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己二酮

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L-prolinamide/PPTS system was developed to catalyze Robinson annulation of 1,3-cyclohexanedione derivatives. Using this system, the functionalized carbon chain of Wieland-Wiescher ketone could be synthesized in high enantioselectivity, which was a useful synthon for structural diversity of total synthesis of natural product.

二、发现了L-prolinamide/PPTS体系可以催化Ronbinson环化1,3-环己二酮衍生物,实现含季碳且具有多官能团侧链的Wieland-Wiescher酮高对映选择性的合成,为天然产物结构多样性的合成奠定了基础。

THE FIRST TOTAL SYNTHESIS OF TAXAMAIRIN B Taxamairin B, representive of rare naturally-occuring rearrang-ed 9(10→20)-abeo-8, 11, 13-triene diterpenoids, has been firstsynthesized by a eleven-step route in an overall yield of 8.19%,starting from commercially available catechol and 1,3-cyclohexan-dione. The improved Friedel-Crafts annulation, thermodynamicallycontrolled-geminal pairing methylation, the selective oxidation ofallyl group and the selective reduction of the less-hindrancecarbon-carbon double bond are the key steps.

二。美丽红豆杉素B的全合成研究 1,美丽红豆杉素B的首次全合成以价廉,易得的邻苯二酚和1,3-环己二酮为原料,经过改良的Friedel-Crafts烷基化反应,热力学控制的α,β-不饱和酮结构的α一位双烷基化,烯丙位的选择性氧化,以及选择性还原位阻较小的碳碳双键等十一步反应,以8.19%的总收率首次完成了美丽红豆杉素B的全合成。

The effects of the intensity of basicity and the molar proportion of reactants on the reaction are discussed.

对1,3-环己二酮在碱性条件下的甲基化反应进行了对比研究,利用IR和1H NMR对产物结构进行了表征,讨论了碱性强弱和反应物物质的量之比对该反应产物的影响

Six 3,6-dichloropyridazine-derivatized cinchona alkaloid catalysts were synthesized and applied in IFB reaction.

二氢奎宁二聚体2c最差(56%ee),与环己二酮相比,环戊二酮作为反应原料时,产物的ee值降低。

Additionally, the quantum chemical study on the isomeriaation mechanism of the enol ester of 2-acyl-l,3-cyclohexanedione was performed, which was discovered by Yang when he synthesized the derivate of 2-acyl-l,3-cyclohexanedione.

第三部分工作是对杨定亚在合成2-酰基-1,3-环己二酮类化合物的衍生物时意外发现的烯酯异构化反应机理进行了研究。

Firstly, 3-ethylthiobutanal was prepared from crotonaldehyde reacting with ethanehiol in triethylamine with high yield. Secondly, methyl acetoacetate was converted to 6-ethylthiohept-3-en-2-one by three steps via hydrolysis, condensation with 3-ethyltio-butanal and dehydration, then 6-ethylthiohept-3-en-2-one was cycloco ndensed with dimethyl malonate by Michael addition and Claisen condensation, followed by saponification and decarboxylation to give the intermediate of 5-(2-ethylthiopropyl)-cyclohexane-1,3-dione.

首先,以巴豆醛与乙硫醇为原料,在三乙胺的催化作用下高收率制得3-乙硫基丁醛;然后从乙酰乙酸甲酯出发,通过碱水解、与3-乙硫基丁醛缩合、脱水三步反应合成6-乙硫基-3-烯-2-庚酮,接着6-乙硫基-3-烯-2-庚酮与丙二酸二甲酯通过Michael加成和Claisen缩合成环,再通过皂化和脱羧反应生成中间体5-[2-丙基]-1,3-环己二酮;再与丙酸酐反应丙酰化,最后与0-3-氯-2-丙烯基羟胺肟化,得到目标化合物烯草酮。

A series of 3 - aryl - 3 -( 5,5 - dimethyl - 3 - hydroxy - 2 - cyclohexene - 1 - one - 2 - yl) propanoic ester s were synthesized by reaction between aromatic aldehydes ,5,5- dimethyl -1,3-cyclohexanedione and isopropylidene malonate catalyzed by KF - Al2O3 in alcohols.

在KF-Al_2O_3催化下,将芳香醛3,5-二甲基-1,3-环己二酮及丙二酸亚异丙酯在醇中反应,一锅式合成了一系列的3-芳基-3-(5,5-二甲基-3-羟基-2-环己烯-1-酮-2-基)丙酸酯。

Using the chemical reaction route selection method proposed by the authors, a reaction route of using commercial methylglyoxal as the starting material to produce Furaneol was chosen.

今采用作者提出的化学反应路径选择因子对呋喃酮的合成方法进行计算比较,确定了以丙酮醛为原料,通过偶联反应合成中间体苏式3,4-二羟基-2,5-己二酮,再由成环反应制备产物呋喃酮的合成路线。

A series of 3,3,6,6 tetramethyl 1,8 dioxo 9 aryl 1,2,3,4,5,6,7,8,9,10 decahydro acridines have been synthesized by the condensation of aromatic aldehydes, 5,5 dimethyl 1,3 cyclohexanedione and ammonium acetate in the presence of triethylbenzylammonium chloride as catalyst in water.

芳醛、5 ,5 二甲基 1,3 环己二酮与醋酸铵在三乙基苄基氯化铵催化下以水作为溶剂反应,生成一系列 3 ,3 ,6,6 四甲基 1,8 二氧代 9 芳基 1,2 ,3 ,4,5 ,6,7,8,9,10 十氢吖啶,与其它溶剂相比,水作为该反应的溶剂具有价格便宜,不易燃和无毒等优点,而且产率较高,产物的结构通过单晶X射线确

Then we applied these chrial ligands to asymmetric borane reduction of w-bromoacetophenone and diketones.

将其应用于前手性单酮及二酮的还原中,其中双方酰化脯氨酸在1,6-二苯基-1,6-己二酮的还原反应中可获得最高为90%的ee值。

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