2-allyl-4-(tert-butyl)phenyl allyl ether | 94374-53-5

• 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-allyl-4-(tert-butyl)phenyl allyl ether
• 英文别名: 2-allyl-1-allyloxy-4-tert-butylbenzene；4-Tert-butyl-1-prop-2-enoxy-2-prop-2-enylbenzene
• CAS: 94374-53-5
• 化学式: C₁₆H₂₂O
• 分子量: 230.35
• InChiKey: CJPCLINUXFPUJB-UHFFFAOYSA-N

物化性质

• 沸点：
  137 °C(Press: 16 Torr)
• 密度：
  0.911±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-allyl-4-(tert-butyl)phenyl allyl ether 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 [RuHCl(CO)(PPh₃)₃] 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 20.0h， 生成 5-tert-butylbenzofuran
  参考文献：
  名称：

  An isomerization-ring-closing metathesis strategy for the synthesis of substituted benzofurans

  摘要：

  Twelve substituted benzofurans were synthesized from their corresponding substituted l-allyl-2-allyloxybenzenes using ruthenium-mediated G and O-allyl isomerization followed by ring-closing metathesis. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.05.090
• 作为产物：
  描述：

  allyl p-cymyl ether 在 甲醇 、 sodium 、 三氯化硼 作用下， 以 乙醇 为溶剂， 反应 4.0h， 生成 2-allyl-4-(tert-butyl)phenyl allyl ether
  参考文献：
  名称：

  细胞色素P-450活性位点的合成模型。第一次沟通。一个双向桥接铁（II） -卟啉携带紧密结合的硫醇盐配位体的合成†

  摘要：

  所述双桥接铁（II）-tetraphenylporphyrin衍生物6，携带空间位固定小号-配体中的“近侧”位置，并在“远侧”现场基板，合成作为细胞色素P-450酶的模型。化合物36（6的CO配合物）显示出类似于天然细胞色素P-450的Soret分离带（403和457 nm）。

  DOI：

  10.1002/hlca.19870700425

文献信息

• A New One-Pot Synthetic Approach to the Highly Functionalized (<i>Z</i>)-2-(Buta-1,3-dienyl)phenols and 2-Methyl-2<i>H</i>-chromenes: Use of Amine, Ruthenium and Base-Catalysis
  作者：Dhevalapally B. Ramachary、Vidadala V. Narayana、Kinthada Ramakumar

  DOI：10.1002/ejoc.200800472

  日期：2008.8

  (Z)-2-(buta-1,3-dienyl)phenols 6 and 2-methyl-2H-chromenes 7 from simple starting materials was achieved for the first time through ring-closing metathesis/base-induced ring opening/[1,7]-sigmatropic hydrogen shift reactions. The synthesis of privileged (Z)-2-(buta-1,3-dienyl)phenols 6 via base-induced ring opening of highly functionalized benzo[b]oxepines 5 is described(© Wiley-VCH Verlag GmbH &

  一种用于合成高度取代的苯并[b]氧杂环庚烷 5、(Z)-2-(buta-1,3-dienyl)phenols 6 和 2-methyl-2H-chromenes 7 的实用且简单的一锅多催化工艺首次通过闭环复分解/碱诱导开环/[1,7]-σ-σ 氢位移反应从简单的起始材料中获得。描述了通过碱诱导的高度官能化苯并 [b] 氧杂环庚烷 5 开环合成特权 (Z)-2-(buta-1,3-dienyl)phenols 6 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 魏因海姆，德国，2008）
• [EN] PROCESS FOR THE PREPARATION OF AN ALLYL ARYL ETHER BY CATALYTIC O-ALLYLATON<br/>[FR] PROCÉDÉ DE PRÉPARATION D'UN ALLYL ARYL ÉTHER PAR O-ALLYLATION CATALYTIQUE
  申请人：RESOLUTION RES NEDERLAND BV

  公开号：WO2010086137A1

  公开（公告）日：2010-08-05

  The invention provides a process for the preparation of an allyl aryl ether comprising the O-allylation of an aromatic hydroxyl containing compound with an allyl source in the presence of a catalyst, wherein the catalyst is a transition metal complex with a bidentate diphosphine ligand, and wherein the bidentate diphosphine ligand has 2 to 4 bridging atoms between the phosphorus atoms and wherein at least one of the bridging atoms is substituted. This invention further provides novel transition metal complexes that may be used in the above process. This invention further provides a process for the preparation of epoxy resins wherein as intermediate use is made of the allyl aryl ethers prepared by the process of the invention.

