2-Methoxy-2-methyl-5,5-dipropyl-Δ³-1,3,4-oxadiazoline | 138723-85-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 原羧酸衍生物
• 英文名称: 2-Methoxy-2-methyl-5,5-dipropyl-Δ³-1,3,4-oxadiazoline
• 英文别名: 2-Methoxy-2-methyl-5,5-dipropyl-1,3,4-oxadiazole
• CAS: 138723-85-0
• 化学式: C₁₀H₂₀N₂O₂
• 分子量: 200.281
• InChiKey: YUPSINFLOQLIKN-UHFFFAOYSA-N

物化性质

• 沸点：
  238.4±40.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  43.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-Methoxy-2-methyl-5,5-dipropyl-Δ³-1,3,4-oxadiazoline 以 正戊烷 为溶剂， 反应 4.0h， 生成 4-methoxyheptane
  参考文献：
  名称：

  Chemistry and Kinetics of Dipropylcarbene in Solution

  摘要：

  The photochemistry of 2-methoxy-2-methyl-5,5-dipropyl-Delta(3)-1,3,4-oxadiazoline (1a) and 2,2-dimethoxy-5,5-dipropyl-Delta(3)-1,3,4-oxadiazoline (1b) was investigated. Photolysis (300 nm) of these compounds in solution leads to fragmentation to 4-diazoheptane (major), which slowly forms the corresponding azine. Fragmentation to form 4-heptanone is also observed. Yields of 4-diazoheptane in CH2Cl2 are much larger than those in pentane. 4-Diazoheptane can be trapped with 1-pentene to form a pyrazoline or with methanol to form 4-methoxyheptane. The pyrazoline can be decomposed photochemically to form 1,1,2-tripropylcyclopropane. In solution, 4-diazoheptane is inefficiently photolyzed to dipropylcarbene (DPC), which can be trapped with piperidine or with pyridine in laser flash photolysis experiments. Analysis of the piperidine and pyridine data indicates that the lifetime of DPC in cyclohexane, methylene chloride, or Freon-113 (CF2ClCFCl2) solution at ambient temperature is controlled by 1,2 hydrogen migration to form Z- and E-3-heptene. The lifetime deduced under these conditions is approximate to 300 ps, which is about 20-fold shorter than that of dimethylcarbene in perfluorohexane at ambient temperature. Upon photolysis (254 nm) of oxadiazoline 1a in argon, 4-diazoheptane and 1-methoxydiazoethane are formed. These diazo compounds undergo subsequent photolysis that revealed the formation of methoxy(methyl)carbene and E- and Z-3-heptene. It was not possible to detect DPC in argon at 14 K.

  DOI：

  10.1021/jp990198d
• 作为产物：
  描述：

  4-庚酮 在 lead(IV) acetate 作用下， 以 苯 为溶剂， 反应 4.0h， 生成 2-Methoxy-2-methyl-5,5-dipropyl-Δ³-1,3,4-oxadiazoline
  参考文献：
  名称：

  Chemistry and Kinetics of Dipropylcarbene in Solution

  摘要：

  The photochemistry of 2-methoxy-2-methyl-5,5-dipropyl-Delta(3)-1,3,4-oxadiazoline (1a) and 2,2-dimethoxy-5,5-dipropyl-Delta(3)-1,3,4-oxadiazoline (1b) was investigated. Photolysis (300 nm) of these compounds in solution leads to fragmentation to 4-diazoheptane (major), which slowly forms the corresponding azine. Fragmentation to form 4-heptanone is also observed. Yields of 4-diazoheptane in CH2Cl2 are much larger than those in pentane. 4-Diazoheptane can be trapped with 1-pentene to form a pyrazoline or with methanol to form 4-methoxyheptane. The pyrazoline can be decomposed photochemically to form 1,1,2-tripropylcyclopropane. In solution, 4-diazoheptane is inefficiently photolyzed to dipropylcarbene (DPC), which can be trapped with piperidine or with pyridine in laser flash photolysis experiments. Analysis of the piperidine and pyridine data indicates that the lifetime of DPC in cyclohexane, methylene chloride, or Freon-113 (CF2ClCFCl2) solution at ambient temperature is controlled by 1,2 hydrogen migration to form Z- and E-3-heptene. The lifetime deduced under these conditions is approximate to 300 ps, which is about 20-fold shorter than that of dimethylcarbene in perfluorohexane at ambient temperature. Upon photolysis (254 nm) of oxadiazoline 1a in argon, 4-diazoheptane and 1-methoxydiazoethane are formed. These diazo compounds undergo subsequent photolysis that revealed the formation of methoxy(methyl)carbene and E- and Z-3-heptene. It was not possible to detect DPC in argon at 14 K.

