dimethyl 1-hydroxy-1-(3-bromophenyl)methylphosphonate

• 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: dimethyl 1-hydroxy-1-(3-bromophenyl)methylphosphonate
• 英文别名: (3-Bromophenyl)-dimethoxyphosphorylmethanol；(3-bromophenyl)-dimethoxyphosphorylmethanol
• 化学式: C₉H₁₂BrO₄P
• 分子量: 295.07
• InChiKey: SWPZVCAWSFYHIL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(2,6-二氯苯氧基)乙酰氯 、 dimethyl 1-hydroxy-1-(3-bromophenyl)methylphosphonate 在 吡啶 作用下， 以 氯仿 为溶剂， 以53%的产率得到O,O-dimethyl α-(2,4-dichlorophenoxyacetoxy)-3-bromobenzylphosphonate
  参考文献：
  名称：

  Studies of O,O-Dimethyl α-(2,4-Dichlorophenoxyacetoxy)ethylphosphonate (HW02) as a New Herbicide. 1. Synthesis and Herbicidal Activity of HW02 and Analogues as Novel Inhibitors of Pyruvate Dehydrogenase Complex

  摘要：

  On the basis of the previous work for optimization of O,O-diethyl alpha-(substituted phenoxyacetoxy)alkylphosphonates, further extensive synthetic modifications were made to the substituents in alkylphosphonate and phenoxy moieties of the title compounds. New O,O-dimethyl alpha-(substituted phenoxyacetoxy)alkylphosphonates were synthesized as potential inhibitors of pyruvate dehydorogenase complex (PDHc). Their herbicidal activity and efficacy in vitro against PDHc were examined. Some of these compounds exhibited significant herbicidal activity and were demonstrated to be effective inhibitors of PDHc from three different plants. The structure-activity relationships of these compounds including previously reported analogous compounds were studied by examining their herbicidal activities. Both inhibitory potency against PDHc and herbicidal activity of title compounds could be increased greatly by optimizing substituent groups of the title compounds. O,O-Dimethyl alpha-(2,4-dichlorophenoxyacetoxy)ethylphosphonate (I-5), which acted as a competitive inhibitor of PDHc with much higher inhibitory potency against PDHc from Pisum sativum and Phaseolus radiatus than from Oryza sativa , was found to be the most effective compound against broadleaf weeds and showed potential utility as herbicide.

  DOI：

  10.1021/jf104247w
• 作为产物：
  描述：

  间溴苯甲醛 、 二甲基三甲硅基膦酸酯 在 1,3-双(2,6-二异丙基苯基)咪唑-2-烯 、 盐酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 24.5h， 以74%的产率得到dimethyl 1-hydroxy-1-(3-bromophenyl)methylphosphonate
  参考文献：
  名称：

  N-杂环碳催化醛的氢膦酰化

  摘要：

  已开发出N-杂环卡宾催化的亚甲基三甲基甲硅烷基亚磷酸酯与醛的Pudovik型反应，以构建碳-磷键，从而以中等至优异的产率提供α-羟基膦酸酯。 N-杂环卡宾-Pudovik型反应-α-羟基膦酸酯-醛-CP键

  DOI：

  10.1055/s-0030-1260045

文献信息

• Phospho-transfer catalysis
  作者：Stephen R Davies、Michael C. Mitchell、Christopher P Cain、Paul G Devitt、Roger J Taylor、Terence P Kee

  DOI：10.1016/s0022-328x(97)00176-9

  日期：1998.1

  9×10−2 mol−1 dm3 h−1, 293 K). However, one of the major limitations of this model is that competitive product inhibition dominates after some 15 turnovers (75% completion). Model studies reveal that hydrophosphonylation catalysis via a nitrogen Lewis base is accelerated up to 10-fold upon the introduction of [Zn(OSO2CF3)2] as co-catalyst. Consequently, Class II.1 systems employ metal salts [Zn(OSO2CF3)2]

