草酸依地普仑的合成

以5-氰基苯酞为起始原料,经亲核加成、水解、手性拆分,环化和成盐等反应制得抗抑郁药草酸依地普仑,以5-氰基苯酞计,总收率为19%.该方法工艺简单,条件温和,收率较高,适合工业化生产.     

炔基苯基高碘盐的合成与应用

芳基乙炔与羟基对甲苯磺酰氧基碘苯在分子筛催化下反应,生成苯乙炔基对甲苯磺酰氧基碘苯,产率44%-49%。1-三甲基硅基炔与亚碘酰苯在三氟化硼乙醚溶液中反应,经对甲苯磺酸钠水溶液处理后,得炔基对甲苯磺酰氧基碘苯,产率46%-65%。     

6,11-二氢二苯骈[b,e]氧杂-11-酮-2-乙酸的合成

采用对羟基苯乙酸(Ⅱ)和苯酞为原料,在甲醇钠的催化下,以n(Ⅱ)∶n(苯酞)∶n(甲醇钠)=1.0∶1.1∶2.2,于130℃反应7h制备4-(2-羧基苄氧基)苯乙酸(Ⅲ)。Ⅲ与乙酰氯经氯化、环合得6,11-二氢二苯骈[b,e]氧杂-11-酮-2-乙酸(Ⅰ),该步优化的反应条件为:n(Ⅲ)∶n(乙酰氯)=1∶1.25,反应温度为100℃,反应时间为6h。以Ⅱ计,总收率达48.16%,Ⅰ的结构经IR、1H NMR和MS确证。     

液晶单体4-(反-4-正丙基环己基)-氟苯的合成

以新蒸馏过的环己烯和丙酰氯为原料,与三氯化铝和氟苯一起采用“一锅法”制备4-(4-丙酰基环己基)-氟苯。首先将环己烯与丙酰胺的混合物在搅拌下于-10℃逐滴加入到三氯化铝的氟苯悬浮液中,而后将该反应混合物在40℃下搅拌反应2h即可得4-(4-丙酰基环己基)-氟苯。环己烯、丙酰氯、三氯化铝、氟苯投料摩尔比为1∶1∶1.5∶2。第二步反应是用黄鸣龙法将4-(4-丙酰基环己基)-氟苯还原为4-(反-4-正丙基环己基)-氟苯。最后经减压蒸馏和数次重结晶得到纯度大于99.5%的产品4-(反-4-正丙基环己基)-氟苯。     

苯嗪草酮的合成

以苯甲酰腈为起始原料,经水解酯化、希夫碱反应、成酰肼和环合等4步反应合成苯嗪草酮(四步总收率72.2%,以苯甲酰腈计)。通过工艺改进,简化了操作,提高了产品品质(HPLC纯度99.23%),降低了生产成本,改进后的工艺适合工业化生产。     

5-氰基苯酞的合成

以邻苯二甲酰亚胺为起始原料经过硝化、还原、环合、Sandmeyer反应合成5-氰基苯酞,其结构经1HNMR、13CNMR、MS确定.总收率达24.5%.     

苯嗪草酮的合成

苯甲酰甲酸甲酯首先与乙酰肼、水合肼反应得到2-乙酰肼腙-2-苯基-乙酰肼,然后以正丁醇为溶剂,在无水乙酸钠存在下环化脱水得苯嗪草酮。反应总收率71．3％（以苯甲酰甲酸甲酯计）,苯嗪草酮的含量为98％。     

6，11-二氢二苯骈[6，e]氧杂[艹卓]革-11-酮-2二乙酸的合成

采用对羟基苯乙酸（Ⅱ）和苯酞为原料，在甲醇钠的催化下，以n（Ⅱ）：n（苯酞）：n（甲醇钠）=1．0：1．1：2．2，于130℃反应7h制备4-（2碳基苄氧基）苯乙酸（Ⅲ）。Ⅲ与乙酰氯经氯化、环合得6，11-二氢二苯骈[b，e]氧杂[艹卓]-11-酮-2-乙酸（Ⅰ），该步优化的反应条件为：n（Ⅲ）：n（乙酰氯）=1：125，反应温度为100％，反应时间为6h。以Ⅱ计，总收率达48．16％。Ⅰ的结构经IR、^1H NMR和MS确证。     

活性炭负载CuO催化氧化苯偶姻反应研究

以活性炭为载体制备负载型CuO催化剂,将其作为过氧化氢氧化苯偶姻合成苯偶酰催化剂。研究了氧化剂用量、反应温度、催化剂用量等条件对氧化反应的影响,并采用傅里叶变换红外光谱和熔点测定对产物进行了表征,实验结果表明:该催化剂催化性能良好。较优实验条件为:负载量为6.4%(占负载型催化剂总质量比),氧化铜负载量约0.13g,总反应时间共4h,反应初始温度为50℃,反应1h后,升至90℃反应1h,最后至110℃反应2h,过氧化氢与苯偶姻摩尔比2∶1,苯偶酰收率可达96%以上。     

