1-acetoxy-2,2,6,6-tetramethylpiperidine | 96927-53-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 1-acetoxy-2,2,6,6-tetramethylpiperidine
• 英文别名: (2,2,6,6-Tetramethylpiperidin-1-yl) acetate
• CAS: 96927-53-6
• 化学式: C₁₁H₂₁NO₂
• 分子量: 199.293
• InChiKey: FIGUZKWTMKRWJI-UHFFFAOYSA-N

物化性质

• 沸点：
  232.2±23.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-acetoxy-2,2,6,6-tetramethylpiperidine 在 哌啶 、 溶剂黄146 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 5.33h， 生成 3-Oxo-2-[1-phenyl-meth-(Z)-ylidene]-butyric acid 2,2,6,6-tetramethyl-piperidin-1-yl ester
  参考文献：
  名称：

  E- or Z-Selective Knoevenagel Condensation of Acetoacetic Derivatives:  Effect of Acylated Substituent, that is, TEMPO and Amines, as an Auxiliary, and New Accesses to Trisubstituted E- and Z-2-Alkenals and Furans

  摘要：

  Knoevenagel condensation of O-acetoacetylTEMPOs (2,2,6,6-tetramethylpiperidine-1-oxyl) with aldehydes substituted with an electron-withdrawing group such as aromatic and heteroaromatic ones leads preferentially to E-adducts, while acylacetoamides including Weinreb amides produce Z-adducts, exclusively. These E- and Z-adducts are selectively converted to the corresponding (2E)- and (2Z)-2hyroxyalkyl-2-alkenals, respectively, by stepwise reductions of the acyl group with DIBALH and then the carboxylic functions after protection of the hydroxy group. Transformation of the Knoevenagel products by taking advantage of the E-geometry to trisubstituted furans is also developed.

  DOI：

  10.1021/jo051952w
• 作为产物：
  描述：

  2,2,6,6-四甲基哌啶氧化物 在 碳酸氢钠 、 sodium ascorbate 作用下， 反应 0.08h， 生成 1-acetoxy-2,2,6,6-tetramethylpiperidine
  参考文献：
  名称：

  Anderson, J. Edgar; Corrie, John E. T., Journal of the Chemical Society. Perkin transactions II, 1992, # 7, p. 1027 - 1031

  摘要：

  DOI：

文献信息

• Copper nitrate-catalyzed oxidative coupling of unactivated C(sp³)–H bonds of ethers and alkanes with <i>N</i>-hydroxyphthalimide: synthesis of <i>N</i>-hydroxyimide esters
  作者：Xiaohe Xu、Jian Sun、Yuyan Lin、Jingya Cheng、Pingping Li、Yiyan Yan、Qi Shuai、Yuanyuan Xie

  DOI：10.1039/c7ob02249b

  日期：——

  between N-hydroxyphthalimide (NHPI) and ethers/alkanes has been described. The reaction is accomplished smoothly by using simple and green molecular oxygen as the oxidant, providing an alternative for the efficient synthesis of N-alkoxyphthalimides. In addition, it was found that when tert-butyl ethers were used as substrates, unexpected N-hydroxyimide ester derivatives were obtained in moderate to

  已经描述了N-羟基邻苯二甲酰亚胺（NHPI）与醚/烷烃之间的硝酸铜催化的交叉脱氢偶联反应。通过使用简单的绿色分子氧作为氧化剂，可以顺利完成反应，为有效合成N-烷氧基邻苯二甲酰亚胺提供了一种选择。另外，发现当将叔丁基醚用作底物时，以中等至优异的产率获得了意想不到的N-羟基酰亚胺酯衍生物。为了进一步理解这种不寻常的转化，进行了对照实验并提出了合理的机制。
• Reactions of Sulfoxides with Magnesium Amides. Transformation of Sulfoxides into Sulfides, Dithioacetals, and Vinyl Sulfides
  作者：Kazuhiro Kobayashi、Masataka Kawakita、Kouichi Yokota、Tohru Mannami、Koji Yamamoto、Osamu Morikawa、Hisatoshi Konishi

  DOI：10.1246/bcsj.68.1401

  日期：1995.5

  ethylmagnesium bromide and secondary amines, such as diisopropylamine (DIPA) or 2,2,6,6-tetramethylpiperidine (TMP) in diethyl ether, were examined. Diaryl sulfoxides were heated with the diisopropylaminomagnesium reagent in diethyl ether to give the corresponding diaryl sulfides in 42—52% yields. Sulfoxides bearing hydrogens at the α-positon only (RSOCH2R1) reacted with the tetramethylpiperidinomagnesium

