2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphinoyl radical | 178817-47-5

• 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: 2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphinoyl radical
• CAS: 178817-47-5
• 化学式: C₁₇H₂₆O₄P
• 分子量: 325.365
• InChiKey: KCSAIHNLSYMLGZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.74
• 重原子数：
  22.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphinoyl radical 在 百草枯 作用下， 以 乙腈 为溶剂， 生成 (2,6-Dimethoxy benzoyl)-2,4,4 trimethylpentylphosphineoxide
  参考文献：
  名称：

  膦酰基自由基：结构和反应性。激光闪光光解和时间分辨 ESR 研究

  摘要：

  通过激光闪光光解研究了一系列双（酰基）氧化膦的光化学及其磷自由基与丙烯酸正丁酯、苯硫酚、溴三氯甲烷、氧和甲基紫精的反应速率常数。将结果与单(酰基)氧化膦((2,4,6-三甲基苯甲酰基)二苯基氧化膦)进行比较。不同磷自由基反应性的变化与磷原子上自由基定位的程度和 s 特征相关，这反映在 31P 超精细耦合常数上，通过时间分辨 ESR 测量。在 σ 轨道中观察到高度自旋定位的高 31P 超精细分裂。结果表明，典型的自由基反应（加入单体和氧，和原子抽象）与 31P 超精细耦合密切相关。观察到电子转移反应（甲基紫精的还原）呈负相关，局部轨道具有较高的 p 特征，...

  DOI：

  10.1021/ja982463z
• 作为产物：
  描述：

  二(2,6-二甲氧基苯甲酰基)(2,4,4-三甲基戊基)氧膦 以 乙腈 为溶剂， 生成 2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphinoyl radical
  参考文献：
  名称：

  A Steady-State and Picosecond Pump-Probe Investigation of the Photophysics of an Acyl and a Bis(acyl)phosphine Oxide

  摘要：

  The photophysics (2,4,6-trimethylbenzoyl)diphenylphosphine oxide(1) and bis(2,6-dimethoxybenzoyl)2,4,4-trimethylpentylphosphine oxide (4) have been investigated by fluorescence, phosphorescence, and low temperature time resolved electron spin resonance. Both 1 and 4 undergo a-cleavage to produce benzoyl and phosphorous centered radicals. The photochemistry of 1 and 4 has been investigated by nanosecond laser flash photolysis, picosecond pump-probe spectroscopy, and steady-state photolysis. The singlet states of 1 and 4 and the phosphorous centered radicals produced by alpha-cleavage were characterized directly by time resolved absorption spectroscopy. The triplet states of 1 and 4 were characterized indirectly by quenching with 1-phenylnaphthalene as a selective triplet quencher. The use of 1-phenylnaphthalene indicates that alpha-cleavage occurs mainly from the triplet states of 1 and 4. However, the observed rate of formation of phosphorous centered radicals derived from picosecond investigations is experimentally indistinguishable from the rate of disappearance of the singlet states of 1 and 4. The results are compatible with mechanisms for which the rate of intersystem crossing of the S-1 states of 1 and 4 limits the observed rate of alpha-cleavage, because the rate of alpha-cleavage is of the same order or faster than the rate of intersystem crossing. This relatively uncommon situation appears to have an analogy in the well investigated photochemistry of dibenzyl ketone.

  DOI：

  10.1021/ja971630c

文献信息

• Probing the Reactivity of Photoinitiators for Free Radical Polymerization:  Time-Resolved Infrared Spectroscopic Study of Benzoyl Radicals
  作者：Christopher S. Colley、David C. Grills、Nicholas A. Besley、Steffen Jockusch、Pavel Matousek、Anthony W. Parker、Michael Towrie、Nicholas J. Turro、Peter M. W. Gill、Michael W. George

  DOI：10.1021/ja026099m

  日期：2002.12.1

  of substituted benzoyl radicals has been generated by laser flash photolysis of alpha-hydroxy ketones, alpha-amino ketones, and acyl and bis(acyl)phosphine oxides, all of which are used commercially as photoinitiators in free radical polymerizations. The benzoyl radicals have been studied by fast time-resolved infrared spectroscopy. The absolute rate constants for their reaction with n-butylacrylate

  通过 α-羟基酮、α-氨基酮以及酰基和双（酰基）氧化膦的激光闪光光解产生了一系列取代的苯甲酰基自由基，所有这些都在商业上用作自由基聚合中的光引发剂。苯甲酰基自由基已通过快速时间分辨红外光谱进行了研究。在乙腈溶液中测量它们与丙烯酸正丁酯、苯硫酚、溴三氯甲烷和氧气反应的绝对速率常数。苯甲酰基自由基加成到丙烯酸正丁酯的速率常数范围从 1.3 x 10(5) 到 5.5 x 10(5) M(-1) s(-1) 并且比丙烯酸正丁酯低约 2 个数量级除了由所研究酮的 α 裂解产生的反自由基之外。已经进行了密度泛函理论计算，以使观察到的引发自由基的反应性合理化。通过酰基和双（酰基）氧化膦的光解产生的磷中心自由基的计算表明，P原子马利肯自旋群是磷中心自由基相对反应性的指标。(2,4,6-三甲基苯甲酰基) 氧化膦的 α 裂解通过皮秒泵浦探针和纳秒步进扫描时间分辨红外光谱进行了研究。结果支持一种机制，其中 α