N-methyl-2-aminothiotropone | 17561-05-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-methyl-2-aminothiotropone
• 英文别名: 2-(Methylamino)cyclohepta-2,4,6-triene-1-thione
• CAS: 17561-05-6；3480-10-2
• 化学式: C₈H₈NS*H
• 分子量: 151.232
• InChiKey: AWURXEXTSBUSQH-UHFFFAOYSA-N

物化性质

• 熔点：
  67-68 °C(Solv: cyclohexane (110-82-7))
• 沸点：
  265.7±43.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.125
• 拓扑面积：
  44.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-methyl-2-aminothiotropone 、 三溴化硼 以 not given 为溶剂， 生成
  参考文献：
  名称：

  Chelate Chemistry. V. Metal Chelates Based on Tropolone and Its Derivatives

  摘要：

  DOI：

  10.1021/ja00973a019

文献信息

• Studies on Seven-membered Ring Compounds. XX. Reactions of Troponeimine Derivatives. (2)
  作者：Hideo Nakao、Nobuo Soma、Genshun Sunagawa

  DOI：10.1248/cpb.13.828

  日期：——

  The reaction of 2-methoxytroponeimine (I) and its N-methyl derivative (II) with active methylene compounds were carried out. The reaction of I with malononitrile, ethyl cyanoacetate or cyanoacetamide in the presence of sodium ethoxide afforded rearrangemet products, that is 3-phenylacrylic acid derivatives. The same reaction in the absence of sodium ethoxide gave mainly 2-imino-1, 2-dihydrocyclohepta[b]pyrrole derivatives. However, the reaction of I with diethyl malonate afforded ethyl 2-oxo-8-methoxy-1, 2-dihydrocyclohepta[b]pyrrole-3-carboxylate. II showed some different reactivity from I. Namely, the reaction of II with active methylene compounds in the presence of sodium ethoxide afforded 2-imino-1, 2-dihydrocyclohepta[b]pyrrole derivatives besides rearrangement products.

  2-甲氧基托品酮亚胺（I）及其N-甲基衍生物（II）与活性甲基酮化合物的反应进行了研究。I与丙二腈、氰乙酸乙酯或氰乙酰胺在乙醇钠存在下反应，得到了重排产物，即3-苯基丙烯酸衍生物。同样条件下，在无乙醇钠时主要生成2-亚胺基-1,2-二氢环庚[b]吡咯衍生物。然而，I与丙二酸二乙酯反应生成了乙酯2-氧代-8-甲氧基-1,2-二氢环庚[b]吡咯-3-羧酸酯。II显示出与I不同的反应活性，在乙醇钠存在下，II与活性甲基酮化合物的反应除了重排产物外，还主要生成2-亚胺基-1,2-二氢环庚[b]吡咯衍生物。
• General Synthesis, Spectroscopic Properties, and Dipole Moments of 2-Substituted Tropothiones
  作者：Takahisa Machiguchi、Toshio Hasegawa、Yuichi Kano

  DOI：10.1246/bcsj.66.3699

  日期：1993.12

  Several 2-substituted tropothiones (2,4,6-cycloheptatriene-1-thiones) having an electron-donating group (Me, Ph, NH2, NHMe, OH, OMe, or SMe) were synthesized by direct sulfurization from the corresponding tropones in a one-pot reaction. In contrast to the instability of the parent tropothione (1a), most of these 2-substituted derivatives were insensitive to air and were thermally stable compounds which can be handled at room temperature. These tropothione derivatives were characterized by spectroscopic and dipole moment measurements. The IR spectra showed ν(C=S) vibrations at around 1100—1040 cm−1. The UV-vis spectra displayed three π–π* transitions accompanied by n–π* transitions. The 400-MHz 1H NMR spectra of the thiones showed that only protons at the 7 position resonate well-separated downfield from the other ring protons due to the strong C=S anisotropy. In the 13C NMR (100.6 MHz) spectra, the C=S carbon signals appeared at < δ = 183 and the other ring carbons resonated at δ = 154—112. Variable-temperature 13C as well as 14N NMR spectroscopic studies clarified that 2-amino- and 2-(methylamino)tropothiones exist as an equilibrium mixture of the thione and enethiol structures in an approximate ratio of 64 : 36. This is different from the results of a previous investigation showing that the structures exist as the thione form exclusively. Dipole moments of some derivatives of 1a were measured and compared with those of the corresponding tropones. These tropothione derivatives obtained were more ionic than both the parent compound 1a and the corresponding tropones.

  几种具有电子给体基团（如甲基、苯基、氨基、甲氨基、羟基、甲氧基或硫甲基）的2-取代类萜烯硫酮（2,4,6-环七烯-1-硫酮）通过从相应的类萜酮直接硫化反应合成，采用一锅法。在与不稳定的母体类萜烯硫酮（1a）相比，这些大多数2-取代衍生物对空气不敏感，并且是热稳定化合物，可以在室温下处理。这些类萜烯硫酮衍生物通过光谱和偶极矩测量进行了表征。红外光谱显示在约1100—1040 cm−1处有ν(C=S)的振动。紫外-可见光谱显示伴随n–π*跃迁的三个π–π*跃迁。400-MHz的1H NMR光谱显示，仅有7位的质子因强C=S各向异性而与其他环上的质子分开共振。13C NMR（100.6 MHz）光谱中，C=S碳信号出现在< δ = 183，其他环碳的共振在δ = 154—112。变温13C和14N NMR光谱研究表明，2-氨基和2-(甲氨基)类萜烯硫酮以大约64 : 36的比例存在于硫酮与烯硫醇结构的平衡混合物中。这与之前的研究结果不同，后者表明这些结构仅存在于硫酮形态。对一些1a衍生物的偶极矩进行了测量，并与相应类萜酮的偶极矩进行了比较。这些获得的类萜烯硫酮衍生物比母体化合物1a和相应类萜酮更具离子性。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: B: B-Verb.10, 3.11.2, page 191 - 192
  作者：

  DOI：——

  日期：——
• Machiguchi, Takahisa; Kano, Yuichi; Hasegawa, Toshio, Chemistry Letters, 1990, # 4, p. 563 - 566
  作者：Machiguchi, Takahisa、Kano, Yuichi、Hasegawa, Toshio

  DOI：——

  日期：——
• Kajigaeshi,Shoji; Matsuoka, Shingo; Kanemasa, Shuji, Heterocycles, 1984, vol. 22, # 3, p. 461 - 465
  作者：Kajigaeshi,Shoji、Matsuoka, Shingo、Kanemasa, Shuji、Noguchi, Michihiko

  DOI：——

  日期：——