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氧碘化物

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The effects of above-mentionedconditions on alkylene reaction are studied to obtain the optimum reactive conditionsby orthogonal experiments having seven factors and three levels. GCLE is chosen as material to prepare 7-phenyl acetamideyl vinyl cephalkyl acidp-methoxy benyl eatsr in the experiment. The process is as follow: GCLE reacts withiodide in solvent, and produce 3-iodid, then reacts with PPh_3 to produce Witting agent,and reacts with HCHO to produce 7-phenyl acetamideyl vinyl cephalkyl acid p-methoxy benyl eatsr in alkaline conditions.

试验选用GCLE作为原料制备7-苯乙酰氨基-3-乙烯基头孢烷酸对甲氧苄酯,反应过程如下:GCLE与碘化物、PPh3在溶剂中反应生成3位膦盐,在碱性条件下生成Wittig试剂再与HCHO反应生成7-苯乙酰氨基-3-乙烯基头孢烷酸对甲氧苄酯。

Started from D-tyrosine, we obtained the tetramic acid 96 using Jouin reaction. The assembly of the second fragment 109 was stared from 1,4-butandiol,using asymmetric alkylation reaction developed by Oppolzer as a key step. Coupling of the tetramic acid 96 with 109 provided the key intermediate 110 according to Yoshii\'s procedure. After remove protective group and Sharpless epoxidation, we obtained the key intermediate 113. Its macrocyclization to form the final product is in progress.

本论文的第二章主要对Macrocidin A开展了合成工作,我们从D构型的酪氨酸出发,经过官能团转换;利用Jouin反应生成Tetramic acid 96,另外一个片断从1,4-丁二醇开始经过多步反应生成碘化物104,利用Oppolzer发展的手性樟脑磺酰胺为辅基参与的不对称烷基化反应,引入手性甲基,生成关键中间体109,接着通过Yoshii发展的方法连接96和109生成110,经过Sharpless不对称环氧化反应建立环氧化合物,然后脱去保护基得到关环前体113,分子内的Mitsunobu反应进行关大环反应正在进行之中。

A process for the carbonylation of allylic butenyl ether (for example, methyl crotyl ether, 3-methoxybutene-1 and mixtures thereof) or mixture of butadiene and alcohol and production of beta-gamma unsaturated carboxylic acid esters (for example, methyl-3-pentenoate) utilizing a rhodium-containing catalyst for example, dicarbonylacetylacetonate rhodium(I or the like promoted with an iodide-containing compound (for example, HI, AlI3, SnI4, TiI4, CrI3, and CoI2 or the like).

一种将烯丙型丁烯基醚(如甲基巴豆基醚、3-甲氧基丁烯-1及其混合物)或者丁二烯与醇的混合物羰基化的方法,以及由含碘化物化合物(如HI、AlI3、SnI4、TiI4、CrI3和CoI2或等效物)促进,用含铑催化剂如二羰基乙酰丙酮酸铑(I或其等效物制备β-γ不饱和羧酸酯(如甲基-3-戊烯酸酯)的方法。

And to make the product be easy of purification, the excess of amine was reduced to 50% from 150%. Then the diiodoalkane reacted with dialkylmethylamine into diquaternary ammonium iodide, and obtained three diquaternary compounds whose spacer groups were -(CH2)6-, N,N"-dimethyl- N,N,N",N"-tetraoctyl-1,6-hexane diammonium diiodide, N,N"-dimethyl-N,N,N",N"-tetradecyl-1,6-hexane diammonium diiodide, N,N"-dimethyl-N,N,N",N-tetradodecyl -1,6-hexane diammonium diiodide.

对于更长间隔链的双子型季铵盐,一方面为了加快亲核取代反应速率,先将1,6-二氯己烷、3-氧杂-1,5-二氯戊烷转化成1,6-二碘己烷、3-氧杂-1,5-二碘戊烷,另一方面为了降低产物提纯的难度,将叔胺的过量由150%降到50%,使二碘代烷与双长烷基甲基叔胺在相同的温度下、反应相同的时间,经过相同的后处理,得到3个间隔链为-(CH2)6-的双子型季铵碘化物,(C8H17)2N+(CH3)(CH2)6 (CH3)N+(C8H17)2·2I-、(C10H21)2N+(CH3)(CH2)6(CH3)N+(C10H21)2·2I-和(C12H25)2N+(CH3)(CH2)6(CH3)N+(C12H25)2·2I-。

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