2,6-Dimethyl-benzochinon-(1,4)-diazid-(4) | 937-37-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,6-Dimethyl-benzochinon-(1,4)-diazid-(4)
• 英文别名: 2,5-Cyclohexadien-1-one, 4-diazo-2,6-dimethyl-；4-diazonio-2,6-dimethylphenolate
• CAS: 937-37-1
• 化学式: C₈H₈N₂O
• 分子量: 148.164
• InChiKey: FDJXHMXREUSGSY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  51.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,6-Dimethyl-benzochinon-(1,4)-diazid-(4) 在 硫酸 作用下， 生成 Acetic acid 4-(4-acetoxy-3,5-dimethyl-phenyl)-2,5-diphenyl-furan-3-yl ester
  参考文献：
  名称：

  3,5-二烷基-螺[2.5] Octa-2,5-dien-4-ones的酸催化反应

  摘要：

  用对甲苯磺酸对螺二烯酮（2a）和（2b）进行酸催化的开环得到苯乙烯衍生物（3a）和（3b），而用乙酸酐/ H 2 SO 4处理得到呋喃衍生物（4a） ）和（4b）。

  DOI：

  10.1016/s0040-4039(01)92356-1
• 作为产物：
  描述：

  2,6-二甲基-2,5-环己二烯-1,4-二酮 生成 2,6-Dimethyl-benzochinon-(1,4)-diazid-(4)
  参考文献：
  名称：

  Direct observation of the cyclopropene-vinylcarbene rearrangement. Matrix isolation of bicyclo[3.1.0]hexa-3,5-dien-2-ones

  摘要：

  4-Oxocyclohexa-2,5-dienylidenes 4b-g have been generated in argon matrices at 10 K by visible-light irradiation of the corresponding quinone diazides 5. Carbenes 4 have been characterized by IR and UV-vis spectroscopy and by their characteristic thermal reaction with molecular oxygen. On irradiation into the longest-wavelength absorption (420-700 nm), carbenes 4c-g rearrange to give the highly strained bicyclo[3.1.0]hexa-3,5-dien-2-ones 3c-g, while 4b is photostable under the same conditions. The photochemical 4 --> 3 rearrangement is completely reversible: infrared irradiation or visible light irradiation (lambda > 470 nm) of the cyclopropenes 3 lead back to triplet carbenes 4 quantitatively. In addition, several of the 1,3-bridged cyclopropenes 3 undergo a thermal rearrangement to give carbenes 4. This indicates that the highly strained cyclopropenes 3 are thermodynamically less stable than the corresponding carbenes 4 and kinetically only stabilized by a shallow energy barrier. Even under the conditions of matrix isolation at cryogenic temperatures, cyclopropenes 3 are metastable compounds.

  DOI：

  10.1021/jo00031a009

文献信息

• An Efficient Procedure for the Synthesis of Crystalline Aryldiazonium Trifluoroacetates – Synthetic Applications
  作者：Christophe Colas、Maurice Goeldner

  DOI：10.1002/(sici)1099-0690(199906)1999:6<1357::aid-ejoc1357>3.0.co;2-p

  日期：1999.6

  spectra have been recorded for all the synthesized salts; the data are in good agreement with the rather limited published data and constitute a first extensive report of 13C-NMR chemical shifts in diazonium salts. An excellent linear relationship emerged between Brown's substituent constants s+p and the 13Cipso chemical shifts. The diazonium salts obtained proved to be much more soluble in organic

