一种新的手性氨基醇配体的合成

利用生产氯霉素的副产物( )-(1S,2S)-1-(对硝基苯基)-2-氨基-1,3-丙二醇经过四步反应合成了一种新的手性氨基醇催化剂———(1S,2S)-1-对硝基苯基-2-[(N-甲基-3’,4’-甲叉二氧基苯甲胺基)]-3-(叔丁基二甲基硅氧基)-1-丙醇.四步的总产率为43%.其结构经IR1、HNMR1、3CNMR确证.     

木瓜蛋白酶作用下酰基氨基酸酰苯胺的不对称合成的研究 Ⅱ.外消旋丝氨酸的析解

1.在木瓜蛋白酶作用下,N-酰基-DL-丝氨酸与苯胺作用合成了N-异戊酰-、N-正己酰-、N-苯甲酰-及N-苯甲氧羰酰-L-丝氨酸酰苯胺。 2.脂肪族取代基,正己酰-,取代的丝氨酸酰苯胺不对称合成反应的最适pH为4.9～5.1;芳香族取代基,苯甲氧羰酰-,取代的丝氨酸酰苯胺不对称合成反应的最适pH为5.0～5.2。 3.比较了四种酰基-丝氨酸的酰苯胺合成的速度。N-苯甲氧羰酰-L-丝氨酸酰苯胺最快;N-苯甲酰-,N-正己酰-其次;N-异戊酰-最慢。 4.在最适pH,酶浓度自1.31毫克蛋白N/毫升反应液提高到2.27毫克蛋白N/毫升反应液时,N-苯甲氧羰酰-L-丝氨酸酰苯胺的产率,在24小时自76.43％提高到100％。 5.在pH=5.0～5.2,柠檬酸缓冲液浓度自0.2M提高到1.0M时,N-苯甲氧羰酰-L-丝氨酸酰苯胺的产率,在12小时提高了1％。 6.选定了苯甲氧羰酰基为取代基;反应最适pH=5.0～5.2;酶浓度为2.2毫克蛋白N/毫升反应液;缓冲液浓度为0.2M;作为丝氨酸酰苯胺不对称合成的最适条件,在此条件下进行了实际析解,得到中间产物N-苯甲氧羰酰-L-丝氨酸酰苯胺,与此同时,还得到了N-苯甲酰-、N-正己酰-、N-异戊酰-L-丝氨酸酰苯胺。 7.水解N-苯甲氧羰酰-、N-苯甲酰-、N-正己酰-、N-异戊酰-L-丝氨酸酰苯胺,得到了L-丝氨酸,水解N-苯甲氧羰酰-D-线氨酸,得到了D-丝氨酸,两个旋     

3-(二甲基叔丁基硅氧基)戊二酸酐的合成

介绍了以柠檬酸为起始原料合成3-（二甲基叔丁基硅氧基）戊二酸酐的方法。该路线经脱羧反应、加氢还原、羟基保护、酯水解和再闭环,以总收率为30．3％得到目的产物。同时讨论了合成过程中发烟硫酸的浓度、加氢还原的催化剂、反应时间对环合收率的影响,得到合成3-（二甲基叔丁基硅氧基）戊二酸酐的的适宜条件。认为该法工艺路线简单,是适合工业生产的合成路线。     

合成恩替卡韦重要中间体工艺的优化

以(1S, 2R)-2-［(苄氧基)甲基］-3-环戊烯-1-醇为起始原料,经环氧化、上苄基保护基、环氧开环、上4-对甲氧基苯基二苯基（MMT）保护、Dess Martin氧化反应得到中间体(2R, 3S, 5S)-5-［2-［［(4-甲氧基苯基)二苯甲基］氨基］-6-苄氧基-9H-嘌呤-9-基］-3-苄氧基-2-［(苄氧基)甲基］环戊酮。产物结构经氢谱测试确证。与文献报导相比,该工艺操作简便,适宜放大生产。     

