Synthesis of 2-phenylbenzotriazole-type mutagens, PBTA-5 and PBTA-6, and their detection in river water from Japan.
We previously determined the chemical structures of four 2-phenylbenzotriazole mutagens (PBTA-1, -2, -3 and -4) in blue rayon-adsorbed material from the Nishitakase River in Kyoto prefecture and the Nikko River in Aichi prefecture in Japan. On the basis of a synthesis study, these four PBTA derivatives were deduced to have originated from corresponding dinitrophenylazo dyes by reduction and chlorination. 2-[(2-Bromo-4,6-dinitrophenyl)azo]-5-[bis(2-acetoxyethyl) amino]-4-methoxyacetanilide (Color Index Name, Disperse Blue 79:1; CAS Registry Number, 75497-74-4) is a very common dinitrophenylazo dye used in textile dyeing factories. In the present study, we synthesized 2-[4-[bis(2-acetoxyethyl)amino]-2-(acetylamino)-5-methoxyphenyl]-5-amino-7-bromo-4-chloro-2H-benzotriazole (PBTA-5) from Disperse Blue 79:1 by reduction with sodium hydrosulfite and subsequent chlorination with sodium hypochlorite. On hydrolysis of PBTA-5 with alkali, 2-[2-(acetylamino)-4-[bis(2-hydroxyethyl)amino]-5-methoxyphenyl]-5-amino-7-bromo-4-chloro-2H-benzotriazole (PBTA-6) was obtained. Both PBTA-5 and -6 were potent mutagens, inducing 723,000 revertants and 485,000 revertants per microgram of Salmonella typhimurium YG1024, respectively, in the presence of S9 mix. To clarify whether PBTA-5 and -6 exist in the environment, water samples were collected from five rivers flowing through regions where textile dyeing industries are developed. PBTA-6 was detected at levels of 3-134 ng/g blue rayon in all water samples that were examined. On the other hand, the amount of PBTA-5 in the samples was less than the detection limit.
Watanabe
T
T
Department of Public Health, Kyoto Pharmaceutical University, 5 Nakauchicho, Misasagi, Yamashina-ku, Kyoto 607-8414, Japan. watanabe@mb.kyoto-phu.ac.jp
Nukaya
H
H
Terao
Y
Y
Takahashi
Y
Y
Tada
A
A
Takamura
T
T
Sawanishi
H
H
Ohe
T
T
Hirayama
T
T
Sugimura
T
T
Wakabayashi
K
K
D000327:Adsorption; D002482:Cellulose / Q000031:analogs & derivatives* / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid; D004396:Coloring Agents / Q000737:chemistry; D005618:Fresh Water / Q000737:chemistry; D007211:Indoles / Q000737:chemistry; D007564:Japan; D009152:Mutagenicity Tests; D009153:Mutagens / Q000032:analysis / Q000138:chemical synthesis / Q000633:toxicity; D009942:Organometallic Compounds / Q000737:chemistry; D014230:Triazoles / Q000032:analysis* / Q000138:chemical synthesis* / Q000737:chemistry* / Q000633:toxicity
C115463:2-(2-(acetylamino)-4-(N-(2-cyanoethyl)ethylamino)-5-methoxyphenyl)-5-amino-7-bromo-4-chloro-2H-benzotriazole; C438665:2-(2-(acetylamino)-4-(bis(2-hydroxyethyl)amino)-5-methoxyphenyl)-5-amino-7-bromo-4-chloro-2H-benzotriazole; C438664:2-(4-(bis(2-acetoxyethyl)amino)-2-(acetylamino)-5-methoxyphenyl)-5-amino-7-bromo-4-chloro-2H-benzotriazole; D004396:Coloring Agents; D007211:Indoles; D009153:Mutagens; D009942:Organometallic Compounds; D014230:Triazoles; C079284:blue rayon; D002482:Cellulose