Condensation of D-glucose, o-phenylenediamine and N,N-benzylphenylhydrazine hydrochloride (NNBPHH) in a one-pot reaction, or condensation of 2-(D-arabino-tetritol-1-yl) quinoxaline and NNBPHH, gave 3-(D-erythro-glycer...Condensation of D-glucose, o-phenylenediamine and N,N-benzylphenylhydrazine hydrochloride (NNBPHH) in a one-pot reaction, or condensation of 2-(D-arabino-tetritol-1-yl) quinoxaline and NNBPHH, gave 3-(D-erythro-glycerol-1- yl)-1-phenyl-1H-pyrazolo[3,4-b]quinoxaline. The structure of the latter was determined by 1H NMR spectroscopy and by synthesis using phenylhydrazine hydrochloride instead of NNBPHH. Condensation of D-glucose and 4,5-dichloro-o-phenylenediamine gave 6,7-dichloro-2-(D-arabino-tetritol-1-yl)quinoxaline, which upon condensation with NNBPHH gave the corresponding 6,7-dichloro-3-(D-erythro-glycerol-1-yl)-1-phenyl-1H-pyrazolo[3,4-b]quinoxaline. The structure and mechanism of formation of these compounds are discussed.展开更多
The reactions of Co（C1O4）2·6H2O and Co（NO3）2.6H2O with the di-Schiff base ligand N,N＇-bis-（1-benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine （LA） in ethanol have been investigated. The reactions of LA wi...The reactions of Co（C1O4）2·6H2O and Co（NO3）2.6H2O with the di-Schiff base ligand N,N＇-bis-（1-benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine （LA） in ethanol have been investigated. The reactions of LA with excess amount of cobalt salts yield the six-coordinate complexes [CoL2]（ClO4）E·H2O 1 and [CoL2]（NO3）E·H2O 2 as isolatable products （L= N-（1- benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine）, where L is a tri-dentate mono-Schiff base ligand, resulting from the hydrolysis of the precursor di-Schiff base LA. Both complexes were characterized by X-ray crystallography. Crystal data for complex 1： monoclinic, space group P21/c, a = 11.9214（10）, b = 23.5828（17）, c = 14.0387（12）A, β = 135.219（4）°, C22H30Cl2CoN8O9, Mr = 680.37, V = 2780.1（4） A^3 ,Z = 4, Dc = 1.625 g/cm^3,μ（MoKa） = 0.876 mm^-1, F（000） = 1404, the final R = 0.0725 and wR = 0.1530 for 5726 observed reflections （I 〉 2σ（I））. Crystal data for complex 2： monoclinic, space group P21/c, a = 18.2162（16）, b = 10.0610（6）, c = 18.593（2）A, β = 130.099（3）°, C22H30CoN10O7, Mr = 605.49, V = 2606.5（4） A3 Z = 4, Dc = 1.543 g/cm^3,μ（MoKa） = 0.722 mm^-1, F（000） = 1260, the final R = 0.0619 and wR = 0.1429 for 5194 observed reflections （I 〉 2σ（I））. X-ray diffraction analysis reveals that each cobalt atom in the two complexes is chelated by six nitrogen atoms from two tridentate iigands L, exhibiting a slightly distorted octahedral coordination sphere. In both complexes, the strong hydrogen-bonding interactions between the lattice waters and N-H groups of the ligands result in 1D chains which are further connected by ClO4^- （or NO3^-） groups to form a 3D framework. In complex 2, the strong π-π interactions increase the stability of the structure.展开更多
<span style="font-family:Verdana;">The present work describes the synthesis of a novel heterocyclic azo dye by </span><span style="font-family:Verdana;">general diazonization of 2...<span style="font-family:Verdana;">The present work describes the synthesis of a novel heterocyclic azo dye by </span><span style="font-family:Verdana;">general diazonization of 2-amino-4,5-dimethylthiazole followed by the di</span><span style="font-family:Verdana;">azo-</span><span><span><span style="font-family:;" "=""> </span></span></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;">coupling of the resulting diazonium ion with 5-methyl-2-(propan-2-</span><span><span style="font-family:Verdana;">yl)phenol to obtain ligand </span><b><span style="font-family:Verdana;">L</span></b><span style="font-family:Verdana;">. This was characterized using Fouri</span></span><span style="font-family:Verdana;">er-transformed infrared and electronic spectrophotometry. Ligand </span><b><span style="font-family:Verdana;">L </span></b><span style="font-family:Verdana;">was further coordinated with five </span><span style="font-family:Verdana;">metal ions, M:L, 1:2 </span></span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">[</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">M</span></span></span><span><span><span