rac-2-(3-tosyl-1,2,3,4-tetrahydroquinazolin-2-yl)quinolin-8-ol | 1355955-70-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: rac-2-(3-tosyl-1,2,3,4-tetrahydroquinazolin-2-yl)quinolin-8-ol
• 英文别名: 2-(3-tosyl-1,2,3,4-tetrahydroquinazolin-2-yl)quinolin-8-ol；2-[3-(4-methylphenyl)sulfonyl-2,4-dihydro-1H-quinazolin-2-yl]quinolin-8-ol
• CAS: 1355955-70-2
• 化学式: C₂₄H₂₁N₃O₃S
• 分子量: 431.515
• InChiKey: GJBHCMCBPTXRNI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  31
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  90.9
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  rac-2-(3-tosyl-1,2,3,4-tetrahydroquinazolin-2-yl)quinolin-8-ol 在 水 、 palladium diacetate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 24.0h， 生成 3-tosyl-1,2,3,4-tetrahydroquinazoline
  参考文献：
  名称：

  Serendipitous formation of 3-tosyl-1,2,3,4-tetrahydroquinazoline

  摘要：

  通过实验和计算研究阐明了 Pd(LBS)·3H2O 的甲醇母液中 3-甲苯磺酰基-1,2,3,4-四氢喹唑啉的形成过程，其中 LBS 是亚胺配体 N- 的双阴离子形式{2-[(8-羟基喹啉-2-基)亚甲基氨基]苄基}-4-甲基苯磺酰胺。实验研究表明，四氢喹唑啉是由2-甲苯磺酰氨基甲基苯胺与甲醛缩合而得，甲醛分别来自亚胺配体LBS的酸催化水解和甲醇的金属介导的有氧氧化。计算研究揭示了反应途径中的相关中间体和关键步骤。

  DOI：

  10.1039/c3nj00658a
• 作为产物：
  描述：

  2-tosylaminomethylaniline 、 8-羟基喹啉-2-甲醛 以 氯仿 为溶剂， 反应 4.5h， 以88%的产率得到rac-2-(3-tosyl-1,2,3,4-tetrahydroquinazolin-2-yl)quinolin-8-ol
  参考文献：
  名称：

  Metal-Assisted Ring-Closing/Opening Process of a Chiral Tetrahydroquinazoline

  摘要：

  The ring-chain tautomerism of a 2-aryl-1,2,3,4-tetrahydroquinazo-line has been exploited to induce reversible changes in the aminal-imine equilibrium, as desired, by coordination of a suitable metal ion. This process was studied by NMR and UV-vis spectroscopies, X-ray crystallography, and molecular modeling approach. The results obtained show that the imine H2Li undergoes a selective ring-closing reaction upon complexation with Ni2+. As a result, complexes of the type Ni(HLa)(2) are obtained, whose chirality arises from the chiral ligand H2La and the helicity of the structure. Hence, helical enantiomers form the following racemates: [Delta-C(R,R)N(S,S),Lambda-C(S,S)N(R,R)]-Ni(HLa)(2)center dot 2HOAc and [Delta,Lambda-C(S,R)N(R,S)]-Ni(HLa)(2)center dot 4MeOH. In contrast to the situation observed for Ni2+, the cyclic tautomer of the ligand, H2La, undergoes a selective ring-opening reaction upon complex formation with Pd2+, ultimately yielding Pd(HLi)(2)center dot MeOH, in which the open-chain imine ligand is bidentate through the N,O donor set of the quinoline residue. Density functional theory calculations were conducted to provide insight into the different behavior of both coordinated metals (Ni2+ and Pd2+) and to propose a mechanism for the metal-assisted opening/closing reaction of the tetrahydroquinazoline ring.

  DOI：

  10.1021/ic2017038

文献信息

• Serendipitous formation of 3-tosyl-1,2,3,4-tetrahydroquinazoline
  作者：Jesus Sanmartín-Matalobos、Ana M. García-Deibe、Lucía Briones-Miguéns、Emilio Lence、Concepcion González-Bello、Cristina Portela-García、Matilde Fondo

  DOI：10.1039/c3nj00658a

  日期：——

  Both experimental and computational studies were undertaken to elucidate the formation process of 3-tosyl-1,2,3,4-tetrahydroquinazoline from methanolic mother liquors of Pd(LBS)·3H2O, where LBS is the dianionic form of the imine ligand N-2-[(8-hydroxyquinolin-2-yl)methyleneamino]benzyl}-4-methylbenzenesulfonamide. Experimental studies have shown that the tetrahydroquinazoline is obtained by condensation of 2-tosylaminomethylaniline and formaldehyde, which come from the acid-catalyzed hydrolysis of the imine ligand LBS and metal-mediated aerobic oxidation of methanol, respectively. Computational studies have revealed relevant intermediates and key steps in the reaction pathway.