酰基保护的4-氨基-3,4-二氢-1(2H)-萘酮的立体选择性还原反应

1,2,3,4-四氢-1-萘胺及其衍生物是一类重要的药物合成中间体.从光学纯的(R)-和(S)-1,2,3,4-四氢-1-萘胺出发,首先经乙酰化、苯甲酰化和邻苯二甲酰化反应制备相应酰胺,然后在高锰酸钾作用下氧化生成了氨基萘酮衍生物,收率为65%～85%.这些不同酰基保护的氨基萘酮衍生物经硼氢化钠(NaBH4)和二异丁基氢化铝(DIBAL-H)还原后得到两种构型的氨基萘醇混合产物,经二维核磁共振氢谱的核磁欧沃豪斯效应(NOE)推断,此还原反应的主产物是顺式构型的氨基萘醇,当(R)-或(S)-邻苯二甲酰化的氨基萘酮经DIBAL-H还原后主产物为顺式的氨基萘醇4ca和7ba,其非对映异构体过量(de)百分比分别为92.6%和98.2%.     

骨髓增殖性肿瘤治疗药物TG101348的合成工艺研究

研究了骨髓增殖性肿瘤治疗药物TG101348的合成工艺.将2,4-二羟基-5-甲基嘧啶与三氯氧磷、氨水发生氯化、取代反应生成2-氯-4-氨基-5-甲基嘧啶（Ⅲ）,而后Ⅲ与N-叔丁基-3-溴苯磺酰胺（Ⅰ）发生Buchwald偶联反应得到3-[（2-氯-5-甲基-4-嘧啶基）胺基]-N-（叔丁基）苯磺酰胺（Ⅳ）,Ⅳ再与CH3 OH-HCl反应得到3-[（2-氯-5-甲基-4-嘧啶基）胺基]-N-（叔丁基）苯磺酰胺盐酸盐（Ⅴ）,最后Ⅴ与1-（4-氨基苯氧乙基）吡咯烷（Ⅵ）发生亲核取代反应得到TG101348,HPLC测得TG101348的纯度为99.7;.     

染料中间体4-羟基-6-氨基-N-甲基-2-萘磺酰胺的合成研究

以4-羟基-6-氨基-2-萘磺酸为原料,经乙酰化保护氨基和羟基,再将4-乙酰氧基-6-乙酰氨基-2-萘磺酸钠用氯磺酸/氯化亚砜将磺酸基转变为磺酰氯,然后与脂肪胺甲胺缩合生成磺酰胺,最后经水解除去乙酰基合成了染料中间体4-羟基-6-氨基-N-甲基-2-萘磺酰胺.产物结构经红外光谱、元素分析与质谱确证.     

线型聚苯乙烯支载(4S)-[4″-(4′-(4-乙烯基苄氧基)苄氧基)苄基]-1,3-噁唑烷酮的合成

以L-酪氨酸为原料,经过羧基酯化、氨基保护、还原、关环、聚合等6步反应得到了结构新颖的手性助剂——线型聚苯乙烯(NCPS)支载(4S)-[4″-(4′-(4-乙烯基苄氧基)苄氧基)苄基]-1,3-噁唑烷酮.中间产物用IR,1H NMR,13C NMR,元素分析等方法进行了结构表征,波谱解析结果与化合物结构相符合.     

THP保护拉坦前列素内半缩醛的合成

以商品化的(1S,5R,6R,7R)-7-苯甲酰氧基-6-[3(S)-3-羟基-5-苯基-1(E)-戊基]-2-氧杂双环[3.3.0]辛烷-3-酮为原料,经4步反应合成一种四氢呋喃(THP)保护的拉坦前列素内半缩醛,并用核磁共振氢谱(1 H NMR)、核磁共振碳谱(13 C NMR)、红外光谱(IR)和质谱(MS)对产物进行表征.结果表明,终产物的收率为65.7%,纯度为99.0%.     

7(6)-羟基黄酮的简便合成及相关谱学分析

以2,4（5）-二羟基苯乙酮和苯甲酰氯为原料,在碳酸钾催化下-步合成了相应的β-丙二酮型化合物1-[4-（苯甲酰氧基）-2-羟基苯基]-3-苯基-l,3-丙二酮（8a）和1-[5-（苯甲酰氧基）-2-羟基苯基]-3-苯基-1,3-丙二酮（8b）。化合物8a和8b分别在l％氢氧化钾水溶液中回流处理,分别得到7-羟基黄酮（9a）和6-羟基黄酮（9b）。用红外光谱、核磁共振氢谱和质谱对所合成的化合物进行了结构表征。     

Markedness and its Interpretation in Language Use

Language markedness is a common phenomenon in languages, and is reflected from hearing, vision and sense, i.e. the variation in the three aspects such as phonology, morphology and semantics. This paper focuses on the interpretation of markedness in language use following the three perspectives, i.e. pragmatic interpretation, psychological interpretation and cognitive interpretation, with an aim to define the function of markedness.     

