JPH0430935B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to 4-bromo-3-tert-butylphenol and a method for producing the same.

The 4-bromo-3-tert-butylphenol of the present invention is useful as an intermediate for substances that can be used in medicines or agricultural chemicals.

[Conventional technology]

4-Bromo-3-tert-butylphenol of the present invention is a new compound that has not been described in any literature.

[Problems to be solved by the present invention]

The object of the present invention is to develop novel compounds 4-bromo-
The objective is to obtain 3-tert-butylphenol in good yield.

[Means for solving problems]

The gist of the present invention is to produce the desired product, 4-bromo-3-tert-butylphenol, by brominating a boric acid ester of 3-tert-butylphenol with bromine.

That is, the present invention comprises: (1) 4-bromo-3-tert-butylphenol (2) A boric acid ester obtained by reacting 3-tert-butylphenol with boric acid is brominated with bromine, and then hydrolyzed. A method for producing 4-bromo-3-tert-butylphenol, characterized by:

It provides:

[Effect]

4-Bromo-3-tert-butylphenol of the present invention can be produced by reacting 3-tert-butylphenol with boric acid, brominating a boric acid ester with bromine, and then hydrolyzing it. .

The reaction to obtain the boric acid ester of 3-tert-butylphenol involves adding 3-tert-butylphenol and boric acid to a solvent such as benzene, toluene, or xylene that forms an azeotrope with water and is immiscible with water. This is carried out by dehydration treatment by heating under reflux to obtain borate esters such as orthoborate, cyclic borate, etc. singly or as a mixture in various proportions.

In the bromination reaction of borate ester of 3-tert-butylphenol with bromine, a solvent can be used to facilitate the reaction. Suitable solvents include halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and dichloroethane. Reaction temperature is preferably from -10℃
Approximately 80℃ is appropriate, and the reaction time is several minutes to 24℃.
An appropriate amount of time is required.

After the bromination reaction is completed, an appropriate amount of water is added to carry out hydrolysis to obtain a reaction product.

〔Example〕

Next, the method for producing 4-bromo-3-tert-butylphenol of the present invention will be specifically explained using Examples, but the present invention is not limited to these Examples.

Example 1 8.25 g of 3-tert-butylphenol and 1.5 g of boric acid were added to 50 ml of toluene, a moisture meter was attached, and the mixture was heated to reflux with stirring to perform dehydration treatment until water was no longer produced. . Then, toluene was distilled off under reduced pressure, leaving 3-
A boric acid ester of tert-butylphenol was obtained. Subsequently, 50 ml of chloroform was added as a solvent to this boric acid ester, and while stirring under ice cooling,
A solution of 9 g of bromine dissolved in 20 ml of chloroform was added dropwise. After completion of the dropwise addition, stirring was continued at room temperature for 16 hours. 100 ml of water was added to the reaction mixture, and stirring was continued for an additional 4 hours at room temperature. Separate the chloroform layer and wash with water and saturated sodium chloride solution in that order.
After drying over anhydrous calcium chloride, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, developed with benzene) to obtain 4-bromo-3-tert-butylphenol.
2.39g was obtained. n ²⁵ _D 1.5601 IR spectrum characteristic absorption (NaClcm ^-1 ) 3340, 2960, 1595, 1575, 1470, 1365, 1285,
1225 NMR spectrum (CDCl ₃ , δ=ppm) 1.40 (9H, S) 5.51 (1H, S) 6.45 (1H,
dd) 6,88 (1H, d) 7.33 (1H, d) Elemental analysis value (%) Actual value C: 52.53 H: 5.82 Calculated value C: 52.42 H: 5.71 Example 2 15 g of 3-tert-butylphenol and Ho acid
4.7 g was added to 100 ml of toluene, and the same reaction procedure as in Example 1 was carried out to obtain a boric acid ester of 3-tert-butylphenol. 100 ml of carbon tetrachloride was added to this boric acid ester, and a solution of 17 g of bromine dissolved in 50 ml of carbon tetrachloride was added dropwise while stirring at room temperature. After the dropwise addition was completed, the mixture was stirred at 60°C for 1 hour. Hereinafter, the same reaction operation as in Example 1 was carried out, and 4
5.3 g of -bromo-3-tert-butylphenol was obtained.

Next, reference examples and application examples of specific carbamate derivatives using 4-bromo-3-tert-butylphenol of the present invention will be shown.

