CN106397379A - 一种2‑苯基‑1,4‑苯并哌喃酮的制备方法 - Google Patents

一种2‑苯基‑1,4‑苯并哌喃酮的制备方法 Download PDF

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CN106397379A
CN106397379A CN201610503544.9A CN201610503544A CN106397379A CN 106397379 A CN106397379 A CN 106397379A CN 201610503544 A CN201610503544 A CN 201610503544A CN 106397379 A CN106397379 A CN 106397379A
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molal quantity
phenyl
reaction
alanine
cod
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Inventor
贾宏葛
唐亚楠
马立群
王雅珍
何子健
杨熠
来伟伟
朱广宇
张辉
臧雨
徐双平
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Qiqihar University
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Qiqihar University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
    • C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
    • C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
    • C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

本发明属于催化工程领域，特别涉及一种新的黄酮衍生物的制备方法，利用新型手型铑催化剂催化邻醛基苯酚和苯乙炔反应合成2‑苯基‑1,4‑苯并哌喃酮，解决了目前黄酮类化合物合成路线长，反应过程中副产物多，总收率低的问题，本发明专利属一步合成法，反应过程短，避免了中间体的合成，收率高。

Description

一种2-苯基-1,4-苯并哌喃酮的制备方法
技术领域
本发明专利属于催化工程领域，特别涉及一种黄酮衍生物的制备方法，利用新型手型铑催化剂催化裂解苯乙炔与邻醛基苯酚合成2-苯基-1,4-苯并哌喃酮，解决了现有的合成苯并酮类化合物过程中副产物多的问题。
背景技术
近年来，许多新技术新方法在黄酮类化合物合成中得到广泛应用，如利用硅烷等保护基催化多酮的方法构建黄酮化合物的骨架，但是，其合成路线长，反应过程中副产物多，总收率低。
为了克服黄酮类衍生物合成时存在的问题，本发明专利提供了一种利用新型手型铑催化剂合成2-苯基-1,4-苯并哌喃酮的方法，该方法一步合成，反应过程短，避免了中间体的合成，收率高。
发明内容
本发明专利采用的技术方案是：先在反应瓶中加入以L-丙氨酸(L-alanine)和1,5-环辛二烯(cod)为配体的手型铑催化剂[Rh(cod)(L-alanine)] 0.002～0.01份(摩尔数)、乙酸铜2份(摩尔数)、1,2,3,4-四苯基1,3-环戊二烯0.02～0.1份(摩尔数)，抽真空进行氮气保护后，依次向反应瓶注入邻醛基苯酚1份(摩尔数)、苯乙炔1份(摩尔数)、邻二甲苯0.02～0.04份(摩尔数)，在120℃下加热回流反应5.5小时，用乙醚进行萃取，有机相经旋蒸干燥后得到粗产物，最后通过柱层析法提纯得到白色针状的2-苯基-1,4-苯并哌喃酮，收率为85%，其核磁共振氢谱见说明书附图1。
本发明专利产物是制备黄酮类药品的重要中间体，黄酮类化合物具有重要的生物活性和药理作用，有显著的抗心血管疾病活性、抗肝脏病毒、抗菌等活性，降血压、降血脂、提高机体免疫力的作用。

Claims (1)

1.一种2-苯基-1,4-苯并哌喃酮的制备方法，其特征在于先在反应瓶中加入以L-丙氨酸(L-alanine)和1,5-环辛二烯(cod)为配体的手型铑催化剂[Rh(cod)(L-alanine)]0.002～0.01份(摩尔数)、乙酸铜2份(摩尔数)、1,2,3,4-四苯基1,3-环戊二烯0.02～0.1份(摩尔数)，抽真空进行氮气保护后，依次向反应瓶注入邻醛基苯酚1份(摩尔数)、苯乙炔1份(摩尔数)、邻二甲苯0.02～0.04份(摩尔数)，在120℃下加热回流反应5.5小时，用乙醚进行萃取，有机相经旋蒸干燥后得到粗产物，最后通过柱层析法提纯得到白色针状的2-苯基-1,4-苯并哌喃酮。
CN201610503544.9A 2016-07-01 2016-07-01 一种2‑苯基‑1,4‑苯并哌喃酮的制备方法 Pending CN106397379A (zh)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2230312A1 (en) * 2009-03-19 2010-09-22 Helmholtz-Zentrum für Infektionsforschung GmbH Probe compound for detecting and isolating enzymes and means and methods using the same
CN104324750A (zh) * 2014-08-07 2015-02-04 齐齐哈尔大学 1,5-环辛二烯/l-丙氨酸为配体铑催化剂的制备

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2230312A1 (en) * 2009-03-19 2010-09-22 Helmholtz-Zentrum für Infektionsforschung GmbH Probe compound for detecting and isolating enzymes and means and methods using the same
CN104324750A (zh) * 2014-08-07 2015-02-04 齐齐哈尔大学 1,5-环辛二烯/l-丙氨酸为配体铑催化剂的制备

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
GOURHARI MAITI，等: "A novel one pot route to flavones under dual catalysis, an organo-and a Lewis acid catalyst", 《TETRAHEDRON LETTERS》 *
MARIE HOFFMANN，等: "Assigning regioisomeric or diastereoisomeric relations of problematic trisubstituted double-double bonds through heteronuclear 2D selective J-resolved NMR spectroscopy", 《RSC ADV.》 *
MASAHITO YOSHIDA，等: "A concise total synthesis of biologically active frutinones via tributylphosphine-catalyzed tandem acyl transfer-cyclization", 《TETRAHEDRON》 *
QIAN YANG，等: "Synthesis of Chromones via Palladium-Catalyzed Ligand-Free Cyclocarbonylation of o-Iodophenols with Terminal Acetylenes in Phosphonium Salt Ionic Liquids", 《J.ORG.CHEM.》 *
SWAGATA BARUAH，等: "Ru(II)-Catalyzed C–H activation and annulations of salicylaldehydes with monosubstituted and disubstituted alkynes", 《THE ROYAL SOCIETY OF CHEMISTRY》 *

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