methyl 2-(Z)-chloro(spiropent-1-ylidene)acetate | 152530-87-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 2-(Z)-chloro(spiropent-1-ylidene)acetate
• 英文别名: methyl (Z)-2-chlorospiropentylideneacetate；methyl (2Z)-2-chloro-2-spiro[2.2]pentan-2-ylideneacetate
• CAS: 152530-87-5
• 化学式: C₈H₉ClO₂
• 分子量: 172.611
• InChiKey: ZPDNNEPMIVICKL-WAYWQWQTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-pyrroline N-oxide 、 methyl 2-(Z)-chloro(spiropent-1-ylidene)acetate 以 二氯甲烷 为溶剂， 反应 120.0h， 以70%的产率得到(3''S^*,3''aS^*)-3''-chloro-3''-(methoxycarbonyl)tetrahydrodispiroisoxazole>
  参考文献：
  名称：

  A new cascade ring enlargement of isoxazolidines formed from 2-chloro-2-cyclopropylideneacetates

  摘要：

  通过 2-氯-2-环丙基亚基乙酸酯 1 和螺环戊烷类似物 2 环载吡咯啉 N-氧化物 3 得到螺[环丙烷-1,5′-异恶唑烷]4 和 5，收率很高；由于在螺环丙烷环的碳α上存在一个氯取代基，从而促进了环丙基到环丁基环的增大，这些化合物经过级联重排后可直接得到吲嗪酮衍生物 8 和 9（收率为 70-73%），为吲嗪骨架的合成提供了一种新方法。

  DOI：

  10.1039/a801168k
• 作为产物：
  描述：

  1-Chloro-1-(trichloroethenyl)spiropentane 在 acidic ion-exchange resin (BAYER LEWATIT 118) 作用下， 以 甲醇 为溶剂， 反应 120.0h， 生成 methyl 2-(Z)-chloro(spiropent-1-ylidene)acetate
  参考文献：
  名称：

  Cyclopropyl building blocks for organic synthesis. Part 22. Facile synthesis of stable analogs of 2-oxocyclobutanecarboxylates: 2-[(diphenylmethylene)amino]cyclobutenecarboxylates, derivatives and reactions

  摘要：

  An efficient two-step synthesis of 2-[(diphenylmethylene)amino]cyclobutenecarboxylate (4a) and some analogous derivatives from 2-chloro-2-cyclopropylideneacetates 2, 17, 22, and 25 and nonenolizable ketimines, especially diphenylmethyleneamine (DPMA-H), is described. A likely mechanism for the formation of 4a from the primary Michael adduct 3 of DPMA-H to 2 and its substituted analogues is presented. The unique neighboring group effect of the DPMA moiety to allow formation of an azaspiropentane intermediate and its regioselective rearrangement to cyclobutenamine derivatives is discussed and further exemplified by an extremely facile SET alpha-chlorination. Compound 4a and derivatives undergo a thermal ring-opening reaction to the corresponding butadienes with subsequent formation of 1,3-disubstituted 3,4-dihydroisoquinolines 39. Further transformations of 4a and some derivatives include transesterification, hydrolysis to methyl 2-oxocyclobutanecarboxylates, and addition of N-phenyltriazolinedione.

  DOI：

  10.1021/jo00075a047

文献信息

• Switching the Reaction Mode of 4-Methoxycarbonyl-4-chloro-5-spirocyclopropaneisoxazolidines by N-Aryl Substitution
  作者：Alberto Brandi、Stefano Cicchi、Julia Revuelta、Ina Objartel、Armin de Meijere

  DOI：10.1055/s-0030-1258136

  日期：2010.8

  4-Methoxycarbonyl-4-chloro-5-spirocyclopropaneisoxazolidines, easily obtained by in situ cycloadditions of nitrones to methyl 2-chlorocyclopropylideneacetate and 2-chlorospiropentyl-ideneacetate, in contrast to their known thermal rearrangements leading to δ-lactams, undergo rearrangement to their respective tetrahydropyridones, when the nitrone nitrogen is substituted by an aryl moiety.

