11-(3',4'-methylenedioxyphenyl)-undeca-2(E),4(E),10(E)-trienoic acid | 72967-09-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 11-(3',4'-methylenedioxyphenyl)-undeca-2(E),4(E),10(E)-trienoic acid
• 英文别名: (2E,4E,10E)-11-(1,3-benzodioxol-5-yl)undeca-2,4,10-trienoic acid
• CAS: 72967-09-0
• 化学式: C₁₈H₂₀O₄
• 分子量: 300.354
• InChiKey: SFSUJWUEOWHWSJ-FCGWLDPVSA-N

物化性质

• 熔点：
  128.0-130.0 °C
• 沸点：
  527.8±39.0 °C(Predicted)
• 密度：
  1.175±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.19
• 重原子数：
  22.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  55.76
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  11-(3',4'-methylenedioxyphenyl)-undeca-2(E),4(E),10(E)-trienoic acid 在 草酰氯 作用下， 以 苯 为溶剂， 反应 1.0h， 生成 (2E,4E,10E)-11-(benzo[d][1,3]dioxol-5-yl)undeca-2,4,10-trienoyl chloride
  参考文献：
  名称：

  A Practical and Efficient Synthetic Route to Dihydropipercide and Pipercide¹

  摘要：

  Dihydropipercide 1 and Pipercide 2 are examples of hydrophobic insecticidal isobutylamide derivatives isolated from Piper Nigrum L. which have received synthetic attention over the past decade. Novel structural features combining the N-isobutyldieneamide array, found in related natural products such as Pellitorine, with the 3,4-methylenedioxyphenyl moiety, found in insecticide synergists including Piperonyl Butoxide and Sesamex, render these as attractive targets for synthesis. Although a variety of synthetic routes to related natural products have appeared in the literature, practical methods for the preparation of the title compounds were lacking. Convenient and convergent 10-11-step protocols were developed which provided access to gram quantities of the targets. Methyl 6-oxohexanoate 4 was prepared from cyclohexanone enol acetate 3 via a tandem ozonolysis, methanolysis, hydrolysis process. Subsequent olefination and olefin isomerization steps followed by further elaboration provided the targets 1 and 2. Noteworthy features of this methodology include the convenient synthesis of oxoester intermediate 4 and the phenythio radical-induced olefin isomerization of intermediate 6 which afforded high yields of >99.5% E-olefin 13. These are both somewhat uncommon but potentially useful processes which may find further application in organic synthesis.

  DOI：

  10.1021/jo981039d
• 作为产物：
  描述：

  6-氧代己酸甲酯 在 氢氧化钾 、 lithium aluminium tetrahydride 、 正丁基锂 、 草酰氯 、 air 、 二甲基亚砜 、 苯硫酚 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 水 、 苯 为溶剂， 反应 8.5h， 生成 11-(3',4'-methylenedioxyphenyl)-undeca-2(E),4(E),10(E)-trienoic acid
  参考文献：
  名称：

  A Practical and Efficient Synthetic Route to Dihydropipercide and Pipercide¹

  摘要：

  Dihydropipercide 1 and Pipercide 2 are examples of hydrophobic insecticidal isobutylamide derivatives isolated from Piper Nigrum L. which have received synthetic attention over the past decade. Novel structural features combining the N-isobutyldieneamide array, found in related natural products such as Pellitorine, with the 3,4-methylenedioxyphenyl moiety, found in insecticide synergists including Piperonyl Butoxide and Sesamex, render these as attractive targets for synthesis. Although a variety of synthetic routes to related natural products have appeared in the literature, practical methods for the preparation of the title compounds were lacking. Convenient and convergent 10-11-step protocols were developed which provided access to gram quantities of the targets. Methyl 6-oxohexanoate 4 was prepared from cyclohexanone enol acetate 3 via a tandem ozonolysis, methanolysis, hydrolysis process. Subsequent olefination and olefin isomerization steps followed by further elaboration provided the targets 1 and 2. Noteworthy features of this methodology include the convenient synthesis of oxoester intermediate 4 and the phenythio radical-induced olefin isomerization of intermediate 6 which afforded high yields of >99.5% E-olefin 13. These are both somewhat uncommon but potentially useful processes which may find further application in organic synthesis.

  DOI：

  10.1021/jo981039d

文献信息

• Concise, efficient new synthesis of pipercide, an insecticidal unsaturated amide from Piper nigrum, and related compounds
  作者：George M. Strunz、Heather Finlay

  DOI：10.1016/s0040-4020(01)89414-x

  日期：1994.1

  Pipercide and piperolein A, unsaturated amides from Piper nigrum, were prepared in overall yields of 21% and 35% respectively, by a new, short and efficient strategy, in which the key step was the aldol-Grob-type fragmentation sequence recently reported by Sakai et al.. (but using propylene- rather than ethylene glycol). The nor-homologues of these natural products were similarly prepared. In the final

  通过新的，短而有效的策略，分别从Piper nigrum制备了总产率分别为21％和35％的Pipercide和Piperolein A（不饱和酰胺），其中的关键步骤是最近报道的aldol-Grob型片段化序列。 Sakai等人（但使用丙二醇而不是乙二醇）。这些天然产物的非同源物以类似方式制备。在最后的步骤中，可以通过Roskamp的方法（包括用Sn [N（TMS）2 ] 2和适当的胺处理）直接从酯中制备酰胺，或者通过常规方法从相应的羧酸中制备酰胺。
• Sabharwal; Dogra; Sharma, Journal of the Indian Chemical Society, 1990, vol. 67, # 4, p. 318 - 320
  作者：Sabharwal、Dogra、Sharma、Kalra、Vig、Kad

  DOI：——

  日期：——
• SABHARWAL, ARUN;DOGRA, VIJAV;SHARMA, SANJIV;KALRA, RAHMI;VIG, O. P.;KAD, +, J. INDIAN CHEM. SOC., 67,(1990) N, C. 318-320
  作者：SABHARWAL, ARUN、DOGRA, VIJAV、SHARMA, SANJIV、KALRA, RAHMI、VIG, O. P.、KAD, +

  DOI：——

  日期：——
• A Practical and Efficient Synthetic Route to Dihydropipercide and Pipercide¹
  作者：Lloyd W. Rotherham、J. Edward Semple

  DOI：10.1021/jo981039d

  日期：1998.9.1

  Dihydropipercide 1 and Pipercide 2 are examples of hydrophobic insecticidal isobutylamide derivatives isolated from Piper Nigrum L. which have received synthetic attention over the past decade. Novel structural features combining the N-isobutyldieneamide array, found in related natural products such as Pellitorine, with the 3,4-methylenedioxyphenyl moiety, found in insecticide synergists including Piperonyl Butoxide and Sesamex, render these as attractive targets for synthesis. Although a variety of synthetic routes to related natural products have appeared in the literature, practical methods for the preparation of the title compounds were lacking. Convenient and convergent 10-11-step protocols were developed which provided access to gram quantities of the targets. Methyl 6-oxohexanoate 4 was prepared from cyclohexanone enol acetate 3 via a tandem ozonolysis, methanolysis, hydrolysis process. Subsequent olefination and olefin isomerization steps followed by further elaboration provided the targets 1 and 2. Noteworthy features of this methodology include the convenient synthesis of oxoester intermediate 4 and the phenythio radical-induced olefin isomerization of intermediate 6 which afforded high yields of >99.5% E-olefin 13. These are both somewhat uncommon but potentially useful processes which may find further application in organic synthesis.