Synthetic building blocks for the production of materials for organic electroluminescence devices

Abstract

The present invention relates to compounds which are suitable as synthesis precursors for the production of electronically active materials for use in organic electroluminescence devices.

Claims

1. A compound of the formula (1), formula (2) or formula (3), ##STR00325## where the following applies to the symbols and indices used: L stands for a single bond, NR, BR, P(═O)R, a straight-chain alkylene or alkylidene group having 1 to 10 C atoms or a branched or cyclic alkylene or alkylidene group having 3 to 10 C atoms, which may be substituted by in each case substituted by one or more radicals R, where one or more non-adjacent CH.sub.2 groups may be replaced by —RC═CR—, —C≡C—, Si(R).sub.2, C═O, —O—, —S— or —CONR— and where one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted by one or more radicals R; R is selected on each occurrence, identically or differently, from the group consisting of H, D, Cl, Br, I, NAr.sub.2, N(R.sup.1).sub.2, where R.sup.1 is not equal to H, C(═O)Ar, C(═O)R.sup.1, BR.sup.1, P(═O)Ar.sub.2, PAr.sub.2, OAr, SAr, S(═O)Ar, S(═O).sub.2Ar, Si(R.sup.1).sub.3, a straight-chain alkyl or alkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.1, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═NR.sup.1, P(═O)(R.sup.1), NR.sup.1, O, S or CONR.sup.1 and where one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1; two or more adjacent substituents R here may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R.sup.1; Ar is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5-30 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1; two radicals Ar here which are bonded to the same N atom or P atom may also be bridged to one another by a single bond or a bridge selected from N(R.sup.1), C(R.sup.1).sub.2, O, S or BR.sup.1; R.sup.1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO.sub.2, N(R.sup.2).sub.2, P(═O)(R.sup.2).sub.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.2, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, C═NR.sup.2, P(═O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, S or CONR.sup.2 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2; two or more adjacent substituents R.sup.1 here may optionally form a monocyclic or polycyclic, aliphatic ring system, which may be substituted by one or more radicals R.sup.2; R.sup.2 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN, where two or more adjacent substituents R.sup.2 may form a mono- or polycyclic, aliphatic ring system with one another; n is 0, 1, 2, 3, 4 or 5, with the proviso that L is not present if n=0 and furthermore with the proviso that, for n≧1, L is in each case bonded to the benzene skeleton instead of a radical R and the corresponding group R is thus not present; with the proviso that the following compounds are excluded from the invention: ##STR00326## ##STR00327##

2. The compound according to claim 1, wherein n=0, 1, 2 or 3.

3. The compound according to claim 1, wherein n=0, 1 or 2.

4. The compound according to claim 1, selected from the compounds of the formulae (1a) to (1h), (2a) to (2l) and (3a) to (3f), ##STR00328## ##STR00329## ##STR00330## ##STR00331## ##STR00332## where the symbols used has the meanings given in claim 1.

5. The compound according to claim 1, wherein two adjacent radicals R form a ring of the formula (4) with one another, ##STR00333## where R.sup.1 has the meanings given above, the dashed bonds indicate the linking of the group to the benzene skeleton and furthermore: E is selected from the group consisting of C(R.sup.1).sub.2, NR.sup.1, O, S, BR.sup.1 or Si(R.sup.1).sub.2.

6. The compound according to claim 1, wherein R is selected on each occurrence, identically or differently, from the group consisting of H, NAr.sub.2, C(═O)Ar, C(═O)R.sup.1, P(═O)Ar.sub.2, PAr.sub.2, Si(R.sup.1).sub.3, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an alkenyl group having 2 to 10 C atoms, each of which may be substituted by one or more radicals R.sup.1, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1 or O and where one or more H atoms may be replaced by F, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1; two or more adjacent substituents R here may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R.sup.1.

7. The compound according to claim 1, wherein none of the radicals R, R.sup.1 or R.sup.2 contains condensed aryl or heteroaryl groups in which six-membered rings are condensed directly onto one another.

