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 CS2CO3 or CsHC03.

BACKGROUND OF THE INVENTION

Organofluorine chemistry plays an importance role in medicinal, agricultural, and material sciences and fields. Fluoroalkyl groups have strong effects such as high stability and lipophilicity, in addition, longer fluoroalkyl groups have high water-, oil-resistance and low fricition.

Homogeneous catalysis still suffers from the inherent problems associated with homogeneous catalyzed reactions due to the use of unrecoverable metals and ligands, as well as

inconveniences with regard to catalyst handling, recyclability, and separation of the catalyst from products, impede the transfer of these advances to large-scale industrial processes. Furthermore expensive and structurally complicated ligands are required in homogeneous catalysis, which are often not even comnmercially available for use on industrial scale.

EP O 114 359 A1 discloses a process for the manufacture of perfluoralkyl substituted carbocyclic or heterocyclic compounds by reaction of perfluoroalkyl iodides with

unsubstituted or substituted carbocyclic or heterocyclic compounds at elevated temperatures and in presence of at least one alkaline salt, characterized by carrying out the reaction in the presence of at least one metal of the first or eight auxiliary group of the periodic table or in the presence of a complex compound containing said metal as the central atom.

The examples show the use of K2C03 as base and reaction temperatures of 150°C, 160°C and 170°C for the heterogeneously catalyzed reactions. For the preparation of C^Fn- eiis in Example 1 using a Ru/C catalyst a yield of 89.2% is disclosed.

In case of Pt/C in examples 5 to 7 a yield of 55 to 76 mol% is disclosed for the conversion of benzene with three different perfluoroalkyl iodides.

WO 93/16969 A discloses a process for the catalytic perfluoroalkylation of aromatic compounds, wherein a perfluoroalkyl iodide or mixture of iodides is reacted with an aromatic compound in the presence of an aqueous base, such as an alkali metal hydroxide or carbonate, and discloses that further improvements in rate and yield are secured by employing, as the catalyst, a noble metal supported on porous silica microspheres.

The examples show the use of K2C03 and KOH as bases and reaction temperature of 170°C, 180°C and 200°C.

Example 1 reports a yield of 93% using a catalyst consisting of 2% Pd and 0.1% Pt on a silica support.

The use of a support different from silica is reprted in example 2, 17 and 18, example 2 discloses a yield of only 55% using 5% Ru/C as catalyst, example 17 and 18 disclose a yield of only 4.5%) and 2.5% respectively using 2% Pd/C as catalyst.

Example 19 and 20 disclose the use of 5% Pd and 1% cobalt respectively on high surface area carbon (surface area 2000 m2/gram) and a yield of 87% and 88% respectively.

A special procedure for the preparation of the silica supported catalyst is disclosed.

EP 1 947 092 Al discloses perfluoroalkylation of nucleobases with a perfluoroalkyl halide in the presence of a sulfoxide, a peroxide and an iron compound. A specifically mentioned catalytic system is a Fe2(S04)3/H2S04/H202 system.

There was a need for a heterogeneously catalyzed process for the preparation of

perfluoroalkylated compounds, which provides high yields, which does not require high temperatures and does not require the use of catalysts prepared according to special procedures. The method should be applicable to a wide variety of substrates and should be compatible with a wide variety of functional groups. Furthermore the method should not be restricted to iodides as alkylating agent only, but should also work with other halides. And the method should work not only with perfluorinated alkyl iodides, but also with fluorinated and chlorinated alkyl halides.

Unexpectedly the use of Cs2C03 or CsHC03 as base together with Pt/C as catalyst meets these requirements. No dialkylated products are observed. The reaction does not mandatorily require inert atmosphere but can even be done under air atmosphere. The catalyst can be reused and is not deactivated by the reaction.

