4-diazo-2,2,6,6-tetramethylheptane-3,5-dione | 60681-09-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-diazo-2,2,6,6-tetramethylheptane-3,5-dione
• 英文别名: (E)-4-diazonio-2,2,6,6-tetramethyl-5-oxohept-3-en-3-olate
• CAS: 60681-09-6
• 化学式: C₁₁H₁₈N₂O₂
• 分子量: 210.276
• InChiKey: ZGJJLWVPCGYATR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  36.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-diazo-2,2,6,6-tetramethylheptane-3,5-dione 以 solid matrix 为溶剂， 反应 0.17h， 生成 tert-butyl-(2,2-dimethyl-propionyl)-ketene
  参考文献：
  名称：

  Direct observation of .alpha.-oxo ketenes from the photolysis of .alpha.-diazo .beta.-diketones

  摘要：

  Monitoring by IR spectroscopy of the broad-band irradiation of the symmetrically substituted 2-diazo-cyclohexane-1,3-dione (I 1), 3-diazopentane-2,4-dione (19), and 4-diazo-2,2,6,6-tetramethylheptane-3,5-dione (24) in Ar matrices at 12 K showed the formation of 2-carbonylcyclopentanone (s-Z-12), acetyl(methyl)ketene (s-E-20), and tert-butyl(pivaloyl)ketene (s-E-25), respectively, in less than 10 min. On increasing the photolysis time to >3 h, the alpha-oxo ketenes 12,20, and 25 decarbonylated to the corresponding oxocarbenes which underwent Wolff rearrangement to carbonylcyclobutane (15), dimethylketene (23), and di-tert-butylketene (28), respectively. The reaction of 2-carbonylcyclopentanone (12) with CH3OH was monitored by IR spectroscopy. Thus, it was found that the reaction started at ca. 100 K and was essentially complete at 140 K, involving the initial formation of the enol form (9) of methyl 2-oxocyclopentanecarboxylate.

  DOI：

  10.1021/jo00044a019
• 作为产物：
  描述：

  4-amino-2,2,6,6-tetramethyl-heptane-3,5-dione; hydrochloride 在 盐酸 、 sodium nitrite 作用下， 生成 4-diazo-2,2,6,6-tetramethylheptane-3,5-dione
  参考文献：
  名称：

  Korobitsyna,I.K.; Nikolaev,V.A., Journal of Organic Chemistry USSR (English Translation), 1976, vol. 12, p. 1245 - 1251

  摘要：

  DOI：

文献信息

• Solvent-Directed Transition Metal-Free C–C Bond Cleavage by Azido-1,3,5-triazines and Their Stability-Reactivity Paradox
  作者：Fulei Ma、Xiaoyu Xie、Yuanheng Li、Ziqiang Yan、Mingming Ma

  DOI：10.1021/acs.joc.0c02342

  日期：2021.1.1

  We report a solvent-directed and regioselective carbon–carbon bond cleavage of aryl ketones by azido-1,3,5-triazines (ATs), which is typically completed within 10 min in DMSO at room temperature, without using transition metal catalysts. The cleavage is driven by the steric hindrance in the adducts of aryl ketones and ATs, which is substantiated by DFT calculation. Our recent results showed that ATs

  我们报道了叠氮基1,3,5-三嗪（ATs）对芳基酮的溶剂定向和区域选择性碳-碳键裂解，该反应通常在室温下于DMSO中于10分钟内完成，无需使用过渡金属催化剂。裂解是由芳基酮和ATs加合物中的空间位阻驱动的，这可通过DFT计算得到证实。我们最近的结果表明，ATs在溶液中具有高反应活性，在固态时具有高稳定性。鉴于ATs的分子和晶体结构，已经解释了这种“稳定性-反应性悖论”。
• Lauer, Wolfgang; Krause, Volker; Wegenroth, Horst, Chemische Berichte, 1988, vol. 121, p. 465 - 470
  作者：Lauer, Wolfgang、Krause, Volker、Wegenroth, Horst、Meier, Herbert

  DOI：——

  日期：——
• Nikolaev,V.A. et al., Journal of Organic Chemistry USSR (English Translation), 1978, vol. 14, p. 1338 - 1346
  作者：Nikolaev,V.A. et al.

  DOI：——

  日期：——
• LAUER, WOLFGANG;KRAUSE, VOLKER;WENGENROTH, HORST;MEIER, HERBERT, CHEM. BER., 121,(1988) N 3, 465-469
  作者：LAUER, WOLFGANG、KRAUSE, VOLKER、WENGENROTH, HORST、MEIER, HERBERT

  DOI：——

  日期：——
• NIKOLAEV V. A.; FRENX YU.; KOROBITSINA I. K., ZH. ORGAN. XIMII, 1978, 14, HO 7, 1433-1441
  作者：NIKOLAEV V. A.、 FRENX YU.、 KOROBITSINA I. K.

  DOI：——

  日期：——