  我们在这里报告了一种精确的原位31 P 1 H} -NMR方法，用于测定α-羟基膦酸酯（羰基羰基膦酰化反应（Pudovik）反应的产物）的对映体纯度。该方法基于二氮杂膦烷手性衍生剂（CDA），该试剂满足精确测定的所有标准；（i）α-羟基膦酸酯的衍生既快速又干净，（ii）缺乏动力学拆分，并且（iii）31 P 1 H}化学位移分散体非常出色（> 5ppm）。通过交叉引用从CDA衍生的（MeO）2的酯获得的31 P 1 H} -NMR信号，实现了该测定的校准从脂肪酶催化的（MeO）2 P（= O）CHPh（OAc）水解（F-AP 15，米根霉（Rhizopuus oryzae））获得的鳞状物质中，用P（= O）CHPh（OH）进行旋光度测量。对一系列密切相关的衍生化α-羟基膦酸酯的NMR化学位移和偶合参数的分析在推断的基础上支持进一步的构型分配。我们还报告了在酸，有机氮碱和金属盐存在下α-羟基膦酸酯的构型稳定性。2
• Biocatalytic Promiscuity of Lipases in Carbon‐Phosphorus Bond Formation
  作者：Dominik Koszelewski、Ryszard Ostaszewski

  DOI：10.1002/cctc.201900397

  日期：2019.5.20

  A promiscuous lipase‐catalyzed carbon‐phosphorus bond formation is presented. The developed enzymatic Pudovik‐Abramov reaction of various aromatic and aliphatic aldehydes with dialkyl phosphonates provides biologically and pharmacologically relevant α‐hydroxy phosphonates with the yields from 11 % to 85 %. The developed protocol proceeds in the presence of porcine pancreas lipase under environmentally

  提出了混杂的脂肪酶催化的碳-磷键形成。各种芳香族和脂肪族醛与二烷基膦酸酯的发达的酶促Pudovik‐Abramov反应可提供生物学上和药理学上相关的α-羟基膦酸酯，产率为11％至85％。所开发的方案在环境可持续的条件下在猪胰腺脂肪酶存在下进行。研究了包括酶来源，有机溶剂和温度在内的反应条件对反应过程的影响。制定的协议适用于多种醛，包括与合成有关的杂环糠醛和2-噻吩甲醛。
• Accurate in situ 31P{1H} assay of enantiopurity in α-hydroxyphosphonate esters using a diazaphospholidine derivatizing agent
  作者：Paul G. Devitt、Michael C. Mitchell、John M. Weetman、Roger J. Taylor、Terence P. Kee

  DOI：10.1016/0957-4166(95)00265-q

  日期：1995.8

  A rapid, convenient and efficient in situ assay of enantiomeric excess in alpha-hydroxyphosphonate esters is reported exploiting P-31/H-1} NMR analysis of the diastereoisomers formed upon condensation with a phosphorochloridite reagent containing a chiral diazaphospholidine ring. Use of this chiral framewark affords chemical shift dispersions >5 ppm between diastereoisomers. Accurate integrations are thus possible once account is taken of differential n.O.e. effects and spin lattice T-1 relaxation rimes of the phosphorus nuclei.
• Synthesis, characterization and catalytic properties of magnetic nanoparticle supported guanidine in base catalyzed synthesis of α-hydroxyphosphonates and α-acetoxyphosphonates
  作者：Amin Rostami、Bahareh Atashkar、Darush Moradi

  DOI：10.1016/j.apcata.2013.07.001

  日期：2013.10

  Magnetic nanoparticle Fe3O4-immobilized guanidine (MNPs-Guanidine) as a novel magnetically interphase nanocatalyst was synthesized and characterized. MNPs-Guanidine catalyzed the synthesis of alpha-hydroxyphosphonates from aldehydes and dimethyl phosphite in solvent-free condition at 80 degrees C. The synthesis of alpha-acetoxyphosphonates through a one-pot reaction of aldehydes, dimethyl phosphite and acetic anhydride was also achieved using this catalyst in PEG at room temperature. The catalyst was recycled up to 10 times with little loss of activity. (C) 2013 Elsevier B.V. All rights reserved.
• <i>N</i>-Heterocyclic Carbenes Catalyzed Phospho-Aldol Reaction of Aldehydes
  作者：Lin He、Zhihua Cai、Xiaowei Ma、Guangfen Du

  DOI：10.1002/cjoc.201300615

  日期：2013.12

  AbstractAn efficient phospho‐aldol reaction of aldehydes catalyzed by N‐heterocyclic carbenes (NHCs) has been developed. With 10 mol% stable NHC 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene, various aldehydes reacted with dialkylphosphites smoothly to provide α‐hydroxy phosphonates in 59% –99% yield. In this process, NHC was assumed to function as a carbon‐centered br?nsted base.