JPS6160627A - 3-tert-butyl-4-chlorophenol - Google Patents

Abstract

NEW MATERIAL:3-tert-Butyl-4-chlorophenol. USE:Intermediate of pharmaceuticals and agricultural chemicals, etc. PREPARATION:The objective 3-tert-butyl-4-chlorophenol can be prepared in high yield by chlorinating 3-tert-butylphenol with sulfuryl chloride. The reaction is carried out e.g. by using a catalyst such as metal chloride (e.g. ferric chloride, aluminum chloride, zinc chloride, cuprous chloride, cupric chloride, cobalt chlo ride, nickel chloride, etc.), metal complex compound [e.g. iron (III) acetylace tonate, etc.], etc., and a solvent such as halogenated hydrocarbon (e.g. dichloromethane, chloroform, carbon tetrachloride, dichloroethane, etc.), prefer ably at about 0-120 deg.C, especially about 30-80 deg.C for several tens min-about 48hr.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to 5-tert-butyl-4-chlorophenol and its production method. It is useful as an intermediate for substances that can be used in other applications.

[Conventional technology]

The s-tert-butyl-4-chlorophenol of the present invention is a new compound that has not been described in any literature.

[Problem that the invention seeks to solve]

An object of the present invention is to obtain a novel compound, S-tert-butyl-4-chlorophenol, in a high yield.

[Means for solving problems]

The gist of the present invention is to chlorinate 3-tert-butylphenol with sulfuryl chloride to obtain the target product 5-tert-butylphenol.
The process is for producing butyl-4-chlorophenol.

That is, the present invention is characterized in that (1) 3-tert;-butyl-4-chlorophenol (2) 5-tert-7' tylphenol is chlorinated with sulfuryl chloride.
A complete method for producing -tert-butyl-4-chlorophenol is provided.

[Effect]

The s-tert-butyl-4-chlorophenol of the present invention can be produced by chlorinating 5-tθi-butylphenol with sulfuryl chloride or various chlorinating agents such as chlorine, or by chlorinating 5-tθi-butylphenol with boric acid. It can be produced by converting it into an ester, chlorinating it, and then hydrolyzing it.

In the present invention, 5-tert-butylphenol is chlorinated with sulfuryl chloride.
A method for producing t-7'thyl-4-chlorophenol is provided.

A catalyst can be used for the reaction between 3-tert-butylphenol and sulfuryl chloride. Catalysts that can be used include metal chlorides such as ferric chloride, aluminum chloride, zinc chloride, cuprous chloride, cupric chloride, cobalt chloride, and nickel chloride, and metals such as iron (2) acetylacetonate. Examples include complex compounds.

A solvent can be used to facilitate the reaction.

Suitable solvents include norogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and dichloroethane.

The reaction temperature is preferably about O'C to 120'C, more preferably about 30C to 80C.

Appropriate reaction time is several tens of minutes to about 48 hours.

〔Example〕

Next, the method for producing S-tere-butyl-4-chlorophenol of the present invention will be specifically explained using Examples, but the present invention is not limited to these Examples.

Example 1 5-tert-butylphenol 9 and carbon tetrachloride 3
0- and heated to 70'C. While stirring at this temperature, sulfuryl chloride IQ, 59 was added dropwise. After dropping, stir at 70°C for 48 hours. I got it. After the reaction mixture was cooled to room temperature, it was poured into cold water and the product was extracted with carbon tetrachloride. After drying over anhydrous calcium chloride, carbon tetrachloride was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, developed with benzene).
- tert -butyl-4-chlorophenol t59
I got ft.

Na04 c1rr' 1.5424 Engineering R spectrum characteristic absorption
5340, 2980.1605.1580.1470.
1570.1285°NMR spectrum (CNC4
, δ-ppm) 1.35 (9E, a) C41 (1 Mr. 8
) &51(11!, cud) &85(11,C1)
7.11 (1B, a) Elemental analysis value (4) Actual value C: 65.12 H near, 27 calculated value
0:6! SO4H Near, 09 Example 2 30 g of S-tert-7' tylphinol was dissolved in 50 g of dichloroethane, and ferric chloride α19 was further added. The reaction mixture was heated to 60° CIC, and 311 g of sulfuryl chloride was added dropwise while stirring at this temperature. After the dropwise addition was completed, stirring was continued at 60°C for 8 hours. After the reaction mixture was cooled to room temperature, it was poured into cold water and the product was extracted with dichloroethane.

After drying over anhydrous calcium chloride, dichloroethane was distilled off under reduced pressure. The residue was purified by vacuum distillation to a boiling point of 1
156 g of 5-tert-butyl-4-chlorophenol having a temperature of 01 to 102°C/α8 Hg was obtained.

Next, reference examples and application examples of specific carbamate derivatives using 5-tert-butyl-4-chlorophenol of the present invention will be shown.

