Process for polymerising (hetero)aromatic compounds

1. A process for polymerizing or copolymerizing, the process comprising polymerizing at least one (hetero)aromatic compound in the presence of a mixture comprising:

a) a catalyst/ligand system comprising a palladium catalyst and an organic phosphine or phosphonium compound;

b) a base, which is a lithium salt; and

c) at least one solvent;

wherein:

the organic phosphine is a trisubstituted phosphine of formula (VI)

or phosphonium salt thereof;

X independently of Y represents a nitrogen atom or a C—R 2 group;

Y independently of X represents a nitrogen atom or a C—R 9 group;

R 1 for each of the two R 1 groups independently of the other represents a radical selected from the group consisting of C 1 -C 24 -alkyl, C 3 -C 20 -cycloalkyl, which includes mono-, bi-, and tri-cyclic cycloalkyl radicals, C 5 -C 14 -aryl, which includes the phenyl, naphthyl, fluorenyl radical, and C 2 -C 13 -heteroaryl, wherein a number of heteroatoms, at least one selected from the group consisting of nitrogen, oxygen, and sulfur, is from 1 to 2;

the two radicals R 1 are optionally linked to one another;

the radicals R 1 may themselves each be independently of one another mono- or poly-substituted by at least one substituent selected from the group consisting of hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 3 -C 8 -cycloalkyl, C 2 -C 9 -hetero-alkyl, C 5 -C 10 -aryl, C 2 -C 9 -heteroaryl, wherein the number of heteroatoms, at least one selected from the group consisting of nitrogen, oxygen and sulfur, is from 1 to 4, C 1 -C 20 -alkoxy, C 1 -C 10 -haloalkyl, hydroxy, amino of the forms NH—(C 1 -C 20 -alkyl), NH—(C 5 -C 10 -aryl), N(C 1 -C 20 -alkyl) 2 , N(C 1 -C 20 -alkyl) (C 5 -C 10 -aryl), N(C 5 -C 10 -aryl) 2 , N(C 1 -C 20 -alkyl/C 5 -C 10 -aryl 3 ) 3 + , NH—CO—C 1 -C 20 -alkyl, NH—CO—C 5 -C 10 -aryl, carboxylato of the forms COOH and COOQ, wherein Q represents either a monovalent cation or C 1 -C 8 -alkyl, C 1 -C 6 -acyloxy, sulfinato, sulfonato of the forms SO 3 H and SO 3 Q′, wherein Q′ represents a monovalent cation, C 1 -C 20 -alkyl, or C 5 -C 10 -aryl, and tri-C 1 -C 6 -alkylsilyl, wherein two of the mentioned substituents may also be bridged with one another;

R 2 -R 9 each independently of each other represent a hydrogen, alkyl, alkenyl, cycloalkyl, aromatic or heteroaromatic aryl, O-alkyl, NH-alkyl, N-(alkyl) 2 , O-(aryl), NH-(aryl), N-(alkyl)(aryl), O—CO-alkyl, O—CO-aryl, F, Si(alkyl) 3 , CF 3 , CN, CO 2 H, CHO, SO 3 H, CONH 2 , CONH(alkyl), CON(alkyl) 2 , SO 2 (alkyl), SO(alkyl), SO(aryl), SO 2 (aryl), SO 3 (alkyl), SO 3 (aryl), S-alkyl, S-aryl, NH—CO(alkyl), CO 2 (alkyl), CONH 2 , CO(alkyl), NHCHO, NHCO 2 (alkyl), CO(aryl), or CO 2 (aryl) radical, wherein

two or more adjacent radicals R 2 -R 9 each independently of the other are optionally linked to one another to form a condensed ring system;

the R 2 -R 9 alkyl represents a hydrocarbon radical having from 1 to 20 carbon atoms and optionally linear or branched;

the R 2 -R 9 alkenyl represents a mono- or poly-unsaturated hydrocarbon radical having from 2 to 20 carbon atoms and optionally linear or branched;

the R 2 -R 9 cycloalkyl represents a hydrocarbon having from 3 to 20 carbon atoms;

the R 2 -R 9 aryl represents a 5- to 14-membered aromatic radical, wherein from one to four carbon atoms in the aryl radical are optionally substituted with at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur so that a 5- to 14-membered heteroaromatic radical is present, and

the radicals R 2 to R 9 optionally comprise at least one further substituent as defined for R 1 ; and

the (hetero)aromatic compound comprises at least one functional halide group and at least one functional boron group.

