methyl 4-(4-oxopentyl)benzoate | 103094-70-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 4-(4-oxopentyl)benzoate
• 英文别名: 1-4-carbomethoxyphenyl pentan-4-one
• CAS: 103094-70-8
• 化学式: C₁₃H₁₆O₃
• 分子量: 220.268
• InChiKey: PCANUTXUTRHVTG-UHFFFAOYSA-N

物化性质

• 沸点：
  345.2±35.0 °C(Predicted)
• 密度：
  1.065±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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 4-(4-oxopentyl)benzoate 在 lithium hydroxide 作用下， 以 甲醇 、 水 为溶剂， 以91%的产率得到4-(4-oxopentyl)benzoic acid
  参考文献：
  名称：

  Samarium(II)-Promoted Radical Spirocyclization onto an Aromatic Ring

  摘要：

  Samarium(II)-mediated spirocyclization onto an aromatic ring was achieved by the reaction of methyl 4-(4-oxoalkyl)benzoates with SmI2 in the presence of i-PrOH and HMPA, yielding methyl 1-alkyl-1-hydroxyspiro[4.5]dec-6-ene-8-carboxylates in moderate to high yields. Utilizing this chemistry, spiro[3.5] and -[5.5] systems, and sterically congested spiro[4.5] systems, were easily synthesized. For the successful conversion, appropriate activation of the aromatic ring has proven to be extremely important: while an ester or amide functionality on the aromatic ring can promote the spirocyclization, a sulfonamide substituent causes ortho cyclization.

  DOI：

  10.1021/jo034767w
• 作为产物：
  描述：

  对甲基苯甲酸甲酯 在 盐酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.0h， 生成 methyl 4-(4-oxopentyl)benzoate
  参考文献：
  名称：

  Electroreductive intramolecular coupling of nonconjugated aromatic ketones

  摘要：

  The electroreduction of nonconjugated aromatic ketones gave intramolecularly coupled products. The best result was obtained using an Sn cathode in i-PrOH containing tetraalkylammonium salt as a supporting electrolyte. This reductive cyclization proceeded with remarkable stereoselectivity, and the cis isomer was obtained exclusively. A variety of new bi- and polycyclic compounds were synthesized. The reaction mechanism was studied, and it was suggested that the anion radical generated by one-electron transfer to a carbonyl group attacks an aromatic ring intramolecularly. The choice of counter cation of the anion radical was critical for the reductive cyclization. Other reductive methods employing metal reducing agents were also studied. Reduction with Na in HMPA-THF gave the same cyclized product, though the yield was lower than that with the electroreduction.

  DOI：

  10.1021/jo00085a033

文献信息

• Samarium Diiodide Mediated Ketyl-Aryl Coupling Reactions - Influence of Substituents and Trapping Experiments
  作者：Ulrike K. Wefelscheid、Mathias Berndt、Hans-Ulrich Reißig

  DOI：10.1002/ejoc.200800293

  日期：2008.7

  derivatives as single diastereoisomers in most cases. The position of the substituents was also of crucial influence on the outcome; in several cases ipso-substitution leading to the formation of spiro compounds was observed. Electron-donating substituents at the aromatic moiety are less favourable for the ketyl–aryl couplings. They apparently impede the second electron transfer that is involved in this multi-step

  这项综合研究描述了芳基部分的取代基对 SmI2 介导的分子内酮基-芳基偶联反应的影响。不同取代的γ-芳基酮被用作前体，其通过4-戊烯-2-醇与相应的溴苯或碘苯的Heck反应直接制备。在用两当量的二碘化钐γ-芳基酮处理后，带有吸电子取代基，如氰基、三氟甲基或羰基，在大多数情况下，得到预期的六氢化萘衍生物，为单一的非对映异构体。取代基的位置对结果也有至关重要的影响。在一些情况下，观察到导致形成螺环化合物的 ipso 取代。芳族部分的给电子取代基对酮基-芳基偶联不太有利。它们显然阻碍了这个多步骤过程中涉及的第二次电子转移。在这些观察的基础上，详细讨论了 SmI2 促进的酮基-芳基偶联的机制。对于在间位具有吸电子取代基的前体，SmI2 促进的环化的相当稳定的碳负离子中间体可以用丙酮或烯丙基溴作为亲电试剂捕获，以区域选择性地提供相应的加成产物。我们的结果对于立体选择性生成的六氢化萘衍生物的合成应用应该是有价值的。（©
• Electroorganic chemistry. 98. Novel intramolecular stereoselective addition of electrogenerated radical species to the aromatic ring
  作者：Tatsuya. Shono、Naoki. Kise、Takeshi. Suzumoto、Toshio. Morimoto

  DOI：10.1021/ja00275a084

  日期：1986.7

  La reduction electrochimique de derives de l'aryl-5 pentanone-2 conduit a des derives de l'(hexahydro-1,2,3,4,6,8a methyl-1) naphtol-1

