diethyl (2-bromo-4-tolyl)phosphonate | 1615710-02-5

• 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: diethyl (2-bromo-4-tolyl)phosphonate
• 英文别名: Diethyl (2-Bromo-4-methylphenyl)phosphonate；2-bromo-1-diethoxyphosphoryl-4-methylbenzene
• CAS: 1615710-02-5
• 化学式: C₁₁H₁₆BrO₃P
• 分子量: 307.124
• InChiKey: OQYNMYUCIXXMJY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  diethyl (2-bromo-4-tolyl)phosphonate 在 正丁基锂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 7.0h， 生成
  参考文献：
  名称：

  Copolymerization of Ethylene and Methyl Acrylate by Cationic Palladium Catalysts That Contain Phosphine-Diethyl Phosphonate Ancillary Ligands

  摘要：

  A series of benzo-linked phosphine-diethyl phosphonate (P-PO) and phosphine-bis(diethyl phosphonate) (P-(PO)2) ligands and the corresponding (P-PO)PdMe(2,6-lutidine)(+) and (P(PO)(2))PdMe(2,6-lutidine)+ complexes were synthesized. Cationic (P-PO)PdMe(2,6-lutidine)+ complexes are active for ethylene oligomerization/polymerization, with activities of 2 kg mol(-1) h(-1) for {k(2)-1-PiPr(2)-2-P(O)(OEt)(2)-5-Me-Ph}PdMe(2,6-lutidine)(+) (3c), 125 kg mol(-1) h(-1) for {k(2)-1-PPh2-2-P(O)(OEt)(2)-5-Me-Ph}PdMe(2,6-lutidine) (3a), and 1470 kg mol(-1) h(-1) for {k(2)-1-P(2-OMe-Ph)(2)-2-P(O)(OEt)(2)-Ph}PdMe(2,6-lutidine) (3b). The polyethylene is highly linear, with over 80% terminal unsaturation and low (230-1890 Da) molecular weight in all cases. 3b copolymerizes ethylene with methyl acrylate, exhibiting highly selective (95%) in-chain (rather than chain-end) acrylate incorporation. The P-(PO)2 catalyst {k(2)-1-P(4-Bu-t-Ph)(2-P(O)(OEt)(2)-5-Me-Ph)-2-P(O)(OEt)(2)-5-Me-Ph}PdMe(2,6-lutidine) (3d) is more active for ethylene homopolymerization (2640 kg mol(-1) h(-1)), yielding linear, low-molecular-weight polymer (1280-1430 Da) with predominantly internal olefin placement. In ethylene/methyl acrylate copolymerization, 3d incorporates 2.6 mol % methyl acrylate, 60% of which is in-chain. Both 3b and 3d catalyze ethylene/acrylic acid copolymerization, albeit with low (<10 kg mol(-1) h(-1)) activities and acrylic acid incorporation up to 1.1 mol %.

  DOI：

  10.1021/om5004489
• 作为产物：
  描述：

  2-溴-4-甲基苯酚 在 吡啶 、 tris-(dibenzylideneacetone)dipalladium(0) 、 1,3-双(二苯基膦)丙烷 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 40.0h， 生成 diethyl (2-bromo-4-tolyl)phosphonate
  参考文献：
  名称：

  钯催化不对称去对称同时构建手性磷和季碳立构中心

  摘要：

  已开发出钯催化的双烯丙基氧化膦的不对称串联 Heck 和羰基化反应。这种去对称化过程提供了一种有效的途径，以良好的产率同时合成手性 P-立体中心和手性季碳立体中心，并具有良好的非对映和对映选择性。

  DOI：

  10.1021/acs.orglett.4c01863

文献信息

• Multinuclear Palladium Olefin Polymerization Catalysts Based on Self-Assembled Zinc Phosphonate Cages
  作者：Qian Liu、Richard F. Jordan

  DOI：10.1021/acs.organomet.8b00683

  日期：2018.12.24

  four [(κ2-OP-P-SO)PdMe(4-tBu-py)]2– units are arranged on the periphery of a double-four-ring (D4R) Zn4P4O12 cage. Analogous 4-L species were generated by the reaction of Zn[1-H]}4, (COD)PdMe2, and other pyridine ligands. 4-py reacts with CH3OH to form a trimeric cluster 3-py, which adopts a cage structure based on Zn3P3O6 and Pd3O3 rings. In the presence of B(C6F5)3 to sequester the pyridine ligands

  膦-膦酸酯-磺酸酯配体HP +（4- t Bu-Ph）（2-PO 3 H 2 -5-Me-Ph）（2-SO 3 – -5-Me-Ph）（H 3 [OP- [P-SO]，1 -H 3）被研究作为基于膦酸锌支架的多核Pd化合物自组装的基础。1层-H 3发生反应以Zn（OAc）2 ·2H 2 O操作得到的Zn [ 1 -H]} 4，其采用的Zn 4 P 4 ø 8，其中锌中心由μ联环结构2-κ 1，κ 1 -bridging（芳基）PO 3个H ^ -配体。的Zn [ 1 -H]} 4种发生反应与乙二胺（TMEDA）PDME 2和吡啶以产生[（κ 2 - ö P- P -SO）PDME（PY）] [锌（TMEDA）]} 2（2），其中两个[（κ 2 - ö P- P -SO）PDME（PY）] 2-单元通过链接的Zn 2 P 2 ö 4环。无CH 3 OH的Zn [ 1 -H]} 4的顺序反应用（COD）PDME
• Lewis Acid Modification and Ethylene Oligomerization Behavior of Palladium Catalysts That Contain a Phosphine-Sulfonate-Diethyl Phosphonate Ancillary Ligand
  作者：Nathan D. Contrella、Richard F. Jordan

  DOI：10.1021/om5009988

  日期：2014.12.22

  The multifunctional phosphine-sulfonate-diethyl phosphonate ligand [1-(P(4-Bu-t-Ph)(2-PO3Et2-5-Me-Ph)-2-SO3-5-Me-Ph](-) ([OP-P-SO](-)) was used to form complexes of type [kappa(2)-(OP-P-SO)]PdMe(L) (L = 2,6-lutidine, 2b; L = pyridine, 2c). B(C6F5)(3) abstracts the Pd-bound sulfonate group of 2b and induces a switch to a phosphine-diethyl phosphonate coordination mode, affording [kappa(2)-(OP-P-SO-B(C6F5)(3))]PdMe(2,6-lutidine) (3). In contrast, MgCl2 binds to the sulfonate and diethyl phosphonate units of 2b, generating the dipalladium species [kappa(2)-(OP-P-SO)PdMe}(2)(mu-Cl)][MgCl] (4) by simple self-assembly. AgB(C6F5)4 reacts with 4 in the presence of THF to selectively abstract the Mg-Cl to form [kappa(2)-(OP-P-SO)PdMe}(2)(mu-Cl)Mg(THF)][B(C6F5)(4)] (5). The ethylene polymerization behaviors of 2b, 2c, 3, and 5 are quite similar (M-n: 120-1170 Da, activity: 60-290 kg (mol Pd)(-1) h(-1)). All of these catalysts produce low-molecular-weight polyethylene with predominantly internal unsaturation, but little branching. The reaction of 4 with 2 equiv of AgB(C6F5)(4) to abstract both chloride ions generates an active ethylene polymerization catalyst that produces linear polyethylene with a bimodal molecular weight distribution.