methyl S-nitrosomercaptoacetate | 166667-91-0

• 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: methyl S-nitrosomercaptoacetate
• 英文别名: methyl-S-nitrosomercaptoacetate；methyl 2-nitrososulfanylacetate
• CAS: 166667-91-0
• 化学式: C₃H₅NO₃S
• 分子量: 135.144
• InChiKey: IEDOGLKUYHAKSG-UHFFFAOYSA-N

物化性质

• 沸点：
  177.0±42.0 °C(Predicted)
• 密度：
  1.35±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  81
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl S-nitrosomercaptoacetate 生成 methyl mercaptoacetate
  参考文献：
  名称：

  Nitroso group transfer from N-nitrososulfonamides to thiolate ions. Intrinsic reactivity

  摘要：

  The nitroso group transfer from N-nitrososulfonamides to thiolate ions was studied. Based on the results, the reaction rate is strongly dependent on the nature of the leaving group (alpha(1g) approximate to -1.30), but virtually independent of the basicity of the thiol (beta(nuc) approximate to 0-10)This dependence is ascribed to the presence of a nucleophile desolvation equilibrium (beta(d)) that is followed by the attack of the thiolate ion on the nitroso group (beta'(nuc)) via a concerted mechanism. The equilibrium constants for the loss of a nitroso group from a nitrosothiol and an N-nitrososulfonarni de were used to obtain the equilibrium constants for the different reactions involved. By using rate-equilibrium correlations, the parameters alpha(norm)(1g) ,beta(d), and beta('norm)(nuc) were obtained. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.06.060
• 作为产物：
  描述：

  巯基乙酸甲酯 在 氧化亚氮 作用下， 生成 methyl S-nitrosomercaptoacetate
  参考文献：
  名称：

  Nitroso group transfer from N-nitrososulfonamides to thiolate ions. Intrinsic reactivity

  摘要：

  The nitroso group transfer from N-nitrososulfonamides to thiolate ions was studied. Based on the results, the reaction rate is strongly dependent on the nature of the leaving group (alpha(1g) approximate to -1.30), but virtually independent of the basicity of the thiol (beta(nuc) approximate to 0-10)This dependence is ascribed to the presence of a nucleophile desolvation equilibrium (beta(d)) that is followed by the attack of the thiolate ion on the nitroso group (beta'(nuc)) via a concerted mechanism. The equilibrium constants for the loss of a nitroso group from a nitrosothiol and an N-nitrososulfonarni de were used to obtain the equilibrium constants for the different reactions involved. By using rate-equilibrium correlations, the parameters alpha(norm)(1g) ,beta(d), and beta('norm)(nuc) were obtained. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.06.060

文献信息

• Barnett, D.Jonathan; Rios, Ana; Williams, D. Lyn H., Journal of the Chemical Society. Perkin transactions II, 1995, # 7, p. 1279 - 1282
  作者：Barnett, D.Jonathan、Rios, Ana、Williams, D. Lyn H.

  DOI：——

  日期：——
• Thiolytic decomposition of the carcinogen N-methyl-N'-nitro-N-nitrosoguanidine. A change in rate-limiting step with nucleophile basicity controls alkylating activity
  作者：Taina Santala、James C. Fishbein

  DOI：10.1021/ja00049a017

  日期：1992.11

  The kinetics of the reaction of seven alkanethiolates with N-methyl-N'-nitro-N-nitrosoguanidine over the pH range 3-8.5 at 40-degrees-C, ionic strength 1 M (KCl), are reported. Plots of k(obs) against total thiol concentration are linear, and the slopes of these plots change as a function of pH. The changes in slope with pH are well-described by a rate law for decomposition of MNNG that is first-order in thiolate ion and first-order in neutral MNNG. Rate constants k2' for the reaction of the thiolates are determined. There is no significant buffer catalysis of the reactions of any of the thiolates in the pH range studied. In the case of the reactions of propanethiolate and trifluoroethanethiolate, two products, methylnitroguanidine (MNG) and the thiol ((RS)-N-nitroformamidine) adducts 1, were found to account quantitatively (98 +/- 3%) for the nitroguanidine skeleton of the starting material. In the case of the other five thiolates, the percent yield of MNG was determined. The yields of MNG are independent of thiolate ion concentration or buffer concentration. The yield of MNG changes from 5% for the reaction of propanethiolate, the most basic thiolate, to 90% for the reaction of pentafluoropropanethiolate, the least basic thiolate. On the basis of the yields of MNG, which indicate the extent of reaction at the nitroso nitrogen for the different thiolates, specific second-order rate constants for the thiolate ion reaction at the nitroso nitrogen, k(DN), and for the thiolate ion reaction at the guanidino carbon, k(DA), are calculated from the total second-order rate constant, k2'. The plot of log k(DN) against pK(aRSH) is linear with a slope beta(nuc) = 0.54 +/- 0.02. A similar plot for log k(DA) shows a downward break with decreasing thiol pK(a). The plot is consistent with a reaction that involves an anionic intermediate, T-, the formation of which is rate-limiting for basic thiolates and the decomposition of which is rate-limiting for weakly basic thiolates. Limiting values of beta(nuc) consistent with the data were determined to be beta(nuc) = 0.70 +/- 0.12 and 2.4 +/- 0.2 for rate-limiting formation and breakdown reactions, respectively. The latter value is attributed to a late transition state for leaving group expulsion with a large imbalance in which C-N double bond formation lags behind leaving group expulsion. The results represent a good chemical model for the recently reported chemoprotective denitrosation reaction between glutathione and MNNG that is catalyzed by a glutathione S-transferase.
• Nitroso group transfer from N-nitrososulfonamides to thiolate ions. Intrinsic reactivity
  作者：C. Adam、L. García-Río、J.R. Leis、J.A. Moreira

  DOI：10.1016/j.tet.2006.06.060

  日期：2006.9

  The nitroso group transfer from N-nitrososulfonamides to thiolate ions was studied. Based on the results, the reaction rate is strongly dependent on the nature of the leaving group (alpha(1g) approximate to -1.30), but virtually independent of the basicity of the thiol (beta(nuc) approximate to 0-10)This dependence is ascribed to the presence of a nucleophile desolvation equilibrium (beta(d)) that is followed by the attack of the thiolate ion on the nitroso group (beta'(nuc)) via a concerted mechanism. The equilibrium constants for the loss of a nitroso group from a nitrosothiol and an N-nitrososulfonarni de were used to obtain the equilibrium constants for the different reactions involved. By using rate-equilibrium correlations, the parameters alpha(norm)(1g) ,beta(d), and beta('norm)(nuc) were obtained. (c) 2006 Elsevier Ltd. All rights reserved.