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炔烃

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The average relativeerror was 3.63%, less much than mostly used group-contribution methods for alkyne, chlorine derivative, iodine derivative, especially for alkane, bromine derivative, aromatic hydrocarbon, alicyclic hydrocarbon and sulfur-containing organic compounds.

对4068种有机物的正常沸点进行了估算,其平均相对误差为3.63%,总体估算精度明显优于相比较的基团贡献法,对炔烃、氯衍生物、碘衍生物,尤其是对烷烃类、溴衍生物、芳烃、脂环烃和含硫化合物的估算误差明显减小。

We have studied the transition metal complexes catalyzed sequential cross coupling reactions of these new difunctional group reagents with electrophiles and nucleophiles, respectively; developed some convenient and practical new methods for the stereoselective synthesis of disubstituted alkenes, trisubstituted alkenes, conjugated dienes containing heteroatom, conjugated enyne containing heteroatom etc., enriching methodologies for organic synthesis.

继而研究了这些新型双官能试剂在过渡金属配合物催化下分别与亲电试剂、亲核试剂的顺序交叉偶联反应,为双取代烯烃、三取代烯烃、杂原子取代的共轭二烯烃、杂原子取代的共轭烯炔烃等的立体选择合成提供了方便实用的新方法,丰富了烯烃立体选择合成的方法学。

The catalytic system composed of NHPI and transition metal ion can catalyze effectively ethane into acetic acid,cyclane into dicarboxylic acid,toluene into benzoic acid,alkene into epoxide,alkyne into acetylenic ketone,and amide into imide;NHPI used alone can catalyze adamantane to be carbonylated,hydrogen peroxide prepared by oxidization alcohol;NHPI combined with as...

NHPI与过渡金属离子组成的催化体系能高效地催化乙烷氧化为乙酸、环烷烃氧化为二元羧酸、甲苯氧化为苯甲酸、烯烃氧化为环氧化物、炔烃氧化为炔酮、酰胺氧化为酰亚胺;NHPI单独使用能催化金刚烷发生氧化羰基化反应、催化氧化醇制取过氧化氢;NHPI与有机助催化剂如偶氮二异丁腈、溴化季铵盐、蒽醌和醇等也能催化分子氧氧化反应。

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。

In addition, the new phosphine-catalyzed cyclization reactions of dimethylacetylenedicarboxylate and methyl propiolate with N-tosylimines are also described.

发展了膦催化下丁炔二酸二甲酯和丙炔酸甲酯与贫电子亚胺的环化反应,这对2-炔酸酯的反应又是一个补充,进一步丰富了膦催化下贫电子炔烃的反应化学。

One technique commonly used to reduce the amount of acetylenes and diolefins in an unsaturated hydrocarbon stream primarily comprising monoolefins involves selectively hydrogenating the acetylenes and diolefins to monoolefins.

用于降低主要包含单烯烃的不饱和烃料流中的炔烃和二烯烃的量的一种通用技术涉及将炔烃和二烯烃选择性加氢成单烯烃。

Also included is the study of characteristics of organic compounds such as alkanes, cycloalkanes, alkyl halides, alkenes alcohols, alkynes and the practical application of these materials to everyday life.

这门荣誉课还包括有机化合物特质的研究,如烷烃、环烷烃、卤代烃,醇烯烃、炔烃和日常生活中实际应用的材料。

The result of potassium malonyloxyborohydride as a new hydroboration reagent reacts with terminal alkenes and alkynes is described.

介绍新的硼氢化试剂丙二酰氧基硼氢化钾与链端烯炔烃的作用,烯烃的硼氢化物在PTC条件下,插入∶CCl2 ,可得饱和羧酸;炔烃则难以与之硼氢化。

In the fifth part, asymmetric synthesis of β,γ-trans-alkenyl α-amino esters was achieved by chiral phosphoric acid catalyzed transfer hydrogenation of β,γ-alkynyl α-imino esters. Utilizing Hantzsch ester as the hydrogen donor, both the alkyne and imine moieties of β,γ-alkynyl α-imino esters were reduced to yield β,γ-trans-alkenyl α-amino esters with up to 96% ee.

第五部分工作中,使用手性磷酸作为催化剂,Hantzsch酯作为氢源,β,γ-炔烃取代的α-酮酸酯亚胺中的炔键和亚胺官能团均被还原,以中等的收率和优秀的对映选择性(up to 96% ee)得到β,γ-反式烯烃取代的α-氨基酸衍生物。

According to the geometric evolution of the substituted polyynes from theacetylenic-like resonance form to the cumulenic-like (charge-separated)resonance form, it is obtained that there are two kinds of resonance form of thesubstituted polyyne.

根据取代多炔几何构型从多炔烃共振结构逐渐演变到累接双键烃共振结构的过程,表明取代多炔存在着两种共振形式。

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