# US 2021/0276969 A1 · Continuous method for preparing carbonate esters

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- Number: US 2021/0276969 A1
- Document ID: US20210276969A1
- Status: Published application
- Kind: A1
- Application number: 17/209,742
- Filed: 2021-03-23
- Published: 2021-09-09
- Earliest claimed: 2020-03-09
- Assignees: Uchicago Argonne, LLC
- Applicants: Uchicago Argonne, LLC
- Inventors: Trevor L. DZWINIEL; Krzysztof PUPEK
- Web page: https://patentgrep.com/patent/US20210276969A1

## CPC

- C07D 317/40: Vinylene carbonate; Substituted vinylene carbonates
- B01J 31/0232: {also containing elements or functional groups covered by B01J31/0201 - B01J31/0228 (perfluorinated sulfonyl compounds or moieties B01J31/0224; perfluorosulfonic acids B01J31/0227)}
- B01J 31/0237: {Amines}
- B01J 31/0239: {Quaternary ammonium compounds}
- B01J 31/0244: {with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine}
- C07C 68/00: Preparation of esters of carbonic or haloformic acids
- C07C 68/02: from phosgene or haloformates
- C07C 69/96: Esters of carbonic or haloformic acids
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

In one embodiment, a continuous process for preparing organic carbonate solvent of Formula (I) as described herein comprises contacting a first reactant (an alcohol) with a reactive carbonyl source (carbonyldiimidazole (CDI) or an alkylchloroformate) in the presence of a catalyst in reaction stream flowing through a continuous flow reactor at temperature 20° C. to about 160° C. and at a flow rate providing a residence time in the range of about 0.1 minute to about 24 hours; collecting a reactor effluent exiting from the continuous flow reactor; recovering a crude product from the reactor effluent; and distilling the crude product to obtain the organic carbonate compound of Formula (I). In another embodiment, the first reactant is an epoxide and the carbonyl source is carbon dioxide.

## Claims

### Claim 1

A continuous process for preparing organic carbonate solvent of Formula (I):
comprising the steps of:
(a) contacting a first reactant with a reactive carbonyl source in reaction stream containing a catalyst flowing through a continuous flow reactor at a temperature in the range of about 20° C. to about 160° C., and at a flow rate providing a residence time in the range of about 0.1 minute to about 24 hours;
(b) optionally quenching any remaining reactive carbonyl source;
(c) collecting a reactor effluent exiting from the continuous flow reactor;
(d) recovering a crude product from the reactor effluent; and
(e) purifying the crude product to obtain the organic carbonate compound of Formula (I);
wherein:
the reactive carbonyl source is carbon dioxide; and the first reactant is an epoxide of Formula (III):
the catalyst comprises at least one material selected from the group consisting of a bicyclic amidine, an acid addition salt of a phosphazene, an acid addition salt of a bicyclic guanidine, a quaternary ammonium halide, and a quaternary phosphonium halide;
Z is a covalent bond;
x is 1;
R and R1 are the same and are selected from the group consisting of (a) C1-C6 alkyl and (b) C1-C6 fluoroalkyl comprising at least one fluoro substituent;
R2 is H;
R3 and R4 both are CH and are directly connected by the covalent bond Z.

### Claim 2 (depends on 1)

The process of claim 1, wherein the reaction stream further comprises an aprotic organic solvent in which the first reactant, the carbonyl source, and the catalyst are dissolved.

### Claim 3 (depends on 2)

The process of claim 2, wherein the aprotic organic solvent comprises at least one material selected from the group consisting of an ether, a nitrile, an ester, an organic carbonate ester, an amide, a ketone, a sulfone, a sulfoxide, a hydrocarbon, a halogenated hydrocarbon, and a phosphoramide.

### Claim 4 (depends on 2)

The process of claim 2, wherein the aprotic organic solvent is selected from the group consisting of a nitrile, an ester, an organic carbonate ester, an amide, a ketone, a sulfone, a sulfoxide, and a halogenated hydrocarbon.

### Claim 5 (depends on 2)

The process of claim 2, wherein the aprotic organic solvent comprises acetonitrile.

### Claim 6 (depends on 2)

The process of claim 2, wherein the epoxide is dissolved in the aprotic organic solvent at a concentration of about 0.5 to about 6 molar (M).

### Claim 7 (depends on 1)

The process of claim 1, wherein R and R1 are C1 to C4 alkyl.

### Claim 8 (depends on 1)

The process of claim 1, wherein R and R1 are C1 to C4 fluoroalkyl comprising at least one fluoro substituent.

### Claim 9 (depends on 1)

The process of claim 1, wherein the catalyst is present in the reaction stream at a concentration of about 1 to 20 mol % relative to the epoxide.

### Claim 10 (depends on 9)

The process of claim 9, wherein the catalyst is present at a concentration of about 1 to about 15 mol % relative to the epoxide.

### Claim 11 (depends on 1)

The process of claim 1, wherein the carbon dioxide is present in the reaction stream at a pressure in the range of about 1 to about 10 bar.

### Claim 12 (depends on 1)

The process of claim 1, wherein the reaction stream flowing through the continuous flow reactor is heated in step (a) at a temperature in the range of about 50° C. to about 120° C.

### Claim 13 (depends on 1)

The process of claim 1, wherein the catalyst is selected from the group consisting of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, and benzyltriethylammonium bromide.

### Claim 14 (depends on 1)

The process of claim 1, wherein the epoxide is 3,3,3,-trifluoropropylene-1,2-oxide.

### Claim 15 (depends on 1)

The process of claim 1, wherein the compound of Formula (I) is purified in step (e) by distillation.

### Claim 16 (depends on 1)

The process of claim 1, wherein the epoxide is dissolved in an aprotic organic solvent at a concentration of about 0.5 to about 6 molar (M); the catalyst is selected from the group consisting of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, and benzyltriethylammonium bromide; the catalyst is present in the reaction stream at a concentration of about 1 to about 15 mol % relative to the epoxide; the carbon dioxide is present in the reaction stream at a pressure in the range of about 1 to about 10 bar; and the continuous flow reactor is heated in step (a) at a temperature in the range of about 50° C. to about 120° C.

### Claim 17 (depends on 16)

The process of claim 16, wherein the aprotic organic solvent is selected from the group consisting of a nitrile, an ester, an organic carbonate ester, an amide, a ketone, a sulfone, a sulfoxide, and a halogenated hydrocarbon.

### Claim 18 (depends on 16)

The process of claim 16, wherein the aprotic organic solvent is acetonitrile.

### Claim 19 (depends on 16)

The process of claim 16, wherein the epoxide is 3,3,3,-trifluoropropylene-1,2-oxide.