  研究了亚砜与由溴化乙基镁和仲胺（例如二异丙胺 (DIPA) 或 2,2,6,6-四甲基哌啶 (TMP) 在乙醚中的反应）原位生成的氨基镁的反应。二芳基亚砜与二异丙基氨基镁试剂在乙醚中一起加热，得到相应的二芳基硫化物，产率为 42-52%。仅在 α 位带有氢的亚砜 (RSOCH2R1) 在室温下与四甲基哌啶镁试剂反应，生成相应的二硫缩醛 (RSCHR1SR)，产率为 47-86%。在室温下用氨基镁处理在 α 位和 β 位都带有氢的亚砜 (RSOCHR1CHR2R3) 得到相应的乙烯基硫化物 (RSCR1=CR2R3)，产率为 52-72%，伴随着 2。3-27% 的相应二硫代缩醛的产率。讨论了导致形成硫稳定碳正离子中间体的产物的途径。
• Dual Photoredox/Palladium-Catalyzed C–H Acylation of 2-Arylpyridines with Oxime Esters
  作者：Xiao-Peng Liu、Jia-Rong Chen、Bin-Qing He、Yuan Gao、Peng-Zi Wang、Hong Wu、Hong-Bin Zhou

  DOI：10.1055/s-0040-1707252

  日期：2021.3

  unprecedented dual photoredox/palladium-catalyzed iminyl-radical-mediated C–C bond cleavage and directed ortho C–H acylation of 2-arylpyridines by using oxime esters is described. Oxime esters can serve as efficient acyl sources through formation of the corresponding acyl radicals by photoredox-catalyzed iminyl-radical-mediated C–C bond cleavage. This redox-neutral protocol features excellent regioselectivity

  描述了一种前所未有的双光氧化还原/钯催化亚胺基-自由基介导的 C-C 键裂解和使用肟酯的 2-芳基吡啶的定向邻位 C-H 酰化。肟酯可以通过光氧化还原催化亚胺基介导的 C-C 键裂解形成相应的酰基自由基作为有效的酰基来源。这种氧化还原中性方案具有出色的区域选择性、广泛的底物范围和对两种组分的良好官能团耐受性，提供广泛的芳基酮，通常具有良好的产率。
• Reaction of aromatic nitroso compounds with chemical models of ‘thiamine active aldehyde’
  作者：Luísa M. Ferreira、M. Manuel B. Marques、Paulo M.C. Glória、Humberto T. Chaves、João-Pedro P. Franco、Isabel Mourato、José-Rafael T. Antunes、Henry S. Rzepa、Ana M. Lobo、Sundaresan Prabhakar

  DOI：10.1016/j.tet.2008.06.008

  日期：2008.8

  Aromatic nitroso compounds in the presence of base and 2-(α-hydroxyalkyl)-3,4-dimethylthiazolium trifluoromethanesulfonate and related salts furnish in variable yields O- and N-acyl-aryl hydroxylamines and 3,4-dimethylthiazolium trifluoromethanesulfonate. A primary kinetic isotope effect of 4.9, obtained for the appropriate 2α-deuterated thiazolium salt, points to the C2α–H bond cleavage as the rate

  在碱和2-（α-羟基烷基）-3,4-二甲基噻唑三氟甲烷磺酸盐和相关盐存在下的芳族亚硝基化合物，其收率可变，可得到O-和N-酰基-芳基羟胺以及3,4-二甲基噻唑三氟甲烷磺酸盐。对于适当的2α氘代噻唑鎓盐而言，一次动力学同位素效应为4.9，指向C2α-H键断裂作为速率确定步骤。通过ESR检测到的自由基种类明确地鉴定为苯基氢硝基氧化物，但是用TEMPO尝试捕获相应的C-杂环自由基没有成功，并且带有潜在的环丙基自由基钟的底物得到了具有完整的环丙基环的产物。理论计算表明，这种反应具有很大的活化能，因此本身不能排除这类自由基的干预。涉及两种同时存在的机制的可能操作的证据，自由基和优势离子途径涉及噻唑鎓盐的共轭碱基，是“活性硫胺素”的化学模型，而ArNO则可用于形成反应产物。
• Catalyst-free generation of acyl radicals induced by visible light in water to construct C–N bonds
  作者：Maogang Ran、Jiaxin He、Boyu Yan、Wenbo Liu、Yi Li、Yunfen Fu、Chao-Jun Li、Qiuli Yao

  DOI：10.1039/d0ob02364g

  日期：——

  for the direct generation of acyl radicals from α-diketones, and its selective conversion of nitrosoarenes to hydroxyamides or amides with AcOH or NaCl as an additive. The reaction was carried out under mild conditions in water with purple LEDs as the light source. A broad scope of substrates was demonstrated. Mechanistic experiments indicate that α-diketones cleave to give acyl radicals, with hydroxyamides

  我们在这里描述了无催化剂和氧化还原中性的光化学策略，用于直接从α-二酮生成酰基自由基，以及将亚硝基芳烃选择性转化为羟酰胺或酰胺，并以AcOH或NaCl作为添加剂的方法。该反应在温和的条件下在水中以紫色LED为光源进行。展示了广泛的基板范围。机理实验表明，α-二酮裂解产生酰基，而羟酰胺被进一步还原为酰胺。