JPH02282383A - Thioamide derivative and agricultural and horticultural germicide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R represents 3-6C alkyl, 3-6C alkenyl, 3-6C alkynyl, 3-6C cycloalkyl, 4-6C cycloalkylalkyl, 2-6C halogenated alkyl or 3-6C alkoxyalkyl; M is S or O) or an optical isomer thereof. EXAMPLE:N-[2-Thienyl(thiocarbamoyl)methyl]-1-isopropyl-3-methyl-1H-pyr azole-5- carboxamide. USE:An agriculture and horticultural germicide. PREPARATION:An aldehyde expressed by the formula B-CHO, aqueous ammonia, etc., and an alkali cyanide are reacted with each other to form an amino- acetonitrile derivative expressed by formula II, which is then reacted with an acid halide expressed by the formula A-COX in the presence of an acid receptor to give an amide-substituted acetonitrile derivative expressed by formula III. The resultant product is further reacted with H2S in the presence of a base.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel thioamide-substituted derivative, a method for producing the same, and an agricultural and horticultural fungicide containing the derivative as an active ingredient.

[Conventional technology and problems]

One of the important problems in agricultural production, especially in the cultivation of fruit trees and cane vegetables, is diseases caused by plant pathogenic bacteria belonging to the periphery (eg, downy mildew, late blight, etc.).

Diseases caused by these bacteria are difficult to control due to the physiological and ecological characteristics of seedlings, and the development of excellent control agents is desired. Many crops are affected by downy mildew and late blight, and the damage caused is extremely large.

Currently, cabtan (common name), captafor (common name),
Dithiocarbamate fungicides such as zineb (generic name) and chlorocuronil (generic name) are widely used. However, these fungicides mainly have a preventive effect and can hardly be expected to have a curative effect, so they have the major drawback that if they are used only when a disease outbreak is observed, sufficient effects cannot be expected. There is. Antibacterial agents containing acylalanine compounds that have been recently developed and put into practical use, such as metalaxyl (generic name), have both preventive and curative effects, but resistant bacteria have already emerged. However, its control effect has been considerably reduced.

Conventionally, amide-substituted acetonitrile derivatives chemically similar to the compounds of the present invention have been disclosed in Japanese Patent Application Laid-Open No. 57167978.
No. 1, JP-A-58-69866 and JP-A-Sho 6
Although this prior art is reported in Publication No. 0-255759, etc., it cannot be said to be sufficient as a practical fungicide for agricultural and horticultural purposes.
This remains a major unsolved problem.

[Problem that the invention seeks to solve]

The present invention provides a fungicide that simultaneously has preventive and curative effects against diseases caused by plant pathogenic bacteria belonging to the periphyton (e.g., downy mildew, late blight, etc.), and which does not cause phytotoxicity to useful crops. The purpose is to

Means and action for solving problem C] As a result of intensive research on the above-mentioned thioamide derivatives in order to solve the above-mentioned problem, the following compound group of general formula [1] has been found to be effective against late blight and downy mildew on various plants. The present invention has been completed based on the discovery that it has both preventive and curative effects on plants, and has extremely low phytotoxicity to crops.

The compound of the present invention is a new compound that has not been described in any literature.

That is, the present invention provides (1) general formula [1]: [wherein R is an alkyl group having 3 to 6 carbon atoms, 3 to 6 carbon atoms]
an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkylalkyl group having 4 to 6 carbon atoms, a halogenated alkyl group having 2 to 6 carbon atoms, or a halogenated alkyl group having 3 to 6 carbon atoms. represents an alkoxyalkyl group, M
represents a sulfur atom or an oxygen atom. ] Thioamide derivatives and optical isomers thereof.

(2) The present invention provides an agricultural and horticultural fungicide containing as an active ingredient one or more of the thioamide derivative and its optically active substance according to claim (1).

Next, the production method of the present invention is shown in a reaction scheme and explained below.

2-Synthesis of tolyl intermediate to AI) [Production method 1] [4] [5] [Production method 2] [6] [7] [8] [5] [7] Synthesis of derivatives) [5
] [2] BN112 (2) [6) [Manufacturing method 4] N112 [7] Nlh [1] (However, R represents the above meaning), (However,
M represents the above meaning. ), and X represents a halogen atom. ] [Production method 1] The intermediate aminoacetonitrile derivative [5] in the first step is synthesized by two methods.

Method a-1 is a method for obtaining by Strecker reaction. The starting material aldehyde [3], aqueous ammonia and/or ammonium chloride, and alkali cyanide such as sodium cyanide and potassium cyanide are combined with ethers such as ethyl ether and tetrahydrofuran, aromatic hydrocarbons such as benzene and toluene, and water. The reaction is carried out in a binary solvent system. The reaction temperature is usually preferably around 0-100°C.

