Process for functionalizing biomass using molybdenum catalysts

Patent metadata

Field	Value
Publication number	US-9676737-B2
Application number	US-201414915114-A
Country	US
Kind code	B2
Filing date	Aug 29, 2014
Priority date	Aug 29, 2013
Publication date	Jun 13, 2017
Grant date	Jun 13, 2017

Abstract

The present invention concerns a process for converting biomass into useful organic building blocks for the chemical industry. The process involves the use of molybdenum catalysts of the formula A a+ a(Mo v X x R 1 y R 2 z R 3 e) a*3− , which may be readily prepared from industrial molybdenum compounds.

First claim

The invention claimed is:

1. A process for producing a reduced polyol comprising:
reaction of the polyol with a substrate in the presence of a molybdenum catalyst at a temperature of at least 175° C., wherein the substrate is the polyol itself, a polyol different from the polyol being reduced, H 2 , or a diol different from the polyol, wherein said molybdenum catalyst has the formula:
A α+ a (Mo v X x R 1 y R 2 z R 3 e ) α*a− ,
and wherein
A α+ is a mono-, di-, or trivalent counterion;
X is CO, O, OH, S, or Se;
R 1 is selected from the group consisting of H, F, Cl, Br, I, CN, N 3 , NCS, dithiocarbamates, CH 3 , BF 4 , PF 6 , SbF 6 , and AsF 6 ;
R 2 is a mono-, bi- or tridentate ligand;
R 3 is a ligand coordinating to the central molybdenum atom through its π-system selected from the group consisting of an alkene, a diene, a cyclopentadienyl, methylcyclopentadienyl, a pentamethylcyclopentadienyl radical, benzene, naphthalene, anthracene, and an aromatic;
a is 0, 1, 2, 3, 4, 5, or 6;
v is 1, 2, 3, 4, 5, 6, or 7;
x is in the range 2v to 6v;
y is 0, 1, 2, 3, 4, 5, 6, 7, or 8;
z is 0, 1, 2, or 3;
e is 0, 1, 2, or 3; and
α*a− is a negative charge, which balances the positive charge of A α+ a,

and wherein the process is carried out with a solvent, said polyol, said substrate, and said molybdenum catalyst being fully dissolved in said solvent;
and wherein the polyol is an alcohol containing a plurality of hydroxyl groups, wherein at least two of the hydroxyl groups are located on adjacent carbon atoms.

2. The process according to claim 1 , wherein the temperature is in the range 175 to 250° C.

3. The process according to claim 1 , wherein the polyol is a diol or a triol.

4. The process according to claim 3 , wherein the polyol is selected from the group consisting of 1,2-hexanediol, 1,2-tetradecanediol, and glycerol.

5. The process according to claim 4 , wherein the polyol is glycerol.

6. The process according to claim 1 , wherein the substrate is the polyol itself, H 2 , or a diol different from the polyol.

7. The process according to claim 6 , wherein the substrate is a diol different from the polyol.

8. The process according to claim 1 , wherein the amount of molybdenum catalyst is in the range 0.1 to 20 mol %.

9. The process according to claim 1 , wherein A α+ is Na + or NH 4 + .

10. The process according to claim 1 , wherein R 2 has one or more donor atoms selected from the group consisting of N, P, and S.

11. The process according to claim 10 , wherein R 2 is 2,2′-bipyridine.

12. The process according to claim 1 , wherein v is 1 or 7.

13. The process according to claim 1 , wherein a is 0, 2, or 6.

14. The process according to claim 1 , wherein the molybdenum catalyst is selected from the group consisting of Mo(CO) 6 , Mo(CO) 4 (bipy), MoO 2 Cl 2 (bipy), MoO 2 Br 2 (bipy), MoO 2 (CH 3 ) 2 (bipy), (NH 4 ) 6 Mo 7 O 24 .4H 2 O, Na 2 MoO 4 , and mixtures thereof, wherein bipy is 2,2′-bipyridine.

15. The process according to claim 1 , wherein the resulting product having the highest molar percentage is the corresponding compound wherein at least one α,β-dihydroxyl group has been converted into an α,β-carbon-carbon double bond.

16. The process according to claim 2 , wherein the temperature is in the range 180 to 220° C.

17. The process according to claim 2 , wherein the temperature is in the range 190 to 210° C.

18. The process according to claim 2 , wherein the temperature is in the range 195 to 205° C.

19. The process according to claim 8 , wherein the amount of molybdenum catalyst is in the range 1 to 15 mol %.

20. The process according to claim 8 , wherein the amount of molybdenum catalyst is in the range 2 to 10 mol %.

21. The process according to claim 8 , wherein the amount of molybdenum catalyst is in the range 3 to 8 mol %.

22. The process according to claim 8 , wherein the amount of molybdenum catalyst is in the range 4 to 7 mol %.

Assignees

• Univ Danmarks Tekniske
• Danmarks Tekniska Univ

Inventors

• Dethlefsen Johannes Rytter
• Fristrup Peter

Classifications

• C07D301/02 Primary

  Synthesis of the oxirane ring · CPC title

• C07C2527/24

  Nitrogen compounds · CPC title

• C07C2531/16

  containing coordination complexes · CPC title

• C07C45/00

  Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds · CPC title

• C07C2531/18

  containing nitrogen, phosphorus, arsenic or antimony · CPC title