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-氨基-10-羟基-5,10-二氢磷杂吖嗪-10-氧化物的合成、诱变性及应用

2-氨基-10-羟基-5;10-二氢磷杂吖嗪-10-氧化物的合成、诱变性及应用;二氢磷杂吖嗪; 吡唑啉酮; 合成; 结构鉴定; 诱变性     

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.     

新型含磷阻燃剂的合成及阻燃PC/ABS的热稳定性能

通过9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、乙烯基甲基二甲氧基硅烷(WD-23)和γ-氨丙基甲基二乙氧基硅烷(DB902)之间的反应,合成了一种新型含磷阻燃剂:10-(乙基甲基二甲氧基硅烷)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物/γ-氨丙基甲基二乙氧基硅烷共聚物(DPWDF).利用热重分析(TGA)研究了阻燃剂及阻燃PC/ABS的热稳定性.结果表明:480 ℃以后,阻燃剂在空气氛围中的残炭量比在氮气氛围中的高;阻燃剂提前于基体PC/ABS分解,有利于促进基体成炭,提高基体的高温残炭量.     

1,8-二羟基-9,10-二氢蒽的合成

以1,8-二羟基葸醌为原料,经甲醚化,锌粉和金属钠还原,去甲基等4步反应合成1,8-二羟基-9,10-二氢蒽,总产率为37％．1,8-二甲氧基葸醌用NaBH4／CF3C00H还原生成二聚产物,并测定了其单晶结构。     

4-氯-1,7-二羟基二氢化茚的合成及意外醚化反应的研究

以对氯苯酚(8)为原料、三乙胺作缚酸剂，与丙烯酰氯反应生成对氯苯酚丙烯 酸酯(7)，7与A1Ck共热155℃，首先发生Fries重排，然后关环得到4-氯-7-羟基二 氢化茚-1-酮(6)，再用NaBHl／CH_3OH或LiAlH_4／THF还原6的羰基得到4-氯-1，7- 二羟基二氢化茚(5)．条件控制不当易产生两个意外的醚化产物4-氯-1-甲氧基-7- 羟基二氢化茚(9)和自身醚化产物10，9的结构经x射线单晶衍射分析确证，并提出 生成10的可能机理为5的醇羟基极易通过分子内催化形成碳正离子、进而与另一分 子5形成自身醚化产物10．因此，还原反应完成后的后处理应避免长时间放置和加 热，以减少醚化产物的生成．化合物5，9，10均为未见文献报道的新化合物．     

Ⅲ.1,4,4a,5,12,12a-六氢-6-羟基-11-甲基-5,12-二羰基-并四苯的合成

本文报告脱水四圜素同型物合成工作中一个模型试验,1,4,4a,5,12,12a-六氢-6-羟基-11-甲基-5,12-二羰基-并四苯合成的结果。 2-(2′,5′-二甲氧基苯甲酰)-苯甲酸(Ⅴ)经与碘化甲基镁作用,得3-甲基-3(2′,5′-二甲氧基苯)-隣苯甲醇甲酸内酯(Ⅵ),再经锌粉-氢氧化钠还原,得隣(α-甲基-2′,5′-二甲氧基)-苄基-苯甲酸(Ⅶ),浓硫酸环化变成1,4-二甲氧-10-甲基葱酮-[9](Ⅷ),用氢溴酸去甲基得1,4-二羟基-10-甲基蒽酮-[9](Ⅸ),以四乙酸铅氧化几乎全部变成9,10-二氢-9-羰基-10-甲基-蒽醌[1,4](Ⅹ)。Ⅹ和丁二烯-[1,3] 作用变为1,4,4a,5,12,12a-六氢-6-羟基-11-甲基-5,12-二羟基并四苯(Ⅺ)。     

