炔丙基自由基 | 2932-78-7

• 分子结构分类: 有机化合物 - 叠烯 - 无环联烯
• 中文名称: 炔丙基自由基
• 英文名称: propynyl radical
• 英文别名: propargyl radical；Allenyl-Radikal
• CAS: 2932-78-7
• 化学式: C₃H₃
• 分子量: 39.0568
• InChiKey: DITHIFQMPPCBCU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  3
• 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：

  炔丙基自由基 在 甲烷 作用下， 以 gaseous matrix 为溶剂， 生成 丁二炔
  参考文献：
  名称：

  Crossed beam reaction of atomic carbon, C(3Pj), with the propargyl radical, C3H3(X 2B2): Observation of diacetylene, C4H2(X 1Σg+)

  摘要：

  The reaction of ground-state carbon, C(3Pj), with the propargyl radical, C3H3(X 2B2), is investigated at an average collision energy of 42.0 kJmol−1 employing the crossed molecular beams technique and a universal mass spectrometric detector. The laboratory angular distribution and time-of-flight spectra of the C4H2 product are recorded at m/e=50. Forward-convolution fitting of our data reveals the formation of diacetylene, HCCCCH, in its X1Σg+ electronic ground state. The reaction dynamics are governed by an initial attack of C(3Pj) to the π-electron density at the acetylenic carbon atom of the propargyl radical, followed by a [1,2]-hydrogen migration to the n-C4H3 isomer. A final carbon–hydrogen bond rupture yields atomic hydrogen and diacetylene through a tight exit transition state located 30–60 kJmol−1 above the products. This first successful crossed molecular beams study of a reaction between an atom and a free radical marks the beginning of the next generation of crossed beams experiments elucidating the formation of molecular species in combustion processes, chemical vapor deposition, in the interstellar medium, outflows of carbon stars, and hydrocarbon-rich planetary atmospheres via radical–radical reactions.

  DOI：

  10.1063/1.475025
• 作为产物：
  描述：

  环己三烯 在 H 作用下， 生成 炔丙基自由基
  参考文献：
  名称：

  Detailed kinetics of cyclopentadiene decomposition studied in a shock tube

  摘要：

  Mixtures of cyclopentadiene diluted with argon were used to investigate its decomposition pattern in a single pulse-shock tube. The temperatures ranged from 1080 to 1550 K and pressures behind the shock were between 1.7-9.6 atm. The cyclopentadiene concentrations ranged from 0.5 to 2%. Gas-chromatographic analysis was used to determine the product distribution. The main products in order of abundance were acetylene, ethylene, methane, allene, propyne, butadiene, propylene, and benzene. The decomposition of cyclopentadiene was simulated with a kinetic scheme containing 44 species and 144 elementary reactions. This was later reduced to only 36 reactions. The ring opening process of the cyclopentadienyl radical was found to be the crucial step in the mechanism. (C) 1997 John Wiley and Sons, Inc.

  DOI：

  10.1002/(sici)1097-4601(1997)29:7<505::aid-kin4>3.0.co;2-y

文献信息

• Kinetics of the Reactions of Allyl and Propargyl Radicals with CH₃
  作者：Vadim D. Knyazev、Irene R. Slagle

  DOI：10.1021/jp003890d

  日期：2001.4.1

  The allyl-methyl and propargyl-methyl cross-radical reactions were studied by laser photolysis/photoionization mass spectroscopy. Overall rate constants were obtained in direct real-time experiments in the temperature region 301−800 K and bath gas (helium) density (3−36) × 1016 atom cm-3. The observed overall C3H5 + CH3 (1) and C3H3 + CH3 (2) rate constants demonstrate negative temperature dependencies

  通过激光光解/光电离质谱研究了烯丙基-甲基和炔丙基-甲基的交叉自由基反应。总体速率常数是在 301-800 K 温度区域和浴气（氦）密度 (3-36) × 1016 atom cm-3 的直接实时实验中获得的。观察到的整体 C3H5 + CH3 (1) 和 C3H3 + CH3 (2) 速率常数表明负温度依赖性。碰撞效应的主方程模型表明，在所有使用的实验条件下，C3H5 + CH3 反应都接近其高压极限。对实验值的衰减效应（在最高温度下平均为 18%）进行较小的修正导致反应 1 的速率常数的高压极限温度依赖性：k1∞ = 1.55 × 10-9 T - 0.54exp(117 K/T) cm3 分子-1 s-1。
• Homolytic dissociation of 1-substituted cyclohexa-2,5-diene-1-carboxylic acids: an EPR spectroscopic study of chain propagation†
  作者：Leon V. Jackson、John C. Walton

  DOI：10.1039/b104859g

  日期：——

  Hydrogen abstraction from 1-substituted cyclohexa-2,5-diene-1-carboxylic acids containing linear, branched and cyclic alkyl substituents, as well as allyl, propargyl (prop-2-ynyl), cyanomethyl and benzyl substituents, has been studied by EPR spectroscopy. For each carboxylic acid, EPR spectra of the corresponding cyclohexadienyl radicals were observed at lower temperatures, followed by spectra due to ejected carbon-centred radicals at higher temperatures. Rate constants, for release of the carbon-centred radicals from the cyclohexadienyl radicals, were determined from radical concentration measurements for the above range of substituents. The rate of cyclohexadienyl radical dissociation increased with branching in the 1-alkyl substituent and with electron delocalisation in the ejected carbon-centred radical; 3,5- and 2,6-dimethyl-substitution of the cyclohexadienyl ring led to reductions in the dissociation rate constants. Rate data for abstraction of bisallylic hydrogens from the cyclohexadienyl acids were also obtained for ethyl, n-propyl and isopropyl radicals. These results indicated a sharp drop in the rate of hydrogen abstraction as the degree of branching in the attacking radical increased. Small decreases in the hydrogen abstraction rate constants were observed for cyclohexadienes containing CO2R substituents.

