3-tert-butyl-8-cyclohexyl-1-diisopropylamino-5-(4-methoxyphenyl)-6,7-bis(methoxycarbonyl)-bicyclo[3,2,1]-1-phospha-2,8-diaza-1,3,6-octatriene | 177651-26-2

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 3-tert-butyl-8-cyclohexyl-1-diisopropylamino-5-(4-methoxyphenyl)-6,7-bis(methoxycarbonyl)-bicyclo[3,2,1]-1-phospha-2,8-diaza-1,3,6-octatriene
• 英文别名: Dimethyl 3-tert-butyl-8-cyclohexyl-1-[di(propan-2-yl)amino]-5-(4-methoxyphenyl)-2,8-diaza-1lambda5-phosphabicyclo[3.2.1]octa-1,3,6-triene-6,7-dicarboxylate；dimethyl 3-tert-butyl-8-cyclohexyl-1-[di(propan-2-yl)amino]-5-(4-methoxyphenyl)-2,8-diaza-1λ5-phosphabicyclo[3.2.1]octa-1,3,6-triene-6,7-dicarboxylate
• CAS: 177651-26-2
• 化学式: C₃₂H₄₈N₃O₅P
• 分子量: 585.724
• InChiKey: FDZGCYDAONCQKB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  41
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  80.7
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  3-tert-butyl-8-cyclohexyl-1-diisopropylamino-5-(4-methoxyphenyl)-6,7-bis(methoxycarbonyl)-bicyclo[3,2,1]-1-phospha-2,8-diaza-1,3,6-octatriene 在 二氟氯乙酸 作用下， 以 二氯甲烷 为溶剂， 以70%的产率得到
  参考文献：
  名称：

  Reactivity of dihydrodiazaphosphinines towards unsaturated substrates: Addition, [5 + 2] cycloaddition and rearrangement processes

  摘要：

  Treatment of 4-amino-1-azadienes 1 with dichloro (diisopropylamino)phosphane gave 1,2-dihydro- 1,3,2-diazaphosphinines 3, which cycloadded in a [5 + 2] fashion to dimethyl acetylenedicarboxylate to furnish bicyclic iminophosphoranes 5. The single addition compound 6 was formed by reaction of 3a with (CO)(5)Cr=C(OMe)(C equivalent to CPh). Compounds 5 underwent formal 1,7-rearrangement to 7 at room temperature. In turn, 5a reacted with electrophiles (difluorochloroacetic acid and methyl iodide) through the valence isomer 5a' to give polycyclic structures 13 and 14, which led to 16 by fluoride-induced [4 + 2] cycloreversion. Other reactive electrophilic substrates, Like diethyl azodicarboxylate and N-phenyltriazolinedione, led to the oxidized derivative 9 and to the addition product 12 respectively. The X-ray structures of 7a and 12 are discussed.

  DOI：

  10.1016/s0022-328x(96)06618-1
• 作为产物：
  描述：

  在 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 18.0h， 生成 3-tert-butyl-8-cyclohexyl-1-diisopropylamino-5-(4-methoxyphenyl)-6,7-bis(methoxycarbonyl)-bicyclo[3,2,1]-1-phospha-2,8-diaza-1,3,6-octatriene
  参考文献：
  名称：

  Barluenga, Jose; Tomas, Miguel; Bieger, Klaus, Angewandte Chemie, 1996, vol. 108, # 8, p. 977 - 979

  摘要：

  DOI：

文献信息

• Reaction of Dihydrodiazaphosphinines with Acetylenic Diesters: A Direct Synthesis of the λ5-Diazaphosphaazulene Skeleton
  作者：José Barluenga、Miguel Tomás、Klaus Bieger、Santiago García-Granda、Rafael Santiago-García

  DOI：10.1002/(sici)1099-0690(199807)1998:7<1425::aid-ejoc1425>3.0.co;2-0

  日期：1998.7

  depending on the reaction conditions. Compound 6a is alternatively synthesized by treatment of equimolecular amounts of the previously described monoadduct 3(3′) and dimethyl acetylenedicarboxylate. A reaction pathway is proposed based primarily on i) the isolation and characterization of intermediate 8(8′) and ii) the reactivity of 3(3′) towards electrophiles, in particular with tetracyanoethylene (compound

  根据反应条件，1,2-二氢-1,3,2-二氮杂膦2与乙炔-二羧酸酯反应生成化学选择性的加合物5或6a，b。或者，通过等摩尔量的前述单加合物3（3'）和乙炔二羧酸二甲酯的处理来合成化合物6a。提出的反应途径主要基于以下方面：i）中间体8（8'）的分离和表征，以及ii）3（3'）对亲电试剂，特别是四氰基乙烯（化合物10）的反应性）。