In method a-2, the starting material aldehyde [3] and a trialkylsilyl nitrile represented by trimethylsilyl nitrile are reacted in the presence of a catalytic amount of a Lewis acid such as zinc iodide as necessary to form an intermediate [4]. obtain. Subsequently, the aminoacetonitrile derivative [5] is obtained by reacting with ammonia dissolved in a solvent such as methanol or ethanol. The obtained aminoacetonitrile derivative [5] can also be purified and isolated by forming a salt with a hydrogen halide such as hydrogen chloride in an ether solvent such as diethyl ether.

Next, in the second step, the aminoacetonitrile derivative [5] obtained in the first step is reacted with the acid halide represented by the general formula [6] in the presence of an acid acceptor.

Examples of acid acceptors include organic bases such as triethylamine, dimethylaniline, and pyridine, and inorganic bases such as ammonia, potassium carbonate, sodium carbonate, ammonium hydrocarbons, sodium hydroxide, and ammonium carbonate. .

This reaction is preferably carried out in the presence of a solvent, such as ethers such as diethyl ether, tetrahydrofuran, diisopropyl ether, methyl acetate,
Esters such as ethyl acetate, methylene chloride,
Halogenated hydrocarbons represented by chloroform, 1.2 dichloroethane, etc., acetyl nitrile, etc. can be used. Since the reaction is an exothermic reaction, the reaction temperature is desirably carried out under cooling, preferably around -30°C to around 50°C, and practically desirably around -20 to 30°C. In this way, an intermediate amide-substituted acetonyl-lyl derivative is obtained.

[Production method 2] A method in which the starting material carboxylic acid derivative [8] and the aminoacetonitrile derivative [5] obtained in [Production method 1] are dehydrated and condensed in the presence of a dehydrating agent to obtain an intermediate amide-substituted acetonitrile derivative. be.

As a dehydrating agent, dicyclohexylcarbodiimide (D
Particularly preferred are carbodiimides such as CC), l-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and inorganic dehydrating agents such as silicon tetrachloride.

[Manufacturing method 3] (a) The desired thioamide derivative can be easily obtained from the aminoacetonyl lylyl derivative [5] obtained in [manufacturing method 1] and hydrogen sulfide. The base to be used is preferably an organic base such as triethylamine, pyridine, or dimethylaniline, and the reaction will proceed satisfactorily within the range of 0.01 to 1 mole per mole of raw material [5]. .

Although the reaction may proceed without using a solvent,
Usually, it is preferable to use them, and the types thereof are not particularly limited, but examples include hydrocarbons such as benzene and toluene, ethers such as tetrahydrofuran and dioxane, and aromatic amines such as pyridine and dimethylaniline. are listed as preferred. Further, two or more of these may be used as a mixed solvent.

As hydrogen sulfide, one of the raw materials, commercially available gaseous hydrogen sulfide can be used as is, and the amount of feed is determined by the raw material [
5] can be fed in an equimolar amount or in a slightly excess amount to cause the reaction. The reaction temperature is -20 to 100
℃ is desirable, and 0 to 50°C is particularly preferable.

When the reaction is carried out at room temperature, the reaction is usually completed in 5 to 6 hours.

Intermediate [2] thus obtained can be easily isolated and purified by recrystallization.

(b) The reaction between the intermediate [2] obtained in (a) and the acid halide [6] can be carried out under the same conditions as in [Production method 1] (b).

[Production method 4] The reaction to obtain the desired thioamide derivative (1) from the intermediate amide-substituted acetonitrile derivative (7) and hydrogen sulfide can be carried out under the same conditions as in [Production method 3:l (a)].

The thioamide derivative thus obtained can be made into a pure product by a conventional purification method such as recrystallization column chromatography.

Next, the method for producing the compound of the present invention will be explained using specific examples, but the present invention is not limited to these.

2 11 Hito! ! ! LL- (a) N Ammonium chloride (7.7 g) and potassium cyanide (4
, 9g) was added with aqueous ammonia (80 mj2) under water cooling, and after stirring, the mixture was dissolved in toluene (80 m!!,), 1-2-thiophene aldehyde (8.0 g) was added, and the mixture was stirred at room temperature for 20 hours. After the reaction was completed, the I.luene layer was separated, and the aqueous layer was extracted three times with toluene.

These toluene layers were combined, dehydrated and dried, and then the solvent was distilled off to obtain α-(2-thienyl)aminoacetonitrile. (6,9g) (b) 112NclIcN +H85-1→11□
IJcHcsNII□This crystal was found to be the target α-(2-thienyl) by mass spectrometry and nuclear magnetic resonance spectroscopy.
It was confirmed that it was aminoacetothioamide.

Melting point 95-97°C α-(2-thienyl)aminoacetonitrile (13,8
g) (0,1 mol), triethylamine 10.1 g (0
, 1 mol) and 10 ml of lysine in toluene I00 ml
hydrogen sulfide (5.1 g) while stirring under water cooling.
) (0.15 mol) was introduced.

