4,5-dihydro-2-benzoxepin-1(3H)-one | 5651-62-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噁庚英
• 英文名称: 4,5-dihydro-2-benzoxepin-1(3H)-one
• 英文别名: 4,5-dihydrobenzo[c]oxepin-1(3H)-one；2-Benzoxepin-1(3H)-one, 4,5-dihydro-；4,5-dihydro-3H-2-benzoxepin-1-one
• CAS: 5651-62-7
• 化学式: C₁₀H₁₀O₂
• 分子量: 162.188
• InChiKey: DVKWMWZIAMTAPL-UHFFFAOYSA-N

物化性质

• 熔点：
  53-55 °C(Solv: ligroine (8032-32-4))
• 沸点：
  95-99 °C(Press: 0.01 Torr)
• 密度：
  1.145±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2932999099

反应信息

• 作为反应物：
  描述：

  4,5-dihydro-2-benzoxepin-1(3H)-one 在 三氯氧磷 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 31.0h， 生成 3,13-Diazapentacyclo[11.9.0.02,10.04,9.017,22]docosa-2(10),4,6,8,17,19,21-heptaene
  参考文献：
  名称：

  Dopamine/Serotonin Receptor Ligands. 13:  Homologization of a Benzindoloazecine-Type Dopamine Receptor Antagonist Modulates the Affinities for Dopamine D₁−D₅ Receptors

  摘要：

  Enlarging the 10-membered ring of 7-methyl-6,7,8,9,14,15-hexahydro-5H-indolo[3,2-f][3] benzazecine (1, LE 300) yielded two homologue antagonists. Their affinities and inhibitory activities at D-1-D-5 receptors were measured by radioligand binding experiments and a functional Ca2+ assay. Compared to 1, phenylpropyl homologue 3 was superior in selectivity and affinity for the D5 subtype (K-i = 0.6 nM), whereas the affinity of the indolylpropyl homologue 2 for all subtypes decreased. Compounds 2, 3, 10, 11, 17, and 18 are derivatives of novel heterocyclic ring systems.

  DOI：

  10.1021/jm060213k
• 作为产物：
  描述：

  3-(2-羧基苯基)丙酸 在 锂硼氢 、 硫酸 作用下， 以 1,4-二氧六环 为溶剂， 反应 44.5h， 生成 4,5-dihydro-2-benzoxepin-1(3H)-one
  参考文献：
  名称：

  Synthesis and antifungal activity of 7-methyl-7-hydroxy-2,3-benzo[c]octa-1,6-olide

  摘要：

  The racemic 7-methyl-7-hydroxy-2,3-benzo[c]octa-1,6-olide, the analog of natural product (6R)-3,7-dimethyl-7-hydroxy-2-octen-1,6-olide, was totally synthesized using easily available (E)-2-(2-carboxyvinyl)benzoic acid as a raw material in nine-step reactions including three key steps of Wittig reaction, epoxidation, and cyclization, with an overall yield of 10.3%. The bioassay results showed that (+/-)-2 exhibited stronger antifungal activity than the natural product (+/-)-1 and (R)-1 against Alternaria solani with an EC50 value of 27.36g/ml.

  DOI：

  10.1080/10286020.2013.879121

文献信息

• Electron-Transfer-Induced Intramolecular Heck Carbonylation Reactions Leading to Benzolactones and Benzolactams
  作者：Ilhyong Ryu、Takahide Fukuyama、Takanobu Bando

  DOI：10.1055/s-0037-1609964

  日期：2018.8

  Radical Methods and their Strategic Applications in Synthesis Abstract A metal-catalyst-free intramolecular Heck carbonylation reaction of benzyl alcohols and benzyl amines with carbon monoxide under heating at 250 °C affords the corresponding benzolactones and benzolactams in good to excellent yields. A hybrid radical/ionic chain mechanism, involving electron transfer from radical anions generated by nucleophilic

