Phosphoric acid 1-cyano-1-methyl-hept-2-ynyl ester diethyl ester | 140421-18-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: Phosphoric acid 1-cyano-1-methyl-hept-2-ynyl ester diethyl ester
• 英文别名: 2-Cyanooct-3-yn-2-yl diethyl phosphate；2-cyanooct-3-yn-2-yl diethyl phosphate
• CAS: 140421-18-7
• 化学式: C₁₃H₂₂NO₄P
• 分子量: 287.296
• InChiKey: JUJGYVVMZQJYBB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  19
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  68.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Phosphoric acid 1-cyano-1-methyl-hept-2-ynyl ester diethyl ester 在 samarium diiodide 、 叔丁醇 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 oct-3-yne-2-carbonitrile
  参考文献：
  名称：

  Cyano phosphate: an efficient intermediate for the chemoselective conversion of carbonyl compounds to nitriles

  摘要：

  Cyanohydrin diethyl phosphates, readily obtained from various ketones and aldehydes by reaction with diethyl phosphorocyanidate and lithium cyanide, reacted chemoselectively with samarium(II) iodide in THF to give the corresponding nitriles in excellent yields. This method was also found applicable to alpha,beta-unsaturated carbonyl compounds via cyano phosphates to give beta,gamma-unsaturated nitriles, not obtainable by standard methods, without isomerization of the double bonds.

  DOI：

  10.1021/jo00005a031
• 作为产物：
  描述：

  3-辛炔-2-酮 、 氰基磷酸二乙酯 在 锂丁酯 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 生成 Phosphoric acid 1-cyano-1-methyl-hept-2-ynyl ester diethyl ester
  参考文献：
  名称：

  A New Synthesis of Allenic Nitriles from Ynones via Cyano Phosphates.

  摘要：

  炔酮氰基炔诺酮二乙基磷酸盐（氰基磷酸盐）2 与由 2-噻吩基（氰基）铜锂和正丁基锂生成的高硼铜酸盐 3 发生了区域选择性反应，通过 SN2'反应生成了三取代的异烯腈 4，产率良好。另一方面，过量的二烷基铜锂与炔酮氰基磷酸盐 2 反应，通过异链腈 4 得到烯丙基腈 5。

  DOI：

  10.1248/cpb.40.21

文献信息

• Cyano phosphate: an efficient intermediate for the chemoselective conversion of carbonyl compounds to nitriles
  作者：Ryuji Yoneda、Shinya Harusawa、Takushi Kurihara

  DOI：10.1021/jo00005a031

  日期：1991.3

  Cyanohydrin diethyl phosphates, readily obtained from various ketones and aldehydes by reaction with diethyl phosphorocyanidate and lithium cyanide, reacted chemoselectively with samarium(II) iodide in THF to give the corresponding nitriles in excellent yields. This method was also found applicable to alpha,beta-unsaturated carbonyl compounds via cyano phosphates to give beta,gamma-unsaturated nitriles, not obtainable by standard methods, without isomerization of the double bonds.
• A New Synthesis of Allenic Nitriles from Ynones via Cyano Phosphates.
  作者：Ryuji YONEDA、Noriko INAGAKI、Shinya HARUSAWA、Takushi KURIHARA

  DOI：10.1248/cpb.40.21

  日期：——

  Ynone cyanohydrin diethyl phosphates (cyano phosphates) 2 reacted regioselectively with higher-ordr cuprates 3, generated from 2-thienyl(cyano)copper lithium and n-butyl lithium, to give trisubstituted allenic nitriles 4 through an SN2' process in good yields. On the other hand, reaction of an excess of dialkyl copper lithium with ynone cyano phosphates 2 afforded allylic nitriles 5, via allenic nitriles 4.

  炔酮氰基炔诺酮二乙基磷酸盐（氰基磷酸盐）2 与由 2-噻吩基（氰基）铜锂和正丁基锂生成的高硼铜酸盐 3 发生了区域选择性反应，通过 SN2'反应生成了三取代的异烯腈 4，产率良好。另一方面，过量的二烷基铜锂与炔酮氰基磷酸盐 2 反应，通过异链腈 4 得到烯丙基腈 5。