Thereafter, stirring was continued overnight at room temperature, and crystals were precipitated. Subsequently, it is concentrated as it is, and the obtained crystals are recrystallized from a mixed solvent of toluene and ethyl acetate, and further dried (1
1.0 g) of crystals were obtained.

α-(2-thienyl)aminoacetothioamide (3,4
4g) (0.02 mol) in tetrahydrofuran (TH
F) dissolved in 50 mf followed by triethylamine (2
,4g) (0,024 mol).

While stirring this mixture under water cooling, 1-isopropyl-3-methyl-IH-pyrazole-5-carboxylic acid chloride (3,72 g) (0,02 mol) was added to tetrahydrofuran (THF) 6.211I! ! A solution dissolved in , was added dropwise.

Thereafter, stirring was continued for 5 hours at room temperature to complete the reaction. Subsequently, the reaction solution was concentrated, and the residue was washed with water.

The obtained crystals were further recrystallized from toluene-ethyl acetate to obtain crystals (5.35 g) (liquid chromatography purity 99%).

This crystal was analyzed by mass spectrometry and 'H-NMR to reveal the target N
-(2-thienyl(thiocarbamoyl)methyl)-1-
It turned out to be isopropyl-3-methyl-I H pyrazole-5-carboxamide.

2 Person No. 2 (a) A catalytic amount (about 5+++ g) of zinc iodide was added to silyl cyanide (11 g) under water cooling, and the mixture was stirred at room temperature for 1 hour.

Then add 80mβ of ammonia-saturated methanol and 40°
The mixture was stirred at C for 2 hours. The reaction mixture was concentrated, extracted with ethyl acetate, dried, and the solvent was distilled off to obtain α(3-furanyl)aminoacetonitrile (11.6 g).

(c) 3-Furanaldehyde (10g) and trimethyl α-(3
1-isopropyl 3-methyl-IH-pyrazole-5-carboxylic acid chloride (3.05 g) was added to an acetonitrile solution of (furyl) aminoacetonitrile (2.15 g) and triethylamine (1.75 g) under water cooling.
After stirring for an hour, the mixture was stirred at room temperature for 5 hours. After filtering off the resulting solid, the solvent was distilled off, and the resulting oil was purified by column chromatography to obtain N-(cyano-3-furanylmethyl)-1-isopropyl-3-methyl IH-pyrazole-5- Crystals of carboxamide (3.42 g) were obtained.

mp: 130-132"C'H-NMR: (Solvent CDCl23 ・DMSO-d
6) δ (ppm) −1,44, (d, 6B, J=6
．． 6Hz), 2.28(s, 311L5.45(qq
, IFl+J=6.6tlz), 6.02(d, IH,
J=7.8tlz) 6.62(s, l1l), 6.5
0-6.75 (+++, 1l-1) 7.40-7.55
(m, 1ll), 7.65-7.80 (m, III)
.

8.23 (d, Ill, J=7.811z) (C) N-(cyano-3-furanylmethyl)-1-isopropyl-3-methyl-IH-pyrazole-5 carboxamide (2,72 g) and triethylamine 1. Hydrogen sulfide is bubbled into 2 g of toluene solution over water for 15 minutes. Stirring was continued for 1 hour under water cooling and for 10 hours at room temperature, and then the formed crystals were collected by filtration.

When this crystal is washed with chloroform and dried, the desired N
-(3-furanyl(thiocarbamoyl)methylcou 1-
Isopropyl-3-methyl-I H pyrazole-5-carboxamide (2.47 g) was obtained.

Racemic 11-(2-thienyl(thiocarbamoyl)methyl)-1-isopropyl-3-methyl-IH-pyrazole-5-carboxamide (compound No. 3) obtained in Example 1 of Person No. 3 340 mg of the body was added to an optical isomer separation column (Daicel Chemical (1:1 LRAL (:EL 0)
After fractionation using 8't9M solution ethanol:hexane-1=4), the solvent was distilled off under reduced pressure, the obtained crystals were washed with isopropyl ether, and the compound 'h No. 3 (-
) body 131 mg and compound No. 3 (+) body 14
7 mg was obtained.

These physical property values are shown below.

Compound No., (-) form of 3' H-N M R (CDCP,) 1.38 (d, 611.J=6.611z L2.23
(s 311) 5.16 (quint, II, J=6.
61(z), 6.20(d, ILJ=6.61(z
) 6.34 (s, IH), 6.70-6.94 (m,
111), 7.00-7.24 (+++, 211).

7.67 (d, 111.J=6.611z), 7.7
9(brs, LH) 7.98(brs 1tD [α], ”=-184,2(,methanol)>
99.9χee decomposition point 208-209.5°C Compound No. 3 (''-) form 'I-r NMR (CDCj2+) 1.38 (d, 61 (, J = 6.6 Hz), 2.2
3(s, 31i), 5.14(quint, IN, J=
6.6Hz), 6.22(d, ll'l, J4.8H
z).

