Octahedral iridium complex catalyzed α-chlorination of 2-acyl imidazoles with tosyl chloride

An efficient and catalytic α-chlorination of 2-acyl imidazoles with readily available tosyl chloride catalyzed by an octahedral iridium complex under mild condition was reported. A range of 2-acyl imidazoles were converted to their corresponding α-chlorination products in good to excellent yields.     

Synthesis and antitumor activity of 6- and 2- （ 1-acyl sulfanylalkyl）-5,8-dimethoxy- 1,4-naphthoquinones

Sixteen novel 6- and 2-（1-acylsulfanylalkyl）-5,8-dimethoxy-l,4-naphthoquinones were designed and synthesized. Their cytotoxicities were evaluated in vitro against BEL-7402, HT-29 and SPC-Al cell lines. The pharmacological results showed that most of the prepared compounds displayed the excellent selectivity for HT-29 cell line. Compound lab exhibited the most potent antitumor activity among the tested compounds.     

Practical synthesis of β-acyl and β-alkoxycarbonyl heterocyclic sulfones

A short and efficient synthesis for β-acyl and β-alkoxycarbonyl heterocyclic sulfones containing benzothiazol (BT) and phenyltetrazol (PT) heterocyclic core is presented here. The method seems to be general and provides the desired C-nucleophiles in very good to excellent yields from readily available starting materials.     

Ab initio Study of H2O–HCl (1:1, 1:2, 2:1) Complexes

This paper reports on an ab initio (6-31G**) study of 1:1, 1:2, and 2:1 (H₂O) _n (HCl) _m complexes. Stable configurations of the 1:2 and 2:1 (H₂O) _n (HCl) _m complexes and their geometrical and energy characteristics were determined. The vibrational analysis of the complexes was carried out. The effect of hydrogen bonding due to S₁S₀ and T₀T₁ electronic excitations is considered.     

Reaction of 1, 1-Di-p-methoxyphenyl-2, 2-dinitroethylene and 1, 1-Di-O-methoxyphenyl-2, 2-dinitroethylene with 1-Benzyl-1, 4-dihydronicotinamide： Evidence for Concerted Electron-hydrogen Atom Transfer Mechanism

1,1-Di-p-methoxyphenyl-2, 2-dinitroethylene reacts with 1-benzyl-1, 4-dihydronicotinamide (BNAH) in deaerated acetonitrile to give 1,1-di-p-methoxyphenyl-2, 2-dinitroethane,while 1,1-di-O-methoxyphenyl-2, 2-dinitroethylene fails to react with BNAH under the same conditions, which provides evidence for a concerted electron-hydrogen atom transfer mechanism.     

A practical synthesis of 3-acyl cyclobutanones by [2 + 2] annulation. Mechanism and utility of the Zn(II)-catalyzed condensation of α-chloroenamines with electron-deficient alkenes

New conditions for the conversion of simple tertiary amides to α-chloroenamines and their use in Zn(II)-catalyzed cycloaddition reactions with commercial α,β-unsaturated carbonyl compounds allows rapid, regiocontrolled access to 3-acyl cyclobutanones. Reactions take place at ambient temperature without solvent, giving strained [2 + 2] adducts with all-carbon-substituted quaternary carbon atoms. Ab initio calculations of the putative keteniminium intermediate and studies with styrenyl olefins suggest a dual role for Zn(OTf)(2) during catalysis.     

Synthesis and Crystal Structure of 1-Methylsulfinyl-1-methylthio-2-cyano-2-phenylethylene

