cis-2,6-diphenyl-trans-3-isopropylpiperidin-4-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: cis-2,6-diphenyl-trans-3-isopropylpiperidin-4-one
• 英文别名: r-2,c-6-diphenyl-t-3-isopropylpiperidin-4-one；(2R,3S,6S)-2,6-diphenyl-3-propan-2-ylpiperidin-4-one
• 化学式: C₂₀H₂₃NO
• 分子量: 293.409
• InChiKey: LXVGVXNRKSJPEM-SXLOBPIMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-2,6-diphenyl-trans-3-isopropylpiperidin-4-one 在 盐酸 、 sodium azide 、 硫酸 作用下， 以86%的产率得到t-3-isopropyl-2,c-7-diphenylhexahydro-1,4-diazepin-5-one
  参考文献：
  名称：

  Chemistry of N-Nitroso Compounds. 7. Conformational Preferences of Hexahydro-N1,N4- dinitroso-r-2,c-7-diphenyl-1H-1,4-diazepines: Use of Modified 1D HOHAHA and NOE Techniques

  摘要：

  Modified HOHAHA and NOE experiments on three N,N'-dinitrosohexahydrodiazepines, at temperatures ranging from -50 degrees C to +120 degrees C, indicated that each of the title compounds exists as an equilibrium mixture of two families of conformations, the major family consisting of four rotamers and the minor consisting of, possibly, four rotamers resulting from two parallel dynamic processes viz., the restricted N-N rotation at two N-NO bonds and the pseudorotation of the seven-membered ring. The 3-isopropyl derivative 10, at +50 degrees C, exhibited only four resonances for each kind of proton/carbon, indicating that the rate of pseudorotation is fast compared to the NMR time scale. The H-1 resonances, broad at room temperature, became decoalesced at -50 degrees C as a result of the slow pseudorotation process. In all the three dinitroso compounds, of the two sets of twist-chair conformers, the major rotamers (similar to 95%) have the alkyl group (at C3) axially disposed while the minor rotamers have quasiequatorial alkyl groups. On the other hand, the alkyl group at C6 of the 3,6-dimethyl derivative 11 adopts equatorial orientation in all its conformers.

  DOI：

  10.1021/jo00128a018
• 作为产物：
  描述：

  2,6-diphenyl-3-propan-2-ylpiperidin-4-one,hydrochloride 在 氨 作用下， 以 水 、 丙酮 为溶剂， 生成 cis-2,6-diphenyl-trans-3-isopropylpiperidin-4-one
  参考文献：
  名称：

  NMR spectral study of some 2r,6c-diarylpiperidin-4-one (3′-hydroxy-2′-naphthoyl)hydrazones with special reference to γ-syn effect

  摘要：

  H-1 and C-13 NMR spectra have been recorded for 2r,6c-diarylpiperidin-4-one (3'-hydroxy-2'-naphthoyl)hydrazones 10-17 and 3,3-dimethyl-2r,6c-bis(p-methoxyphenyl)piperidin-4-one (5). For selected compounds 20 NMR spectra have been recorded. The spectral data along with those reported for related compounds are used to study the effect of a heteroatom X on the C-13 chemical shift of a gamma-carbon with X C-alpha C-beta C-gamma torsional angle close to 0 degrees, termed as gamma-syn effect. Also gamma-gauche and delta-effects of the alkyl groups at C-3 on the carbons of the aryl group at C-2 have been studied. The chemical shifts for the naphthalene ring are in accord with the mesomeric and steric effects of the carbonyl and hydroxy groups. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.saa.2010.09.015

文献信息

• Conformational analysis of 2,6-diarylpiperidin-4-one hydrazones by X-ray diffraction and NMR spectroscopy
  作者：C. Sankar、S. Umamatheswari、K. Pandiarajan

  DOI：10.1016/j.molstruc.2014.10.015

  日期：2015.3

  derived from the condensation of 3t-alkyl-2r,6c-diarylpiperidin-4-ones with isoniazid (INH) is reported. Newly synthesized compounds have been characterized by using elemental analysis, IR, 1H, 13C and 2D NMR spectral analysis. Moreover, representative crystal structure of 3,3-dimethyl-2r,6c-diarylpiperidin-4-one N-isonicotinoylhydrazone has been determined by X-ray diffraction analysis. NMR data revealed

  摘要 由 3t-烷基-2r,6c-diarylpiperidin-4-ones 与异烟肼 (INH) 缩合得到的一系列新的 3t-烷基-2r,6c-diarylpiperidin-4-one N-异烟酰腙 (12-22) 是报道。新合成的化合物已通过元素分析、IR、1H、13C 和 2D NMR 光谱分析进行了表征。此外，3,3-二甲基-2r,6c-diarylpiperidin-4-one N-异烟酰腙的代表性晶体结构已通过 X 射线衍射分析确定。核磁共振数据显示，在所有情况下都形成了两种几何异构体（E 和 Z），并且哌啶环采用椅子构象。而在固态下，化合物在 CN 键周围具有 E 构型。这些结论也得到了化合物 16 的 X 射线数据的证实。
• Facile synthesis of N-benzylated 3-alkyl-2,6-diarylpiperidin-4-ones: Stereochemical investigation by 1D/2D NMR and single-crystal XRD
  作者：Someshwar D. Dindulkar、Paramasivam Parthiban、Vedavati G. Puranik、Yeon Tae Jeong

  DOI：10.1016/j.molstruc.2010.12.054

  日期：2011.3

  1H and 13C NMR spectral studies. Of them, the 1-benzyl-3-ethyl-2,6-diphenylpiperidin-4-one 22 was completely characterized by 2D NMR techniques such as 1H 1H COSY, 1H 13C COSY and NOESY to assign the signals, unambiguously. The proton coupling constants and NOE correlations provided the complete stereochemistry of 22, which is further witnessed by its single-crystal XRD analysis. The NMR and XRD studies

