JPH02300157A - Benzylcarbazate derivative and germicide for agriculture and horticulture containing same derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X is H, halogen, lower alkyl, lower alkoxy or halogen-substituted lower alkyl; Y is X except H; n is 0-2, provided that when X is H, Y is lower alkyl except methyl or halogen substituted lower alkyl). EXAMPLE:4-Chlorobenzyl 3-phenyl carbazate. USE:A germicide for agriculture and horticulture useful for rice blast, wheat powdery mildew, wheat rust, etc. PREPARATION:A compound expressed by formula II is reacted with a compound expressed by formula III in a solvent such as dichloromethane in the presence of a base (e.g. triethylamine) at 0-150 deg.C for several min to 48hr to provide the compound expressed by formula I.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a fungicide for agriculture and horticulture.

[Prior Art] The fungicidal activity of certain pendylcarbazate derivatives is known from German Patent No. 2 246 282. However, because the bactericidal activity is not sufficient,
It has not been put into practical use.

[Problems to be Solved by the Invention] Agricultural and horticultural fungicides are generally widely used and contribute to protecting plants and increasing crop production. However, by continuously spraying the same fungicide on crops, resistant bacteria become widespread, reducing the control effect of the fungicide and often making it practically unusable. Therefore, the development of a highly practical agricultural and horticultural fungicide that does not develop drug resistance and exhibits excellent pest control effects is eagerly awaited. An object of the present invention is to provide a novel agricultural and horticultural fungicide with high practical value.

[Means for Solving the Problems and Work 1] The present inventors have discovered that penzylcarbazate derivatives having a specific substituent have excellent bactericidal activity, and have completed the present invention. did.

That is, the present invention provides general formula (I) H (wherein X is a hydrogen atom, a halogen atom, a lower alkyl group,
Represents a lower alkoxy group or a lower alkyl group substituted with a halogen atom. Y represents a halogen atom, a lower alkyl group, a lower alkoxy group, or a halogen-substituted lower alkyl group. n is an integer from 0 to 2.

However, when X is a hydrogen atom, Y represents a lower alkyl group excluding a methyl group or a lower alkyl group substituted with a halogen atom. ) and a penzylcarbazate derivative represented by the general formula (1) as active ingredients.

Specific examples of the penzylcarbazate derivative represented by the general formula (1) according to the present invention are shown in Table 1, but the compounds of the present invention are not limited thereto.

The compound of the general formula (1) can be synthesized, for example, according to the reaction formula below.

H (If) (III) → General formula (I
) X, Yn in general formula (■) and general formula (m) in the above reaction formula
is the same as general formula (1).

The above reaction is carried out in a solvent or in the absence of a solvent, in the presence of a base or in the absence of a base, preferably from 0°C to 1°C.
This can be carried out by reacting at 50°C, more preferably from 20°C to 100°C for several minutes to 48 hours.

As a solvent, aliphatic hydrocarbons such as hexane, heptane, ligroin, petroleum ether, benzene, toluene,
Aromatic hydrocarbons such as xylene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl eat butyl ketone, cyclohexanone, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, Halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, esters such as ethyl acetate and butyl acetate,
Nitriles such as acetonitrile and isobutyronitrile, dimethylformamide, dimethyl sulfoxide, and the like are used.

As a base, pyridine, triethylamine, N, N-
Organic bases such as diethylaniline, sodium hydroxide,
Alkali metal hydroxides such as potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and the like are used.

The amount of the reagent used in the reaction is usually 1 equivalent to 1 equivalent of the compound of general formula (I [[)] to 1 equivalent of the compound of general formula (n).
0 equivalents, base is 1 equivalent to 10 equivalents.

The fungicide of the present invention, which contains the pendylcarbazate derivative represented by the general formula (I) as an active ingredient, has excellent bactericidal activity against a wide range of types of filamentous fungi, so it is effective against various types of fungi that occur in agriculture and horticulture. It can be used to control pathogenic bacteria.

Furthermore, the pendylcarbazate derivative represented by the general formula (I) can be safely used on useful crops such as rice and wheat without causing any phytotoxicity.

In the disinfectant of the present invention, the penzylcarbazate derivative represented by the general formula (I) can be used as it is, but it is usually mixed with a solid carrier, liquid carrier, surfactant or other formulation auxiliary, and It is used in formulations such as wettable powders, emulsions, granules, and powders.

These preparations contain the pendylcarbazate derivative represented by the above general formula (1) as an active ingredient at a weight ratio of 0.1.
~99.9%, preferably 1~99%.

