α—氯芳基乙酮的合成

α┐氯芳基乙酮的合成ＩＭＰＲＯＶＥＤＳＹＮＴＨＥＳＩＳＯＦα┐ＣＨＬＯＲＯＡＲＹＬＭＥＴＨＹＬＫＥＴＯＮＥＳ曹松＊王蔚ａ樊爱龙ａ（滁州师专化学系，安徽２３９０１２；ａ南京大学化学系，江苏２１００９３）ＣＡＯＳｏｎｇ＊，ＷＡＮＧＷｅｉａ，ＦＡＮＡｉ－Ｌ...     

雷酚酮内酯的半合成研究

以雷酚内酯为原料，经甲基化。氧化和去甲基化三步反应合成了雷酚酮内酯，它是新一代抗白血病药物一雷公藤甲素全合成的重要中间体。     

邻乙基苯肼盐酸盐的合成

邻乙基苯肼盐酸盐的合成ＳＹＮＴＨＥＳＩＳＯＦ２┐ＥＴＨＹＬＰＨＥＮＹＬＨＹＤＲＡＺＩＮＥＨＹＤＲＯＣＨＬＯＲＩＤＥ潘富友＊杨建国（台州师范专科学校化学系，浙江３１７０００）ＰＡＮＦｕ－Ｙｏｕ＊ＹＡＮＧＪｉａｎ－Ｇｕｏ（Ｄｅｐｔ．ｏｆＣｈｅｍｉｓｔｒｙ...     

应用固定化D-氨基酸氧化酶转化头孢菌素C为7-ACA

D-氨基酸氧化酶（DAAO）是两步酶法催化头孢菌素C（CPC）生成7-氨基头孢霉烷酸（7-ACA）的重要酶之一。利用固定化DAAO催化CPC的转化液中，酮酸中间体随批次的增加逐渐减少，反应至第13批时，转化基本完全。当转化液pH由7．2升至7．6时，终止反应，转化率和收率分别达99．6％和93％。分次补加固定化DAAO，可连续转化132批。     

4′-溴甲基-2-联苯甲酸叔丁酯的合成

4′-溴甲基-2-联苯甲酸叔丁酯（1）是降压药替米沙坦（telmisartan）的合成中间体。本研究参考文献，用4′-甲基-2-氰基联苯（2）经水解、酯化、溴代制得1（图1），并进行了改进。2在乙醇-水（5：1）中于80℃反应16h，得粗品纯度99％，可直接用于下步反应。酯化时，文献用浓硫酸催化或直接通入异丁烯制取，用HPLC跟踪反应进程，经试验结果不理想。现改在0℃用叔丁醇加DCC酯化，收率90％（文献：86．1％）。溴化时用氯仿代替四氯化碳㈨作溶剂。改进后的1总收率61％。     

Long-term application of diethylstilbestrol upregulates expressions of μ- and m-calpains in pituitary intermediate lobe of female Wistar rats

