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以对苯二甲醛、丙二腈、季戊四醇和毗咯为原料,合成了含有螺环结构单元的中间体3-[4-(2,2-二氰基)乙烯基]苯基-9-(4-甲酰基)苯基-2,4,8,10-四氧杂螺[5.5]十一烷(3)和α,β,γ,δ-四-(4-甲酰基苯基)卟啉(4).4与过量的季戊四醇反应,得到α,β,γ,δ-四-{4-[2-(5,5-二羟甲基-1,3-二噁烷基)]}苯基卟啉(5),5与3的反应产物经10%NaOH处理后,再与过量的季戊四醇反应,得到α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二羟甲基-1,3-二噁烷基))))苯基一2,4,8,10.四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]]苯基卟啉(6),6与乙酐、丙酐、苯甲酰氯反应,得到α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二乙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基])苯基卟啉(7),α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二丙酰氧基甲基-1,3-二噁烷基))))苯基.2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(8)和α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二苯甲酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(9)等三种卟啉星形化合物.中间体1~6和星形化合物7~9均进行了IR,1H NMR,MS和元素分析等结构表征.对影响反应的诸因素进行了讨论. 相似文献
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呋咱并[3,4-e]-4,6-二氧化-1,2,3,4-四嗪新法合成与表征 总被引:1,自引:0,他引:1
自行设计了呋咱并[3,4-e]-1,2,3,4-四嗪-4,6-二氧化(FTDO)新的合成路线,采用3,4-二氨基呋咱(DAF)为起始原料,经过氧化﹑缩合﹑硝化﹑成环4步反应合成了FTDO,总收率为30.89%,并采用核磁共振光谱﹑红外光谱﹑质谱及元素分析等进行了结构表征.探讨了成环反应的机理,并研究了硝化及成环反应条件,确定硝化反应的最佳条件为:硝化试剂为100%HNO3,25℃下反应2 h,收率为99.54%;成环反应的最佳条件为:55℃下反应5 h,n(化合物4)∶n(P2O5)为1∶16,溶剂量为160 mL/g,收率为46.37%. 相似文献
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α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5] 十一烷基]}苯基卟啉星形化合物的合成 总被引:1,自引:1,他引:0
以对苯二甲醛、丙二腈、季戊四醇和吡咯为原料, 合成了含有螺环结构单元的中间体3-[4-(2,2-二氰基)乙烯基]苯基-9-(4-甲酰基)苯基-2,4,8,10-四氧杂螺[5.5]十一烷(3)和α,β,γ,δ-四-(4-甲酰基苯基)卟啉(4). 4与过量的季戊四醇反应, 得到α,β,γ,δ-四-{4-[2-(5,5-二羟甲基-1,3-二噁烷基)]}苯基卟啉(5), 5与3的反应产物经10% NaOH 处理后, 再与过量的季戊四醇反应, 得到α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二羟甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(6), 6与乙酐、丙酐、苯甲酰氯反应, 得到α,β,γ,δ-四-{4-[3-(9-(4-(3- (9-(4-(2-(5,5-二乙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(7), α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二丙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(8)和α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二苯甲酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(9)等三种卟啉星形化合物. 中间体1~6和星形化合物7~9均进行了IR, 1H NMR, MS和元素分析等结构表征. 对影响反应的诸因素进行了讨论. 相似文献
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Merz 首先报道了二苯乙烯基型冠醚化合物2,3,11,12-四苯基-1,4,7,10,13,16-六氧杂-环十八-2,11-二烯(1)的合成。吴成泰等采用不同的相转移催化剂合成了2,3,14,15-四苯基-1,4,7,10,13,16,19,22-八氧杂-环廿四-2,14-二烯(2),并初步探讨了其反应机理。Inoue 等研究了1、2和2,3,17,18-四苯基-1,4,7,10,13,16,19,22,25,28-十氧杂-环卅-2,17-二烯(3)的合成和反应。由于此类冠醚环内含有双键的结构特征,引起人们的兴趣。周性尧、吴成泰等以2作为中性离子载体,研制出比商品电极内阻低、pH 范围宽和响应灵敏高的钠离子选择电极。为进一步改善中性离 相似文献
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F. Firoozi K. Javidnia M. Kamali A. Fooladi A. Foroumadi A. Shafiee 《Journal of heterocyclic chemistry》1995,32(1):123-128
Starting from readily available ethyl-4-nitropyrrole-2-carboxylate ( 1 ), substituted 1-methyl-2-(1,3,4-thiadiazol-2-yl)-4-nitropyrroles and 1-methyl-2-(1,3,4-oxadiazol-2-yl)-4-nitropyrroles were prepared. The reaction of 1 with diazomethane gave ethyl 1-methyl-4-nitropyrrole-2-carboxylate ( 2 ). Reaction of compound 2 with hydrazine hydrate afforded the corresponding hydrazide 3 . The reaction of 3 with formic acid yielded 1-(1-methyl-4-nitropyrrole-2-carboxyl)-2-(formyl)hydrazine ( 7 ). Refluxing of the latter with phosphorus pentasulfide in xylene yielded compound 6 in 40% yield. Reaction of compound 7 with phosphorus pentoxide afforded compound 9 . Reaction of compound 3 with 1,1′-carboxyldiimidazole in the presence of triethylamine yielded 2-(1-methyl-4-nitro-2-pyrrolyl)-1,3,4-oxadiazoline-4(H)-5-one ( 11 ). Refluxing compound 3 with cyanogen bromide in methanol gave compound 12 . Compound 13 could be obtained through the reaction of compound 3 with carbon disulfide in basic medium. Alkylation of compound 13 afforded the correspanding alkylthio derivative 14 . Reaction of 1-methyl-4-nitropyrrole-2-carboxylic acid ( 15 ) with thiosemicarbazide and phosphorus oxychloride gave 2-amino-5-(1-methyl-4-nitro-2-pyrrolyl)-1,3,4-thiadiazole ( 16 ). Sandmeyer reaction of compound 16 yielded 2-chloro-5-(1-methyl-4-nitro-2-pyrrolyl)-1,3,4-thiadiazole ( 17 ). Refluxing of the latter with thiourea afforded 2-(1-methyl-4-nitro-2-pyrrolyl)-1,3,4-thiadiazoline-4(H)-5-thione ( 18 ). Alkylation of compound 18 gave the corresponding alkylthio derivative 19 . Oxidation of the latter with hydrogen peroxide in acetic acid yielded 2-(1-methyl-4-nitro-2-pyrrolyl)-5-methylsulfonyl-1,3,4-thiadiazole ( 20 ). 相似文献
