JPS63154649A - Amide compound, production thereof and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [X is H or halogen; R1 and R2 are H, alkyl, phenyl or group shown by formula (R3 is 1-3C alkyl), etc.]. EXAMPLE:beta,beta-Dimethylatropic acid anilide. USE:A herbicide showing excellent herbicidal effects independently of target soil and treating method, exhibiting actions especially on paddy fields with a small amount and not providing crops with phytotoxicity. PREPARATION:A compound shown by formula III [Z is OR7 (R7 is H or 1-10C alkyl) or halogen] is reacted with an amine compound shown by formula IV in a solventless state or in an organic solvent optionally in the presence of a base at 0-200 deg.C for 0.1-5hr to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an amide compound (β,β-dimethymethitropic acid amide derivative), a manufacturing method, and a herbicide.

[Conventional technology]

Phenylacetamide derivative herbicides are known as herbicides.

[Problems to be Solved by the Invention] The present inventors conducted a dosage study in order to find a herbicide with a structure different from those hitherto, which has an excellent herbicidal effect and is not harmful to crops, and as a result, the present invention was developed. Reached.

[Failure to solve the problem]

That is, the present invention is based on the general formula (In the formula, X is a hydrogen atom or a halogen atom.

Rt, Rt is a hydrogen atom, an alkyl group, or a phenyl group.

R9 R,, R, is an alkyl group having 1 to 8 carbon atoms, R11, R,
Y is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms; ) (first invention).

general formula In formula C, X is a hydrogen atom or a halogen atom.

Z is 0R-I or a halogen atom. R-! is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ) and the general formula (in the formula R1, R2 hydrogen atom, alkyl group, phenyl R
1+ R3, R, is an alkyl group having 1 to 8 carbon atoms, R,, R
.

is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; Y is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms. ) and a method for producing an amide compound represented by the general formula (%) (second invention), which is characterized by reacting the amide compound with an amine compound represented by the general formula (%) and the general formula (where X is a hydrogen atom or a halogen atom).

R,,R, are hydrogen atoms, alkyl groups, and phenyl groups.

R1 island Rs, R4 is an alkyl group having 1 to 8 carbon atoms, R,, R6
is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; Y is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms. ) is a herbicide (third invention) characterized by containing an amide compound represented by the following as an active ingredient.

In the general formula (1), examples of the halogen atom of X include fluorine, chlorine, and bromine. Preferred is a chlorine atom.

Examples of the alkyl group for R, , R, include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl and octyl groups.

Preferred are methyl, ethyl and isopropyl groups.

Examples of the alkyl group having 1 to 8 carbon atoms for Rs and R4 include methyl, ethyl, propyl and isopropyl groups. Among these, isopropyl group is preferred.

Ra, the alkyl group having 1 to 8 carbon atoms of Ra is R3
゜The same alkyl groups as R4 can be mentioned. Preferred is a methyl group.

Examples of the halogen atom of Y include fluorine, chlorine, and bromine atoms. Preferred is a chlorine atom.

Examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as R3 and R. Preferred is a methyl group.

The alkyl group having 1 to 10 carbon atoms for R't is methyl.

Examples include ethyl, propyl, butyl and octyl groups. Preferred are methyl and ethyl groups.

Examples of the amide compound represented by general formula (1), which is a new compound of the present invention, include the following compounds (Table 1)
.

In addition, the analytical values (Mp, elemental analytical values) of those compounds.

NMR) are shown in Tables 2 and 8.

Table-1 Table-2! Table 8 Table 8 (continued) The novel amide derivative of the present invention represented by general formula (1) can be produced by various methods.

The compound represented by the general formula (]) can be produced by reacting the compound represented by the general formula (2) with the amino compound represented by the general formula (3).

The method for synthesizing the carboxylic acid represented by the general formula (2) is described in the applicant's patent application dated December 5, 1986 (title of the invention “β-
``Method for producing substituted atropic acids'').

