2-(4'-methoxy-[1,1'-biphenyl]-4-yl)-2-methyl-1,3-dioxolane | 117530-17-3

• 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: 2-(4'-methoxy-[1,1'-biphenyl]-4-yl)-2-methyl-1,3-dioxolane
• 英文别名: 2-[4-(4-Methoxyphenyl)phenyl]-2-methyl-1,3-dioxolane
• CAS: 117530-17-3
• 化学式: C₁₇H₁₈O₃
• 分子量: 270.328
• InChiKey: HICYOIVLZCCMBM-UHFFFAOYSA-N

物化性质

• 沸点：
  395.8±42.0 °C(Predicted)
• 密度：
  1.113±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(4'-methoxy-[1,1'-biphenyl]-4-yl)-2-methyl-1,3-dioxolane 生成 1-(4-甲氧基-联苯-4-基)-乙酮
  参考文献：
  名称：

  2-Methoxy-4-nitrobenzenediazonium Salt as a Practical Diazonium-Transfer Agent for Primary Arylamines via Tautomerism of 1,3-Diaryltriazenes: Deaminative Iodination and Arylation of Arylamines without Direct Diazotization

  摘要：

  1,3-二芳基三氮烯是由2-甲氧基-4-硝基苯胺盐和一元芳香胺制备的，以“偶氮转移”互变异构体的形式存在，其中2-甲氧基-4-硝基苯基基团位于饱和氮原子上，并在2-甲氧基基团和N–H部分之间形成氢键。通过1,3-二芳基三氮烯的互变异构反应，已证明该重氮盐作为一元芳香胺的实用重氮转移试剂的合成实用性，能够在不直接进行重氮化的情况下，完成一元芳香胺的去氨碘化和芳基化。反应后起始的2-甲氧基-4-硝基苯胺可以很容易地回收。

  DOI：

  10.1246/bcsj.78.1654
• 作为产物：
  描述：

  4-溴苯甲醚 、 2-(4-chlorophenyl)-2-methyl-1,3-dioxolane 在 2,2'-联吡啶 、 nickel diacetate 、 sodium hydride 、 potassium iodide 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 1.5h， 以62%的产率得到2-(4'-methoxy-[1,1'-biphenyl]-4-yl)-2-methyl-1,3-dioxolane
  参考文献：
  名称：

  还原剂的活化。含氢化钠的复合还原剂25.芳基卤化物的一锅一试剂交叉偶联反应

  摘要：

  在2,2'-联吡啶和KI存在下制备NiCRA [NaH-AtmONa-Ni（OAc）2 ]会产生一种试剂（称为NiCRA-bpy-KI），被证明是最有效的Ni之一迄今已报道了含有芳基卤化物交叉偶联反应的试剂。

  DOI：

  10.1016/s0040-4039(00)80145-8

文献信息

• Mixed NHC/Phosphine Ni(II) Complexes: Synthesis and Their Applications as Versatile Catalysts for Selective Cross-Couplings of ArMgX with Aryl Chlorides, Fluorides, and Methyl Ethers
  作者：Jie Zhang、Jin Xu、Yanchao Xu、Hongmei Sun、Qi Shen、Yong Zhang

  DOI：10.1021/acs.organomet.5b00874

  日期：2015.12.28

  New methods for the preparation of mixed NHC/phosphine Ni(II) complexes have been developed. It was shown that the quaternary ammonium cation in the easily available Ni(II) complexes [NEt4] [Ni(PPh3)X-3] (X = Cl and Br) can act as a good leaving group in reactions of [NEt4][Ni(PPh3)X-3] with the bulky ItBu (ItBu = 1,3-ditertbutylimidazol-2-ylidene) or IPr [IPr = 1,3-bis (2,6-diisopropylphenyl)imidazol-2-ylidene] ligarid, resulting in the corresponding mixed NHC/PPh3 Ni(II) complexes Ni(PPh3)-(ItBu)X-2 (X = Cl, 1; X = Br, 2) or Ni(PPh3)(IPr)Br-2 (3) in high yields. The PPh3 ligand in these obtained mixed NHC/PPh3 Ni(II) complexes can be easily substituted by a more electron-donating phosphine ligand, i.e., PC)T, resulting in the corresponding mixed NHC/PCy3 Ni(II) complexes Ni(PCy3)(ItBu)Br-2 (4) and Ni(PCy3)(IPr)Br-2 (5) in high yields. The crystal structures of these NO) complexes have been characterized, which revealed a trans disposition of the NHC ligand to the phosphine ligand. The catalytic behaviors of them on varying the carbene ligand (ItBu vs IPr) as well as the phosphine ligand (PPh3 vs PCy3) were investigated in the cross-coupling of aryl Grignard reagents with a wide range of electrophiles. In addition to a significant synergic effect on their catalytic activities, high selectivity for the activation and transformation of C-Cl, C-F and C-O bonds was achieved based on the rational structural design. Complex 2 showed the highest catalytic activity for the cross, coupling of aryl chlorides and fluorides with aryl Grignard reagents, but exhibit little activity for the cross-coupling of aryl methyl ethers with aryl Grignard reagents. On contrast, complex 4 showed great potential for the aryl methyl ethers involved cross-coupling reactions, although its reactivity for the activation of the C-X bond is very poor. The difference in catalytic activity between 2 and 4 has been successfully employed to construct oligoarenes by selective cross-coupling reactions.