WO2010043148A1

WO2010043148A1 - 2-cyano-3-(substituted) amino-3-phenyl acrylic ester compound, preparing method and use thereof

Info

Publication number: WO2010043148A1
Application number: PCT/CN2009/074216
Authority: WO
Inventors: 王凤云; 李刚; 沈菲; 王耀良; 贺鹰
Original assignee: 江苏中旗化工有限公司
Priority date: 2008-10-15
Filing date: 2009-09-25
Publication date: 2010-04-22
Also published as: CN101381326A

Abstract

Disclosed is a 2-cyano-3-(substituted) amino-3-phenyl acrylic ester compound, preparing method and use thereof. The compound，which has the structure of formula (I), has good fungicidal activity, and may be used for preventing and curing diseases caused by various fungi, such as fusarium, rust fungus or grey mold fungus and so on.

Description

Instruction manual

2-cyano-3-(substituted)amino-3-phenyl acrylate compound, preparation method and application thereof

The present invention relates to the field of agricultural fungicides, and more particularly to a 2-cyano-3-(substituted)amino-3-phenyl acrylate compound, a composition, a process for the preparation thereof, and the use of a crop fungicide. Background technique

2-cyanoacrylates were first seen in French patents in 1969, but it was not until 1981 that the hill reaction inhibitory activity of compound 1 was first reported. Such compounds have attracted great interest and synthesis. , the activity and mode of action have been studied in depth. Many of the 2-cyano-3-(substituted)amino-3-substituted phenylacrylic acids and their derivatives have a 3-substituted amine group such as Compound IV, Compound V and Compound VI. However, the structure of such a compound is different from that of the present invention.

Compound

Compound VI

European Patent EP 885.45 reports that certain other compounds such as 2-cyano-3-(substituted)amino-3-substituted anilino acrylates are reported to have bactericidal activity, but the structures of these compounds are also different from the structure of the present invention.

Compound VII

In 2001, the Chinese patent CN1317483A and the like disclose that a compound having the following general formula has bactericidal activity.

(Compound VIII)

Wherein, X and Y are respectively fluorine, chlorine, bromine, an alkyl group having 1 to 3 carbon atoms and an alkoxy group, a nitro group or a trifluoromethyl group. This patent is the first to report that such compounds have bactericidal activity, but the compound of the formula I does not include the compound of the formula I in which the X and hydrazine are all hydrogen atoms.

2004 Patent Publication No. CN 1559210A Application of 2-cyano-3-amino-3-phenylethyl acrylate to control crop diseases as a fungicide application and patent application number: CN200410065145.6 reported compound 2-cyano-3 -Amino-3-phenyl acrylate ethyl ester for controlling rice seedling disease and application of methyl 2-cyano-3-amino-3-phenyl acrylate reported in application number CN200810023843.8 for controlling crop diseases as a fungicide Application, both compounds are known compounds. These two compounds are also not included in the compounds of the formula I of the present patent application. Summary of the invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a 2-cyano-3-(substituted)amino-3-phenylacrylate compound which can control various crop diseases at a small dose.

Another object of the present invention is to provide a process for the preparation of the above compounds.

Still another object of the present invention is to provide the use of the above compounds in crop bactericides.

The object of the invention can be achieved by the following measures:

A 2-cyano-3-(substituted)amino-3-phenyl acrylate compound having the structure of formula (I):

Ri or R ₂ are each independently hydrogen, dC ₆ unsubstituted or substituted alkyl, Ci-C ₆ alkoxy, C ₂ -C ₆ ester, d-C ₆ carboxylic, C ₃ -C ₆ naphthenic a heterocyclic methyl group, a C ₃ -C ₆ allyl group, a C ₃ -C ₆ propargyl group or a benzyl group, wherein the substituent of the substituted alkyl group is a halogen, a hydroxyl group or a cyano group Or alkoxy, said substituent of said substituted heterocyclylmethyl is halogen or monocyclic aryl; R ₃ is C ₃ -C ₈ alkyl, C ₃ -C ₆ haloalkyl, C ₃ - C ₆ Alkoxyalkyl, C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ heterocycloalkylmethyl.

