1-[4-((2)H3)methyl((2)H4)phenyl]ethan-1-one | 179990-85-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-[4-((2)H3)methyl((2)H4)phenyl]ethan-1-one
• 英文别名: 4'-(Methyl-d3)acetophenone-2',3',5',6'-d4；d7-4-methylacetophenone；1-[2,3,5,6-Tetradeuterio-4-(trideuteriomethyl)phenyl]ethanone
• CAS: 179990-85-3
• 化学式: C₉H₁₀O
• 分子量: 141.122
• InChiKey: GNKZMNRKLCTJAY-HRDWIZOWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-[4-((2)H3)methyl((2)H4)phenyl]ethan-1-one 在 N-溴代丁二酰亚胺(NBS) 作用下， 生成 d6-4-bromomethylacetophenone
  参考文献：
  名称：

  Fragmentations of protonated acetophenones via intermediate ion-molecule complexes

  摘要：

  AbstractProtonated acetophenones, substituted with a methoxymethyl group in the para and meta positions, have been generated by electron impact induced fragmentation of the correspondingly substituted 2‐phenylpropan‐2‐ols. The metastable ions, formed in the second field‐free region of a VG ZAb 2F mass spectrometer, react unimolecularly by elimination of CH3OH, formation of CH3CO+ and magnified image ions, loss of CH3COOCH3, and loss of CH2O. The mechanisms of these fragmentations have been elucidated with the aid of deuterated analogues of the protonated acetophenones. It is shown that these reactions are initiated by an endothermic transfer of the proton at the carbonyl group of the protonated acetophenones to the benzene ring. A further migration of the proton to the ether O atom of the methoxymethyl side‐chain leads eventually to the elimination of CH3OH. Protolytic bond cleavages of either side‐chain gives rise to the CH3CO+ and magnified image ions. At low internal energies both these ions may be trapped by the aromatic neutral fragment in ion‐molecule complexes. Reactions within these complexes result in the energetically favourable losses of CH3COOCH3 and CH2O, respectively. With respect to these reactions, the protonated acetophenones behave analogously to the correspondingly substituted and protonated benzaldehydes.

  DOI：

  10.1002/oms.1210220711
• 作为产物：
  描述：

  氘代甲苯 、 乙酰氯 在 三氯化铝 作用下， 以 二硫化碳 为溶剂， 生成 1-[4-((2)H3)methyl((2)H4)phenyl]ethan-1-one
  参考文献：
  名称：

  Fragmentations of protonated acetophenones via intermediate ion-molecule complexes

  摘要：

  AbstractProtonated acetophenones, substituted with a methoxymethyl group in the para and meta positions, have been generated by electron impact induced fragmentation of the correspondingly substituted 2‐phenylpropan‐2‐ols. The metastable ions, formed in the second field‐free region of a VG ZAb 2F mass spectrometer, react unimolecularly by elimination of CH3OH, formation of CH3CO+ and magnified image ions, loss of CH3COOCH3, and loss of CH2O. The mechanisms of these fragmentations have been elucidated with the aid of deuterated analogues of the protonated acetophenones. It is shown that these reactions are initiated by an endothermic transfer of the proton at the carbonyl group of the protonated acetophenones to the benzene ring. A further migration of the proton to the ether O atom of the methoxymethyl side‐chain leads eventually to the elimination of CH3OH. Protolytic bond cleavages of either side‐chain gives rise to the CH3CO+ and magnified image ions. At low internal energies both these ions may be trapped by the aromatic neutral fragment in ion‐molecule complexes. Reactions within these complexes result in the energetically favourable losses of CH3COOCH3 and CH2O, respectively. With respect to these reactions, the protonated acetophenones behave analogously to the correspondingly substituted and protonated benzaldehydes.