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M Fujita A Ota S Ito K Yamamoto Y Kawashima T Iso J Iwao 《Chemical & pharmaceutical bulletin》1990,38(4):936-941
SA2572 ((+)-1), 3-acetyl-2-[5-methoxy-2-[4-[N-methyl-N-(3,4,5-trimethoxyphenethyl) amino] butoxy]phenyl]-benzothiazoline hydrochloride is a newly synthesized Ca2+ antagonist having a inhibitory effect on the fast Na+ inward channel. In order to clarify the absolute configurations and the pharmacological properties of both enantiomers, compounds ((+)-1 and (-)-1) were synthesized. The configurations of these compounds were assigned on the basis of an X-ray crystallographic analysis of synthetic precursor (5). The in vitro Ca2+ channel blocking activities of (+)-1 and (-)-1 were evaluated in terms of the inhibitory activities on depolarization-induced contraction of guinea pig taenia cecum and rabbit aorta. The in vivo efficacy of the enantiomers was evaluated with their hypotensive effects in spontaneously hypertensive rats. Compound (-)-1 showed more potent Ca2+ antagonistic activities on guinea pig taenia cecum and rabbit aorta and the hypotensive effect than those activities of (+)-1. In the electrophysiological study of Langendorff perfused rabbit hearts, compound (+)-1 showed more potent inhibitory effect on the fast Na+ inward channel than that of compound (-)-1, and an approximately equal potent inhibitory effect on the slow Ca2+ inward channel as compared with compound (-)-1. Stereoselectivity of the pharmacological activity was found. 相似文献
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Gökhan Alpaslan Hasan Tanak Ayşen Alaman Ağar Ahmet Erdönmez Şamil Işık 《Structural chemistry》2010,21(5):1027-1036
The Schiff base compound (E)-2-(1-(2-(4-methylphenylsulfonamido)ethyliminio)ethyl) phenolate has been synthesised and characterized
by IR, UV–Vis, and X-ray single-crystal determination. Ab initio calculations have been carried out for the title compound
using the density functional theory (DFT) and Hartree–Fock (HF) methods at 6-31G(d) basis set. The calculated results show
that the DFT/B3LYP and HF can well reproduce the structure of the title compound. Using the TD-DFT and TD-HF methods, electronic
absorption spectra of the title compound have been predicted and a good agreement with the TD-DFT method and the experimental
ones is determined. Molecular orbital coefficient analyses reveal that the electronic transitions are mainly assigned to n → π* and π → π* electronic transitions. To investigate the tautomeric stability, optimization calculations at B3LYP/6-31G(d)
level were performed for the NH and OH forms of the title compound. Calculated results reveal that the OH form is more stable
than NH form. In addition, molecular electrostatic potential and NBO analysis of the title compound were performed at B3LYP/6-31G(d)
level of theory. 相似文献
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A new sulfonyl group-containing heterocyclic compound 2-(2-chloro-4-nitrophenylsulfonyl)-1-(2-thienyl)ethanone 2 was prepared from the corresponding sulfide 2-(2-chloro-4-nitrophenylthio)-1-(2-thienyl)ethanone 1 . Two different cyclization reactions of the compound 2 were discussed. In contrast to the tandem alkylation-cyclization process [1], another cyclic procedure was described. In the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene as a base and dimethylformamide as a solvent, compound 2 was treated with ethyl acrylate or methyl methacrylate at 50–55° to give the 1,4-benzoxathiin 4,4-dioxide 5 or 6 respectively via a tandem Michael conjugate addition-cyclization process. 相似文献
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Tanak H 《The journal of physical chemistry. A》2011,115(47):13865-13876
