5-甲基环戊-2-烯-1-酮 | 14963-40-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 5-甲基环戊-2-烯-1-酮
• 英文名称: 5-methylcyclopent-2-en-1-one
• 英文别名: 5-methyl-cyclopent-2-enone；5-Methyl-cyclopent-2-enon；5-methyl-2-cyclopenten-1-one；2-methyl-4-cyclopentenone；2-Cyclopenten-1-one, 5-methyl-
• CAS: 14963-40-7
• 化学式: C₆H₈O
• 分子量: 96.1289
• InChiKey: OOJIJAGFQCKGCL-UHFFFAOYSA-N

物化性质

• 沸点：
  140°C (estimate)
• 密度：
  0.9420

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  5-甲基环戊-2-烯-1-酮 在 正丁基锂 、 硫酸 、 溴 、 silica gel 、 对甲苯磺酸 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 14.05h， 生成 (R)-5-Methyl-2-(2,4,6-triisopropyl-benzenesulfinyl)-cyclopent-2-enone
  参考文献：
  名称：

  Diastereomer-Differentiating Radical β-Addition to 4- or 5-Methyl-2-[(2,4,6-triisopropylphenyl)sulfinyl]-2-cyclopentenones

  摘要：

  Addition of alkyl radicals to a diastereomeric mixture of(4R)- and (4S)-4-methyl-2-[(2,4,6-triisopropylphenyl)sulfinyl]-2-cyclopentenones gave the diastereomerically pure addition product derived from the (4R)-isomer, while the (4S)-isomer remained unreacted. The tel tert-butyl radical addition to a diastereomeric mixture of (5R)- and (5S)-5-methyl-2-[(2,4,6-triisopropylphenyl)sulfinyl]-2- cyclopentenones also gave the diastereomerically pure addition product. These results show that (4R) and (4S) or (5R) and (5S) diastereomers were kinetically separated in the radical beta-addition. The 1,2- and 1,3-steric interactions in the radical addition to 4- or 5-methyl-2-cyclopentenones were also examined.

  DOI：

  10.1021/jo9721507
• 作为产物：
  描述：

  (+/-)-5-chloro-5-methyl-2-cyclopentenone 在 镍 氢气 作用下， 生成 5-甲基环戊-2-烯-1-酮
  参考文献：
  名称：

  Rabiller,C. et al., Bulletin de la Societe Chimique de France, 1974, p. 3055 - 3058

  摘要：

  DOI：

文献信息

• Cyclocarbonylation of acyclic 1,3-dienes via their tricarbonyl iron complexes : Cyclopenten-2-ones and dicarbonyl cyclopentadienyl iron halides
  作者：Michel Franck-Neumann、Enrique Luis Michelotti、Roland Simler、Jean-Michel Vernier

  DOI：10.1016/s0040-4039(00)60188-0

  日期：1992.11

  of acyclic 1,3-dienes can be converted to conjugated cyclopentenones by decomplexation with aluminium halides. Most complexes of a simple dienes need drastic conditions for the cyclocarbonylation to occur (100 Atm CO, 1000° C), with the exception of 1,1,3-trialkylbutadiene complexes which are nearly quantitatively converted into cyclopentenones at room temperature, even in the absence of a CO atmosphere

  无环1，3-二烯的三羰基铁配合物可通过与卤化铝解络而转化为共轭的环戊烯酮。大多数简单的二烯络合物都需要苛刻的条件才能发生环羰基化反应（100 Atm CO，1000°C），除了1,1,3-三烷基丁二烯络合物几乎可以在室温下定量转化为环戊烯，即使在室温下也是如此。没有CO气氛。在相同的温和条件下，其他配合物通过环羰基化反应以中等收率生成环戊二烯基二羰基卤化铁，然后通过卤化铝促进脱氧。
• 1,4-Addition Ugi Reaction Using Cyclic α,β-Unsaturated Ketone as Substrate
  作者：Kui Lu、Yantao Ma、Meile Gao、Yan Liu、Ming Li、Chuanming Xu、Xia Zhao、Peng Yu

