3-甲基-2-(-2-丙烯基)环戊烯-1-酮 | 3569-36-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 3-甲基-2-(-2-丙烯基)环戊烯-1-酮
• 英文名称: 2-allyl-3-methyl-2-cyclopentenone
• 英文别名: allylrethrone；allethron；allethrone；desoxyallethrolone；2-Allyl-3-methylcyclopent-2-en-1-one；3-methyl-2-prop-2-enylcyclopent-2-en-1-one
• CAS: 3569-36-6
• 化学式: C₉H₁₂O
• 分子量: 136.194
• InChiKey: PVHNZNUYNVXVLR-UHFFFAOYSA-N

物化性质

• 沸点：
  80-86 °C(Press: 3 Torr)
• 密度：
  0.948±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-甲基-2-(-2-丙烯基)环戊烯-1-酮 以 正己烷 为溶剂， 反应 72.0h， 生成 2-Cyclopropyl-3-methyl-cyclopent-2-enone
  参考文献：
  名称：

  2-（丙-2-烯基）环戊-2-烯酮的光化学

  摘要：

  已经研究了几种取代的2-（丙-2-烯基）环戊-2-烯酮的光化学。2-（丙-2-烯基）环戊-2-烯酮（2a; R = OMe或OAc），（6a）和（21）进行二-π-甲烷重排为乙烯基环丙烷[[3a和b），（ 7）和（29）]，而侧链取代的类似物（2b; R = OMe或OAc），（2c; R = OAc）和（6b）在相似条件下进行Z – E异构化。用（2a; R = OAc）进行的敏化和淬灭实验表明（3）源自（2a）的三重激发态。在（2a），（6a）和（21）以及（2b），（2c）和（6b）之间的反应性差异是基于在（分子的侧链。

  DOI：

  10.1039/p19760000249
• 作为产物：
  描述：

  allyl cyclopentadiene 在 chromium(VI) oxide 、 溴 作用下， 以 甲醇 为溶剂， 反应 0.5h， 生成 3-甲基-2-(-2-丙烯基)环戊烯-1-酮
  参考文献：
  名称：

  Liu, Zhu-Jin; Rong, Guo-Bin, Synthetic Communications, 1986, vol. 16, # 8, p. 871 - 876

  摘要：

  DOI：

文献信息

• Abnormal Nazarov Reaction. A New Synthetic Approach to 2,3-Disubstituted 2-Cyclopentenones
  作者：Shigeo Hirano、Seiji Takagi、Tamejiro Hiyama、Hitosi Nozaki

  DOI：10.1246/bcsj.53.169

  日期：1980.1

  Acid-catalyzed reaction of β,β′-disubstituted cross conjugated dienones or the corresponding ethylene acetals gives mainly 2,3-disubstituted 2-cyclopentenones in stead of the simple Nazarov cyclization products, 3,4-disubstituted 2-cyclopentenones. This transformation is explained in terms of electrocyclic ring-closure, addition of hydroxylic solvent(s), tautomerization of the resulting 2-hydroxycyclopentanone

  β,β'-二取代的交叉共轭二烯酮或相应的乙烯缩醛的酸催化反应主要产生 2,3-二取代的 2-环戊烯酮，而不是简单的 Nazarov 环化产物，即 3,4-二取代的 2-环戊烯酮。这种转变是根据电环闭环、羟基溶剂的添加、所得 2-羟基环戊酮中间体的互变异构化，然后是溶剂分解和异构化来解释的。基于该工作假设，公开了一种获得茉莉酮类化合物的新途径，该途径涉及对衍生自取代戊二酸酯的丙烯酰二甲硅烷基醚进行酸处理。
• Process for preparing oxocyclopentene derivatives
  申请人：Sumitomo Chemical Company, Limited

  公开号：US04970345A1

  公开（公告）日：1990-11-13

  A process for preparing oxocyclopentenes of the formula: ##STR1## wherein R.sup.1 is hydrogen, lower alkyl or lower alkenyl and R.sup.2 is hydrogen, lower alkyl, lower alkenyl, lower alkynyl, substituted or unsubstituted aryl, ar(lower)alkyl, thienyl or cycloalkyl, which comprises subjecting a furan-carbinol of the formula: ##STR2## wherein R.sup.1 is as defined above and R.sup.3 is hydrogen, lower alkyl, lower alkenyl, lower alkynyl, substituted or unsubstituted aryl, ar(lower)alkyl, thienyl or cycloalkyl to rearrangement, subjecting the resultant hydroxycyclopentenone of the formula: ##STR3## wherein R.sup.1 and R.sup.3 are each as defined above to hydrogenation and subjecting the resulting hydroxycyclopentanone of the formula; ##STR4## wherein R.sup.1 and R.sup.2 are each as defined above to dehydration.

