2,8-二氨基-10-甲氧基-5,10-二氢磷杂吖嗪-10-氧化物的合成、诱变性及应用性能研究

10-羟基-5，10-二氢磷杂吖嗪-10-氧化物(1)经酰氯化、甲基化得到10-甲氧基-5，10-二氢磷杂吖嗪-10-氧化物(2)，2经硝化得到10-甲氧基-2，8-二硝基，5，10-二氢磷杂吖嗪-10-氧化物(3.62％)．3在Pd／C(u=0．05)存在下，用氢气还原为2，8-二氨基-10-甲氧基-5，10-二氢磷杂吖嗪-10-氧化物(4.71％)，考察了Bd／C(w=0．05)用量对氢化还原反应的影响．经过Salmonella／mammalian microsome assay测试，4表现为非诱变性，用4与乙酰J-酸作用得到新型双偶氮酸性染料(5)．5对羊毛和丝绸分别在2％与3％色度下浸染郜得到黑色染样，考察了5的上染曲线，并对染样进行了测色研究，发现该染料属于酸性蓝黑染料，其黑度优于目前市场上流行的酸性黑10B．     

2-硝基-10-羟基-5,10-二氢磷杂吖嗪-10-氧化物的还原研究

10-羟基-5,10-二氢磷杂吖嗪-10-氧化物硝基衍生物的还原反应研究报道始见于1978年.尹志刚等进一步对2-硝基-10-羟基-5,10-二氢磷杂吖嗪-10-氧化物进行了催化加氢研究,结果发现,催化剂用量达到底物质量的7.5%以上,反应介质为中性或弱碱性,该化合物能够被顺利还原[1].该还原方法缺点是Pd/C催化剂不能够回收利用,还原成本高,需要较高氢气压力,危险性大,从而不利于该染料中间体工业化生产.     

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

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.     

新型磷杂菲基反应型阻燃剂的合成及其在聚氨酯阻燃中的应用

以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物和1,4-丁二醇二缩水甘油醚为原料,合成了一种新型的反应型阻燃剂1-（2-羟基-3-磷杂菲）丙氧基-4-环氧丙氧基丁烷(1),其结构和性能经¹H NMR, ³¹P NMR, FT-IR和TG表征。以1为封端剂,聚氨酯（PU）为基材,制备了1/PU阻燃复合材料（2）,研究了1对2阻燃性能和力学性能的影响,初步探讨了1的阻燃机理。结果表明:1具有气相和凝聚相阻燃作用,2燃烧后可形成致密光滑炭层,使点燃时间延长,改善了燃烧熔滴现象。1含量为1%时,2¹的LOI为27%, UL-94燃烧等级为V-0级。     

新型含磷阻燃剂DOPO-PPO的合成及其阻燃性能

以苯基磷酰二氯,对羟基苯甲醛及9,10-二氢-9-氧杂-10-磷杂菲(DOPO)为原料,合成了一种新型含磷阻燃剂——二[4-(次甲基-羟基-磷杂菲)苯氧基]苯基氧化磷(DOPO-PPO),其结构经1H NMR和IR表征。通过TGA和DTG研究了DOPO-PPO的热稳定性,热降解行为及成炭性能。结果表明:DOPO-PPO的起始热分解温度为210℃,在700℃时残炭为30.4%。以环氧树脂为基材,DOPO-PPO为阻燃剂,二氨基二苯硫砜为固化剂,制备了阻燃环氧树脂(3)。通过极限氧指数(LOI)和垂直燃烧(UL-94)测试了3的阻燃性能。结果表明:当DOPOPPO的添加量为12.0%(质量百分数,即312)时,阻燃级别为V-0级,LOI为34.0%。     

纳米二氧化硅表面接枝9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物以及对聚甲基丙烯酸甲酯复合材料阻燃性能和透明性的影响

