Zinc-Promoted Barbier-Type Reaction of Propargyl Bromide with Aldehydes in Aqueous Media

In the prese of metallic zinc, propargyl bromide is found to react with aldehydes at room temperature in tetrahydrofurane-saturated aqueous ammonium chloride (5:2) to afford the corresponding homopropargylic alcohols in moderate to high yields together with small amounts of α-allenic alchohols.     

Trimethylsilylation of Propargyl Chloride and Propargyl Bromide

Me₃SiC[tbnd]CCH₂Cl and Me₃SiC[tbnd]CCH₂Br are obtained in high yields by treating propargyl chloride and bromide, respectively, with n-butyllithium and lithium diisopropylamide and subsequently adding chlorotrimethylsilane in the presence of hexamethylphosphoric triamide (HMPT). An effective method for the purification of HMPT is described.     

Reaction of Propargyl Bromide with Aldehydes in the Presence of Metallic Tin. Synthesis of Homopropargylalcohols and Homoallenylalcohols

In the presence of water, metallic tin and propargyl bromide reacted smoothly with aldehydes to give the corresponding homopropargyl alcohols (a) and homoallenyl alcohols (b). High Chemospecifity to bifounctional carbonyl compounds containing -OH, -X and -NO₂ etc. was obtained.     

锡-铟促进和微波辐射辅助下醛和炔丙基溴的炔丙基化反应

A rapid and regioselective preparation of homopropargyl alcohols was reported. In the presence of SnCl2C6HsMe3NBr and microwave irradiation, the mixture of tin-indium and propargyl bromide reacted quickly with aldehydes in aqueous media to produce the homopropargyl alcohols exclusively in high yields. For benzaldehydes bearing different substituents, electronic effect of the substituents affected the reaction, the electron-withdrawing groups promoting the reaction and the electron-donating groups impeding the reaction. The reactions of benzaldehydes bearing an ortho substituent group on the phenyl ring with propargyl bromide may yield a mixture of regioisomers （homopropargyl and homoallenyl alcohols） or a single homoallenic alcohol due to the steric effect.     

Triphenylphosphine-Catalyzed Isomerisation of Propargyl Bromide to 1-Bromopropadiene

Pure bromopropadiene, BrCH=C=CH₂ has been obtained by isomerisation of propargyl bromide in the presence of catalytic amounts of triphenylphosphine.     

有机高价碘盐参与的炔丙醇的交叉偶联反应

有机高价碘在钯（Ⅱ）／铜（Ⅰ）共催化作用下与炔丙醇发生交叉偶联反应生成3－取代炔丙醇。该反应不仅条件温和，产率很高，而且具有良好的区域选择性。所得产物均经熔点，IR及^1H NMR验证。     

炔丙型硫Ylide环丙烷化反应及其立体选择性

炔丙型硫Ylide与丙烯酸酯的反应是一个多反应竞争的复杂反应, 通常环丙烷化产物收率很低. 本文通过对反应底物的优化, 成功获得了高收率、高选择性的反式环丙烷化产物. 同时利用Gaussian 03程序, 选择密度泛函BHHLYP方法, 6-31G**基组对反应路径及过渡态模型进行了计算, 进而采用密度泛函理论中的B3LYP方法, 选择6-31G**基组, 对顺、反式产物的热稳定性进行了分析, 明确了该反应的高非对映选择性是由过渡态的能量差异和产物的热稳定性两个因素共同决定的, 而过渡态的能量差异可以归于分子内弱的立体电子效应的不同.     

The Reaction of Indole Magnesium Bromide with Ketones I. The Reaction of Indole Magnesium Bromide with Cyclohexanone

Indole magnesium bromide, produced by reacting indole with n-butyl magnesium bromide in ether, was reacted with cyclohexanone at ice or room temperature to yield 1-(indol-I-yl)-cyclohexanol (I), which is unstable and may be decomposed easily into indole and cyclohexanone in acidic condition. Indole magnesium bromide reacted with cyclohexanone in refluxing benzene or in anisole at 80°C, to form two products, 1-(indol-3-yl)-cyclohexanol (II) and 1-(indol-3-yl)-cyclohexene (III). (II) could be converted to (III) by heating (II) in phosphoric acid. Reaction of III with maleic anhydride gave a Diels-Alder adduct (IV). Reaction of indole magnesium bromide with cyclohexanone in anisole at 130°C yielded (III) and a trimolecular condensation product of cyclohexanone (V).     

Reaction of Silver Metaborate with Trimethyltin Bromide

The reaction between trimethyltin bromide and silvermetaboratc leads to the formation of trimethyltin metaborate, (CH₃)₃SnBO₂, and AgBr. The properties of the isolated new trimethyltin metaborate have also been studied. U.V. and I.R. spectra of (CH₃)₃SnBO₂ has also been recorded.     

