Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Patent
1996-09-19
1999-07-13
O'Sullivan, Peter
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
564507, C07C21302
Patent
active
059229179
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to a process for the preparation of 2-amino-1,3-propanediol and, more particularly, it relates to a process for the preparation of 2-amino-1,3-propanediol starting from 1,3-dihydroxyacetone oxime.
2-Amino-1,3-propanediol, a compound better known as serinol, is a useful intermediate for the preparation of non-ionic iodinated contrast media (British patent No. 1472050 -Savac A. G.), in particular for the synthesis of Iopamidol (The Merck Index, XI Ed., page 799, No. 4943).
Several syntheses of serinol are known in the literature.
The U.S. Pat. No. 4,221,740 (Schering A. G.) and U.S. Pat. No. 4,448,999 (Dynamit Nobel A. G.), for instance, describe a process for the preparation of serinol through the reduction of the sodium salt of 2-nitro-1,3-propanediol.
U.S. Pat. No. 4,978,793 (W.R. Grace & Co.) describes a synthetic process comprising at first the preparation of ketals of 2-nitro-1,3-propanediol starting from nitromethane and formaldehyde and, subsequently, their reduction to the corresponding amino ketals which, in turn, can be hydrolyzed to serinol.
The patent application EP 0238961 (Merck Patent GmbH) describes a process for the preparation of serinol comprising the reduction of the corresponding ketimine which is obtained, in turn, by reacting 1,3-dihydroxyacetone with ammonia or with a primary amine.
It is also known in the literature, for instance as reported by Piloty et reduction of 1,3-dihydroxyacetone oxime with sodium amalgam, in the presence of aluminum sulphate. (1989)!, serinol can be prepared by electrochemical reduction of 1,3-dihydroxyacetone oxime.
Said processes are of difficult industrial application and, with particular reference to the electrochemical reduction, remarkable quantities of by-products, variable depending on the selected operating conditions, were identified.
Catalytic hydrogenations of oximes in the presence of heterogeneous catalysts are also known in the literature as reported, for instance, by P. Rylander in "Catalytic Hydrogenation in Organic Syntheses", Academic Press, 1979, page 153-164.
Methods for the reduction of 1,3-dihydroxyacetone oxime by hydrogenation under heterogeneous catalysis, however, are not reported in the literature.
In this connection, we carried out hydrogenation reactions in the presence of conventional catalysts based on platinum or palladium. Independently from the selected operating conditions, the results were completely unsatisfactory affording, in the most favourable cases, the formation of serinol in traces.
We have instead surprisingly found that the catalytic hydrogenation reaction of 1,3-dihydroxyacetone oxime for the preparation of serinol can be easily carried out in the presence of a catalyst consisting of rhodium supported on alumina.
It is therefore the object of the present invention a process for the preparation of 2-amino-1,3-propanediol comprising the catalytic hydrogenation of 1,3-dihydroxyacetone oxime in a suitable solvent and in the presence of a catalyst consisting of rhodium supported on alumina.
The serinol thus prepared is a useful intermediate in the synthesis of Iopamidol, for instance, as described in the aforementioned British patent No. 1472050.
The process object of the present invention is of easy industrial application and 1,3-dihydroxyacetone oxime is a well-known compound, easily obtainable, according to conventional methods.
A convenient method for the preparation of 1,3-dihydroxyacetone oxime is (1972), 183-205! and comprises the reaction between 1,3-dihydroxyacetone and hydroxylamine hydrochloride.
The reagents and the reaction products used in the process object of the present invention are stable and allow to operate on an industrial scale without using unusual technologies.
The reaction parameters of the process object of the present invention are reported and described as follows.
The hydrogenation reaction is carried out into a reactor suitable to sustain relatively high pressures, for instance into an autoclave, at a pressure preferably comprised between 40 and 70 bars (
REFERENCES:
patent: 3737462 (1973-06-01), Cheema et al.
patent: 5580993 (1996-12-01), Villa et al.
Piloty et al., Berichte der Deutschen Chemischen Gesellschaft, vol. 30, "Ueber Einige Aminoalkohole der Fettreihe", pp. 2057-2068, 1897.
Rylander, P., Catalytic Hydrogenation in Organic Synthesis, Academic Press, pp. 153-164, 1979.
Chemical Papers, vol. 43 (2)(1989),M.Fedoronko,et al.,"Electroreduction of Triose Oximes" pp. 335-341 and p. 340.
Berichte der Deutschen Chemischen Gesellschaft, vol. 30 (1897) O.Piloty,et al.,"Ueber Einige Aminoalkohole Der Fettreihe" pp. 2057-2068 and p. 2061.
Nardi Antonio
Villa Marco
Bracco International B.V.
O'Sullivan Peter
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