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芬太尼类化合物中4-取代基作用的研究 总被引:1,自引:0,他引:1
用量子力学方法对非极性取代的4-正丙基芬太尼和极性取代的4-甲氧甲基芬太尼及4-甲氧羰基芬太尼的电子结构和构象进行了研究.结果表明, 4-取代基对提高活性的贡献表现在电性因素方面, 构象变化不是主要因素. 4-非极性取代基对提高活性没有贡献.4-极性取代基增加了新的负电荷集中部位, 这新的负电势区域可能是同受体相互作用的一个重要辅助部位, 该区域既可与受体的另一部位作用, 也可能同酰胺氧原子作用于同一受体部位, 无论是哪一种情况均有利于提高活性。 相似文献
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1,3-偶极环加成反应合成1-(取代苄基)-1,2,3-三唑类化合物 总被引:10,自引:0,他引:10
利用苄氯和取代苄氯与叠氮化钠的亲核取代反应合成了一系列苯环上带有不同取代基团的苄基叠氮化合物,亲核取代反应速率受苯环上取代基的影响:吸电子基团的存在,可以促使反应更容易进行.合成的叠氮化合物与苯乙炔经1,3-偶极环加成反应得到了相应的取代苄基1,2,3-三唑类化合物,反应条件温和.这些1,2,3-三唑类目标化合物具有对热稳定的优点.用红外、核磁、元素分析、质谱等对合成的叠氮化合物和1,2,3-三唑类化合物的结构进行了表征,重点研究了1,3-环加成反应的规律.加成反应速率取决于叠氮化合物(偶极物)的极性,即与取代基的电负性有关:苯乙炔(亲偶极物)易于与缺电子的叠氮反应,反之亦然.同时在反应过程中观察到空间位阻效应:反应可以生成两种同分异构体,其中4-苯基-1,2,3-三唑是主要产物. 相似文献
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通过密度泛函理论计算比较性地研究了5,15-二(4-(5-乙酰基硫戊氧基)苯基)自由卟啉及其锌配合物的分子结构、电荷性质、分子轨道、电子吸收光谱和红外光谱.这类化合物具有在卟啉相对的两个中位的苯环上连有5-乙酰基硫戊氧基的新颖结构.模拟得到的这两个化合物的分子结构和电子吸收光谱以及红外光谱都与实验测得的符合得很好.通过与未取代的自由卟啉和卟啉锌的结构和性质进行比较,研究了中位取代基、极性溶剂和中心金属取代对此类卟啉化合物结构和性质的影响规律.对化合物的电子吸收光谱中的电子跃迁本质进行了归属,并通过基于正则坐标分析产生的动画对红外光谱的振动模式进行了指认.目前的工作将对理解此类新颖卟啉化合物的结构和性质以及取代基和溶剂效应提供很大的帮助. 相似文献
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4H-甲基咪唑苯二氮(艹卓)酮类抗HIV-1药物的量子化学研究 总被引:3,自引:0,他引:3
用分子力学MM3方法、量子化学MNDO法和从头算STO-3G基组计算了20个4H-甲基咪唑苯二氮(廿卓)酮HIV-1逆转录酶抑制剂的优势构型和电子结构,用逐步回归方法和BP神经网络方法得到其抗HIV-1活性与电子结构的定量构效关系.结果表明:(1)TIBO类衍生物的体积越大,极性越小,即流水性越大对抑制HIV-1活性越有利.(2)C环N上H原子可能是化合物的正电活性部位.(3)R′原子与受体作用时可能作为电子给予体,前线轨道中S的贡献比O大得多,故含S的TIBO化合物比含O化合物的活性高.(4)苯环上连接吸电子基团对活性有利,由于分子的正负电荷中心距离较近,极性较小,疏水性较大,故3位取代比2位取代活性更高. 相似文献
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类杂芪染料分子第一超极化率的溶剂效应研究 总被引:2,自引:0,他引:2
从实验上证明了反式-(2-N-甲基吡咯基)-(4-N-甲基吡啶基)杂芪碘(MPPSI),反式-(2-吡咯基)-(4-N-甲基吡啶基)杂芪碘(PPSI),反式-(2-呋喃基)-(4-N-甲基吡啶基)杂芪碘(FPSI)和反式-(2-噻吩基)-(4-N-甲基吡啶基)杂芪碘(TPSI)在15种溶剂中的分子第一超极化率(β~χ~χ~χ)与给电子取代基的富电子性间的线性关系,得到了β~χ~χ~χ值与溶剂极性间的线性相关性,从以上两个线性相关中得到了溶剂极性影响类杂芪分子给/吸电子取代基的给/吸电子能力的溶剂系数δ~A和δ~D,以及分子内电荷转移对溶剂极性的敏感因子η。 相似文献
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三烃基锡β-2, 8, 9-三氧杂-5-氮杂-1-锗杂三环[3.3.3.0^1.5]十一碳烷基(β-取代)丙酸酯的研究 总被引:4,自引:0,他引:4
本文合成了15个含锡锗杂恶唑烷化合物,N(CH~2CH~2O)~3GeCHR^1CH~2CO~2SnR(R=Cy~3, Bu~3^n, Ph~3, Cy~2Bu^n,CyBu~2^n; R^1=H, C~6H~5, p-CH~3C~6H~4, p-ClC~6H~4)。通过对产物的IR、1^HNMR、MS和元素的分析测定, 确定了它们的组成和结构。三丁基锡羧酸酯具有五配位的结构。生物活性测定结果表明, 这些化合物具有较好的杀螨和除草活性, 同时对植物病原菌也有一定的防治效果。 相似文献
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研究了不同碱金属离子对CaO的促进作用,发现以Na~+的添加效果最好。在此基础上,研究了不同含钠化合物对CaO的促进作用,并用脉冲反应技术研究Na~+/CaO催化剂表面氧物种的特性及其作用。CaO表面上存在非选择性氧化的氧物种。Na~+对CaO的修饰作用是抑制非选择性氧化。当表面上的非选择性氧化的氧物种消耗后,体相的晶格氧会向表面迁移,以补充消耗掉的表面氧物种。消耗掉的表面氧物种也可由气相氧补充。CH_4脉冲和混合气脉冲说明仅靠[Na~+O~-]中心不足以使甲烷转化成C_2产物,必须有气相氧的参与才能使甲烷转化成C_2产物。 相似文献