聚甲基丙烯酸甲酯(PMMA)是一种重要的透明高分子材料,但是PMMA的易燃性限制了其应用。 本工作在纳米二氧化硅表面接枝含磷阻燃剂9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO),并用于聚甲基丙烯酸甲酯(PMMA)的改性。 极限氧指数(LOI)、垂直燃烧(UL-94)和锥形量热(CCT)测试结果表明,制备的PMMA复合材料的阻燃性能大幅度提高,这主要归因于纳米粒子和含磷阻燃剂的协同阻燃作用,形成致密的炭保护层结构。 同时,二氧化硅接枝DOPO的加入可以保持PMMA良好的透明性,这有利于材料在光学透明性要求较高的领域的应用。     

阻燃剂9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物合成中酯化反应和酰基化反应的优化

有机磷杂环化合物9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物(DOPO)因性能优异而作为无卤阻燃剂得到广泛应用。为了提升和改进DOPO的合成,不少文献对合成中的4个反应,即酯化反应、酰基化反应、水解反应和关环反应进行了大量研究,但是由于缺少合适的分析方法和仪器,对酯化反应和酰基化反应仍没有得出明确的结论。本文则采用了核磁共振磷谱以及测量反应产物HCl吸收碱液的温度变化两种方法,精确地得到了酯化反应和酰基化反应的优化条件。首先采用核磁共振磷谱,讨论了酯化反应温度、原料配比和加料方式对酯化反应产物组成的影响,得出了邻苯基苯氧基二氯化磷(CC)含量高的工艺条件:反应温度80℃,PCl3过量25%~50%,采用邻苯基苯酚(OPP)加入PCl3的反滴法;并得出酯化反应产物的组成直接决定了6-氯-(6氢)-二苯并-(c,e)-氧磷杂己环(CDOP)在酰基化反应产物中的含量。另通过测量HCl吸收碱液的温度变化,间接表征酰基化反应的反应速度,由此得出合适的酰基化反应温度和催化剂用量。结果为:当催化剂固定为0.2 g时,酰基化反应在150℃几乎不反应,随温度升高,反应变快,180℃下4 h完全,190℃下1.5 h即可完成;温度180℃下,1~1.5 g/1 mol OPP的催化剂较为合适,酰基化反应在3~4 h结束。     

新型侧基含磷共聚酯的合成、表征及性能

以精制对苯二甲酸（TPA）、乙二醇（EG）和含磷反应型阻燃剂9,10-二氢-9-氧杂-10-[2,3-二（2-羟基乙氧基）羰基丙基]-10-磷杂菲-10-氧化物为原料,利用熔融缩聚法合成了含磷量分别为0．35％、0．65％的阻燃聚酯。通过熔融纺丝法将聚酯制成纤维及织物,研究了纤维的染色性能,并通过极限氧指数法和垂直燃烧法研究了织物的阻燃性能。FT-IR和NMR研究结果表明：阻燃共聚酯含磷量为0．35％时,其氧指数（LOI）达31．5％,并无熔滴、烟雾产生,具有优异的阻燃性能和抗熔滴性能。DSC、TG和XPS的研究结果表明：侧基舍磷单元的引入降低了聚酯的Tg和Tm,较低的Tm将有利于材料加工性能的改善;阻燃聚酯侧基上的P-C、P-O键易断裂并挥发至气相中,从而降低了聚酯热稳定性,阻燃聚酯可能以气相阻燃机理为主发挥阻燃作用。此外,含磷共聚酯纤维具有较优异的染色性能。     

一种新型含磷-溴-氮阻燃剂的合成

以三氯氧磷、季戊四醇、2 ,3-二溴丙醇及三聚氰胺等为原料合成了一种新型磷 -溴 -氮阻燃剂 0 - (2 ,4,6 -三氧杂 - 1-氧基磷杂双环 [2 .2 .2 ]辛烷 - 4-亚甲基 ) - 0 - 2 ,3- (二溴丙基 )磷酸三聚氰胺盐 (Ⅲ ) .改进了中间体 4-羟甲基 - 2 ,6 ,7-三氧杂 - 1-氧基磷杂双环 [2 .2 .2 ]辛烷 (Ⅰ )的合成条件 ,元素分析、红外光谱等确定了结构     

