2,5-二甲氧基苯基烷基酮与t-BuMgCl反应的机理研究

2,5-二甲氧基苯基烷基酮1_(a-d)(烷基分别为甲基、乙基、异丙基和叔丁基)与t-BuMgCl反应后,主要生成了1,2-加成产物、1.6-共轭加成产物及还原产物,产物及其分布在不同程度上受酮的结构、反应介质以及金属镁中过渡金属杂质的含量等因素的影响。据此,提出了反应的可能机理。     

二-(4-溴-2,5-二烷氧基苯基)甲烷及其类似物的合成

报道二-(4-溴-2,5-二烷氧基苯基)甲烷的一种简便合成方法.1,4-二乙氧基-2,5-二(烷氧基甲基)苯(1)在对甲苯磺酸催化下生成柱形杯[5]芳烃化合物2;2与N-溴代丁二酰亚胺(NBS)反应,生成二-(4-溴-2,5-二烷氧基苯基)甲烷(3).该方法反应条件温和、操作简单、选择性好、收率高.2与硝酸发生硝化反应,生成二-(4-硝基-2,5-二甲氧基苯基)甲烷(4).所合成的二-(4-溴-2,5-二烷氧基苯基)甲烷和二-(4-硝基-2,5-二甲氧基苯基)甲烷经过1H NMR,13C NMR和MS表征确认.     

新型手性双功能有机催化剂的合成及其催化不对称Henry反应合成(R)-aegeline

以(S)-2-氨甲基-1-乙基吡咯烷为原料,合成了新型手性双功能有机催化剂(S)-1-[3,5-二(三氟甲基)苯基]-3-(1-乙基吡咯烷基-2-甲基)硫脲(2,产率82.2%).用2催化对甲氧基苯甲醛与硝基甲烷的不对称Henry反应,制得(R)-1-(4-甲氧基苯基)-2-硝基乙醇(3, 84%ee);3经Pd/C催化氢化得到(R)-2-氨基-1-(4-甲氧基苯基)乙醇(4);4与反式肉桂酰氯反应合成了(R)-aegeline,总产率37.6%(以对甲氧基苯甲醛计).化合物的结构经1H NMR, 13C NMR和MS表征.     

仙茅素A的全合成

首次报道了仙茅素A[2,5-双(3,4-二羟基苯基)呋喃-3-甲醛]的全合成。以3,4-二甲氧基苯乙酮为起始原料,经Paal-Knorr反应,选择性溴代及还原等反应合成了仙茅素A,其结构经1H NMR,13C NMR和ESI-MS表征。     

新型六[间-(β-噻吩基)苯基]苯衍生物的合成

3,3’-二溴二苯乙炔与β-噻吩频哪醇硼酸酯发生Suzuki偶联反应制得3,3’-二(2,5-二十二烷基-3-噻吩)二苯乙炔(7);Co2(CO)8催化7自身环三聚合成了新型六[间-(β-噻吩基)苯基]苯衍生物——六{3-[2’,5’-二(十二烷基)-3-噻吩]苯基}苯,产率86%,其结构经1H NMR和MS表征。     

延胡索素乙有关化合物的合成 Ⅲ.2,3,9,11-四甲氧基-5,6,13,13a-四氢-8H-二苯并[a,g]喹诺里嗪的合成

β-(3,4-二甲氧基苯基)乙胺(Ⅲ)与3,5-二甲氧基-α-重氮苯乙酮(Ⅳ)在氧化银存在下作用,生成N-(3',5'-二甲氧基苯乙酰基)-β-(3,4-二甲氧基苯基)乙胺(Ⅴ).以磷酰氯行Bischler-Napieralski反应,得1-(3',5'-二甲氧基苄基)-6,7-二甲氧基-3,4-二氢异喹啉(Ⅵ),再用锌粉与盐酸还原,生成1-(3',5'-二甲氧基苄基)-6,7-二甲氧基-1,2,3,4-匹氢异喹啉(Ⅶ),用甲醛行Pictet-Spengler反应得2,3,9,11-四甲氧基-5,6,13,13 a-匹氢-8 H-二苯并[a,g]喹诺里嗪(Ⅷ).     

新型扶手型分子石墨烯的合成

3,4-二苯基-2,5-二(3,5-二溴苯基)环戊二烯酮与二苯乙炔经Diels-Alder环加成反应制得1,2,4,5-四苯基-3,6-二(3,5-二溴苯基)苯(6);6经Suzuki偶联反应制得1,2,4,5-四苯基-3,6-二[3,5-二(4-十二烷基苯基)]苯基苯(8);8经路易斯酸催化的Scholl氧化脱氢关环反应合成了一个新的扶手型分子石墨烯,其结构经1H NMR,13C NMR和MALDI-TOF-MS表征。     

2,5-二甲氧基苯基烷基酮, 4-叔丁基-2,5-二甲氧基苯基烷基酮, 2,5-二甲基苯基烷基酮及其还原产物和加成产物的合成及光谱研究

本文报道一系列芳基烷基酮, 如2,5-二甲氧基苯基烷基酮, 4-叔丁基-2,5-二甲氧基苯基烷基酮2,5-二甲基苯基烷基酮及相应的一些衍生物的合成及MS, NMR,IR和UV光谱的分析结果. 并讨论了一些改进后的合成方法和有意义的副反应以及由光谱数据所揭示的这些化合物的特征结构.     

N-(2, 5-二甲氧基苯基)N-对甲苯磺酰基-β-氨酸甲酯在多聚磷酸中反应产物的结构测定

发现N-(2,5二甲氧基苯基)N-对甲苯磺酰基-β-丙氨酸甲酯(1)在多聚磷酸作用下,产生了两个新化合物。经过核磁共振、质谱、红外光谱、紫外光谱和化学性质的研究,证实了两个化合物的结构分别为N-(2,5二甲氧基-4-对甲苯基砜基苯基)β-丙氨酸甲酯(2)和N,N'-[4,4'-(2,2',5,5'-四甲氧基)-联苯亚基]双丙氨酸甲酯(4)。在多聚磷酸作用下,发生这样的反应是很少见的。     

氟烷基磺酰氟和(2S,3R)-2,3-二羟基-3-苯基丙酸甲酯的脱水环氧化反应的研究

考察了(2S,3R)-2,3-二羟基-3-苯基丙酸甲酯和几种常用的氟烷基磺酰氟试剂在有机碱存在下的脱水环氧化反应.实验结果表明,氟烷基磺酰氟能够诱导(2S,3R)-2,3-二羟基-3-苯基丙酸甲酯发生脱水环氧化反应而生成(2R,3R)-2,3-环氧-3-苯基丙酸甲酯,得率80%～92%,且产物的不对映过量(ee)值大于97%.该方法具有工业化应用前景.     

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。