JPS58216148A - Anilide acid derivative, its preparation and herbicide containing it - Google Patents

Abstract

NEW MATERIAL:A hexahydrophthalanilde acid derivative shown by the formula I (R is alkali metal, alkali earth metal, H, or 1-4C alkyl). EXAMPLE:4'-Chloro-2'-fluoro-1,2,3,4,5,6-hexahydro-phthalanilide acid ethyl ester. USE:A herbicide. Useful for dry field farming and cultivation of paddy-rice plant, showing high selectivity especially for leguminous plants. PROCESS:A 2-haloformyl-1-cyclohexanecarboxylic ester shown by the formula II(X is halogen) is reacted with 4-chloro-2-fluoro-aniline shown by the formula IIIin the presence of a base such as triethylamine, pyridine, etc. in a solvent such as dioxane, benzene, etc. at 0-100 deg.C to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a herbicide characterized by containing this as an active ingredient.

More specifically, the present invention relates to a hexahydro compound represented by the general formula (wherein R represents an alkali metal, an alkaline earth metal, a hydrogen atom, or an alkyl group having the number of carbon atoms/-1 that may have a side chain) The present invention relates to a phthalanilide acid derivative (hereinafter referred to as the compound of the present invention), a method for producing the same, and a herbicide characterized by containing one or more of them as an active ingredient.

The object of the present invention is to obtain this compound industrially advantageously and furthermore to provide a herbicide that is extremely useful in upland cultivation and rice cultivation.

The compounds of the present invention are, for example, Japanese grasshopper, Japanese violet, pigweed, Japanese knotweed, sperihyu, hackberry, chickweed, sycamore, Japanese commonweed, Japanese commonweed,
Against upland weeds such as Asiatica and Sparrow
Also, for example, Takunubie, Japanese cypress, Japanese azalea, Kikashigusa, Japanese tree spruce, Japanese cypress, Japanese cypress,
While it has excellent herbicidal power against paddy field weeds, such as Paddy weeds and Paddy weeds, it also has high selectivity, especially when used in pre-emergence soil treatment for leguminous crops.
In transplanted paddy rice, it shows excellent herbicidal power against weeds when used in soil treatment after the rice takes root but before weeds emerge.
The present invention was completed after discovering that it can be safely used for paddy rice.

The compound of the present invention is a novel compound that has not been described in any literature, and can be produced by various methods. Among the compounds of the present invention, R
An ester derivative in which is an alkyl group having 7 to 9 carbon atoms which may have a side chain can be prepared, for example, by the reaction of the following formula (wherein X is a chlorine atom, a bromine atom, etc., and R is a ) In other words, co-haloformyl-cyclohexanecal? 4'-
It can be produced by reacting with chlorocofluoroaniline. Examples of the inert solvent include ethers such as ethyl ether, dioxane, and tetrahydrofuran, aromatic hydrocarbons such as h-7-L'' and xylene, and ketones such as acetone and methyl ethyl ketone. Examples include amines such as triethylamine, pyridine, and dimethylaniline, the raw material aniline, sodium hydroxide,
Potassium hydroxide, sodium carbonate, potassium carbonate, etc. can be mentioned. The reaction temperature is O~/θOoc, preferably io-rooC.

The ester obtained here is hydrolyzed to obtain the compound of the present invention (') in which R is a hydrogen atom in the general formula
(hereinafter referred to as anilide acid).

In addition, this anilide acid can be easily produced by the reaction of the following formula, that is, by reacting anhydrous cis-/co-cyclohexanedicarboxylic acid and dichloro-co-fluoroaniline in the same solvent as in the reaction of formula (1). be able to.

The alkali metal salt of the compound of the present invention can be obtained by reacting the anilide acid thus obtained with a caustic alkali in water or an organic solvent.

