4,9-dibromo-7-tert-butyl-10b,10c-dihydro-trans-10b,10c-dimethylpyren-2-yl 9-anthracenyl ketone

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 4,9-dibromo-7-tert-butyl-10b,10c-dihydro-trans-10b,10c-dimethylpyren-2-yl 9-anthracenyl ketone
• 英文别名: anthracen-9-yl-[(10bR,10cS)-4,9-dibromo-7-tert-butyl-10b,10c-dimethylpyren-2-yl]methanone
• 化学式: C₃₇H₃₀Br₂O
• 分子量: 650.453
• InChiKey: AKBHTLXHKDGTPC-PQQNNWGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.8
• 重原子数：
  40
• 可旋转键数：
  3
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4,9-dibromo-7-tert-butyl-10b,10c-dihydro-trans-10b,10c-dimethylpyren-2-yl 9-anthracenyl ketone 在 氯氟磺酰 、 氟磺酸 作用下， 生成
  参考文献：
  名称：

  Stable Ion NMR and GIAO-DFT Study of Novel Cations from 8,16-Dicyano[2.2]metacyclophanedienes and from Strategically Substituted/Benzannelated Dihydropyrenes:  Charge-Induced Tropicity Modulation and π-Switching

  摘要：

  [GRAPHICS]The dicyanometacyclophanediene 1 is diprotonated at the cyano groups (1H(2)(2+)) in various superacid media. Upon quenching, intact 1 and the ring-closed CPD 2 were obtained in a 3:2 or 3:1 ratio, depending on the superacid system. Compound 2 undergoes ring opening in the superacid to give the ipso-monoprotonated 2H(+), which on quenching furnishes 1-cyanopyrene as a major product together with 2 and 1. The dication 3(2+), with strongly deshielded internal methyls, was generated from the epoxyannulene 3. Ketones 4-6 and ester 7 are O/C diprotonated to give paratropic carboxonium-annulenium dications (4H(2)(2+), 5H(2)(2+), 6H(2)(2+), and -7H(2)(2+), respectively). Ester 8 gives a trication by two-electron oxidation and O-protonation. Conjugated carboxylic acid 9 gives a mixture of two dications by CO and ring protonation. The dibromo derivatives 10 and 11 form carboxoniurn ions, whereas the monobromo derivative 12 is O/C diprotonated to give an oxonium-annulenium dication. Charge delocalization modes and tropicity in the resulting species are evaluated by NMR and GIAO-DFT. Facile formation of 2 from I in quenching experiments indicates that thermal closing can be achieved with the diprotonated dinitrile, without imposing skeletal rearrangement.

  DOI：

  10.1021/jo701932j
• 作为产物：
  描述：

  9-蒽甲酰氯 、 4,9-dibromo-2,7-di-tert-butyl-trans-10b,10c-dimethyl-10b,10c-dihydropyrene 以 二氯甲烷 为溶剂， 反应 24.0h， 以13%的产率得到4,9-dibromo-7-tert-butyl-10b,10c-dihydro-trans-10b,10c-dimethylpyren-2-yl 9-anthracenyl ketone
  参考文献：
  名称：

  Stable Ion NMR and GIAO-DFT Study of Novel Cations from 8,16-Dicyano[2.2]metacyclophanedienes and from Strategically Substituted/Benzannelated Dihydropyrenes:  Charge-Induced Tropicity Modulation and π-Switching

  摘要：

  [GRAPHICS]The dicyanometacyclophanediene 1 is diprotonated at the cyano groups (1H(2)(2+)) in various superacid media. Upon quenching, intact 1 and the ring-closed CPD 2 were obtained in a 3:2 or 3:1 ratio, depending on the superacid system. Compound 2 undergoes ring opening in the superacid to give the ipso-monoprotonated 2H(+), which on quenching furnishes 1-cyanopyrene as a major product together with 2 and 1. The dication 3(2+), with strongly deshielded internal methyls, was generated from the epoxyannulene 3. Ketones 4-6 and ester 7 are O/C diprotonated to give paratropic carboxonium-annulenium dications (4H(2)(2+), 5H(2)(2+), 6H(2)(2+), and -7H(2)(2+), respectively). Ester 8 gives a trication by two-electron oxidation and O-protonation. Conjugated carboxylic acid 9 gives a mixture of two dications by CO and ring protonation. The dibromo derivatives 10 and 11 form carboxoniurn ions, whereas the monobromo derivative 12 is O/C diprotonated to give an oxonium-annulenium dication. Charge delocalization modes and tropicity in the resulting species are evaluated by NMR and GIAO-DFT. Facile formation of 2 from I in quenching experiments indicates that thermal closing can be achieved with the diprotonated dinitrile, without imposing skeletal rearrangement.

  DOI：

  10.1021/jo701932j

文献信息

• Stable Ion NMR and GIAO-DFT Study of Novel Cations from 8,16-Dicyano[2.2]metacyclophanedienes and from Strategically Substituted/Benzannelated Dihydropyrenes:  Charge-Induced Tropicity Modulation and π-Switching
  作者：Kenneth K. Laali、Takao Okazaki、Reginald H. Mitchell、Khurshid Ayub、Rui Zhang、Stephen G. Robinson

  DOI：10.1021/jo701932j

  日期：2008.1.1

  [GRAPHICS]The dicyanometacyclophanediene 1 is diprotonated at the cyano groups (1H(2)(2+)) in various superacid media. Upon quenching, intact 1 and the ring-closed CPD 2 were obtained in a 3:2 or 3:1 ratio, depending on the superacid system. Compound 2 undergoes ring opening in the superacid to give the ipso-monoprotonated 2H(+), which on quenching furnishes 1-cyanopyrene as a major product together with 2 and 1. The dication 3(2+), with strongly deshielded internal methyls, was generated from the epoxyannulene 3. Ketones 4-6 and ester 7 are O/C diprotonated to give paratropic carboxonium-annulenium dications (4H(2)(2+), 5H(2)(2+), 6H(2)(2+), and -7H(2)(2+), respectively). Ester 8 gives a trication by two-electron oxidation and O-protonation. Conjugated carboxylic acid 9 gives a mixture of two dications by CO and ring protonation. The dibromo derivatives 10 and 11 form carboxoniurn ions, whereas the monobromo derivative 12 is O/C diprotonated to give an oxonium-annulenium dication. Charge delocalization modes and tropicity in the resulting species are evaluated by NMR and GIAO-DFT. Facile formation of 2 from I in quenching experiments indicates that thermal closing can be achieved with the diprotonated dinitrile, without imposing skeletal rearrangement.