Synthesis of carbamate or urea compounds

Patent metadata

Field	Value
Publication number	US-10597358-B2
Application number	US-201615544165-A
Country	US
Kind code	B2
Filing date	Jan 18, 2016
Priority date	Jan 16, 2015
Publication date	Mar 24, 2020
Grant date	Mar 24, 2020

Abstract

The invention pertains to the synthesis of carbamate and urea compounds. In particular the invention is directed to the synthesis of carbamate and urea compounds which may be used in the production of compounds that are used to stabilize nitrocellulose. The method of the invention comprises preparing a carbamate or urea derivative comprising reacting an amine and a carbonate or carbamate in the presence of an ionic liquid.

First claim

The invention claimed is:

1. A method for preparing an N,N-diaryl substituted urea derivative for nitrocellulose stabilization, said method comprising a first step of preparing a carbamate according to formula I, comprising reacting an amine according to formula II and a compound according to formula III, in the presence of a catalyst that comprises an N,N-dialkylimidazolium ionic liquid or a non-nucleophilic base

wherein
Ar 1 is an aryl that is optionally substituted with one or more of halide, alkoxy, alkyl, nitro, sulfonate, ester, amide and/or carboxylate;
Ar 2 is Ar 1 or an aryl that is optionally substituted with one or more of halide, alkoxy, alkyl, nitro, sulfonate, ester, amide and/or carboxylate;
X is an alkoxy, or an aryloxy and is optionally substituted with one or more of halide, alkoxy, alkyl, nitro, sulfonate, ester, amide and/or carboxylate; and
LG is an alkoxy, an aryloxy, an amine that is optionally substituted with one or two C 1 -C 4 alkyl groups, an amide, a sulfonate, a halide, a nitrate, a phosphate or a carboxylate;
wherein the catalyst is present in less than 50 mol % with respect to the amine according to formula II; and
followed by a second step wherein the carbamate according to formula I is reacted with an amine to form said N,N-diaryl substituted urea derivative for nitrocellulose stabilization.

2. The method according to claim 1 , wherein the catalyst comprises an N,N-dialkylimidazolium ionic liquid.

3. The method according to claim 2 , wherein the ionic liquid comprises a cation and an anion and wherein the cation is a N,N-dialkyl imidazolium, and the anion is selected from the group consisting of hydroxide, chloride, bromide, iodate, acetate, hexafluorophosphate, tetrafluoroborate and combinations thereof.

4. The method according to claim 1 , wherein the catalyst comprises a non-nucleophilic base.

5. The method according to claim 1 , wherein Ar 1 is a phenyl, optionally substituted with one or more of halide, alkoxy, nitro, sulfonate, ester, amide, and carboxylate and Ar 2 is Ar 1 or a phenyl that is optionally substituted with one or more of halide, alkoxy, nitro, sulfonate, ester, amide, and/or carboxylate.

6. The method according to claim 1 , wherein X is a C 1 -C 4 alkoxy or a C 6 -C 10 aryloxy.

7. The method according to claim 1 , wherein the amine according to formula II and compound according to formula III are reacted at a temperature of at least 90° C.

8. The method according to claim 1 , wherein the reaction between the amine according to formula II and the compound according to formula III also forms a protonated LG product and the protonated LG product is removed during said reaction.

9. The method according to claim 1 , wherein the amine reacted with the carbamate according to formula I in the second step is ammonia or methylamine.

10. The method according to claim 1 , wherein the carbamate according to formula I is converted into —N-methyl-N′,N′-diphenylurea (Akardite II), wherein Ar 1 and Ar 2 are both phenyl and X is —NHMe.

11. The method according to claim 4 , wherein the non-nucleophilic base is a superbase selected from the group consisting of amidines, phosphazenes, and guanidines.

12. The method according to claim 3 , wherein the cation is 1-ethyl-3-methylimidazolium or 1-butyl-3-methylimidazolium (BMIm).

13. The method according to claim 3 , wherein the anion is a hydroxide or a chloride.

14. The method according to claim 5 , wherein both Ar 1 and Ar 2 are phenyl such that the amine according to formula II is diphenylamine.

15. The method according to claim 1 , wherein the catalyst is present in less than 25 mol % with respect to the amine according to formula II.

16. The method according to claim 1 , wherein the catalyst is present in less than 10 mol % with respect to the amine according to formula II.

Assignees

• TNO

Inventors

• Van Der Heijden Antonius Eduard Dominicus Maria
• Van Geest Erik
• Van Den Elshout Jos Johan Matthijs Hugo

Classifications

• C07C273/1836 Primary

  from derivatives of carbamic acid · CPC title

• B01J31/0251

  Guanidides (R2N-C(=NR)-NR2) · CPC title

• B01J31/0284

  of an aromatic ring, e.g. pyridinium · CPC title

• C07C271/58

  with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring · CPC title

• B01J31/0265

  Phosphazenes, oligomers thereof or the corresponding phosphazenium salts (polyphosphazenes per se C07F9/067) · CPC title