N-(2,3-Dimethyl-2-phenyl-3-butenyl)toluene-4-sulfonamide

• 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: N-(2,3-Dimethyl-2-phenyl-3-butenyl)toluene-4-sulfonamide
• 英文别名: N-(2,3-dimethyl-2-phenylbut-3-enyl)-4-methylbenzenesulfonamide
• 化学式: C₁₉H₂₃NO₂S
• 分子量: 329.463
• InChiKey: NSDQQLUFIPXQPQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  54.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  甲醇 、 2-叔丁基-2-苯基-1-(4-甲苯磺酰基)氮丙啶 在 高氯酸 作用下， 反应 20.0h， 以19%的产率得到N-(2,3-Dimethyl-2-phenyl-3-butenyl)toluene-4-sulfonamide
  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

• Two-Step 1,2-Shifts by β-Cleavage of Carbenium Ions and Recombination in Friedel−Crafts Reactions of 2-<i>tert</i>-Butyl-1-tosylaziridines¹
  作者：Konstantinos Bellos、Helmut Stamm

  DOI：10.1021/jo980774m

  日期：1998.10.1

  AlCl3-induced ring cleavage of two 2-tert-butyl-1-tosylaziridines in benzene (PhH) or anisole (AnH) generates carbenium ions (CIs). Subsequent neopentyl rearrangement forms CIs 3a,b, whose beta-cleavage generates +CH2NTsAlC3- (14) and an alkene. The intermediate 14 can recombine with the alkene at either C=C carbon, resulting in a reversal of the cleavage (3a,b) or in a formal 1,2-shift (CIs 12a,b). AnH rapidly removes 14 from these interconverting systems by formation of a methoxybenzylamide species that undergoes fragmentation into TsNHAlCl3- and methoxybenzyl cation, which gives dianisylmethane (main product). PhH reacts slowly with 14, leaving CIs 3a,b and 12a,b more time for other reactions. Unreacted 14 can even be trapped by AnH at the end of a PhH run. Protonation of each alkene forms N-free CIs that react with PhH and AnH. Replacing tosyl in one of the aziridines by benzoyl makes the beta-cleavage markedly slower than both the classic phenyl shift and the internal trapping of CIs.
• 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).