Solid carriers include fine powders or granules such as kaolin clay, attabulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob flour, walnut flour, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Liquid carriers include aromatic hydrocarbons such as xylene, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, Examples include acetonitrile and water.

Surfactants used for emulsification, dispersion, humidity, etc. include alkylaryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, alkyl sulfate ester salts, and naphthalene sulfonic acid formalin condensates. and nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, and sorbitan fatty acid ester.

Formulation adjuvants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethylcellulose), PAP (isopropyl acid phosphate), and the like.

Bacteria that can be controlled by using the fungicide of the present invention include, for example, rice blast (Pyrlcular lao).
ryzae), sheath blight (Rh1zocton1a 5
olani), apple powdery mildew (Podospha
era Ieucotrleha) s scabosis (Ve
Ventura nashlcola, Seleroslnia +eali, GIoeosporlum kaki,
Sclerotlnla clnerea
), CIadosporum carp
ophilum), Grape Botrytis (Botryt)
is einerea), black rot (EIslnoe)
aspellna), late rot disease (GloIIerel)
la ctngulata) 1 Sugar beet brown spot (Ce
rcospora betlcola), peanut brown spot CCerQO8pOra arachldlc
ola), Cercospora per
sonata), barley powdery mildew (Eryslp
he graslnis f', sp, hordei
), eye spot disease (Cercosporella
herpotricholdes) s purple snow rot (Pusariu+in1vale), wheat powdery mildew (Er)'5iphe graa+1nis
f', sp, tritlcI), Fusarium rust (Pu
ceinla recondita), cucumber and disease (Pseudoperonospora euben)
sis), powdery mildew (sphaerotheca
'uliglnea), vine blight () lycosph
aerella a+elonls), Botrytis blight (
Botrytis clnerea) Cl
adosporum cucumerinum), tomato late blight (Phytophthora 1nfesta)
ns), leaf mold (CIadosporius+ f
ulvuw), Botrytis c.
lnerea), strawberry powdery mildew (5phaero
theca hu+wull), hop gray mold (Botrytls clnerea), tobacco powdery mildew (Eryslphe eichoraeearu)
a) Diplocarpon ros
ae), citrus scab (EIslnoe fav)
cetli)% Blue mold (Penlcilllum)
itallcum), green mold (Penlcllll1
um digitatum ), etc.

The application amount of the fungicide of the present invention varies depending on the type of compound used, the target disease, the tendency of occurrence, the degree of damage, environmental conditions, the dosage form used, etc., but when used as is, such as powders and granules, contains 0 per 10 are as an active ingredient.
．． The weight should be selected from the range of 1 to 5 kg, preferably 0.3 to 1 kg. In addition, when ultimately used in liquid form such as an emulsion or a wettable powder, 0.1 to 110,000 pp,
Preferably, it is selected from the range of 10 to 3000 ppm.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 Synthesis of 4-chlorobenzyl 3-phenylcarbazate (Compound No. 4) 1.1 g of phenylhydrazine was added to 30 ml of dichloromethane.
Add 1.2 g of triethylamine to the solution dissolved in
While stirring, add 4-chlorobenzyl chloroformate 2
, 1g was added. After the addition, the mixture was stirred at room temperature for 4 hours. After the reaction was completed, water was added, the organic layer was separated, the solvent was distilled off, and the mixture was purified by column chromatography to obtain 2.1 g of 4-chlorobenzyl 3-phenylcarbazate.

Melting point: 114.5-116°C IR data: 3260 cm-' (NH)170
0cm" (C-0) Elemental analysis (%): CHClN2O2 Calculated value: C; 80.7B, H; 4.73.N, 10.
12 Actual value: C; 61.02. H:4.72. N;9
．． 97 Example 2 Synthesis of 4-chlorobenzyl 3-(2-chlorophenyl)carbazate (Compound No. 6) 1.8 g of 2-chlorophenylhydrazine hydrochloride was suspended in 10 ml of water, 40 ml of dichloromethane was added, and 4% caustic soda was added. 10 ml of aqueous solution was added. While stirring under cooling with cold water, 2.1 g of 4-chlorobenzyl chloroformate was added.

After the addition, the mixture was stirred at room temperature for 4 hours. After the reaction was completed, water was added, the organic layer was separated, the solvent was distilled off, and the mixture was purified by column chromatography to obtain 1.8 g of 4-chlorobenzyl 3-(2-chlorophenyl)carbazate.

Melting point: 107-108°C IR data: 3200cm-1 (NH) 1740c
m-1 (C-0) Elemental analysis (%): C14H1□C12N 20□ Calculated value: C; 54.04. H; 3.88. N; 9.00 Actual value: C; 54.25. H; 3.92. N: 8.8B Representative examples of the compounds of the present invention obtained by a similar method and their physical properties are shown in Table 2.

