文献类型：专利

英文题名：Preparing fluorescent dyes comprises e.g. reacting 2-oxo-2H-chromene-3-carbaldehyde compound and 5-butyl-8,8,9-trimethyl-8H-5,10-diaza cyclopenta(a)phenalene-4,6-dione and post-processing

作者：CHANG S;CHEN R;LI C;LIU Y;TIAN B;ZHANG Z;ZHANG J;FENG J;XIANG K

机构：[1]UNIV EAST CHINA SCI & TECHNOLOGY

申请号：CN105566942-A

申请日：2015-10-13

公开日：2016-05-11

语种：英文

收录：DERWENT

摘要：NOVELTY - Preparing long emission wavelength fluorescent dyes (A) comprises e.g. (i) reacting 6-bromobenzo(de)isochromene-1,3-dione (I), ethanol and n-butylamine to obtain 6-bromo-2-butyl-1H-benzo(de)isoquinoline-1,3(2H)-dione (II), (ii) reacting (II) with 2-methoxyethanol, hydrazine hydrate to obtain 2-butyl-6-hydrazinyl-1H-benzo(de)isoquinoline-1,3(2H)-dione (III), (iii) reacting (III) and 3-methyl-2-butanone to obtain 5-butyl-8,8,9-trimethyl-8H-5,10-diaza cyclopenta(a)phenalene-4,6-dione (IV), and then reacting with 2H-chromen-2-one compounds to obtain (X). USE - The dyes are useful in laser, electroluminescent and fluorescent probes. ADVANTAGE - The dyes have near-infrared emission spectra; and Stokes shift of up to 150 nm. DETAILED DESCRIPTION - Preparing long emission wavelength fluorescent dyes (A) i.e. substituted 9-((Z)-2-(7-amino-2-oxo-2H-chromen-3-yl)-vinyl)-5-butyl-8,8-dimethyl-8H-5,10-diaza-cyclopenta(a)phenalene-4,6-dione compounds (Xa), 5-butyl-8,8-dimethyl-9-((Z)-2-(10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo(de)anthracen-9-yl)-vinyl)-8H-5,10-diaza-cyclopenta(a) (Xb) and 5-butyl-8,8-dimethyl-9-((Z)-2-(5,7,7-trimethyl-2-oxo-7,8-dihydro-2H-1-oxa-8-aza-anthracen-3-yl)-vinyl)-8H-5,10-diaza-cyclopenta(a)phenalene-4,6-dione (Xc) using naphthalimide and coumarin precursor comprises (i) dissolving 6-bromobenzo(de)isochromene-1,3-dione of formula (I) in 40-50 times ethanol, then adding 2-3 times n-butylamine and reacting at 90 degrees C for 12 hours to obtain 6-bromo-2-butyl-1H-benzo(de)isoquinoline-1,3(2H)-dione of formula (II), (ii) dissolving (II) in 5-10 times 2-methoxyethanol, then adding 2-3 times hydrazine hydrate and reacting at 120 degrees C for 4 hours, and then suction filtering to obtain 2-butyl-6-hydrazinyl-1H-benzo(de)isoquinoline-1,3(2H)-dione of formula (III), (iii) dissolving (III) in 20-30 times 3-methyl-2-butanone, then adding 2-3 times catalysts and reacting at 90 degrees C for 4 hours, removing excess solvent by rotary evaporation, then dispersing in ethanol, adding ammonium hydroxide and filtering to obtain 5-butyl-8,8,9-trimethyl-8H-5,10-diaza cyclopenta(a)phenalene-4,6-dione of formula (IV), (iv) adding phenol compound (Va), 2,2,4-trimethyl-1,2-dihydroquinolin-7-ol of formula (Vb) or (IV) into dimethylformamide 2,2,4-trimethyl-1,2-dihydroquinolin-7-ol of formula (V) in dimethylformamide, then adding into phosphoryl chloride/dimethylformamide and stirring at 70 degrees C on ice bath for 2 hours, pouring reaction mixture into 5-10 equivalents water, and suction filtering to obtain benzaldehyde compound (VIa), 7-hydroxy-2,2,4-trimethyl-1,2-dihydroquinoline-6-carbaldehyde (VIb) or 8-hydroxy-1,2,3,5,6,7-hexahydropyrido(3,2,1-ij)quinoline-9-carbaldehyde of formula (VIc), (v) dissolving compound (VI) in 30-50 times ethanol, adding 20-30 times diethyl malonate, reacting at 85 degrees C for 3 hours under the action of catalyst, rotary evaporating to remove excess solvent to obtain dihydronaphthalene compounds (VIIa), 10-oxo-2,3,5,6,10,11-hexahydro-1H,4H-3a-aza-benzo(de)anthracene-9-carboxylic acid ethyl ester (VIIb) or ethyl 6,8,8-trimethyl-2-oxo-8,9-dihydro-2H-pyrano(3,2-g)quinoline-3-carboxylate of formula (VIIc), (vi) dissolving (VII) in 18% hydrochloric acid, reacting at 100 degrees C for 7 hours and filtering to obtain 2H-chromen-2-one compound (VIIIa), 2,3,5,6-Tetrahydro-1H,4H-11-oxa-3a-aza-benzo(de)anthracen-10-one (VIIIb) or 6,8,8-trimethyl-8,9-dihydro-2H-pyrano(3,2-g)quinolin-2-one of formula (VIIIc), (vii) adding (VIII) in dimethylformamide, then adding phosphoryl chloride/dimethylformamide, reacting at 70 degrees C, stirring for 2 hours on ice bath, then pouring reaction mixture into 5-10 equivalents water and filtering to obtain 2-oxo-2H-chromene-3-carbaldehyde compounds (IXa), 10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo(de)anthracene-9-carbaldehyde (IXb)or 6,8,8-trimethyl-2-oxo-8,9-dihydro-2H-pyrano(3,2-g)quinoline-3-carbaldehyde of formula (IXc), and (viii) dissolving compound (IX) and compound (IV) in 20-50 times ethanol, reacting for 4 hours under the action of catalyst, cooling and filtering to obtain 9-((Z)-2-(7-amino-2-oxo-2H-chromen-3-yl)-vinyl)-5-butyl-8,8-dimethyl-8H-5,10-diaza-cyclopenta(a)phenalene-4,6-dione compound, 5-butyl-8,8-dimethyl-9-((Z)-2-(10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo(de)anthracen-9-yl)-vinyl)-8H-5,10-diaza-cyclopenta(a)phenalene-4,6-dione or 5-butyl-8,8-dimethyl-9-((Z)-2-(5,7,7-trimethyl-2-oxo-7,8-dihydro-2H-1-oxa-8-aza-anthracen-3-yl)-vinyl)-8H-5,10-diaza-cyclopenta(a)phenalene-4,6-dione to obtain (X). R1 and R2 = not defined.