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丙二烯

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This dissertation focused on two types of reactions, oxidative allylation of 1, 3-dicarbonyl compounds and ring-opening allylation of epoxides.

我们重点考察了两类反应:1, 3-二羰基类化合物的不对称烯丙基化反应和环氧化合物的开环烯丙基化反应。

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。

Given the current complexity of industrial recovery of 3'-methyl-2'-butenyl 3, 3-dimethyl-pentenoate and the decomposition problems with 2-methyl-1-butene, research was conducted on a process for direct recycling of MBDP involving an ester exchange reaction of MBDP with either methanol, trimethyl orthoacetate, or solutions of methanol and trimethyl orthoacetate.

针对目前工业上回收3,3-二甲基-4-戊烯酸-3'-甲基-2'-丁烯酯工艺复杂、异戊烯大量分解问题,研究了MBDP直接返回循环使用工艺,MBDP与甲醇、原乙酸三甲酯或与甲醇原乙酸三甲酯混合溶液进行酯交换反应的回收新工艺,比较了四异丙基钛酸酯、甲醇钠、氢氧化钾用作酯交换催化剂的效果,筛选出回收MBDP&一锅煮&最佳工艺:按照n:n:n:n=1.0:9.8:9.2:0.05物质的量比投料,74℃~78℃反应21h,MBDP转化为贲亭酸甲酯和异戊烯醇,单程转化率87.7%,用85%的磷酸中和甲醇钠,蒸出甲醇,直接用于合成贲亭酸甲酯。

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

In the presence of alkalinity and tetraethyl ammonium bromide, 2,4-dihydroxy benzophenone reacts with allyl glycidyl ether to form an ethylenic derivative of benzophenone, 2-hydroxy-4-(β-hydroxy-γ-allyloxy) propyloxy benzophenone, which can further undergo hydrosilylation with polyhydromethylsiloxane.

在相转移催化剂四乙基溴化按作用下,利用2,4-二羟基二苯甲酮与烯丙基缩水甘油醚在碱性水溶液中的开环加成反应,合成了中间体4-丙氧基-2-羟基二苯甲酮,将其进一步与聚甲基氢硅氧烷进行硅氢化加成反应。

In order to enhance the compatibility of ABS/PP/CaCO3 composites, the effects of reactive blends of the composites were studied by using Haake rheometer. The effects of various assistant cross-linkingers, such as castor oil, triallyl isocyanurate, turpentine (JS-1) and glycol dimethacrylate, and the used amount of cross-linkinger-dicumyl peroxide on the torques of the melting composites were investigated.

为提高ABS/PP/CaCO3复合材料相容性,采用转矩流变仪观察了ABS/PP/CaCO3三元复合物反应性共混后的扭矩,考察了不同的助交联剂蓖麻油、异氰脲酸三烯丙酯、松香酯(JS-1)、二甲基丙烯酸乙二醇酯以及交联剂过氧化二异丙苯的用量对共混物的影响。

The volatile components were separated and identified using GC-MS technique. RESULTS Seven ingredients were. isolated: 2-ethyl-hexyl-adipate (66.5%), 1-methoxy-4-(1-propenyl)benzene (12.5%), isopropyl isothiocyanate (6%), isobutylisothiocyanate (6%), 6-methyl-5-heptene-2-one (3.5%), benzaldehyde (1.4%), phenylacetaldehyde (0.8%).

结果 分离出7个成分,采用峰面积归一化法确定了各成分的相对含量,分别为66.5%双-2-乙基己基-己二酸、12.5%1-甲氧基-4-(1-丙烯基)苯、6%异硫氰酸异丙酯6%、6%异硫氰酸异丁酯、3.5%6-甲基-5-庚烯-2-酮、1.4%苯甲醛、0.8%苯乙醛。

A novel chiral diallylic diamine has been synthesized through double addition of allyl zinc bromide to chiral imines in this contribution.

通过烯丙基溴化锌对手性亚胺的两次不对称加成,合成了光活性的双烯丙基化的新型手性二胺。

In addition, 65% ee was obtained for 1, 3-dimethylprop-2-enyl acetate. Interestingly, the reactivities of these ligands are all very high.

对于1, 3-二苯基烯丙基醋酸酯的烷基化和胺化反应, ee 值最高分别为93%和98%,此外,在对1, 3-二甲基烯丙基醋酸酯的烷基化反应中 ee 值最高也可达65%。

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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。

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这不是纸上谈兵式的交易,这是人与人的业务,而且涉及金额巨大。