Preparation of substituted aromatic compounds

1. A process for preparing compounds of the formula (II),

where the substituents R 1 to R 5 are each independently H, CH 3 , straight-chain or branched C 1 –C 8 -alkyl, CH(OC 1 –C 6 -alkyl) 2 , CH(C 1 –C 5 -alkyl)(OC 1 –C 5 -alkyl), CH 2 (OC 1 –C 5 -alkyl), CH(CH 3 )(OC 1 –C 5 -alkyl), C 1 –C 8 -alkoxy, N(C 1 –C 5 -alkyl) 2 , phenyl, substituted phenyl, aryl, heteroaryl, S(C 1 –C 5 -alkyl) or a radical C aryl, alkyl , and the symbols X 1 to 5 are each carbon with at least one X 1-5 being nitrogen or with at least one X 1-5 being nitrogen and X 1 R 1 and X 2 R 2 together are O, NH, N(C 1 –C 5 -alkyl), N(C═O—C 1 –C 5 -alkyl), N(SiR 3 ) 2 or S,

or where neighboring radicals R 1 to R 5 form the following structural unit,

where X 6 to X 9 and R 6 to R 9 have the same meaning as X 1 to X 5 and R 1 to R 5 and

the radical C aryl, alkyl is straight-chain or branched, substituted or unsubstituted C 1 –C 8 -alkyl, 1-hydroxyalkyl having from 1 to 8 carbon atoms, CN, 2-hydroxyalkyl having from 2 to 5 carbon atoms, 3-hydroxyalkyl having from 3 to 5 carbon atoms, 1-NHR-, CH(OC 1 –C 5 -alkyl) 2 , C(C 1 –C 5 -alkyl)(OC 1 –C 5 -alkyl), CH 2 (OC 1 –C 5 -alkyl), CH(CH 3 )(OC 1 –C 5 -alkyl), C 1 –C 5 -alkoxy, N(C 1 –C 5 -alkyl) 2 , phenyl, substituted phenyl, aryl, heteroaryl, CO 2 H, CO 2 alkyl, (C═O) 0.5 , substituted 1-vinylalkyls, CH 3 —C(═O), R—C(═O) or CHO, wherein R is an alkyl having from 1 to 5 carbon atoms,

which comprises reacting chloro- or fluoroaromatics of the formula (I) with carbon electrophiles and lithium metal.

2. The process as claimed in claim 1 , wherein the carbon electrophile is selected from the group consisting of:

aryl or alkyl cyanates (C aryl,alkyl =CN)

oxirane, substituted oxiranes (C aryl,alkyl =CH 2 CH 2 OH, substituted CR 2 CR 2 OH)

azomethines (C aryl,alkyl =CR 1 2 —NR 1 H)

nitroenolates (C aryl,alkyl =oximes)

immonium salts (C aryl,alkyl =amines)

haloaromatics, aryl triflates, other arylsulfonates (C aryl,alkyl =aryl, heteroaryl)

carbon dioxide (C aryl,alkyl =COOH)

carbon monoxide (C aryl,alkyl =(—CO—) 0.5 )

aldehydes, ketones (C aryl,alkyl +CHR 1 —OH, CR 1 2 —OH)

α,β-unsaturated aldehydes/ketones (C aryl,alkyl =CH(OH)-vinyl, CR 1 (OH)-vinyl)

ketenes (C aryl,alkyl =C(═O)CH 3 in ketene, C(═O)—R, wherein R is an alkyl having from 1 to 5 carbon atoms in substituted ketenes)

alkali metal and alkaline earth metal salts of carboxylic acids (C aryl,alkyl =CHO in formates, COCH 3 in acetates, R 1 CO in R 1 COOCH 3 )

aliphatic nitriles (C aryl,alkyl =COCH 3 in acetonitrile, R 1 CO in R 1 CN)

aromatic nitriles (C aryl,alkyl =COAr − )

amides (C aryl,alkyl =CHO in HCONR 1 2 , C(═O)R 1 in R 1 CONR 1 2 )

esters (C aryl,alkyl =[C(OH)R 1 ] 0.5 ),

alkylating agents (C aryl,alkyl =alkyl), and mixtures thereof.

3. The process as claimed in claim 1 , wherein the reaction is performed at a temperature in the range from −100 to +80° C.

4. The process as claimed in claim 1 , wherein lithium is used in the form of a dispersion, powder, turnings, sand, granules, pieces or in the form of bars.

5. The process as claimed in claim 1 , wherein the solvent used is an aliphatic or aromatic ether, a hydrocarbon or an amine which does not carry a hydrogen on the nitrogen atom, selected from the group consisting of triethylamine, diethyl ether, tetrahydrofuran, toluene, toluene-THF mixtures, anisole, diisopropyl ether, and mixtures thereof.

6. The process as claimed in claim 1 , wherein the process is performed as a one-pot process.

7. The process as claimed in claim 1 , wherein the organolithium compound is first generated and then reacted with the carbon electrophile at the same or a slightly different temperature.

8. The process as claimed in claim 2 , wherein the reaction is performed at a temperature in the range from −100 to +80° C.

9. The process as claimed in claim 2 , wherein lithium is used in the form of a dispersion, powder, turnings, sand, granules, pieces or in the form of bars.

10. The process as claimed in claim 2 , wherein the solvent used is an aliphatic or aromatic ether, a hydrocarbon or an amine which does not carry a hydrogen on the nitrogen atom, selected from the group consisting of triethylamine, diethyl ether, tetrahydrofuran, toluene, toluene-THF mixtures, anisole, diisopropyl ether, and mixtures thereof.

11. The process as claimed in claim 2 , wherein the process is performed as a one-pot process.

12. The process as claimed in claim 2 , wherein the organolithium compound is first generated and then reacted with the carbon electrophile at the same or a slightly different temperature.

13. The process as claimed in claim 3 , wherein lithium is used in the form of a dispersion, powder, turnings, sand, granules, pieces or in the form of bars.

14. The process as claimed in claim 3 , wherein the solvent used is an aliphatic or aromatic ether, a hydrocarbon or an amine which does not carry a hydrogen on the nitrogen atom, selected from the group consisting of triethylamine, diethyl ether, tetrahydrofuran, toluene, toluene-THF mixtures, anisole, diisopropyl ether, and mixtures thereof.

15. The process as claimed in claim 3 , wherein the process is performed as a one-pot process.

16. The process as claimed in claim 3 , wherein the organolithium compound is first generated and then reacted with the carbon electrophile at the same or a slightly different temperature.

17. The process as claimed in claim 4 , wherein the solvent used is an aliphatic or aromatic ether, a hydrocarbon or an amine which does not carry a hydrogen on the nitrogen atom, selected from the group consisting of triethylamine, diethyl ether, tetrahydrofuran, toluene, toluene-THF mixtures, anisole, diisopropyl ether, and mixtures thereof.

18. The process as claimed in claim 4 , wherein the process is performed as a one-pot process.

19. The process as claimed in claim 4 , wherein the organolithium compound is first generated and then reacted with the carbon electrophile at the same or a slightly different temperature.