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

Patent metadata

Field	Value
Publication number	US-9771367-B2
Application number	US-201515310295-A
Country	US
Kind code	B2
Filing date	Jun 4, 2015
Priority date	Jun 6, 2014
Publication date	Sep 26, 2017
Grant date	Sep 26, 2017

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 2 CO 3 or CsHCO 3 .

First claim

The invention claimed is:

1. 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 1-20 alkyl or a C 1-20 alkyl wherein in the alkyl chain at least one hydrogen is substituted by F or Cl;
CAESCARB is Cs 2 CO 3 , CsHCO 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 is 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 1-10 alkyl, C 3-8 cycloalkyl, C 1-4 alkoxy, OH, N(R10)R11, CN, NH—OH, NO, NO 2 , F, Cl, Br, I, CF 3 , (CH 2 ) m —C(O)Y1, S(O) 2 R50, CH═C(H)R28,

 benzyl, phenyl and naphthyl;
RINGA can be condensed with a ring RINGB, RINGB is a 5 or 6 membered carboryclic 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 1-10 alkyl, C 3-8 cycloalkyl, C 1-4 alkoxy, OH, N(R17)R18, CN, NH—OH, NO, NO 2 , F, Cl, Br, I, CF 3 , (CH 2 ) n —C(O)Y2, S(O) 2 R51, CH═C(H)R38,

 benzyl, phenyl and naphthyl;
any of said C 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, O—C(O)—C 1-5 alkyl, O—C 1-10 alkyl, S—C 1-10 alkyl, S(O)—C 1-10 alkyl, S(O 2 )—C 1-10 alkyl, O—C 1-6 alkylen-O—C 1-6 alkyl, C 3-8 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, C 1-4 alkoxy, NO 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 2-6 alkyl, O—C 1-6 alkyl, phenyl, benzyl, O-phenyl, O—C 1-6 alkylen-O—C 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 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 1-6 alkyl and C 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 1-10 alkyl, C(R25)(R26)—O—R27;
R25, R26 and R27 are identical or different and independently from each other selected from the group consisting of H and C 1-10 alkyl.

2. 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

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 1-10 alkyl, C 3-8 cycloalkyl, C 1-4 alkoxy, OH, C(H)═O, N(R10)R11, CN, NH—OH, NO, NO 2 , F, Cl, Br, I, CF 3 , (CH 2 ) m —C(O)Y1, S(O) 2 R50, CH═C(H)R28,

 benzyl, phenyl and naphthyl,
said C 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, O—C(O)—C 1-5 alkyl, O—C 1-10 alkyl, S—C 1-10 alkyl, S(O)—C 1-10 alkyl, S(O 2 )—C 1-10 alkyl, O—C 1-6 alkylen-O—C 1-6 alkyl, C 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 1-4 alkoxy, NO 2 and CN.

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

4. The method according to claim 1 , wherein
COMPSUBST is selected from the group consisting of benzene, pyrazole,

 and
polystyreneR44 is selected from the group consisting of C.

5. The method according to claim 1 , wherein
X is Br or I.

6. The method according to claim 1 , wherein
X is I.

7. The method according to claim 1 , wherein
compound FCLALKYLHADLIDE is a perfluoroalkyl halide, F 2 HC—Cl or F 2 HC—Br.

8. The method according to claim 1 , wherein
X is Cl, Br or I, and
R3 is perfluoro C 1-20 alkyl; or
FCLALKYLHADLIDE is F 2 HC—Cl or F 2 HC—Br.

9. The method according to claim 1 , wherein
FCLALKYLHALIDE is selected from the group consisting of F 21 C 10 —I, F 17 C 8 —I, F 13 C 6 —I, F 9 C 4 —I, F 3 C—I, F 3 C—Br, F 3 C—Cl, F 2 HC—Cl and F 2 HC—Br.

10. The method according to claim 1 , wherein
the reaction is done in the presence of a compound COMPSALT;
wherein COMPSALT is selected from the group consisting of Nal, Kl, Csl and N(R30)(R31)

Assignees

• Lonza Ag

Inventors

• Taeschler Christoph
• Beller Matthias
• Neumann Helfried
• He Lin
• Natte Kishore
• Ellinger Stefan
• Zaragoza Doerwald Florencio

Classifications

• C07D207/323

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms · CPC title

• C07D213/127

  Preparation from compounds containing pyridine rings · CPC title

• C07C45/68

  by increase in the number of carbon atoms · CPC title

• C07B37/04

  Substitution · CPC title

• C07D213/26

  Radicals substituted by halogen atoms or nitro radicals · CPC title