Or R ₂ is preferably independently hydrogen, CC ₆ unsubstituted or substituted alkyl, CC ₆ alkoxy, C ₂ -Q^, d-C ₆ carboxylic acid, C ₃ -C ₆ cycloalkyl, non a substituted or substituted heterocyclylmethyl, allyl, propargyl or benzyl group, wherein the substituent of the substituted alkyl group is a halogen, a hydroxyl group, a cyano group or an alkoxy group, and the substituted heterocyclic group The substituent of the group is 13⁄4 or benzyl, and the heterocyclylmethyl group is pyrrole or hydrogenated pyrrolemethyl, pyridylmethyl or thiazolylmethyl. R ₃ is preferably a C ₃ -C ₆ alkyl group, a C ₃ -C ₆ cycloalkyl group or an oxocyclopentanylmethyl group.

Ri or R _{2 is} further preferably independently hydrogen, dC ₆ alkyl, dC ₆ chloroalkyl, dC ₆ hydroxyalkyl, C-Ce cyanoalkyl, dC ₆ alkoxyalkyl, d-C ₆ alkane, respectively. Oxyl, ethyl acetate, d-C ₄ carboxylic acid, cyclopropyl, cyclohexyl, benzyl substituted hydropyrrole methyl, chloropyridylmethyl, chlorothiazole methyl, allyl; R _{3 is} further preferably a C ₃ -C ₆ alkyl group, a cyclohexyl group or an oxocyclopentanyl group.

A most preferred class of compounds of the invention wherein R _{2 is} independently hydrogen; R ₃ is C ₃ -C ₆ alkyl such as n-propyl, isopropyl, n-butyl, isobutyl or sec Butyl.

A process for preparing a 2-cyano-3-(substituted)amino-3-phenyl acrylate compound, the general reaction equation of which is as follows:

Wherein R ₂ or R ₃ is as defined above.

In the preparation of compound II, cyanoacetate is first added to a solution containing ethylene glycol in ethylene glycol dimethyl ether, and then benzoyl chloride is added to carry out the reaction, and finally acidified to obtain 2-cyano-3-hydroxy-3-benzene. Base acrylate; another method for preparing compound II is: in a solvent containing cyanoacetate in dichloroethane, simultaneously adding benzoyl chloride and an acid binding agent triethylamine, finally filtering, and concentrating the filtrate to acidify 2-cyano-3-hydroxy-3-phenyl acrylate.

In the preparation of the compound hydrazine, 2-cyano-3-hydroxy-3-phenyl acrylate is reacted with phosphorus oxychloride in an inert solvent of dichloromethane or dichloroethane, and the acid bonding agent triethylamine is added dropwise. 2-Chloro-3-chloro-3-phenyl acrylate was obtained. A. The intermediate 2-cyano-3-chloro-3-phenyl acrylate of the present invention (hereinafter referred to as compound III) is specifically prepared by the following method:

(1) The intermediate 2-cyano-3-hydroxy-3-phenyl acrylate (hereinafter referred to as compound II) is prepared by the following two methods:

(Compound II)

Wherein: R ₃ is a C ₃ - 0>alkylalkyl group and various substituted alkoxyalkyl groups and a -^substituted alkyl group containing one or more halogen atoms such as fluorine, chlorine, bromine and iodine.

Preparation method one:

After adding an equimolar amount of cyanoacetate at 20 ° C in a solution of ethylene glycol dimethyl ether in the configuration, after cooling to 0 ° C, an equimolar amount of benzoyl chloride is added to react at room temperature. After stirring, the product is finally acidified to give 2-cyano-3-hydroxy-3-phenyl acrylate (hereinafter referred to as compound Π). The chemical reaction equation is as follows:

(Compound II)

Preparation method two:

