JPH0429957A - Production of biaryl derivative - Google Patents

Abstract

PURPOSE:To obtain the title compound readily and in high yield, by using pyridine as a solvent and ligand, and dechlorinating and coupling a chlorobenzene derivative in the presence of triphenylphosphine, an anhydrous nickel compound and a reducing metal. CONSTITUTION:A chlorobenzene derivative shown by the formula (R is lower alkoxycarbonyl, aldehyde, nitrile or lower alkylcarbonyl) is dechlorinated and coupled in the presence of an anhydrous nickel compound such as anhydrous nickel chloride, a reducing metal such as zinc powder and preferably twice as much triphenylphosphine as the anhydrous nickel compound in a dry pyridine at 0-250 deg.C, preferably at room temperature-100 deg.C to give the objective compound such as 1,1'-biphenyl-4,4'-dicarboxylic acid dimethyl ester, useful as a copolymerizable component for heat-resistant polymer, an improver for polyethylene terephthalate or a raw material for liquid crystal polymer, by a simple operation industrially, advantageously and in high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION (Object of the Invention) The present invention provides an industrial method for producing biaryl derivatives.

(Industrial Application Field) The present invention relates to a method for producing a biphenyl derivative useful as a copolymer component of a heat-resistant polymer, a modifier for polyethylene terephthalate, or a raw material for a liquid crystal polymer.

(Prior Art) As a method for producing a diaryl derivative by dehalogenation coupling of an aryl halide, a method using a nickel phosphine complex as a catalyst has been known for a long time, as described by CM, Iyoda et al., Bull.

Chem, Soc, Jpn, 63.80 (199
0):].

Also, in recent years, a method has been developed that does not require separate preparation of a nickel phosphine complex. That is, a method has been proposed in which aryl halides are coupled in an aprotic polar solvent such as dimethylformamide or dimethylacetamide in the presence of a metal such as zinc or magnesium using an anhydrous nickel compound as a catalyst [J , Org, Ch.
em, , 51.2627 (1986), Japanese Patent Publication No. 5
No. 6-40615, published by Kosho]. In this case, large amounts of aromatic bidentate compounds such as phosphines, 2'2'-dipyridyl or phenanthroline had to be used as ligands for the nickel catalyst.

(Problems to be Solved by the Invention) Although the above-mentioned method has high reactivity, the phenylaryl derivative derived from triphenylphosphine is produced as a by-product and reduces the yield. Moreover, triphenylphosphine is expensive and requires four times the amount of the nickel compound used as a ligand.

Therefore, the present invention provides a method for producing biaryl derivatives in high yield by reducing the amount of triphenylphosphine used and suppressing the by-product of phenylaryl derivatives.

(Means for Solving the Problems) In order to solve the above problems, the present inventor has conducted research over many years on an industrial method for producing biaryl derivatives. The inventors recognized that the above problems could be solved and completed the present invention.

That is, the present invention provides a method for producing a biaryl derivative by dechlorocoupling a chlorobenzene derivative, which is characterized in that the reaction is carried out in pyridine in the presence of triphenylphosphine, an anhydrous nylacel compound, and a reducing metal. It's a method.

The chlorobenzene derivative used is (in the formula, R is
Lower alkoxycarbonyl group, aldehyde group, 2) IJ
represents a lower alkylcarbonyl group. ) is a chlorobenzene derivative represented by For example, 4-substituted or 3-substituted 4-chlorobenzene derivatives such as methyl 4-chlorobenzoate, 4-chlorobenzaldehyde, 4-chlorobenzonitrile, and 4-chloroacetophenone;
A 2-substituted product or the like may also be used.

In addition, as the anhydrous nickel compound, organic or inorganic nickel compounds such as /'% nickel halogenide, nickel carbonate, nickel acetate compounds, etc. can be used, but among them, anhydrous dimethyl chloride, anhydrous nickel bromide, etc. The use of anhydrous nickel compound is preferred (1
It can be used in an amount of o, ooi mole or more, preferably 0.005 to 0.1 mole, per mole of the chlorobenzene derivative.

Further, as the reducing metal, zinc, manganese, and magnesium can be used, and among them, finely powdered zinc is preferable. The amount used is preferably equimolar or more. Further, the reaction temperature is preferably room temperature to 100°C, especially from 0 to 250°C.

Furthermore, it is preferable to use dried pyridine in the reaction. However, although the method of the present invention requires triphenylphosphine as a ligand for the nickel catalyst, the amount used can be twice that of nickel, and there is no need to separately prepare a nickel phosphine complex. .

