JPS6061563A - Thiocarbamate derivative - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R1, R2 are halogen, lower alkyl, lower alkoxy; R3 is lower alkyl; R4, R5 are H, halogen, lower alkyl, lower alkoxy). EXAMPLE:O-4-ethyl-3-methylphenyl N-methyl N-(3-methylphenyl) thiocarbamate. USE:Herbicide: it shows very good herbicidal activity against a number of weeds including barnyard grass in rice paddy fields filled with water substantially without injury to rice plant. It can be used as a herbicide in vegetable fields, too. PREPARATION:The reaction between a compound of formula II and another compound of formula III is conducted in the presence of a dehydrohalogenation reagent such as sodium or potassium hydroxide to give the compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to thiocarbamate derivatives and methods for their production.

It has been well known that O-aryl N-arylthiocarbamate compounds have antibacterial and nematocidal effects as medicines. Furthermore, it is generally known that carbamate, thiocarbamate and dithiocarbamate compounds have herbicidal activity. Also, JP-A-48-4992
No. 5 discloses that certain aryl 14-aryl carbamate compounds can be used as herbicides. However, it is not known that O-aryl N-arylthiocarbamate compounds can be used as effective herbicides.

The present inventors have conducted intensive research to develop compounds that have sufficient herbicidal effects and high selectivity among O-aryl N-arylthiocarbamate derivatives, and as a result, various compounds of the present invention have been developed. It was discovered that this product exhibits excellent herbicidal activity against weeds, and the present invention was completed.

That is, the present invention relates to the general formula (■): (in the formula, R1 and R2 are each) - rogen atom, lower alkyl group, lower alkoxy group, lower alkenyloxy group, lower alkynyloxy group, lower alkylthio group, or nitro group , R3 represents a lower alkyl group, and R2 and R2 each represent a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group. R1 and R7 and R4 and R6 are the same or Different.However, if R8 and R2 are both lower alkyl groups, at least one of them is
The present invention provides a thiocarbamate derivative (hereinafter referred to as the compound of the present invention) produced by the present invention and a method for producing the same.

The compound of the present invention is a novel compound that has not been described in any literature, and no literature suggesting its useful physiological activity is known.

The herbicide containing the compound of the present invention as an active ingredient exhibits extremely excellent herbicidal activity against many weeds including field weed, especially in flooded rice fields, and is virtually harmless to transplanted paddy rice. , suitable as a herbicide for paddy fields. In addition, when treated with upland soil, it showed an excellent selective weeding effect between grass weeds and broad-leaved weeds, and was recognized to have applicability as a herbicide for upland.

The compound of the present invention represented by the general formula (D) can be produced according to the following reaction formula.

(In the formula, R1 and R2 represent a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a lower alkylthio group, or a nitro group, n represents a lower alkyl group, R1 and R
, 4"l hydrogen atom, halogen atom, respectively.

Indicates a lower alkyl group, lower alkoxy group or trifluoromethyl group. R1 and R7 and melon and horse are the same but different. However, when R1 and R1 are both lower alkyl groups, at least one of them is a lower alkyl group having 2 or more carbon atoms. Hal represents a halogen atom. ) The above reaction is carried out in the presence of a dehydrohalogenating agent and in the presence or absence of a reaction solvent, usually at temperatures between 0°C and 1°C.
The reaction temperature is 50'C, and the reaction time is several minutes to 4 minutes.
It takes about 8 hours.

As a dehydrohalogenating agent, hydroxide) IJum,
Alkali hydroxides such as potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, alkali carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, metal hydrides such as sodium hydride, triethylamine, Examples include tertiary amines such as dimethylaniline and pyridine. In reaction formula (2),
The raw material aniline derivative can be used as a dehydrohalogenating agent.

As a reaction solvent, water, methanol, ethanol,
Alcohols such as Impropatol, ketones such as acetone, methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene, xylene, ethers such as ethyl ether, tetrahydrofuran, dioxane, chlorobenzene, chloroform, carbon tetrachloride, dichloroethane, etc. Polar solvents such as chlorogenated hydrocarbons, dimethylformamide, and dimethyl sulfoxide are used.

The chlorothioformate derivative as a raw material in reaction formula (2) can be obtained, for example, by reacting a corresponding phenol derivative with thiophosgene.

Next, the method for producing the compound of the present invention will be specifically explained.

