diethyl (4-methoxyphenyl)phosphonite | 67103-60-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: diethyl (4-methoxyphenyl)phosphonite
• 英文别名: (4-methoxy-phenyl)-phosphonous acid diethyl ester；(4-Methoxy-phenyl)-phosphonigsaeure-diaethylester；Diaethoxy-(4-methoxy-phenyl)-phosphin；diethyl p-anisylphosphonite；(diethoxy) (p-methoxyphenyl)-phosphine；di-ethyl p-methoxyphenylphosphonite；Diethyl 4-methoxyphenylphosphonite；diethoxy-(4-methoxyphenyl)phosphane
• CAS: 67103-60-0
• 化学式: C₁₁H₁₇O₃P
• 分子量: 228.228
• InChiKey: DOOWFJFNVFZABJ-UHFFFAOYSA-N

物化性质

• 沸点：
  136-138 °C(Press: 13 Torr)
• 密度：
  1.0529 g/cm3(Temp: 0 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  diethyl (4-methoxyphenyl)phosphonite 在 盐酸 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以10.6 g的产率得到ethyl (4-methoxyphenyl)phosphinate
  参考文献：
  名称：

  重新合成芳基-H-次膦酸酯

  摘要：

  报道了由Sander最初开发并由Petneházy优化的制备纯芳基-H-次膦酸酯的反应条件的系统研究。通过将亚磷酸三乙酯直接添加到适当的格氏试剂中，研究了反应浓度对亚膦酸酯中间体形成的影响。亚膦酸酯随后在酸性条件下的水解以高产率和纯度得到各种芳基-H-次膦酸酯。 亚膦酸酯-次膦酸酯-芳基-H-次膦酸酯-亚磷酸三乙酯-水解-格氏试剂

  DOI：

  10.1055/s-0030-1260109
• 作为产物：
  描述：

  乙醇 、 (4-甲氧基苯基)亚膦酸二氯化物 生成 diethyl (4-methoxyphenyl)phosphonite
  参考文献：
  名称：

  Kamai, Doklady Akademii Nauk SSSR, 1949, vol. 66, p. 389,391

  摘要：

  DOI：

文献信息

• Nuclear magnetic resonance, luminescence and structural studies of lanthanide complexes with octadentate macrocyclic ligands bearing benzylphosphinate groups
  作者：Silvio Aime、Andrei S. Batsanov、Mauro Botta、Rachel S. Dickins、Stephen Faulkner、Clive E. Foster、Alice Harrison、Judith A. K. Howard、Janet M. Moloney、Timothy J. Norman、David Parker、Louise Royle、J. A. Gareth Williams

  DOI：10.1039/a703065g

  日期：——

  The solution and solid-state structures of lanthanide complexes of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetryltetramethylenetetra(benzylphosphinate), L1a, and of its o-, m- and p-methoxybenzyl analogues (L2, L3, L4) have been investigated by NMR, relaxometry, crystallographic and photophysical methods. It has been shown that the number of proximate water molecules is dependent on the size of the bound lanthanide ion: the complex [LaL1a]– is nine-co-ordinate and adopts a twisted square-antiprismatic structure with one bound water molecule. The analogous [YL1a]–, [YbL1a]–, [GdL1a]– and [EuL1a]– complexes also adopt a twisted square-antiprismatic geometry, but are eight-co-ordinate, with no metal-bound water. Relaxivity studies with the gadolinium complexes showed that they are purely ‘outer-sphere’ contrast agents, but they associate strongly with proteins leading to a pronounced relaxivity enhancement. Detailed biodistribution studies with [GdL1a]– revealed avid biliary uptake at low doses and a well defined tendency for the complex to be cleared more slowly from tumour tissue, allowing tissue differentiation.

  利用NMR、弛豫测量、晶体学和光物理方法研究了1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙撑四(苄基膦酸酯), L1a及其邻、间、对甲氧基苄基类似物(L2、L3、L4)的镧系配合物的溶液和固态结构。结果表明，邻近的水分子数目取决于结合的镧系离子的大小：配合物[LaL1a]–是九配位的，具有一个结合水分子，呈扭曲的方形反棱柱结构。类似的[YL1a]–、[YbL1a]–、[GdL1a]–和[EuL1a]–配合物也采取扭曲的方形反棱柱几何结构，但为八配位，没有金属结合水。对钆配合物的弛豫率研究表明，它们是纯粹的“外球”对比剂，但与蛋白质强相互作用导致弛豫率显著提高。详细生物分布研究揭示[GdL1a]–在低剂量下有强烈胆汁摄取，且该配合物从肿瘤组织中的清除速度较慢，这有利于组织区分。
• Selective conversion of acrylonitrile into 1,4-dicyano-1-butene
  申请人：Allied Corporation

  公开号：US04574060A1

  公开（公告）日：1986-03-04

  Selective conversion of acrylonitrile into 1,4-dicyano-1-butene by contacting a liquid phase comprising acrylonitrile with an effective amount of a polymer-bound alkyl diarylphosphinite catalyst having the formula I: ##STR1## wherein the trivalent phosphorus is substituted by one alkoxy group and one aryl group and wherein the third bond of phosphorus is a P--C bond to a pendant aryl group of the polymer matrix, such as polystyrene cross-linked with divinylbenzene is disclosed. Treatment of the liquid phase, prior to contacting same with the polymer-bound catalyst, with a drying agent comprising a polymer-bound dialkyl arylphosphonite and regeneration of the drying agent are also disclosed.

