CN115710244B - Preparation method of coumarin - Google Patents
Preparation method of coumarin Download PDFInfo
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- CN115710244B CN115710244B CN202211374288.XA CN202211374288A CN115710244B CN 115710244 B CN115710244 B CN 115710244B CN 202211374288 A CN202211374288 A CN 202211374288A CN 115710244 B CN115710244 B CN 115710244B
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- chlorophenol
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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 76
- 235000001671 coumarin Nutrition 0.000 title claims abstract description 40
- 229960000956 coumarin Drugs 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 26
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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 15
- 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 57
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 13
- 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
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 230000008569 process Effects 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
- 238000002156 mixing Methods 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
- 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
- 239000013049 sediment Substances 0.000 claims description 2
- 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 5
- 239000002253 acid Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000007086 side reaction Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000002994 raw material Substances 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
- 239000007850 fluorescent dye Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002596 lactones Chemical group 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
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000203 mixture Substances 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
- 241000196324 Embryophyta Species 0.000 description 1
- 238000007341 Heck reaction Methods 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
- 235000000556 Paullinia cupana Nutrition 0.000 description 1
- 240000003444 Paullinia cupana 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
- 125000005396 acrylic acid ester group Chemical group 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
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 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
- 239000003086 colorant Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005265 energy consumption Methods 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
- 230000006872 improvement Effects 0.000 description 1
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- IQPNAANSBPBGFQ-UHFFFAOYSA-N luteolin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(O)C(O)=C1 IQPNAANSBPBGFQ-UHFFFAOYSA-N 0.000 description 1
- LRDGATPGVJTWLJ-UHFFFAOYSA-N luteolin Natural products OC1=CC(O)=CC(C=2OC3=CC(O)=CC(O)=C3C(=O)C=2)=C1 LRDGATPGVJTWLJ-UHFFFAOYSA-N 0.000 description 1
- 235000009498 luteolin Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 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
- 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
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst 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 performing 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, the catalyst is not easy to run off, the occurrence of side reaction is effectively inhibited, the catalyst can be recycled, the operation is simple, and the economic benefit is good.
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 and the first natural coumarin was obtained from luteolin of guarana by Vogel, the english name of which is "coumarou". W.h.perkin developed coumarin from salicylaldehyde, and h.s.biff did not suggest the correct structure for coumarin until 1872. The natural coumarin mainly exists in flowers and plants, can be prepared into natural perfume, has carbon-carbon double bonds, carbon-oxygen double bonds and lactone structures in coumarin and derivative structures, is an organic compound, has three forms of appearance, is generally needle-shaped, leaf-shaped and columnar, and has aromatic smell. Industrial synthesis of coumarin was invented by Perkin in 1868, and a number of synthetic routes were developed. The biosynthesis of coumarin is through metabolism of phenylalanine, and coumarin compound has special structure, rigid conjugated plane structure, so that the coumarin compound has strong fluorescence in visible light range and different colors according to different light rays. Fluorescent light of blue-violet color under ultraviolet light irradiation, light yellow crystal under natural light irradiation may be colorless, and is widely used as fluorescent whitening agent, fluorescent dye, laser dye, etc. Meanwhile, the fluorescent dye has the characteristics of high emission intensity, strong fluorescence and the like, becomes one of hot spots for researching organic fluorescent dyes in recent years, and has the following structure:
coumarin has many synthetic methods, of which the most common is the Perkin, witting, knoevenagel, pechmann reaction. The starting material typically required for these reactions is salicylaldehyde or phenol, which forms the pyran ring by building up a lactone structure in the benzene ring.
