7-phenyl-1,6-diazabicyclo<4.3.0>nona-7-dien-9-one | 141991-04-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 7-phenyl-1,6-diazabicyclo<4.3.0>nona-7-dien-9-one
• 英文别名: 3-phenyl-5,8-dihydro-1H-pyrazolo[1,2-a]pyridazin-1-one；1-Phenyl-5,8-dihydropyrazolo[1,2-a]pyridazin-3-one
• CAS: 141991-04-0
• 化学式: C₁₃H₁₂N₂O
• 分子量: 212.251
• InChiKey: FRIVVCGKDVBJNJ-UHFFFAOYSA-N

物化性质

• 沸点：
  351.1±52.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  23.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  7-phenyl-1,6-diazabicyclo<4.3.0>nona-7-dien-9-one 在 platinum(IV) oxide 、 palladium on activated charcoal 、 Raney-Ni (W-7) 盐酸 、 氢氧化钾 、 氢气 、 sodium ethanolate 、 对甲苯磺酸 作用下， 以 甲醇 、 乙醇 、 溶剂黄146 、 xylene 、 苯 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 36.0h， 生成 2-phenyl-1,5,9-triazacyclotridecan-4-one
  参考文献：
  名称：

  Synthesis of the spermidine alkaloid (±)-N-acetyl-N(1)-deoxymayfoline

  摘要：

  The total synthesis of the spermidine alkaloid (+/-)-N(1)-acetyl-N(1)-deoxymayfoline ((+/-)-1) was achieved by expansion of rings. The 5-membered cyclic compound 2 was fused with butadiene by intermolecular Diels-Alder cycloaddition. The resulting 7-phenyl-1,6-diazabicyclo[4.3.0]nona-3,7-dien-9-one (4) was reductively cleaved with Raney-Ni in alcoholic KOH to afford the mono-cyclic lactam 6. This was selectively alkylated in high yields to the cyano derivative 7. Reduction of the nitrile group to the amine derivative 8 went smoothly by use of Adam's catalyst in the presence of acid. Intramolecular transamidation was then accomplished by acid catalysis with TsOH to furnish the 13-membered diazalactam 9. The synthesis of (+/-)-1 was completed by the selective acetylation of the more nucleophilic amino group.

  DOI：

  10.1016/s0040-4020(01)92268-9
• 作为产物：
  描述：

  N-(2,5-dihydro-1H-pyrrol-1-yl)-3-phenylpropiolamide 在 2,9-二甲基-4,7二苯基-1,10-菲啰啉 、 copper(ll) bromide 作用下， 以 氯苯 为溶剂， 反应 0.5h， 以90%的产率得到7-phenyl-1,6-diazabicyclo<4.3.0>nona-7-dien-9-one
  参考文献：
  名称：

  铜催化顺序环化/炔化肼的迁移，用于环扩环NN熔融吡唑啉酮的构建。

  摘要：

  开发了铜催化的酰肼的连续环化/迁移反应，用于合成环扩环的N-N稠合吡唑啉酮。对照实验表明，铜-配体络合物在反应中起重要作用。该方法具有广泛的应用范围，包括一定的官能团耐受性以及亲核加成/ 1,3-迁移/正式的1,2-迁移序列。由于高产率和原子经济性，该协议提供了简单的操作并减少了浪费。N–N融合的吡唑啉酮的合成效用也通过进一步的转化得到了证明。

  DOI：

  10.1021/acs.orglett.0c02378

文献信息

• Copper-Catalyzed Sequential Cyclization/Migration of Alkynyl Hydrazides for Construction of Ring-Expanded N–N Fused Pyrazolones
  作者：Keiji Konishi、Motohiro Yasui、Hitomi Okuhira、Norihiko Takeda、Masafumi Ueda

  DOI：10.1021/acs.orglett.0c02378

  日期：2020.9.4

  copper-catalyzed sequential cyclization/migration reaction of alkynyl hydrazides for the synthesis of ring-expanded N–N fused pyrazolones was developed. Control experiments indicate that the copper–ligand complex plays an essential role in the reaction. This approach features a broad scope including some functional group tolerance as well as a nucleophilic addition/1,3-migration/formal 1,2-migration sequence. This

  开发了铜催化的酰肼的连续环化/迁移反应，用于合成环扩环的N-N稠合吡唑啉酮。对照实验表明，铜-配体络合物在反应中起重要作用。该方法具有广泛的应用范围，包括一定的官能团耐受性以及亲核加成/ 1,3-迁移/正式的1,2-迁移序列。由于高产率和原子经济性，该协议提供了简单的操作并减少了浪费。N–N融合的吡唑啉酮的合成效用也通过进一步的转化得到了证明。
• Synthesis of the spermidine alkaloid (±)-N-acetyl-N(1)-deoxymayfoline
  作者：Bassem F. Tawil、Armin Guggisberg、Manfred Hesse

  DOI：10.1016/s0040-4020(01)92268-9

  日期：1992.1

  The total synthesis of the spermidine alkaloid (+/-)-N(1)-acetyl-N(1)-deoxymayfoline ((+/-)-1) was achieved by expansion of rings. The 5-membered cyclic compound 2 was fused with butadiene by intermolecular Diels-Alder cycloaddition. The resulting 7-phenyl-1,6-diazabicyclo[4.3.0]nona-3,7-dien-9-one (4) was reductively cleaved with Raney-Ni in alcoholic KOH to afford the mono-cyclic lactam 6. This was selectively alkylated in high yields to the cyano derivative 7. Reduction of the nitrile group to the amine derivative 8 went smoothly by use of Adam's catalyst in the presence of acid. Intramolecular transamidation was then accomplished by acid catalysis with TsOH to furnish the 13-membered diazalactam 9. The synthesis of (+/-)-1 was completed by the selective acetylation of the more nucleophilic amino group.