CN115710244A - Preparation method of coumarin - Google Patents
Preparation method of coumarin Download PDFInfo
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- CN115710244A CN115710244A CN202211374288.XA CN202211374288A CN115710244A CN 115710244 A CN115710244 A CN 115710244A CN 202211374288 A CN202211374288 A CN 202211374288A CN 115710244 A CN115710244 A CN 115710244A
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- coumarin
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- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 235000001671 coumarin Nutrition 0.000 title claims abstract description 37
- 229960000956 coumarin Drugs 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 24
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 16
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005859 coupling reaction Methods 0.000 claims abstract description 7
- 238000007259 addition reaction Methods 0.000 claims abstract description 6
- 230000008878 coupling Effects 0.000 claims abstract description 6
- 238000010168 coupling process Methods 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 66
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- UUCLVSDUMKMBSM-UHFFFAOYSA-N 3-benzylpyridine Chemical compound C=1C=CN=CC=1CC1=CC=CC=C1 UUCLVSDUMKMBSM-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 abstract description 8
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000007086 side reaction Methods 0.000 abstract 1
- 239000012043 crude product Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000007850 fluorescent dye Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- -1 coumarin compound Chemical class 0.000 description 3
- 150000004775 coumarins Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OIKUPYQBJLSNAS-VOTSOKGWSA-N (e)-4-(2-hydroxyphenyl)but-3-en-2-one Chemical compound CC(=O)\C=C\C1=CC=CC=C1O OIKUPYQBJLSNAS-VOTSOKGWSA-N 0.000 description 2
- IRTLROCMFSDSNF-UHFFFAOYSA-N 2-phenyl-1h-pyrrole Chemical compound C1=CNC(C=2C=CC=CC=2)=C1 IRTLROCMFSDSNF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003684 Perkin reaction Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000002596 lactones Chemical group 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- KQDJTBPASNJQFQ-UHFFFAOYSA-N 2-iodophenol Chemical compound OC1=CC=CC=C1I KQDJTBPASNJQFQ-UHFFFAOYSA-N 0.000 description 1
- 240000004507 Abelmoschus esculentus Species 0.000 description 1
- 235000003934 Abelmoschus esculentus Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 241000544583 Heterococcus <yellow-green algae> Species 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- 241000426519 Myleus rhomboidalis Species 0.000 description 1
- 241000282806 Rhinoceros Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PQCJPAROZVFPIL-UHFFFAOYSA-N ethyl phosphanylformate Chemical compound CCOC(P)=O PQCJPAROZVFPIL-UHFFFAOYSA-N 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- PMOWTIHVNWZYFI-AATRIKPKSA-N trans-2-coumaric acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1O PMOWTIHVNWZYFI-AATRIKPKSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of coumarin, which comprises the step of carrying out coupling addition reaction on 2-chlorophenol and acrolein under the action of a metal complex catalyst to generate coumarin. The invention provides a novel method for synthesizing coumarin, which avoids the use of strong acid and strong alkali, reduces the generation of three wastes and has no pollution to the environment; the metal complex catalyst has high activity, is not easy to run off, can effectively inhibit the occurrence of side reactions, can be recycled, and has simple operation and good economic benefit.
Description
Technical Field
The invention belongs to the field of coumarin preparation, and particularly relates to a coumarin preparation method.
Background
Coumarin, also known as coumarins, was originally extracted in 1820, the first natural coumarin, obtained from gumbo rhinoceros of guyana by Vogel, under the english name "coumarou". Perkin developed coumarin through salicylaldehyde, and the correct structure of coumarin was proposed only by 1872 in h.s.biff. The natural coumarin mainly exists in flowers and plants and can be prepared into natural perfume, and the coumarin and the derivative structure thereof have carbon-carbon double bonds, carbon-oxygen double bonds and lactone structures, are organic compounds, have three forms in appearance, are generally needle-shaped, leaf-shaped and columnar, and have aromatic odor. The industrial synthesis of coumarin was invented by Perkin in 1868, and subsequently opened up many synthetic routes. The biosynthesis of coumarin is realized through the metabolism of phenylalanine, and the coumarin compound has special structural characteristics and a rigid conjugated planar structure, so that the coumarin compound has strong fluorescence in a visible light region, and can show different colors according to different light rays. Under the irradiation of ultraviolet light, the fluorescent material is blue-violet fluorescent light, and under the irradiation of natural light, the crystal is light yellow, and the crystal is possible to be colorless, and the fluorescent material is widely used as a fluorescent whitening agent, a fluorescent dye, a laser dye and the like. Meanwhile, the fluorescent dye has the characteristics of high emission intensity, strong fluorescence and the like, and becomes one of the hot spots of organic fluorescent dye research in recent years, and the structure of the fluorescent dye is as follows:
coumarin has many synthetic methods, and the most common of them are Perkin, witting, knoevenagel, pechmann, etc. The starting material typically required for these reactions is salicylaldehyde or phenol, which forms the pyran ring by building up a lactone structure on the benzene ring.