style="font-family:;" "=""> </span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">= Cu(II), Mn(II), Zn(II), Ni(II) and Co(II)</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">]</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">. The </span></span></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;">coordination compounds obtained were characterized by electronic, IR spectrophotometry, magnetic susceptibility and percentage metal analyses. The results obtained suggested that a thiazoylazo dye was obtained as ligand </span><b><span style="font-family:Verdana;">L</span></b><span style="font-family:Verdana;">. It was proposed that two molecules of the solvent coordinated to the metal ion in addition with the ligands to give an octahedral geometry for copper(II), manganese(II) and nickel(II) complexes. On the other hand, square planar </span><span style="font-family:Verdana;">geometry was suggested for zinc(II) and cobalt(II) complexes. The an</span><span style="font-family:Verdana;">ti-infla</span></span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">- </span></span></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;">mmatory activity of the ligand and coordination compounds was evaluated using four </span><i><span style="font-family:Verdana;">in</span></i> <i><span style="font-family:Verdana;">vitro</span></i><span style="font-family:Verdana;">-based assays viz: </span><span><span style="font-family:Verdana;">xanthine oxidase and lipoxygenase inhibition assay, membrane stability and protein denaturation assay. The synthesized compounds generally exhibited good anti-inflammatory activity in all </span><span style="font-family:Verdana;">the assays carried out. However, the reference standards, in this instance,</span><span style="font-family:Verdana;"> were more effective in the case of xanthine oxidase, lipoxygenase and protein denaturation inhibitory assays. For the membrane stability study, the </span><span><span style="font-family:Verdana;">coordination compounds and ligand </span><b><span style="font-family:Verdana;">L </span></b><span style="font-family:Verdana;">elicited more potent anti-inflammatory</span></span><span style="font-family:Verdana;"> activity than the standard drug.</span></span></span></span></span>展开更多
A visible-light-catalyzed synthesis of indol-3-yl aryl ketones from aryldiazonium salts, CO and indoles at room temperature was developed. This process provides a useful method for the preparation of diverse indol-3-y...A visible-light-catalyzed synthesis of indol-3-yl aryl ketones from aryldiazonium salts, CO and indoles at room temperature was developed. This process provides a useful method for the preparation of diverse indol-3-yl aryl ketones from readily accessible reactants under base-free, acid-free and transition-metalfree conditions.展开更多
The title compound, （E）-1-（7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl）- 3-（2-methoxyphenyl）-2-（1H-1,2,4-triazol-1-yl）propenol （3a）, was synthesized by the Aldol con- densation reaction of 1-（7-methox...The title compound, （E）-1-（7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl）- 3-（2-methoxyphenyl）-2-（1H-1,2,4-triazol-1-yl）propenol （3a）, was synthesized by the Aldol con- densation reaction of 1-（7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl）-2-（1,2,4-triazol- 1-yl）ethanone with 2-methoxybenzaldehyde and then reduced with NaBH4, and its crystal structure was determined by single-crystal X-ray diffraction： monoclinic system, space group P21 with a = 6.2002（3）, b = 12.8452（7）, c = 13.2257（7） ？, Z = 2, V = 1031.23（9） ？3, Mr = 407.46, Dc = 1.312 Mg/m3, S = 1.054, μ = 0.091 mm-1, F（000） = 432, the final R = 0.0353 and wR = 0.0769 for 3161 observed reflections （I 〉 2σ（I））. X-ray analysis displays that the title compound adopts an E configuration for the C（7）=C（8） double bond and S configuration for the chirality center with the specific rotation of –63.75°. Furthermore, the stability of the crystal was maintained through the intermolecular hydrogen bond O（1）–H？？？N（3）. The antitumor assay exhibits that the title compound 3a （E configuration） has a good antitumor activity against the Hela cell line with the IC50 value of 36.9 μM, which is better than that of 3b （Z configuration）.展开更多
