methyl 2-acetononanoate | 172159-96-5

• 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: methyl 2-acetononanoate
• 英文别名: methyl 2-acetylnonanoate；methyl 2-hexylacetoacetate；methyl (RS)-2-acetylnonanoate
• CAS: 172159-96-5
• 化学式: C₁₂H₂₂O₃
• 分子量: 214.305
• InChiKey: CWUSXSYQJSNZAL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  15
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 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 2-acetononanoate 在 盐酸 、 sodium methylate 作用下， 反应 8.0h， 生成 2-癸酮
  参考文献：
  名称：

  A new approach to the synthesis of 3,6- and 5,6-dialkyl derivatives of 4-hydroxy-2-pyrone. Synthesis of rac-germicidin

  摘要：

  A new approach to the synthesis of 3,6- and 5,6-dialkyl-4-hydroxy-2-pyrones has been developed. The method includes the formation of acylated Meldrum's acids (5-(2-alkyl-3-oxoacyl)-2,2-dimethyl-1,3-dioxane-4,6-diones) followed by their thermal transformation. Introduction of 3-alkyl substituents was accomplished by acylation of 4-hydroxy-2-pyrones and ionic hydrogenation of the 3-acyl derivatives obtained. The effectiveness of this new approach has been demonstrated in the synthesis of rac-germicidin, an autoregulative germination inhibitor of Streptomyces viridochromogenes NRRL B-1551. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(99)00150-7
• 作为产物：
  描述：

  乙酰乙酸甲酯 、 alkaline earth salt of/the/ methylsulfuric acid 在 sodium 作用下， 以 甲醇 为溶剂， 生成 methyl 2-acetononanoate
  参考文献：
  名称：

  天然产物的小型组合图书馆的合成：菊粉（Inula helenium L。）（菊科）根精油中新的长链3-甲基-2-链烷酮的鉴定和定量

  摘要：

  最近，有报道称菊粉菊（Inula helenium L.（Asteraceae））根精油具有强大的抗葡萄球菌活性。此外，油的生物测定指导分馏指出，杜仲倍半萜烯内酯和一系列未确定的成分是观察到的活性的主要载体。

  DOI：

  10.1002/pca.2466

文献信息

• Electrophilic Iron Catalyst Paired with a Lithium Cation Enables Selective Functionalization of Non‐Activated Aliphatic C−H Bonds via Metallocarbene Intermediates
  作者：Alberto Hernán‐Gómez、Mònica Rodríguez、Teodor Parella、Miquel Costas

  DOI：10.1002/anie.201905986

  日期：2019.9.23

  Combining an electrophilic iron complex [Fe(F pda)(THF)]2 (3) [F pda=N,N'-bis(pentafluorophenyl)-o-phenylenediamide] with the pre-activation of α-alkyl-substituted α-diazoesters reagents by LiAl(ORF )4 [ORF =(OC(CF3 )3 ] provides unprecedented access to selective iron-catalyzed intramolecular functionalization of strong alkyl C(sp3 )-H bonds. Reactions occur at 25 °C via α-alkyl-metallocarbene intermediates

  将亲电子配合物[Fe（F pda）（THF）] 2（3）[F pda = N，N'-双（五氟苯基）-邻苯二甲酰胺]与α-烷基取代的α-的预活化结合LiAl（ORF）4 [ORF =（OC（CF3）3]金属碳烯中间体，其活性/选择性与羧酸铑催化剂相似，机理研究表明，锂阳离子在决定亲电性铁碳卡宾中间体的形成速率中起着至关重要的作用，然后通过协同插入CH中进行键。
• METHOD FOR PURIFYING PYRUVIC ACID COMPOUNDS
  申请人：SUMITOMO CHEMICAL COMPANY LIMITED

  公开号：EP0937703A1

  公开（公告）日：1999-08-25

  The present invention is directed to a method for purifying pyruvic acid compounds, which method comprises reacting a pyruvic acid compound of general formula (I): wherein R1 is an optionally substituted lower alkyl group, a lower alkenyl group, a lower alkynyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and R2 is a lower alkyl group, with a bisulfite of general formula (II):         MHSO3     (II) wherein M is NH4 or an alkali metal, to give a bisulfite adduct of the pyruvic acid compound and then decomposing the adduct with an acid. According to the present invention, pyruvic acid compounds can be purified by simple and easy procedures without using purification techniques such as distillation or column chromatography, and the above method is advantageous as a process for the production on an industrial scale.

