JPS6160626A - 4-bromo-3-tert-butylphenol - Google Patents

Abstract

NEW MATERIAL:4-Bromo-3-tert-butylphenol. USE:Intermediate of pharmaceuticals and agricultural chemicals, etc. PREPARATION:The objective 4-bromo-3-tert-butylphenol can be prepared in high yield, by (1) dehydrating 3-tert-butylphenol with boric acid in a solvent immiscible with water and capable of forming an azeotropic mixture with water, e.g. benzene, toluene, xylene, etc., under heat-refluxing, to obtain a boric acid ester in the form of orthoborate, cycloborate, etc. or their mixture, (2) brominating the boric acid ester with bromine in a solvent such as halogenated hydrocarbon (e.g. dichloromethane, chloroform, tetrachloro-hydrocarbon, dichlo roethane, etc.) preferably at about -10-+80 deg.C for several min-24hr, and (3) hydrolyzing the brominated product with a proper amount of water.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to 4-bromo5-tert-butylphenol and a method for producing the same.

The 4-bromo-5-tert-butylphenol of the present invention is useful as an intermediate for substances that can be used in medicines or agricultural chemicals.

[Conventional technology]

The 4-bromo-3-t·rt-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 a novel compound of 4-bromo-5-te.
The objective is to obtain rt-butylphenol in good yield.

[Means for solving problems]

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

That is, the present invention provides the following methods: (1) 4-Bromo-5-tert-butyl 7-ethyl VIS-tert-butylphenol is reacted with boric acid to form a boric acid ester, which is subjected to fA hydrogenation with bromine, and then hydrated. The present invention provides a method for producing 4-bromo-3-tert-butylphenol, which is characterized by decomposition.

[For production]

The 4-bromo-3-tert-butylphenol of the present invention can be produced by reacting 3-tert-butylphenol with boric acid to aborate a boric acid ester with bromine, and then hydrolyzing the boric acid ester.

The reaction to obtain the boric acid ester of 5-tert-butylphenol involves adding 5-tert-butyl, phenol, and boric acid to a solvent that forms an azeotrope with water and is immiscible with water, such as benzene, toluene, or xylene. , is carried out by dehydration treatment by heating under reflux, orthoborate,
Boric acid esters such as cyclic borates can be obtained singly or as mixtures in various proportions.

of boric acid ester of 5-tert-butylphenol,
In the bromination reaction using bromine, a solvent can be used to facilitate the reaction. As a solvent, dichloromethane, chloroform, carbon tetrachloride.

Halogenated hydrocarbons such as dichloroethane are suitable. The reaction temperature is preferably about -10°C to about 80°C, and the reaction time is about several minutes to 24 hours.

After the bromination reaction is complete, add an appropriate amount of water to perform hydrolysis.
Obtain the 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 Add 25 g of 5-tert-butylphenol and 1.59 g of boric acid to 5 toluene (ltJ), attach a water quantitative receiver, and heat to reflux while stirring to perform dehydration treatment until water is no longer produced. Ta.

Then, toluene was distilled off under reduced pressure, leaving 5-t as a residue.
A boron ester of ert-butylphenol was obtained. Subsequently, chloroform 5 was added to this boric acid ester as a solvent.
0alj was added, and a solution of bromine 99 dissolved in chloroform 20IILt was added dropwise while stirring under water cooling. After the dropwise addition was completed, stirring was continued at room temperature for 16 hours. 100 id of water was added to the reaction mixture and stirring continued for 4 hours at room temperature. The chlorotetraform layer was separated, washed successively with water and a saturated aqueous sodium chloride solution, dried over anhydrous calcium chloride, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, developed with benzene) to obtain 2.599 g of 4-bromo-3-tert-butylphenol. -1,5601 Engineering R spectrum characteristic absorption (NILOI z-') NMR spectrum (o
pal, δ=ppm) 1.40 (9H,S) 5.
51 (IH, S) & 45 (IH, da) & 88
(IH, a) 7.33 (11 (, tl) elemental analysis value (support)) Actual value 0:52.55 H:5.82 Calculated value 0:
52.42 H:5.71 Example 2 3-tert-butylphenol 159 and boric acid 4
79 was added to 100 tnl of toluene, and the same reaction procedure as in Example 1 was carried out to obtain a boric acid ester of 5-tert-butylphenol. 100-carbon tetrachloride was added to this boric ester, and while stirring at room temperature, bromine-17
A solution prepared by dissolving 50 g of carbon tetrachloride in 50 Lnl of carbon tetrachloride was added dropwise.