  本发明提供了一种制备烯丙基芳基醚的方法，包括在催化剂的存在下，通过芳香族羟基含有物与烯丙基源进行O-烯丙基化反应，其中，所述催化剂是一种具有双膦配体的过渡金属配合物，所述双膦配体在磷原子之间具有2到4个桥连原子，并且至少一个桥连原子被取代。本发明还提供了新型过渡金属配合物，可用于上述方法。本发明还提供了一种制备环氧树脂的方法，其中使用本发明方法制备的烯丙基芳基醚作为中间体。
• Cationic Ruthenium-Cyclopentadienyl-Diphosphine Complexes as Catalysts for the Allylation of Phenols with Allyl Alcohol; Relation between Structure and Catalytic Performance in<i>O</i>-<i>vs. C</i>-Allylation
  作者：Jimmy A. van Rijn、Martin Lutz、Lars S. von Chrzanowski、Anthony L. Spek、Elisabeth Bouwman、Eite Drent

  DOI：10.1002/adsc.200900085

  日期：2009.7

  With the use of new cationic ruthenium(II) complexes as catalyst, both reactions can be performed with good selectivity. Active cationic Ru(II) complexes, having cyclopentadienyl and bidentate phosphine ligands are generated from the corresponding Ru(II) chloride complexes with a silver salt. The structures of three novel (diphosphine)Ru(II)CpCl catalyst precursor complexes are reported. It appears that

  研究了一种新的催化方法以获得O或C使用烯丙醇或二烯丙基醚作为烯丙基供体的烯丙基化酚醛产品。通过使用新的阳离子钌（II）配合物作为催化剂，两个反应都可以良好的选择性进行。由具有银盐的相应的氯化钌（II）配合物产生具有环戊二烯基和二齿膦配体的活性阳离子钌（II）配合物。报道了三种新型（二膦）Ru（II）CpCl催化剂前体配合物的结构。看起来双齿配体的结构对催化活性以及化学选择性具有主要影响。另外，揭示了少量酸的强共催化作用。描述了用于建立反应网络的模型实验，该网络解释了O的起源和时间演变。烯丙基化和C烯丙基化的酚醛产品。讨论了[（二膦）RuCp] +配合物的结构与性能关系与所加质子的助催化作用之间的力学关系。
• [EN] PROCESS FOR THE PREPARATION OF AN ALLYL ARYL ETHER BY CATALYTIC O-ALLYLATION<br/>[FR] PROCÉDÉ DE PRÉPARATION D'UN ALLYL ARYL ÉTHER PAR O-ALLYLATION CATALYTIQUE
  申请人：RESOLUTION RES NEDERLAND BV

  公开号：WO2010086138A1

  公开（公告）日：2010-08-05

  The invention provides a process for the preparation of an allyl aryl ether comprising the O-allylation of an aromatic hydroxyl containing compound with an allyl source in the presence of a catalyst, wherein the catalyst is a transition metal complex with a phosphine ligand, and wherein the phosphine ligand is either a monodentate phosphine P(X)3, wherein each X independently is a an aliphatic substituent having from 1 to 9 carbon atoms, a cycloaliphatic substituent having from 5 to 9 carbon atoms or aromatic substituent having from 6 to 9 carbon atoms, or wherein two substituents X together form a divalent alkylene group, with from 3 up to 6 carbon atoms, or a bidentate diphosphine X2P-R-PX2 wherein each X has the same meaning as defined for the monodentate phosphine, wherein the divalent alkylene group is attached to the same or different phosphorus atom(s), and R is a bridging group having at least 4 bridging atoms between the phosphorus atoms, wherein the O-allylation is carried out in the presence of an acid in an amount of at least 0.1 mol% calculated on the aromatic hydroxyl containing compound. This invention further provides a process for the preparation of epoxy resins wherein as intermediate use is made of the allyl aryl ethers prepared by the process of the invention.