Compared to prior art, various advantages are observed as outlined in the examples below, e.g. in case of naphtalene not only the yield is higher but also the the selectivity is better, only the alpha position is substituted. The method is applicable both to aromatic and non-aromatic compounds. Also heteroaromatic compounds can be converted, even nonactivated thiophenes react smoothly at comparably low temperatures, n-methyl pyrrole reacts under mild conditions at 50°C. Also the notoriously difficult pyridines, which are very stable to many alkylating reagents and even can be used as a solvent in some perfluoroalkylation reactions, were converted with high yields. Also with caffeine high yields are obtained.

In this text, the following meanings are used, if not otherwise stated:

alkyl linear or branched alkyl;

DBU 1 , 8-diazabicyclo [5.4.0]undec-7-en

halide F , CI , Br or I , preferably CI , Br , and I , more preferably Br and I ;

halogen F, CI, Br or I; preferably F, CI or Br; more preferably F or CI;

HRMS EI: High Resolution Mass Spectrometry Electron Impact

"linear" and "n-" are used synonymously with respect to the respective isomers of alkanes; MTBE methyl tert-butyl ether;

Pt/C platinum on charcoal

RT room temperature, it is used synonymously with the expression ambient

temperature;

THF tetrahydrofurane

"wt%", "% by weight" and "weight-%" are used synonymously and mean percent by weight.

SUMMARY OF THE INVENTION

Subject of the invention is a method for the preparation of a alkylated or 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;

FCLALKYLHALIDE is a compound of formula (III);

R3-X (III)

X is CI, Br or I;

R3 is Ci_2o alkyl or a Ci_2o alkyl wherein in the alkyl chain at least one hydrogen is substituted by F or CI;

CAESCARB is Cs2C03, CsHC03 or a mixture thereof;

CAT is Pt/C;

COMPSUBST is selected from the group consisting of a compound COMPSUBST-I,

compound of formula (II), compound of formula (IV), polystyrene,

ethene and ethine;

the ethene being unsubstituted or substituted by 1 , 2 or 3 substitutents selected from the group consisting of Ci_io alkyl, C3_s cycloalkyl, Ci_4 alkoxy, N(R10)R1 1 , CN, NO, N02, F, CI, Br, I, CF3, (CH2)m-C(0)Yl , S(O)2R50, CH=C(H)R28, C=C-R24 ? benzyl, phenyl and naphthyl;

the ethine being unsubstituted or substituted by 1 substitutent selected from the group consisting of CMO alkyl, C3_8 cycloalkyl, Ci_4 alkoxy, N(R10)R1 1 , CN, NO, N02, F, CI, Br, I, CF3, (CH2)m-C(0)Yl , S(O)2R50, CH=C(H)R28, C=C-R24 ? benzyl, phenyl and naphthyl;

R40 and R41 are identical or different and independently from each other selected from the group consisting of (CH2)q-C(0)R13 and CN;

R42 is selected from the group consisting of (CH2)q-C(0)R13, CN, R13;

COMPSUBST-I contains a ring RINGA;

RINGA is a 5 or 6 membered carbocyclic or heterocyclic 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 ia a 5 membered ring, then RINGA is unsubstituted or substituted by 1 , 2, 3 or 4 identical or different subsitutents,

when RINGA is a 6 membered ring then RINGA is unsubstituted or substituted by 1 , 2, 3, 4 or 5 identical or different subsitutents,

any of said subsitutents of RINGA is independently from any other of said substitutent of RINGA selected from the group consisting of C1-10 alkyl, C3-8 cycloalkyl, Ci_4 alkoxy, OH, N(R10)R1 1 , CN, NH-OH, NO, N02, F, CI, Br, I, CF3, (CH2)m- C(0)Y1 , S(O)2R50, CH=C(H)R28, C=C-R24 ? 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 substitutents independently from each other selected from the group consisting of Ci_io alkyl, C3-8 cycloalkyl, Ci_4 alkoxy, OH, N(R17)R18, CN, NH-OH, NO, N02, F, CI, Br, I, CF3, (CH2)n-C(0)Y2, S(0)2R51 , CH=C(H)R38, C^__zC-R34 s benzyl, phenyl and naphthyl;

any of said C1-10 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, 0-C(0)-Ci_5 alkyl, O-C1-10 alkyl, S-C1-10 alkyl, S(0)-Ci_io alkyl, S(O2)-Ci_i0 alkyl, 0-Ci_6 alkylen-0-Ci_6 alkyl, C3_8 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, Ci_4 alkoxy, N02 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;

