16β-唑取代-3β-羟基-5α-雄甾-17-酮的绿色合成

表雄酮经16-位溴化后与唑在无溶剂条件下经亲核取代反应合成了5个新型的16β-唑取代-3β-羟基-5α-雄甾-17-酮(3a ～3e),其结构经1H NMR和13C NMR表征.3β-羟基-16β-咪唑-5α-雄甾-17-酮(3a)的绝对构型经X-射线单晶衍射证实其16β-构型.     

2,3α-环氧-3β-咪唑-5α-雄甾-17-酮的合成及其晶体结构

5α-表雄甾经Jones氧化与溴化反应制得2α-溴-5α-雄甾-3,17-二酮(3);3与咪唑在DMF/K2CO3体系中反应成功地合成了2,3α-环氧-3β-咪唑-5α-雄甾-17-酮(4),其结构经1H NMR,13C NMR,IR,MS和XRD表征。4属单斜晶系,空间群P21,晶胞参数a=1.061 5 nm,b=0.581 7 nm,c=1.628 9 nm,α=γ=90°,β=105.594°,R1=0.042 9,ωR2=0.114 3。     

3β,17-二羟基-16-氨基-5α-雄甾烷四个立体异构体的合成

以表雄酮(1)为原料,由中间体3β-羟基-5α-雄甾-16-烯(3)合成3β,17α-二羟基-16α-氨基-5α-雄甾烷(7)和它的16β-氨基异构体(10a);由中间体3β-羟基-16α-溴-5α-雄甾-17-酮(12)合成3β,17β-二羟基-16α-氨基-5α-雄甾烷(21)和它的16β-氨基异构体(15)。上述四个立体异构体均通过化学转化以及波测试谱确证了其构型。     

一些氢化茚酮和氢化萘酮物的环氧立体构型

在不同浓度的三乙胺乙酸乙酯溶液中2-甲基环戊-1,3-二酮与氯代甲基乙烯酮(1b)反应可分别得三酮、α-氯代醇或环氧双酮. α-氯代醇经X射线单晶衍射分析结果推断出环氧双酮的环氧是β构型, 其异构体为α, 用相似的方法制得的同系环氧物也经X射线单晶衍射分析, 结果表明其环氧为β构型.     

基于乙烯基环氧构建雄甾6β,7β-亚甲基的方法

设计了简便构建甾体分子中6β,7β-亚甲基结构的合成路线.以4,6-雄二烯-3,17-二酮为起始原料,依次经硼氧化钠还原、间氯过氧苯甲酸环氧化、氢化铝锂还原性开环、Simmons-Smith加成等4步反应得到目标结构化合物6β,7β-亚甲基雄甾-3β,5β,17-三醇.中间体4β,5β-环氧-6-雄烯-3β,17-二醇经C-4-O还原开环得到顺式产物6-雄烯-3β,5β,17β-三醇,产率93.0%.没有检测到C-5-O裂解产物,从而高效地得到了高立体选择性定位导向Simmons-Smith加成所需的5β-羟基-6-甾烯结构.中间体和目标物经红外光谱、核磁共振氢谱、质谱及元素分析确证了其化学结构.     

合成4-雄甾烯-3,17-二酮-19-酸的工艺改进

以米非司酮中间体Ⅱ(19-羟基-4-雄甾烯-3,17-二酮)为原料,2,2,6,6-四甲基哌啶氧(自由基)为催化剂,磷酸盐为缓冲溶液,亚氯酸钠为氧化剂制得米非司酮中间体Ⅰ——4-雄甾烯-3,17-二酮-19-酸,产率80%,其结构经1H NMR,13C NMR和MS确证。     

5α-雄甾-16-烯-3β-对甲苯磺酸酯的溶剂解反应

5α-雄甾-16-烯-3β-对-甲苯磺酸酯(1a)和亚硝酸钠在二甲基甲酰胺(DMF)中加热反应,可生成5α-雄甾-16-烯-3α-醇(2a)及其甲酸酯(2b)和5α-雄甾-16-烯-3-酮(3)等产物。由于 DMF 参与了反应,所以推测这是一种溶剂解反应,并对反应机理进行了讨论。     

17α-羟基-16β-甲基-5,9(11)-孕甾二烯-3,20-二缩酮的D环高碳化

报导了17α-羟基-16β-甲基-4,9(11)孕甾二烯-3,20-二缩酮(1)用70%醋酸进行的水解反应. 结果得相应的3,20-二酮化合物(2). 当用98%醋酸处理(1)不能获得(2). 而是重排成17α-羟基-16β, 17β-二甲基-D-高孕甾二烯二酮(3). 当化合物(1)和(2)与含有CaCl2的70%醋酸反应获得16β, 17β-二甲-D-高-4,9(11), 15-孕甾三烯-3,17-二酮, 其得率取决于CaCl2的浓度和反应时间.     

16,17α-环氧-5α-和5β-孕甾-3β-醇-20-酮和16,17α-环氧-16β-甲基-5α-⊿9(11)-孕甾烯-3β-醇-20-酮的微生物脱氢

16,17α-环氧-5α-和5β-孕甾-3β-醇-20-酮(1,2)用诺卡氏菌脱氢分别得到4,5,6,7和8,5,6,7四个化合物,其中16,17α-环氧-⊿⁴-孕甾烯-3,20-双酮(5)是主要产物.1和2分别用节杆菌脱氢时则均得到两个20α-羟基的不饱和化合物15和16,其中⊿^1,4-双酮16是主要产物.16,17α-环氧-16β-甲基-5α-⊿⁹⁽¹¹⁾-孕甾烯-3β-醇-20-酮(3)用诺卡氏菌脱氢可得到12,13,14三个化合物,其中16,17α-环氧-16β-甲基_-⊿^4,9(11)-孕甾二烯-3,20-双酮(13)是主要产物.综上所述,5α和5β甾族化合物用诺卡氏菌脱氢主要脱去C_4,5两个氢原子形成⊿⁴-烯-3-酮化合物,而采用节杆菌可使C_l,2和C₄,5位同时脱氢形成⊿^1,4-双烯-3-酮化合物.     

6β-卤代-19-羟基-4-雄甾烯-3,17-双酮的分子内亲核取代反应

具有4-烯-3-酮结构的6β-卤代甾体化合物经强酸处理可以转变为大约1∶1的6β与6α卤代甾体化合物的混合物,混合物经分步结晶、柱层或薄层分离可以得到一定量的6α-卤代化合物。例如,6β-溴-4-雄甾烯-3,17-双酮在含有盐酸的甲醇中,45℃反应1小时,约50%的化合物转化为6α-溴代化合物。在寻     

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.     

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.     

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^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。