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The synthesis and structures of metal aminocarboxylates prepared in acidic, neutral, or alkaline media have been explored with the purpose of isolating coordination polymers with linear chain and two-dimensional layered structures. Metal glycinates of the formulae [CoCl2(H2O)2(CO2CH2NH3)] (I), [MnCl2(CO2CH2NH3)2] (II), and [Cd3Cl6(CO2CH2NH3)4] (III) with one-dimensional chain structures have been obtained by the reaction of the metal salts with glycine in an acidic medium under hydro/solvothermal conditions. These chain compounds contain glycine in the zwitterionic form. 4-Aminobutyric acid transforms to a cyclic amide under such reaction conditions, and the amide forms a chain compound of the formula [CdBr2(C4H7NO)2] (IV). Glycine in the zwitterionic form also forms a two-dimensional layered compound of the formula [Mn(H2O)2(CO2CH2NH3)2]Br2 (V). 6-Aminocaproic acid under alkaline conditions forms layered compounds with metals at room temperature, the metal being coordinated both by the amino nitrogen and the carboxyl oxygen atoms. Of the two layered compounds [Cd{CO2(CH2)5NH2}2]2 H2O (VI) and [Cu{CO2(CH2)5NH2}2]2 H2O (VII), the latter has voids in which water molecules reside. 相似文献
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采用溶胶-凝胶法和浸渍法制备了V2O5/SiO2催化剂,并用XRD,IR,TPD和活性评价等手段对催化剂的表面构造、化学吸附性能和异丁烷选择氧化反应性能进行了研究.结果表明:催化剂表面由Lewis碱位V=O双键的端氧和Lewis酸位V5+构成,异丁烷分子主要通过甲基中的H双位吸附在催化剂表面的Lewis碱位上,异丁烯分子可通过甲基的H吸附在催化剂表面的Lewis碱位,也可通过C=C双键吸附在催化剂表面的Lewis酸位上.在常压条件下,异丁烷选择氧化产物主要有异丁烯、甲基丙烯醛和甲基丙烯酸,其中深度氧化产物CO2主要由通过C=C吸附的异丁烯继续反应生成. 相似文献
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Jinhai Xie Minming Huang Serge Kaliaguine 《Reaction Kinetics and Catalysis Letters》1996,58(2):217-227
The basicity of alkali-exchanged zeolites has been characterized by chloroform adsorption using FTIR spectroscopy. The chloroform is adsorbed on the basic oxygen site through its hydrogen atom, while a weak interaction also exists between the adjacent cation and the chlorine atom of chloroform. The charge on the oxygen atoms (basic sites) was calculated using the electronegativity equivalence method. The CH stretching frequency of chloroform adsorbed on basic sites is well correlated with this oxygen charge. 相似文献
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甲烷氧化偶联La-Me-O(Me=Mg,Ca,Sr,Ba)系催化剂表面氧种的研究 总被引:2,自引:0,他引:2
利用CO_2-TPD法考察了La-Me-O(Me=Mg,Ca,Sr,Ba)系催化剂的表面碱性,并用O_2-TPD、CH_4-TPD法对该体系的表面活性氧种进行了表征,并与催化性能相关联。结果表明,La-Ba-O催化剂由于表面强碱性中心数目多,产生活性氧种的数目也多,有利于甲烷的活化,因而具有最高的甲烷转化率和C_2烃选择性。脉冲反应表明,在无气相氧存在下,表面晶格氧参与了氧化偶联,而且是选择氧化的活性氧种。 相似文献
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Green IX Tang W McEntee M Neurock M Yates JT 《Journal of the American Chemical Society》2012,134(30):12717-12723
