O-亚苯基硼酸盐 | 37737-62-5

• 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: O-亚苯基硼酸盐
• 中文别名: 邻苯硼酸硼
• 英文名称: tris(catecholato)diboron
• 英文别名: (1,2-bis(benzo[d][1,3,2]dioxaborol-2-yloxy)benzene)；o-Phenylendioxy-2,2'-bis(benzodioxa-1,3-borol-2)；Bis-borsaeure-tris-(o-phenylenester)；Tri-o-phenylen-bisborat；tris(o-phenylenedioxa)bisborate；2,2'-o-phenylenedioxy-bis-benzo[1,3,2]dioxaborole；1,2-bis-benzo[1,3,2]dioxaborol-2-yloxy-benzene；bis(benzo-1,3,2-dioxaboranyl)pyrocatecholate；phenylene-1,2-dioxo-bis(1,3,2-dioxaborolane)；o-Phenylendioxy-bis(1,3,2-benzodioxaborol)；Di-O-([1.3.2]benzodioxaborolyl-(2))-brenzcatechin；1.2-Di-([1.3.2]benzodioxaborolyl-(2)-oxy)-benzol；1,2-Bis-benzo[1,3,2]dioxaborol-2-yloxy-benzol；tricatecholdiborane；1,2-Bis(benzo[d][1,3,2]dioxaborol-2-yloxy)benzene；2-[2-(1,3,2-benzodioxaborol-2-yloxy)phenoxy]-1,3,2-benzodioxaborole
• CAS: 37737-62-5
• 化学式: C₁₈H₁₂B₂O₆
• 分子量: 345.912
• InChiKey: WKEXSQGNCGXAHZ-UHFFFAOYSA-N

物化性质

• 熔点：
  102-109 °C(lit.)
• 沸点：
  170 °C.03 mm Hg(lit.)
• 密度：
  1.37±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.36
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

安全信息

• 安全说明：
  S22,S24/25
• WGK Germany：
  3
• 海关编码：
  2909309090

反应信息

• 作为反应物：
  描述：

  O-亚苯基硼酸盐 在 diborane(6) 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以86%的产率得到儿萘酚硼烷
  参考文献：
  名称：

  用于合成儿茶酚硼烷的新经济、便捷方法

  摘要：

  儿茶酚硼烷可通过三邻苯二硼酸酯 (2) 与乙硼烷在三甘醇二甲醚或四甘醇二甲醚中在中等温度（70-80 °C）下方便地合成。产物儿茶酚硼烷可以以 85% 的收率和 >97% 的纯度蒸馏出来。三邻苯二硼酸盐还与硼烷-路易斯碱配合物（例如 BH3:DMS、BH3:THF 和 BH3:NR3）反应，无论是否使用溶剂，都能以良好的收率提供高纯度的儿茶酚硼烷。

  DOI：

  10.1021/op000291w
• 作为产物：
  描述：

  B-氯-1,2-苯二酚硼烷 以 neat (no solvent) 为溶剂， 生成 O-亚苯基硼酸盐
  参考文献：
  名称：

  Gerrard, W.; Lappert, M. F.; Mountfield, B. A., Journal of the Chemical Society

  摘要：

  DOI：

文献信息

• Aluminum-Hydride-Catalyzed Hydroboration of Carbon Dioxide
  作者：Cher-Chiek Chia、Yeow-Chuan Teo、Ning Cham、Samuel Ying-Fu Ho、Zhe-Hua Ng、Hui-Min Toh、Nicolas Mézailles、Cheuk-Wai So

  DOI：10.1021/acs.inorgchem.0c03507

  日期：2021.4.5

  time: 60 min (5 min); yield: 97.6% (>99%); TOF: 292.8 h–1 (356.4 h–1)] and B2O3 (3f). Mechanistic studies show that the Al–H bond in complex 2 activated CO2 to form [ClC(PPh2NMes)2Al(H)OC(O)H}] (4), which was subsequently reacted with BH3·SMe2 to form 3e and 3f, along with the regeneration of complex 2. Complex 2 also shows good catalytic activity toward the hydroboration of carbonyl, nitrile, and

