(2H3)甲基3-氧代丁酸酯 | 107694-22-4

• 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
• 中文名称: (2H3)甲基3-氧代丁酸酯
• 中文别名: N-(正丁基)磷酸三酰胺
• 英文名称: methyl-d-3 acetoacetate
• 英文别名: methyl-d3 acetoacetate；Methyl-d3 3-Oxobutanoate；trideuteriomethyl 3-oxobutanoate
• CAS: 107694-22-4
• 化学式: C₅H₈O₃
• 分子量: 119.093
• InChiKey: WRQNANDWMGAFTP-BMSJAHLVSA-N

物化性质

• 溶解度：
  可溶于氯仿、可溶于二氯甲烷、四氢呋喃

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：

  (2H3)甲基3-氧代丁酸酯 在 potassium tert-butylate 作用下， 以 乙醚 为溶剂， 反应 12.02h， 生成
  参考文献：
  名称：

  Carbanion rearrangements. Collison induced dissociations of deprotonated alkyl acetoacetates

  摘要：

  AbstractDeprotonation of methyl acetoacetate yields two enolate ions MeCOC̄HCO2Me (a) and C̄H2COCH2CO2Me (b). On collisional activation, ions a and b fragment differently. The major fragmentation of a is specific loss of MeOH through a four‐centred transition state to form −O(Me)CCCO. In contrast, ion b eliminates CH2CO to give −CH2CO2Me. Some rearrangement of b to a is also noted. Rearrangement of a to b is very minor under single collision conditions but at high collision gas pressure rearrangement of a to b is strongly promoted. Similar effects are observed in the collisional activation spectra of MeCOC̄(Me)CO2Me (c) and −CH2COC(Me)CO2Me (d). The loss of MeOH from (c) proceeds via a six membered transition state to −CH2COC(Me)CO; this is a stepwise process in which the deprotonation (step two) is not rate determining. A number of other decompositions occur, these have also been studied by deuterium labelling.

  DOI：

  10.1002/oms.1210220210
• 作为产物：
  描述：

  氘代甲醇 、 5-乙酰基-2,2-二甲基-1,3-二恶烷-4,6-二酮 以 苯 为溶剂， 以38%的产率得到(2H3)甲基3-氧代丁酸酯
  参考文献：
  名称：

  M（NO 3）2 · X H 2 O，TNCB，TBAP和HMTAI对1,4-二氢吡啶进行快速有效的芳构化，并由硝苯地平d 3制备氘标记的脱氢硝苯地平

  摘要：

  在100°C的乙酸中，使用各种金属硝酸盐，溴化三硝酸铈（IV）溴酸盐（TNCB）和高碘酸四丁铵（TBAP）作为氧化剂，研究了各种1,4-二氢吡啶的简便有效芳构化。碘（HMTAI）在甲醇中回流。nifedipine-的有效转化d 3至dehydronifedipine- d 3作为内标可以以硝苯地平浓度的在体内测定中使用。

  DOI：

  10.1016/j.bmcl.2010.04.096

文献信息

• Facile and efficient aromatization of 1,4-dihydropyridines with M(NO3)2·XH2O, TNCB, TBAP and HMTAI and preparation of deuterium labeled dehydronifedipine from nifedipine-d3
  作者：Ajam C. Shaikh、Chinpiao Chen

  DOI：10.1016/j.bmcl.2010.04.096

  日期：2010.6

  The easy and efficient aromatization of various 1,4-dihydropyridines was investigated using various metal nitrates, trinitratocerium(IV) bromate (TNCB), and tetrabutyl ammonium periodate (TBAP) as oxidant in acetic acid at 100 °C, as well as hexamethylenetetramine-iodine (HMTAI) reflux in methanol. The efficient conversion of nifedipine-d3 to dehydronifedipine-d3 as an internal standard can be used

  在100°C的乙酸中，使用各种金属硝酸盐，溴化三硝酸铈（IV）溴酸盐（TNCB）和高碘酸四丁铵（TBAP）作为氧化剂，研究了各种1,4-二氢吡啶的简便有效芳构化。碘（HMTAI）在甲醇中回流。nifedipine-的有效转化d 3至dehydronifedipine- d 3作为内标可以以硝苯地平浓度的在体内测定中使用。
• Carbanion rearrangements. Collison induced dissociations of deprotonated alkyl acetoacetates
  作者：Peter C. H. Eichinger、John H. Bowie

  DOI：10.1002/oms.1210220210

  日期：1987.2

  AbstractDeprotonation of methyl acetoacetate yields two enolate ions MeCOC̄HCO2Me (a) and C̄H2COCH2CO2Me (b). On collisional activation, ions a and b fragment differently. The major fragmentation of a is specific loss of MeOH through a four‐centred transition state to form −O(Me)CCCO. In contrast, ion b eliminates CH2CO to give −CH2CO2Me. Some rearrangement of b to a is also noted. Rearrangement of a to b is very minor under single collision conditions but at high collision gas pressure rearrangement of a to b is strongly promoted. Similar effects are observed in the collisional activation spectra of MeCOC̄(Me)CO2Me (c) and −CH2COC(Me)CO2Me (d). The loss of MeOH from (c) proceeds via a six membered transition state to −CH2COC(Me)CO; this is a stepwise process in which the deprotonation (step two) is not rate determining. A number of other decompositions occur, these have also been studied by deuterium labelling.