消旋正丁基苯酞拆分方法的改进

对消旋正丁基苯酞的化学拆分方法进行了改进,提高了终产物的光学纯度和总收率。方法如下:先将消旋正丁基苯酞在氢氧化钠水溶液中开环、酸化,再与拆分试剂——左旋α-苯乙胺反应得到2个非对映异构体胺盐的混合物,然后用丙酮和左旋α-苯乙胺的混合溶液重结晶,得到左旋正丁基苯酞的左旋α-苯乙胺盐,酸性条件下将其解离并环合,减压蒸馏得到左旋正丁基苯酞,并通过对比实验确定了最优化的工艺条件。改进后的拆分方法有效抑制了左旋正丁基苯酞的左旋α-苯乙胺盐在重结晶过程中的热分解,提高了产物左旋正丁基苯酞的光学纯度(99%ee)和总收率(25%)。     

硫双威原药中杂质成分分析

用高效液相色谱/质谱联用技术及紫外光谱法分离并鉴定了硫双威原药中的主要杂质,确定了硫双威原药中的主要杂质为灭多威(杂质1),吡啶盐酸(杂质2),硫双威异构体(E,Z)(杂质3),硫双威异构体(E,E)(杂质4)及硫(杂质5)。     

盐酸头孢唑兰的合成研究

盐酸头孢唑兰是第四代头孢菌素类抗菌素.以7h氨基头孢烷酸(7-ACA)为原料,经硅烷化反应后,与1-三甲基硅基咪唑并[1,2-b]哒嗪氢盐酸盐反应,得到中间体3-氨基-3-[(3-咪唑并[1,2-b]哒嗪)甲基]-3-头孢烯-4-羧酸盐酸盐(7-ACP),然后与(Z)-2-(5-氨基-1,2,4-噻二唑-3-基)-2-甲氧亚氨基硫代乙酸(S-2-苯并噻唑)酯进行缩合反应,得到盐酸头孢唑兰.反应条件优化后总收率可达25％,产品纯度在98％以上.     

Isomerization of silyl ketene acetals: Models for the propagating chain end in group transfer polymerization

The rate of E/Z isomerization for the propagating end in group transfer polymerization (GTP) of methyl methacrylate (MMA) is comparable to the rate of propagation for bifluoride catalysis, in contrast to bibenzoate catalysis where propagation is faster. Methyl 2,2,4-trimethyl-5-methoxy-5-(trimethylsiloxy)pent-4-enoate, 4 (the product of the initiation step in the GTP of MMA), was used as the model of the GTP living end. The rate of monomer addition to 4 was independent of the starting E/Z isomer ratio. The observation of random tacticity in the polymers prepared via anionically catalyzed GTP can be adequately explained by comparable rates of E/Z isomerization and propagation or in the case of bibenzoate catalysis, by the assumption that E and Z propagating ends react with similar stereochemistry. Silyl ketene acetal 2 (a model of the polyacrylate propagating end) underwent HgI₂ catalyzed E/Z isomerization at a rate comparable to the polymerization of ethyl acrylate.     

HPLC在红霉素肟的醚化反应中的应用

在克拉霉素合成工艺中,红霉素肟的醚化保护是最重要的一步。作者研究确立了一种反相高效液相色谱法,能有效地对醚化产物红霉素A9 (1 异丙氧环己基)肟及其与工艺相关的化合物进行分离和定量分析。色谱柱为DIKMA公司的InertsilODS-3(150mm×4 6mm,粒径5μm)。流动相为V(乙腈)∶V〔c(KH2PO4)=0 033mol/L〕=48∶52,流速1 5mL/min,UV检测波长205nm,柱温30℃。肟醚在进样量为10～50μg内具有良好的线性关系,为醚化反应的工艺优化和监控提供了一个可在10min内快速而可靠的检测方法。作者还对红霉素A9 (1 异丙氧环己基)肟的E和Z异构体进行了定性分离和色谱行为研究,结果表明Z异构体比E的保留时间短,流动相V(乙腈)∶V〔c(KH2PO4)=0 033mol/L〕=45∶55时,分离度最好。     