乙烯基溴化镁与苯基取代氯甲烷反应的CIDNP效应

化学诱导动态核极化(CIDNP)巳广泛地用于研究溶液中的各种自由基反应。CIDNP研究表明,在Grignard试剂的生成以及Grignard试剂与卤代烃的反应中,很多是按自由基历程进行的。我们曾报道,乙烯基溴化镁(1)与三苯基氯甲烷(2)反应时,生成三苯基甲烷(4)和乙炔(5),并检测到反应溶液中三苯甲基自由基的ESR谱;1与二苯基氯甲烷(6)反应生成1,1,2,2-四苯基乙烷(7),二苯基甲烷(8),3,3-二苯基丙烯(9),1,3-丁二烯(10)和溴乙烯(11),并提出这些反应可能是通过自由基中间体进行的。为了进一步探讨反应机理,我们对题目化合物的反应进行了CIDNP实验,取得了一些很有意义的结果。     

金属锡作用下炔丙基碘与醛类化合物的反应

金属锡作用下的烯丙基卤代物与羰基化合物的加成反应以其反应条件温和及能选择性地与含有其他反应活性基团的羰基化合物加成等特点而显示出在有机合成上的应用价值。但目前这类反应还只局限于烯丙基卤代物反应的范围内。本文首次报道金属锡作用下的炔丙     

Regioselective Propargylation of Aldehydes with Propargyl Bromide Mediated by Sn-In in Aqueous Media under Microwave Irradiation

Tin-indium were employed in the propargylations of various aldehydes with propargyl bromide in the presence of SnCl2 and C6H5（CH3）3NBr under microwave irradiation to afford the corresponding homopropargyl alcohols exclusively in high yields. All the reactions were completed smoothly in predominantly aqueous media in 200 seconds only.     

Structures and Chemical Bonding in Antimony(III) Bromide Complexes with Pyridine

Weakly or “partially” bonded molecules are an important link between the chemical and van der Waals interactions. Molecular structures of six new SbBr₃-Py complexes in the solid state have been determined by single-crystal X-ray diffraction analysis. In all complexes all Sb atoms adopt a pseudo-octahedral coordination geometry which is completed by additional Sb⋅⋅⋅Br contacts shorter than the sum of the van der Waals radii, with Br−Sb⋅⋅⋅Br angles close to 180°. To reveal the nature of Sb–Br and Sb–N interactions, the DFT calculations were performed followed by the analysis of the electrostatic potentials, the orbital interactions and the topological analysis. Based on Natural Bond Orbital (NBO) analysis, the Sb–Br interactions range from the covalent bonds to the pnictogen bonds. A simple structural parameter, non-covalence criterion (NCC) is defined as a ratio of the atom-atom distance to the linear combination of sums of covalent and van der Waals radii. NCC correlates with E(2) values for Sb−N, Sb−Cl and Sb−Br bonds, and appears to be useful criterion for a preliminary evaluation of the bonding situation.     

Photorearrangement of Propargyl Bromide as a Probe to Study Propargylic and Allenic Radicals by Infrared Matrix Isolation Technique

The photolysis of propargyl bromide in Ar matrix to form allenyl bromide proceeded with a radical mechanism. The deuterium label study and radical scavenger were used to investigate the mechanism. Neither propargyl nor allenyl radical was trapped in Ar matrix at 8 K. The rates of propargyl and allenyl radicals coupled with bromo radical are significantly fast. The stability of propargyl and allenyl radicals is discussed.     

Theoretical Study on the Mechanism of the Gas-phase Reaction of Sc＋ with Propargyl Alcohol

In order to elucidate the reaction mechanisms of reaction Sc^＋ with propargyl alcohol (PPA), the triplet potential energy surface for the reactions has been theoretically investigated using a DFT method. The geometries for the reactants, intermediates, transition states and products were completely optimized at B3LYP/DZVP level. The single point energy of each stationary point was calculated at MP4/(6-311＋G** for C, H, O and Lanl2dz for Sc^＋) level. All the transition states were verified by the vibrational analysis and the internal reaction coordinate (IRC) calculations. The present results show that the reaction takes an insertion-elimination mechanism both along the O—H and C—O bond activation branches, but the C—O bond activation is much more favorable in energy than the O—H bond activation. All theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction.     

Cyclization-Carbonylation-Cyclization Coupling Reaction of Propargyl Ureas with Palladium(II)-Bisoxazoline Catalyst

The cyclization-carbonylation-cyclization coupling reaction (CCC-coupling reaction) of propargyl ureas catalyzed by Pd^II(box) complexes afforded symmetrical ketones bearing two 2-amino-2-oxazoline groups in good to moderate yields.     

一个异常的吡啶环的酰化反应

吡啶环作为一种缺π电子的芳杂环,其酰化反应一般需要在较强烈的反应条件下才能进行,且酰化主要发生在β位上.本文报道了一个温和条件下发生的吡啶环α位上的酰化反应,即在室温下,将3,5,6-三甲基-2-吡嗪甲酸(川芎酸)加入到三氯氧磷和吡啶的混合物中,迅速发生反应,产物经MS,IR,1HNMR,13CNMR等谱图表征,为吡啶的α位酰化物.     

2-Halo-2,4-dinitrothiolene-1,1-dioxides in Reaction with Pyridine

Russian Journal of Organic Chemistry -