diazoethane | 138308-51-7

• 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: diazoethane
• 英文别名: 2-Diazonio-1-[2-(phenylethynyl)phenyl]prop-1-en-1-olate；2-diazo-1-[2-(2-phenylethynyl)phenyl]propan-1-one
• CAS: 138308-51-7
• 化学式: C₁₇H₁₂N₂O
• 分子量: 260.295
• InChiKey: AJJGOLFGGVUXPZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  19.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  diazoethane 以 二氯甲烷 为溶剂， 以60%的产率得到1-methyl-3-phenylnaphthalen-2-ol
  参考文献：
  名称：

  邻炔基取代的α-重氮苯乙酮的重排。通过芳基烯酮中间体转化为β-萘酚

  摘要：

  与铑（II）介导的邻炔基取代的α-二重氮苯乙酮的环异构化相反，辐射导致生成β-萘酚，后者是通过芳基烯酮中间体的环化反应而形成的。

  DOI：

  10.1016/s0040-4039(00)79427-5
• 作为产物：
  描述：

  2-苯基乙炔基苯甲酸甲酯 在 potassium trimethylsilonate 、 氯甲酸甲酯 作用下， 以 乙醚 为溶剂， 反应 20.0h， 生成 diazoethane
  参考文献：
  名称：

  A comparative study of the decomposition of o-alkynyl-substituted aryl diazo ketones. Synthesis of polysubstituted .beta.-naphthols via arylketene intermediates

  摘要：

  The photochemical, thermal, and rhodium-catalyzed decomposition reactions of several closely related o-alkynyl or o-alkenyl alpha-diazoaceto- and propiophenone derivatives have been studied. The reaction outcome is markedly dependent upon the reaction conditions employed for nitrogen extrusion. Thermolysis or photolysis of o-alkynyl alpha-diazopropiophenone derivatives yields polysubstituted beta-naphthols. These products are derived from Wolff rearrangement of the initially formed carbene to give an aryl ketene which undergoes intramolecular cyclization onto the o-alkynyl substituent. In direct contrast to the thermal and photochemical results, Rh(II)-catalyzed decomposition yields products derived from direct attack of a rhodium carbenoid onto the tethered pi-system producing a vinyl carbenoid intermediate. Further reaction of the cyclized carbenoid with the starting diazo compound furnishes a vinyl indenone which undergoes a rapid intramolecular Diels-Alder reaction to produce a novel dimer whose structure was elucidated by an X-ray crystal analysis. Replacement of the methyl group on the diazo center with a sterically less demanding hydrogen atom was also found to play an important role in controlling the outcome of the Rh(II)-catalyzed reaction.

  DOI：

  10.1021/jo00075a045

文献信息

• A Tandem Cyclization-Onium Ylide Rearrangement-Cycloaddition Sequence for the Synthesis of Benzo-Substituted Cyclopentenones
  作者：Albert Padwa、Jamal M. Kassir、Mark A. Semones、M. David Weingarten

  DOI：10.1021/jo00106a014

  日期：1995.1

  A new annulation sequence leading to benzo-substituted cyclopentenones is effected by treating o-alkynyl-substituted alpha-diazoacetophenones containing tethered heteroatoms with Rh(II) carboxylates. The reaction involves addition of the initially formed keto carbenoid onto the acetylenic pi-bond to give a rearranged vinyl carbenoid. Sulfonium ylide formation occurred both intra- and intermolecularly when the reaction was carried out in the presence of a sulfide. In the case where an ether oxygen was present on the backbone of the vinyl carbenoid, the resulting oxonium ylide underwent a [1,2]- or [2,3]-shift to give the rearranged product. These cyclic metallocarbenoids were also found to interact with a neighboring carbonyl or oximino pi-bond to produce carbonyl or azomethine ylides. The 1,3-dipoles generated in this manner were trapped with dimethyl acetylenedicarboxylate. The domino transformation was also performed intramolecularly by attaching a trapping agent directly to the carbonyl group. Incorporation of an amido carbonyl on the alkyne side chain was found to dramatically alter the course of the tandem annulation reaction. A novel rearranged cycloadduct was formed in high yield whose structure was elucidated by X-ray crystallography. The mechanism for its formation involves the opening of a transient intermediate oxabicyclo[2.2.1]heptane followed by a Wagner-Meerwein rearrangement.
• Rhodium carbenoid mediated cyclizations of o-alkynyl-substituted .alpha.-diazoacetophenones
  作者：Albert Padwa、Keith E. Krumpe、Jamal M. Kassir

