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从豆甾醇出发,通过10步反应,合成得到具有显著细胞毒活性的24-亚甲基胆甾-5-烯-3β,19-二醇(1),总产率为16%.目标产物1的熔点、[α]值和波谱数据与天然产物一致.化合物1的合成是首次报道,它对人体鼻咽癌(CN2)和胃癌(Mgc803)细胞有显著抑制活性. 相似文献
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5α,11-二羟基-2-氧代桉烷-3-(5α-Hydroxy—isopterocarpolone,1)是由贾忠建等于1996年从中药南牡蒿中首次分离得到的一种桉烷型倍半萜类天然产物.桉烷型倍半萜类化合物广泛分布于天然植物中,具有较好的昆虫拒食、抑制细胞繁殖和植物生长调节等多种生理活性.天然产物1的合成研究尚未见报道. 相似文献
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运用可靠的B3LYP/DZP++方法研究了2'-脱氧腺苷-5'-单磷酸(dAMP)与羟基自由基(HO·)的反应中所产生的20余种自由基. 结果表明, 反应的初始产物包括HO·加成到dAMP碱基C8、C4位上所形成的羟基加合物自由基, 以及dAMP碱基环上氨基的脱氢自由基. 而且,反应最初形成的C4位羟基加合物自由基具有脱水产生dAMP碱基环上氨基脱氢自由基的热力学趋势, 脱水形成的两种氨基脱氢自由基都是强氧化剂.尽管HO·加成到dAMP碱基C2位上所形成的加成产物比C4位的加成产物更稳定, 但dAMP与HO·的氧原子间较强的静电排斥作用却使得HO·难以靠近C2原子, 导致C2位的羟基加成产物难以形成. 上述结论不但与有关实验结果一致, 而且还对一些实验现象作出了合理的解释. 相似文献
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L-核苷是天然核苷的对映异构体,虽然早在20世纪60年代就有人报道L-核苷的合成,但直到最近人们对它才开始重视.生物活性研究发现,在合成核苷和DNA的酶中,细胞脱氧胞苷激酶(deK)缺乏立体专一性,它可对一些核苷类如3TC,FTC和ddC的2个对映体同时磷酸化,细胞脱氧胞苷激酶不仅可活化胞嘧啶衍生物,而且可活化腺嘌呤类的2个对映体(如D-,L-ddA;D-,L-d4A). 相似文献
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以1,3,5-三羟基苯、新戊二醇、三氯氧磷等为原料,采用简洁、高效的合成路线,通过两步反应合成了新型阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂己内磷酸酯基)苯.通过红外光谱、核磁共振氢谱、质谱、元素分析以及热失重分析等对产物结构和热性能进行了表征和研究.热失重分析表明:该阻燃剂起始分解温度为295.26℃ ,在295.26℃ ~343.38℃和350.40℃ ~578.04℃温区迅速炭化;当阻燃剂被加热到681.03℃时,炭残余量高达43.33 %. 相似文献
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The protonation constants of adenosine 5′‐monophosphate, guanosine 5′‐monophosphate, and inosine 5′‐monophosphate were determined in binary mixtures of H2O containing 0, 10, 15, 20, 25, 30, 35, 40, 45, and 50% MeOH, using a combination of potentiometric and spectrophotometric methods at a constant temperature (25°) and constant ionic strength (0.1 mol?dm?3 NaClO4). The protonation constants were analyzed using the normalized polarity parameter (E ), and Kamlet, Abboud, and Taft (KAT) parameters. A linear correlation of log K vs. the normalized polarity parameter was obtained. Dual‐parameter correlation of log K vs. π* (dipolarity/polarizability) and α (H‐bond‐donor acidity), as well as π* and β (H‐bond‐acceptor basicity) also gives good results in various aqueous organic solvent mixtures. Finally, the results are discussed in terms of the effect of solvent on the protonation equilibria. 相似文献
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3, 5, 6-哌嗪三酮-2-甲酰胺(5)经与PCl5-POCl3反应制得3, 5, 6-三氯-2-氰基吡嗪(6)。6经转化为甲酯(7)再水解为3, 5, 6-三氯-2-吡嗪甲酸(8)。由8出发合成了两个2, 3-二氯-5-取代-5, 8-二氢-8-氧-吡啶并[2, 3-b]吡嗪-7-羧酸乙酯(11a~b)。其中5, 7~11均为新化合物, 其组成和结构经元素分析、IR、^1H NMR、MS证实。 相似文献
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Synthesis and Fungicidal Activities of 2-Alkylthio-5- (3, 4, 5-tribenzyloxyphenyl)-1, 3, 4-oxadiazoles 总被引:1,自引:0,他引:1
De Qing LONG De Jiang LI Wei Quan CAI Sheng Sheng CHEN 《中国化学快报》2006,17(11):1427-1430
Abstract: Ten novel 2-alkylthio-5-(3, 4, 5-tribenzyloxyphenyl)-1, 3, 4-oxadiazole derivatives (5a-j) were synthesized from methyl 3, 4, 5-trihydroxybenzoate by ethedfication, hydrazidation, cyclization and thioetherification reactions. The structures of 5a-j were confirmed by 1HNMR, MS spectra and elemental analysis. The results indicated that most of the compounds 5 exhibited good fungicidal activities. The activity of 5h is higher than 90% against Fusarium oxysporum and Botrytis cinereapers in 50 mg/L. 相似文献
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Density functional calculations at the BP86/TZ2P level are reported for the pseudo-octahedral heteroarene complexes M(η1-EC5H5)6 and for the sandwich complexes M(η6-EC5H5)2 (M = Cr, Mo, W; E = N, P, As, Sb, Bi). The complexes M(CO)6 and M(η6-C6H6)2 have been calculated for comparison. The nature of the metal–ligand interactions was analyzed with the EDA (energy decomposition analysis) method. The calculated bond dissociation energies (BDE) of M(η1-EC5H5)6 have the order for E = P > As > N > Sb ? Bi and for M = Cr < Mo < W. All hexaheteroarenes bind more weakly than CO in M(CO)6. Except for pyridine, which is the weakest η6-bonded ligand, the trend in the BDE of the M(η6-EC5H5)2 