JPH01207289A - Production of acylaminoacetonitrile derivative - Google Patents

Abstract

PURPOSE:To industrially and advantageously obtain the title compound useful as an agricultural and horticultural germicide, etc., by reacting nitrogen- containing heterocyclic amides with a glyoxilic acid ester, followed by acetosylation, and then reaction with a heterocyclic compound, further treatment with NH3 and dehydration. CONSTITUTION:An amide expressed by formula I [A represents pyrozolyl group expressed by formula II (R<1> represents alkyl, phenyl, etc.; R<2> and R<3> represents H, halogen, alkyl, etc.), etc.] is reacted with a glyoxilic acid ester expressed by formula III (R<7> represents lower alkyl) and converted into an acetoxy derivative to afford an acetoxamide derivative expressed by formula IV (Ac represents acetyl). Then this compound is reacted with a heterocyclic composed expressed by formula V (R<6> represents H, halogen or alkyl; X represents O or S) in the presence of a Lewis acid, treated with ammonia to amidate the ester group and dehydrated with a customary dehydrating agent to afford the aimed compound expressed by formula VI.

Description

[Detailed Description of the Invention] C Industrial Application Field] The present invention is a novel agricultural and horticultural fungicide useful for late blight and downy mildew, general formula (9): (wherein A is the general formula ( 2): (wherein R1 represents an alkyl group, a haloalkyl group, an alkoxyalkyl group, or a phenyl group, and R2 and R3 are a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkoxyalkyl group, respectively) or a pyrazolyl group represented by -form (3): (In the formula, one of Y and Z represents a carbon atom, and the other represents an oxygen atom or a sulfur atom. , R4 and R
5 represents a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, or a phenyl group), R6 represents a hydrogen atom, a halogen atom, or an alkyl group, and X represents an oxygen atom or a sulfur atom. The present invention relates to a method for producing an acylaminoacetonitrile derivative represented by:

[Prior Art] Many studies have been conducted on organic synthetic compounds useful in agriculture and horticulture, and many compounds exhibiting physiological activity have been discovered and put into practical use. Compounds with various chemical structures are in practical use as agricultural and horticultural fungicides.
The role that these synthetic compounds have played in controlling plant diseases and, ultimately, in the development of agriculture is immeasurable. A large number of active compounds have been found as amide compounds, and some are used as herbicides or fungicides. However, it is a fact that these conventional synthetic compounds cannot be said to have sufficient control action or safety. Furthermore, all of these compounds mainly have a preventive effect against late blight and downy mildew, and cannot be expected to have any therapeutic effects. Therefore, by the time disease outbreaks are observed, sufficient effects can already be expected. It has the disadvantage of not being possible. In reality, when considering the spraying of chemicals to control crop diseases, they are more or less sprayed after the disease has appeared, and it is difficult to completely control the disease with these compounds. In addition, these compounds have extremely high concentrations that exhibit pesticidal effects;
The safe use of pesticides is also viewed as a problem, and there are some drugs whose toxicity to fish cannot be ignored. In order to improve these points, research into new pesticidal agents has continued, and for example, N-phenylalanine derivatives, such as metalaxyl (N-(2,6 -dimethylphenyl)-N-(2-methoxyacetyl)alanine methyl ester] have been developed and are being put into practical use around the world. However, these N-phenylalanine derivatives have already lost their control effects due to the emergence of drug-resistant bacteria. The decline is seen as a problem.

[Problem that the invention seeks to solve]

As a result of intensive studies to overcome these drawbacks and find a compound with excellent properties as an agricultural and horticultural fungicide, we have found that it has both preventive and therapeutic effects against late blight, downy mildew, etc. of various crops. It is a compound that has a wide range of applications and has an excellent pesticidal effect, or does not cause phytotoxicity to cultivated plants.
The general formula (9) is not toxic to warm-blooded animals or fish.
):0 The present invention provides a method for producing an acylaminoacetonitrile derivative represented by the above-mentioned formula (9), which is safe,
The objective is to provide an inexpensive manufacturing method.

