Process for functionalizing biomass using molybdenum catalysts

Patent metadata

Field	Value
Publication number	US-2016200641-A1
Application number	US-201414915114-A
Country	US
Kind code	A1
Filing date	Aug 29, 2014
Priority date	Aug 29, 2013
Publication date	Jul 14, 2016
Grant date	—

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

1 . A process for the reduction of a 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 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 rt-system selected from the group consisting of an alkene, a diene, a cyclopentadienyl, methylcyclopentadienyl, or pentamethylcyclopentadienyl radical, benzene, naphthalene, anthracene, or other aromatics;
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; and
e is 0, 1, 2, or 3, such as 0;
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 - 15 . (canceled)

16 . The process according to claim 1 , wherein the temperature is in the range 175 to 250° C., 180 to 220° C., 190 to 210° C., or 195 to 205° C.

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

18 . The process according to claim 17 , wherein the polyol is selected from the group consisting of 1,2-hexanediol, 1,2-tetradecanediol, and glycerol.

19 . The process according to claim 18 , wherein the polyol is glycerol.

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

21 . The process according to claim 20 , wherein the substrate is a diol different from the polyol.

22 . The process according to claim 1 , wherein the amount of molybdenum catalyst is in the range 0.1 to 2.0 mol %, 1 to 15 mol %, 2. to 10 mol %, 3 to 8 mol %, or 4 to 7 mol %.

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

24 . 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.

25 . The process according to claim 24 , wherein R 2 is 2,2′-bipyridine.

26 . The process according to claim 1 , wherein V is 1 or 7.

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

28 . 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, and Na 2 MoO 4 , or mixtures thereof, wherein bipy is 2,2′-bipyridine.

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

Assignees

• Univ Danmarks Tekniske

Inventors

• Dethlefsen Johannes Rytter
• Fristrup Peter

Classifications

• C07C2531/18

  containing nitrogen, phosphorus, arsenic or antimony · CPC title

• C07C29/60

  by elimination of -OH groups, e.g. by dehydration (C07C29/34 takes precedence) · CPC title

• C07C1/22 Primary

  by reduction · CPC title

• C07D301/02 Primary

  Synthesis of the oxirane ring · CPC title

• C07D303/04

  containing only hydrogen and carbon atoms in addition to the ring oxygen atoms · CPC title