4-乙酰氧基-3-氧代丁酸甲酯 | 87730-99-2

• 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: 4-乙酰氧基-3-氧代丁酸甲酯
• 英文名称: 4-acetoxy-3-oxo-butyric acid methyl ester
• 英文别名: methyl 4-acetoxy-3-oxobutyrate；methyl 4-acetoxyacetoacetate；Methyl 4-(acetyloxy)-3-oxobutanoate；methyl 4-acetyloxy-3-oxobutanoate
• CAS: 87730-99-2
• 化学式: C₇H₁₀O₅
• mdl: MFCD24388406
• 分子量: 174.153
• InChiKey: YGSVVJZHBIUMSG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  12
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.571
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-乙酰氧基-3-氧代丁酸甲酯 在 氨 作用下， 以 甲醇 、 异丙醇 为溶剂， 反应 0.5h， 生成 isopropyl 2-hydroxymethyl-1,4-dihydro-6-methyl-4-(3-nitrophenyl)-3-methoxycarbonyl-5-piperidinecarboxylate
  参考文献：
  名称：

  Asymmetric Synthesis of (R)-Nilvadipine and (S)-NB 818 via Regioselective Bromination of Chiral 1,4-Dihydropyridines as a Key Step and Enzymatic Resolution of Racemic 2-Hydroxymethyl-1,4-dihydropyridine Derivatives.

  摘要：

  通过脂肪酶催化外消旋物质的水解或酯交换反应得到光学活性的2-羟甲基-1,4-二氢吡啶。手性 NB 818 和尼伐地平是由手性 2-羟甲基-1, 4-二氢吡啶合成的。另一方面，从前手性底物获得的手性 1, 4-二氢吡啶在温和条件下通过甲基的区域选择性溴化转化为 (S)-NB 818 和 (R)-尼伐地平。

  DOI：

  10.1248/cpb.45.869
• 作为产物：
  描述：

  sodium dihydrogenphosphate 、 4-氯乙酰乙酸甲酯 在 苄基三乙基氯化铵 、 potassium acetate 、 溶剂黄146 作用下， 以 乙腈 为溶剂， 生成 4-乙酰氧基-3-氧代丁酸甲酯
  参考文献：
  名称：

  Acetoacetic acid ester derivatives for the manufacture of

  摘要：

  这项发明涉及一种用于制备以下化合物的新型工艺：其中R.sup.1表示C.sub.1-5-烷基，特别是甲基、乙基、丙基或异丙基，基团R.sup.2分别独立地代表氢或C.sub.1-5-烷基，特别是氢或甲基、乙基、丙基或异丙基。该工艺的特点在于，化合物的公式为：其中R代表C.sub.1-4-烷氧基、氯、溴或C.sub.1-4-烷酰氧基，R.sup.1和R.sup.2具有上述含义，R.sup.3代表C.sub.1-4-烷基。经水解和醛缩反应处理化合物后，其中R=C.sub.1-4-烷氧基时，反应产物随后经酸处理。这些化合物I大多数是已知的调味物质。

  公开号：

  US04892966A1

文献信息

• 2,3-bridged 1,4-dihydropyridines, and their use as medicaments
  申请人：Bayer Aktiengesellschaft

  公开号：US06121284A1

  公开（公告）日：2000-09-19

  The present invention relates to new 2,3-bridged 1,4-dihydropyridines of the general formula (I), ##STR1## in which R, R.sup.1, R.sup.2, D and E have the meaning given in the description, processes for their preparation and their use as medicaments, preferably for treatment of the central nervous system.

  本发明涉及一般式（I）的新型2,3-桥联1,4-二氢吡啶，其中R、R.sup.1、R.sup.2、D和E的含义如描述中所示，以及它们的制备方法和作为药物的用途，优选用于治疗中枢神经系统。
• Construction of Highly Substituted Nitroaromatic Systems by Cyclocondensation. Part I. Synthesis of 4-nitro-3-oxobutyrate
  作者：Rudolf O. Duthaler

  DOI：10.1002/hlca.19830660516

  日期：1983.7.27

  Methyl 4-nitro-3-oxobutyrate (1) is prepared by substitution of 4-bromo- and 4-iodo-3-oxobutyrate enol ether or enol acetate derivatives with nitrite and deprotection of the keto function (Schemes 2 and 3). A much more convenient access to 1 is, however, the nitration of acetoacetate dianion with alkyl nitrates (Scheme 4). Compound 1 is stable and storable, and can be handled safely. Its use in cyclocondensations