[Means and effects for solving the problems] The compound represented by the general formula (9) produced by the production method of the present invention is (wherein A is mm). represents an alkyl group, a haloalkyl group, an alkoxyalkyl group, or a phenyl group, and R2 and R3 each represent a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkoxyalkyl group, or a nitro group. ) (In the formula, one of Y and Z represents a carbon atom, the other represents an oxygen atom or a sulfur atom, and R4 and R
5 represents a hydrogen atom, a halogen atom, Al-114, a haloalkyl group, or a phenyl group), R6 represents a hydrogen atom, a halogen atom, or an alkyl group, and X represents an oxygen atom or a sulfur atom. ) and are all new compounds.

The compound represented by the general formula (9) is usually prepared by the following reaction formula (a
) is manufactured by the method.

Reaction formula (a) CN CN (13) In the method of acid acceptor reaction formula (a), aldehyde) (10) is reacted with sodium cyanide to form cyanohydrin (11),
Then, the amine derivative (12) is obtained by reacting with ammonia in a suitable solvent (for example, methanol). This is then reacted with a suitable acid chloride (13) in the presence of an acid acceptor to obtain the desired compound (9).

However, in this method, the amino derivative (12
), problems include low yield, expensive raw material aldehyde (10), and use of highly toxic sodium cyanide.

In order to eliminate these drawbacks, as a result of intensive studies, we have found a route to solving the above problems and completed the present invention.

That is, the present invention provides general formula (1): % formula % (wherein A is general formula (2): (wherein, R1 represents an alkyl group, a haloalkyl group, an alkoxylalkyl group, or a phenyl group, and R2 and R
1 represents either a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkoxyalkyl group or a nitro group, respectively) or a pyrazolyl group represented by the general formula (in which Y and Z are either One represents a carbon atom, the other represents an oxygen atom or a sulfur atom, and R4 and R5 represent a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, or a phenyl group). The amide represented by the general formula (2) is reacted with a glyoxylic acid ester represented by HCOCOOR7 (in the formula, R7 represents a lower alkyl group) to produce the general formula (4): (wherein A and R7 are each represented by the above-mentioned A hydroxyamide derivative represented by (indicating the meaning above) is obtained, which is then converted into an acetoxy compound, and -i is represented by formula (5): (wherein A2 and R7 each have the above-mentioned meaning). An acetoxyamide derivative is obtained, and then this is converted into a heterocyclic compound represented by the following formula (6): (wherein, R6 represents a hydrogen atom, a halogen atom, or an alkyl group, and X represents an oxygen atom or a sulfur atom) is reacted with in the presence of a Lewis acid to obtain an ester represented by the general formula (7): (wherein A, R', R7 and By treatment with ammonia, an amide represented by the formula (8): (wherein A, R' and χ each have the meanings given above) is obtained, and this amide is then dehydrated with a conventional dehydrating agent. This is a method for producing an acylaminoacetonitrile derivative represented by mm formula (9): (wherein A, , Rh and X each have the above-mentioned meanings).

The production method of the present invention can be easily carried out according to the route shown in reaction formula (b).

Reaction formula (b) 1) A-CONH2+ HCOCO, R5→The production method of the present invention will be explained in more detail below. The starting amide can be easily synthesized from the corresponding carboxylic acid. This amide (1) is reacted with an ester of glyoxylic acid to obtain a hydroxyamide derivative (4). This reaction is performed using hydrocarbons such as benzene, toluene, xylene, hexane, and ligroin, or esters such as ethyl acetate and butyl acetate, or dimethyl sulfoxide, N,
aprotic polar solvents such as N-dimethylformamide;
Alternatively, the reaction can be carried out in various solvents such as ethers such as dioxane and tetrahydrofuran, but it is particularly preferable to carry out the reaction in an ether solvent.
It is desirable to carry out at 120°C, especially 50 to 100°C. The reaction time is related to the reaction temperature and is between 1 and 20 hours. The thus obtained hydroxyamide jA It form (4) is treated with a conventional halogenating agent (e.g. thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, hydrogen chloride, hydrogen bromide) to replace the hydroxyl group with a halogen, and further Treatment with an alkali salt of acetic acid (eg sodium acetate) yields the acetoxyamide derivative (5).