  通过实验和计算研究阐明了 Pd(LBS)·3H2O 的甲醇母液中 3-甲苯磺酰基-1,2,3,4-四氢喹唑啉的形成过程，其中 LBS 是亚胺配体 N- 的双阴离子形式2-[(8-羟基喹啉-2-基)亚甲基氨基]苄基}-4-甲基苯磺酰胺。实验研究表明，四氢喹唑啉是由2-甲苯磺酰氨基甲基苯胺与甲醛缩合而得，甲醛分别来自亚胺配体LBS的酸催化水解和甲醇的金属介导的有氧氧化。计算研究揭示了反应途径中的相关中间体和关键步骤。
• Structural variety of zinc and copper complexes based on a 2,3-disubstituted 1,2,3,4-tetrahydroquinazoline ligand
  作者：Jesús Sanmartín-Matalobos、Cristina Portela-García、Luis Martínez-Rodríguez、Concepción González-Bello、Emilio Lence、Ana M. García-Deibe、Matilde Fondo

  DOI：10.1039/c2dt30550j

  日期：——

  Zn(HLring)2·2MeOH·0.5H2O shows O,N-donor behaviour of the ring tautomer. The 1,2,3,4-tetrahydroquinazoline undergoes a ring-opening reaction upon formation of phenoxo-bridged dinuclear complexes M2(Lchain)2 in which the chain tautomer is acting as O,N,N,N-donor. The crystal structure of Cu2(Lamide)(Lquinazoline)(MeOH)·2MeOH evidenced the sensitivity of H2Lring to the copper-mediated aerobic oxidation, which results

  2-（3-甲苯磺酰基-1,2,3,4-四氢喹唑啉-2-基）喹啉-8-ol（H 2 L环）的环链互变异构已被用于生产单核复合物或双核。根据需要，通过改变配体的化学计量配合物。Cu 2+和Zn 2+在其单核络合物M（HL环）2中稳定配体的环互变异构形式。Zn（HL环）2 ·2MeOH·0.5H 2 O的结构表征显示了环互变异构体的O，N-供体行为。这1,2,3,4-四氢喹唑啉在形成苯氧基桥联的双核配合物M 2（L链）2时发生开环反应，其中互变异构体充当O，N，N，N供体。Cu 2（L酰胺）（L喹唑啉）（MeOH）·2MeOH的晶体结构证明了H 2 L环对铜介导的需氧氧化的敏感性，这导致了配体的两种衍生物，喹唑啉和酰胺。这喹唑啉配体通过其O，N，N结合位点充当单阴离子并单核化，而酰胺配体通过Cu 2（L酰胺）中的O，N，N，N和O，O结合位点充当三阴离子并成核。L喹唑啉）（MeOH）·2MeOH。
• Tuning the ring-chain tautomerism of a tetrahydroquinazoline/Schiff base system with unexpected methanol oxidation
  作者：Jesús Sanmartín-Matalobos、Cristina Portela-García、Ana M. García-Deibe、Matilde Fondo、Lucía Briones-Miguéns

  DOI：10.1016/j.poly.2013.08.034

  日期：2013.11

  The ring-chain tautomerism of a tetrahydroquinazoline/Schiff base (H2Lgrin/H2Lchain) system can be controlled by metal coordination through varying ligand stoichiometry of the reaction H2L + M-2(+) [H2Lring: 2-(3-tosyl-1,2,3,4-tetrahydroquinazolin-2-yl)quinolin-8-ol; H2Lchain: N-(2-[(8-hydroxyquinolin-2-yl) methyleneamino]benzyl}-4-methylbenzenesulphonamide and M: Co2+ and Cd2+]. The ring tautomer H2Lring undergoes a ring-opening reaction upon formation of dinuclear complexes M-2(L-chain)(2), while Co2+ and Cd2+ stabilise the tetrahydroquinazoline ligand in their mononuclear complexes M(HLring)(2). The detection of 3-tosyl-1,2,3,4-tetrahydroquinazoline on the methanolic mother liquors of Co-2(L-chain)(2) revealed the acid-catalysed hydrolysis of the Schiff base ligand and the cobalt-mediated aerobic oxidation of methanol to formaldehyde. (C) 2013 Elsevier Ltd. All rights reserved.
• Metal-Assisted Ring-Closing/Opening Process of a Chiral Tetrahydroquinazoline
  作者：Ana M. García-Deibe、Jesús Sanmartín-Matalobos、Concepción González-Bello、Emilio Lence、Cristina Portela-García、Luis Martínez-Rodríguez、Matilde Fondo

  DOI：10.1021/ic2017038

  日期：2012.2.6

  The ring-chain tautomerism of a 2-aryl-1,2,3,4-tetrahydroquinazo-line has been exploited to induce reversible changes in the aminal-imine equilibrium, as desired, by coordination of a suitable metal ion. This process was studied by NMR and UV-vis spectroscopies, X-ray crystallography, and molecular modeling approach. The results obtained show that the imine H2Li undergoes a selective ring-closing reaction upon complexation with Ni2+. As a result, complexes of the type Ni(HLa)(2) are obtained, whose chirality arises from the chiral ligand H2La and the helicity of the structure. Hence, helical enantiomers form the following racemates: [Delta-C(R,R)N(S,S),Lambda-C(S,S)N(R,R)]-Ni(HLa)(2)center dot 2HOAc and [Delta,Lambda-C(S,R)N(R,S)]-Ni(HLa)(2)center dot 4MeOH. In contrast to the situation observed for Ni2+, the cyclic tautomer of the ligand, H2La, undergoes a selective ring-opening reaction upon complex formation with Pd2+, ultimately yielding Pd(HLi)(2)center dot MeOH, in which the open-chain imine ligand is bidentate through the N,O donor set of the quinoline residue. Density functional theory calculations were conducted to provide insight into the different behavior of both coordinated metals (Ni2+ and Pd2+) and to propose a mechanism for the metal-assisted opening/closing reaction of the tetrahydroquinazoline ring.