Dibenzopyrrometheneboron difluoride dyes

A fluorescent dye of the formula:

• ##STR41## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.1', R.sup.2', R.sup.3', and R.sup.4' are optionally and independently H, halogen, cyano, sulfo, alkali or ammonium salts of sulfo, carboxy, alkyl, perfluoroalkyl, alkoxy, alkylthio, nitro, amino, monoalkylamino, dialkylamino, alkylamido;
• or substituted or unsubstituted ARYL, ARYL-oxy, HETEROARYL, HETEROARYL-oxy, ARYL-amino, HETEROARYL-amino, ARYL-amido or HETEROARYL-amido;
• or two adjacent substituents are fused to form BENZO;
• wherein
• BENZO is --CR.sup.7 .dbd.CR.sup.8 --CR.sup.9 .dbd.CR.sup.10 -- bonded to any two adjacent positions of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.1', R.sup.2', R.sup.3', and R.sup.4', up to a maximum of four BENZO moieties;
• R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are independently selected from H, halogen, cyano, sulfo, alkali or ammonium salts of sulfo, carboxy, alkyl, perfluoroalkyl, alkoxy, alkylthio, nitro, amino, monoalkylamino, dialkylamino, alkylamido;
• ARYL is an aromatic or polyaromatic substituent containing 1 to 4 aromatic rings having 6 conjugated carbon atoms and no heteroatoms that are optionally fused to each other or bonded to each other by carbon-carbon single bonds and attached by a single bond, and is optionally and independently substituted by H, halogen, cyano, sulfo, alkali or ammonium salt of sulfo, carboxy, nitro, alkyl, perfluoroalkyl, alkoxy, alkylthio, amino, monoalkylamino, dialkylamino or alkylamido;
• HETEROARYL is a 5- or 6-membered aromatic heterocycle that is optionally fused to additional six-membered aromatic rings, or is fused to one 5- or 6-membered heteroaromatic ring, said heteroaromatic rings contain at least 1 and as many as 3 heteroatoms that are selected from the group consisting of O, N or S in any combination and HETEROARYL is attached by a single bond, and is optionally and independently substituted by H, halogen, cyano, sulfo, alkali or ammonium salt or sulfo, carboxy, alkyl, perfluoroalkyl, alkoxy, alkylthio, amino, monoalkylamino, dialklamino or alkylamido;
• R.sup.5 and R.sup.5' are independently alkyl, cycloalkyl having 3-6 carbons, perfluoroalkyl, ARYL or HETEROARYL;
• R.sup.6 is H, alkyl, cycloalkyl having 3-6 carbons, perfluoroalkyl, ARYL or HETEROARYL;
• all alkyl and perfluoro groups have 1-18 carbon atoms in an arrangement that is either linear or branched;
• all alkyl substituents and alkyl portions of substituents are optionally further substituted by H, halogen, cyano, amino, hydroxy, carboxy, mercapto, sulfo, or alkali or ammonium salt of sulfo;
• wherein such dye is further modified such that at least one substituent contains an amino, an isocyanate, a dichloro-1,3,5-triazine, a maleimide, a haloacetamide, a carboxy, an anhydride, an acid halide, an acyl azide, an acyl hydrazide, an activated ester, a sulfo, a sulfonyl chloride, a sulfonyl fluoride, an alcohol, an alkylating agent, a thiol, or a disulfide group;
• or said compound is covalently attached to a conjugant.

A fluorescent composition, comprising:

• a fluorescent dye of the formula:
• ##STR42## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.1', R.sup.2', R.sup.3', and R.sup.4' are optionally and independently H, halogen, cyano, sulfo, alkali or ammonium salts of sulfo, carboxy, alkyl, perfluoroalkyl, alkoxy, alkylthio, nitro, amino, monoalkylamino, dialkylamino, alkylamido, or substituted or unsubstituted ARYL, ARYL-oxy, HETEROARYL, HETEROARYL-oxy, ARYL-amino, HETEROARYL-amino, ARYL-amido or HETEROARYL-amido;
• or two adjacent substituents are fused to form BENZO or HETERO;
• wherein
• BENZO is --CR.sup.7 .dbd.CR.sup.8 --CR.sup.9 .dbd.CR.sup.10 -- bonded to any two adjacent positions of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.1', R.sup.2', R.sup.3', and R.sup.4', up to a maximum of four BENZO moieties;
• R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are independently selected from H, halogen, cyano, sulfo, alkali or ammonium salts of sulfo, carboxy, alkyl, perfluoroalkyl, alkoxy, alkylthio, nitro, amino, monoalkylamino, dialkylamino, alkylamido;
• HETERO is a combination of 1 to 3 carbon atoms and 1 to 3 hetero atoms selected from the group consisting of O, S and N to form a fused 5- or 6-membered heteroaromatic ring bonded to any two adjacent positions of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.1', R.sup.2', R.sup.3' that is optionally and independently substituted by H, halogen, cyano, sulfo, alkali or ammonium salt of sulfo, carboxy, alkyl, perfluoroalkyl, alkoxy, alkylthio, amino, monoalkylamino, dialkylamino or alkylamido;
• ARYL is an aromatic or polyaromatic substituent containing 1 to 4 aromatic rings having 6 conjugated carbon atoms and no heteroatoms that are optionally fused to each other or bonded to each other by carbon-carbon single bonds and attached by a single bond, and is optionally and independently substituted by H, halogen, cyano, sulfo, alkali or ammonium salt of sulfo, carboxy, nitro, alkyl, perfluoroalkyl, alkoxy, alkylthio, amino, monoalkylamino, dialkylamino or alkylamido;
• HETEROARYL is a 5- or 6-membered aromatic heterocycle that is optionally fused to additional six-membered aromatic rings, or is fused to one 5- or 6-membered heteroaromatic ring, said heteroaromatic rings contain at least 1 and as many as 3 heteroatoms that are selected from the group consisting of O, N or S in any combination and HETEROARYL is attached by a single bond, and is optionally and independently substituted by H, halogen, cyano, sulfo, alkali or ammonium salt or sulfo, carboxy, alkyl, perfluoroalkyl, alkoxy, alkylthio, amino, monoalkylamino, dialklamino or alkylamido;
• R.sup.5 and R.sup.5' are independently alkyl, cycloalkyl having 3-6 carbons, perfluoroalkyl, ARYL or HETEROARYL;
• R.sup.6 is H, alkyl, cycloalkyl having 3-6 carbons, perfluoroalkyl, ARYL or HETEROARYL;
• all alkyl and perfluoro groups have 1-18 carbon atoms in an arrangement that is either linear or branched;
• all alkyl substituents and alkyl portions of substituents are optionally further substituted by H, halogen, cyano, amino, hydroxy, carboxy, mercapto, sulfo, or alkali or ammonium salt of sulfo;
• associated with a polymeric microparticle, in an amount sufficient to make said microparticle fluorescent.