In a solvent containing cyanoacetate in dichloroethane, cool to 0 ° C, while adding an equimolar amount of benzoyl chloride and tribasic acid to the solution, and then stirring at room temperature for several hours. After filtration, the filtrate is concentrated and acidified to obtain 2-cyano-3-hydroxy-3-substituted-3-phenyl acrylate (hereinafter referred to as compound Π). The chemical reaction equation is as follows:

(Compound II)

(2) Preparation of the intermediate 2-cyano-3-chloro-3-phenyl acrylate (hereinafter referred to as compound III) having the following structural formula:

(Compound III)

Wherein: R ₃ containing C ₃ - C _6; ¾ an alkyl group and various substituted alkyl and alkoxy containing one or more halogen atoms such as fluorine, chlorine, bromine, iodine C ₃ - C ₆ alkoxy substituted base. Preparation:

The compound II and phosphorus oxychloride are placed in a 1:1.1 molar configuration in an inert solvent of dichloromethane or dichloroethane as a solvent, and the acid-binding agent triethylamine is added dropwise. After the completion of the dropwise addition, the reaction is continued for several hours, and then the alkali is used. And, extract, dry. Distilled liquid 2-cyano-3-chloro-3-phenyl acrylate (the following compound ΙΠ), the chemical reaction is as follows:

(Compound II) (Compound ΙΠ)

B. 2-Cyano-3-substituted amino-3-phenyl acrylate (Compound I) is specifically prepared by the following method and has the following structural formula:

(Compound I)

The compound in is stirred with a variety of substituted amines or ammonia in an inert solvent such as dichloromethane, dichloroethane or tetrahydrofuran at 0 to 70 ° C for several hours, filtered, desolvated, and washed with water to give Compound I. The chemical reaction equation is as follows:

(Compound III) (Compound I) The compound of the present invention has a systemic activity and can be used as a foliar and soil fungicide. Can be applied to control a variety of crop diseases, such as wheat scab, cotton blight, pepper Phytophthora, 7J rice seedling disease, melon gray mold, wheat sheath blight, 7J rice blast, wheat rust Other diseases have better control effects.

The invention also provides a fungicide composition prepared by using the above compound as an active ingredient and other auxiliary agents (carriers), And a process for the preparation of the composition, the compound of formula I is admixed with a carrier which may comprise a single compound of the invention or a mixture of several compounds.

The composition according to the invention is preferably present in an amount of from 1 to 99% by weight of active ingredient. The carrier of the composition of the present invention is a substance which satisfies the following conditions; it is formulated with the active ingredient to facilitate application to the site to be treated, for example, plant, seed, or soil; or is advantageous for storage, transportation or handling. The carrier may be a solid or a liquid, and includes a material which is usually a gas but which has been compressed into a liquid, and a carrier which is usually used in the preparation of the germicidal composition can be used.

Suitable solid carriers include natural and synthetic clays and silicates such as diatomaceous earth, talc, attapulgite, aluminum silicate (kaolin), montmorillonite and mica; calcium carbonate; calcium sulfate; ammonium sulfate; And synthetic calcium silicate or aluminum silicate; elements such as carbon and sulfur; naturally synthesized resins such as benzofuran resins, polyvinyl chloride and styrene polymers and copolymers; solid polychlorinated phenols; asphalt; waxes such as beeswax , paraffin.

Suitable liquid carriers include water; alcohols such as isopropanol and ethanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexyl ketone; ethers; aromatic hydrocarbons such as benzene, toluene and xylene; petroleum fractions such as Kerosene and mineral oils; chlorinated hydrocarbons such as carbon tetrachloride, perchloroethylene and trichloroethane, usually mixtures of these liquids are also suitable.

The pesticidal composition is usually processed into the form of a concentrate and used for transport, which is diluted by the user prior to use. The presence of a small amount of surfactant carrier aids in the dilution process. Thus, in the composition according to the invention, at least one of the carriers is preferably a surfactant, for example the composition may contain at least two carriers, at least one of which is a surfactant.

