Diallyl ethers of 2,5bis(hydroxymethyl)tetrahydrofuran and processes for making the same

Patent metadata

Field	Value
Publication number	US-9139545-B2
Application number	US-201314401199-A
Country	US
Kind code	B2
Filing date	Jun 10, 2013
Priority date	Jun 11, 2012
Publication date	Sep 22, 2015
Grant date	Sep 22, 2015

Abstract

The diallyl ether derivatives of the cis and trans stereoisomers of 2,5-bis(hydroxymethyl)tetrahydrofuran are produced. These materials are expected to be useful for making a variety of biobased polymers. Processes are further described for producing these diallyl ether derivatives in substantially quantitative yields.

First claim

The invention claimed is:

1. (2R,5S)-2,5-bis((allyloxy)methyl)tetrahydrofuran.

2. (2S,5S)-2,5-bis((allyloxy)methyl)tetrahydrofuran.

3. A process for making a diallyl ether derivative of at least one of the cis and trans stereoisomers of 2,5-bis(hydroxymethyl)tetrahydrofuran, comprising reacting at least one of the cis and trans isomers of 2,5-bis(hydroxymethyl)tetrahydrofuran with a Brønsted base whose conjugate acid has an acid dissociation constant pK a greater than 16 to form at least one corresponding conjugate base of an isomer of 2,5-bis(hydroxymethyl)tetrahydrofuran, then reacting the conjugate base or bases so formed with allyl bromide to form the corresponding diallyl ether derivative.

4. The process according to claim 3 , wherein the yield of the diallyl ether derivative or derivatives is substantially quantitative.

5. The process as in claim 3 , wherein the Brønsted base is a Bronsted base whose conjugate acid has an acid dissociation constant pK a of at least about 18.

6. The process as in claim 5 , wherein the Bronsted base is potassium t-butoxide and is reacted with the at least one of the cis and trans isomers of 2,5-bis(hydroxymethyl)tetrahydrofuran.

7. The process as in any one of claims 3 - 6 , which is carried out in a nonaqueous solvent system and in the absence of water.

8. The process as in claim 7 , carried out at a temperature of about 25 degrees Celsius or less.

9. The process as in claim 8 , carried out at a temperature of about 20 degrees Celsius or less.

10. The process as in claim 7 , wherein allyl bromide is added gradually over time.

11. The process as in claim 10 , wherein not more than about 13.3 percent of the allyl bromide is added per minute.

Assignees

• Archer Daniels Midland Co

Inventors

• Stensrud Kenneth

Classifications

• C07D493/04

  Ortho-condensed systems · CPC title

• B01J31/02

  containing organic compounds or metal hydrides · CPC title

• C07D307/12 Primary

  Radicals substituted by oxygen atoms · CPC title

• G06F1/1632 Primary

  External expansion units, e.g. docking stations · CPC title