O-phenyl morpholine-4-carbothioate | 75528-03-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: O-phenyl morpholine-4-carbothioate
• CAS: 75528-03-9
• 化学式: C₁₁H₁₃NO₂S
• 分子量: 223.296
• InChiKey: HBKSEYHMIVUXBX-UHFFFAOYSA-N

物化性质

• 熔点：
  125-126 °C(Solv: ethanol (64-17-5))
• 沸点：
  323.1±52.0 °C(Predicted)
• 密度：
  1.243±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  53.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  硫代氯甲酸苯酯 以60%的产率得到
  参考文献：
  名称：

  MARTIN D.; WENZEL A., J. PRAKT. CHEM., 1980, 322, NO 2, 253-260

  摘要：

  DOI：

文献信息

• Phenyl Chloro(thionoformate): a New Dealkylating Agent of Tertiary Amines
  作者：David S. Millan、David S. Millan、Rolf H. Prager、Rolf H. Prager

  DOI：10.1071/ch98147

  日期：——

  Phenyl chloro(thionoformate) reacts rapidly with unhindered tertiary aliphatic amines at 20° to give a thiocarbamate and an alkyl chloride. Dialkylcyclohexylamines react surprisingly rapidly to form predominantly cyclohexene. The thiocarbamates are converted into the secondary amine salt by treatment with dimethyl sulfate, followed by hydrolysis with water. Rates of reaction and alkyl group cleavage selectivity in amines were found to be superior or comparable to those previously reported with chloroformates.

  苯基氯代(硫代甲酸酯)在20°下与无障碍的三级脂肪胺迅速反应，生成硫代氨酸酯和烷基氯化物。二烷基环己胺出奇地迅速反应，主要生成环己烯。硫代氨酸酯经过甲基硫酸二甲酯处理后，再用水水解转化为二级胺盐。在氨基中，反应速率和烷基团裂解选择性被发现优于或与以前报道的氯代甲酸酯相媲美。
• The dealkylation of tertiary aliphatic amines with phenyl chlorothionoformate
  作者：David S. Millan、Rolf H. Prager

  DOI：10.1016/s0040-4039(98)00743-6

  日期：1998.6

  Phenyl chlorothionoformate reacts rapidly with aliphatic amines at 20°C to give a thiourethane and an alkyl chloride. The urethanes are readily converted to the secondary amine salt by reaction with dimethyl sulfate, followed by hydrolysis with water. Rates of reaction, and alkyl group cleavage selectivity, are comparable to those reported for 1-chloroethyl chloroformate.

  苯基氯硫代甲酸酯在20°C下与脂肪胺迅速反应，生成硫代氨基甲酸酯和烷基氯​​。氨基甲酸酯通过与硫酸二甲酯反应，然后用水水解，很容易转化为仲胺盐。反应速率和烷基裂解选择性与报道的氯甲酸1-氯乙基酯相当。
• Kinetics and Mechanism of the Aminolysis of Phenyl and 4-Nitrophenyl Chlorothionoformates
  作者：Enrique A. Castro、María Cubillos、José G. Santos

  DOI：10.1021/jo970276y

  日期：1997.6.1

  for the aminolysis of both substrates are linear with the same slope, beta = 0.26. From this value, the kinetic law, and the analysis of products, it is deduced that these reactions proceed through a zwitterionic tetrahedral addition intermediate (T(+/-)) on the reaction path, and its formation is the rate-determining step. From a comparison of the present reactions with the concerted aminolysis of substituted

  一系列仲脂环族胺与标题底物的反应在25°C的离子强度0.2 M（用KCl维持）的水溶液中进行动力学研究。在胺下，发现过量的伪一阶速率系数（k（obsd））。在恒定pH下，k（obsd）对游离胺浓度的曲线是线性的，其斜率（k（N））与pH无关。获得的两种底物的氨解布朗斯台德型图（log k（N）与胺pK（a））呈线性，斜率相同，β= 0.26。根据该值，动力学定律和产物分析，可以推断这些反应在反应路径上通过两性离子四面体加成中间体（T（+/-））进行，其形成是决定速率的步骤。
• Structure−Reactivity Correlations in the Aminolysis and Pyridinolysis of Bis(phenyl) and Bis(4-nitrophenyl) Thionocarbonates
  作者：Enrique A. Castro、José G. Santos、Jimena Téllez、María I. Umaña

  DOI：10.1021/jo970624w

  日期：1997.9.1

  The reactions of a series of secondary alicyclic amines with bis(phenyl) and bis(4-nitrophenyl) thionocarbonates (BPTOC and BNPTOC, respectively), and a series of pyridines with the latter substrate, are subjected to a kinetic investigation in water, 25.0 degrees C, ionic strength 0.2 M (KCl). All the reactions obey pseudo-first-order kinetics under amine excess over the substrate. The reactions of piperidine with BPTOC are first order in amine, but those of the same substrate with the other secondary alicyclic amines exhibit a complex order, consistent with the existence of both a zwitterionic (T+/-) and an anionic (T-) tetrahedral intermediates on the reaction pathway. Deprotonation of T+/- by a secondary amine to give T- (rate coefficient k(3)) competes with expulsion of the amine moiety from T+/- (k(-1)), except in the reactions of 1-formylpiperazine whereby k(-1) much greater than k(3) [1-formylpiperazine], and a kinetics second order in amine is observed. The reactions of secondary alicyclic amines with BNPTOC are all first order in amine and show a nonlinear Bronsted-type plot with limiting slopes beta = 0.1 (high amine pK(a)) and beta = 0.5 (low amine pK(a)). This slight curvature is consistent with a concerted mechanism (one step). The intermediate T+/- is not formed because of its high kinetic instability due to a large k(-1) value. The pyridinolysis of BNPTOC exhibits a first order in amine kinetics and a linear Bronsted-type plot of slope beta = 1.0, which is consistent with the existence of T+/- whereby the expulsion of the leaving group from T+/- is the rate-determining step. This intermediate is less unstable than that with a secondary amine due to the fact that k(-1) is smaller for a pyridine compared to an isobasic secondary alicyclic amine.
• Martin, D.; Wenzel, A., Journal fur praktische Chemie (Leipzig 1954), 1980, vol. 322, # 2, p. 253 - 260
  作者：Martin, D.、Wenzel, A.

  DOI：——

  日期：——