The obtained acetoxy compound is reacted with a heterocyclic compound (6) in the presence of a Lewis acid to obtain an ester (7). This reaction is carried out using a solvent that is inert to the reaction (e.g. tetrahydrofuran).
Although the process can be carried out indoors and can be accelerated by raising the temperature, it is preferable to carry out the process at around room temperature. Lewis acids include zinc chloride,
Examples include ferrous chloride, ferric chloride, aluminum chloride, stannous chloride, titanium tetrachloride, and boron trifluoride. The reaction time depends on the temperature, but is preferably 5 to 70 hours.

The resulting ester (7) is then converted to the corresponding amide (8) by treatment with ammonia in solution by known methods. This amide (8) is then treated with a conventional dehydrating agent to yield the nitrile (9).

Examples of dehydrating agents include phosphorus oxychloride, acetic anhydride in pyridine, p-)luenesulfonyl chloride in pyridine, phosphorus pentachloride, phosgene, dicyclohexylcarbodiimide, sodium hydroxide, and triphenylphosphine in the presence of carbon tetrachloride. Can be mentioned. Although the reaction proceeds at room temperature, it is desirable to raise the temperature to 50 to 100°C.

〔Example〕

The manufacturing method of the present invention will be specifically explained below with reference to Examples.

Example I Synthesis of N-(α-cyanofurfuryl)-1,3-dimethylpyrazole-4-carboxylic acid amide Step 1 1.3-dimethylpyrazole-4-carboxylic acid amide 2
．． 0 g (14+ nmol) was dissolved in dioxane 20d, and 1.46 g (14n+
The reaction mixture was heated and stirred at 50°C for 3 hours, poured into water, saturated with sodium chloride, and extracted with chloroform. The solvent was distilled off under reduced pressure and subjected to silica gel column chromatography [chloroform/methanol-
2071 (v/v)] to obtain hydroxyamide as a colorless oil.

Yield 2.92g (yield 84.4%) NMR (DMSO-da, δppm): 1.23 (31
(,t,J-7,6Hz),2.37(3H,s),3
．． 76 (3H, s).

4.09 (28,q, J-7,6Hz), 5.81 (I
H, d, J-7, 7Hz).

8.06(1)1. s), 8.28 (18, d, J=7
．． 7 Hz) Second step 7.0 g (29 m
mo+) was dissolved in 100 mff1 of thionyl chloride and stirred at room temperature for 3 hours. Thionyl chloride was distilled off under reduced pressure, and the residue was dissolved in 100 m of glacial acetic acid. 4.0 g (60+++ mol) of anhydrous sodium acetate was added, and the mixture was stirred at room temperature for 3 hours. The solvent was distilled off under reduced pressure, ethyl acetate was added to the residue, washed with water, and then dried over anhydrous magnesium sulfate.

Silica gel column chromatography [chloroform/
methanol-20/1 (v/v)] to obtain the acetoxy compound as a colorless oil.

Yield 7.5g (yield 91.55%) NMR (CDCl2.δPPII+): 1.33 (3H
,t,J-7,0Hz),2.50(311,s),3
．． 49 (3H, s).

3.83 (3H, s), 4.28 (2H, q, J-7
, 0Hz), 5.67 (IH, d.

J-9Hz), 7.03 (LH, d, J-91(z),
7.85 (18,s).

3rd step 2.0g of acetoxy compound obtained in the 2nd step (7n+ao
l) into 40 m2 of anhydrous tetrahydrofuran,
Furan 10 and boron trifluoride ether complex 0.17 were added and the reaction mixture was left at room temperature for 50 hours. The reaction mixture was poured into water, extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to obtain the ester as a light brown oil.

