methyl 2,2-bisdeuterioacetoacetate | 93530-72-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: methyl 2,2-bisdeuterioacetoacetate
• 英文别名: methyl 2,2-d2-3-oxobutanoate；methyl α,α-dideuterioacetoacetate；Methyl Acetoacetate-2-²H2；Methyl 2,2-dideuterioacetylacetate；Methyl 2,2-dideuterio-3-oxobutanoate
• CAS: 93530-72-4
• 化学式: C₅H₈O₃
• 分子量: 118.101
• InChiKey: WRQNANDWMGAFTP-SMZGMGDZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2,2-bisdeuterioacetoacetate 生成
  参考文献：
  名称：

  Photochemistry of Deuterated Acetylketenes:  Matrix Isolation Infrared Spectroscopic and ab Initio Studies

  摘要：

  The partially deuterated s-Z and s-E conformers of acetylketene (1 and 2) were generated by flash vacuum pyrolysis of two different deuterated precursors, 3 and 4. The conformer mixture was characterized by low-temperature FTIR spectroscopy in Ar, N-2, and Xe matrices. The observed frequencies and intensities are in excellent agreement with ab initio calculations at the MP2/6-31G* and B-LYP/6-31G* levels. Irradiation of Ar matrices in the UV (313 nm) caused the appearance of new sets of absorptions, which disappeared upon annealing of the matrices to 35 K. Difference spectra revealed no new absorptions due to OD bands arising from photoisomers 7-10, thereby rigorously proving that no C-D/O-D tautomerism takes place and that the new absorptions observed are due to exceptionally prominent photochemically populated matrix sites.

  DOI：

  10.1021/jp9529026
• 作为产物：
  描述：

  乙酰乙酸甲酯 在 氘代甲醇 作用下， 反应 2.0h， 生成 methyl 2,2-bisdeuterioacetoacetate
  参考文献：
  名称：

  碳酸钾促进乙酰乙酸酯与苯甲醛缩合反应制备6-苯基-2,4-二氧四氢吡喃的机理研究

  摘要：

  在醇溶剂中用碳酸钾处理苯甲醛和乙酰乙酸酯是通过γ-C-烷基化而不是α-C-烷基化进行的，导致形成6-苯基-2,4-二氧代四氢吡喃。根据氘交换实验，碳13标记实验，1 H NMR监测研究和反应性研究的结果，我们提出的该反应机理涉及α-碳的去质子化，分子内质子转移形成γ-阴离子，添加生成的γ阴离子与苯甲醛的羰基碳发生分子内酯交换反应。

  DOI：

  10.1021/jo400213s

文献信息

• A new furan annelation reaction by the palladium-catalyzed reaction of 2-alkynyl carbonates or 2-(1-alkynyl)oxiranes with β-keto esters
  作者：Ichiro Minami、Masami Yuhara、Hiroyuki Watanabe、Jiro Tsuji

  DOI：10.1016/0022-328x(87)80052-9

  日期：1987.11

  A new furan annelation by the palladium-catalyzed reaction of 2-alkynyl carbonates with β-keto esters is described. The reaction proceeds under mild neutral conditions and hence unstable 3-alkylidene-2,3-dihydrofurans can be prepared in this way. Similarly, reaction of 2-(1-alkynyl)oxiranes with β-keto esters gives alkylidene furans.

  描述了通过碳酸2-炔基碳酸酯与β-酮酯的钯催化反应的新的呋喃脱嵌。反应在温和的中性条件下进行，因此可以以这种方式制备不稳定的3-亚烷基-2，3-二氢呋喃。类似地，使2-（1-炔基）氧杂环戊烷与β-酮酯反应，得到亚烷基呋喃。
• Synthesis of sequentially deuterated 1-n-Butyl-3-methylimidazolium ionic liquids
  作者：Alexander Khrizman、Hiu Yan Cheng、Guillermo Moyna

  DOI：10.1002/jlcr.1884

  日期：2011.6.30

  Deuterium isotopologues of the ionic liquid (IL) 1–n-butyl-3-methylimidazolium chloride ([C4mim]Cl) sequentially labeled on the C-1″, C-1′, C-2′, C-3′, and C-4′ positions of the N-alkyl groups were prepared following a strategy that minimizes the number of distinct reactions through the use of analogous synthetic routes. In several cases, good yields after the initial deuterium incorporation reaction were achieved by combining well-established chemical transformations into efficient single-step processes. Copyright © 2011 John Wiley & Sons, Ltd.

