JPH07145112A - Nitro compounds - Google Patents

Abstract

PURPOSE:To obtain a novel nitro compound which is useful as a synthetic intermediate for a novel tetrahydrophthalimide derivative having herbicidal effect. CONSTITUTION:A nitro compound of formula I (R is an alkyl), for example, 4fluoro-2-hydroxy-5-nitro-2'-methylpropiophenone. The compound of formula I is obtained, for example, by nitrating a compound of formula II using nitric acid in sulfuric acid at -5 to +5 deg.C for 0.1 to 1 hour. The nitro compound of formula I is used as an intermediate to give a tetrahydrophthalimide derivative of formula III.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a nitro compound which is an intermediate for the production of a novel tetrahydrophthalimide derivative having herbicidal activity.

2. Description of the Related Art Up to now, it has been described in JP-B-48-11940 that certain tetrahydrophthalimide derivatives can be used as active ingredients of herbicides.

However, these compounds are not necessarily satisfactory because they have insufficient herbicidal efficacy and poor selectivity between crops and weeds.

[0002]

The inventors of the present invention have made various studies in view of such a situation, and as a result, the general formula 2

[Chemical 2] [In the formula, R represents an alkyl group. ] It was found that the tetrahydrophthalimide derivative represented by the above formula is a compound having few above-mentioned drawbacks, excellent herbicidal efficacy, and excellent selectivity between crops and weeds. The inventors have found that the nitro compound shown is a useful intermediate in the production of the compound, and completed the present invention. That is, the present invention provides a compound represented by the general formula

[Chemical 3] [In the formula, R represents the same meaning as described above. ] The nitro compound shown by these (Hereafter, it describes with this invention compound.) Is provided.

The compounds of the present invention have the general formula

[Chemical 4] [In the formula, R represents the same meaning as described above. ] It can manufacture by nitrating the compound shown by these. The nitration reaction is carried out, for example, by using nitric acid in concentrated sulfuric acid.
The reaction is carried out at 5 to 5 ° C for 0.1 to 1 hour. The amount of the reagent used for the reaction is 1 to 3 equivalents, preferably 1.0 to 1.1 equivalents, relative to 1 equivalent of the compound represented by the general formula. This nitration reaction is performed at the o-position and p-position of phenol
A positional isomer is generated because it occurs at the position, and the resulting isomer can be separated by means such as column chromatography. The compound represented by the general formula 4 can be produced, for example, according to the method described in Beilstein Vol. 8, page 85. Next, Table 1 shows some of the compounds of the present invention that can be produced by the above method.

[Table 1]

The compounds of the present invention have the general formula

[Chemical 5] [In the formula, R represents the same meaning as described above. ] It can lead to the tetrahydrophthalimide derivative shown by the above-mentioned general formula 2 through the aniline derivative shown by the above. The aniline derivative represented by the general formula 5 can be produced by reducing the compound of the present invention. Examples of the reduction method include a metal reduction method using iron powder or the like. The reaction is usually 50 to 150 in a solvent.
C., preferably at a temperature of 80 to 120.degree. C., the reaction time is usually 0.5 to 10 hours, and the amount of iron powder used in the reaction is 2.5 to 10 equivalents per 1 equivalent of the compound of the present invention. Target. As the reaction solvent, acetic acid, propionic acid, or the like is used, and toluene, ethyl acetate, water, or the like can also be mixed and used. General formula obtained by the above reaction
The aniline derivative represented by Chemical formula 5 can be isolated without isolation.
A tetrahydrophthalimide derivative represented by the general formula 2 can be obtained by reacting with 3,4,5,6-tetrahydrophthalic anhydride. Table 2 shows some of the aniline derivatives represented by the general formula:

[Table 2]

The tetrahydrophthalimide derivative represented by the general formula 2 can be produced by reacting the aniline derivative represented by the general formula 5 with 3,4,5,6-tetrahydrophthalic anhydride. This reaction is usually carried out in a solvent, the reaction temperature range is 50 to 150 ° C, preferably 80 to 120 ° C, and the reaction time range is 0.5 to 10 ° C.
Time is standard. The amount of the reagent used in the reaction is 1 equivalent of the aniline derivative represented by the general formula:
3,4,5,6-tetrahydrophthalic anhydride is usually 1.0 ~
1.2 equivalents. As the reaction solvent, aromatic hydrocarbons such as benzene, toluene and xylene, fatty acids such as formic acid, acetic acid, propionic acid and oleic acid, esters such as ethyl formate, ethyl acetate and butyl acetate, water and the like or a mixture thereof. Is mentioned. After completion of the reaction, the reaction solution is poured into water and the resulting crystals are filtered off or subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary purified by chromatography, recrystallization or the like. A tetrahydrophthalimide derivative represented by the formula 2 can be obtained. Next, Table 3 shows some of the tetrahydrophthalimide derivatives represented by the general formula 2 produced by the above production method.

