Method of preparing thiazolines-3
专利摘要:
Thiazoline-(3) compounds of the formula <IMAGE> (I) in which R1, R2, R3, R4 and R5 are hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl or aralkyl or R1 and R2 or R3 and R4 or R3 and R5 or R4 and R5 are joined together to form a saturated or unsaturated ring are prepared by reacting (1) an oxo compound having a halogen atom on the carbon adjacent to the carbonyl group and having the formula <IMAGE> (II) where X is halogen, (2) an oxo compound of the formula <IMAGE> (III) (3) a metal or ammonium sulfide and (4) ammonia. 公开号:SU843745A3 申请号:SU772528007 申请日:1977-10-07 公开日:1981-06-30 发明作者:Шерберих Пауль 申请人:Дегусса Аг (Фирма); IPC主号:
专利说明:
(54) METHOD FOR OBTAINING TIAZOLINS-3 The invention relates to a process for the preparation of thiazolines-3 of the general formula Yaz. . B4J JURi where R and Rgi independently of each other are a hydrogen atom or a lower alkyl of R and RO together are cyclohexyl or cyclopentyl; R - is a hydrogen atom, lower alkyl or phenyl; Rj and R5 are a hydrogen atom or a lower alkyl, which are used as oxidation stabilizers for oxidation, as well as starting materials for the production of sulfur containing amino acids. A known method for the preparation of thiazolines-3 of the general formula is where R and R are lower alkyl or lower aralkyl; K, and Rj together - alkylene; Ri is a hydrogen atom, lower alkyl or lower aralkyl; R is lower alkyl or lower areshkyl; or RJ and jointly alkylene, i.e. compounds of general formula (I), where Rn, is a hydrogen atom, which consists in the fact that 1,1-diformyldisulfide of the general formula,: cssc i- ° to where R and Rl have the above values, are reacted with an oxo compound of the general formula h where rl and r are as defined above, hydrogen sulfide and ammonia in the presence of an amine and an ammonium salt in an organic solvent medium. The disadvantage of this method is the inaccessibility of the original diformyldisulfides, which is why it is impossible to obtain 5-thiazolines-3. The purpose of the invention is to simplify the process technology, as well as to expand the range of target products. This goal is achieved by the fact that in the method of producing thiazone-3 of the general formula, which ends in the fact that the oxo compound of the general formula Cs-c for R, where R - 5 has the above values; X is a halogen, is reacted with an oxidation of the general formula RJ-C-RZ about where R, and Co have the above values, with an alkali metal hydrosulfide, as well as ammonia. Example 1. To a suspension of 67 (1.2 mol) sodium hydrosulfide in 110 g (1.5 mol) 2-methylpropanal -1 add 106 g (1.0 mol) 2-chloro-2-methylpropanal dropwise and ammonia is introduced. At this, the temperature is maintained at 15-25 seconds by cooling. The supply of ammonia is continued until heat dissipation from the reaction mixture continues. From the reaction mixture by fractional distillation, the resulting 2-isopropyl-5,5-dimethylthiazolin-3-s bp is obtained. at 16 mbar 68-72s. The yield is 120 g, i.e. 76% relative to the loaded 2-chloro-2-methylpropanal Example 2. The method is carried out kaK in example 1, but load 120g (1.4 mol) of diethyl ketone with 80 g (1.1 mol), potassium hydrosulfide and ibe g (1.0 1 mol) 2-chloro-2-methylpbopanal -1. The yield of 2,2-diethyl-5,% dimethylthiazolin-3 is 135 g, i.e. 79% relative to the loaded 2-chloro-2-methylpropanal-1, bp. 50-52tC at 1.3 mbar. Example 3. The method is carried out as in Example 1, but 70 g (1.2 mol) of propionic aldehyde, 80 g (1.1 mol) of potassium hydrosulfide and 137 g (1.0 mol) are loaded. bromoacetone. The yield of 2-ethyl-4-methylthiazoline-3 is 90 g, which corresponds to 70% relative to the loaded bromoacetone, bp B-B3 C at 7 mbar. Example 4. The method is carried out as in Example 1 , but 70 g (1.2 mol) of propionic aldehyde, 58 g (1.0 mol) of sodium hydrosulfide and 199 g of phenacyl bromide are loaded in. The resulting 