  通过将含有丙烯腈的液相与具有以下式I的聚合物结合烷基二芳基膦酰胺催化剂的有效量接触，将丙烯腈选择性地转化为1,4-二氰基-1-丁烯。其中，三价磷被一个烷氧基和一个芳基取代，磷的第三键是与聚合物基体的悬挂芳基之一形成P-C键，例如与二乙烯基苯交联的聚苯乙烯。还披露了在与聚合物结合的催化剂接触之前，对液相进行处理，其中处理液相采用包含聚合物结合的二烷基芳基膦酸酯的干燥剂，并且还披露了对干燥剂进行再生。
• Efficient Synthesis of Phosphonamidates through One‐Pot Sequential Reactions of Phosphonites with Iodine and Amines
  作者：Xunwei Chen、Wenjun Luo、Yanlin Wang、Zikang Li、Xiaorui Ma、Ai‐Yun Peng

  DOI：10.1002/chem.202002934

  日期：2020.11.11

  one‐pot sequential strategy to construct phosphonamidates has been developed by generating phosphonites in situ from arylmagnesium bromides and triethyl phosphite followed by treatment with iodine and amines. A variety of phosphonamidates were obtained with good to excellent yields at room temperature from easily available materials.

  通过从芳基溴化镁和亚磷酸三乙酯原位生成亚膦酸酯，然后用碘和胺进行处理，已经开发出了一种构建磷酸亚酰胺的顺序方法。从室温容易获得的材料在室温下以良好或优异的产率获得了多种膦酰胺盐。
• Alkyl aryl arylphosphonites, process for the preparation thereof and use
  申请人：Hoechst Aktiengesellschaft

  公开号：US05498741A1

  公开（公告）日：1996-03-12

  Monoalkyl monoaryl arylphosphonites of the formula (I); ##STR1## in which R.sub.1 is the radical ##STR2## in which R' is identical or different and is (.sub.1 -C.sub.6)-alkyl, (C.sub.1 -C.sub.6)-alkoxy, (C.sub.1 -C.sub.6)-alkylthio, or halogen, and n is an integer from 0 to 3, or is the naphthyl radical which can bear 1 to 3 substituents R'; R.sub.2 is a (C.sub.1 -C.sub.6)-alkyl radical, and R.sub.3 is as R.sub.1, where R.sub.1 and R.sub.2 can be identical or different with respect to one another; is described.

  化合物的名称为(I)的单烷基单芳基芳基膦酸酯；其中R.sub.1为基团##STR2##在其中R'相同或不同，为(.sub.1-C.sub.6)-烷基，(C.sub.1-C.sub.6)-烷氧基，(C.sub.1-C.sub.6)-烷硫基或卤素，n为0到3的整数，或为萘基，可以承载1到3个取代基R'；R.sub.2为(C.sub.1-C.sub.6)-烷基基团，R.sub.3与R.sub.1相同，其中R.sub.1和R.sub.2可以相同或不同。
• Photoinduced Decarboxylative Radical Phosphinylation
  作者：Yulu Cheng、Jingsen Zhen、Linxiang Chai、Jian Wang、Junyue Yin、Lin Zhu、Chaozhong Li

  DOI：10.1002/anie.202316764

  日期：2024.2.19

  Reported herein is an unprecedented protocol for C(sp³)‐phosphinylation. With 1 mol % 4CzIPN (1,2,3,5‐tetrakis(carbazol‐9‐yl)‐4,6‐dicyanobenzene) as the catalyst, the visible light induced reaction of redox‐active esters of aliphatic carboxylic acids with dimethyl arylphosphonites or diethyl alkylphosphonites at room temperature provides the corresponding decarboxylative phosphinylation products in satisfactory yields. The protocol exhibits broad substrate scope and wide functional‐group compatibility, enabling the late‐stage modification of complex molecules and rapid synthesis of bioactive phosphinic acids such as glutamine synthetase phosphinothricin and a kynureninase inhibitor. A radical‐polar crossover mechanism involving the formation and subsequent oxidation of phosphoranyl radicals followed by nucleophilic demethylation (or deethylation) is proposed.

  摘要 本文报告了一种前所未有的 C(sp3)-膦酰化协议。以 1 mol % 4CzIPN （1,2,3,5-四（咔唑-9-基）-4,6-二氰基苯）为催化剂，在室温下，脂肪族羧酸的氧化还原活性酯与二甲基芳基亚膦酸盐或二乙基烷基亚膦酸盐在可见光的诱导下发生反应，以令人满意的收率得到相应的脱羧膦化产物。该方案具有广泛的底物范围和宽泛的官能团兼容性，能够对复杂分子进行后期修饰，并快速合成具有生物活性的膦酸，如谷氨酰胺合成酶phosphinothricin 和一种犬尿素酶抑制剂。提出了一种自由基-极性交叉机制，其中涉及磷酰自由基的形成和随后的氧化，然后是亲核去甲基化（或脱乙基化）。