N,N-diethyl-2-(phenylthio)acetamide | 53136-40-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: N,N-diethyl-2-(phenylthio)acetamide
• 英文别名: Acetamide, N,N-diethyl-2-(phenylthio)-；N,N-diethyl-2-phenylsulfanylacetamide
• CAS: 53136-40-6
• 化学式: C₁₂H₁₇NOS
• mdl: MFCD02576198
• 分子量: 223.339
• InChiKey: IUKLUPXCEUXOIW-UHFFFAOYSA-N

物化性质

• 沸点：
  337.4±25.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.416
• 拓扑面积：
  45.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N,N-diethyl-2-(phenylthio)acetamide 在 selenium(IV) oxide 、 双氧水 作用下， 以 甲醇 、 水 为溶剂， 反应 8.0h， 生成 2-(苯磺酰基)-N,N-二乙基乙酰胺
  参考文献：
  名称：

  Spectroscopic and theoretical studies of some N,N-diethyl-2-[(4′-substituted)phenylsulfonyl]acetamides

  摘要：

  The analysis of the IR carbonyl band of the N,N-diethyl-2-[(4'-substituted)phenylsulfonyl]acetamides Et(2)NC(O)CH(2)S(O)(2)-C(6)H(4)-Y (Y = OMe 1, Me 2,1-13, Cl 4, Br 5, NO(2) 6) supported by B3LYP/6-31G(d,p) calculations for 3, indicated the existence of three pairs (anti and syn) of cis (c) and gauche (g(1) and g(2)) conformers in the gas phase, being the gauche conformers significantly more stable than the cis ones. The anti geometry is more stable than the syn one, for each pair of cis and gauche conformers. The summing up of the orbital (NBO analysis) and electrostatic interactions justifies quite well the populations and the v(CO) frequencies of the anti and syn pairs of c, g(1) and g(2) conformers. The IR higher carbonyl frequency component whose population is ca. 10%, in CCl(4), may be ascribed to the least stable and most polar cis conformer pair (in the gas phase) and the lower frequency component whose population is ca. 90%, to the summing up of the populations of the two most stable and least polar gauche conformer pairs (g(1) and g(2)) (in the gas phase). The reversal of the cis(c)/gauche (g(1) + g(2)) population ratio observed in chloroform ca. 60% (cis)/40% (gauche) and the occurrence of the most polar cis(c) conformer only, in acetonitrile, strongly suggests the coalescence of the two gauche components in a unique carbonyl band in solution. A further support to this rationalization is given by the single point PCM solvation model performed by HF/6-31G(d,p) method, which showed a progressive increase of the c/(g(1) + g(2)) ratio going from gas to CCl(4), to CHCl(3) and to CH(3)CN. X-ray single crystal analysis of 4 indicates that this compound assumes, in the solid state, the syn-clinal (gauche) conformation with respect to the [O=C-CH(2)-S] moiety, and the most stable anti geometry relative to the [C(O)N(CH(2)CH(3))(2)] fragment. In order to obtain larger energy gain from the crystal packing the molecules of 4 are linked in centrosymmetric dimers through two C-H center dot center dot center dot O interactions (C-H([O-Ph])center dot center dot center dot O([SO2])) forming a step ladder. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molstruc.2011.06.051
• 作为产物：
  描述：

  苯硫基乙酸 在 吡啶 、 氯化亚砜 作用下， 以 二氯甲烷 为溶剂， 反应 10.0h， 生成 N,N-diethyl-2-(phenylthio)acetamide
  参考文献：
  名称：

  铑催化的α-重氮亚胺的Sommelet-Hauser型重排：官能化酰胺的合成。

  摘要：

  由α-硫代酸酯和N-磺酰基-1,2,3-三唑衍生的硫鎓的高效铑催化的Sommelet-Hauser型重排反应已成功完成，用于合成各种官能化的酰胺。发达的反应涉及具有亚胺基序的硫酰化物的前所未有的[2,3]-σ重排。重要的是，该方法与各种取代的α-硫代酯/酰胺/酮和取代的N-磺酰基-1,2,3-三唑类均能很好地起作用，并且可以良好的收率合成各种烯酰胺衍生物。该反应还成功地扩展到由末端炔烃的一锅法合成酰胺。

  DOI：

  10.1039/d0cc00016g

文献信息

• Conformational analysis of some N,N-diethyl-2-[(4′-substituted) phenylthio] acetamides
  作者：Elisângela Vinhato、Paulo R. Olivato、Julio Zukerman-Schpector、Maurizio Dal Colle

