Process for the synthesis of fluoralkyl sulfonate salts

Patent metadata

Field	Value
Publication number	US-9944593-B2
Application number	US-201415027167-A
Country	US
Kind code	B2
Filing date	Sep 30, 2014
Priority date	Oct 4, 2013
Publication date	Apr 17, 2018
Grant date	Apr 17, 2018

Abstract

A process for the preparation of the fluoroalkyl sulfonate salt of a nitrogen-based organic base said process comprising the step of reacting a fluoroalkyl sulfonyl halide with an organic base selected from the group consisting of tertiary amines, pyridines, amidines and guanidines.

First claim

The invention claimed is:

1. A process for the preparation of a fluoroalkyl sulfonate salt of any one of formula (VII), formula (VIII) or formula (IX):

wherein:
R f is selected from the group consisting of C 1 to C 25 straight-chain, branched or cyclic fluorinated alkyl or alkenyl, optionally substituted and/or optionally comprising heteroatoms selected from the group consisting of O, N and S in the chain;
each of R 4 , R 5 , R 6 , R 7 and R 8 , is independently selected from the group consisting of H, halogen, C 1 to C 25 straight-chain, branched or cyclic, optionally substituted, alkane or alkene, and C 6 to C 25 , optionally substituted, aryl or heteroaryl;
each of R 9 , R 10 , R 11 and R 12 , is independently selected from group consisting of H, C 1 to C 25 straight-chain, branched or cyclic, optionally substituted, alkane or alkene, optionally containing heteroatoms, wherein up to four of R 9 , R 10 , R 11 and R 12 may be bonded to one another in pairs by single or double bond; and
each of R 13 , R 14 , R 15 , R 16 and R 17 , is independently selected from the group consisting of H, C 1 to C 25 straight-chain, branched or cyclic, optionally substituted, alkane or alkene, optionally containing heteroatoms, wherein up to four of R 13 , R 14 , R 15 , R 16 and R 17 may be bonded to one another in pairs by single or double bond;

said process comprising the step of reacting a fluoroalkyl sulfonyl halide with an organic base selected from the group consisting of:
pyridines of formula (III):

amidines of formula (IV):

and
guanidines of formula (V):

wherein R 4 -R 17 are as defined above,
in the presence of an alcohol when using a pyridine or amidine organic base; or in the presence of water under basic conditions when using a guanidine organic base.

2. The process of claim 1 wherein the fluoroalkyl sulfonyl halide is selected from the group consisting of the fluoroalkyl sulfonates of formula (I) R f SO 2 X, wherein X is selected from F, Cl and Br; and R f is selected from the group consisting of C 1 to C 25 straight-chain, branched or cyclic fluorinated alkyl or alkenyl, optionally substituted and/or optionally comprising heteroatoms selected from the group consisting of O, N and S in the chain.

3. The process of claim 1 , wherein the fluoroalkyl sulfonyl halide is reacted with the organic base in the presence of an alcohol.

4. The process of claim 3 wherein the organic base is selected from the group consisting of pyridines and amidines.

5. The process of claim 3 , wherein fluroalkyl sulfonates of formulae (VII) and (VIII) are prepared by reacting a fluoro alkyl sulfonate of formula (I) with pyridines of formula (III) and amidines of formula (IV), and an alcohol of formula R′OH:

wherein R f is selected from the group consisting of C 1 to C 25 straight-chain, branched or cyclic fluorinated alkyl or alkenyl, optionally substituted and/or optionally comprising heteroatoms selected from the group consisting of O, N and S in the chain; each of R 4 , R 5 , R 6 , R 7 and R 8 , is independently selected from the group consisting of H, halogen, C 1 to C 25 straight-chain, branched or cyclic, optionally substituted, alkane or alkene, and C 6 to C 25 , optionally substituted, aryl or heteroaryl; each of R 9 , R 10 , R 11 and R 12 , is independently selected from group consisting of H, C 1 to C 25 straight-chain, branched or cyclic, optionally substituted, alkane or alkene, optionally containing heteroatoms, wherein up to four of R 9 , R 10 , R 11 and R 12 may be bonded to one another in pairs by single or double bond; and R′ is selected from the group consisting of C 1 -C 20 straight-chain, branched or cyclic, optionally substituted, alkyl optionally containing additional —OH groups, and C 6 -C 20 optionally substituted aryl or heteroaryl.

