3-methyl-5-phenyl-1,3,4-oxadiazoline-2-thione | 7111-93-5

• 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: 3-methyl-5-phenyl-1,3,4-oxadiazoline-2-thione
• 英文别名: 3-methyl-5-phenyl-3H-[1,3,4]oxadiazole-2-thione；2-Phenyl-4-methyl-1,3,4-oxadiazolin-5-thion；5-Phenyl-3-methyl-oxadiazolin-2-thion；3-Methyl-5-phenyl-1,3,4-oxadiazole-2(3H)-thione；3-methyl-5-phenyl-1,3,4-oxadiazole-2-thione
• CAS: 7111-93-5
• 化学式: C₉H₈N₂OS
• 分子量: 192.241
• InChiKey: IHYKGPXSEWWQBW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  56.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-methyl-5-phenyl-1,3,4-oxadiazoline-2-thione 在 双氧水 、 溶剂黄146 作用下， 生成 3-甲基-5-苯基-1,3,4-恶二唑-2-酮
  参考文献：
  名称：

  一氯化硫对2-酰基-1,1-二甲基肼的作用；四氮唑和恶二唑啉的形成

  摘要：

  Tetrazans是一氯化硫作用于2-酰基-1,1-二甲基肼的主要产物。在某些情况下，还以较小的产率形成1,3,4-恶二唑啉-2-硫酮。

  DOI：

  10.1039/j39670002636
• 作为产物：
  描述：

  methyl N-benzamido-N-methylcarbamodithioate 在 三乙胺 作用下， 以 乙醇 为溶剂， 反应 4.0h， 生成 3-methyl-5-phenyl-1,3,4-oxadiazoline-2-thione
  参考文献：
  名称：

  Alkyl 2-Methyldithiocarbazates in Heterocyclic Synthesis: Preparation of 2-Alkylthio-1,3,4-thiadiazolium Cations and 2-Thioxo-2,3-dihydro-1,3,4-Oxadiazole Derivatives

  摘要：

  烷基 3-酰基-2-甲基二硫代卡巴肼 2 可由烷基 2-甲基二硫代卡巴肼和酰基氯化物制得，在高氯酸/乙酸酐的作用下发生闭环反应，生成 2-烷硫基 3-甲基-1,3,4-噻二唑鎓盐 4。化合物 2 还会在碱催化下发生环化反应，生成 4-甲基-2-硫酮-2,3-二氢-1,3,4-恶二唑 3，再与四氟硼酸三甲基锍反应，生成 3-甲基-2-甲硫基-1,3,4-恶二唑阳离子 5。1-Aroyl-2-ethoxyoxalyl-1-phenylhydrazines 6 在三氟甲磺酸/乙酸酐的作用下发生环化反应，生成 2-芳基-5-乙氧羰基-3-苯基-1,3,4-恶二唑鎓盐 7。

  DOI：

  10.1055/s-1988-27672

文献信息

• Platinum assisted cyclization of S-methyl 3-acyl-2-methyldithiocarbazates under mild conditions. Crystal structure of [Pt2(μ-SMe)(terpy)2][ClO4]3 †
  作者：Giuliano Annibale、Paola Bergamini、Valerio Bertolasi、Michela Cattabriga、Antonio Lazzaro、Andrea Marchi、Gianni Vertuani

  DOI：10.1039/a904859f

  日期：——

  The reaction of the newly synthesized aqua complex [Pt(terpy)(OH2)][BF4]2 with S-methyl 3-acyl-2-methyldithiocarbazates under a variety of experimental conditions has been studied. Using a 2∶1 metal to ligand ratio in methanol, a platinum assisted cyclization was observed. The reaction products were Δ2-1,3,4-oxadiazoline-5-thione derivatives and the binuclear tricationic complex [Pt2(µ-SMe)(terpy)2]3+ whose molecular structure has been determined by X-ray crystallography. This platinum assisted transformation is proposed as a new synthetic route to Δ2-1,3,4-oxadiazoline-5-thiones under mild conditions. In the presence of an excess of a non-co-ordinating acid (HClO4, CH3SO3H or CF3SO3H) the cyclization is completely quenched and complexes with co-ordinated S-methyl 3-acyl-2-methyldithiocarbazates have been isolated. A general mechanism which accounts for the observed transformations is proposed on the basis of 1H NMR and UV/Vis evidence.

