JPS6160633A - 3-tert-butyl-4-chlorophenyl chloroformate - Google Patents

Abstract

NEW MATERIAL:3-tert-Butyl-4-chlorophenyl chloroformate. USE:Useful as an intermediate of a substance which can be used as pharma ceuticals and agricultural chemicals, etc. PREPARATION:The titled compound can be prepared by reacting 3-tert- butylphenol with phosgene or trichloromethyl chloroformate. The reaction is carried out in a solvent such as dichloromethane, chloroform, etc., at -10-80 deg.C, especially 0-60 deg.C, preferably in the presence of a dehydrohalogenation agent such as potassium hydroxide. The amount of phosgene is 1-0.5mol-equivalent per 1mol of 3-tert-butyl-4-chlorophenol used as the raw material. The amount of trichloromethyl chloroformate is about 0.5-0.75mol-equivalent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to 5-tart-butyl-4-chloro-72-2-chloroformate and a method for producing the same.

The 3-tart-butyl-4-chlorophenyl chloroformate of the present invention is useful as an intermediate for substances that can be used in medicines or agricultural chemicals.

[Conventional technology]

5-tart-butyl-4-chlorophenyl of the present invention
Chloroformate is a new compound that has not been described in any literature.

[Problem that the invention seeks to solve]

The object of the present invention is to develop novel compounds 3-tart-buf
To obtain tv-4-40 lophenyl chloroformate in good yield.

[Means to solve the problem]

The gist of the present invention is to react 3-tart-butylphenol with phosgene or trichloromethyl chloroformate to produce the desired product, 3-tart-butyl-4-chlorophenyl chloroform/-.

That is, the present invention provides 3-tert-butyl chloroformate (r) 3-tert-butyl-4-chlorophenyl chloroformate (2) 3-tert-butyl phenol, which is characterized by reacting S-tert-butylphenol with phosgene or trichloromethyl chloroformate. A method for producing -4-chlorophenyl chloroformate is provided.

[Effect]

The 3-tert-butyl-4-chloro7dynyl chloroformate of the present invention can be produced by reacting 5-tert-butyl-4-chlorophenol with phosgene or trichloromethyl chloroformate. .

The reaction between 5-tert-7'f-4-chlorophenol and phosgene or trichloromethyl chloroformate can proceed easily in the presence of a dehydrohalogenating agent9.

As the dehydrohalogenating agent, sulfur hydroxide is used.

Alkali hydroxides such as potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, carbonic acid).

Examples include alkali carbonates such as potassium carbonate, metal hydrides such as IJium, alkali metal hydrides 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 tetrahydro-7rane, and acetone. , ketones such as methyl ethyl ketone, or water.

The reaction temperature is preferably about -10°C to 80°C, more preferably about 0°C to 60°C. Appropriate reaction time is about several minutes to 24 hours.

Various methods are used for the reaction, for example: r=
5. A method of adding a dehydrohalogenating agent to a mixture of tert-butyl-4-chlorophenol and phosgene or trichloromethyl chloroformate dissolved in an appropriate solvent; 3-t dissolved in a suitable solvent
Examples include a method of adding a mixed solution of art-butyl-4-chlorophenol and a dehydrohalogenating agent to a suitable solvent.

The appropriate amount of phosgene to react with 5-tart-7'thyl-4-chlorophenyl is about 1 to 1.5 molar equivalents, and the reaction amount of phosgene with respect to s-tore-butyl-4-chlorophenol is approximately 1 to 1.5 molar equivalents. The reaction amount is suitably from α5 molar equivalents to about 175 molar equivalents.

5-tert +, which is the raw material for 3-tert-butyl-4-chlorophenyl chloroformate of the present invention;
Butyl-4-chlorophenol can be synthesized by various methods, but for example, it can be produced by chlorinating 5-tart-butylphenol in the presence or absence of a catalyst such as ferric chloride or aluminum chloride. You can do it.

〔Example〕

Next, the method for producing 5-tart-butyl-4-chlorophenyl chloroformate 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 50- was dissolved in 50 Int of carbon tetrachloride and further ferric chloride (L19) was added. The reaction mixture was heated to 60"C and while stirring at this temperature, sulfuryl chloride 55 .19 was added dropwise. After the addition, 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 carbon tetrachloride. With anhydrous calcium chloride. After drying, carbon tetrachloride was distilled off under reduced pressure.The residue was purified by vacuum distillation to give a boiling point of 101-102°C/11.811IIIH.
g of 3-tert-butyl-4-chlorophenol 1
I got 569.

