Electrochemical synthesis of dicarbamates

Patent metadata

Field	Value
Publication number	US-2018347055-A1
Application number	US-201515527901-A
Country	US
Kind code	A1
Filing date	Nov 25, 2015
Priority date	Nov 28, 2014
Publication date	Dec 6, 2018
Grant date	—

Abstract

The invention relates to an electrochemical process for preparing bis-O-alkyl-carbamates from primary amines with CO 2 as carbonyl source and at least one alkyl halide with at least three carbon atoms in the alkyl group as alkylating agent.

First claim

1 . An electrochemical process for preparing bis-O-alkyl-carbamates comprising alkylating a primary diamines with CO 2 as carbonyl source and with an alkylating agent containing at least one alkyl halide having at least three carbon atoms in the alkyl group in the presence of at least one iodide source, wherein the process is carried out at 10° C. to 215° C.

2 . The electrochemical process according to claim 1 , wherein the process is carried out at 20° C. to 215° C.

3 . The electrochemical process according to claim 1 , wherein the iodide source is used in an amount of at least 0.5 mol-%, relative to the alkyl halide/the sum of the alkyl halides.

4 . The electrochemical process according to claim 1 , wherein the iodide source is selected from the group consisting of symmetrically-substituted tetralkyl ammonium iodides, asymmetrically-substituted tetralkyl ammonium iodides and sodium iodide.

5 . The electrochemical process according to claim 1 , wherein the iodide source is selected from the group consisting of tetrabutyl ammonium iodide (TBAI) and tetraethyl ammonium iodide (TEAI).

6 . The electrochemical process according to claim 1 , wherein the alkyl halide is activated by heat treatment at 60° C. to 215° C.

7 . The electrochemical process according to claim 1 , wherein the primary diamine is selected from aliphatic primary diamines and aromatic primary diamines.

8 . The electrochemical process according to claim 1 , wherein the primary diamine is selected from the group consisting of 1,6-diaminohexane, 4,4′-methylenebis(cyclohexylamine), 5-Amino-1,3,3-trimethylcyclo-hexanemethyl-amine, 1,4-diaminobenzene and 2,4-diaminotoluene.

9 . The process according to claim 1 , wherein the alkyl halide is selected from the group consisting of alkyl iodides and alkyl chlorides.

10 . The process according to claim 1 , wherein the alkyl halide is selected from the group consisting of n-butyl chloride, iso-butyl chloride and t-butyl chloride.

11 . The process according to claim 1 , wherein the process is carried out in a solvent.

12 . The process according to claim 11 , wherein the solvent is selected from the group consisting of DMF, DMSO, 1,2-dimethoxy ethane and N-methyl-2-pyrrolidone.

13 . The process according to claim 11 , wherein the solvent is acetonitrile.

14 . The process according to claim 6 , wherein the heat treatment is carried under reflux.

15 . The process according to claim 1 , wherein the process is carried out under normal pressure (1 atm).

16 . The electrochemical process according to claim 1 , wherein the process is carried out 60° C. to 195° C.

17 . The electrochemical process according to claim 1 , wherein the iodide source is in an amount of 1 to 5 mol-% relative to the alkyl halide/the sum of the alkyl halides.

18 . The electrochemical process according to claim 4 , wherein the iodide source is in pure form.

19 . The electrochemical process according to claim 4 , wherein the iodide source is in association with one selected from the group consisting of 15-crown-5, 18-crown-6, and potassium iodide.

Assignees

• Covestro Deutschland Ag

Inventors

• Richter Frank
• Heckroth Heike
• Trieu Vinh
• Feroci Marta
• Forte Gianpiero
• Inesi Achille
• Chiarotto Isabella

Classifications

• C07C269/04 Primary

  from amines with formation of carbamate groups · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• C25B3/07

  Oxygen containing compounds · CPC title

• C25B3/09

  Nitrogen containing compounds · CPC title

• C25B3/25 Primary

  Reduction · CPC title