Propylthionitrit | 88871-35-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: Propylthionitrit
• 英文别名: thionitrous acid propyl ester；1-nitrososulfanyl-propane；1-Nitrososulfanylpropane
• CAS: 88871-35-6
• 化学式: C₃H₇NOS
• 分子量: 105.161
• InChiKey: ZBBFIGBOZFBYFN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  6
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  54.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  丙烷-1-硫醇 在 三缩四乙二醇 、 silica gel 、 dinitrogen tetraoxide 作用下， 以 叔丁醇 为溶剂， 生成 Propylthionitrit
  参考文献：
  名称：

  二氧化硅-聚乙二醇/N 2 O 4 配合物作为多相硝化剂和亚硝化剂

  摘要：

  氯化硅与不同量的 H(OCH 2 CH 2 ) n OH (n = 2-4) 反应以提供基于二氧化硅的线性聚乙二醇和环状聚乙二醇醚。选择了二氧化硅-四甘醇醚 (III) 的 N 2 O 4 络合物，并将其用作一种稳定、廉价且非均相的二氧化硅基试剂，用于苯酚的选择性单硝化和二硝化以及硫醇的亚硝化。

  DOI：

  10.1080/10426500307863

文献信息

• Silica-Acetate Complex of N₂O₄: A Heterogeneous Reagent for the Selective Nitration of Phenols and Nitrosation of Thiols
  作者：N. Iranpoor、H. Firouzabadi、R. Heydari

  DOI：10.1081/scc-120016310

  日期：2003.1.4

  Abstract Complexation of gaseous N2O4 with acylated silica gel affords an addition compound, which is an efficient heterogeneous reagent for the selective mono- and dinitration of phenol, substituted phenols and nitrosation of thiols.

  摘要 气态 N2O4 与酰化硅胶络合得到加成化合物，这是一种有效的多相试剂，用于苯酚、取代苯酚的选择性单硝化和二硝化以及硫醇的亚硝化。
• Efficient Conversion of Thiols to S-Nitrosothiols with the 18-Crown-6 Complex of N2O4 as a New Nitrosating Agent
  作者：N. Iranpoor、H. Firouzabadi、R. Heydari

  DOI：10.1039/a904784k

  日期：——

  Gaseous N2O4 reacts with 18-crown-6 to afford a stable ionic complex of NO+·18-crown-6·H(NO3)2–; this complex is an efficient nitrosating agent for the conversion of thiols to their corresponding S-nitrosothiols in different organic solvents.

  气态N2O4与18-冠-6反应，形成稳定的离子复合物NO+·18-冠-6·H(NO3)2–；该复合物是有效的亚硝化试剂，可将硫醇转化为相应的S-亚硝基硫醇，适用于不同的有机溶剂。
• 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.