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We have used GC to follow up the formation of epoxy acid and established the acidify condition; we have done series of parallel experiments to better the pivotal condensation reaction between acid and amine; In the cyclization step, we use cheap and available reagent-Lithium amide , rather than expensive LiHMDS, to proceed the reaction; and at last, we introduced green reagent-ozone to clear the phenyl group of nitrogen to avoid using heavy metal reagent-CAN. The total yield for this method is 29.8%.

通过GC监测,确定环氧酸的最佳酸化条件;对关键的酸和胺的缩合步骤,平行试验了多种条件;在环合一步,用价廉易得的氨基锂及催化量的HMDS代替昂贵的LiHMDS进行反应;氮上苯基的脱除采用臭氧,避免了重金属试剂-硝酸铈铵的使用,总收率为29.8%。

Chapter two: Using 5-(4-aminophenyl)-10,15,20-triphenylporphyrin as thestarting compound, the classical diazotization of aniline and the resulting reaction ofdiazo salts were applied to porphyrin for the first time, and a series of asymmetriclysubstituted meso-tetraarylporphyrins including 5-(4-chlorophenyl)-10,15,20-triphenylporphyrin, 5-(4-iodinphenyl)-10,15,20-triphenylporphyrin, 5-(4-cyanophenyl)-10,15,20-triphenylporphyrin, 5-(4-bisphenyl)-10,15,20-triphenylporphyrin and 5-(4-hydroxylphenyl)-10,15,20-triphenylporphyrin were synthesized.

第二章:在已合成的5-(4-氨基苯基)-10,15,20-三苯基卟啉基础上,首次将芳胺的重氮化及重氮盐反应应用于卟啉,合成了5-(4-氯苯基)-10,15,20-三苯基卟啉、5-(4-碘基苯基)-10,15,20-三苯基卟啉、5-(4-氰基苯基)-10,15,20-三苯基卟啉、5-(4-联苯基)-10,15,20-三苯基卟啉和5-(4-羟基苯基)-10,15,20-三苯基卟啉等一系列不对称取代的meso-四芳基卟啉。

Chromatographic behaviors of six cationic thulium porphyrin complexes have been firstly investigated in different mobile phase.

2首次以六个不同的铥卟啉配合物(四(4-羟基苯基)卟啉铥、四(4-甲氧基苯基)卟啉铥、四苯基卟啉铥、四(4-甲基苯基)卟啉铥、四(4-氯苯基)卟啉铥和四(4-异丙基苯基)卟啉铥)为研究对象进行HPLC分离。

Among the open-chain crown ethers and cryptands with a same structure, the compounds disubstituted at the amide nitrogen atoms show the larger extractability for Am and Eu than the monosubstituted ones. The compounds disubstituted at the amide nitrogen atoms by two phenyl groups show the larger extractability for Am and Eu than those by two alkyl groups.

3在结构相同的开链冠醚和开链穴醚中,酰胺氮原子上二取代化合物对Am和Eu的萃取能力大于一取代化合物;酰胺氮原子上两个取代基都是苯基的化合物对Am和Eu的萃取能力大于两个取代基都是烷基的化合物。

The copolymer of N isopropylacrylamide and acrylamido azobenzene was synthesized for the study of the effect of the photoisomerization of a water soluble copolymer containing azobenzene groups on the photocontrolled release behavior of liposomes.

为了研究侧链含有偶氮苯基的水溶性共聚物的光异构化对脂质体内包容物的光控释放的影响,设计合成了N-异丙基丙烯酰胺和丙烯酰胺基偶氮苯的共聚物。

The obtained potential energy curves disclosed that a four-state cycle existed in the ground and excited states. It was also found that the activation energy for the methyl transfer was higher compared to the phenyl transfer, which was consistent to the experimental results that the photoisomerization of the phenyl substituted derivative was more rapid than the methyl substituted derivatives.

对反应势能面的研究发现,在光异构化反应中化合物M21和M21、M31的基态和激发态虽然都可以构成四能级反应过程,但由于M21异构化过程的活化能较高,使其所构成的四能级反应难以进行,这就从理论上解释了迁移基团为甲基的M21变色性能低于迁移基团为苯基的M31的实验结果。

In comparison with 〓ligand the substitution of one phenyl groupby pyridyl ligand renders this cluster a self defocusing effect different with previousbutterfly shaped clusters, so the peripheral ligands may also play an important role onthe NLO effects.

配体中的吡啶取代基取代苯基的微小改变使标题化合物具有了不同于以往蝴蝶状簇合物的非线性折射性质,即表现为自散焦,从而说明外围配体对非线性也具有大的影响作用。

By following the "self-assisted molecular editing" protocol first established in our labs,a number of Aphos ligands were efficiently prepared from a single starting material and they were screened for catalytic efficacy, leading to the discovery of the best-performing Aphos appended with a 3-nitrophenyl group at the C4 position.Combination of this Aphos with Pd_2 offers a precatalyst for successful cross-coupling of unactivated aryl chlorides with aryl boronic acids at room temperature.The reactions took place under mild basic conditions to produce the products in high yields.

通过我们首次提出的&自助分子剪裁&的概念从单一起始物快速合成和筛选了一系列膦配体,并发现C4位含3-硝基苯基的的膦配体和醋酸钯联用可以在室温下顺利地催化不活泼氯代芳烃和芳基硼酸的偶联反应,反应条件温和且产物收率很高。

Using classical diazotisation of anilines, 5-(4-aminophenyl)-10,15,20-triphenyl-porphyrin was converted to a series of meso-tetraarylporphyrins with different substituents, including 5-(4-hydroxylphenyl)-10,15,20-triphenylporphyrin (80%), 5-(4-chlorophenyl)-10,15,20-triphenylporphyrin (74%), 5-(4-iodinphenyl)-10,15,20-triphenylporphyrin (76%), 5-(4-hydrazinephenyl)-10,15,20-triphenylporphyrin (67%) and 5-(4-bisphenyl)-10,15,20-triphenylporphyrin (32%). Therefore an efficient way of synthesizing unsymmetrically substituted TAPs was developed.

利用芳胺的重氮化及重氮盐反应,研究了5-(4-氨基苯基)-10,15,20-三苯基卟啉上氨基官能团的转化反应,以较高产率合成了5-(4-羟基苯基)-10,15,20-三苯基卟啉(80%)、5-(4-氯苯基)-10,15,20-三苯基卟啉(74%)、5-(4-碘基苯基)-10,15,20-三苯基卟啉(76%)、5-(4-肼基苯基)-10,15,20-三苯基卟啉(67%)和5-(4-联苯基)-10,15,20-三苯基卟啉(32%)等一系列含单个para-取代基的meso-四芳基卟啉,为合成不对称取代的芳基卟啉提供一条有效途径。

According to the results of the examination, the stronger the electron-withdrawing protective group of imines, the better the cis-selectivity of the reaction, 68% yield, trans:cis is 99:1 diastereoselectivity could be leaded by Ts-imines (4-methyl-N-methylene-benzenesulfonaides) with a substituent [2,4-(CH3O)2C6H3], Substrate scope investigation revealed that a wide variety of ketenes and imines could react smoothly to afford corresponding,β-lactams.

实验结果表明,亚胺的保护基团吸电子能力越强,越有利于顺式产物的生成。对甲苯磺酰基保护的取代基为2,4-二甲氧苯基的亚胺参与的该反应可得到68%的产率,反式:顺式=99:1的非对映选择性。底物拓展过程中发现Staudinger反应适用于多种不同的亚胺与烯酮。

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