The surfactant can be an emulsifier, dispersant or wetting agent; it can be a nonionic or ionic surfactant. Examples of suitable surfactants include polyacrylic acid and sodium and lignosulfonate salts and calcium salts; condensation of fatty acids or fatty amines or amides having at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide a mixture of glycol, sorbitol, sucrose and pentaerythritol fatty acid esters and fatty amines or amides with ethylene oxide and/or propylene oxide; fatty alcohols or alkylphenols such as p-octylphenol or p-octylcresol a condensation with ethylene oxide and/or propylene oxide; a sulfate or a sulphate of these condensation products; an alkali or alkaline earth metal containing at least 10 carbon atoms of sulfuric acid or sulfonate in the molecule, preferably sodium Salts such as sodium lauryl sulfate, sodium secondary alkyl sulfate, sodium sulfonated castor oil, sodium alkyl aryl sulfonate such as sodium lauryl benzene.

Examples of the compositions of the present invention are wettable powders, powders, granules and solutions, emulsifiable concentrates, emulsions, suspension concentrates, aerosols, and aerosols. Wettable powders usually contain 25, 50 or 75% by weight of active ingredient, and usually contain 3-10% by weight of dispersing agent in addition to the inert carrier, and if necessary, 0-10% by weight of stabilizer, and/or other additives are added. Such as penetrants or adhesives. The powder may usually be formed into a powder concentrate having a composition similar to that of the wettable powder but without a dispersing agent, and further diluted with a solid carrier in the field to give a composition usually containing 0.5 to 10% by weight of the active ingredient. Granules are usually prepared to have a size of 10-100 mesh (1.676-0.152 mm), which can be made by agglomeration or injection technology. Ready. Typically, the granules will contain from 0.5 to 75% by weight of active ingredient and from 0 to 10% by weight of additives such as stabilizers, surfactants, sustained release modifiers. The so-called "flowable dry powder" has a relatively small particle composition with a relatively high concentration of active ingredient. Emulsifying concentrates, in addition to solvents, usually contain a cosolvent, 1-50% W/V active ingredient, 2-20% W/V emulsifier and 0-20% W/V other additives such as stabilizers, infiltration when needed. And corrosion inhibitors, suspension concentrates usually contain 10-75% by weight of active ingredient, 0.5-15% by weight of dispersant, 0.1-10% by weight of other additives such as antifoaming agent, corrosion inhibitor, stabilizer, penetration Agents and adhesives. Aqueous dispersions and emulsions, for example compositions obtained by diluting a wettable powder or concentrate according to the invention with water, are also within the scope of the invention. The emulsion may be of two types, water-in-oil or oil-in-water.

The compounds of the present invention are useful for controlling diseases caused by fungi (such as Fusarium, Rust or Botrytis, etc.) on plants. As can be seen from the bactericidal activity test, the compound represented by the compound I of the present invention is against Gibberella zeae, Fusarium oxysporum, Phytophthora capsici, and rice blast disease. Gibberella fujikuroi), Botrytis cinerea, Rhizoctonia solani have good inhibitory activity. ^

The following specific examples further illustrate the invention.

Synthesis example

Synthesis Example: 1 Preparation of Compound No 1 2-cyano-3-(substituted)amino-3-amino-3-phenylpropenyl acrylate: (a) 2-cyano-3-hydroxy-3-benzene Method for preparing n-propyl propyl propionate

A-1: Preparation method of 2-cyano-3-hydroxy-3-phenylpropionate n-propyl ester 1 :

24.3 g of magnesium (1.0 mol) was placed in a 2-liter three-necked flask containing 500 ml of absolute ethanol and 500 ml of ethylene glycol dimethyl ether and 2 g of carbon tetrabromide, and the reaction was stirred at 90 ° C for 12 hours, minus After evaporating ethanol and ethylene glycol dimethyl ether, 500 ml of ethylene glycol dimethyl ether was added, and 127 g of n-propyl cyanoacetate (1.0 mol) was added dropwise at less than 20 ° C, and the solution was cooled to 0 °. C, 140.5 g of benzoyl chloride (1.0 mol) was added dropwise. After the completion of the dropwise addition, the reaction mixture was stirred at room temperature for 15 hours. The solvent was evaporated under reduced pressure, and the residue was acidified with 325 ml of 5M hydrochloric acid, and extracted with 3 X 150 ml of chloroform. The organic layer was combined, washed with water, dried over anhydrous sodium sulfate, evaporated, evaporated, evaporated, evaporated, evaporated, evaporated. IR ( nujol ) 2220 cm" ¹ ,1660 cm" ¹ ,

