Mono- and dialkyl ethers of furan-2,5-dimethanol and (tetra-hydrofuran-2,5-diyl)dimethanol and amphiphilic derivatives thereof

Patent metadata

Field	Value
Publication number	US-9670174-B2
Application number	US-201415038066-A
Country	US
Kind code	B2
Filing date	Dec 12, 2014
Priority date	Dec 19, 2013
Publication date	Jun 6, 2017
Grant date	Jun 6, 2017

Abstract

Linear mono- and dialkyl ethers of furan-2,5-dimethanol (FDM) and/or 2,5-bis(hydroxymethyl)tetrahydrofuran (bH-MTHF), methods for their preparation, and derivative chemical compounds thereof are described. In general, the synthesis process entails a reaction of FDM or bHMTHFs in a polar aprotic organic solvent having a permittivity ( )>8, at a temperature ranging from about −25 C to about 100 C, with either a) an unhindered Brnsted base with a pKa?15 or b) a hindered Brnsted base having minimum pKa of about 16, and a nucleophile.

First claim

I claim:

1. A process for preparing linear mono- and di-alkyl ethers of either furan-2,5-dimethanol (FDM) or 2,5-bis(hydroxymethyl)tetrahydrofuran (bHMTHF) comprising: contacting either FDM or bHMTHF in a polar aprotic organic solvent with a permittivity (∈)>8, at a temperature ranging from about −25° C. to about 100° C., with either a) an unhindered Brønsted base having a difference in pKa (ΔpKa)≧15 relative to the pKa of a hydroxyl group of either said FDM or bHMTHF, or b) a hindered Brønsted base and a nucleophile.

2. The process according to claim 1 , wherein said unhindered Brønsted base is a metallic hydride.

3. The process according to claim 2 , wherein said unhindered Brønsted base is at least one of a lithium, sodium, or potassium hydride.

4. The process according to claim 1 , wherein said unhindered Brønsted base is an organometallic base.

5. The process according to claim 4 , wherein said unhindered Brønsted base is at least one of an alkyl lithium, alkyl magnesium, or alkyl cuprate compound.

6. The process according to claim 1 , wherein said unhindered Brønsted base is a metal amide or Grignard reagent.

7. The process according to claim 1 , wherein said hindered Brønsted base is at least one of sodium or potassium t-butoxide, or lithium diisopropylamide.

8. The process according to claim 1 , wherein said hindered Brønsted base has a pKa of at least 16.

9. The process according to claim 8 , wherein said hindered Brønsted base has a pKa ≧20.

10. The process according to claim 1 , wherein said polar, aprotic organic solvent has a permittivity (∈)>30.

11. The process according to claim 1 , wherein said polar, aprotic organic solvent is at least one of: dimethylformamide (DMF), dimethylsulfoxide (DMSO), dimethylacetamide (DMA), N-methylpyrrolidone (NMP), hexamethylphosphoramide (HMPA), acetone, acetonitrile (ACN), nitromethane, sulfolane, tetrahydrofuran (THF), 1,4-dioxane, and ethyl acetate.

12. The process according to claim 1 , wherein said nucleophile is at least one of:
an alkyl halide or sulfonate with an alkyl chain length between C 5 -C 25 .

13. The process according to claim 12 , wherein said alkyl halide or sulfonate has an alkyl chain length between C 8 -C 18 .

14. The process according to claim 12 , wherein said halide is at least one of: Cl, Br, or I.

15. The process according to claim 12 , wherein said sulfonate is at least one of: a -OTf (triflate), -OMs (mesylate), -OTs (tosylate), -OBs (brosylate), or -OEs (esylate).

16. The process according to claim 1 , wherein said temperature is in a range from about
−10° C. to about 70° C.

17. The process according to claim 1 , wherein said temperature is in a range from about
−5° C. to about 35° C.

18. The process according to claim 1 , wherein said mono- and diethers of FDM and bHMTHF have linear hydrocarbon chain lengths of C 5 -C 25 .

19. The process according to claim 18 , wherein said mono- and diethers of bHMTHF and FDM have linear hydrocarbon chain lengths of C 6 -C 18 .

20. A method of preparing a mono-ether comprising: contacting FDM with a Brønsted base and 1 or less molar equivalents of an alkyl-X species according to the following:

wherein: “X” is the leaving group, “n” is an integer from 5 to 25, and “CA” is a conjugate acid.

21. A mono-ether of FDM prepared according to claim 20 , wherein said mono-ether of FDM is at least one of the following compounds:
a. (5-((octadecyloxy)methyl)furan-2-yl)methanol

b. (5-((dodecyloxy)methyl)furan-2-yl)methanol

and
a. (5-((hexyloxy)methyl)furan-2-yl)methanol

22. A method of preparing a di-ether comprising: contacting FDM with a Brønsted base and a minimum of 2 molar equivalents of an alkyl-X species according to the following:

wherein: “X” is the leaving group, “n” is an integer from 5 to 25, and “CA” is a conjugate acid of the base.

23. A di-ether of FDM prepared according to claim 22 , wherein said di-ether of FDM is at least one of the following compounds:
a. 2,5-bis((hexyloxy)methyl)furan

b. 2,5-bis((dodecyloxy)methyl)furan

24. A method of preparing a mono-ether comprising: contacting bHMTHFs with a Brønsted base and 1 or less molar equivalents of an alkyl-X species according to at least one of the following:

wherein: “X” is the leaving group, “n” is an integer from 5 to 25, and “CA” is a conjugate acid.

25. A mono-ether of bHMTHF prepared according to claim 24 , wherein said mono-ether of bHMTHF is at least one of the following compounds:
a. ((2S,5R)-5-((hexyloxy)methyl)tetrahydrofuran-2-yl)methanol

b. ((2S,5S)-5-((hexyloxy)methyl)tetrahydrofuran-2-yl)methanol

c. ((2S,5S)-5-((hexyloxy)methyl)tetrahydrofuran-2-yl)methanol

d. ((2S,5R)-5-((dodecyloxy)methyl)tetrahydrofuran-2-yl)methanol

e. ((2S,5S)-5-((dodecyloxy)methyl)tetrahydrofuran-2-yl)methanol

f. ((2S,5S)-5-((dodecyloxy)methyl)tetrahydrofuran-2-yl)methanol

26. A method of preparing a di-ether comprising: contacting bHMTHFs with a Brønsted base and a minimum of 2 molar equivalents of an alkyl-X species according to the following:

wherein: “X” is the leaving group, “n” is an integer from 5 to 25, and “CA” is a conjugate acid.

27. A di-ether of bHMTHF prepared according to claim 26 , wherein said di-ether of bHMTHF is at least one of the following compounds:
a. (2R,5S)-2,5-bis((hexyloxy)methyl)tetrahydrofuran

b. (2S,5S)-2,5-bis((hexyloxy)methyl)tetrahydrofuran

c. (2R,5S)-2,5-bis((dodecyloxy)methyl)tetrahydrofuran

d. (2S,5S)-2,5-bis((dodec

Assignees

• Archer Daniels Midland Co

Inventors

• Stensrud Kenneth

Classifications

• C07D307/12 Primary

  Radicals substituted by oxygen atoms · CPC title

• C07D307/52

  Radicals substituted by nitrogen atoms not forming part of a nitro radical · CPC title

• C07D307/42

  Singly bound oxygen atoms · CPC title

• C07D307/14 Primary

  Radicals substituted by nitrogen atoms not forming part of a nitro radical · CPC title