Synthesis of coumarin by Perkin reaction
Perkin developed coumarin in 1868 from salicylaldehyde and acetic anhydride using sodium acetate as a catalyst, however, the reaction yield of this method 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 is obtained by o-hydroxybenzaldehyde/ketone and acetic acid derivatives having an active methylene group, very similar to aldol condensation, and by using a basic substance as a catalyst. In this reaction, since an acetic acid derivative of a more active methylene group is contained, the catalyst is only required to use a common organic base (such as piperidine, pyridine, primary amine, secondary amine, etc.), thereby reducing the reaction duration and temperature. The reaction scheme is as follows:
synthesis of coumarin by Pechmann reaction
The german chemist Pechmann originally developed coumarin from malic acid and phenol in 1884, using dry zinc dichloride and concentrated sulfuric acid as catalysts. The reaction scheme is as follows:
synthesis of coumarin by Witting reaction
The method is to reflux a solution of salicylaldehyde and ethoxycarbonyl phosphonium ylide as raw materials to form an intermediate, namely o-hydroxy cinnamate, and then to exchange molecular lactone of the intermediate to form coumarin. The synthetic route is as follows:
synthesis of coumarin by heck reaction
Documents Heterocyclic Communications (2010), 16 (2-3), 113-120 and Advanced Synthesis & Catalysis (2012), 354 (4), 627-641 report that coumarin is synthesized by performing Heck coupling reaction of 2-iodophenol or 2-bromophenol with acrylic acid ester as raw materials under the action of hydrochloric acid and palladium catalyst. The synthetic route is as follows:
in summary, the coumarin is synthesized by using strong acid or alkali as the catalyst, so that the requirements on equipment materials are high, the equipment is corroded greatly, the catalyst cannot be recycled, the yield is low, the cost is high, and meanwhile, the three wastes are more and the method is not friendly to the environment. The improvement of the synthesis process has important significance for the coumarin synthesis process. Therefore, the research on a new, efficient and environment-friendly coumarin preparation method has important significance.
In view of the shortcomings of the above processes, there is a need to develop a novel method for synthesizing coumarin.
Disclosure of Invention
The invention aims to provide the preparation method of coumarin, which avoids the use of strong acid or alkali catalysts, reduces the requirements on equipment, reduces the generation of three wastes, and simultaneously can apply the metal complex catalyst and reduce the cost. The method uses the metal complex catalyst, is easy to separate, effectively inhibits the selectivity of 4- (2-hydroxyphenyl) but-3-ene-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 object, the present 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 a coupling addition reaction to generate coumarin.
As a preferred embodiment, the metal complex catalyst according to the present invention is selected from one or more of the following 1a, 1b, 2a, 2b, 3a, 3 b:
the reaction route of the invention is as follows:
as a preferred embodiment, the catalyst is used in an amount of 1 to 10% by weight relative to 2-chlorophenol.
As a preferred embodiment, the molar ratio of 2-chlorophenol to acrolein in the preparation process is 1:1.1-2.3, preferably 1:1.2-1:1.9.
As a preferred embodiment, the preparation method is characterized in that the condition of the coupling addition reaction 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 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 preferred embodiment, the solvent is used in an amount of 2 to 5 times the mass of 2-chlorophenol.
The second aspect of the invention relates to a metal complex catalyst for use in the preparation of coumarin.
A metal complex catalyst, expressed as M-X, wherein 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.
In the invention, the preparation method of the metal complex catalyst comprises the following steps:
(1) Mixing a metal M precursor compound and a ligand X in acetonitrile/dichloromethane solvent, fully stirring at 50-80 ℃ and reacting for 1-3 hours;
(2) After the reaction is finished, filtering to remove sediment; 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) Washing the clear solution with water, drying, filtering and concentrating to obtain the catalyst.
In the preparation method of the catalyst, in the step (1), the volume ratio of the acetonitrile solvent to the dichloromethane solvent is 1:2-1:3, and the use amount of the solvent is not particularly limited, for example, the added metal M precursor compound and the ligand X can be completely dissolved.
In the preparation method of the catalyst, in the step (1)The metal M precursor compound 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 the following.
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-benzyl pyridine 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 invention forms a metal complex structure of a coordination saturated twisted square plane by using a large C-N heterocyclic ring donor ligand, and simultaneously, the N heterocyclic ring ligand has strong sigma-electron donating ability, and metal or metal ions combined with the N heterocyclic ring ligand show stronger stability and the ability of catalyzing substrate activation, so that the catalyst is more preferably applied to the catalytic coupling addition reaction of 2-chlorophenol and acrolein.
The invention has the beneficial effects that:
(1) The invention has the advantages of simple process route, simple operation and low raw material cost; avoiding the influence caused by using strong acid and strong alkali.
(2) The metal complex catalyst is environment-friendly, is easy to separate, can be recycled, and reduces the cost.
(3) The invention can produce coumarin at lower operating temperature, the raw material conversion rate reaches more than 97%, and the product selectivity is more than 95%.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the scope of the present invention is not limited to these examples.
