5-Benzyl-5,6,6-trimethyl-2-phenyl-4,5-dihydro-6H-oxazine

• 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: 5-Benzyl-5,6,6-trimethyl-2-phenyl-4,5-dihydro-6H-oxazine
• 英文别名: 5-benzyl-5,6,6-trimethyl-2-phenyl-4H-1,3-oxazine
• 化学式: C₂₀H₂₃NO
• 分子量: 293.409
• InChiKey: AVIWPEOJHHQWAY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 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：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-benzyl-1-benzoyl-2-tert-butylaziridine 在 高氯酸 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以22%的产率得到N-(2-tert-Butyl-3-phenylallyl)benzamide
  参考文献：
  名称：

  Reactions of a tertiary carbon carrying a tert-butyl Group: Acid-catalyzed alcoholyses of activated aziridines with and without solvent assistance.

  摘要：

  Acid-catalyzed ring opening of tosylated and acylated 2-tert-butylaziridines 1 (2-phenyl) and 2 (2-benzyl) generates carbenium ions 18 (from 1) and 19 (from 2) which rearrange by a neopentyl rearrangement to carbenium ions 20 (18 --> 20) and 21 (19 --> 21). Reactions of 18-21 farm the final products: (1) deprotonation yields allylamides, homoallylamides, and enamides; (2) external trapping of 18 or 19 by a solvent molecule yields ethers; (3) internal trapping (only acylated 1 and 2) yields oxazolines and dihydrooxazines. The amount of external trapping with 1a,b depends on the activation: 1a (tosyl activation) yields more methyl ether (75% vs 51%) than 1b (benzoyl), but 1a yields less isopropyl ether (0% vs 25%) than 1b. The latter finding is in accord with an intramolecular interaction of the carbenium center of 18a with one of the tosyl oxygen atoms provided that this interaction distorts the carbenium plane to a pyramid which sterically retards external trapping. The former finding is not observed with 2a and 2b. This points to at least some methanol-assisted ring opening of 1a-H+ that must be supported by a benzylic effect. The required conformation of the phenyl ring is fixed in 1a-H+ (N-protonation and bulky SO2 cis to phenyl) but not in 1b-H+ (O-protonation and planar nitrogen conformation).

  DOI：

  10.1021/jo00122a057

文献信息

• Reactions of a tertiary carbon carrying a tert-butyl Group: Acid-catalyzed alcoholyses of activated aziridines with and without solvent assistance.
  作者：Konstantinos Bellos、Helmut Stamm

  DOI：10.1021/jo00122a057

  日期：1995.9

  Acid-catalyzed ring opening of tosylated and acylated 2-tert-butylaziridines 1 (2-phenyl) and 2 (2-benzyl) generates carbenium ions 18 (from 1) and 19 (from 2) which rearrange by a neopentyl rearrangement to carbenium ions 20 (18 --> 20) and 21 (19 --> 21). Reactions of 18-21 farm the final products: (1) deprotonation yields allylamides, homoallylamides, and enamides; (2) external trapping of 18 or 19 by a solvent molecule yields ethers; (3) internal trapping (only acylated 1 and 2) yields oxazolines and dihydrooxazines. The amount of external trapping with 1a,b depends on the activation: 1a (tosyl activation) yields more methyl ether (75% vs 51%) than 1b (benzoyl), but 1a yields less isopropyl ether (0% vs 25%) than 1b. The latter finding is in accord with an intramolecular interaction of the carbenium center of 18a with one of the tosyl oxygen atoms provided that this interaction distorts the carbenium plane to a pyramid which sterically retards external trapping. The former finding is not observed with 2a and 2b. This points to at least some methanol-assisted ring opening of 1a-H+ that must be supported by a benzylic effect. The required conformation of the phenyl ring is fixed in 1a-H+ (N-protonation and bulky SO2 cis to phenyl) but not in 1b-H+ (O-protonation and planar nitrogen conformation).