acetoxyacetic acid methyl ester | 126774-13-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: acetoxyacetic acid methyl ester
• 英文别名: acetoxy[N-(3-butenyl)-N-(ethoxycarbonyl)amino]acetic acid methyl ester；methyl 2-acetyloxy-2-[but-3-enyl(ethoxycarbonyl)amino]acetate
• CAS: 126774-13-8
• 化学式: C₁₂H₁₉NO₆
• 分子量: 273.286
• InChiKey: XHFCQXMQMPQYRJ-UHFFFAOYSA-N

物化性质

• 沸点：
  347.6±42.0 °C(Predicted)
• 密度：
  1.139±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.08
• 重原子数：
  19.0
• 可旋转键数：
  7.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  82.14
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  acetoxyacetic acid methyl ester 在 三乙基硅烷 、 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 以52%的产率得到allyllactic acid methyl ester
  参考文献：
  名称：

  Tin tetrachloride-induced π-cyclizations of glycine cation equivalents to substituted pipecolic acid derivatives

  摘要：

  Cationic pi-cyclization reactions of N-(3-alkenyl)-N-(methoxycarbonyl)acetoxyglycine esters induced by tin tetrachloride in dichloromethane are described. Reactions started and quenched with water at -78-degrees-C mainly yield cis-4-hydroxypipecolic esters, whereas reactions quenched after warm-up to room temperature provide trans-4-chloropipecolic esters as major products. A mechanistic scheme is advanced which adequately explains these results. The essentials are a rapid cationic aza-Cope equilibrium of the incipient iminium cation, and participation of the ester moiety through formation of a relatively stable bicyclic dioxycarbenium cation as pivotal intermediate.

  DOI：

  10.1016/s0040-4020(01)86443-7
• 作为产物：
  描述：

  ethyl N-(3-butenyl)carbamate 在 吡啶 、 4-二甲氨基吡啶 作用下， 以 苯 为溶剂， 反应 21.0h， 生成 acetoxyacetic acid methyl ester
  参考文献：
  名称：

  Tin tetrachloride-induced π-cyclizations of glycine cation equivalents to substituted pipecolic acid derivatives

  摘要：

  Cationic pi-cyclization reactions of N-(3-alkenyl)-N-(methoxycarbonyl)acetoxyglycine esters induced by tin tetrachloride in dichloromethane are described. Reactions started and quenched with water at -78-degrees-C mainly yield cis-4-hydroxypipecolic esters, whereas reactions quenched after warm-up to room temperature provide trans-4-chloropipecolic esters as major products. A mechanistic scheme is advanced which adequately explains these results. The essentials are a rapid cationic aza-Cope equilibrium of the incipient iminium cation, and participation of the ester moiety through formation of a relatively stable bicyclic dioxycarbenium cation as pivotal intermediate.

  DOI：

  10.1016/s0040-4020(01)86443-7

文献信息

• Reductive cyclization of carbon-centered glycine radicals; a novel synthetic route to cyclic α-amino acids
  作者：Peter M. Esch、Henk Hiemstra、Richard F. de Boer、W.Nico Speckamp

  DOI：10.1016/s0040-4020(01)81240-0

  日期：1992.1

  Reductive cyclizations (tributylin hydride, AIBN) of several α-(penthylthio)glycine derivatives with a 30alkenyl substituent at nitrogen are reported. These reactions proceed via 2-aza-5-alken-1-yl radicals as intermediates which bear electron-withdrawing carbonyl substituents at the radical center and at nitrogen. Such radicals can be considered as relatively stable captodative radicals, but are reactive

  报道了几种在氮上具有30个烯基取代基的α-（苯硫基）甘氨酸衍生物的还原环化作用（氢化三丁基氢化物，AIBN）。这些反应通过2-氮杂-5-烯-1-基作为中间体进行，该中间体在自由基中心和氮上带有吸电子羰基取代基。这样的基团可以被认为是相对稳定的Capdudative基团，但是对于烯烃环化而言是足够反应性的。主要产物通常来自5- exo环化，是脯氨酸在结构上令人关注的类似物。经由6-哌啶酸类似物的不同量的内切在某些情况下，也可以得到环化。乙炔的类似环化是成功的，而腈则不能环化。
• Synthesis of cyclic α-amino acids through ring closure of glycine derived free radicals
  作者：Peter M. Esch、Henk Hiemstra、W. Nico Speckamp

  DOI：10.1016/s0040-4039(00)94622-7

  日期：1990.1

  Cyclizations of 1-methoxycarbonyl-2-aza-5-hexenyl (and related) radical intermediates proceed in good yields and constitute a novel synthetic route to proline and pipecolic acid analogues.

  1-甲氧基羰基-2-氮杂-5-己烯基（及相关基团）自由基中间体的环化收率很高，并构成了脯氨酸和胡椒酸类似物的新型合成途径。
• ESCH, PETER M.;HIEMSTRA, HENK;SPECKAMP, W. NICO, TETRAHEDRON LETT., 31,(1990) N, C. 759-762
  作者：ESCH, PETER M.、HIEMSTRA, HENK、SPECKAMP, W. NICO

  DOI：——

  日期：——
• ESCH, PETER M.;BOSKA, ILONA M.;HIEMSTRA, HENK;, SPECKAMP W. NICO, SYNLETT.,(1989) N, C. 38-40
  作者：ESCH, PETER M.、BOSKA, ILONA M.、HIEMSTRA, HENK、, SPECKAMP W. NICO

  DOI：——

  日期：——