Yield 1.63 g (yield 79.2%) IR (neat
, cm-'), 3300,2900.2800,17
40,1640°1550,1520.1370.13
30.1210.1180.1150.1020°4O NMR (CDCh, δppm+): 1.27 (3H
,t,J-7,01(z),2.47(3H,s),3
．． 80 (3tl, s).

4.27 (2H, q, J-7,0Hz), 5.
86 (LH, d, J=7.6Hz).

6.35 (2H, m), 6.83 (18, d, J-7,
6Hz).

7.30 (IH, br s), 7.73 (IH, s) 4th step Ester obtained in 3rd step 1.4 g (4.8 mm
ol) in 10 m2 of 5.5% ammonia-methanol solution
and left overnight. The solvent was distilled off under reduced pressure, and the residue was crystallized by adding isopropyl ether to obtain the amide as light brown crystals.

Yield 0.94 g (Yield 74.6%) Melting point 162~
165°C [R(KBr, cm-Re: 3390, 3240, 16
70,1620,1540°1410,1390.12
70.1175.1150.1010.73ONMR(
DMSO-d61δppts>:2.36 (3H, s)
, 3.77 (3H, s), 5.75 (IH, d, J=7
．． 5) 1z).

6.37 (2H, m), 7.16 (IH, s).

7.43 (LH, br　s), 7.52 (IH, s).

7.98 (IH, d, J = 7.5Hz), 8.18 (L
H,s) Fifth step Amide 200 obtained in the fourth step [(0,76mno
+) was dissolved in pyridine 511&, 0.25 (1,31m+io+) of p-toluenesulfonyl chloride was added, and the mixture was heated and stirred at 50°C for 10 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with a 10% aqueous citric acid solution, water, a saturated aqueous sodium bicarbonate solution, and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography [chloroform/methanol = 20/1 (v
/v)) to obtain the desired product as colorless crystals.

Yield 150 mg (yield 80.5%) Melting point 121.5-122.5"C IR (KBr, cl'): 3400, 3200, 31
80,2980,2840°1650,1520.14
40.1360.1310.1280.1250.11
? 0°1150, 1130.1010,970,950
,860,840,810,740,72ONMR(C
DCl1I δppI11): 2.39 (3H, s)
, 3.74 (3H, s), 6.24 (IH, d, J=8
．． 0Hz).

6.28-6.52 (2H, m), 7.36 (II (,
br s),? , 53(1)1. d.

J=8.0Hz), 7.83(LH,s).

Example 2 Synthesis of N-(α-cyanofurfuryl)-2,4-dimethylthiazole-5-carboxylic acid amide 1st step 2.4-dimethylthiazole-5-carboxylic acid amide 6
, Og (38,4m+*ol) in 60m2 of ethyl acetate
4.0 g (38 mmo) of ethyl glyoxylate
The reaction mixture was heated and stirred at 50°C for 4 hours, poured into water, saturated with sodium chloride, and extracted with chloroform. The solvent was distilled off under reduced pressure and subjected to silica gel column chromatography [chloroform/methanol = 10
/ 1 (v/v)] to obtain hydroxyamide as a colorless oil.

Yield 8.23 g (yield 83.0%) NMR (DMS
O-da, δppm): 1.25 (3H, t, J
=7.8Hz), 2.57(3H,s), 2.66(3
H,s＞.

4.05 (2H, q, J = 7.8Hz), 5.79 (I
H, d, J = 7.5Hz).

8.30 (18, d, J = 7.5 Hz) Second step 8.0 g of hydroxyamide obtained in the first step (31+
1...ol) was dissolved in 100 mf of thionyl chloride and stirred at room temperature for 3 hours. Thionyl chloride was distilled off under reduced pressure, and the residue was dissolved in 100 ml of glacial acetic acid. 4.3 g (65 mmo+) of anhydrous sodium acetate was added, and the mixture was stirred at room temperature for 3 hours. The solvent was distilled off under reduced pressure, and ethyl acetate was added to the residue, which was washed with water and dried over anhydrous magnesium sulfate.