Yl , Y2 and R13 are identical or different and independently from each other selected from the group consisting of H, OH, C(R14)(R15)R16, Ci_6 alkyl, 0-Ci_6 alkyl, phenyl, benzyl, O-phenyl, 0-Ci_6 alkylen-0-Ci_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, CI and Br;

RIO, Rl 1 , R17, R18, R19 and R20 are identical or different and are independently from

each other H or Ci_6 alkyl, or RIO and Rl 1 , 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, Ci_6 alkyl and Ci_6 alkoxy;

R24, R34, R28 and R38 are identical or different and independently from each other selected from the group consisting of H, Ci_io alkyl, C(R25)(R26)-0-R27;

R25, R26 and R27 are identical or different and independently from each other selected from the group consisting of H and Ci_io alkyl.

DETAILED DESCRIPTION OF THE INVENTION

Preferably, COMPSUBST is selected from the group consisting of compound

COMPSUBST-I, compound of formula (II), compound of formula (IV), polystyrene, ethene and ethine;

the ethene being unsubstituted or substituted by 1 or 2 substitutents selected from the group consisting of Ci_i0 alkyl, C3_6 cycloalkyl, Ci_4 alkoxy, N(R10)R1 1 , CN, F, CI, Br, I, CF3, (CH2)m-C(0)Yl , S(O)2R50, benzyl, phenyl and naphthyl;

the ethine being unsubstituted or substituted by 1 substitutent selected from the group consisting of CMO alkyl, C3_6 cycloalkyl, Ci_4 alkoxy, N(R10)R1 1 , CN, F, CI, Br, I, CF3, (CH2)m-C(0)Yl , S(O)2R50, benzyl, phenyl and naphthyl;

with COMPSUBST-I bein selected from the group consisting of

with COMPSUBST-I being 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,

preferably, COMPSUBST I is unsubstituted or substituted by 1 , 2, 3, 4 or 5, identical or different substituents independently from each other selected from the group consisting of CMO alkyl, C3_8 cycloalkyl, Ci_4 alkoxy, OH, C(H)=0, N(R10)R1 1 , CN, NH-OH, NO, N02, F, CI, Br, I, CF3, (CH2)m-C(0)Yl , S(O)2R50,

CH=C(H)R28, ί =C-R24 ? benzyl, phenyl and naphthyl;

said Ci_io 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, 0-C(0)-Ci_5 alkyl, O-CMO alkyl, S-CMO alkyl, S(O)-Ci_i0 alkyl, S(O2)-Ci_i0 alkyl, 0-Ci_6 alkylen-0-Ci_6 alkyl, C3_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, Ci_4 alkoxy, N02 and CN

CLAIMS

1. Method for the preparation of a alkylated or 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;

FCLALKYLHALIDE is a compound of formula (III);

R3-X (III)

X is CI, Br or I;

R3 is Ci_2o alkyl or a Ci_2o alkyl wherein in the alkyl chain at least one hydrogen is

substituted by F or CI;

CAESCARB is Cs2C03, CsHC03 or a mixture thereof;

CAT is Pt/C;

COMPSUBST is selected from the group consisting of a compound COMPSUBST-I,

compound of formula (II), compound of formula (IV), polystyrene,

ethene and ethine;

the ethene being unsubstituted or substituted by 1 , 2 or 3 substitutents selected from the group consisting of C1-10 alkyl, C3_8 cycloalkyl, Ci_4 alkoxy, N(R10)R11, CN, NO,

