SU1004365A1

SU1004365A1 - Process for producing naphthalenethioles

Info

Publication number: SU1004365A1
Application number: SU813342424A
Authority: SU
Inventors: Степан Васильевич Савчишин; Владимир Борисович Голубко; Валентина Васильевна Руденко; Леонид Иванович Рассыльный; Александр Анатольевич Писклов; Виктор Лаврентьевич Пистуненко; Лидия Сергеевна Свистула; Татьяна Владимировна Курдюмова; Владимир Владимирович Резниченко; Тамара Николаевна Подрезова; Людмила Владимировна Галич
Original assignee: Предприятие П/Я В-8611
Priority date: 1981-07-16
Filing date: 1981-07-16
Publication date: 1983-03-15

Description

(Sk) СПОСОБ ПОЛУЧЕНИЯ НАФТАЛИНТИОЛОВ(Sk) METHOD FOR PRODUCING NAPHTHALINTHIOLS

1. one.

Изобретение относитс к усовер- шенствованному способу получени нафталинтиолое формулы IThis invention relates to an improved process for the preparation of naphthalene thiol of formula I

RR

(I)(I)

Где R - водород или хлор, которые наход т применение в производстве тиоиндигоидных красите- Q лей.Where R is hydrogen or chlorine, which are used in the manufacture of thioindigoid dyes Q.

Известен способ получени 2-нафталинтиола , взаимодействием хлорбензольного раствора 2-нафталинсульфохлорида и 20-25 -ного раствора сер-15 ной кислоты с цинковой пылью при 7075 С и последующим нагреванием при 9S 100°C. Выход целевого продукта 92% 1.A known method for the preparation of 2-naphthalentiol, the interaction of a chlorobenzene solution of 2-naphthalenesulfonyl chloride and a 20-25 solution of sulfuric acid with zinc dust at 7075 ° C and subsequent heating at 9 ° C is 100 ° C. The yield of the target product is 92% 1.

Известен способ получени 1-хлор- 20 -8-нафталинтиола, заключающийс во взаимодействии смеси бО-б5 -ной серной кислоты и хлорбензольной суспензий 1-хлор-8-нафталинсульфохлоридаA method of producing 1-chloro-20 -8-naphthalentiol is known, which consists in the interaction of a mixture of sulfuric acid BS-5 and chlorobenzene suspensions of 1-chloro-8-naphthalenesulfonyl chloride

с цинком при 90-96С и последующем нагревании. Выход целевого продукта 73,5Х 2.with zinc at 90-96C and subsequent heating. The yield of the target product 73,5X 2.

Недостатком указанных способов где используетс обработка смеси .сульфохлорида с минеральной кислотой и цинком, вл етс трудность регулировани температуры при подаче цинка , что сказываетс на стабильности выхода целевого продукта.The disadvantage of these methods, where the treatment of a mixture of sulfochloride with mineral acid and zinc is used, is the difficulty of controlling the temperature when feeding zinc, which affects the stability of the yield of the target product.

Наиболее близким к предлагаемому вл етс способ получени одного из прерставителей нафталинтиолоа формуг. лы 1), в частности 2-нафталинтиола, заключающийс в том, что 2-нафталин- сульфохлорид подвергают взаимодействию с цинком, смесь выдерживают приClosest to the present invention is a method for preparing one of the naphthalenethiol formulas. 1), in particular 2-naphthalentiol, which consists in that 2-naphthalene sulfonyl chloride is reacted with zinc, the mixture is kept at

