2-Methyl-naphthochinon-(1,4)-diazid | 99230-11-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-Methyl-naphthochinon-(1,4)-diazid
• 英文别名: (4E)-4-diazo-2-methylnaphthalen-1-one
• CAS: 99230-11-2
• 化学式: C₁₁H₈N₂O
• 分子量: 184.197
• InChiKey: FQSGCURFMOZJIX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.09
• 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-Methyl-naphthochinon-(1,4)-diazid 在 水 、 sodium acetate 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 24.25h， 生成 3-Methyl-2-<3-methyl-4-(trifluormethylsulfonyloxy)-1-naphthylazo>-4-(trifluormethylsulfonyloxy)-1-naphthol
  参考文献：
  名称：

  Maas, Gerhard; Tretter, Andreas, Liebigs Annalen der Chemie, 1985, # 9, p. 1866 - 1873

  摘要：

  DOI：
• 作为产物：
  描述：

  甲萘醌 生成 2-Methyl-naphthochinon-(1,4)-diazid
  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

• Synthesis, Molecular Structure, and Reactivity of Rhodium(I) Complexes with Diazoalkanes and Related Substrates as Ligands
  作者：Helmut Werner、Norbert Mahr、Justin Wolf、Arno Fries、Matthias Laubender、Elke Bleuel、Raquel Garde、Pascual Lahuerta

  DOI：10.1021/om0302037

  日期：2003.8.1

  A series of (diazoalkane)rhodium(I) compounds of the general composition trans-[RhCl(N2CRR‘)(PiPr3)2] with R = R‘ = Ph, p-C6H4Me, p-C6H4Cl and R = Ph, R‘ = p-C6H4Me, o-C6H4Me, CH3, CH2Ph, CF3 has been prepared from the dimer [RhCl(PiPr3)2]2 (1) and the diazoalkane. This preparative route has also been extended to complexes in which the N2C unit(s) of 1,4-C6H4C(Ph)N2}2, 9-diazofluorene, 9,10-anthraquinone-9-diazide

  一般组成的一系列（重氮烷）铑（I）化合物反式-[RhCl（N 2 CRR'）（P i Pr 3）2 ]，R = R'= Ph，p -C 6 H 4 Me，p -C 6 H 4 Cl和R = Ph，R'= p -C 6 H 4 Me，o -C 6 H 4 Me，CH 3，CH 2 Ph，CF 3由二聚体[RhCl（P i Pr 3）2 ]2（1）和重氮烷。该制备途径也已扩展到其中1,4-C 6 H 4 C（Ph）N 2 } 2的N 2 C单元，9-重氮芴，9,10-蒽醌-9-的配合物。二叠氮化物和3-甲基-1,4-萘醌-1-二叠氮与14电子[RhCl（P i Pr 3）2 ]片段连接。C（CO 2 Et）2 N 2的行为与预期相同，用1处理后即可得到复杂的反式-[RhCl N 2 C（CO 2 Et）2 }（Pi Pr 3）2），CH（CO 2 Et）N 2与相同的原料反应，生成二氮衍生物反式-[RhCl（N
• Ried,W.; Dietrich,R., Chemische Berichte, 1961, vol. 94, p. 387 - 391
  作者：Ried,W.、Dietrich,R.

  DOI：——

  日期：——
• Ried,W.; Trummlitz,H., Justus Liebigs Annalen der Chemie, 1966, vol. 692, p. 100 - 104
  作者：Ried,W.、Trummlitz,H.

  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.
• Reductive Electrochemistry of Spiromethanofullerenes
  作者：Marcel W. J. Beulen、José A. Rivera、M. Ángeles Herranz、Beatriz Illescas、Nazario Martín、Luis Echegoyen

  DOI：10.1021/jo010297z

  日期：2001.6.1

  The synthesis and electrochemical properties of spiromethanofullerenes 1-6 are described. The syntheses were achieved via the diazomethane route, and the regioisomeric distribution of bis-adducts 3 was determined by H-1 NMR, UV-vis, and HPLC analysis. The electrochemistry of these compounds in dichloromethane exhibits, besides several reversible reductions, some irreversible waves. Reductive electrolysis of 1 and 3-5 in dichloromethane leads to the removal of the addend and thus to the formation of C-60 Reductive electrolysis of 1, 2 and 6 in dichloromethane leads to a different reaction, which we tentatively assign to a reaction with the solvent to form fullerene-CH2Cl products. Electrolyses in the less reactive solvent THF lead to adduct removal for 1 and 3-5. Interestingly, significant formation of bis-adducts from the corresponding monoadducts was observed for 4 and 5. These electrochemically induced reactions, namely addend removal, reaction with the solvent, and addend transfer are influenced by the structure of the addend and by the choice of solvent.