Synthesis of coumarin by Perkin reaction
In 1868, perkin developed coumarin from salicylaldehyde and acetic anhydride using sodium acetate as a catalyst, but the reaction yield of this process was not high. In order to improve the yield of coumarin, researchers improve and optimize the reaction conditions of the Perkin synthesis method, so that the yield of the method is obviously improved compared with that of the original method. The reaction scheme is as follows:
synthesis of coumarin by knoevenagel reaction
The Knoevenagel reaction is also a base-catalyzed condensation reaction. Coumarin can be obtained by o-hydroxybenzaldehyde/ketone and acetic acid derivatives with active methylene group, similar to aldol condensation, using basic substance as catalyst. In this reaction, since the acetic acid derivative containing a relatively active methylene group is used, the catalyst only needs to use a general organic base (e.g., piperidine, pyridine, primary amine, secondary amine, etc.), thereby reducing the reaction time and temperature. The reaction scheme is as follows:
synthesis of coumarin by Pechmann reaction
The german chemist Pechmann developed coumarin in 1884 initially from malic acid and phenol, with the catalysts being dry zinc dichloride and concentrated sulfuric acid. The reaction scheme is as follows:
synthesizing coumarin by witting reaction
The method comprises refluxing solution of salicylaldehyde and ethoxycarbonylphosphonium ylide as raw materials to form an intermediate, namely o-hydroxycinnamate, and performing intramolecular exchange on the intermediate to form coumarin. The synthetic route is shown as follows:
synthesis of coumarin by heck reaction
The documents Heterococcus Communications (2010), 16 (2-3), 113-120 and Advanced Synthesis & Catalysis (2012), 354 (4), 627-641 report the Synthesis of coumarins starting from 2-iodophenol or 2-bromophenol and acrylates by a Heck coupling reaction under the action of hydrochloric acid and a palladium catalyst. The synthetic route is as follows:
in conclusion, strong acid or strong base is used as a catalyst for synthesizing coumarin, so that the method has the advantages of high requirements on equipment materials, high corrosion on equipment, incapability of recycling the catalyst, low yield, high cost, more three wastes and environmental friendliness. The improvement of the synthesis process has important significance for the process of synthesizing the coumarin. Therefore, the research on a new, efficient and environment-friendly preparation method of coumarin is of great significance.
In view of the above-mentioned disadvantages, a new method for synthesizing coumarin is needed.
Disclosure of Invention
The invention aims to provide a preparation method of coumarin, which avoids the use of strong acid or strong base catalysts, reduces the requirements on equipment, reduces the generation of three wastes, and can mechanically apply a metal complex catalyst to reduce the cost. In addition, the method uses a metal complex catalyst, is easy to separate, effectively inhibits the selectivity of 4- (2-hydroxyphenyl) butyl-3-alkene-2-ketone, can effectively reduce the operation steps of post-reaction treatment, reduces the energy consumption, is environment-friendly, and avoids the problem of environmental pollution.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of coumarin comprises the following steps: under the action of a metal complex catalyst, 2-chlorophenol and acrolein undergo coupling addition reaction to generate coumarin.
As a preferred embodiment, the metal complex catalyst of the present invention is selected from one or more of the following 1a, 1b, 2a, 2b, 3a, and 3 b:
the reaction route of the invention is as follows:
as a preferable mode, in the preparation method, the catalyst is used in an amount of 1 to 10wt% with respect to 2-chlorophenol.
As a preferred embodiment, in the preparation method, the molar ratio of 2-chlorophenol to acrolein is 1.1 to 2.3, preferably 1.
As a preferable scheme, in the preparation method, the coupling addition reaction condition is that the reaction is carried out for 2 to 5 hours at the reaction temperature of 40 to 60 ℃.
As a preferred embodiment, the preparation method is carried out in the presence of a solvent. The solvent is one or more of acetonitrile, N-dimethylformamide, dioxane, dichloromethane and dichloroethane.
As a preferable mode, the solvent is used in an amount of 2 to 5 times the mass of 2-chlorophenol.
A second aspect of the invention relates to metal complex catalysts used in the preparation of coumarins.
