1-(溴甲基)-3,5-双[(4-乙烯基苯基)甲氧基]苯 | 199277-76-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1-(溴甲基)-3,5-双[(4-乙烯基苯基)甲氧基]苯
• 英文名称: 3,5-bis(p-vinylphenylmethyloxy)benzyl bromide
• 英文别名: 3,5-Di(4-vinylbenzyloxy)benzyl bromide；3,5-Bis(4-vinylbenzyloxy)benzyl bromide；1-(bromomethyl)-3,5-bis[(4-ethenylphenyl)methoxy]benzene
• CAS: 199277-76-4
• 化学式: C₂₅H₂₃BrO₂
• 分子量: 435.36
• InChiKey: JVFMELGYXCXKQW-UHFFFAOYSA-N

物化性质

• 熔点：
  78-79 °C
• 沸点：
  564.6±45.0 °C(Predicted)
• 密度：
  1.279±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  28
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(溴甲基)-3,5-双[(4-乙烯基苯基)甲氧基]苯 在 18-冠醚-6 、 四溴化碳 、 potassium carbonate 、 三苯基膦 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 97.0h， 生成 3,5-Di[3,5-di(4-vinylbenzyloxy)benzyloxy]benzyl bromide
  参考文献：
  名称：

  Immobilization of BINOL by Cross-Linking Copolymerization of Styryl Derivatives with Styrene, and Applications in Enantioselective Ti and Al Lewis Acid Mediated Additions of Et2Zn and Me3SiCN to Aldehydes and of Diphenyl Nitrone to Enol Ethers

  摘要：

  The chiral ligand 1,1'-bi-2-naphthol (BINOL) has been succesfully immobilized on polystyrene. Several dendritic and non-dendritic BINOL derivatives (3, and 13-17), bearing at least two polymerizable styryl groups, were prepared and fully characterized. Suspension copolymerization of the MOM- or TIPS-protected cross-linking BINOL ligands (MOM = methyloxymethyl, TIPS = triisopropylsilyl) with styrene, cleavage of the protecting-groups, and loading with a Lewis-acid afforded catalytically active polystyrene-supported BINOLates. The polymer-bound BINOLs p-3, and p-13-p-16 were tested in the Ti-BINOLate-mediated addition of Et2Zn to PhCHO. The enantioselectivities (up to 93%) and conversions obtained with the polymer-bound catalysts were in most cases identical (within experimental error) to those obtained with the unsubstituted 1,1'-bi-2-naphthol and with the non-polymerized BINOL cross-linkers under homogeneous conditions. Special focus was put on the reusability of the supported catalyst: the polymer-beads were used in up to 20 consecutive catalytic runs, with the best polymers showing no or only minor loss of selectivity. BINOL-polymers p-17, obtained by copolymerization of a 3,3'-distyryl-substituted BINOL 17a with styrene, were used in the BINOL AlMe-mediated cycloaddition of diphenyl nitrone with alkyl vinyl ethers. In all cases the exolendo selectivity (greater than or equal to 92:8) and the enantioselectivities with which the exo-cycloadducts were formed (greater than or equal to 95%) correspond to those observed in the homogeneous reactions. A dendritically cross-linked BINOL-polymer was also employed in the Ti-BINOLate-mediated cyanosilylation of pivalaldehyde. The enantiopurity of the cyanohydrine obtained in the first run was as high as in the homogeneous reaction (72%); surprisingly the catalytic performance of the supported catalyst increased steadily during the first catalytic cycles to reach 83%. Thus, cross-linking BINOLs can be succesfully incorporated into a polystyrene matrix (without racemization!) to give poly mer-bound BINOL ligands that give excellent performance over many catalytic cycles with catalytic activities comparable with those of soluble analogues.

  DOI：

  10.1002/1521-3765(20001016)6:20<3692::aid-chem3692>3.0.co;2-0
• 作为产物：
  描述：

  3,5-二羟基苯甲酸甲酯 在 lithium aluminium tetrahydride 、 18-冠醚-6 、 四溴化碳 、 potassium carbonate 、 三苯基膦 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 84.0h， 生成 1-(溴甲基)-3,5-双[(4-乙烯基苯基)甲氧基]苯
  参考文献：
  名称：

  Immobilization of BINOL by Cross-Linking Copolymerization of Styryl Derivatives with Styrene, and Applications in Enantioselective Ti and Al Lewis Acid Mediated Additions of Et2Zn and Me3SiCN to Aldehydes and of Diphenyl Nitrone to Enol Ethers

