bromonitrile oxide | 74213-25-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: bromonitrile oxide
• 英文别名: bromonitriloxide；bromofulminate；Bromoformonitrile oxide
• CAS: 74213-25-5
• 化学式: CBrNO
• 分子量: 121.921
• InChiKey: OPEBOTYCWHBJJL-UHFFFAOYSA-N

物化性质

• 密度：
  1.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  30.7
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  bromonitrile oxide 反应 0.17h， 生成 bromine isocyanate
  参考文献：
  名称：

  Maier, Guenther; Teles, Joaquim Henrique, Angewandte Chemie, 1987, vol. 99, # 2, p. 152 - 153

  摘要：

  DOI：
• 作为产物：
  描述：

  1,1-二溴甲醛肟 以 neat (no solvent, gas phase) 为溶剂， 生成 bromonitrile oxide
  参考文献：
  名称：

  毫米波光谱法检测不稳定卤代溴化物BrCNO的气相

  摘要：

  在Br 2 CNOH的低压热解过程中，观察到不稳定的卤代硼酸盐BrCNO的毫米波光谱。确定的79 BrCNO和81 BrCNO的基态旋转常数分别为1739.93007（10）和1726.96186（11）MHz。溴四极超细分裂的最小二乘拟合分别给出了79 BrCNO和81 BrCNO基态的χ值656.8（88）和551（10）MHz 。观察到的由BrCN弯曲模式引起的振动卫星模式表明该分子表现出极准的拟线性行为，大致类似于OCCCO。

  DOI：

  10.1016/s0009-2614(98)00085-2

文献信息

• Efficient regioselective synthesis of 4- and 5-substituted isoxazoles under thermal and microwave conditions
  作者：Jamal Lasri、Suman Mukhopadhyay、M. Adflia Januário Charmier、M. Adflia Januário Charmier

  DOI：10.1002/jhet.5570450521

  日期：2008.9

  The [2+3] cycloaddition reaction between nitrile oxides 2 and the captodative olefins 1 or the methyl crotonate derivatives 4 is regioselective and leads to the formation of the 5-substituted amino-isoxazole 3 or the 4-substituted methoxycarbonyl-isoxazole 5 derivatives, respectively. All these reactions are greatly accelerated by microwave irradiation without changing their regioselectivity with respect

  腈氧化物2与俘获性烯烃1或巴豆酸甲酯衍生物4之间的[2 + 3]环加成反应是区域选择性的，并导致形成5-取代的氨基-异恶唑3或4-取代的甲氧基羰基-异恶唑5的衍生物，分别。微波辐照极大地加速了所有这些反应，而没有改变它们相对于热条件的区域选择性。
• Substituted oximes and furoxans as precursors to unstable nitrile oxides. electronic and geometric structures by ultraviolet photoelectron spectroscopy, infrared spectroscopy and ab initio calculations
  作者：T. Pasinszki、N.P.C. Westwood

  DOI：10.1016/s0022-2860(96)09631-7

  日期：1997.6

  phase is discussed. HeI photoelectron and mid-infrared spectroscopy are used, for the first time, to obtain spectra of the oxime and furoxan precursors, and of the thermolysis products, the substituted nitrile oxides. Assessment of the structures for these three apparently disparate groups of compounds is assisted by conventional ab initio calculations, and also by calculations employing density functional

  摘要 讨论了二卤代甲醛肟和二取代呋喃烷在气相中作为瞬态氧化腈发生剂之间的关系。HeI 光电子和中红外光谱首次用于获得肟和呋喃前体的光谱，以及热解产物取代的腈氧化物的光谱。这三个明显不同的化合物组的结构评估通过常规的从头计算以及使用密度泛函理论的计算来辅助。
• Total Synthesis of Vinigrol
  作者：Thomas J. Maimone、Jun Shi、Shinji Ashida、Phil S. Baran

  DOI：10.1021/ja908194b

  日期：2009.12.2

  longstanding challenge posed by the complex diterpene vinigrol has been answered for the first time. The notorious difficulty in synthesizing vinigrol stems from its unprecedented decahydro-1,5-butanonaphthalene ring system, eight contiguous stereocenters, and highly congested functionality. This Communication delineates a stereocontrolled 23-step route to vinigrol that is scalable (>5 g prepared of a late-stage

