# US 11,028,065 B1 · Continuous method for preparing carbonate esters

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- Number: US 11,028,065 B1
- Document ID: US11028065B1
- Status: Granted
- Kind: B1
- Application number: 16/812,628
- Filed: 2020-03-09
- Granted: 2021-06-08
- 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/US11028065B1

## 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 processes for preparing an 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:
Z is a covalent bond;
x is 0;
R is C1-C6 alkyl or C1-C6 fluoroalkyl bearing at least one fluoro substituent;
R2 is H, C1-C6 alkyl or C1-C6 fluoroalkyl bearing at least one fluoro substituent;
both R3 and R4 are CH2 and are not directly bonded together;
R and R′ independently are C1-C6 alkyl or C1-C6 fluoroalkyl comprising at least one fluoro substituent;
and wherein the first reactant is an alcohol of Formula (II):
the carbonyl source is a chloroformate of formula Cl(CO)OCH2R′; the catalyst is selected from the group consisting of a tertiary amine, an aromatic nitrogen-containing heterocycle, and quaternary ammonium hydroxide, the catalyst is present in the reaction stream at a concentration of about 100 to 150 mol % relative to the alcohol; and the reaction stream comprises an aprotic organic solvent selected from the groups consisting of a nitrile, a glycol ether, and ketone in which the alcohol, the chloroformate, and the catalyst are dissolved.

### Claim 2 (depends on 1)

The process of claim 1, wherein the alcohol is dissolved in the solvent at a concentration of about 0.5 to about 6 molar (M).

### Claim 3 (depends on 1)

The process of claim 1, wherein the solvent comprises acetonitrile.

### Claim 4 (depends on 1)

The process of claim 1, wherein the catalyst comprises diisopropylethylamine.

### Claim 5 (depends on 4)

The process of claim 4, wherein the alcohol is 2,2,2-trifluoroethanol; the carbonyl source is methylchloroformate; the catalyst is diisopropylethylamine; the solvent is acetonitrile; the alcohol is dissolved in the solvent at a concentration of about 0.5 to 6 M; and the continuous flow reactor is heated at a temperature in the range of about 30° C. to about 110° C.

### Claim 6

A continuous processes for preparing an 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:
Z is a covalent bond;
x is 0;
R1 is C1-C6 alkyl or C1-C6 fluoroalkyl bearing at least one fluoro substituent;
R2 is H, C1-C6 alkyl or C1-C6 fluoroalkyl bearing at least one fluoro substituent;
both R3 and R4 are CH2 and are not directly bonded together;
R is C1-C6 alkyl or C1-C6 fluoroalkyl comprising at least one fluoro substituent;
and wherein the first reactant is an alcohol of Formula (II):
the carbonyl source is carbonyldiimidazole (CDI); the catalyst is selected from the group consisting tertiary amine, an aromatic nitrogen-containing heterocycle, and a quaternary ammonium hydroxide; the catalyst is present in the reaction stream at a concentration of about 2 to 15 mol % relative to the alcohol; and the reaction stream comprises an aprotic organic solvent selected from the group consisting of a nitrile, an ester, an organic carbonate ester, an amide, a ketone, a sulfone, a sulfoxide, a halogenated hydrocarbon, a phosphoramide, and an ionic liquid, in which the alcohol, the CDI, and the catalyst are dissolved.

### Claim 7 (depends on 6)

The process of claim 6, wherein the alcohol is 2,2,2-trifluoroethanol.

### Claim 8 (depends on 6)

The process of claim 6, wherein the solvent comprises dimethylformamide.

### Claim 9 (depends on 6)

The process of claim 6, wherein the alcohol is present in the reaction stream in a respective molar ratio of alcohol-to-CDI of about 1.8:1 to about 2.6:1.

### Claim 10 (depends on 6)

The process of claim 6, wherein the alcohol is 2,2,2-trifluoroethanol; the solvent is selected from the group consisting of dimethylformamide, acetonitrile, acetone, and dimethylsulfoxide; the alcohol is present in the reaction stream in a respective molar ratio of alcohol to CDI of about 2:1 to about 3:1; and the continuous flow reactor is heated at a temperature in the range of about 50 to about 120° C.

### Claim 11 (depends on 1)

The process of claim 1, wherein the first reactant is the epoxide of Formula (III); the carbonyl source is carbon dioxide; the catalyst is selected from the group consisting of an acid addition salt 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; the catalyst is present in the reaction stream at a concentration of about 1 to 20 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 reaction stream comprises an aprotic organic solvent 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 and wherein the epoxide is 3,3,3,-trifluoropropylene-1,2-oxide.

### Claim 12 (depends on 11)

The process of claim 11, wherein the reaction stream flowing through the continuous flow reactor is heated at a temperature in the range of about 50° C. to about 120° C.

### Claim 13 (depends on 11)

The process of claim 11, wherein the solvent comprises acetonitrile.

### Claim 14 (depends on 11)

The process of claim 11, wherein the solvent is acetonitrile; the catalyst is selected from the group consisting of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, and benzyltriethylammonium bromide; the catalyst is present at a concentration of about 1 to about 15 mol % relative to the epoxide; and the continuous flow reactor is heated at a temperature in the range of about 50° C. to about 120° C.