  摘要：

  The chiral ligand 1,1'-bi-2-naphthol (BINOL) has been succesfully immobilized on polystyrene. Several dendritic and non-dendritic BINOL derivatives (3, and 13-17), bearing at least two polymerizable styryl groups, were prepared and fully characterized. Suspension copolymerization of the MOM- or TIPS-protected cross-linking BINOL ligands (MOM = methyloxymethyl, TIPS = triisopropylsilyl) with styrene, cleavage of the protecting-groups, and loading with a Lewis-acid afforded catalytically active polystyrene-supported BINOLates. The polymer-bound BINOLs p-3, and p-13-p-16 were tested in the Ti-BINOLate-mediated addition of Et2Zn to PhCHO. The enantioselectivities (up to 93%) and conversions obtained with the polymer-bound catalysts were in most cases identical (within experimental error) to those obtained with the unsubstituted 1,1'-bi-2-naphthol and with the non-polymerized BINOL cross-linkers under homogeneous conditions. Special focus was put on the reusability of the supported catalyst: the polymer-beads were used in up to 20 consecutive catalytic runs, with the best polymers showing no or only minor loss of selectivity. BINOL-polymers p-17, obtained by copolymerization of a 3,3'-distyryl-substituted BINOL 17a with styrene, were used in the BINOL AlMe-mediated cycloaddition of diphenyl nitrone with alkyl vinyl ethers. In all cases the exolendo selectivity (greater than or equal to 92:8) and the enantioselectivities with which the exo-cycloadducts were formed (greater than or equal to 95%) correspond to those observed in the homogeneous reactions. A dendritically cross-linked BINOL-polymer was also employed in the Ti-BINOLate-mediated cyanosilylation of pivalaldehyde. The enantiopurity of the cyanohydrine obtained in the first run was as high as in the homogeneous reaction (72%); surprisingly the catalytic performance of the supported catalyst increased steadily during the first catalytic cycles to reach 83%. Thus, cross-linking BINOLs can be succesfully incorporated into a polystyrene matrix (without racemization!) to give poly mer-bound BINOL ligands that give excellent performance over many catalytic cycles with catalytic activities comparable with those of soluble analogues.

  DOI：

  10.1002/1521-3765(20001016)6:20<3692::aid-chem3692>3.0.co;2-0

文献信息

• Preparation of Dendritic and Non-Dendritic Styryl-Substituted Salens for Cross-Linking Suspension Copolymerization with Styrene and Multiple Use of the Corresponding Mn and Cr Complexes in Enantioselective Epoxidations and Hetero-Diels–Alder Reactions
  作者：Holger Sellner、Jaana K. Karjalainen、Dieter Seebach

  DOI：10.1002/1521-3765(20010702)7:13<2873::aid-chem2873>3.0.co;2-c

  日期：2001.7.2

  than 95% of the Salen incorporated being actually accessible for complexation (by elemental analysis). The polymer-bound Mn and Cr complexes were used as catalysts for epoxidations of six phenyl-substituted olefins (m-CPBA/NMO; products 22a-f), and for dihydropyranone formation from the Danishefsky diene and aldehydes (PhCHO, C5H11CHO, C6H11CHO, products 23a-c). There are several remarkable features

  在使用TADDOL和BINOL之后，我们现在制备了带有两个至八个苯乙烯基的Salen衍生物（2、3、14、15、18、19、20、21），用于与苯乙烯交联共聚。Salen核要么衍生自（R，R）-二苯基乙二胺（3，15，19，21），要么衍生自（R，R）-环己烷二胺（2，14，18，20）。使用Suzuki（cf.1）或Sonogashira交叉偶联（cf.11）和/或用树状苯乙烯基取代的Fréchet型苄基进行酚醚化（cf.5、7）将苯乙烯基连接到水杨醛部分上分支溴化物。随后与二胺的缩合提供手性Salens。还制备了缺少外围乙烯基的相应Salens（参见12、13、16、17），用于比较均相溶液中的催化活性和聚苯乙烯中的催化活性。按照Itsuno和Fréchet的程序，苯乙烯和苯乙烯基Salens的交联自由基悬浮共聚，得到的珠子（直径约400微米）装有Mn或Cr（每克聚合物约0.2 mmo
• Speeding up heterogeneous catalysis with an improved highly reusable catalyst for the preparation of enantioenriched secondary alcohols
  作者：Esther M. Sánchez-Carnerero、Rafael Sandoval-Torrientes、Javier Urieta-Mora、Florencio Moreno、Beatriz L. Maroto、Santiago de la Moya

