CN107915704A - A kind of synthetic method of simple coumarin kind compound - Google Patents

A kind of synthetic method of simple coumarin kind compound Download PDF

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Publication number
CN107915704A
CN107915704A CN201610882203.7A CN201610882203A CN107915704A CN 107915704 A CN107915704 A CN 107915704A CN 201610882203 A CN201610882203 A CN 201610882203A CN 107915704 A CN107915704 A CN 107915704A
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CN
China
Prior art keywords
synthetic
compound
coumarin
reaction
alundum
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Pending
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CN201610882203.7A
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Chinese (zh)
Inventor
杨绍祥
田红玉
刘永国
孙宝国
郝颜峰
王嘉琳
王皓
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Beijing Technology and Business University
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Beijing Technology and Business University
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Application filed by Beijing Technology and Business University filed Critical Beijing Technology and Business University
Priority to CN201610882203.7A priority Critical patent/CN107915704A/en
Publication of CN107915704A publication Critical patent/CN107915704A/en
Pending legal-status Critical Current

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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
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulfur atoms in positions 2 or 4

Abstract

The invention discloses a kind of synthetic method of simple coumarin kind compound, with fortified phenol and 3,3 diethoxy ethyl propionates are raw material, and under the catalysis of alundum (Al2O3) and methanesulfonic acid, single step reaction synthesizes simple coumarin kind compound.Compared with the existing methods, synthesis step is few, environmental pollution is small by the present invention.

Description

A kind of synthetic method of simple coumarin kind compound
Technical field
The present invention relates to a kind of synthetic method of simple coumarin kind compound, specifically with fortified phenol and 3,3- diethyls Epoxide ethyl propionate is raw material, and under the catalysis of alundum (Al2O3) and methanesulfonic acid, single step reaction synthesizes simple Coumarins chemical combination Thing.
Background technology
Simple coumarin kind compound refers to the cumarin of the only substituted base on phenyl ring, and chemical constitution is shown below：
Benzene ring substituents include hydroxyl, methoxyl group, methylene-dioxy and isopentene group etc., the aesculetin in the bark of ash (esculetin), auraptene (aurapten) in the angelica lactone in levisticum (angelicone) and shaddock ped etc. belongs to Simple coumarin kind compound.
The synthesis of simple coumarin kind compound is mainly using fortified phenol or substituted salicylic aldehydes as starting material, through electrophilic Substitution, the method for cyclodehydration prepared, mainly using Perkin reaction, Pechmann reaction, Wittig reaction, Knoevenagal is reacted to complete to prepare.
The synthesis of simple coumarin kind compound is there is low yield, accessory substance is more, chemo-selective is not high, environmental pollution The shortcomings of serious, with being rooted in the hearts of the people for environmental protection concept, green chemical synthesis method is increasingly rooted in the hearts of the people.In simple Coumarins In the new synthetic method of compound, uninanned platform method is a kind of important synthetic method, and this method needs suitably be catalyzed It can just be smoothly completed under agent catalysis, therefore the selection for catalyst has obtained people and more and more paid attention to.
The content of the invention
A kind of the shortcomings that the present invention seeks to overcome traditional simple coumarin kind compound synthetic method, there is provided processing step Less, the novel synthesis of non-environmental-pollution.
To realize above-mentioned purpose, the technical solution adopted by the present invention is, with fortified phenol and 3,3- diethoxies third Acetoacetic ester is raw material, and under the catalysis of alundum (Al2O3) and methanesulfonic acid, single step reaction synthesizes simple coumarin kind compound, synthesis Route is shown below：
R=3- methyl, 3- ethyls, 4- hydroxyls, 2- methyl -3- hydroxyls, 2,3- dihydroxy, 2,4- dihydroxy, 3,5- dihydroxies Base, 3- hydroxy-5-methyl bases.
The ratio of heretofore described catalyst combination alundum (Al2O3) and methanesulfonic acid is 1: 0.1-10.The reaction temperature For 40 DEG C -150 DEG C.The catalyst amount is 10%-0.1%.The reaction time for 1 it is small when -10 it is small when.
Compared with the existing methods, processing step is few, the reaction time is short, non-environmental-pollution by the present invention.
Embodiment
Illustrated by taking R=3- hydroxy-5-methyl bases as an example.
Embodiment 1：
Reaction equation is as follows：
In the 250ml glass there-necked flasks equipped with stirring, reflux condenser and thermometer, 3- hydroxy-5-methyl base benzene is added Phenol 1.24g (10mmol) and 3,3- diethoxy ethyl propionate 1.90g (10mmol), adds and then adds 0.25mmol first Sulfonic acid and 0.25mmolAl2O3.90 DEG C are heated to, reacts 3h, stops reaction, toluene extraction, revolving, removes solvent, column layer Separating-purifying is analysed, obtains 1.41g white solids, yield 80%.
The those of ordinary skill of this professional domain can method according to the present invention, with reference to above-described embodiment, to catalyst phosphorus The selection of wolframic acid and its dosage, reaction temperature, reaction time are arbitrarily chosen within the scope of the invention, provide one or more tools The synthetic method of body, within the scope of the present invention.
Product is characterized by nucleus magnetic hydrogen spectrum.
1H NMR(300MHz；MeOD-d6)δ：8.14 (1H, d, J=9.6Hz), 6.63 (1H, s), 6.60 (1H, s), 6.23 (1H, d, J=9.6Hz), 2.35 (3H, s, CH3)。