[Table 3]

The tetrahydrophthalimide derivative represented by the general formula (2) has an excellent herbicidal effect and is
Shows excellent selectivity between weeds. That is, the general formula 2
The tetrahydrophthalimide derivative represented by is a variety of problematic weeds in foliar treatment and soil treatment of upland fields, for example, buckwheat vine, sanaetade, purslane, chickweed, white locust, Aogateto, Japanese radish, red peach, red horned worm, shrimp, hibiscus, Broad-leaved weeds such as American stag deer, field pansy, field grass, yellow-billed morning glory, white-billed morning glory, red throated petrel, red-footed puffin, Onami fir, sunflower, dog camphor, etc.
The tetrahydrophthalimide derivative represented by the general formula 2 has a herbicidal effect on grass family weeds such as crabgrass, chinensis, chinensis, oats, oats, sorghum, and Cyperaceae weeds such as Kogomegayatsu. It does not cause harmful phytotoxicity to major crops such as wheat, rice, soybean, cotton and sugar beet. Further, the tetrahydrophthalimide derivative represented by the general formula 2 is a variety of weeds that pose a problem in flooding paddy fields, for example,
It has a herbicidal effect on grass weeds such as the northern grass, broad-leaved weeds such as Azena, scabbard, and Mizohabe, cyperaceae weeds such as pine nuts, and eels, and does not show any harmful effects to rice. .

When the tetrahydrophthalimide derivative represented by the general formula (2) is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid carrier, a surfactant or other formulation auxiliary agents to prepare an emulsion or wettable powder. , Suspensions, granules, etc. These formulations contain the tetrahydrophthalimide derivative represented by the general formula 2 as an active ingredient in a weight ratio of 0.1 to 80%, preferably 1 to 70%.
Examples of the solid carrier include kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, fine powder or granules of synthetic hydrous silicon oxide, and the like. As the liquid carrier, aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol and cellosolve, ketones such as acetone, cyclohexanone and isophorone, vegetable oil such as soybean oil and cottonseed oil, dimethyl sulfoxide, N ，
Examples include N-dimethylformamide, acetonitrile, water and the like. Surfactants used for emulsification, dispersion, wet extension, etc. include alkyl sulfate ester salts, alkyl sulfonates, alkylaryl sulfonates, dialkylsulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, etc. Anionic surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, nonionic surfactants such as sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters. . Other formulation adjuvants include lignin sulfonate,
Alginate, polyvinyl alcohol, gum arabic,
Examples include CMC (carboxymethyl cellulose), PAP (acidic isopropyl phosphate) and the like.

The tetrahydrophthalimide derivative represented by the general formula (2) is usually formulated and subjected to soil treatment, foliar treatment or flooding treatment before or after emergence of weeds. The soil treatment includes a soil surface treatment, a soil admixture treatment, and the like, and the foliage treatment includes a treatment from above the plant body and a local treatment for treating only the weeds so as not to adhere to the crop. In addition, it can be expected to enhance herbicidal efficacy by mixing with other herbicides. Furthermore, it can be used by mixing with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners and the like. The tetrahydrophthalimide derivative represented by the general formula 2 is used in paddy fields, upland fields,
It can be used as an active ingredient in orchards, meadows, lawns, forests or non-croplands. When the tetrahydrophthalimide derivative represented by the general formula (2) is used as an active ingredient of a herbicide, the treatment amount is usually different depending on weather conditions, formulation form, treatment time, method, place, target weeds, target crops, etc. 0.1 g to 80 g per are,
The amount is preferably 0.5 g to 70 g, and emulsions, wettable powders, suspensions and the like are usually added in a predetermined amount of 1 liter to 10 liters per 1 are (adding auxiliary agents such as spreading agents if necessary). Diluted with water and treated. Granules and the like are usually treated as they are without any dilution. Examples of the spreading agent include polyoxyethylene resin acid (ester), ligninsulfonic acid salt, abietic acid salt, dinaphthylmethanedisulfonic acid salt, and paraffin in addition to the above-mentioned surfactant.

