Method for preparation of alkylated or fluoro, chloro and fluorochloro alkylated compounds by heterogeneous cobalt catalysis

A method for the preparation of fluoro alkylated, chloro alkylated or fluorochloro alkylated compound ALKYLCOMPSUBST with heterogeneous catalysis by a reaction of a compound COMPSUBST with an alkylating agent ALKHAL in the presence of a catalyst CAT;

• ALKHAL is a compound of formula (III);
• R3-X (III)
• wherein
• X is Br or I;
• R3 is C1-20 alkyl;
• wherein the C1-20 alkyl residue R3 of ALKHAL is either unsubstituted, or at least one hydrogen residue of the C1-20 alkyl residue R3 of ALKHAL is substituted by F or Cl;
• CAT is Co-L1/C;
• L1 is 1,10-phenanthroline;
• COMPSUBST is selected from the group consisting of a compound COMPSUBST-I, compound of formula (II), compound of formula (IV), polystyrene, ethene and ethine;
• wherein
• COMPSUBST-I is a ring RINGA or is a RINGA condensed with a ring RINGB;
• RINGA is a 5 or 6 membered carbocyclic aromatic 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 substitutents,
• when RINGA is a 6 membered ring then RINGA is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substitutents,
• any of said substitutents of RINGA is independently from any other of said substitutent of RINGA selected from the group consisting of C1-20 alkyl, C3-8 cycloalkyl, C1-4 alkoxy, OH, N(R10)R11, CN, NH—OH, NO, NO2, F, Cl, Br, I, CF3, (CH2)m—C(O)Y1, S(O)2R50,
• CH═C(H)R28, benzyl, phenyl and naphthyl;
• RINGB is a 5 or 6 membered carbocyclic or heterocyclic ring, resulting in a bicyclic having 8, 9 or 10 ring members in total,
• when RINGB is a heterocyclic ring, then RINGB 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 identical or different substituents in case of RINGB being a 5 membered ring, with 1, 2, 3 or 4 identical or different substituents in case of RINGB being a 6 membered ring, which identical or different substitutents are independently from each other selected from the group consisting of C1-10 alkyl, C3-8 cycloalkyl, C1-4 alkoxy, OH, N(R17)R18, CN, NH—OH, NO, NO2, F, Cl, Br, I, CF3, (CH2)n—C(O)Y2, S(O)2R51, CH═C(H)R38,
• 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, O—C(O)—C1-5 alkyl, O—Ch1-10 alkyl, S—Ch1-10 alkyl, S(O)—Ch1-10 alkyl, S(O2)—C1-10 alkyl, O—C1-6 alkylen-O—C1-6 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, C1-4 alkoxy, NO2 and CN;
• m and n are identical or different and independently from each other an integer from 0 to 10;
• wherein
• the compound of formula (II) and the compound of formula (IV) being
• R40 and R41 are identical or different and independently from each other selected from the group consisting of —(CH2)q—C(O)R13 and —CN;
• R42 is selected from the group consisting of —(CH2)q—C(O)R13, —CN and R13;
• q is independently an integer from 0 to 10;
• wherein
• the ethene being unsubstituted or substituted by 1, 2 or 3 substitutents selected from the group consisting of C1-10 alkyl, C3-8 cycloalkyl, C1-4 alkoxy, N(R10)R11, CN, NO, NO2, F, Cl,
• Br, I, CF3, (CH2)p—C(O)Y1, S(O)2R50, CH═C(H)R28, benzyl, phenyl and naphthyl;
• the ethine being unsubstituted or substituted by 1 substitutent selected from the group consisting of C1-10 alkyl, C3-8 cycloalkyl, C1-4 alkoxy, N(R10)R11, CN, NO, NO2, F, Cl, Br, I, CF3,
• (CH2)p-C(O)Y1, S(O)2R50, CH═C(H)R28, benzyl, phenyl and naphthyl;
• p is independently an integer from 0 to 10;
• any of the R24, R34, R28 and R38 are identical or different and independently from each other selected from the group consisting of H, C1-10 alkyl, C(R25)(R26)-O-R27;
• any of the R25, R26 and R27 are identical or different and independently from each other selected from the group consisting of H and C1-10 alkyl;
• any of the R50 and R51 are identical or different and independently from each other selected from the group consisting of OH, C1-6 alkyl and C1-6 alkoxy;
• any of the Y1, Y2 and R13 are identical or different and independently selected from the group consisting of H, OH, C(R14)(R15)R16, C1-6 alkyl, O—C1-6 alkyl, phenyl, benzyl, O—phenyl, O—C1-6 alkylen-O—C1-6 alkyl and N(R19)R20;
• any of the R14, R15 and R16 are identical or different and independently from each other selected from the group consisting of H, F, Cl and Br;
• any of the R10, R11, R17, R18, R19 and R20 are identical or different and are independently from each other H or C1-6 alkyl, or R10 and R11, R17 and R18 or R19 and R20 represent together tetramethylene or pentamethylene.