Method for reduction of organic molecules

Patent metadata

Field	Value
Publication number	US-10166534-B2
Application number	US-201515549908-A
Country	US
Kind code	B2
Filing date	Feb 11, 2015
Priority date	Feb 11, 2015
Publication date	Jan 1, 2019
Grant date	Jan 1, 2019

Abstract

A method for the reduction organic molecules comprising a Ruthenium-Triphosphine complex with aromatic ligands at the phosphors which are ortho or meta substituted.

First claim

The invention claimed is:

1. A method for the reduction of organic molecules, comprising the step of
a) hydrogenating at least one organic molecule in the presence of a Ruthenium-Triphosphine-complex whereby the triphosphine-complex comprises at least one aryl and/or heteroaryl moeity bound to a phosphine which is substituted in ortho and/or meta position to the phosphine, wherein the organic molecules are selected from the group consisting of carbonic acids, derivatives of carboxylic acids and derivatives of carbonic acids, wherein the carboxylic acid derivatives are selected from the group consisting of free acids, salts of free acids, acyclic anhydrides, cyclic anhydrides, lactames and imides and wherein the carbonic acid derivatives are selected from the group consisting of salts of carbonic acid, acyclic organic carbonates, cyclic organic carbonates, carbamic acids and salts of carbamic acids.

2. The method according to claim 1 , wherein the salts of carbonic acid are bicarbonates or carbonates.

3. The method according to claim 1 , wherein the Ruthenium-Triphosphine-complex comprises a phosphororganic compound where two or all three phosphors have an aryl and/or heteroaryl moeity which is substituted in ortho and/or meta position to the phosphine bound thereto.

4. The method according to claim 1 , wherein the Ruthenium-Triphosphine-complex comprises a phosphororganic compound of the following structure

whereby R 1 to R 6 are independent from each other substituted or unsubstituted aryl or heteroaryl provided that one of R 1 and R 2 , R 3 and R 4 , R 5 and R 6 is substituted in ortho and/or meta position to the phosphine, and R 7 is hydrogen or an organic moiety selected from the group consisting of an alkyl moiety, a cycloalkyl moiety and an aryl moiety.

5. The method according to claim 1 , wherein step a) is performed under acidic conditions.

6. The method according to claim 1 , wherein step a) is performed under acidic conditions whereby the initial concentration of acid is ≥0.5 to ≤20 times the concentration of Ruthenium in mol:mol.

7. The method according to claim 6 , wherein step a) is performed under acidic conditions whereby the acid is a sulfonic acid.

8. The method according to claim 1 , wherein step a) is carried out at an initial hydrogen pressure of ≥1 bar.

9. The method according to claim 1 , wherein step a) is carried out in a dipolar protic or aprotic solvent or in CO 2 .

10. The method according to claim 7 , wherein the sulfonic acid is selected from the group consisting of methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, p-bromobenzosulfonic acid, p-nitrobenzosulfonic acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, trifluoroacetic acid, perchloric acid, bis(trifluoromethane)sulfonimide and mixtures thereof.

Assignees

• Rwth Aachen
• Rheinisch Westfalische Technische Hochschule Rwth Aachen

Inventors

• Klankermayer Jürgen
• Leitner Walter
• Meuresch Markus

Classifications

• C07C67/303 Primary

  by hydrogenation of unsaturated carbon-to-carbon bonds · CPC title

• B01J2531/821

  Ruthenium · CPC title

• B01J31/2409 Primary

  with more than one complexing phosphine-P atom · CPC title

• C07C29/177

  with simultaneous reduction of a carboxy group · CPC title

• C07D307/06

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms · CPC title