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- Nachgewiesen in: USPTO Patent Grants
- Sprachen: English
- Patent Number: 6,248,889
- Publication Date: June 19, 2001
- Appl. No: 09/196,512
- Application Filed: November 20, 1998
- Assignees: 3M Innovative Properties Company (St. Paul, MN)
- Claim: What is claimed is
- Claim: 1. A process for preparing a fluoride from its corresponding alcohol comprising the steps of (a) forming a mixture comprising (i) at least one fluorinated, saturated aliphatic or alicyclic sulfonyl fluoride and (ii) at least one primary or secondary alcohol; and (b) adding a molar excess of at least one strong, aprotic, non-nucleophilic, hindered, double bond-containing, organic base to said mixture.
- Claim: 2. The process of claim 1 further comprising the step of cooling said mixture to a temperature in the range of about -30.degree. C. to about 0.degree. C. before adding said base.
- Claim: 3. The process of claim 1 wherein said sulfonyl fluoride is represented by the general formula R.sub.f SO.sub.2 F, where R.sub.f is selected from the group consisting of perfluorinated alkyl groups having from 1 to about 10 carbon atoms; partially-fluorinated alkyl groups having from 1 to about 10 carbon atoms; unsubstituted or perfluoroalkyl-substituted, perfluorinated cycloalkyl groups having from about 4 to about 8 carbon atoms; and unsubstituted or perfluoroalkyl-substituted, partially-fluorinated cycloalkyl groups having from about 4 to about 8 carbon atoms.
- Claim: 4. The process of claim 3 wherein said R.sub.f is a perfluorinated alkyl group having from 1 to about 10 carbon atoms.
- Claim: 5. The process of claim 1 wherein said sulfonyl fluoride is selected from the group consisting of CF.sub.3 SO.sub.2 F, C.sub.2 F.sub.5 SO.sub.2 F, C.sub.4 F.sub.9 SO.sub.2 F, C.sub.6 F.sub.13 SO.sub.2 F, C.sub.8 F.sub.17 SO.sub.2 F, C.sub.10 F.sub.21 SO.sub.2 F, cyclo-(C.sub.6 F.sub.11)SO.sub.2 F, C.sub.2 F.sub.5 -cyclo-(C.sub.6 F.sub.10) SO.sub.2 F, H(CF.sub.2).sub.4 SO.sub.2 F, H(CF.sub.2).sub.8 SO.sub.2 F, and mixtures thereof.
- Claim: 6. The process of claim 5 wherein said sulfonyl fluoride is selected from the group consisting of perfluorobutanesulfonyl fluoride, perfluorohexanesulfonyl fluoride, perfluorooctanesulfonyl fluoride, and mixtures thereof.
- Claim: 7. The process of claim 6 wherein said sulfonyl fluoride is perfluorobutanesulfonyl fluoride.
- Claim: 8. The process of claim 1 wherein said alcohol is represented by the general formula R.sub.1 R.sub.2 CH--OH where R.sub.1 and R.sub.2 are independently selected from the group consisting of branched or linear aliphatic groups, alicyclic groups, araliphatic groups, aromatic groups, hydrogen, branched or linear fluoroaliphatic groups, fluoroalicyclic groups, fluoroaraliphatic groups, and fluoroaromatic groups; wherein said aliphatic, alicyclic, araliphatic, fluoroaliphatic, fluoroalicyclic, and fluoroaraliphatic groups can contain catenary heteratoms and/or one or two olefinic double bonds.
- Claim: 9. The process of claim 8 wherein said R.sub.1 and R.sub.2 are independently selected from the group consisting of branched or linear aliphatic groups, branched or linear fluoroaliphatic groups, araliphatic groups, and alicyclic groups.
- Claim: 10. The process of claim 9 wherein said R.sub.1 and R.sub.2 are independently selected from the group consisting of branched or linear aliphatic groups, branched or linear fluoroaliphatic groups, and araliphatic groups.
- Claim: 11. The process of claim 8 wherein said fluoroaliphatic groups comprise a moiety that is represented by the formula --D--R.sub.f ', where D is selected from the group consisting of a covalent bond, --O--, --OC.sub.r H.sub.2r --, --O(C.sub.r H.sub.2r O).sub.t --C.sub.r H.sub.2r --, --C.sub.r H.sub.2r --, and --(C.sub.r H.sub.2r O).sub.t --C.sub.r H.sub.2r --, where r is an integer of 1 to about 20 and t is an integer of 1 to about 6; and R.sub.f ' is selected from the group consisting of --(C.sub.x F.sub.2x O).sub.z C.sub.y F.sub.2y+1 and --C.sub.q F.sub.2q X, where x is independently an integer of 1 to about 10 for each C.sub.x F.sub.2x O group, y is an integer of 1 to about 10, z is an integer of 1 to about 10, q is an integer of 1 to about 15, and X is selected from the group consisting of hydrogen and fluorine.
- Claim: 12. The process of claim 1 wherein said alcohol is selected from the group consisting of
- Claim: CH.sub.3 CHOHCH(CH.sub.3).sub.2
- Claim: C.sub.6 H.sub.11 OH
- Claim: C.sub.6 F.sub.11 CHOHCH.sub.3
- Claim: C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OH
- Claim: C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 OH
- Claim: C.sub.6 H.sub.5 CHOHC.sub.6 H.sub.5
- Claim: C.sub.6 F.sub.5 CHOHC.sub.6 H.sub.5
- Claim: CH.sub.3 OCOCH.sub.2 CHOHCH.sub.2 CH.sub.3
- Claim: C.sub.10 H.sub.11 OH(1,2,3,4-tetrahydro-2-hydroxynaphthalene)
- Claim: CH.sub.2.dbd.CH(CH.sub.2).sub.n CH(OH)CH.sub.2 OCH.sub.2 --(C.sub.x F.sub.2x O).sub.z C.sub.y F.sub.2y+1
- Claim: C.sub.6 H.sub.5 CH.sub.2 O(CH.sub.2).sub.n CH(OH)CH.sub.2 --(C.sub.x F.sub.2x O).sub.z C.sub.y F.sub.2y+1
- Claim: CH.sub.3 C(.dbd.O)O(CH.sub.2).sub.n CH(OH)CH.sub.2 OCH.sub.2 --(C.sub.x F.sub.2x O).sub.z C.sub.y F.sub.2y+1
- Claim: THP--O(CH.sub.2).sub.n CH(OH)CH.sub.2 OCH.sub.2 --(C.sub.x F.sub.2x O).sub.z C.sub.y F.sub.2y+1
- Claim: C.sub.8 H.sub.17 --C.sub.4 H.sub.2 N.sub.2 --C.sub.6 H.sub.4 O(CH.sub.2).sub.n CH(OH)CH.sub.2 OCH.sub.2 (C.sub.x F.sub.2x O).sub.z C.sub.y F.sub.2y+1
- Claim: C.sub.7 H.sub.15 --C.sub.4 H.sub.2 N.sub.2 --C.sub.6 H.sub.4 O(CH.sub.2).sub.n CH(OH)CH.sub.2 OCH.sub.2 (C.sub.x F.sub.2x O).sub.z C.sub.y F.sub.2y+1
- Claim: C.sub.6 H.sub.13 --C.sub.4 H.sub.2 N.sub.2 --C.sub.6 H.sub.4 O(CH.sub.2).sub.n CH(OH)CH.sub.2 OCH.sub.2 (C.sub.x F.sub.2x O).sub.z C.sub.y F.sub.2y+1
- Claim: C.sub.8 H.sub.17 O--C.sub.4 H.sub.2 N.sub.2 --C.sub.6 H.sub.4 O(CH.sub.2).sub.n CH(OH)CH.sub.2 OCH.sub.2 (C.sub.x F.sub.2x O).sub.z C.sub.y F.sub.2y+1
- Claim: C.sub.7 H.sub.15 O--C.sub.4 H.sub.2 N.sub.2 --C.sub.6 H.sub.4 O(CH.sub.2).sub.n CH(OH)CH.sub.2 OCH.sub.2 (C.sub.x F.sub.2x O).sub.z C.sub.y F.sub.2y+1
- Claim: C.sub.6 H.sub.13 O--C.sub.4 H.sub.2 N.sub.2 --C.sub.6 H.sub.4 O(CH.sub.2).sub.n CH(OH)CH.sub.2 OCH.sub.2 (C.sub.x F.sub.2x O).sub.z C.sub.y F.sub.2y+1
- Claim: CH.sub.3 (CH.sub.2).sub.b CH(OH)(CH.sub.2).sub.m CH.dbd.CH.sub.2
- Claim: CH.sub.3 (CH.sub.2).sub.b CH(OH)(CH.sub.2).sub.m OC(.dbd.O)CH.sub.3, CH.sub.3 (CH.sub.2).sub.b CH(OH)(CH.sub.2).sub.m O--THP
- Claim: CH.sub.3 (CH.sub.2).sub.b CH(OH)(CH.sub.2).sub.m OCH.sub.2 C.sub.6 H.sub.5, 16alpha-hydroxyestone, 3beta-hydroxycholestan, 3alpha-andostan, 16beta-hydroxy-3-[[(trifluoromethyl)sulfonyl]oxy]esta-1,3,5(10)-trien-17-o ne, thymidine, 5'-deoxythymidine, uridine, 2'-deoxyuridine, 2'-deoxy-5-(trifluoromethyl)uridine, guanosine, 2'-deoxyguanosine, adenosine, 2'-desoxyadensoine, 5'-deoxyadenosine, and mixtures thereof, where x is independently an integer of 1 to about 10 for each C.sub.x F.sub.2x O group, y is an integer of 1 to about 10, and z is an integer of 1 to about 10, where n and m are independently integers of one to about ten, b is an integer of zero to about 10, and THP=tetrahydropyranyl.
- Claim: 13. The process of claim 1 wherein said alcohol is selected from the group consisting of
- Claim: CH.sub.2.dbd.CH(CH.sub.2).sub.2 CH(OH)CH.sub.2 OCH.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OC.sub.4 F.sub.9
- Claim: C.sub.6 H.sub.5 CH.sub.2 O(CH.sub.2).sub.2 CH(OH)CH.sub.2 OCH.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OC.sub.4 F.sub.9
- Claim: CH.sub.3 C(.dbd.O)O(CH.sub.2).sub.2 CH(OH)CH.sub.2 OCH.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OC.sub.4 F.sub.9
- Claim: THP--OCH.sub.2 CH(OH)CH.sub.2 OCH.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OC.sub.4 F.sub.9
- Claim: CH.sub.2.dbd.CH(CH.sub.2).sub.2 CH(OH)CH.sub.2 OCH.sub.2 CF.sub.2 O(CF.sub.2 CF.sub.2 O).sub.2 CF.sub.3
- Claim: CH.sub.3 C(.dbd.O)O(CH.sub.2).sub.2 CH(OH)CH.sub.2 CH.sub.2 OCH.sub.2 CF.sub.2 O(CF.sub.2 CF.sub.2 O).sub.2 CF.sub.3
- Claim: C.sub.6 H.sub.5 CH.sub.2 O(CH.sub.2).sub.2 CH(OH)CH.sub.2 CH.sub.2 OCH.sub.2 CF.sub.2 O(CF.sub.2 CF.sub.2 O).sub.2 CF.sub.3
- Claim: THP--O(CH.sub.2).sub.2 CH(OH)CH.sub.2 CH.sub.2 OCH.sub.2 CF.sub.2 O(CF.sub.2 CF.sub.2 O).sub.2 CF.sub.3
- Claim: CH.sub.2.dbd.CH(CH.sub.2).sub.2 CH(OH)CH.sub.2 OCH.sub.2 CF.sub.2 CF.sub.2 OC.sub.2 F.sub.5
- Claim: C.sub.6 H.sub.5 CH.sub.2 O(CH.sub.2).sub.2 CH(OH)CH.sub.2 OCH.sub.2 CF.sub.2 CF.sub.2 OC.sub.2 F.sub.5
- Claim: CH.sub.3 C(.dbd.O)O(CH.sub.2)CH(OH)CH.sub.2 OCH.sub.2 CF.sub.2 CF.sub.2 OC.sub.2 F.sub.5
- Claim: THP--O(CH.sub.2).sub.2 CH(OH)CH.sub.2 OCH.sub.2 CF.sub.2 CF.sub.2 OC.sub.2 F.sub.5
- Claim: C.sub.6 H.sub.5 CH.sub.2 O(CH.sub.2).sub.2 CH(OH)CH.sub.2 OCH.sub.2 C.sub.7 F.sub.15
- Claim: C.sub.6 H.sub.5 CH.sub.2 O(CH.sub.2).sub.2 CH(OH)CH.sub.2 OCH.sub.2 C.sub.3 F.sub.7
- Claim: C.sub.8 H.sub.17 --C.sub.4 H.sub.2 N.sub.2 --C.sub.6 H.sub.4 OCH.sub.2 CH(OH)CH.sub.2 OCH.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OC.sub.4 f.sub.9
- Claim: C.sub.8 H.sub.17 --C.sub.4 H.sub.2 N.sub.2 --C.sub.6 H.sub.4 OCH.sub.2 CH(OH)CH.sub.2 OCH.sub.2 CF.sub.2 O(CF.sub.2 CF.sub.2 O).sub.2 CF.sub.3
- Claim: C.sub.8 H.sub.17 O--C.sub.4 H.sub.2 N.sub.2 --C.sub.6 H.sub.4 OCH.sub.2 CH(OH)CH.sub.2 OCH.sub.2 CF.sub.2 CF.sub.2 OC.sub.2 F.sub.5
- Claim: C.sub.8 H.sub.17 --C.sub.4 H.sub.2 N.sub.2 --C.sub.6 H.sub.4 OCH.sub.2 CH(OH)CH.sub.2 OCH.sub.2 C.sub.7 F.sub.15
- Claim: CH.sub.3 CH(OH)(CH.sub.2).sub.4 OCH.sub.2 C.sub.6 H.sub.5, CH.sub.3 CH.sub.2 CH(OH)(CH.sub.2).sub.4 OCH.sub.2 C.sub.6 H.sub.5
- Claim: CH.sub.3 CH.sub.2 CH.sub.2 CH(OH)(CH.sub.2).sub.4 OCH.sub.2 C.sub.6 H.sub.5
- Claim: CH.sub.3 (CH.sub.2).sub.3 CH(OH)(CH.sub.2).sub.4 OCH.sub.2 C.sub.6 H.sub.5, CH.sub.3 CH.sub.2 CH(OH)(CH.sub.2).sub.3 CH.dbd.CH.sub.2, and mixtures thereof, where THP=tetrahydropyranyl.
- Claim: 14. The process of claim 1 wherein said alcohol is chiral or racemic.
- Claim: 15. The process of claim 14 wherein said alcohol is chiral.
- Claim: 16. The process of claim 1 wherein said base is capable of enabling the formation of a sulfonate ester without substantially inducing elimination.
- Claim: 17. The process of claim 16 wherein said base exhibits a gas phase proton affinity of at least about 1000 kJ/mole.
- Claim: 18. The process of claim 1 wherein said base is selected from the group consisting of N-alkyl pyrrolidines, guanidines, and mixtures thereof.
- Claim: 19. The process of claim 18 wherein said N-alkyl pyrrolidines are selected from the group consisting of 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and 1,8-diazabicyclo[5.4.0]dec-7-ene (DBU); and said guanidine is N,N,N',N',N"-pentamethylguanidine.
- Claim: 20. The process of claim 19 wherein said base is selected from the group consisting of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), and mixtures thereof.
- Claim: 21. The process of claim 20 wherein said base is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
- Claim: 22. The process of claim 1 wherein said molar excess is at least about 1.2 equivalents per equivalent of alcohol.
- Claim: 23. The process of claim 1 wherein said process is carried out using less than about 2 equivalents of both sulfonyl fluoride and base per equivalent of alcohol.
- Claim: 24. The process of claim 1 wherein said base is added sufficiently slowly that said mixture is maintained at a temperature below about 10.degree. C.
- Claim: 25. The process of claim 1 further comprising the step of adding at least one inert solvent.
- Claim: 26. The process of claim 1 further comprising the step of recovering the resulting fluoride product.
- Claim: 27. A process for preparing a fluoride from its corresponding alcohol comprising the steps of (a) forming a mixture comprising (i) a sulfonyl fluoride represented by the general formula R.sub.f SO.sub.2 F, where R.sub.f is a perfluorinated alkyl group having from 1 to about 10 carbon atoms and (ii) at least one primary or secondary alcohol represented by the general formula R.sub.1 R.sub.2 CH--OH where R.sub.1 and R.sub.2 are independently selected from the group consisting of branched or linear aliphatic groups, alicyclic groups, araliphatic groups, aromatic groups, hydrogen, branched or linear fluoroaliphatic groups, fluoroalicyclic groups, fluoroaraliphatic groups, and fluoroaromatic groups, wherein said aliphatic, alicyclic, araliphatic, fluoroaliphatic, fluoroalicyclic, and fluoroaraliphatic groups can contain catenary heteratoms and/or one or two olefinic double bonds; and (b) adding to said mixture a molar excess of a strong, aprotic, non-nucleophilic, hindered, double bond-containing, organic base selected from the group consisting of N-alkyl pyrrolidines, guanidines, and mixtures thereof.
- Claim: 28. A process for preparing a fluoride from its corresponding alcohol comprising the steps of (a) forming a mixture comprising (i) at least one primary or secondary alcohol and (ii) a molar excess of at least one strong, aprotic, non-nucleophilic, hindered, double bond-containing, organic base, said molar excess being less than 2 equivalents of said base per equivalent of said alcohol; and (b) adding at least one fluorinated, saturated aliphatic or alicyclic sulfonyl fluoride to said mixture.
- Current U.S. Class: 544/335; 568/607; 568/615; 568/616; 568/618; 568/623; 568/663; 570/136; 570/142
- Current International Class: C07D23902; C07C 4315; C07C 4109; C07C 2118
- Patent References Cited: 2732398 January 1956 Brice et al. ; 3419595 December 1968 Hanson ; 5474705 December 1995 Janulis et al. ; 5702637 December 1997 Johnson et al. ; 5760255 June 1998 Vorbruggen et al.
- Other References: Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, vol. 11, pp. 562-563, John Wiley & Sons, New York, (1994). No month provided. ; Bennua-Skalmowski et al., "The Reaction of Perfluorobutanesulfonyl Fluoride with Alcohols in the Presence of 4-Dialkylaminopyridines," Bull. Soc. Chim. Belg. vol. 103, No. 7-8, (1994). No month provided. ; Zimmer et al., "Das Reagenz--The Reagent, Nonafluoro-1-butanesulfonyl Fluoride: More than a Fluorinating Reagent", J. prakt. Chem. 340, pp. 274-777 (1998). No month provided. ; Bennua-Skalmowski et al., "A Facile Conversion of Primary or Secondary Alcohols with n-Perfluorobutanesulfonyl Fluoride/1,8-Diazabicyclo[5.4.0]undec-7-ene into their Corresponding Fluorides," Tetrahedron Letters, vol. 36, No. 15, pp. 2611-2614, (1995). No month provided. ; Kiesewetter et al., "Synthesis of 16-Fluoroestrogens by Unusually Facile Fluoride Ion Displacement Reactions: Prospects for the Preparation of Fluorine-18 Labeled Estrogens," J. Org. Chem., 49, pp. 4900-4905 (1984). No month provided. ; Nohira et al., "Synthesis and Mesomorphic Properties of Ferrolectric Liquid Crystals with a Fluorinated Asymmetric Frame (1)", Mot. Cryst. Liq. Cryst., vol. 180B, pp. 379-388 (1990). No month provided. ; Middleton, "New Fluorinating Reagents, Dialkylaminosulfur Fluorides," J. Org. Chem., vol. 40, No. 5, pp. 574-578 (1975). No month provided. ; Trott et al., 126 .sup.th National Meeting of the American Chemical Society, pp. 42M-43M, New York, (1954)-abstract only. ; Abe et al., Electrochemical Fluorination (Simons Process) as a Route to Perfluorinated Organic Compounds of Industrial Interest, Preparation, Properties, and Industrial Applications of Organofluorine Compounds, Ellis Howard, pp. 37-43 (1982). No month provided. ; E.P. Hunter and S.G. Lias, Proton Affinity Evaluation, NIST Chemistry WebBook, NIST Standard Reference Database No. 69, Eds. W.G. Mallard and P.J. Linstrom, Mar. 1988 (internet address: webbook.nist.gov/cgi/cbook.cgi).
- Primary Examiner: Keys, Rosalynd
- Attorney, Agent or Firm: Weiss, Lucy C.
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