4-[2-(benzylamino)ethyl]-2(1H)-quinolone | 100342-54-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 4-[2-(benzylamino)ethyl]-2(1H)-quinolone
• 英文别名: 4-[2-(benzylamino)ethyl]-1H-quinolin-2-one
• CAS: 100342-54-9
• 化学式: C₁₈H₁₈N₂O
• 分子量: 278.354
• InChiKey: ZZGSPAMESMAAQC-UHFFFAOYSA-N

物化性质

• 熔点：
  132-133 °C(Solv: water (7732-18-5); ethyl ether (60-29-7))
• 沸点：
  496.7±45.0 °C(Predicted)
• 密度：
  1.142±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.86
• 重原子数：
  21.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  44.89
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  4-[2-(benzylamino)ethyl]-2(1H)-quinolone 在 lithium aluminium tetrahydride 、 三乙胺 、 三氟乙酸 作用下， 以 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 0.5h， 生成 (+/-)-(1R,2aS,8bS)-8b-[2-(benzylamino)ethyl]-1-(hydroxymethyl)-1-methyl-2,2a,4,8b-tetrahydrocyclobuta[c]quinoline-3(1H)-one
  参考文献：
  名称：

  Photochemistry of 4-(2‘-Aminoethyl)quinolones:  Enantioselective Synthesis of Tetracyclic Tetrahydro-1aH-pyrido[4‘,3‘:2,3]- cyclobuta[1,2-c] Quinoline-2,11(3H,8H)-diones by Intra- and Intermolecular [2 + 2]-Photocycloaddition Reactions in Solution

  摘要：

  Enantioselective [2 + 2]-photocycloaddition reactions on 4-(2'-aminoethyl) quinolones in solution were studied using the enantiomerically pure complexing agent 1 as source of chirality. The intermolecular reactions of fully N-protected substrates 5a-5c with different 2-alkyl-substituted acrylates 12-15 represent the first systematic study on the diastereoselectivity of their intermolecular [2 + 2]-photocycloadditions to unsymmetrically 1,1-disubstituted olefins (75-91% yield, d.r. = 58/42-95/5). N-Benzylic-protected photoproducts exo-16a/b-19a/b could easily be converted into lactams 20a/b-23a/b by a sequence of Boc deprotection and thermal lactamization (74-98% yield). Identical products 20a-22a were directly accessible by the intramolecular [ 2 + 2]-photocycloaddition of acrylic acid amides 2-4 (41-61% yield). The suitability of both pathways for an enantioselective reaction variant was proven (70-92% ee). Thus, tetracyclic lactams possessing the carbon framework C were obtained with good yields and enantio-selectivities of up to 92% ee in intramolecular reactions. Comparative investigation of both routes showed that quinolone dimerization was the single most decisive factor preventing a complete chirality transfer. Functional group manipulations were successfully conducted with the primary photoproduct exo-17a. Finally, a new and unexpected type of benzylic hydrogen abstraction-radical cyclization reaction was discovered for substrate 5a, which explains the photochemical instability of substrates 2-5 under short wavelength irradiation (lambda = 300 nm).

  DOI：

  10.1021/jo0606608
• 作为产物：
  描述：

  2-羟基-4-甲基喹啉 在 lithium aluminium tetrahydride 、 正丁基锂 、 氯化亚砜 、 氢溴酸 作用下， 反应 4.0h， 生成 4-[2-(benzylamino)ethyl]-2(1H)-quinolone
  参考文献：
  名称：

  Photochemistry of 4-(2‘-Aminoethyl)quinolones:  Enantioselective Synthesis of Tetracyclic Tetrahydro-1aH-pyrido[4‘,3‘:2,3]- cyclobuta[1,2-c] Quinoline-2,11(3H,8H)-diones by Intra- and Intermolecular [2 + 2]-Photocycloaddition Reactions in Solution

  摘要：

  Enantioselective [2 + 2]-photocycloaddition reactions on 4-(2'-aminoethyl) quinolones in solution were studied using the enantiomerically pure complexing agent 1 as source of chirality. The intermolecular reactions of fully N-protected substrates 5a-5c with different 2-alkyl-substituted acrylates 12-15 represent the first systematic study on the diastereoselectivity of their intermolecular [2 + 2]-photocycloadditions to unsymmetrically 1,1-disubstituted olefins (75-91% yield, d.r. = 58/42-95/5). N-Benzylic-protected photoproducts exo-16a/b-19a/b could easily be converted into lactams 20a/b-23a/b by a sequence of Boc deprotection and thermal lactamization (74-98% yield). Identical products 20a-22a were directly accessible by the intramolecular [ 2 + 2]-photocycloaddition of acrylic acid amides 2-4 (41-61% yield). The suitability of both pathways for an enantioselective reaction variant was proven (70-92% ee). Thus, tetracyclic lactams possessing the carbon framework C were obtained with good yields and enantio-selectivities of up to 92% ee in intramolecular reactions. Comparative investigation of both routes showed that quinolone dimerization was the single most decisive factor preventing a complete chirality transfer. Functional group manipulations were successfully conducted with the primary photoproduct exo-17a. Finally, a new and unexpected type of benzylic hydrogen abstraction-radical cyclization reaction was discovered for substrate 5a, which explains the photochemical instability of substrates 2-5 under short wavelength irradiation (lambda = 300 nm).

  DOI：

  10.1021/jo0606608

文献信息

• Stereoselective Intra- and Intermolecular [2+2] Photocycloaddition Reactions of 4-(2′-Aminoethyl)quinolones
  作者：Thorsten Bach、Sebastian Brandes、Philipp Selig

  DOI：10.1055/s-2004-834817

  日期：——

  The 4-(2'-aminoethyl)quinolones 6, 8 and 9 were prepared starting from 4-(2'-bromoethyl)quinolone (4) in two steps and overall yields of 56-93%. They underwent inter- and intramolecular [2+2] photocycloaddition reactions with an alkene to provide the cyclobutanes 1-3 in racemic form (61-89% yield). The photochemical reaction proceeded with very good chemo-, regio- and stereoselectivity. It was in one

  4-(2'-氨基乙基)喹诺酮6、8和9以4-(2'-溴乙基)喹诺酮(4)为原料，分两步制备，总产率为56-93%。他们与烯烃进行分子间和分子内 [2+2] 光环加成反应，以提供外消旋形式的环丁烷 1-3（产率 61-89%）。光化学反应以非常好的化学选择性、区域选择性和立体选择性进行。在一种情况下 (8b → 2b) 也进行了对映选择性 (93% ee)。