N-benzoyl-3,4-dihydro-1H-2,1-benzoxazine | 95207-34-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并恶嗪类
• 英文名称: N-benzoyl-3,4-dihydro-1H-2,1-benzoxazine
• 英文别名: Cupioyrnnuvjae-uhfffaoysa-；3,4-dihydro-2,1-benzoxazin-1-yl(phenyl)methanone
• CAS: 95207-34-4
• 化学式: C₁₅H₁₃NO₂
• 分子量: 239.274
• InChiKey: CUPIOYRNNUVJAE-UHFFFAOYSA-N

物化性质

• 熔点：
  149-151 °C
• 沸点：
  363.7±45.0 °C(Predicted)
• 密度：
  1.224±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-benzoyl-3,4-dihydro-1H-2,1-benzoxazine 反应 2.0h， 生成 N-benzoyl-2-methoxymethylaniline
  参考文献：
  名称：

  Rearrangement of N-acyl-3,4-dihydro-1H-2,1-benzoxazines to 2-substituted-4H-3,1-benzoxazines through a retro-Diels–Alder extrusion of formaldehyde

  摘要：

  N-Acyl-3,4-dihydro-1H-2,1-benzoxazines (3) undergo a thermal decomposition involving loss of formaldehyde in a retro-Diels-Alder reaction. The resultant N-acylazaxylylenes dagger (4) undergo a 6 pi electrocyclisation to give 2-substituted-4H-3, 1-benzoxazines (5) rather than a 4 pi electrocyclisation to give the N-acyl-1,2-dihydrobenzazetes (6). Compounds 5 have been fully characterised spectroscopically and their data is inconsistent with that reported previously by other workers for what are purported to be the same compounds. 2-Methyl-4H-3,1-benzoxazine (5b) and other 2-alkyl-substituted compounds undergo facile hydrolysis to o-aminobenzyl esters (9) which rearrange to the thermodynamically more stable o-hydroxymethylanilides (10). 2-Phenyl-4H-3,1-benzoxazine (5a) is relatively stable to hydrolysis but undergoes a novel photochemical ring opening (> 254 nm) to give the N-benzoylazaxylylene (12) which can be trapped with alcohols giving o'-alkoxymethylbenzanilides (11). In cyclohexanol at 160 degrees C, the intermediate in the thermal rearrangement of 3a to 5a, N-benzoylazaxylylene (12), was trapped as o'-cyclohexyloxymethylbenzanilide (11b). The rearrangements in mesitylene are unimolecular with activation energies of 35, 37 and 42 kcal mol(-1)double dagger for 3a; 3c and 3d,.respectively. The extrusion and electrocyclisation reaction pathways for N-acetyl-3,4-dihydro-2, 1-benzoxazine (3b) have been modelled using AM1 molecular orbital theory which predicts both a non-synchronous transition state for the retro-Diels-Alder reaction and the preferred mode of ring closure to be the 6 pi rather than the 4 pi electrocyclisation.

  DOI：

  10.1039/p29960001367
• 作为产物：
  描述：

  O-2-phenylethyl benzohydroxamate 在 次氯酸叔丁酯 、 silver perchlorate 作用下， 以 苯 为溶剂， 反应 5.0h， 生成 N-benzoyl-3,4-dihydro-1H-2,1-benzoxazine
  参考文献：
  名称：

  Glover, Stephen A.; Goosen, Andre; McCleland, Cedric W., Journal of the Chemical Society. Perkin transactions I, 1984, # 10, p. 2255 - 2260

  摘要：

  DOI：

文献信息

• N-alkoxy-n-acylnitrenium ions in intramolecular aromatic addition reactions
  作者：Stephen A. Glover、Andre Goosen、Cedric V. McClei、Johan L. Schoonraad

  DOI：10.1016/s0040-4020(01)81665-3

  日期：——

  solvents. These intermediates readily cyclise onto aromatic nuclei on alkozy side-chains to give benzoxazines and benzoxazepines and on the acyl side-chains to give γ, δ and ϵ benzolactams. Spirane products are formed by ipso addition When a 4-methoxy substituent ia present on the side-chain aromatic rings. The yields and regioselectivities of these reactions have been ascribed to different transition structures