Elemental analysis value (4) Actual value c: 6a12 H near, 27 calculated value C: 6
5.04 Hnia, 095-tart-butyl-4
-Chlorophenol 9.22 and trichloromethyl
Dissolve chloroformate 5.59 in benzene Sod,
While stirring under water cooling, a solution of triethylamine S and B9 in benzene at 20 dK 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. -Water the liquid.

After washing with an aqueous solution of IJum (saturated chloride) 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.
/1as<Hg, 5-tart-butyl-,4-chlorophenyl chloroform-)9.529 was obtained. Fan ff1.5252 Engineering R spectrum characteristic absorption (Na(!tcm-')2
960.1780,1470,1185,1110,1
01035N spectrum (ODO4, δ-ppm) 1
．． 41 (9H, s) & 95 (IH, da) 7.18
(IL (1) 731 (IH, cL) Elemental analysis value (%) Actual value C: 5 engineering 11H: 4.91 Calculated value C: 5 engineering 46H: 4.B9 Example 2 3-tert-butyl-4- Chlorophenol 5.5
and phosgene 552 were dissolved in 50 dK of benzea, and added to a 1N aqueous sodium hydroxide solution 55a while stirring under water cooling.
g was added dropwise. After the dropwise addition was completed, stirring was continued for 2 hours. After separating the benzene layer from the reaction solution, the same experimental operations as in Example 1 were carried out to obtain s-tert-butyl-4-chlorophenyl chloroforme-h'La.

Example 3 Trichloromethyl chloroformate &69 was dissolved in chloroform 100- and while stirring at room temperature, 5-
A solution of 119 grams of tart-butyl-4-chlorophenol and 9 grams of quinoline dissolved in 100 grams of chloroform was added dropwise. After dropping, stir at room temperature for 16 hours, and then stir for 6 hours.
The mixture was stirred at 0°C for 4 hours. After cooling to room temperature, the precipitated crystals were collected from door to door. Thereafter, the same reaction operation as in Example 1 was performed to obtain 3-tert-fluor 4-10 lophenyl chloroformate a59.

Next, reference examples and application examples of specific carbamate derivatives using 3-tart nibutyl-4-chlorophenyl chloroformate of the present invention will be shown.

Reference Example 4-Fluoro-N-methylaniline 1.259 and anhydrous potassium carbonate 1.589 were added to 20d of acetone,
5-tert-buty with stirring at room temperature.

, 4-chlorophenyl chloroformate 2.59
was dissolved in acetone 20TRt and added. 30 like this
After stirring for a minute, 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 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) and further recrystallized from ethanol to give 5-tart-butyl-4-chlorophenyl H-(4-fluorophenyl)-N-methylcarbamate. I got 79. Melting point: 92 to 94°C Specific examples of the specific carbamate derivative represented by the general formula (1) obtained by the same reaction procedure as in the above reference example will be described below. The specific carbamate derivatives produced from 3-tart-fluor-4-chlorophenyl chloroformate of the present invention are not limited to these examples.

5-tart-butyl-4-chlorophenyl N-methyl-N-phenylcarbamate Melting point 595-6a5°C Elemental analysis value (→ Actual value (1!: 6a33 H: &45 N: 4.
67 calculated value C! :6a02 H:&54 N:4.
403-tert-7” f-4-40 Lofenil
N-(5-chlorophenyl)-N-nor-1-lucano(mate Melting point 65-67°C Elemental analysis value (Actual measurement value 0:61.74 H:5.45 N:59
6 calculations [0:6t37 H:5.45 N:597
3-tart-butyl-4-chlorophenyl N-methyl-N-(3-methylphenyl)car/<, 71-t Melting point 49.5~StS°C2 Elemental analysis value (→ Actual value 0:69.04 H: &83 N:4.47
Calculated value 0:6&77 H:&68 N:4.223
- tart-butyl-4-chlorophenyl l? −
.

