2,2-二甲氧基-1-氧杂-3,4-二氮杂螺[4.5]癸-3-烯 | 138723-92-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2,2-二甲氧基-1-氧杂-3,4-二氮杂螺[4.5]癸-3-烯
• 英文名称: 2,2-dimethoxy-5,5-pentamethylene-1,3,4-Δ³-oxadiazoline
• 英文别名: 3,4-diaza-2,2-dimethoxy-1-oxa<4.3>spirodec-3-ene；3,4-diaza-2,2-dimethoxy-1-oxaspiro[3,4]dec-3-ene；4-Oxa-1,2-diazaspiro[4.5]dec-1-ene, 3,3-dimethoxy-；2,2-dimethoxy-1-oxa-3,4-diazaspiro[4.5]dec-3-ene
• CAS: 138723-92-9
• 化学式: C₉H₁₆N₂O₃
• 分子量: 200.238
• InChiKey: IBLDAXZFLLUYMS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  52.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,2-二甲氧基-1-氧杂-3,4-二氮杂螺[4.5]癸-3-烯 以 乙腈 为溶剂， 生成 diazocyclohexane
  参考文献：
  名称：

  Δ³-1,3,4-Oxadiazolines:  Photochemical Precursors to Diazoalkanes and sec-Alkanediazonium Ions in Acidic Solution¹

  摘要：

  DOI：

  10.1021/ja962550w
• 作为产物：
  描述：

  环己酮 、 alkaline earth salt of/the/ methylsulfuric acid 在 lead(IV) acetate 作用下， 生成 2,2-二甲氧基-1-氧杂-3,4-二氮杂螺[4.5]癸-3-烯
  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

• UV Light Is No Longer Required for the Photoactivation of 1,3,4-Oxadiazolines
  作者：Katarzyna Orłowska、João V. Santiago、Piotr Krajewski、Kacper Kisiel、Irena Deperasińska、Katarzyna Zawada、Wojciech Chaładaj、Dorota Gryko

  DOI：10.1021/acscatal.2c05319

  日期：2023.2.3

  the activation of these compounds that permit the use of UV-light-sensitive substrates are highly valued. Herein, we report the visible-light-induced activation of oxadiazolines by triplet energy transfer catalysis that, in contrast to UV-induced processes, alters their reactivity and enables the generation of carbenes. The formed reactive species react with electron-poor olefins, thereby giving valuable

  卡宾在大量有机转化中起着关键作用。尽管稳定的重氮羰基化合物作为亲电子卡宾的来源占主导地位，但不稳定的类似物的危险性要求它们从稳定的前体原位生成。其中，1,3,4-恶二唑啉在紫外光照射下可作为重氮烷烃的替代物。鉴于它们的高稳定性、多样的反应性和简单的合成，允许使用紫外光敏感底物的更温和的激活这些化合物的方法受到高度重视。在此，我们报告了可见光诱导的三重态能量转移催化对恶二唑啉的活化，与紫外线诱导的过程相反，它改变了它们的反应性并能够产生卡宾。形成的活性物质与缺电子烯烃反应，从而得到有价值的螺环丙烷。理论和实验的机理研究揭示了可能的途径，并强调了三重态能量转移步骤的重要性。
• 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.
• Epo×ide of a ketene acetal. The first 2,2-dialko×yo×irane to be isolated
  作者：Malgorzata Dawid、Paul C. Venneri、John Warkentin

  DOI：10.1139/cjc-79-2-110

  日期：——

  Dimethoxycarbene, generated at 110 degreesC in benzene by thermolysis of 2,2-dimethoxy-5,5-dimethyl-Delta (3)-1,3,4- oxadiazoline, reacted with cyclohexanone to afford 2,2-dimethoxyspiro[2.5]-1-oxaoctane. It is the first oxirane of a ketene acetal that could be isolated and characterized by H-1 NMR-, C-13 NMR-, and IR spectroscopy. The identical oxirane might be expected from conrotatory cyclization of the appropriate carbonyl ylide. That ylide was generated under identical conditions by thermolysis of an oxadiazoline precursor (3,4-diaza-2,2-dimethoxy-1-oxaspiro[4.5]dec-3-ene) (14). The ylide could either cyclize or fragment to dimethoxycarbene and cyclohexanone. Addition of 4-tert-butylcyclohexanone, to trap dimethoxycarbene in competition with the cyclohexanone generated from 14 and, to leave the ylide closure pathway as the only route to the oxirane, showed that the carbonyl ylide does cyclize. However, fragmentation of the carbonyl ylide is relatively fast compared to its cyclization and most of it fragments to dimethoxycarbene and cyclohexanone. Oxirane formation from the carbene and ketone is probably either a concerted cycloaddition or it occurs in two steps, by nucleophilic attack at the carbonyl carbon to form the C-C bond first, prior to ring closure. If the carbene is bonded first to O of the carbonyl group, as it is in the carbonyl ylide, subsequent formation of the C-C bond is too slow, relative to fragmentation of the ylide, to afford the oxirane ring efficiently.
• 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.
• Δ³-1,3,4-Oxadiazolines:  Photochemical Precursors to Diazoalkanes and <i>sec</i>-Alkanediazonium Ions in Acidic Solution¹
  作者：John Paul Pezacki、Brian D. Wagner、Calvin S. Q. Lew、John Warkentin、Janusz Lusztyk

  DOI：10.1021/ja962550w

  日期：1997.2.1