Gas chromatographic analysis conditions of the product: island jin gas chromatograph, RTX-DB-5 column, 10 ℃/min rise to 120 ℃; raising the temperature to 240 ℃ at 20 ℃/min; heating to 320 ℃ at 20 ℃/min, and keeping for 5min.
The instrument sources in the following examples are shown in table 1 below:
TABLE 1
| Instrument and reagent | Source | Specification of specification |
| Gas chromatograph | Shimadzu (Shimadzu) | GC-2014C |
| Nuclear magnetic resonance spectrometer | Bruker | Advance Bruker 400M |
Unless otherwise indicated, the inorganic salts and reagents used in the examples below were all commercially available.
Example 1
Will 59.83g H 2 CuCl 4 89.52g of 2-phenylpyridine in acetonitrileIn a dichloromethane mixed solvent, wherein acetonitrile is 200ml and dichloromethane is 400ml. Heating to 60 ℃, stirring and fully mixing for reaction for 2 hours, filtering the mixed solution, distilling and desolventizing to obtain a crude catalyst product. The crude product is added into dichloromethane solvent to be fully dissolved to obtain clear solution, and then the catalyst 1 is obtained after repeated distillation, water washing, concentration, filtration and drying.
Example 2
Will be 74.6g K 2 CuCl 4 133.6g of 3-benzylpyridine are mixed in an acetonitrile/dichloromethane mixture, wherein acetonitrile is 150ml and dichloromethane is 450ml. Heating to 70 ℃, stirring and fully mixing for reaction for 2 hours, filtering the mixed solution, distilling and desolventizing to obtain a crude catalyst product. The crude product is added into dichloromethane solvent to be fully dissolved to obtain clear solution, and then the catalyst 2 is obtained after repeated distillation, water washing, concentration, filtration and drying.
Example 3
Will 40.57g H 2 PtCl 6 61.42g of 2-phenylpyridine was mixed in a mixed solvent of acetonitrile/dichloromethane, wherein the mixture was 150ml of acetonitrile and 450ml of dichloromethane. Heating to 80 ℃, stirring and fully mixing for reaction for 2 hours, filtering the mixed solution, distilling and desolventizing to obtain a crude catalyst product. The crude product is added into dichloromethane solvent to be fully dissolved to obtain clear solution, and then the catalyst 3 is obtained after repeated distillation, water washing, concentration, filtration and drying.
Example 4
40.04g of ZnCl 2 176.04g of 2-phenylquinoline are mixed in an acetonitrile/dichloromethane mixed solvent, wherein acetonitrile is 200ml and dichloromethane is 400ml. Heating to 80 ℃, stirring and fully mixing for reaction for 2 hours, filtering the mixed solution, distilling and desolventizing to obtain a crude catalyst product. The crude product is added into dichloromethane solvent to be fully dissolved to obtain clear solution, and then the catalyst 4 is obtained after repeated distillation, water washing, concentration, filtration and drying.
Example 5
Catalyst 1 (5.14 g,4 wt%) was added to a 1000mL three-necked flask equipped with a mechanical stirrer and a thermocouple, 2-chlorophenol (128.56 g,1 mol), acrolein (67.27 g,1.2 mol) and acetonitrile (257.12 g) were added to the three-necked flask, and the three-necked flask was placed in an oil bath, then mechanical stirring was started, the temperature of the oil bath was raised to 40℃and the reaction was carried out for 3 hours. Filtering to remove the solid catalyst after the reaction is finished, separating out the reaction liquid, distilling the reaction liquid to remove the solvent acetonitrile, placing the reaction liquid in a baking oven at 50 ℃ for 6 hours to obtain the product coumarin of white solid, and confirming that the product is coumarin through nuclear magnetism.
Results of nuclear magnetic analysis 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 (6.43 g,10 wt%) was added to a 1000mL three-necked flask equipped with a mechanical stirrer and a thermocouple, 2-chlorophenol (64.28 g,0.5 mol), acrolein (47.65 g,1.7 mol) and acetonitrile (128.56 g) were added to the three-necked flask, and the three-necked flask was placed in an oil bath, then mechanical stirring was started, the temperature of the oil bath was raised to 50℃and the reaction was carried out for 3 hours.
Example 7
Catalyst 3 (7.71 g) was charged into a 1000mL three-necked flask equipped with a mechanical stirrer and a thermocouple, 2-chlorophenol (128.59 g), acrolein (72.88 g,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 started, and the oil bath was set to be heated to 60℃for 2 hours of reaction.