  制备氧代环戊烯的方法，其化学式为：其中R.sup.1为氢、低烷基或低烯基，R.sup.2为氢、低烷基、低烯基、低炔基、取代或未取代芳基、芳基(低)烷基、噻吩基或环烷基，包括将化学式为的呋喃-碳醇经过重排，得到化学式为的羟基环戊烯酮，然后将化学式为的羟基环戊烷酮进行氢化，最后将化学式为的羟基环戊酮进行脱水。
• Synthesis of mono- and 1,4-dicarbonyl compounds based on the oxygenation of phosphonate carbanions. Synthesis of dihydrojasmone, allethrone and methylenomycin b
  作者：Marian Mikołajczyk、Wanda Midura、Sławomir Grzejszczak

  DOI：10.1016/s0040-4039(01)81212-0

  日期：1984.1

  Oxidation of the α-alkylthio-substituted phosphonate carbanions was found to give the corresponding carbonyl compounds. A new synthesis of 1,4-dicarbonyl systems involving the oxygenation of phosphonate carbanions as a key step is described. Total synthesis of dihydrojasmone and allethrone and formal synthesis of methylenomycin B is reported.

  发现α-烷硫基取代的膦酸酯碳负离子的氧化得到相应的羰基化合物。描述了涉及膦酸碳负离子的氧化作为关键步骤的1,4-二羰基系统的新合成。报道了二氢茉莉酮和烯丙酮的全合成和甲基新霉素B的正式合成。
• Reaction of β-halo α, β-unsaturated ketones with cuprate reagents. Efficient syntheses of β, β-dialkyl ketones and β-alkyl α,β-unsaturated ketones. A synthesis of (<i>Z</i>)-jasmone
  作者：Edward Piers、Kin Fai Cheng、Isao Nagakura

  DOI：10.1139/v82-185

  日期：1982.5.15

  Treatment of the 3-halo-2-cyclohexen-1-ones 11–15 and 17 with an excess of lithium dimethylcuprate provided good to excellent yields of the corresponding 3,3-dimethylcyclohexanones 21–24. Similar reactions involving the β-bromo cyclopentenones 19 and 20 stopped at the monoaddition stage, producing the cyclopentenones 40 and 43. Reaction of the β-bromo cyclohexenones 12 and 15 with 1.1 equiv. of lithium dimethylcuprate did not effect clean conversion of these substrates into the corresponding 3-methyl-2-cyclohexen-1-ones. When a series of β-bromo enones 12, 14–19 were allowed to react with the lithium (phenylthio)(alkyl)cuprates 44–47, the corresponding β-alkyl enones were, in general, produced cleanly and efficiently. However, reaction of 3-bromo-2-methyl-2-cyclopenten-1-one (19) with the cuprate reagent 44 gave mainly the β-phenylthio enone 49. This undesired result could be avoided by employing, in the place of 19, the β-iodo cyclopentenone 50, which reacted smoothly with 44 to give a high yield of 2,3-dimefhyl-2-cyclopenten-1-one (40). Reaction of 3-bromo-2-cyclohexen-1-one (14) with 3 equiv. of the mixed vinylcuprate reagent 48 gave 3-(3-butenyl)-2-cyclohexen-1-one (32). Alkylation of 1,3-cyclopentanedione with (Z)-1-chloro-2-pentene afforded compound 51, which was converted into the β-bromo enone 52. Treatment of the latter substance with lithium dimethylcuprate provided (Z)-jasmone (53).

  将3-卤代-2-环己烯-1-酮11-15和17与过量的二甲基溴化锂处理，得到相应的3,3-二甲基环己酮21-24，收率良好至优良。涉及β-溴代环戊烯酮19和20的类似反应在单加成阶段停止，产生环戊烯酮40和43。β-溴代环己烯酮12和15与1.1当量的二甲基溴化锂反应未对这些底物进行干净转化为相应的3-甲基-2-环己烯-1-酮产生影响。当一系列β-溴代烯酮12、14-19与苯基硫代烷基铜盐44-47反应时，通常产生相应的β-烷基烯酮，而且效率高。然而，3-溴代-2-甲基-2-环戊烯-1-酮（19）与铜盐试剂44反应主要产生β-苯基硫代烯酮49。通过使用β-碘代环戊烯酮50代替19，可以避免这种不良结果，后者与44反应顺利，产生高收率的2,3-二甲基-2-环戊烯-1-酮（40）。3-溴代-2-环己烯-1-酮（14）与混合乙烯铜盐试剂48的3当量反应产生3-(3-丁烯基)-2-环己烯-1-酮（32）。1,3-环戊二酮与(Z)-1-氯-2-戊烯烷基化生成化合物51，进一步转化为β-溴代烯酮52。后一物质经二甲基溴化锂处理得到(Z)-茉莉酮（53）。
• Synthesis of Pyrethroids and Jasmonoids through Palladium-Catalyzed Cross-Coupling Reactions
  作者：Viviana Heguaburu、Florencia Parpal、Ana Paula Paullier、Enrique Pandolfi

  DOI：10.1055/a-1736-1749

  日期：2022.6

  The synthesis of jasmone and related jasmonoids and pyrethroids is described. These compounds play a defensive role in plants and share a common cyclopentenone core with variations in the side chains. Jasmone, cinerone, allylrethrone, and derivatives were synthesized through π-allyl palladium cross-coupling of stannane derivatives. With selective hydrogenation, dihydrojasmone, and dihydrocinerone were

  描述了茉莉酮和相关茉莉酮类和拟除虫菊酯的合成。这些化合物在植物中起防御作用，并具有共同的环戊烯酮核心，侧链有所不同。通过锡烷衍生物的 π-烯丙基钯交叉偶联合成茉莉酮、香樟酮、烯丙基甲胺和衍生物。通过选择性加氢，还合成了二氢茉莉酮和二氢桂皮酮。

表征谱图