Reference Example 1 N-(3-chlorophenyl)-N-mercarbamoyl chloride 2-049, 5-tert-butyl-4-chlorophenol t84g and anhydrous potassium carbonate t69
was added to acetone 3arnt and 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. Benzene solution in water, fi!
After washing with an aqueous solution of sodium 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) and further recrystallized from hexane to obtain s-tert-butyl-4-chlorophenyl N-(5-chlorophenyl)-N-methylcarbamate. 29 was obtained. Melting point 65-67°C Reference Example 2 5-tert-butyl-4-chlorophenol 9.2
2 and thiophosgene 1. ．． 59 with chloroform 50d
(1N-hydroxylated while stirring at room temperature)
60 ml of IJum aqueous solution was added dropwise. 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, O-3-tert- with a boiling point of 103-106°C/α5g
Butyl-4-chlorophenyl chlorothioformate 9
．． 5g was obtained.

n211゜5665 Elemental analysis value (@Actual value C: 5α25 H: 4.45 Calculated value C
! :51120 H:4.59N-methylaniline 1
．． 079 and 1.589 anhydrous potassium carbonate were added to acetone 20-, and while stirring at room temperature, O-5-ter
2.659 t-butyl-4-chlorophenyl chlorothioformate was dissolved in acetone zogK 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).

0-3-
tert-butyl-4-chlorophenyl N-methyl-
64 g of N-phenylthiocarbamate L was obtained. Melting point 65-67°C Reference example 5 5-tert-butyl-4-chlorophenol 9.2
5.
Dissolve 5g of benzene 50IRtllC, stir while cooling with water, and dissolve triethylamine s, ag in benzene 20It
The dissolved K was added dropwise. After the dropwise addition was completed, stirring was continued at room temperature for 12 hours. 70 d of hexane was added to the reaction solution, and the precipitated crystals were collected from door to door. Add liquid F to water.

After washing with saturated aqueous sodium chloride solution and drying with anhydrous calcium chloride, the solvent was distilled off under reduced pressure. By distilling the residue under reduced pressure, the boiling point is 105-108°C/
1 amgg of 5-tert-butyl-4-chlorophenyl sigma formate 9.322 was obtained. Nobu'
1.5252 Elemental analysis value (@ Actual value C: 5A11 H: 4.91 Calculated value C
:5546 H:4.894-Fluoro-N-methylaniline 1.259 and anhydrous potassium carbonate 1.389
was added to 2011 t of acetone, and while stirring at room temperature,
5-tert-butyl-4-chlorophenyl chlorophor, I'-)2-57 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 Benose/. Benzene solution in water.

After washing with an aqueous solution of IJ (saturated chloride) and drying with anhydrous magnesium sulfate, benzene was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, developed with benzene) and further recrystallized from ethanol to give 5-tert-butyl-4-chlorophenyl N-(4-fluorophenyl)-N-methylcarbame)2. I got .79. Melting point: 92 to 94° C. Specific examples of the specific carbamate derivative represented by the general formula (T1) obtained by the same reaction procedure as in the above reference example will be described below. 3-tert-7' of the present invention
The specific carbamate derivatives produced from thyl-4-chlorophenol are not limited to these examples.