Example 1 0-4-ethyl-3-methylphenyl N-methyl-N
-Production method of (!1-methylphenyl)thiocarbamate (Compound AI of the present invention) N-methyl-N"-(3-methylphenyl)thiocarbamoyl chloride')-009,4-ethyl-3-methylphenol1. 569 and anhydrous potassium carbonate 1.5
89 was added to 50IRt of methyl ethyl ketone and heated under reflux for 15 hours. After the reaction mixture was cooled to room temperature, it was poured into cold water and the product was extracted with vine. The benzene solution was washed with a 10% monosodium hydroxide aqueous solution, water, and a saturated sodium chloride aqueous solution in this order, dried over anhydrous magnesium sulfate, and then benzene was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, developed with benzene/hexane-171 (V/V)) to give 0-4-4-
Thyl-3-methylphenyl N-methyl-N-(s-methylphenyl)thiocarbamate Example 2 0-4-chloro-3-methylphenyl N-methyl-N
-Production method of (s-methylphenyl)thiocarbamate
(Compound A4 of the present invention) 4-chloro-3-methylphenol 2959 and thiophosgene 259 were dissolved in 50% of chloroform, and while stirring under cooling with water, a 100% aqueous solution of 10% sodium hydroxide was added.
was dripped. After the dropwise addition was completed, stirring was continued at room temperature for 12 hours. The dichloroform layer was separated from the reaction solution, dried over anhydrous calcium chloride, and then chloroform was distilled off under reduced pressure. By distilling the residue under reduced pressure, the boiling point is 104-106℃15
0-4-chloro-6-methylphenyl chlorothioformate 369 of nimHg was obtained.

Elemental analysis value @) OH Analysis value 4525 2.65 Calculated value 4545 2.75 Add 1.38 ml of glacial potassium carbonate to acetone 20-
0-4-chloro-3-methylphenyl chlorothioformate 2.219 was dissolved in acetone 20 with stirring at room temperature.
7 and added. After stirring for 60 minutes,
The mixture was heated to reflux for an hour. After cooling the reaction mixture to room temperature,
Poured into cold water and extracted the product with benzene. Benzene solution in water.

After washing with an aqueous solution of IJ (saturated chloride) and drying over anhydrous magnesium sulfate, benzene was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, developed with benzene/hexane-1/1 (V/V)) to give 0-4-chloro-6-methylphenyl N-methyl-
N-(3-methylphenyl)thiocarbamate 2.11
9 (yield 69 cm) was obtained. A part of this product was recrystallized in hexane to obtain colorless crystals with a melting point of 10α5 to 102°C.

Next, representative examples of the compounds of the present invention represented by the general formula (I) and their physical properties are shown in Table 1 below. The compounds of the present invention are not limited to the compounds of this specific example.

The compound of the present invention exhibits excellent herbicidal activity against various weeds and does not cause any phytotoxicity to crops such as paddy rice, soybeans, and cotton, and is thus suitable as an active ingredient in herbicides. In other words, the action of the compound of the present invention is that it kills weeds or stops their growth without causing chemical damage to crops.
Alternatively, by significantly suppressing or delaying growth, growth competition with crops may be lost.

The compound of the present invention is particularly useful for plants such as wildflowers, snails, cypresses, Japanese grasses, and botanicals, especially in flooded paddy fields.
50 to 5009/1 against many weeds such as tarui
It was observed that extremely excellent herbicidal activity was exhibited at an active ingredient amount of 0 a. On the other hand, it is extremely safe for young rice seedlings (no effect was observed even at an amount of 1,000 g/10a of active ingredient, and its properties as a herbicide for paddy fields are extremely excellent).

Furthermore, when the compound of the present invention is used as a soil treatment agent after sowing general broad-leaved crops such as soybeans, which are upland crops, it will not cause any chemical damage to the crops and will reduce the number of wild plants.

It was found that it can effectively control grass weeds such as grasshopper and foxtail grass, and has applicability as a herbicide for upland fields.

Next, the herbicidal effects of the compounds of the present invention will be explained using usage examples. In the usage examples, "parts" are parts by weight.

Use Example 1 Herbicidal effect test under flooded conditions 10 parts of each of the compounds of the present invention were used as a carrier material and Zikrite [
Product name, manufactured by Kunimine Kogyo ■ 815 parts, surfactant: Neoperex [product name, manufactured by Kao Atlas ■] 1.55
Part and Tsurupol 800A [Product name, Toho Chemical Industry ■
Mixed and crushed with 1.55 parts (manufactured by) and 10 parts of water conservancy was obtained.

Next, put paddy soil in a porcelain pot with a diameter of 9 cm, add water and plow through the soil, sow weed seeds on the soil surface layer, and plant two paddy rice seedlings (variety, Nipponbare) at the two-leaf stage at a depth of 16 m. I planted it. The next day, watering was carried out for 2 cn1, and 10 t of the prescribed amount of the irrigation agent of each of the compounds of the present invention obtained as described above was added per pot.
The solution was diluted with 1.5 nt of water and dropped onto the water surface. Thereafter, the plants were left in a greenhouse, and the herbicidal effects and effects on paddy rice were investigated 6 weeks after treatment with the chemical solution.

