N—芳基—N‘—取代噻唑基脲的合成与结构表征

由于植物细胞分裂素在植物生长发育中非常重要的作用 ,一直得到人们的重视 ,但其天然存在量微难以大量应用 ,故人工合成的化学结构类似物相继出现 ,主要有嘌呤类 ,如 6-苄氨基嘌呤 ( 6-BA)等 [1]和脲类化合物 ,如二苯脲类 ( DPU) [2 ]和N-苯基 -N′-( 1 ,2 ,3 -噻二唑 -5 -基 )脲 ( TDZ) [3]。人工合成嘌呤类植物细胞分裂素的结构改造一般以苯并杂环代替嘌呤环或嘌呤环上取代基进行结构变化 ,脲素细胞分裂素结构改造 ,通常是改变 N-取代基的化学结构 ,为寻找化学结构更类似天然植物细胞分裂素的化合物 ,在合成 N-取代苯基 -N′-( 6-苯…     

N，N‘—二—（3,5—二甲基苯基）—3，6—二甲基—1，4—二氢—1，2，4，5—四嗪—1，4—二甲酰胺的合成

1 ,2 ,4,5—四嗪衍生物具有抗肿瘤 ,杀菌 ,杀虫等活性 ,我们曾合成了具有抗肿瘤活性的Ｎ ,Ｎ′ 二苯基 3 ,6 二甲基 1 ,4 二氢 1 ,2 ,4,5 四嗪 1 ,4 二甲酰胺 (3ａ) [1,2 ,3] ,合成路线见图 1。研究它们的抗肿瘤活性时发现该化合物的苯环间位若以Ｎ ,Ｎ 二甲基取代 ,对小鼠白血病细胞 (Ｐ 3 88)和人肺腺癌细胞 (Ａ 5 49)有很强的抗肿瘤活性。为此我们合成了苯环上有两个间位供电子基取代的四嗪类标题化合物 (3ｂ) ,以此研究四嗪类苯环取代基的构效关系。合成过程中 ,发现原料 3 ,5 二甲基苯异氰酸酯 (2ｂ)在溶剂氯仿中的溶解度良好 ,浓缩…     

盐酸金刚乙胺的合成

盐酸金刚乙胺(1)是一种抗病毒和镇静药物,主要用于预防和治疗Ａ型流感病毒感染[1]。文献[2,3]以溴代金刚烷(3)为原料,在浓硫酸存在下与乙炔气体反应,然后水解得到中间体1 金刚烷甲基酮(7),且产物需经过柱分离,总收率40%。本文参考文献[4,5],按如下路线合成了标题化合物。1　实验部分1.1　主要仪器和试剂ＩＲ(60ＳＸＲ ＦＴＩＲ);1Ｈ ＮＭＲ(ＦＸ 90Ｑ);ＭＳ(ＭＡＴ 2000)。熔点用毛细管法测定,温度计未经校正。金刚烷(工业品)98%;浓硫酸(工业品)98 4%;其它试剂为化学纯。1.2　合成1 溴代金刚烷(3)　在烧瓶中,依次加入2(320ｇ,2.35ｍｏｌ…     

相转移催化合成对甲氧基肉桂酸-2-乙基己酯的研究

对甲氧基肉桂酸 2 乙基己酯是一种有效的ＵＶＢ防晒剂[1 ,2 ] ,一般采用Ｃｌａｉｓｅｎ Ｓｃｈｍｉｄｔ缩合反应制得[3] ,但由于催化剂ＫＯＨ处于水相 ,对反应物不能充分起到催化作用导致产率较低[4] 。我们利用乙二醇 (ＰＥＧ)为相转移催化剂合成立体专一的反式对甲氧基肉桂酸 2 乙基己酯 ,产率提高到 72 .5 %。合成路线如下 :1　实验部分1 .1　仪器与试剂ＢＩＯ ＲＡＰＦＴ45 0红外光谱仪 ,用液膜法测试 ;Ｂｒｕｒｅｒ ＡＭ 30 0超导核磁共振仪 (溶剂ＤＣ Ｃｌ3) ;ＭＡＴ/44Ｓ ,ＧＣ ＭＳ型色质联用谱仪 ;试剂均为分析纯 ,上海化学试剂…     

新试剂HABST分光光度法测定铜

硫脲类试剂因含有Ｓ ,Ｎ配位原子而可与无机离子形成配合物 ,近年来已被用于定性分析和定量测定。对氨基苯磺酸钠类硫脲因其良好的水溶性而避免了以往测铜试剂需有机相中进行的繁琐处理。Ｎ 庚基 Ｎ′ (对氨基苯磺酸钠 )硫脲(ＨＡＢＳＴ) [1 ] 是继Ｎ 烯丙基 Ｎ′ (对氨基苯磺酸钠 )硫脲 (ＡＳＡＴＵ) [2 ] 后又合成的一种水溶性光度试剂 ,通过初步研究 ,发现它与Ａｇ+、Ｃｕ2 +有特征性反应。在此基础上 ,对其与铜的显色反应作进一步研究 ,探讨了ＨＡＢＳＴ分光光度法测定铜的最佳条件 ,在ｐＨ4.5～ 6.0的ＨＡｃ ＮａＡｃ缓冲溶液中 ,Ｃ…     