  这项研究描述了首次使用双（磷烷基）甲氨基铝氢化物[ClC（PPh 2 NMes）2 AlH 2（2，Mes = Me 3 C 6 H 2），用于CO 2的催化加氢硼化。通过在-78°C下在甲苯中使类胡萝卜素锂[Li（Cl）C（PPh 2 NMes）2 ]与2当量的AlH 3 ·NEtMe 2反应，合成了配合物2。2（10 mol％）能够催化HBpin在C 6 D 6中还原CO 2在110°C的温度下放置2天，得到甲氧基硼烷[MeOBpin]（3a；产率：78％，TOF：0.16 h –1）和双（硼基）氧化物[pinBOBpin]（3b）的混合物。当使用更有效的[BH 3 ·SMe 2 ]代替HBpin时，催化反应极纯，导致形成硼酸三甲酯[B（OMe）3 ]（3e）[催化负载量：1 mol％（10 mol） ％）; 反应时间：60分钟（5分钟）；产率：97.6％（＞ 99％）；TOF：292
• Rhodium catalysed diboration of unstrained internal alkenes and a new and general route to zwitterionic [L2Rh(η6-catBcat)] (cat = 1,2-O2C6H4) complexes†
  作者：Chaoyang Dai、Todd B. Marder、Edward G. Robins、Dmitri S. Yufit、Judith A. K. Howard、Todd B. Marder、Andrew J. Scott、William Clegg

  DOI：10.1039/a804710c

  日期：——

  Reactions of [L2Rh(acac)] (L = alkene or phosphine) with B2cat3 yield the zwitterionic complexes [L2Rh(η6-catBcat)] and [(acac)Bcat] cleanly; [(dppm)Rh(η6-catBcat)], the X-ray structure of which is reported, is an excellent catalyst for the diboration of vinylarenes and unstrained internal alkenes cis- and trans-stilbene and trans-β-methylstyrene.

  [L2Rh(acac)]（L = 烯烃或膦）与B2cat3反应生成净化的两性离子配合物[L2Rh(η6-catBcat)]和[(acac)Bcat]；其中，[(dppm)Rh(η6-catBcat)]的X射线结构已被报道，是一种优异的催化剂，用于乙烯基芳烃和不饱和内烯烃（顺式和反式二苯乙烯以及反式β-甲基苯乙烯）的二硼化反应。
• Phosphine promoted substituent redistribution reactions of B-chlorocatechol borane: molecular structures of ClBcat, BrBcat and L·ClBcat (cat = 1,2-O2C6H4; L = PMe3, PEt3, PBut3, PCy3, NEt3)†
  作者：R. Benjamin Coapes、Fabio E. S. Souza、Mark A. Fox、Andrei S. Batsanov、Andrés E. Goeta、Dimitrii S. Yufit、Michael A. Leech、Judith A. K. Howard、Andrew J. Scott、William Clegg、Todd B. Marder

  DOI：10.1039/b010025k

  日期：——

  In order to evaluate the potential for side reactions when using B-chlorocatechol borane (ClBcat) in stoichiometric or catalytic transformations involving metal phosphine complexes, we examined the interaction between ClBcat and a series of PR3 compounds. Reactions of ClBcat with the basic phosphines PMe3, PEt3, PMe2Ph and PBut3, in exactly 1 ∶ 1 stoichiometry, all afforded crystalline adducts of the form R3P·ClBcat, which have been characterised spectroscopically. All display broad singlets at room temperature in both 11B1H} and 31P1H} NMR spectra with no B–P coupling observed. The low temperature 11B1H} and 31P1H} NMR spectra, however, do show B–P coupling, suggesting rapid dissociation at room temperature. The compounds ClBcat, BrBcat, and the adducts between ClBcat and PMe3, PEt3 and PBut3 have been characterised by single crystal X-ray diffraction. In ClBcat and BrBcat, the halogen contributes little π-bonding to boron as the B–O bond lengths are identical in both compounds. The reaction of ClBcat with a small excess of PCy3 yielded Cy3P·ClBcat, which has also been characterised by single crystal X-ray diffraction and shows considerable distortion. The reaction between ClBcat and the less basic phosphines PPh3 and PPh2Me yielded only the redistribution products R3P·BCl3 and B2cat3. In fact, reaction of all of the phosphines with an excess of ClBcat gave only redistribution products, although there was evidence for an intermediate in the 11B1H} NMR spectra, with PMe3 and PEt3. The isolated R3P·ClBcat adducts proved unstable, even at low temperature in the solid state, eventually leading to R3P·BCl3 and B2cat3. Reaction of ClBcat with NEt3 afforded Et3N·ClBcat, which was characterised spectroscopically and by single crystal X-ray diffraction. This adduct is stable both in solution and in the solid state.

