SU368211A1 - LIBRARY fM. Cl. From 07c 13 / 16UDK 547.592-125: 541.63 (088.8) - Google Patents

Description

one

The invention relates to the synthesis of diaryl cyclop raffins, which can be used as model compounds and intermediates for the preparation of high molecular compounds.

A known method for the preparation of 1,1-diarylcyclohexanes is that phenol OR anisole is reacted with cyclohexanone at -50 ° C in the presence of a complex of BP3-IsP04 and the molar ratio of reactants to catalyst is 6: 1: 1. The yield of 1,1-bis- (4-methoxyphenyl) -diclohexane is 30% of theory.

In order to increase the yield of the target product according to the proposed method, phenol or aljylphenyl ethers are reacted with farylclohexenes in the presence of the catalyst complex VRh-HzPO4, and phenol or alkylphenyl ethers, 1-arylcyclohexes and the catalyst are preferably taken in a molar ratio of 3 - 7: 1: , 2 -0.5.

The method is simple, single-stage, does not require complicated equipment and allows to obtain high-purity 1,1-diarylcyclohexanes with yields of 86-91% of theory.

The proposed method is carried out as follows.

In a three-necked flask-reactor equipped with a stirrer, thermometer, and dropping funnel, the VRZ – H3PO4 complex is preliminarily prepared by saturating the anhydrous phosphoric acid with boron fluoride. To the resulting complex is added phenol or

alkylphenyl ether and then 1-arylcyclohexene is added over 1 hour with stirring at a predetermined temperature from the addition funnel. In the case of the use of crystalline olefins, a solution of the latter is added in an equal volume of carbon tetrachloride. The reaction mixture is further stirred at the same temperature for 3 to 4 hours, diluted with water, the organic layer is separated, and the aqueous layer is extracted twice.

in small portions of ether, the ether extracts are washed successively with water, 10% soda solution, water, and dried over CaClz. The ether and unreacted reagents are distilled off at atmospheric pressure, and the residue is distilled under vacuum or recrystallized. The structure of 1,1-diarylcyclohexanes is confirmed by the data of IR and NMR spectrocopy.

Example 1. 1-Phenyl-1- (p-hydroxyphenyl) -cyclohexane.

To a mixture of 47.0 g (0.5 mol) of phenol and 5.3 g (0.03 mol) of the complex VRZ-NzRO4, heated to 55-60 ° C, 15.8 g (0, 1 mole) 1-fekylcyclohexene, after

which mix the mixture for another 3 hours at that

same temperature and process as indicated in the general .methodika. Obtain 22.4 g of the desired product IB as colorless needles, so pl. 125.5 - 12b ° С (from a mixture of actane-toluene). Output 89% of theory.

Found,%: C 85.80; H 7.97. Cigaoo

Calculated,%: C 85.67; H 7.99.

Example 2. 1-Phenyl-1 - (/ g-methoxyphenyl) cyclohexane.

To a mixture of 54.0 g (0.5 mol) of anisole and 5.3 g (0.03 mol) of the complex VRZ-HzP04 heated to 5.5-60 ° C, 15.8 g (0, 1 mol of bphenylschiclohexene, after which the mixture is stirred for another 4 hours at the same temperature and treated according to the general procedure.This gives 23.9 g of the desired product as a colorless viscous liquid, ie, kilo 189-190 ° C / 3 mm Hg Art., ng 1.5867; df 1.0861. Yield 90% of theory.

Found,%: C 85.60; H 8.29. MRo 82.26.

Ci9H220

Calculated,%: C 85.67; H 8.32. MRo 82.17.

Approx. 3. 1- (w-Chlorophenyl) -1 - ((g-oxyphenyl) -cy1K Lohexane.

To a mixture of 23.5 g (0.25 mol) of phenol and 4.5 g (0.025 mol) of the complex VRZ-NzR04 heated

to 65-70 ° C., 9.65 g (0.05 mol) of 1- (l-chlorophenyl) - cyclohexene is added over 1 hour, after which the mixture is stirred for 4 hours more at the same temperature and treated in the usual way . Obtain 13.1 g of the desired product in 1 kind of colorless needles, so pl. 93.5-94 ° C (from petroleum ether). Found,%: C 75.51; H 6.70; C1 12.44.

Cigigigl

Calculated,%: C 75.38; H 6.68; C1 12.36.

Various phenols and alkylphenyl ethers can be used for the reaction, as well as other 1-arylcyclohexenes; the corresponding 1,1-diarylcyclohexanes will be obtained.

Subject And s about b-e te "and

Claims (2)

1. A process for the preparation of 1,1-diarylcycloxanes, characterized in that, in order to increase the yield of the target product, phenol or alkylphenyl esters are reacted with 1-aryl-1-cyclohexenes in the presence of a catalyst complex BPZ-HzP04. 2. A method according to claim 1, characterized in that the phenol or alkylphenyl ethers, 1-arylcyclohexene and the catalyst are taken in a matrix ratio of 3 to 7: 1: 0.2 - 0.5.