  摘要 以 87-92% 的高产率方便地合成了一系列 13 个 1-benzyl-3-alkyl-2,6-diarylpiperidin-4-ones 14-26。为了找到对哌啶酮立体化学的影响，除了 N-苄基化之外，还引入了 C-3 上的甲基/乙基/异丙基和 C-2/C-6 上苯环上的卤素/烷基/烷氧基/苄氧基。所有合成的化合物均通过质量、1H 和 13C NMR 光谱研究进行表征。其中，1-benzyl-3-ethyl-2,6-diphenylpiperidin-4-one 22 通过 1H 1H COSY、1H 13C COSY 和 NOESY 等 2D NMR 技术完全表征，明确分配信号。质子耦合常数和 NOE 相关性提供了 22 的完整立体化学，其单晶 XRD 分析进一步证明了这一点。NMR 和 XRD 研究表明，化合物 22 以椅子构象存在，所有取代基在溶液和固态下均呈赤道取向。根据它们的邻位偶联常数，所有化合物
• Synthesis of polyfunctionalized piperidone oxime ethers and their cytotoxicity on HeLa cells
  作者：Paramasivam Parthiban、Ramjee Pallela、Se-Kwon Kim、Dong Ho Park、Yeon Tae Jeong

  DOI：10.1016/j.bmcl.2011.09.063

  日期：2011.11

  the phenyl at C-2 and C-6 in association with/without methyl substituent on the secondary amino group and methyl/ethyl/isopropyl substituents on the active methylene centers. Regardless of their substitution all compounds predominantly exist in the chair conformation except 3m, which adopts a twist-boat conformation. All the synthesized compounds were evaluated for their in vitro antiproliferative activity

  合成了一系列二十个2,6-二芳基哌啶-4-一O-甲基肟，在C-2和C-6的苯基的各个位置上都有氟/氯/溴/甲基/甲氧基/乙氧基/异丙基取代基，与/在仲氨基上没有甲基取代基，在活性亚甲基中心上没有甲基/乙基/异丙基取代基。不论它们的取代方式是什么，所有化合物都主要存在于椅子构象中，除了3m，它采用的是扭曲船构型。评价所有合成的化合物对人宫颈癌（HeLa）细胞系的体外抗增殖活性。通过用MTT测定法测量处理24小时后的活细胞数来确定测试化合物的细胞毒性。初步的SAR结果表明，一些铅分子3c-f，3j-k，4d-g和4i具有对哌啶酮药效团进一步结构优化的范围，以促进抗癌药物合成的发展。
• Effects of protonation and co-anion on the ¹ H and ¹³ C chemical shifts of 2<i>r</i> ,6<i>c</i> - diphenylpiperidin-4-ones: evidence for the formation of ion pair
  作者：V. Vimalraj、K. Pandiarajan

  DOI：10.1002/mrc.2814

  日期：2011.10

  recorded. In DMSO-d(6) the protons of the piperidine ring and the ortho protons of the phenyl groups are markedly deshielded due to protonation. Protonation shields all the carbons of the piperidine ring and the ipso carbons of the phenyl groups markedly but deshields the other aromatic carbons slightly. The deshieldings on H-3a, H-5a and the ortho protons of the phenyl groups are less in the nitrate

  已经记录了2r，6c-二苯基哌啶-4-酮（1a），3t-烷基-2r，6c-二苯基哌啶-4-酮1b-d，3t-烷基-2r的（1）H和（13）C NMR光谱DMSO-d中的，6c-二苯基-4-氧代哌啶鎓硝酸盐2b和2d，3t-烷基-2r，6c-二苯基哌啶-4-酮盐酸盐3a-c和3t-甲基-2r，6c-二苯基-4-氧代哌啶鎓苦味酸盐4b （6）。对于1b，2b和3b，也已在CH（3）OD中记录了（1）H和（13）C NMR光谱。对于1b，1d，2b，2d，3b和4b，还记录了2D光谱。在DMSO-d（6）中，哌啶环的质子和苯基的邻位质子由于质子化而显着脱保护。质子化显着地屏蔽了哌啶环的所有碳和苯基的ipso碳，但略微屏蔽了其他芳族碳。H-3a上的屏蔽 硝酸盐和苦味酸中的H-5a和苯基的邻质子比相应的盐酸盐中的H-5a和苯基的质子少。对（13）C化学位移的影响不受共阴离子的影响。这些观察结果表明，
• Synthesis, spectral and conformational studies of some N-arylsulfonyl-t(3)-isopropyl-r(2),c(6)-diarylpiperidin-4-ones
  作者：A. Manimekalai、S. Sivakumar

  DOI：10.1002/mrc.2829

  日期：——

  preferences of 1-8 have been discussed on the basis of the coupling constants, and they suggest normal chair conformation with equatorial orientations of all the substituents in 1-8. The preferred conformation of aryl sulfonyl group at nitrogen and isopropyl group at C-3 was determined theoretically using density functional calculations.

  合成了一系列N-芳基磺酰基-t（3）-异丙基-r（2），c（6）-二芳基哌啶-4-酮1-8，并通过（1）H，（13）C NMR，2D明确表征-COSY和HSQC NMR光谱。已经基于偶联常数讨论了1-8的构象偏好，并且它们暗示了具有1-8的所有取代基的赤道取向的正常椅子构象。理论上使用密度泛函计算确定在氮上的芳基磺酰基和在C-3上的异丙基的优选构象。