  氘同位素的离子液体（IL）1–n-丁基-3-甲基咪唑氯化物（[C4mim]Cl）在N-烷基侧基的C-1″、C-1′、C-2′、C-3′和C-4′位点上逐步标记，采用了一种通过类似合成路径最小化不同反应数量的策略。在多个案例中，通过将成熟的化学转化结合为高效的单一步骤过程，初步氘掺入反应后获得了良好的产率。版权 © 2011 John Wiley & Sons, Ltd.
• Retracted Article: Synthesis of deuterated isopentyl pyrophosphates for chemo-enzymatic labelling methods: GC-EI-MS based 1,2-hydride shift in epicedrol biosynthesis
  作者：Madhukar S. Said、Govinda R. Navale、Jayant M. Gajbhiye、Sandip S. Shinde

  DOI：10.1039/c9ra00163h

  日期：——

  coupled to electron impact mass spectrometry fragmentation data of deuterated (2H) epicedrol analogues. The chemo-enzymatic method was applied for the specific synthesis of 8-position labelled farnesyl pyrophosphate and epicedrol. EI-MS fragmentation ions compared with non-labelled and isotopic mass shift fragments suggest that the 2H of C6 migrates to the C7 position during the cyclization mechanism

  基于气相色谱与氘代( 2 H) 表白醇类似物的电子碰撞质谱碎裂数据相结合，阐明了倍半萜表白醇环化酶机制。采用化学-酶法特异性合成8位标记法呢基焦磷酸和表白醇。EI-MS 碎片离子与未标记和同位素质量转移碎片相比表明 C6 的2 H 在环化机制期间迁移到 C7 位置。
• Novel palladium-catalyzed reactions of propargyl carbonates with carbonucleophiles under neutral conditions
  作者：Jiro Tsuji、Hiroyuki Watanabe、Ichiro Minami、Isao Shimizu

  DOI：10.1021/ja00293a075

  日期：1985.4

  La reaction de carbonates de propargyl(I) avec des carbonucleophiles doux en presence de palladium donne des propenes disubstitues en 2,3 dans des conditions neutres. Les β-cetoesters et les β-dicetones portant deux hydrogenes actifs reagissent avec I dans le rapport 1/1. Il se produit a la fois une C- et une O-alkylation avec ces composes pour donner des methylene-4 dihydro-4,5 furannes et methyl-4

  La 反应 de carbonates de propargyl(I) avec des carbonucleophiles doux en存在 de palladium donne des propenes dissubstitues en 2,3 dans des conditions neutres。Les β-cetoesters et les β-dicetones portant deux hydroes actifs reagissent avec I dans le rapport 1/1。Il se produit a la fois une C- et une O-烷基化反应组成浇注 donner des methylene-4 dihydro-4,5 furranes etmethyl-4 furanes
• A mass spectrometric study of the dimethyl ester trimethylsilyl enol ether derivatives of some 3-oxodicarboxylic acids
  作者：John S. Svendsen、Jon E. Whist、Leiv K. Sydnest

  DOI：10.1002/oms.1210220803

  日期：1987.8

  AbstractThe fragmentation pathways for the dimethyl ester trimethylsilyl enol ether derivatives of some 3‐oxodicarboxylic acids have been found by using B/E and B2/E linked scans, collisional activated decomposition and isotope substitution techniques. The trimethylsilyloxy group strongly directs the decomposition processes, and induces a fragmentation pattern that intimately reflects the structure of the compounds.