Preparation method of a-2 2-cyano-3-hydroxy-3-phenylpropionic acid n-propyl ester 2:

28.2 g of benzoyl chloride (0.20 mol) and 25.4 g of n-propyl cyanoacetate (0,20 mol) were dissolved in 200 ml of dichloromethane, cooled to 0-5 ° C, and 40.4 g of triethylamine was added dropwise with stirring. (0.40 mol), at room temperature after dripping

- 1 - The reaction was continued for 10 hours, and 100 ml of 5M hydrochloric acid was added dropwise under cooling, the layers were separated, and the organic layer was combined, washed with water, dried over anhydrous sodium sulfate and evaporated. %. MP 157.5.2-158.8 V. IR ( nujol ) 2220 cm" ¹ ,1660 cm" ¹ ,

(b) Preparation of 2-cyano-3-chloro-3-phenylpropionate n-propyl ester:

36.8 g of phosphorus oxychloride (0.24 mol) and 50.8 g of 2-cyano-3-3-hydroxy-3-phenyl-n-propyl acrylate (0.22 mol) were dissolved in 200 ml of dichloromethane, and 48.5 was added dropwise with stirring. Triethylamine (0.48 mol), the reaction was refluxed for 15 hours, and 100 ml of 5M hydrochloric acid was added dropwise under cooling. The solvent was evaporated under reduced pressure. The residue was dissolved in diethyl ether. After washing to neutrality, the organic phase was dried over anhydrous sodium sulfate. After evaporation of solvent under reduced pressure, 49.9 g of product was distilled out, yield 91.1%, bpl63.4~165.8 °C (5mmHg) ₀ IR ( nujol ) 2220 cm ^{^{"1, 2220 cm" 1,}} EI-MS (m / e) 249 (m +) 221, 120, 216, 2214, 186, 142,141, 119,91,77.

(c) Preparation of 2-cyano-3-amino-3-phenyl-n-propyl acrylate (Compound NO.l):

5.0 g of 2-cyano-3-chloro-3-phenyl propyl acrylate (0.02 mol) and 2.7 g of 25% aqueous ammonia (0.04 mol) were reacted in 30 ml of tetrahydrofuran under stirring at about 20 to 25 °C. After the hour, the layer chromatography was carried out until the reaction was completed. The filtrate was evaporated under reduced pressure. The residue was dissolved in dichloromethane (30 ml), washed with water, dried over anhydrous sodium sulfate, and then evaporated and evaporated. 4.9 g of white crystals (Y=92%), melting point: 99.2~100.5