TiO(2)-supported gold nanoparticles exhibit surprising catalytic activity for oxidation reactions compared to noble bulk gold which is inactive. The catalytic activity is localized at the perimeter of the Au nanoparticles where Au atoms are atomically adjacent to the TiO(2) support. At these dual-catalytic sites an oxygen molecule is efficiently activated through chemical bonding to both Au and Ti(4+) sites. A significant inhibition by a factor of 22 in the CO oxidation reaction rate is observed at 120 K when the Au is preoxidized, caused by the oxygen-induced positive charge produced on the perimeter Au atoms. Theoretical calculations indicate that induced positive charge occurs in the Au atoms which are adjacent to chemisorbed oxygen atoms, almost doubling the activation energy for CO oxidation at the dual-catalytic sites in agreement with experiments. This is an example of self-inhibition in catalysis by a reactant species. 相似文献
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Mareque Rivas JC Salvagni E Parsons S 《Dalton transactions (Cambridge, England : 2003)》2004,(24):4185-4192
Amide oxygen co-ordination to a zinc(II) ion around a hydrogen bonding microenvironment is a common structural/functional feature of metalloproteases. We report two strategies to position hydrogen bonding groups in the proximity of a zinc(II)-bound amide oxygen, and we investigate their effect on the stability of the amide group. Polydentate tripodal ligands (6-R1-2-pyridylmethyl)-R2 (R1= NHCOtBu, R2= N(CH2-py-6-X)2 X = H L1, X = NH2, H L2, X = NH2 L3) form [(L)Zn]2+ cations (L =L1, 1; L2, 2; L3, 3) with intramolecular amide oxygen co-ordination (1-3), and intramolecular N-H...O=C(amide) hydrogen bonding (2, 3) rigidly fixed by the ligand framework. 1-3 undergo cleavage of the tert-butyl amide upon addition of Me4NOH.5H2O (1 equiv.) in methanol at 50(1) degrees C. Under these conditions the half-life, t(1/2), of the amide bond is 0.4 h for 1, 9 h for 2 and 320 h for 3. Mononuclear zinc(II) complexes of (6-NHCOtBu-2-pyridylmethyl)-R2(R2= N(CH2CH2)2S) L4 and chelating N2 ligands without hydrogen bonding groups (1,10-phenanthroline L5, 2-(aminomethyl)pyridine L6) as control compounds, and with an amino hydrogen bonding group (6-amino-2-(aminomethyl)pyridine L7) have been synthesised. Amide cleavage is in this case faster at the zinc(II) complex with the amino hydrogen bonding group. Thus, hydrogen bonding environments can both accelerate and slow down amide bond cleavage reactions at zinc(II) sites. Importantly, the magnitude of the effect exerted by the hydrogen bonding environments was found to be significant; 800-fold rate difference. This result highlights the importance of hydrogen bonding environments around metal centres in amide cleavage reactions, which may be relevant to the chemistry of natural metalloproteases and applicable to the design of more efficient artificial protein cleaving agents. 相似文献