薄层色谱法在2-氨基葡萄糖-四乙酸酯合成中的应用

有关ＬｉｐｉｄＡ结构类似物的合成 ,是医药界新兴的一个重要研究热点。而 β ｄ 葡萄糖 1 溴 2 氨基 2 ,3 ,4,6 四乙酸酯是合成ＬｉｐｉｄＡ系列类似物的关键[1,2 ] 。已知 β ｄ 2 氨基葡萄糖中含有四个羟基 (图 1 ) ,就单个基团取代而言 ,这四个羟基的相对活性顺序为Ｃ1>Ｃ6 >Ｃ4>Ｃ3。但在实际反应过程中 ,其活性顺序还与反应条件密切相关。图 1　β ｄ 2 氨基葡萄糖分子结构图Ｆｉｇ .1　Ｔｈｅｓｔｒｕｃｔｕｒｅｏｆβ ｄ 2 ａｍｉｎｏｇｌｕｃｏｐｙｒａｎｏｓｅ　　　　　因此区域选择性合成 β ｄ 葡萄糖 1 溴 2 氨基 …     

双(1,4-二酰基氨基硫脲)化合物的合成

酰氨基硫脲及其相关化合物通常具有广泛的生物活性 ,如抗菌[1～ 3] ,抑制神经紧张[4] ,治疗血糖过低[5] ,植物生长调节[6～ 9] 等。迄今为止 ,鲜有关于双 (1 ,4 二酰基氨基硫脲 )合成的报道。为了考查该类化合物的生物活性 ,我们设计合成了一系列双 (1 ,4 二酰基氨基硫脲 )化合物 ,以下图所示的两条合成路线合成了该类化合物 :二酰氯 (1 )、异硫腈酸酰酯 (2 )等中间体可不经进一步纯化直接用于下一步反应。所生成的产物 3ａ 3ｆ、3′ｄ 3′ｇ经ＤＭＦ Ｈ2 Ｏ ＥｔＯＨ重结晶 ,产率达 81 %～ 98%。在合成化合物 (1 )时 ,对于一些用ＳＯＣｌ2 …     

Crystal Structure of Complex （Et4N）[VFe3S4Cl3（CH3CN）3]

1　ＩＮＴＲＯＤＵＣＴＩＯＮＳｉｎｃｅ1980,ｍａｎｙＶ/Ｆｅ/Ｓｈｅｔｅｒｏｍｅｔａｌｌｉｃｓｕｌｆｕｒｃｌｕｓｔｅｒｃｏｍｐｏｕｎｄｓｈａｖｅｂｅｅｎｒｅｐｏｒｔｅｄ.ＲａｕｃｈｆｕｓｓｅｔａｌｏｂｔａｉｎｅｄｔｗｏｋｉｎｄｓｏｆＶ/Ｆｅ/Ｓｃｏｍｐｏｕｎｄｓ[1]ｕｓｉｎｇ(ＣＨ3Ｃ5Ｈ4)2Ｖ2Ｓ4ａｓａｎｏｒｇａｎｏｍｅｔａｌｌｉｃｌｉｇａｎｄ,ｏｎｅｉｓ(ＭｅＣｐ)2Ｖ2Ｆｅ2(ＮＯ)2Ｓ4ｗｉｔｈａｃｕｂａｎｅｌｉｋｅｓｔｒｕｃｔｕｒｅａｎｄａｎｏｔｈｅｒｉｓ(ＭｅＣｐ)2Ｖ2Ｓ4Ｆｅ(ＮＯ)2ａｎｄ(ＭｅＣｐ)2Ｖ2Ｓ4…     

微波辐射快速合成2-(2′-羟苯基)-5(6)取代苯并咪唑衍生物

苯并咪唑衍生物具有一定的抗病毒能力[1 ] ,一些苯并咪唑衍生物已用作农用抗植物病毒剂[2 ] 。一锅煮合成反应时间较长 ,产率中等[3,4] 。本文用取代邻苯二胺和水杨酸为原料 ,吡啶为溶剂 ,ＰＯＣｌ3为催化剂 ,微波辐射法合成了标题化合物。合成路线如下 :1　实验部分1 1　仪器ＷＣ 1型熔点测定仪 (温度计未校正 ) ;日本岛津ＩＲ 435红外光谱仪 (ＫＢｒ压片 ) ;ＴＥＯＬ ＦＸ90Ｑ核磁共振仪 ,ＤＭＳＯ ｄ6 为溶剂 ;日本柳公Ｃ·Ｈ·Ｎ元素分析仪ＭＴ 3;苏州三星电子有限公司产新天地Ｍ9Ｋ88型微波炉 ,输出功率 85 0Ｗ ,2 4 5 0Ｈｚ。1 2　…     

黄烷酮衍生物的合成及杀灭钉螺活性研究

许多黄烷酮类化合物具有抗菌[1 ] 、抗炎[2～ 3] 、抗ＨＩＶ[4] 、抗肿瘤[5] 、抗氧化[6] 、抗诱变[7] 等诸多活性 ,还可以用于制作热敏材料[8]等。黄烷酮类化合物大多从植物中分离获得[9] ,目前 ,文献报道的合成方法也在逐渐增多[1 0～ 1 2 ] ,本文是采用肉桂酸衍生物与间苯三酚反应关环得到 3ａ～ 3ｈ一系列化合物并考察了它们杀灭钉螺的活性。其合成反应路线如下 :1　实验部分1 1　仪器与试剂81 0 0系列数字显示熔点仪 (温度计未经校正 ) ;2 4 0 0元素分析仪 ;日本岛津ＦＴＩＲ 82 0 1红外光谱仪 (ＫＢｒ压片法 ) ;ＦＸ 90Ｑ型核磁共振…     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

解决能源问题的新途径——光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。