A metal complex catalyst is expressed as M-X, in the catalyst, metal M is an active component and is selected from one or more of Cu, zn and Pt; and X is a ligand selected from one or more of pyridine, quinoline and derivative compounds thereof.
The preparation method of the metal complex catalyst comprises the following steps:
(1) Mixing a metal M precursor compound and a ligand X in an acetonitrile/dichloromethane solvent, fully stirring at the temperature of 50-80 ℃, and reacting for 1-3 hours;
(2) After the reaction is finished, filtering to remove precipitates; distilling the filtrate to remove the solvent to obtain a crude catalyst, and dissolving the crude catalyst into dichloromethane again to obtain a clear solution;
(3) And washing the clear solution with water, drying, filtering and concentrating to obtain the catalyst.
In the preparation method of the catalyst of the present invention, in the step (1), the volume ratio of the solvent acetonitrile and dichloromethane is 1:2-1:3, and the amount of the solvent is not particularly limited, and for example, the added precursor compound of the metal M and the ligand X may be completely dissolved.
In the preparation method of the catalyst of the present invention, in the step (1), the precursor compound of the metal M is selected from one or more of metal chloride, chlorate and chlorate, preferably H 2 CuCl 4 、K 2 CuCl 4 、H 2 PtCl 6 、K 2 PtCl 6 、ZnCl 2 One or more of (a).
In the preparation method of the catalyst, in the step (1), the ligand X is selected from one or more of pyridine, quinoline and derivative compounds thereof, preferably, the ligand X is selected from one or more of 2-phenylpyridine, 3-benzylpyridine and 2-phenylquinoline.
In the preparation method of the catalyst, in the step (1), the molar ratio of the metal M precursor compound to the ligand X is 1:2-1:4.
As a preferred embodiment, the metal complex catalyst of the present invention is selected from one or more of the following structural formulas 1a, 1b, 2a, 2b, 3a, 3 b:
the preferred metal complex catalyst of the present invention forms a metal complex structure of a coordinately saturated distorted square plane by using a large C-N heterocyclic donor ligand, and at the same time, since the N heterocyclic ligand has a strong sigma-electron donating ability, the metal or metal ion bound thereto exhibits stronger stability and an ability to catalyze the activation of a substrate, thereby being more preferably applied to a catalytic coupling addition reaction of 2-chlorophenol and acrolein.
The invention has the beneficial effects that:
(1) The method has the advantages of simple process route, simple operation and low raw material cost; the influence caused by using strong acid and strong alkali is avoided.
(2) The metal complex catalyst disclosed by the invention is environment-friendly, easy to separate, recyclable and low in cost.
(3) The method can produce coumarin at a lower operation temperature, the conversion rate of raw materials reaches more than 97%, and the selectivity of products is more than 95%.
Detailed Description
The present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited to these examples.
Gas chromatography analysis conditions of the product: shimadzu gas chromatograph, RTX-DB-5 column, 10 ℃/min up to 120 ℃; raising the temperature to 240 ℃ at a speed of 20 ℃/min; raising the temperature to 320 ℃ at the temperature of 20 ℃/min, and keeping the temperature for 5min.
The instrument sources in the following examples are given in table 1 below:
TABLE 1
| Instrument and reagent | Source | Specification of |
| Gas chromatograph | Shimadzu | GC-2014C |
| Nuclear magnetic resonance spectrometer | Bruker | Advance Bruker 400M |
The inorganic salts and reagents used in the following examples are commercially available unless otherwise specified.
Example 1
Mixing 59.83g H 2 CuCl 4 89.52g of 2-phenylpyridine was mixed with a mixed solvent of acetonitrile/dichloromethane (200 ml of acetonitrile and 400ml of dichloromethane). Heating to 60 ℃, stirring and fully mixing for reaction for 2 hours, filtering the mixed solution, and distilling to remove the solvent to obtain a crude catalyst. And adding the crude product into a dichloromethane solvent to fully dissolve the crude product to obtain a clear solution, and repeatedly distilling, washing with water, concentrating, filtering and drying to obtain the catalyst 1.
Example 2
74.6g K 2 CuCl 4 133.6g of 3-benzylpyridine was mixed with a mixed solvent of acetonitrile/dichloromethane (150 ml of acetonitrile and 450ml of dichloromethane). Heating to 70 ℃, stirring and fully mixing for reaction for 2 hours, filtering the mixed solution, and distilling to remove the solvent to obtain a crude catalyst. And adding the crude product into a dichloromethane solvent to fully dissolve the crude product to obtain a clear solution, and repeatedly distilling, washing with water, concentrating, filtering and drying to obtain the catalyst 2.