(Effects of the Invention) In the method of the present invention, since the pyridine used acts as a solvent and a ligand, the amount of triphenylphosphine, which was conventionally required four times as much as in the case of a nickel compound, can be reduced to twice the amount. As a result, the by-product of phenylaryl derivatives derived from triphenylphosphine is extremely suppressed, and biaryl derivatives can be produced with high yield and simple operation, making this method highly valuable as an industrial production method for biaryl derivatives. .

(Example) The present invention will be specifically explained below using Examples.

Example 1 (1,1"-biff to 11.-4,4'-deer lb bomb
Synthesis of dimethic acid) b) In a 100 ml flask under nitrogen atmosphere, 50 ml of dry pyridine 8.53 g (0.05 mol) of methyl 1.4-chlorobenzoate, 0.32 g of anhydrous dimethyl chloride (0,()025 mole), triphenylphosphine 1.31g (0,005 mole), zinc powder 4
90 g (0,075 mol) was added and stirred at room temperature for 20 minutes. The mixture was heated in an oil bath and reacted at 85°C for 7 hours. When the reaction solution was analyzed by gas chromatography, it was found that the starting material methyl 4-chlorobenzoate had completely disappeared, and 3% of methyl benzoate, 1% of methyl 1,1゜biphenyl-4-carboxylate, and 1% of the target product were found. ,1゛-biphenyl-4,4
It was found that dimethyl dicarboxylate was produced at a rate of 96%.The reaction solution was cooled to room temperature, extracted with chloroform, worked up, concentrated, and filtered to obtain a dimethyl dicarboxylate with a melting point of 216-218°C. 1.1゛-biphenyl-4,4°
-6.21 g of dimethyl dicarboxylate (yield 91.9%)
)Obtained.

Example 2 (Synthesis of 4,4°-diformylbiphenyl) The same procedure as in Example 1 was repeated except that 7.03 g of 4-chlorobenzaldehyde was used in place of methyl 4-chlorobenzoate. As a result, 4.86 g (yield 92.4%) of 4,4°-diformyl biphenyl was obtained. By recrystallization, melting point 145-14
3.88g of 4°4”-diformyl biphenyl at 7℃
(yield 73.8%).

Comparative Example 1 (Synthesis of dimethyl 1,1°-pipheniIt-4,4"-dicarboxylate) In a 100 ml flask under nitrogen atmosphere,
50 ml of dry dimethylacetamide 8.53 g (0,05 mol) of methyl 1,4-chlorobenzoate, 0.32 g (0,0025 mol) of anhydrous nickel chloride, 2.75 g (0,0105 mol) of triphenylphosphine, 4 zinc powder .90g (0,075 mol) was added and stirred for 20 minutes. The mixture was heated in an oil bath and reacted at 85° C. for 3 hours. Analysis of the reaction solution by gas chromatography revealed that methyl benzoate was 4%, biphenyl was 1%, methyl 1.1'-biphenyl-4-carboxylate was 5%, and 1.1'-
87% dimethyl biphenyl-4°4°-dicarboxylate
, and other high boiling point substances were produced at a rate of 3%. After cooling to room temperature, extraction with chloroform, post-treatment, concentration, and filtration gave 5.50 g (yield: 81.5%) of dimethyl 1.1°-biphenyl-4°4°-dicarboxylate. .

In addition, the above reaction is J, ○rg, Chem, 51°26
27 (1990).

Comparative Example 2 [Synthesis of dimethyl 1,1'-biphenyl-4,4''-dicarboxylate] Triphenylphosphine of Comparative Example 1 2.7
5 g (0,0105 mol) was added to the same amount of 1.31 as in Example 1.
g (0,005 mol) and reacted in dimethylacetamide for 5 hours in the same manner, but the reaction was not completed. When the reaction solution was analyzed by gas chromatography,
73% of the raw material methyl 4-chlorobenzoate remains, and 1
, 1''-biphenyl 4.4°-dimethyl dicarboxylate was produced in an amount of only 24%.

Claims (1)

[Scope of Claims] 1) A method for producing a biaryl derivative by dechlorocoupling a chlorobenzene derivative, which is characterized in that the biaryl derivative is reacted in pyridine in the presence of triphenylphosphine, an anhydrous nickel compound, and a reducing metal. manufacturing method. 2) A method for producing a biaryl derivative according to claim 1, characterized in that triphenylphosphine is used in twice the amount of the anhydrous nickel compound.