Silica gel column chromatography [chloroform/
The acetoxy compound was obtained as a colorless oil by purification with methanol (10/1 (v/v)).

Yield 8.8g (yield 94.6%) NMR ((:DClz, δIIPm): 1.35
(3H, t, J=7.5Hz), 2.52(3H
,s) , 2.60(3H,s) 3.50(3H,s
), 4.20 (2H, Q, J=7.5Hz), 5.72
(lit, d.

J=8.3Hz), 7.25(ILd, J=8.3)
1z) Third step 8.0 g (26 mmo) of the acetoxy compound obtained in the second step
Dissolve l) in 150 mff1 of anhydrous tetrahydrofuran, add 38 mL of furan and 0.4 m of boron trifluoride ether complex.
The reaction mixture was poured into water, extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to obtain the ester as a light brown oil.

Yield 6.6g (yield 80.3%) NMR (CDC131δppm): 1.25 (3H, t, J = 7.0Hz), 2.55 (3
11,s), 2.62(3H,s).

4.20 (2H, Q, J = 7.0Hz), 5.94 (1
)1. d, J=7.5Hz).

6.30 (21 (, m), 7.04 (ltl, d, J=
7.5 Hz), 7.25 (LH, br s) 4th step 5.0 g (16.2 mmo) of the ester obtained in the 3rd step
+) to 5.5% ammonia-methanol yg? a 3
4 rm? I made 8 squares and left it overnight. The solvent was distilled off under reduced pressure, and the residue was crystallized by adding isopropyl ether to obtain the amide as colorless crystals.

Yield 3.65 g (yield 80.6%) Melting point: 14
3-144°C NMR (CDCh, δppm): 2.60. (
311, s), 2.65. (3H,s), 5
．． 70 (18,d, J=7.6Hz)6.45(
2H, m), 7.20 (211, s), 7.48 (il
l, br s), 7.55 (18, s), 7.90 (1
B, d, J-7,6Hz) Fifth step Amide obtained in the fourth step 1. Og(3,6mff1) was dissolved in anhydrous pyridine 25, and 1.5 g of trifluoroacetic anhydride was added dropwise while stirring and cooling at -25°C. After gradually raising the temperature to 0°C, the reaction mixture was dissolved in water. Pour into
After extraction with ethyl acetate, it was dried using magnesium sulfate. It was purified by silica gel column chromatography (chloroform/methanol = 10/1 (v/v)) to obtain the acetoxy compound as colorless crystals.

Yield 0.61g (yield 65.2%) Melting point: 103°
C IR (KBr, cm-'): 2225, 1655 NMR (CDC1ff δppm): 2.61 (3
H,s), 2.64 (3H,s), 6.34
(IH, d, J-8, 0) 1z).

6.40 (LH, br s), 6.58 (IH, br s)
s), 7.48 (IH, br s).

7.96 (IH, d, J-8,0 Hz) Below, examples of compounds obtained by the same procedure are shown in Table 1.

The acylaminoacetonitrile derivative represented by the general formula (9) produced by the production method of the present invention has preventive and therapeutic effects against late blight and downy mildew of various crops, and has a preventive and therapeutic effect on cultivated plants. It does not cause drug damage and is not toxic to warm-blooded animals or Class 8.

Next, for reference, the efficacy of the compound of the present invention as a fungicide for agricultural and horticultural purposes will be explained using test examples. In addition, the following compounds were used as control compounds in the test examples.

