2-methyldibenzothiepin-11(6H)-one | 5202-11-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并硫平类
• 英文名称: 2-methyldibenzothiepin-11(6H)-one
• 英文别名: 2-methyldibenzo[b,e]thiepin-11(6H)-one；2-Methyl-dibenzothiepin-11-on；2-methyl-6H-benzo[c][1]benzothiepin-11-one
• CAS: 5202-11-9
• 化学式: C₁₅H₁₂OS
• 分子量: 240.326
• InChiKey: KFGAXGZXARTZRX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-methyldibenzothiepin-11(6H)-one 在 氢溴酸 、 magnesium 作用下， 以 溶剂黄146 为溶剂， 生成 11-(2-bromoethylidene)-2-methyl-6,11-dihydrodibenzothiepin
  参考文献：
  名称：

  Polivka, Zdenek; Licha, Irena; Taufmann, Petr, Collection of Czechoslovak Chemical Communications, 1987, vol. 52, # 6, p. 1566 - 1581

  摘要：

  DOI：
• 作为产物：
  描述：

  AE-477/13519093 在 氢氧化钾 、 磷酸 、 盐酸羟胺 、 phosphorus pentoxide 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 为溶剂， 反应 3.0h， 生成 2-methyldibenzothiepin-11(6H)-one
  参考文献：
  名称：

  Acid-catalyzed reactions of ortho-substituted benzohydroxamic acids in polyphosphoric acid (PPA)

  摘要：

  DOI：

  10.1021/jo00373a022

文献信息

• Synthesis of benzyl sulfides<i>via</i>substitution reaction at the sulfur of phosphinic acid thioesters
  作者：Yoshitake Nishiyama、Takamitsu Hosoya、Suguru Yoshida

  DOI：10.1039/d0cc02039g

  日期：——

  An ambident electrophilicity of phosphinic acid thioesters is disclosed. Unexpected carbon-sulfur bond formation took place in the reaction between phosphinic acid thioesters and benzyl Grignard reagents. The developed method for benzyl sulfides has a wide substrate scope and was applicable for the synthesis of a drug analog.

  公开了次膦酸硫酯的亲环境亲电性。次膦酸硫酯与苄基格氏试剂之间的反应发生了意外的碳硫键形成。所开发的苄基硫的方法具有广泛的底物范围，可用于合成药物类似物。
• Friedel–Crafts reactions of acyl trifluoromethanesulfonates and cyclic acylsulfonium cations generated from acyl fluorides
  作者：K.V. Raghavendra Rao、Yannick Vallée

  DOI：10.1016/j.tet.2016.06.029

  日期：2016.7

  Reactive acyl trifluoromethanesulfonates are formed from the reaction of acyl fluorides with trimethylsilyl trifluoromethanesulfonate (TMSOTf). These electrophiles undergo Friedel–Crafts reactions with electron-rich aromatics at room temperature. When a sulfur atom is present at their γ position, their cyclization to acylsulfonium cations is observed and is followed by a rearrangement leading to benzothiepinones

  反应性酰基三氟甲磺酸盐是由酰基氟与三甲基甲硅烷基三氟甲磺酸盐（TMSOTf）反应形成的。这些亲电试剂在室温下与富电子芳族化合物发生Friedel-Crafts反应。当硫原子存在于其γ位置时，观察到它们被环化为酰基ls阳离子，随后发生重排，生成苯并噻吩酮（或二苯并[ b，e ]噻吩酮），产率为40-85％。
• Über neuartige tricyclische Thiazepin- und Thiepin-Derivate Untersuchungen über synthetische Arzneimittel, 8. Mitteilung
  作者：F. Gadient、E. Jucker、A. Lindenmann、M. Taeschler

  DOI：10.1002/hlca.19620450616

  日期：——

  Es werden Synthesen und die pharmakologischen Eigenschaften von neuartigen tricyclischen Verbindungen, und zwar von Derivaten des 5,11-Dihydro-benzo[b]-pyrido [2,3-e]thiazepins[1,4] und des 6,11-Dihydro-dibenzo[b, e]thiepins, beschrieben.

  Es werden Synthesen和Pharmacologischen Eigenschaften von Neuartigen Tricyclischen Verbindungen，以及Zwar von Derivaten des 5,11-Dihydro-benzo [b] -pyrido [2,3-e] thiazepins [1,4]和des 6,11-Dihydro-二苯并[b，e]噻吩类化合物，贝司列本。
• N,N-diethyl-N'-{dibenzo[b,e]thiepin-11(6H)-ylidene}-1,3-propanediamine
  申请人：Hoffmann-La Roche Inc.

  公开号：US03985895A1

  公开（公告）日：1976-10-12

  Dibenzo[b,e]thiepin derivatives of the formula ##SPC1## Wherein X is sulfur or sulfonyl and R is hydrogen or methyl, are described. The compounds of formula I are useful as diuretic agents.

  描述了具有以下公式的二苯并[b,e]噻吩衍生物##SPC1##其中X是硫或磺酰基，R是氢或甲基。公式I的化合物可用作利尿剂。
• Reactions of 11-chloro-11-phenyl-6,11-dihydrodibenzo[b,e]-thiepin with piperidine and some further nucleophiles
  作者：Miroslav Protiva、Karel Šindelář、Vladimír Valenta、Jiří Holubek、Emil Svátek、Miroslav Ryska、Jiří Schlanger、Jiří Urban、Marta Hrubantová

  DOI：10.1135/cccc19823094

  日期：——

  The title compound Vb affords with piperidine normal nucleophilic substitution product and the isomeric 3-piperidino derivative XXXII. The structure of XXXII was proven by (1) the ¹H NMR and ¹³C NMR spectra, (2) an independent synthesis via the intermediates XXXV, XXXVI, XXX, IV and VIIIa, and (3) with the help of model reactions of the 2-methyl derivative VIb and the 3-methyl derivative VIIb with piperidine. The rearranged cation XXXVII is considered a precursor of the product XXXII. Similar mixtures are apparently formed in reactions of the chloro derivative Vb with a series of further amines where, however, mostly the normal substitution products (XV-XXI) were isolated and only in two cases the formation of the 3-substituted compounds (XXXIII, XXXIV) was noted. The 11-amino derivatives of the type XIII are unstable in ethanol in the presence of hydrogen chloride; the product of their acid catalyzed solvolysis is the ethoxy derivative XIV. Potassium phthalimide reacts with the compound Vb under the formation of the normal product XXII accompanied by 9-phenylanthracene (XXXVIII). Reaction of Vb with 3-dimethylaminopropylmagnesium chloride affords on the one hand the normal product XXIV, and the isomer on the other, to which the structure XXXIX is ascribed. The biological screening of the amines prepared showed with some compounds a rather significant antimicrobial activity in vitro (e.g. XXXIII) and some structurally less specific neurotropic effects, especially the spasmolytic (XXII, XXXIX) and the central depressant one (XX, XXXIII).

  标题化合物Vb通过哌啶正常亲核取代产物和异构体3-哌啶衍生物XXXII。 XXXII的结构经由（1）1H NMR和13C NMR光谱证明，（2）经由中间体XXXV、XXXVI、XXX、IV和VIIIa的独立合成，以及（3）通过2-甲基衍生物VIb和3-甲基衍生物VIIb与哌啶的模型反应来证实。重排的阳离子XXXVII被认为是产物XXXII的前体。在Vb的氯衍生物与一系列进一步胺类反应中，显然会形成类似的混合物，然而，大多数情况下只分离出正常取代产物（XV-XXI），只有在两种情况下才注意到3-取代化合物（XXXIII、XXXIV）的形成。在乙醇存在氯化氢的情况下，XIII型的11-氨基衍生物是不稳定的；它们在酸催化的溶剂解作用下的产物是乙氧基衍生物XIV。邻苯二甲酰亚胺钾与化合物Vb反应生成伴随着9-苯基蒽的正常产物XXII。Vb与3-二甲氨基丙基镁氯化物反应，一方面生成正常产物XXIV，另一方面生成异构体，其结构被归因为XXXIX。所制备的胺类的生物筛选表明，一些化合物在体外显示出相当显著的抗菌活性（例如XXXIII），以及一些结构上不太特异的神经效应，特别是解痉作用（XXII、XXXIX）和中枢抑制作用（XX、XXXIII）。