Other compounds were synthesized by the methods described above. Replacing n-propyl cyanoacetate with isopropyl cyanoacetate to prepare compound Ν0.2, replacing n-propyl cyanoacetate with n-butyl cyanoacetate to prepare compound Ν0.3, replacing n-propyl cyanoacetate with isobutyl cyanoacetate to prepare compound Ν0.4, replacing compound n-propyl cyanoacetate with neobutyl cyanoacetate to prepare compound Ν0.5, replacing n-propyl cyanoacetate with t-butyl cyanoacetate to prepare compound Ν0.6, replacing cyanoacetic acid with chloroethyl cyanoacetate Preparation of compound Ν0.7 from propyl ester, preparation of compound Ν0.8 with chloroethyl cyanoacetate and replacement of ammonia with aminomethyl, and preparation of compound Ν0.9 by replacing n-propyl cyanoacetate with n-amyl cyanoacetate Compound NO.10 was prepared by replacing cyanoacetic acid with n-propyl cyanoacetate, and compound NO.11 was prepared by replacing cyanoacetic acid with n-propyl cyanoacetate, and replacing cyanoacetic acid with octyl cyanoacetate. Preparation of compound N0.12 with propyl ester, compound N0.13 with n-propyl cyanoacetate replaced by heptyl cyanoacetate, compound N0.14 with n-propyl cyanoacetate replaced with cyanoacetate, replacing cyanoacetic acid with octyl cyanoacetate Preparation of compound N0.15 with n-propyl ester, using isopropyl cyanoacetate The compound N0.16 was prepared by replacing the aqueous solution with n-propyl cyanoacetate, replacing the ammonia with aminoethyl, preparing the compound N0.17 by replacing the ammonia with aminoethyl, and preparing the compound N0.18 by replacing the ammonia with the aminooxymethyl group, using hydrazine-benzyl- 3-N-methylmethyltetrahydropyrrole was replaced with ammonia to prepare compound N0.19, and hydrazine-n-propyl-2-chloro-pyridine-5-methylamine was used to replace ammonia to prepare compound ΝΟ.20 with Ν-isopropyl-2 chloro -pyridine-5-methylamine was replaced with ammonia to prepare compound N0.21, and hydrazine-n-propyl-2 chloro-thiazol-5-methylamine was used to replace ammonia to prepare compound Ν0.22, and amino propylene was used to replace ammonia to prepare compound Ν0. 23, replacing ammonia with aminocyclohexane to prepare compound Ν0.24, using aminocyclopropane Compound N0.2 was prepared by changing ammonia water, compound N0.26 was prepared by replacing ammonia with aminoethanol, compound N0.27 was prepared by replacing ammonia with aminomethyl ether, and compound N0.28 was prepared by replacing ammonia with amino (di)ethyl ether. Compound N0.29 was prepared by replacing ammonia water, compound NO.30 was prepared by replacing ammonia water with aminoacetonitrile, and compound N0.31 was prepared by replacing ammonia water with aminoacetic acid.

Table 1 Structural formula of a compound of formula I

(Compound I)

- II -

( HDQD [^- 'sm '3⁄4^ΝΗ _Τ )

91Z L0/600Z 13/I3d 8 £Ϊ0Ϊ OAV - z\ -

91Z L0/600Z 13/I3d 8 £Ϊ0Ϊ OAV 23 72-74 1.04( t, 3H ) , 1.75( m, 2H ), 3.72(m, 2H), 4,27(q, 2H),

5.19 (m, 2H), 5.75(m, 1H), 7.34~7.54(m, 5H), 9.85((br., 1H)

24 131.5-132.2 1.16~1.79(m, 10H), 1.35(t,3H), 1.75( m, 2H),

3.11(m,1H), 4,28(q, 2H), 7.28~7.65(m,5H), 10.04(br. 1H)

25 86.7~88.3°C 0.60~0.67( m, 4H), 1.04( t, 3H ) , 1.75( m, 2H ),

2.49~2.55(m,1H), 4,25(q,2H) 7.28~7.57(m,5H), 9.91 (br.1H)

26 74.2-75.9 1.04( t, 3H ) , 1.75( m, 2H ), 3.22(m, 2H),

3.36 (br., 1H), 3.62 (m, 2H), 4, 27 (q, 2H), 7.34 to 7.54 (m, 5H), 9.85 ((br.1H)

27 56.7-58.9 1.17( t, 3H ), 1.95( m, 2H ), 3.24(m, 2H), 3.31(S,3H),

3.69 (m, 2H), 4, 22 (q, 2H), 7.31 to 7.64 (m, 5H), 9.94 ((br.1H)

28 89.4-91.1 1.08( t, 3H ), 1.89( m, 2H ), 2.35(t, 3H), 3.24(m, 2H),

3.45(t., 2H), 3.69(m, 2H) 4.22(q, 2H), , 7.31~7.64(m,5H), 9.94((br.1H)

29 78.2-80.1 1.16( t, 3H), 1.34(t, 3H), 1.75( m, 2H ), 3.36(m, 2H),

3.95(q,2H), 4.22( q, 2H ), 7.50~7.63(m, 5H) , 10.10(br., 1H)

