1-(benzyloxy)octan-3-one | 1311463-07-6

• 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: 1-(benzyloxy)octan-3-one
• 英文别名: 1-Phenylmethoxyoctan-3-one
• CAS: 1311463-07-6
• 化学式: C₁₅H₂₂O₂
• 分子量: 234.338
• InChiKey: DULDKMRWITVRQC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(benzyloxy)octan-3-one 在 palladium 10% on activated carbon 、 氢气 、 [双(2-甲氧基乙基)胺]三氟化硫 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 80.0 ℃ 、101.33 kPa 条件下， 反应 24.25h， 生成 3,3-difluorooctan-1-ol
  参考文献：
  名称：

  Regio-selective hydroxylation of gem-difluorinated octanes by alkane hydroxylase (AlkB)

  摘要：

  gem-Difluoromethylene substituted molecules constitute a distinct class of fluorinated compounds. In this study, special chemistry has been developed for their preparation based on the highly selective terminal hydroxylation of these gem-difluorinated octanes by AlkB (alkane hydroxylase) from Pseudomonas putida Gpo1 to form gem-difluorinated octan-1-ols. The hydroxylation reaction is performed by whole-cell catalysis. Identification of the distal- and proximal-hydroxylation products was made by H-1, C-13, and F-19 NMR; GC and GC/MSD; and/or by comparison with authentic standards in GC. To the best of our knowledge, we have obtained the first synthesis of 2,2-, 3,3- and 4,4-difluorooctan-1-ols, from simple and inexpensive starting materials. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.03.101
• 作为产物：
  描述：

  1,3-辛二醇 在 sodium hydride 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 19.0h， 生成 1-(benzyloxy)octan-3-one
  参考文献：
  名称：

  Regio-selective hydroxylation of gem-difluorinated octanes by alkane hydroxylase (AlkB)

  摘要：

  gem-Difluoromethylene substituted molecules constitute a distinct class of fluorinated compounds. In this study, special chemistry has been developed for their preparation based on the highly selective terminal hydroxylation of these gem-difluorinated octanes by AlkB (alkane hydroxylase) from Pseudomonas putida Gpo1 to form gem-difluorinated octan-1-ols. The hydroxylation reaction is performed by whole-cell catalysis. Identification of the distal- and proximal-hydroxylation products was made by H-1, C-13, and F-19 NMR; GC and GC/MSD; and/or by comparison with authentic standards in GC. To the best of our knowledge, we have obtained the first synthesis of 2,2-, 3,3- and 4,4-difluorooctan-1-ols, from simple and inexpensive starting materials. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.03.101

文献信息

• Bis‐Alkoxycarbonylation of Acrylic Esters and Amides for the Synthesis of 2‐Alkoxycarbonyl or 2‐Carbamoyl Succinates
  作者：Diego Olivieri、Riccardo Tarroni、Nicola Della Ca'、Raffaella Mancuso、Bartolo Gabriele、Gilberto Spadoni、Carla Carfagna

  DOI：10.1002/adsc.201900918

  日期：2020.2.6

  The first example of the bis‐alkoxycarbonylation of acrylic esters and acrylic amides, leading to differently substituted 1,1,2‐ethanetricarboxylate compounds and 2‐carbamoylsuccinates respectively, is reported. The catalyst is formed in situ by mixing Pd(TFA)2 (TFA=trifluoroacetate) and the ligand bis(2,6‐dimethylphenyl)butane‐2,3‐diimine. The reaction, that proceeds using p‐benzoquinone as oxidant

  据报道，丙烯酸酯和丙烯酸酰胺的双烷氧基羰基化的第一个例子分别导致了不同取代的1,1,2-乙烷三羧酸酯化合物和2-氨基甲酰基琥珀酸酯的取代。通过混合Pd（TFA）2（TFA =三氟乙酸盐）和配体bis（2,6-二甲基苯基）丁烷-2,3-二亚胺原位形成催化剂。使用对苯醌作为氧化剂和对苯并在非常温和的反应条件下（20°C，4 bar一氧化碳），使用甲苯磺酸作为添加剂，已使用各种醇作为亲核试剂，用于各种取代的电子贫乏烯烃。值得注意的是，这种催化系统能够促进丙烯酸酯和酰胺的β-位和通常不反应的α-位的羰基化，从而形成双烷氧基羰基化产物，收率高至优异（高达98％）。在提出的催化循环和DFT计算的基础上，已经合理化了用不同的缺电子烯烃观察到的反应性趋势。
• PROCESS FOR THE SYNTHESIS OF KETONES FROM INTERNAL ALKENES
  申请人：CALIFORNIA INSTITUTE OF TECHNOLOGY

  公开号：US20140194604A1

  公开（公告）日：2014-07-10

  The present invention is directed to methods for oxidizing internal olefins to ketones. In various embodiments, each method comprising contacting an organic substrate, having an initial internal olefin, with a mixture of (a) a biscationic palladium salt; and (b) an oxidizing agent; dissolved or dispersed in a solvent system to form a reaction mixture, said solvent system comprising at least one C 2-6 carbon nitrile and optionally at least one secondary alkyl amide, said method conducted under conditions sufficient to convert at least 50 mol % of the initial internal olefin to a ketone, said ketone positioned on a carbon of the initial internal olefin. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed oil derivatives and a bioactive natural product are described.

  本发明涉及将内烯烃氧化为酮的方法。在各种实施方式中，每种方法包括将具有初始内烯烃的有机底物与（a）双阳离子钯盐的混合物；和（b）氧化剂接触，溶解或分散在溶剂体系中形成反应混合物，所述溶剂体系包括至少一种C2-6碳腈和可选地至少一种次烷基酰胺，所述方法在足以将初始内烯烃的至少50摩尔％转化为酮的条件下进行，所述酮位于初始内烯烃的碳上。该转化在室温下发生，并显示出广泛的底物范围。描述了将其应用于种子油衍生物和生物活性天然产物的氧化。
• Regioselective Wacker Oxidation of Internal Alkenes: Rapid Access to Functionalized Ketones Facilitated by Cross-Metathesis
  作者：Bill Morandi、Zachary K. Wickens、Robert H. Grubbs

  DOI：10.1002/anie.201303587

  日期：2013.9.9

  Wacka wacka: The title reaction makes use of a wide range of directing groups (DG) to enable the highly regioselective oxidation of alkenes, and occurs predictably at the distal position. Both E and Z alkenes afford valuable functionalized ketones and cross‐metathesis was shown to facilitate the preparation of the starting materials. BQ=benzoquinone.

  Wacka wacka：标题反应利用了广泛的导向基团（DG）来实现烯烃的高度区域选择性氧化，并且可预测地发生在末端位置。既Ë和Ž 烯烃得到有价值官能酮和交叉复分解显示出促进起始原料的制备。BQ ＝苯醌。
• NAKANO, TATSUYA;ISHII, YASUTAKA;OGAWA, MASAYA, J. ORG. CHEM., 52,(1987) N 22, 4855-4859
  作者：NAKANO, TATSUYA、ISHII, YASUTAKA、OGAWA, MASAYA

  DOI：——

  日期：——