Rylene dyes

A process for preparing rylene dyes of the general formula I′

• where the variables are defined as follows:
• R is hydrogen;
• C1-C30-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —NR1—, —CO— and/or —SO2— moieties and may be mono- or polysubstituted by carboxyl, sulfo, hydroxyl, cyano, C1-C6-alkoxy and/or a 5- to 7-membered heterocyclic radical which is bonded via a nitrogen atom and may contain further heteroatoms and be aromatic;
• C5-C8-cycloalkyl whose carbon framework may be interrupted by one or more —O—, —S— and/or —NR1— moieties and may be mono- or polysubstituted by C1-C6-alkyl;
• aryl or hetaryl which may each be mono- or polysubstituted by C1-C18-alkyl, C1-C6-alkoxy, halogen, hydroxyl, cyano, carboxyl, —CONHR2, —NHCOR2 and/or aryl- or hetarylazo, each of which may be substituted by C1-C10-alkyl, C1-C6-alkoxy, halogen, hydroxyl, cyano or carboxyl;
• R′ is bromine;
• cyano;
• —NR32;
• aryloxy, arylthio, hetaryloxy or hetarylthio, each of which may be mono- or polysubstituted by C1-C12-alkyl, C1-C12-alkoxy, cyano, —CONHR2 and/or —NHCOR2;
• C3-C18-alk-1-ynyl whose carbon chain may be interrupted by one or more —O—, —S—, —NR1—, —CO— and/or —SO2— moieties and may be mono- or polysubstituted by —COOR1, —SO3R1, hydroxyl, cyano, C1-C6-alkoxy, C5-C8-cycloalkyl, aryl and/or a 5- to 7-membered heterocyclic radical which is bonded via a nitrogen atom and may contain further heteroatoms and be aromatic;
• R1 is hydrogen or C1-C6-alkyl;
• R2 is hydrogen;
• C1-C18-alkyl;
• aryl or hetaryl, each of which may be substituted by C1-C8-alkyl, C1-C6-alkoxy, halogen, hydroxyl or cyano;
• R3 is hydrogen;
• C1-C18-alkyl;
• aryl or hetaryl, each of which may be substituted by C1-C8-alkyl, C1-C6-alkoxy, halogen, hydroxyl and/or cyano;
• both R3 radicals may be joined to give a 5- to 7-membered heterocyclic radical which contains the nitrogen atom and is bonded via it;
• n is2,3or4;
• m is from 0 to 6,
• which comprises
• a) reacting a rylene derivative monobrominated in the peri-position of the general formula II′
• with 1-aminoanthraquinone in a cross-coupling reaction in the presence of an aprotic organic solvent, of a transition metal catalyst system and of a base,
• b) cyclizing the rylenanthramine formed in step a) of the general formula III′
• in the presence of a polar organic solvent and of a base to give the rylene dye of the formula I′ which is unsubstituted in the rylene core and where m is 0, and
• c) if desired, converting the rylene dye I′ unsubstituted in the rylene core and obtained in step b) to the rylene dye of the formula I′ brominated in the rylene core where R′ is bromine and m does not equal 0 by reacting with elemental bromine, and
• d) if desired, converting the rylene dye I′ brominated in the rylene core and obtained in step c)
• d1) by reacting with a compound of the general formula IV
• where Z is sulfur or oxygen and the ring A is an aryl or hetaryl radical, each of which may be mono- or polysubstituted by C1-C12-alkyl, C1-C12-alkoxy, cyano, —CONHR2 and/or —NHCOR2,
• in the presence of an inert nitrogen-basic organic solvent and of a base to give the rylene dye of the formula I′ which is substituted in the rylene core and where R′ is aryloxy, arylthio, hetaryloxy or hetarylthio, each of which may be mono- or polysubstituted by C1-C12-alkyl, C1-C12-alkoxy, cyano, —CONHR2 and/or —NHCOR2, and m does not equal 0,
• d2) by reacting with copper(I) cyanide in the presence of a dipolar aprotic organic solvent to give the rylene dye of the formula I′ which is substituted in the rylene core and where R′ is cyano and m does not equal 0,
• d3) by reacting with an alkyne of the general formula V
• H—C≡C—R″ V
• where R″ is a C1-C16-alkyl radical which may be interrupted by one or more —O—, —S—, —NR1—, —CO— and/or —SO2— moieties and may be mono- or polysubstituted by —COOR1, —SO3R1, hydroxyl, cyano, C1-C6-alkoxy, C5-C8-cycloalkyl, aryl and/or a 5- to 7-membered heterocyclic radical which is bonded via a nitrogen atom and may contain further heteroatoms and be aromatic,
• in the presence of an aprotic organic solvent, of a palladium complex as a catalyst, of a copper salt as a cocatalyst and of a base to give the rylene dye of the formula I′ which is substituted in the rylene core and where R′ is —C≡C—R″ and m does not equal 0, or
• d4) by reacting with ammonia or an amine of the general formula VI
• in the presence of a dipolar aprotic organic solvent to give the rylene dye of the formula I′ which is substituted in the rylene core and where R′ is —NR32 and m does not equal 0.

