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In some cases, its epimer 4 was also obtained. 22 compounds were synthesized, among them 18 were new.3. Using the intramolecular Pictet-Spengler reaction to form the pentacyclic skeleton of Et-743, the byproducts 25 were obtained under various conditions. The structures of them were determined to be 1, 2-dihydro-isoquinoline compounds, and the mechanism of the reaction was proposed.B. The synthesis of the analogs of Et-743Because of the failure of removing the protective groups in compounds 14, the synthetic strategy was adjusted.

对于苄基保护的羟基化合物13a,顺利得到化合物30,然后与不同的羧酸反应得到18个酯化合物33-50;对于苄氧羰基保护的氨基化合物13b,由于脱除保护基的化合物31在空气中不稳定,所以我们采取不经分离纯化,直接与羧酸反应得到酰胺化合物53-62,然后再分别对其C-21位的羰基进行还原氰基化,得到10个酰胺目标化合物63-72,另外,我们还对羟基转化为氨基的反应进行了探索。3。

During the manufacturing of the critical intermediate cephalosporin nucleus --7-amino-3-chloro-cephalosporanic acid diphenylmethyl ester hydrochloride salt, first the feasibility of the one-pot synthetic route of open loop, closed loop and ozonization when chlorine is passed over is qualified by experiments. Then the critical factors that will influence this reaction are studied as follows: the mol ratio of triphenyl phosphite and Diphenylmethyl 3-hydroxy-7-phenylacetaminoceph-3-em-4-carboxylate-l-oxide is four to one; the quantity of the stablizer should be at least more than two to one. The temperature of the system must be 25℃ when chlorine is passed over so that the hydrochloride can be precipitated to obtain cephalosporin nucleus of cefaclor--7-amino-3-chloro-cephalosporanic acid diphenylmethyl ester hydrochloride salt.

在制备关键中间体头孢母核7-氨基-3-氯头孢烷酸二苯甲酯盐酸盐时,先通过实验验证把开环、闭环、臭氧化三步在通入氯气时并为一锅煮的合成路线的可行性之外,又研究了影响该反应的几个重要因素:亚磷酸三苯酯与3-羟基-7-头孢烷-5-亚砜-2-甲酸二苯甲酯的摩尔比为4:1;稳定剂2-甲基-2-丁烯的用量至少大于2:1,通入氯化氢气体时体系温度在25℃时盐酸盐则能够顺利析出,获得头孢克洛的头孢母核—7-氨基-3-氯头孢烷酸二苯甲酯盐酸盐。

This dissertation is mainly focused on the reactivity of methylenecyclopropanes and comprises six parts. 1 The reactions of methylenecyclopropanes with phenylsulfenyl chloride, phenylselenyl chloride and diphenyl diselenide; 2 The coupling reactions of the ring-opening products derivated from methylenecyclopropanes; 3 The palladium-catalyzed ring-enlargement of mono-aryl group substituted methylenecyclopropanes to cyclobutenes. 4 The gold-catalyzed domino ring-opening and ring-closing hydroamination of methylenecyclopropanes with sulfonamides; 5 The Lewis acid-catalyzed reactions of mono-aryl group substituted methylenecyclopropanes with diethyl ketomalonate in the presence of water; 6 The iodobenzene diacetate mediated novel 1,3-dipolar cycloaddition of methylenecyclopropanes, vinylidenecyclopropanes, and methylenecyclobutane with phthalhydrazine.

本论文主要研究了亚甲基环丙烷类化合物的一些化学反应性能,共由以下六部分组成:1、亚甲基环丙烷类化合物与苯硫氯、苯硒氯及二苯基二硒的反应;2、亚甲基环丙烷类化合物开环产物的偶联反应;3、单芳基取代的亚甲基环丙烷类化合物在钯催化剂作用下的扩环反应;4、金化合物催化磺酰胺对亚甲基环丙烷类化合物的串联开环关环氨氢化反应;5、路易斯酸催化亚甲基环丙烷类化合物与丙酮二羧酸二乙酯在有水存在下的反应;6、醋酸碘苯促进的亚甲基环丙烷类化合物、亚乙烯基环丙烷类化合物及亚甲基环丁烷类化合物与邻苯二甲酰肼的新型1,3-偶极环加成反应。

Methods Explore the optimal concentration of phurbol-12-myristate-acetate and calcium ionophore (A23817) inducing time, and optimal concentration of biotinyl sheep anti mouce IgG (bio-SAM-IgG) and horse radish peroxidasestreptavidin. The CD4(superscript +) cell enriched from peripheral blood mononuclear cells using solid phase anti-CDs monoclonal antibodies were induced by PMA and A23817 under influence of monensin and harvested in vary hours.

从健康人外周血单个核细胞中富集CD4细胞,加入莫能霉素,用不同浓度的佛波醇酯和钙离子载体(A23817)诱导CD4细胞不同时间,比较其胞内表达白细胞介素-2(IL-2)/白细胞介素-4(IL-4)的细胞百分率,确定最适诱生条件;用不同稀释度的IL-2McAb、IL-4McAb、不同浓度的生物素化羊抗鼠IgG(bio-SAM IgG)和辣根过氧化物酶标记的链霉亲和素作棋盘配比试验,确认McAb、bio-SAM IgG和HRP-SA的最适浓度,根据上述结果建立了检测细胞内细胞因子的BSA-ICC法。

The results showed that the hypoglycaemic and the urine glucose lowering effect of PCE-C in alloxan-diabetes rabbits were excellently and long-lasting. PCE-C could also reduce the serum total cholesterol and the serum triglyceride in experimental rabbits to normal level, and delay the loss of body weight of the rabbits. The glycosylated hemoglobin is the true index that reflects the long-term controlling effect for diabetes, and the experiment result affirmed the veracity and reliability of the results of the blood glucose.

结果表明,PCE-C对实验家兔血糖和尿糖的降低效果具有高效性和持续性;当血糖控制不良时,可并发血脂水平的升高,PCE-C可以使血清总胆固醇和甘油三酯恢复正常水平,同时能减缓实验家兔的体重下降;糖化血红蛋白是真正反映糖尿病长期控制效果的指标,PCE-C对实验家兔GHb的作用影响充分证实了血糖测定结果的准确性和可靠性。

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