vinylidene biradical | 2143-69-3

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: vinylidene biradical
• 英文别名: vinylidene diradical；vinylidene；ethene-1,1-diyl；methylenecarbene；methylene carbon；Ethyliden；Ethen-1,1-diyl
• CAS: 2143-69-3；67321-66-8
• 化学式: C₂H₂
• 分子量: 26.0379
• InChiKey: SNVLJLYUUXKWOJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  2
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  vinylidene biradical 在 氧气 作用下， 生成 1-氨基-4-[(3-氨基-2,4,6-三甲基-5-磺基苯基)氨基]-9,10-二氧代-9,10-二氢-2-蒽磺酸 、 二氧化碳
  参考文献：
  名称：

  乙炔激波管氧化的实验与建模研究

  摘要：

  在 1150–2132 K 的温度和 0.9–1.9 atm 的压力下，在反射冲击波后面研究了九种稀释在氩气中的乙炔和氧气混合物。初始成分从非常贫油到中等富油不等，当量比为 0.0625-1.66。使用另外两种添加乙烯的混合物来提高对乙烯基氧化反应的敏感性。通过二氧化碳分子的激光吸收监测反应进程。收集的实验数据进行了广泛详细的化学动力学分析。最初的动力学模型是根据最近的文献数据组装的，然后使用解决方案映射技术进行优化。分析扩展到包括 Hidaka 和同事最近的实验观察 (Combust Flame 1996, 107, 401)。导出的模型紧密地再现了两组实验数据，通过修改九个速率系数和三个中间物质的形成焓获得的结果。讨论了确定的参数权衡和更改的理由。© 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 391–414, 2003

  DOI：

  10.1002/kin.10141
• 作为产物：
  描述：

  丙烯腈-2-d 生成 vinylidene biradical
  参考文献：
  名称：

  The 1,1-elimination of hydrogen cyanide and formation of triplet vinylidene from the photolysis of acrylonitrile

  摘要：

  The single-photon photodissociation of acrylonitrile-1-d has been investigated by flash photolysis and kinetic absorption spectroscopy in the vacuum-ultraviolet region. Both electronically excited triplet vinylidene and DCN were observed. The result provides further evidence that a "vinylidene" type structure with an extended lifetime exists. Alternative primary processes were considered, particularly those involving vinyl radical or molecular acetylene formation, but they were not observed.

  DOI：

  10.1021/j100190a022

文献信息

• 193 nm photolysis of vinyl bromide: Nascent product distribution of the C2H3Br→C2H2 (vinylidene)+HBr channel
  作者：Dean-Kuo Liu、Laura T. Letendre、Hai-Lung Dai

  DOI：10.1063/1.1382812

  日期：2001.7.22

  content of the photofragments HBr and C2H2 from the minor channel of the photolysis of C2H3Br with 193 nm radiation has been measured using time-resolved infrared Fourier transform IR emission spectroscopy with 0.5 μs resolution. Vibrational level population and the rotational population of the HBr fragment are determined from 1.0 μs following the photolysis until complete HBr relaxation. The nascent

  使用具有 0.5 μs 分辨率的时间分辨红外傅里叶变换红外发射光谱测量了来自具有 193 nm 辐射的 C2H3Br 光解的小通道的光碎片 HBr 和 C2H2 的内能含量。HBr 片段的振动水平种群和旋转种群是从光解后 1.0 μs 到 HBr 完全弛豫期间确定的。从具有玻尔兹曼分布的碰撞淬火模型推断出 HBr 的初始分布，振动和旋转分别为 8690 和 7000 K。产物振动能量分布支持基于产生亚乙烯基和 HBr 的 3 中心 HBr 消除过程的反应机制。亚乙烯基的新生内能推导出为 24 kcal/mol。
• Site-specific dissociation dynamics of ethylene at 157 nm: Atomic and molecular hydrogen elimination
  作者：Jim J. Lin、Chia C. Wang、Yuan T. Lee、Xueming Yang

  DOI：10.1063/1.1321044

  日期：2000.12

  The atomic and molecular hydrogen elimination processes from ethylene have been studied using a molecular beam apparatus. Site and isotope effects on the molecular hydrogen elimination from ethylene have been clearly observed from the photodissociation of ethylene at 157 nm. Experimental results show that there are three different types of molecular elimination processes: 1,1 elimination, 1,2-cis elimination

  已经使用分子束装置研究了从乙烯中消除原子和分子氢的过程。从乙烯在 157 nm 的光解中可以清楚地观察到位点和同位素对乙烯分子氢消除的影响。实验结果表明存在三种不同类型的分子消除过程：1,1消除、1,2-顺消除和1,2-反消除。已检测到 1,1 消除和 1,2 消除之间的动能分布存在显着差异。分子氘消除的 1,2-顺式消除和 1,2-反式消除之间也存在显着差异。还确定了乙烯及其同位素异构体的原子和分子氢消除过程的支化比。已观察到同位素和位点对不同分子消除通道的支化率的影响。实验结果也与最近的理论研究进行了比较。
• Kinetics of reactions of chlorinated vinyl radicals (CH2CCl and C2Cl3) with molecular oxygen
  作者：J. J. Russell、J. A. Seetula、D. Gutman、S. M. Senkan

  DOI：10.1021/j100342a047

  日期：1989.3
• The ultraviolet photodissociation dynamics of <i>d</i>₁‐vinyl chloride
  作者：Yibo Huang、Yung‐an Yang、Guo‐xin He、Robert J. Gordon

  DOI：10.1063/1.465183

  日期：1993.8.15

  We have used partially deuterated vinyl chloride to elucidate the photodissociation mechanism of this molecule. We have found that 75% of the HCl fragments are produced by three-center α,α elimination. Surprisingly, the rotational energy distributions of HCl are the same for both elimination pathways. One possible explanation is that H atom migration in the parent molecule results in similar transition states for the two pathways. Alternatively, dissociation and fragment isomerization may be strongly coupled so that the product angular momentum distribution is determined late in the reaction coordinate. Very different rotational state distributions were observed for v″=0 and v″≳0. We speculate that this dichotomy is caused by formation of a hydrogen-bonded π complex between HCl(v″≳0) and acetylene. We have also determined that HCl+ ions are produced primarily by an α,β mechanism. This mechanism consists of electronic excitation of vinyl chloride, followed by photoelimination and photoionization of electronically excited HCl*. Finally, we determined that H atoms are preferentially produced by detachment from the β carbon, as predicted from the relative stabilities of the α- and β-chlorovinyl radicals.  
• Photodissociation of vinyl chloride: formation and kinetics of vinylidene H2CC(3B2)
  作者：Askar Fahr、Allan H. Laufer

  DOI：10.1021/j100259a039

  日期：1985.6