6.34 (s, IH), 6.68-6.91 (m, I
H), 6.98-7.21 (m, 2H).

7.66 (d, IH, J=7.811z), 7.87
(brs, LH) 8.17 (brs l1l) [α] o ”=+181.9 (methanol) >
98.3! ee decomposition point 208-210.5°C Compounds of the present invention that can be synthesized in the same manner as described below are shown in Table 1.

(Hereafter, margin) Table 1 CsHq-cycl.

Compound No.

A1 to A7 and B1 to B4 in Table 1 above are represented by the following structural formulas.

I (Hereafter, margin) next, Table 2 shows the physical properties of the compounds of the present invention.

Compound no.

Solvent 10DMSOd-6 CDCffiz 10DMSOd-6 CDCI! , 3''-DMSOd-6 CDCffiz 10DMSOd-6 Table 2 ('H-NMR data and melting point) δppm (standard material TMS) Melting point (°C) 5.48 (qq, Ill, J=6.611 z ), 6
．． 17 (d, IIIJ=7.8Hz), 6.35~
6.75 (m, 2t+), 6.65 (s, l1l)
181-1837.45-7.65 (m, 111),
8.30 (d, IH, J=7.8Hz).

9.50 (hrs, 111), 9.78 (brs, l1
l) 1.44 (cl, 611J=6.611z), 2
．． 28 (s, 311) 5.46 (qq, III, J=6
．． 617), 6.34(d, 111.J=7.8)(
z), 6.60 (s, 111), 6.90-7.20 (
m, III), 209-2107.20-7.50
(m, 21+), 8.33 (d, 111J=7.811
z).

9.62 (brs, 211) 1.44 (d, 6H, J-6, 611z), 2.28
(s, 311) 5.46 (qq, 111J=6.6Hz
), 6.01 (d, ill, J=7,8Hz),
6.50-6.80 (m, 2H), 7.40-7
゜60 (m, IH), 7.60-7.85 (m, 1B)
, 8.23 (d, 1B, J=7.8Hz), 9.48
(brs, 18), 9.61 (brs, 1ll) 191
~193 1.43 (d, 611J=6.611z), 2.26
(s, 311) 5.36 (qq, 111.J=6.61
+□) +6.07 (d, III,, r.

7.811z), 6.49(s, 1tD, 7.10-7
．． 40 (m, 2H), 202-2047.40'7
．． 65 (m, IH), 8.08 (d, Ill J=
7.811z).

9.51 (brs, 2H) Compound no.

solvent δppm (standard material TMS) DCffs ten DMSOd-6 CDCn,.

10 DMSOd-6 DCnz + D member So d-6 CDCj! 3 + Open SOd-6 0.50-0.90 (m, 3tl), 1.38 (d, 3
H, J=7.2Hz).

1.5 (1-2, 10 (m, 2) 1), 2.21 (s,
311), 4.75-5.40 (m, IH), 6.12
(d, 111.J=7.211 z ), 6.34(s
.

III), 6.65-6.95 (m, IH)
, 6.95-7.25 (m, 2H) 8.00 (d
, lt(, J=7.2Hz), 9.24(brs
, 21+) 0.80 (d, 3H, J=6.611□),
2.18(s, 31().

1.80-2.35 (m, IH) 14.19 (d, 2H
, J=7.2Hz).

6-10(d+IH1J=7.2Hz), 6.45(
s, l1l) 6.70-6.95 (m, 1B), 7.0
0-7.25 (m, 2H).

8, 16 (d, III, J=7.2Hz),
9.32 (brs, LH).

9.60 (brs, IB) 0.20-0.65 (m, 4H), 1.00-1.60
(m, IH) 2.21 (s, 3H), 4.28 (d,
2H, J4.2Hz).

6.01 (d, IH, J=7.21(z), 6
．． 35-6.60 (a+, 2+1).

6.72 (s, IH), 7.50-7.70 (m, I
H).

8.43(d, IH, J=7.2)1z), 9.
50 (brs, IH).

9.93 (brs, 1tl) 0.10-0.65 (a+, 4■), 0.95-1.5
6(m,1)1).

2.19(s, 3t0.4.23(d, 2LJ=7.2
1(z)5.81(d, IHJ=7.2Hz), 6
．． 35J, 650m, 2 losses.

7.20-7.40 (++, IH), 7.40-7.6
5(m, II).

8.15 (d, LH, J-7, 2Hz), 9.20 (
brs, 1. H).

9.48 (brs, IH) Melting point (°C) 168-170 203-205 169-171 189-191 Compound no.

solvent δppm (standard material TMS) Melting point (C) Compound no.

Solvent δppm <Standard material TMS) Melting point (°C) DCL + DMSOd-6 CDCj2+ 10DMSOd-6 DCjh + DMSOd-6 0,15-0.60 (m, 4H), 0.9f)-1,5
0 (m, l1l) 2.18 (s, 311), 4.22
(d, 2H, J=6.611 z ), 6.08 (d.

