4,4'-((4-methoxy-1,3-phenylene)bis(methylene))bis(methoxybenzene) | 72046-76-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 4,4'-((4-methoxy-1,3-phenylene)bis(methylene))bis(methoxybenzene)
• 英文别名: 1-methoxy-2,4-bis(4-methoxybenzyl)-benzene；1-Methoxy-2,4-bis[(4-methoxyphenyl)methyl]benzene
• CAS: 72046-76-5
• 化学式: C₂₃H₂₄O₃
• 分子量: 348.442
• InChiKey: ROQIHCFJLVHVIC-UHFFFAOYSA-N

物化性质

• 沸点：
  481.5±40.0 °C(Predicted)
• 密度：
  1.088±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 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：

  4,4'-((4-methoxy-1,3-phenylene)bis(methylene))bis(methoxybenzene) 在 三溴化硼 作用下， 以 二氯甲烷 为溶剂， 以83%的产率得到2,4-bis(4-methoxybenzyl)-phenol
  参考文献：
  名称：

  Palladium-Catalyzed Cross-Coupling of B-Benzyl-9-borabicyclo[3.3.1]nonane To Furnish Methylene-Linked Biaryls

  摘要：

  [GRAPHICS]Benzylboranes are noticeably uncommon partners within Suzuki-Miyaura coupling reactions. B-Benzyl-9-BBN was successfully coupled to a range of aryl/heteroaryl bromides, chlorides, and triflates to give pharmacologically important methylene-linked biaryl structures. Activated, deactivated, and sterically hindered substrates were successfully coupled in high yield using Pd(PPh3)(4) or Pd(OAc)(2) with SPhos as the catalyst system.

  DOI：

  10.1021/ol051929x
• 作为产物：
  描述：

  4-methoxybenzylmagnesium chloride 在 2-双环己基膦-2',6'-二甲氧基联苯 、 palladium diacetate 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 20.0h， 生成 4,4'-((4-methoxy-1,3-phenylene)bis(methylene))bis(methoxybenzene)
  参考文献：
  名称：

  Palladium-Catalyzed Cross-Coupling of B-Benzyl-9-borabicyclo[3.3.1]nonane To Furnish Methylene-Linked Biaryls

  摘要：

  [GRAPHICS]Benzylboranes are noticeably uncommon partners within Suzuki-Miyaura coupling reactions. B-Benzyl-9-BBN was successfully coupled to a range of aryl/heteroaryl bromides, chlorides, and triflates to give pharmacologically important methylene-linked biaryl structures. Activated, deactivated, and sterically hindered substrates were successfully coupled in high yield using Pd(PPh3)(4) or Pd(OAc)(2) with SPhos as the catalyst system.

  DOI：

  10.1021/ol051929x

文献信息

• Catalytic dehydrative etherification and chlorination of benzyl alcohols in ionic liquids
  作者：Hassan A. Kalviri、Chad F. Petten、Francesca M. Kerton

  DOI：10.1039/b909866f

  日期：——

  Dibenzyl ethers and benzyl chloride can be obtained in moderate to excellent yields through Pd-catalysed reactions in hydrophobic ionic liquids using microwave or conventional heating.

  在疏水性离子液体中，通过钯催化的反应，利用微波或常规加热，可以中等至优异的产率获得二苄醚和苄氯。
• Ligand‐Facilitated Reductive Coupling of Benzyl Chlorides with Aryl Chlorides Catalyzed by Well‐Defined Heteroleptic Ni (II)‐NHC Complexes
  作者：Gusheng Lu、Ruipeng Li、Zhengwang Shen、Qinjia Wu、Hongmei Sun

  DOI：10.1002/aoc.5741

  日期：2020.9

  3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene), complex 1 exhibited superior catalytic activity in the magnesium‐mediated reductive coupling of benzyl chlorides with aryl chlorides, featuring outstanding tolerance of both coupling partners with steric demand. This study discloses a ligand‐facilitated reductive coupling of benzyl chlorides with aryl chlorides, which provides a new and practical synthetic

  新型杂合Ni（II）配合物，带有高度受阻但具有柔性的IPr *配体，Ni（IPr *）（PPh 3）Br 2（1）和Ni（IPr *）（PCy 3）Br 2（2）（IPr * = 1,3-双（2,6-双（二苯甲基）-4-甲基苯基）咪唑-2-亚基可以轻松制备，产率分别为78％和89％。两者均通过元素分析和NMR光谱进行了表征，并对1进行了X射线晶体学分析。与2及其类似物相比，其空间要求较低的IPr配体（IPr = 1,3-二（2,6-二异丙基苯基）咪唑-2-亚基）复杂1在苄基氯与芳基氯的镁介导的还原偶联中表现出卓越的催化活性，这两种偶联伙伴均具有出色的空间耐受性。这项研究揭示了苄基氯与芳基氯的配体促进还原偶联，为二芳基甲烷的合成提供了一种新的实用合成工具。
• Nickel-Catalyzed Reductive Cross-Coupling of Benzyl Chlorides with Aryl Chlorides/Fluorides: A One-Pot Synthesis of Diarylmethanes
  作者：Jie Zhang、Gusheng Lu、Jin Xu、Hongmei Sun、Qi Shen