  DOI：

  10.1021/jp990198d

文献信息

• A surprising rearrangement of a carbene-ethylene sulfide ylide
  作者：Eunju Lee Tae、Zhendong Zhu、Matthew S Platz

  DOI：10.1016/s0040-4039(99)00859-x

  日期：1999.7

  Photolysis of 2-methoxy-2-methyl-5,5-dipropyl-Δ3-1,3,4 oxadiazoline in methylene chloride produces 4 diazo-heptane which can undergo secondary photolysis to form dipropylcarbene. Dipropylcarbene reacts with ethylene sulfide to form a ylide which rearranges to form a vinyl sulfide. Calculations indicate that this rearrangement is a concerted and asynchronous process in the gas phase.

  的光解2-甲氧基-2-甲基-5,5-二丙基Δ 3 -1,3,4-恶二唑啉在二氯甲烷中产生4重氮基庚烷，其可以经历二次光解以形成dipropylcarbene。二丙基卡宾与硫化亚乙基反应形成叶立德，该叶立德重排形成硫化亚乙烯基。计算表明，这种重排是气相中的协调和异步过程。
• Electrooxidative cyclization of N-acylhydrazones of aldehydes and ketones to .DELTA.3-1,3,4-oxadiazolines and 1,3,4-oxadiazoles
  作者：Toshiro Chiba、Mitsuhiro Okimoto

  DOI：10.1021/jo00031a014

  日期：1992.2

  The electrolytic oxidation of ketone N-acylhydrazones (1) in methanolic sodium acetate induced their intramolecular cyclization to the corresponding 2-methoxy-DELTA(3)-1,3,4-oxadiazolines 3. The thermal stability of a given oxadiazoline and what products were formed by its thermal decomposition was found to depend on the natures of the substituents at C-2. Thus, 2-methoxy-2-phenyloxadiazolines preferentially yielded oxiranes 5, whereas 2-alkyl-2-methoxyoxadiazolines preferentially gave enol ethers 6. 2,2-Dimethoxyoxadiazolines decomposed to the parent ketones and many unidentified products. The electrolytic oxidation of aldehyde N-acylhydrazones 2 gave 2,5-disubstituted 1,3,4-oxadiazoles 4. The oxidative cyclization of the N-benzoylhydrazones of aliphatic aldehydes gave especially high yields of the corresponding heterocycles.
• Chemistry and Kinetics of Dipropylcarbene in Solution
  作者：Eunju Lee Tae、Zhendong Zhu、Matthew S. Platz、John Paul Pezacki、John Warkentin

  DOI：10.1021/jp990198d

  日期：1999.7.1

  The photochemistry of 2-methoxy-2-methyl-5,5-dipropyl-Delta(3)-1,3,4-oxadiazoline (1a) and 2,2-dimethoxy-5,5-dipropyl-Delta(3)-1,3,4-oxadiazoline (1b) was investigated. Photolysis (300 nm) of these compounds in solution leads to fragmentation to 4-diazoheptane (major), which slowly forms the corresponding azine. Fragmentation to form 4-heptanone is also observed. Yields of 4-diazoheptane in CH2Cl2 are much larger than those in pentane. 4-Diazoheptane can be trapped with 1-pentene to form a pyrazoline or with methanol to form 4-methoxyheptane. The pyrazoline can be decomposed photochemically to form 1,1,2-tripropylcyclopropane. In solution, 4-diazoheptane is inefficiently photolyzed to dipropylcarbene (DPC), which can be trapped with piperidine or with pyridine in laser flash photolysis experiments. Analysis of the piperidine and pyridine data indicates that the lifetime of DPC in cyclohexane, methylene chloride, or Freon-113 (CF2ClCFCl2) solution at ambient temperature is controlled by 1,2 hydrogen migration to form Z- and E-3-heptene. The lifetime deduced under these conditions is approximate to 300 ps, which is about 20-fold shorter than that of dimethylcarbene in perfluorohexane at ambient temperature. Upon photolysis (254 nm) of oxadiazoline 1a in argon, 4-diazoheptane and 1-methoxydiazoethane are formed. These diazo compounds undergo subsequent photolysis that revealed the formation of methoxy(methyl)carbene and E- and Z-3-heptene. It was not possible to detect DPC in argon at 14 K.