[0009]

EXAMPLES The present invention will be described in more detail with reference to production examples, but the present invention is not limited to these examples. Preparation Example 1 10 g of 4-fluoro-2-hydroxy-2'-methylpropiophenone was added to 50 ml of concentrated sulfuric acid at 0 ° C. Furthermore, 3.8 g of ice-cooled fuming nitric acid (d = 1.50) was added at -5 to 0 ° C.
The mixture was added dropwise with, then stirred at 0 ° C. for 30 minutes, poured into ice water and extracted with ether. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography (eluent; hexane: ethyl acetate = 2: 1 mixed solvent) to give 4-fluoro-2-hydroxy-5-nitro-2'-methylpropiophenone (4 g). mp 59.9 ° C. ¹ H-NMR (deuterated chloroform solvent, TMS internal standard) δ value (ppm): 1.25 (6H, d), 3.5 (1H, m), 6.7 (1H, d), 8.
55 (1H, d), 13.25 (1H, bs) Some of the compounds of the present invention that can be produced in this manner are shown in Table 4.

[Table 4]

An example of producing a tetrahydrophthalimide derivative represented by the general formula 2 will be shown. Reference Production Example 1 (Production of Compound 1) 1.2 g of reduced iron was suspended in 3 ml of 5% acetic acid water to 60 to 70.
Heated to ° C. 2-hydroxy-4-fluoro-
A solution prepared by dissolving 1 g of 5-nitroacetophenone in 10 ml of acetic acid was added dropwise. The reaction temperature was kept at 70 to 80 ° C. for 0.5 hour, 0.9 g of 3,4,5,6-tetrahydrophthalic anhydride was added, and the reaction was carried out for 3 hours. The reaction solution is filtered and water is added,
The mixture was extracted with ethyl acetate, the organic layer was washed with saturated brine and aqueous sodium hydrogen carbonate, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The concentrated residue is purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 1: 1), and then (2-
Fluoro-4-hydroxy-5-acetylphenyl)-
3,4,5,6-Tetrahydrophthalimide (Compound 1) 1.2
g was obtained. mp 176 to 178 ° C. Next, some of the tetrahydrophthalimide derivatives represented by the general formula 2 produced according to this production method are shown in Table 5.
Shown in.

[Table 5]

Next, formulation examples are shown. The tetrahydrophthalimide derivative represented by the general formula 2 is shown by the compound number in Table 5. Parts are parts by weight. Formulation Example 1 Compound 1, 50 parts, calcium lignin sulfonate 3
Parts, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain a wettable powder. Formulation Example 2 An emulsion is obtained by thoroughly mixing 5 parts of compound 3, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzene sulfonate, 30 parts of xylene and 45 parts of cyclohexanone. Formulation Example 3 2 parts of compound 2, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are well pulverized and mixed, and water is added and kneaded well, and then granulated and dried. To obtain granules. Formulation Example 4 Compound 4, 25 parts, polyoxyethylene sorbitan monooleate 3 parts, CMC 3 parts, and water 69 parts are mixed and wet-milled until the particle size becomes 5 microns or less to obtain a suspension agent.

Next, it is shown in Test Examples that the tetrahydrophthalimide derivative represented by the general formula 2 is useful as an active ingredient of a herbicide. The tetrahydrophthalimide derivative represented by the general formula 2 is represented by the compound number in Table 5, and the compound used for comparison and control is represented by the compound symbol in Table 6.

[Table 6] For the evaluation of herbicidal efficacy and phytotoxicity, the test plants (weeds and crops) at the time of the survey were evaluated as "0" if they had no or almost no emergence and growth condition compared to those of the untreated plants. A plant whose plant is completely killed or whose budding or growth is completely suppressed is defined as "5", and it is 0 to 5
It is divided into 6 stages and is shown as 0, 1, 2, 3, 4, 5.

Reference Test Example 1 Field Stem / Leaf Treatment Test Field soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and seeds of millet, Malaga morning glory, Japanese radish, and hibiscus were sown and grown in a greenhouse for 10 days. Thereafter, the test compound was made into an emulsion in accordance with Formulation Example 2 and the predetermined amount was 1
It was diluted with water containing a spreader equivalent to 10 liters per are, and foliage treatment was performed from above the plant with a small sprayer. After the treatment, the plants were grown in a greenhouse for 20 days and the herbicidal efficacy was investigated. The results are shown in Table 7.