  DOI：10.1021/acs.orglett.6b01134

  日期：2016.6.17

  The first nickel-catalyzed, magnesium-mediated reductive cross-coupling between benzyl chlorides and aryl chlorides or fluorides is reported. A variety of diarylmethanes can be prepared in good to excellent yields in a one-pot manner using easy-to-access mixed PPh3/NHC Ni(II) complexes of Ni(PPh3)(NHC)Br2 (NHC = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, IPr, 1a; 1,3-di-tert-butylimidazol-2-ylidene

  报道了苄基氯与芳基氯或氟化物之间第一个镍催化的，镁介导的还原性交叉偶联。多种二芳基甲烷的可以用很好的制备使用在一锅方式优异的产率易于访问混合PPH 3 / NHC镍（II）镍（PPH的络合物3）（NHC）溴2（NHC = 1，作为催化剂前体的3-双（2,6-二异丙基苯基）咪唑-2-亚烷基，IPr，1a ; 1,3-二叔丁基咪唑-2-亚烷基，ItBu，1b）。基于1a和1b之间催化活性的差异激活多氯芳烃或进行化学选择性交叉偶联来构建寡聚体-二芳基甲烷图案。
• Direct C(sp²)C(sp³) Cross-Coupling of Diaryl Zinc Reagents with Benzylic, Primary, Secondary, and Tertiary Alkyl Halides
  作者：Jay J. Dunsford、Ewan R. Clark、Michael J. Ingleson

  DOI：10.1002/anie.201411403

  日期：2015.5.4

  The direct C(sp2)C(sp3) cross‐coupling of diaryl zinc reagents with benzylic, primary, secondary, and tertiary alkyl halides proceeded in the absence of coordinating ethereal solvents at ambient temperature without the addition of a catalyst. The C(sp2)C(sp3) cross‐coupling showed excellent functional‐group tolerance, and products were isolated in high yields, generally without the requirement for

  二芳基锌试剂与苄基，伯，仲和叔烷基卤化物的直接C（sp 2）C（sp 3）直接交叉偶联在环境温度下不加配醚溶剂的情况下进行，无需添加催化剂。C（sp 2）C（sp 3）交叉偶联显示出极好的官能团耐受性，并且通常以色谱法纯化的产物，收率很高。该过程代表了构造新的C（sp 2）C（sp 3）键的便捷，操作简单的方法。
• Heteroleptic Ni(II) Complexes Bearing a Bulky Yet Flexible IBiox-6 Ligand: Improved Selectivity in Cross-Electrophile Coupling of Benzyl Chlorides with Aryl Chlorides/Fluorides
  作者：Zheng-Wang Shen、Die-Die Meng、Sajid Imran、Chun-Hui Yan、Hong-Mei Sun

  DOI：10.1021/acs.organomet.0c00515

  日期：2020.10.12

  Ni(PPh3)2Br2 to give the respective heteroleptic Ni(II) complexes Ni(IBiox-6)[P(OEt)3]Br2 (1) and Ni(IBiox-6)(PPh3)Br2 (2) in yields of 60% and 71%. Their crystal structures were characterized to reveal a rare cis disposition of the IBiox-6 ligand to the phosphite ligand in 1, while 2 possessed the more common trans configuration. Both complexes catalyzed the cross-electrophile coupling of benzyl chlorides

  名为IBiox-6的双恶唑啉衍生的NHC与Ni [P（OEt）3 ] 2 Br 2和Ni（PPh 3）2 Br 2平稳反应，分别得到杂配的Ni（II）配合物Ni（IBiox-6）[ P（OEt）3 ] Br 2（1）和Ni（IBiox-6）（PPh 3）Br 2（2）的产率分别为60％和71％。它们的晶体结构进行了表征揭示一种罕见的顺式的IBiox-6配体在亚磷酸盐配体的布置1，而2所具有的较常见的反式组态。两种配合物均通过“真正的一锅法”在50°C的Mg车削条件下催化了苄基氯与芳基氯和氟化物的亲电子交联偶联，其特点是不需要温度变化或分批添加任何偶联伴侣。特别地，配合物1在催化活性和选择性之间显示出更好的平衡。研究了由1和Mg车削催化的程序范围，为合成具有高位阻和各种官能团的二芳基甲烷提供了一种高度选择性，简单和实用的方法，包括具有不对称结构的低聚二芳基甲烷。