  本发明涉及一种纯化丙酮酸化合物的方法，该方法包括使通式(I)的丙酮酸化合物反应： 其中 R1 是任选取代的低级烷基、低级烯基、低级炔基、环烷基、芳基或杂环基，R2 是低级烷基，与通式（II）的亚硫酸氢盐反应： MHSO3 (II) 其中 M 为 NH4 或碱金属，以得到丙酮酸化合物的亚硫酸氢盐加合物，然后用酸分解该加合物。根据本发明，丙酮酸化合物可以通过简单易行的程序进行纯化，而无需使用蒸馏或柱层析等纯化技术，上述方法作为一种工业规模的生产工艺是非常有利的。
• A study on the mechanism and scope of the radical-mediated oxidation of arylacetoacetates
  作者：Mercè Tona、Marisa Guardiola、Lluis Fajarí、Angel Messeguer

  DOI：10.1016/0040-4020(95)00576-t

  日期：1995.1

  Arylacetoacetate 1a undergoes an oxidative degradation in the presence of K(t)BuO, THF, catalytic I-2 and O-2, to give keto ester 4 as major compound. Hydrolysis and decarboxylation of this intermediate led to the corresponding arylcarboxylic acid 3a in satisfactory overall yields. By experiments conducted in the presence of O-18(2), incorporation of atmosphere oxygen into the benzylic position of 4 was evidenced. Furthermore, spin-trap experiments showed that benzyl radical 7 was generated in the reaction medium, which supports its role as intermediate in the pathway leading to the observed oxidation products. A plausible mechanism for this process is presented. On the other hand, appropriate conditions for achieving the alkylation of these arylacetoacetates with no concomitant formation of oxidation side-products are reported. Finally, arylacetates suffer also this degradative oxidation process leading to the corresponding arylcarboxylic acids without isolation of the intermediate keto ester derivative.
• Asymmetric Hydrogenation of Substituted 2-Pyrones
  作者：Matthias J. Fehr、Giambattista Consiglio、Michelangelo Scalone、Rudolf Schmid

  DOI：10.1021/jo982215l

  日期：1999.8.1

  Various substituted 2-pyrones have been hydrogenated with high enantioselectivity (up to 97% ee) to the corresponding 5,6-dihydropyrones using cationic ruthenium catalysts containing the (6,6'-dimethoxybiphenyl-2,2'diyl)bis[3,5-di(tert-butyl)phenylphosphine] ligand. When substituents at position 3 are absent, 5,6-dihydropyrones are further hydrogenated to the fully saturated delta-lactones. In the case of 4,6-dimethyl-2H-pyran-2-one, the diastereoselectivity of the second hydrogenation step was determined by the chirality of the applied catalyst, while for the 4,5,6-trimethyl-2H-pyran-2-one a double asymmetric induction effect was observed. Other cyclic substrates with endo- or exocyclic double bonds were hydrogenated, although with substantially lower enantioselectivity with respect to the 2-pyrones.
• Synthesis and Pharmacology of 3-Isoxazolol Amino Acids as Selective Antagonists at Group I Metabotropic Glutamic Acid Receptors
  作者：Ulf Madsen、Hans Bräuner-Osborne、Karla Frydenvang、Lise Hvene、Tommy N. Johansen、Birgitte Nielsen、Connie Sánchez、Tine B. Stensbøl、Francois Bischoff、Povl Krogsgaard-Larsen

  DOI：10.1021/jm000441t

  日期：2001.3.1

  Using ibotenic acid (2) as a lead, two series of 3-isoxazolol amino acid ligands for (S)-glutamic acid (Glu, 1) receptors have been developed. Whereas analogues of (RS)-2-amino-3-(3-hydroxy5-methyl-4-isoxazolyl)propionic acid [AMPA, (RS)-3] interact selectively with ionotropic Glu receptors (iGluRs), the few analogues of (RS)-2-amino-3-(3-hydroxy-5-isoxazolyl)propionic acid [HIBO, (RS)-4] so far known typically interact with iGluRs as well as metabotropic Glu receptors (mGluRs). We here report the synthesis and pharmacology of a series of 4-substituted analogues of HIBO. The hexyl analogue 9 was shown to be an antagonist at group I mGluRs. The effects of 9 were shown to reside exclusively in (S)-9 (K-b = 30 muM at mGlu(1) and K-b = 61 muM at mGlu(5)). The lower homologue of 9, compound 8, showed comparable effects at mGluRs, but 8 also was a weak agonist at the AMPA subtype of iGluRs. Like 9, the higher homologue, compound 10, did not interact with iGluRs, but 10 selectively antagonized mGlu(1) (K-b = 160 muM) showing very weak antagonist effect at mGlu(5) (K-b = 990 muM). The phenyl analogue 11 turned out to be an AMPA agonist and an antagonist at mGlu(1) and mGlu(5), and these effects were shown to originate in (S)-11 (EC50 = 395 muM, K-b = 86 and 90 muM, respectively). Compound 9, administered icy, but not sc, was shown to protect mice against convulsions induced by N-methyl-D-aspartic acid (NMDA). Compounds 9 and 11 were resolved using chiral HPLC, and the configurational assignments of the enantiomers were based on X-ray crystallographic analyses.