高等学校化学学报

高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (7): 1210.

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2,8-二氨基-10-羟基-5-甲基-5,10-二氢磷杂吖嗪-10-氧化物的合成及其诱变性研究

尹志刚1, 靳焜2, 赵德丰2, 彭勤纪2, FreemanH.S.3   

  1. 1. 郑州轻工业学院化工系, 郑州 450002;
    2. 大连理工大学精细化工国家重点实验室, 大连 116012;
    3. 美国北卡罗来那卅立大学纺织化学系, Raleigh, N C 27965-8302
  • 收稿日期:2002-06-28 出版日期:2003-07-24 发布日期:2003-07-24
  • 通讯作者: 尹志刚(1965年出生),男,博士,副教授,从事中间体合成及非诱变染料研究.E-mail:yinck@263.net E-mail:yinck@263.net
  • 基金资助:

    国家自然科学基金(批准号:29972006);河南省教育厅骨干教师基金;郑州轻工业学院科研基金资助

Studies on the Synthesis and Mutagenicity of 2,8-Diamino-10-hydroxy-5-methyl-5,10-dihydrophenophosphazine-10-oxide

YIN Zhi-Gang1, JIN Kun2, ZHAO De-Feng2, PENG Qin-Ji2, Freeman H. S.3   

  1. 1. Department of Chemical Engineering, Zhengzhou Institute of Light Industry, Zhengzhou 450002, China;
    2. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, China;
    3. Department of Textile Engineering, Chemistry and Science, North Carolina State University, Raleigh, NC 27695-8302, USA
  • Received:2002-06-28 Online:2003-07-24 Published:2003-07-24

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被引次数

12

摘要：

在升温条件下,二苯胺和三氯化磷反应,产物经水解、氧化得次膦酸:10-羟基-5,10-二氢磷杂吖嗪-10-氧化物(产率45%).经酰化后,与甲醇钠作用,生成相应的次膦酸甲酯.次膦酸甲酯经NaH处理后,在120℃下发生甲基迁移,形成5-甲基次膦酸(产率62%).用45倍摩尔量的硝化剂将5-甲基次膦酸硝化,得到双硝基产物(产率59%).在5%Pd/C催化下,双硝基产物又被氢气还原.考察催化剂用量对该还原反应的影响,并在最佳催化剂用量时得到2,8-二氨基-10-羟基-5-甲基-5,10-二氢磷杂吖嗪-10-氧化物(产率70%).用NMR,IR和质谱确定了所合成的5个中间体结构.对合成的氨基化合物进行Salmonella/mam-malianmicrosomeassay测试,结果表明,该氨基化合物表现为非诱变性.

关键词: 5,10-二氢磷杂吖嗪, 合成, 结构鉴定, 诱变性, Salmonella/mamalian microsomeassay

Abstract:

Diphenylamine and phosphorus trichloride interacted on each other at slow-elevated temperatures and then the brown solution obtained was treated with H2O, followed by oxidization to produce a phosphinic acid, viz, 10-hydroxy-5,10-dihydrophenophosphazine-10-oxide(yield 45%) which could be converted to a methyl phosphinate in yield 70% by reacting with SOCl2 and then with MeONa in MeOH. After being treated with NaH in anhydrous DMF and then heating the reaction mixture to 120 ℃, the methyl phosphinate obtained above could also be transformed into N-methyl phosphinic acid with a yield of 62%. On nitrating the new phosphinic acid with 45 equimolar amount of nitrating agent, a dinitro compound will be obtained in a yield 59%. And this dinitro compound could further be reduced to 2,8-diamino-10-hydroxy-5-methyl-5,10-dihydrophenophosphazine-10-oxide with hydrogen over 5% Pd/C. The effect of the amount of 5% Pd/C on the hydrogenation was investigated and the title compound was ultimately synthesized in a yield 70% by using the optimum amount of catalyst. All five intermediates obtained from this study were identified by NMR and mass spectroscopy. The title compound was proved to be a nonmutagenic aromatic diamine via Salmonella/mammalian microsome assay.

Key words: 5,10-Dihydrophenophosphazine, Synthesis, Structure identification, Mutagenicity, Salmonella/mammalian microsome assay

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