JPS62281837A - Production of 3,4'-dichlorodiphenyl ether - Google Patents

Abstract

PURPOSE:To obtain the titled substance useful as an intermediate for 3,4'- diaminodiphenyl ether, etc., which are medicines and highly functional high polymer materials, etc., by reacting sodium salt of p-chlorophenol with m- chlorobenzene in the presence of a copper catalyst in an organic polar medium. CONSTITUTION:Sodium salt of p-chlorophenol is reacted with m-dichlorobenzene in an equivalent amount of preferably large excess such as 5-50 times based on the sodium salt of the p-chlorophenol in the presence of a copper catalyst, e.g. CuO, CuCl, etc., in an organic polar solvent, e.g. N,N-dimethylformamide, etc., preferably in an inert gas to afford the aimed 3,4'-dichlorodiphenyl ether. EFFECT:Gives high yield.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention Field of Industrial Application The present invention is directed to the production of intermediate 3,4'-diaminodiphenyl ether, which is used in a wide range of fields such as agriculture, medicine, and highly functional polymer materials. The present invention relates to a method for producing 3,4'-dichlorodiphenyl ether, which can be used as a 3,4'-dichlorodiphenyl ether.

BACKGROUND ART Conventionally, the Williamson reaction, in which phenol and halogenated benvin are reacted in the presence of an alkali salt, has been known as a method for synthesizing diphenyl ethers. The reaction temperature can be lowered by neutralizing the polar solvent, but the reaction progresses easily only in the case of activated halogenated benzene, and with less active halogenated benzene, the target compound cannot be produced. I don't get much.

On the other hand, the Ullmann (Ull+nan) reaction, in which an alkali salt of phenol and a halogenated benzene are reacted at high temperature in the presence of copper or a copper salt, is also known, but the reaction between dichlorobenzene and an alkali salt of chlorophenol, which have low activity, is Does not react even in the presence of copper or copper salts. In other words, it is thought that halogenated benzene has neither the ability to dissolve phenolate nor convert copper salt into a reactive form. Therefore, there is an example (JP-A-49-62434) in which the reaction is carried out by adding an excess of chlorophenol as a solvent, but the yield of diphenyl ether is not necessarily high. An example of adding a sequestering agent to a metal ion in the reaction of inert halogenated benzene (Japanese Unexamined Patent Publication No. 56-2953)
9), but it requires the use of an expensive sequestering agent.

As a result of various studies, the present inventors have found that when sodium salt of p-chlorophenol and m-dichlorobenzene are reacted in the presence of an organic polar medium in the presence of a copper catalyst, 3.4'-dichlorosiftenyl is produced in extremely high yield. It was discovered that nyl ether can be obtained, leading to the present invention.

Structure of the Invention The present invention is a method for producing 3,4'-dichlorophenyl ether, which is characterized by reacting sodium salt of p-chlorophenol and m-dichlorobenzene in the presence of a paid polar medium and a copper catalyst.

Various types of paid polar media can be used in the method of the present invention, but aprotic polar media are preferred, such as N,N-dimethylformamide (DM
F), N,N-dimethylacetamide (DMA),
N-methyl-2-pyrrolidone (NMP), hegisamethylphosphoramide (HMPA), dimethyl sulfoxide (
DMS○) etc. These media can be used alone or in combination of two or more. Sufficiently good results can be obtained with the amount of polar medium used in the range of 0.5 to 20 times equivalent to the sodium metal salt of p-chlorophenol, but preferably in the range of 1 to 5 times equivalent. Copper catalysts used in the reaction include metallic copper (cu), CLI
Suitable examples include O, Cu2O, cucr, cuC12・2H20, diacetic acid vA (Cu(OAC>2・t(20), etc.), but even the weaker copper compounds can be used in this reaction. Yes, half of the copper catalyst is 0.001~ based on the sodium metal salt of p-chlorophenol.
1.0 damage, preferably 0.005 to 0.10
It's double the amount.

The term m-dichlorobenzene refers to 5 to 50 equivalents based on the sodium metal salt of p-chlorophenol, and the sodium metal salt is reacted with the 3,4'-dichlorophenyl ether produced by using a large excess. You can suppress the next reaction. The sodium metal salt used in the reaction may be produced by reacting ρ-chlorophenol with a sodium compound in m-dichlorobenzene and removing water from the system, or may be produced by reacting with an aromatic hydrocarbon such as benzene or toluene. Alternatively, p-chlorophenol and a sodium compound may be reacted using a solvent such as the like, and water may be generated by removing the solvent.

The reaction temperature varies slightly depending on the type of medium used, but is in the range of 100-200'C, preferably 130-18'C.
It is in the range of 0°C. The reaction time depends on the reaction temperature, type of medium, etc., but is usually in the range of 1 to 30 hours, preferably in the range of 1 to 20 hours.

Further, the reaction of the present invention is preferably carried out in an inert gas, and if oxygen (02) is present, a tar compound will be produced. Nitrogen, argon, helium, etc. are used as the inert gas.

As described above, 3,4'-dichlorodiphenyl ether can be obtained in high yield according to the present invention, which can be used as a starting material for the production of the corresponding diaminodiphenyl ether, and this diamine compound can be used for the production of polymer compounds. It has extremely high industrial value as a raw material for.

The present invention will now be described in detail with reference to Examples.

Example 1 p-chlorophenol 20.49 (0,159 mol
).

m-dichlorobenzene 232.7g (L583 mol
) and aqueous sodium hydroxide solution (Na OH01174
mol) is heated to reflux to remove water from the system. Next, DM F24.0g (0,328mol>) and copper acetate (
Cu(OAC) 2 ・H2C) 0.3g (1,55
mmol) and heated and stirred at 155-160°C for 18 hours. Non-isolated compounds are removed by filtering the reaction solution. The filtrate was then distilled to obtain 33,7 Lj (0,141 mol) of 3,4'-dichlorodiphenyl ether, which corresponds to 88.8% of the theoretical value based on p-chlorophenol. The boiling point of ether (B,
p) is 110 to b Examples 2 to 4 ■-dichlorobenzene to p-chlorophenol,
Table 1 shows the results obtained under the same conditions as in Example 1 except that 5.20.40 times the equivalent was added.

Comparative Example 1 The same conditions as in Example 1 were carried out except that DMF was not added.

Comparative Example 2 CI(OAC)2 ・Example 1 except that H2C is not added
It was carried out under the same conditions.

Further, the results of Comparative Examples 1 and 2 are also shown in Table 1.

Table 1 Examples 5 to 10 CIJ(OAC)2 Reactions were carried out under the same conditions as in Example 1 except that various copper catalysts listed in Table 2 were used instead of H2C. The results are shown in Table 2.

Table 2 Examples 10 to 13 Reactions were carried out under the same conditions as in Example 1, except that the same molar amounts of the various media listed in Table 3 were used instead of DMF. The results are shown in Table 3.

Table 3 Patent applicant Teijin Yuka Co., Ltd.
Company representative Patent attorney 1)
June 1986, June 10th, 1985

Claims (1)

[Claims] 1. A method for producing 3,4'-dichlorodiphenyl ether, which comprises reacting a sodium metal salt of p-chlorophenol and m-dichlorobenzene in the presence of an organic polar medium and a copper catalyst. 2. The method according to item 1, wherein the organic polar medium is an aprotic organic polar medium.