Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Patent
1992-09-04
1994-01-11
Hollrah, Glennon H.
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
564215, 564500, 564501, C07C23508
Patent
active
052783413
DESCRIPTION:
BRIEF SUMMARY
DESCRIPTION
The invention relates to N-acylaminoalkyl 2-hydroxyethyl sulfides of the formula (A) is an integer from 3 to 6, and to a process for their preparation by reaction of compounds of the formula (B) mercaptoethanol in the presence of a free-radical initiator.
The N-acylaminoalkyl 2-hydroxyethyl sulfides according to the invention are precursors for the preparation of aminoalkyl ethyl sulfones of the formula (C) preferably a group or an element from the series comprising --OH, --OSO.sub.3 H, --Cl or --OCOCH.sub.3, which in turn serve as components for the preparation of reactive dyes (DE 2,040,620 or EP 0,141,776).
Hitherto it has been possible to obtain the compounds of the formula (C) as mentioned by oxidation of the non-acylated aminoalkyl sulfides of the general formula (D)
Several processes for preparing the sulfides of the abovementioned formula (D) are already known. Thus, according to J. Med. Chem. 9, 217 (1966), 3-aminopropyl 2-hydroxyethyl sulfide is obtained by reaction of mercaptoethanol with 3-bromoaminopropane hydrobromide. However, the disadvantage of this method is the formation of 2 equivalents of sodium bromide. An improved process for the preparation of this sulfide operating without the formation of salt is described in DE 2,040,620: allylamine is reacted with mercaptoethanol at 50.degree.-150.degree. C. with the addition of azoisobutronitrile (AIBN). No yields are given in this publication. Upon repeating this process (see Example 9 below), yields of only 56.6% of theory were obtained. Thus, it may be stated that this preparation process does not meet the demands of an industrial process either.
A modification of this preparation process is described by the reaction of 4-nitro-N-allylbenzamide at 120.degree.-140.degree. C. with mercaptoethanol, also with the addition of free-radical formers (DE 2,040,620, Example 1). In this case, too, no yields are given. Repetition of this reaction (see Example 11 below) gave a crude yield of 78.3% of theory. However, this modified process is no economically feasible route for preparing 3-aminopropyl 2-hydroxyethyl sulfide, due to the formation of 3-nitrobenzoic acid.
U.S. Pat. No. 3,278,526 describes the reaction of N-alkenylamides with hydrogen sulfide and thiols with the addition of free-radical initiators, in which the maximum yields of 66% are unsatisfactory. Japanese Patent 44/10,770 also teaches that in the reaction of N-acylalkenylamides with mercaptans the addition of special free-radical initiators is necessary. The yields of these reactions are 57-91% of theory.
For the reasons mentioned above, there was a need for an economical and technically feasible process for the preparation of N-acylaminoalkyl 2-hydroxyethyl sulfides.
It has now been found that N-acylaminoalkyl 2-hydroxyethyl sulfides of the formula (1) -C.sub.4) radical and n is an integer of from 3 to 6 can be prepared in high yields and in high purity by reacting compounds of the general formula (2) equivalent amount of mercaptoethanol at temperatures of about 15.degree. to about 150.degree. C., preferably of about 20.degree. to about 100.degree. C., particularly preferably of about 25.degree. to about 80.degree. C., in the presence of a free-radical initiator in the presence or in the absence of a solvent which is inert towards the reactants and towards free-radical reactions.
Oxygen preferably serves as the free-radical former. It can be introduced into the reaction mixture, for example, in pure form or as a mixture with an inert gas or inert gas mixture, preferably in the form of air.
According to the process, the procedure is either such that both reactants are mixed and brought to the reaction temperature in the presence of air and/or oxygen, or such that one of the two reactants is initially introduced and the second reactant is metered in within the temperature ranges mentioned. It is in principle immaterial whether the compound of the formula (2) mentioned is initially introduced and the mercaptoethanol is metered in or whether the procedure is the other way round
REFERENCES:
patent: 3278526 (1966-10-01), Louthan et al.
Kandror et al, Selective Inhibition of the Radical Addition of Thiols to Olefins . . . , CA 77 (23): 151194g, 1972.
Angenendt Heinrich
Meier Michael
Mischke Peter
Hoechst Aktiengesellschaft
Hollrah Glennon H.
Lambkin Deborah
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