  研究了新合成的含水配合物 [Pt(terpy)(OH2)][BF4]2与 S-甲基 3-酰基-2-甲基二硫代咔嗪盐在各种实验条件下的反应。在甲醇中，金属与配体的比例为 2∥1，观察到了铂辅助环化反应。反应产物是δ2-1,3,4-噁二唑啉-5-硫酮衍生物和双核三阳离子配合物[Pt2(µ-SMe)(terpy)2]3+，其分子结构已通过 X 射线晶体学确定。这种铂辅助转化被认为是在温和条件下合成δ2-1,3,4-噁二唑啉-5-硫酮的新途径。在过量的非配位酸（HClO4、CH3SO3H 或 CF3SO3H）存在下，环化反应被完全淬灭，并分离出配位的 S-甲基 3-酰基-2-甲基二硫代氨基甲酸酯络合物。根据 1H NMR 和 UV/Vis 证据，提出了解释所观察到的转化的一般机制。
• Specific Molecular Orbital Contributions to Nucleophilicity. The Thiocarbonyl Group as Priviledged Monitor to Pinpoint Active and Less Active Molecular Orbitals in Reactions with Methylating Agents
  作者：M. Arbelot、A. Allouche、K. F. Purcell、M. Chanon

  DOI：10.1021/jo00113a010

  日期：1995.4

  The rate constants for 41 compounds bearing a C=S function reacting with MeX (X = I, Tos) span 7 orders of magnitude. The PES spectra of these compounds display two very low energy peaks, which stand clearly apart from the other peaks. These two peaks correspond to the pi orbitals of the C-S group; one is its CS pi bonding orbital oriented out of the molecular plane (pi(CS)) and the other its p-type in-plane lone pair orbital (pi(S)). For some of the compounds, the HOMO is the pi(CS) orbital and for others the HOMO is the ns lone pair orbital. The best correlation (R = 0.96) between rate constants h and PES data is obtained when In(k) is plotted against the inverse of PES energy of the pi(S) lone pair orbital. Whether this lone pair orbital is the HOMO or the next lower HOMO has no importance. A modest correlation (R = 0.78) is obtained when In(k) is plotted against the inverse of PES energy of the pi(CS) bonding orbital, An attempt to correlate the calculated energy of the third highest occupied orbital (from AM1 calculations) with In(h) provides a complete scattering of data (R < 0.1), but the calculated energy of the second lone pair orbital sigma(S) (approximate to 90 kcal mol-l deeper than the HOMO) correlates reasonably with In(h) (R = 0.88). The energies of the S 2s and 2p core orbitals (calculated for 13 cyclic compounds with the HF/3-21G technique to be 4000 to 5500 kcal mol(-1) deeper than HOMO) correlate with In(k) (R = 0.86) as well as does that of the second lone pair orbital os. These results are the first where both frontier orbitals and core orbitals display correlation with overall reactivity. They are discussed in terms of direct (perturbational) versus indirect (nonperturbational) concepts.
• Sandstroem,J.; Wennerbeck,I., Acta Chemica Scandinavica (1947), 1966, vol. 20, p. 57 - 71
  作者：Sandstroem,J.、Wennerbeck,I.

  DOI：——

  日期：——
• Ziyaev, A. A.; Galust'yan, G. G.; Sabirov, K., Russian Journal of Organic Chemistry, 1992, vol. 28, # 7, p. 1221 - 1225
  作者：Ziyaev, A. A.、Galust'yan, G. G.、Sabirov, K.、Nasirov, S.、Tashkhodzhaev, B.、Yagudaev, M. R.

  DOI：——

  日期：——
• The action of sulphur monochloride on 2-acyl-1,1-dimethylhydrazines; the formation of tetrazans and oxadiazolines
  作者：P. Hope、L. A. Wiles

  DOI：10.1039/j39670002636

  日期：——

  Tetrazans are the main products of the action of sulphur monochloride on 2-acyl-1,1-dimethylhydrazines. In some cases 1,3,4-oxadiazoline-2-thiones are also formed, in smaller yields.

  Tetrazans是一氯化硫作用于2-酰基-1,1-二甲基肼的主要产物。在某些情况下，还以较小的产率形成1,3,4-恶二唑啉-2-硫酮。

表征谱图