Method for reduction of organic molecules

Patent metadata

Field	Value
Publication number	US-10434504-B2
Application number	US-201816201519-A
Country	US
Kind code	B2
Filing date	Nov 27, 2018
Priority date	Feb 11, 2015
Publication date	Oct 8, 2019
Grant date	Oct 8, 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 such that the ruthenium center of the Ruthenium-Triphosphine-complex is shielded to prevent inactivation due to formation of a ruthenium dimer, wherein the organic molecules are selected from the group consisting of carboxylic acids, derivatives of carboxylic acids selected from the group consisting of esters, lactones and amides and derivatives of carbonic acids selected from the group consisting of CO2, carbamates, urethanes and ureas.

2. 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 moiety which is substituted in ortho and/or meta position to the phosphine bound thereto.

3. 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.

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

5. 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.

6. The method according to claim 5 , wherein step a) is performed under acidic conditions whereby the acid is a sulfonic acid.

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

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

9. The method according to claim 6 , 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.

10. The method according to claim 1 , wherein the carboxylic acid derivatives are selected from the group consisting of esters, lactones and amides and wherein the carbonic acid derivatives are selected from the group consisting of CO 2 , carbamates, urethanes and ureas.

11. The method according to claim 10 , 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.

12. The method according to claim 10 , 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.

13. The method according to claim 10 , wherein step a) is performed under acidic conditions.

14. The method according to claim 10 , 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.

15. The method according to claim 14 , wherein step a) is performed under acidic conditions whereby the acid is a sulfonic acid.

16. The method according to claim 10 , wherein step a) is carried out at an initial hydrogen pressure of ≥1 bar.

17. The method according to claim 10 , wherein step a) is carried out in a dipolar protic or aprotic solvent or in CO 2 .

18. The method according to claim 15 , 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

Inventors

• Klankermayer Jürgen
• Leitner Walter
• Meuresch Markus

Classifications

• B01J31/2409 Primary

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

• C07D307/33

  in position 2, the oxygen atom being in its keto or unsubstituted enol form · CPC title

• B01J2531/821

  Ruthenium · CPC title

• C07D307/06

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

• C07C67/303 Primary

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