ethyl 5-oxo-4-oxaspiro<2.3>hexane-1-carboxylate | 79930-26-0

• 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: ethyl 5-oxo-4-oxaspiro<2.3>hexane-1-carboxylate
• 英文别名: 1-ethoxycarbonyl-5-oxo-4-oxaspiro<2.3>hexane；Ethyl 5-oxaspiro[2.3]hexane-1-carboxylate；5-oxo-4-oxa-spiro[2.3]hexane-1-carboxylic acid ethyl ester；Ethyl 5-oxo-4-oxaspiro[2.3]hexane-2-carboxylate
• CAS: 79930-26-0
• 化学式: C₈H₁₀O₄
• 分子量: 170.165
• InChiKey: MIVHZRXBGHDLIA-UHFFFAOYSA-N

物化性质

• 沸点：
  275.4±33.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 5-oxo-4-oxaspiro<2.3>hexane-1-carboxylate 在 sodium hydroxide 作用下， 以 乙醇 为溶剂， 生成 α-ethoxycarbonyl-β-oxoadipic acid
  参考文献：
  名称：

  Kato,T. et al., Journal of the Chemical Society. Perkin transactions I, 1979, p. 525 - 528

  摘要：

  DOI：
• 作为产物：
  描述：

  双乙烯酮 、 重氮乙酸乙酯 在 二苯甲酮 作用下， 生成 ethyl 5-oxo-4-oxaspiro<2.3>hexane-1-carboxylate
  参考文献：
  名称：

  Kato, Tetsuzo; Chiba, Takuo; Sato, Masayuki, Heterocycles, 1980, vol. 14, # 1, p. 90

  摘要：

  DOI：

文献信息

• The reactions of diazo compounds with lactones. Part 1. Cyclopropanespiro-β-lactones from diketene: synthesis and reactions
  作者：Paul V. Murphy、Timothy J. O’Sullivan、Niall W. A. Geraghty

  DOI：10.1039/b001393p

  日期：——

  The cyclopropanespiro-β-lactones 3, 4 and 12 can be prepared by the metal catalysed, or photochemically promoted decomposition reactions of diazocompounds in the presence of diketene. The thermal reactions of these compounds give a variety of products depending on the nature of the spirolactone; these include a furan 9a, 1,4-dicarbonyl compounds 18a–c and 19b, a pyranone 20b, furanones 21a, 21f and 22a and the enol 16. The boron trifluoride promoted reaction of a mixture of 3b and 4b gives a β-ketoacid. Mechanisms are proposed for the formation of these products. The rearrangment of the cyclopropanespiro-β-lactones to furan-2(5H)-ones and furan-2-(3H)-ones 6–8, 21a, 21f, 22a and 24 is shown to be a general reaction that involves metal catalysis. A mechanism based on formation of a metallocycle by a novel insertion of the metal into the C–O bond of the β-lactone ring is proposed for this rearrangement. This accounts for the observed features of the reaction.

  环丙烷螺-β-内酯3、4和12可以通过金属催化或光化学促进的双氮化合物在二酮存在下的分解反应制备。该类化合物的热反应根据螺内酯的性质会产生多种产品，包括呋喃9a、1,4-二酮化合物18a–c和19b、吡喃酮20b、呋喃酮21a、21f和22a以及烯醇16。三氟化硼促进的3b和4b混合物的反应产生β-酮酸。针对这些产物的形成提出了反应机理。环丙烷螺-β-内酯转变为呋喃-2(5H)-酮和呋喃-2-(3H)-酮6–8、21a、21f、22a和24的重排被证明是一个涉及金属催化的一般反应。对于这一重排，提出了一种基于金属通过新颖的插入方式进入β-内酯环的C–O键形成金属环的机理。这解释了反应中观察到的特征。
• Ring transformation of 5-oxo-4-oxaspiro(2.3)hexanes.
  作者：TETSUZO KATO、NOBUYA KATAGIRI、RENZO SATO

  DOI：10.1248/cpb.29.2361

  日期：——

  1-Ethoxycarbonyl-5-oxo-4-oxaspiro [2.3] hexane (3), on treatment with sodio methyl acetoacetate in THF, was transformed into 3-hydroxy-4-ethoxycarbonyl-2-cyclopenten-1-one (5) in 82% yield. Reaction of compound 3 with malononitrile (4a) in the presence of sodium hydride in THF gave the cyclopentenone 5 and 2-amino-3-cyano-6-ethoxycarbonylethyl-4-pyrone (6) in 49% and 24% yields, respectively. Similarly, reaction of compound 3 with ethyl cyanoacetate (4b) afforded compound 5 and 2-amino-3-ethoxycarbonyl-6-(2-ethoxycarbonylethyl)-4-pyrone (7) in 63% and 19% yields, respectively. Reaction of 1-dimethylphosphono-1-methyl-5-oxo-4-oxaspiro [2.3] hexane (1c) with 4a and 4b under similar conditions gave 2-amino-3-cyano-6-(2-dimethylphosphonopropyl)-4-pyrone (10) and 2-amino-3-ethoxycarbonyl-6-(2-dimethylphosphonopropyl)-4-pyrone (11) in 58% and 63% yields, respectively.

  1-乙氧羰基-5-氧代-4-氧杂螺[2.3]己烷（3）在四氢呋喃中与乙酰乙酸甲酯钠反应，生成3-羟基-4-乙氧羰基-2-环戊烯-1-酮（5），收率82%。化合物3与丙二腈（4a）在四氢呋喃中氢化钠存在下反应，分别生成环戊烯酮5和2-氨基-3-氰基-6-乙氧羰基乙基-4-吡喃酮（6），收率分别为49%和24%。类似地，化合物3与氰乙酸乙酯（4b）反应，分别生成化合物5和2-氨基-3-乙氧羰基-6-(2-乙氧羰基乙基)-4-吡喃酮（7），收率分别为63%和19%。1-二甲基膦酰基-1-甲基-5-氧代-4-氧杂螺[2.3]己烷（1c）与4a和4b在类似条件下反应，分别生成2-氨基-3-氰基-6-(2-二甲基膦酰基丙基
• KATO, TETSUZO;KATAGIRI, NOBUYA;SATO, RENZO, CHEM. AND PHARM. BULL., 1981, 29, N 8, 2361-2366
  作者：KATO, TETSUZO、KATAGIRI, NOBUYA、SATO, RENZO

  DOI：——

  日期：——