3-tert-butyl-4-chlorophenyl N-methyl-N-phenylcarbamate Melting point 59.5-6α5°C Elemental analysis value (@actual value C:6a55 H:&45 N:467calculated value C!+6a02)I:&34 N: 4.4
OS-tert-phthyl-4-chlorophenyl N -
(3-chlorophenyl)-N-methylcarbamate Melting point 65-67°C Elemental analysis value (actual measured value C!: 61.74 H: 145 N: 59
6 Calculated value 0:61j7 H:a45 N:597
5-tert-butyl-4-chlorophenyl N-methyl-N-(5-methylphenyl)carbamate melting point
495-51.5°C Elemental analysis value @) Actual measurement value C: 69. Q4 H:&85 N:4.4
7 Calculated value 0:6a77 H:&68 N:4.2
23-, tert-butyl-4-chlorophenyl N
-(5-methoxyphenyl)-N-methylcarbamate Melting point 55-38°C Elemental analysis value (H) Actual value C: 65.20 H: '& 29H: 4.55
Calculated value 0:65.60 H:&37 N:4.0
23-tert-butyl-4-chlorophenyl N-
(6-Medoxy 2-pyridyl)-N-methylcarbamate Melting point 54-56°C Elemental analysis value C) Actual measurement value C! :62.04 H:5.95 N near, 74 calculated value C:61. ? 7 H:&06 N:
1lLO50-5-t+9rt-butyl-4-chlorophenyl N-methyl-N-phenylthiocarbamate Melting point 65-67°C Elemental analysis value ←) Actual value C: 64.48 FI: 5.94 N: 4
．． 52 calculated value C: 64.75 H: &05 N:
4.19o -s -tert-butyl-4-chlorophenyl N-methyl-N-(5-methylphenyl) thiocarbamate Melting point 855~8&5℃ Elemental analysis value (actual value C: 6al H132N: 412 calculated value C
! :65.59 H:6.57 N:4.020-
5-tert-butyl-4-chlorophenyl N-(
3-Methoxyphenyl)-N-methylthiocarbamate Melting point 110-111.5°C Elemental analysis value (H) Actual value C! :62.67 H:S, 91 N:4
．． 1! Calculated value (!:62.71 H:&09 N
:584o -s -tert-butyl-4-chlorophenyl N-(6-medoxy-2-pyridyl)-N-methylthiocarbamate Melting point 123-124°C Elemental analysis value (2)) Actual value (!: 59.61 H : S, 72 N near, 54 calculated value C: 59.25 H: 5.80 N
Nia, 675-tore-butyl-4-chlorophenyl N-methyl-N-(2-methylphenyl)carbamate oil elemental analysis value @) Actual value C! :611L71 H:&70 N:4
．． 56 calculated value 0:6a77 H:6.68 N:
4.223-tirt-butyl-4-chlorophenyl N-methyl-N-(4-methylphenyl)carbamate oil elemental analysis value (H) Actual value C! :6a42'Fl:6.62 N:
i4 calculated value 0:6a77 1168 N:4.22
5-tert-butyl-4-chlorophenyl N-(
2-Fluorophenyl)-N-methylcarbamate Melting point 70-71°C Elemental analysis value (H) Actual value C: 64.52 H: 5.71 N: 4.
55 Calculated value C: 64. S8 H:5.70 N:
4.173-1θre-F-7-# -4-chlorophenyl N-(5-fluorophenyl)-N-methylcarbamate Melting point 61-62.5"C Elemental analysis value (H) Actual value 0:64.21H :5.65 N:A9
2 Calculated value 0:6438 H:5.70 N:4.
173-tert-butyl-4-chlorophenyl N
-(4-fluorophenyl)-N-methylcarbamate Melting point 92-94°C Elemental analysis value (%) Actual value C: 64.31 H: 5.56 N: A7
9 calculated value 0:64.58 H:a70 N-:4
．． 173-t13rt-Butyl-4-chlorophenyl N-(3-7'romophenyl)-N-methylcarbamate Melting point 80-82℃ Elemental analysis value (actual snout value C: 54.12 H: 4.96 N: i2
Calculation Direct 0:54.49 Et:4.82
N:5555-tert-butyl-4-chlorophenyl N-methyl-N-(3,4-')methylphenyl)carbamate oil elemental analysis value (actual measured value by burning 0:69.53 ■:i85 N:4.1
4 Calculated value C: 69.45 H199N: 4.045
- tert-butyl-4-ri aa7e=/L/N-
Mefk-N-(As-dimethylphenyl)carbamate Melting point 69-71"C Elemental analysis value (Actual measured value 0:69.D9 FI: 6.87 N: 4
．． 01 Calculated value 0:69.45 H:&99 N:
4.043-tert-butyl-4-chlorophenyl N-(3-chloro-4-methylphenyl)-N-methylcarbamate Melting point 116-117°C Elemental analysis value (a) Actual value C: 62.54 H: 5. 86 N:X6
5 Calculated value 0:62-50 H:5.77' N:
125-tert-butyl-4-chlorophenyl N
-Ethyl-N-phenylcarbamate Melting point 85-88°C Elemental analysis value (@actual value c: 6FL6cJ H: 682 N: 4.
42 calculated value 1:! :6a77 T1:&6B N
:4.223-tert-butyl-4-chlorophenyl N-ethyl-N-(3-methylphenyl)carbamate Melting point 69-71°C Elemental analysis value ←) Actual value 0:69.21 H:&97 N:4. 05
Calculated value 0:69.45 H:&99 N:4.0
4 Application examples A 10% water conservancy containing these carbamate derivatives as active ingredients was prepared, and a porcelain pot with a diameter of 9 cm was used to conduct a water overflow treatment test immediately after transplanting seedlings of paddy rice and before weed germination under paddy field conditions. We investigated 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 5009
It was possible to control paddy field weeds such as field weeds, Japanese cypress, Japanese grass weed, and Japanese grass weed with an amount of the active ingredient of about 10 a.

〔Effect of the invention〕

As is clear from the above explanation, according to the present invention, 3-te
rt-Butyl-4-chlorophenol can be obtained in good yield.

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

Patent applicant: Toyo'W: Jv Industries Co., Ltd. Procedural Amendment March 4, 1985

Claims (2)

[Claims] (1) 3-tert-butyl-4-chlorophenol. (2) A method for producing 3-tert-butyl-4-chlorophenol, which comprises chlorinating 3-tert-butylphenol with sulfuryl chloride.