[Table 7]

Reference test example 2 Field and foliage treatment test Field vat having an area of 33 × 23 cm ² and a depth of 11 cm was filled with field soil, and seeds of Malaga morning glory, Prunus chinensis, velvetleaf, Ebisugusu, Acacia serrata, Siamese edulis and Enocorogosa were cultivated for 18 days. did. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with 10 liters of water equivalent to 1 are containing a spreading agent, and was uniformly applied to the entire foliage from above the plant with a small sprayer. Processed. At this time, the growth conditions of weeds and crops differ depending on the grass species,
At the 1 to 4 leaf stage, the plant height was 2 to 12 cm. The herbicidal efficacy was investigated 20 days after the treatment. The results are shown in Table 8. The test was conducted in a greenhouse throughout the entire period.

[Table 8]

Reference Test Example 3 Upland Field Soil Treatment Test Field up soil was packed in a vat having an area of 33 × 23 cm ² and a depth of 11 cm, soybean, corn, velvetleaf and physalis physalis were sown and covered with a thickness of 1 to 2 cm. The test compound is made into an emulsion according to Formulation Example 2, and the predetermined amount is 1 per 1 are.
The soil surface was diluted with 0 liter of water and treated with a small sprayer. After the treatment, the plants were grown in a greenhouse for 20 days and the herbicidal efficacy was investigated. The results are shown in Table 9.

[Table 9] Reference Test Example 4 Field Soil Treatment Test Field soil was packed in a vat having an area of 33 × 23 cm ² and a depth of 11 cm, and wheat, sanaetade, yaemgra, field pansy, and Enokologsa were sown and covered with a thickness of 1 to 2 cm. The test compound was made into an emulsion according to Formulation Example 2, and the predetermined amount thereof was diluted with 10 liters of water per are.
The soil surface was treated with a small sprayer. After the treatment, the plants were grown in a greenhouse for 27 days and the herbicidal efficacy was investigated. The results are shown in Table 10.
Shown in.

[Table 10]

Reference Test Example 5 Upland Field Soil Treatment Test Field up soil was packed in a vat having an area of 33 × 23 cm ² and a depth of 11 cm, and wheat, sugar beet, sunflower seed, yaemgra, field pansy and green crocodile were sowed to a thickness of 1 to 2 cm. Covered with soil. The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with water equivalent to 10 liters per are, and the soil surface was treated with a small sprayer. After treatment,
It was grown in a greenhouse for 27 days, and herbicidal efficacy was investigated. The results are shown in Table 11.

[Table 11] Reference Test Example 6 Paddy Water Submersion Treatment Test Paddy soil was packed in a cylindrical plastic pot with a diameter of 8 cm and a depth of 12 cm, and seeds of rice ball millet and broad-leaved weeds (Azena, Kishigusa, Mizojabe) were mixed at a depth of 1 to 2 cm. . After flooding and making it into a paddy field, it was grown in a greenhouse. 6
After a day (the initial stage of the development of each weed), the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with 5 ml of water and treated on the water surface. Grow in the greenhouse for 20 days after treatment,
The herbicidal efficacy was investigated. The results are shown in Table 12.

[Table 12]

Reference Test Example 7 Paddy Water Submersion Treatment Test 1 / 5000a Wagner pots were filled with paddy soil, and rice ball millet, broad-leaved weeds (Azena, Prickly Pear, Mizochabe) and pine pine overwintering stems were mixed to a depth of 1-2 cm. After flooding to make it into a paddy field, rice at the 3-leaf stage was transplanted and grown in a greenhouse. Five days later (the germination stage of Laevis mellifera), the compound to be tested was made into an emulsion according to Formulation Example 2, and the predetermined amount was adjusted to 10
Dilute it with milliliters of water and treat it on the surface of the water.
cm. After the treatment, the plants were grown in a greenhouse for 20 days, and herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 13. In addition,
From the day after the treatment, the amount of water leaked was equivalent to a water depth of 3 cm per day for 2 days.

[Table 13]

[0018]

INDUSTRIAL APPLICABILITY The compound of the present invention is a useful intermediate in the production of a tetrahydrophthalimide derivative represented by the general formula 2 having excellent herbicidal activity.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Koichi Morita 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Ryo Sato 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd.

Claims (1)

[Claims] 1. A general formula: ## STR1 ## [In the formula, R represents an alkyl group. ] The nitro compound shown by these.