Reference Example 1 1.7 g of N-methyl-N-phenylcarbamoyl chloride, 2.29 g of 4-bromo-3-tert-butylphenol and 1.4 g of anhydrous potassium carbonate were added to 30 ml of acetone, and the mixture was heated under reflux for 48 hours. After the reaction mixture was cooled to room temperature, it was poured into cold water and the product was extracted with benzene. The benzene solution was washed with water and a saturated aqueous sodium chloride solution in that 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) to give 4-bromo-3-tert-butylphenyl N-methyl-N-
3.04 g of phenyl carbamate was obtained. Oil reference example 2 4-bromo-3-tert-butylphenol 11.5
g and 6.5 g of thiophosgene in 50 ml of chloroform.
60 ml of 1N aqueous sodium hydroxide solution was added dropwise while stirring at room temperature. After the dripping is finished,
Stirring was continued for 3 hours at room temperature. The chloroform layer was separated from the reaction solution, dried over anhydrous calcium chloride, and then chloroform was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, developed with hexane) to obtain 10.3 g of O-4-bromo-3-tert-butylphenyl chlorothioformate. n ²⁵ _D 1.5823 Elemental analysis value (%) Actual value C: 42.59 H: 3.89 Calculated value C: 42.94 H: 3.93 1.37 g of 3-methoxy-N-methylaniline and 1.38 g of anhydrous potassium carbonate were added to 20 ml of acetone, and the mixture was heated to room temperature. O-4-bromo-3- while stirring with
tert-butylphenyl chlorothioformate
3.08g was dissolved in 20ml 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. Benzene solution in water,
After washing with saturated aqueous sodium chloride solution and drying over anhydrous magnesium sulfate, benzene was distilled off. The residue was purified by column chromatography (silica gel, developed with benzene/hexane = 1/1 (V/V)) and further recrystallized from benzene-hexane to obtain O-4-bromo-3-tert-
Butylphenyl N-(3-methoxyphenyl)-
2.61 g of N-methylthiocarbamate was obtained. melting point
115-116°C A specific example of a specific carbamate derivative represented by the general formula () obtained by the same reaction procedure as in the above reference example will be described below. 4- of the present invention
The specific carbamate derivatives produced from bromo-3-tert-butylphenol are not limited to these examples.

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 4-Bromo-3 -tert-butylphenyl N-methyl-N-phenyl carbamate Oil elemental analysis value (%) Actual value C: 59.28 H: 5.51 N: 3.48 Calculated value C: 59.67 H: 5.56 N: 3.86 4-bromo-3-tert- Butylphenyl N-
(3-chlorophenyl)-N-methylcarbamate Oil elemental analysis value (%) Actual value C: 54.11 H: 4.93 N: 3.80 Calculated value C: 54.49 H: 4.82 N: 3.53 4-Bromo-3-tert-butylphenyl N- Methyl-N-(3-methylphenyl)carbamate Oil elemental analysis value (%) Actual value C: 60.71 H: 6.01 N: 4.00 Calculated value C: 60.64 H: 5.89 N: 3.72 4-Bromo-3-tert-butylphenyl N-
(3-methoxyphenyl)-N-methylcarbamate Oil elemental analysis value (%) Actual value C: 57.96 H: 5.56 N: 3.68 Calculated value C: 58.17 H: 5.65 N: 3.57 4-Bromo-3-tert-butylphenyl N-
(6-Methoxy-2-pyridyl)-N-methylcarbamate Melting point 78-79℃ Elemental analysis value (%) Actual value C: 55.06 H: 5.47 N: 7.16 Calculated value C: 54.97 H: 5.38 N: 7.12 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-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 Application examples 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 varies depending on the active ingredient, the amount of active ingredient is approximately 15 to 500g/10a.
It was possible to control paddy field weeds such as Kikashigusa.

〔Effect of the invention〕

As is clear from the above explanation, according to the present invention, 4
-Bromo-3-tert-butylphenol can be obtained in good yield.

In addition, compounds derived from this compound have industrial utility.

Claims (1)

[Claims] 1 4-Bromo-3-tert-butylphenol. 2 4- characterized in that a boric acid ester obtained by reacting 3-tert-butylphenol with boric acid is brominated with bromine and then hydrolyzed.
Method for producing bromo-3-tert-butylphenol.