  为了评估B-氯儿茶酚硼烷（ClBcat）在与金属膦配合物的定量或催化转化中可能产生的副反应，我们研究了ClBcat与一系列PR3化合物的相互作用。在严格的1∶1化学计量比下，ClBcat与基本膦类物质如PMe3、PEt3、PMe2Ph和PBut3的反应，均生成了晶体形态的加合物R3P·ClBcat，这些加合物已通过光谱学进行了表征。所有这些加合物在室温下的11B1H}和31P1H}核磁共振谱中均显示出宽的单峰，未观察到B-P偶合。然而，在低温下的11B1H}和31P1H}核磁共振谱中确实出现了B-P偶合现象，表明室温下快速解离。ClBcat、BrBcat以及ClBcat与PMe3、PEt3和PBut3之间的加合物已通过单晶X射线衍射进行了表征。在ClBcat和BrBcat中，卤素对硼的π键贡献很小，因为这两种化合物中的B-O键长度相同。ClBcat与少量过量的PCy3反应生成了Cy3P·ClBcat，该加合物也通过单晶X射线衍射进行了表征，并显示出显著的扭曲。ClBcat与较弱的碱性膦类物质PPh3和PPh2Me反应仅生成了重分配产物R3P·BCl3和B2cat3。实际上，所有膦类物质与过量ClBcat反应仅生成重分配产物，尽管在11B1H}核磁共振谱中存在中间体的证据，如PMe3和PEt3的情况。分离得到的R3P·ClBcat加合物在固态甚至低温下也表现出不稳定性，最终会生成R3P·BCl3和B2cat3。ClBcat与NEt3反应生成了Et3N·ClBcat，该加合物通过光谱学和单晶X射线衍射进行了表征，且在溶液和固态中均表现出稳定性。
• Reactions of catecholborane with Wilkinson's catalyst: implications for transition metal-catalyzed hydroborations of alkenes
  作者：Kevin Burgess、Wilfred A. Van der Donk、Stephen A. Westcott、Todd B. Marder、R. Thomas Baker、Joseph C. Calabrese

  DOI：10.1021/ja00050a015

  日期：1992.11

  Reactions of catecholborane (HBO 2 C 6 H 4 ) with RhCl(PPh 3 ) 3 (1) yield a variety of products depending on the B/Rh ratio, solvent, and temperature. Of particular relevance to catalyzed alkene hydroboration is degradation of HBO 2 C 6 H 4 to B 2 (O 2 C 6 H 4 ) 3 /«BH 3 » and the dihydride RhH 2 Cl(PPh 3 ) 3 (3). The molecular structure of 3, determined by X-ray diffraction, has meridional phosphine

  儿茶酚硼烷 (HBO 2 C 6 H 4 ) 与 RhCl(PPh 3 ) 3 (1) 的反应会根据 B/Rh 比、溶剂和温度产生多种产物。与催化的烯烃硼氢化特别相关的是 HBO 2 C 6 H 4 降解为 B 2 (O 2 C 6 H 4 ) 3 /«BH 3 » 和二氢化物 RhH 2 Cl(PPh 3 ) 3 (3)。3的分子结构，由X射线衍射确定，具有经向膦配体和顺式氢化物
• Catalyzed hydroboration of nitrostyrenes and 4-vinylaniline: a mild and selective route to aniline derivatives containing boronate esters
  作者：Christopher M. Vogels、Andreas Decken、Stephen A. Westcott

  DOI：10.1016/j.tetlet.2006.01.144

  日期：2006.4

  from competing hydrogenation and hydroboration of the alkene unit along with reduction of the nitro group. Hydroboration of 4-vinylaniline gave regioselective formation of either the branched or the linear organoboronate ester depending upon the catalyst precursors (i.e., RhCl(PPh3)3 or Rh(acac)(dppe) vs [Cp∗IrCl2]2) used to facilitate this reaction. Hydroboration products were converted to air-stable

  儿茶酚硼烷（HBcat； cat = 1,2-O 2 C 6 H 4）与β-硝基苯乙烯和3-硝基苯乙烯的过渡金属催化反应，导致烯烃单元竞争性氢化和氢硼化以及硝基还原而生成的产物。4-乙烯基苯胺的氢硼化反应可根据所用催化剂前体（即RhCl（PPh 3）3或Rh（acac）（dppe）vs [Cp ∗ IrCl 2 ] 2）而形成支链或线性有机硼酸酯的区域选择性形成。促进这一反应。通过添加频哪醇将硼氢化产物转化为空气稳定的伯胺。