2-phenylethyl acetoacetate | 24370-84-1

• 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
• 英文名称: 2-phenylethyl acetoacetate
• 英文别名: phenethyl 3-oxobutanoate；phenylethyl acetoacetate；2-Phenylethyl 3-oxobutanoate
• CAS: 24370-84-1
• 化学式: C₁₂H₁₄O₃
• 分子量: 206.241
• InChiKey: QOMFXOOKFCCSND-UHFFFAOYSA-N

物化性质

• 沸点：
  151.5-153 °C(Press: 6 Torr)
• 密度：
  1.091±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  2-phenylethyl acetoacetate 在 dirhodium tetraacetate 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以 乙腈 、 苯 为溶剂， 反应 7.5h， 生成 trans-3-acetyl-4,5-dihydro-4-phenylfuran-2-(3H)-one
  参考文献：
  名称：

  Electronic and steric control in carbon-hydrogen insertion reactions of diazoacetoacetates catalyzed by dirhodium(II) carboxylates and carboxamides

  摘要：

  Carboxylate and carboxamide ligands on dirhodium(II) catalysts can provide enormous regiocontrol in carbon-hydrogen insertion reactions of diazoacetate esters. Whereas 2,3,4-trimethyl-3-pentyl diazoacetoacetate (1) forms gamma-lactone products from insertion into primary and tertiary C-H bonds in a statistical distribution (61:39) with dirhodium(II) tetrakis(perfluorobutyrate), only tertiary C-H insertion is observed with dirhodium(II) tetraacetamide. Similar results are obtained with 2-methyl-2-octyl diazoacetoacetate (3), where competition for insertion exists between secondary and primary C-H bonds and electronic factors govern regioselection. However, with 2-methyl-3-isopropyl-3-heptyl diazoacetoacetate (2) and 2-methyl-1-phenyl-2-propyl diazoacetoacetate (4), product distributions from C-H insertion are invariant with the dirhodium(II) ligands; insertion into a secondary C-H bond is favored over tertiary C-H insertion with 2 (95:5), and insertion into a primary C-H bond is preferred to benzylic secondary C-H insertion with 4 (70:30). In such cases, which are amenable to analyses by MM2 calculations, regioselectivity is determined by conformational preferences for which C-H insertion selectivity can be as random as that found with 2 and 4. When only one C-H bond site is available for insertion to form a five-membered ring product, only one gamma-lactone is observed from reactions catalyzed by dirhodium(II) tetraacetate, and that product is not necessarily the one predicted by presumed electronic preferences.

  DOI：

  10.1021/ja00056a021
• 作为产物：
  描述：

  乙酸苯乙酯 在 乙醚 、 氨 、 potassium amide 作用下， 生成 2-phenylethyl acetoacetate
  参考文献：
  名称：

  β-Elimination and Other Types of Reaction with Certain β-Phenylethyl Esters and Potassium Amide in Liquid Ammonia

  摘要：

  DOI：

  10.1021/ja01219a017

文献信息

• Enzymatic Synergism in the Synthesis of β-Keto Esters
  作者：Catalina Wiśniewska、Dominik Koszelewski、Małgorzata Zysk、Szymon Kłossowski、Anna Żądło、Anna Brodzka、Ryszard Ostaszewski

  DOI：10.1002/ejoc.201500676

  日期：2015.8

  Reaction of alcohols with ethyl and tert-butyl acetoacetate catalyzed by a combination of commercially available enzymes is shown to be a convenient method for the preparation of a range of acetoacetic acid derivatives. Systematic studies proved that the combination of two or more enzymes enhances the yield of the reaction. Application of the selected enzyme mixture for enzymatic transesterification

  由市售酶的组合催化的醇与乙酰乙酸乙酯和叔丁酯的反应被证明是制备一系列乙酰乙酸衍生物的方便方法。系统研究证明，两种或多种酶的组合提高了反应的产率。将所选的酶混合物用于各种 β-酮酯的酶促酯交换，分别在 24 和 48 小时内以高达 96% 的优异产率和定量提供了相应的产品。该方法简单温和，可用于从伯醇和仲醇制备乙酰乙酸酯。
• Design and synthesis of new 1,4-dihydropyridines containing 4(5)-chloro-5(4)-imidazolyl substituent as a novel calcium channel blocker
  作者：Maryam Iman、Asghar Davood、Ali Reza Nematollahi、Ahmad Rerza Dehpoor、Abbas Shafiee

  DOI：10.1007/s12272-011-0902-9

  日期：2011.9

  New analogues of nifedipine, in which the ortho-nitro phenyl group at position 4 has been replaced by 4(5)-chloro-5(4)-imidazolyl substituent and which are able to interact with the receptor by hydrogen binding were designed, synthesized, and evaluated as calcium channel antagonists. The designed dihydropyridines were synthesized using the Hantzsch condensation and evaluated as calcium channel antagonists