IH, J=7.8Hz), 6.49(s, 1ll),
6.70-6.95 187-190 (m, IH),
6.95-7.30 (m, 211), 8.22 (d, 1
1LJ=7.8Hz), 9.35(brs, 1ll)
, 9.65 (brs, 1ll) 0.10-0.65 (
m, 4H), 0.90-1.50 (m, III).

2.16 (s, 311), 4.20 (d, 211.J=
7.2Hz ) 5.90 (d, III, J = 7.2Hz
), 6.49(s, III), 210-21
26.90-7.55 (m, 31118.17 (dlI
H, J=7.211z).

9.33 (brs, 1lI), 9.48 (brs, I
II) 1.48 (d, 311), 2.22 (s, 311
), 3.45-4.10 (m, 211) 5.25-55
-70(,IH)+6.13(d,IH1J=7.8H
z) 6.45 (s, IB), 6.70-6.95 (m
, LH) 7.00-7.30 178-180 (m,
2H), 9.19 (d, IH, J=7.8Hz)9.
31(brs, 11(), 9.49(brs, l
1l) (hereinafter, blank) DMSOd-6 IIMSOd-6 DCj2a + DMSOd-6 DMSOd-6 1,6 (1 to 1.88 (m, 2tD, 2.27
(s, 3H) 1.99-2.44 (m, 4■), 5
．． 52 (quint, IH, J=8.311z)6.
20 (d, 111J-8, 111°), 6.69 (s,
1ll) 7, OO~7.08 (m, IH), 7.
22-7.29 (m, 1]I).

7.42-7.51 (m, IH) 18.43 (d, IH
, J=8.11+z)19.53(brs, 111)
, 9.83 (brs, ltl) 1.34-2.18 (
m, 8H), 2.25 (s, 311).

5.30-5.88 (m, IJI), 6.30 (d, 1
N, J-8,4Hz)6,64 (s, 1ll)
, 6.92-7.18 (m, 1it).

7.22-7.55 (m, 2B), 8.33 (d, IH
, J=8.4Hz)9.53(brs IB)9.
70 (brs, LH) 1.48-2.84 (m, 6H)
, 2.24 (s, 311).

5.56 (qutnt, 18.J=8.411z)6
．． 01 (altl, J-8,411z), 6.28
~6.45 (mI2H).

6.66 (s, LH), 7.46-7.63 (m, LH
).

8.47 (d, IH, J=8.411z), 9.
49 (brs, l1l) 10.02 (brs, 1)
1) 1.47-2.84 (m, 611), 2.24 (s,
3)l).

5.48 (qutnt, IH, J=8.4Hz).

5.80 (d, LH, J-8, 4Hz), 6.25~
6.65 (m, 28).

7, 15~7.30 (m, IH), 7.41~
7.54 (m, IH) 8.01 (d, II (, J=8
．． 411z), 9.16 (brs, 1ll).

9.37 (brs, IH) 201-205 (Disassembly) 165-180 (Bunxun 173-182 (Disassembly) 193-195 Compound no.

solvent CDCj! .

Ten-open SOd-6 DMSOd-6 δppm <Standard material TMS) Melting point (°C) 1.5'7~2.83 (m, 611), 2.2
2 (s, 3H).

5.51 (qujnt, 11LJ=8.411z).

5.96 (d, 1i1J=8.411z), 6.56
(s, l1l).

7.08-7.54 (m, 311), 8.29 (d, I
IIJ=8.4tlz).

9.38(brs, 1ll), 9.66(brs, 1l
l) 199-202 (decomposition) 1.46-2.12 (m, 811), 2.19 (s, 3
H).

5.14=5.71 (m, IH), 5.96 (d,
IH, J□8.411z)6,64 (s, IH)
, 7.08-7.34 (m, III).

7.35-7.72 (m, 21118.40 (d, II
I, J-8, 411z) 9.43 (brs, IH),
9.70 (brs. The present invention provides an agricultural and horticultural fungicide characterized by:

The agricultural and horticultural fungicide of the present invention is not only effective against downy mildew and late blight of various crops, but also effective against other diseases. The main diseases include cucumber downy mildew, grape downy mildew, lettuce downy mildew, Chinese cabbage downy mildew, hop downy mildew, potato late blight, tomato late blight, cucumber gray late blight, green pepper late blight, tomato caused by Visium blight,
Examples include seedling damping-off of cucumbers and rice, and seedling damping-off of beets caused by Aphanomyces bacteria.

Application methods for the agricultural and horticultural fungicide of the present invention include seed treatment, foliage spraying, soil application, and the like.

The amount and concentration of application will vary depending on the target crop, target disease, degree of disease occurrence, application method, etc., but when spraying, the amount of active ingredient should be 2 to 2 per hectare.
Applicable at 2000g, preferably 10-1.000g.