2. The process of to claim 1 , wherein the base is at least one selected from the group consisting of a lithium alkoxide, a lithium hydroxide, carboxylate, carbonate, fluoride and phosphate.

3. The process of claim 2 , wherein the base is LiOH or LiOH.xH 2 O.

4. The process of claim 1 , wherein:

X represents a CR 2 group and Y represents a CR 9 group, or X is nitrogen and Y represents a CR 9 group;

R 1 is selected from the group consisting of a phenyl, C 1 -C 10 -alkyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-adamantyl, and 2-adamantyl;

R 2 to R 9 are selected from the group consisting of hydrogen, C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl, C 1 -C 10 -haloalkyl, C 3 -C 8 -cycloalkyl, C 6 -C 10 -aryl, and C 2 -C 6 -heteroaryl, wherein from 1 to 3 nitrogen atoms or an oxygen or sulfur atom is optionally present as heteroatom; and

two adjacent radicals R 2 to R 9 are optionally bridged with one another.

5. The process of claim 4 , wherein the catalyst/ligand system comprises an organic phosphine which is a trisubstituted phosphine of formula

Cpd.

R 1

R 5

R 6

R 3

R 4

A-1

H

H

H

H

A-2

cyclohexyl

H

H

H

H

A-3

phenyl

H

H

H

H

A-4

adamantyl

H

H

H

H

A-5

cyclohexyl

—OCH 3

H

H

H

A-6

cyclohexyl

1)

1)

H

H

A-7

H

H

A-8

phenyl

1)

1)

H

H

A-9

adamantyl

1)

1)

H

H

A-10

cyclohexyl

H

H

2)

2)

A-11

H

H

2)

2)

A-12

phenyl

H

H

2)

2)

A-13

adamantyl

H

H

2)

2)

wherein:

6. The process claim 1 , wherein the palladium catalyst is selected from the group consisting of a Pd(II) halide, a Pd(II) carboxylate, a Pd(II) diketonate, Pd 2 (dba) 3 , Pd(dba) 2 , Pd(PR 3 ) 2 , Pd(OAc) 2 , PdCl 2 (PR 3 ) 2 , PdCl 2 (PhCN) 2 , PdCl 2 (CH 3 CN), and PdCl 2 (COD), wherein PR 3 is the organic phosphine of formula (VI).

7. The process of claim 1 , wherein the solvent is at least one selected from the group consisting of toluene, xylene, anisole, THF, 2-methyltetrahydrofuran, dioxane, chlorobenzene, fluorobenzene, and water.

8. The process of claim 7 , wherein the solvent is at least one selected from the group consisting of THF and water.

9. The process of claim 1 , wherein the at least one functional halide and the at least one boron group are attached to a 5-membered heteroaromatic ring that is optionally substituted and optionally fused to another ring.

10. The process of claim 9 , wherein the at least one heteroaromatic compound is selected from the group consisting of

wherein:

R 1′ and R 2′ may be the same or different and are selected from the group consisting of hydrogen, a C 1 -C 100 alkyl group, —COOR 124′ , a C 1 -C 100 alkyl group which is substituted by one or more halogen atoms, hydroxyl groups, nitro groups, —CN, or C 6 -C 18 aryl groups and/or interrupted by —O—, —COO—, —OCO, or —S—, a C 7 -C 100 arylalkyl group, a carbamoyl group, a C 5 -C 12 cycloalkyl group which can be substituted one to three times with C 1 -C 8 alkyl, C 1 -C 8 alkoxy, or both, a C 6 -C 24 aryl group, a phenyl or 1- or 2-naphthyl group which can be substituted one to three times with C 1 -C 8 alkyl, C 1 -C 24 thioalkoxy, and/or C 1 -C 24 alkoxy, pentafluorophenyl;

R 124′ is a hydrogen or a C 1 -C 50 alkyl group;

R 123 is a C 1 -C 25 alkyl group optionally interrupted by one or more oxygen atoms, or a C 1 -C 25 alkoxy group;