2-ethyl-4-phenylthiazoline-3 is purified by recrystallization from methanol.T, pl. -52 ° C, in Output 140 g, corresponding to 73% relative to the phenacyl bromide loaded. Example 5. The method is carried out as in Example 1, but 90 g (1.6 mol) of acetone, 67 g (1.2 mol) of sodium hydrosulfide and 151 g are loaded (1.0 mol) 2-bromo-2-methylpropanal - (1). Yield 2.2, 5, 5-tetramethylthiazoline 110 g or 77% relative to the loaded 2-bromo-2-methylpropanal-1, t. mp 50-52 C. Example B. The method is carried out as in Example 1, but loading 87 g (1.5 mol), acetone, a solution of 67 g (1.2 mol) sodium hydrosulfide in 100 ml of water and 175 g 45 % aqueous solution of chloroacetaldehyde (1.0 mol). From the reaction mixture, the resulting 2,2-dimethylthiazolin-3 is isolated in the form of an oil, which is separated and subjected to fractional distillation. Bp 40-45 ° C at 16 mbar. The output of 85 g, which corresponds to 74% relative to the loaded chloroacetaldehyde. Example 7. The method is carried out as in Example 1, but loading 130 g (1.5 mol) of diethyl ketone, a solution of 67 g (1.2 mol) of sodium hydrosulfide in 100 ml of water and 175 g of a 45% aqueous solution of chloroacetaldehyde (1 , 0 mole). The yield of 2,2-diethylthiazoline-3 .100 g, which corresponds to 70% relative to the loaded chloroacetaldehyde. Bp 7780Ос at 16 mbar. Example 8. The method is carried out as in Example 1, but loading 120 g (1.2 mol) of cyclohexanone, a solution of 80 g (1.1 mol) of potassium hydrosulfide in 100 ml of water and 105 g of a 75% aqueous solution of chloroacetaldehyde (1 , 0 mole). The yield of 2.2-pentametal Lentiazolin-3 115 g, which is 73% relative to the loaded chloroacetaldehyde. Bp 100-105s at 16 mbar. Example 9. The method is carried out analogously to example 1, but 110 g (1.5 mol) of butanol-2, a solution of 80 g (1.1 mol) of potassium hydrosulfide in 100 ml of water and 175 g of a 45% aqueous solution of chloroacetaldehyde ( 1.0 mol). The yield of 2-methyl-2-ethylthiazolin-3 112 g, which corresponds to 80% relative to the loaded chloroacetaldehyde. Bp 52-55CC at 16 mbar.
权利要求:
Claims (1) [1] 1. Patent. USA 3931208, cl. C 07 D 277/10, published 06/01/76 (prototype).
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同族专利:
公开号 | 公开日 DE2645731A1|1978-04-13| CH630372A5|1982-06-15| FR2367070B1|1982-08-06| JPS5346974A|1978-04-27| GB1537955A|1979-01-10| FR2367070A1|1978-05-05| JPS5850218B2|1983-11-09| BE859516A|1978-04-07| DE2645731C2|1986-05-07| US4153606A|1979-05-08| IT1143607B|1986-10-22| NL7710350A|1978-04-11|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 FR1175412A|1955-11-30|1959-03-26|Leuna Werke Veb|Process for the preparation of thiazolines delta-3, 4, products conforming to those thus obtained and applications of said products| US3004981A|1957-08-09|1961-10-17|Leuna Werke Veb|Process for the preparation of delta-3, 4-thiazolines| CH529162A|1968-09-06|1972-10-15|Degussa|Process for the preparation of thiazolines 3| DE2254701C3|1972-11-09|1978-12-07|Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt|Process for the preparation of thiazolines substituted in the 2- and 5-positions|US4477674A|1980-01-16|1984-10-16|Petrolite Corporation|Preparation of dihydrothiazoles| DE3026334A1|1980-07-11|1982-02-11|Degussa Ag, 6000 Frankfurt|METHOD FOR PRODUCING THIAZOLINES- | US4355169A|1981-03-02|1982-10-19|Polaroid Corporation|Thiazolidinyl-substituted phenyl sulfonamides| JPH0352680Y2|1984-09-12|1991-11-15| JPH0331728Y2|1985-07-31|1991-07-05| JPH0443669Y2|1986-03-08|1992-10-15| DE4423485A1|1994-07-05|1996-01-11|Basf Ag|Thiazole methine dyes| CN104177307B|2014-09-02|2016-10-05|北京工商大学|A kind of method preparing 2-replacement-4-methyl-3-Thiazoling type compound|
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申请号 | 申请日 | 专利标题 DE19762645731|DE2645731C2|1976-10-09|1976-10-09|Process for the preparation of thiazolines- | 相关专利
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