Example 3
Mixing 40.57g H 2 PtCl 6 61.42g of 2-phenylpyridine was mixed in a mixed solvent of acetonitrile/dichloromethane (150 ml of acetonitrile and 450ml of dichloromethane). Heating to 80 ℃, stirring and fully mixing for reaction for 2 hours, filtering the mixed solution, and distilling to remove the solvent to obtain a crude catalyst. And adding the crude product into a dichloromethane solvent to fully dissolve the crude product to obtain a clear solution, and repeatedly distilling, washing with water, concentrating, filtering and drying to obtain the catalyst 3.
Example 4
40.04g of ZnCl 2 176.04g of 2-phenylquinoline was mixed with a mixed solvent of acetonitrile/dichloromethane (200 ml of acetonitrile and 400ml of dichloromethane). Heating to 80 ℃, stirring and fully mixing for reaction for 2 hours, filtering the mixed solution, distilling and removing the solvent to obtain a crude catalyst. And adding the crude product into a dichloromethane solvent to fully dissolve the crude product to obtain a clear solution, and repeatedly distilling, washing with water, concentrating, filtering and drying to obtain the catalyst 4.
Example 5
Catalyst 1 (5.14g, 4wt%) was charged into a 1000mL three-necked flask equipped with a mechanical stirrer, a thermocouple, 2-chlorophenol (128.56g, 1mol), acrolein (67.27g, 1.2 mol), and acetonitrile (257.12 g) were charged into the three-necked flask, and the three-necked flask was placed in an oil bath, and then mechanical stirring was turned on, the temperature of the oil bath was raised to 40 ℃ and reacted for 3 hours. And after the reaction is finished, filtering to remove the solid catalyst, separating out reaction liquid, distilling the reaction liquid to remove the solvent acetonitrile, placing the reaction liquid in an oven at 50 ℃ for 6 hours to obtain a white solid product coumarin, and confirming that the product is coumarin through nuclear magnetism.
And (3) nuclear magnetic analysis result of the product:
1 H NMR(CDCl 3 ,400MHz):δ7.80(d,J＝10.9Hz,1H),7.63(m,1H),7.45(m,1H),7.20-7.22(m,2H),6.45(d,J＝10.8Hz,1H).
example 6
Catalyst 2 (6.43g, 10wt%) was charged in a 1000mL three-necked flask equipped with a mechanical stirrer and a thermocouple, 2-chlorophenol (64.28g, 0.5 mol), acrolein (47.65g, 1.7 mol) and acetonitrile (128.56 g) were charged in the three-necked flask, and the three-necked flask was placed in an oil bath, and then mechanical stirring was turned on, and the temperature of the oil bath was raised to 50 ℃ to react for 3 hours.
Example 7
Catalyst 3 (7.71 g) was charged into a 1000mL three-necked flask equipped with a mechanical stirrer, a thermocouple, 2-chlorophenol (128.59 g), acrolein (72.88g, 1.3 mol), and acetonitrile (257.14 g) were added to the three-necked flask, and the three-necked flask was placed in an oil bath, and then mechanical stirring was turned on, and the temperature of the oil bath was raised to 60 ℃ to react for 2 hours.
Example 8
Catalyst 4 (1.93g, 1wt%) was charged into a 1000mL three-necked flask equipped with a mechanical stirrer, a thermocouple, 2-chlorophenol (192.84g, 1.5 mol), acrolein (100.91g, 1.8 mol), and acetonitrile (385.68 g) were added to the three-necked flask, and the three-necked flask was placed in an oil bath, and then mechanical stirring was turned on, and the temperature of the oil bath was raised to 50 ℃ to react for 3 hours.
Comparative example 1
Catalyst 1 in example 5 was replaced with 2-phenylpyridine (5.14 g), and the reaction was carried out for 3 hours at 40 ℃ in the same manner as in example 5. Coumarin is not produced.
Comparative example 2
Catalyst 1 from example 5 was replaced by H 2 CuCl 4 (5.14 g), the same conditions as in example 5 were repeated. The reaction was carried out at 40 ℃ for 3 hours.
Comparative example 3
Mixing 40.57g H 2 PtCl 6 56.67g of 2-phenylpyrrole (CAS. RTM. No.: 3042-22-6) was mixed in an acetonitrile/dichloromethane mixed solvent of 150ml of acetonitrile and 450ml of dichloromethane. Heating to 80 ℃, stirring and fully mixing for reaction for 2 hours, filtering the mixed solution, and distilling to remove the solvent to obtain a crude catalyst. And adding the crude product into a dichloromethane solvent to fully dissolve the crude product to obtain a clear solution, and repeatedly distilling, washing with water, concentrating, filtering and drying to obtain the catalyst 5.
