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Part 2. Annulation reaction of 3, 4-dichlorocoumarin (1) and 3, 4-dichloromaleimide (8) by a new general annulation strategy developed in this group with 2-phenylbenzofuran (15), 3-phenylbenzofuran (16), 2, 5-diphenyloxazole (17), 2, 5-diphenylthiazole (18), 2-methyl-4-phenylthiazole (19) and 2, 3-dimethoxy-1, 3-butadiene (40) were investigated.

二。在本课题组前一阶段提出的从二氯代环烯酮与1,1-二芳基乙烯的光化反应以及光化反应中得到的环丁烷产物的连续电环化反应对3,4-二氯马来酰亚胺以及3,4-二氯香豆素进行增环反应的工作基础上,研究了3,4-二氯香豆素(1)和3,4-二氯马来酰亚胺(8)与5个α-苯基取代的环烯烃2-苯基苯并呋喃(15),3-苯基苯并呋喃(16),2,5-二苯基噁唑(17),2,5-二苯基噻唑(18),2-甲基-4-苯基噻唑(19),以及一个丁二烯——2,3-二甲氧基丁二烯(40)进行的芳香族增环反应。

The epoxidation of of various olefins was carried out using LDH-F with Mg/Al=5 as the catalyst and H2O2 and benzonitrile as the oxidants. This catalytic system has excellent catalytic activity. The conversion and selectivity are both above 95% when using styrene, indene, allyl alcohol, and allyl chloride as the substrates.

以Mg/Al=5的LDH-F为催化剂,H2O2和苯甲腈为氧化剂对不同官能团化烯烃进行环氧化反应,结果表明,此催化体系具有良好的催化性能,在苯乙烯、茚、丙烯醇和烯丙基氯环氧化反应中转化率和选择性均在95%以上。

1A series ofω-alkylmercapo acid were synthesized by two methods:one involved the reaction of the appropriateω-bromoalkyl acid with mercaptide under the presence of base;the other method was used only for the long alkyl compound by the reaction ofω-alkenyl acid and alkanethiol in the presence of AIBN.

正是基于以上考虑,本论文探索了合成下沿带有硫醚官能团,而上沿带有偶氮官能团的杯[4]芳烃衍生物的方法,进行了以下研究: 1采用ω-溴代羧酸和烃基硫醇在碱性条件下发生反应,或由ω-烯基羧酸和硫醇在AIBN的存在下反应,得到了ω-硫醚羧酸,使用氯化亚砜将羧酸转化为酰氯。

The alkaloids were studied by gas chromatography coupled to mass spectrometry. Six major venom alkaloids were detected in worker venom which are all trans 2-methyl-6-alkyl or alkenyl pepdine according to mass spectral data and relative report on S.invicta.

通过保留时间和质谱离子碎片数据,并与国外相关报道比较分析得出:入红火蚁毒液中主要成分为2-甲基-6-烷基或烯基哌啶生物碱,仅有6位取代烃基碳链长短和烯键有无及顺反异构的差异。

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。

The yields were 67~89% and 61~90% respectively, and the ees were 66~99. 9% and 68~99. 9% respectively (except for trans-5-decene and ally naphthyl ether). With trans-stilbene as the substrate, chiral ligands and OsO〓 could be recovered and reused five times in the AD reaction with high catalytic activity and stereoselectivity.

4在PF〓/NMO体系中,将配体8和10分别用于八种烯烃的AD反应,配体、OsO〓和底物的摩尔比为0.02/0.015/1时,化学产率分别为67~91%和61~90%,ee值分别为66~99.9%和68~99.9%(反式-5-癸烯和萘基烯丙基醚除外)。

Selected novel olefinic orthoesters, may be copolymerized with other olefins using certain late metal transition catalysts, to form novel polyolefins containing orthoester pendant groups.

利用某些后过渡金属催化剂,可以使选择的新颖烯烃原酸酯与其它的烯烃共聚合,以形成含原酸酯侧基的新颖聚烯烃。

A one-step method for the synthesis of aromatic indolizine derivatives byintramolecular 1,5-dipolar cyclization reaction of 2-(2-arylethenyl)pyridinium N-ylidesin the presence of an oxidant has been studied for the first time. In the presence ofelectron-deficient olefins, however, 2-(2-phenylethenyl)pyridinium N-ylides underwent1,3-dipolar cycloadditions and then aromatized in situ by TPCD to produce indolizinederivatives, indicating 1,3-dipolar cycloaddition proceed more readily than 1 ,5-dipolarcyclization in these conditions. Pyridinium disubstituted N-ylides, readily obtainedfrom corresponding pridinium and β-chlorovinyl ketone, underwent thermalintramolecular 1,5-dipolar cyclization to give indolizine derivatives easily.Indolizinecarbaldehyde derivatives were synthesized starting from 2-pyridinecarbaldehyde in four-steps involving 1,3-dipolar cycloaddition reaction.

本文首次研究了2-(2-芳基乙烯基)吡啶N-叶立德在氧化剂存在下的分子内1,5-偶极环化反应,采用一锅法合成了中氮茚衍生物;研究了这些N-叶立德的1,5-偶极环化和1,3-偶极环加成反应的选择性,发现当有缺电子烯烃存在时,优先进行1,3-偶极环加成反应,而不再发生分子内1,5-偶极环化反应;由β-氯乙烯酮方便地得到了烯丙基N-叶立德,他们在加热时进行分子内1,5-偶极环化反应而得到中氮茚衍生物;由2-吡啶甲醛为起始原料,通过1,3-偶极环加成反应等四步反应,得到了重要的中氮茚甲醛衍生物,这些反应都具有条件温和和操作简便的特点,是合成中氮茚衍生物的新方法。

Zinc diamyl dithiocarbamate antioxidant showed good synergism with antimony diakyl dithiocarbamate antiwear additive in improving the oxidation stability of modified soybean oils. The incipient oxidation temperature and induction period time of genetically modified soybean oils were improved significantly by adding polyalphaolefin and additives, and they were even better than that of the synthetic base oil PAO with the same additive formulation.

结果表明,改性大豆油的不饱和脂肪酸含量越高,其氧化安定性越差;抗氧剂二戊基二硫代氨基甲酸锌和抗磨剂二烷基二硫代氨基甲酸锑在改性大豆油中均表现出了良好的抗氧协同性能,尤其在基因改性大豆油中,聚-α-烯烃和添加剂的复配使其起始氧化温度和氧化诱导时间均超过了相同配方的聚-α-烯烃油样。

In order to decrease copolymerization loss of isoprene during thermal dimerization of cyclopentadiene in C5-fraction,the effect of three inhibitors,diethylhydroxylamine,p-tert-butylcatechol and o-nitrophenol,on dienes' polymerization in the process was investigated by experiment with sealed glasstube.

为减少C5馏分环戊二烯热二聚过程中异戊二烯的聚合损失,采用封管实验方法考察了添加阻聚剂二乙基羟胺、对叔丁基邻苯二酚、邻硝基苯酚对热二聚过程中各二烯烃组分聚合程度的影响。

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