  作为特别主题“现代自由基方法及其在合成中的战略应用”的一部分发布 抽象的 苄醇和苄胺与一氧化碳的无金属催化剂的分子内Heck羰基化反应在250°C加热下以良好或极好的收率得到相应的苯并内酯和苯并内酰胺。提出了一种杂合自由基/离子链机制，该机制涉及电子转移，该自由基是由醇或胺对中间酰基自由基的亲核攻击所产生的自由基阴离子转移而来的。 苄醇和苄胺与一氧化碳的无金属催化剂的分子内Heck羰基化反应在250°C加热下以良好或极好的收率得到相应的苯并内酯和苯并内酰胺。提出了一种杂合自由基/离子链机制，该机制涉及电子转移，该自由基是由醇或胺对中间酰基自由基的亲核攻击所产生的自由基阴离子转移而来的。
• Radical isomerization via intramolecular ipso substitution of aryl ethers: Aryl translocation from oxygen to carbon
  作者：Lee Eun、Lee Chulbom、Sung Tae Jin、Sung Whang Ho、Sok Li Kap

  DOI：10.1016/s0040-4039(00)77609-x

  日期：1993.4

  Bromopropyl aryl ethers an converted to 3-arylpropanols under standard radical generating conditions in the presence of tributylstannane and AIBN. This rearrangement involves intramolecular ipso attack of the alkyl radicals which generates spiro cyclohexadienyl radical intermediates.

  在三丁基锡烷和AIBN存在下，在标准自由基产生条件下，将溴丙基芳基醚转化为3-芳基丙醇。该重排涉及烷基的分子内ipso攻击，其产生螺环己二烯基自由基中间体。
• Supramolecular Control of Selectivity in Hydroformylation of Vinyl Arenes: Easy Access to Valuable β-Aldehyde Intermediates
  作者：Paweł Dydio、Joost N. H. Reek

  DOI：10.1002/anie.201209582

  日期：2013.4.2

  flow! A rationally designed regioselective hydroformylation catalyst, [Rh/L], in which noncovalent ligand–substrate interactions allow the unprecedented reversal of selectivity from the typical α‐aldehyde to the otherwise unfavored product β‐aldehyde, is reported. This catalytic system opens up novel and sustainable synthetic pathways to important intermediates for the fine‐chemicals industry.

  逆流而上！据报道，一种合理设计的区域选择性加氢甲酰化催化剂[Rh / L]，其中非共价配体-底物的相互作用使选择性从典型的α-醛到其他不利的产物β-醛发生了前所未有的逆转。该催化体系为精细化工行业的重要中间体开辟了新的，可持续的合成途径。
• Pd/C-Catalyzed Carbonylative Esterification of Aryl Halides with Alcohols by Using Oxiranes as CO Sources
  作者：Byul-Hana Min、Dong-Su Kim、Hyo-Soon Park、Chul-Ho Jun

  DOI：10.1002/chem.201600570

  日期：2016.4.25

  A carbonylative esterification reaction between aryl bromides and alcohols, promoted by Pd/C and NaF in the presence of oxiranes, has been developed. In this process, oxiranes serve as sources of carbon monoxide by their conversion to aldehydes through a palladium‐promoted Meinwald rearrangement pathway. Intramolecular versions of this process serve as methods for the synthesis of lactones and phthalimides

  在环氧乙烷的存在下，Pd / C和NaF促进了芳基溴化物与醇类之间的羰基化酯化反应。在此过程中，环氧乙烷通过钯促进的Meinwald重排途径转化为醛，从而成为一氧化碳的来源。该方法的分子内形式用作合成内酯和邻苯二甲酰亚胺的方法。
• Regioselective biocatalytic self-sufficient Tishchenko-type reaction <i>via</i> formal intramolecular hydride transfer
  作者：Erika Tassano、Kemal Merusic、Isa Buljubasic、Olivia Laggner、Tamara Reiter、Andreas Vogel、Mélanie Hall

  DOI：10.1039/d0cc02509g

  日期：——

  A self-sufficient nicotinamide-dependent intramolecular bio-Tishchenko-type reaction was developed. The reaction is catalyzed by alcohol dehydrogenases and proceeds through formal intramolecular hydride transfer on dialdehydes to deliver lactones. Regioselectivity on [1,1′-biphenyl]-2,2′-dicarbaldehyde substrates could be controlled via the electronic properties of the substituents. Preparative scale

  开发了一种自给自足的烟酰胺依赖性分子内生物-季申科型反应。该反应由醇脱氢酶催化，并通过在二醛上的正式分子内氢化物转移进行，以递送内酯。可以通过取代基的电子性质控制[1,1'-联苯] -2,2'-二甲醛的底物的区域选择性。制备规模的合成提供了对取代的二苯并[ c，e ] oxepin-5（7 H）-的访问。