苯甲胺,N-(1,1-二甲基乙基)-N-羟基-a-甲基- | 102564-44-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 苯甲胺,N-(1,1-二甲基乙基)-N-羟基-a-甲基-
• 英文名称: N-tert-Butyl-N-(1-phenylethyl)hydroxylamine
• CAS: 102564-44-3
• 化学式: C₁₂H₁₉NO
• 分子量: 193.289
• InChiKey: PYVQUIXLZRWWNT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  23.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  苯甲胺,N-(1,1-二甲基乙基)-N-羟基-a-甲基- 在 二硫化碳 作用下， 以 乙腈 为溶剂， 反应 0.5h， 以90%的产率得到N-(tert-butyl)-N-(α-phenylethyl)amine
  参考文献：
  名称：

  Deoxygenation of N,N-disubstituted hydroxylamines by carbon disulfide

  摘要：

  Hindered N,N-dialkylhydroxylamines react rapidly with CS2 to give the corresponding 2-degrees-amines.

  DOI：

  10.1016/s0040-4039(00)91706-4
• 作为产物：
  描述：

  N-叔丁基苄胺 在 sodium tungstate 双氧水 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 为溶剂， 反应 20.0h， 生成 苯甲胺,N-(1,1-二甲基乙基)-N-羟基-a-甲基-
  参考文献：
  名称：

  Tungstate-catalyzed oxidation of secondary amines to nitrones. .alpha.-Substitution of secondary amines via nitrones

  摘要：

  DOI：

  10.1021/jo00293a013

文献信息

• ¹H NMR of (α-Substituted benzyl-<i>t</i>-butyl)hydroxylamines and EPR of Their Oxidized Forms
  作者：Gatherina T. Migita、Masaharu Nakayama、Makoto Takeuchi、Kotaro Ogura

  DOI：10.1246/cl.1991.737

  日期：1991.5

  1H NMR study of several (benzyl-t-butyl)hydroxylamine derivatives (BBHA) was performed, which were obtained through the addition of Grignard agents to α-phenyl-N-t-butylnitrone (PEN) or the reduction of PEN. Concomitantly, EPR of their oxidized forms (nitroxide radicals, BEN) was measured. It was proved that the joint application of 1H NMR and EPR provides decisive evidences to assign the α-substituents.

  对几种（苄基-t-丁基）羟胺衍生物（BBHA）进行了1H NMR研究，这些衍生物是通过Grignard试剂与α-苯基-N-t-丁基亚胺（PEN）反应或对PEN进行还原获得的。同时，测量了它们的氧化形式（亚硝基自由基，BEN）的EPR。研究证明，1H NMR与EPR的联合应用为α-取代基的分配提供了决定性证据。
• Synthesis of hindered secondary amines via Grignard reagent addition to ketonitrones
  作者：Martin A. Schwartz、Xiufeng Hu

  DOI：10.1016/s0040-4039(00)91707-6

  日期：1992.3

  Grignard reagents add to ketonitrones in a nonpolar solvent to afford N,N-dialkylhydroxylamines in good yields and with little competing proton transfer. Deoxygenation of the crude hydroxylamines with carbon disulfide then completes an efficient general synthetic route to hindered sec-alkyl-tert-alkylamines and to di-tert-alkylamines.

  格氏试剂在非极性溶剂中加到酮硝酮中，以良好的收率和极少的质子转移竞争性获得N，N-二烷基羟胺。然后用二硫化碳对粗羟胺进行脱氧，从而完成了一条有效的通用合成路线，可生成受阻的仲烷基叔烷基胺和二叔烷基胺。
• An ESR and HPLC-EC Assay for the Detection of Alkyl Radicals
  作者：Christo P. Novakov、Dennis Feierman、Arthur I. Cederbaum、Detcho A. Stoyanovsky