1　ＩＮＴＲＯＤＵＣＴＩＯＮＤｉｔｈｉｏａｃｅｔａｌｓ[1 3]ｈａｖｅｄｅｍｏｎｓｔｒａｔｅｄｔｈｅｉｒｐｏｔｅｎｔｉａｌｆｏｒｔｈｅｓｙｎｔｈｅｓｉｓｏｆｈｅｔｅｒｏｃｙ ｃｌｅｓ,ｔｈｅｒｅｆｏｒｅ ,ｔｈｅｉｒｓｙｎｔｈｅｓｉｓａｎｄｒｅａｃｔｉｏｎｓｈａｖｅａｔｔｒａｃｔｅｄｍｕｃｈａｔｔｅｎｔｉｏｎ ,ｂｕｔｖｅｒｙｌｉｔｔｌｅｈａｓｂｅｅｎｒｅｐｏｒｔｅｄａｂｏｕｔｔｈｅｏｘｉｄａｔｉｏｎｏｆｄｉｔｈｉｏａｃｅｔａｌｓ[4].Ａｃｃｏｒｄｉｎｇｔｏｔｈｅｐｒｅｖｉ ｏｕｓｒｅｐｏｒｔ,ｔｈｅｏｘｉｄ…     

A_a_1,A_a_2-B_b_1B_b_2缩聚反应的固化理论

本文讨论了A_(a_1),A_(a_2)-B_(b_1)B_(b_2)型缩聚反应的固化理论。给出了溶胶-凝胶分配公式、凝胶化条件、分布函数及适合固化全过程的高分子矩的循环公式和k次矩的解析表示式。     

DiastereoselectiveandEnantioselectiveSynthesisof(1S,2S)-2-Ethyl-1-aminocyclopropaneCarboxylicAcid

During the last decade, 1-aminocyclopropanecarboxylic acid and its derivatives (ACCS) have attracted increasing attention of organic and bioorganic chemists due to their outstanding biological properties, ranging from antimicrobial, insecticidal, plant growth and fruit ripening controls, etc.1. Moreover, the three-membered carbocycle provides building blocks of unprecedented synthetic potential because it undergoes selective ring opening, ring enlargement or cycloaddition reactions2. The mo…     

Solubility of Oxygen in Some 1-1, 2-1, 1-2, and 2-2 Electrolytes as a Function of Concentration at 25°C

The solubility of oxygen has been measured in a number of electrolytes [(LiCl, KCl, RbCl, CsCl, NaF, NaBr, NaI, NaNO₃, KBr, KI, KNO₃, CaCl₂, SrCl₂, BaCl₂, Li₂SO₄, K₂SO₄, Mn(NO₃)₃)] as a function of concentration at 25°C. The solubilities, mol (kg-H₂O)^–1, have been fitted to a function of the molality m (standard deviation < 3mol-kg^–1)

Uncommon expansion of piperidine ring into hydroazocine ring in reactions of some piperidine β-acyl derivatives with acetylenecarboxylic acids esters

Cyclohexanone condensation with formaldehyde and methylamine led to the formation of 4ahydroxy-2-methyloctahydrospiro[isoquinoline-4,1'-cyclohexan]-2'-one whose structure was established by means of X-ray diffraction (XRD) analysis. This spiro compound reacted with acetylenecarboxylic acids esters with unexpected conversion of its piperidine ring into a hexahydroazocine cycle. The uncommon expansion reaction of the β-acyl-substituted piperidine ring into a hexahydroazocine cycle is confirmed by the analogous conversion of 4-hydroxy-1-methyl-4-phenylpiperidin-3-yl(phenyl)methanone into azocine derivative at treating with methyl propiolate.     

Conductivities of 1∶1 salts in 2-cyanopyridine

Electrolytic conductivities of eight simple 11 electrolytes have been measured in dilute solutions of 2-cyanopyridine (2CNP) at 30°. Infinite dilution mobilities and association constants were calculated using the Fuoss-Hsia equation. With the exception of LiCF₃SO₃ all salts show very little association, consistent with the very high dielectric constant of 2CNP. The weak association which does occur is attributed to weak ion-solvent interactions. No evidence was found for triple ion formation. Conductivities of concentrated solutions of LiAsF₆ in 2CNP increase slowly with concentration reaching a maximum at a concentration of around 0.65 mol-dm^–3. These conductances are slightly lower than those in propylene carbonate which has a lower dielectric constant and a higher viscosity. Conductivities of concentrated LiAsF₆ solutions in 2CNP mixtures with acetonitrile vary monotonically, consistent with solution viscosities, and show no sign of the maximum commonly observed in mixed organic solvents.     

