N-methyl-O-(trimethylsilyl)hydroxylamine | 22737-30-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: N-methyl-O-(trimethylsilyl)hydroxylamine
• 英文别名: N-methyl-O-trimethylsilylhydroxylamine；O-trimethylsilyl-N-methylhydroxylamine；O-trimethylsilyl-hydroxylamine；O-Trimethylsilyl-N-methylhydroxylamin；O-Trimethylsilyl-N-methyl-hydroxylamin；N-trimethylsilyloxymethanamine
• CAS: 22737-30-0
• 化学式: C₄H₁₃NOSi
• 分子量: 119.239
• InChiKey: DJFMCNNAIBLYDP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.97
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  21.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-噻吩基锂 、 N-methyl-O-(trimethylsilyl)hydroxylamine 在 CuCN 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以60%的产率得到噻吩-2-甲胺
  参考文献：
  名称：

  A General and Convenient Procedure for the Synthesis of N-Alkylarylamines and N-Alkylheteroarylamines by Electrophilic Amination of Cuprates with N-Alkylhydroxylamines

  摘要：

  DOI：

  10.1021/jo981412h
• 作为产物：
  描述：

  三甲基氯硅烷 、 N-甲基羟胺 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 生成 N-methyl-O-(trimethylsilyl)hydroxylamine
  参考文献：
  名称：

  Ergiebige Synthese N-substituierter Arylglyoxylohydroxamsäuren

  摘要：

  DOI：

  10.1002/ardp.19883210516
• 作为试剂：
  描述：

  在 N-methyl-O-(trimethylsilyl)hydroxylamine 作用下， 以 氯仿 为溶剂， 反应 0.5h， 生成 (R)-2-[4-(4-trifluoromethyl-phenoxy)-benzenesulfonyl]-1,2,3,4-tetrahydro-isoquinoline-1-carbonic acid-hydroxyamide
  参考文献：
  名称：

  [DE] SUBSTITUIERTE TETRAHYDROISOCHINOLINE ALS MMP-INHIBITOREN, VERFAHREN ZU IHRER HERSTELLUNG UND IHRE VERWENDUNG ALS MEDIKAMENT
  [EN] SUBSTITUTED TETRAHYDROISOCHINOLINES USED IN THE FORM OF MMP INHIBITORS, METHOD FOR THE PRODUCTION AND USE THEREOF IN THE FORM OF DRAGS
  [FR] TETRAHYDRO-ISOQUINOLEINES SUBSTITUEES, UTILISEES COMME INHIBITEURS MMP, LEUR PROCEDE DE FABRICATION ET LEUR UTILISATION COMME MEDICAMENTS

  摘要：

  公开号：

  WO2006002763A3

文献信息

• New anionic rearrangements. XV. 1.2-Anionic rearrangement of organosilylhydroxylamines
  作者：Robert. West、Philip. Boudjouk

  DOI：10.1021/ja00793a026

  日期：1973.6
• Electrophilic amination of catecholboronate esters formed in the asymmetric hydroboration of vinylarenes
  作者：Frances I. Knight、John M. Brown、Dario Lazzari、Alfredo Ricci、A. John Blacker