  本发明提供了一种制备烯丙基芳基醚的方法，该方法包括在催化剂存在下，使用烯丙基源对含芳香族羟基的化合物进行O-烯丙基化反应，其中催化剂是一种过渡金属配合物，其配体为膦，所述膦配体为单齿膦P（X）3，其中每个X独立地是具有1至9个碳原子的脂肪基取代基，具有5至9个碳原子的环脂肪基取代基或具有6至9个碳原子的芳香族取代基，或其中两个取代基X共同形成一个具有3至6个碳原子的二价烷基链，或为双齿二膦X2P-R-PX2，其中每个X具有单齿膦所定义的相同含义，所述二价烷基链连接到相同或不同的磷原子上，R是具有至少4个桥接原子的桥接基团，其中O-烯丙基化反应在存在酸的情况下进行，所述酸的用量至少为计算在含芳香族羟基的化合物上的0.1摩尔％。本发明还提供了一种制备环氧树脂的方法，其中使用本发明方法制备的烯丙基芳基醚作为中间体。
• Process for the preparation of an allyl aryl ether by catalytic o-allylation
  申请人：Hexion Specialty Chemicals Research Belgium S.A.

  公开号：EP2213645A1

  公开（公告）日：2010-08-04

  The invention provides a process for the preparation of an allyl aryl ether comprising the O-allylation of an aromatic hydroxyl containing compound with an allyl source in the presence of a catalyst, wherein the catalyst is a transition metal complex with a phosphine ligand, and wherein the phosphine ligand is - either a monodentate phosphine P(X)3, wherein each X independently is a an aliphatic substituent having from 1 to 9 carbon atoms, a cycloaliphatic substituent having from 5 to 9 carbon atoms or aromatic substituent having from 6 to 9 carbon atoms, or wherein two substituents X together form a divalent alkylene group, with from 3 up to 6 carbon atoms, - or a bidentate diphosphine X2P-R-PX2 wherein each X has the same meaning as defined for the monodentate phosphine , wherein the divalent alkylene group is attached to the same or different phosphorus atom(s), and R is a bridging group having at least 4 bridging atoms between the phosphorus atoms, wherein the O-allylation is carried out in the presence of an acid in an amount of at least 0.1 mol% calculated on the aromatic hydroxyl containing compound. This invention further provides a process for the preparation of epoxy resins wherein as intermediate use is made of the allyl aryl ethers prepared by the process of the invention.

  本发明提供了一种制备烯丙基芳基醚的工艺，该工艺包括在催化剂存在下，芳香族含羟基化合物与烯丙基源发生 O-烯丙基化反应，其中催化剂为带有膦配体的过渡金属络合物，膦配体为 - 单齿膦 P(X)3，其中每个 X 独立地是具有 1 至 9 个碳原子的脂肪族取代基、具有 5 至 9 个碳原子的环脂族取代基或具有 6 至 9 个碳原子的芳香族取代基，或两个取代基 X 共同形成具有 3 至 6 个碳原子的二价亚烷基、 - 或双齿二膦 X2P-R-PX2，其中每个 X 的含义与单齿膦的定义相同，二价亚烷基连接到相同或不同的磷原子上，R 是桥基，在磷原子间至少有 4 个桥基原子、 其中，O-烯丙基化是在酸的存在下进行的，酸的量至少为含芳烃羟基化合物的 0.1 摩尔%。 本发明进一步提供了一种制备环氧树脂的工艺，其中使用了本发明工艺制备的烯丙基芳基醚作为中间体。