JPS5852236A - Dichlorostyrene derivative and its preparation - Google Patents

Abstract

NEW MATERIAL:4-Hydroxy-beta,beta-dichlorostyrene of formulaI. USE:An intermediate which can be easily converted to p-hydroxyphenyl-acetic acid or p-hydroxyphenylacetic acid amide, etc. useful as pharmaceutical intermediate. PROCESS:The compound of formulaIcan be obtained, easily, safely, in high yield from an easily available raw material, by the electrolytic reduction of 4-hydroxyphenyl trichloromethyl carbinol of formula II in an organic solvent or a mixture of water and organic solvent under acidic conditions, preferably at 10-70 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel zig-o-rustireshi derivative and a method for producing the same.

The zig-o-rustireshi derivative of the present invention is a novel compound that has not been described in any literature, and is represented by the following formula.

By hydrolyzing 4-styrene, β-dichlorstyrene can be converted into F, which is important as a pharmaceutical intermediate.
-t, diphenylacetic acid, P-diphenylacetic acid anide, etc. can be easily derived. Therefore, 4-dichloride β, β-dichloride is extremely valuable as a raw material for the synthesis of P-diphenylacetic acid, F-diphenylacetic acid amide, etc.

From phenyltrimethyl lupinol derivatives! ,
Anlawr, Chant, Int, Ed, E.
Road g1. .

There is L←57-58 (1977). However, this document does not consider any compounds having chemically active substituents on the bechizene nucleus. Therefore, it is extremely difficult to predict how 4-human0+diphenyltrichlormethylcarpinol, which has a chemically active hydroxyl group, will react.

Moreover, the method of the above-mentioned document requires the use of mercury in the electrode, which is currently causing problems in terms of pollution and toxicity, and whose use is likely to be discontinued; the current efficiency is extremely poor and it cannot be used economically; It also has drawbacks in terms of production, such as the fact that the actual yield is about 80. In contrast, according to the method of the present invention, diphenyltrichloromethylcarbinol in 4-hydro, which is easily obtained from various raw materials and manufacturing methods, is electrolytically reduced, thereby safely and easily producing 4-dichloromethane in high yield. Doro+C β, β-dichlorostyrene can be produced.

Diphenyltrichloromethylcarbinol in 4-hydrochloride, which is used as a starting material in the present invention, is a known compound that can be prepared by addition reaction of 05-ol to acyl, for example, phenol, or from p-hydro+dibenzaldehyde and 00-carbonyl form. It can be easily obtained by phase transfer catalyst or electrolysis method.

The electrolytic reduction reaction of the present invention is carried out in an organic solvent or in a water-organic solvent.
It is carried out under acidic conditions. As an organic solvent [alcohols such as methanol and ethanol, ethers such as dioxane and methyl solp, acetonitrile, dimethylformanide, etc., solvents that dissolve water to some extent and are inert during electrolysis are used. Ru. To maintain acidic conditions,
For example, all kinds of inorganic acids and organic acids can be used, but mineral acids such as hydrochloric acid and sulfuric acid, and organic acids such as benzenesulfonic acid and tornidisulfonic acid are usually preferred.

In the present invention, the supporting electrolyte is not particularly limited, and any acid used to maintain acidity can be used as the supporting electrolyte, or ethyl ammonium Salts such as tertiary aesi O hydrochloride, sulfate, etc., balatoluenesulfosic acid tetraethylacet7ium salt, Bat 119
14 Quaternary ammonium salts such as 5-methylammonium salt of teto-hydroborate, 5-methylant-5-methylammonium salt of sodium perchlorate, sodium fluorocarbonate, 5-methyl teto-hydroborate
Usual supporting electrolytes such as fluoroboric acid salts such as methylammonium salts, alkali metal salts such as becisesysulnesic acid and toluesysulfosic acid, and other salts of alkali metals and alkaline earth metals can be used. The amount of supporting electrolyte to be used can be selected from a wide range, but is preferably in the range of about 0.01 to 10 volts per 1° C. of the raw material.

As the electrode material, ordinary electrodes such as carbon, platinum, titanium, iron, stainless steel, nickel, and lead can be used. Taking economic efficiency into consideration, a preferable example is to use lead for the i-electrode.
Mention may be made of the use of carbon in the anode.