Example 3 10 parts by weight of the compound (1) of the present invention was added to a gel as a carrier material.
87.3 parts by weight of Clyte [trade name, manufactured by Kunimine Kogyo Co., Ltd.], 11.35 parts by weight of Neoperex [trade name, manufactured by Kao Atlas Co., Ltd.] as a surfactant, and Tsurupol 800
A [Product name, manufactured by Toho Chemical Industry Co., Ltd.] Mix and pulverize with 1.35 parts by weight to obtain a 10% permanent agent.

Example 4 (Emulsion) 25 parts by weight of the compound (2) of the present invention, 65 parts by weight of benzene, and 10 parts by weight of Tsurpol 800A as a surfactant were mixed and dissolved to obtain a 25% emulsion.

Example 5 (Powder) 2 parts by weight of the compound (3) of the present invention was added to 5 parts of diatomaceous earth! 1 part of j and 93 parts by weight of clay were uniformly mixed and ground to obtain a powder.

Example 6 (Granules) 10 parts by weight of the compound (4) of the present invention was mixed and pulverized with 50 parts by weight of bentonite, 35 parts by weight of Kunilite [trade name, manufactured by Kuniho Kogyo Co., Ltd.], and 5 parts by weight of Tsurupol 800A as a surfactant. After that, 10 parts by weight of water was added, stirred uniformly, extruded through a merchant with a diameter of 0.7 fins, dried,
Cut into lengths of mm to obtain 10% granules.

Example 7 Tomato late blight control effect test Tomato seeds (
Variety: Fukuju) was sown and grown for 3 weeks. A hydrating powder prepared according to Example 3 was diluted with water to a predetermined concentration, and 2 ml per bot was sprayed onto the seedlings. After air-drying, tomato late blight fungus (Phytophthora infestans)
) spores were inoculated and kept in a constant temperature room at 25° C. and 100% relative humidity for 24 hours. The plants were then placed in a greenhouse and the damage level was investigated 7 days after inoculation.

Damage level (%) = 100x N N: Total number of leaves investigated No: No disease Nl: Number of affected leaves with a lesion area rate of less than 25% N2: Number of affected leaves with a lesion area rate of 25 to 50% 03: Spot area Rate 50-75
Number of affected leaves in % 04: Number of affected leaves with a lesion area rate of 75% or more Control value (%) - 100X The test results are shown in Table 3.

Table 3 Example 8 Wheat powdery mildew control effect test Wheat seeds (
Variety: Norin No. 61) was sown and grown in a greenhouse for 10 days. A hydrating powder prepared according to Example 3 was diluted with water to a predetermined concentration, and 2 ml per pot was sprayed onto the seedlings. After air drying, wheat powdery mildew fungus (Erysiphae
graminls r, sp, trltlcl) inoculated with conidia and kept in a thermostatic chamber at 25°C and 100% relative humidity for 2 hours.
I left it for 4 hours. The plants were then placed in a greenhouse, and damage caused by dust was investigated 7 days after inoculation. The damage dust investigation method and the control value calculation method were performed in the same manner as in Example 7.

The test results are shown in Table-4.

Example 9 Wheat rust control effect test Wheat seeds (
Variety: Norin No. 61) was sown and grown in a greenhouse for 10 days. A hydrating powder prepared according to Example 3 was diluted with water to a predetermined concentration, and 2 ml per bot was sprayed onto the seedlings. After air drying, wheat rust fungus (Puccinia rec
ondlta) and placed in a constant temperature room at 20° C. and 100% relative humidity for 24 hours. Thereafter, the plants were placed in a greenhouse, and the number of lesions was investigated 7 days after inoculation, and the control value was calculated using the following formula.

Control value (%) - 100X The test results are shown in Table-5.

Table-5

Claims (2)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X is a hydrogen atom, a halogen atom, a lower alkyl group,
Represents a lower alkoxy group or a lower alkyl group substituted with a halogen atom. Y represents a halogen atom, a lower alkyl group, a lower alkoxy group, or a halogen-substituted lower alkyl group. n is an integer from 0 to 2. However, when X is a hydrogen atom, Y represents a lower alkyl group excluding a methyl group or a lower alkyl group substituted with a halogen atom. ) A benzylcarbazate derivative represented by (2) A fungicide for agriculture and horticulture, which contains a benzylcarbazate derivative represented by the general formula (I) according to claim 1 as an active ingredient.