Methyl benzoylphosphonochloridate | 134420-56-7

• 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: Methyl benzoylphosphonochloridate
• 英文别名: [chloro(methoxy)phosphoryl]-phenylmethanone
• CAS: 134420-56-7
• 化学式: C₈H₈ClO₃P
• 分子量: 218.576
• InChiKey: DTOITFYTUJQHFU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl benzoylphosphonochloridate 在 吡啶 、 盐酸羟胺 、 N,N-二乙基苯胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 {[(E)-Hydroxyimino]-phenyl-methyl}-phosphonic acid benzyl ester methyl ester
  参考文献：
  名称：

  Photoinduced phosphorylation by [.alpha.-(hydroxyimino)benzyl]phosphonates through fragmentation to monomeric metaphosphates

  摘要：

  DOI：

  10.1021/jo00015a040
• 作为产物：
  描述：

  methyl hydrogen benzoylphosphonate 在 氯化亚砜 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 Methyl benzoylphosphonochloridate
  参考文献：
  名称：

  Photoinduced phosphorylation by [.alpha.-(hydroxyimino)benzyl]phosphonates through fragmentation to monomeric metaphosphates

  摘要：

  DOI：

  10.1021/jo00015a040

文献信息

• Beckmann rearrangement of N-(α-hydroxyiminoalkylphosphonyl)amino acids. A convenient synthetic approach to novel peptide-transition-state analogs.
  作者：Eli Breuer、Hisham Zaher、Zeev Tashma

  DOI：10.1016/0040-4039(92)88143-s

  日期：1992.4

  Thermal Beckmann rearrangement of N-(α-hydroxyiminoalkylphosphonyl)amino acid derivatives () yields acylphosphordiamidates (), which represent a new type of peptide analogs.

  N-（α-羟基亚氨基烷基膦酰基）氨基酸衍生物的热贝克曼重排（）产生酰基磷二酰胺化物（），代表一种新型的肽类似物。
• Mahajna, Mahmoud; Breuer, Eli, Journal of the Chemical Society. Perkin transactions I, 1994, # 13, p. 1847 - 1850
  作者：Mahajna, Mahmoud、Breuer, Eli

  DOI：——

  日期：——
• BREUER, ELI;MAHAJNA, MAHMOUD;QUIN, LOUIS D.;QUIN, GYONGYI S., J. ORG. CHEM., 56,(1991) N5, C. 4791-4793
  作者：BREUER, ELI、MAHAJNA, MAHMOUD、QUIN, LOUIS D.、QUIN, GYONGYI S.

  DOI：——

  日期：——
• Mahajna Mahmound, Breuer Eli, J. Chem. Soc. Dalton Trans, (1994) N 13, S 1847-1849
  作者：Mahajna Mahmound, Breuer Eli

  DOI：——

  日期：——
• Thermal fragmentation of trihaloethyl and hexafluoro-2-propyl .alpha.-hydroxyiminobenzylphosphonates. Solvent effects and the trapping of metaphosphate
  作者：Mahmoud Mahajna、Eli Breuer

  DOI：10.1021/jo00079a029

  日期：1993.12

  Reactions of 2,2,2-trihaloethyl or 1,1,1,3,3,3-hexafluoro-2-propyl benzoylphosphonate anions 7 or 10 with hydroxylamine gave the corresponding (alpha-hydroxyiminobenzyl)phosphonates, 3 or 11, respectively, as predominantly (E)-isomers. Refluxing (E)-3a or (E)-3b in EtOH or 2-PrOH caused them to fragment to benzonitrile and mixed phosphodiesters: ethyl trihaloethyl phosphate (12) or 2-propyl trihaloethyl phosphate (13), respectively. (E)-3a did not undergo any fragmentation in boiling water or MeOH. Refluxing (E)-3a in aprotic solvents led to the formation of benzonitrile and P,P'-bis(2,2,2-trifluoroethyl)pyrophosphate (4a). The rate of fragmentation increased with solvent polarity. Similar behavior was exhibited by 11. The fragmentation of anions 3 and 11 is interpreted in terms of a dissociative mechanism leading to the formation of metaphosphate in the first step. The lack of reactivity in water and methanol is rationalized by assuming stabilization of the starting material by H-bond formation, while the rate enhancement by polar solvent is attributed to stabilization of the transition state and solvation of the departing OH- by the solvent. The metaphosphate formed in the thermal fragmentation of 3a in MeCN was trapped by styrene oxide, as evidenced by the isolation and identification of 2-oxo-2-(2',2',2'-trifluoroethyl)-4-phenyl-1,3,2-dioxaphospholane as a mixture of diastereoisomers 18 and 19.