  4-硝基-3-氧代丁酸乙酯（1）是通过4-溴-和取代制备的4-碘代-3-氧代丁酸烯醇醚或与亚硝酸盐和酮官能团脱保护（烯醇乙酸酯衍生物方案2和3）。然而，更方便地获得1是用烷基硝酸盐硝化乙酰乙酸二阴离子（方案4）。化合物1稳定且可储存，可以安全处理。通过与乙酰丙酮反应建立其在环缩合中的应用（方案5），以70％的产率提供4,6-二甲基-3-硝基水杨酸酯48。卤素取代法合成1还可以访问该结晶（ë）烯醇醚18的1，以及它的二甲基缩醛25，（Ž）烯醇醋酸盐32，和（ë）烯醇乙酸酯33。由4-溴-3-氧代丁酸酯12制备3-取代的4-溴丁烯酸酯15、16和26，这是使用N-溴-琥珀酰亚胺的现有方法的有用替代品。
• Visible-light-mediated aerobic oxidative dimerizative annulation of β-carbonylketones: a facile strategy to construct highly functionalized furans
  作者：Zhen-Peng Shang、Gao-Feng Zha、Xiao-Qing Chen、Hua-Li Qin

  DOI：10.1016/j.tetlet.2016.09.008

  日期：2016.10

  A green and convenient method for the synthesis of highly functionalized furans is developed through visible-light-mediated aerobic oxidative dimerizative annulation of β-carbonylketones. This protocol represents a novel and efficient way to construction of highly functionalized furans from basic starting materials under mild conditions.

  通过可见光介导的β-羰基酮的好氧氧化二聚环化反应，开发了一种绿色且方便的合成高度官能化呋喃的方法。该协议代表了在温和条件下从基本起始原料构建高度官能化呋喃的新颖有效途径。
• Method of preparing thieno[3,2-c]pyridine derivatives and intermediates used therein
  申请人：Yun Sangmin

  公开号：US20070197789A1

  公开（公告）日：2007-08-23

  Ticlopidine and clopidogrel having high blood platelet aggregation inhibitory and anti-thrombotic activities are simply prepared by reacting a substituted thiophene derivative with a 2-chlorobenzylamine derivative.

  Ticlopidine和clopidogrel具有高血小板聚集抑制和抗血栓活性，可通过将取代噻吩衍生物与2-氯苯甲胺衍生物反应来简单制备。
• Calcium Entry Blockers and Activators: Conformational and Structural Determinants of Dihydropyrimidine Calcium Channel Modulators
  作者：George C. Rovnyak、S. David Kimball、Barbara Beyer、Gabriella Cucinotta、John D. DiMarco、Jack Gougoutas、Anders Hedberg、Mary Malley、James P. McCarthy

  DOI：10.1021/jm00001a017

  日期：1995.1

  Dihydropyrimidines 4, 6, and 15, uniquely designed to unambiguously establish structural and conformational determinants for DHP receptor occupation and for modulation of calcium channel function, were prepared and examined for calcium channel modulation. Our results confirm and firmly establish a preference for syn-orientation of an unsymmetrically substituted aryl moiety at the DHP receptor (15d vs 15e). We propose a normal vs capsized DHP boat model to explain structural and conformational requirements for modulation of calcium channel function that requires an obligatory left-hand side alkoxy cis-carbonyl interaction for maximal DHP receptor affinity, the effect on channel function being determined by orientation of the 4-aryl group. Enantiomers having an up-oriented pseudoaxial aryl group (normal DHP boat) will elicit calcium antagonist activity, whereas enantiomers having a down-oriented pseudoaxial aryl group (capsized DHP boat) will elicit calcium agonist activity. Single enantiomers of macrocyclic lactone 15b demonstrate opposite channel activity. Antagonist activity resides in enantiomer 15b-A (S-configuration, left-hand side alkoxy cis-carbonyl with up-oriented pseudoaxial aryl group and normal DHP boat), whereas agonist activity resides in enantiomer 15b-B (R-configuration, left-hand side alkoxy cis-carbonyl with down-oriented pseudoaxial aryl group and capsized DHP boat). Moreover, this model is consistent with and provides a rational explanation of previous literature in this area, most notably the observation of chiral inversion and potency diminution upon replacement of ester by hydrogen in the Bay K 8644 series.