butyl-4 dihydro-3,4 coumarine | 90778-35-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 3,4-二氢香豆素
• 英文名称: butyl-4 dihydro-3,4 coumarine
• 英文别名: 4-Butyldihydrocoumarin；4-Butyl-3,4-dihydrochromen-2-one
• CAS: 90778-35-1
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: AGPPDVJEVKETSL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  正丁基锂 、 香豆素 生成 butyl-4 dihydro-3,4 coumarine
  参考文献：
  名称：

  Iodotrimethylsilane-promoted additions of monoorganocopper compounds to .alpha.,.beta.-unsaturated ketones, esters, and lactones

  摘要：

  Conjugate additions with the efficient monoorganocopper-iodotrimethylsilane combination, exemplified plified mainly with methylcopper, butylcopper, and tert-butylcopper, proceed cleanly, smoothly, and rapidly to a variety of alpha,beta-unsaturated carbonyl compounds; cyclic and acyclic enones, beta-alkoxy enones, enoates and lactones in ether, THF, and dichloromethane, often at -78-degrees-C. The RCu-(LiI)-TMSI reagent gives a good economy of group transfer with good to excellent yields of conjugate adducts. Lithium iodide, present from preparation of the organocopper compounds, increases the rate of the reactions and is a favorable component. Additions are faster, but somewhat less selective, in THF than in ether. Careful workup after addition of triethylamine or pyridine at low temperature permits isolation of TMS enol ethers and TMS ketene acetals. Acyclic enones preferentially give the Z-silyl enol ethers. The RCu(LiI)-TMSI system is a most useful alternative to the conventional lithium diorganocuprates in conjugate additions.

  DOI：

  10.1021/jo00077a055

文献信息

• Addition conjuguee des α, ω-bis(bromomagnesio)alcanes sur les coumarines
  作者：P. Canonne.、H. Caron、G. Foscolos

  DOI：10.1016/s0040-4020(01)91475-9

  日期：1984.1

  4-dihydrocoumarin. A large difference in product distribution was observed between the two bifunctional reagents. Annelation was favored by the use of 1,4-bis(bromomagnesio))butane, whereas conjugate addition was observed with 1,5-bis(bromomagnesio)pentane and even In the use of 4-methylcoumarin.

  1，4-双（溴镁）丁烷和1，5-双（溴镁）戊烷与香豆素和6-甲基香豆素的反应得到了1-（邻羟基苯乙烯基）环烷醇和4-烷基-3,4-二氢香豆素的混合物。在两种双功能试剂之间观察到产物分布的巨大差异。使用1,4-双（溴镁）丁烷有利于退火，而使用1,5-双（溴镁）戊烷甚至在使用4-甲基香豆素时观察到共轭加成。
• CANONNE, P.;CARON, H.;FOSCOLOS, G., TETRAHEDRON, 1984, 40, N 5, 865-871
  作者：CANONNE, P.、CARON, H.、FOSCOLOS, G.

  DOI：——

  日期：——
• Iodotrimethylsilane-promoted additions of monoorganocopper compounds to .alpha.,.beta.-unsaturated ketones, esters, and lactones
  作者：Mikael Bergdahl、Magnus Eriksson、Martin Nilsson、Thomas Olsson

  DOI：10.1021/jo00077a055

  日期：1993.12

  Conjugate additions with the efficient monoorganocopper-iodotrimethylsilane combination, exemplified plified mainly with methylcopper, butylcopper, and tert-butylcopper, proceed cleanly, smoothly, and rapidly to a variety of alpha,beta-unsaturated carbonyl compounds; cyclic and acyclic enones, beta-alkoxy enones, enoates and lactones in ether, THF, and dichloromethane, often at -78-degrees-C. The RCu-(LiI)-TMSI reagent gives a good economy of group transfer with good to excellent yields of conjugate adducts. Lithium iodide, present from preparation of the organocopper compounds, increases the rate of the reactions and is a favorable component. Additions are faster, but somewhat less selective, in THF than in ether. Careful workup after addition of triethylamine or pyridine at low temperature permits isolation of TMS enol ethers and TMS ketene acetals. Acyclic enones preferentially give the Z-silyl enol ethers. The RCu(LiI)-TMSI system is a most useful alternative to the conventional lithium diorganocuprates in conjugate additions.