It can be applied at a spraying concentration of 1 to 11,000 pp.
5 to 500 ppm is desirable.

In addition, since the agricultural and horticultural fungicide of the present invention has both preventive and curative effects, it can be applied both preventively and after the onset of disease, and there is a wide range of suitable times for its application. have.

The agricultural and horticultural fungicides of the present invention may optionally contain other biologically active compounds, such as similar or complementary fungicides, or agricultural chemicals such as insecticides, herbicides, plant growth regulators, and fertilizers. Not only can it be used in combination with effective substances, soil conditioners, etc., but also mixed formulations with these are also possible.

The agricultural and horticultural fungicide of the present invention can be used in a suitable carrier, such as a solid carrier such as clay, talc, bentonand, diatom, or water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.). etc.), chlorinated hydrocarbons, ethers, ketones, esters (
ethyl acetate, etc.) acid amides (dimethylformamide, etc.)
It can be applied by mixing with liquids such as emulsifiers, dispersants, suspending agents, penetrants, spreading agents, stabilizers, etc., if desired, to form emulsions, oils, dihydrates, powders, etc. .

It can be put to practical use in any dosage form such as granules or flowables.

Next, the range of each component and the type of each component in formulation examples of these compositions will be shown, but the agricultural and horticultural fungicide of the present invention is not limited to these.

In addition, in the following formulation examples, "parts" mean parts by weight.

(1) Wettable powder Compound of the present invention: 5 to 75 parts Solid portion: 9 to 86 parts Surfactant
・・・・・・ Parts 5 to 10 Others
... As the 1- to 5-hedral carrier, calcium carbonate, kaolinite, gicrite A1 dicrite PFP.

Examples include diatomaceous earth and talc.

As surfactants, Lunox 1000 C, Tsurupol 5039, Tsurupol 5050, Tsurupol O05 are used.
[].

Examples include Trupol 5029-0, calcium sulfonate, sodium dodecyl sulfonate, and the like.

Other components include Carplex 1180 and the like.

(2) Emulsion Compound of the present invention: 5 to 50 parts Liquid carrier: 35 to 90 parts Surfactant
・・・・・・ 5 to 15 parts As a liquid carrier,
xylene, dimethylborumamide, methylnaphthalene,
Examples include isophorone.

Examples of the surfactant include Tsurupol 2680, Tsurupol 3005X, and Tsurupol 3346.

(3) Flowable agent Compound of the present invention: 5 to 75 parts Liquid carrier: 14.5 to 68 parts Surfactant: 5 to 10 parts Others
... 5 to 10 parts Water is used as the liquid carrier.

Examples of the surfactant include Lunox 100OC, Tsurubol 3353, Sorbohol FL, Nippol, Agrisol S-710, sodium ligninsulfonate, and the like.

Other ingredients include ethylene glycol, propylene glycol, xanthan gum, and the like.

(4) Powder Compound of the present invention: 0.03 to 3-hedral carrier: 94-98.97 parts Others: 1- to 3-hedral carrier: carbonic acid; Calcium, kaolinite, gicrite,
Examples include talc.

Other ingredients include diisopropyl phosphate,
Examples include Carplex #80.

(5) Granules Compound of the present invention: 0.3 to 10 parts Solid part: 92 to 98.7 parts Others: 1 to 5 parts As a hedral carrier: , calcium carbonate, kaolinite, bentonite, talc, etc.

Other ingredients include calcium lignin sulfonate, polyvinyl alcohol, and the like.

Next, specific formulation examples of the agricultural and horticultural fungicide containing the thioamide derivative represented by the general formula [1] according to the present invention as an active ingredient will be shown.
It is not limited only to these. In addition, in the following formulation examples, "parts" means parts by weight.

l5±earth Wettable powder Compound of the present invention 5 parts Sieglite PPP 87
Part (Mixture of kaolinite and sericite: Sieglite Industries ■Product name) Tsurupol 5039 5039
Part (mixture of anionic surfactant and white carbon: Toho Chemical ■trade name) Carplex #80 ...... 3 parts (white carbon: Shionogi & Co., Ltd. ■trade name) or more are uniformly mixed and pulverized. and use it as a hydrating agent. When using, add the above hydrating agent to 100~
It is diluted 10,000 times and applied so that the amount of active ingredient is 10 to 1000 g per hectare.

Preparation beans (wettable powder: compound of the present invention: 25 parts Sieglite PPP: 69
(Mixture of kaolinite and sericite: Sieglite Industries ■Product name) Tsurupol 5039 3
Part (mixture of anionic surfactant and white carbon; Toho Chemical ■ trade name) Carplex #80... 3 parts (white carbon; Shionogi & Co., Ltd. (II trade name) or more are uniformly mixed and pulverized. to make a hydrating agent.When using, add 50% of the above hydrating agent.
It is diluted 0 to 50,000 times and sprayed so that the amount of active ingredient is 10 to 1000 g per hectare.

