| This dissertation is concerned with the synthesis and evaluation of direct dyes and pigments in which diamines 4,4'-diamino- para-terphenyl (DATP) and 4,4'-diamino- para-quaterphenyl (DAQP) were employed as potential alternatives to benzidine. DATP (113) was synthesized by direct nitration of para-terphenyl and reduction of the resultant dinitro compound using hydrazine and Pd catalyst. DAQP (117) was synthesized in three steps from biphenyl: (1) simultaneous nitration and iodination, (2) Cu-induced coupling of 4-iodo,4'-nitrobiphenyl to give 4,4'-dinitro-para-quaterphenyl (116), (3) reduction DNQP to the target diamine ( 117) using SnCl2/HCl.*; Organic dyes were prepared by coupling DATP (cf. 121--125 ) or DAQP (cf. 127--131) to the widely used dye intermediates: naphthionic acid, J-acid, H-acid, chromotropic acid and Chicago acid. Diazotizations were conducted at 0--5°C using conc. HCl or H2SO 4. Couplings were conducted by adding the tetrazonium salt to the couplers at pH 8--9. Analogs of the commercially important dye C.I. Direct Black 38 were also made from DATP (cf. 126) and DAQP (cf. 132 ). These two dyes were synthesized through a four-step procedure: (1) diazotization of the diamines, (2) coupling with H-acid at 10°C and pH 2, (3) coupling with the diazonium salt of aniline at pH 8--9, and (4) addition of meta-phenylenediamine at 10°C and pH 7--8.; Organic pigments were prepared by coupling or condensing DATP (cf. 133--137) or DAQP (cf. 138--142) with intermediates such as 2-mercapto-4,6-dihydroxypyrimidine, acetoacetanilide, 1-phenyl-3-methyl-5-pyrazolone, 5-acetoacetylaminobenzimidazolone and 4-[(2,5-dichlorophenyl)azo]-3-hydroxy-2-naphthoyl chloride.; The standard Ames test and Prival modification were used to assess mutagenicity. The results showed that DATP was mutagenic, while DAQP was nonmutagenic. All pigments based on DATP and DAQP were nonmutagenic, which may be accounted for in part by the extremely low solubility of the pigments in the test media.; The results of this study indicated that both diamines can be used to make disazo and azomethine organic colorants; however due to the mutagenicity of DATP, only DATQ could be accepted as a synthetic intermediate, despite the lack of mutagenicity in organic pigments derived from the former diamine. Further, the high melting and decomposition temperatures associated with organic pigments derived from DAQP suggest that they are suitable for applications requiring high performance pigments, such as the coloration of fibers and plastics during melt extrusion. (Abstract shortened by UMI.); *Please refer to dissertation for diagrams. |