  DOI：10.1021/tx015507h

  日期：2001.9.1

  The correlation of lipid peroxidation with release of alkanes (RH) is considered a noninvasive method for the in vivo evaluation of oxidative stress. The formation of RH is believed to reflect a lipid hydroperoxide (LOOH)-dependent generation of alkoxyl radicals (LO.) that undergo, beta -scission with release of alkyl radicals (R-.). Alternatively, R-. could be spin-trapped with a nitrone before the formation of RH and analyzed by ESR. Extracts from the liver and lung of CCl4- and asbestos-treated rats that were previously loaded with nitrones exhibited ESR spectra suggesting the formation of iso-propyl, n-butyl, ethyl, and pentyl radical-derived nitroxides. In biological systems, various nitroxides with indistinguishable ESR spectra could be formed. Hence, experiments with N-tert-butyl-alpha -phenylnitrone (PBN) for spin trapping of R-. were carried out in which the nitroxides formed were separated and analyzed by HPLC with electrochemical detection (EC). The C1-5 homologous series of PBN nitroxides and hydroxylamines were synthesized, characterized by ESR, GC-MS, and HPLC-EC, and used as HPLC standards. For in vivo generation and spin trapping of R-., rats were loaded with CCl4 and PBN. The HPLC-EC chromatograms of liver extracts from CCl4-treated rats demonstrated the formation of both the nitroxide and hydroxylamine forms of PBN/(CCl3)-C-., as well as the formation of a series of unidentified PBN nitroxides and hydroxylamines. However, formation of PBN adducts with retention times similar to these of the PBN/C2-5 derivatives was not observed. In conclusion, we could not correlate the production of PBN-detectable alkyl radicals with the reported CCl4-dependent production Of C1-5 alkanes. We speculate that the major reason for this is the low steady-state concentrations of R-. produced because only a small fraction of LO. undergo,beta -scission to release R-..
• Comparative Metabolism of <i>N-tert-</i>Butyl-<i>N</i>-[1-(1-oxy-pyridin-4-yl)-ethyl]- and <i>N-tert</i>-Butyl-<i>N</i>-(1-phenyl-ethyl)-nitroxide by the Cytochrome P450 Monooxygenase System
  作者：Christo P. Novakov、Detcho A. Stoyanovsky

  DOI：10.1021/tx025510g

  日期：2002.5.1

  The use of spin-trapping agents for a direct ESR detection of (OH)-O-. in biological systems is limited by the low stability of the hydroxyl radical-derived nitroxides. Among the various probes used for trapping of (OH)-O-., DMSO has proven to be highly efficient. The reaction between (OH)-O-. and DMSO yields methyl radical (CH3.), which can react with N-tert-butyl-alpha-phenylnitrone (PBN) and alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone (POBN) to form stable, ESR-detectable nitroxides. The latter approach has been successfully used in in vivo experiments for analysis of (OH)-O-.; in these experiments, POBN/.CH3 and PBN/.CH3 were detected in the bile duct and the urine of the treated animals. However, the sites of generation of (OH)-O-. produced in vivo are unknown. Currently, no ESR data is available for the formation of (OH)-O-. in liver of animals subjected to oxidative stress. Since nitroxides containing aromatic rings are likely to be substrates of cytochrome P450, experiments were carried out for assessing the ability of the cytochrome P450 monooxygenase system to metabolize PBN/.CH3 and POBN/.CH3, respectively. In the presence of NADPH, rat liver microsomes catalyzed the reduction of POBN/.CH3 to the corresponding hydroxylamine (POBN/CH3), while PBN/.CH3 was metabolized without accumulation of its hydroxylamine form (PBN/CH3). The metabolism of PBN/.CH3 was inhibited by 4-methylpyrazole and ketoconasole, suggesting that cytochrome P450-catalysis was required for the consumption of this nitroxide. Under anaerobic conditions, both the nitroxide and hydroxylamine forms of PBN/CH3 were metabolized, implying that these adducts may undergo reductive cytochrome P450-catalyzed biotransformation. On the basis of the susceptibility of PBN/.CH3 to undergo irreversible metabolic transformation, it is discussed that POBN may prove to be a more efficient spin-trapping agent for the in vivo detection of .OH.