A process for preparing symmetrical rylene dyes of the general formula I″

• where the variables are defined as follows:
• R is hydrogen;
• C1-C30-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —NR1—, —CO— and/or —SO2— moieties and may be mono- or polysubstituted by carboxyl, sulfo, hydroxyl, cyano, C1-C6-alkoxy and/or a 5- to 7-membered heterocyclic radical which is bonded via a nitrogen atom and may contain further heteroatoms and be aromatic;
• C5-C8-cycloalkyl whose carbon framework may be interrupted by one or more —O—, —S— and/or —NR1— moieties and may be mono- or polysubstituted by C1-C6-alkyl;
• aryl or hetaryl which may each be mono- or polysubstituted by C1-C18-alkyl, C1-C6-alkoxy, halogen, hydroxyl, cyano, carboxyl, —CONHR2, —NHCOR2 and/or aryl- or hetarylazo, each of which may be substituted by C1-C10-alkyl, C1-C6-alkoxy, halogen, hydroxyl, cyano and/or carboxyl;
• R′ is bromine;
• cyano;
• —NR32;
• aryloxy, arylthio, hetaryloxy or hetarylthio, each of which may be mono- or polysubstituted by C1-C12-alkyl, C1-C12-alkoxy, cyano, —CONHR2 and/or —NHCOR2;
• C3-C18-alk-1-ynyl whose carbon chain may be interrupted by one or more —O—, —S—, —NR1—, —CO— and/or —SO2— moieties and may be mono- or polysubstituted by —COOR1, —SO3R1, hydroxyl, cyano, C1-C6-alkoxy, C5-C8-cycloalkyl, aryl and/or a 5- to 7-membered heterocyclic radical which is bonded via a nitrogen atom and may contain further heteroatoms and be aromatic;
• R1 is hydrogen or C1-C6-alkyl;
• R2 is hydrogen;
• C1-C18-alkyl;
• aryl or hetaryl, each of which may be substituted by C1-C8-alkyl, C1-C6-alkoxy, halogen, hydroxyl and/or cyano;
• R3 is hydrogen;
• C1-C18-alkyl;
• aryl or hetaryl, each of which may be substituted by C1-C8-alkyl, C1-C6-alkoxy, halogen, hydroxyl and/or cyano;
• both R3 radicals may be joined to give a 5- to 7-membered heterocyclic radical which contains the nitrogen atom and is bonded via it;
• n is 1,2,3 or4;
• m is from 0 to 6,
• which comprises
• a) reacting a rylene derivative monobrominated in the peri-position of the general formula II′
• with 1,5-diaminoanthraquinone in a double cross-coupling reaction in the presence of an aprotic organic solvent, of a transition metal catalyst system and of a base,
• b) cyclizing the rylenanthramine formed in step a) of the general formula III″
• in the presence of a polar organic solvent and of a base to give the rylene dye of the formula I″ where m is 0, and
• c) if desired, converting the rylene dye I′ unsubstituted in the rylene core and obtained in step b) to the rylene dye of the formula I″ brominated in the rylene core where R′ is bromine and m is equal to 0 by reacting with elemental bromine, and
• d) if desired, converting the rylene dye I″ brominated in the rylene core and obtained in step c)
• d1) by reacting with a compound of the general formula IV
• where Z is sulfur or oxygen and the ring A is an aryl or hetaryl radical, each of which may be mono- or polysubstituted by C1-C12-alkyl, C1-C12-alkoxy, cyano, —CONHR2 and/or —NHCOR2,