Control compound A: α-(2,6-cyclopyridin-4-ylcarbonylamino)-(2-furyl)acetonitrile B: α-(2-furylcarbonylamino)-(2-furyl)acetonitrile C: 4- C2,4-dichlorobenzoyl)-5-benzoylmethoxy-1,3-dimethylpyrazole D: α-benzoylaminopropioacetonitrile E: zinc ethylene bis(dithiocarbamate) [zineb] F: tetrachloroisophthalonitrile [TPN] Control compounds A and B are compounds described in JP-A-57-167978, C is a compound commercially available as a herbicide for paddy fields, and control compound A is a compound commercially available as a herbicide for paddy fields.
nn, Chew, ), 1972, 764.69-9
The compounds described on page 3 and control compounds E and F are commercially available agents for controlling potato late blight, cucumber rot, etc.

The formulation used in this test example is as follows.

Formulation Example 1 Wettable powder compound (1): 50 parts, sodium ligninsulfonate = 10 parts, sodium alkylnaphthalenesulfonate 5
parts, white carbon: 10 parts and diatomaceous earth: 25 parts
The mixture was mixed and ground to obtain 100 parts of a wettable powder.

Test Example 1 Potato late blight control test (preventive effect) Potatoes grown in pots in a greenhouse (variety Nibaron, plant height 25
A spray gun (approximately 1.0 kg/cm) was applied with a prescribed concentration of the drug (preparing a wettable powder of the test compound according to the method of Formulation Example 1 above, and diluting this with water to a prescribed concentration).
) was used to spray 50 d per 3 pots and air dry. A zoospore suspension was prepared from potato Phytophthora blight which had been previously cultured on potato sections for 7 days. This suspension was sprayed and inoculated onto the potato plants sprayed with the drug, and the test plants were grown from 17 to 19
After being kept at 95% humidity or higher for 6 days at 1°C, the degree of lesion formation was investigated. The results are shown in Table-2.

The disease severity index was determined by observing and evaluating the lesion area ratio for each leaf, and the disease severity was determined for each plot using the following formula.

The evaluation criteria are as follows.

Disease severity index O: Lesion area ratio 0%1: 〃
1 to 5% 2: 〃 6 to 25% 3: 26 to 50% 4: 51% or more no: Number of leaves with severity index O nI: //1 horn nz; // 2 //ngo:〃3〃 n4: // 4 // N ”' no + n + + n z +
n 3 + na Test Example 2 Potato Phytophthora control test (therapeutic effect) Zoospores were generated from Potato Phytophthora blight bacteria that had been cultured for 7 days on potato sections on potatoes grown in pots in a greenhouse (variety Nibaron, approximately 25 cm in height). A suspension was prepared and inoculated by spray. 20 hours 17°C ~ 19
After keeping the temperature at /'
cm") was used to spray 50m1 per 3 pots and air dry. After being kept at 17-19°C and humidity of 95% or higher for 6 days, the degree of lesion formation was investigated.Evaluation criteria and disease severity display method is as shown in Test Example 1.The results are shown in Table-
Shown in 2.

Test Example 3 Cucumber and disease control test (preventive effect) Cucumbers grown in pots in a greenhouse (variety: Wasumi Hanshiro, Konoha 2)
A predetermined concentration of the drug (test compound) was added to the above Formulation Example 1.
Prepare a hydrating agent according to the method of
30 d per 3 pots was sprayed using the following method and air-dried. Downy mildew bacteria were collected from lesions on cucumber leaves infected with downy mildew, a spore suspension was prepared with demineralized water, and the suspension was inoculated by spraying. The inoculated pots were immediately kept at 18-20°C, humidity 95% or higher for 24 hours, then transferred to a greenhouse (room temperature 18-27°C), and the extent of lesion formation was examined after 7 days.

The evaluation criteria and disease severity display method were as shown in Test Example 1. The results are shown in Table-2.

Test Example 4 Cucumber and disease control test (therapeutic effect) Cucumber and disease spore suspension were prepared and sprayed on the same cucumber as used in Test Example 3.