  N-烷氧基-N-酰基硝鎓离子是通过在醚溶剂中用银离子处理N-烷氧基-N-氯酰胺类生成的。这些中间体很容易环化到醇酸侧链上的芳香核上，得到苯并恶嗪和苯并x氮平，以及酰基侧链上的γ，δ和ϵ苯并内酰胺。当在侧链芳环上存在4-甲氧基取代基时，通过ipso加成形成尖晶石产物。这些反应的产率和区域选择性归因于不同的过渡结构，用于环化到分别涉及胞外和环内N-0π键的酰基和烷氧基侧链上。从MNDO计算中获得了这种极高的π键特性的证据，该计算预测π键阶为0.9，旋转势垒为29.7 kcalmol -1
• GLOVER, S. A.;GOOSEN, A.;MCCLELAND, C. W.;SCHOONRAAD, J. L., J. CHEM. SOC. PERKIN TRANS., 1984, N 10, 2255-2260
  作者：GLOVER, S. A.、GOOSEN, A.、MCCLELAND, C. W.、SCHOONRAAD, J. L.

  DOI：——

  日期：——
• GLOVER, STEPHEN A.;GOOSEN, ANDRE;MCCLELAND, CEDRIC W.;SCHOONRAAD, JOHAN L+, TETRAHEDRON, 43,(1987) N 11, 2577-2592
  作者：GLOVER, STEPHEN A.、GOOSEN, ANDRE、MCCLELAND, CEDRIC W.、SCHOONRAAD, JOHAN L+

  DOI：——

  日期：——
• Glover, Stephen A.; Goosen, Andre; McCleland, Cedric W., Journal of the Chemical Society. Perkin transactions I, 1984, # 10, p. 2255 - 2260
  作者：Glover, Stephen A.、Goosen, Andre、McCleland, Cedric W.、Schoonraad, Johan L.

  DOI：——

  日期：——
• Rearrangement of N-acyl-3,4-dihydro-1H-2,1-benzoxazines to 2-substituted-4H-3,1-benzoxazines through a retro-Diels–Alder extrusion of formaldehyde
  作者：Stephen A. Glover、Katherine M. Jones、Ian R. McNee、Colleen A. Rowbottom

  DOI：10.1039/p29960001367

  日期：——

  N-Acyl-3,4-dihydro-1H-2,1-benzoxazines (3) undergo a thermal decomposition involving loss of formaldehyde in a retro-Diels-Alder reaction. The resultant N-acylazaxylylenes dagger (4) undergo a 6 pi electrocyclisation to give 2-substituted-4H-3, 1-benzoxazines (5) rather than a 4 pi electrocyclisation to give the N-acyl-1,2-dihydrobenzazetes (6). Compounds 5 have been fully characterised spectroscopically and their data is inconsistent with that reported previously by other workers for what are purported to be the same compounds. 2-Methyl-4H-3,1-benzoxazine (5b) and other 2-alkyl-substituted compounds undergo facile hydrolysis to o-aminobenzyl esters (9) which rearrange to the thermodynamically more stable o-hydroxymethylanilides (10). 2-Phenyl-4H-3,1-benzoxazine (5a) is relatively stable to hydrolysis but undergoes a novel photochemical ring opening (> 254 nm) to give the N-benzoylazaxylylene (12) which can be trapped with alcohols giving o'-alkoxymethylbenzanilides (11). In cyclohexanol at 160 degrees C, the intermediate in the thermal rearrangement of 3a to 5a, N-benzoylazaxylylene (12), was trapped as o'-cyclohexyloxymethylbenzanilide (11b). The rearrangements in mesitylene are unimolecular with activation energies of 35, 37 and 42 kcal mol(-1)double dagger for 3a; 3c and 3d,.respectively. The extrusion and electrocyclisation reaction pathways for N-acetyl-3,4-dihydro-2, 1-benzoxazine (3b) have been modelled using AM1 molecular orbital theory which predicts both a non-synchronous transition state for the retro-Diels-Alder reaction and the preferred mode of ring closure to be the 6 pi rather than the 4 pi electrocyclisation.

表征谱图