• in the presence of an inert nitrogen-basic organic solvent and of a base to give the rylene dye of the formula I″ which is substituted in the rylene core and where R′ is aryloxy, arylthio, hetaryloxy or hetarylthio, each of which may be mono- or polysubstituted by C1-C12-alkyl, C1-C12-alkoxy, cyano, —CONHR2 and/or —NHCOR2, and m does not equal 0,
• d2) by reacting with copper(I) cyanide in the presence of a dipolar aprotic organic solvent to give the rylene dye of the formula I″ which is substituted in the rylene core and where R′ is cyano and m does not equal 0,
• d3) by reacting with an alkyne of the general formula V
• H—C≡C—R″ V
• where R″ is a C1-C16-alkyl radical which may be interrupted by one or more —O—, —S—, —NR1—, —CO— and/or —SO2— moieties and may be mono- or polysubtituted by —COOR1, —SO3R1, hydroxyl, cyano, C1-C6-alkoxy, C5-C8-cycloalkyl, aryl and/or a 5- to 7-membered heterocyclic radical which is bonded via a nitrogen atom and may contain further heteroatoms and be aromatic,
• in the presence of an aprotic organic solvent, of a palladium complex as a catalyst, of a copper salt as a cocatalyst and of a base to give the rylene dye of the formula I″ which is substituted in the rylene core and where R′ is —C≡C—R″ and m does not equal 0, or
• d4) by reacting with ammonia or an amine of the general formula VI
• in the presence of a dipolar aprotic organic solvent to give the rylene dye of the formula I″ which is substituted in the rylene core and where R′ is —NR32 and m does not equal 0.

A process for preparing nonsymmetrical rylene dyes of the general formula I′″

• where the variables are defined as follows:
• R is hydrogen;
• C1-C30-alkyl whose carbon chain may be interrupted by one or more —O—, —S—, —NR1—, —CO— and/or —SO2— moieties and may be mono- or polysubstituted by carboxyl, sulfo, hydroxyl, cyano, C1-C6-alkoxy and/or a 5- to 7-membered heterocyclic radical which is bonded via a nitrogen atom and may contain further heteroatoms and be aromatic;
• C5-C8-cycloalkyl whose carbon framework may be interrupted by one or more —O—, —S— and/or —NR1— moieties and may be mono- or polysubstituted by C1-C6-alkyl;
• aryl or hetaryl which may each be mono- or polysubstituted by C1-C18-alkyl, C1-C6-alkoxy, halogen, hydroxyl, cyano, carboxyl, —CONHR2, —NHCOR2 and/or aryl- or hetarylazo, each of which may be substituted by C1-C10-alkyl, C1-C6-alkoxy, halogen, hydroxyl, cyano and/or carboxyl;
• R′ is bromine;
• cyano;
• —NR32;
• aryloxy, arylthio, hetaryloxy or hetarylthio, each of which may be mono- or polysubstituted by C1-C12-alkyl, C1-C12-alkoxy, cyano, —CONHR2 and/or —NHCOR2;
• C3-C18-alk-1-ynyl whose carbon chain may be interrupted by one or more —O—, —S—, —NR1—, —CO— and/or —SO2— moieties and may be mono- or polysubstituted by —COOR1, —SO3R1, hydroxyl, cyano, C1-C6-alkoxy, C5-C8-cycloalkyl, aryl and/or a 5- to 7-membered heterocyclic radical which is bonded via a nitrogen atom and may contain further heteroatoms and be aromatic;
• R1 is hydrogen or C1-C6-alkyl;
• R2 is hydrogen;
• C1-C18-alkyl;
• aryl or hetaryl, each of which may be substituted by C1-C8-alkyl, C1-C6-alkoxy, halogen, hydroxyl and/or cyano;
• R3 is hydrogen;
• C1-C18-alkyl;
• aryl or hetaryl, each of which may be substituted by C1-C8-alkyl, C1-C6-alkoxy, halogen, hydroxyl and/or cyano;