A compound represented by general formula (2) [where X is the same as X in general formula (1)] and a halogenating agent (
thionyl chloride, phosphorus trichloride, phosphorus pentachloride, etc.) and R, O
It can be produced by reacting an alcohol having 1 to 10 carbon atoms, represented by H, by a normal etherification method.

In the reaction of the compound represented by general formula (2) and the compound represented by general formula (3), the reaction temperature is usually 0 to 200°C.
, preferably 5 to 180°C, the reaction time is usually 0.
The time is 1 to 5.0 hours, preferably 0.2 to 1.0 hours.

The reaction can be carried out without a solvent or in a solvent, such as an organic solvent or an aqueous solution.

Also necessary are polybasic compounds (caustic soda, pyridine,
Triethylamine, etc.), N-methyl-2-chloropyridinium iosite, etc. can also be added thereto. The amount added is usually 0.1 to 0.1 based on the weight of the compound of general formula (2).
The amount is 10.0 mol, preferably 0.2 to 2 mol.

In order to isolate the target compound from the reaction mixture obtained in this way, first add an aqueous solution of 5-dihydrochloric acid, filter out the precipitate,
The dried product is recrystallized with methanol, ether, benzene, etc. to obtain the desired product.

The herbicide of the present invention contains the amide derivative represented by the general formula (1) as an active ingredient, and if necessary, other herbicides such as the 1,4-dihydrohydrochloride described in JP-A-60-161905 are used. α-naphthoic acid, salts of so and/or esters thereof; amide compounds described in JP-A-60-246852; phenoxy-based, diphenyl ether-based, amide-based compounds described in Japanese Patent Application No. 59-208191;
Carbamate, diasol, virazole, urea and triazine herbicides; patent application No. 59-24752
1.2.3.4-Tetrahydro α-naphthoic acid, its salts and/! ! , Takeso Ntel, amino acid derivatives described in Japanese Patent Application No. 59-258118, hydrazide compounds described in Japanese Patent Application No. 59-261855, and amide compounds described in Japanese Patent Application No. 60-68008. Or two or more types can be used together. When used in combination, the amount of herbicide of the present invention is usually 20 g or more, based on the weight of total herbicide.

Also, if necessary, inert carriers (solid, liquid or gaseous carriers such as talc, clay, kaolin).

Diatomaceous earth, calcium carbonate, potassium chlorate.

Saltpeter, wood flour, nitrocellulose, starch, benzene, xylene, n-hexane, gum arabic.

(vinyl chloride, carbon dioxide, freon, propane, butane, etc.) surfactants, water-soluble polymers, disinfectants.

Insecticides, other concentrated chemicals, fertilizers (urea, ammonium sulfate, ammonium phosphorus, potassium salt, etc.) soil conditioners, antifreeze agents, antifungal agents, 9 pigments,
It can contain an antifoaming agent and the like. The carrier, surfactant, water-soluble polymer and their blending amounts are described in the specifications of Japanese Patent Application No. 59-208190 and No. 59-208191.

The dosage form of the herbicide includes any dosage form such as 9-grain powder, emulsion, water-containing tablet, 2-tablet flowable preparation, aerosol, and smoke.

The preparation can be done by the usual methods, such as adding a solid carrier to the active ingredient to make a powder, adding a solid carrier and a surfactant to make an aqueous solution or granules, or adding a solid carrier, a solvent, and a surfactant. Examples include a method of adding an agent to form an emulsion.

The manufacturing method and content of each component of granules, irrigants, flowable preparations, etc. are also disclosed in Japanese Patent Application No. 59-208190 and No. 59.
-208191. It is described in each specification.

Weeds to which the herbicide of the present invention can be applied include paddy field weeds and upland weeds.

Examples of paddy weeds include the Asteraceae (e.g., Asteraceae), the Asteraceae (e.g., the Asteraceae), the Lythraceae (e.g., the Lythrum, the Japanese Lythrum, the Japanese Lythrum, the Japanese Lythrum).