The inoculated pot was immediately kept at 18-20°C and 95% humidity for 24 hours, and then the drug at a predetermined concentration (the test compound was prepared on the aqueous phase side according to the method of Formulation Example 1 above). diluted with water to a specified concentration) with a spray gun (1,
0kg/cm") and sprayed 30ml per 3 pots and air-dried. Furthermore, the bond was placed in a greenhouse (room temperature 18-27°C).
), and the extent of lesion formation was examined 7 days later.

The evaluation criteria and disease severity display method were as shown in Test Example 1. The results are shown in Table-2.

Test Example 5 Tomato late blight control test (soil irrigation treatment) Tomatoes grown in pots in a greenhouse (variety Nisei-1 plant height 20 cm)
A predetermined amount of the drug (test compound was prepared as a wettable powder according to the method of Formulation Example 1 above, and diluted with water to a predetermined concentration) in a pot (about 7.5 cm in diameter). Two plants per pot were irrigated using a pipette and kept in a greenhouse for 5 days. A zoospore suspension was prepared from a late blight tomato surface that had been previously cultured on potato sections for 7 days. This suspension was spray-inoculated onto drug-treated tomato plants, and the test plants were kept at 17-19°C and a humidity of 95% or higher for 6 days, and then the degree of lesion formation was investigated.

The evaluation criteria and disease display method were as shown in Test Example 1. The results are shown in Table-2.

In addition, in the case of chemical application in the above test example, in the case of spraying, the active ingredient concentration was 1100 pp, and in the case of soil irrigation, the active ingredient dosage was 15 g/are.

Table 2 Disease control test results Table 2 (Continued) Table 2 (Continued) [Effects of the invention] The method of synthesizing an aminoacetonitrile derivative and then acylating it with an appropriate acid chloride has a low yield. Although there are problems such as the use of toxic sodium cyanide and/or expensive raw materials, the method for producing acylaminoacetonitrile derivatives of the present invention uses a completely different route from these, and allows the desired product to be produced safely and inexpensively. This is a method that can supply Since the acylaminoacetonitrile derivative produced by the production method of the present invention has excellent preventive and therapeutic efficacy against various plant diseases,
The production method of the present invention is extremely useful in agricultural industry.

Claims (1)

[Claims] General formula (1): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (However, A in the formula is general formula (2): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2 ) (In the formula, R^1 represents an alkyl group, haloalkyl group, alkoxylalkyl group, or phenyl group, and R^2 and R^3 each represent a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, or an alkoxyalkyl group. or a pyrazolyl group represented by the general formula (3): ▲Mathematical formulas, chemical formulas, tables, etc.▼(3) (In the formula, one of Y and Z is , carbon atom,
The other represents an oxygen atom or a sulfur atom, and R^4 and R^5 represent a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, or a phenyl group). and a glyoxylic acid ester represented by the general formula: HCOCOOR^7 (in the formula, R^7 represents a lower alkyl group) to form the general formula (4): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ( 4) Obtain a hydroxyamide derivative represented by (in the formula, A and R^7 each have the above-mentioned meanings), and then convert this into an acetoxy compound to form the general formula (5): ▲ mathematical formula, chemical formula , tables, etc. ▼(5) (In the formula, A and R^7 respectively indicate the above meanings) An acetoxyamide derivative represented by the following is obtained, and then this is converted into the general formula (6): ▲Mathematical formula, chemical formula , tables, etc.▼(6) (In the formula, R^6 represents a hydrogen atom, a halogen atom, or an alkyl group, and X represents an oxygen atom or a sulfur atom.) By reacting in the presence of the general formula (7): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (7) (In the formula, A, R^6, R^7 and X each have the above meanings.) The general formula (8): ▲Mathematical formula, chemical formula, table, etc.▼(8) The general formula (9) is characterized in that it is an amide represented by (each having the above meaning) and then this amide is dehydrated with a conventional dehydrating agent: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (9) A method for producing an acylaminoacetonitrile derivative represented by the formula (wherein A, R^6 and X each have the above meanings).