The alkaline earth metal salts of the compounds of the present invention can be prepared by reacting the water-soluble salts obtained as described above with a suitable water-soluble salt of an alkaline earth metal such as calcium or barium in an aqueous solvent, or It is obtained by directly reacting a metal carbonate or hydroxide with an anilide acid in an inert solvent.

Furthermore, the ester of the compound of the present invention can also be obtained by reacting the nineanilide acid or its salt obtained as described above with a diazoalkane, dialkyl sulfuric acid, or alkyl halide.

Table 1 shows representative compounds of the present invention.

Table 1: When using the compounds of the present invention as herbicides, the active ingredient should be sog to 10θog per IO, preferably SO
g to lIoog are usually mixed with various adjuvants, such as diluents, solvents, surfactants, etc., and formulated into emulsions, aqueous solutions, powders, granules, etc., and used.

In addition, herbicides containing the compound of the present invention include other types of herbicides, plant growth regulators, fungicides, insecticides, acaricides, nematicides, synergists, attractants, repellents, pigments, fertilizers, etc. Combined with
Can be used mixedly.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Synthesis example/1-chloroco'-fluoro-7,co, 3. g, 5, 6
-Ethyl hexahydrophthalanilide (compound stock)/3. Monoethyl, s, b-hexahydrophthalate, x, o g was heated under reflux in 10 rmt of thionyl chloride, and then excess thionyl chloride was distilled off under reduced pressure.

20 mt of chloroform and pyridine o,
q g was added. To this, t-chloro-fluoroaniline/, 111. 9 was added dropwise at room temperature, and the mixture was stirred for 2 hours. The reaction mixture was washed with water, and the resulting chloroform solution was washed with aqueous sodium carbonate, diluted hydrochloric acid, and water, and then dried over anhydrous magnesium sulfate.

After concentrating the chloroform solution, it was purified by column chromatography (silica dal, developer, ethyl acetate/n-hexane = 4) to obtain 6 g (yield: 9%) of the desired product. nD=1.536S.

Synthesis example koda'-chloroco'-fluoro-1,2,3,g,S,
O-hexahydrophthalanilide acid (compound %lO) anhydride cis-/, J-cyclohexane dicarboxylic acid s, hg
Acetone 3! In addition to wI4, dark fluoroaniline Sg was then added dropwise at room temperature, after 9 minutes,...! ? O
Stirred on oc for 1 hour. Collect f of the precipitated target products, g,
0 g (yield ratio) was obtained. When this product was recrystallized from acetone, the melting point was 15 g-1 tooc.

Synthesis Example 3 Ri'-chloroa'-fluoro-I, co, 3. 'I,
S, A-hexahydrophthalanilide acid calcium salt (
Compound angle, 2) To the anilide acid obtained in Synthesis Example 2, 5,9 was dissolved in methanol IOmt/3 mt of N-caustic soda was added and stirred at room temperature, and then methanol was distilled off. 10 parts water to the residue
Add and dissolve mt, and add anhydrous calcium acetate θ, l
Ig was added to water and mixed.

After stirring for 30 minutes at room temperature, the precipitate was filtered and washed with water. Dry under reduced pressure overnight at 60 oc, white crystals/g
I got g.

The elemental analysis value is (c 1a Hl 4Ct Fo 3 N
)20 a-u20 as HN Calculated value (correspondence),! ;/, 30 LA/
Actual value (%) S θ gu, t gu, tsu. Yield: 4t%. This one is /Sg~/1,2
Melted at cc.

Formulation Example 1 Wettable powder Compound &2 of the present invention in 30 parts (means parts by weight, the same applies hereinafter), 30 parts of diatomaceous earth, 3.2 parts of clay, 3 parts of sodium ligninsulfonate, polyoxyethylene nonylphenol ether (white car 3 parts of the powder (50% powder) were ground and mixed to make a wettable powder.

Formulation Example Emulsion An emulsion is prepared by dissolving 30 parts of the compound of the present invention, 3 parts of xylephthalate, 3 parts of polyoxyethylene nonylphenol ether, and 3 parts of calcium dodecylbenzenesulfonate.

