SU572449A1 - Method for preparing asymmetric ethers of hemglycols - Google Patents

Description

The invention relates to a new process for the preparation of phenylalkyl or phenylaryl esters of gemglycols that are not described in the literature, which can be found in agriculture. A method is known for producing phenylalkyl or phenylaryl methylene glycol ethers by reacting α-chloromethylphenyl ethers with alcohols or phenols in a water-free adetonic medium at the boiling point: solvent 1. k-d not readily available, which limits the production of: non-metric hemglycol ethers. In addition, there is a low yield of the target product due to the formation of side symmetric ethers. The proposed method and the pursuit of asymmetric hemglycol esters of formula I The target product is isolated by known methods, for example, by distillation in vacuum. The yield of the final product reaches 70% of theory. This method allows to obtain unsymmetrical phenylalkyl or phenylaryl esters of hemglycols of variational R, R, R in formula I and oxosoydipy, as a result of sequential operations in one system, without processing AND isolation of intermediate products. The proposed method is illustrated by the lower pp iB units and pr and meperam. Example 1. Obtaining n-butyl 2-chlorophenyl ether 1,1- | Cyclohecoylideneglycol. In a three-neck reaction flask equipped with a mechanical stirrer, a dropping funnel, a thermometer and water separation under reflux were placed 26 g (0.2 gm) of 2-chlorophenol, 150 ml of benzene and 60% aqueous solution of caustic potash in 20 g The mixture, with vigorous stirring, is heated under conditions of benzene condensation until the evolution of water ceases. Reaction lasts for 3 hours. After separation of 11 ml of water, the main part of benzene is distilled off, and to the resulting anhydrous crystalline potassium 2-chlorophenol, 50 ml (0.5 gm) of cyclohexaHiHa are added and the mixture is stirred for 1 hour at 90 ° C until complete dissolution 2-chlorofol “al ta -kali. 46 g (0.26 gm) of butyl iodide are added to the resulting mass and the mixture is not stirred at 80-90 ° C for 3 hours, followed by separation as a precipitate, potassium iodide salt, which is then washed on the filter with cyclohexanone. Benzene and cyclohexanone are distilled off from the filtrate using a water-jet pump, and the residue in an amount of 100 g is subjected to vacuum (mm Hg) distillation. In tab. 1 are shown the phyico-chemical coefficients of the obtained ester. T a b l II c a 1

The results of the microelement analysis. Paydeno. %: C, 67.80; 67.82; H 8, 20; 8.26; C1 12.60; 12.55.

Ci4H2l02Cli.

Calculated,%: C 67.96; H 8.14; C1 12.57.

The identity of the obtained target product is established chromatographically. The analysis was carried out on an LCM7A chromatograph. The length of the column is 1 m. Polyethylene glycol-4000 applied on a kirnich INZ-600 in the amount of 5% of the 190A detector was used as the liquid phase. The yield of the target product per 2-chlorophenol is 35 g (62%), the selectivity of the process is 100%.

Example 2. Obtaining benzyl 2-chlorophenyl ether 1,1-cyclohexylideneglycol. In the reaction flask of the installation described above, 26 g (0.2 gm) of 2-chlorophenol, 150 ml of benzene and 12 g (0.2 g-m) of dry and non-powdery caustic potash are placed. The mixture is intensively mixed without heating

for 1 h (20-45 °). The transfer is then continued with heating under conditions of benzene condensation until the emission stops.

water. The reaction lasts 2 hours and during this time 4 ml of water are released. Then the main part of benzene is distilled off and 70 g (0.7 gm) of cyclohexanone are added to the anhydrous potassium 2-chlorophenol potassium obtained. 26 g (0.2 gm) of benzyl chloride was added dropwise to the resulting liquid and the mixture was stirred at 80-90 ° C for 3 hours. 250 ml of benzene was added to the cooled reaction mixture and the mixture was stirred with water while stirring.

The upper layer is separated from the lower aqueous layer, and which is extracted once with benzene and combined with the upper layer. The organic layer is washed twice with a 5% aqueous solution of potassium hydroxide and once

water, then dried over anhydrous Na2S04. After drying and distilling off the solvent, the residue in the amount of 97 g is distilled under vacuum. In tab. 2 shows the physico-chemical constants of the resulting ether.

table 2

The results of the trace element analysis: Found,%: C 72.00; 71.98; H 6.70; 6.75; C1 11.07; 11.03.

Ci9H2lO2Cli.

Calculated,%: C 72.04; H 6.63; C1 11.22.

The identity of the obtained target product is established chromatographically. The analysis was carried out on an LCM7A chromatograph. Under the above conditions, the yield of the target ester based on o-chlorophenol is 38 g (60%).

The yield and physicochemical constants of asymmetric hemglycol ethers are presented in Table. 3

Claims (1)

1. Patent of England No. 771064, cl. C 2C, pub. in 1957