Process for the preparation of 3'-aminopropyl 2-sulfatoethyl sul

Details Process for the preparation of 3'-aminopropyl 2-sulfatoethyl sul Process for the preparation of 3'-aminopropyl 2-sulfatoethyl sul

1993-08-25

1995-05-16

Chan, Nicky

Organic compounds -- part of the class 532-570 series

Organic compounds

Sulfate esters

C07C30504

Patent

active

054162343

DESCRIPTION:

BRIEF SUMMARY
This application is a 371 of PCT/EP92/00349 filed Feb. 19, 1992.
The invention relates to an improved process for the preparation of 3'-aminopropyl 2-sulfatoethyl sulfone by an addition reaction of mercaptoethanol with allylamine in aqueous sulfuric acid in the presence of free-radical initiators, oxidation of the reaction mixture thus obtained with hydrogen peroxide in the presence of catalytic amounts of transition metal compounds and esterification with sulfuric acid or oleum or chlorosulfonic acid, using free-radical initiators which are soluble in the reaction medium.
3'-Aminopropyl 2 -sulfatoethyl sulfone is an important precursor for the preparation of reactive dyes (EP 0141776).
The preparation of 3'-aminopropyl 2-sulfatoethyl sulfone is described in European Patent 0,518,889, in which allylamine is reacted with mercaptoethanol in aqueous sulfuric acid in a one-pot process at temperatures from about 50.degree. C. to the boiling point of the reaction mixture in the presence of free-radical initiators, the reaction mixture formed is oxidized with hydrogen peroxide in the presence of catalytic amounts of a compound of a transition metal of the periodic table of elements at temperatures from about 70.degree. to about 100.degree. C., further sulfuric acid is added until the total amount of sulfuric acid in the mixture is at least 1 mol, relative to the allylamine used, and the 3'-aminopropyl 2-hydroxyethyl sulfone hemisulfate is esterified by evaporation to dryness.
The reaction times of the free-radical addition reaction of mercaptoethanol with allylamine are in this reaction between 35 and 45 hours.
Surprisingly, it has now been found that the reaction time of the process described can be considerably shortened and high yields can be obtained by using free-radical initiators, preferably 2,2'-azobis[2-(2-imidazolin-2-yl)propane] or its dihydrochloride or 2,2'-azobis(2-amidinopropane) dihydrochloride, which are soluble in the reaction medium and carrying out the reaction of allylamine with mercaptoethanol in aqueous sulfuric acid at about 25.degree. C. to the boiling point of the reaction mixture, preferably at the temperature at which the free-radical initiator has a half-life of about 1 to about 5 hours, followed by oxidation and esterification.
Accordingly, the invention relates to an improved process for the preparation of 3'-aminopropyl 2-sulfatoethyl sulfone in high yields and in a relatively short reaction time by reaction of allylamine with mercaptoethanol in aqueous sulfuric acid in a one-pot process at temperatures from about 25.degree. C. to the boiling point of the reaction mixture in the presence of free-radical initiators which are soluble in the reaction medium, oxidation of the reaction mixture thus obtained with hydrogen peroxide in the presence of catalytic amounts of a compound of a transition metal of the periodic table of elements as oxidation catalyst to give 3'-aminopropyl 2-hydroxyethyl sulfone hemisulfate, addition of further sulfuric acid until the total amount of sulfuric acid in the mixture is at least 1 mol, relative to the allylamine used, and esterification of the 3'-aminopropyl 2-hydroxyethyl sulfone hemisulfate obtained after oxidation by evaporation to dryness or with sulfuric acid or oleum or chlorosulfonic acid in solution.
It is advantageous to initially introduce 1 mol of allylamine in aqueous sulfuric acid at a temperature at which the free-radical initiator has a half-life of about 1 to about 5 h, and to meter in 0.9 to about 1.5 mol, preferably about 0.95 to about 1.05 mol, of mercaptoethanol, in which 0.1 to about 5 g, preferably about 0.5 to about 1.5 g, of free-radical initiator are dissolved per mole of mercaptoethanol. It is also possible to initially introduce mercaptoethanol, in which 0.1 to about 5 g, preferably about 0.5 to about 1.5 g, of free-radical initiator are dissolved per mole of mercaptoethanol, and to meter in 1 mol of allylamine in aqueous sulfuric acid at a temperature at which the free-radical initiator has a half-life of about 1 to 5 h. How

REFERENCES:
patent: 5281740 (1994-01-01), Meier et al.

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