  DOI：10.1016/s0040-4020(97)00722-9

  日期：1997.8

  (S)-(4-Methoxyphenyl)-ethyl-1,3,2-benzodioxaborole, (S)-1-(4-chlorophenyl)ethyl-1,3,2-benzodioxaborole and (S)-1-indanyl-1,3,2-benzodioxaborole. intermediates in the catalytic asymmetric hydroboration of 4-chloro-and 4-methoxystyrene, were isolated as pure oils in 75%, 84% and 49% yield respectively. For the first example, amination with N-chloromagnesio-N-methyl-O-trimethylsilhydroxylamine gave a mixture of (S)-1-(4-methoxyphenyl)-N-methylethylamine in 33% yield, 88% e.e. and (S)-1-(4-methoxyphenyl) ethanol in 31% yield, 86% e.e.. Related results were obtained in the other cases, and the steps of catalytic hydroboration and amination could be combined in a single sequence without isolation of the intermediate. Numerous variants were carried out in the amination procedure with only marginal improvements in chemoselectivity. An investigation of the mechanism was carried out using low temperature heteronuclear NMR on C-13-1-(S)-1-(4-chlorophenyl)ethyl-1,3,2-benzodioxaborole. The dual pathway is a result of an irreversible and unselective initial step. (C) 1997 Elsevier Science Ltd.
• Oxidative Bioactivation of Methamidophos Insecticide:  Synthesis of <i>N</i>-Hydroxymethamidophos (A Candidate Metabolite) and Its Proposed Alternative Reactions Involving N → O Rearrangement or Fragmentation through a Metaphosphate Analogue
  作者：Mahmoud Mahajna、John E. Casida

  DOI：10.1021/tx9701135

  日期：1998.1.1

  The systemic insecticide methamidophos, MeO(MeS)P(O)NH2, is a very weak inhibitor of acetylcholinesterase (AChE) in vitro relative to in vivo suggesting bioactivation. This hypothesis is supported by finding that brain AChE inhibition and poisoning signs from methamidophos are greatly delayed in mice and houseflies pretreated with oxidase inhibitors in an order for effectiveness of methimazole > N-benzylimidazole >> piperonyl butoxide. In contrast, the order for delaying parathion-induced AChE inhibition and toxicity is N-benzylimidazole >> piperonyl butoxide or methimazole, suggesting that different oxidases are involved in methamidophos and parathion activation. N-Hydroxylation is examined here as an alternative to the controversial S-oxidation proposed earlier for methamidophos activation. N-Hydroxymethamidophos [MeO(MeS)P(O)NHOH], synthesized by coupling MeO(MeS)P(O)Cl and Me-3-SiNHOSiMe3 followed by desilylation, is unstable at pH 7.4 (t(1/2) = 10 min at 37 degrees C) with decomposition by two distinct and novel mechanisms. The first mechanism (A) is N --> O rearrangement to MeO(MeS)P(O)ONH2 and then hydrolysis to MeO(MeS)P(O)OH, a sequence also established in the analogous series of (MeO)(2)P(O)NHOH --> (MeO)(2)P(O)ONH2 --> (MeO)(2)P(O)OH. The second mechanism (B) is proposed to involve tautomerism to the phosphimino form [MeO(MeS)P(OH)=NOH] that eliminates MeSH forming a metaphosphate analogue [MeOP(O)=NOH] trapped by water to give MeO(HO)P(O)NHOH that undergoes the N --> O rearrangement as above and hydrolysis to MeOP(O)(OH)(2). As a metaphosphate analogue, the metaphosphorimidate generated from MeO(MeS)P(O)NHOH in aqueous ethanol yields MeOP(O)(OH)(2) and MeO(EtO)P(O)OH in the same ratio as the solvents on a molar basis. Reactions of the N- and O-methyl derivatives of MeO(MeS)P(O)NHOH and (MeO)(2)P(O)NHOH are consistent with proposed mechanisms A and B. N-Hydroxymethamidophos is less potent than methamidophos as an AChE inhibitor and toxicant possibly associated with its rapid hydrolysis. Bioactivation of methamidophos via a metaphosphate analogue would directly yield a phosphorylated and aged AChE resistant to reactivating agents, an intriguing hypothesis worthy of further consideration.
• Trimethylsilylderivate von O- und N-Alkylhydroxylaminen
  作者：O. Smrekar、U. Wannagat

  DOI：10.1007/bf00904128

  日期：——
• Wilson, Michael W.; Hodges, John C., Organic Preparations and Procedures International, 1993, vol. 25, # 6, p. 665 - 672
  作者：Wilson, Michael W.、Hodges, John C.

  DOI：——

  日期：——