8. The compound according to claim 1, wherein at least one radical R is selected from the group consisting of an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1.

9. The compound according to claim 1, wherein at least one radical R is selected from the group consisting of triarylamine, carbazole, indenocarbazole, indolocarbazole, azacarbazole, indole, furan, benzofuran, dibenzofuran, thiophene, benzothiophene or dibenzothiophene, each of which may be substituted by one or more radicals R.sup.1, or at least one substituent R stands for —NAr.sub.2, where the two groups Ar may also be bridged to one another by a group selected from NR.sup.1, O, S, C(R.sup.1).sub.2, Si(R.sup.1).sub.2 or BR.sup.1.

10. A process for the preparation of the compound according to claim 1, comprising the reaction steps: a) oxidation of a fluoro-meta-xylene to give the carboxylic acid; and b) conversion of the carboxylic acid functionalities into nitrile groups.

11. A process for the preparation of a compound according to claim 1 which comprises reacting a fluoro-meta-dihalobenzene with Zn(CN).sub.2 and Zn in the presence of a catalyst.

12. A starting material in a nucleophilic aromatic substitution reaction which comprises the compound according to claim 1.

13. The compound according to claim 1, wherein at least one radical R is selected from the group consisting of benzene, biphenyl, terphenyl, quaterphenyl, 1-spirobifluorene, 2-spirobifluorene, 3-spirobifluorene, 4-spirobifluorene, 1-fluorene, 2-fluorene, 3-fluorene, 4-fluorene, 1-naphthyl, 2-naphthyl, pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, triazine, imidazole, benzimidazole, pyrazole, thiazole, oxazole, oxadiazole, triazole, phenanthrene, triphenylene or combinations of two or three of these groups, each of which may be substituted by one or more radicals R.sup.1.

14. The compound according to claim 1, wherein at least one radical R is selected from the group consisting of benzene, ortho-biphenyl, meta-biphenyl, para-biphenyl, ortho-terphenyl, meta-terphenyl, para-terphenyl, branched terphenyl, ortho-quaterphenyl, meta-quaterphenyl, para-quaterphenyl, branched quaterphenyl, 1-spirobifluorene, 2-spirobifluorene, 3-spirobifluorene, 4-spirobifluorene, 1-fluorene, 2-fluorene, 3-fluorene, 4-fluorene, 1-naphthyl, 2-naphthyl, pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, triazine, imidazole, benzimidazole, pyrazole, thiazole, oxazole, oxadiazole, triazole, phenanthrene, triphenylene or combinations of two or three of these groups, each of which is optionally substituted by one or more radicals R.sup.1, or in that at least one substituent R is selected from one of the groups of the formulae (7) to (18) ##STR00334## ##STR00335## where the symbols used have the meanings given in claim 1, * indicates the position of the bonding of the group and furthermore: A is on each occurrence, identically or differently, CR.sup.1 or N, with the proviso that one, two or three groups A stand for N; Ar.sup.1 is, identically or differently on each occurrence, a divalent aromatic or heteroaromatic ring system having 5 to 16 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1; m is 0 or 1.

15. The compound according to claim 1, wherein at least one radical R is selected from the group consisting of the formulae (19) to (33), ##STR00336## ##STR00337## ##STR00338## where the symbols used have the meanings given in claim 1 and furthermore: G is selected from the group consisting of NR.sup.1, O or S; where in each case one or two groups CR.sup.1 may be replaced by N.

Description

EXAMPLES

(1) The following syntheses are carried out, unless indicated otherwise, in dried solvents under a protective-gas atmosphere. The solvents and reagents can be purchased from Sigma-ALDRICH or ABCR. The respective numbers in square brackets or the numbers indicated for individual compounds relate to the CAS numbers of the compounds which are known from the literature, but are not commercially available.