30 70.2-73.4 1.06( t, 3H ), 1.75( m, 2H ), 4.02(d, J =6.5Hz), 4.34, (q ,2H),

7.30-7.63 (m., 5H), 10.12 (br, 1H)

31 145-147 1.16( t, 3H ) , 1.75( m, 2H ), 3.36(m,2H), 4.22(t, 2H ),

7.50~7.63(m, 5H), 10.10(br., 1H) Formulation examples (The active ingredient in the formula is added after the whitening, all percentages are by weight)

Formulation Example 1: 10% emulsifiable concentrate

Compound No.1 10 parts Tween 80 12 copies

Ν,Ν-dimethyl phthalamide 3 parts

Xylene to make up 100 parts

Formulation Example 2: 90% soluble liquid

Compound No.1 90 parts

N-methylpyrrolidone 10 parts

Formulation Example 3: 70% soluble liquid

Compound No.1 70 parts

Methyl ethyl ketone 30 parts

Formulation Example 4: 15% Suspending Agent

Compound No.1 15 parts

Ethylene glycol 10 parts

Sodium dodecyl benzoate 5 parts

Xanthan gum 0.5 parts

Stabilizer 4.5 parts

Water 65 parts

Formulation Example 5: 25% wettable powder

Compound No.2 25 parts

Stabilizer 3 parts

Sodium lauryl sulfate 12 parts

Lignin calcium silicate 10 parts

Kaolin 50 parts of biological activity determination examples

As can be seen from the experiment below, the compound represented by the compound I of the present invention is against the wheat scab Gibberella zeae. cotton blight ox_3⁄4ro /w), ji3⁄4 ((Phytophthora capsici). rice blast disease

( Gibberella fujikiiroi ). Botrytis cinerea and Rhizoctonia solani have good inhibitory activity. Among them, the compounds Nol, No2, No3 and No 4 have the best effects.

Biological activity example

Bactericidal activity test: Toxic medium method The drug compound Nol 2-cyano-3-(substituted)amino-3-phenyl acrylate was prepared into a concentration of 2 μg/ml to prepare a drug-containing medium, and then transferred to wheat after 8 hours. Scab (C/Me e//s ^3⁄4e ), cotton {Fusarium oxysporum >> (Phytoph thora capsicl) ·, rice blast disease

( Gibberella fu jikuroi ) , Bo try t is cinerea , 6 fresh stalks of Rhizoctonia solani , and placed in a 25 ° C incubator for 4 days to measure the colony growth diameter. The mycelial growth inhibition rate was calculated. The results of the measurements are shown in Table 3.

In vitro inhibition of mycelial growth activity of various pathogens

No wheat red cotton withered Phytophthora capsici rice seedlings cucumber gray mold wheat

mother

1 100 100 88 100 95 75

2 100 100 90 100 85 82

3 100 100 86 100 90 85

4 100 100 89 100 90 84

5 80 70 78 70 95 69

6 85 73 71 73 85 72

7 100 100 67 100 60 70

8 84 72 69 73 54 55

9 88 75 72 75 65 58

10 89 85 70 85 55 64

11 86 82 55 82 50 69

12 84 75 58 75 68 45

13 73 65 64 65 55 35

14 80 76 45 76 55 63

15 100 88 76 76 45 75

16 85 75 72 75 45 79

17 86 67 54 67 45 65

18 56 43 34 43 0 20

19 68 54 43 54 0 35

20 24 25 15 25 0 0 21 26 25 12 25 0 9

22 27 0 12 0 0 0

23 85 60 54 60 56 45

24 70 65 55 65 57 34

25 87 75 65 75 67 64

26 76 64 67 64 67 65

27 79 67 70 67 56 63

28 80 76 54 76 57 54

29 86 80 63 80 68 45

30 76 70 54 70 88 56

31 77 60 74 60 57 67 Compound A* 85 73 71 73 85 72 Remarks: Compound A* is a known compound: 2-cyano-3-amino-3-phenyl acrylate