Example 8
Catalyst 4 (1.93 g,1 wt%) was added to a 1000mL three-necked flask equipped with a mechanical stirrer and a thermocouple, 2-chlorophenol (192.84 g,1.5 mol), acrolein (100.91 g,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, then mechanical stirring was started, the temperature of the oil bath was raised to 50℃and the reaction was carried out for 3 hours.
Comparative example 1
Catalyst 1 in example 5 was replaced with 2-phenylpyridine (5.14 g) and the remaining conditions were the same as in example 5 at 40℃for 3 hours. Coumarin is not produced.
Comparative example 2
Replacement of catalyst 1 in example 5 with H 2 CuCl 4 (5.14 g) and the other conditions were the same as in example 5. The reaction was carried out at 40℃for 3 hours.
Comparative example 3
Will 40.57g H 2 PtCl 6 56.67g of 2-phenylpyrrole (CAS number: 3042-22-6) were mixed in an acetonitrile/dichloromethane mixed solvent, wherein acetonitrile was 150ml and dichloromethane was 450ml. Heating to 80 ℃, stirring and fully mixing for reaction for 2 hours, filtering the mixed solution, distilling and desolventizing to obtain a crude catalyst product. The crude product is added into dichloromethane solvent to be fully dissolved to obtain clear solution, and then the catalyst 5 is obtained after repeated distillation, water washing, concentration, filtration and drying.
Catalyst 1 in example 7 was replaced with catalyst 5 (7.71 g) and the rest of the conditions were the same as in example 5. The reaction was carried out at 40℃for 3 hours.
The chromatographic analysis results of examples 5-8 corresponding to comparative examples 2, 3 are shown in Table 2:
TABLE 2
| Conversion of 2-chlorophenol% | Coumarin selectivity% | * By-product selectivity% | |
| 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 |
* By-product 4- (2-hydroxyphenyl) but-3-en-2-one (CAS: 6051-53-2).
Claims (12)
1. A preparation method of coumarin comprises the following steps: under the action of a metal complex catalyst, 2-chlorophenol and acrolein undergo a coupling addition reaction to generate coumarin;
the metal complex catalyst is selected from one or more of the following structural formulas:
2. the process according to claim 1, wherein the catalyst is used in an amount of 1 to 10% by weight relative to the 2-chlorophenol.
3. The method according to claim 1, wherein the molar ratio of 2-chlorophenol to acrolein is 1:1.1-2.3.
4. The method according to claim 1, wherein the molar ratio of 2-chlorophenol to acrolein is 1:1.2-1:1.9.
5. The process of claim 1, wherein the conditions for the coupling addition reaction are reaction at a reaction temperature of 40-60 ℃ for 2-5 hours.
6. The process according to claim 1, 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 method of claim 1, wherein the method of preparing the metal complex catalyst comprises the steps of:
(1) Mixing a metal M precursor compound and a ligand X in acetonitrile/dichloromethane solvent, fully stirring at 50-80 ℃ and reacting for 1-3 hours;
(2) After the reaction is finished, filtering to remove sediment; 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) Washing the clear solution with water, drying, filtering and concentrating to obtain the catalyst.
8. The method of claim 7, wherein in step (1), the metal M precursor compound is selected from one or more of metal chlorides, chlorates.
9. The method of claim 7, wherein in step (1), the metal M precursor compound is selected from the group consisting of H 2 CuCl 4 、K 2 CuCl 4 、H 2 PtCl 6 、K 2 PtCl 6 、ZnCl 2 One or more of the following.
10. The method of claim 7, wherein in step (1), the ligand X is selected from one or more of pyridine, quinoline, and derivatives thereof.
11. The method according to claim 7, wherein in step (1), the ligand X is selected from one or more of 2-phenylpyridine, 3-benzylpyridine, 2-phenylquinoline.
12. The method of claim 7, wherein in step (1), the molar ratio of the metal M precursor compound to ligand X is from 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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| 4-甲基香豆素类化合物的合成方法探析;陈达平;;中国高新技术企业(03);81-83 * |
| Domino Heck/Lactonization-Catalyzed Synthesis of 3- C -Linked Mannopyranosyl Coumarins;Denis Giguere et al.;J. Org. Chem.;第74卷;8480–8483 * |
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