methylthio radical | 7175-75-9

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: methylthio radical
• 英文别名: Methylthio-Radikal；methylthiyl radical；Methylthiyl-Radikal
• CAS: 7175-75-9
• 化学式: CH₃S
• 分子量: 47.1008
• InChiKey: QSLPNSWXUQHVLP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  2
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  methylthio radical 在 氧气 作用下， 以 gas 为溶剂， -36.1 ℃ 、10.67 kPa 条件下， 生成 甲基硫化物过氧自由基
  参考文献：
  名称：

  在气相中观察到氧气中甲基噻吩基加成

  摘要：

  The formation of a weakly bound adduct between CH3S and 02 was observed between 216 and 258 K using the technique of pulsed laser photolysis/laser-induced fluorescence. The equilibrium constant for the gas-phase reaction, CH3S + O2 half arrow right over half arrow left CH3SOO (If, Ir), was measured. The CH3S-OO bond is measured to be almost-equal-to 11 kcal mol-1. This is one of the first weakly bound radical-O2 adducts that has been observed which could be of significance in the atmosphere. The atmospheric implications of this adduct are briefly discussed.

  DOI：

  10.1021/j100198a006
• 作为产物：
  描述：

  氯甲烷 在 S^-* 作用下， 24.9 ℃ 、66.66 Pa 条件下， 生成 methylthio radical
  参考文献：
  名称：

  Hypovalent radicals. 13. Gas-phase nucleophilic reactivities of phenylnitrene (PhN^- •) and sulfur anion radicals (S^-•) at sp³ and carbonyl carbon

  摘要：

  DOI：

  10.1021/ja00340a010

文献信息

• Gas-phase reactions of iron(1-) and cobalt(1-) with simple thiols, sulfides, and disulfides by Fourier-transform mass spectrometry
  作者：L. Sallans、K. R. Lane、B. S. Freiser

  DOI：10.1021/ja00185a013

  日期：1989.2

  products, H-Fesup minus}}-SH and Fesup minus}}-SH. Some of the thermochemical data derived from this study include Ddegree}(Msup minus}}-S) > 103 kcal/mol and Ddegree}(Msup minus}}-SH) = 83 plus minus}9 kcal/mol. Finally, a brief survey of the reactivity of Vsup minus}}, Crsup minus}}, and Mosup minus}} with selected organosulfur compounds is also reported. 79 refs., 3 figs., 7 tabs

  发现 Fesup minus}} 和 Cosup minus}} 会与简单的硫醇、硫化物和二硫化物反应。由这些金属阴离子 Msup minus}} 和硫醇形成的主要反应产物包括 MSsup minus}}、MSHsup minus}} 和 MSHsub 2}sup minus}} 和提出了一种涉及金属初始插入弱 CS 键的机制。类似地，CS 插入是与硫化物和二硫化物反应的主要攻击模式，类似于观察到的金属阳离子反应。碰撞诱导解离用于支持主要产物 H-Fesup minus}}-SH 和 Fesup minus}}-SH 的拟议结构。本研究得出的一些热化学数据包括 Ddegree}(Msup minus}}-S) > 103 kcal/mol 和 Ddegree}(Msup minus}}-SH) = 83 plus减去}9 kcal/mol。最后，还报告了
• Radical adducts of dibenzofulvenes and 9-methylenanthrone - an esr study
  作者：Angelo Alberti、Gian Franco Pedulli、Rino Leardin、Antonio Tundo、Giuseppe Zanardi

  DOI：10.1016/0040-4020(86)80018-7

  日期：1986.1

  R3M. radicals (M=C, Si, Ge, Sn, P, O, S) to give the corresponding paramagnetic adducts. In the case of 9-methylenanthrone radical addition occurred selectively at the exocyclic carbon-carbon double bond even with Group IV B organometallic radicals for which attack at the carbonyl oxygen would give rise to thermodynamically more stable adducts. When irradiating solutions of 9-methylenanthrone a photoinduced

  使标题化合物与一系列R 3 M.基团（M = C，Si，Ge，Sn，P，O，S）反应，得到相应的顺磁性加合物。在9-亚甲基蒽酮基团的情况下，即使在IV B族有机金属基团上，环碳-碳双键选择性地发生加成，其对羰基氧的攻击将产生热力学上更稳定的加合物。辐射9-甲基蒽酮溶液时，发生了光致自反应，导致形成了二聚体。根据测得的ESR光谱参数，讨论了加合物的结构，以及R n M基团对β-质子超细分裂常数的影响。
• Channeling of Products in the Hot Atom Reaction H + (CN)₂ → HCN/HNC + CN and in the Reaction of CN with CH₃SH
  作者：Brian K. Decker、R. Glen Macdonald

  DOI：10.1021/jp0108061

  日期：2001.7.1

  for the gas-phase hot atom reaction H + (CN)sub 2} yields} HCN/HNC + CN (a) and the reaction CN + CHsub 3}SH yields} HCN/HNC + CHsub 3}S/CHsub 2}SH (b) at 293 K. The reactive H atoms had an initial mean translational energy of 92 kJ mol-1, with a 38 kJ molsup -1} fwhm Gaussian energy distribution. The branching fractions determined for the product channels forming HCN and HNC, respectively, are

