Reduction of HMF ethers with metal catalyst

Patent metadata

Field	Value
Publication number	US-9422258-B2
Application number	US-201414215157-A
Country	US
Kind code	B2
Filing date	Mar 17, 2014
Priority date	Oct 30, 2008
Publication date	Aug 23, 2016
Grant date	Aug 23, 2016

Abstract

Methods of making reduced derivatives of hydroxymethyl furfural using metal catalysts are described. The derivatives may have tetrahydrofuran or furan nucleus with alkoxymethyl ether or ester moieties on the 5′ carbon and methanol on the 2′ carbon. Suitable metal catalyst include Raney nickel, a nickel catalyst with a zirconium promoter, a chromite catalyst with a barium, a palladium catalyst, such as palladium on carbon, or a ruthenium catalyst. Also provided are a new class of compounds, which are n-alkoxy hexane diols (i.e., 1,2 or 1,5 hexane diol ethers) and methods of making the same by reduction of furan or tetrahydrofuran derivatives.

First claim

The invention claimed is:

1. A method of making at least one desired compound selected from the group consisting of a (5-acyloxymethyl)-tetrahydrofuran-2-methanol compound of the formula:

and a (5-acyloxymethyl)-furan-2-methanol compound of the formula:

wherein R is an alkyl group of 1 to 5 carbons, comprising contacting a source of R-5′acyloxymethylfurfural ester with hydrogen and a catalyst selected from the group consisting of: a nickel catalyst, a nickel catalyst with a zirconium promoter, a copper chromite catalyst with a barium promoter, a ruthenium catalyst, and a palladium catalyst, at a temperature and a pressure and for a time selected to convert the R-5′acyloxymethylfurfural ester to at least one desired compound in a single step.

2. The method of claim 1 , where the source contains at least 40% of the R-5′acyloxymethylfurfural ester as a fraction of dissolved solutes in the source and the desired compound formed is predominantly the (5-acyloxymethyl)-tetrahydrofuran-2-methanol.

3. The method of claim 1 , where the source contains at least 40% of the R-5′acyloxymethylfurfural ester as a fraction of dissolved solutes in the source and the desired compound formed is predominantly the (5-acyloxymethyl)-furan-2-methanol.

4. The method of claim 1 , where the source contains less than 40% of the R-5′acyloxymethylfurfural ester as a fraction of dissolved solutes in the source and additionally contains at least 20% of a combination of alkyl levulinates and humins as a fraction of dissolved solutes in the source and the desired compound formed is predominantly the (5-acyloxymethyl)-furan-2-methanol.

5. The method of claim 1 , wherein the temperature is 140-250° C., the pressure is 500-1500 psi, the time is 30 min to 14 hours, the source is greater than 80% pure, and the reaction converts the acyloxymethylfurfural ester to the (5-acyloxymethyl)-tetrahydrofuran-2-methanol compound.

6. The method of claim 1 , wherein the temperature is 170-205° C., the source is less than 80% pure, the pressure is 950-1500 psi, the time is 3-7 hours, the catalyst is Raney nickel, and the reaction converts the acyloxymethylfurfural ester to the 5-(acyloxymethyl)-tetrahydrofuran-2-methanol compound.

7. The method of claim 1 , wherein the metal catalyst is on a substrate support.

8. The method of claim 1 , wherein the temperature is 140-250° C., the pressure is 500-1500 psi, the time is 30 min to 8 hours, the catalyst is barium promoted copper chromite, and the source is less than 80% pure.

9. The method of claim 1 , wherein the metal catalyst comprises nickel with a zirconium promoter on an inert substrate.

10. The method of claim 1 , wherein the contacting is in a solvent selected from the group consisting of methanol, ethanol, n-propanol, i-propanol, n-butanol, butanol, acetone, and ethyl acetate, fusel oil alcohols, and any combinations thereof.

Assignees

• Archer Daniels Midland Co

Inventors

• Bloom Paul
• Sanborn Alexandra

Classifications

• C09K3/00

  Materials not provided for elsewhere · CPC title

• C07D307/44

  Furfuryl alcohol · CPC title

• C07D307/12

  Radicals substituted by oxygen atoms · CPC title

• C08K5/06

  Ethers; Acetals; Ketals; Ortho-esters · CPC title

• C07C41/26

  by introduction of hydroxy or O-metal groups · CPC title