4-氨基-8-去氮杂四氢叶酸二乙酯的新合成方法

针对4-氨基-8-去氮杂四氢叶酸二乙酯现有合成方法中化合物极性大、溶解度差、收率低的缺点,采用在2,4位氨基引入保护基的方法进行改进。以6-乙酰氧基-2,4-二氯吡啶并[3,2-d]嘧啶为原料,在2,4-位引入苄基后与对氨基苯甲酰谷氨酸二乙酯连接,经硼氢化钠和氯化镍还原后再脱保护,生成叶酸类抑制剂关键中间体4-氨基-8-去氮杂四氢叶酸二乙酯。此方法所需时间短,收率较高,操作及后处理方便。并对6-乙酰氧基-2,4-二氯吡啶并[3,2-d]嘧啶苄基化的选择性、硼氢化钠和氯化镍还原方法进行了讨论。此方法对于四氢叶酸类化合物的合成有重要参考意义。     

Syntheses of 10-Hydroxy-5,10-dihydrophenophosphazine 10-Oxide and Its Methyl Derivatives

Ph2NH and PCl3 interacted at a molar ratio of 1:1.05 and slow-elevated temperature and then at 210-220 ℃ for 6h.The brown solution obtained was treated with H2O to produce a very hard brown solid believed to be a mixture of 5,10-dihydrophenophosphazine 10-oxide(1a) and 10,10′(5H,5H′）-spirobipenophosphazinium chloride(1b).This brown solid was directly oxidized with peracetic acid in HOAc prior to the separation of them to give compound 10-hydroxy-5,10-dihydropheno-phosphazine 10-oxide(2) with a higher yield(45%) than that of the literature(27%).When treated with excess SOCl2.compound 2 could quantitatively be converted to the corresponding phosphinyl chloride and the latter could further be transformed into 10-methoxy-5,10-dihydrophenophosphazine 10-oxide in 70% as treated with NaOMe in methanol.Compound 2 could also be converted to a bisanion when treated with NaH in DMF.The resulted bisanion reacted with MeI to give 5-methyl-10-hydroxy-5,10-dihydrophenophosphzine 10-oxide in a 73% yield which would be converted to 5-methyl-10-methoxy-5,10-dihydrophenophosphazine 10-oxide.All these compounds obtained were identified by surveying their melting points.and spectra and elemental analysis.     

A New Technique of Synthesizing 10—Hydroxy—5—methyl—5,10—dihydrophenophosphazine 10—Oxide

10-Hydroxy-5-methyl-5,10-dihydrophenophosphazine 10-oxide(1)was prepared by a new technique of treating 10-methoxy-5,10-dihydrophenophosphazine 10-oxide(2)with an equivalent of NaH in anhydrous DMF,and then at 120℃ for 3-4h,which not only avoided poisonous and expensive methyl iodide used in literature,but made the consumption of NaH greatly decrease as well.The possible reaction mechanism was also described.The chemical structure of 1 was confiremed by IR,NMR,and mass spectroscopy.     

Synthesis of trifluoromethylthiazoles and their application to azo dyes

3-Bromo-1,1,1-trifluoropropan-2-one ( 2 ) reacted with thiourea and N-monosubstituted thioureas to give the corresponding 4-trifluoromethylthiazoles, respectively. In the reactions with N,N'-diphenylthiourea and thioamides, the considerably stable intermediates, 4-hydroxy-4-trifluoromethylthiazoline derivatives 7 and 8 , were isolated. The reaction of ethyl 2-bromo-4,4,4-trifluoro-3-oxobutanoate ( 4 ) with thiourea was carried out under the gentle conditions to give both thiazole-5-carboxylate 10 and 4-hydroxythiazoline 11 . The thiazole 10 was applied to the azo dye synthesis and the absorption maxima of thus obtained azo dyes were discussed.     

Synthesis of 6-chloro and 6-fluoro-4-hydroxyl-2-quinolone and their azo disperse dyes

<正>In this study,6-chloro-4-hydroxy-2-quinolone and 6-flouro-4-hydroxy-2-quinolone were synthesized from corresponding dianilides.These compounds were coupled with some diazotized aromatic amines to give the corresponding azo disperse dyes.The structures of the quinolone derivatives and new azo dyes were confirmed by UV-vis,FT-IR,~1H NMR and elemental analysis.     