1-benzoyl-2-(2-naphthyl)-selenourea

During our synthesis of N-benzoyl-N'-aryl selenourea derivatives, we isolated the title compound. One of them was selected optically for the diffraction study. The crystal belongs to the Monoclinic space group P21/n, Mr = 353.27, a = 11.073(1)? , b = 5.745(1) ?, c = 24.356(5) ?, β = 92.10 (1) , V = 1548.3 (4) ?3, Z = 4, Dx=1.515 Mg/m3,λ(Mo Kα)=0.71073 ?,θ = 1.67-25,μ o = 2.428 mm-1 , T = 296 (2) K. View of the molecule showing the labeling of the non-H atoms are described as: The se…     

李春艳1,李建华1,申贵隽2*

氰化物是一种快速、剧毒的化合物,能够引起组织衰竭以至机体死亡。氰化物一旦污染环境及食用源,会严重危害人体健康,当吸入或口服较大剂量氰化物时,会引起“闪电式”骤死,中毒者在10~60S内突然发出尖叫随即昏倒,出现强直性与阵发性痉挛,2-3min后呼吸停止而死亡[1]。因此加强对氰化物检测是一项重要的安全检测指标,为此,建立准确、快速,特别是能用于现场操作的氰化物测定方法有重要意义。     

CONVERSION OF KETONES INTO1，1－DISUBSTITUTED－2，3，3－TRIFLUORO－2－PROPEN －1－OLSWITH1，1－DIBROMO－1，2，2，2－TETRLUORO ETHANE／MAGNESIUM REAGENT

ＣＯＮＶＥＲＳＩＯＮ　ＯＦ　ＫＥＴＯＮＥＳ　ＩＮＴＯ１，１－ＤＩＳＵＢＳＴＩＴＵＴＥＤ－２，３，３－ＴＲＩＦＬＵＯＲＯ－２－ＰＲＯＰＥＮ　－１－ＯＬＳＷＩＴＨ１，１－ＤＩＢＲＯＭＯ－１，２，２，２－ＴＥＴＲＬＵＯＲＯ　ＥＴＨＡＮＥ／ＭＡＧＮＥＳＩＵＭ...     

Synthesis of 2-(3-hydroxy-2-methyl-1-alkenyl)-1-pyrrolines and 2-(3-hydroxybutyl)-1-pyrroline using α-lithiated 2-methyl-1-pyrroline

Condensation of 2-methyl-1-pyrroline with chloroacetone or 3-chloro-2-butanone using LDA in THF afforded novel 2-(3-hydroxy-2-methyl-1-alkenyl)-1-pyrrolines via a peculiar reaction mechanism instead of the anticipated 2-(3-oxobutyl)-1-pyrrolines. The intermediacy of 2-(2,3-epoxy-2-methylalkyl)-1-pyrrolines in the latter transformation was demonstrated by immediate reductive epoxide ring opening utilizing lithium aluminium hydride in diethyl ether. Furthermore, 2-(3-oxobutyl)-1-pyrroline was prepared via an alternative approach through alkylation of 2-methyl-1-pyrroline with 3-chloro-2-(methoxymethyloxy)-1-propene using LDA in THF, followed by acid hydrolysis. Reduction of 2-(3-oxobutyl)-1-pyrroline by sodium borohydride in methanol afforded the corresponding 2-(3-hydroxybutyl)-1-pyrroline in good yield.     

CHINESE JOURNAL OF CHEMISTRY Vol.2 0 No .1 1 November 2 0 0 2 AUTHOR INDEX

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电子激发态SO2(A^1A2, B^1B1)分子的碰撞猝灭动力学研究

用四倍频YAG激光(266nm)把SO2分子从电子基态X^1A1激励到电子激发态A^1A2和B^1B1的高振动耦合区, 通过检测自发辐射SO2(B^1B1→X^1A1)的时间分辨信号, 测定了室温(290K)下SO2(A^1A2, B^1B1)被He, 氯代甲烷分子和某些烷烃分子猝灭的速率常数。此外, 还从碰撞配合物模型出发, 对SO2(A^1A2, B^1B1)的猝灭机制进行了讨论。