烯化

The third part of this thesis is reactive simulating calculation In this section, some well-known auxiliaries are selected to compute in density functional theory B3LYP on Gaussian 03, from which the relationship between reaction active energies of transition states and enantiomeric excess of chiral products homoallylic alcohols isobtained based on relative reactive ratio theory. Using this relationship, calculations on the reaction of more than eight auxiliaries with four other aldehydes are carried out in AMI and MNDO, proving that N,N\'-dibenzyl tartamide has higher enantioselectivity than others in this reaction.

第三部分为计算化学部分，运用密度泛函理论B3LYP方法在Gaussian03软件上对已经报道的几种手性配体参与的醛不对称烯丙基化反应过程进行模拟计算，基于相对反应速率理论找出两种构型过渡态间活化能的差异与产物光学收率之间的关系；并以此为基础，用AM1和MNDO方法对上述合成的几种配体控制的反应过程进行量化计算，从而在理论上证实了N-苄基酒石酸二酰胺配体在醛的不对称烯丙基化反应中具有较高的立体选择性。

In a similar way, using N,N\'-dibenzyl tartamide as auxiliary,-(2-methyl)allyl-2-chloro-phenyl-methyl azide, a vital intermediate of Repaglinide, can be prepared via asymmetric allylation of o-chlorobenzaldehyde in

产物经氧化和碘加成内酯化反应得到阿伐他汀中间体(3R，5S)-3-羟基-5-碘甲基戊内酯(10)；将N-苄基酒石酸二酰胺用于邻氯苯甲醛的不对称烯丙基化反应以较高光学收率得-甲基烯丙基-2-氯苯基-甲基醇

An alicyclolic epoxy resin with endocyclic structure,namely hydrogenated terpinene-maleic ester type epoxy resin, was synthesized from the raw material hydrogenated terpinene-maleic anhydride.

以氢化萜烯马来酸酐为原料与环氧氯丙烷反应合成一种含桥环结构的饱和脂环基环氧树脂——氢化萜烯酯型环氧树脂。

Other methyl nucleophiles includingMeMgBr, MeCeCl2, MeTiCl3, Me3Al, Me3ZnMgCl, MeMnClwere tried, but in all these cases no detectable amount of exo-C8-methylated product was obtained. Although protecting C3-carbonyl as 1,3-dioxolanes could be achieved, the serious enolization of C8-carbonyl was still problematic. Converting C9-furan ring to α,β-butenolide did depress the enolization, but desired C8-methylation was completely replaced by migration of the double bond of the butenolide.

在本论文的早期阶段，主要着眼于解决二环[3.2.1]-C8-羰基加成甲基所遇到的C9-呋喃环差向异构化和C3与C8两个羰基之间化学选择性的问题：通过引入不同金属降低甲基试剂的碱性并没有取得甲基化的成功；通过不同的方法将C3-羰基掩蔽，但是C8-羰基的烯醇化依然无法抑制；虽然通过将呋喃环转化为α，β-不饱和-γ-丁内酯可以抑制烯醇化，但内酯环上的双键迁移又成了新的竞争反应。

The dissertation mainly consists of two parts:1. The Reaction Chemistry of Alkynes under Palladium Catalysis Part 1 studies the reaction α,β-unsaturated carbonyl compounds with alkenylpalladium intermediate generated by nucleopalladation, and discovered 1 the Pd-catalyzed tandem addition reaction of halides, alkynes and α,β-unsaturated carbonyls,2 the four-component tandem addition reaction of halides, alkynes and α,β-unsaturated carbonyls, 3 the tandem intramolecular oxypalladation-conjugate additionreaction of alkynoic acids with α,β-enals. These new reactions provide notonly efficient highly stereoselective methods for the synthesis of γ,δ-unsaturated,polyunsaturated carbonyl compounds and γ-lactonic aldehydes, but also thebasic transformations for a number of C-C bond formation reactions which can be usedto design synthesis of many acyclic, cyclic or polycyclic compounds.