  La 还原电化学 de 衍生 de l'aryl-5 pentanone-2 导管 a des 衍生 de l'(hexahydro-1,2,3,4,6,8amethyl-1)naphtol-1
• Design, Synthesis, and Biological Activities of Classical <i>N</i>-{4-[2-(2-Amino-4-ethylpyrrolo[2,3-<i>d</i>]pyrimidin-5-yl)ethyl]benzoyl}-<scp>l</scp>-glutamic Acid and Its 6-Methyl Derivative as Potential Dual Inhibitors of Thymidylate Synthase and Dihydrofolate Reductase and as Potential Antitumor Agents
  作者：Aleem Gangjee、Jianming Yu、Roy L. Kisliuk、William H. Haile、Giulia Sobrero、John J. McGuire

  DOI：10.1021/jm0203534

  日期：2003.2.1

  3-d]pyrimidin-5-yl)ethyl]benzoyl]-l-glutamic acid (2) and N-[2-amino-4-ethyl-6-methyl[(pyrrolo[2,3-d]pyrimidin-5-yl)ethyl]benzoyl]-l-glutam ic acid (4), were designed and synthesized as potent dual inhibitors of thymidylate synthase (TS) and dihydrofolate reductase (DHFR) and as antitumor agents. Compound 2 had inhibitory potency against human DHFR similar to N-[4-[2-(amino-3,4-dihydro-4-oxo-7H-pyrrolo[2,

  两种新颖的类似物，N- [2-氨基-4-乙基[（吡咯并[2,3-d]嘧啶-5-基）乙基]苯甲酰基] -1-谷氨酸（2）和N- [2-氨基-设计并合成了4-乙基-6-甲基[（吡咯并[2,3-d]嘧啶-5-基）乙基]苯甲酰基] -1-谷氨酸（4），作为有效的胸苷酸合酶双重抑制剂（TS ）和二氢叶酸还原酶（DHFR）并用作抗肿瘤药。化合物2具有类似于N- [4- [2-（氨基-3,4-二氢-4-氧代-7H-吡咯并[2,3-d]嘧啶-5-基）乙基]苯甲酰基的对人DHFR的抑制能力。 ] -L-谷氨酸（LY231514）和1，而4对人DHFR没有活性。2和4都比LY231514更能抵抗大肠杆菌。抗人TS的功效比LY231514低7倍，而4表现出与LY231514相似的抑制活性。与2相比，它是人类草氨酸谷氨酸合成酶（FPGS）的有效底物，4是FPGS的不良底物。在标准的NCI临床前体外筛选中，化合物2
• The first samarium(ii)-mediated stereoselective spirocyclization onto an aromatic ring
  作者：Hiroaki Ohno、Shin-ichiro Maeda、Mitsuaki Okumura、Ryutaro Wakayama、Tetsuaki Tanaka

  DOI：10.1039/b110633c

  日期：2002.2.12

  The first samarium(II)-mediated spirocyclisation onto an aromatic ring was achieved by the reaction of methyl 4-(4-oxoalkyl)benzoates with SmI2 in the presence of i-PrOH and HMPA, yielding methyl 1-alkyl-1-hydroxyspiro[4.5]dec-6-ene-8-carboxylates in moderate to high yields.

  在 i-PrOH 和 HMPA 存在下，4-(4-氧代烷基)苯甲酸甲酯与 SmI2 发生反应，首次实现了钐(II)介导的芳环螺环化反应，以中等至高产率生成了 1-烷基-1-羟基螺[4.5]癸-6-烯-8-羧酸甲酯。
• Secondary amines, their preparation, pharmaceutical compositions containing them and their use
  申请人：BEECHAM GROUP PLC

  公开号：EP0006735A1

  公开（公告）日：1980-01-09

  The compounds of the formula (II): and their pharmaceutically acceptable salts wherein R, is a hydrogen, fluorine or chlorine atom or a hydroxyl, hydroxymethyl. methyl, methoxy, amino. formamido. acetamido. methylsulphonylamido, nitro, benzyloxy, methyisuiphonylmethyl. ureido, trifluoromethyl or p-methoxybenrylamino group; R2 is a hydrogen, fluorine or chlorine atom or a hydroxyi group; R3 is a hydrogen or chlorine atom or a hydroxyl group; R4 is a carboxylic acid group or a salt, ester or amide thereof; R5 is a hydrogen. chlaine or fluorine atom or a methyl, methoxyl or hydroxyl group or a carboxylic acid group or a salt, ester or amide thereof: R5 is a hydrogen atom or a methyl, or propyl group; X is an oxygen atom or a bond: and Y is an alkylene group of up to 6 carbon atoms or a bond have been found to possess anti-obesity and/ or antihypergtycaemic activity.

  分子式为（II）的化合物及其药用盐，其中R为氢、氟或氯原子，或羟基、羟甲基、甲基、甲氧基、氨基、甲酰胺基、乙酰胺基、甲磺酰胺基、硝基、苄氧基、甲基磺酰甲基、脲基、三氟甲基或对甲氧基苯基氨基基团；R2为氢、氟或氯原子，或羟基基团；R3为氢或氯原子，或羟基基团；R4为羧酸基团或其盐、酯或酰胺；R5为氢、氯或氟原子，或甲基、甲氧基或羟基基团，或羧酸基团或其盐、酯或酰胺；R6为氢原子或甲基、丙基基团；X为氧原子或键；Y为长度不超过6个碳原子的烷基团或键，已被发现具有抗肥胖和/或抗高血糖活性。