carboxy-methylsulfanyl | 14310-40-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: carboxy-methylsulfanyl
• CAS: 14310-40-8
• 化学式: C₂H₃O₂S
• 分子量: 91.1106
• InChiKey: HTOWSIOVJLEWNQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.27
• 重原子数：
  5.0
• 可旋转键数：
  1.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1,4-二巯基-2,3-丁二醇 、 carboxy-methylsulfanyl 以 水 为溶剂， 生成 巯基乙酸 、
  参考文献：
  名称：

  巯基自由基和二硫键阴离子自由基的还原电势和交换反应

  摘要：

  DOI：

  10.1021/j100310a022
• 作为产物：
  描述：

  二硫醇二羟基乙酸 以 水 为溶剂， 生成 carboxy-methylsulfanyl 、
  参考文献：
  名称：

  Perthiyl radicals, trisulfide radical ions, and sulfate formation: a combined photolysis and radiolysis study on redox processes with organic di- and trisulfides

  摘要：

  The formation of perthiyl and thiyl radicals has been studied in a combined photochemical and radiation chemical investigation of the di- and trisulfides of penicillamine and cysteine, together with glutathione disulfide, cystamine dihydrochloride, and dithiodiglycolic acid in aqueous solution. The highest RSS. yields are found from the trisulfides with little difference between PenSSSPen and CySSSCy in the case of photolysis, but with a (4-5):1 ratio in favor in PenSS. over CySS. upon radiation chemically induced processes. Thiyl radicals are the other major species formed. The RSS./RS. ratio changes significantly depending on the nature of the di- or trisulfide and the method of radical generation employed. Perthiyl radicals are found to be moderately good oxidants, weaker though than thiyl radicals, and readily react with molecular oxygen in an addition process. The following absolute rate constants have been measured: k(PenSS. + ascorbate) = (4.1 +/- 1.0) x 10(6) M-1 s-1 and k(PenSS. + O2) = (5.1 +/- 1.0) x 10(6) M-1 s-1. Probably the most interesting finding about perthiyl radicals is that inorganic SO42- is formed in their reaction with molecular oxygen. The mechanism of sulfate formation is suggested to proceed via the perthioperoxyl radical, RSSOO., structural rearrangement of this transient into the corresponding sulfonyl-type radical, RSSO2., addition of oxygen to the latter to yield a sulfonyl peroxyl, RSSO2OO., followed by a bimolecular radical-radical reaction of these peroxyl radicals (in analogy to the fate of peroxyl radicals in general) leading to RSSO3.. Cleavage of SO3 from RSSO3. and hydrolysis would then result in SO42-. Reduction of trisulfides yields (RSSSR).- radical anions which decay into either RSS. + RS- (preferred pathway in case of PenSSSPen reduction; k{PenSSSPen + e(aq)-} = 2.0 x 10(10) M-1 s-1, k{PenSSSPen + CO2.-} = 2.3 x 10(8) M-1 s-1), or RS. + RSS- (preferred pathway in case of CySSSCy reduction). Trisulfide radical anions could directly be identified in the case of the cysteine compound with (CySSSCy).- absorbing at 425 nm and exhibiting a half-life of ca 4-mu-s. Radical cations (PenSSSPen).+ are indicated in the oxidation of penicillamine trisulfide.

  DOI：

  10.1021/j100180a058

文献信息

• Direct observation of a 1,4-hydrogen shift in vinyl radicals derived from the reaction of alkynes with thiyl radicals
  作者：Bruce C. Gilbert、David J. Parry、Loris Grossi

  DOI：10.1039/f19878300077

  日期：——

  E.s.r. experiments demonstrate that in vinyl radicals generated from thiyl radicals and alkynes, intermolecular abstraction of a thiol hydrogen (k≈ 107 dm3 mol–1 s–1) is in competition with 1,n-hydrogen shifts. A rapid 1,4-shift (k≈ 105 s–1) is shown to occur in cases where the resulting radical is stabilized by the presence of α-sulphur and α-carboxy substituents, whereas in other examples a 1,5-shift

  ESR实验表明，在乙烯的基团，从含硫基团和炔烃，硫醇氢（分子间的抽象产生ķ ≈10 7分米3摩尔-1小号-1）与1竞争，ñ -氢移位。一种快速1,4-移（ķ ≈10个5小号-1）被示出在其中所得基团是由存在稳定的情况下发生α -sulphur和α羧基的取代基，而在其他示例中，1,5-转变为主。
• EPR and proton ENDOR studies in single crystals of potassium hydrogen thiodiacetate
  作者：M. Ravi Kumar、K. V. Lingam、T. K. Gundu Rao

  DOI：10.1039/ft9918700273

  日期：——

  Radicals trapped in a γ-irradiated single crystal of potassium hydrogen thiodiacetate have been investigated using the techniques of EPR and ENDOR. A radical of the type HO2C—CH2—S—ĊH—CO2H was observed and analysed. The second radical could not be analysed, owing to overlap of the spectrum and only information about the g factors could be obtained. The third radical observed was of the type RCH2—S, formed by the scission of the S—C bond, and was observable only at low temperatures (below –100 °C), and was characterized by highly anisotropic g factors.

  利用 EPR 和 ENDOR 技术研究了滞留在经过 γ 辐照的硫代二乙酸氢钾单晶体中的自由基。观察并分析了一个 HO2C-CH2-S-ĊH-CO2H 型自由基。由于光谱重叠，无法对第二个自由基进行分析，只能获得有关 g 因子的信息。观察到的第三个自由基属于 R -S 类型，由 S-C 键裂解形成，只能在低温（低于 -100 °C）下观察到，其特征是 g 因子高度各向异性。