5,7-dihydro-1,5,11-trimethyl-6H-dibenzocyclohepten-6-one | 106863-59-6

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 5,7-dihydro-1,5,11-trimethyl-6H-dibenzocyclohepten-6-one
• 英文别名: 3,8,15-Trimethyltricyclo[9.4.0.02,7]pentadeca-1(15),2,4,6,11,13-hexaen-9-one；3,8,15-trimethyltricyclo[9.4.0.02,7]pentadeca-1(15),2,4,6,11,13-hexaen-9-one
• CAS: 106863-59-6
• 化学式: C₁₈H₁₈O
• 分子量: 250.34
• InChiKey: HPAXZPPUVDZQBP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5,7-dihydro-1,5,11-trimethyl-6H-dibenzocyclohepten-6-one 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 1.0h， 生成 1,5,11-Trimethyl-6,7-dihydro-5H-dibenzo[a,c]cyclohepten-6-ol
  参考文献：
  名称：

  Stereodependence of the Effect of α Substituents on the Face Reactivity of Conformationally Rigid Ketones toward Metal Hydrides. Is There an Antiperiplanar (Cieplak) Effect?

  摘要：

  The relative rates of hydride addition to the carbonyl group of the conformationally fixed bridged biaryl ketone, 1, and its alpha derivatives bearing methyl, methylthio, methoxy, chloro, and fluoro substituents in axial-like and equatorial-like orientations have been measured for three different reactions. The derived rate constants were partitioned, on the basis of diastereoselectivity, to provide reactivities for each face antiperiplanar to the axial substituents and anticlinal to the equatorial substituents. These face reactivities gave reasonably linear correlations with the inductive substituent parameter, sigma(I). The strength of the inductive effects as indicated by the slopes of the Taft plots were large and positive, small and positive, and negative for the reductions involving lithium aluminum hydride, sodium borohydride, and triethylsilane, respectively. The substituent effects on face reactivity and their stereodependencies failed to follow either the theory of Cieplak or that of Anh. The major influences of substituents can be explained on the basis of through-bond interactions with the transition state and the differences between axial and equatorial effects on electrostatic (through-space) interactions with the transition state.

  DOI：

  10.1021/jo970428p
• 作为产物：
  描述：

  4',1'-Dimethyl-1,2,3,4-dibenzylcyclohepta-1,3-dien-6-on 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 11.0h， 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

文献信息

• Antiperiplanar effect in 1,2-asymmetric induction
  作者：Robert R. Fraser、Maria Stanciulescu

  DOI：10.1021/ja00239a054

  日期：1987.3

  On apporte la preuve que l'interaction n-σ + entre le nucleophile (eau) et une liaison C-C antiperiplanaire est au moins 1,9 kcal/mol plus forte que celle avec une liaison C-H antiperiplanaire. Ceci est en accord avec les calculs theoriques de Anh et Eisenstein et le modele de Felkin pour l'induction asymetrique-1,2

  在 apporte la preuve que l'interaction n-σ + entre le le nucleophile (eau) et une liaison CC antiperiplanaire est au moins 1,9 kcal/mol plus forte que celle avec une liaison CH antiperiplanaire。Ceci est en Agreement avec les calculs theoriques de Anh et Eisenstein et le modele de Felkin pour l'induction asymetrique-1,2
• Stereodependence of the Effect of α Substituents on the Face Reactivity of Conformationally Rigid Ketones toward Metal Hydrides. Is There an Antiperiplanar (Cieplak) Effect?
  作者：Robert R. Fraser、Neil C. Faibish、Fanzuo Kong、Krzysztof Bednarski

  DOI：10.1021/jo970428p

  日期：1997.9.1

  The relative rates of hydride addition to the carbonyl group of the conformationally fixed bridged biaryl ketone, 1, and its alpha derivatives bearing methyl, methylthio, methoxy, chloro, and fluoro substituents in axial-like and equatorial-like orientations have been measured for three different reactions. The derived rate constants were partitioned, on the basis of diastereoselectivity, to provide reactivities for each face antiperiplanar to the axial substituents and anticlinal to the equatorial substituents. These face reactivities gave reasonably linear correlations with the inductive substituent parameter, sigma(I). The strength of the inductive effects as indicated by the slopes of the Taft plots were large and positive, small and positive, and negative for the reductions involving lithium aluminum hydride, sodium borohydride, and triethylsilane, respectively. The substituent effects on face reactivity and their stereodependencies failed to follow either the theory of Cieplak or that of Anh. The major influences of substituents can be explained on the basis of through-bond interactions with the transition state and the differences between axial and equatorial effects on electrostatic (through-space) interactions with the transition state.
• Experimental and theoretical studies of acid-catalyzed oxygen-18 exchange rates of conformationally rigid ketones. Is the antiperiplanar effect important?
  作者：Robert R. Fraser、Fanzuo Kong、Maria Stanciulescu、Yun Dong Wu、K. N. Houk

  DOI：10.1021/jo00068a044

  日期：1993.7

  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.