The same conditions as in example 5 were used except that catalyst 1 in example 7 was replaced with catalyst 5 (7.71 g). The reaction was carried out at 40 ℃ for 3 hours.
The results of the chromatographic analyses of examples 5 to 8 corresponding to comparative examples 2 and 3 are shown in Table 2:
TABLE 2
| 2-chlorophenol conversion% | Coumarin selectivity% | * Selectivity of by-product% | |
| Example 5 | 98 | 97 | 2.67 |
| Example 6 | 99 | 97 | 2.39 |
| Example 7 | 98 | 99 | 0.08 |
| Example 8 | 97 | 98 | 0.73 |
| Comparative example 2 | 62 | 73 | 25.26 |
| Comparative example 3 | 76 | 80 | 17.98 |
* 4- (2-hydroxyphenyl) but-3-en-2-one (CAS: 6051-53-2) as a by-product.
Claims (10)
1. A preparation method of coumarin comprises the following steps: under the action of a metal complex catalyst, 2-chlorophenol and acrolein undergo coupling addition reaction to generate coumarin.
2. The process of claim 1 wherein the metal complex catalyst is selected from one or more of the following structural formulas:
3. the process according to claim 1 or 2, characterized in that the amount of catalyst used is 1-10% by weight with respect to 2-chlorophenol.
4. A process according to any one of claims 1 to 3, characterized in that the molar ratio of 2-chlorophenol to acrolein is from 1.1 to 2.3, preferably from 1.2 to 1.9.
5. The process according to any one of claims 1 to 4, wherein the coupling addition reaction is carried out under conditions of a reaction temperature of 40 to 60 ℃ for 2 to 5 hours.
6. The process according to any one of claims 1 to 5, wherein the process is carried out in the presence of a solvent which is one or more of acetonitrile, N-dimethylformamide, dioxane, dichloromethane, dichloroethane.
7. The process of any one of claims 1 to 6, wherein the process for preparing the metal complex catalyst comprises the steps of:
(1) Mixing a metal M precursor compound and a ligand X in an acetonitrile/dichloromethane solvent, fully stirring at the temperature of 50-80 ℃, and reacting for 1-3 hours;
(2) After the reaction is finished, filtering to remove precipitates; distilling the filtrate to remove the solvent to obtain a crude catalyst product, and dissolving the crude catalyst product into dichloromethane again to obtain a clear solution;
(3) And washing the clear solution with water, drying, filtering and concentrating to obtain the catalyst.
8. According to claimThe process of claim 7, wherein in step (1), the metal M precursor compound is selected from one or more of metal chlorides, chlorites, chlorates, preferably H 2 CuCl 4 、K 2 CuCl 4 、H 2 PtCl 6 、K 2 PtCl 6 、ZnCl 2 One or more of (a).
9. The method according to claim 7 or 8, wherein in step (1), the ligand X is selected from one or more of pyridine, quinoline and derivative compounds thereof, preferably, the ligand X is selected from one or more of 2-phenylpyridine, 3-benzylpyridine and 2-phenylquinoline.
10. The method according to any one of claims 7 to 9, wherein in step (1), the molar ratio of the metal M precursor compound to the ligand X is 1:2 to 1:4.
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| CN104447654A (en) * | 2014-11-21 | 2015-03-25 | 安徽华业香料股份有限公司 | Synthetizing method of coumarin compound |
| CN114716371A (en) * | 2022-03-10 | 2022-07-08 | 上海应用技术大学 | N-containing active center metal organic catalyst for synthesizing cyclic carbonate and preparation method and application thereof |
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| CN114716371A (en) * | 2022-03-10 | 2022-07-08 | 上海应用技术大学 | N-containing active center metal organic catalyst for synthesizing cyclic carbonate and preparation method and application thereof |
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| DENIS GIGUERE ET AL.: "Domino Heck/Lactonization-Catalyzed Synthesis of 3- C -Linked Mannopyranosyl Coumarins", J. ORG. CHEM., vol. 74, pages 8480 * |
| 孙丽;胡云楚;唐智勇;苏燕艳;: "香豆素的合成、应用及其理论研究", 应用化工, no. 02, 28 February 2010 (2010-02-28), pages 264 - 269 * |
| 孙丽;胡云楚;唐智勇;苏燕艳;: "香豆素的合成、应用及其理论研究", 应用化工, no. 02, pages 264 - 269 * |
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