Ligand free open air copper(II) mediated aryl formamidation and amination of aryl halides

A simple synthetic procedure for direct formamidation and amination of aryl halides mediated by copper(II) salts was developed in open air, without an external ligand in formamide with potassium carbonate as a base. This approach is particularly efficient when electron active aryl halides are used as substrates. In these cases almost quantitative formamidation was observed.     

交联聚苯乙烯树脂固载甲酰基的微波辅助还原

在微波照射的相转移催化(MI-PTC)条件下,3种甲酰基功能化的交联聚苯乙烯树脂——对甲酰基苯氧基甲基树脂、对甲酰基-2-甲氧基苯氧基甲基树脂和对甲酰基-3-甲氧基苯氧基甲基树脂固载的甲酰基被NaBH4还原,得到相应的3种苄羟基功能化的树脂——Wang树脂、Sasrin树脂和新型的对苄羟基-3-甲氧基苯氧基甲基树脂.考察了溶剂、相转移催化剂等因素对反应的影响,优化的反应介质为THF/H2O混合溶剂,相转移催化剂为苄基三羟乙基氯化铵(BTHAC).然而,在传统加热和微波辐射条件下,最有效混合溶剂的配比有所不同.在水浴加热条件下,最有效的反应溶剂为12 mL THF+3 mL H2O;而在微波加热的条件下,最有效的反应溶剂却是3 mL THF+12 mL H2O.在优化的溶剂、催化剂条件下,微波功率为60 W时,高分子固载的甲酰基30 min之内几乎被定量地还原成羟基.与传统加热方式比较,MI-PTC还原聚苯乙烯固载甲酰基可以大大缩短反应时间,提高反应效率,是一种进行高分子化合物官能团转化的良好方法.     

HOCl…HCOCl复合物的结构和电子性质

在DFT-B3LYP/6-311++G**水平上求得HOCl+HCOCl复合物势能面上的四种稳定构型(S1,S2,S3和S4).其中,在复合物S1和S3中,HOCl单体的5H原子作为质子供体,与HCOCl单体中作为质子受体的10原子相互作用,形成红移氢键复合物;在复合物S4中,HOCl单体的7Cl原子作为质子供体,与HCOCl单体中作为质子受体的IO原子相互作用,形成红移卤键复合物;而在复合物S2中,同时存在2C-3H…6O蓝移氢键和4Cl…5O相互作用.在MP2/6-311++G**水平上计算的单体间的相互作用能考虑了基组重叠误差(BSSE)和零点振动能(ZPVE)校正,其值在-5.05与-14.76 kJ·mol-1之间.采用自然键轨道理论(NBO)对两种单体间相互作用的本质进行了考查,并通过分子中原子理论(AIM)分析了复合物中氢键和卤键键鞍点处的电子密度拓扑性质.     

Vergleichbare Kraftfelder vieratomiger Formylverbindungen

Comparable force fields for HCOO^–, HFCO, HClCO and HDCO have been calculated on the basis of internal coordinates. Linear relations between (i) the carbonyl bond order and the carbonyl stretching force constant, (ii) the sum of the three in-plane bending force constants and the hydrogen out-of-plane force constantf , (iii) a combination of orbital electronegativities andf , have been obtained. The observed in-plane vibrational frequencies have been calculated with an average error of 6.3 cm^–1 or 0.4%.

     

铑催化合成气转化为乙醇反应中甲酰基中间体的化学捕获

本文采用化学捕获法对铑基催化剂上合成气转化反应中的甲酰基中间体进行了化学捕获,在CO+2D_2反应后,用CH_3I进行的化学捕获反应中生成了CH_3CHO、CH_3CDO两种形式的乙醛;补充的Ar吹扫实验显示DCO的甲基化反应对生成的CH_3CDO有重要贡献。因此,甲酰基的确是合成气反应中的C_1含氧中间体。根据这一结果,初步探讨了合成气反应中CH_x物种的生成途径。     

Synthesis of some new purine-related compounds: Regioselective one-pot synthesis of new tetrazolo[1,5-a]pyrimidine,pyrazolo[1,5-a]pyrimidine and pyrimido[1,6-a]pyrimidine derivatives

An easy and efficient route for the synthesis of some tetrazolo[1,5-a]-, pyrazolo[1,5-a]- and pyrimido[1,6-a] pyrimidine derivatives was described through the reaction of sodium salts of formyl ketones with 5-aminotetrazole, 5-aminopyrazole derivatives and 6-aminothiouracil, respectively. The antimicrobial screening of some derivatives of the prepared compounds has been achieved, and it exhibited a moderate activity against the tested microorganisms.     