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-p4mo5-tert
-Butylphenol 5.69% 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 N-methyl-N-phenylcarbamoyl chloride 1.
79.4-Bromo-3-tert-butylphenol'
1.299 and 1.42 of anhydrous potassium carbonate were added to 50 ml of amethane, 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 obtain 4-bromo-3-tert-butylphenyl N-methyl-N-7x, nylcarbamate 5049. Oil Reference Example 2 4-Plumo-3-tert-butylphenol 11,5
9 and thiophosgene &59 were dissolved in chloroform 50-, and 60 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 5 hours. Separate the chloroform layer from the reaction solution,
After drying over anhydrous calcium chloride, chloroform was distilled off under reduced pressure. The residue was purified by column chromatography (-(silica gel).

0-4-bromo-3-ter
t-Butylphenyl chlorothioformate ICL! 5
I got a 9. sDl, 5825 yuan red minute digit value ($) Actual value 0:42.59 H:589 Calculated value Q:4
2.94 H: 1.579 of 5935-methoxy N-methylaniline and 1.389 of anhydrous potassium carbonate were added to 20 d of amethane, and while stirring at room temperature, 0-4-
508 ml of bromo 5-tert-buty/l/phenyl chlorothioformate was dissolved in 20 ml of amethane and added. After stirring as it was for 50 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. 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. The residue was purified by column chromatography (silica gel, benzene/hexane = 1/1 (V/l exhibition gFJ), and further recrystallized from benzene-hexane to obtain 0-4-bromo3tllrt-butylphenyl N- (3-methoxyphenyl)-N-methylthiocarbamate 2.619
I got it. A specific example of the specific carbamate derivative represented by the general formula (0) obtained by the same reaction procedure as in the above reference example is described below. 1
The specific carbamate derivatives mentioned above are not limited to these examples.

Melting point 117-119℃ Elemental analysis value (4) Actual value 0:52.83 H:a07 N:&70
Calculated values 0:52.81 H:5.17 N:6.
84 Melting point 91-95°C Elemental analysis value (1) Actual measurement (d a:5a1a H:S, 78 N:1
94 calculated value 0:51L16'H:a65 N:A
364-pro%-3-tert-)9
N-Mezazole N-Phenylgut→(Mate oil elemental analysis value (A) Actual value 0:59.28 H:5.51 N:54
8 calculated value 0:59.67 Hia56 N:58
64-promo 5-tert-butyl 7er4yl N-(
5-Jl Roro 7 Process) -N-Mesazo to Car-(Mate Oil Elemental Analysis Value (A) Actual Value 0:54.11 H:4.93 N:580
Calculated value 0:54.49 H:4.82 N:55
34-Buri%-5-t8rt-Furipre7e=J117
N-mezazoμ-N-(5-methylphenylene)car-(mate oil elemental analysis value (4) Actual value C: 6α71 H:il N: 4.00 Calculated value 0; 6 (L64 H: 5.89 N: 72
4-Furo'%-5-tert-FuchitsV7z:J'
N-(3-metho-+>yx-a)-M-oil elemental analysis value (1) Actual value 0:57.96 H:a56 N:18 Calculated value a:51L17 H:a65 N:557 Melting point 78 ~79℃ Elemental analysis value (4) Actual value 0:5Fh06 H:&47N near, 1
6 Calculated value 0:5497 H:S58 N near, 1
20-4-Fr bar E-3-tert-F) Shire 7 engineering=J
N-Mezzarelay M-7 22--6 opt-bamate Melting point 60-62℃ Elemental analysis value &) Actual value 0:57.27 H:S56 M:578
Calculated value 0:5 S14 H:5.52 N2570
0-4→Act s-t s rt-%/l/7EQILz
11- (S-Meiteshifuzaki)-N-Mesemate Melting point 115-116°C Elemental analysis value ($) Actual value 0:5&09 u:s, s7 H: Engineering 55 calculated value 0:55. B8 H:a43 N:A43 Application example A 10% hydrating powder containing these carbamate derivatives as an active ingredient was prepared, and a porcelain pot with a diameter of 9 crn was used to apply it to rice seedlings immediately after transplanting under paddy field conditions. A flood treatment test was conducted before weed germination to investigate the herbicidal effects on various weeds and the effects on paddy rice. As a result, for all active ingredients, 10,009
Even at a dosage of /10a, virtually no drug damage was observed.

Also, although it varies depending on the active ingredient, it is approximately 15 to 50 G.
It was possible to control paddy field weeds such as field weeds, cyperus japonica, snapper, and weed grass with an amount of active ingredient of about q/IQ&.

〔Effect of the invention〕

As is clear from the above description, 4-promo S-t@rt-butylphenol can be obtained in good yield according to the present invention.

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

Patent applicant: Toyo Soda Kogyo Co., Ltd. Procedural amendment March 4, 1985

Claims (2)

[Claims] (1) 4-bromo-3-tert-butylphenol. (2) Brominating a boric acid ester obtained by reacting 3-tert-butylphenol with boric acid using bromine,
4-bromo-3-, which is then hydrolyzed
Method for producing tert-butylphenol.