| 151114-12-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• CAS: 151114-12-4
• 化学式: C₂₀H₂₈N₂
• 分子量: 296.456
• InChiKey: HGJGUOLOPHWMCI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  在 2,6-二叔丁基吡啶 、 (p-Br-C₆H₄)4N(1+.)*Sb₆^(1-) 作用下， 以 二氯甲烷 为溶剂， 反应 0.01h， 以90%的产率得到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：

  adamantylidene-adamantane triazolinedione addukt 在 nickel(IV) oxide 、 三乙基硼氢化锂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 7.0h， 生成
  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

文献信息

• 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.