BACKGROUND: During formation of prolactin neoplasia, how cells and its structure in adenohypophysis affect prolactin cells should be further studied. Intermediate lobe can be regarded as a driving region to release prolactin (PRL) and may promote formation of prolactin neoplasia in pituitary anterior lobe. OBJECTIVE: To observe the effect of diethylstilbestrol (DES) on the expressions of μ and m-calpains in pituitary intermediate lobe of female Wistar rats. DESIGN: Observational contrast animal study. SETTING: Beijing Neurosurgical Institute. MATERIALS: A total of 21 female Wistar rats, 3 weeks old weighing 70–80 g were housed with free access to tap water and standard pellet food. They were kept in a CL-grade condition, at (24±1)℃ and a humidity of (55±5)%, and with a 12 hours day-night cycle. Caprine anti-μ- and m-calpains antibodies were provided by Santa Cruz Biotechnology, CA, USA; rabbit-anti-PRL antibodies by Dako, Denmark; rabbit-anti-ACTH antibody by Boster Company, Wuhan. METHODS: The experiment was carried out in Pathophysiological Department and Animal Laboratory, Beijing Neurosurgical Institute from August 2006 to January 2007. ① Rats were randomly divided into groups with 7 in each group, including vehicle control group, in which rats were injected intraperitoneally with sun-flower seed oil (1 mL/kg, twice a week) for 16 weeks; DES group, where animals were administered with DES (5 mg/kg, twice a week) for 16 weeks; DES + vehicle control group, in which DES was administered for 12 weeks at the same dose with those in DES group, and then was discontinued and replaced by sun-flower seed oil (1 mL/kg, twice a week) for the following 4 weeks. ② At 16 weeks later, pituitary tissue was dealt with HE staining and PRL immunohistochemical examination to observe evoke of tumor; meanwhile, immunohistochemical examination was used to observe expression of PRL of pituitary anterior lobe, expressions of μ- and m-calpains of pituitary intermediate lobe and distribution of adrenocorticotropin. MAIN OUTCOME MEASURES: ① Expression of PRL of pituitary anterior lobe, expressions of μ- and m-calpains of pituitary intermediate lobe and distribution of adrenocorticotropin. ② Morphological observation of pituitary tissue. RESULTS: All 21 rats were involved in the final analysis. ① Results of immunohistochemical examination: Morphological changes of neoplasia in DES group were strongly positive to PRL, and this suggested that formation of prolactin adenoma was observed in pituitary tissue. As compared with vehicle control group, expression of adrenoeorticotropic hormone (ACTH) was increased in both DES group and DES + vehicle control group. In addition, expressions of μ- and m-calpains in pituitary intermediate lobe were higher in DES group than that in vehicle control group. Otherwise, expressions of m-calpains in pituitary intermediate lobe was decreased in DES + vehicle control group, but expression of μ-calpains was still increased. ② Morphological observation of pituitary tissue: Gland tubes were orderly arranged in rats in vehicle control group. Anterior pituitary gland in rats of DES group demonstrated an apparent disappearance of gland tubes and a relatively large-scaled vasculature formation, namely the vascular lake lined by tightly arranged endothelial cells. Local integrated tumor cell arrangements were also detected. In addition, the border between the IL and the anterior lobe was locally blurred. The definite tumor-like changes in pituitary tissues were confirmed in 6 of 7 female Wistar rats in DES group, and one spontaneous occurrence of tumor formation was found in vehicle control group. In DES + vehicle control group, DES withdrawal led to the subtile emergence of gland tube cavity, although tumor-like cells still existed in 4 of 7 rats, suggesting occurrence of the tumor regression due to the withdrawal of DES. CONCLUSION: A long-term application of DES can enhance the expressions of ubiquitours neutral cysteine protease in pituitary intermediate lobe and this suggests that both of them play a key role in release of hormone and formation of prolactin neoplasia through directly promoting PRL expression and release of neighboring pituitary intermediate lobe.     

金龟子绿僵菌对甾族化合物的11α—羟化

研究筛选金龟子绿僵菌及其的１１α－羟化作用与生物氧化条件之间关系和底物分次添加方式影响。生物转化条件如培养基组成、菌龄、接种量等因素。在培养结果时取样作ｐＨ、菌丝量和转化率检测。结果：当底物浓度为０．２％转化率为３６％。结论：金龟子绿僵菌作为１９－去甲基－１３－乙基－雄甾－４－烯－３，１７－双酮（ＦＡ）的１１α－羟化是很有效的。     

高效液相色谱法测定头孢拉定中间体环己烯甘氨酸

环己烯甘氨酸是头孢拉定合成反应中的重要中间体，ＰＨＧ是产物中的主要杂质。我们采用ＨＰＬＣ法，以７－ＡＤＣＡ为内标，对其进行了定量分析，结果表明：内标法与外法结果基本一致。     

(E)-3-〔3-4-(氟苯基)-1-(1-甲基乙基)-1H-吲哚-2-基〕-2-丙烯醛的合成

（Ｅ）３〔３（４氟苯基）１（１甲基乙基）１Ｈ吲哚２基〕２丙烯醛（２）是合成氟伐他汀的关键中间体．从苯胺经异丙基化、与２氯１（４氟苯基）乙酮缩合、氯化锌催化的分子内环合、在Ｖｉｌｓｍｅｉｅｒ反应条件下与３（Ｎ甲基Ｎ苯基）丙烯醛反应合成（２），四步反应总收率为５４％．