  通过电子顺磁共振（EPR）光谱研究了从含有线性、支化、环状烷基取代基以及烯丙基、炔丙基（丙-2-炔基）、氰基甲基和苄基取代基的1-取代环己-2,5-二烯-1-羧酸中提取氢的反应。对于每种羧酸，在较低温度下观察到相应的环己二烯基自由基的EPR谱，随后在较高温度下观察到由喷出的碳中心自由基引起的谱。通过对于上述范围的取代基的自由基浓度测量，确定了从环己二烯基自由基释放碳中心自由基的速率常数。环己二烯基自由基解离速率随着1-烷基取代基的分支增加和喷出的碳中心自由基的电子离域程度增加而加快；环己二烯环的3,5-和2,6-二甲基取代导致解离速率常数降低。还获得了从环己二烯羧酸中提取双烯丙基氢的速率数据，涉及乙基、正丙基和异丙基自由基。这些结果表明，随着攻击自由基的分支程度增加，氢提取速率急剧下降。环己二烯中含有CO2R取代基时，氢提取速率常数略有下降。
• 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。
• Decomposition of Picolyl Radicals at High Temperature: A Mass Selective Threshold Photoelectron Spectroscopy Study
  作者：Engelbert Reusch、Fabian Holzmeier、Marius Gerlach、Ingo Fischer、Patrick Hemberger

  DOI：10.1002/chem.201903937

  日期：2019.12.20

  The reaction products of the picolyl radicals at high temperature were characterized by mass-selective threshold photoelectron spectroscopy in the gas phase. Aminomethylpyridines were pyrolyzed to initially produce picolyl radicals (m/z=92). At higher temperatures further thermal reaction products are generated in the pyrolysis reactor. All compounds were identified by mass-selected threshold photoelectron

  通过气相质量选择阈值光电子能谱对吡啶甲基自由基在高温下的反应产物进行了表征。氨甲基吡啶热解最初产生吡啶自由基(m/z=92)。在较高温度下，在热解反应器中进一步产生热反应产物。所有化合物均通过质量选择阈值光电子能谱进行鉴定，并对几种迄今尚未探索的反应分子进行了表征。计算中概述了几种解离途径的机制。m/z=91 的光谱，由吡啶甲基氢损失产生，显示四种异构体，两种乙炔基吡咯，其绝热电离能 (IEad ) 为 7.99 eV (2-乙炔基-1H-吡咯) 和 8.12 eV (3-乙炔基-) 1H-吡咯）和两种环戊二烯甲腈，IE 分别为 9.14 eV（环戊-1,3-二烯-1-甲腈）和 9.25 eV（环戊-1,4-二烯-1-甲腈）。第二个连续的氢损失形成氰基环戊二烯基自由基，IE 为 9.07 eV (T0) 和 9.21 eV (S1)。该化合物进一步解离为乙炔和氰基丙炔基(IE=9.35 e
• Formation of fulvene in the reaction of C2H with 1,3-butadiene
  作者：Jessica F. Lockyear、Martin Fournier、Ian R. Sims、Jean-Claude Guillemin、Craig A. Taatjes、David L. Osborn、Stephen R. Leone

  DOI：10.1016/j.ijms.2014.08.025

  日期：2015.2

  with 1,3-butadiene at 4 Torr and 298 K are probed using photoionization time-of-flight mass spectrometry. The reaction takes place in a slow-flow reactor, and products are ionized by tunable vacuum-ultraviolet light from the Advanced Light Source. The principal reaction channel involves addition of the radical to one of the unsaturated sites of 1,3-butadiene, followed by H-loss to give isomers of C

  摘要 使用光电离飞行时间质谱法探测 C 2 H 自由基与 1,3-丁二烯在 4 Torr 和 298 K 反应中形成的产物。反应在慢流反应器中进行，产物被高级光源发出的可调真空紫外光电离。主要的反应通道包括将自由基加成到 1,3-丁二烯的不饱和位点之一，然后失去 H，得到 C 6 H 6 的异构体。C 6 H 6 产物的光电离谱表明形成了支化分数为(57±30)%的富烯。形成至少一种或多种异构体，其可能是 3,4-二亚甲基环丁-1-烯、3-亚甲基-1-戊烯-4-炔或 3-甲基-1,2-戊二烯-4 中的一种或多种-恩。实验光电离谱为 3，4-二亚甲基环丁-1-烯和3-亚甲基-1-戊烯-4-炔和3-甲基-1,2-戊二烯-4-炔的模拟光电离谱用于拟合测量数据并获得最大支化分数这些异构体分别为 74%、24% 和 31%。苯和 1,3-己二烯-5-炔的总和的支化分数的上限为 45%。还通过计算研究了反应势能表面。计算了生成富烯