Decolorization and partial degradation of selected azo dyes by methanogenic sludge

The toxicity potential and decolorization of three acid azo dyes (Acid Orange 6, Acid Orange 7, and Acid Orange 52) by methanogenic granular sludge from an anaerobic expanded granular sludge bed reactor was assayed. Complete bioreduction was found for all three azo dyes. Sulfanilic acid and 4-aminoresorcinol were detected from the decolorization of Acid Orange 6, sulfanilic acid and 1-amino-2-naphtol were detected from the reduction of Acid Orange 7, and sulfanilic acid and N,N-dimethyl-1,4-phenylenediamine (DMP) were found to be intermediates of Acid Orange 52 degradation. Sulfanilic acid and 1-amino-2-naphtol were persistent in the anaerobic conditions, whereas 4-aminoresorcinol was completely mineralized by anaerobic sludge and DMP was transformed into 1,4-phenylenediamine. Enrichment cultures obtained via consecutive passages on basal medium with only azo dye as a carbon and an energy source seemed to be morphologically heterogeneous. Baculiform and coccus cells were found when viewed under a light microscope. Cocci were joined in chains. Because anaerobic sludge contains sulfate-reducing bacteria and therefore may generate sulfide, azo dyes were tested for chemical decolorization by sulfide to compare rates of chemical and biologic reduction.     

Approaches to phenazine-derived N-isosteres of anthracyclinones

1-Hydroxyphenazine 5,10-dioxide showed antitumor properties against mouse leukemia P388. It also participated in biochemical mechanisms of quinoid antitumor agents, as indicated by inhibition of radiolabeled DNA-RNA precursors in cultured leukemia L1210 cells and by stimulation of oxygen consumption in mammalian microsomes. This suggests that the isosteric di-N-oxide system may be a biologically active substitute for 1,4-quinone, and that di-N-oxides of tetrahydrobenzo[b]phenazines can be explored as anthracyclinone N-isosteres. As potential synthetic intermediates, 7,8,9,10-tetrahydro-6,11-dihydroxybenzo[b]-phenazines have been prepared by 1) Diels-Alder addition of phenazine-1,4-quinone and 1-methoxy-3-(trimethylsilyloxy)-1,3-butadiene to give isolable but labile adducts and 2) condensation of 6,7-diamino-1,2,3,4-tetrahydro-2-hydroxy-5,8-dimethoxy-2-naphthoic acid with 3-methoxy-1,2-quinone. Attempts at N-oxidation gave instead oxidation of the 6,11-hydroquinone ring to quinone, regardless of hydroxyl protection. Despite previous literature indications, we have been unable to synthesize the 1,4-dihydroxyphenazine 5,10-dioxide system. We conclude that this hydroxyl substitution pattern (1,4) in an adjacent ring must be avoided in the redesign of anthracyclinone isosteres that have di N-oxide in place of quinone.     

Synthesis,characterization, and dyeing performance of some azo thienopyridine and thienopyrimidine dyes based on wool and nylon

A string of novel heterocyclic mono azo dyes were synthesized and their utilization in dyeing different fabrics as wool and nylon were discussed. Thienopyridine azo dyes 4 and 6 were prepared by reaction of chloro acetamidederivative 2 with diamino compounds to yield 3 and 5 , followed by reaction with NaNO₂/HCl and coupling with nucleophilic reagent. One-pot reaction of chloro acetamide 2 with ammonium thiocyanat in solvent ethanol gave the unexpected thienopyrimidine derivative 7 , which contain two active sites, the former is primary amine that was able to form diazonium salt that coupled with N,N-dimethylaniline, resorcinol, and/or self-coupling to afford the azo dyes 8-10 , and the latter is active methylene group that underwent coupling with different diazonium salts to give the azo thienopyrimidine derivative dye 11-15 . The dyeing performance of these azo dyes had been investigated in terms of their dyeing behavior and fastness properties on different fabrics. Results showed that the color strength (K/S) values, as well as, washing, rubbing, and resistance to acid, alkali and light showed high efficiency of these heterocyclic mono azo dyes to dye wool rather than nylon fibers.