Method for producing quaterrylene-3,4:13, 14-tetracarboxy diimides by direct synthesis

A process for preparing quaterrylene-3,4:13,14-tetracarboximides of the general formula I

• in which the variables are each defined as follows:
• R, R′ are each independently:
• hydrogen;
• (A) C1-C30-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —NR1—, —N═CR1—, —C≡C—, —CR1═CR1—, —CO—, —SO— and/or —SO2— moieties and which may be mono- or polysubstituted by:
• (i) C1-C12-alkoxy C1-C6-alkylthio, —C≡CR1, —CR1═CR12, hydroxyl, mercapto, halogen, cyano, nitro, —NR2R3, —NR2COR3, —CONR2R3, —SO2NR2R3, —COOR2, —SO3R2, —PR2R3 and/or —POR2R3;
• (ii) aryl or hetaryl, to which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR1—, —N═CR1—, —CR1═CR1—, —CO—, —SO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by:
• C1-C18-alkyl, C1-C12-alkoxy, C1-C6-alkylthio, —C≡CR1, —CR1═CR12, hydroxyl, mercapto, halogen cyano, nitro, —NR2R3, —NR2COR3, —CONR2R3, —SO2NR2R3, —COOR2, —SO3R2, —PR2R3, —POR2R3, aryl and/or hetaryl, each of which may be substituted by C1-C18-alkyl, C1-C12-alkoxy, hydroxyl, mercapto, halogen, cyano, nitro, —NR2R3, —NR2COR3, —CONR2R3, —SO2NR2R3, —COOR2, —SO3R2, —PR2R3 and/or —POR2R3;
• (iii) C3-C8-cycloalkyl whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR1—, —N═CR1—, —CR1═CR1—, —CO—, —SO— and/or —SO2— moieties and to which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR1—, —N═CR1—, —CR1═CR1—, —CO—, —SO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by:
• C1-C18-alkyl, C1-C12-alkoxy, C1-C6-alkylthio, —C≡CR1, —CR1═CR12, hydroxyl, mercapto, halogen, cyano, nitro, —NR2R3, —NR2COR3, —CONR2R3, —SO2NR2R3, —COOR2, —SO3R2, —PR2R3 and/or —POR2R3;
• (iv) a -U-aryl radical which may be mono- or polysubstituted by the above radicals specified as substituents for the aryl radicals (ii), where U is an —O—, —S—, —NR1—, —CO—, —SO— or —SO2— moiety;
• (B) C3-C8-cycloalkyl, to which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR1—, —N═CR1—, CR1═CR1—, —CO—, —SO— and/or —SO2— moieties, where the entire ring system may be substituted once or more than once by:
• the (i), (ii), (iii), (iv) radicals, and/or
• (v) C1-C30-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —NR1—, —N═CR1—, —C≡C—, —CR1═CR1—, —CO—, —SO— and/or —SO2— moieties and which may be mono- or polysubstituted by:
• C1-C12-alkoxy C1-C6-alkylthio, —C≡CR1, —CR1CR12, hydroxyl, mercapto, halogen, cyano, nitro, —NR2R3, —NR2COR3, —CONR2R3, —SO2NR2R3, —COOR2, —SO3R2, —PR2R3, —POR2R3, aryl and/or saturated or unsaturated C4-C7-cycloalkyl whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR1—, —N═CR1—, —CR1═CR1—, —CO—, —SO— and/or —SO2— moieties, where the aryl and cycloalkyl radicals may each be mono- or polysubstituted by C1-C18-alkyl and/or the above radicals specified as substituents for alkyl;
• (C) aryl or hetaryl, to which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —NR1, —N═CR1—, —C≡C—, —CR1═CR1—, —CO—, —SO— and/or —SO2— moieties, where the entire ring system may be substituted by the (i), (ii), (iii), (iv), (v) radicals, and/or aryl- and/or hetarylazo, each of which may be substituted by C1-C10-alkyl C1-C6-alkoxy and/or cyano;
• R1 is hydrogen or C1-C18-alkyl, where the R1 radicals may be the same or different when they occur more than once;
• R2, R3 are each independently hydrogen;
• C1-C18-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —CO—, —SO— and/or —SO2— moieties and which may be mono- or polysubstituted by C1-C12-alkoxy, C1-C6-alkylthio, hydroxyl, mercapto, halogen, cyano, nitro and/or —COOR1;
• aryl or hetaryl, to each of which may be fused further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton may be interrupted by one or more —O—, —S—, —CO— and/or —SO2— moieties, where the entire ring system may be mono- or polysubstituted by C1-C12-alkyl and/or the above radicals specified as substituents for alkyl,
• which comprises reacting a perylene-3,4-dicarboximide of the general formula IIa
• in the presence of a base-stable, high-boiling, organic solvent and of a strong alkali metal base or alkaline earth metal base, at a temperature of from 50 to 210° C., with a perylene-3,4-dicarboximide of the general formula IIb
• in which X is hydrogen, bromine or chlorine.