R 99 is a C 1 -C 25 alkyl group optionally interrupted by one or more oxygen atoms;

one of X 1 and X 2 is N and the other is CH;

R 116 is H, C 1 -C 25 alkyl, or a phenyl optionally substituted one to three times with C 1 -C 8 alkyl, C 1 -C 24 alkoxy, or both;

X 11 is independently in each occurrence —B(OH) 2 , —B(OY 1 ) 2 , —B(OH) 3 − , —BF 3 − ,

wherein Y 1 is independently in each occurrence a C 1 -C 10 alkyl group and Y 2 is independently in each occurrence a C 2 -C 10 alkylene group, and Y 13 and Y 14 are independently of each other hydrogen, or a C 1 -C 10 alkyl group; and

X 11′ is a halogen.

11. The process of claim 1 , wherein the at least one (hetero)aromatic compound is selected from the group consisting of

wherein:

X 7 is —O—, —S—, —NR 115− , or —Si(R 117 ) 2 —;

a is an integer of 1 to 5;

one of X 1 and X 2 is N and the other is CH;

one of X 5 and X 6 is N and the other is CR 14 ;

Ar 1 is

 or a heteroarylene group;

R 115 is H, C 1 -C 25 alkyl, or phenyl optionally substituted one to three times with C 1 -C 8 alkyl, C 1 -C 24 alkoxy, or both;

R 117 is C 1 -C 25 alkyl;

R 12 and R 12′ are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, optionally interrupted by one or more oxygen or sulphur atoms, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or

R 13 is a C 1 -C 10 alkyl group or a tri(C 1 -C 8 alkyl)silyl group;

R 15 and R 15′ are independently of each other H, or a C 1 -C 25 alkyl group optionally interrupted by one or more oxygen atoms;

R 14 is a C 1 -C 25 alkyl group optionally interrupted by one or more oxygen atoms, or a C 1 -C 25 alkoxy group;

R 18 and R 18′ independently of each other are a hydrogen, halogen, C 1 -C 25 alkyl optionally interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 aralkyl, or C 1 -C 25 alkoxy;

R 19 is hydrogen, C 7 -C 25 aralkyl, C 6 -C 18 aryl, C 6 -C 18 aryl substituted by a C 1 -C 18 alkyl, C 1 -C 18 alkoxy, or C 1 -C 25 alkyl optionally interrupted by one or more oxygen or sulphur atoms;

R 20 and R 20′ are independently of each other a hydrogen, C 7 -C 25 aralkyl, C 1 -C 25 alkyl, optionally interrupted by one or more oxygen or sulphur atoms;

X 11 is independently in each occurrence —B(OH) 2 , —B(OY 1 ) 2 , —B(OH) 3 − , —BF 3 − ,

 —BF 4 Na, or —BF 4 K, wherein Y 1 is independently in each occurrence a C 1 -C 10 alkyl group and Y 2 is independently in each occurrence a C 2 -C 10 alkylene group, or a C 1 -C 10 alkyl group, and Y 13 and Y 14 are independently of each other hydrogen or a C 1 -C 10 alkyl group; and

X 11′ is a halogen.

12. The process of claim 10 , wherein R 124′ is a C 8 -C 36 alkyl group.

13. The process of claim 10 , wherein R 123 is a C 6 -C 25 alkyl optionally interrupted by one or more oxygen atoms.

14. The process of claim 10 , wherein R 99 is a C 6 -C 25 alkyl group optionally interrupted by one or more oxygen atoms.

15. The process of claim 11 , wherein:

Y 2 is a —CY 3 Y 4 —CY 5 Y 6 —, or —CY 7 Y 8 —CY 9 Y 10 —CY 11 Y 12 —, wherein Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 and Y 12 are hydrogen, or Y 2 is —C(CH 3 ) 2 C(CH 3 ) 2 —, —C(CH 3 ) 2 CH 2 C(CH 3 ) 2 —, or —CH 2 C(CH 3 ) 2 CH 2 —.

16. The process of claim 1 , wherein two radicals R 1 are linked to one another with P to form a 5H-dibenzo-phospholyl, 9-phosphabicyclo[3.3.1]nonanyl, or 9-phospha-bicyclo[4.2.1]nonanyl.