4,4-Dimethyl-4,5-dihydro-3H-4-azonia-cyclohepta[2,1-a;3,4-a']dinaphthalene; bromide | 1020592-49-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯氮卓类
• 英文名称: 4,4-Dimethyl-4,5-dihydro-3H-4-azonia-cyclohepta[2,1-a;3,4-a']dinaphthalene; bromide
• 英文别名: 13,13-dimethyl-13-azoniapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene;bromide
• CAS: 1020592-49-7
• 化学式: Br*C₂₄H₂₂N
• 分子量: 404.349
• InChiKey: MNTBAPSXZSNERQ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.75
• 重原子数：
  26
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4,4-Dimethyl-4,5-dihydro-3H-4-azonia-cyclohepta[2,1-a;3,4-a']dinaphthalene; bromide 在 sodium sulfide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.17h， 以89%的产率得到(R,R)-bis<<2-<(N,N-dimethylamino)methyl>-1,1'-binaphthyl-2'-yl>methyl> sulfide
  参考文献：
  名称：

  Nucleophilic cleavage of 4,5-dihydro-3H-dinaphth[2,1-c:1',2'-e]azepinium quaternary salts. A convenient approach to new axially dissymmetric and axially asymmetric ligands

  摘要：

  DOI：

  10.1021/jo00051a053
• 作为产物：
  描述：

  (S)-2,2'-双(溴甲基)-1,1'-联萘 、 二甲胺 以 乙腈 、 苯 为溶剂， 反应 12.0h， 以90%的产率得到4,4-Dimethyl-4,5-dihydro-3H-4-azonia-cyclohepta[2,1-a;3,4-a']dinaphthalene; bromide
  参考文献：
  名称：

  Nucleophilic cleavage of 4,5-dihydro-3H-dinaphth[2,1-c:1',2'-e]azepinium quaternary salts. A convenient approach to new axially dissymmetric and axially asymmetric ligands

  摘要：

  DOI：

  10.1021/jo00051a053

文献信息

• Reductive cleavage of axially disymmetric tertiary amines and quaternary ammonium salts by lithium aluminium hydride. Synthesis of new 1,1′-binaphthyl substituted amines
  作者：Frédéric Cottineau、Nicole Maigrot、Jean-Paul Mazaleyrat

  DOI：10.1016/s0040-4039(00)61900-7

  日期：1985.1

  Axially disymmetric tertiary amines or quaternary ammonium salts A are synthesized by double alkylation of primary or secondary amines with racemic or optically pure 2,2′-bis (bromomethyl)-1,1′-binaphthyl. Their reductive cleavage by lithium aluminium hydride in refluxing THF leads to chiral secondary or tertiary amines B, substituted by a binaphthyl unit, with high yields and absence of racemization

  轴向二对称的叔胺或季铵盐A是通过将伯胺或仲胺与外消旋或光学纯的2,2'-双（溴甲基）-1,1'-联萘基进行双烷基化反应而合成的。它们在回流的THF中被氢化铝锂还原裂解，得到手性仲或叔胺B，被双萘基单元取代，收率高且没有外消旋作用。
• Stereochemical Dichotomy in the Stevens Rearrangement of Axially Twisted Dihydroazepinium and Dihydrothiepinium Salts. A Novel Enantioselective Synthesis of Pentahelicene
  作者：Irena G. Stara、Ivo Stary、Milos Tichy、Jiri Zavada、Vladimir Hanus

  DOI：10.1021/ja00091a009

  日期：1994.6

  Evidence is presented indicating that the stereochemistry of the Stevens rearrangement of the axially chiral onium salts 1a-d and 5 is dramatically structure-dependent. Thus, the binaphthyl ammonium salts (S)-(+)-1a-c react with a strong base with exclusive (100% de) formation of the corresponding rearranged amines (R,3R)-(+)-2a-c, demonstrating a complete transfer of the (S) axial dissymmetry/asymmetry into (R) asymmetry of the newly formed carbon center. Exactly opposite stereochemistry was established in an earlier study by Mislow of the biphenyl analogue (S)-(+)-5, yielding the rearranged products (S,9S)-(+)-6 and (R,9S)-(-)-7 with exclusive (S) configuration at the carbon center. Rearrangement of the sulfonium salt 1d is found to be intermediate between the two extremes, yielding a mixture of diastereoisomeric products 2d and 3d, which differ in configuration at the asymmetric carbon center. A direct proof is thus provided that two stereochemically different pathways can participate in the Stevens rearrangement. An explanation is suggested in terms of competition between suprafacial (concerted) and antarafacial (nonconcerted) mechanism.
• COTTINEAU, F.;MAIGROT, N.;MAZALEYRAT, J. -P., TETRAHEDRON LETT., 1985, 26, N 4, 421-424
  作者：COTTINEAU, F.、MAIGROT, N.、MAZALEYRAT, J. -P.

  DOI：——

  日期：——
• Nucleophilic cleavage of 4,5-dihydro-3H-dinaphth[2,1-c:1',2'-e]azepinium quaternary salts. A convenient approach to new axially dissymmetric and axially asymmetric ligands
  作者：Irena G. Stara、Ivo Stary、Jiri Zavada

  DOI：10.1021/jo00051a053

  日期：1992.12