diisopropyl (2ξ)-(3-carboethoxy-2-methyl-2-propenyl)phosphonate | 40597-28-2

• 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: diisopropyl (2ξ)-(3-carboethoxy-2-methyl-2-propenyl)phosphonate
• 英文别名: ethyl 4-(diisopropoxyphosphoryl)-3-methylbut-2-enoate；Ethyl 4-(diisopropoxy-phosphoryl)-3-methylbut-2-enoate；ethyl 4-di(propan-2-yloxy)phosphoryl-3-methylbut-2-enoate
• CAS: 40597-28-2
• 化学式: C₁₃H₂₅O₅P
• 分子量: 292.312
• InChiKey: KONRHKAOVIOPGU-UHFFFAOYSA-N

物化性质

• 沸点：
  365.4±35.0 °C(Predicted)
• 密度：
  1.052±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 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：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3,7-二甲基-辛醛 、 diisopropyl (2ξ)-(3-carboethoxy-2-methyl-2-propenyl)phosphonate 在 四丁基氢氧化铵 作用下， 以 苯 为溶剂， 生成 Ethyl-3,7,11-Trimethyl-cis-2,trans-4-dodecadienoat 、 hydroprene
  参考文献：
  名称：

  On the stereochemistry of the Horner?Emmons reaction between 3-functionally substituted 2-methyl-2-propenylphosphonates and aliphatic aldehydes

  摘要：

  The reaction of diethyl 3-ethoxycarbonyl-2-methyl-2-propenylphosphonate (1a) with 3-methylbutanal (2) in heterogeneous MOH (solid)-benzene systems in the presence of 5-10 mol.% of benzyltriethylammonium chloride (BTEAC) gives the reaction product (3) with a higher, for M = K, or lower, for M = Li, ratio of 2E,4E- and 2Z,4E-stereoisomers than that observed in the absence of BTEAC. Tetrabutylammonium bromide (TBAB) as a catalyst of the reaction 1a + 2 --> 3 in the system KOH (solid)-wet benzene leads to a higher [2E,4E-3]:[2Z,4E-3] ratio than BTEAC; this ratio grows from 44:56 without TBAB to 80:20 at 100 mol.96 of TBAB. In the latter case the stereochemical outcome of the reaction is similar to that obtained when tetrabutylammonium hydroxide in dry benzene is used as the deprotonating agent. The corresponding diisopropyl phosphonate (1b) and 3,7-dimethyloctanal (4a) interact in the system KOH (solid)-wet benzene-TBAB to give hydroprene (5) containing 88 % of the 2E,4E-isomer (5a) while in the case of 1 equiv. of [(n-Bu4)N]OH in dry benzene the content of 5a is 92 %. Diisopropyl 3-isopropoxycarbonyl-2-methyl-2-propenylphosphonate (1c) and 7-methoxy-3,7-dimethyloctanal (4b) under either of these conditions afford methoprene (6) containing 93 % of the 2E,4E-isomer.

  DOI：

  10.1007/bf00704196
• 作为产物：
  描述：

  三异丙基亚磷酸酯 、 ethyl 4-bromo-3-methylcrotonate 以51%的产率得到diisopropyl (2ξ)-(3-carboethoxy-2-methyl-2-propenyl)phosphonate
  参考文献：
  名称：

  Stereochemistry of the Horner-Emmons reaction of 3-functionalized 2-methyl-2-propenylphosphonates with aliphatic aldehydes. 1. Effect of size of the alkoxy group attached to the phosphorus atom

  摘要：

  DOI：

  10.1007/bf00953422

文献信息

• Synthesis of aryl-containing terpenoids based on 1,4-dihydronaphthalene
  作者：O. S. Kukovinets、M. I. Kislitsyn、R. A. Zainullin、A. A. Mukhamedzyanova、F. Z. Galin、M. I. Abdullin

  DOI：10.1134/s1070428008030093

  日期：2008.3

  Successive transformations including oxidation of 1,4-dihydronaphthalene into 1,2,3,4-tetrahydronaphthalen-2-one, Reformatskii reaction of the latter with methyl bromoacetate, ozonolysis of the Reformatsky reaction product, and Emmons olefination of the aldehyde group in methyl 3-oxo-5-(2-formylphenyl)pentanate thus formed gave analogs of highly active dienoate juvenoids having an aromatic ring in their molecules.

  通过连续的转化，包括将 1,4- 二氢萘氧化成 1,2,3,4-四氢萘-2-酮，后者与溴乙酸甲酯发生 Reformatskii 反应，Reformatsky 反应产物的臭氧分解，以及由此形成的 3-氧代-5-(2-甲酰基苯基)戊酸甲酯中醛基的埃蒙斯烯化反应，得到了分子中含有一个芳香环的高活性二烯酸酯类幼体类似物。
• Novel products
  申请人：Zoecon Corporation

  公开号：US03948996A1

  公开（公告）日：1976-04-06

  Aliphatic di-unsaturated esters and acids, and derivatives thereof, substituted with thiol (mercapto) or hydrocarbon thio group useful for the control of insects.

  具有巯基（硫醇）或烃硫基取代的脂肪族二烯酸酯和酸以及它们的衍生物，可用于控制昆虫。
• Kukovinets; Zainullin; Kasradze, Russian Journal of Bioorganic Chemistry, 1999, vol. 25, # 10, p. 705 - 706
  作者：Kukovinets、Zainullin、Kasradze、Odinokov、Tolstikov

  DOI：——

  日期：——