  红外瞬态吸收光谱用于确定气相热原子反应 H + (CN)sub 2} 产率} HCN/HNC + CN (a) 和反应 CN + CHsub 3 的总产物支化分数}SH 产率} HCN/HNC + CHsub 3}S/CHsub 2}SH (b) 在 293 K。反应性 H 原子的初始平均平移能量为 92 kJ mol-1，38 kJ molsup -1} fwhm 高斯能量分布。为形成 HCN 和 HNC 的产物通道确定的支化分数分别为反应 (a) 的 0.88 和 0.12 (+-}0.05) 和反应 (b) 的 0.81 和 0.19 (+-}0.08)。反应 (b) 的双分子速率常数在 293 K 时测量为 (2.7 +-} 0.3) x 10sup -10} cmsup 3}molecsup -1} ssup -1}。观察到的反应 (a) 的产物支化分
• Kinetics of the reaction of the methylthiyl radical (CH3S) with unsaturated hydrocarbons
  作者：R. Jeffrey Balla、Brad R. Weiner、H. H. Nelson

  DOI：10.1021/ja00250a008

  日期：1987.8

  produce equilibrium constants for a range of temperatures. Arrhenius parameters for the forward reaction, k(+/- 2sigma) = (4.5 +/- 1.3) x 10/sup -13/ exp((0.60 +/- 0.21 kcal/mol)/RT)cm/sup 3//s, and the reverse reaction, k(+/- 2sigma) = (3.7 +/- 22) x 10/sup +13/ exp((-18.4 +/- 4.6 kcal/mol)/RT) s/sup -1/, have also been obtained. Thermodynamic values for the reaction of CH/sub 3/S with 1,3-butadiene

  通过使用激光诱导，研究了甲基硫基自由基 CH/sub 3/S 与 1,3-丁二烯和丙二烯的反应作为温度 (296-455 K) 和压力 (20-60 Torr) 的函数荧光 (LIF) 作为动力学探针。CH/sub 3/S 自由基与 1,3-丁二烯加成形成加合物。在更高的温度下，观察到平衡，并在实时实验中监测 CH/sub 3/S 自由基接近其平衡浓度。这些数据产生了一系列温度的平衡常数。正向反应的 Arrhenius 参数，k(+/- 2sigma) = (4.5 +/- 1.3) x 10/sup -13/ exp((0.60 +/- 0.21 kcal/mol)/RT)cm/sup 3// s 和逆反应，k(+/- 2sigma) = (3.7 +/- 22) x 10/sup +13/ exp((-18.4 +/- 4.6 kcal/mol)/RT) s/sup -1 /, 也得到了。CH/sub
• Transient spectra and primary processes in the flash photolysis of CH3SSCH3, CH3SCH3, CH3SH and C2H5SH
  作者：A. B. Callear、D. R. Dickson

  DOI：10.1039/tf9706601987

  日期：——

  From direct observation of the CH3, CH3S, CH2S and S2 produced in the flash photolysis of CH3SSCH3(∼1950 Å) it was concluded that the primary processes are : [graphic ommitted] The relative degree of S—S to C—S bond scission was recorded as ∼1.35. The stability of CH3S and the instability of CH3SS are consistent with statistical partitioning of the excess energy. From the independence of the CH3S and CH3 on total pressure in the ∼1950 Å flash photolysis of CH3SCH3, it was concluded that the primary process is predominantly CH3SCH3+hν→CH3+CH3S. The stability of the generated CH3S is consistent with the statistical energy partitioning. By assuming equal yields of CH3 and CH3S radicals, the oscillator strength of the CH3S band at 2185 Å was 1.3(±0.2)× 10–3. Two primary processes were identified in the ∼1950 Å flash photolysis of CH3SH, [graphic ommitted] and the relative degree of C—S to S—H bond cleavage was 1:1.7. It was suggested that in this case the excited CH3SH finds a configuration in which the S—H potential is repulsive more rapidly than the rate at which the energy is partitioned. To account for the pressure dependent formation of CH3 and CH2S in the ∼1950 Å flash photolysis of C2H5SH, and also the independence of CH2S on added nitric oxide, the primary processes [graphic ommitted] were postulated.

  通过直接观察 CH3SSCH3（∼1950 Å）在闪烁光解过程中产生的 CH3、CH3S、CH2S 和 S2，可以得出结论：主要过程是......：[图略] S-S 与 C-S 键裂解的相对程度为 ∼1.35。CH3S 的稳定性和 CH3SS 的不稳定性与过剩能量的统计分配是一致的。 根据 CH3S 和 CH3 对 CH3SCH3 ∼1950 Å 闪光光解总压力的独立性，可以得出结论：主要过程主要是 CH3SCH3+hν→CH3+CH3S 。生成的 CH3S 的稳定性与统计能量分配一致。假设 CH3 和 CH3S 自由基的产率相等，2185 Å 处 CH3S 波段的振荡器强度为 1.3(±0.2)× 10-3。在 CH3SH 的 ∼1950 Å 闪光光解过程中发现了两个主要过程，[图形省略]C-S 与 S-H 键裂解的相对程度为 1:1.7。有人认为，在这种情况下，激发的 CH3SH 找到一种 S-H 势排斥的构型的速度比能量分配的速度更快。为了解释 C2H5SH 在 ∼1950 Å 的闪光光解过程中形成的 CH3 和 CH2S 与压力有关，以及 CH2S 与添加的一氧化氮无关，推测了以下主要过程[图略]。