Elementary reactions of formyl (HCO) radical studied by laser photolysis—transient absorption spectroscopy

Several elementary reactions of formyl radical of combustion importance were studied using pulsed laser photolysis coupled to transient UV–Vis absorption spectroscopy: HCO → H + CO (1), HCO + HCO → products (2), and HCO + CH₃ → products (3). One-pass UV absorption, multi-pass UV absorption as well as cavity ring-down spectroscopy in the red spectral region were used to monitor temporal profiles of HCO radical. Reaction (1) was studied over the buffer gas (He) pressure range 0.8–100 bar and the temperature range 498–769 K. Reactions (2a), (2b), (2c), (3a) and (3b) as well as the UV absorption spectrum of HCO, were studied at 298 and 588 K, and the buffer gas (He) pressure of 1 bar. Pulsed laser photolysis (308, 320, and 193 nm) of acetaldehyde, propionaldehyde, and acetone was used to prepare mixtures of free radicals. The second-order rate constant of reaction (1) obtained from the data at 1 bar is: k₁(He) = (0.8 ± 0.4) × 10⁻¹⁰exp(−(66.0 ± 3.4) kJ mol⁻¹/RT) cm³ molecule⁻¹ s⁻¹. The HCO dissociation rate constants measured in this work are lower than those reported in the previous direct work. The difference is a factor of 2.2 at the highest temperature of the experiments and a factor of 3.5 at the low end. The experimental data indicate pressure dependence of the rate constant of dissociation of formyl radical 1, which was attributed to the early pressure fall-off expected based on the theory of isolated resonances. The UV absorption spectrum of HCO was revised. The maximum absorption cross-section of HCO is (7.3 ± 1.2) × 10⁻¹⁸ cm² molecule⁻¹ at 230 nm (temperature independent within the experimental error). The measured rate constants for reactions (2a), (2b), (2c), (3a) and (3b) are: k₂ = (3.6 ± 0.8) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ (298 K); k₃ = (9.3 ± 2.3) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹(298 and 588 K).     

Synthesis of Novel Photochromic 6‐Benzyloxo‐spirobenzopyran Compounds

The synthesis of four novel derivatives of 1′,3′,3′‐trimethylspiro‐[2H‐1]‐benzopyran‐6‐benzyloxo‐2,2′‐indoline is reported. The synthetic approach to these compounds involves the preparation of the key compound, 3‐formyl‐4‐hydroxybenzophenone, by means of the Reimer–Tiemann reaction. The photochromic compounds were isolated and characterized by ¹H and ¹³C NMR as well as FT‐IR and UV‐VIS spectrometry. Comparative studies performed in these compounds showed a higher molar extinction coefficient and red shift of maximum absorption wavelength when the benzyloxo group is introduced in the spirobenzopyran molecule.     

Carbon-Carbon Bond Formation from Carbon Monoxide and Hydride: The Role of Metal Formyl Intermediates**

Current examples of carbon chain production from metal formyl intermediates with homogeneous metal complexes are described in this Minireview. Mechanistic aspects of these reactions as well as the challenges and opportunities in using this understanding to develop new reactions of CO and H₂ are also discussed.     

HCO+和HOC+与C2H2气相质子转移反应的理论研究

在 HF,B3LYP和 QCISD(T)水平上研究了 HCO+和 HOC+与 C2 H2 的气相质子转移反应 .结果表明 :高级电子相关效应对研究质子转移过程极为重要 ;HCO+和 HOC+通过质子垂直进攻 C2 H2 的 π-键分别生成中间体 OC· HC2 H+2 和 CO· HC2 H+2 ,最终生成主要产物为π-质子化的乙炔 HC(H) CH+;对于质子转移反应 HOC+比 HCO+更为活泼 .计算结果与实验结果符合得较好 ,这将有助于理解星际化学以及燃烧化学中的质子转移过程