(4-Ethyl-2-methyl-5-oxo-cyclopent-1-enyl)-acetic acid | 180690-41-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4-Ethyl-2-methyl-5-oxo-cyclopent-1-enyl)-acetic acid
• 英文别名: 2-(4-Ethyl-2-methyl-5-oxocyclopenten-1-yl)acetic acid
• CAS: 180690-41-9
• 化学式: C₁₀H₁₄O₃
• 分子量: 182.219
• InChiKey: IEPGKPBYUISMKD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  二环己胺 、 (4-Ethyl-2-methyl-5-oxo-cyclopent-1-enyl)-acetic acid 以 乙醚 、 正戊烷 为溶剂， 反应 24.0h， 生成 dicyclohexylammonium (+/-)-2-(4-ethyl-2-methyl-5-oxocyclopentenyl)acetate
  参考文献：
  名称：

  Conversion of 2-Alkyl-2-(2-oxopropyl)cyclopentane-1,3-diones into 2,3,5- and 2,3,4-Trisubstituted Cyclopent-2-enones by Intramolecular Aldolizations to 2,3-Diacylcyclopropanolates Followed by Remarkable Skeletal Rearrangements¹

  摘要：

  2-Alkyl-2-(prop-2-ynyl)cyclopentane-1,3-diones 2, conveniently prepared from 2-alkylcyclopentane-1,3-diones 1 and prop-2-ynyl bromide, afford the triketones 3 by Hg2+-catalyzed hydration of the acetylenic triple bond. Treatment of these triketones with aqueous sodium hydroxide gives rise to the 2,3,5-trisubstituted cyclopent-2-enones 5, which are accompanied by the isomeric 2,3,4-trisubstituted cyclopent-2-enones 7 as byproducts. The formation of these isomers can be avoided, when the 2,2-disubstituted cyclopentane-1,3-diones 2 are first converted by ring cleavage into the 5-alkyl-4-oxooct-7-ynaic acids 4 and then by subsequent hydration into the 5-alkyl-4,7-dioxoalkanoic acids 6. An intramolecular aldolization of the latter forms exclusively the cyclopentenones 5. A mechanism explaining the simultaneous formation of 5 and 7 from 3 is based on the formation of the 2,3-diacylcyclopropanolates 11 and 16 by intramolecular aldolization and subsequent ring opening to the 2-acetylcyclohexane-1,4-diones 13 and 18. A further ring opening to the 4,7-dioxoalkanoates 15 and 20 followed by intramolecular aldol condensation then gives rise to the isomeric trisubstituted cyclopent-2-enones 5 and 7.

  DOI：

  10.1021/jo960189q
• 作为产物：
  描述：

  methyl (+/-)-2-(4-ethyl-2-methyl-5-oxocyclopentenyl)acetate 在 sodium hydroxide 、 水 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以75%的产率得到(4-Ethyl-2-methyl-5-oxo-cyclopent-1-enyl)-acetic acid
  参考文献：
  名称：

  Conversion of 2-Alkyl-2-(2-oxopropyl)cyclopentane-1,3-diones into 2,3,5- and 2,3,4-Trisubstituted Cyclopent-2-enones by Intramolecular Aldolizations to 2,3-Diacylcyclopropanolates Followed by Remarkable Skeletal Rearrangements¹

  摘要：

  2-Alkyl-2-(prop-2-ynyl)cyclopentane-1,3-diones 2, conveniently prepared from 2-alkylcyclopentane-1,3-diones 1 and prop-2-ynyl bromide, afford the triketones 3 by Hg2+-catalyzed hydration of the acetylenic triple bond. Treatment of these triketones with aqueous sodium hydroxide gives rise to the 2,3,5-trisubstituted cyclopent-2-enones 5, which are accompanied by the isomeric 2,3,4-trisubstituted cyclopent-2-enones 7 as byproducts. The formation of these isomers can be avoided, when the 2,2-disubstituted cyclopentane-1,3-diones 2 are first converted by ring cleavage into the 5-alkyl-4-oxooct-7-ynaic acids 4 and then by subsequent hydration into the 5-alkyl-4,7-dioxoalkanoic acids 6. An intramolecular aldolization of the latter forms exclusively the cyclopentenones 5. A mechanism explaining the simultaneous formation of 5 and 7 from 3 is based on the formation of the 2,3-diacylcyclopropanolates 11 and 16 by intramolecular aldolization and subsequent ring opening to the 2-acetylcyclohexane-1,4-diones 13 and 18. A further ring opening to the 4,7-dioxoalkanoates 15 and 20 followed by intramolecular aldol condensation then gives rise to the isomeric trisubstituted cyclopent-2-enones 5 and 7.

  DOI：

  10.1021/jo960189q

文献信息

• Transformation of cyclopentane-1,3-diones into cyclohexane-1,4-diones - a novel ring enlargement process
  作者：Siegfried Schramm、Birgit Roatsch、Egon Gründemann、Hans Schick

  DOI：10.1016/s0040-4039(00)74081-0

  日期：1993.7

  4-diones (3-acetyl-2-alkylcyclohex-3-en-4-olones) by treatment with an equimolar amount of sodium hydroxide in water or sodium methoxide in methanol. This ring enlargement can be considered as the result of an intramolecular aldol reaction followed by a ring opening of the formed bicyclo[3.1.0]hexane system.

  将2-烷基-2-（2-氧丙基）环戊烷-1,3-二酮平稳地转化为2-乙酰基-3-烷基环己烷-1,4-二酮（3-乙酰基-2-烷基环己基-3-en-4-用等摩尔量的氢氧化钠水溶液或甲醇钠的甲醇溶液处理。这种环的扩大可以认为是分子内羟醛反应随后形成的双环[3.1.0]己烷体系开环的结果。
• Conversion of 2-Alkyl-2-(2-oxopropyl)cyclopentane-1,3-diones into 2,3,5- and 2,3,4-Trisubstituted Cyclopent-2-enones by Intramolecular Aldolizations to 2,3-Diacylcyclopropanolates Followed by Remarkable Skeletal Rearrangements¹
  作者：Hans Schick、Birgit Roatsch、Siegfried Schramm、Hans-Detlev Gilsing、Matthias Ramm、Egon Gründemann

  DOI：10.1021/jo960189q

  日期：1996.1.1

  2-Alkyl-2-(prop-2-ynyl)cyclopentane-1,3-diones 2, conveniently prepared from 2-alkylcyclopentane-1,3-diones 1 and prop-2-ynyl bromide, afford the triketones 3 by Hg2+-catalyzed hydration of the acetylenic triple bond. Treatment of these triketones with aqueous sodium hydroxide gives rise to the 2,3,5-trisubstituted cyclopent-2-enones 5, which are accompanied by the isomeric 2,3,4-trisubstituted cyclopent-2-enones 7 as byproducts. The formation of these isomers can be avoided, when the 2,2-disubstituted cyclopentane-1,3-diones 2 are first converted by ring cleavage into the 5-alkyl-4-oxooct-7-ynaic acids 4 and then by subsequent hydration into the 5-alkyl-4,7-dioxoalkanoic acids 6. An intramolecular aldolization of the latter forms exclusively the cyclopentenones 5. A mechanism explaining the simultaneous formation of 5 and 7 from 3 is based on the formation of the 2,3-diacylcyclopropanolates 11 and 16 by intramolecular aldolization and subsequent ring opening to the 2-acetylcyclohexane-1,4-diones 13 and 18. A further ring opening to the 4,7-dioxoalkanoates 15 and 20 followed by intramolecular aldol condensation then gives rise to the isomeric trisubstituted cyclopent-2-enones 5 and 7.