(5-Me)xyphenyl)-N-methylcarbamate Melting point 65-58"C Elemental analysis value (4) Actual value 0:65.20 1129 N:4.55 Calculated value 0:65.60 H: &37 N:4 .02
5-tart-butyl-4-chlorophenyl N-(
6-Medoxy (2-pyridyl)-N-methylcarbamate Melting point 54-56℃ Elemental analysis value (→ Actual value C: 6λ04 H: 5.95 N near, 7
4 calculations [Cj:61,97 H:i6 N:a03
3-tart-butyl-4-chlorophenyl N-methyl-N-(2-methylphenyl)carbamate oil elemental analysis value) Actual value Cj: 6 & 71 H: & 70 N: 4.5
6 Calculated value 0:6&77 H:&lS8 N:4.2
23-tert-butyl-4-chlorophenyl N-
Methyl-N-(4-methylphenyl)carbamate oil elemental analysis value (qg) Actual value 0:6&42 H:6.62 N:584
Calculated value C: 6FL77 H: &68 N: 4.2
23-tort;-butyl-4-chlorophenyl N
-(2-Fluorophenyl)-N-methylcarbamate Melting point 70-71°C Elemental analysis value (→ Actual value C: 64.52 H: S, 71 N: 4.3
! 1 Calculated value Cj: 64J8 H: a70 N: 4.
173-tert-butyl-4-chlorophenyl N
-(5-fluorophenyl)-N-methylcarbamate Melting point 61-62.5°C Elemental analysis value (actual measurement value 0:64.21 Fi: S65 N: 592
Calculated value 0:64.38 H:5.70 N:4.1
75-tore-butyl-4-chlorophenyl N-methylcarbamate (4-fluorophenyl)-N-methylcarbamate Melting point 92-94°C Elemental analysis value ←) Actual value CI4.51 Fi:5.56 N257
9 Calculated value 0:64. S8 H:5.70 N:4
．． 175-to-butyl-4-chlorophenyl N
-(3-bromophenyl)-N-methylcarbamate Melting point 80-82°C Elemental analysis value (%) Actual value Cj: 54.12 H: 4.96 N: 542 Calculated value C: 54.49 H: 4.82 N: Engineering 53s
-tart-butyl-4-chlorophenyl N-methyl-N-(L4-dimethylphenyl)carbamate oil elemental analysis value ((conversion) Actual value C: 69.53 H185N: 4.14 Calculated value Cj: 69.45 H: &99 N:4.04
3-tart-butyl-4-chlorophenyl N-methyl-N-(L5-dimethylphenyl)carbamate Melting point 69-71°C Elemental analysis value □□□) Actual value 0:69.09 H:&87 N;4.0
1 Calculated value 0:69.45 H:&99 N:4.
045- tert-butyl-4-chlorophenyl N
-(3-chloro-4-methylphenyl)-N-methylcarbamate Melting point 116-117°C Elemental analysis value (→ Actual value C: 6Z, 54 H: S86 N: Engineering 65
Calculated value C: 62.30 H: 5.77 N: 58
2S-tart-butyl-4-chlorophenyl N
-Ethyl-N-phenylcarbamate Melting point 85-88°C Elemental analysis value (→ Actual value C: 6 [IL60 H: & 82 N: 4.
42 Calculated value C! 1a77 H168N: 4.225-
tert-butyl-4-chlorophenyl N-ethyl-N-(5-methylphenyl) force ~ Bamate melting point 69
~71°C Elemental analysis value (actual measured value 0:69.21 1(:&97 N:4.0
5 Calculated value 0:69.45 H:6.99 N:4
．． 04 Application example A 10% hydrating powder containing these carbamate derivatives as an active ingredient was prepared, and a porcelain pot with a diameter of 9α was used to treat flooding immediately after transplanting young rice seedlings and before weed germination under paddy field conditions. Tests were conducted to investigate the herbicidal effects on various weeds and the effects on paddy rice. As a result, for all active ingredients, 10009/1 for transplanted paddy rice
Substantially no drug damage was observed even at a dose of 0a.

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 weed, Japanese cypress, Japanese grass weed, and Japanese grass weed with an amount of about 10a of the active ingredient.

〔Effect of the invention〕

As is clear from the above explanation, according to the present invention, 5-te
rt -7'f -4-chlorophenyl Chloroformate can be obtained in high yield.

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) 3-tert-butyl-4-chlorophenyl chloroformate. (2) 3-tert characterized by reacting 3-tert-butyl-4-chlorophenol with phosgene or trichloromethyl chloroformate
-Production method of butyl-4-chlorophenyl chloroformate.