Method for preparing cyclic carbonate

Patent metadata

Field	Value
Publication number	US-11292777-B2
Application number	US-201816316616-A
Country	US
Kind code	B2
Filing date	Jan 12, 2018
Priority date	Nov 30, 2017
Publication date	Apr 5, 2022
Grant date	Apr 5, 2022

Abstract

The present invention provides a method for preparing a cyclic carbonate, which has the advantages of high yield, mild reaction conditions, high catalytic efficiency under room temperature and 1 atm pressure conditions, and wide substrate scopes. It is not only suitable for monosubstituted epoxides, but also suitable for disubstituted epoxides. The method comprises the step of reacting epoxides of Formula (I) with carbon dioxide in the presence of a quaternary ammonium salt and a catalyst, to obtain a cyclic carbonate of Formula (II). The reaction formula is:

First claim

What is claimed is:

1. A method for preparing a cyclic carbonate, comprising a step of:
reacting an epoxide of Formula (I) with carbon dioxide in the presence of a quaternary ammonium salt and a catalyst, to obtain a cyclic carbonate of Formula (II), the reaction formula being:

and
the catalyst being an ethylenediamino bridged tetra(phenolate) rare earth-zinc heterobimetallic compound of Formula (III),

wherein:
R 1 and R 2 are independently selected from the group consisting of hydrogen, an alkyl, alkoxy, aryl and ester group; or
R 1 and R 2 are independently selected from alkyl and alkoxy, and R 1 and R 2 , together with the atoms to which they are attached, form a ring;
Ln is yttrium, ytterbium or samarium;
wherein the quaternary ammonium salt is selected from the group consisting of tetrabutylammonium iodide, tetrabutylammonium bromide, tetraoctylammonium bromide, bis(triphenylphosphine)ammonium chloride and any combination thereof; and
wherein a molar amount of the quaternary ammonium salt is 3-4 times a molar amount of the ethylenediamino bridged tetra(phenolate) rare earth-zinc heterobimetallic compound of formula (III).

2. The method for preparing a cyclic carbonate as claimed in claim 1 , wherein the alkyl group is a substituted or non-substituted linear or branched C 1-18 alkyl group, and the alkoxy group a substituted or non-substituted linear or branched C 1-18 alkoxy group.

3. The method for preparing a cyclic carbonate as claimed in claim 1 , wherein the aryl group is a substituted or non-substituted C 6-14 aryl group; and the ester group is —COO—R 3 , in which R 3 is H, C 1-10 alkyl or aryl group.

4. The method for preparing a cyclic carbonate as claimed in claim 2 , wherein the alkyl, alkoxy, or aryl group has one or more substituent(s) that is/are nitro, cyano, hydroxyl or halo, in which the halo is fluoro, chloro, bromo or iodo.

5. The method for preparing a cyclic carbonate as claimed in claim 1 , wherein:
R 1 and R 2 , together with the atoms to which they are attached, form a C 3-18 carbocyclic ring or a C 217 heterocyclic ring containing an oxygen atom.

6. The method for preparing a cyclic carbonate as claimed in claim 1 , wherein the temperature of addition reaction is 25-90° C.

7. The method for preparing a cyclic carbonate as claimed in claim 1 , wherein a molar ratio of the bridged tetra(phenolate) rare earth-zinc heterobimetallic compound to the epoxide of Formula (I) is 1:100-500.

8. The method for preparing a cyclic carbonate as claimed in claim 1 , wherein the catalyst of ethylenediamino bridged tetra(phenolate) rare earth-zinc heterobimetallic compound is synthesized by steps of:
1) synthesis of ethylenediamino bridged tetra(phenol) LH 4 : heating ethylenediamine, formaldehyde and 2, 4-di-tert-butylphenol at 75-85° C. for 60-72 h to obtain the ethylenediamino bridged tetra(phenol) LH 4 , wherein the molar ratio of ethylenediamine, formaldehyde and 2,4-di-tert-butylphenol is 1:4:6-1:4:8; and the reaction formula is:

2) synthesis of bridged tetra(phenolate) rare earth metal compound LLn (THF): reacting the ethylenediamino bridged tetra(phenol) with LnCp 3 (THF) in ether at 20-50 ° C. for 4-12 h in the absence of water and oxygen, to obtain the bridged tetra(phenolate) rare earth metal compound LLn(THF), wherein the molar ratio of the ethylenediamino bridged tetra(phenol) to LnCp 3 (THF) is 1:1-1:1.05, and the reaction formula is:

and
3) synthesis of bridged tetra(phenolate) rare earth-zinc heterobimetallic compound LnZnL(THF): reacting a solution of diethyl zinc in hexane or toluene with a solution of LnL(THF) in tetrahydrofuran at −5-50° C. for 8-12 h in the absence of water and oxygen, to obtain the bridged tetra(phenolate) rare earth-zinc heterobimetallic compound LnZnL(THF), wherein the molar ratio of diethyl zinc to LnL(THF) is 1:1-1.05:1, and the reaction formula is:

Assignees

• Univ Soochow

Inventors

• Yao Yingming
• Qu Liye

Classifications

• B01J2231/32

  Addition reactions to C=C or C-C triple bonds · CPC title

• B01J2531/36

  Yttrium · CPC title

• C07D317/44

  ortho- or peri-condensed with carbocyclic rings or ring systems · CPC title

• B01J31/2243

  At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand · CPC title

• B01J2531/26

  Zinc · CPC title