Claims (5)

1. a kind of synthetic method of simple coumarin kind compound, it is characterized in that：With fortified phenol and 3,3- diethoxy propionic acid Ethyl ester is raw material, and under the catalysis of alundum (Al2O3) and methanesulfonic acid, single step reaction synthesizes simple coumarin kind compound.
2. synthetic method according to claim 1, the ratio of the catalyst combination alundum (Al2O3) and methanesulfonic acid is 1: 0.1-10。
3. synthetic method according to claim 1, it is characterized in that：The reaction temperature is 40 DEG C -150 DEG C.
4. synthetic method according to claim 1, it is characterized in that：The catalyst amount is 10%-0.1%.
5. synthetic method according to claim 1, it is characterized in that：The reaction time for 1 it is small when -10 it is small when.
CN201610882203.7A 2016-10-10 2016-10-10 A kind of synthetic method of simple coumarin kind compound Pending CN107915704A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610882203.7A CN107915704A (en) 2016-10-10 2016-10-10 A kind of synthetic method of simple coumarin kind compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610882203.7A CN107915704A (en) 2016-10-10 2016-10-10 A kind of synthetic method of simple coumarin kind compound

Publications (1)

Publication Number Publication Date
CN107915704A true CN107915704A (en) 2018-04-17

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Country Status (1)

Country Link
CN (1) CN107915704A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004075643A (en) * 2002-08-22 2004-03-11 Ube Ind Ltd Method for producing coumarin compound
CN101497593A (en) * 2009-03-18 2009-08-05 华南理工大学 5-hydroxy coumarin and pyranoid type coumarin compounds, synthesizing method and use
CN102134247A (en) * 2011-01-19 2011-07-27 浙江凯普化工有限公司 Xanthotoxol derivative and new composite method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004075643A (en) * 2002-08-22 2004-03-11 Ube Ind Ltd Method for producing coumarin compound
CN101497593A (en) * 2009-03-18 2009-08-05 华南理工大学 5-hydroxy coumarin and pyranoid type coumarin compounds, synthesizing method and use
CN102134247A (en) * 2011-01-19 2011-07-27 浙江凯普化工有限公司 Xanthotoxol derivative and new composite method thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DONALD G. CROSBY等: "New Syntheses in the Coumarin Series", 《J. ORG. CHEM.》 *
HASHEM SHARGHI等: "Al2O3/MeSO3H (AMA) AS A NOVEL HETEROGENEOUS SYSTEM FOR SYNTHESIS OF COUMARINS UNDER MILD CONDITIONS", 《HETEROCYCLES》 *
JINQIAN WANG等: "Synthesis of 5-epi-Taiwaniaquinone G", 《J. ORG. CHEM.》 *
MORINA ADFA等: "Antitermite Activities of Coumarin Derivatives and Scopoletin from Protium javanicum Burm. f.", 《J CHEM ECOL》 *
黄仲九等: "《化学工艺学》", 30 September 2008, 高等教育出版社 *

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Application publication date: 20180417