SU1442520A1 - Method of producing asymmetrical diarylsulfides - Google Patents

Abstract

The invention relates to substituted sulfides, in particular, a process for the preparation of asymmetric diarylsulfides, which can be used in various organic syntheses. The chain is a product of target substances and ensuring the universality of the process. The latter is carried out by the reaction of diphenylsulfide and aryl bromide in the liquid phase while bubbling H, S at a rate of 1.5-2 l / h at 125-230 C. The method allows to increase the yield of target products from 44-76 to 51-84% and use in the synthesis not only bromophenols and bromonaphthols, but also other bromo-aromatic compounds, in particular 1-bromonaphthalene and netol-4-bromo that do not react with thiophene by a known method. S (L with

Description

The invention relates to a method for producing asymmetric diarylsulfides, which are used in the synthesis of biologically active substances, as well as in various organic syntheses.

The purpose of the invention is to increase the versatility of the process and increase the yields of target products by reacting aryl bromide with diphenyldisulfide while sparging hydrogen sulfide at a rate of 1.5-2.0 l / h and a temperature of 125-230 ° C.

Example 1. Synthesis of phenyl 4-oxyphenyl) sulfide.

A mixture consisting of 4.6 g (0.024 mol) of 4-bromophenol and 2.6 g (0.012 mol) of diphenyl disulfide is heated to 220 ° C with stirring and sparging and hydrogen sulfide at a rate of 2.0 l / h. The reaction starts immediately or after a certain induction period and lasts for 6 hours. During the distillation of the reaction mixture in vacuum, 3.19 g (66.3% of the original and 77% of the reacted diphenyl disulfide) phenyl (4-hydroxy-1) sulfide with bp 158-1b2 ° С (2 mmHg).

Example 2. Under the conditions described in Example 1, but with a hydrogen sulfide sparging rate of 1.5 l / h, phenyl (4-hydroxyphenyl) sulfide was obtained in a yield of 65% for the reacted diphenyl disulfide.

Example 3. Under the conditions described in Example 1, but within 5 hours, the phenyl (4-hydroxyphenyl) sulfide was obtained in 69% yield.

Example 4. Synthesis of Fe1Sl (2-oxyphenyl) sulfide.

A mixture consisting of 17.9 g (0.1 mol) of Z-bromophenol and 10.9 g (0.05 mol) of diphenyl disulfide is heated to 205 ° C with stirring and bubbling of hydrogen sulfide at a rate of 2 l / h. After a certain The i-duction period (about 30 min) begins the intense hydrogen bromide, which ceases after 8 hours. When the reaction mixture was distilled in vacuum, 12.1 g (60.1% of the original and 70% of the reacted diphenyl disulfide) were released ( 2-oxyphenyl) sulfide with so Kip. 120-123 C (mm Hg).

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Example 5. Analogously to the conditions of example 4, but with a sparging rate of hydrogen sulfide of 1.5 l / h, phenyl (2-hydroxyphenyl) sulfide was obtained with a yield of 52% to the initial and 64% to the reacted diphenyl disulfide.

Example 6. Synthesis of phenyl f1- - (2-hydroxynaphthyl) sulfide.

A mixture of 4.46 g (0.02 mol) of 1-bromo-, -2-naphthol, 2.18 g (0.01 mol) of diphenyl disulfide in 3 ml of DCT is heated with stirring and bubbling of hydrogen sulfide at a rate of 2 l / hr. Immediately, the rapid release of hydrogen bromide begins, which ceases after 5 hours. During the distillation of the reaction mixture in vacuo, phenyl 1- (2-hydroxynaphthyl)} sulfide with boiling point is ignited. 205-210 ° C (1 mm Hg), so pl. 58 60 s. Yield 59.1% calculated on the basis of taken and 84% on the reacted diphenyl disulfide.

Example 7. Similar to the conditions of Example 5, but without the solvent, phenyl (1- (2-hydroxyaphthyl) sulfide) was obtained in 58% yield, calculated on the reaction of diphenyl disulfide and 81.3% on the reaction of diphenyl disulfide.

Example 8, Synthesis of phenyl (1- -naphthyl) sulfide.

A mixture consisting of 12.3 g (0.06 mol) of 1-bromonaphthalene and 6.6 g (0.03 mol) of diphenyldisulfide is heated with stirring and bubbling of the sulfur feed with a rate of 5 L / h. The reaction starts at 230 ° C and continues at this temperature for 7 hours. During the distillation of the reaction mixture in vacuo, 9.7 g of phenyl (1-naphthyl) sulfide with a boiling point are isolated. 161-162 ° C (1 mm Hg). Yield 70% for taken and 73.9% for reacted diphenyl disulfide.

Example 9. Synthesis of phenyl (4--ethoxyphenyl) sulfide.

A mixture consisting of 20.1 g (0.1 mol) of P-bromphenetol and 10.9 g (0.05 mol) of diphenyl sulfide is heated with stirring and bubbling of hydrogen sulfide at a rate of 2 l / h to 230 ° C and at this temperature is held for 10-12 hours until complete elimination of hydrogen bromide. During the distillation of the reaction mixture in vacuo, phenyl (4-α-ethoxyphenyl) sulfide is separated off, t, bp. 170172 ° C (3 mm Hg). The yield is 44% calculated on the taken and 51.3% calculated on the diphenyl disulfide entered into the reaction.

Thus, the proposed method is more versatile than the known one, since it allows not only bromophenols and bromo-naptoles to be involved in the interaction with diphenyl disulfide, but also various bromo-naphthalene and 4-bromophenol, which by a known method does not react with thiophenol. In addition, according to the proposed method, the target

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Claims (1)

products are obtained with high yields of 51-84% against 44-76%. Invention Formula 5 A method for producing asymmetric diarylsulfides by reacting an aromatic tio compound with an aryl bromide in the liquid phase when heated, characterized by 10 by the fact that, in order to increase the universality of the process and the yields of the target products, diphenyl disulfide is used as the aromatic tio-compound and the process is carried out at 15 bubbling of hydrogen sulfide at a rate of 1.5-2.0 l / h and a temperature of 125-230 ° C.