多种植物病原菌具有抑菌活性， 尤其对水稻纹枯病、 麦腐霉根腐 病、 黄瓜黑星病、 黄瓜炭疽病、 稻瘟病、 稻曲病、 玉米小斑病等的效果较为突出。
实施例 11 防治香瓜白粉病（S toerot/iec /z^g^ea ) 田间小区试验结果
供试药剂为化合物 13的 15%乳袖， 处理剂量为 50、 75、 100g a.i/lim2, 对照药剂为 50% 醚菌酯干悬浮剂 （BASF公司）， 处理剂量为 75 g a.i/hm2， 另设喷清水的空白对照， 供试 5个 处理， 4次重复， 随机排列。 施药器具为"工农 16"手动喷雾器， 施药 4次， 间隔 7天， 喷施药 液量为 1000 L hm2。第 4次施药后 6天进行防治效果调查， 调査方法、 病害分级及防治效果计 算均执行中华人民共和国国家标准《农药田间药效试验准则》。 田间试验结果表明, 15 %化合物 13乳油对防治香瓜白粉病具有优异的防治效果， 处理剂量 50〜100g a.i./hm2对香瓜白粉病的 防效略好于对照药剂 50%醚菌酯千悬浮剂相应处理的防治效果见表 7。
表 7 :
Figure imgf000014_0001
50 5.056 92.97
化合物 13
75 1.556 97.84
15% EC
100 0.778 98.92
醚菌酯 50% DF 75 4.361 93.94
CK 71.959

Claims

1. N- (2-取代苯基) -N-甲氧基氨基甲酸酯类化合物， 如通式 I所示:
Figure imgf000015_0001
权
式中-
X选自 0、 S、 C00或 NRa， 其中 Ra为氢、 d- C3烷基、 C2-CJ 烯基或 C2- C4炔基;
n选自 1-4; 当 n大于 1时， R可以相同或不同， 分别选自卤素或氨基；
要
及其盐。
2.按照权利要求 1所述的通式 I化合物， 其特征在于- ,
X选自 0或 NRa， 其中 Ra为氢、 d-C3垸基、 C2-C4链烯基书或 C2- ( 炔基;
R选自 1-4个卤原子， 卤原子可以相同或不同， 分别选自氟、 氯或溴。
3. 按照权利要求 2所述的通式 I化合物， 其特征在于：
X选自 0;
R选自 1-4个卤原子， 卤原子可以相同或不同， 分别选自氟或氯。
4. 按照权利要求 3所述的通式 I化合物， 其特征在于：
X选自 0且位于吡啶环上氮原子的邻位；
R选自 1-4个卤原子， 卤原子可以相同或不同， 分别选自氟或氯。
5. 权利要求 1所述的通式 I化合物的制备方法， 包括： 在碱存在下化合物 ΠΙ与化合物 II 反应生成化合物 I， 反应式如下：
Figure imgf000015_0002
π
式中：
L选自可被亲核置换的基团；
X选自 0、 S、 C00或 NRa， 其中 Ra为氢、 垸基、 C厂 C4链烯基或(：2- C4炔基; R可以相同或不同， 分别选自卤素或氨基； n选自 1 - 4。
6. 一种根据权利要求 1所述的 N- (2-取代苯基) - N-甲氧基氨基甲酸甲酯类化合物在防治 作物有害真菌方面的应用。
7. 一种杀菌组合物， 其特征在于： 活性组分为权利要求 1所述的 N- (2-取代苯基) - N-甲 氧基氨基甲酸甲酯类化合物； 活性组分的重量百分含量为 0.1-99%。
8. 一种根据权利要求 7所述的组合物在防治作物有害真菌方面的应用。
PCT/CN2006/000150 2005-02-06 2006-01-25 N-(2-substituted phenyl)-n-methoxycarbamates and their preparation as well as use Ceased WO2006081759A1 (en)

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Cited By (4)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58154561A (ja) 1982-03-09 1983-09-14 Seitetsu Kagaku Co Ltd ２−ヒドロキシハロゲノピリジンの製造方法
WO1993015046A1 (de) 1992-01-29 1993-08-05 Basf Aktiengesellschaft Carbamate und diese enthaltende pflanzenschutzmittel
US5354883A (en) 1992-02-05 1994-10-11 Basf Aktiengesellschaft Preparation of E-oxime ethers of phenylglyoxylic esters
JPH07278090A (ja) * 1994-04-11 1995-10-24 Nippon Nohyaku Co Ltd Ｎ−置換フェニルカルバミン酸誘導体及びその製造方法並びに農園芸用殺菌剤
WO1996001256A1 (de) 1994-07-06 1996-01-18 Basf Aktiengesellschaft 2-[(dihydro)pyrazolyl-3'-oxymethylen]-anilide als schädlingsbekämpfungsmittel und fungizide
JP2001055304A (ja) * 1999-08-18 2001-02-27 Nippon Soda Co Ltd ピリジルピリジン化合物、製造方法および農園芸用殺菌剤
WO2002046142A1 (en) 2000-12-08 2002-06-13 Dow Agrosciences Llc Aryl and heteroarylcyclopropyl oxime ethers and their use as fungicides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY110439A (en) * 1991-02-07 1998-05-30 Ishihara Sangyo Kaisha N-phenylcarbamate compound, process for preparing the same and biocidal composition for control of harmful organisms

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58154561A (ja) 1982-03-09 1983-09-14 Seitetsu Kagaku Co Ltd ２−ヒドロキシハロゲノピリジンの製造方法
WO1993015046A1 (de) 1992-01-29 1993-08-05 Basf Aktiengesellschaft Carbamate und diese enthaltende pflanzenschutzmittel
US5824705A (en) 1992-01-29 1998-10-20 Basf Aktiengesellschaft Carbamates and crop protection agents containing them
US5354883A (en) 1992-02-05 1994-10-11 Basf Aktiengesellschaft Preparation of E-oxime ethers of phenylglyoxylic esters
JPH07278090A (ja) * 1994-04-11 1995-10-24 Nippon Nohyaku Co Ltd Ｎ−置換フェニルカルバミン酸誘導体及びその製造方法並びに農園芸用殺菌剤
WO1996001256A1 (de) 1994-07-06 1996-01-18 Basf Aktiengesellschaft 2-[(dihydro)pyrazolyl-3'-oxymethylen]-anilide als schädlingsbekämpfungsmittel und fungizide
JP2001055304A (ja) * 1999-08-18 2001-02-27 Nippon Soda Co Ltd ピリジルピリジン化合物、製造方法および農園芸用殺菌剤
WO2002046142A1 (en) 2000-12-08 2002-06-13 Dow Agrosciences Llc Aryl and heteroarylcyclopropyl oxime ethers and their use as fungicides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1845086A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101874485A (zh) * 2010-06-30 2010-11-03 浙江工业大学 一种双酰肼类化合物作为杀菌剂的应用
CN101874496A (zh) * 2010-06-30 2010-11-03 浙江工业大学 一种酰腙衍生物作为杀菌剂的应用
WO2015012245A1 (ja) 2013-07-22 2015-01-29 住友化学株式会社 植物病害防除組成物およびその用途
EP4154714A2 (en) 2013-10-03 2023-03-29 Syngenta Participations Ag Fungicidal compositions

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