SU1735263A1 - Method of 1-phenyl-1-chloro-3-methoxypropane synthesis - Google Patents

Abstract

The invention relates to ethers, in particular the preparation of 1-phenyl-1-chloro-3-methoxypropane, used in organic synthesis of fragrances. The goal is to increase the yield of the target product and simplify the process. Synthesis is carried out by the reaction of styrene with a-chloromethyl ether in the presence of a catalyst ZnCb and triztil-benzylammonium (molar ratio (1–2): 1) at their molar ratio of 1: (1-1.2) :( 4-6) and room temperature. These conditions increase the yield of the target product from 75 to 92-93% with the exception of the final treatment of the reaction mass and the use of a solvent. 1 tab

Description

The invention relates to organic chemistry, and specifically to a method for producing 1-phenyl-1-chloro-3-methoxypropane of the formula

1 gSN-CH2-SNgOSN5

 h

which can be used in organic synthesis, in particular, as an intermediate product for the synthesis of fragrance 1-phenyl-3-methoxyprop-1-ene.

The closest in technical essence and the achieved result to the proposed is a method of obtaining 1-phenyl-1-chloro-3-methoxypropane from styrene and a-chloromethyl methyl ethyl in the presence of anhydrous zinc chloride as a catalyst in a ratio of 1: 1: 0.009 in a CCU medium as a solvent, for 4 h, with stirring and cooling (15-20 ° C). After treating the mixture with water

and a 3% sodium hydroxide solution, the target product is isolated in 75% yield.

The disadvantages of this method are the relatively low yield of the target product, the use of a solvent, the need for treatment and, therefore, the presence of large quantities of wastewater.

The purpose of the invention is to increase the yield of the target product and simplify the process.

This goal is achieved in that according to the method for producing 1-phenyl-1-chloro-3-methoxypropane by reacting styrene and a-chloromethyl methyl ether at room temperature in the presence of zinc chloride as a catalyst in a mixture with triethyl benzylammonium chloride at a molar ratio of 1.0: 1.0-2.0 and molar ratio of styrene: a-chloromethyl methyl ether equal to 1.0: 1.0-2.0: 4, respectively.

The difference of this method is that the process is carried out in the presence of chloride

Yo

VI

WITH

ate

N0

ON GJ

triethylbenzylammonium with a molar ratio of zinc chloride: triethylbenzylammonium chloride of 1.0: 1.0-2.0 and a molar ratio of styrene; a-chloromethyl methyl ether; catalyst 1.0: 1.0-1.2: 4.

Example 1. Preparation of 1-phenyl-1-chloro-3-methoxypropane.

To a mixture of 10.4 g (0.1 mol) of styrene, 0.027 g (0.0002 mol) of ZnCl2 and 0.046 g (0.0002 mol) of TEBAH (ratio of ZnCl2: T35AX 1: 1) was added dropwise 8.1 g (0, 1 mol) og-chloromethyl methyl ether at such a rate that the temperature of the reaction mixture does not rise above 20 ° C. At the same temperature, the mixture is stirred for 4 hours and the reaction mixture is distilled under vacuum. This gives 17.2 g (93%) of 1-phenyl-1-chloro-3-methoxy-propane, boil. 104-105 ° / 8 mm, po 20 20 1,5176, d420 1; 0786.

Spectrum PMR, d (in C C C); 1.97-2.38 m- (2H, CH2), 3.26 s (1H, OCHz). 3.3-3.63 m (2H, OCH2), 5.05 t (1H, CHCI, J 8 Hz), 7.4 s (5H.

SbH5).

Found,%: C 64.90; H 7.01; CI 19.31

SyuN1ZOS1

Calculated.%: C 65.04, H 7.04; CI 19.24

Purity on GLC 100%.

Example 2. Analogously to example 1, with the only difference that they take 10.4 g (0.1 mol) of styrene, 0.027 g (0.0002 mol) ZnCl2, 0.092 g (0.0004 mol) TEBAH (ratio ZnCl2: T35AX 1: 2), 8.1 g (0.1 mol) of a-chloromethyl ether and get 17 g (92%) of 1-phenyl-1-chloro-3-methoxypropane with mp. 104-105 ° / 8 mm, according to 20 1.5175.

Purity on GLC 100%.

Example 3. Analogously to example 1, with the only difference that they take 5.2 g (0.05 mol) of styrene, 0.0135 g (0.0001 mol) of ZnCl2, 0.0345 g (0.00015 mol) of TEBAH ( the ratio of ZnCl2: TEBACH 1: 1.5) 4.05 g (0.05 mol) a. -chloromethyl methyl ether and receive 17.1 g (92.5%) of 1-phenyl-1-chloro-3-methoxypropane with bp. 102-103 ° / 7 mm, 20 ~ 1,5178.

Purity on GLC 100%.

Example 4. Under the conditions of Example 1, with the only difference being that they take 10.4 g (0.1 mol) of tyrol, 0.027 g (0.0002 mol) of ZnCl2, 0.046 g 50; 1.0-1.2.

There is a mutual interaction between the 40th air and the chlorine tour, from the increase it is simpler 45

Mr. Soo Chlormet

(0.0002 mol) TEBAH (ratio of ZnCl2: T3BAX 1: 1) and 9.7 g (0.12 mol) of a-chloromethyl methyl ether, get 17.2 g (93%) of 1-phenyl-1-chloro-3 -methoxypropane with

bp 97-98 ° / 5 mm, according to 20 1,5174, GLC purity 100%. Test cases confirming the stated limits of the ratio of reagents and process temperature are presented in the table.

As can be seen from the table, both an increase and a decrease in the amount of catalyst, as well as a change in the ratio of the catalyst leads to a decrease in the yield of the target product, a decrease in temperature below 20 ° C (15 ° C) and an increase above 20 ° C (25 ° C) also leads to to a decrease in the yield of the target product (80 and 87 instead of 92-93%).

The use of the proposed method for the preparation of 1-phenyl-1-chloro-3-methoxypropane as compared with the known ones allows to increase the yield of the target product to 92-93% instead of 75%, and also provides

simplification of the process technology, which consists in excluding the final treatment of the reaction mixture and the use of undesirable solvent in the technology.

Claims (1)

The invention The method of obtaining 1-phenyl-1-chloro-3-methoxypropane formula 35 -S СК-СН2-ВН7ОСНз С1 reacting styrene with cr-chloromethyl ether in the presence of a catalyst — zinc chloride at room temperature, characterized by that. that, in order to increase the yield of the target product and simplify the process, the latter is carried out in the presence of triethylbenzylammonium chloride at a molar ratio of the latter and zinc chloride of 1.0-2.0: 1.0 and mol p; 1, 0-1.2. the nominal ratio of the sterolization catalyst: a- chloromethyl ether 1,0: 4- 10 3-6-10 3: