Method For Preparation of Alkylated or Fluoro, Chloro and Fluorochloro Alkylated Compounds By Heterogeneous Catalysis

Abstract

The invention discloses a method for preparation of alkylated or fluoro, chloro and fluorochloro alkylated compounds by a heterogeneous Pt/C-catalyzed alkylation or fluoro, chloro and fluorochloro alkylation with alkyl halides or with fluoro, chloro and fluorochloro alkyl halides in the presence of Cs.sub.2C0.sub.3 or CsHC0.sub.3.

Claims

1-16. (canceled)

17. A method for the preparation of a fluoro, chloro or fluorochloro alkylated compound by a reaction of a compound COMPSUBST with a compound FCLALKYLHALIDE with heterogeneous catalysis using a catalyst CAT in the presence of a compound CAESCARB; wherein FCLALKYLHALIDE is a compound of formula (III);
R3-X(III) X is Cl, Br or I; R3 is C.sub.1-20 alkyl or a C.sub.1-20 alkyl wherein in the alkyl chain at least one hydrogen is substituted by F or Cl; CAESCARB is Cs.sub.2CO.sub.3, CsHCO.sub.3 or a mixture thereof; CAT is Pt/C; COMPSUBST is selected from the group consisting of a compound COMPSUBST-I, ethene, propene, ethine, and polystyrene; COMPSUBST-I contains a ring RINGA; RINGA is a 5 or 6 membered carbocyclic or heterocyclic aromatic ring, when RINGA is a heterocyclic ring, then RINGA has 1, 2 or 3 identical or different endocyclic heteroatoms independently from each other selected from the group consisting of N, O and S, when RINGA is a 5 membered ring, then RINGA is unsubstituted or substituted by 1, 2, 3 or 4 identical or different substituents, when RINGA is a 6 membered ring then RINGA is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents, any of said substituents of RINGA is independently from any other of said substituent of RINGA selected from the group consisting of C.sub.1-10 alkyl, C.sub.3-8 cycloalkyl, alkoxy, OH, N(R10)R11, CN, NHOH, NO, NO.sub.2, F, Cl, Br, I, CF.sub.3, (CH.sub.2).sub.mC(O)Y1, S(O).sub.2R50, CHC(H)R28, ##STR00070## benzyl, phenyl and naphthyl; RINGA can be condensed with a ring RINGB, RINGB is a 5 or 6 membered carbocyclic or heterocyclic ring, when RINGB is a heterocyclic ring, is contains 1, 2 or 3 identical or different endocyclic heteroatoms independently from each other selected from the group consisting of N, O and S; RINGB is unsubstituted or substituted with 1, 2 or 3 in case of RINGB being a 5 membered ring, with 1, 2, 3 or 4 in case of RINGB being a 6 membered ring, identical or different substituents independently from each other selected from the group consisting of C.sub.1-10 alkyl, C.sub.m cycloalkyl, C.sub.1-4 alkoxy, OH, N(R17)R18, CN, NHOH, NO, NO.sub.2, F, Cl, Br, I, CF.sub.3, (CH.sub.2).sub.nC(O)Y2, S(O).sub.2R51, CHC(H)R38, ##STR00071## benzyl, phenyl and naphthyl; any of said C.sub.1-10 alkyl substitutent of RINGA or RINGB is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, OH, OC(O)C.sub.1-5 alkyl, OC.sub.1-10 alkyl, SC.sub.1-10 alkyl, S(O)C.sub.1-10 alkyl, S(O.sub.2)C.sub.1-10 alkyl, OC.sub.1-6 alkylen-OC.sub.1-6 alkyl, C.sub.m cycloalkyl and 1,2,4-triazolyl; any of said benzyl, phenyl and naphthyl substitutent of RINGA or RINGB is independently from each other unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, C.sub.1-4 alkoxy, NO.sub.2 and CN; m, n and q are identical or different and independently from each other 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; Y1, Y2 and R13 are identical or different and independently from each other selected from the group consisting of H, OH, C(R14)(R15)R16, C.sub.2-6 alkyl, OC.sub.1-6 alkyl, phenyl, benzyl, O-phenyl, OC.sub.1-6 alkylen-OC.sub.1-6 alkyl and N(R19)R20; R14, R15 and R16 are identical or different and independently from each other selected from the group consisting of H, F, Cl and Br; R10, R11, R17, R18, R19 and R20 are identical or different and are independently from each other H or C.sub.1-6 alkyl, or R10 and R11, R17 and R18 or R19 and R20 represent together a tetramethylene or a pentamethylene chain; R50 and R51 are identical or different and independently from each other selected from the group consisting of OH, C.sub.1-6 alkyl and C.sub.1-6 alkoxy; R24, R34, R28 and R38 are identical or different and independently from each other selected from the group consisting of H, C.sub.1-10 alkyl, C(R25)(R26)-OR27; R25, R26 and R27 are identical or different and independently from each other selected from the group consisting of H and C.sub.1-10 alkyl.

18. The method according to claim 1, wherein COMPSUBST is selected from the group consisting of compound COMPSUBST-I and polystyrene; wherein COMPSUBST-I is selected from the group consisting of ##STR00072## wherein COMPSUBST-I is unsubstituted or substituted by 1, 2, 3 or 4 in case of COMPSUBST-I being a monocyclic compound with 5 endocyclic atoms, by 1, 2, 3, 4 or 5 in case of COMPSUBST-I being a monocyclic compound with 6 endocyclic atoms, by 1, 2, 3, 4, 5 or 6 in case of COMPSUBST-I being a bicyclic compound wherein a 5-membered and a 6-membered ring are ortho-fused, by 1, 2, 3, 4, 5, 6 or 7 in case of COMPSUBST-I being a bicyclic compound wherein two 6-membered rings are ortho-fused, identical or different substituents independently from each other selected from the group consisting of C.sub.1-10 alkyl, C.sub.3-8 cycloalkyl, C.sub.1-4 alkoxy, OH, C(H)O, N(R10)R11, CN, NHOH, NO, NO.sub.2, F, Cl, Br, I, CF.sub.3, (CH.sub.2).sub.mC(O)Y1, S(O).sub.2R50, CHC(H)R28, ##STR00073## benzyl, phenyl and naphthyl, said C.sub.1-10 alkyl substitutent of COMPSUBST-I is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, OH, OC(O)C.sub.1-5 alkyl, OC.sub.1-10 alkyl, SC.sub.1-10 alkyl, S(O)C.sub.1-10 alkyl, S(O.sub.2)C.sub.1-10 alkyl, OC.sub.1-6 alkylen-OC.sub.1-6 alkyl, C.sub.3-8 cycloalkyl and 1,2,4-triazolyl; said benzyl, phenyl and naphthyl substitutent of COMPSUBST-I is independently from each other unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, C.sub.1-4 alkoxy, NO.sub.2 and CN.

19. The method according to claim 17, wherein m, n and q are identical or different and independently from each other 0, 1, 2, 3 or 4.

20. The method according to claim 17, wherein COMPSUBST is selected from the group consisting of benzene, pyrazole, ##STR00074## ##STR00075## ##STR00076## ##STR00077## and polystyreneR44 is selected from the group consisting of C.

21. The method according to claim 17, wherein X is Br or I.

22. The method according to claim 17, wherein X is I.

23. The method according to claim 17, wherein compound FCLALKYLHADLIDE is a perfluoroalkyl halide, F.sub.2HCCl or F.sub.2HCBr.

24. The method according to claim 17, wherein X is Cl, Br or I, and R3 is perfluoro C.sub.1-20 alkyl; or FCLALKYLHADLIDE is F.sub.2HCCl or F.sub.2HCBr.

25. The method according to claim 17, wherein FCLALKYLHALIDE is selected from the group consisting of F.sub.21C.sub.10I, F.sub.17C.sub.8I, F.sub.13C.sub.6I, F.sub.9C.sub.4I, F.sub.3CI, F.sub.3CBr, F.sub.3CCl, F.sub.2HCCl and F.sub.2HCBr.

26. The method according to claim 17, wherein the reaction is done in the presence of a compound COMPSALT; wherein COMPSALT is selected from the group consisting of NaI, KI, CsI and N(R30)(R31)(R32)R33I; and R30, R31, R32 and R33 are identical or different and independently from each other selected from the group consisting of H and C.sub.1-10 alkyl.

27. The method according to claim 26, wherein R30, R31, R32 and R33 are identical or different and independently from each other selected from the group consisting of H and C.sub.2-6 alkyl.

28. The method according to claim 26, wherein COMPSALT is selected from the group consisting of NaI and (n-Bu).sub.4NI.

29. The method according to claim 17, wherein the amount of Pt in CAT is from 0.1 to 20%, the % are % by weight and are based on the combined weight of Pt and C in CAT.

30. The method according to claim 17, wherein from 0.001 to 20% of Pt are used in the reaction, the % are % by weight % and are based on the weight of FCLALKYLHALIDE.

31. The method according to claim 17, wherein from 1 to 20 mol equivalents of COMPSUBST are used in the reaction, the mol equivalents are based on the molar amount of FCLALKYLHALIDE.

32. The method according to claim 17, wherein from 0.1 to 10 mol equivalents of CAESCARB are used in the reaction, the mol equivalents are based on the molar amount of FCLALKYLHALIDE.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0058] Preferably, COMPSUBST is selected from the group consisting of compound COMPSUBST-I, compound of formula (II), compound of formula (IV), polystyrene, ethene and ethine; [0059] the ethene being unsubstituted or substituted by 1 or 2 substitutents selected from the group consisting of C.sub.1-10 alkyl, C.sub.3-6 cycloalkyl, C.sub.1-4 alkoxy, N(R10)R11, CN, F, Cl, Br, I, CF.sub.3, (CH.sub.2).sub.mC(O)Y1, S(O).sub.2R50, benzyl, phenyl and naphthyl; [0060] the ethine being unsubstituted or substituted by 1 substitutent selected from the group consisting of C.sub.1-10 alkyl, C.sub.3-6 cycloalkyl, C.sub.1-4 alkoxy, N(R10)R11, CN, F, Cl, Br, I, CF.sub.3, (CH.sub.2).sub.mC(O)Y1, S(O).sub.2R50, benzyl, phenyl and naphthyl;
with COMPSUBST-I being selected from the group consisting of

##STR00006##

with COMPSUBST-I being unsubstituted or substituted [0061] by 1, 2, 3 or 4 in case of COMPSUBST-I being a monocyclic compound with 5 endocyclic atoms, [0062] by 1, 2, 3, 4 or 5 in case of COMPSUBST-I being a monocyclic compound with 6 endocyclic atoms, [0063] by 1, 2, 3, 4, 5 or 6 in case of COMPSUBST-I being a bicyclic compound wherein a 5-membered and a 6-membered ring are ortho-fused, [0064] by 1, 2, 3, 4, 5, 6 or 7 in case of COMPSUBST-I being a bicyclic compound wherein two 6-membered rings are ortho-fused, [0065] preferably, COMPSUBST I is unsubstituted or substituted by 1, 2, 3, 4 or 5, [0066] identical or different substituents independently from each other selected from the group consisting of C.sub.1-10 alkyl, C.sub.3-8 cycloalkyl, C.sub.1-4 alkoxy, OH, C(H)O, N(R10)R11, CN, NHOH, NO, NO.sub.2, F, Cl, Br, I, CF.sub.3, (CH.sub.2).sub.mC(O)Y1, S(O).sub.2R50, CHC(H)R28,

##STR00007## benzyl, phenyl and naphthyl; [0067] said C.sub.1-10 alkyl substitutent of COMPSUBST-I is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, OH, OC(O)C.sub.1-5 alkyl, OC.sub.1-10 alkyl, SC.sub.1-10 alkyl, S(O)C.sub.1-10 alkyl, S(O.sub.2)C.sub.1-10 alkyl, OC.sub.1-6 alkylen-OC.sub.1-6 alkyl, C.sub.3-8 cycloalkyl and 1,2,4-triazolyl; [0068] said benzyl, phenyl and naphthyl substitutent of COMPSUBST-I is independently from each other unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, C.sub.1-4 alkoxy, NO.sub.2 and CN; [0069] compound of formula (II), compound of formula (IV), R10, R11, m, n, Y1, Y2, R28, R50 and R24 are defined as above, also with all their embodiments.

[0070] Preferably, m, n and q are identical or different and independently from each other 0, 1, 2, 3 or 4;

more preferably, m, n and q are 0 or 4.

[0071] In another embodiment, Y1, Y2 and R13 are identical or different and independently from each other selected from the group consisting of H, OH, C(R14)(R15)R16, C.sub.2-6 alkyl, OC.sub.1-6 alkyl, phenyl, benzyl, O-phenyl, OC.sub.1-6 alkylen-OC.sub.1-6 alkyl and N(R19)R20.

[0072] Preferably, Y1, Y2 and R13 are identical or different and independently from each other selected from the group consisting of H, OH, C.sub.1-2 alkyl, and OC.sub.1-2 alkyl.

[0073] More preferably, COMPSUBST-I is unsubstituted or substituted [0074] by 1, 2 or 3 in case of COMPSUBST-I being a monocyclic compound with 5 endocyclic atoms, [0075] by 1, 2, 3, 4 or 5 in case of COMPSUBST-I being a monocyclic compound with 6 endocyclic atoms, [0076] by 1, 2, 3, 4 or 5 in case of COMPSUBST-I being a bicyclic compound wherein a 5-membered and a 6-membered ring are ortho-fused, [0077] by 1, 2, 3 or 4 in case of COMPSUBST-I being a bicyclic compound wherein two 6-membered rings are ortho-fused, [0078] identical or different substituents independently from each other selected from the group consisting of C.sub.1-4 alkyl, C.sub.1-4 alkoxy, OH, C(H)O, N(R10)R11, CN, F, Cl, Br, CF.sub.3, (CH.sub.2).sub.mC(O)Y1, and S(O).sub.2R50; [0079] said C.sub.1-4 alkyl substitutent of COMPSUBST-I is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of halogen; [0080] with R10, R11, Y1 and R50 as defined above, also with all their embodiments.

[0081] Especially, COMPSUBST is selected from the group consisting of benzene, pyrazole,

##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012## [0082] compound of formula (V), compound of formula (VI), polystyrene, ethene and ethine; [0083] Y is C.sub.1-6 alkyl; [0084] the ethene being unsubstituted or substituted by 1 or 2 substitutents selected from the group consisting of C.sub.1-10 alkyl, C.sub.1-4 alkoxy, N(R10)R11, CN, F, Cl, Br, I, CF.sub.3, (CH.sub.2).sub.mC(O)Y1, benzyl and phenyl; [0085] the ethine being unsubstituted or substituted by 1 substitutent selected from the group consisting of C.sub.1-10 alkyl, C.sub.1-4 alkoxy, N(R10)R11, CN, F, Cl, Br, I, CF.sub.3, (CH.sub.2).sub.mC(O)Y1, benzyl and phenyl;

##STR00013##

wherein [0086] R43 is H or CH.sub.3; [0087] R44 is selected from the group consisting of C.sub.1-10 alkyl, C.sub.1-4 alkoxy, OH, N(R10)R11, CN, NO, NO.sub.2, F, Cl, Br, I, CF.sub.3, (CH.sub.2).sub.mC(O)Y1, S(O).sub.2R50; [0088] with R10, R11, m, Y1 and R50 as defined above, also with all their embodiments.

[0089] Embodiments of the substituted ethene are propene, ethene-1,1-diyldibenzene and 3,3-dimethylbut-1-ene.

[0090] An embodiment of the substituted ethine is 1-octyne.

[0091] Preferably, Y is methyl or ethyl.

[0092] An embodiment of COMPSUBST is

##STR00014##

[0093] Y is methyl or ethyl, preferably ethyl.

[0094] The alkylated or fluoro, chloro or fluorochloro alkylated compound is called compound ALKYLCOMPSUBST in the following.

[0095] Preferably, FCLALKYLHALIDE is a compound of formula (III);

R3-X(III) [0096] X is Cl, Br or I; [0097] R3 is C.sub.1-20 alkyl or a C.sub.1-20 alkyl, wherein any of the hydrogens is substituted by F or Cl; more preferably, [0098] R3 is C.sub.1-15 alkyl or C.sub.1-15 alkyl, wherein any of the hydrogens is substituted by F or Cl; even more preferably, [0099] R3 is C.sub.1-10 alkyl or C.sub.1-10 alkyl, wherein any of the hydrogens is substituted by F or Cl.

[0100] The expression wherein any of the hydrogens is substituted by F or Cl means, that at least one hydrogen in the alkyl chain is substituted by F or Cl, and any other hydrogen in the alkyl chain can independently from any other hydrogen in the alkyl chain also be substituted by F or Cl.

[0101] Therefore, preferably, FCLALKYLHALIDE is a compound of formula (III);

R3-X(III) [0102] X is Cl, Br or I; [0103] R3 is C.sub.1-20 alkyl or a C.sub.1-20 alkyl wherein in the alkyl chain at least one hydrogen is substituted by F or Cl;
more preferably, [0104] R3 is C.sub.1-15 alkyl or C.sub.1-15 alkyl wherein in the alkyl chain at least one hydrogen is substituted by F or Cl;
even more preferably, [0105] R3 is C.sub.1-10 alkyl or C.sub.1-10 alkyl wherein in the alkyl chain at least one hydrogen is substituted by F or Cl.

[0106] Preferably, [0107] X is Br or I;
more preferably, [0108] X is I;
also with R3 in all its embodiments.

[0109] In an especial ambodiment, compound FCLALKYLHADLIDE is a perfluoroalkyl halide, F.sub.2HCCl or F.sub.2HCBr, preferably FCLALKYLHADLIDE is a perfluoroalkylated bromide or iodide, F.sub.2HCCl or F.sub.2HCBr;

preferably [0110] X is Cl, Br or I, and [0111] R3 is perfluoro C.sub.1-20 alkyl; or [0112] FCLALKYLHADLIDE is F.sub.2HCCl or F.sub.2HCBr;
more preferably, [0113] X is Br or I, and [0114] R3 is perfluoro C.sub.1-20 alkyl; or [0115] FCLALKYLHADLIDE is F.sub.2HCCl or F.sub.2HCBr;
even more preferably, [0116] X is Br or I, and [0117] R3 is perfluoro C.sub.1-15 alkyl; or [0118] FCLALKYLHADLIDE is F.sub.2HCCl or F.sub.2HCBr.

[0119] In particular, FCLALKYLHALIDE is selected from the group consisting of F.sub.21C.sub.10I, F.sub.17C.sub.8I, F.sub.13C.sub.6I, F.sub.9C.sub.4I, F.sub.3CI, F.sub.3CBr, F.sub.3CCl, F.sub.2HCCl, and F.sub.2HCBr;

more in particular, FCLALKYLHALIDE is selected from the group consisting of n-F.sub.21C.sub.10I, n-F.sub.17C.sub.8I, n-F.sub.13C.sub.6I, n-F.sub.9C.sub.4I, F.sub.3CI, F.sub.3CBr, F.sub.3CCl, F.sub.2HCCl, and F.sub.2HCBr.

[0120] In one embodiment, the reaction is done in the presence of a compound COMPSALT; [0121] COMPSALT is selected from the group consisting of NaI, KI, CsI and N(R30)(R31)(R32)R33I; [0122] R30, R31, R32 and R33 are identical or different and independently from each other selected from the group consisting of H and C.sub.1-10 alkyl; [0123] preferably, R30, R31, R32 and R33 are identical or different and independently from each other selected from the group consisting of H and C.sub.2-6 alkyl; [0124] more preferably, COMPSALT is selected from the group consisting of NaI and (n-Bu).sub.4NI.

[0125] The reaction is preferably done in the presence of a compound COMPSALT and X is Cl or Br, preferably X is Cl.

[0126] CAT is Pt/C, that is CAT is platinum supported on carbon.

[0127] Preferably, CAT is Pt supported on charcoal, more preferably on activated charcoal.

[0128] Preferably, the amount of Pt in CAT is from 0.1 to 20%, more preferably from 0.5 to 15%, even more preferably from 1 to 12.5%, especially from 2 to 12.5%, the % are % by weight and are based on the combined weight of Pt and C in CAT.

[0129] Preferably, from 0.001 to 20%, more preferably from 0.01 to 15%, even more preferably from 0.025 to 12.5%, especially from 0.05 to 10%, of Pt are used in the reaction, the % are % by weight % and are based on the weight of FCLALKYLHALIDE.

[0130] Preferably, from 1 to 20 mol equivalents, more preferably 1 to 15 mol equivalents, even more preferably from 1 to 10 mol equivalents, of COMPSUBST are used in the reaction, the mol equivalents are based on the molar amount of FCLALKYLHALIDE.

[0131] Preferably, from 0.1 to 10 mol equivalents, more preferably 0.5 to 5 mol equivalents, even more preferably from 0.75 to 2.5 mol equivalents, of CAESCARB are used in the reaction, the mol equivalents are based on the molar amount of FCLALKYLHALIDE.

[0132] The reaction temperature of the reaction is preferably from 20 to 200 C., more preferably from 20 to 150 C., even more preferably from 30 to 140 C., especially from 30 to 130 C.

[0133] The reaction time of the reaction is preferably from 30 min to 48 h, more preferably from 1 h to 48 h, even more preferably from 2 h to 36 h.

[0134] Preferably, the reaction is done under inert atmosphere. Preferably, the inert atmosphere is achieved by the use if an inert gas preferably selected from the group consisting of argon, another noble gas, lower boiling alkane, nitrogen and mixtures thereof.

[0135] The lower boiling alkane is preferably a C.sub.1-3 alkane, i.e. methane, ethane or propane.

[0136] The reaction can be done in a closed system, it can be done at a pressure caused by the chosen temperature in a closed system. It is also possible to apply pressure with said inert gas. It is also possible to carry out the reaction at ambient pressure.

[0137] The reaction can be done in a solvent SOL, SOL is preferably selected from the group consisting of alkanes, chlorinated alkanes, ketones, ethers, esters, aliphatic nitrils, aliphatic amides, sulfoxides, and mixtures thereof;

preferably SOL is selected from the group consisting of C.sub.5-8 alkane, chlorinated C.sub.5-8 alkane, acetone, methylethylketone, diethylketone, MTBE, tetrahydrofuran, methyltetrahydrofuran, ethylacetate, butylacetate, valeronitril, acetonitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and mixtures thereof.

[0138] It is also possible to use COMPSUBST simultaneously as substrate and as solvent.

[0139] As an alternative, the reaction can also be carried out in the absence of a solvent. In another embodiment, COMPSUBST is used as SOL.

[0140] The amount of SOL is preferably from 0.1 to 100 fold, more preferably from 1 to 50 fold, even more preferably from 1 to 25 fold, of the weight of FCLALKYLHALIDE.

[0141] After the reaction, ALKYLCOMPSUBST can be isolated by standard methods such as evaporation of volatile components, extraction, washing, drying, concentration, crystallization, chromatography and any combination thereof, which are known per se to the person skilled in the art.

[0142] COMPSUBST, CAESCARB, CAT and FCLALKYLHALIDE, are commercially available and can be prepared according to known procedures.

EXAMPLES

Yield:

[0143] The yield is given as a molar yield of the expected ALKYLCOMPSUBST based on molar amount of FCLALKYLHALIDE and was determined by quantitative GC analysis with hexadecane as internal standard, if not otherwise stated.

Conversion:

[0144] Conversion was determined by dection of the remaining FCLALKYLHALIDE by quantitative GC analysis with hexadecane as internal standard, if not otherwise stated.

Ratio of Isomers and Position of Alkylation

[0145] were determined by NMR spectroscopy

Example 1: Perfluoralkylation of Benzene

[0146] A mixture of benzene (0.44 g, 5.6 mmol), n-C.sub.10F.sub.21I (0.13 g, 0.2 mmol), Pt/C (Sigma-aldrich 330159, with 5 wt % Pt, the wt % are based on the combined weight of Pt and C, with ca. 50 wt % water, the wt % based on the combined amount of Pt, C and water, 78 mg, 0.01 mmol, 5 mol % Pt based on n-C.sub.10F.sub.21I), and Cs.sub.2CO.sub.3 (65 mg, 0.2 mmol) were placed in a magnetically stirred Wheaton vial, the Wheaton vial was placed in a well-plate in a Parr autoclave (Parr Instruments 4560 series). After replacing the air in the autoclave with nitrogen and increasing the pressure to 10 bars with nitrogen, the reaction mixture was stirred at 100 C. for 20 h. Then the reaction mixture was cooled, and then the pressure was released from the autoclave. After the addition of 25 ml dichloromethane the solids were removed by filtration. The filtrate showed a yield of 96%. Conversion of the n-C.sub.10F.sub.21I was 100%. The filtrate was then extracted with water, concentrated, dissolved in a minimal amount of benzene and purified by pipette column chromatography using FluoroFlash reverse phase silica gel (eluting with a gradient of 4:1 MeOH:H.sub.2O (10 mL), then MeOH (10 mL), then acetone (10 mL). The methanol fraction and the aceton fraction were collected, dried with MgSO.sub.4, filtered and concentrated under vacuum to give 107 mg product with a content of 99 wt % of compound of formula (1)

##STR00015##

according to quantitative GC analysis. The identity of the product was confirmed using HRMS EI (m/z): [M]+ calculated for C.sub.16H.sub.5F.sub.21; 596.00504. found: 596.00502.

Example 2: Trifluormethylation of Benzene

Step (a) Preparation of CF.SUB.3.Br Stock Solution

[0147] A stock solution of CF.sub.3Br in benzene was prepared by bubbling CF.sub.3Br into a 5 mL benzene. The solution was weighed before and after the CF.sub.3Br was added to measure the amount of CF.sub.3Br in the CF.sub.3Br stock solution.

Step (b) Reaction

[0148] CF.sub.3Br stock solution (0.5 mL, 0.2 mmol, prepared according to step (a)), Pt/C (Sigma-aldrich 330159, with 5 wt % Pt, the wt % are based on the combined weight of Pt and C, with ca. 50 wt % water, the wt % based on the combined amount of Pt, C and water, 78 mg, 0.01 mmol, 5 mol % Pt based on CF.sub.3Br), and Cs.sub.2CO.sub.3 (65 mg, 0.2 mmol) were placed in a magnetically stirred Wheaton vial, the Wheaton vial was placed in a well-plate in a Parr autoclave (Parr Instruments 4560 series). After replacing the air in the autoclave with nitrogen and increasing the pressure to 15 bars with nitrogen, the reaction mixture was stirred at 100 C. for 20 h. Then the reaction mixture was cooled, and then the pressure was released from the autoclave, and the solids were removed by filtration. The crude reaction mixture was analyzed by .sup.19F-NMR using as internal standard 1,4-difluorobenzene showing an yield of 21% of trifluormethyl benzene.

Example 3: Perfluoroalkylation of Polystyrene

[0149] A mixture of polystyrene (0.10 g, corresponding to 1 mmol styrene), n-C.sub.10F.sub.21I (0.13 g, 0.2 mmol), THF (1 mL), Pt/C (Sigma-aldrich 330159 with 5 wt % Pt, the wt % are based on the combined weight of Pt and C, with ca. 50 wt % water, the wt % based on the combined amount of Pt, C and water, 78 mg, 0.01 mmol, 5 mol % Pt based on n-C.sub.10F.sub.21I), and Cs2CO3 (65 mg, 0.2 mmol) were placed in a magnetically stirred Wheaton vial, the Wheatopn vial was placed in a well-plate in a Parr autoclave (Parr Instruments 4560 series). After replacing the air in the autoclave with nitrogen and increasing the pressure to 10 bars with nitrogen, the reaction mixture was stirred at 80 C. for 20 h. Then the reaction mixture was cooled, and then the pressure was released from the autoclave, and the solids were removed by filtration. Analysis of the product by .sup.19F-NMR using as internal standard 1,4-difluorobenzene showed a yield of 95% based on the consumption of C.sub.10F.sub.21I and a perfluoroalkylation of the polystyrene. Perfluoroalkylation ratio is ca. 20%, measured by .sup.19F NMR using as internal standard 1,4-diflourobenzene.

Examples 4, 5 and 6

[0150] Example 1 was repeated with the differences given in table 1.

TABLE-US-00001 TABLE 1 T t Conversion Yield Example [ C.] [h] [%] [%] 4 80 36 95 92 5 80 36 91 90 6 80 36 87 84

[0151] Further differences were:

[0152] Example 5 was not inertized and was stirred under atmospheric pressure and under air atmosphere.

[0153] Example 6 shows the results of the third run of CAT.

Comparative Examples 1 to 14

[0154] Comparative examples 1 to 14 were done according to example 1 with the conditions and any differences given in table 2.

TABLE-US-00002 TABLE 2 Comparative T t Conversion Yield example Catalyst Bases [ C.] [h] [%] [%] 1 Pd/C Cs.sub.2CO.sub.3 100 20 63 61 2 Ru/C Cs.sub.2CO.sub.3 100 20 27 24 3 Ru/Al.sub.2O.sub.3 Cs.sub.2CO.sub.3 100 20 25 21 4 Rh/C Cs.sub.2CO.sub.3 100 20 41 39 5 Pt/TiO.sub.2 Cs.sub.2CO.sub.3 100 20 46 45 6 Pt/Al.sub.2O.sub.3 Cs.sub.2CO.sub.3 100 20 79 77 7 Pt/ZrO.sub.2 Cs.sub.2CO.sub.3 100 20 62 61 8 Pt/CeO.sub.2 Cs.sub.2CO.sub.3 100 20 51 49 9 Pt/C DBU 100 8 100 56 10 Pt/C K.sub.3PO.sub.4 100 20 67 60 11 Pt/C K.sub.2CO.sub.3 100 20 54 49 12 Pt/C NEt.sub.3 100 20 74 51 13 PtCl.sub.2 Cs.sub.2CO.sub.3 80 36 19 18 14 PtI.sub.2 Cs.sub.2CO.sub.3 80 36 15 14

[0155] The comparative examples, when compared with the inventive examples, show that the combination Pt/C with Cs.sub.2CO.sub.3 according to instant invention gives superior results, the catalysts different from Pt/C or bases different from Cs.sub.2CO.sub.3 give lower yields. In case of Example 12, where NEt.sub.3 was used as base, undesired formation of appreciable amount of C.sub.10F.sub.21H was observed.

Example 10: Perfluoroalkylation of 1,4-dibromobenzene

[0156] A mixture of 1,4-dibromobenzene (0.236 g, corresponding to 1 mmol 1,4-dibromobenzene), n-C.sub.10F.sub.21I (0.13 g, 0.2 mmol), DMSO (0.5 mL), (Sigma-aldrich 330159 with 5 wt % Pt, the wt % are based on the combined weight of Pt and C, with ca. 50 wt % water, the wt % based on the combined amount of Pt, C and water, 78 mg, 0.01 mmol, 5 mol % Pt based on n-C.sub.10F.sub.21I), and Cs.sub.2CO.sub.3 (65 mg, 0.2 mmol) were placed in a magnetically stirred Wheaton vial, the Wheatopn vial was placed in a well-plate in a Parr autoclave (Parr Instruments 4560 series). After replacing the air in the autoclave with nitrogen and increasing the pressure to 10 bars with nitrogen, the reaction mixture was stirred at 100 C. for 24 h. Then the reaction mixture was cooled, and then the pressure was released from the autoclave, and the solids were removed by filtration. Analysis of the product by .sup.19F-NMR using the internal standard 1,4-difluorobenzene showed a conversion of 21% based on the perfluorodecyl iodide.

[0157] Examples 17 to 44 show the versatility of the method with different compounds ALKYLCOMPSUBST and FCLALKYLHALIDES, they were done in analogy to example 1, reaction conditions were 0.2 mmol of FCLALKYLHALIDE, CAT was Pt/C (Pt: 5 mol % relative to FCLALKYLHALIDE) and Cs.sub.2CO.sub.3 (1 molar equivalent based on FCLALKYLHALIDE). ALKYLCOMPSUBST was used in the amount of 0.5 mL in case of a ALKYLCOMPSUBST being liquid and 1 mmol in case of ALKYLCOMPSUBST being solid, reaction was done under N.sub.2 atmosphere at 10 bar. Yield is isolated yield, in example 28 the yield was determined with .sup.19F NMR with 1,4-difluorobenzene as an internal standard.

[0158] The reaction of example 44 was done with caffeine (1 mmol) in DMSO (0.5 mL) as SOL. The yield according to .sup.19F-NMR with 1,4-difluorobenzene as an internal standard was 61%, isolated yield by pipette column using perfluorinated reverse phase silica gel was 49%.

[0159] Further details such as COMPSUBST, FCLALKYLHALIDE, ALKYLCOMPSUBST, T, t, yield and ratio of isomers of examples 17 to 44 are given in Tables 3 and 4.

TABLE-US-00003 TABLE 3 FCLALKYL- Example COMPSUBST HALIDE ALYKLCOMPSUBST 17 [00016] n-F.sub.21C.sub.10I [00017] 18 [00018] n-F.sub.21C.sub.10I [00019] 19 [00020] n-F.sub.17C.sub.8I [00021] 20 [00022] n-F.sub.13C.sub.6I [00023] 21 [00024] n-F.sub.21C.sub.10I [00025] 22 [00026] n-F.sub.17C.sub.8I [00027] 23 [00028] n-F.sub.13C.sub.6I [00029] 24 [00030] n-F.sub.9C.sub.4I [00031] 25 [00032] n-F.sub.21C.sub.10I [00033] 26 [00034] n-F.sub.17C.sub.8I [00035] 27 [00036] n-F.sub.9C.sub.4I [00037] 29 [00038] n-F.sub.21C.sub.10I [00039] 30 [00040] n-F.sub.21C.sub.10I [00041] 31 [00042] n-F.sub.21C.sub.10I [00043] 32 [00044] n-F.sub.21C.sub.10I [00045] 33 [00046] n-F.sub.21C.sub.10I [00047] 34 [00048] n-F.sub.21C.sub.10I [00049] 35 [00050] n-F.sub.21C.sub.10I [00051] 36 [00052] n-F.sub.21C.sub.10I [00053] 37 [00054] n-F.sub.21C.sub.10I [00055] 38 [00056] n-F.sub.21C.sub.10I [00057] 39 [00058] n-F.sub.21C.sub.10I [00059] 40 [00060] n-F.sub.21C.sub.10I [00061] 41 [00062] n-F.sub.13C.sub.6I [00063] 42 [00064] n-F.sub.21C.sub.10I [00065] 43 [00066] n-F.sub.21C.sub.10I [00067] 44 [00068] n-F.sub.21C.sub.10I [00069]

TABLE-US-00004 TABLE 4 T t Yield in [%] Ex. [ C.] [h] (Ratio of Isomers in [%]) 17 100 20 90 18 100 15 87 19 100 15 81 20 100 30 59 21 100 15 73 22 100 15 71 23 100 30 54 24 100 15 70 25 100 20 81 26 100 20 80 27 100 20 79 28 100 20 21 29 100 20 75 30 100 24 77 (2-, 3-, 4- = 24, 39, 37) 31 120 20 75 (2, 3-, 4- = 18, 41, 41) 32 120 20 81 (2-, 4- = 11, 89) 33 100 24 71 (2-, 3- = 23, 77) 34 100 24 77 (2-, 4, 5-, 6- = 12, 54, 5, 29) 35 100 24 73 (2-, 4, 5-, 6- = 4, 80, 1, 15) 36 120 20 69 (2-, 4, 5-, 6- = 24, 24, 17, 35) 37 100 20 78 (2-, 4- = 62, 38) 38 120 20 65 39 120 20 47 (2-, 3, 4- = 81, 11, 8) 40 50 20 94 41 50 30 68 42 100 20 65 (2-, 3, 4- = 45, 46, 9) 43 100 20 63 (2-, 3- = 80, 20) 44 100 20 49

Example 45: Perfluoralkylation of ethene-1,1-diyldibenzene

[0160] A mixture of 1,1-diphenylethylene (180 mg, 1 mmol), n-C.sub.10F.sub.21I (130 mg, 0.2 mmol), Pt/C (Sigma-aldrich 330159, with 5 wt % Pt, the wt % are based on the combined weight of Pt and C with ca. 50 wt % water, the wt % based on the combined amount of Pt, C and water, 78 mg, 0.01 mmol, 5 mol % Pt based on n-C.sub.10F.sub.21I), and Cs.sub.2CO.sub.3 (65 mg, 0.2 mmol) were placed in a Parr autoclave (25 mL capacity). After replacing the air in the autoclave with nitrogen and increasing the pressure to 10 bars with nitrogen, the reaction mixture was stirred at 100 C. for 20 h. Then the reaction mixture was cooled, and then the pressure was released from the autoclave. The solids were removed by filtration. The filtrate was extracted 4 times with CH.sub.2Cl.sub.2. The combined organic phase dried with MgSO.sub.4, filtered, and concentrated under vacuum. The crude product was purified by column chromatography on silica gel to give 119 mg fluorinated product. The major product is the (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-henicosafluorododec-1-ene-1,1-diyl)dibenzene. The identity of the product was confirmed using HRMS EI (m/z): [M]+ calculated for C.sub.24H.sub.11F.sub.21, 698.051999. found, 698.05131. The minor product is (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-henicosafluorododecane-1,1-diyl)dibenzene. The identity of the product was confirmed using HRMS EI (m/z): [M]+ calculated for C.sub.24H.sub.13F.sub.21, 700.06764. found, 700.06668. The position of C.sub.10F.sub.21 was determined by NMR of the major product. .sup.1H NMR (300 MHz, CDCl.sub.3) delta=7.44 to 7.26 (m, 10H), 6.14 (t, J=14.7, 1H). .sup.19F NMR (282 MHz, CDCl.sub.3) delta=80.33 (3F), 103.13 (2F), 120.90 to 122.59 (14F), 125.79 (2F).

Example 46: Perfluoralkylation of 3,3-dimethylbut-1-ene

[0161] A mixture of 3,3-dimethylbut-1-ene (374 mg, 3.39 mmol), n-C.sub.10F.sub.21I (130 mg, 0.2 mmol), Pt/C (Sigma-aldrich 330159, with 5 wt % Pt, the wt % are based on the combined weight of Pt and C with ca. 50 wt % water, the wt % based on the combined amount of Pt, C and water, 78 mg, 0.01 mmol, 5 mol % Pt based on n-C.sub.10F.sub.21I), and Cs.sub.2CO.sub.3 (65 mg, 2 mmol) were placed in a magnetically stirred Wheaton vial, the Wheaton vial was placed in a Parr autoclave (Parr Instruments 4560 series). After replacing the air in the autoclave with nitrogen and increasing the pressure to 10 bars with nitrogen, the reaction mixture was stirred at 60 C. for 20 h. Then the reaction mixture was cooled, and then the pressure was released from the autoclave. The solids were removed by filtration. The filtrate was extracted 4 times with CH.sub.2Cl.sub.2. The combined organic phase dried with MgSO.sub.4, filtered, and concentrated under vacuum to give 102 mg fluorinated mixture (determined by .sup.19F NMR). The major identified product is 5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-henicosafluoro-2,2-dimethyltetradec-3-ene. The identity of the product was confirmed using HRMS EI (m/z): [M]+ calculated for C.sub.16H.sub.11F.sub.21, 602.05199. found, 602.05105.

Example 47: Perfluoralkylation of 1-octyne

[0162] A mixture of 1-octyne (327 mg, 3.88 mmol), n-C.sub.10F.sub.21I (130 mg, 0.2 mmol), Pt/C (Sigma-aldrich 330159, with 5 wt % Pt, the wt % are based on the combined weight of Pt and C with ca. 50 wt % water, the wt % based on the combined amount of Pt, C and water, 78 mg, 0.01 mmol, 5 mol % Pt based on n-C.sub.10F.sub.21I), and Cs.sub.2CO.sub.3 (65 mg, 2 mmol) were placed in a magnetically stirred Wheaton vial, the Wheaton vial was placed in a Parr autoclave (Parr Instruments 4560 series). After replacing the air in the autoclave with nitrogen and increasing the pressure to 10 bars with nitrogen, the reaction mixture was stirred at 60 C. for 20 h. Then the reaction mixture was cooled, and then the pressure was released from the autoclave. The solids were removed by filtration. The filtrate was extracted 4 times with CH.sub.2Cl.sub.2. The combined organic phase dried with MgSO.sub.4, filtered, and concentrated under vacuum to give 111 mg fluorinated product. The identity of the product was confirmed using NMR. .sup.1H NMR (300 MHz, CDCl.sub.3) delta=2.61 to 2.51 (m, 2H), 1.89 to 1.42 (m, 2H), 1.23 (s, 6H), 0.82 (t, J=6.5, 3H). .sup.19F NMR (282 MHz, CDCl.sub.3) delta=80.65 (3F), 105.04 (2F), 121.16 to 123.01 (14F), 125.93 (2F).