The Schiff base compound (E)-2-[(2-chlorophenyl)iminomethyl]-4-trifluoromethoxyphenol has been synthesized and characterized by IR, UV-vis, and X-ray single-crystal determination. The molecular geometry from X-ray experiment in the ground state has been compared using the density functional theory (DFT) with the 6-311++G(d,p) basis set. The calculated results show that the DFT can well reproduce the structure of the title compound. Using the TD-DFT method, electronic absorption spectra of the title compound have been predicted, and a good agreement is determined with the experimental ones. To investigate the tautomeric stability, optimization calculations at the B3LYP/6-311++G(d,p) level were performed for the enol and keto forms of the title compound. Calculated results reveal that its enol form is more stable than its keto form. The predicted nonlinear optical properties of the title compound are much greater than those of urea. The changes of thermodynamic properties for the formation of the title compound with the temperature ranging from 200 to 500 K have been obtained using the statistical thermodynamic method. At 298.15 K, the change of Gibbs free energy for the formation reaction of the title compound is -824.841 kJ/mol. The title compound can spontaneously be produced from the isolated monomers at room temperature. The tautomeric equilibrium constant is also computed as 3.85 × 10(-4) at 298.15 K for enol?keto tautomerization of the title compound. In addition, a molecular electrostatic potential map of the title compound was performed using the B3LYP/6-311++G(d,p) method. 相似文献
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Starting from readily available 1-methyl-5-nitroimidazole-2-carboxylic acid hydrazide (1), 1-methyl-2-(1,3,4-thiadiazol-2-yl)-5-nitroimidazole (4) and 1-methyl-2-(1,3,4-oxadiazol-2-yl)-5-nitroimidazole (10) were prepared. The reaction of 1 with formic acid gave 1-(1-methyl-5-nitroimidazole-2-carboxyl)-2-(formyl)hydrazine ( 8 ) in high yield. Refluxing of the latter with phosphorus pentasulfide in xylene yielded compound 4 in 50% yield. Reaction of compound 8 with phosphorus pentoxide afforded compound 10 in 60% yield. 相似文献
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Albayrak C Odabaşoğlu M Ozek A Büyükgüngör O 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2012,85(1):85-91
In this study, the molecular structure and spectroscopic properties of the title compound were characterized by X-ray diffraction, FT-IR and UV-vis spectroscopies. These properties were also investigated using DFT method. The most convenient conformation of title compound was firstly determined. The geometry optimizations in gas phase and solvent media were performed by DFT methods with B3LYP adding 6-31G(d) basis set. The differences between crystal and computational structures are due to crystal packing in which hydrogen bonds play an important role. UV-vis spectra were recorded in different organic solvents. The results show that title compound exists in both keto and enol forms in DMSO, EtOH but it tends to shift towards enol form in benzene. The polar solvents facilitate the proton transfer by decreasing the activation energy needed for Transition State. The formation of both keto and enol forms in DMSO and EtOH is due to decrease in the activation energy. TD-DFT calculations starting from optimized geometry were carried out in both gas and solution phases to calculate excitation energies of the title compound. The non-linear optical properties were computed at the theory level and the title compound showed a good second order non-linear optical property. In addition, thermodynamic properties were obtained in the range of 100-500K. 相似文献
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利用丙氨酸和2,5-二羟基苯甲醛所形成的亚胺叶立德与C60发生1,3-偶极环加成反应, 合成并分离、纯化制备了一种新的C60吡咯烷衍生物: 2-(2-5-二羟基苯基)-5-甲基-2,5-二氢吡咯并[3,4]富勒烯. 通过1H NMR, FT-IR, UV-vis和元素分析确定了其结构, 研究了体系的电化学和荧光性质. 采用密度泛函的方法, 在B3LYP/6-31G水平上对分子的几何构型进行了优化, 得到稳定的几何构型; 运用INDO/S方法计算了化合物的电子光谱, 计算结果434.2 nm与实验值432.0 nm基本一致. 相似文献