替诺昔康中间体的合成

以3-氯磺酰基-2-甲氧羰基噻吩为原料,用甘氨酸甲酯盐酸盐代替肌氨酸甲酯盐酸盐,经缩合、闭环、与硫酸二甲酯进行N-甲基化反应合成了替诺骨康的中间体4-羟基-2-甲基-2H-噻吩并[2,3-e]-1,2-噻嗪-3-甲酸甲酯-1,1-二氧化物。通过^1H NMR确认了产物的结构。     

Field evidence of synergism and inhibition in the sesiidae sex pheromone system

The E,Z, Z,Z, and Z,E geometric isomers of 3,13 octadecadien-1-ol acetate were used singly and in binary combinations to trap sesiids in Wisconsin cherry orchards. The Z,E isomer alone did not capture any sesiids. A synergistic effect, however, of Z,E onSynanthedon pictipes response to its pheromone E,Z was demonstrated for the first time. Strong inhibitory effects of the Z,Z isomer onS. pictipes response to E,Z, and of the E,Z isomer onS. scitula response to Z,Z, were found. As little as 0.5% of Z,Z in E,Z completely inhibited theS. pictipes response. This species' response was also reduced by 85% when Z,Z was evaporated at 4 points, each ca. 6 m from the pheromone trap. Consistencies and discrepancies of the data with relevant experimental results from other geographical areas are briefly discussed.Lepidoptera: Sesiidae (=Aegeriidae), the clearwing moths.Research supported by the College of Agriculture and Life Sciences, University of Wisconsin, Madison, and by the Wisconsin Red Tart Cherry Ind. Market. Order.     

Autoxidation of Methyl α-Eleostearate – Identification of the Low Molecular Weight Decomposition Products

Methyl α-eleostearate dissolved in pentane was stored at room temperature in the darkness. The low molecular weight products formed were compared with those resulting form reductive ozonolysis of methyl α-eleostearate. Pentanal, 2(E)-heptenal, 2(E),4(E)-nonadienal, methyl 9-oxononanoate, methyl 11-oxo-9(Z)-undecenoate and methyl 13-oxo-9(Z), 11(E)-tridecadienoate were formed in both processes. The storage experiment also yielded isomers of 2,4-nonadienal and methyl 13-oxo-9, 11-tridecadienoate, whose sterochemistry was not clarified.     

The preparation and characterization of the methoxy derivatives of polyunsaturated fatty acids: Stabilized product analogs of lipoxygenase catalysis

The products from the action of soybean lipoxygenase on a series of polyunsaturated fatty acids have been converted in 2 steps into the corresponding methoxy derivatives. The product hydroperoxides were reduced in situ to alcohols with sodium borohydride. The ethers were generated by treatment of the alcohols with sodium hydride and methyl iodide in tetrahydrofuran. 13-Methoxy-9(Z),11(E)-octadecadienoic, 15-methoxy-11(Z),13(E)-eicosadienoic and 15-methoxy-5(Z),8(Z),11(Z), 13(E)-eicosatetraenoic acids were thus prepared. The methyl ethers were analyzed and the structures established by high performance liquid chromatography, nuclear magnetic resonance and infrared spectrometry, polarimetry and mass spectroscopy (as methyl esters). The methylation reaction proceeds without molecular rearrangements or racemiziation.     

Synthesis of methylidene phthalide, its polymerization, and properties of poly(methylidene phthalide)

Different approaches to the synthesis of methylidene phthalide, which shows promise as a monomer for the obtainment of polymerization heat-resistant (co)polymers, are considered. Regularities are established for the best variant of methylidene phthalide synthesis through the action of thionyl chloride on o-acetylbenzoic acid in DMF. Optimum conditions are found for the synthesis of methylidene phthalide with a high yield and purity. Polymerization of high-purity methylidene phthalide yields (co)polymers in the form of absolutely colorless optically transparent heat-resistant glasses. Methylidene phthalide copolymers with styrene, methyl methacrylate, acrylonitrile, and methyl acrylate containing ≥40 mol % methylidene phthalide units have glass-transition temperatures as high as 220–260°C. In addition, methylidene phthalide (co)polymers are promising as smart polymers.     

色氨酸酯类盐酸盐的合成及其经皮促渗活性

以对甲苯磺酰氯(PTSC)、甲醇和色氨酸为原料,采用一锅法合成他达那非重要中间体色氨酸甲酯盐酸盐,对合成工艺进行了优化,且利用该方法成功合成其他目标化合物。结构均经红外、核磁以及质谱确定。同时考察了目标产物的体外透皮促渗活性及其对应的最佳用量,结果显示,色氨酸甲酯盐酸盐无论单独使用还是和薄荷醇共同作用均对阿昔洛韦的经皮渗透吸收有明显促进作用,当色氨酸甲酯盐酸盐的用量为0. 6%时,无论单独使用还是和薄荷醇共同作用效果均是最好的。