N'-(1,11-Dimethyl-5,7-dihydro-dibenzo[a,c]cyclohepten-6-ylidene)-N,N-dimethyl-hydrazine | 149878-81-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: N'-(1,11-Dimethyl-5,7-dihydro-dibenzo[a,c]cyclohepten-6-ylidene)-N,N-dimethyl-hydrazine
• CAS: 149878-81-9
• 化学式: C₁₉H₂₂N₂
• 分子量: 278.397
• InChiKey: AZQWDGYVFRGTRN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.99
• 重原子数：
  21.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  15.6
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  N'-(1,11-Dimethyl-5,7-dihydro-dibenzo[a,c]cyclohepten-6-ylidene)-N,N-dimethyl-hydrazine 在 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 5,7-dihydro-1,5,11-trimethyl-6H-dibenzocyclohepten-6-one
  参考文献：
  名称：

  Experimental and theoretical studies of acid-catalyzed oxygen-18 exchange rates of conformationally rigid ketones. Is the antiperiplanar effect important?

  摘要：

  The relative rates for the acid-catalyzed addition of (H2O)-H-18 to the carbonyl group of the conformationally fixed bridged biaryl ketone, 1, and several derivatives bearing methyl, chloro, and methoxy substituents in axial-like and equatorial-like orientations have been measured. The effects of axial-versus diaxial-like methyl and chloro substituents produce rate decreases which are consistent with the antiperiplanar (hyperconjugative) interaction proposed by Cieplak; however, the negligible influence of a methoxy group when antiperiplanar is not consistent. Theoretical calculations suggest an unsymmetrical structure for the transition state. On the basis of this structure, the results may be rationalized by a large steric interaction for the first axial methyl or chloro substituent (synperiplanar to the nucleophile) and a small one for the second (antiperiplanar) substituent. An axial methoxy can stabilize the transition state by hydrogen bonding when syn but can only exert the observed small steric retardation in the transition state involving antiperiplanar attack.

  DOI：

  10.1021/jo00068a044
• 作为产物：
  描述：

  4',1'-Dimethyl-1,2,3,4-dibenzylcyclohepta-1,3-dien-6-on 、 偏二甲肼 反应 6.0h， 生成 N'-(1,11-Dimethyl-5,7-dihydro-dibenzo[a,c]cyclohepten-6-ylidene)-N,N-dimethyl-hydrazine
  参考文献：
  名称：

  Experimental and theoretical studies of acid-catalyzed oxygen-18 exchange rates of conformationally rigid ketones. Is the antiperiplanar effect important?

  摘要：

  The relative rates for the acid-catalyzed addition of (H2O)-H-18 to the carbonyl group of the conformationally fixed bridged biaryl ketone, 1, and several derivatives bearing methyl, chloro, and methoxy substituents in axial-like and equatorial-like orientations have been measured. The effects of axial-versus diaxial-like methyl and chloro substituents produce rate decreases which are consistent with the antiperiplanar (hyperconjugative) interaction proposed by Cieplak; however, the negligible influence of a methoxy group when antiperiplanar is not consistent. Theoretical calculations suggest an unsymmetrical structure for the transition state. On the basis of this structure, the results may be rationalized by a large steric interaction for the first axial methyl or chloro substituent (synperiplanar to the nucleophile) and a small one for the second (antiperiplanar) substituent. An axial methoxy can stabilize the transition state by hydrogen bonding when syn but can only exert the observed small steric retardation in the transition state involving antiperiplanar attack.

  DOI：

  10.1021/jo00068a044