JPS6347706B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to chlorothioformate derivatives and methods for producing the same. The chlorothioformate derivatives of the present invention are useful as intermediates for substances that can be used in medicines, agricultural chemicals, and the like. The inventors have discovered that certain new carbamate derivatives have herbicidal activity. The chlorothioformate derivative of the present invention is an important intermediate for these carbamate derivatives, and is a new compound that has not been described in any literature. That is, the present invention is based on the general formula () The present invention provides a chlorothioformate derivative represented by the formula (wherein R represents a lower alkyl group having 2 or more carbon atoms, and X represents a halogen atom) and a method for producing the same. The chlorothioformate derivative represented by the above general formula () has the general formula () (In the formula, R represents a lower alkyl group having 2 or more carbon atoms, and X represents a halogen atom.) It can be produced by reacting a phenol derivative represented by the formula with thiophosgene. The reaction between the phenol derivative represented by the above general formula () and thiophosgene can be facilitated by the presence of a dehydrohalogenating agent. Dehydrohalogenation agents include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, alkali carbonates such as sodium carbonate and potassium carbonate, and hydrogenation agents such as sodium hydride. Examples include metals, alkali metals such as sodium and potassium, and tertiary amines such as triethylamine, dimethylaniline, pyridine, quinoline, and isoquinoline. A solvent can be used to facilitate the reaction. Examples of solvents include halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, and chlorobenzene, aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as ethyl ether, dioxane, and tetrahydrofuran, acetone, and methyl ethyl ketone. Various types of ketones, such as Ketones, water, etc., are used.
The reaction temperature is preferably about 0°C to 100°C, more preferably about 5°C to 50°C. Appropriate reaction time is from several minutes to about 48 hours. Various methods are used for the reaction, including a method in which a dehydrohalogenating agent is added to a mixture of the phenol derivative represented by the above general formula () and thiophosgene dissolved in an appropriate solvent, and a method in which a dehydrohalogenating agent is added to a thiophosgene solution. Examples include a method of adding a mixed solution of a phenol derivative represented by formula () and a dehydrohalogenating agent in an appropriate solvent. The reaction amount of thiophosgene with respect to the phenol derivative represented by the general formula () is suitably about 1 molar to 1.5 molar. The phenol derivative represented by the above general formula () can be synthesized by various methods, for example, by converting the corresponding 3-alkyl phenol into a borate ester, halogenating it, and then hydrolyzing it, or by It can be advantageously produced by halogenating phenols in the presence of a catalyst such as iodine, aluminum chloride, or ferric chloride. Next, the method for producing the compound of the present invention will be specifically explained using Examples, but the present invention is not limited to these Examples. Example 1 4-chloro-3-ethylphenol (boiling point 87~
89℃/2mmHg) 9.39g and thiophosgene 7.5g
was dissolved in 50 ml of chloroform, and 70 ml of 1N aqueous sodium hydroxide solution was added dropwise while stirring at room temperature. After the dropwise addition was completed, stirring was continued at room temperature for 3 hours. The chloroform 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 100~
11.1 g of O-4-chloro-3-ethylphenyl chlorothioformate was obtained at 103° C./1.2 mmHg. Example 2 5.0 g of thiophosgene was dissolved in 40 ml of carbon tetrachloride,
While stirring under ice-cooling, add 8.0 g of 4-bromo-3-ethylphenol (boiling point 104-105℃/2.3mmHg).
A solution dissolved in 50 ml of 1N aqueous sodium hydroxide solution was added dropwise. After the dropwise addition was completed, stirring was continued for 12 hours. After that, the same experimental operation as in Example 1 was performed,
O-4-Bromo-3 with boiling point 111-114℃/1mmHg
-Ethyl phenyl chlorothioformate 7.8g
I got it. Example 3 5.5 g of 3-tert-butyl-4-chlorophenol (boiling point 101-102°C/0.8 mmHg) and 4.0 g of thiophosgene were dissolved in 40 ml of chloroform, and 28 ml of 20% potassium carbonate aqueous solution was added dropwise while stirring at room temperature. did. After the dropwise addition was completed, stirring was continued for 24 hours. After that, the same experimental operation as in Example 1 was carried out, and the boiling point was 103.
~106℃/0.5mmHg O-3-tert-butyl-4-
3.2 g of chlorophenyl chlorothioformate was obtained. Table 1 shows representative examples of the chlorothioformate derivatives represented by the general formula () and their physical properties.