N02, F, CI, Br, I, CF3, (CH2)m-C(0)Yl, S(O)2R50, CH=C(H)R28, C=C-R24 ? benzyl, phenyl and naphthyl;

the ethine being unsubstituted or substituted by 1 substitutent selected from the group consisting of CMO alkyl, C3_8 cycloalkyl, Ci_4 alkoxy, N(R10)R11, CN, NO, N02, F,

CI, Br, I, CF3, (CH2)m-C(0)Yl, S(O)2R50, CH=C(H)R28, C=C-R24 ? benzyl, phenyl and naphthyl;

(II) (IV)

R40 and R41 are identical or different and independently from each other selected from the group consisting of (CH2)q-C(0)R13 and CN;

R42 is selected from the group consisting of (CH2)q-C(0)R13, CN, R13;

COMPSUBST-I contains a ring RINGA;

RINGA is a 5 or 6 membered carbocyclic or heterocyclic 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 ia a 5 membered ring, then RINGA is unsubstituted or substituted by 1 , 2,

3 or 4 identical or different subsitutents,

when RINGA is a 6 membered ring then RINGA is unsubstituted or substituted by 1 , 2,

3, 4 or 5 identical or different subsitutents,

any of said subsitutents of RINGA is independently from any other of said substitutent of

RINGA selected from the group consisting of C1-10 alkyl, C3-8 cycloalkyl, Ci_4 alkoxy, OH, N(R10)R1 1 , CN, NH-OH, NO, N02, F, CI, Br, I, CF3, (CH2)m- C(0)Y1 , S(O)2R50, CH=C(H)R28, C=C-R24 ? 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 substitutents independently from each other selected from the group consisting of Ci_io alkyl, C3-8 cycloalkyl, Ci_4 alkoxy, OH, N(R17)R18, CN, NH-OH, NO, N02, F, CI, Br, I, CF3, (CH2)n-C(0)Y2, S(0)2R51 , CH=C(H)R38, C^__zC-R34 s benzyl, phenyl and naphthyl;

any of said C1-10 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, 0-C(0)-Ci_5 alkyl, O-C1-10 alkyl, S-C1-10 alkyl, S(0)-Ci_io alkyl, S(O2)-Ci_i0 alkyl, 0-Ci_6 alkylen-0-Ci_6 alkyl, C3_8 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, Ci_4 alkoxy, N02 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;

Yl , Y2 and R13 are identical or different and independently from each other selected from the group consisting of H, OH, C(R14)(R15)R16, Ci_6 alkyl, 0-Ci_6 alkyl, phenyl, benzyl, O-phenyl, 0-Ci_6 alkylen-0-Ci_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, CI and Br;

RIO, Rl 1 , R17, R18, R19 and R20 are identical or different and are independently from

each other H or Ci_6 alkyl, or RIO and Rl 1 , 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, Ci_6 alkyl and Ci_6 alkoxy;

R24, R34, R28 and R38 are identical or different and independently from each other selected from the group consisting of H, Ci_io alkyl, C(R25)(R26)-0-R27;

R25, R26 and R27 are identical or different and independently from each other selected from the group consisting of H and Ci_io alkyl.

2. Method according to claim 1 , wherein

COMPSUBST is selected from the group consisting of compound COMPSUBST-I,

compound of formula (II), compound of formula (IV), polystyrene, ethene and ethine;

the ethene being unsubstituted or substituted by 1 or 2 substitutents selected from the group consisting of Ci_io alkyl, C3-6 cycloalkyl, Ci_4 alkoxy, N(R10)R1 1 , CN, F, CI, Br, I, CF3, (CH2)m-C(0)Yl , S(O)2R50, benzyl, phenyl and naphthyl;

the ethine being unsubstituted or substituted by 1 substitutent selected from the group consisting of CMO alkyl, C3_6 cycloalkyl, Ci_4 alkoxy, N(R10)R11, CN, F, CI, Br, I, CF3, (CH2)m-C(0)Yl, S(O)2R50, benzyl, phenyl and naphthyl;

with COMPSUBST-I being 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 CMO alkyl, C3_8 cycloalkyl, Ci_4 alkoxy, OH, C(H)=0, N(R10)R11, CN, NH-OH, NO, N02, F, CI, Br, I, CF3, (CH2)m-C(0)Yl, S(O)2R50, CH=C(H)R28, L-K24 s benzyl, phenyl and naphthyl;

said Ci_io 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, 0-C(0)-Ci_5 alkyl, O-CMO alkyl, S-CMO alkyl, S(O)-Ci_i0 alkyl, S(O2)-Ci_i0 alkyl, 0-Ci_6 alkylen-0-Ci_6 alkyl, C3_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, Ci_4 alkoxy, N02 and CN.

3. Method according to claim 1 or 2, wherein

m, n and q are identical or different and independently from each other 0, 1 , 2, 3 or 4.

4. Method according to one or more of claims 1 to 3, wherein

COMPSUBST is selected from the group consisting of benzene, pyrazole,

of formula (VI), polystyrene, ethene and ethine;

Y is C I -6 alkyl;

the ethene being unsubstituted or substituted by 1 or 2 substitutents selected from the group consisting of CMO alkyl, Ci_4 alkoxy, N(R10)R11, CN, F, CI, Br, I, CF3, (CH2)m- C(0)Y1, benzyl and phenyl;

the ethine being unsubstituted or substituted by 1 substitutent selected from the group

consisting of CMO alkyl, Ci_4 alkoxy, N(R10)R11, CN, F, CI, Br, I, CF3,

(CH2)m-C(0)Yl, benzyl and phenyl;

(V) (VI)

wherein

R43 is H or CH3;

R44 is selected from the group consisting of Ci_i0 alkyl, Ci_4 alkoxy, OH, N(R10)R11, CN, NO, N02, F, CI, Br, I, CF3, (CH2)m-C(0)Yl, S(O)2R50.

5. Method according to one or more of claims 1 to 4, wherein

X is Br or I.

6 Method according to one or more of claims 1 to 5, wherein

X is I.

7. Method according to one or more of claims 1 to 6, wherein

compound FCLALKYLHADLIDE is a perfluoroalkyl halide, F2HC-C1 or F2HC-Br.

8 Method according to one or more of claims 1 to 7, wherein

X is CI, Br or I, and

R3 is perfluoro Ci_20 alkyl; or

FCLALKYLHADLIDE is F2HC-C1 or F2HC-Br.

9. Method according to one or more of claims 1 to 8, wherein

FCLALKYLHALIDE is selected from the group consisting of F2iCio-I, FnCs-I, F13C6-I, F9C4-I, F3C-I, F3C-Br, F3C-C1, F2HC-C1 and F2HC-Br.

10. Method according to one or more of claims 1 to 9, wherein

the reaction is done in the presence of a compound COMPSALT;

COMPSALT is selected from the group consisting of Nal, KI, Csl and

N(R30)(R31)(R32)R33I;

R30, R31, R32 and R33 are identical or different and independently from each other selected from the group consisting of H and Ci_io alkyl.

11. Method according to claim 10, wherein

R30, R31, R32 and R33 are identical or different and independently from each other selected from the group consisting of H and C2_6 alkyl.

12. Method according to claim 10 or 11, wherein

COMPSALT is selected from the group consisting of Nal and (n-Bu)4NI.

13. Method according to one or more of claims 1 to 12, 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.

14. Method according to one or more of claims 1 to 13, 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.

15. Method according to one or more of claims 1 to 14, 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.
16. Method according to one or more of claims 1 to 15, 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