5,5-Dimethyl-9,12,14,17-tetra(propan-2-yl)-4-oxonia-3-azapentacyclo[9.6.2.02,6.08,18.015,19]nonadeca-1,3,6,8,10,12,14,16,18-nonaene | 209624-82-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 5,5-Dimethyl-9,12,14,17-tetra(propan-2-yl)-4-oxonia-3-azapentacyclo[9.6.2.02,6.08,18.015,19]nonadeca-1,3,6,8,10,12,14,16,18-nonaene
• CAS: 209624-82-8
• 化学式: C₃₁H₃₈NO
• 分子量: 440.649
• InChiKey: LYANCXSUPXASRC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  33
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  13.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5,5-Dimethyl-9,12,14,17-tetra(propan-2-yl)-4-oxonia-3-azapentacyclo[9.6.2.02,6.08,18.015,19]nonadeca-1,3,6,8,10,12,14,16,18-nonaene 在 水 作用下， 生成 1,3,5,10-Tetraisopropyl-7,7-dimethyl-7H-8-oxa-9-aza-cyclopenta[a]pyren-9-ol
  参考文献：
  名称：

  Nitration of isopropylpyrenes. Strained models for protonation and transfer-nitration in the condensed phase

  摘要：

  Protic mono- and dinitration of 1,3,5,7,9-pentaisopropylpyrene (1) occurred at the available alpha positions to give 2 and 3. Despite steric crowding, 2 and 3 did not exhibit a torsional barrier to i-Pr rotation at ambient temperatures; however, buttressing of the peri i-Pr groups was evident (H-1 NMR, UV, and force field energy minimizations). Persistent (dihydroxyiminium)pyrenium dications 2a+2 and 3a+2 were formed by low temperature protonation of 2 and 3 with CF3SO3H (TfOH)/SO2 or with FSO3H/SO2. Intramolecular cyclization of the nitro group of 2a+2 gave the rearranged pyrenium ion 2c+. 1 reacted with NO2+BF4- in acetonitrile solvent to give two pyrenium ions stable at rt, viz. the Wheland intermediate of alpha-nitration 2b+2 and the (dihydroxyiminium)pyrenium dication 2a+2; the latter was also the predominant pyrenium ion formed in the reaction of 1 with NO+BF4- in acetonitrile. Reaction of 1 with NO2+BF4- in chloroform solvent gave alpha-nitration products and a persistent radical cation RC. The simultaneous presence of alpha-nitration products and a persistent pyrenium RC was also observed in the reaction of 1 with NO+BF4- in chloroform, where broader NMR line widths and a stronger ESR signal suggested more extensive oxidation. Protic and aprotic nitrations of 1,3,6,8-tetraisopropylpyrene (10) occurred at the alpha-beta positions; a minor addition product (26) was also found. A mixture of isomeric dinitropyrenes was obtained in NO2+ nitration of 1-isopropylpyrene (13). In line with low temperature protonation studies, aprotic nitrations of 2-isopropyl- and 4-isopropylpyrenes occurred predominantly at the alpha positions. The crowded pyrenium ion of 3 and 2 transfer nitrate to aromatics (toluene, mesitylene, benzene) under mild conditions in competition with a more facile transalkylation.

  DOI：

  10.1021/jo00035a022
• 作为产物：
  描述：

  2,4,6,8,10-pentaisopropyl-1,3-dinitropyrene 在 三氟甲磺酸 作用下， 以 liquid sulphur dioxide 为溶剂， 生成 5,5-Dimethyl-9,12,14,17-tetra(propan-2-yl)-4-oxonia-3-azapentacyclo[9.6.2.02,6.08,18.015,19]nonadeca-1,3,6,8,10,12,14,16,18-nonaene
  参考文献：
  名称：

  Nitration of isopropylpyrenes. Strained models for protonation and transfer-nitration in the condensed phase