Chickweed family (e.g. Chickweed), Polygonaceae (e.g. Chickweed), Polygonaceae (e.g. Stylish Polygonum), Polygonaceae (Example: Willow Polygonum), Polygonaceae C (Example: Coconutiaceae), Polygonaceae (Example: Styxiaceae, Porphyllidae), Lepidopteraceae (
Examples: duckweed, hingimo, duckweed), Cyperaceae (Example: hyderico, scallop, cyperus, pine), Poaceae (e.g., Poaceae, novienne), Aceridae (e.g., Nisbuta, water plantain), Cyperaceae (e.g., Helaomodacaceae), Examples of these include the family Aridaceae (e.g. Alocatinidae) and the family Alocatidae (e.g. Aomidae).

In addition, upland weeds include, for example, Chenopodiaceae (e.g., Coaxiaceae), Brassicaceae (e.g., shepherd's purse, St. radish, wild Japanese radish), Hydraaceae (e.g., Japanese radish), Polygonaceae (e.g., Polygonaceae)
Gishigishi, /S rutade), Rubiaceae (e.g. Nyaemgura)
, Caryophyllaceae (e.g., Caryophyllaceae, Caryophyllaceae, Ko/S
Cobaceae), Sesameaceae (e.g., Asteraceae), Asteraceae (e.g., Asteraceae (e.g.) Asteraceae, Mugwort, dandelion, Chamomile), Convolvulaceae (e.g., Convolvulus),
Oxalis (e.g. Oxalis), Poaceae (e.g. Sparrow gnome, Poaceae, Poaceae), Euphorbiaceae (e.g. Oxalis), Solanaceae (e.g. Physalis)
, Cyperaceae (e.g. Cyperaceae), etc.

Target crops for herbicides include paddy rice and field crops.

The amount of herbicide used is 1 to 50 g, preferably 1 to xog, of the active ingredient. Herbicides can be used directly or diluted. As a treatment method, either foliage treatment or soil treatment can be used. Herbicidal effects are usually achieved within at least one week after herbicide treatment.

〔Example〕

The present invention will be further explained below with reference to Examples and Test Examples, but the present invention is not limited thereto.

, Parts in Examples indicate parts by weight.

Example 1 β,β-dimethymethitropic acid anilide (
8) Add 9.8 g of aniline and 50 m/m of pyridine to a 200 m/' colben equipped with a thermometer, stirrer and dropping tube, and add 19.
5I! was added dropwise under vigorous stirring at a temperature below 20°C. After dropping, add 5-dihydrochloric acid and wash the precipitated white solid with water.

After drying, recrystallize from methanol-water to yield 23.7ji.
(yield: 94.5).

Example 2 (Irrigation agent) Compound Nn4 (10 parts, kaolin 55 parts, bentonite)
80 parts and 5 parts of sodium ligninsulfonate were mixed and ground to obtain the herbicide (wettable powder) of the present invention.

Example 8 (Granules) After mixing and pulverizing 10 parts of Compound 1VI117, 55 parts of bentonite, 82 parts of talc, and 8 parts of sodium naphthalene sulfonate, an appropriate amount of water was added and the mixture was kneaded and granulated using a granulator. The herbicide (granules) of the present invention was obtained.

Test example 1 [Paddy field conditions (soil treatment test)] 115000
I filled a pot with R's pot with Mizutakami II (clay loam), and the surface layer was covered with wild grass and broad-leaved weeds (Kikashigusa).

Seeds of various weeds such as A. japonica), bulrush, cypress, and Japanese cypress were uniformly mixed and sown, and paddy rice seedlings at the 2- to 8-leaf stage were transplanted to a depth of 2 cm and water was added to create a flooded state of 80°C. Then, three days later, at the beginning of the emergence of various weeds, a predetermined amount of the chemical prepared according to the example was uniformly sprayed on the flooded surface. Eight weeks after spraying, the herbicidal effects of each test compound were investigated.

