SU1766913A1 - Method of 4-(adamanthyl-1)-benzenesulfochloride synthesis - Google Patents

Abstract

The essence of the invention: the product is 4- (adamantyl-1) -benzenesulfonate. B and) CieHi & CIOaS, so pl. 177-178.5 ° C, yield 86 9- 91.7%. Reagent 1: benzene. Reagent 2: Bromo-Damantane. Reagent 3: Chlorosulfonic acid. Reaction conditions: molar ratio of reagents respectively 1: 1: (3-b) and temperature (-I5) -0 ° C.

Description

Yo

The invention relates to a sulfur-containing derivative of adamantane, namely, a new method of producing 4- (adamantyl-1) -benzenesulfonyl chloride, which has not been described previously in the literature, which can be used as an intermediate in the synthesis of practically important compounds of inclusion 1, as well as a convenient synthon in chemistry anticancer drugs 2.

Among all possible methods for producing alkyl aryl sulfochlorides in the practice of organic synthesis, preference is given to the method of directly introducing the sulfochloride group into the aromatic nucleus by the effect of an excess of chlorosulfonic acid on the corresponding alkyl benzene 3.

If you follow the generally accepted scheme, then to synthesize the desired 4- (adamantyl-1) -benzenesulfonyl chloride, you need to take 1-phenyladamantane, which is obtained by 4 interaction of benzene with bromadomantane in the presence of a ferric chloride - iron trichloride. The catalyst is also pre-sublimated. the reaction is required 16 hours. After treating the reaction mixture with a solution of HCl, extraction with benzene, the organic extracts are dried with CaCl2, the solvent is distilled off, the residue is crystallized, and ruled from methanol under cooling with a mixture of dry ice and trichlorethylene, followed by sublimation under high vacuum at 60 ° C. Output 80% /

The disadvantages of this method include the duration of the process, the use of a large excess of benzene, special preparation of the catalyst, and the complicated procedure for the isolation of the product.

 ABOUT

 about

 cho

V

th

Thus, the scheme for the synthesis of 4- (adamantyl-1) -benzenesulfonyl chloride within the framework of the existing methods should consist of two stages: the interaction of bromide manganese with benzene and the sulfochlorination of the obtained 1-phenyladamantane.

The purpose of the invention is the development of a new technological method for the production of 4- (adamantyl-1) benzenesulfonorcin, which is not described in literature.

This goal is achieved by treating chlorosulfonic acid with a mixture of benzene and 1-bromadomantane in chloroform or without it at 0 ° C. The preparative process is as follows. Chlorosulfonic acid was added to a mixture of benzene and bromadomamantane in chloroform cooled to (-15 ° C), keeping the temperature no higher than 0 ° C. The molar ratio of benzene: bromadamantane: chlorosulfonic acid is 1: 1: (3-5). After completion of the reaction (TLC control), the mixture is treated and 4- (adamantyl-1) -benzenesulfonyl chloride is obtained in a yield of 87-92% (for benzene).

The advantages of the method are the simplicity of the apparatus, single stage, ease of carrying out the process, availability of starting materials. Due to these characteristics, this method can be widely used for the synthesis of various adamantyl-containing substances. In addition, these qualities allow us to develop a cheap technological scheme for the synthesis of the target product.

The invention is illustrated by the following examples.

Example 1. To a mixture of 35.0 g (0.162 mol) of 1-bromoamantane and 12.65 g (0.162 mol) of benzene in 15 ml, cooled to –15 ° C, 35 ml (0.49 mol) of chlorosulfonic acid are added dropwise, maintaining temperature not higher than 0 ° C. After adding the total amount of acid, stirring is continued for 1 hour at 0 ° C, then the mixture is allowed to spontaneously warm to room temperature. The reaction is monitored by the TCX method (Silufol UV-254, Petr. Effect: effect, 6: 1 , UV radiation). After completion of the reaction, the mixture is poured onto crushed ice (200 g), the chloroform layer is separated, the aqueous is extracted (3 x 50 ml), the organic layers are combined, dried with Na2SO4, the solvent is distilled off and 46.2 g (91.7%) of product are obtained , after purification by chromatography (Silicagel 40/100, n-hexane), a white crystalline solid is isolated. square 177-178,5 ° C.

PMR spectrum, 250 MHz, CDCIa, d, ppm: 1.80-2.14 m. (15H, CioHis), 7.60 d. (2H, Hz, 5 arom.), 7.98 d. ( 2H, H2.6 arom.) 9.0 Hz.

Found,%: C 61.57; H6.10; CI 11.52; S 10.30.

Ci6Hi9CI02S

Calculated,%: C, 61.82; H 6.16; CI 11.41; S 10.32,

The yield of 4- (adamantyl-1) -benzenesulfonyl chloride is 91.7% ka benzene.

Example 2. Under the conditions of Example 1, 35.0 g (0.162 mol) of 1-bromoadamantane, 12.65 g (0.162 mol) of benzene, and 60 ml (0.74 mol) of HFCC 43.8 g (86.9%) 4- (adamantyl-1) -benzenesulfonyl chloride.

Claims (1)

The method of obtaining 4- (adamantyl-1) -benzene sulfonyl chloride, characterized in that the bromadomantane is reacted with benzene and chlorosulfonic acid at a molar ratio of 1: 1: 3.5, respectively, and temperature (-15) - 0 ° C