  设计、合成了硝苯地平的新类似物，其中 4 位的邻硝基苯基已被 4(5)-氯-5(4)-咪唑基取代，并且能够通过氢键与受体相互作用，并评估为钙通道拮抗剂。设计的二氢吡啶是使用 Hantzsch 缩合合成的，并使用豚鼠回肠纵向平滑肌的高 K+ 收缩评估为钙通道拮抗剂。使用 AutoDock4 程序进行对接研究，并使用多元线性回归获得 QSAR 方程。我们的计算研究表明，酯的氧 (O10) 和咪唑环的 N3' 分别与 HIS 363 的 NH 和 LYS354 的 NH 形成氢键相互作用，BEHp5 和 RDF075p 的总和是最重要的描述符。钙通道拮抗剂评估的结果表明，增加 C3 和 C5 酯取代基的链长会增加活性。最有效的化合物是双苯丙酯 (5l) 衍生物，因为它比参考药物硝苯地平的活性更强，而且双苯乙酯 (5k) 衍生物的活性与硝苯地平相当。目前的研究表明，4(5)-氯-5(4)-咪唑基部
• NEW ANALOGS AS ANDROGEN RECEPTOR AND GLUCOCORTICOID RECEPTOR MODULATORS
  申请人：Oncostellae, S.L.

  公开号：EP3480201A1

  公开（公告）日：2019-05-08

  The present invention relates to novel dihydropyridine derivatives of formula (I): as modulators of nuclear receptors selected from androgen receptor and glucocorticoid receptor, to processes for their preparation, to pharmaceutical compositions comprising said compounds and to the use of said for manufacturing a medicament for the treatment of pathological conditions or diseases that can improve by modulation of androgen receptor and/or glucocorticoid receptor, selected from cancer, metastasizing cancers, benign prostate hyperplasia, polycystic ovary syndrome (PCOS), hair loss, hirsutism, acne, hypogonadism, muscle wasting diseases, cachexia, Cushing's syndrome, anti-psychotic drug induced weight gain, obesity, post-traumatic stress disorder and alcoholism.

  本发明涉及一种新型的二氢吡啶衍生物，其化学式为(I)：作为选择的核受体调节剂，所述核受体包括雄激素受体和糖皮质激素受体，以及其制备方法，包括所述化合物的制药组合物和利用所述化合物制造用于治疗可以通过调节雄激素受体和/或糖皮质激素受体改善的病理情况或疾病的药物，所述病理情况或疾病包括癌症、转移性癌症、良性前列腺增生、多囊卵巢综合征（PCOS）、脱发、多毛症、痤疮、性腺功能减退、肌肉消耗性疾病、虚弱、库欣综合征、抗精神病药物诱导的体重增加、肥胖、创伤后应激障碍和酗酒。
• Simple and high yielding syntheses of β-keto esters catalysed by zeolites
  作者：B.S. Balaji、Bhanu M. Chanda

  DOI：10.1016/s0040-4020(98)00804-7

  日期：1998.10

  Simple and high yielding syntheses of several β-keto esters, catalysed by zeolite Hβ are reported. The methods developed include condensation of aldehydes with ethyl diazoacetate and transesterification of β-keto esters with primary, secondary, allylic and benzylic alcohols etc., all catalysed by Hβ. It was further observed that under microwave irradiation the yields of many aromatic β-keto esters

  报道了由沸石Hβ催化的几种β-酮酯的简单和高产率的合成。所开发的方法包括醛与重氮乙酸乙酯的缩合以及β-酮酯与伯，仲，烯丙基和苄基醇等的酯交换反应，所有这些反应均由Hβ催化。进一步观察到，在微波辐射下，许多芳族β-酮酯的产率明显提高。
• Carbenoid Reactions in Rhodium(II)-Catalyzed Decomposition of Iodonium Ylides
  作者：Paul Müller、Daniel Fernandez

  DOI：10.1002/hlca.19950780417

  日期：1995.6.28

  intermediacy of metallocarbenes in decomposition reactions of iodonium ylides with [Rh2(OAc)4] was established by comparison with reactions of the corresponding diazo compounds. The sensitivity of the RhII-catalyzed intermolecular cyclopropane formation from substituted styrenes and bis(methoxycarbonyl)(phenyliodono)methanide (1a) or dimethyl diazomalonate (1b) is identical. The Hammett plot (with σ+)

  通过与相应的重氮化合物的反应进行比较，确定了碘化亚烷基碘与[Rh 2（OAc）4 ]的分解反应中金属卡宾的中间体。由取代的苯乙烯和双（甲氧基羰基）（苯基碘基）甲烷（1a）或重氮丙二酸二甲酯（1b）形成的Rh II催化的分子间环丙烷的敏感性相同。的哈米特图（与σ +）具有-0.47的斜率。碘鎓碘化物和重氮化合物在[Rh 2（OAc）4]催化的环丙烷形成，环加成反应和分子内CH插入，并且在分子内竞争中对环丙烷形成和插入表现出相同的选择性。当在手性催化剂（[Rh 2 （-）-（（S）-ptpa} 4 ]）的存在下进行时，叶立德20c的分子内CH插入导致形成ee为67％的21a，与用重氮化合物20b得到的ee相同。