  DOI：10.1016/j.reactfunctpolym.2017.02.008

  日期：2017.4

  A new catalytic heterogeneous system, very efficient and highly reusable, for the preparation of enantioenriched secondary alcohols through the addition of diethylzinc to benzaldehyde has been developed. This system is based on a chiral bis(hydroxyamide) ligand supported on crosslinked polystyrene. The catalyst has been shown to be very efficient, leading to the corresponding secondary alcohol with

  已经开发出一种非常有效且高度可重复使用的新型催化多相体系，该体系通过将二乙基锌添加到苯甲醛中来制备对映体富集的仲醇。该系统基于负载在交联聚苯乙烯上的手性双（羟酰胺）配体。已显示该催化剂非常有效，在短至2小时的时间内即可产生对映体过量93％的相应仲醇，并且仅使用4％的多相催化剂和1.5当量的有机锌试剂即可。我们已经证明，新催化剂非常稳定，可以有效地循环使用，而不会降低收率或对映选择性。对于通过使用催化流化床反应器将反应潜在地转移到工业中，所提出的系统具有毫无疑问的兴趣。
• Preparation of Polystyrene Beads with Dendritically Embedded TADDOL and Use in EnantioselectiveLewis Acid Catalysis
  作者：Holger Sellner、P. Beat Rheiner、Dieter Seebach

  DOI：10.1002/1522-2675(200201)85:1<352::aid-hlca352>3.0.co;2-d

  日期：2002.1

  of TADDOLates, which are dendritically incorporated in polystyrene beads (Scheme 1). A series of styryl-substituted TADDOLs with flexible, rigid, or dendritically branching spacers between the TADDOL core and the styryl groups (2–16 in number) has been prepared (5–7, 20, 21, 26 in Schemes 2–4 and Fig. 1–3). These were used as cross-linkers in styrene-suspension polymerization, leading to beads of ca

  对 TADDOLates 的制备和使用进行了完整的说明，TADDOLates 以树枝状掺入聚苯乙烯珠粒中（方案 1）。已经制备了一系列苯乙烯基取代的 TADDOL，在 TADDOL 核心和苯乙烯基（数量为 2-16）之间具有柔性、刚性或树枝状支化间隔物（方案 2-4 中的 5-7、20、21、26 和图 1-3)。这些被用作苯乙烯悬浮聚合中的交联剂，导致约珠。400-μm 直径（方案 5 和 6，b）。这些依次负载钛酸盐并用于路易斯酸催化将 Et2Zn 添加到 PhCHO 作为测试反应（方案 6）。在标准条件下获得的对映选择性和转化度（均高达 99%）的比较，表明这些掺入聚合物的 Ti-TADDOLates 是该过程的高效催化剂（表 1）。鉴于制备新型固定化催化剂所需的努力，重点放在了它们的多种用途上。从 TADDOL 获得的聚合物在 20 次测试反应循环中的性能最好，该聚合物带有四个第一代
• Taddol and titanium (IV) taddolate dendrimers
  申请人：Novartis AG

  公开号：US06211316B1

  公开（公告）日：2001-04-03

  TADDOL dendrimers are described. Their use as crosslinkers in polymerisation reactions and the use of Ti salts of polymer-bound TADDOL dendrimers as catalysts in enantioselective addition reactions is disclosed.

  本文介绍了TADDOL树枝状聚合物。它们作为聚合反应中的交联剂以及聚合物支持的TADDOL树枝状聚合物的Ti盐在对映选择性加成反应中作为催化剂的使用被揭示。
• TADDOL and titanium ( ) taddolate dendrimers and composition
  申请人：Novartis AG

  公开号：US06441112B1

  公开（公告）日：2002-08-27

  TADDOL dendrimers are described. Their use as crosslinkers in polymerisation reactions and the use of Ti salts of polymer-bound TADDOL dendrimers as catalysts in enantioselective addition reactions is disclosed.

  介绍了TADDOL树枝状聚合物。它们作为聚合反应中的交联剂以及聚合物- TADDOL树枝状聚合物的Ti盐作为手性选择性加成反应催化剂的用途被揭示。