A: Synthesis

Example S1

5-Bromo-2-fluoroisophthalonitrile, S1

(2) ##STR00068##

a) S1a: 5-Bromo-2-fluoroisophthalic acid, S1a

(3) ##STR00069##

(4) Procedure analogous to H. G. Menzella, J. Med. Chem., 2009, 52 (6), 1518. 663.8 g (4.2 mol) of potassium permanganate are added spoonwise with vigorous stirring to a mixture, warmed to 90° C., of 203.1 g (1 mol) of 5-bromo-2-fluoro-m-xylene [99725-44-7] and 2000 ml of water (attention: slightly exothermic reaction). When the addition is complete, the reaction mixture is stirred under reflux for a further 12 h. The mixture is allowed to cool to 70° C., the manganese dioxide formed is filtered off with suction through a Celite layer, rinsed twice with 300 ml of warm water each time and rendered acidic using conc. 300 ml of HCl with stirring. The water phase is allowed to cool, and the product which has precipitated out is then filtered off with suction, rinsed three times with 300 ml of water each time and then dried in vacuo. Yield: 205.7 g (782 mmol), 78%. Purity: about 98% according to .sup.1H-NMR.

(5) The following compounds are prepared analogously:

(6) TABLE-US-00001 Ex. Starting material Product Yield S2a 0 66% 1416549-07-9 S2a S3a 69% 26584-26-9 S3a S4a 76% 1407493-64-4 S4a S5a 70% 67205-30-5 S5a S6a 63% 2366-75-8 S6a S7a 0 46% 1314888-40-8 S7a Use of 500 mmol S8a 81% 344-16-1 S8a S9a 67% 26829-82-3 S9a

b) S1b: 5-Bromo-2-fluoroisophthaloyl chloride, S1 b

(7) ##STR00086##

(8) Procedure analogous to W. P. Hellmann, J. Med. Chem., 1978, 21 (9), 906. 20 drops of DMF are added with stirring to a mixture of 131.5 g (500 mmol) of 5-bromo-2-fluoroisophthalic acid, S1a and 500 ml of thionyl chloride, and the mixture is then slowly warmed to 70° C. When the evolution of HCl is complete, the mixture is stirred for a further 4 h, and the excess thionyl chloride is then distilled off until the residue solidifies to give a pale-yellow crystalline mass. The acid chloride is used without further purification. Yield: quantitative. Purity: about 98% according to .sup.1H-NMR.

(9) The following compounds are prepared analogously:

(10) TABLE-US-00002 Ex. Starting material Product Yield S2b quantitative S2a S2b S3b 0 quantitative S3a S3b S4b quantitative S4a S4b S5b quantitative S5a S5b S6b quantitative S6a S6b S7b quantitative S7a S7b Use of 250 mmol S8b 00 quantitative S8a S8b S9b 01 02 quantitative S9a S9b

c) S1c: 5-Bromo-2-fluoroisophthalamide, S1c

(11) ##STR00103##

(12) Procedure analogous to W. P. Heilmann, J. Med. Chem., 1978, 21 (9), 906. A solution of 150.0 g (500 mmol) of 5-bromo-2-fluoroisophthaloyl chloride, S1b in 300 ml of dioxane is added dropwise to a vigorously stirred mixture of 300 ml of conc. ammonium hydroxide and 800 ml of dioxane with ice-cooling at such a rate that the temperature does not exceed 50° C. When the exothermic reaction is complete, the cooling bath is removed, the reaction mixture is stirred further until an internal temperature of 25° C. has been reached, the solid which has precipitated out is filtered off with suction, washed three times with 200 ml of water and then dried in vacua. Yield: 87.5 g (335 mmol) 67%. Purity: about 98% according to .sup.1H-NMR

(13) The following compounds are prepared analogously:

(14) TABLE-US-00003 Ex. Starting material Product Yield S2c 04 05 64% S2b S2c S3c 06 07 70% S3b S3c S4c 08 09 66% S4b S4c S5c 0 68% S5b S5c S6c 73% S6b S6c S7c 59% S7b S7c Use of 250 mmol S8c 79% S8b S8c S9c 77% S9b S9c

d) S1: 5-Bromo-2-fluoroisophthalonitrile, S1

(15) ##STR00120##

(16) Procedure analogous to W. P. Hellmann, J. Med. Chem., 1978, 21 (9), 906.