  DOI：

  10.1002/oms.1210220711

文献信息

• Selective electrolytic fluorinations in 70% HF/30% pyridine
  作者：Sarah M. Lee、Jamie M. Roseman、C. Blair Zartman、Eamonn P. Morrison、Sean J. Harrison、Corrie A. Stankiewicz、W.J. Middleton

  DOI：10.1016/0022-1139(95)03379-3

  日期：1996.3

  The selective fluorination of compounds containing benzylic hydrogen atoms was accomplished by electrolysis in a mixture of 70% HF and 30% pyridine (Olah's reagent) using a square wave alternating current (1.76–2.75 V, 0.02–0.05 Hz) and Pt electrodes. This method can be used in the laboratory to prepare conveniently gram-size quantities of monofluorinated products. An ion radical mechanism has been

  使用方波交流电（1.76-2.75 V，0.02-0.05 Hz）和Pt电极，在70％HF和30％吡啶（Olah试剂）的混合物中进行电解，即可完成含苄基氢原子的化合物的选择性氟化。此方法可在实验室中用于方便地制备克级量的单氟化产物。已经提出了离子自由基机理。
• Triplet-Sensitized Photoreactivity of a Geminal Diazidoalkane
  作者：Ranaweera A. A. Upul Ranaweera、Jagadis Sankaranarayanan、Lydia Casey、Bruce S. Ault、Anna D. Gudmundsdottir

  DOI：10.1021/jo201304c

  日期：2011.10.21

  Photolysis of 1 in chloroform yielded 2 as the major product and a small quantity of 3. Laser flash photolysis demonstrated that upon irradiation, the first excited triplet state of the ketone (T1K) of 1 is formed and decayed to form radical 4, which has a λmax at 380 nm (τ = 2 μs). Radical 4 expelled a nitrogen molecule to yield imine radical 5 (λmax at 300 nm). Density functional theory (DFT) calculations

  在氯仿中1的光解产生2作为主要产物，少量3产生。激光闪光光解表明在照射时，该酮的第一激发三重态（T 1K的）1形成并衰减到形成自由基4，其具有λ最大在380nm处（τ= 2微秒）。自由基4排出氮分子以产生亚胺基5（在300nm处的λmax）。密度泛函理论（DFT）计算表明，形成5的过渡态势垒约为4 kcal / mol。相比之下，1的光解在氩气基质中生成三重态氮6，进一步用15 N和D同位素标记以及DFT计算对其进行了表征。长时间辐照6会产生三重亚胺亚硝基7。
• DEUTERIUM-ENRICHED CELECOXIB
  申请人：Czarnik Anthony W.

  公开号：US20090062364A1

  公开（公告）日：2009-03-05

  The present application describes deuterium-enriched celecoxib, pharmaceutically acceptable salt forms thereof, and methods of treating using the same.
• Fragmentations of protonated acetophenones via intermediate ion-molecule complexes
  作者：U. Filges、Hans-Fr. Grützmacher

  DOI：10.1002/oms.1210220711

  日期：1987.7

  AbstractProtonated acetophenones, substituted with a methoxymethyl group in the para and meta positions, have been generated by electron impact induced fragmentation of the correspondingly substituted 2‐phenylpropan‐2‐ols. The metastable ions, formed in the second field‐free region of a VG ZAb 2F mass spectrometer, react unimolecularly by elimination of CH3OH, formation of CH3CO+ and magnified image ions, loss of CH3COOCH3, and loss of CH2O. The mechanisms of these fragmentations have been elucidated with the aid of deuterated analogues of the protonated acetophenones. It is shown that these reactions are initiated by an endothermic transfer of the proton at the carbonyl group of the protonated acetophenones to the benzene ring. A further migration of the proton to the ether O atom of the methoxymethyl side‐chain leads eventually to the elimination of CH3OH. Protolytic bond cleavages of either side‐chain gives rise to the CH3CO+ and magnified image ions. At low internal energies both these ions may be trapped by the aromatic neutral fragment in ion‐molecule complexes. Reactions within these complexes result in the energetically favourable losses of CH3COOCH3 and CH2O, respectively. With respect to these reactions, the protonated acetophenones behave analogously to the correspondingly substituted and protonated benzaldehydes.