4-甲基-7，10-二氢苯并[h]香豆素的合成研究

以1-萘酚(6)为起始原料，经过Birch还原得到5，8-二氢-1-萘酚(7)；7与乙酰 乙酸乙酯在不同条件下缩合合成了4-甲基-7，10-二氢苯并[h]香豆素(4)．研究结 果表明，无氧和酸催化的反应条件对缩合反应是至关重要的．在没有酸催化的条件 下，反应生成3-乙酰基-2-羟基-6-甲基-吡喃-4-酮(8)，并通过单晶X射线衍射分析 确定了产物的结构；在酸催化的条件下，除了生成产物4外，还伴随生成脱氢芳构 化产物4-甲基苯并[h]香豆素(5)，而且在不同条件下二者的比例不同，其中以甲磺 酸为催化剂、在氮气保护下并加入抗氧化剂无水Na_2SO_3为最佳反应条件，化学选 择性约为70：30(4：5)，收率49．1％．     

2,2-二(4-羟基-3-氨基)苯基丙烷的合成

在乙醇介质中，以Fe(OH)3／C为催化剂，用80％水合肼将2，2-二(4-羟基-3-硝基)苯基丙烷还原为2，2-二(4-羟基-3-氨基)苯基丙烷。产率99．0％，纯度98．5％。考察了10种金属离子对催化剂活性的影响，结果发现Pb^2 会引起催化剂中毒；Mg^2 ，Cu^2 和Zn^2 钝化了催化剂的催化活性；Ba^2 和Cr^3 不影响催化剂的活性；Al^3 ，Ni^2 ,Ti^3 和Ti^4 能活化催化剂，使反应速度加快，但它们单独使用时无催化活性。     

10,10-二吡啶甲基-9,10-二氢蒽的合成研究

蒽酮1和氯甲基吡啶盐酸盐2在甲苯中回流反应生成10,10-二吡啶甲基-9(10H)蒽酮(3),收率63％～68％;3用硼氢化钠还原生成10,10-二吡啶甲基-9,l0-二氢蒽-9-醇(4),收率87％～90％;蒽醇4在酸催化下发生歧化反应,得到还原产物10,10-二吡啶甲基-9,10-二氢蒽(5)和氧化产物蒽酮3.该歧化反应受催化剂、溶剂和反应温度等影响.当蒽醇4用三氟化硼为催化剂、甲苯为溶剂、回流反应,5的收率达到74％.所合成的新化合物都经1H NMR,13C NMR,MS和元素分析表征确认.     

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.     

Study on the Methyl Migration of 10-Methoxy-5,10-dihydrophenophosphazine 10-oxide

The title compound (1) was treated with NaH at room temperature in anhydrous DMF to give a sodium salt (containing nitrogen anion)which could shift the methyl group from oxygen to nitrogen atom to form N-methyl phosphinic acid as the reaction temperature was increased to 120 ℃.Three nitro derivatives containing 5,10-dihydrophenophosphazine ring system were prepared for the investigation on the above reaction mechanism which would be possible regarded as a special inter-molecular substitution.viz.,the nucleophilic nitrogen anion from one molecule of 1 attacked the cabon atom of the O-methyl of another 1.In addition,the chemical structures of seven compounds containing 5,10-dihydrophenophosphazine ring system involved in the experiment were confirmed by IR,^1 H NMR,^31P NMR and mass spectroscopy.     

Quantification of key red blood cell folates from subjects with defined MTHFR 677C>T genotypes using stable isotope dilution liquid chromatography/mass spectrometry

