Process for the preparation of polyoxyalkylated amines

Details Process for the preparation of polyoxyalkylated amines Process for the preparation of polyoxyalkylated amines

1994-12-05

1997-05-13

Burn, Brian M.

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

Organic compounds

Amino nitrogen containing

564504, C07C21103

Patent

active

056294522

DESCRIPTION:

BRIEF SUMMARY
This application is a 371 of PCT/FR93/00364, filed Apr. 9, 1993.
The present invention concerns a preparation process for compounds containing at least one primary or secondary amine function and at least one polyoxyalkylated chain.
For the synthesis of such compounds, several pathways have been proposed in the prior art.
The first of these pathways consists of treating a polyoxyalkylated molecule having a terminal group that can be transformed into an amine function.
Thus the preparation of polyoxyethylated amines from polyethylene glycol is known. The study "Eur. Polym. J. Vol. 19, No. 12, pp. 1177-1183, 1983" of Zalipsky describes the preparation of amino-polyethylene glycol from polyethylene glycol by modifying the terminal hydroxyl function by a chlorine atom, then replacing this chlorine atom by an azide function, which is reduced in the presence of a catalysts.
Other more recent processes such as that of Yinglin, in "Synthetic Communications 21, (1), 79-84 (1991 )" effect the preparation of amino-polyethylene glycol from polyethylene glycol. According to these processes, a tosyl radical is fixed onto the terminal hydroxyl function and then the product obtained is reacted with potassium phthalimide or sodium diformamide to arrive at the desired aminated compound.
Belgian patent No. 849,343 describes the preparation of polyoxyethylenes of secondary amines conforming to the following formula (I): atoms, a cyclohexyl radical or an aryl radical possibly bearing alkyl groups, designate a methyl radical, and, a whole number from 2 to 15.
To prepare these compounds, ox[y]alkylates conforming to the following formula (II) are reacted: with ammonia and hydrogen in the presence of hydrogenation-dehydrogenation catalysts, at a temperature of 150.degree. C. to 250.degree. C. and under an absolute pressure of 0.5 to 1.5 atmosphere.
Such processes, while they are economically acceptable, present, however, the principal disadvantage of requiring several steps, because amination can only be realized in last place, when the polyoxyethylate part has reached the desired length.
A second synthesis pathway for polyoxyalkylated amines consists of preparing compounds according to formula (I) by adding propylene or ethylene oxide onto molecules already having an amine function.
This generally leads to additions of oxide onto the nitrogen atom of the amine function, which then loses its primary or secondary nature.
In order to prevent polyoxyalkylation on the nitrogen atom of the amine function, it has been proposed to begin with secondary or primary amines protected by steric hindrance by means of a branched group.
Thus U.S. Pat. No. 2,871,266 describes a preparation process for secondary mono(polyoxyalkylated) amines from encumbered amines in the form of tert-carbinamine of the formula: ##STR1## in which R1, R2 and R3 are alkyl radicals whose total number of carbon atoms varies from 7 to 23.
In order to form the secondary mono(polyoxyalkylated) amine, it is necessary to first form an N-hydroxyethylated derivative from this tert-carbinamine and then to react this intermediate product with ethylene or propylene oxide in the presence of an alkaline catalyst.
Such a process therefore has the disadvantage of requiring the presence of a carbon encumbered at alpha of the nitrogen by groups having at least 7 carbon atoms and only permits obtaining secondary polyoxyalkylated amines whose hydrogen is poorly reactive.
A third synthesis pathway of polyoxyalkylated amines consists of starting with an amino-alcohol whose amine function is protected and transforming it into an inert function with epoxides, and then effecting the addition of propylene or ethylene oxide.
This third pathway is notably described in "Makromol. Chem. 184, 1849-1859, 1983" in the case of preparation of polyoxiranes having primary terminal amine functions from amino-alcohol.
The amine function of the initial amino-alcohol is first protected by means of a succinyl group. Then a potassium alcoholate is formed by means of potassium dihydronaphthylide. The alcoholat

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