DE1063602B - Process for the preparation of 1, 5, 5-trialkyl-substituted delta 3,4-thiazolines - Google Patents

Description

It was found to be 1,5,5-trialkyl substituted , d ^ -Thiazolines from alkylidene vinylamines and sulfur can be produced. Such alkylidenevinylamines can, for example, by exposure to ammonia Aldehydes are formed which are branched on the cc-C atom (see Beilstein's Handbook of Organic Chemistry, Vol. 4, p. 221 and U.S. Patent 2,319,848). For example, isobutyraldehyde reacts with ammonia to form l-ButyMen - /?, / 9-dimethylvinylamine. General is the Formulate the formation of the alkylidenevinylamines as follows:

Method of manufacture

of 1,5,5-trialkyl-substituted

Zl ³ > ⁴ thiazolines

Applicant:

VEB Leuna-Werke »Walter Ulbricht«,
Leuna (Kr.Merseburg)

R ₂

R ,.

XH-CHO + NH ₃

= CH = N = CH
(I)

ch:

+ 2H ₂ O

R ₅ .

Substituted vinylamines of type I react with sulfur to form Zl ⁸ '* -thiazolines of structure II, that is, for every mole of amine there is 1 gram atom of sulfur:

HC

R-2

K-2

R ₂

R ₂

R ₁ and R ₂ can generally be alkyl groups. The reaction of the Alkylidenvinylamine (I) with sulfur is advantageously carried out between 100 and 15O ⁰ C. At lower temperatures the conversion decreases, and increased at higher resin formation takes place.

The 4 ³ ' ⁴ -thiazoline formation can also take place in such a way that a polysulfide solution is used instead of the elemental sulfur. The advantage is that the reaction of acylidenevinylamines (I) with polysulphide begins with self-heating at room temperature and ends below 100X.

Dr. Hubert Schade and Dr. Max Thiel,

Leuna (Kr. Merseburg),
have been named as inventors

Finally, the synthesis of the above-defined Zl ³ ' ⁴ -thiazolines (II) can be started directly from the aldehydes branched on the aC atom by adding 1 gram atom of sulfur to 2 moles of the aldehyde in question and _{introducing NH 3} into this mixture, with the alkylidene vinylamine (I) and water are formed according to reaction scheme 1, the latter being removed by distillation. During the subsequent heating at 100 to 150 ⁰ C, the reaction proceeds according to reaction scheme 2, and it forms Zl ^{3 '4} -thiazoline (II) in place of the sulfur can also be a polysulphide used in the above portrayed method addition to the Zl ³ - ⁴ -Thiazoline (II) is used in all cases

A second product of significantly higher boiling point, which also contains sulfur and nitrogen and has twice the molecular weight of ^{I 3} ' ⁴ -thiazoline, is regularly isolated in more or less high yield Analyze only the general molecular formula with

(R ₁ R ₂ ) X ₈ H ₄ N ₂ S ₂

can be specified.

In the same way, aldehyde mixtures, for example those which are obtained by dehydrogenation of isobutyl oil fractions and which are aldehydes branched on aC atom according to their structure, can be reacted with ammonia] to give alkylidene vinylamines. This mixture of aldehydes or the resulting with NH ₃ ent

909 608/4!

Any alkylidenevinylamines that have been found react with sulfur or polysulfide solution under the conditions described to form Zl ^{3> 4} -thiazolines.

example 1

800 g isobutylidene - ^, j3-dimethylvinylamin are heated for 4 hours at 150 ⁰ C and 205 g of sulfur. The red-brown reaction product is distilled in vacuo. This gives 400 g of 2-isopropyl-5,5-dimethyl-zl ^{3 '4} -thiazoline of boiling ₅ 55 to 56 ° C, picrate F. 116 ° C, and 280 g of a body of boiling. ₅ 115 ° C (. C ₁₆ H ₂₈ N ₂ S ₂ ).

Example 2

800 g of N - (^ - methyl - ^ - propyl-ethylidene) - (^ - methyl - /? - propylvinyl) amine and 140 g of sulfur are heated according to Example 1 and then distilled in vacuo. This gives about 400 g of 2- [pentyl (2 ')] - ^{5-methyl-5-propyl-3} zl> ⁴ -thiazoline, bp ₃ 90 ° C as well as 290 g of a higher-boiling, bp body ₃ 150 ° C.. .

Example 3

_{Gaseous NH 3} is passed into a mixture of 1704 g of isobutyraldehyde and 384 g of sulfur. The reaction temperature rises and remains constant for a few hours. It is allowed to cool in a stream of _{NH 3.} The water of reaction is then driven off by slow heating and the residue is heated to 150 ° C. for 3 hours. The red-brown reaction mixture is worked up by fractionation in vacuo. This gives 800 g of 2-isopropyl-5,5-dimethyl-Zl ^3J4 -thiazoline from Kp. ₆ 55 to 56 ° C, picrate F. 116 ° C, and about 350 g of a higher-boiling body from Kp. ₅₁₁₅ ° C (C ₁₆ H ₂₈ N ₂ S ₂ ).

Example 4

700 cm ^{3 of} ammonium polysulphide solution with 250 g of polysulphide sulfur per liter are mixed with 576 g of isobutyraldehyde _{with simultaneous introduction of NH 3 gas and vigorous stirring.} The temperature rises to about 70 ° C. The reaction mixture is kept at this temperature for a further hour. Two layers are formed, of which the lower, aqueous, is discarded and the upper is distilled in vacuo. This gives 300 g of 2-isopropyl-5,5-dimethyl-Zl ^{3 '4} -thiazoline, Kp. _Lo 65 to 70 ° C.

Example 5

865 g of isobutylidene / 5, / 5-dimethylvinylamine and 900 g of ammonium polysulphide solution with 250 g of polysulphide sulfur per liter are mixed with vigorous stirring. The temperature rises to over 50 ° C. As soon as the temperature begins to fall, the mixture is heated to 70 ° C for 1 hour and the two layers formed are separated. The lower, aqueous, is discarded, the upper is distilled in vacuo. This gives 600 g of 2-isopropyl-5,5-dimethyl- _/ d ³ - ⁴ -thiazoline, Kp _{2, 5} 45-46 ° C.

_ις example 6

660 g of a mixture of alkylidenevinylamines, which can be prepared from the aldehydes obtained by dehydrating the C ₇ to C ₉ isobutyl oil alcohol fraction, are heated to 150 ° C. with 90 g of sulfur for 3 hours and the reaction product is distilled in vacuo. This gives about 350 g of a / I ^{3 '1} -Thiazolingemisches from Kp. _4130-136 ° C.

Claims (3)

Patent claims: 1. A process for the preparation of 1,5,5-trialkyl-substituted zl ³ ' ⁴ -thiazohnen, characterized in that alkylidenevinylamines of the general formula R ₁ R ₂ C-CH = N-CH = CHR ₁ R ₂ where R ₁ and R _{2 are} alkyl radicals, are reacted with elemental sulfur at temperatures between 100 and 150 ° C. 2. The method according to claim 1, characterized in that instead of sulfur, aqueous poly-sulfide solution is used below 100 ° C. 3. Modification of the method according to claim 1 and 2, characterized in that one is on on a-carbon atom lets branched aldehydes ammonia and sulfur or polysulfide act.