苯并膦嗪系芳胺及其染料诱变性的研究

The forming mechanism of the dihydrophenophosphazine by the interaction of Ph2NH and PCl3 was studied and the possible mechanism of forming spiro phosphonium chloride at the same reaction system was also proposed. It was especially found that 5,10-dihydrophenophosphazine 10-oxide existed the tautomeric equilibrium between enol and ketone by studying some reaction system on it. The spiro phosphonium chloride can be dissolved in HOAc, and not be in alkali media and not be oxidized by oxidant, which converted the traditional "two-step" synthetic technique of 10-hyroxy-5,10-dihydrophenophosphazine 10-oxide to an "one-step" technique in which the yield (40%~50%) of target molecule was increased by 20%~25%, the consumption of raw materials was clearly decreased, and this new technique can easily be repeated within one day rather than over three days in literature. The structure of the obtained compound was also identified by surveying its melting point, IR, NMR and Mass spectra..The product obtained from the interaction of (N-methyl-) 10-hydroxy-5,10-di- hydrophenophosphazine 10-oxide and SOCl2 was refluxed with RONa in ROH to give five corresponding esters phosphinic acid which had double melting points except for methyl ester (see also Fig. 1~3). However the esters derived from N-methyl phosphinic acid exhibited exothermic phenomena while melting at second temperature (see also Fig. 3). When substituting MeOH for MeONa on above technology, the methyl ester phosphinic acid with double melting points was also obtained, and its crystal phase was clearly different from its counterpart with single melting point by surveying their X-ray diffraction. The recrystallization from iso-propanol did hardly change the crystal phase of the methyl ester but change that of the other esters.The dark green bis-anion obtained from treatment of 10-hydroxy-5,10-dihydro- phenophosphazine 10-oxide with NaH reacted with MeI at about 120℃ in anhydrous DMF to give N-methyl phosphinic acid. However, the similar N-methylation of the methyl ester phosphinate was not to give the expected product but to give N-methyl phosphinic acid too. It was found that the green N-anion obtained from the methyl ester phosphinate shifted its methyl group from oxygen to nitrogen at the same reaction conditions, and the reaction would be more possibly carried out in a special inter-molecular substitution than in intramolecular substitution.(see also Scheme 1~2).It was found in nitrating the methyl derivatives containing 5,10-dihydro- phenophosphazine ring system that the consumption of nitrating reagent was the most important factor influencing the nitration. In the case of the raction time and temperature, and reaction media unchanged, when a 9~11-fold excess of HNO3 was used, the mono nitro product was mainly obtained and the dinitro compound obtained when over 40-fold excess of HNO3 was used. Nitration with between 11- and 40-fold excess of HNO3 gave the mixing nitro products. Prolonging nitration time and increasing reaction temperature would promote the formation of dinitro products while shorting nitration time and decreasing reaction temperature would promote the formation of mono-nitro products It was found in reducing the resulting nitro compounds over 5%Pd/C catalyst that the nitro phosphinic acids required more catalyst than the esters nitro phosphinic acid, and dinitro compounds required more catalyst than mono-nitro compounds in the case of all nitro groups completely changed into amino groups. In addition, the pH value of reaction media markedly influenced the catalytic hydrogenation. So, the pH value of reaction media was usually adjusted to 7.00~7.20 before hydrogenation, otherwise the catalytic hydrogenation would not carry out because of possible catalyst poison.The NMR of 20 intermediates containing 5,10-dihydrophenophosphazine ring system involved in the present dissertation was studied by using several correlated techniques such as gradient correlated spectroscopy (gCOSY), gradient 1H-detected heteronuclear single quantum coherence (gHSQC), an

诱变性（致癌性）芳胺和染料已在国际市场上禁用。本项目研究用非诱变性的苯并膦嗪系的胺化物代替诱变性芳胺研制各类性能良好的非诱变的染料新品种，并对研制出的胺化物及染料样品进行诱变性的测试与评价。苯并膦嗪系的胺化物在我国首次用于非诱变性染料的研制中，芳胺染料的诱变性的测试与评价的研究在我国尚属空白，开展了我国染料新领域。