methyl 2-(6,8-difluorophenanthren-1-yl)-2-hydroxypropionate | 843614-70-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: methyl 2-(6,8-difluorophenanthren-1-yl)-2-hydroxypropionate
• 英文别名: Methyl 2-(6,8-difluorophenanthren-1-yl)-2-hydroxypropanoate
• CAS: 843614-70-0
• 化学式: C₁₈H₁₄F₂O₃
• 分子量: 316.304
• InChiKey: ZPTWEEUOMPWVJH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2-(6,8-difluorophenanthren-1-yl)-2-hydroxypropionate 在 氢氧化钾 、 二乙胺基三氟化硫 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 2-(6,8-difluorophenanthr-1-yl)-2-fluoropropionic acid
  参考文献：
  名称：

  Regioselectively Nucleus and/or Side-Chain Fluorinated 2-(Phenanthryl)propionic Acids by an Effective Combination of Radical and Organometallic Chemistry

  摘要：

  Regioselectively nucleus and/or side-chain fluorinated 2-(phenanthr-1-yl)- and 2-(phenanthr-2-yl)-propionic acids 1-5 were prepared using phenanthren-1(2H)-ones 6a-c as key intermediates. Thus. ethyl 2-(fluorophenanthryl)propionates 11 were obtained in good yields by Reformatsky reaction of 6a-c with ethyl 2-bromopropionate followed by dehydratation and DDQ-promoted aromatization of the resulting beta-hydroxyesters. Side-chain alkyl 2-hydroxy-2-(phenanthr-1-yl)propionates 14 were obtained by bromine/lithium permutation of dihydrophenanthryl bromides 12a-c with butyllithium followed by quenching of the lithiated intermediates with methyl pyruvate or ethyl 3,3,3-trifluoropyruvate and subsequent DDQ-promoted aromatization. The alkyl 2-hydroxy-2-(phenanthr-1-yl)propionates 25 were prepared by reacting 8-bromo-1,3-difluorophenanthrene 24 with butyllithium for 10 seconds at -110degreesC and subsequent addition of the suitable pyruvate to the lithiated intermediates. Alkyl 2-hydroxy-2-(phenanthr-2-yl)propionates 26 and 29 were suitably obtained by site-selective metalation of 1,3-difluorophenanthrene 28 and the bromophenanthrene 24: respectively, with LDA followed by quenching of the metalated intermediates with the Suitable alkyl pyruvate. Fluorination of the above alpha-hydroxypropionates with DAST, followed by the alkaline hydrolysis, allowed the expected 2-(phenanthryl)propionic acids 1-5 to be obtained in satisfactory overall yields.

  DOI：

  10.1021/jo048294k
• 作为产物：
  描述：

  6,8-difluoro-3,4-dihydrophenanthren-(2H)-1-one 在 正丁基锂 、 一水合肼 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 copper(ll) bromide 、 lithium tert-butoxide 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 甲苯 、 苯 为溶剂， 反应 8.0h， 生成 methyl 2-(6,8-difluorophenanthren-1-yl)-2-hydroxypropionate
  参考文献：
  名称：

  Regioselectively Nucleus and/or Side-Chain Fluorinated 2-(Phenanthryl)propionic Acids by an Effective Combination of Radical and Organometallic Chemistry

  摘要：

  Regioselectively nucleus and/or side-chain fluorinated 2-(phenanthr-1-yl)- and 2-(phenanthr-2-yl)-propionic acids 1-5 were prepared using phenanthren-1(2H)-ones 6a-c as key intermediates. Thus. ethyl 2-(fluorophenanthryl)propionates 11 were obtained in good yields by Reformatsky reaction of 6a-c with ethyl 2-bromopropionate followed by dehydratation and DDQ-promoted aromatization of the resulting beta-hydroxyesters. Side-chain alkyl 2-hydroxy-2-(phenanthr-1-yl)propionates 14 were obtained by bromine/lithium permutation of dihydrophenanthryl bromides 12a-c with butyllithium followed by quenching of the lithiated intermediates with methyl pyruvate or ethyl 3,3,3-trifluoropyruvate and subsequent DDQ-promoted aromatization. The alkyl 2-hydroxy-2-(phenanthr-1-yl)propionates 25 were prepared by reacting 8-bromo-1,3-difluorophenanthrene 24 with butyllithium for 10 seconds at -110degreesC and subsequent addition of the suitable pyruvate to the lithiated intermediates. Alkyl 2-hydroxy-2-(phenanthr-2-yl)propionates 26 and 29 were suitably obtained by site-selective metalation of 1,3-difluorophenanthrene 28 and the bromophenanthrene 24: respectively, with LDA followed by quenching of the metalated intermediates with the Suitable alkyl pyruvate. Fluorination of the above alpha-hydroxypropionates with DAST, followed by the alkaline hydrolysis, allowed the expected 2-(phenanthryl)propionic acids 1-5 to be obtained in satisfactory overall yields.

  DOI：

  10.1021/jo048294k

文献信息

• Regioselectively Nucleus and/or Side-Chain Fluorinated 2-(Phenanthryl)propionic Acids by an Effective Combination of Radical and Organometallic Chemistry
  作者：Giacomo Ricci、Renzo Ruzziconi

  DOI：10.1021/jo048294k

  日期：2005.1.1

  Regioselectively nucleus and/or side-chain fluorinated 2-(phenanthr-1-yl)- and 2-(phenanthr-2-yl)-propionic acids 1-5 were prepared using phenanthren-1(2H)-ones 6a-c as key intermediates. Thus. ethyl 2-(fluorophenanthryl)propionates 11 were obtained in good yields by Reformatsky reaction of 6a-c with ethyl 2-bromopropionate followed by dehydratation and DDQ-promoted aromatization of the resulting beta-hydroxyesters. Side-chain alkyl 2-hydroxy-2-(phenanthr-1-yl)propionates 14 were obtained by bromine/lithium permutation of dihydrophenanthryl bromides 12a-c with butyllithium followed by quenching of the lithiated intermediates with methyl pyruvate or ethyl 3,3,3-trifluoropyruvate and subsequent DDQ-promoted aromatization. The alkyl 2-hydroxy-2-(phenanthr-1-yl)propionates 25 were prepared by reacting 8-bromo-1,3-difluorophenanthrene 24 with butyllithium for 10 seconds at -110degreesC and subsequent addition of the suitable pyruvate to the lithiated intermediates. Alkyl 2-hydroxy-2-(phenanthr-2-yl)propionates 26 and 29 were suitably obtained by site-selective metalation of 1,3-difluorophenanthrene 28 and the bromophenanthrene 24: respectively, with LDA followed by quenching of the metalated intermediates with the Suitable alkyl pyruvate. Fluorination of the above alpha-hydroxypropionates with DAST, followed by the alkaline hydrolysis, allowed the expected 2-(phenanthryl)propionic acids 1-5 to be obtained in satisfactory overall yields.