[Table] From the chlorothioformate derivatives of the present invention represented by the general formula (), for example, (In the formula, R ₁ represents a lower alkyl group, R ₂ represents a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and Y represents a CH group or an N group.) , useful as an active ingredient in herbicides, general formula () (In the formula, R represents a lower alkyl group having 2 or more carbon atoms, X represents a halogen atom, R ₁ represents a lower alkyl group, R ₂ represents a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and Y represents a CH group or an N group.) Specific carbamate derivatives can be prepared. Next, a method for producing this particular carbamate derivative will be shown as a reference example. Reference example 1.21 g of N-methyl-3-toluidine and 1.38 g of anhydrous potassium carbonate were added to 20 ml of acetone, and while stirring at room temperature, O-4-bromo-3-tert-
3.08 g of butylphenyl chlorothioformate was dissolved in 20 ml of acetone and added. After stirring as it was for 30 minutes, the mixture was heated under reflux for 2 hours. After the reaction mixture was cooled to room temperature, it was poured into cold water and the product was extracted with benzene. Wash the benzene solution with water and saturated saline in that order, dry with anhydrous magnesium sulfate,
After distilling off benzene, it is purified by column chromatography and recrystallization to obtain O-4-bromo-3-
tert-butylphenyl N-methyl-N-(3-
2.58 g of methylphenylthiocarbamate was obtained. Melting point 91-93°C Obtained by the same reaction procedure as the above reference example,
Specific examples of the specific carbamate derivative represented by the above general formula () are described below. The specific carbamate derivatives produced from the chlorothioformate derivatives of the present invention are not limited to these examples. O-4-chloro-3-ethyl phenyl N-
(6-methoxy-2-pyridyl)-N-methylthiocarbamate Melting point 69.5-70.5℃ Elemental analysis value (%) Actual value C: 57.23 H: 5.16 N: 8.23 Calculated value C: 57.05 H: 5.08 N: 8.31 O- 4-Bromo-3-isopropylphenyl
N-(6-methoxy-2-pyridyl)-N-methylthiocarbamate Melting point 82-84℃ Elemental analysis value (%) Actual value C: 51.37 H: 4.64 N: 7.33 Calculated value C: 51.65 H: 4.84 N: 7.08 O-4-bromo-3-tert-butylphenyl
N-(6-methoxy-2-pyridyl)-N-methylthiocarbamate Melting point 117-119℃ Elemental analysis value (%) Actual value C: 52.83 H: 5.07 N: 6.70 Calculated value C: 52.81 H: 5.17 N: 6.84 O-4-bromo-3-tert-butylphenyl
N-Methyl-N-(3-methylphenyl)thiocarbamate Melting point 91-93℃ Elemental analysis value (%) Actual value C: 58.18 H: 5.78 N: 3.94 Calculated value C: 58.16 H: 5.65 N: 3.56 O-4 -Bromo-3-isopropylphenyl
N-Methyl-N-(3-methylphenyl)thiocarbamate Melting point 99.5-101.5℃ Elemental analysis value (%) Actual value C: 57.27 H: 5.26 N: 3.59 Calculated value C: 57.14 H: 5.32 N: 3.70 O-4 -Bromo-3-isopropylphenyl
N-(3-methoxyphenyl)-N-methylthiocarbamate Melting point 68.5-70℃ Elemental analysis value (%) Actual value C: 55.08 H: 5.23 N: 3.19 Calculated value C: 54.82 H: 5.11 N: 3.55 O- 4-Chloro-3-ethylphenyl N-methyl-N-(3-methylphenyl)thiocarbamate Melting point 61-63℃ Elemental analysis value (%) Actual value C: 63.97 H: 5.71 N: 4.11 Calculated value C: 63.83 H: 5.67 N: 4.37 O-4-chloro-3-ethylphenyl N-
(3-methoxyphenyl)-N-methylthiocarbamate Melting point 64-65℃ Elemental analysis value (%) Actual value C: 60.92 H: 5.55 N: 4.52 Calculated value C: 60.79 H: 5.40 N: 4.17 O-4- Bromo-3-ethyl phenyl N-
(6-methoxy-2-pyridyl)-N-methylthiocarbamate Melting point 84-85℃ Elemental analysis value (%) Actual value C: 50.46 H: 4.31 N: 7.03 Calculated value C: 50.40 H: 4.49 N: 7.34 O- 4-Bromo-3-ethylphenyl N-methyl-N-(3-methylphenyl)thiocarbamate Melting point 93-94℃ Elemental analysis value (%) Actual value C: 55.90 H: 4.83 N: 3.85 Calculated value C: 56.04 H: 4.98 N: 3.84 O-4-chloro-3-ethyl phenyl N-methyl-N-phenyl thiocarbamate oil elemental analysis value (%) Actual value C: 62.76 H: 5.24 N: 4.44 Calculated value C: 62.83 H: 5.27 N: 4.58 O-4-bromo-3-isopropylphenyl
