6-methoxy-2-methyl-3H-azepine | 919515-24-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吖庚因类
• 英文名称: 6-methoxy-2-methyl-3H-azepine
• 英文别名: 6-Methoxy-2-methyl-3H-azepine
• CAS: 919515-24-5
• 化学式: C₈H₁₁NO
• 分子量: 137.181
• InChiKey: NAKNYZFLEHLIOE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  allyl N-isopropyl-2-methoxybuta-2,3-dienimidothioate 在 potassium tert-butylate 作用下， 以 四氢呋喃 、 正己烷 、 二甲基亚砜 为溶剂， 反应 0.67h， 生成 6-methoxy-2-methyl-3H-azepine 、 2-[(Z)-1-methoxyprop-1-enyl]-4,4-dimethyl-5-vinyl-4,5-dihydro-1,3-thiazole
  参考文献：
  名称：

  2-Aza-1,3,5-三烯与超碱的反应的进一步发展：通过串联去质子化-环化竞争性形成新的4,5-二氢-1,3-噻唑，二氢氮杂环庚烷和氮杂环庚烷

  摘要：

  摘要 烯丙基-和苄基硫烷基取代的2-氮杂-1,3,5-三烯很容易转化为多官能化的4,5-二氢-1,3-噻唑（ 2-噻唑啉），方法是用超碱处理使活化的SCH 2基团去质子化，然后进行分子内[1,5]环闭合。同一分子的酮亚胺功能的甲基或亚甲基片段竞争性去质子化，然后进行[1,7]电环化，形成七元氮杂杂环，二氢氮杂和/或氮杂。 烯丙基-和苄基硫烷基取代的2-氮杂-1,3,5-三烯很容易转化为多官能化的4,5-二氢-1,3-噻唑（ 2-噻唑啉），方法是用超碱处理使活化的SCH 2基团去质子化，然后进行分子内[1,5]环闭合。同一分子的酮亚胺功能的甲基或亚甲基片段竞争性去质子化，然后进行[1,7]电环化，形成七元氮杂杂环，二氢氮杂和/或氮杂。

  DOI：

  10.1055/s-0034-1378805

文献信息

• Simultaneous synthesis of 4,5-dihydro-3H-azepines and 3H-azepines, bearing alkoxy and alkylsulfanyl substituents, through metallation of 2-aza-1,3,5-trienes by t-BuOK
  作者：Nina A. Nedolya、Ol’ga A. Tarasova、Ol’ga G. Volostnykh、Alexander I. Albanov、Boris A. Trofimov

  DOI：10.1016/j.jorganchem.2011.07.016

  日期：2011.10

  and 3H-azepines have simultaneously been obtained from conjugated 2-aza-1,3,5-trienes by treatment with t-BuOK under mild reaction conditions (THF/DMSO, ∼−30 °C, 30 min). One-pot synthesis of 1-aza-1,3,4-trienes from α-lithiated alkoxyallenes, isopropyl isothiocyanate and alkyl iodides, followed by the thermally induced sigmatropic [1,5]-H shift, easily leads to starting 2-aza-1,3,5-trienes. The reaction

  通过在温和的条件下用t -BuOK处理，同时从共轭2-氮杂-1,3,5-三烯中同时获得了一系列新的烷氧基和烷基硫烷基取代的4,5-二氢-3 H-氮杂环庚烷和3 H-氮杂环庚烷。反应条件（THF / DMSO，〜-30°C，30分钟）。由α-锂化的烷氧基丙二烯，异硫氰酸异丙酯和烷基碘化物一锅合成1-氮杂-1,3,4-三烯，然后热诱导σ[1,5] -H转变，很容易导致2-氮杂-1,3,5-三烯。该反应通过氮杂三烯基阴离子的产生和[1,7]-电环化而进行，并且代表了一种新颖的简单方法来同时处理氮杂环庚二烯和氮杂环庚烯。
• Reactions of 2-aza-1,3,5-trienes with superbases: competition between formation of thiazoles and azepines
  作者：N. A. Nedolya、O. A. Tarasova、O. G. Volostnykh、A. I. Albanov、B. A. Trofimov

  DOI：10.1007/s10593-012-0930-5

  日期：2012.2
• Structural reorganization of (allyl-, benzyl-, and propargylsulfanyl)-substituted 2-aza-1,3,5-trienes in t-BuOK/THF/DMSO: access to rare functionalized 2-thiazolines
  作者：Nina A. Nedolya、Ol’ga A. Tarasova、Alexander I. Albanov、Boris A. Trofimov

  DOI：10.1016/j.tetlet.2014.03.015

  日期：2014.4

  Treatment of (allyl-, benzyl-, and propargylsulfanyl)-substituted 2-aza-1,3,5-trienes, which are readily accessible from lithiated methoxyallene, isopropyl isothiocyanate, and allyl, benzyl, or propargyl bromide, respectively, with t-BuOK in THF/DMSO resulted in the unexpected formation of 2-thiazoline derivatives along with seven-membered azaheterocycles [in the case of (allyl- and benzylsulfanyl)-substituted 2-aza-1,3,5-trienes]. An unprecedented structural reorganization of the azatrienes into 2-thiazolines presumably occurs via alpha-deprotonation of the substituents at the sulfur atom followed by intramolecular [1,5]-cyclization. Deprotonation of the ketimine fragment of the same molecule followed by [1,71-electrocyclization resulted in azepine ring formation. (C) 2014 Elsevier Ltd. All rights reserved.
• Reactions of lithiated allenes with isothiocyanates: First example of deprotonation of 2-aza-1,3,5-trienes. Synthesis of 6-methoxy-2-methyl-3H-azepine and 3-methoxy-7-methyl-2-methylsulfanyl-4,5-dihydro-3H-azepine
  作者：N. A. Nedolya、L. L. Dmitrieva、A. I. Albanov、L. V. Klyba、O. A. Tarasova、I. A. Ushakov

  DOI：10.1134/s1070428006030250

  日期：2006.3
• Rearrangement of benzylsulfanyl-substituted 2-aza-1,3,5-triene into 5-phenyl-4,5-dihydro-1,3-thiazole in the t-BuOK-THF-DMSO system
  作者：N. A. Nedolya、O. A. Tarasova、A. I. Albanov、B. A. Trofimov

  DOI：10.1134/s1070428013100151

  日期：2013.10

  Benzylsulfanyl-substituted 2-aza-1,3,5-triene prepared according to one-pot procedure from methoxyallene, isopropyl isothiocyanate, and benzyl bromide underwent unexpected rearrangement in the superbasic t-BuOK-THF-DMSO system with formation of 2-[(Z)-1-methoxyprop-1-en-1-yl]-4,4-dimethyl-5-phenyl-4,5-dihydro-1,3-thiazole via alpha-deprotonation of the benzylsulfanyl substituent, followed by intramolecular [1,5]-cyclization. Concurrent deprotonation of methyl group in the ketone imine fragment and subsequent [1,7]-electrocyclization of the resulting azatriene carbanion afforded 2-(benzylsulfanyl)-3-methoxy-7-methyl-4,5-dihydro-3H-azepine and 6-methoxy-2-methyl-3H-azepine.