  DOI：10.1016/j.saa.2013.06.118

  日期：2013.11

  component observed at the lower frequency can be ascribed to the gauche conformers g(anti; syn) for 3-6 in n-C6H14, which is in agreement with the gauche and cis relative stabilities and frequencies resulting from the PCM calculations. Similarly, the single IR band for 1 and 2 in n-hexane may be attributed to the gauche conformers. The PCM calculations compared well with the IR data for the compounds

  通过νCOIR分析，对一些带有取代基OMe 1，Me 2，H 3，Cl 4，Br 5和NO26的N，N-二乙基-2 [（（4'-取代）苯硫基]乙酰胺进行了构象分析。使用B3LYP / 6-311 ++ G（d，p）和可极化连续体模型（PCM）进行计算，并对1、3和6进行NBO分析，对4进行X射线衍射。计算结果表明在气相中存在两个稳定构象对，即gauche（anti; syn）（最稳定）和顺式（anti; syn）。与1和3的顺式构象的极性相比，gauche构象的极性较小，但对6而言，极性更强。在较低频率下观察到的最强烈的IR羰基双峰组分可归因于3的gauche构象构形g（anti; syn）在n-C6H14中为-6，这与PCM计算得出的gauche和cis相对稳定性和频率一致。类似地，正己烷中1和2的单个IR谱带可归因于gauche构象异构体。PCM计算结果与溶液中化合物的IR数据进行了很
• Direct access to α-sulfenylated amides/esters <i>via</i> sequential oxidative sulfenylation and C–C bond cleavage of 3-oxobutyric amides/esters
  作者：Yi Jiang、Jie-dan Deng、Hui-hong Wang、Jiao-xia Zou、Yong-qiang Wang、Jin-hong Chen、Long-qing Zhu、Hong-hua Zhang、Xue Peng、Zhen Wang

  DOI：10.1039/c7cc09026a

  日期：——

  An efficient, environmentally benign and unprecedented synthesis of various α-sulfenylated amides/esters has been developed under oxygen atmosphere. The reaction shows good functional group tolerance and excellent chemo/regioselectivity. All the desired products were obtained in moderate to excellent yields, even on the gram scale. Practically, the related α-thiol Weinreb amide can be readily transferred

  在氧气气氛下，已经开发出一种高效，环境友好的和前所未有的合成各种α-亚磺酰化酰胺/酯的方法。该反应显示出良好的官能团耐受性和优异的化学/区域选择性。即使在克规模上，也以中等至极好的收率获得了所有所需的产品。实际上，相关的α-硫醇Weinreb酰胺可以很容易地转移到一系列预期的化合物中，并且硒原子可以高产率地引入到酰胺的α-位。
• Electrolytic Partial Fluorination of Organic Compounds. 17. Regiospecific Anodic Fluorination of Sulfides Bearing Electron-Withdrawing Substituents at the Position .alpha. to the Sulfur Atom
  作者：Toshio Fuchigami、Moriyasu Shimojo、Akinori Konno

  DOI：10.1021/jo00116a037

  日期：1995.6

  Regiospecific monofluorination of various sulfides bearing electron-withdrawing substituents, cyano, ester, acyl, amino, and phosphonate groups,at their alpha-positions was successfully carried out by the anodic oxidation of the sulfides in Et(3)N . 3HF/MeCN using an undivided cell. Fluorine was introduced at the position alpha to the sulfur atom selectively. Fluorination of alpha-(phenylthio)-substituted cyclic carbonyl compounds was also successful. Furthermore, anodic alpha,alpha-difluorination of ethyl alpha-(phenylthio)acetate was also successfully carried out although a large amount of electricity was required.
• Electrolytic reactions of fluoro organic compounds. 9. Fluoride ion promoted anodic substitutions of chalcogeno compounds. 1. Regioselective anodic alkoxylation of sulfides
  作者：Toshio Fuchigami、Hidetoshi Yano、Akinori Konno

  DOI：10.1021/jo00024a002

  日期：1991.11

  Anodic alpha-alkoxylation of sulfides was remarkably promoted in the presence of fluoride ions: When Et3N.3HF was used as a supporting electrolyte, simple alkyl phenyl sulfides and sulfides bearing weak electron-withdrawing groups underwent anodic alkoxylation via fluorosulfonium ions as key intermediates in a unique Pummerer-type mechanism with reasonable or high yields for the first time.