complexes is opposite to the trend of the M(η1-EC5H5)6 complexes NC5H5 < PC5H5 < AsC5H5 < SbC5H5 < BiC5H5. The opposite trend is explained with the different binding modes in M(η6-EC5H5)2 and M(η1-EC5H5)6. The bonding in the former complexes mainly takes place through the π electrons of the ligand which are delocalized over the ring atoms while the bonding in the latter takes place through the lone-pair electrons of the heteroatoms E. The Lewis basicity of the group-15 heterobenzenes EC5H5 becomes weaker for the heavier elements E. The occupied π orbitals of the heterobenzene ring become gradually more polarized toward the five carbon atoms in the heavier arenes EC5H5 which induces stronger metal-carbon bonds in M(η6-EC5H5)2 and weaker metal-E bonds. The EDA calculations show that the nature of the M-EC5H5 bonding in M(η1-EC5H5)6 is similar to the M–CO bonding in M(CO)6. Both types of bonds have a slightly more covalent than electrostatic character. The π orbital interactions in the chromium and molybdenum complexes of CO and heterobenzene are more important than the σ interactions. This holds true also for the tungsten complexes of CO and the lighter heteroarenes while the σ- and π-bonding in the heavier W(η1-EC5H5)6 species have similar strength. The EDA results also show that the nature of the bonding in the sandwich complexes M(η6-EC5H5)2 is very similar to the bonding in the bisbenzene complexes M(η6-C6H6)2. The orbital interactions contribute for all metals and all arene ligands about 60% of the attractive interactions while the electrostatic attraction contributes about 40%. The largest contribution to the orbital term comes always from the δ orbitals. The calculations predict that the relative stability of the sandwich complexes M(η6-EC5H5)2 over the octahedral species M(η1-EC5H5)6 increases when E becomes heavier and it increases from W to Mo to Cr when E = N, P, As. 相似文献
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Prof. Dr. Tarun K. Mandal Siddhartha Samanta Sourav Chakraborty Prof. Dr. Ayan Datta 《Chemphyschem》2013,14(6):1149-1154
Mixed cation (Li+, Na+ and K+) and anion (F?, Cl?, Br?) complexes of the aromatic π‐surfaces (top and bottom) are studied by using dispersion‐corrected density functional theory. The selectivity of the aromatic surface to interact with a cation or an anion can be tuned and even reversed by the electron‐donating/electron‐accepting nature of the side groups. The presence of a methyl group in the ? OCH3, ? SCH3, ? OC2H5 in the side groups of the aromatic ring leads to further cooperative stabilization of the otherwise unstable/weakly stable anion???π complexes by bending of the side groups towards the anion to facilitate C? H???anion interactions. The cooperativity among the interactions is found to be as large as 100 kcal mol?1 quantified by dissection of the three individual forces from the total interaction energy. The crystal structures of the fluoride binding tripodal and hexapodal ligands provide experimental evidence for such cooperative interactions. 相似文献
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A. T. Gubaidullin L. M. Burnaeva V. F. Mironov I. A. Litvinov Yu. Yu. Kotorova G. A. Ivkova E. I. Goryunov I. V. Konovalova T. A. Mastryukova 《Russian Journal of General Chemistry》2004,74(12):1861-1867
The reaction with chloral of 2-[1-(3-chlorophenyl)-2,2,2-trifluoroethoxy]-5,6-benzo-1,3,2-dioxaphosphorinan-4-one containing a chiral fluorinated exocyclic substituent on phosphorus leads to formation of 2-[1-(3-chlorophenyl)-2,2,2-trifluoroethoxy]-3-(trichloromethyl)-6,7-benzo-1,4,25-dioxaphosphepin-5-one 2-oxide with a high regio- and stereoselectivity. The molecular and supramolecular structure of the isolated diastereomer was established by means of X-ray diffraction.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 12, 2004, pp. 1973–1980.Original Russian Text Copyright © 2004 by Gubaidullin, Burnaeva, Mironov, Litvinov, Kotorova, Ivkova, Goryunov, Konovalova, Mastryukova.This revised version was published online in April 2005 with a corrected cover date. 相似文献