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We transformed RMgBr into R-Ti derivatives with the production of byproduct MgBrO~(i-Pr at the same time, but we didn\'t need romove the Mg salt by centrifugation or chelating reagents, for bis[2-(N,N-dimethylamino)ethyl] ether could chelate with Mg atom and thereby reduced the Louis acidity of Mg salt, so we used R-Ti derivatives produced in situ to alkylate the aldehydes induced by BINOL-Ti complexes..

我们通过利用TiO~(i-Pr_4使格氏试剂转化成烷基钛,同时产生具有亲核加成促进作用的副产物MgBrO~(i-Pr,由于BDMAEE能与MgBrO~(i--Pr络合降低其路易酸活性,所以不需要离心或者借助络合试剂完全除去镁盐,而使用原位生成的烷基钛在BINOL-Ti诱导下对醛进行不对称加成。

A novel carbonyl transposition led by anilines'nucleophilic addition to methyl 2-keto α-D-glucopyranoside was discovered. And the mechanism of the reaction concerned to an enol rearrangment was provided through tracing the change of 〓H-NMR and 〓C-NMR of a hemiacetal intermediate which was obtained in the reaction of o-phenylene diamine with 2-keto glycoside. Both the intermediate and the converting product were identified by 〓H-NMR,〓C-NMR,〓H-〓H COSY and HMQC.

一、发现了2-位氧化α-甲基D-葡萄糖苷的芳胺亲核加成引起羰基转位的新方法,利用核磁共振氢谱及碳谱对邻苯二胺与2-位氧化α-甲基D-葡萄糖苷加成生成的稳定中间体半缩酮化合物在氘代丙酮中的变化进行跟踪,结合对转化产物的氢氢相关谱和HMQC结构确证,提出了该反应中2-位羰基通过烯醇化互变而转至3-位的机理并得到了验证。

Analyse and compare what adopt a variety of pair of methods, the Michael addition reaction of ester of acerbity second of second of hydroxyl of protection of benzyl of the response of close nucleus addition that uses second nitrile and ester of formic acid second certainly, chloridize, cyanogen, reaction that take off carboxyl generates 3- benzyl oxygen radical the fifth of the ten Heavenly Stem the method of 2 nitrile, detailed discussion the action that wait and the by-product that arise possibly reach the reactant in each pace reaction, activator, dissolvent avoid a method.

通过对多种方法的分析和比较,确定采用乙腈和甲酸乙酯的亲核加成反应、氯化苄保护羟基、氰乙酸乙酯的Michael加成反应、脱羧反应生成3-苄氧基戊二腈的方法,并具体的讨论了每一步反应中反应物、催化剂、溶剂等的功能和可能产生的副产物及避免方法。

These results were veryreasonable considering the fact that cyclohexene and 1-octene can not bepolymerized with Ziegler-Natta catalyst.

产物的FD-MS分析结果表明:〓和辛烯-l的加成物为加成数从1到16的混合物;〓和环己烯主要生成加成数为9的加成物。

Both catalytic activity and selectivity of Ru(PPh_3)_3Cl_2 were improved in ionic liquid BMImPF_6/DME medium.The conversion of hexene and selectivity ofβ-adduct for the hydrosilylation reaction of 1-hexene with triethoxysilane catalyzed by Ru(PPh_3)_3Cl_2 in ionic liquid BMImPF_6DME (V/V=1/4) medium at 90℃were 100% and 89.0%,respectively.

实验结果表明,在乙二醇二甲醚/离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMImBF_6)(V/V =1/4)介质中,于90℃下,己烯与三乙氧基硅烷反应的转化率为100%,β加成物的选择性可达89.0%,而用Rh(PPh_3)_3Cl作为反应的催化剂,在纯离子液体BMImPF_6中,就可以高效催化烯烃与三乙氧基氢硅烷的加成反应,过渡金属Rh(PPh_3)_3Cl,Ru(PPh_3)_3Cl_2催化剂/离子液体BMImPF_6催化体系,不仅解决了产物与催化剂分离困难这一难题,同时,离子液体BMImPF_6的存在提高了过渡金属Rh(PPh_3)_3Cl,Ru(PPh_3)_3Cl_2催化硅氢加成反应的活性,特别是β加成物的选择性。

Based on our early work, we will discuss the coupling the reaction of α-cyano ketenedithioacetals with Baylis-Hillman adducts.

基于以上的研究,本文着重讨论了α-氰基二硫缩烯酮与Baylis-Hillman加成产物的偶联反应。

A conjugate addition of alkadienyl carbonyl compound with vinyl palladium intermediates which can be formed from oxypalladation of alkynes or allenes was studied, and 1, 6-addition products were obtained.

发现不饱和烃的分子内氧钯化得到的烯基钯中间体能够与不饱和共轭双烯的醛酮反应,选择性的得到1,6-加成产物

Alkylbenzene, normal alkanes and alkylcyclohexane on the pyrolysates of P. Boryanum at 300℃ had uniform distribution and the relative content of them was similar, indicating that they originated from same precursors. Fatty acids, alcohol and ketone in algal cell are the possible precursors. For example, the precursor of relatively abundant C〓 alkylbenzene and alkylbenzene with C〓 side chain perhaps related with palmitic acid. N-alkylnaphthalene in pyrolysates at 300℃ probably derived from alkylation of cleavage products of aromatic steranes and terpanes.

在盘星藻300℃热解产物中,烷基苯、正烷烃和烷基环己烷碳数分布一致、各化合物的相对含量接近,表明它们有相同的来源,藻类体内的脂肪酸、醇和酮及细胞壁等物质可能是其母质,相对含量较高的碳数为16及侧链碳数为16的烷基苯类化合物,其前身物可能与软脂酸有关。300℃热解产物中的正烷基萘类化合物,可能由芳香甾、萜类的降解产物与直链烃类加成烷基化而形成。

In the CsF promoted Strecker reactions of 2-aziridinesulfinimines, the sulfinyl group controlled the diastereoselective addition.

加成产物经氮杂环丙烷开环可合成所有构型的一系列α、β-二氨基酸和α、β-二氨基膦酸。

This dissertation is concerned with the approaches to a new high density liquid fuel , tetrahydrotricyclopentadiene, which can be synthesized with dicyclopentadiene as raw materials by three steps: Diels-Alder reaction, separation and hydrogenation.

本文以双环戊二烯为原料,通过双烯加成、分离、加氢反应得到目的产物——新型高密度液体燃料四氢三环戊二烯,主要研究内容包括: 1。三环戊二烯的合成采用两种方式对TCPD的合成进行了研究:DCPD直接热聚法、DCPD与环戊二烯双烯加成法。

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