  复杂的二萜乙烯醇所带来的长期挑战首次得到了解答。合成长春醇的困难源于其前所未有的十氢-1,5-丁萘环系统、八个连续的立体中心和高度拥挤的官能团。该通讯描述了一种立体控制的 23 步合成维尼醇的路线，该路线可扩展（> 5 g 后期中间体制备），对保护基化学的依赖程度最低，并通过许多独特的化学选择性转化来促进。
• Reaction of Bromo Dipoles with (<i>Z</i>)-4-(Arylmethylene)azol-5-ones. Substrate-Controlled Synthesis of New Bromo-Substituted Heterocyclic Spirans and Unusual<i>N</i>-Benzoyl α-Aminoacids
  作者：Francesco Foti、Giovanni Grassi、Francesco Risitano、Enrico Rotondo、Domenico Zona

  DOI：10.1055/s-2004-829537

  日期：——

  Bromo spirans 6 and 7 and unusual α-aminoacids 8 were prepared as diastereoisomerically pure compounds from bromo ­dipoles and (Z)-4-arylmethyleneazolones.

  溴代螺环化合物6和7以及不寻常的β-氨基化合物8是从溴代偶极子和（Z）-4-芳基亚甲基唑酮制备而成的非对映异构体纯化合物。
• Structure and spectroscopy of dihaloformaldoximes He I photoelectron, photoionization mass spectroscopy, mid-IR, Raman and ab initio study
  作者：Tibor Pasinszki、Nicholas P. C. Westwood

  DOI：10.1039/a605743h

  日期：——

  The electronic and geometric structures of dichloroformaldoxime, Cl 2 CNOH, dibromoformaldoxime, Br 2 CNOH and bromochloroformaldoxime, BrClCNOH, are investigated for the first time in the gas phase by He I photoelectron, He I andH L α,ß,γ photoionisation mass, and mid-IR spectroscopies, and in the solid state by Raman spectroscopy. Ab initio calculations atthe MP2(fc)/6-31G** level provide an assessment of the geometric structures and, together with the IR and Raman data, permit an almost complete vibrational analysis for each molecule, which appear, in each case, to exist in one isomeric form. The calculations indicate that anti structures for the hydrogen atom position are the most stable in all cases. For BrClCNOH, the calculations just prefer the Z-anti-structure as the thermodynamically more stable, whereas the vibrational spectroscopy, although not unambiguous, suggests the E-anti-isomer as the stereoselectively synthesised conformer. This conclusion is strengthened further by the observation that BrClCNOH (with an exclusive E-structure), favours HCl elimination upon thermolysis, thus making it a good source of the transient BrCNO molecule. Photoelectron spectroscopy, supported by ab initio calculations and trends in the dihalo series, provides an analysis of the effect of halogen substitution on the orbitals of the parent oxime species, H 2 CNOH.

  首次通过He I光电子、He I和H L α,β,γ 离子化质量以及中红外光谱学对二氯甲酰肟、Cl 2 CNOH、二溴甲酰肟、Br 2 CNOH和溴氯甲酰肟、BrClCNOH的电子和几何结构进行了气相研究，并通过拉曼光谱学对固态结构进行了研究。MP2(fc)/6-31G**级别的从头计算对几何结构进行了评估，并与红外和拉曼数据一起，对每个分子进行了几乎完整的振动分析，每个分子似乎都存在一种同分异构体形式。计算表明，在所有情况下，氢原子位置的抗结构是最稳定的。对于BrClCNOH，计算只是倾向于Z-反结构作为热力学上更稳定的结构，而振动光谱学虽然不明确，但表明E-反异构体是立体选择性合成的构象。这一结论通过观察得到进一步证实，即BrClCNOH（具有独特的E-结构）在热解时有利于HCl的消除，从而使其成为瞬态BrCNO分子的良好来源。光电子光谱学在从头计算和二卤素系列趋势的支持下，分析了卤素取代对母体肟物种H 2 CNOH的轨道的影响。