5-(p-Nitrophenyl)adamantan-2-one | 99766-75-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-(p-Nitrophenyl)adamantan-2-one
• 英文别名: 5-(4-nitrophenyl)adamantan-2-one
• CAS: 99766-75-3
• 化学式: C₁₆H₁₇NO₃
• 分子量: 271.316
• InChiKey: CEBYNSWXWYORTH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.24
• 重原子数：
  20.0
• 可旋转键数：
  2.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  60.21
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  5-(p-Nitrophenyl)adamantan-2-one 在 sodium tetrahydroborate 作用下， 以 异丙醇 为溶剂， 生成 (E)-5-(p-Nitrophenyl)adamantan-2-ol
  参考文献：
  名称：

  Face selection in the reduction of p,p'-disubstituted 5,7-diphenyl-2-adamantanones and hydrolysis of the corresponding 2-adamantyl tosylates

  摘要：

  The reduction of 5,7-diphenyl-2-adamantanone with sodium borohydride in 2-propanol is affected by the introduction of a p-nitro substituent in one of the rings: the E-alcohol is obtained in small but easily measurable excess of 1.30:1. Conversely, the introduction of a p-amino group leads to an excess of Z-isomer by roughly the same factor (1.28). When both substituents are present, they evidently cooperate to produce a ratio of 1.64. The tosylates of the alcohols were prepared and their solvolysis rates measured in 3% aqueous hexafluoro-2-propanol and compared with those of the parent and p-substituted 5-phenyl-2-adamantyl tosylates. Additivity of substituent effects was again observed, but the p-aminophenyl group in these reactions was deactivating compared to phenyl, presumably due to II-bonding and/or protonation of the amino group in the acidic medium.

  DOI：

  10.1021/jo00080a012
• 作为产物：
  描述：

  5-phenyladamantan-2-one 在 硫酸 、 硝酸 作用下， 反应 0.5h， 生成 5-(p-Nitrophenyl)adamantan-2-one 、 5-(2,4-Dinitrophenyl)adamantan-2-one
  参考文献：
  名称：

  Face selection in the reduction of p,p'-disubstituted 5,7-diphenyl-2-adamantanones and hydrolysis of the corresponding 2-adamantyl tosylates

  摘要：

  The reduction of 5,7-diphenyl-2-adamantanone with sodium borohydride in 2-propanol is affected by the introduction of a p-nitro substituent in one of the rings: the E-alcohol is obtained in small but easily measurable excess of 1.30:1. Conversely, the introduction of a p-amino group leads to an excess of Z-isomer by roughly the same factor (1.28). When both substituents are present, they evidently cooperate to produce a ratio of 1.64. The tosylates of the alcohols were prepared and their solvolysis rates measured in 3% aqueous hexafluoro-2-propanol and compared with those of the parent and p-substituted 5-phenyl-2-adamantyl tosylates. Additivity of substituent effects was again observed, but the p-aminophenyl group in these reactions was deactivating compared to phenyl, presumably due to II-bonding and/or protonation of the amino group in the acidic medium.

  DOI：

  10.1021/jo00080a012

文献信息

• Reduction of 5-p-anilinoadamantan-2-one. A reinvestigation
  作者：Haifang Li、W.J. le Noble

  DOI：10.1016/s0040-4039(00)97629-9

  日期：1990.1

  Revised data are reported which show that π-donor p-substituents in a phenyl ring located in the 5-position of adamantanone can moderate its ability m affect face selection, but cannot reverse it as claimed earlier.

  据报道，修订的数据表明，位于金刚烷酮5-位的苯环上的π-供体p-取代基可以缓和其影响面部选择的能力，但不能像先前所声称的那样逆转它。
• Electrostatic vs Hyperconjugative Effects as Stereoinductive Factors in the Adamantane Ring System
  作者：William Adcock、Jason Cotton、Neil A. Trout

  DOI：10.1021/jo00086a044

  日期：1994.4

  A series of 5-substituted (X) adamant-2-yl derivatives 1 (Y = O and CH2) have been synthesized and their C-13 NMR spectra measured. The carbonyl and ethylenic C-13 substituent chemical shifts (SCS) are shown to be proportional to substituent field effects (sigma(F)). By use of the polar field susceptibility parameter (rho(F)) for the former shifts, polar field parameters (Delta sigma(F) values) have been calculated for a series of p-SC6H4 substituents. II-Facial diastereoselectivities for the reduction (NaBH4) and methylation (MeLi) of para-substituted (S) phenyl derivatives of 1 (Y = O; X = p-SC6H4) and, as well, for the hydrochlorination of similarly substituted alkenes 1 (Y = CH2; X = p-SC6H4) have been determined and correlated successfully against polar field parameters (Delta sigma(F) values). The slopes of these plots (log(10)[Z]/[E] vs Delta sigma(F)) provide polar-field susceptibility parameters (rho(FS)) which have been deployed to calculate appropriate diastereoselectivities of the aforementioned reactions for 5-substituted (X) derivatives of 1 (Y = O and CH2) in general. A comparison of these calculated values with observed diastereoselectivities for a wide range of substituents reveals that direct electrostatic field interactions play a dominant role in governing the phenomena for nucleophilic additions of the ketones 1 (Y = O) and that it is unnecessary to invoke Cieplak's transition-state hyperconjugative model. This appears to be also the case for electrophilic additions to 1 (Y = CH2) not involving final nucleophilic capture of an intermediate cation. However, hyperconjugation clearly impinges significantly on II-facial diastereoselectivity for those reactions mediated by 2-adamantyl cations. New results for methyl-substituted derivatives of 1 (Y = O and CH2, X = CH3) reinforces the sigma-electron-withdrawing character of this substituent with respect to gamma- and delta-interactions in the neutral ground-state and cationic species.
• Transmission of polar substituent effects in the adamantane ring system as monitored by 19F NMR: hyperconjugation as a stereoinductive factor
  作者：William Adcock、Neil A. Trout

  DOI：10.1021/jo00010a012

  日期：1991.5

  A limited series of (E)- and (Z)-5-substituted adamant-2-yl fluorides 8 and 9, respectively, has been synthesized and characterized, and the F-19 chemical shifts have been measured in several solvents. A wide range of F-19 substituent chemical shifts (SCS, ppm) are obtained for the former system (ca. 9.1 (c-C6H12), 9.6 (CDCl3), and 11.8 (HFIP)) compared to the latter (ca. 0.6 (c-C6H12), 0.7 (CDCl3), and 2.3 (HFIP)). Factorization of the F-19 SCS into polar field (rho-F-sigma-F) and residual contributions (F-19 SCS - rho-F-sigma-F) reveals the predominance of the latter solvent-independent component for the E fluorides (8). Comparison of 8 with a similar dissection of the F-19 SCS of 4-substituted bicyclo[2.2.2]oct-1-yl fluorides 2 strongly suggests that the origin of the large residual contributions for 8 is "through-three-bond" electron delocalization or double hyperconjugation. The importance of this long-range electronic mechanism as a factor governing pi-facial diastereoselection in 2,5-disubstituted adamantanes (1) is discussed. In particular, the assertion that the p-anilino substituent is an electron donor group at remote probe or reaction sites in saturated systems is addressed.