(17) A mixture of 65.3 g (250 mmol) of 5-bromo-2-fluoroisophthalamide, S1c and 142 ml (1.5 mol) of phosphoryl chloride and 10 drops of DMF is slowly heated to 90° C. with vigorous stirring. When the evolution of HCl is complete, the reaction mixture is allowed to cool, then poured into a mixture of 5 kg of ice and 1000 ml of water. The product which has precipitated out is filtered off, washed three times with 200 ml of water each time and dried in vacuo. The purification is carried out by recrystallisation from chlorobenzene. Yield: 49.5 g (220 mmol) 88%. Purity: about 98% according to .sup.1H-NMR

(18) The following compounds are prepared analogously:

(19) TABLE-US-00004 Ex. Starting material Product Yield S2 87% S2c S2 S3 86% S3c S3 S4 82% S4c S4 S5 90% S5c S5 S6 0 84% S6c S6 S7 68% S7c S7 Use of 125 mmol S8 72% S8c S8 S9 77% S9c S9

S10: 5-Phenyl-2-fluoroisophthalonitrile, S10

(20) ##STR00137##
Variant A:

(21) A mixture of 22.5 g (100 mmol) of 5-bromo-2-fluoroisophthalonitrile, S1, 14.6 g (120 mmol) of phenylboronic acid [98-80-6], 42.5 g (200 mmol) of tripotassium phosphate, 1.8 g (6 mmol) of tri-o-tolylphosphine, 224 mg (1 mmol) of palladium(II) acetate, 200 ml of toluene, 50 ml of dioxane and 200 ml of water is heated under reflux until the 5-bromo-2-fluoroisophthalonitrile, S1 has been consumed (about 6 h). After cooling, the aqueous phase is separated off, the organic phase is filtered through a Celite bed in order to remove palladium, the filtrate is washed three times with 200 ml of water each time, once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. The residue obtained after removal of the solvent is recrystallised twice from DMF. Yield: 15.1 g (68 mmol) 68%. Purity: about 99% according to .sup.1H-NMR.

(22) Variant B:

(23) A mixture of 22.5 g (100 mmol) of 5-bromo-2-fluoroisophthalonitrile, S1, 14.6 g (120 mmol) of phenylboronic acid, 17.5 g (300 mmol) of potassium fluoride, anhydrous, 263 mg (1.3 mmol) of tri-tert-butylphosphine, 224 mg (1 mmol) of palladium(II) acetate, 250 ml of THF is heated under reflux until the 5-bromo-2-fluoroisophthalonitrile, S1 has been consumed (about 2 h). After cooling, the mixture is filtered off through a Celite bed and rinsed with 200 ml of THF in order to remove salts and palladium. The filtrate is evaporated to dryness, the residue is washed by stirring with 200 ml of a mixture of water/EtOH (1:1, vv), the solid is filtered off with suction, washed three times with 100 ml of ethanol each time and dried in vacuo. The solid obtained in this way is recrystallised twice from DMF. Yield: 16.9 g (76 mmol) 76%. Purity: about 99% according to .sup.1H-NMR. A further purification can be carried out by repeated recrystallisation or chromatography and by fractional sublimation in vacuo.