N-Methyl-N-phenylthiocarbamate Melting point 74-75.5℃ Elemental analysis value (%) Actual value C: 56.01 H: 4.79 N: 3.52 Calculated value C: 56.04 H: 4.98 N: 3.84 O-4-bromo- 3-Ethyl phenyl N-methyl-N-phenyl thiocarbamate oil Elemental analysis value (%) Actual value C: 55.04 H: 4.64 N: 4.11 Calculated value C: 54.86 H: 4.60 N: 3.99 O-4-Bromo-3 -Ethyl phenyl N-
(3-methoxyphenyl)-N-methylthiocarbamate oil element analysis value (%) Actual value C: 53.56 H: 4.59 N: 3.84 Calculated value C: 53.69 H: 4.77 N: 3.68 O-4-chloro-3- Isopropylphenyl
N-methyl-N-phenylthiocarbamate Melting point 63-64℃ Elemental analysis value (%) Actual value C: 63.96 H: 5.58 N: 4.68 Calculated value C: 63.83 H: 5.67 N: 4.37 O-4-chloro- 3-isopropylphenyl
N-Methyl-N-(3-methylphenyl)thiocarbamate Melting point 77-78.5℃ Elemental analysis value (%) Actual value C: 64.87 H: 5.98 N: 4.31 Calculated value C: 64.75 H: 6.03 N: 4.19 O-4 -Chloro-3-isopropylphenyl
N-(3-methoxyphenyl)-N-methylthiocarbamate Melting point 68-69℃ Elemental analysis value (%) Actual value C: 61.95 H: 5.58 N: 4.31 Calculated value C: 61.79 H: 5.76 N: 4.00 O- 4-chloro-3-isopropylphenyl
N-(6-methoxy-2-pyridyl)-N-methylthiocarbamate Melting point 74-75℃ Elemental analysis value (%) Actual value C: 57.98 H: 5.28 N: 7.63 Calculated value C: 58.19 H: 5.45 N: 7.98 O-4-bromo-3-tert-butylphenyl
N-Methyl-N-phenylthiocarbamate Melting point 60-62℃ Elemental analysis value (%) Actual value C: 57.27 H: 5.36 N: 3.78 Calculated value C: 57.14 H: 5.32 N: 3.70 O-3-tert- Butyl-4-chlorophenyl
N-Methyl-N-phenylthiocarbamate Melting point 65-67℃ Elemental analysis value (%) Actual value C: 64.48 H: 5.94 N: 4.31 Calculated value C: 64.75 H: 6.03 N: 4.19 O-3-tert- Butyl-4-chlorophenyl
N-Methyl-N-(3-methylphenyl)thiocarbamate Melting point 85.5-86.5℃ Elemental analysis value (%) Actual value C: 65.80 H: 6.32 N: 4.12 Calculated value C: 65.59 H: 6.37 N: 4.02 O-3 -tert-butyl-4-chlorophenyl
N-(3-methoxyphenyl)-N-methylthiocarbamate Melting point 110-111.5℃ Elemental analysis value (%) Actual value C: 62.67 H: 5.91 N: 4.13 Calculated value C: 62.71 H: 6.09 N: 3.84 O- 3-tert-butyl-4-chlorophenyl
N-(6-methoxy-2-pyridyl)-N-methylthiocarbamate Melting point 123-124℃ Elemental analysis value (%) Actual value C: 59.61 H: 5.72 N: 7.54 Calculated value C: 59.25 H: 5.80 N: 7.67 O-4-bromo-3-tert-butylphenyl
N-(3-methoxyphenyl)-N-methylthiocarbamate Melting point 115-116℃ Elemental analysis value (%) Actual value C: 56.09 H: 5.57 N: 3.35 Calculated value C: 55.88 H: 5.43 N: 3.43 These A 10% hydrating powder containing a carbamate derivative as an active ingredient was prepared, and a porcelain pot with a diameter of 9 cm was used to conduct a waterlogging test under paddy field conditions immediately after transplanting young paddy rice seedlings and before weed germination. The herbicidal effects on various weeds and the effects on paddy rice were investigated. As a result, in the case of any of the active ingredients, virtually no phytotoxicity was observed on transplanted paddy rice even at a dose of 1000 g/10a. In addition, although it varied depending on the active ingredient, it was possible to control paddy field weeds such as field weeds, snail weeds, Japanese grasshoppers, bulrushes, and other grass weeds with an amount of active ingredients of about 15 to 500 g/10a.

Claims (1)

[Claims] 1 General formula () (In the formula, R represents a lower alkyl group having 2 or more carbon atoms, and X represents a halogen atom.) A chlorothioformate derivative represented by the formula: 2 General formula () (In the formula, R represents a lower alkyl group having 2 or more carbon atoms, and X represents a halogen atom.) General formula () characterized by reacting a phenol derivative represented by the following with thiophosgene. (In the formula, R represents a lower alkyl group having 2 or more carbon atoms, and X represents a halogen atom.) A method for producing a chlorothioformate derivative represented by the formula: