ethyl 2-bromo-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate | 947618-22-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: ethyl 2-bromo-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate
• 英文别名: Ethyl 2-bromo-1-oxo-3,4-dihydronaphthalene-2-carboxylate；ethyl 2-bromo-1-oxo-3,4-dihydronaphthalene-2-carboxylate
• CAS: 947618-22-6
• 化学式: C₁₃H₁₃BrO₃
• 分子量: 297.148
• InChiKey: BNZGGDIFXMHCSK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 2-bromo-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate 在 sodium azide 作用下， 以 二甲基亚砜 为溶剂， 生成 2-azido-2-ethoxycarbonyl-1-tetralone
  参考文献：
  名称：

  Radical Chain Reactions of α-Azido-β-keto Esters with Tributyltin Hydride. A Novel Entry to Amides and Lactams through Regiospecific Nitrogen Insertion

  摘要：

  A variety of acyclic and carbocyclic alpha-azido-beta-keto esters have been readily prepared from the parent dicarbonyl compounds, and their radical chain reactions with tributyltin hydride have been investigated. These reactions normally result in efficient production of alkoxycarbonyl-substituted amides and lactams and thence provide a new, useful method for regiospecific nitrogen insertion of keto ester compounds. The likely mechanism entails initial addition of tributylstannyl radical to the azido moiety to give a stannylaminyl radical, which readily undergoes intramolecular three-membered cyclization onto the ketone group to form an alkoxyl radical. The alkoxyl radical then undergoes regiospecific beta-scissian to form a stable ring-opened radical that is eventually reduced by tributyltin hydride to propagate the chain. With certain substrates, concomitant deazidation occurs to an important extent. This process, which is unusually observed in radical reactions of alkyl azides, is ascribed to addition of the stannyl radical to the terminal azido nitrogen; subsequent fragmentation of the ensuing 1,3-triazenyl adduct gives stannyl azide and a deazidated alkyl radical, resonance-stabilized by the adjacent carbonyl groups. The radical reactions of 2-azido-2-(ethoxy-carbonyl)-1-tetralone with allyltributylstannane and allyltriphenylstannane have also been investigated with the (missed) aim to achieve nitrogen insertion and concomitant allylation.

  DOI：

  10.1021/jo990837g
• 作为产物：
  描述：

  1-氧代-1,2,3,4-四氢萘-2-羧酸乙酯 在 N-chloro-N-fluorobenzenesulfonamide 、 potassium bromide 作用下， 以 乙腈 为溶剂， 反应 0.25h， 以94%的产率得到ethyl 2-bromo-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate
  参考文献：
  名称：

  使用CFBSA / KBr系统进行快速，温和和有效的溴化†

  摘要：

  溴化是有机化学中的一个基本转变，而溴化化合物则是有机合成中最重要的组成部分。在我们的研究中，我们通过在室温下以短反应时间使用CFBSA / KBr系统开发了一种有效的溴化方法。值得注意的是，该方法已被证明适用于一系列底物，包括1,3-二酮和β-酮​​酯，苯酚，芳族胺和杂芳烃，具有良好或优异的收率。

  DOI：

  10.1039/c6ra20217a

文献信息

• Sulfoxide-mediated Umpolung of alkali halide salts
  作者：Sebastian Klimczyk、Xueliang Huang、Christophe Farès、Nuno Maulide

  DOI：10.1039/c2ob25459j

  日期：——

  new protocol for the direct two-electron oxidative Umpolung of alkali halide salts is reported. This procedure, relying on the use of a commercially available sulfoxide as the oxidant, allows the electrophilic halogenation of carbonyl compounds as well as halolactonisation reactions to proceed from the corresponding sodium salts, at room temperature and under mild conditions.

  报道了一种新的直接用于碱金属卤化物盐的双电子氧化Umpolung的协议。该方法依赖于使用可商购的亚砜作为氧化剂，使羰基化合物的亲电子卤化以及卤代内酯化反应在室温下和温和条件下从相应的钠盐开始进行。
• A quick, mild and efficient bromination using a CFBSA/KBr system
  作者：Pan-Pan Jiang、Xian-Jin Yang

  DOI：10.1039/c6ra20217a

  日期：——

  chemistry and brominated compounds as building blocks are of paramount importance in organic synthesis. In our study, we have developed an efficient method of bromination by using a CFBSA/KBr system at room temperature in a short reaction time. Notably, this approach has been proven to be applicable to a range of substrates including 1,3-diketones and β-keto esters, phenols, aromatic amines and heteroarenes

  溴化是有机化学中的一个基本转变，而溴化化合物则是有机合成中最重要的组成部分。在我们的研究中，我们通过在室温下以短反应时间使用CFBSA / KBr系统开发了一种有效的溴化方法。值得注意的是，该方法已被证明适用于一系列底物，包括1,3-二酮和β-酮​​酯，苯酚，芳族胺和杂芳烃，具有良好或优异的收率。
• Radical Chain Reactions of α-Azido-β-keto Esters with Tributyltin Hydride. A Novel Entry to Amides and Lactams through Regiospecific Nitrogen Insertion
  作者：Luisa Benati、Daniele Nanni、Corrado Sangiorgi、Piero Spagnolo

  DOI：10.1021/jo990837g

  日期：1999.10.1

  A variety of acyclic and carbocyclic alpha-azido-beta-keto esters have been readily prepared from the parent dicarbonyl compounds, and their radical chain reactions with tributyltin hydride have been investigated. These reactions normally result in efficient production of alkoxycarbonyl-substituted amides and lactams and thence provide a new, useful method for regiospecific nitrogen insertion of keto ester compounds. The likely mechanism entails initial addition of tributylstannyl radical to the azido moiety to give a stannylaminyl radical, which readily undergoes intramolecular three-membered cyclization onto the ketone group to form an alkoxyl radical. The alkoxyl radical then undergoes regiospecific beta-scissian to form a stable ring-opened radical that is eventually reduced by tributyltin hydride to propagate the chain. With certain substrates, concomitant deazidation occurs to an important extent. This process, which is unusually observed in radical reactions of alkyl azides, is ascribed to addition of the stannyl radical to the terminal azido nitrogen; subsequent fragmentation of the ensuing 1,3-triazenyl adduct gives stannyl azide and a deazidated alkyl radical, resonance-stabilized by the adjacent carbonyl groups. The radical reactions of 2-azido-2-(ethoxy-carbonyl)-1-tetralone with allyltributylstannane and allyltriphenylstannane have also been investigated with the (missed) aim to achieve nitrogen insertion and concomitant allylation.