Formulation Example 3 Granules 3 parts of the compound of the present invention High 7, 1 part of bentonite, talc! 2.3 parts, 3 parts clay, 1 part sodium ligninsulfonate, 1 part dodecylbenzenesulfonic acid) I
3 parts of Jum θ are uniformly mixed and pulverized, some water is added, the mixture is made into granules using an extrusion granulator, and the mixture is dried and sieved to obtain granules.

Next, the herbicidal effects of the compounds of the present invention will be explained using test examples.

Test Example 1 Soil treatment test after sowing in a field Weed seeds of crabgrass, blueberry, and pigweed and soybean seeds were sown in clay pots, and after covering the soil, a predetermined amount of the compound of the present invention was made into an emulsion, diluted with water, and added to the soil using a hand spoon. Processed.

The plants were then grown in a greenhouse, and 20 days after treatment, the herbicidal efficacy and crop damage were observed. The results are shown in Table 2.

Evaluation of herbicidal efficacy was expressed as a number of θ to 3 as shown below. However, phytotoxicity of crops was also expressed using the same criteria as herbicidal efficacy.

O...Weed suppression rate θ~? Person in charge/...
・・・・・・ 〃 lθ〜29θ〜・・・・・・・・・
・ 〃 30〜lI9%3・・・・・・・・・
〃 3θ～Otsu? Hiro...... 〃riθ～g9%!・・・・・・・・・ 〃 deθ〜lθ
θ Section - Table Test Example Ko Soil Treatment Test for Transplanted Paddy Rice Pack paddy soil into a 500-liter Ahl Wagner IT, and after puddling, sow 30 Novie seeds, and then paddy rice (variety:
Nipponbare) was transplanted at 1 plant per 1 pot (1 plant/plant), and tubers of Urikawa and Mizogayatsu were also planted, and about 3 an.
It was managed in a submerged state. The emulsion of the compound of the present invention used in Test Example 1 was diluted with a predetermined amount of water at the early stage of the emergence of wild grass and broad-leaved weeds, and the emulsion was applied uniformly to the water surface.

The herbicidal effect and chemical damage were investigated on the third day after chemical treatment.
Obtained the results in the table.

The herbicidal effect in Table 3 was evaluated using the same method as in Test Example 1.
It is expressed by the numbers on the left.

Regarding chemical damage, the ratio of plant height, number of tillers, and all types (air-dried amount) to the untreated plot was calculated. Drug damage was evaluated on a t scale, expressed as ++.

Table 3 Procedures Amendment Book Showa Year, Month, Day 3, Person making the amendment Relationship to the case Applicant 4, Agent A Address: 3-3-1 Marunouchi, Chiyoda-ku, Tokyo (Telephone number: 211-87419) Name (5995) Patent Attorney Minoru Nakamura 5, Date of Amendment Order From
6°

Claims (3)

[Claims] (1) Hexahydrophthalanilide represented by the general formula (wherein R represents an alkali metal, an alkaline earth metal, a hydrogen atom, or an alkyl group having l-7 carbon atoms which may have a side chain) Acid derivatives. (2) Reacting 2-haloformyl-7-cyclohexanecarboxylic acid ester or anhydride cis-/J-cyclohexanecarboxylic acid with dark chlorocofluoroaniline, and optionally hydrolyzing the product. Characteristic general formula (in the formula, R is an alkali metal, an alkaline earth metal, a hydrogen atom, or the number of carbon atoms that may have a side chain/-
represents p alkyl groups. ) A method for producing a hexahydrophthalanilide acid derivative represented by (3) Hexahydrophthalanilide acid represented by the general formula (wherein R represents an alkali metal, an alkaline earth metal, a hydrogen atom, or an alkyl group having the number of carbon atoms/-1 that may have a side chain) A herbicide characterized by containing one or more derivatives as an active ingredient.