2-oxo-1,3-dioxolane-4-acyl halides, their preparation and use
View Patent ↗The present invention suggests 2-oxo-1,3-dioxolane-4-acyl halides of formula (I), wherein X is selected from F, Cl, Br, I and mixtures thereof, preferably Cl, processes for the preparation of said 2-oxo-1,3-dioxolane-4-acyl halides, the use of said 2-oxo-1,3-dioxolane-4-acyl halides for the preparation of 2-oxo-1,3-dioxolane-4-carboxylic esters of formula (II), the use of said 2-oxo-1,3-dioxolane-4-acyl halides for the preparation of 2-oxo-1,3-dioxolane-4-carboxamides of formula (III), and also the use of said 2-oxo-1,3-dioxolane-4-acyl halides as agents for the blocking of amines.
1. 2-Oxo-1,3-dioxolane-4-acyl halide of formula (I),
wherein X is selected from F, Cl, Br, I and mixtures thereof.
2. The 2-Oxo-1,3-dioxolane-4-acyl halide according to claim 1 , wherein X is Cl.
3. A process for the preparation of the 2-oxo-1,3-dioxolane-4-acyl halide as defined in claim 1 , wherein 2-oxo-1,3-dioxolane-4-carboxylic acid of formula (X)
is reacted with an halogenation agent.
4. The process according to claim 3 , wherein the halogenation agent is SOCl 2 .
5. The process according to claim 4 , wherein the reaction is carried out without a solvent at an elevated temperature.
6. The process according to claim 5 , wherein the halogenation is carried out at about 60° C. in the presence of dimethylformamide as a catalyst.
7. A process comprising reacting the 2-oxo-1,3-dioxolane-4-acyl halide as defined in claim 1 with an alcohol R 1 —OH for the preparation of a 2-oxo-1,3-dioxolane-4-carboxylic ester of formula (II),
wherein R 1 is selected from 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.
8. A process comprising reacting the 2-oxo-1,3-dioxolane-4-acyl halide as defined in claim 1 with a multifunctional polyol comprising R 1 for the preparation of a 2-oxo-1,3-dioxolane-4-carboxylic ester of formula (II),
wherein R 1 is a radical having a valency of 2 to 6, which is substituted with 1 to 5 further 2-oxo-1,3-dioxolane-4-carboxylic ester groups.
9. A process comprising reacting the 2-oxo-1,3-dioxolane-4-acyl halide as defined in claim 1 with an amine NH 2 R 1 for the preparation of a 2-oxo-1,3-dioxolane-4-carboxamide of formula (III),
wherein 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 -aralkyl 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.
10. A process comprising reacting the 2-oxo-1,3-dioxolane-4-acyl halide as defined in claim 1 with a multifunctional amine comprising R 2 for the preparation of a 2-oxo-1,3-dioxolane-4-carboxamide of formula (III),
wherein R 1 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, C 6-12 -alkaryl groups, or a polypeptide residue, and R 2 is a radical having a valency of 2 to 6, which is substituted with 1 to 5 further 2-oxo-1,3-dioxolane-4-carboxamide groups.
11. A process comprising blocking an amine by reaction with the 2-oxo-1,3-dioxolane-4-acyl halide as defined in claim 1 .