  摘要：

  Protic mono- and dinitration of 1,3,5,7,9-pentaisopropylpyrene (1) occurred at the available alpha positions to give 2 and 3. Despite steric crowding, 2 and 3 did not exhibit a torsional barrier to i-Pr rotation at ambient temperatures; however, buttressing of the peri i-Pr groups was evident (H-1 NMR, UV, and force field energy minimizations). Persistent (dihydroxyiminium)pyrenium dications 2a+2 and 3a+2 were formed by low temperature protonation of 2 and 3 with CF3SO3H (TfOH)/SO2 or with FSO3H/SO2. Intramolecular cyclization of the nitro group of 2a+2 gave the rearranged pyrenium ion 2c+. 1 reacted with NO2+BF4- in acetonitrile solvent to give two pyrenium ions stable at rt, viz. the Wheland intermediate of alpha-nitration 2b+2 and the (dihydroxyiminium)pyrenium dication 2a+2; the latter was also the predominant pyrenium ion formed in the reaction of 1 with NO+BF4- in acetonitrile. Reaction of 1 with NO2+BF4- in chloroform solvent gave alpha-nitration products and a persistent radical cation RC. The simultaneous presence of alpha-nitration products and a persistent pyrenium RC was also observed in the reaction of 1 with NO+BF4- in chloroform, where broader NMR line widths and a stronger ESR signal suggested more extensive oxidation. Protic and aprotic nitrations of 1,3,6,8-tetraisopropylpyrene (10) occurred at the alpha-beta positions; a minor addition product (26) was also found. A mixture of isomeric dinitropyrenes was obtained in NO2+ nitration of 1-isopropylpyrene (13). In line with low temperature protonation studies, aprotic nitrations of 2-isopropyl- and 4-isopropylpyrenes occurred predominantly at the alpha positions. The crowded pyrenium ion of 3 and 2 transfer nitrate to aromatics (toluene, mesitylene, benzene) under mild conditions in competition with a more facile transalkylation.

  DOI：

  10.1021/jo00035a022

文献信息

• Mono- and di-nitroalkyl-(cycloalkyl-)pyrenes in superacid media: dihydroxyiminium-(oxoiminium-)pyrenium dications; cyclisation to long-lived oxazoline-(and 1,2-oxazine-)pyrenium ions, ring opening to form nitrosoalkylpyrenium and nitroso radical cation salts with unprecedented stability
  作者：Kenneth K. Laali、Simon Bolvig、Poul Erik Hansen

  DOI：10.1039/p29950000537

  日期：——

  The low temperature protonations of sterically crowded molecules 2,4,6,8,10-pentaisopropyl-1-nitropyrene 1, 2,4,6,8,10-pentaisopropyl-1,3-dinitropyrene 12, 3,6,8,10-tetracyclohexyl-1-nitropyrene 16, 2,7-di-tert-butyl-1-nitropyrene 19, 2,7-di-tert-butyl-1,8-dinitropyrene 21, 1,3,6,8-tetraisopropyl-4-nitropyrene 23 and parent 1-nitropyrene 28, all possessing buttressed nitro groups, were studied in various superacid media under persistent ion conditions. Nitro group diprotonation was observed in all cases to give N,N-dihydroxyiminium-pyrenium (or oxoiminium-pyrenium) dications. The resulting dications derived from 1, 12, 16 and 23 undergo a facile intramolecular nitro group yclisation (which is usually complete within minutes at -75 degrees C --> room temp.) to give oxazoline-(or oxazine-)pyrenium cations 6 (and 11), 14 (and 15), 18 and 25. The charge distribution patterns (probed by C-13 and H-1 chemical shift analysis) for the iminium-pyrenium dications and their cyclised derivatives illustrate extensive charge delocalisation away from the iminium group at the alternating carbons of the periphery, similar to alkylpyrenium and fluoro(alkyl) pyrenium ions. The remote a positions carry substantial positive charge, which increases with the presence of inductively stabilising alkyl (cycloalkyl) substituents. The assignment of the iminium carbon was proved by independent synthesis and protonation of the 15-N labelled 1. Quenching of 6, 18 and 14 (containing 15) does not furnish their N-hydroxyoxazoline derivatives (like 5) nor the alkylnitropyrene precursors. Instead, the corresponding nitroso-alkylpyrenium and its derived radical cation salts (like 9a and 9RC) are obtained (EPR), which when re-dissolved in (CFSOH)-S-3-H-3 or (FSOH)-H-3 reform the cyclised pyrenium ions. Formation of persistent radical cations was also detected in some cases upon storage of the nitroalkylpyrene samples in (CFSOH)-S-3-H-3 ('TfOH') at room temperature.Ring opening of 25 and reduction upon quenching produces a different type of persistent nitrosoalkylpyrene radical (27 <-> 27a) with smaller a(N). The mechanistic aspects of nitro group cyclisation/ring opening are discussed.