  我们开发了一种非常温和的方法，用于在无水条件下以高产率合成结晶芳基重氮三氟乙酸盐。超过 30 种单官能或多官能苯胺衍生物已通过这种方法重氮化，包括对水和酸敏感的底物。衍生自相应苯胺的邻和对羟基芳基重氮盐可以通过用 K2CO3 处理去质子化以产生纯的重氮醌。已记录所有合成盐的 NMR 和 UV/Vis 光谱；这些数据与相当有限的公开数据非常吻合，并构成了重氮盐中 13C-NMR 化学位移的第一份广泛报告。Brown 的取代基常数 s+p 和 13Cipso 化学位移之间出现了极好的线性关系。获得的重氮盐证明比它们的四氟硼酸盐对应物更易溶于有机溶剂。它们在各种碳-碳双键的 Pd 介导的偶联反应中进行了测试，发现在非常温和的条件下，在很短的反应时间内获得了良好的产率。我们相信重氮三氟乙酸盐是重氮四氟硼酸盐的一种非常有吸引力的替代品。
• Ried,W.; Dietrich,R., Chemische Berichte, 1961, vol. 94, p. 387 - 391
  作者：Ried,W.、Dietrich,R.

  DOI：——

  日期：——
• Direct observation of the cyclopropene-vinylcarbene rearrangement. Matrix isolation of bicyclo[3.1.0]hexa-3,5-dien-2-ones
  作者：Goetz Bucher、Wolfram Sander

  DOI：10.1021/jo00031a009

  日期：1992.2

  4-Oxocyclohexa-2,5-dienylidenes 4b-g have been generated in argon matrices at 10 K by visible-light irradiation of the corresponding quinone diazides 5. Carbenes 4 have been characterized by IR and UV-vis spectroscopy and by their characteristic thermal reaction with molecular oxygen. On irradiation into the longest-wavelength absorption (420-700 nm), carbenes 4c-g rearrange to give the highly strained bicyclo[3.1.0]hexa-3,5-dien-2-ones 3c-g, while 4b is photostable under the same conditions. The photochemical 4 --> 3 rearrangement is completely reversible: infrared irradiation or visible light irradiation (lambda > 470 nm) of the cyclopropenes 3 lead back to triplet carbenes 4 quantitatively. In addition, several of the 1,3-bridged cyclopropenes 3 undergo a thermal rearrangement to give carbenes 4. This indicates that the highly strained cyclopropenes 3 are thermodynamically less stable than the corresponding carbenes 4 and kinetically only stabilized by a shallow energy barrier. Even under the conditions of matrix isolation at cryogenic temperatures, cyclopropenes 3 are metastable compounds.
• Ried,W.; Dietrich,R., Justus Liebigs Annalen der Chemie, 1961, vol. 649, p. 57 - 70
  作者：Ried,W.、Dietrich,R.

  DOI：——

  日期：——
• Laser flash photolysis studies on 4-oxocyclohexa-2,5-dienylidenes
  作者：B. R. Arnold、J. C. Scaiano、G. F. Bucher、W. W. Sander

  DOI：10.1021/jo00050a020

  日期：1992.11

  Reactions of 4-oxocyclohexa-2,5-dienylidene (1) and two derivatives have been investigated using laser flash photolysis techniques. Photolysis of 4-diazocyclohexa-2,5-dien-1-one (4) in 1,1,2-trichlorotrifluoroethane allows the indirect detection of the corresponding carbene 1. This carbene reacts with triplet oxygen at close to the diffusion-controlled rate, forming the carbonyl 0-oxide (lambda(max) = 470 nm). Reaction of triplet 1 with moderate concentrations of cyclohexane leads to formation of phenoxyl radical (lambda(max) = 395 nm). At high concentrations or in neat cyclohexane the predominant path appears to be carbene insertion into the C-H bond. Other reactions examined include 0-H insertion in methanol and the indirect formation of ylides from acetone, acetonitrile, and pyridine. The reactivity pattern that emerges indicates that carbene 1 and its derivatives, 2 and 3, have triplet ground states and that the singlet-triplet energy gap is moderately large. Ylide formation is only observed when the reactants are present in low concentrations and involve a two-step reaction from the triplet carbene; no ylides are observed in neat acetone or acetonitrile suggesting that for the singlet carbene insertion into C-H bonds is favored over direct ylide formation.