3,3,6-trimethylhepta-4,5-dien-2-one | 81250-41-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,3,6-trimethylhepta-4,5-dien-2-one
• 英文别名: 4,5-Heptadien-2-one, 3,3,6-trimethyl-
• CAS: 81250-41-1
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: MMLSXKDAXYUEEL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  3,3,6-trimethylhepta-4,5-dien-2-one 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 生成
  参考文献：
  名称：

  Radical cyclization of β-allenic hydrazones. An asymmetric approach

  摘要：

  beta-allenic hydrazones undergo hydrostannylation to afford cyclopentene derivatives and linear rearranged products depending on the substitution of the allenic and hydrazone moieties. A first example of asymmetric radical cyclization of a SAMP beta-allenic hydrazone is described.

  DOI：

  10.1016/s0040-4039(00)73075-9
• 作为产物：
  描述：

  2,2,5-trimethyl-3,4-hexadienal 在 pyridinium chlorochromate 作用下， 生成 3,3,6-trimethylhepta-4,5-dien-2-one
  参考文献：
  名称：

  锡介导的 β-丙二烯基苯甲酰肟的自由基环化

  摘要：

  一组丙二烯系苯甲酰肟 (5) 已用 nBu3SnH 处理过。根据它们的取代模式，已经获得了广泛的化合物。如果甲锡基自由基加成在丙二烯上，则由此形成的以 C 为中心的自由基经历 5-外环闭合以产生环戊烯衍生物 7 或在 N 原子上进行 6-内环闭合以产生二氢吡啶 8。如果甲锡基自由基添加到苯甲酰基部分，形成亚胺基自由基，导致 3H-吡咯 9 和亚烷基-吡咯啉 10。空间效应和极性效应是控制反应过程的因素。

  DOI：

  10.1002/(sici)1099-0690(200001)2000:2<275::aid-ejoc275>3.0.co;2-r

文献信息

• 3H-Pyrroles, Alkylidene-Pyrrolines and Functionalized Pyrrolidines by Radical Cyclization of β-Allenyliminyl Radicals
  作者：Michaël Depature、Jacques Grimaldi、Jacques Hatem

  DOI：10.1002/1099-0690(200103)2001:5<941::aid-ejoc941>3.0.co;2-e

  日期：2001.3

  reaction of allene-tethered dithiosemicarbazides 4 is a convenient method for the preparation of five-membered unsaturated nitrogen heterocycles. The sulfur-directed intermolecular attack of the tin radical at the semicarbazide moiety leads to an allene-tethered iminyl radical, which then undergoes a 5-exo-dig cyclization leading to both the 3H-pyrroles 5 and the alkylidene pyrrolines 6; thermal isomerization

  在这项工作中，我们表明氢化锡介导的丙二烯系二氨基硫脲 4 的反应是制备五元不饱和氮杂环的便捷方法。氨基脲部分的锡自由基的硫导向分子间攻击导致丙二烯系亚胺基自由基，然后进行 5-exo-dig 环化，导致 3H-吡咯 5 和亚烷基吡咯啉 6；在某些情况下会发生 5 到 6 的热异构化。
• Tosyl mediated radical cyclization of allylallenes
  作者：Fatiha El Gueddari、Jacques R. Grimaldi、Jacques M. Hatem

  DOI：10.1016/00404-0399(50)1390-4

  日期：1995.9

  Radical addition of tosyl bromide on vinylallenes affords 1-tosyl cyclopentenes or 1-tosyl cyclohexenes (depending on the substitution of the vinylic moiety) bearing a 4-bromomethyl or a 4-bromo substituant. In some cases dehydrobromination occurs.

  在乙烯基丙二烯上自由基地添加甲苯磺酰基溴可得到带有4-溴甲基或4-溴取代基的1-甲苯磺酰基环戊烯或1-甲苯磺酰基环己烯（取决于乙烯基部分的取代）。在某些情况下会发生脱氢溴化作用。
• Kudrawcew, Walentina; Frei, Bruno; Wolf, Hans Richard, Heterocycles, 1982, vol. 17, p. 139 - 150
  作者：Kudrawcew, Walentina、Frei, Bruno、Wolf, Hans Richard、Jeger, Oskar

  DOI：——

  日期：——
• Tributyltin Hydride-Mediated Free-Radical Cyclization of Allene-Tethered Oxime Ethers and Hydrazones
  作者：José Marco-Contelles、Geneviève Balme、Didier Bouyssi、Christine Destabel、Christiane D. Henriet-Bernard、J. Grimaldi、Jacques M. Hatem

  DOI：10.1021/jo962225r

  日期：1997.3.1

  In this work, we have shown that the tributyltin hydride-mediated cycloisomerization of allene-tethered oxime ethers or hydrazones is a convenient method for the preparation of (vinylstannyl)cyclopentylamine derivatives in terms of simplicity and chemical yields. As a result, the first and detailed analysis of the tributyltin hydride-mediated free-radical cyclization of alkyl-substituted allene-tethered oxime ethers and hydrazones is reported. The site-directed intermolecular attack of the tributyltin radical at the allene moiety and the final size of the ring after cyclization depends on the type of substitution in the substrate. Some general trends can be observed: (1) In crowded substrates having full substitution at C beta or at the terminal-trigonal carbon, the steric hindrance favors attack at the digonal carbon. (2) When different positions in the allene are free for attack, the kinetically more favored irreversible mode of cyclizations (5-exo > 6-exo > 6-endo) determines the ratio of isomers or the final size of the ring. Finally, after acid hydrolysis of the vinyltin products,the resulting O-methyl- or O-benzyl(hydroxylamino)cycloalkanes have been obtained in good yield.
• Oxidative cyclizations of allenic aldehydes
  作者：Jack K. Crandall、Elisa Rambo

  DOI：10.1016/s0040-4039(00)76739-6

  日期：1994.3

  Allenyl aldehydes and ketones are oxidatively cyclized by dimethyldioxirane to provide cyclic acetals and hemiacetals.