本论文的主要工作分为两个部分：一、钯催化下炔烃的反应化学在本小组前人工作的基础上，我们详细研究了炔烃亲核钯化产生的烯基钯中间体与α，β-不饱和羰基化合物的反应，发现两价钯催化下卤离子-炔烃-α，β-不饱和醛酮的串联加成反应、卤离子-炔烃-α，β-不饱和醛酮的西组分串联加成及炔酸分子内氧钯化-串联Michael型加成反应；由此发展了γ，δ-不饱和醛酮、多不饱和羰基化合物和带有醛酮基侧链的γ-丁内酯衍生物的高立体选择性合成方法，这一过量卤离子存在下的烯基钯对α，β-不饱和羰基化合物共轭加成反应的发现，为大量碳-碳键形成反应的实现提供了基础，使我们能够从这一基本反应出发，设计和开发多种分子内、分子间的碳碳成键反应，以好的立体、区域选择性组建开链、环状及多环类型的化合物。

Benzene perfluorous nonene ether was prepared by the reaction of perfluo-rous nonene (C9F18) and phenol,and the molecular structure of which was identified by IR and NMR spectra.

以全氟壬烯、苯酚和氯磺酸为主要原料，经醚化、磺化和中和反应制备对全氟壬烯氧基苯磺酸表面活性剂，用红外光谱和19FNMR，1HNMR对分子结构进行了表征。

In the 29 Aroma material studied, the content of the material having important effect such as norambreinolide, octadecanoic lactone(1), octadecanoic lactone(2), octadecanoic, 8,15-labdanum-1-ol,8,12-external oxidative labdanum-14-en-2-ol(1), 8,12-external oxidative labdanum-14-en-2-ol(2), 8,13-external oxidative labdanum-14-en-13-one(1), 8,13-external oxidative labdanum-14-en-13-one(2) Dihydroactinidiolide, solanone, norsolanone have Significant increasing trend in the aging, the peak of the content of material appear in the 18~21 months in the aging process.

在所测定的29种香气物质中，对香料烟特征香气有重要影响的香味物质如降龙涎香内酯、硬尾内酯2种异构体、硬尾醛、8，15－赖百当醇、2种8，13外氧赖百当－14－烯－13醇异构体和2种8，13外氧赖百当－14－烯－13－酮异构体，二氢猕猴桃内酯、茄酮和降茄二酮等成分在陈化过程中有明显的增加，总的香气物质含量变化的高峰期出现在陈化18~21个月。

This dissertation concentrated on its low-cost synthesis, adjusting of silica to alumina molar ratio and catalytic applications in olefinic alkylation of thiophenic sulfur of simulated FCC gasoline and aromatization of butene in liquefied-petroleum-gas process.

本论文旨在降低MCM-22合成成本，获得硅铝比范围宽泛可调的MCM-22，并拓展其在烯烃烷基化脱硫与液化气丁烯芳构化方面的应用。

Kinetics characteristics of α- pinene isomerization catalyzed by activated carbon supported phosphotungstic acid was studied .

研究了活性炭固载磷钨酸催化α－蒎烯的异构化反应的动力学特征，研究表明，以环己烷作溶剂，α－蒎烯在活性炭固载磷钨酸上的异构化服从准一级动力学模型，其反应的表观活化能为100。

A desulfurization method is proposed for the removal of sulfur compounds from FCC gasoline by alkylation reaction of thiophenic sulfur with olefins over acid catalysts, and the higher boiling sulfur-containing products are removed by fractional distillation.

选择以噻吩的甲基取代衍生物(包括 2-甲基噻吩、3-甲基噻吩及 2，5-二甲基噻吩)与异丁烯的烷基化反应为模型反应，考察了经三氯化铝气相固载法改性的 CT175 树脂催化剂催化噻吩的甲基取代衍生物与烯烃的烷基化反应性能。

We have no common name for a mime of Sophron or Xenarchus and a Socratic Conversation; and we should still be without one even if the imitation in the two instances were in trimeters or elegiacs or some other kind of verse--though it is the way with people to tack on 'poet' to the name of a metre, and talk of elegiac-poets and epic-poets, thinking that they call them poets not by reason of the imitative nature of their work, but indiscriminately by reason of the metre they write in.

索夫农 、森那库斯和苏格拉底式的对话采用的模仿没有一个公共的名称；三音步诗、挽歌体或其他类型的诗的模仿也没有——人们把&诗人&这一名词和格律名称结合到一起，称之为挽歌体诗人或者史诗诗人，他们被称为诗人，似乎只是因为遵守格律写作，而非他们作品的模仿本质。

The relationship between communicative competence and grammar teaching should be that of the ends and the means.

交际能力和语法的关系应该是目标与途径的关系。