3,7-dimethyl-octa-2,6-dienyl diphenyl phosphate | 19451-54-8

• 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: 3,7-dimethyl-octa-2,6-dienyl diphenyl phosphate
• 英文别名: geraniol diphenyl phosphate；Geranyl diphenyl phosphate；Geranyl-diphenyl-phosphat；Geranyl-diphenylphosphat；[(2E)-3,7-dimethylocta-2,6-dienyl] diphenyl phosphate
• CAS: 19451-54-8
• 化学式: C₂₂H₂₇O₄P
• 分子量: 386.428
• InChiKey: VUVYIBOBMXCPIY-LVZFUZTISA-N

物化性质

• 沸点：
  464.1±45.0 °C(Predicted)
• 密度：
  1.111±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  27
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,7-dimethyl-octa-2,6-dienyl diphenyl phosphate 在 lithium bromide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.17h， 以64%的产率得到香叶基溴
  参考文献：
  名称：

  Regio- and Stereoselective Conversion of Allylic Alcohols to Halides via Allylic Phosphates

  摘要：

  DOI：

  10.1055/s-1984-30989
• 作为产物：
  描述：

  氯磷酸二苯酯 在 正丁基锂 、 N,N-双(苯基亚甲基)-1,2-乙二胺 、 copper(II) bis(trifluoromethanesulfonate) 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 50.0h， 生成 3,7-dimethyl-octa-2,6-dienyl diphenyl phosphate
  参考文献：
  名称：

  Phosphorylation of Alcohols with N-Phosphoryl Oxazolidinones Employing Copper(II) Triflate Catalysis

  摘要：

  Phosphoryl transfer from N-phosphoryl 5,5-diphenyl oxazolidinone is efficiently catalyzed by copper(II) triflate. The utility of this method has been demonstrated in the phosphorylation of representative primary, secondary, tertiary, phenolic, and allylic alcohols. These reaction conditions are significantly milder than employing alkoxides and allow the phosphorylation of biologically relevant molecules.

  DOI：

  10.1021/ol051104n

文献信息

• Transition metal-catalyzed substitution reaction of allylic phosphates with Grignard reagents
  作者：Akira Yanagisawa、Nobuyoshi Nomura、Hisashi Yamamoto

  DOI：10.1016/s0040-4020(01)90454-5

  日期：1994.1

  SN2-selective Grignard coupling with primary allylic diphenylphosphates was successfully achieved using Ni or Fe catalyst. In sharp contrast, a catalytic amount of CuCN·2LiCl promoted a SN2′-selective coupling reaction. In the presence of the copper catalyst, stereochemically homogeneous γ- disubstituted allyl Grignard reagents reacted at the less substituted allylic terminus (α-position) with an allylic diphenylphosphate

  使用Ni或Fe催化剂成功地实现了S N 2-选择性格利雅（Grignard）与伯烯丙基二苯基磷酸酯的偶联。与之形成鲜明对比的是，催化量的CuCN·2LiCl促进了S N 2'-选择性偶联反应。在铜催化剂的存在下，立体化学均一的γ-二取代的烯丙基格氏试剂在较少取代的烯丙基末端（α-位）与烯丙基磷酸二苯酯选择性地反应，而不会失去双键的几何形状。
• Reaction of Allyl Diphenyl Phosphates with Soft Bases
  作者：Shuki Araki、Kazuhiro Minami、Yasuo Butsugan

  DOI：10.1246/bcsj.54.629

  日期：1981.2

  The title phosphates were found to react with a variety of soft bases to give nucleophilic substitution products in high yields. The reaction proceeded regiospecifically under mild reaction conditions with preservation of the double bond geometry.

  磷酸酯与多种软碱发生反应，生成高产率的亲核取代产物。该反应在温和的反应条件下进行，具有区域选择性，并保持双键几何形状。
• Regioselectivity of the Coupling of Phenoxyallyllithium with Allylic Electrophiles
  作者：Yasuo Butsugan、Tomokazu Goto、Shuki Araki

  DOI：10.1246/bcsj.58.2137

  日期：1985.7

  The regioselectivity of the coupling of phenoxyallyllithium with allylic electrophiles was investigated. The allylation pattern corresponded with the hardness of the leaving group and the highest α-selectivity was observed in the reaction with allylic phosphate.

  研究了苯氧基烯丙基锂与烯丙基亲电体偶联的区域选择性。烯丙基化模式与离去基团的硬度相对应，在与烯丙基磷酸酯的反应中观察到最高的 α 选择性。
• Organocatalytic Phosphorylation of Alcohols Using Pyridine-N-oxide
  作者：Alan Spivey、James Murray、Rudiger Woscholski

  DOI：10.1055/s-0034-1379993

  日期：——

  Phosphorylation of alcohols by phosphoryl chlorides catalysed by pyridine-N-oxide is reported. The utility of this method is demonstrated through phosphorylation of primary, secondary and a tertiary alcohol as well as phenols under mild reaction conditions and with low catalyst loading (5 mol%).
• An Improved Method for Lewis Acid Catalyzed Phosphoryl Transfer with Ti(<i>t</i>-BuO)₄
  作者：Simon Jones、Dimitrios Selitsianos、Kate J. Thompson、Steven M. Toms

  DOI：10.1021/jo034331g

  日期：2003.6.1

  Several inorganic esters have been evaluated as phosphoryl transfer catalysts. Of these, Ti(t-BuO)(4) was found to be the most effective catalyst giving excellent yields of the desired phosphate esters. The loading of the catalyst could be reduced to a little as 5 mol % for a majority of substrates with no loss in the yield of product. This methodology is significantly more versatile than using TiCl4 and is suitable for the phosphorylation of more complex carbohydrates and molecules of biological interest.