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

1992-09-04

1994-01-25

Chan, Nicky

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

Organic compounds

Sulfate esters

C07C30504

Patent

active

052817407

DESCRIPTION:

BRIEF SUMMARY
The invention relates to a process for the preparation of 3'-aminopropyl 2-sulfatoethyl sulfone in good yields by reacting in a one-pot process allylamine with mercaptoethanol in aqueous sulfuric acid at temperatures of about 50.degree. C. to the boiling point of the reaction mixture in the presence of free-radical initiators, oxidizing the reaction mixture formed with hydrogen peroxide in the presence of catalytic amounts of transitionmetal compounds, then adding sulfuric acid and evaporating the mixture to dryness.
3'-Aminopropyl 2-sulfatoethyl sulfone is an important prerequisite for the preparation of reactive dyes (EP 0,141,776).
The preparation of 3'-aminopropyl 2-sulfatoethyl sulfone has not yet been described in the literature. However, the preparation of 2'-aminoethyl 2-sulfatoetyl sulfone is known from the literature. According to US Pat. No. 2,824,887, it is prepared by reacting 2-chloroethylamine hydrochloride with the sodium salt of mercaptoethanol and oxidizing the 2'-aminoethyl 2-hydroxyethyl sulfide hydrochloride thus obtained with peracetic acid to give 2'-aminoethyl 2-hydroxyethyl sulfone hydrochloride.
European Patent No. 0,141,776 (page 13) describes methods for sulfating 2'-aminoethyl 2-hydroxyethyl sulfone hydrochloride or similar alkyl hydroxyethyl sulfones using sulfuric acid or chlorosulfonic acid at temperatures of 10 to 80.degree. C. If it were desired to prepare 3'-aminopropyl 2-sulfatoethyl sulfone in an analogous manner, the formation of two equivalents of sodium chloride in the preparation of 3'-aminopropyl 2-hydroxyethyl sulfide (precursor) would have to be accepted. An improved process for the preparation of this sulfide which operates without the formation of salt is described in DE 2,040,620, in which allylamine is reacted with mercaptoethanol at 50 to 150.degree. C. with the addition of azoisobutyronitrile (AIBN). The reference cited does not give any yields for this process. Upon repeating the process (Example 4), yields of only 56.6% of theory were obtained. Thus, it can be stated that these known processes for the preparation of 2'-aminoethyl 2-sulfatoethyl sulfone and 3'-aminopropyl 2-hydroxyethyl sulfide (precursor) do not meet the requirements of an industrial process.
Accordingly, there was a need for an economical and technically feasible process for the preparation of 3'-aminopropyl 2-sulfatoethyl sulfone.
It has now been found that 3'-aminopropyl 2-sulfatoethyl sulfone can be prepared in very good yields (>95% of theory) by reacting in a one-pot process allylamine with mercaptoethanol in dilute sulfuric acid at temperatures of about 50.degree. C. to the boiling point, preferably about 70.degree. C. to about 100.degree. C., in the presence of a free-radical initiator, oxidizing the resulting reaction mixture with hydrogen peroxide in the presence of catalytic amounts of a compound of a transition metal of the periodic table of the elements, preferably a compound of tungsten or vanadium, as the oxidation catalyst at temperatures of about 70 to about 100.degree. C., preferably about 80 to about 90.degree. C., and, after sulfuric acid has been added in such an amount that the total amount of sulfuric acid in the mixture is at least 1 mol, relative to the allylamine used, evaporating the mixture to dryness.
The detailed procedure of the process according to the invention can be as follows: it can either be such that both reactants are mixed in aqueous sulfuric acid and brought to the reaction temperature in the presence of air and/or pure oxygen, or such that allylamine is initially introduced in about 0.5 to about 0.7 mol of aqueous sulfuric acid per mole of allylamine and mercaptoethanol is metered in at temperatures of about 50.degree. C. to the boiling point of the reaction mixture, preferably about 70 to about 100.degree. C. It is also possible to initiate the reaction with a free-radical former from the series of azo compounds, such as, for example, azoisobutyronitrile, or of peroxide compounds, such as, for example, benzoyl peroxide. A catalytic amount of,

REFERENCES:
patent: 2824887 (1958-02-01), Klopping

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