2-Oxo-1,3-dioxolane-4-carboxamides, their preparation and use
View Patent ↗The present invention suggests 2-oxo-1,3-dioxolane-4-carboxamides of formula (I), in which R 2 can be, inter alia, an n-valent radical (n>1) which is substituted with n−1 further 2-oxo-1,3-dioxolane-4-carboxamide groups of general formula (II), to processes for the preparation of these 2-oxo-1,3-dioxolane-4-carboxamides, to processes for the preparation of the 2-oxo-1,3-dioxolane-4-carboxylic acids of formula (III), which are suitable starting materials for the above processes, and to the use of said 2-oxo-1,3-dioxolane-4-carboxamides for the preparation of (poly)hydroxyurethanes, -hydroxycarbonates and -hydroxysulfanylformates, and also as end groups for the blocking of amines.
1. 2-Oxo-1,3-dioxolane-4-carboxamide of formula (I),
characterized in that
(i) R 1 and R 2 , in each case independently of one another, are selected from H, straight-chain C 1-12 alkyl groups, branched or cyclic C 3-12 alkyl groups, C 6-10 -aryl groups, C 6-12 -ar-alkyl groups and C 6-12 -alkaryl groups or, together with the N atom to which they are bonded, form a 5- to 8-membered ring, and R 3 is selected from H and straight-chain C 1-12 alkyl groups, branched or cyclic C 3-12 alkyl groups, or
(ii) R 1 and R 3 are each H, and R 2 is a radical having a valency of 2 to 5, which is substituted with an amount equal to the valency minus 1 of further 2-oxo-1,3-dioxolane-4-carboxamide groups of formula (II)
2. 2-Oxo-1,3-dioxolane-4-carboxamide according to claim 1 , characterized in that R 1 and R 3 are each H, and R 2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-ethyl-n-hexyl, n-lauryl, cyclohexyl, phenyl and benzyl.
3. 2-Oxo-1,3-dioxolane-4-carboxamide according to claim 1 , characterized in that the radical has a valency of 2 to 3.
4. 2-Oxo-1,3-dioxolane-4-carboxamide according to claim 1 , characterized in that R 2 is selected from straight-chain or branched C 2-22 -alkylene groups, polyether groups of the formula -(A 1 O) m —, wherein A 1 is C 2-5 -alkylene and m is 1-100, polycarbonate groups, polyester groups, poly(meth)acrylate groups, and combinations thereof.
5. A process for the preparation of a 2-oxo-1,3-dioxolane-4-carboxamide as defined in claim 1 , characterized in that a 2-oxo-1,3-dioxolane-4-carboxylic acid of formula (III)
is reacted with an amine of the formula R 1 —NH—R 2 .
6. The process according to claim 5 , characterized in that it is carried out in the presence of a water-withdrawing agent.
7. A process for the preparation of a 2-oxo-1,3-dioxolane-4-carboxamide as defined in claim 1 , wherein R 1 is H, characterized in that a 2-oxo-1,3-dioxolane-4-carboxylic acid of formula (III) is reacted with an isocyanate of the formula R 2 —NCO.
8. The process according to claim 7 , characterized in that the isocyanate is a monoisocyanate or a polyisocyanate with 2 to 5 NCO groups.
9. The process according to claim 7 , characterized in that the reaction is carried out in the presence of a catalyst selected from tertiary amines, organometallic compounds, and mixtures thereof.
10. A process for the preparation of a 2-oxo-1,3-dioxolane-4-carboxylic acid of formula (III)
characterized in that a 2-oxo-1,3-dioxolane-4-carboxylic acid ester of formula (IV)
is hydrolysed in an acidic medium,
where R 2 is selected from H, straight-chain C 1-12 alkyl groups, branched or cyclic C 3-12 alkyl groups, C 6-10 -aryl groups, C 6-12 -aralkyl groups and C 6-12 -alkaryl groups, and R 3 is selected from H and straight-chain C 1-12 alkyl groups, branched or cyclic C 3-12 alkyl groups.
11. A process for the preparation of a 2-oxo-1,3-dioxolane-4-carboxylic acid of formula (III)
characterized in that a glycerol carbonate of formula (V)
is oxidized,
where R 3 is selected from H and straight-chain C 1-12 alkyl groups, branched or cyclic C 3-12 alkyl groups.
12. The process according to claim 11 , characterized in that the oxidation is effected with a combination of 1,3,5-trichloroisocyanuric acid and an n-oxide, optionally 2,2,6,6-tetramethylpiperidin-1-oxyl.
13. The process according to claim 11 , characterized in that the oxidation is effected as an aerobic oxidation.
14. A process of utilizing the 2-oxo-1,3-dioxolane-4-carboxamides as defined in claim 1 for the preparation of hydroxyurethanes, comprising reacting the 2-oxo-1,3-dioxolane-4-carboxamide with R′—NH 2 , wherein R′—NH 2 is an amine.
15. A process of utilizing the 2-oxo-1,3-dioxolane-4-carboxamides as defined in claim 1 for the preparation of hydroxycarbonates, comprising reacting the 2-oxo-1,3-dioxolane-4-carboxamide with R′—OH, wherein R′—OH is an alcohol.
16. A process of utilizing the 2-oxo-1,3-dioxolane-4-carboxamides as defined in one of claim 1 for the preparation of hydroxysulfanylformates, comprising reacting the 2-oxo-1,3-dioxolane-4-carboxamide with R′—SH, wherein R′—SH is a thiol.
17. A process of utilizing the 2-oxo-1,3-dioxolane-4-carboxamides as defined in claim 1 for the preparation of polymeric hydroxyurethanes, hydroxycarbonates and/or hydroxysulfanylformates, comprising reacting polyvalent 2-oxo-1,3-dioxolane-4-carboxamide with R′—NH 2 , R′—OH, or R′—SH, wherein R′—NH 2 is an amine, R′—OH is an alcohol, and R′—SH is a thiol.
18. A process of utilizing the 2-oxo-1,3-dioxolane-4-carboxamides as defined in claim 1 as end groups for the blocking of amines.