(24) The following compounds are prepared analogously:

(25) TABLE-US-00005 Ex Starting material Boronic acid Product Variant Yield S11   S1   100379-00-8 0 76% B S12   S1   4688-76-0 64% A S13   S1   312968-33-5 Use of 45 mmol 48% A S14   S1   128388-54-5 78% A S15 0   S1   1233200-59-3 63% A S16   S1   197223-39-5 75% A S17   S1   13922-41-3 71% A S18   S1 0   1000869-26-0 70% A S19   S1   68572-87-2 73% A S20   S1   654664-63-8 56% B S21   S1   334658-75-2 0 58% A S22   S1   400607-46-7 53% A S23   S1   402936-15-6 77% A S24   S1   395087-89-5 80% A S25 0   S1   162607-19-4 76% A S26   S1   100124-06-9 69% A S27   S1   668983-97-9 83% A S28   S1 0   1001911-63-2 81% A S29   S1   1370555-65-9 70% A S30   S1   854952-58-2 74% A S31   S1   333432-28-3 00 80% A S32 01   S1 02   1246022-50-3 03 69% A S33 04   S1 05   1251773-34-8 06 77% A S34 07   S1 08   236389-21-2 09 79% A S35 0   S1   1224976-40-2 72% A S36   S1   1421789-05-0 71% A S37   S1   1214723-25-7 66% B S38   S1 0   1313018-07-3 78% A S39   S1   201802-67-7 67% A S40   S1   943836-24-6 69% A S41   823-96-1 0 38% S1 B S42   S2   4612-28-6 Use of 45 mmol 46% A S43   S3   5122-95-2 55% A S44   S4 Use of 50 mmol   98-80-6 34% B S45 0   S5 Use of 30 mmol   98-80-6 23% B S46   S8 64% 123324-71-0 A S47   S9   854952-45-7 75% A S48   17654-69-2 0   1314221-56-1 73%

S49: 5-(N-Diphenylamino)-2-fluoroisophthalonitrile, S49

(26) ##STR00252##

(27) A mixture of 22.5 g (100 mmol) of 5-bromo-2-fluoroisophthalonitrile, S1, 20.3 g (120 mmol) of diphenylamine, 11.5 g (120 mmol) of sodium tert-butoxide, 405 mg (2 mmol) of tri-tert-butylphosphine, 224 mg (1 mmol) of palladium(II) acetate and 300 ml of toluene is heated under reflux until the 5-bromo-2-fluoroisophthalonitrile, S1 has been consumed (about 8 h). After cooling, 100 ml of water are added, the solid which has precipitated out is filtered off with suction, washed three times with 50 ml of ethanol each time and dried in vacuo. The solid obtained in this way is dissolved in 300 ml of dichloromethane, the solution is filtered through a Celite bed in order to remove salts and palladium. The residue obtained after evaporation of the filtrate is recrystallised twice from dioxane/EtOH. Yield: 22.9 g (73 mmol) 73%. Purity: about 99% according to .sup.1H-NMR. A further purification can be carried out by repeated recrystallisation or chromatography and by fractional sublimation in vacuo.

(28) The following compounds can be prepared analogously:

(29) TABLE-US-00006 Ex Starting material Amine Product Yield S50   S1   169224-65-1 68% S51   S1   169224-65-1 53% S52   S1 0   1258515-01-3 49% S53   S1   1290039-78-9 70% S54   S1   355832-04-1 65% S55   S1   1421789-16-3 0 49% S56   S1   1421789-18-5 43% S57   S1   1325195-27-4 46% S58   S1   1318338-47-4 45% S59 0   S1   1259388-68-5 50% S60   S1   56525-79-2 32% S61   S1   1257220-47-5 28% S62   S1 0   1024598-06-8 21% S63   S2   90-30-2 67% S64   S3   4627-22-9 69% S65   S8   1257220-47-5 00 S66 01   S9 02   37500-95-1 03 S67 04   17654-69-2 05   56525-79-2 06

Example S68

Reaction of the Synthetic Building Blocks in a Nucleophilic Aromatic Substitution

(30) ##STR00307##
Variant A:

(31) 20.1 g (120 mmol) of carbazole [51555-21-6] are added in portions to a vigorously stirred suspension of 4.8 g (120 mmol) of sodium hydride, 60% by weight dispersion in mineral oil, in 200 ml of THF with ice-cooling at about +10° C.—care evolution of hydrogen! Foaming! When the addition is complete, the mixture is stirred for a further 30 min., and 20.2 g (100 mmol) with 2-fluoro-5-tert-butylisophthalonitrile, S6 are then added in portions with ice-cooling at such a rate that the temperature does not exceed +20° C. When the addition is complete, the mixture is stirred at +10° C. for a further 2 h, the cooling bath is then removed, the mixture is allowed to warm to 20-25° C. stirred for a further 2 h and then warmed at 40° C. for a further 12 h. After cooling to room temperature, the mixture is quenched by dropwise addition of 30 ml of MeOH, and the reaction mixture is then evaporated virtually to dryness in vacuo. The residue is washed by stirring at elevated temperature twice with a mixture of 100 ml of methanol and 100 ml of water and then once with 200 ml of methanol. The purification is carried out by recrystallisation five times from DMF and fractional sublimation twice (p about 1×10.sup.−5 mbar, T about 180° C.). Yield: 23.1 g (66 mmol) 66%. Purity: 99.9 according to HPLC.

(32) Variant B:

(33) Procedure analogous to variant A, but the carbazole is initially introduced in THE, and 48 ml (120 mmol) of n-BuLi, 2.5 molar in n-hexane are then added dropwise. Yield: 20.6 g (59 mmol) 59%. Purity: 99.9 according to HPLC.

(34) Variant C:

(35) A vigorously stirred suspension of 20.1 g (120 mmol) of carbazole [51555-21-6], 20.2 g (100 mmol) with 2-fluoro-5-tert-butylisophthalonitrile, S6, 31.8 g (150 mmol) of tripotassium phosphate, anhydrous and 100 g of glass beads is stirred at 160° C. for 16 h in 300 ml of dimethylacetamide. After cooling, 500 ml of water are added, the solid which has precipitated out is filtered off with suction, washed twice with 100 ml of water each time, twice with 100 ml of methanol each time and then dried in vacuo. Further purification analogous to variant A. Yield: 22.0 g (63 mmol) 63%. Purity: 99.9 according to HPLC.

(36) The following compounds can be prepared analogously:

(37) TABLE-US-00007 Ex Starting material Product Variant Yield S69 08 09 71% A S70 0 55% S71   S22 69% S72   S45 65% S73   S46 70% S74   S48 66% S75 0   S50 54%

Example S76

Palladium-Catalysed Cyanation of Chlorofluoroaromatic Compounds

(38) ##STR00322##

(39) Procedure analogous to M. Shevlin, Tetrahedron Letters, 2010, 51, 4833.

(40) Catalyst Solution:

(41) 3 ml of a mixture of 2.81 g of concentrated sulfuric acid in 28 ml of N,N-dimethylacetamide are added to a solution of 2.73 g (5.7 mmol) of X-Phos and 643 mg (2.9 mmol) of palladium(II) acetate in 60 ml of N,N-dimethylacetamide, and the mixture is stirred at 80° C. for 30 min., during which a dark-brown solution forms.

(42) 1 ml of the catalyst solution is added to a vigorously stirred mixture of 23.6 g (143 mmol) of 1,3-dichloro-2-fluorobenzene [2268-05-5], 20.2 g (172 mmol) of zinc(II) cyanide, 750 mg (11.5 mmol) of zinc dust and 280 ml of N,N-dimethylacetamide, and the mixture is stirred at 120° C. for 3 h. When the reaction is complete, the solvent is substantially removed in vacuo, the residue is taken up in 500 ml of ethyl acetate, salts remaining are filtered off, the filtrate is washed three times with 300 ml of water and once with 300 ml of sodium chloride solution and dried over magnesium sulfate. The residue remaining after removal of the solvent is recrystallised twice from cyclohexane. Yield: 15.8 g (109 mmol) 76%. Purity: about 97% according to .sup.1H-NMR.

(43) The following compound can be prepared analogously:

(44) TABLE-US-00008 Ex. Starting material Product Yield S77 68% 444-13-3