The evaluation was displayed on a 6-level scale, and the specific rules are as follows. The results are shown in Tables 2 and 3.

Display Paddy rice chemical damage weeding effect 5 Death 100 weed control (residual weed amount 0%) 4 Severe damage 8
0chi control (residual grass amount 20chi) 3 Nakayori 60chi control (remaining grass amount 40%) 2 Kosho 40chi control (remaining grass amount 60chi) 1
Small amount 20-chi control (residual grass amount 80 t) 0 Harmless 0-chi control (remaining grass amount 100 t) Table 2 (1) Table 2-Table (2) Table 2 (clause 3) Table (2) Usage Example 2 Weeding effect test by surface treatment of field soil Field soil was put into a porcelain pot with a diameter of 12 crn, several kinds of plant seeds were sown, and the soil was covered with 1 crn. A predetermined amount of the water-use agent of the invention herbicide diluted in 10 g of water per pot was sprayed on the soil surface, then left in a greenhouse and watered at appropriate times.Three weeks after treatment with the chemical solution, the herbicidal effect and soybean, The effect on cotton was investigated and evaluated according to Use Example 1. The results are shown in Table 4.

Table 4 (1) Table 4 (2) Procedural amendment November 28, 1980 Mr. Manabu Shiga, Commissioner of the Japan Patent Office 1 Display of the case 1982 Patent Application No. 168430 2 Name of the invention Δcarbame 1 - derivative 3.Relationship with famous case for amendment Patent applicant address: 4560 Oaza '12ta, Shinnanyo City, Yamaro Prefecture, 746 (Contact information) Toyo Toyo, 1-7-7 Akasaka, Minato-ku, Tokyo 107 Yumi (Tokuso Building) Soda Kogyo Co., Ltd. Patent Information Department Telephone number (585) 3311 4 Date of amendment order Voluntary amendment 6 Contents of amendment (1) Mei 1111, page 4, line 9, "0-allynyl" is corrected to "0-aryl" .

(2) Same book, line 4012: “Diocarbamate 1 is corrected to ``diolcarbamate.''

(3) In the same book, page 6, line 5, ``There are also documents suggesting and contradicting physiological activity'' is corrected to ``Physiological activity is''.

(4) In III, page 7, line 2, "R1 and R2 are" is corrected to "R1 and R2 are each."

(5) 0), page 10, line 6 Correct r30nrRJ to r300Id,J.

(6) Same book, page 11, line 3 [Corrected Chlordi A formate to [chlorothioformate].

(7) Same f1i, page 15, Table 1 (4) Compound No. of the present invention
, 231R column r1370J is corrected to [1370*J.

(8) Table 1, page 1116 of the same IL (5) Compound No. of the present invention
, 251R column [1385J is corrected to [1385 scoop].

(9) Ibid., page 17, Table 1 (6) Compound No. 3 of the present invention
1 Correct the mp column "oily" to "64-65".

(10) Ibid., page 17, table 1 (6) below the margin [*:
Join NafJJ.

(11) Ibid., page 28, Table 4 (1) Compound No. of the present invention,
Correct the column [3 5] for 14 Mehishiba to ``3 5.''

that's all

Claims (2)

[Claims] (1) General formula (1): represents a kylthio group or a nitro group, the RJ family represents a lower alkyl group, and R4 and RJt each represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, or a trifluoromethyl group. R2 and Ht and R2 and R3 are different from each other. However, when R3 and R7 are both lower alkyl groups, at least one has 2 or more carbon atoms^IPt〃n-+ +, J-m-sweet L-to1
A thiocarbamate derivative represented by 1. (2) General formula (1): (wherein, When both R1 and R6 are lower alkyl groups, at least one is a lower alkyl group having 2 or more carbon atoms. When X in formula (■) is a hydrogen atom, it is a halothiocarbonyl group, and when X in formula (■) is a halothiocarbonyl group, it is a hydrogen atom, R, represents a lower alkyl group, and R4 and R6 are a hydrogen atom and a halogen atom, respectively. atom, lower alkyl group, lower alkoxy group, or trifluoromethyl group. R4 and R6 are the same or different from each other.) General formula (I) characterized by reacting with an aniline derivative represented by: , R1 and R2 are each a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyloxy group,
Lower alkynyloxy group. It represents a lower alkylthio group or a nitro group, R5 represents a lower alkyl group, and R4 and R3 each represent a hydrogen atom, a halogen atom, or a lower alkyl group. Indicates a lower alkoxy group or a trifluoromethyl group. R7 and R7 and R4 and R6 are the same or different from each other. However, if P and R2 are both lower alkyl groups,
At least one of them is a lower alkyl group having 2 or more carbon atoms. ) A method for producing a thiocarbamate derivative represented by