3-Bromo-3-(4-methoxyphenyl)-3H-diazirine | 95911-61-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 3-Bromo-3-(4-methoxyphenyl)-3H-diazirine
• 英文别名: 3-bromo-3-(4-methoxyphenyl)diazirine
• CAS: 95911-61-8
• 化学式: C₈H₇BrN₂O
• 分子量: 227.06
• InChiKey: WRMAOLHDAXVBKI-UHFFFAOYSA-N

物化性质

• 沸点：
  252.1±50.0 °C(Predicted)
• 密度：
  1.65±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  34
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-Bromo-3-(4-methoxyphenyl)-3H-diazirine 在 叠氮化四丁基铵 作用下， 以 乙腈 为溶剂， 以86%的产率得到4-甲氧基苯甲腈
  参考文献：
  名称：

  卤代二氮嗪的叠氮和氟化物交换反应

  摘要：

  制备 d'une 系列 fluoro-3 aryl-3 diazirines etude des反应 d'arylhalogenodiazirines avec l'ion azoture

  DOI：

  10.1021/ja00295a029
• 作为产物：
  描述：

  4-甲氧基苄脒盐酸盐 在 sodium hypochlorite 、 次氯酸叔丁酯 、 lithium bromide 作用下， 以 乙醚 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 24.25h， 生成 3-Bromo-3-(4-methoxyphenyl)-3H-diazirine
  参考文献：
  名称：

  1-氯-3-苯基重氮基的反应性

  摘要：

  对位取代的1-氯-3-苯基重氮（5）是N，N，N'-三氯苯甲m（10）与过量溴离子反应的推定中间体，进一步反应生成3-溴-（4）和3-氯-3-苯基重氮（6）。该6：4的比率用哈米特σ负相关p和σ p +的常数p -取代基。4的形成，建议通过反S N进行2'机理主要是吸电子的p-取代基。化合物6是具有给电子性p取代基的主要产物，它可以由5通过极性过渡结构12进行氯的[1,3]-σ位移而从5中产生。气相DFT（B3LYP / 6-31 + G *）对这两种机理的研究结果与实验一致。

  DOI：

  10.1021/jo060341g

文献信息

• Spin selectivity in the oxygenation of singlet phenylhalocarbenes with oxygen
  作者：Taiki Makihara、Takayuki Nojima、Katsuya Ishiguro、Yasuhiko Sawaki

  DOI：10.1016/s0040-4039(02)02538-8

  日期：2003.1

  Singlet phenylhalocarbenes are shown to react with triplet oxygen and the apparent spin-forbidden oxygenation rates are strongly dependent on substituents, i.e. in the decreasing order of Br>Clmuch greater thanF for halogen and of p-NO2>Hmuch greater thanp-MeO for p-substituents. These results suggest the oxygenation of triplet halocarbene equilibrated with ground-state singlet, resulting in the first estimation of energy difference between the singlet and triplet states. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Reaction of arylhalodiazirines with thiophenoxide: a redox process
  作者：Xavier Creary、Anthony F. Sky、Gillian Phillips、David E. Alonso

  DOI：10.1021/ja00070a003

  日期：1993.8

  Phenylbromodiazirine reacts with thiophenoxide ion in methanol to give benzonitrile, benzamidine, ammonia, and diphenyl disulfide. The reaction is general for arylhalodiazirines, with electron-withdrawing groups on the aromatic ring exerting a small rate-enhancing effect. Three potential mechanisms are suggested for this redox process. These mechanisms include an N-sulfenylated diazirine, a diazirinyl radical, and a diazirinyl anion. Ring opening of these intermediates and subsequent transformations would lead to benzonitriles, benzamidine, and ammonia. A key intermediate in these transformations is PhSNH2, 32. This intermediate has been independently generated and found to rapidly convert to ammonia and diphenyl disulfide under the reaction conditions. Another proposed intermediate, N-(phenylthio)benzamidine, 38, has also been independently generated and subjected to the reaction conditions, where benzamidine and more diphenyl disulfide result. Theoretical calculations suggest the existence of isomeric diazirinyl anions. In addition to a diazirinyl ion with charge essentially on carbon, there is also an allylic-type ion with charge on the two nitrogen atoms. Single-electron reduction of a diazirinyl radical necessarily leads to a nitrogen-centered diazirinyl anion. Conversion of this anion to the carbon-centered diazirinyl anion is a forbidden process. These theoretical studies suggest that the diazirinyl anion may be a viable intermediate in solution.
• CREARY, XAVIER;SKY, ANTHONY F., J. AMER. CHEM. SOC., 112,(1990) N, C. 368-374
  作者：CREARY, XAVIER、SKY, ANTHONY F.

  DOI：——

  日期：——
• Reactivity of 1-Chloro-3-phenyldiazirines
  作者：Tomas Martinu、William P. Dailey

  DOI：10.1021/jo060341g

  日期：2006.6.1

  p-Substituted 1-chloro-3-phenyldiazirines (5), the putative intermediates of the reaction of N,N,N'-trichlorobenzamidines (10) with excess of bromide ions, react further to afford mixtures of 3-bromo- (4) and 3-chloro-3-phenyldiazirines (6). The 6:4 ratios inversely correlate with the Hammett σp and σp+ constants of the p-substituents. The formation of 4, proposed to proceed by anti-SN2‘ mechanism

  对位取代的1-氯-3-苯基重氮（5）是N，N，N'-三氯苯甲m（10）与过量溴离子反应的推定中间体，进一步反应生成3-溴-（4）和3-氯-3-苯基重氮（6）。该6：4的比率用哈米特σ负相关p和σ p +的常数p -取代基。4的形成，建议通过反S N进行2'机理主要是吸电子的p-取代基。化合物6是具有给电子性p取代基的主要产物，它可以由5通过极性过渡结构12进行氯的[1,3]-σ位移而从5中产生。气相DFT（B3LYP / 6-31 + G *）对这两种机理的研究结果与实验一致。
• Azide and fluoride exchange reactions of halodiazirines
  作者：Robert A. Moss、Jacek Terpinski、D. Phillip Cox、Dorothy Z. Denny、Karsten Krogh-Jespersen

  DOI：10.1021/ja00295a029

  日期：1985.5

  Preparation d'une serie de fluoro-3 aryl-3 diazirines et etude des reactions d'arylhalogenodiazirines avec l'ion azoture

  制备 d'une 系列 fluoro-3 aryl-3 diazirines etude des反应 d'arylhalogenodiazirines avec l'ion azoture