An efficient regioselective Friedel-Crafts hydroxyalkylation of N-substituted glyoxylamide with various indoles catalyzed by Lewis acids was developed. The reactions proceeded smoothly at room temperature and the 2-hy...An efficient regioselective Friedel-Crafts hydroxyalkylation of N-substituted glyoxylamide with various indoles catalyzed by Lewis acids was developed. The reactions proceeded smoothly at room temperature and the 2-hydroxy-2-（1H-indol-3-yl）-N-substituted acetamide resulted from the reactions catalyzed by FeSO4 were synthesized in excellent yields （up to 93%）. While the bisindole compounds were obtained when FeCl3 was used as a catalyst in excellent yields （up to 92%）. A possible mechanism was proposed.展开更多
n-Dodecylbenzene sulfonic acid (DBSA) as a novel, biodegradable, and efficient Br?nsted acid catalyst used for the reaction of indoles/4-hydroxy coumarin with aldehydes to obtain a bis(indolyl)methanes/bis(4-hydroxyco...n-Dodecylbenzene sulfonic acid (DBSA) as a novel, biodegradable, and efficient Br?nsted acid catalyst used for the reaction of indoles/4-hydroxy coumarin with aldehydes to obtain a bis(indolyl)methanes/bis(4-hydroxycoumarin-3-yl)methanes, respectively. The catalyst exhibited remarkable activity, and tolerated a wide variety of functional groups providing the desired bis(indolyl)methanes and bis(4-hydroxycoumarin-3-yl)methanes in good to excellent yield (70%-96%) in water.展开更多
文摘Condensation of D-glucose, o-phenylenediamine and N,N-benzylphenylhydrazine hydrochloride (NNBPHH) in a one-pot reaction, or condensation of 2-(D-arabino-tetritol-1-yl) quinoxaline and NNBPHH, gave 3-(D-erythro-glycerol-1- yl)-1-phenyl-1H-pyrazolo[3,4-b]quinoxaline. The structure of the latter was determined by 1H NMR spectroscopy and by synthesis using phenylhydrazine hydrochloride instead of NNBPHH. Condensation of D-glucose and 4,5-dichloro-o-phenylenediamine gave 6,7-dichloro-2-(D-arabino-tetritol-1-yl)quinoxaline, which upon condensation with NNBPHH gave the corresponding 6,7-dichloro-3-(D-erythro-glycerol-1-yl)-1-phenyl-1H-pyrazolo[3,4-b]quinoxaline. The structure and mechanism of formation of these compounds are discussed.
基金the National Natural Science Foundation of China (20425313)the Natural Science Foundation of Fujian Province (2005HZ01-1, 2006L2005, 2006F3135, 2006J0183)
文摘The reactions of Co（C1O4）2·6H2O and Co（NO3）2.6H2O with the di-Schiff base ligand N,N＇-bis-（1-benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine （LA） in ethanol have been investigated. The reactions of LA with excess amount of cobalt salts yield the six-coordinate complexes [CoL2]（ClO4）E·H2O 1 and [CoL2]（NO3）E·H2O 2 as isolatable products （L= N-（1- benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine）, where L is a tri-dentate mono-Schiff base ligand, resulting from the hydrolysis of the precursor di-Schiff base LA. Both complexes were characterized by X-ray crystallography. Crystal data for complex 1： monoclinic, space group P21/c, a = 11.9214（10）, b = 23.5828（17）, c = 14.0387（12）A, β = 135.219（4）°, C22H30Cl2CoN8O9, Mr = 680.37, V = 2780.1（4） A^3 ,Z = 4, Dc = 1.625 g/cm^3,μ（MoKa） = 0.876 mm^-1, F（000） = 1404, the final R = 0.0725 and wR = 0.1530 for 5726 observed reflections （I 〉 2σ（I））. Crystal data for complex 2： monoclinic, space group P21/c, a = 18.2162（16）, b = 10.0610（6）, c = 18.593（2）A, β = 130.099（3）°, C22H30CoN10O7, Mr = 605.49, V = 2606.5（4） A3 Z = 4, Dc = 1.543 g/cm^3,μ（MoKa） = 0.722 mm^-1, F（000） = 1260, the final R = 0.0619 and wR = 0.1429 for 5194 observed reflections （I 〉 2σ（I））. X-ray diffraction analysis reveals that each cobalt atom in the two complexes is chelated by six nitrogen atoms from two tridentate iigands L, exhibiting a slightly distorted octahedral coordination sphere. In both complexes, the strong hydrogen-bonding interactions between the lattice waters and N-H groups of the ligands result in 1D chains which are further connected by ClO4^- （or NO3^-） groups to form a 3D framework. In complex 2, the strong π-π interactions increase the stability of the structure.