Features of Women's language

Language is a means of verbal communication. People use language to communicate with each other. In the society, no two speakers are exactly alike in the way of speaking. Some differences are due to age, gender, statue and personality. Above all, gender is one of the obvious reasons. The writer of this paper tries to describe the features of women＇s language from these perspectives： pronunciation, intonation, diction, subjects, grammar and discourse. From the discussion of the features of women＇s language, more attention should be paid to language use in social context. What＇s more, the linguistic phenomena in a speaking community can be understood more thoroughly.     

低渗透非均质砂岩油藏启动压力梯度研究

理论推导与室内实验相结合,建立了低渗透非均质砂岩油藏启动压力梯度确定方法。首先借助油藏流场与电场相似的原理,推导了非均质砂岩油藏启动压力梯度计算公式。其次基于稳定流实验方法,建立了非均质砂岩油藏启动压力梯度测试方法。结果表明:低渗透非均质砂岩油藏的启动压力梯度确定遵循两个等效原则。平面非均质油藏的启动压力梯度等于各级渗透率段的启动压力梯度关于长度的加权平均;纵向非均质油藏的启动压力梯度等于各渗透率层的启动压力梯度关于渗透率与渗流面积乘积的加权平均。研究成果可用于有效指导低渗透非均质砂岩油藏的合理井距确定,促进该类油藏的高效开发。     

On Tragic Consciousness In The Works By Ernest Hemingway

As an American modern novelist who were famous in the literary world, Hemingway was not a person who always followed the trend but a sharp observer. At the same time, he was a tragedy maestro, he paid great attention on existence, fate and end-result. The dramatis personae's tragedy of his works was an extreme limit by all means tragedy on the meaning of fearless challenge that failed. The beauty of tragedy was not produced on the destruction of life, but now this kind of value was in the impact activity. They performed for the reader about the tragedy on challenging for the limit and the death.     

Achieving Unusual States of Matter Under High Pressure

正The periodicity of the elements and the non-reactivity of the inner-shell electrons are two related principles of chemistry,rooted in the atomic shell structure.Within compounds,Group I elements,for example,invariably assume the+1 oxidation state,and their chemical properties differ completely from those of the p-block elements.These general rules govern our understanding of chemical structures and reactions.Using first principles calcula-     

Exchange-Correlation and Electronic Excitation Energies from Pairing Matrix Fluctuations

We have developed an adiabatic connection to formulate the ground-state exchange-correlation energy in terms of pairing matrix linear fluctuations.This formulation of the exchange-correlation energy opens a new channel for density functional approximations based on the many-body perturbation theory.We illustrate the potential of such approaches with an approximation based on the particle-particle Random Phase Approximation(pp-RPA).This re-     

Density Functional Theory for the Response of Periodic Systems to Electric Fields Based on the Vector Potential Approach

正The electronic and nuclear(structural/vibrational)response of 1D-3D nanoscale systems to electric fields gives rise to a host of optical,mechanical,spectral,etc.properties that are of high theoretical and applied interest.Due to the computational difficulty of treating such large systems it is convenient to model them as infinite and periodic(at least,in first approximation).The fundamental theoretical/computational problem in doing so is that     

On the Thermodynamic Limit for Responses to Static Electromagnetic Fields

For molecular systems,the quantum-mechanical treatment of their responses to static electromagnetic fields usually employs a scalar-potential treatment of the electric field and a vector-potential treatment of the magnetic field.Although the potential for each field separately is associated with the choice of an(unphysical)origin,the precise choice of the origin for the electrostatic field has little consequences for the results.This is different for the     

Call for Papers

<正>"The Journal of Shanghai Normal University:Mathematics"is published by Shanghai Normal University as regular issues of The Journal of Shanghai Normal University each year from 2014 in English.The editors-in-chief of the issues are professors Yuhao Cong and Maoan Han.The Journal of Shanghai Normal University was started in 1958 with     

Journal of Donghua University ( English Edition) Contents of Volume 31

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