  DOI：10.1021/acs.orglett.6b02493

  日期：2016.10.7

  A four-component, 1,4-addition Ugi reaction using cyclic α,β-unsaturated ketones, carboxylic acids, amines, and isocyanides was developed for the first time. By combining this reaction with Michael addition, nucleophilic substitution, and C–N bond formation reactions, bicyclic and tricyclic scaffolds with pyridinone and quinolinone moieties, two basic units among a variety of natural products and pharmaceuticals

  首次开发了使用环状α，β-不饱和酮，羧酸，胺和异氰酸酯的四组分1,4-加成Ugi反应。通过将该反应与迈克尔加成反应，亲核取代反应和C–N键形成反应相结合，构建了吡啶环酮和喹啉酮部分的双环和三环支架，这是多种天然产物和药物中的两个基本单元。
• Hydroxylic additives enhance yield and scalability of silicon-directed Nazarov reaction
  作者：Shaon Joy、Waka Nakanishi、F.G. West

  DOI：10.1016/j.tetlet.2013.07.139

  日期：2013.10

  As a result of difficulties in scaling up silicon-directed Nazarov cyclization for use in the synthesis of taxane natural products, the effect of additives was examined. Hydroxylic additives were found to convey a consistent beneficial effect on the rate, overall yield, and scalability of these reactions. Optimal conditions (1.5 equiv methanol or water with substoichiometric FeCl3), were successfully

  由于难以扩大用于合成紫杉烷天然产物的硅定向Nazarov环化的规模，因此研究了添加剂的作用。发现羟基添加剂对这些反应的速率，总产率和可扩展性具有一致的有益作用。最佳条件（1.5当量甲醇或水和亚化学计量的FeCl 3）已成功应用于一系列β-甲硅烷基二烯酮底物，包括几个复杂的多环实例，以及较简单的二烯酮（以前显示在此条件下产率低或完全不反应）。常规条件。
• Mousseron et al., Bulletin de la Societe Chimique de France, 1946, p. 629,632
  作者：Mousseron et al.

  DOI：——

  日期：——
• A one-step synthesis of 2-norbornanone ethylene acetals from 2-cyclopenten-1-one ethylene acetals and dienophiles via [2 + 4] cycloaddition of in situ generated 2-(2-hydroxyethoxy)cyclopenta-1,3-dienes and intramolecular reacetalization
  作者：Masakazu Ohkita、Osamu Nishizawa、Takashi Tsuji、Shinya Nishida

  DOI：10.1021/jo00071a033

  日期：1993.9

  2-(2-Hydroxyethoxy)cyclopenta-1,3-diene (5) which is generated reversibly from 2-cyclopenten-1-one ethylene acetal (1) under mild, neutral conditions can be intercepted with a variety of dienophiles ultimately to give 2-norbornanone ethylene acetals in 62-100% yields. The addition reactions are highly stereo- and regioselective. Of the several solvents examined, acetonitrile is the most satisfactory. In CHCl3 or CCl4, decomposition of 1 is induced, leading to diminished yields of the adducts. The intermediate 5 is detected by UV spectroscopy, and its content relative to 1 at a stationary state at 70-degrees-C in acetonitrile is estimated to be ca. 0.2%. The reactions of the 2-, 3-, and 5-methyl-substituted derivatives 2-4 with dienophiles similarly led to the production of the corresponding 2-norbornanone acetals through the additions of the dienophiles to the 1,3-cyclopentadien-2-yl ether intermediates 6-8 selectively derived from 2-4 via 1,2-elimination. The formation of isomeric adducts resulting either from 1,4-elimination in 1-4 or from [1,51 hydrogen migration in the enol ether intermediates is not detected. The addition of 2-chloroacrylonitrile, a ketene equivalent, to 1-4 followed by alkaline hydrolysis provides singly acetalized 2,5-norbornadiones in two steps in good yields. 2-Cyclohexen-1-one ethylene acetal (44) also undergoes the addition of dienophiles in the [2 + 4] manner directly to give bicyclo[2.2.2]octan-2-one ethylene acetals, but is substantially less reactive than 1 toward this type of reaction.