Luminescent Nitro Derivatives of 5,11-Dehydro-5H, 11H-benzotriazolo(2,1- alpha)benzotriazole
NEW ORLEANS UNIV LA DEPT OF CHEMISTRY
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Fluorescence was enhanced and laser activity introduced by substitution in 5,11 -dehydro-5H,11Hbenzotriazolo2,1-A-benzotriazole 6 to give 2-nitro, 2,8-dinitro, 2,4,8trinitro, and 2,4,8,10-tetranitro derivatives 9a-d. luminescence for compounds 6, 9a-d, and the 2,8-dinitro-3,9-dimethyl and 2,3,8, 9-tetramethyl-4,10-dinitro derivatives 11a,b was erratically solvent dependent when examined in ethyl acetate, acetonitrile, and acetone, and was most efficient in the 2,8-dinitro derivative 9b, LAMBDA F 479 NM ETHYL ACETATE D 0.98, lambdaf 501 nm acetonitrile D 0.58, and lambdaf 494 mn acetone D 0. 61 and in the tetranitro derivative 9d lambda f 509 mn acetonitrile D 0.81 and lambda f 511 mn acetone D 0.66. With laser activity at 560-590 mn acetonitrile the dye 9b was 30 percent as efficient as rhodamine 6G ethanol in power output. Luminescence was quenched by the reduction of nitro groups to give 2-amino and 2,8-diamino derivatives 9e,f and by the conversion of the tetranitro compound 9d to an unassigned diazido dinitro derivative 9g. Luminescence was not detected in 2,5-dimethyl-3,6-dinitro-1,3a,4,6a- tetraazapentalene 14 and ethyl 2,5-dimethyl-1,3a,4,6a-tetraazapentalene-3,6- dicarboxylate 15. Azidoazobenzenes were obtained from 4-methyl and 4,5-dimethyl diamines via oxidation with lead dioxide to aminoazobenzene derivatives followed by treatment of the diazotized amines with sodium azide and thermolysis of azido intermediates to give 3,9-dimethyl and 2,3,8,9-tetramethyl derivatives 10 a,b of the triazolotriazole 6. Nitration converted the triazole 6 to the 2,4,8-trinitro derivative 9c and the alkyltriazoles to their dinitro derivatives 11 a,b.
- Organic Chemistry
- Physical Chemistry