文摘<span style="font-family:Verdana;">The present work describes the synthesis of a novel heterocyclic azo dye by </span><span style="font-family:Verdana;">general diazonization of 2-amino-4,5-dimethylthiazole followed by the di</span><span style="font-family:Verdana;">azo-</span><span><span><span style="font-family:;" "=""> </span></span></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;">coupling of the resulting diazonium ion with 5-methyl-2-(propan-2-</span><span><span style="font-family:Verdana;">yl)phenol to obtain ligand </span><b><span style="font-family:Verdana;">L</span></b><span style="font-family:Verdana;">. This was characterized using Fouri</span></span><span style="font-family:Verdana;">er-transformed infrared and electronic spectrophotometry. Ligand </span><b><span style="font-family:Verdana;">L </span></b><span style="font-family:Verdana;">was further coordinated with five </span><span style="font-family:Verdana;">metal ions, M:L, 1:2 </span></span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">[</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">M</span></span></span><span><span><span style="font-family:;" "=""> </span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">= Cu(II), Mn(II), Zn(II), Ni(II) and Co(II)</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">]</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">. The </span></span></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;">coordination compounds obtained were characterized by electronic, IR spectrophotometry, magnetic susceptibility and percentage metal analyses. The results obtained suggested that a thiazoylazo dye was obtained as ligand </span><b><span style="font-family:Verdana;">L</span></b><span style="font-family:Verdana;">. It was proposed that two molecules of the solvent coordinated to the metal ion in addition with the ligands to give an octahedral geometry for copper(II), manganese(II) and nickel(II) complexes. On the other hand, square planar </span><span style="font-family:Verdana;">geometry was suggested for zinc(II) and cobalt(II) complexes. The an</span><span style="font-family:Verdana;">ti-infla</span></span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">- </span></span></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;">mmatory activity of the ligand and coordination compounds was evaluated using four </span><i><span style="font-family:Verdana;">in</span></i> <i><span style="font-family:Verdana;">vitro</span></i><span style="font-family:Verdana;">-based assays viz: </span><span><span style="font-family:Verdana;">xanthine oxidase and lipoxygenase inhibition assay, membrane stability and protein denaturation assay. The synthesized compounds generally exhibited good anti-inflammatory activity in all </span><span style="font-family:Verdana;">the assays carried out. However, the reference standards, in this instance,</span><span style="font-family:Verdana;"> were more effective in the case of xanthine oxidase, lipoxygenase and protein denaturation inhibitory assays. For the membrane stability study, the </span><span><span style="font-family:Verdana;">coordination compounds and ligand </span><b><span style="font-family:Verdana;">L </span></b><span style="font-family:Verdana;">elicited more potent anti-inflammatory</span></span><span style="font-family:Verdana;"> activity than the standard drug.</span></span></span></span></span>
基金the financial support from the Educational Bureau of Yunnan Province (No. 2010Y431)the State Ethnic Affairs Commission (No. 12YNZ05)
文摘A visible-light-catalyzed synthesis of indol-3-yl aryl ketones from aryldiazonium salts, CO and indoles at room temperature was developed. This process provides a useful method for the preparation of diverse indol-3-yl aryl ketones from readily accessible reactants under base-free, acid-free and transition-metalfree conditions.
基金Project supported by the National Natural Science Foundation of China(No.21442014)
文摘The title compound, （E）-1-（7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl）- 3-（2-methoxyphenyl）-2-（1H-1,2,4-triazol-1-yl）propenol （3a）, was synthesized by the Aldol con- densation reaction of 1-（7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl）-2-（1,2,4-triazol- 1-yl）ethanone with 2-methoxybenzaldehyde and then reduced with NaBH4, and its crystal structure was determined by single-crystal X-ray diffraction： monoclinic system, space group P21 with a = 6.2002（3）, b = 12.8452（7）, c = 13.2257（7） ？, Z = 2, V = 1031.23（9） ？3, Mr = 407.46, Dc = 1.312 Mg/m3, S = 1.054, μ = 0.091 mm-1, F（000） = 432, the final R = 0.0353 and wR = 0.0769 for 3161 observed reflections （I 〉 2σ（I））. X-ray analysis displays that the title compound adopts an E configuration for the C（7）=C（8） double bond and S configuration for the chirality center with the specific rotation of –63.75°. Furthermore, the stability of the crystal was maintained through the intermolecular hydrogen bond O（1）–H？？？N（3）. The antitumor assay exhibits that the title compound 3a （E configuration） has a good antitumor activity against the Hela cell line with the IC50 value of 36.9 μM, which is better than that of 3b （Z configuration）.
基金the National Natural Science Foundation of China (Nos. 21472130, 81373259) for financial support of this study
文摘An efficient regioselective Friedel-Crafts hydroxyalkylation of N-substituted glyoxylamide with various indoles catalyzed by Lewis acids was developed. The reactions proceeded smoothly at room temperature and the 2-hydroxy-2-（1H-indol-3-yl）-N-substituted acetamide resulted from the reactions catalyzed by FeSO4 were synthesized in excellent yields （up to 93%）. While the bisindole compounds were obtained when FeCl3 was used as a catalyst in excellent yields （up to 92%）. A possible mechanism was proposed.
文摘n-Dodecylbenzene sulfonic acid (DBSA) as a novel, biodegradable, and efficient Br?nsted acid catalyst used for the reaction of indoles/4-hydroxy coumarin with aldehydes to obtain a bis(indolyl)methanes/bis(4-hydroxycoumarin-3-yl)methanes, respectively. The catalyst exhibited remarkable activity, and tolerated a wide variety of functional groups providing the desired bis(indolyl)methanes and bis(4-hydroxycoumarin-3-yl)methanes in good to excellent yield (70%-96%) in water.