Claims

j 85 ° C, 0-chlorobenzene is added, followed by treatment with sulfuric acid and once more simultaneously with sulfuric acid and. hydrochloric acid at temperatures up to (). The target product is recovered by washing with water. The yield is 76%. In addition, the high stability of the yields depends on the quality of the zinc powder used. the invention is to increase the yield of the target product and stabilize the process by eliminating the dependence of the product yield on the quality of zinc dust. This goal is achieved by the fact that according to the method of producing naphthalene thiols of formula 1), consisting in the interaction of the corresponding naphthalenesulfonyl chloride with zinc mineral acids (sulfuric and hydrochloric) in aromatic chlorogluvodine; like at 95-100 ° C, the process is carried out in the presence of lead in a quantity of 0.001-0.005 by weight of zinc. : The desired product was isolated by washing with water at exit 98-99. Example, To a mixture of 201.5 g (0.89 mol) of 2-naphthalenesulfonyl chloride, 933 g (8.28 mol) of chlorobenzene 1000 ml of water, 217 g (3.3 mol) of zinc powder and 0.002 g (0.001 by weight of zinc) UO g (mol) of sulfuric acid is added to lead, the temperature rises to 0 ° C, heated to 95 ° C and kept at this temperature for 5 m, the hot upper layer is separated, and the acid is washed with water. The yield is 1070 ml of solution containing. 1 A 1.5 g (98) naphthalentiol. PRI mme R 2. To a mixture of 201.5 g (0.89 mol) of 2-naphthalenesulfonyl chloride, (8.28 mol) of chlorobenzene, 1000 m of water, 217 g (3.3 mol) of zinc powder and 0.007 g (0.003 From the weight of zinc lead they add g (& 5 mol) of sulfuric acid, the temperature rises to. It is heated to 100 ° C and kept at this temperature for 5 hours, the hot layer is removed and the acid is washed with water. 1070 ml a solution containing Hi, 5 g (98%) of naphthalentiol d Prize, a mixture of 201.5 g (0.89 mol) of 2-naphthalenesulfonyl chloride 933 g (8.28 mol) of chlorobenzene, 1000 ml of water, 21J g (3.3 mole) of zinc powder and .11 g (0.005 by weight; zinc) lead a g (5.5 mol of sulfuric acid) is heated. The hot top layer is separated to a temperature of 5 hours and the acid is washed with water. The yield is 1070 ml of 1 solution containing H 1.5 g (98) of naphthalene thiol. Example. 188.6 g (0.722 mol) of 1-chloro-8-naphthalenesulfonyl chloride, 50 g (48 mol) of chlorobenzene, 300 ml of water, 1 g (5.202 mol) of zinc powder, 0.017 g of syringe (0.005% by weight of zinc) are given g (3.5 mol) of sulfuric acid. It is heated before and stirred at this temperature for 2 hours, then 85 g (2.32 mol) of hydrochloric acid are added. The upper layer is separated, and the acid is washed with hot (50 ° C) water. The yield is 920 g of a solution containing 139.1 g (99) of 1-chloro-8-naphthalentiol. Example5. To a mixture of 188.6 g (0.722 mol) of 1-chloro-8-naphthalenesulfonyl chloride. 50 G 1., 8 mol) of chlorobenzene, 300 ml of water, 1 K5.202 mol) of zinc powder, 0.01 g (0.003% of the weight of zinc) of lead impart g (3.5 mol) of ferric acid. Heat to 100 ° C, stir at this temperature for 2 hours, then 85 g (2.32 mol) of sulfuric acid are added. The upper layer is separated, and the acid is washed with hot (50 ° C) water. Exit 920 g of a solution containing 139.1 g (99%) of 1-chloro-8-naphthalentiol. Example 6. To a mixture of 188 ° 6 g (0.722 mol) of 1-chloro-8-naphthalene sulphochloride, 50 g (8 mol) of chlorobenzene, 300 ml of water, 1 g (5.202 mol) of zinc powder, 0.003 g (0.001% by weight of zinc) lead impart g (3.5f mol) of sulfuric acid. The mixture is heated to 95 ° C and stirred at this temperature for 2 hours, then 85 g (2.32 mol) of hydrochloric acid are added. The upper layer is separated and the acid is washed with hot (,) water. The yield is 920 g of a solution containing 139.1 g (99%) of 1-chloro-8-naphthalentiol. The proposed method allows to increase the yield of target products to a quantitative from 76 to 98-99%, to stabilize the process through the use of passivating additives. The formula of the invention The method of producing naphthalene thiols of the formula 1 r. SH-5GO where R is hydrogen or chlorine, by reacting the corresponding naphthalene sulfonyl chloride with zinc and mineral acids in an aromatic chlorohydrocarbon at a temperature of 95-100 ° C, characterized in that in order to increase the yield of the target product and stabilization process, the latter is carried out in the presence of lead in the amount of 0.00t - 0.005% by weight of zinc. 5. Sources of information taken into account in the examination 1. Technological regulations And the production of thioindigo red-brown, J. Rubezhnoye, 1971.

2. Technological regulations If b produced by black thioindigo. Rubizhne, 1971.

3.Donaldson N. Chemistry and technologist of naphthalene compounds. M., ed. Chemical literature, 1963, p. (prototype). .