Electrolysis may be constant current electrolysis or constant potential electrolysis. Although a diaphragm is not necessarily required in the present invention, when a diaphragm is used, a polymer diaphragm, an ion exchange membrane, a glass filter, a clay plate, or the like can be used as the diaphragm. The reaction temperature is preferably in the range of 10 to 70°C, but other temperatures are also possible. More preferably, 20 to
It is in the range of 60°C. The current density is not particularly limited, but from the viewpoint of production efficiency, reaction time, yield, etc.
00 A/-, preferably 50 to 300 A/-.

The target compound of the present invention can be easily separated and purified from the reaction mixture by conventional methods such as extraction, concentration, distillation, recrystallization, and chromatography.

The present invention will be explained below with reference to Examples.

Example ! Salt production 1110m, balatluecisrunenic acid tet 5ethyl ammonium salt 2.5F and triethylammonyl chloride 5.51 are dissolved in 60MI of ethanol, and this solution is placed in an anode chamber and a cathode chamber separated by a diaphragm. Barahit 0 Shitric 0 lmethylcarpinol 10 in the cathode chamber! :
Constant current electrolysis was performed using lead as the cathode and carbon as the anode. After energizing at 5F and 7℃, add the @polar solution to 200 d of water, extract 4 times with 5Qd hemisphere, and then dry the hemisphere extract with anhydrous magnesium sulfate. After separation and purification of the residue, 1.8Of of β-dichlorostyrene was obtained. Yield: 95.2 excellent, p: 90-91°C IRCcut') 3370, t: 604.15
00.1442.1375.1235.1180.11
09.909.873,821,682 Example 2 50 aJ of methanol containing 3-sulfuric acid is placed in an anode chamber and a cathode chamber separated by a diaphragm. Furthermore, it is disassembled into the cathode chamber +
Add 2.4159 ml of Citricol methyl caldinol. Constant current electrolysis was performed using lead as the anode and cathode. Keep the reaction temperature at 45-50°C.

After energizing 3F/r-ru, the same treatment as in Example 1 is performed to obtain the target product 1.83F (yield: 96.8H).

Example 3 A methanol solution containing 3 parts of sulfuric acid, 20 parts of water
11/ is placed in an anode chamber and a cathode chamber separated by a diaphragm, and further separated.
Add t to the cathode chamber. Constant current electrolysis was performed using lead as the anode and cathode. Keep the reaction temperature at 40-45℃, 3F/
After 7 energization, carry out the same treatment as in Example 1. 5. Target object 1.
79 t (yield 94.7%) is obtained.

Example 4 50 kg of acetonitrile containing 3s sulfuric acid is placed in an anode chamber and a cathode chamber separated by an ion exchange membrane, and then 2.415 f of Droacitolic methylcarbinol is added to the cathode chamber. Constant current electrolysis was performed at a temperature of 50 to 55°C using lead as the anode and cathode, and after 3 F/e current was applied, the same treatment as in Example 1 was performed to obtain the target product of 1.84 f (yield: 97.4 chi). ).

(Above) Procedural Amendment (Screen) October 18, 1980 Commissioner of the Japan Patent Office Kazuinu Wakasugi 1. Indication of the case 1981 Patent Application No. 150152 2. Invention 0 Title 6ri0 Rusutileshi derivatives and their Manufacturing method 3,
Relationship with the case of the person making the amendment Patent applicant: Shu Minji 4, agent, Heiwa Building, 2-10 Hirano-cho, Higashi-ku, Osaka Telephone: 06-203
~0941 (Representative) (6521) Patent Attorney Eiji Saegusa 5, Contents of voluntary amendment of the date of the amendment order: Agricultural specification page 7, lines 9-10, page 8, line 7, intervening pages 15- Line 16 and page 9, line 186, “citrichloromethyl carbinol in loose liquid” are respectively corrected to “diphenyltrichloromethyl b-rubinol in loose liquid” (above)

Claims (1)

[Scope of Claims] 4-dichlorostyrene represented by the formula 0,/-dichlorstyrene. 1. A method for producing 4-human 0+ diphenyltrichloromethylcarbinol represented by the formula 0, which comprises electrolytically reducing 4-human 0+ diphenyltrichloromethylcarbinol. (2) The method according to claim 2, in which electrolytic reduction is carried out under acidic conditions. (2) The method according to claim 2 or 3, wherein the electrolytic reduction is carried out at 10 to 70°C.