2-azido-2-ethoxycarbonyl-1-tetralone | 210166-60-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-azido-2-ethoxycarbonyl-1-tetralone
• 英文别名: Ethyl 2-azido-1-oxo-3,4-dihydronaphthalene-2-carboxylate
• CAS: 210166-60-2
• 化学式: C₁₃H₁₃N₃O₃
• 分子量: 259.265
• InChiKey: XPRIYHNNNIAMGV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  57.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-azido-2-ethoxycarbonyl-1-tetralone 在 偶氮二异丁腈 、 三(三甲基硅基)硅烷 作用下， 以 苯 为溶剂， 反应 3.0h， 以74%的产率得到1-氧代-1,2,3,4-四氢萘-2-羧酸乙酯
  参考文献：
  名称：

  α-叠氮基酮与氢化三丁基锡的自由基链反应：中间N-苯乙烯基丙烯酰基自由基的还原-氮插入和1,2-氢转移

  摘要：

  研究了各种无环和环状α-叠氮基酮与氢化三丁基锡的自由基链反应。衍生的N-（三丁基锡烷基）氨基自由基通常会发生H吸收反应，生成相应的胺，因此通过随后的自缩合反应形成对称的吡嗪，与从α碳到氮的1,2-H迁移竞争，从而导致α-亚氨基酮的分解产物，带有链的三丁基锡自由基的损失。值得注意的是，一个非常不常见的自由基1,2-氢原子移位的发生在很大程度上是由于随后形成了一个高度稳定的，可俘获的碳中心自由基。与我们以前的N相反α-叠氮基-β-酮酯产生的-stannylaminyl自由基，本发明的胺基同类物产生的氮插入酰胺/内酰胺的量很少（甚至根本没有），预计这是由于分子内三元环化到酮部分上而引起的通过β-断裂得到的烷氧基基团。可以推断，最终的开环碳自由基的足够稳定是区域特异性氮插入过程成功获得成功的主要因素。还提供了证据，三（三甲基甲硅烷基）甲硅烷基自由基对α-叠氮基酮的酮氧的化学选择性攻击导致脱叠氮化作

  DOI：

  10.1016/s0040-4020(02)00302-2
• 作为产物：
  描述：

  1-氧代-1,2,3,4-四氢萘-2-羧酸乙酯 在 sodium azide 、 碘 作用下， 以 水 、 二甲基亚砜 为溶剂， 以96 %的产率得到2-azido-2-ethoxycarbonyl-1-tetralone
  参考文献：
  名称：

  α-氨基-β-氧代酯向 δ-丁内酰胺的环转化

  摘要：

  通过环转化获得内酰胺：通过用 Zn−AcOH 还原环状 α-叠氮基-β-氧代环戊烷羧酸酯，获得在 δ 位具有环外酯部分的 δ-丁内酰胺。环的转变在还原条件下很容易进行，这是一个前所未有的过程。

  DOI：

  10.1002/ejoc.202300757

文献信息

• Reactions of Benzocyclic β-Keto Esters with Tosyl and 4-Nitrophenyl Azide. Structural Influence of Dicarbonyl Substrate and Azide Reagent on Distribution of Diazo, Azide and Ring-Contraction Products
  作者：Luisa Benati、Gianluca Calestani、Daniele Nanni、Piero Spagnolo

  DOI：10.1021/jo980223w

  日期：1998.7.1

  The reactions of beta-keto esters derived from 1- and 2-indanone, 1- and 2-tetralone, and benzosuberone with toluene-4-sulfonyl- (tosyl) and 4-nitrobenzenesulfonyl azide (PNBSA) in the presence of Et3N have been investigated in order to evaluate the influence of both dicarbonyl substrate and azide reagent on the product distribution. With tosyl azide the keto esters derived from both 2-benzocycloalkanones exhibit deacylating diazo transfer, but those derived from the 1-benzocycloalkanones undergo additional azido transfer to a significant or even exclusive extent. The finding is mainly explained in terms of the lesser reactivity of the conjugate aryl ketone than alkyl ketone moiety. This would discourage cyclization of the initial sulfonyltriazenyl anion-the presumable azide precursor-to the triazoline adduct, in turn envisaged as the diazo progenitor. With PNBSA both indanones smoothly undergo diazo transfer, whereas their higher homologues lead to ring-contraction products ascribable to corresponding triazolines that curiously prefer to suffer Favorskii-type ring fragmentation. Evidence has been obtained that tosyl azide acts as a azide-transfer reagent superior to PNBSA. A possible explanation of this fact is discussed. An X-ray crystal structure analysis of the phthalazine compound 18 (Ar = 4-Me-C6H4) has been performed.
• 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.
• Radical chain reactions of α-azido ketones with tributyltin hydride: reduction vs nitrogen insertion and 1,2-hydrogen shift in the intermediate N-stannylaminyl radicals
  作者：Luisa Benati、Rino Leardini、Matteo Minozzi、Daniele Nanni、Piero Spagnolo、Samantha Strazzari、Giuseppe Zanardi、Gianluca Calestani

  DOI：10.1016/s0040-4020(02)00302-2

  日期：2002.4

  ketone decomposition products with loss of the chain-carrying tributyltin radical. The noteworthy occurrence of a quite uncommon radical 1,2-hydrogen-atom shift is considered to be largely due to consequent formation of a highly stable, captodative carbon-centred radical. In contrast with our previous N-stannylaminyl radicals produced from α-azido-β-keto esters, the present aminyl congeners give poor

  研究了各种无环和环状α-叠氮基酮与氢化三丁基锡的自由基链反应。衍生的N-（三丁基锡烷基）氨基自由基通常会发生H吸收反应，生成相应的胺，因此通过随后的自缩合反应形成对称的吡嗪，与从α碳到氮的1,2-H迁移竞争，从而导致α-亚氨基酮的分解产物，带有链的三丁基锡自由基的损失。值得注意的是，一个非常不常见的自由基1,2-氢原子移位的发生在很大程度上是由于随后形成了一个高度稳定的，可俘获的碳中心自由基。与我们以前的N相反α-叠氮基-β-酮酯产生的-stannylaminyl自由基，本发明的胺基同类物产生的氮插入酰胺/内酰胺的量很少（甚至根本没有），预计这是由于分子内三元环化到酮部分上而引起的通过β-断裂得到的烷氧基基团。可以推断，最终的开环碳自由基的足够稳定是区域特异性氮插入过程成功获得成功的主要因素。还提供了证据，三（三甲基甲硅烷基）甲硅烷基自由基对α-叠氮基酮的酮氧的化学选择性攻击导致脱叠氮化作
• Ring Transformation of α‐Amino‐β‐oxoesters to δ‐Butyrolactams
  作者：Daniel Krieger、Jens Christoffers

  DOI：10.1002/ejoc.202300757

  日期：2023.10.16

  Lactams by Ring Transformation: δ-Butyrolactams with an exocyclic ester moiety in the δ-position were accessed by reduction of cyclic α-azido-β-oxocyclopentane carboxylates with Zn−AcOH. The ring transformation proceeded readily under the conditions of the reduction which is an unprecedented process.

  通过环转化获得内酰胺：通过用 Zn−AcOH 还原环状 α-叠氮基-β-氧代环戊烷羧酸酯，获得在 δ 位具有环外酯部分的 δ-丁内酰胺。环的转变在还原条件下很容易进行，这是一个前所未有的过程。