methylpropargyl radical | 936346-46-2

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: methylpropargyl radical
• 英文别名: butinyl radical；1-methylallenyl radical；Butin-2-radikal；but-2-ynyl；1-methyl-propadienyl；But-2-yn-1-yl radical
• CAS: 936346-46-2
• 化学式: C₄H₅
• 分子量: 53.0837
• InChiKey: LSOBPYSQSPIQJF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  1-溴-2-丁炔 在 三甲基锡 作用下， 以 various solvent(s) 为溶剂， 生成 methylpropargyl radical
  参考文献：
  名称：

  MacInnes, Iain; Walton, John C., Journal of the Chemical Society. Perkin transactions II, 1987, p. 1077 - 1082

  摘要：

  DOI：

文献信息

• Photofragment translational spectroscopy of 1,2-butadiene at 193 nm
  作者：Jason C. Robinson、Weizhong Sun、Sean A. Harris、Fei Qi、Daniel M. Neumark

  DOI：10.1063/1.1410975

  日期：2001.11.8

  Photofragment translational spectroscopy has been used to investigate the dissociation dynamics of 1,2-butadiene at 193 nm. Ionization of scattered photoproducts was accomplished using tunable VUV synchrotron radiation at the Advanced Light Source. Two product channels are observed: CH3+C3H3 and C4H5+H. The C3H3 product can be identified as the propargyl radical through measurement of its photoionization

  光碎片平移光谱已被用于研究 1,2-丁二烯在 193 nm 处的解离动力学。使用高级光源处的可调谐 VUV 同步加速器辐射完成散射光产物的电离。观察到两个产物通道：CH3+C3H3 和 C4H5+H。通过测量其光电离效率曲线可以将C3H3产物鉴定为炔丙基自由基，而C4H5产物不能明确鉴定。平移能量 P(ET) 分布表明，这两个通道都是由内部转换为基态电子态，然后是解离的结果。C4H5 产物的 P(ET) 分布在 7 kcal/mol 以下被急剧截断，表明最慢的 C4H5 产物的自发分解。
• Factors Influencing C−ON Bond Homolysis in Alkoxyamines:  Unexpected Behavior of SG1 (<i>N</i>-(2-methyl-2-propyl)- <i>N</i>-(1-diethylphosphono-2,2-dimethylpropyl)-<i>N</i>-oxyl)-Based Alkoxyamines
  作者：Denis Bertin、Didier Gigmes、Christophe Le Mercier、Sylvain R. A. Marque、Paul Tordo

  DOI：10.1021/jo0495586

  日期：2004.7.1

  Alkoxyamines and persistent nitroxides are important regulators of nitroxide-mediated radical polymerization (NMP). Since the polymerization time decreases with the increasing equilibrium constant K (kd/kc), i.e., the increasing rate constant kd of the homolysis of the C−ON bond between the polymer chain and the nitroxide moiety, the factors influencing the cleavage rate constants are of considerable

  烷氧基胺和持久性氮氧化物是氮氧化物介导的自由基聚合（NMP）的重要调节剂。由于聚合时间随着平衡常数K（k d / k c）的增加而减少，即聚合物链和氮氧化物部分之间C-ON键均化的速率常数k d的增加，因此影响裂解的因素速率常数引起了极大的兴趣。事实证明，基于SG1的烷氧基胺是用于各种单体NMP的最有效的烷氧基胺家族。因此，确定使SG1衍生物比TEMPO（2,2,6,6-四甲基哌啶-N-氧基）衍生物。与我们对TEMPO衍生物观察到的相反，我们观察到E a与BDE（CH）的关系有两个关系，一个关系是非极性释放的烷基自由基（E a（kJ / mol）= -133.0 + 0.72BDE）和另一个用于极性释放的烷基（E a（kJ / mol）= -137.0 + 0.69BDE）。然而，对于两个家族（SG1和TEMPO衍生物），C-ON键均解的速率常数k d与裂解温度T c相关（log（k d（s
• Electron paramagnetic resonance study of radical formation from cyclopentene and dimethylacetylene following adsorption onto H-mordenite
  作者：Christopher J. Rhodes

  DOI：10.1039/ft9918703179

  日期：——

  Following adsorption of cyclopentene onto H-mordenite at low temperatures an EPR spectrum was recorded at 77 K which can be unequivocally assigned to the radical cation of 1,2,3,4,5,6,7,8-octahydronaphthalene (9-octalin), since it is identical with the spectrum recorded from an authentic sample of 9-octalin following γ-irradiation in a CFCl3 matrix. This radical shows an interesting dynamic behaviour

  在低温下将环戊烯吸附到H-丝光沸石上后，在77 K处记录到EPR光谱，该光谱可以明确地分配给1,2,3,4,5,6,7,8-八氢萘的自由基阳离子（9-八氢萘），因为它与在CFCl 3矩阵中进行γ辐照后从真实的9-八氢萘样品中记录的光谱相同。根据两个环的协调反转，该自由基显示出有趣的动力学行为，该反转调节了伪轴和伪赤道耦合。在195 K初始吸附时，与该过程相关的活化能为14.4 kJ mol –1（实际上比通过ODMR在溶液中测得的活化能低），但令人惊讶地增加到28.3 kJ mol –1 将样品加热至295K。这是根据位于不同吸附位点的自由基来解释的。
• Kinetics of decomposition and interconversion of 3-methylbut-1-yne and 3-methylbuta-1,2-diene. Resonance stabilization energies of propargylic radicals
  作者：Tam T. Nguyen、Keith D. King

  DOI：10.1021/j150621a025

  日期：1981.10
• Crossed-beam reaction of carbon atoms with hydrocarbon molecules. IV. Chemical dynamics of methylpropargyl radical formation, C₄H₅, from reaction of C<i>(³P_j)</i>with propylene, C₃H₆<i>(X ¹A)</i>
  作者：R. I. Kaiser、D. Stranges、H. M. Bevsek、Y. T. Lee、A. G. Suits

  DOI：10.1063/1.473543

  日期：1997.3.22

  The reaction between ground state carbon atoms and propylene, C3H6, was studied at average collision energies of 23.3 and 45.0 kJ mol−1 using the crossed molecular beam technique. Product angular distributions and time-of-flight spectra of C4H5 at m/e=53 were recorded. Forward-convolution fitting of the data yields a maximum energy release as well as angular distributions consistent with the formation of methylpropargyl radicals. Reaction dynamics inferred from the experimental results suggest that the reaction proceeds on the lowest A3 surface via an initial addition of the carbon atom to the π-orbital to form a triplet methylcyclopropylidene collision complex followed by ring opening to triplet 1,2-butadiene. Within 0.3–0.6 ps, 1,2-butadiene decomposes through carbon–hydrogen bond rupture to atomic hydrogen and methylpropargyl radicals. The explicit identification of C4H5 under single collision conditions represents a further example of a carbon–hydrogen exchange in reactions of ground state carbon with unsaturated hydrocarbons. This versatile machine represents an alternative pathway to build up unsaturated hydrocarbon chains in combustion processes, chemical vapor deposition, and in the interstellar medium.