Preparation - Examples Wettable powder Compound of the present invention 20 parts Calcium carbonate (powder) 69 parts (Kaolina 1~ and sericite Tsurupol 5050 10
1 part (mixture of anionic surfactant and white carbon: Toho Chemical ■ trade name) Carplex #80 ... 1 part (white carbon: Shionogi & Co., Ltd. (11 commercial name) or more is uniformly mixed and pulverized to make a hydrating agent.When using, add 15% of the above hydrating agent.
When diluted 00 to 150.000 times, the amount of active ingredient is 1
Spray at 10-1000g per hectare.

■L emulsion Compound of the present invention: 5 parts Xylene: 70 parts N
, N-dimethylformamide 20
Part Tsurupol 2680 ・・・・・・
5 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical σ descendant product name) or more are uniformly mixed to form an emulsion. When using, add 1 of the above emulsion.
It is diluted 0.00 to 10.000 times and sprayed so that the amount of active ingredient is 10 to 1000 g per hectare.

Issei's raw sample emulsion Compound of the present invention: 50 parts Xylene: 25 parts N
, N-dimethylformamide 10
Part Tsurupole 3346 ・・・・・・
15 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■ trade name) The above was mixed uniformly to form an emulsion. When used, the emulsion is diluted 1,000 to 100,000 times and sprayed so that the amount of active ingredient is 10 to 1,000 g per hectare.

1. Flowable agent Compound of the present invention... 5 parts Tsurupol 3353...
5 parts (Nonionic surfactant: Toho Chemical ■Product name) Lunox 100OC... 3 parts (Anionic surfactant: Toho Chemical ■Product name) 1% aqueous solution of xanthan gum ...・ 20 parts (natural polymer) Water ・・・・・・
・57 parts ethylene glycol・・・・・・
- 10 parts The above ingredients except for the active ingredient (the compound of the present invention) are uniformly dissolved, then the compound of the present invention is added, and after stirring well, wet grinding is carried out in a sand mill to obtain a flowable agent. When using, add the above flowable agent to 100 to 1
It is diluted 0,000 times and sprayed so that the amount of active ingredient is 10 to 1000 g per hectare.

Flowable agent Compound of the present invention 75 parts Tsurupol 3353 ・・・・・・
5 parts (Nonionic surfactant: Toho Chemical (l@trade name) Lunox 1oooc...
・ 0.5 parts (anionic surfactant: Toho Chemical ■trade name) 1% aqueous solution of xanthan gum ・・・・・・ 1
0 parts (natural polymer) Water...
・ 4.5 parts propylene glycol ・・・・
... 5 parts The above components except for the active ingredient (the compound of the present invention) are uniformly dissolved, and then the compound of the present invention is added, stirred well, and then wet-pulverized in a sand mill to obtain a flowable agent. When using, add 1,500 ml of the above flowable agent.
Dilute to ~150,000 times and apply at an amount of active ingredient of 10 to 1000 g per hectare.

4-L powder Compound of the present invention: 10 parts Clay: 90 parts or more are mixed uniformly to obtain a powder.

When used, the above-mentioned powder is sprayed as is at an amount of active ingredient of 10 to 1000 g per hectare.

411 Granule Compound of the Invention 5 parts Bentonite 25 parts Tart
・・・・・・ After uniformly mixing and pulverizing 70 parts or more,
Add a small amount of water, stir and mix, granulate using an extrusion granulator, and dry to form granules.

When used, the above-mentioned granules are sprayed as is at an amount of active ingredient of 10 to 1000 g per hectare.

Next, the effects of the compounds of the present invention in biological tests will be specifically described.

Cucumber and disease prevention effect test 1 to 2 cucumbers (variety: Sagami Hanshiro) grown in pots with a diameter of 7 cm
When the leaf stage is reached, the test compound in the form of an emulsion prepared according to Formulation Example 2 is diluted with water to adjust to 1100pp, and a spray gun is used to spray 20m per pot! Spread.

The day after spraying, cucumbers and diseased bacteria (Pseudoperono)
spora cubensis) spore suspension (2x1
05 cells/ml) and placed in an inoculation box at a temperature of 25° C. and a humidity of 95% or higher overnight. After that, it was placed in a greenhouse and the proportion of lesions formed on the inoculated leaves 7 days after inoculation was measured.
The control value was calculated according to the following 2.

Table 3 (Processing concentration: 10100pp The results of this test are shown in Table 3.

(Below, blank space) W-Kyoen I Cucumber and disease-curing efficacy test Diameter 7CITl
1 cucumber (variety: Wasumi Hanshiro) grown in a pot of
~ When the two-leaf stage is reached, cucumbers and Pseud
operonospora cubensts) was sprayed at a temperature of 25°.
The inoculation was carried out by placing it in an inoculation box with a C5 humidity of 95% or higher overnight. The next day, the test compound in the form of an emulsion prepared according to Formulation Example 2 was diluted with water, adjusted to 100 ppm, and sprayed at 20 mI per pot using a spray gun. , scattered. Thereafter, the plants were placed in a greenhouse, and the ratio of lesions formed 7 days after inoculation to the inoculated leaves was measured, and the control value was calculated according to the following formula.

