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With NMR and DFT methods, the Michael additions of alkynyl Fischer carbene complex with a series of substituted pyrazoles as nucleophiles were also studied. All reactions follow the same three-step pathway mechanism described above. Substituents on 3-, 4- and 5- positions of the pyrazolyl ring affect the reaction in the steric and electronic manners, even to change the rate-determining step.

一系列取代吡唑与1-炔基Fischer卡宾化合物的Michael加成反应都遵循前面提出的三步机理,其中吡唑的3-, 4-, 5-位分别从电子效应和立体效应方面不同程度地影响着反应的进行,甚至改变反应的决速步骤。

In the thesis a series ofβ-pyrazolyl-α,β-unsaturated Fischer carbene complexes were synthesized and structurally characterized by NMR, IR and X-ray crystallographic determinations. Based on the dynamic nuclear magnetic resonance and density functional calculation results, a three-step mechanism is proposed for the Michael type addition of pyrazoles to the alkynyl carbene complexes.

本论文合成了一系列β-吡唑基烯基卡宾化合物,并运用核磁共振动力学实验和密度泛函理论计算方法对Michael加成反应的机理及反应速率的影响因素进行了深入探讨。

Simultaneously we prepared benzimidazolines with two methods by the reducton of benzimidazolium salts with NaBH_4 and Grignard addition with benzimidazolium salts. Thus we provided a new biomimic synthetic method for 9 kind of tetrahydro-β-carboline starting from carboxylic aicd and halid. A convenient synthetic method for preparing tetrahydro-β-carboline was provided.

本文以1,3-二甲基苯并咪唑碘盐和2-取代的1,3-二甲基苯并咪唑碘盐为原料,采用了NaBH_4还原和Grignard试剂加成两种方法,制备了9种1,3-二甲基苯并咪唑烷和2-取代的1,3-二甲基苯并咪唑烷作为四氢叶酸辅酶一碳单元转移新模型,在酸性条件下,以色胺作为接受一碳转移的亲核试剂,完成9种四氢-β-咔啉类化合物的新合成方法研究。

Hydroxy-N,N-bis(2-aminoethyl)ethylamine was synthesized by addition alkylation of diethyl triamine with epoxyethane for the first time.

以二乙烯三胺和环氧乙烷为原料,通过加成烷化反应一步合成标题化合物,经多种谱学手段表征确证。

Simultaneously we prepared benzimidazolines with two methods by the of reduction benzimidazolium salts with NaBH_4 and Grignard addition with benzimidazolium salts. Thus we provided a new biomimic synthetic method for 13 kind of tetrahydroisoquinoline starting from carboxylic aicd and halid, gave a new idea of the synthesis for new drugs.It can make many kind ofβ-carboline alkaloids which have bioactivity to antibacterium, antivirus and antitumor to start from 1,2,3,4-tetrahydro -β-carboline.

本文以1,3-二甲基苯并咪唑碘盐和2-取代的1,3-二甲基苯并咪唑碘盐为原料,采用了NaBH_4还原和Grignard试剂加成两种方法,制备了13种1,3-二甲基苯并咪唑烷和2-取代的1,3-二甲基苯并咪唑烷作为四氢叶酸辅酶一碳单元转移新模型,在酸性条件下,以2-(3,4-二甲氧基苯基)乙胺作为接收一碳转移的亲核试剂,完成了13种重要的四氢异喹啉类化合物的新合成方法研究。

In addition, we found that 4-phenyl-l,2,4-triazolinium N-ylides reacted withvarious electron-deficient olefins to afford pyrrole derivatives in good yields via 1,3-dipolar cycloaddition oxidative ring fission, In some cases, tetrahydropyrrolo[1,2-b]triazole and pyrrolo[1,2-b]triazole, which are stable and are not aromatized orcleaved in the reaction conditions, could be isolated, This is a facile and novel route forthe synthesis of pyrrole derivatives.

此外,本文研究了五员三氮杂环化合物4-苯基1,2,4-三氮唑的N-叶立德,发现在氧化剂存在下与缺电子烯烃发生1,3-偶极环加成反应生成的吡咯并[1,2-b]三氮唑,在大多数情况下开环生成吡咯衍生物,反应条件温和,收率良好,是合成吡咯衍生物的一个新的途径。

All ofthese reactions were carried out under mild conditions and are new effective methodsfor the preparation of indolizine derivatives. The reaction of phthalazinium and quinoxalinium N-ylides with electron-deficientolefins in the presence of oxidants have also been studied, it has been found that activemanganese dioxide could behave as a dehydrogenating oxidant. Pyrrolo[2,1-a]phthalazines and pyrrolo[1,2-a]quinoxalines are obtained in this way.

本文还对六员二氮杂环化合物酞嗪和喹喔啉的N-叶立德在氧化剂存在下与缺电子烯烃的l,3-偶极环加成反应作了研究,发现活性二氧化锰也是一个优良的氧化剂,并分别合成得到了吡咯并[2,1-a]酞嗪和吡咯并[1,2-a]喹喔啉衍生物。

In the first part,we studied the nucleophilic addition reactions of aldehyde, amine,Zinc and benzyl bromide in one pot to afford homobenzyl and homoallyl amines in moderate to good yields.

第一部分的工作中,我们研究了Barbier型条件下醛,胺,锌粉,溴试剂一锅法的亲核加成反应。这种反应可以高效的得到高苄基和高烯丙基胺类化合物。

Chapter 6: The analogue of the Squalamine's intermediate was synthesized from desoxycholic acid by using asymmetric addition of alkynes to the aldehydes (ee up to 99%) as key step.

第六章:利用炔对醛的不对称加成反应为工具,我们从方便易得的原料猪胆酸出发,对甾体化合物的侧链进行了改造,合成了Squalamine的中间体类似物。

Recent advances in addition,reduction,and asymmetric reactions of imines were reviewed.

亚胺是一类羰基化合物与氨的缩合产物,作者综述了近年国内外亚胺在加成、还原和不对称反应等方面的研究进展

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