6. The process of claim 1 , wherein the fluoroalkyl sulfonyl halide is reacted with the organic base in the presence of water under basic conditions.

7. The process of claim 6 , wherein the organic base is a guanidine.

8. The process of claim 7 , wherein a guanidinium fluoro alkyl sulfonate of formula (IX) is obtained:

wherein R f is selected from the group consisting of C 1 to C 25 straight-chain, branched or cyclic fluorinated alkyl or alkenyl, optionally substituted and/or optionally comprising heteroatoms selected from the group consisting of O, N and S in the chain; and each of R 13 , R 14 , R 15 , R 16 and R 17 , is independently selected from the group consisting of H, C 1 to C 25 straight-chain, branched or cyclic, optionally substituted, alkane or alkene, optionally containing heteroatoms, wherein up to four of R 13 , R 14 , R 15 , R 16 and R 17 may be bonded to one another in pairs by single or double bond.

9. The process of claim 1 , wherein R f is selected from the group consisting of C 1 to C 16 straight-chain, branched or cyclic fluorinated alkyl, optionally substituted and/or optionally comprising heteroatoms selected from the group consisting of O, N and S in the chain.

10. The process of claim 1 , wherein R f is selected from —CF 3 , —CF 2 CF 3 , —CF 2 CF 2 H, —CF 2 CFHCl, —C 3 F 7 , —CF 2 CFHCF 3 , —CF 2 CFHOCF 3 , —CF 2 CF 2 OCF 2 CF 3 , —CF 2 CFHOCF 2 CF 3 , —CF 2 CF 2 OCFHCF 3 , —CF 2 CF 2 OCF 2 CF 2 H, —CF 2 CF 2 OCF 2 CF 2 CI, —CF 2 CF 2 OCFClCF 2 Cl, —CF 2 CFHOCF 2 CF 2 CF 3 , —CF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 CF 3 , —CF 2 CF 2 OCF(CF 3 )OCF 2 CF 2 CF 3 .

11. The process of claim 1 , wherein R f is CF 2 CF 2 OCFClCF 2 Cl.

12. The process of claim 1 , wherein the organic base is a pyridine of formula (III) and wherein:
R 4 , R 5 , R 6 , R 7 and R 8 are all H; or
R 4 and R 8 are CH 3 and R 5 , R 6 , R 7 are H; or
R 4 , R 6 and R 8 are CH 3 and R 5 and R 7 are H; or
R 4 and R 6 are CH 3 and R 5 , R 7 and R 8 are H.

13. The process of claim 1 , wherein the organic base is an amidine selected from 1, 8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 2,9-diazabicyclo[4.3.0]non-1,3,5,7-tetraene, and 6-(dibutylamino)-1,8-diazabicyclo[5.4.0]undecene-7.

14. The process of claim 1 , wherein the organic base is a guanidine selected from 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1,1-dimethylguanidine, 1,3-dimethylguanidine, 1,2-diphenylguanidine, 1,1,2-trimethylguanidine, 1,2,3-tricyclohexylguanidine, 1,1,2,2-tetramethylguanidine, guanine, 1,5,7-triazabicyclo[4.4.0]-dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-ethyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-propyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-isopropyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-cyclohexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 7-n-octyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.

Assignees

• Solvay Specialty Polymers It

Inventors

• Monzani Cristiano
• Tortelli Vito

Classifications

• C07D213/20 Primary

  Quaternary compounds thereof · CPC title

• C07C309/10

  with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom · CPC title

• C07C303/32 Primary

  of salts of sulfonic acids · CPC title

• C07C279/04

  having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton · CPC title

• C07C277/08

  of substituted guanidines · CPC title