Red blood cell (RBC) folate levels are established at the time of erythropoiesis and therefore provide a surrogate biomarker for the average folate status of an individual over the preceding four months. Folates are present as folylpolyglutamates, highly polar molecules that cannot be secreted from the RBCs, and must be converted into their monoglutamate forms prior to analysis. This was accomplished using an individual's plasma pteroylpolyglutamate hydrolase by lysing the RBCs in whole blood at pH 5 in the presence of ascorbic acid. Quantitative conversion of formylated tetrahydrofolate derivatives into the stable 5,10-methenyltetrahydrofolate (5,10-MTHF) form was conducted at pH 1.5 in the presence of [(13)C(5)]-5-formyltetrahydrofolate. The resulting [(13)C(5)]-5,10-MTHF was then used as an internal standard for the formylated forms of tetrahydrofolate that had been converted into 5,10-MTHF as well any 5,10-MTHF that had been present in the original sample. A stable isotope dilution liquid chromatography-multiple reaction monitoring/mass spectrometry method was validated and then used for the accurate and precise quantification of RBC folic acid, 5-methyltetrahydrofolate (5-MTHF), tetrahydrofolate (THF), and 5,10-MTHF. The method was sensitive and robust and was used to assess the relationship between different methylenetetrahydrofolate reductase (MTHFR) 677C>T genotypes and RBC folate phenotypes. Four distinct RBC folate phenotypes could be identified. These were classified according to the relative amounts of individual RBC folates as type I (5-MTHF >95%; THF <5%; 5,10-MTHF <5%), type II (5-MTHF <95%; THF 5% to 20%; 5,10-MTHF <5%), type III (5-MTHF >55%; THF >20%; 5,10-MTHF >5%), and type IV (5-MTHF <55%; THF >20%; 5,10-MTHF >5%).     

从青藤碱制备具有(＋)-C-Normorphinan骨架的化合物

对青藤碱进行Mitsunobu甲基化反应, 得到O-甲基青藤碱(2); 2经过酸性水解、硼氢化还原以及高碘酸钠氧化开环得到O-甲基青藤碱二醛(5); 在哌啶存在下对5进行羟醛缩合反应, 区域选择性地闭环生成具有(＋)-C-normorphinan骨架的化合物(8S,12S,13R)-6,7-didehydro-3,4-dimethoxy-16-methyl-C-normorphinan-7-carboxaldehyde (7); 经过以上五步反应, 7的总收率约35%. 对7进行硼氢化还原得到化合物8; 化合物8以醋酐进行酯化得到化合物9. 化合物7以5% Pd/C为催化剂、1.01×105 Pa下与氢气作用发生双键氢化反应, 立体定向地得到化合物10, 从化合物10出发获得化合物11和12. 通过对化合物11的1H NMR, 13C NMR, 2D-NMR及NOESY等核磁共振分析确定化合物10, 11和12具有7S绝对构型.     

2-(10-Diazo-10H-anthracen-9-ylidene)-malonodinitrile: A convenient precursor of 9,10-disubstituted anthracenes

Summary The acid promoted decomposition of 2-(10-diazo-10H-anthracen-9-ylidene)-malonodinitrile in the presence of water, methanol, ethanol, acetic and propionic acid, ethyl thioglycolate,p-thiocresole, and acetyl acetone yielding 9,10-disubstituted 9,10-dihydroanthracenes was investigated. Treatment of the reaction products with tri-ethyl amine followed by hydrochloric acid caused their tautomerization to the corresponding 9,10-disubstituted anthracenes. A mechanism for this reaction is proposed. The first example of an intermolecular C-C-bond formation during the protic acid promoted decomposition of a diazo compound in the presence of CH-acids was found. An improved procedure for the preparation of the starting diazo compound, which may serve as a convenient precursor of 9,10-disubstituted anthracenes, is described.Cordially dedicated to Prof. Dr.K. Winsauer on the occasion of his 70^th birthday     

Quintet bis(carbene) from triplet diarylcarbenes introduced at the 1,8-position of anthracene

[9-(10-phenyl)anthryl](4-bromo-2,6-dimethylphenyl)diazomethane was found to be stable enough to survive Sonogashira coupling reaction conditions and was converted to [9-(10-phenyl)anthryl](4-trimethylsilylethynyl-2,6-dimethylphenyl)diazomethane, which was reacted with 1,8-diiodoanthracene to give bis(diazo) compound. Bis(carbene) generated by irradiation of the bis(diazo) compound generated a fairly persistent S = 2 quintet state. [structure: see text]