2-oxo-1, 3-dioxolane-4-carboxylic acid and derivatives thereof, their preparation and use
View Patent ↗Proposed are 2-oxo-1,3-dioxolane-4-carboxylic acid and derivatives thereof, according to the following formula, in which R 1 represents a negative charge, hydrogen or can be preferably Me or Et or a radical having a valency of 2 to 5, which is substituted with an amount of further 2-oxo-1,3-dioxolane-4-carboxyl groups equal to the radical valency minus 1, as well as a process for their preparation by means of carboxylation of the corresponding epoxides, a process for their transesterification and their use for the preparation of hydroxyurethanes and as end groups for the blocking of amines.
1. A 2-Oxo-1,3-dioxolane-4-carboxylic acid ester according to formula (V),
wherein R 1 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, and phenyl.
2. The 2-Oxo-1,3-dioxolane-4-carboxylic acid ester according to claim 1 , selected from 4-methoxycarbonyl-2-oxo-1,3-dioxolane and 4-ethoxycarbonyl-2-oxo-1,3-dioxolane.
3. A 2-Oxo-1,3-dioxolane-4-carboxylic acid ester according to formula (V),
wherein R 1 is a radical having a valency of 2 to 5 derived by abstraction of all OH groups of a polyol having a valency of 2 to 5 and which is substituted by an amount of further 2-oxo-1,3-dioxolane-4-carboxylate groups of formula (VI)
equal to the radical valency minus 1.
4. The 2-Oxo-1,3-dioxolane-4-carboxylic acid ester according to claim 3 , wherein the polyol comprises C 2-4 -(poly)oxyalkylene groups.
5. A process for the preparation of a 2-oxo-1,3-dioxolane-4-carboxylic acid ester according to claim 1 , wherein an epoxide of formula (VII), is reacted with CO 2 ,
wherein R 1 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, and phenyl.
6. The process according to claim 5 , wherein the reaction is carried out at a temperature of from 15° C. to 150° C., optionally from 30° C. to 100° C., and at a pressure of from 1 bar to 100 bars, optionally from 20 bars to 100 bars.
7. The process according to claim 5 , wherein the reaction is carried out without solvent or in a polar aprotic solvent.
8. The process according to claim 5 , wherein the reaction is carried out in the presence of a catalyst selected from metal halides and halogen salts of organic nitrogen compounds and mixtures thereof.
9. The process according to claim 5 , wherein the 2-oxo-1,3-dioxolane-4-carboxylic acid ester is selected from 4-methoxycarbonyl-2-oxo-1,3-dioxolane and 4-ethoxycarbonyl-2-oxo-1,3-dioxolane.
10. The process for the preparation of a 2-oxo-1,3-dioxolane-4-carboxylic acid ester according to claim 3 , wherein the 2-oxo-1,3-dioxolane-4-carboxylic acid ester,
in which R 1 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, and phenyl,
is transesterified with a polyol having a valency of 2 to 5, optionally wherein the polyol comprises C 2-4 -(poly)oxyalkylene groups.
11. The process according to claim 10 , wherein the transesterification is carried out in the presence of an enzymatic catalyst or an acidic cation exchanger.
12. The process according to claim 10 , wherein the 2-oxo-1,3-dioxolane-4-carboxylic acid ester is selected from 4-methoxycarbonyl-2-oxo-1,3-dioxolane and 4-ethoxycarbonyl-2-oxo-1,3-dioxolane.
13. The 2-Oxo-1,3-dioxolane-4-carboxylic acid ester according to claim 3 , wherein the polyol is selected from the group consisting of diol, glycol, triol, tetraol, 1,4-butanediol, neopentyl glycol (2,2-dimethylolpropane), 1,1,1-trimethylolpropane, pentaerythritol and tetramethylolmethane, optionally modified with C 2-4 -alkylene oxide.