adamantylidene-adamantane triazolinedione addukt | 90461-89-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: adamantylidene-adamantane triazolinedione addukt
• CAS: 90461-89-5
• 化学式: C₂₃H₃₁N₃O₂
• 分子量: 381.518
• InChiKey: ZTYDTYIYASLUEA-UHFFFAOYSA-N

物化性质

• 密度：
  1.39±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  28
• 可旋转键数：
  0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  43.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  adamantylidene-adamantane triazolinedione addukt 在 nickel(IV) oxide 、 2,6-二叔丁基吡啶 、 (p-Br-C₆H₄)4N(1+.)*Sb₆^(1-) 、 三乙基硼氢化锂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 7.01h， 生成 2-(2-adamantylidene)adamantane
  参考文献：
  名称：

  Synthesis and decomposition of two cyclic (four-ring) azo compounds (.DELTA.1-1,2-diazetines)

  摘要：

  The DELTA1-1,2-diazetines 1 and 2 have been synthesized in three steps from N-methyltriazolinedione (MeTAD) and the olefins (adamantylideneadamantane, Ad=Ad, for 1; 7-norbornylidene-7-norbornane for 2). Diazetidine 3 (from Ad=Ad + MeTAD) undergoes ring expansion to a pyrazolidine derivative, 5 (subsequently converted to a novel pyrazoline, cyclic (five-ring) azo compound 6). The structurally-related N-methylaminocarbonyl diazetidine 4 undergoes acid-catalyzed ring contraction to N-aminoaziridine derivative 7a. Compound 7a and the corresponding N-aminoaziridine derivative 7b undergo oxidative ring expansion to afford diazetine 1, accompanied by olefin (Ad=Ad). Efforts to extend this novel synthesis of diazetines to other N-aminoaziridines (8,9a, 9b, 10) were unsuccessful, affording only the deazetation product, olefin. Thermal decomposition of diazetine 1 at 137-degrees-C in dodecane (tl/2 = 1.5 h) proceeds by two paths: ring-opening to adamantanone azine and deazetation to the olefin Ad=Ad; azine/olefin = 1.9/1. For diazetine 2, k(overall) is 60-fold slower than for 1 and azine/olefin = 1/14. Diazetine 1 is rapidly converted to olefin (Ad=Ad) at 25-degrees-C by 10 mol% of Ar3N.+ [(p-BrC6H4)3N.+ SbF6-], thought to occur by an electron transfer chain process; diazetine 2 is inert to these conditions. Relative rates of nitrogen loss for 1, 2, and tetramethyldiazetine (15c) at 137-degrees-C are 1:0.05:3. Some aspects of mechanism of thermal and catalyzed decomposition of diazetines are discussed.

  DOI：

  10.1021/jo00072a021
• 作为产物：
  描述：

  以 氘代氯仿 为溶剂， 生成 adamantylidene-adamantane triazolinedione addukt
  参考文献：
  名称：

  Direct observation of the aziridinium imide intermediates in the reaction of biadamantylidene with triazolinediones

  摘要：

  DOI：

  10.1021/ja00305a050

文献信息

• Reaction of electrophiles with unsaturated systems: triazolinedione-olefin reactions
  作者：Chen Chih Cheng、Catherine A. Seymour、Michael A. Petti、Frederick D. Greene、John F. Blount

  DOI：10.1021/jo00190a014

  日期：1984.8
• Mechanism of triazolinedione-olefin reactions. Ene and cycloaddition
  作者：Catherine A. Seymour、Frederick D. Greene

  DOI：10.1021/ja00540a054

  日期：1980.9
• SEYMOUR C. A.; GREENE F. D., J. AM. CHEM. SOC., 1980, 102, NO 20, 6384-6385
  作者：SEYMOUR C. A.、 GREENE F. D.

  DOI：——

  日期：——
• Synthesis and decomposition of two cyclic (four-ring) azo compounds (.DELTA.1-1,2-diazetines)
  作者：Derk J. Hogenkamp、Frederick D. Greene

  DOI：10.1021/jo00072a021

  日期：1993.9

  The DELTA1-1,2-diazetines 1 and 2 have been synthesized in three steps from N-methyltriazolinedione (MeTAD) and the olefins (adamantylideneadamantane, Ad=Ad, for 1; 7-norbornylidene-7-norbornane for 2). Diazetidine 3 (from Ad=Ad + MeTAD) undergoes ring expansion to a pyrazolidine derivative, 5 (subsequently converted to a novel pyrazoline, cyclic (five-ring) azo compound 6). The structurally-related N-methylaminocarbonyl diazetidine 4 undergoes acid-catalyzed ring contraction to N-aminoaziridine derivative 7a. Compound 7a and the corresponding N-aminoaziridine derivative 7b undergo oxidative ring expansion to afford diazetine 1, accompanied by olefin (Ad=Ad). Efforts to extend this novel synthesis of diazetines to other N-aminoaziridines (8,9a, 9b, 10) were unsuccessful, affording only the deazetation product, olefin. Thermal decomposition of diazetine 1 at 137-degrees-C in dodecane (tl/2 = 1.5 h) proceeds by two paths: ring-opening to adamantanone azine and deazetation to the olefin Ad=Ad; azine/olefin = 1.9/1. For diazetine 2, k(overall) is 60-fold slower than for 1 and azine/olefin = 1/14. Diazetine 1 is rapidly converted to olefin (Ad=Ad) at 25-degrees-C by 10 mol% of Ar3N.+ [(p-BrC6H4)3N.+ SbF6-], thought to occur by an electron transfer chain process; diazetine 2 is inert to these conditions. Relative rates of nitrogen loss for 1, 2, and tetramethyldiazetine (15c) at 137-degrees-C are 1:0.05:3. Some aspects of mechanism of thermal and catalyzed decomposition of diazetines are discussed.
• Direct observation of the aziridinium imide intermediates in the reaction of biadamantylidene with triazolinediones
  作者：Stephen F. Nelsen、Daniel L. Kapp

  DOI：10.1021/ja00305a050

  日期：1985.9