1,3-bis(diazoacetyl)benzene | 74048-19-4

• 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: 1,3-bis(diazoacetyl)benzene
• 英文别名: 2,2'-bis-diazo-1,1'-m-phenylene-bis-ethanone；1,3-Bis-diazoacetyl-benzol；1,1'-(1,3-Phenylene)bis(2-diazonioethen-1-olate)；2-diazo-1-[3-(2-diazoacetyl)phenyl]ethanone
• CAS: 74048-19-4
• 化学式: C₁₀H₆N₄O₂
• 分子量: 214.183
• InChiKey: PCTUNNODXVSDML-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  38.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,3-bis(diazoacetyl)benzene 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 22.0h， 生成 (3-Methylsulfanyloxothioacetyl-phenyl)-oxo-dithioacetic acid methyl ester
  参考文献：
  名称：

  Aktivierte Thiocarbonsäure-ester; 8¹. Herstellung von 2-Oxodithiocarbonsäure-estern aus Diazoketonen

  摘要：

  活化硫代羧酸酯； 8. 从重氮酮制备 2-氧代二硫代羧酸酯 在三乙胺存在下，重氮酮（很容易从酸性氯化物中获得）与元素硫发生反应，然后进行烷基化，生成 2-氧代二硫代羧酸烷基酯。

  DOI：

  10.1055/s-1986-31843
• 作为产物：
  描述：

  重氮甲烷 、 间苯二甲酰氯 在 etheric solution 作用下， 生成 1,3-bis(diazoacetyl)benzene
  参考文献：
  名称：

  Über间苯二甘醇。（53. MitteilungüberStickstoff-Heterocyclen）

  摘要：

  DOI：

  10.1002/hlca.194402701140

文献信息

• The Acid Catalyzed Decomposition of Diazo Compounds. I. Synthesis of Oxazoles in the BF₃Catalyzed Reaction of Diazo Carbonyl Compounds with Nitriles
  作者：Toshikazu Ibata、Ryohei Sato

  DOI：10.1246/bcsj.52.3597

  日期：1979.12

  The BF3-catalyzed decomposition of diazo carbonyl compounds in nitriles have afforded the corresponding oxazoles in high yields. This method is applicable to diazo carbonyl compounds such as m- and p-substituted diazoacetophenones, ethyl diazoacetate, 1,2-diphenyl-2-diazoethanone, dibenzoyldiazomethane, and dimethyl diazomalonate. Bis(diazo ketone)s such as terminal bis(diazoacetylated) alkanes (III1−4:

  BF3 催化的腈中重氮羰基化合物的分解以高产率提供了相应的恶唑。该方法适用于间位和对位取代的重氮苯乙酮、重氮乙酸乙酯、1,2-二苯基-2-重氮乙酮、二苯甲酰重氮甲烷和重氮丙二酸二甲酯等重氮羰基化合物。双（重氮酮）如末端双（重氮乙酰化）烷烃（III1-4：n=6, 8, 10, 12）和间和对双（重氮乙酰基）苯也在类似的反应中得到相应的双恶唑。该反应被解释为通过甜菜碱中间体的逐步机制，由 对重氮羰基化合物的羰基氧的攻击引发。描述了恶唑的发射光谱。
• DE724757
  申请人：——

  公开号：——

  公开（公告）日：——
• Spiro-Aziridine and Bislactam Formation from Bisketene−Imine Cycloadditions
  作者：Annette D. Allen、Jazmin Godoy、Nanyan Fu、Michelle Nagy、Sandra Spadaro、Thomas T. Tidwell、Sinisa Vukovic

  DOI：10.1021/ja077623y

  日期：2008.2.1

  1,2-Bisketenes 6 react with imines PhCH=NAr, (E)-2, forming spiro-aziridines 7. DFT computations indicate that this occurs by nucleophilic attack of the imine on the carbonyl carbon of the more reactive arylketene moiety, followed by cyclization, and not by prior cyclization of the 1,2-bisketene forming a carbene lactone intermediate. Computations also indicate that the previously studied bisketene 10 from benzocyclobutadiene 9 is 4.0 kcal/mol less stable than carbene lactone 12 that would result from cyclization but that the failure to observe 12 results from a lower barrier for 10 to instead revert to 9. 1,2-, 1,3-, and 1,4-Bisketenylbenzenes 16, 19, and 22 react with imines forming bis(beta- lactams), with a preference for formation of mixtures of trans, trans chiral (+/-) and achiral diastereomeric products.
• ——
  作者：A. D. Allen、H. Rangwala、K. Saidi、Th. T. Tidwell、J. Wang

  DOI：10.1023/a:1015053418740

  日期：——

  1,2- and 1,3-Bis(ketenyl)benzenes formed by double dehydrochlorination and by double Wolff rearrangement, respectively, gave ketenyl IR absorption at 2115, and 2122, and 2116 cm(-1), respectively. Reaction of these bisketenes with the aminoxyl radical tetramethylpiperidin-1-yloxyl (TEMPO) gave the corresponding tetraadducts as mixtures of meso- and d,l-isomers. The kinetics of the reaction of 1,3-bis(ketenyl)benzene with TEMPO gave a rate constant comparable to that of the monoketene PhCH=C=O. The reactions proceed by the initial attack of TEMPO on the carbonyl carbon of one ketenyl group followed by fast capture of the intermediate radical by a second TEMPO, and then reaction of the remaining ketene.