  DOI：10.1021/jo00044a032

  日期：1992.8

  o-Alkynyl-substituted alpha-diazoacetophenones undergo facile cyclization to indenone derivatives upon treatment with catalytic quantities of Rh(II) carboxylates. A variety of structural influences were encountered by varying the nature of the substituent group attached to the alkyne carbon atom. The cyclization reaction involves addition of a rhodium stabilized carbenoid onto the acetylenic pi-bond to generate a vinyl carbenoid. The vinyl carbenoid was found to undergo both CH and CC migration as well as delta-CH insertion into the alkyl backbone. Different catalysts were shown to result in significant variation in the product ratios for these reactions. Treatment of o-(5-(allyloxy)-1-pentynyl)-alpha-diazoacetophenone with rhodium(II) mandelate afforded 2-(2-propen-1-yl)-2-(1-oxo-1H-indenyl)-2,3,4,5-tetrahydrofuran in high yield. The formation of this compound involves initial formation of a vinyl carbenoid which reacts with the neighboring oxygen atom to give an oxonium ylide which subsequently undergoes a 2,3-sigmatropic rearrangement. When 2-ethynyl-alpha-diazoacetophenone is used, only products derived from 6-endo closure are observed. Substituted o-alkynyl alpha-diazoacetophenones give products derived from 5-exo cyclization. The mode of ring closure is controlled by both steric and electronic factors.
• Padwa Albert, Chiacchio Ugo, Fairfax David J., Kassir Jamal M., Litrico A+, J. Org. Chem, 58 (1993) N 23, S 6429-6437
  作者：Padwa Albert, Chiacchio Ugo, Fairfax David J., Kassir Jamal M., Litrico A+

  DOI：——

  日期：——
• A comparative study of the decomposition of o-alkynyl-substituted aryl diazo ketones. Synthesis of polysubstituted .beta.-naphthols via arylketene intermediates
  作者：Albert Padwa、Ugo Chiacchio、David J. Fairfax、Jamal M. Kassir、Angelo Litrico、Mark A. Semones、Simon L. Xu

  DOI：10.1021/jo00075a045

  日期：1993.11

  The photochemical, thermal, and rhodium-catalyzed decomposition reactions of several closely related o-alkynyl or o-alkenyl alpha-diazoaceto- and propiophenone derivatives have been studied. The reaction outcome is markedly dependent upon the reaction conditions employed for nitrogen extrusion. Thermolysis or photolysis of o-alkynyl alpha-diazopropiophenone derivatives yields polysubstituted beta-naphthols. These products are derived from Wolff rearrangement of the initially formed carbene to give an aryl ketene which undergoes intramolecular cyclization onto the o-alkynyl substituent. In direct contrast to the thermal and photochemical results, Rh(II)-catalyzed decomposition yields products derived from direct attack of a rhodium carbenoid onto the tethered pi-system producing a vinyl carbenoid intermediate. Further reaction of the cyclized carbenoid with the starting diazo compound furnishes a vinyl indenone which undergoes a rapid intramolecular Diels-Alder reaction to produce a novel dimer whose structure was elucidated by an X-ray crystal analysis. Replacement of the methyl group on the diazo center with a sterically less demanding hydrogen atom was also found to play an important role in controlling the outcome of the Rh(II)-catalyzed reaction.
• Rearrangement of o-alkynyl substituted α-diazoacetophenones. Conversion to β-naphthols via arylketene intermediates
  作者：Albert Padwa、David J. Austin、Ugo Chiacchio、Jamal M. Kassir、Antonio Rescifina、Simon L. Xu

  DOI：10.1016/s0040-4039(00)79427-5

  日期：1991.10

  In contrast to the rhodium (II) mediated cycloisomerization of o-alkynyl substituted α-diazoacetophenones, irradiation leads to β-naphthols which are formed via cyclization of an arylketene intermediate.

  与铑（II）介导的邻炔基取代的α-二重氮苯乙酮的环异构化相反，辐射导致生成β-萘酚，后者是通过芳基烯酮中间体的环化反应而形成的。