Claims

Claim

Ri or R ₂ are each independently hydrogen, dC ₆ unsubstituted or substituted alkyl, Ci-C ₆ alkoxy, C ₂ -C ₆ ester, d-C ₆ carboxylic, C ₃ -C ₆ naphthenic a heterocyclic methyl group, a C ₃ -C ₆ allyl group, a C ₃ -C ₆ propargyl group or a benzyl group, wherein the substituent of the substituted alkyl group is a halogen, a hydroxyl group or a cyano group Or an alkoxy group, the substituent of the substituted heterocyclylmethyl group being a halogen or a monocyclic aryl group;

R ₃ is a C ₃ -C ₈ alkyl group, a C ₃ -C ₆ 13⁄4 alkyl group, a C ₃ -C ₆ alkoxyalkyl group, a C ₃ -C ₆ cycloalkyl group or a C ₃ -C ₆ heterocycloalkane group. base.

2. The compound according to claim 1, wherein

Ri or R ₂ are each independently hydrogen, dC ₆ unsubstituted or substituted alkyl, Ci-C ₆ alkoxy, C ₂ -C ₆ ester, d-C ₆ carboxylic, C ₃ -C ₆ naphthenic a heterocyclic methyl group, an allyl group, a propargyl group or a benzyl group, wherein the substituent of the substituted alkyl group is a halogen, a hydroxyl group, a cyano group or an alkoxy group, and the substituted The substituent of the cyclomethyl group is halogen or benzyl;

R ₃ is a C ₃ -C ₆ alkyl group, a C ₃ -C ₆ cycloalkyl group or an oxocyclopentanemethyl group.

3. The compound according to claim 2, wherein

The heterocyclylmethyl group is pyrrole or hydrogenated pyrrole methyl, pyridylmethyl or thiazolylmethyl.

4. The compound according to claim 3, wherein

Or R ₂ are independently independently hydrogen, dC ₆ alkyl, dC ₆ chloroalkyl, dC ₆ hydroxyalkyl, dC ₆ cyanoalkyl, dC ₆ alkoxyalkyl, d-C ₆ alkoxy, acetic acid Ethyl ester group, d-C ₄ carboxylic acid group, cyclopropyl group, cyclohexyl group, benzyl-substituted hydrogenated pyrrole methyl group, chloropyridylmethyl group, chlorothiazole methyl group, allyl group;

R ₃ is a C ₃ -C ₆ alkyl group, a cyclohexyl group or an oxocyclopentanemethyl group.

5. The compound of claim 4, wherein

Ri or R ₂ are each independently hydrogen; R ₃ is a C ₃ -C ₆ alkyl group.

6. A process for the preparation of the compound of claim 1 wherein the reaction equation is as follows:

Wherein R ₂ or R _{3 is} as defined in claim 1.

7. The preparation method according to claim 6, wherein in the preparation of the compound II, the cyanoacetate is added to the solution of the ethylene glycol dimethyl ether containing the magnesium ethoxide, and then the benzoyl chloride is added to carry out the reaction. The final acidification gave 2-cyano-3-hydroxy-3-phenyl acrylate.

The preparation method according to claim 6, wherein in the preparation of the compound II, the benzoyl chloride and the acid-binding agent triethylamine are simultaneously added to the chloroacetate-containing dichloroethane solvent, and finally After filtration, the filtrate was concentrated and acidified to give 2-cyano-3-hydroxy-3-phenyl acrylate.

The method according to claim 6, wherein in the preparation of the compound ruthenium, 2-cyano-3-hydroxy-3-phenyl acrylate and phosphorus oxychloride are used in an inert solvent of dichloromethane or two. In the ethyl chloride, the acid-binding agent triethylamine was added dropwise to obtain 2-cyano-3-chloro-3-phenyl acrylate.

10. A compound according to claim 1 which is an active ingredient and which is formulated into a fungicide composition with a carrier.

11. A compound according to any one of claims 1 to 5 for use in controlling diseases caused by fungi on plants.

12. Use according to claim 11, characterized in that the fungus is Fusarium, Rust or Botrytis.