The results are shown in Table-4.

5: Complete withering 4: Heavy snow 3: Nakayori 2: Small scale 1: Slight damage O: Harmless (normal growth) In addition, the upper row of each column in Table 18 indicates the amount of active ingredient 25g/
The lower column shows the results of an experiment conducted at 12.5 g/are.

Table-4 Test Example 2 [Paddy field conditions (soil treatment test) flooded direct sowing] 17
A 5,000 are pot was filled with paddy soil (clay loam) and the surface layer was covered with novies and broad-leaved weeds (Kikashigusa).

Seeds of various weeds such as Japanese azalea), scallops, Japanese cypress, and Japanese cypress were uniformly mixed and sown, and germinated rice seeds (
Akibare from Japan, Newbonnet from America, and IR-8 from the Philippines) were sown and flooded to a depth of 8 cm. Then, 3 days later, at the beginning of the emergence of various weeds, a diluted hydrating agent solution of each compound was dropped.

Eight weeks after the treatment, the herbicidal effect and phytotoxicity on paddy rice were evaluated according to Test Example 1. The results are shown in Table-5.

Test Example 8 [Paddy field conditions (field test)] A paddy field was plowed for one generation according to the customary method, and paddy rice seedlings were transplanted using a rice transplanter. This rice field was divided into 1 section with a corrugated tin plate of 1 rrLI+ size, and the test compound (formulated in granules) was applied by hand at the time of germination of wild plants 8 days after rice planting and at the 2nd to 3rd leaf stage of wild plants 15 days later. . 20 days after each chemical application, the chemical damage to paddy rice and herbicidal effect were investigated. The results are shown in Table-6.

Table 6 Comparative product test example 4 [Field conditions (soil treatment test)] A clay body was filled with soil containing various weed seeds and tubers of Pisces japonica, corn and soybeans were sown to a depth of 2 cTL, and the soil surface was leveled. I made it. Immediately thereafter test compound (formulated in a hydrating powder)
The solution was diluted to a predetermined dose and applied to the soil surface.

Four weeks after application, crop damage and herbicidal effects were investigated. The results are shown in Table-7.

Table 7 Comparative Product Test Example 5 [Field conditions (stem and foliage treatment test)] A clay body was filled with soil containing various weed seeds, and corn, wheat, and soybean were sown at a depth of 2α. Thereafter, when these crops reached the 8- to 4-leaf stage, the test compound (formulated in an emulsion) was diluted with water and a solution of a predetermined concentration was sprayed over the entire surface. 15 of scattering
After a few days, we investigated the chemical damage to the crops and the herbicidal effect. The results are shown in Table-8.

Table-8 Comparison product 〔Effect of the invention〕

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, X is a hydrogen atom or a halogen atom. R_1 and R_2 are a hydrogen atom, an alkyl group, a phenyl group,
▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Yes R_3 and R_4 are alkyl groups with 1 to 3 carbon atoms, R_5 and R_6 are hydrogen atoms or alkyl groups with 1 to 3 carbon atoms ;Y is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms. )
An amide compound represented by 2 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (In the formula, X is a hydrogen atom or a halogen atom. Z is OR_7 or a halogen atom. R_7 is a hydrogen atom or the number of carbon atoms, 1 to 10 ) and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (3) (In the formula, R_1 and R_2 are hydrogen atoms, alkyl groups, phenyl groups, ▲ Numerical formula, chemical formula, table, etc.) There are ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ where R_3 and R_4 are alkyl groups with 1 to 3 carbon atoms, R_5,
R_6 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; Y
is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms. ) A method for producing an amide compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1). 3 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, X is a hydrogen atom or a halogen atom. R_1 and R_2 are hydrogen atoms, alkyl groups, phenyl groups,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ where R_3 and R_4 are alkyl groups with 1 to 3 carbon atoms, R_5,
R_6 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; Y
is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms. ) A herbicide characterized by containing an amide compound represented by the following as an active ingredient.