  4-甲氧羰基-4-氯-5-螺环丙烷异噁唑烷通过硝酮与 2-氯环丙基亚基乙酸甲酯和 2-氯环丙基亚基乙酸甲酯的原位环加成反应很容易获得，与已知的热重排生成δ-内酰胺不同，当硝酮氮被芳基取代时，它们会重排生成各自的四氢吡啶酮。
• Synthesis of Enantiopure Indolizinones by Cascade Ring Enlargements of 4‘-Chlorospiro[cyclopropane-1,5‘-isoxazolidines]
  作者：Julia Revuelta、Stefano Cicchi、Cristina Faggi、Sergei I. Kozhushkov、Armin de Meijere、Alberto Brandi

  DOI：10.1021/jo052564x

  日期：2006.3.1

  2-Chloro-2-cyclopropylideneacetates (1-Me and 1-Et) and their spiropentane analogues 2 cycloadd enantiopure five-membered cyclic nitrones to give the corresponding adducts (quantitatively, four examples), which undergo cascade ring enlargements to yield indolizinone derivatives (53-70%, four examples). The ring enlargement process is triggered by the abstraction of a bridgehead proton induced by a base and can be suppressed by the presence of a bulky substituent nearby, such as a (triisopropylsilyl)-oxy group.
• A new cascade ring enlargement of isoxazolidines formed from 2-chloro-2-cyclopropylideneacetates
  作者：Chiara Zorn、Andrea Goti、Alberto Brandi、Andrea Goti、Keyji Johnsen、Sergei I. Kozhushkov、Armin de Meijere

  DOI：10.1039/a801168k

  日期：——

  2-Chloro-2-cyclopropylideneacetate 1 and spiropentane analog 2 cycloadd pyrroline N-oxide 3 to give spiro[cyclopropane-1,5′-isoxazolidine]s 4 and 5 in good yields; due to the presence of a chlorine substituent on the carbon α to the spirocyclopropane ring, which facilitates a cyclopropyl to cyclobutyl ring enlargement, these compounds undergo a cascade rearrangement to yield indolizinone derivatives 8 and 9 cleanly (70–73% yield), offering a new method for the synthesis of the indolizine skeleton.

  通过 2-氯-2-环丙基亚基乙酸酯 1 和螺环戊烷类似物 2 环载吡咯啉 N-氧化物 3 得到螺[环丙烷-1,5′-异恶唑烷]4 和 5，收率很高；由于在螺环丙烷环的碳α上存在一个氯取代基，从而促进了环丙基到环丁基环的增大，这些化合物经过级联重排后可直接得到吲嗪酮衍生物 8 和 9（收率为 70-73%），为吲嗪骨架的合成提供了一种新方法。
• Cyclopropyl building blocks for organic synthesis. Part 22. Facile synthesis of stable analogs of 2-oxocyclobutanecarboxylates: 2-[(diphenylmethylene)amino]cyclobutenecarboxylates, derivatives and reactions
  作者：Ludger Wessjohann、Karsten Giller、Bernd Zuck、Lars Skatteboel、Armin de Meijere

  DOI：10.1021/jo00075a047

  日期：1993.11

  An efficient two-step synthesis of 2-[(diphenylmethylene)amino]cyclobutenecarboxylate (4a) and some analogous derivatives from 2-chloro-2-cyclopropylideneacetates 2, 17, 22, and 25 and nonenolizable ketimines, especially diphenylmethyleneamine (DPMA-H), is described. A likely mechanism for the formation of 4a from the primary Michael adduct 3 of DPMA-H to 2 and its substituted analogues is presented. The unique neighboring group effect of the DPMA moiety to allow formation of an azaspiropentane intermediate and its regioselective rearrangement to cyclobutenamine derivatives is discussed and further exemplified by an extremely facile SET alpha-chlorination. Compound 4a and derivatives undergo a thermal ring-opening reaction to the corresponding butadienes with subsequent formation of 1,3-disubstituted 3,4-dihydroisoquinolines 39. Further transformations of 4a and some derivatives include transesterification, hydrolysis to methyl 2-oxocyclobutanecarboxylates, and addition of N-phenyltriazolinedione.