• both R3 radicals may be joined to give a 5- to 7-membered heterocyclic radical which contains the nitrogen atom and is bonded via it;
• n, n′ are each 1,2,3 or 4,and n≠n′;
• m is from 0 to 6,
• which comprises
• a1) initially reacting a rylene derivative monobrominated in the peri-position of the general formula II′
• with excess 1,5-diaminoanthraquinone in a first cross-coupling reaction in the presence of an aprotic organic solvent, of a transition metal catalyst system and of a base,
• a2) reacting the amin orylenanthramine obtained in step a) of the general formula IIIa
• with a rylene derivative monobrominated in the peri-position of the general formula II″
• in the presence of an aprotic organic solvent, of a transition metal catalyst and of a base in a second cross-coupling reaction,
• b) cyclizing the rylenanthramine formed in step a) of the general formula III′″
• in the presence of a polar organic solvent and of a base to give the rylene dye of the formula I′″ which is unsubstituted in the rylene core and where m is 0, and
• c) if desired, converting the rylene dye I′″ unsubstituted in the rylene core and obtained in step b) to the rylene dye of the formula I′″ brominated in the rylene core where R′ is bromine and m does not equal 0 by reacting with elemental bromine, and
• d) if desired, converting the rylene dye I′″ brominated in the rylene core and obtained in step c)
• d1) by reacting with a compound of the general formula IV
• where Z is sulfur or oxygen and the ring A is an aryl or hetaryl radical, each of which may be mono- or polysubstituted by C1-C12-alkyl, C1-C12-alkoxy, cyano, —CONHR2 and/or —NHCOR2,
• in the presence of an inert nitrogen-basic organic solvent and of a base to give the rylene dye of the formula I′″ which is substituted in the rylene core and where R′ is aryloxy, arylthio, hetaryloxy or hetarylthio, each of which may be mono- or polysubstituted by C1-C12-alkyl, C1-C12-alkoxy, cyano, —CONHR2 and/or —NHCOR2, and m does not equal 0,
• d2) by reacting with copper(I) cyanide in the presence of a dipolar aprotic organic solvent to give the rylene dye of the formula I′″ which is substituted in the rylene core and where R′ is cyano and m does not equal 0,
• d3) by reacting with an alkyne of the general formula V
• H—C≡C—R″ V
• where R″ is a C1-C16-alkyl radical which may be interrupted by one or more —O—, —S—, —NR1—, —CO— and/or —SO2— moieties and may be mono or polysubtituted by —COOR1, —SO3R1, hydroxyl, cyano, C1-C6-alkoxy, C5-C8-cycloalkyl, aryl and/or a 5- to 7-membered heterocyclic radical which is bonded via a nitrogen atom and may contain further heteroatoms and be aromatic,
• in the presence of an aprotic organic solvent, of a palladium complex as a catalyst, of a copper salt as a cocatalyst and of a base to give the rylene dye of the formula I′″ which is substituted in the rylene core and where R′ is —C≡C—R″ and m does not equal 0, or
• d4) by reacting with ammonia or an amine of the general formula VI
• in the presence of a dipolar aprotic organic solvent to give the rylene dye of the formula I′″ which is substituted in the rylene core and where R′ is —NR32 and m does not equal 0.