5,5-diethyl-2-methoxy-2-methyl-Δ³-1,3,4-oxadiazoline | 119393-15-6

• 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: 5,5-diethyl-2-methoxy-2-methyl-Δ³-1,3,4-oxadiazoline
• 英文别名: 2,2-Diethyl-5-methoxy-5-methyl-1,3,4-oxadiazole
• CAS: 119393-15-6
• 化学式: C₈H₁₆N₂O₂
• 分子量: 172.227
• InChiKey: VGTWGIORKSEJLR-UHFFFAOYSA-N

物化性质

• 沸点：
  50-52 °C(Press: 1.5 Torr)
• 密度：
  1.06±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  3
• 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：

  5,5-diethyl-2-methoxy-2-methyl-Δ³-1,3,4-oxadiazoline 、 丁炔二酸二甲酯 以 苯 为溶剂， 反应 5.0h， 以67%的产率得到3,4-bis(methoxycarbonyl)-5,5-diethylpyrazole
  参考文献：
  名称：

  Photolysis of 2-alkoxy-.DELTA.3-1,3,4-oxadiazolines. A new route to diazoalkanes

  摘要：

  DOI：

  10.1021/jo00269a019
• 作为产物：
  描述：

  3-戊酮 、 alkaline earth salt of/the/ methylsulfuric acid 在 lead(IV) acetate 作用下， 生成 5,5-diethyl-2-methoxy-2-methyl-Δ³-1,3,4-oxadiazoline
  参考文献：
  名称：

  Rate Constants for 1,2-Hydrogen Migration in Cyclohexylidene and in Substituted Cyclohexylidenes¹

  摘要：

  Laser Bash photolysis (UV-LFP, 308 nm) of suitably substituted oxadiazolines leads to cyclohexylidene (14a), 4-tert-butyl-cyclohexylidene (14b), 2-trifluoromethylcyclohexylidene (14d), 8-aza-8methyl[3.2.1]oct-3-ylidene (14e), diethylcarbene (14f), and ethyl(methyl)carbene (14h). Carbene intermediates were inferred from the products of steady state photolyses, and their pyridinium ylides were inferred from. transient absorption spectra observed when pyridine was present. Yields of the pyridinium ylides 15a-h as a function of pyridine concentration gave the lifetimes (tau) for carbenes 14a-h in cyclohexane, cyclohexane-d(12), and benzene solutions, at 22 degrees C. The intermediacy of cyclohexylidene (14a) was inferred from the observation of cyclohexene formed in both the LFP and steady state (SS) experiments, The major products from dual wavelength irradiation of the oxadiazolines (at 254 and 300 nm) were those of 1,2-migration of hydrogen (1,2-H) in the corresponding carbenes. 2-Trifluromethylcyclohexylidene gave 3-trifluoromethylcyclohexene and 1-trifluoromethylcyclohexene in a 9.8:1 ratio. The kinetic data support the conclusion that 1,2-H in the cyclohexylidenes is accelerated, relative to 1,2-H in dimethylcarbene. A 4-tert-butyl substituent has a negligible effect on the rate constant for 1,2-H, but the CF3 group at the alpha-position decelerates 1,2-H by roughly: 10-fold, as inferred from the distribution of products.

  DOI：

  10.1021/jo990171q

文献信息

• MAJCHRZAK, MICHAEL W.;BEKHAZI, MICHEL;TSE-SHEEPY, IRENE;WARKENTIN, JOHN, J. ORG. CHEM., 54,(1989) N, C. 1842-1845
  作者：MAJCHRZAK, MICHAEL W.、BEKHAZI, MICHEL、TSE-SHEEPY, IRENE、WARKENTIN, JOHN

  DOI：——

  日期：——
• Photolysis of 2-alkoxy-.DELTA.3-1,3,4-oxadiazolines. A new route to diazoalkanes
  作者：Michael W. Majchrzak、Michel Bekhazi、Irene Tse-Sheepy、John Warkentin

  DOI：10.1021/jo00269a019

  日期：1989.4
• Rate Constants for 1,2-Hydrogen Migration in Cyclohexylidene and in Substituted Cyclohexylidenes¹
  作者：John Paul Pezacki、Philippe Couture、James A. Dunn、John Warkentin、Paul D. Wood、Janusz Lusztyk、Francis Ford、Matthew S. Platz

  DOI：10.1021/jo990171q

  日期：1999.6.1

  Laser Bash photolysis (UV-LFP, 308 nm) of suitably substituted oxadiazolines leads to cyclohexylidene (14a), 4-tert-butyl-cyclohexylidene (14b), 2-trifluoromethylcyclohexylidene (14d), 8-aza-8methyl[3.2.1]oct-3-ylidene (14e), diethylcarbene (14f), and ethyl(methyl)carbene (14h). Carbene intermediates were inferred from the products of steady state photolyses, and their pyridinium ylides were inferred from. transient absorption spectra observed when pyridine was present. Yields of the pyridinium ylides 15a-h as a function of pyridine concentration gave the lifetimes (tau) for carbenes 14a-h in cyclohexane, cyclohexane-d(12), and benzene solutions, at 22 degrees C. The intermediacy of cyclohexylidene (14a) was inferred from the observation of cyclohexene formed in both the LFP and steady state (SS) experiments, The major products from dual wavelength irradiation of the oxadiazolines (at 254 and 300 nm) were those of 1,2-migration of hydrogen (1,2-H) in the corresponding carbenes. 2-Trifluromethylcyclohexylidene gave 3-trifluoromethylcyclohexene and 1-trifluoromethylcyclohexene in a 9.8:1 ratio. The kinetic data support the conclusion that 1,2-H in the cyclohexylidenes is accelerated, relative to 1,2-H in dimethylcarbene. A 4-tert-butyl substituent has a negligible effect on the rate constant for 1,2-H, but the CF3 group at the alpha-position decelerates 1,2-H by roughly: 10-fold, as inferred from the distribution of products.