Table 4 (Processing concentration: 10100pp Compound No. Control value (below, margin) The results of this test are shown in Table 4.

(Hereinafter, blank space) - Test for preventive effect on tomato late blight When tomatoes (variety: Fukuju) grown in 8 cm diameter pots reached the 3-leaf stage, preparations were prepared according to Formulation Examples 1 to 3 above. The wettable powder was diluted with water to give a predetermined concentration of active ingredient, and was sprayed using a spray gun to 20 m 2 per pot. The day after spraying, 1
・71・Phytophthora 1nfe
After spraying a spore suspension (2xlO'/ml) of A. stans) and keeping it in an inoculation box at a temperature of 20'C and a humidity of 95% or higher for 5 days, the ratio of the area of lesions formed to the inoculated leaves was measured. The control value was calculated according to the following formula.

Table 5 (Processing concentration: 10100pp Compound No. Control value Drug damage The results of this test are shown in Table 5.

3.14 Tomato Late Blight Curing Effect Test Diameter 8cm
When tomatoes (variety: Fukuju) grown in pots reached the 3-leaf stage, the tomato blight fungus (r'hytophthora
1 nfestans) spore suspension (2 x 105 spores/
m1) was sprayed and kept in an inoculation box at a temperature of 20° C. and a humidity of 95% or higher for one day and night. Thereafter, the wettable powder prepared according to Formulation Examples 1 to 3 above was diluted with water to give a predetermined concentration of the active ingredient, and then sprayed at 20 mff per pot using a spray gun.
Spread.

After air-drying, the pot was placed in the inoculation box described above, and the proportion of the area of lesions formed after 5 days to the inoculated leaves was measured, and the control value was calculated according to the following formula.

The test results are shown in Table 6.

Trial 1u Tsuashi [Phytotoxicity test on cucumbers] When cucumbers (cultivar composition half-white) grown in pots with a diameter of 21c+n reached the 5-6 leaf stage, an emulsion prepared according to Formulation Example 2 was applied. The test compound was adjusted to a predetermined concentration and sprayed at 40rr1 per pot using a spray gun. It was scattered. After growing this cucumber in a greenhouse for 7 days, the degree of chemical damage was investigated according to the following criteria.

5: Cucumber withered 4: Cucumber growth was severely suppressed and withered parts were present 3: Cucumber growth was severely suppressed 2: Cucumber growth was moderately suppressed ■= Small cucumber growth was suppressed 0: Cucumber growth was normal The results are shown in Table 7.

Compound no.

Control value (hereinafter, blank) Table 7 Phytotoxicity test test on cucumber IIi [Phytotoxicity test on potato] When potatoes (variety: Danshaku) grown in bots with a diameter of 21c+++ reached the 5th to 6th leaf stage, the above formulation was applied. The test compound in the form of an emulsion prepared according to Example 2 was adjusted to a predetermined concentration, and 30 m4/pot was sprayed using a spray gun.
Spread. After growing these potatoes in a greenhouse for 7 days, the degree of chemical damage was investigated according to the following criteria.

The evaluation criteria were based on the degree of growth inhibition as described below.

5: Potato withering 4: Large suppression of potato growth and withered parts 3: Large suppression of potato growth 2: Medium suppression of potato growth - Small suppression of potato growth 0: No suppression of potato growth The results are shown in Table 8.

However, the control compounds A to C in Tables 3 to 8 are the following compounds, respectively.

As is clear from the above biological test results, the compound of the present invention exhibited a characteristic that the degree of phytotoxicity was milder than that of the known control compounds AC.

In this way, the uninvented compound exhibits excellent preventive and curative effects against algal and fungal diseases such as downy mildew of cucumbers and late blight of potatoes, and has practical application with little phytotoxicity. It is a useful compound.

Patent applicant: Nissan Chemical Industries, Ltd. Table 8 Phytotoxicity test on potatoes (below, margin)

Claims (2)

[Claims] (1) General formula [1]: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [1] [In the formula, R is an alkyl group with 3 to 6 carbon atoms, 3 to 6 carbon atoms
an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkylalkyl group having 4 to 6 carbon atoms, a halogenated alkyl group having 2 to 6 carbon atoms, or a halogenated alkyl group having 3 to 6 carbon atoms. represents an alkoxyalkyl group, M
represents a sulfur atom or an oxygen atom. ] Thioamide derivatives and optical isomers thereof. (2) A fungicide for agricultural and horticultural use containing one or more of the thioamide derivatives and optically active forms thereof according to claim (1) as active ingredients.