CN115960062B - Preparation method of 9-chloronaphtho [2,3-b ] benzofuran - Google Patents
Preparation method of 9-chloronaphtho [2,3-b ] benzofuran Download PDFInfo
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- CN115960062B CN115960062B CN202310046473.4A CN202310046473A CN115960062B CN 115960062 B CN115960062 B CN 115960062B CN 202310046473 A CN202310046473 A CN 202310046473A CN 115960062 B CN115960062 B CN 115960062B
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- SKBZDPJDERVFJS-UHFFFAOYSA-N 9-chloronaphtho[2,3-b][1]benzofuran Chemical compound C1=2C=3C(OC=2C=C2C(=C1)C=C(Cl)C=C2)=CC=CC=3 SKBZDPJDERVFJS-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 claims abstract description 45
- CNLYNLSYCPWZQY-UHFFFAOYSA-N 6-chloronaphthalen-2-ol Chemical compound C1=C(Cl)C=CC2=CC(O)=CC=C21 CNLYNLSYCPWZQY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003446 ligand Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 150000002815 nickel Chemical class 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 16
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 15
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 15
- 239000012044 organic layer Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 5
- 229940078552 o-xylene Drugs 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- KVRSDIJOUNNFMZ-UHFFFAOYSA-L nickel(2+);trifluoromethanesulfonate Chemical compound [Ni+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F KVRSDIJOUNNFMZ-UHFFFAOYSA-L 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000010168 coupling process Methods 0.000 abstract description 6
- 238000005859 coupling reaction Methods 0.000 abstract description 6
- 230000008878 coupling Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 239000012043 crude product Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000012046 mixed solvent Substances 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 3
- 238000010520 demethylation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000001257 hydrogen Chemical group 0.000 description 3
- 229910052739 hydrogen Chemical group 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- QCSLIRFWJPOENV-UHFFFAOYSA-N (2-fluorophenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1F QCSLIRFWJPOENV-UHFFFAOYSA-N 0.000 description 1
- RICKKZXCGCSLIU-UHFFFAOYSA-N 2-[2-[carboxymethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]ethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]acetic acid Chemical compound CC1=NC=C(CO)C(CN(CCN(CC(O)=O)CC=2C(=C(C)N=CC=2CO)O)CC(O)=O)=C1O RICKKZXCGCSLIU-UHFFFAOYSA-N 0.000 description 1
- ATMGFHJFRAKSQV-UHFFFAOYSA-N 6-chloro-3-iodo-2-methoxynaphthalene Chemical compound ClC=1C=C2C=C(C(=CC2=CC=1)OC)I ATMGFHJFRAKSQV-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
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- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of 9-chloronaphtho [2,3-b ] benzofuran, belonging to the technical field of organic synthesis. The preparation method comprises the following steps: 2-chloro-6-naphthol and o-dibromobenzene are used as raw materials to react under the action of a nickel salt catalyst, a ligand and alkali to prepare the 9-chloronaphtho [2,3-b ] benzofuran. The method synthesizes the 9-chloronaphtho [2,3-b ] benzofuran by a one-pot method through a series reaction of C-O coupling and C-C coupling, and no additional solvent is needed in the whole reaction system. The preparation method has the advantages of simple preparation steps, low production cost, mild reaction conditions, high total yield, environment friendliness and the like, and is favorable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 9-chloronaphtho [2,3-b ] benzofuran.
Background
An Organic Light-Emitting Diode (OLED) is an Organic electroluminescent device with a multi-layer structure, which can be applied to the fields of display and illumination, and is a third generation display technology based on electroluminescence after CRT (picture tube) and LCD (liquid crystal) display. As a new display technology, OLED is currently in the early stage of industrial explosion, and according to the development history of the display technology, OLED is expected to be dominant gradually. 9-chloronaphtho [2,3-b ] benzofuran is a chemical intermediate with excellent optical and electrical properties, can be used for further synthesizing organic photoelectric materials, is widely used in aspects of organic/polymer electroluminescent diodes (OLED/PLED), organic Solar Cells (OSC), organic Field Effect Transistors (OFET) and the like, and is widely paid attention to and studied in recent years. Therefore, research on the synthesis of 9-chloronaphtho [2,3-b ] benzofuran is of great importance for the development of the OLED industry.
According to literature reports, 9-chloronaphtho [2,3-b ] benzofuran is mainly synthesized by the following synthetic route. For example, patent CN202010624467 reports a method for synthesizing 9-chloronaphtho [2,3-b ] benzofuran: the method takes 6-chloro-3-iodo-2-methoxynaphthalene and o-fluorobenzeneboronic acid as raw materials, and prepares 9-chloronaphtho [2,3-b ] benzofuran through three steps of Suzuki coupling reaction, demethylation reaction, cyclization reaction and the like, wherein the total reaction yield is about 53.7%.
The synthetic route has the advantages that the adopted raw materials are high in price, the reaction steps are long, the total reaction yield is low, in addition, 15 times of equivalent pyridine hydrochloride is used in the second-step demethylation process, the smell is large, a large amount of byproducts are generated after the reaction, and the environmental protection problem is outstanding; meanwhile, the reaction is required to be carried out at a high temperature of 230 ℃, the color of the final product is darker, and the purification difficulty is high. In summary, the existing 9-chloronaphtho [2,3-b ] benzofuran synthesis method has the technical problems of overhigh reaction temperature, long reaction steps, low total reaction yield, harsh reaction conditions, outstanding environmental protection problem and high energy consumption. Therefore, there is a need to continuously study the synthesis method of 9-chloronaphtho [2,3-b ] benzofuran in order to obtain a more economical, green and efficient industrial production method of 9-chloronaphtho [2,3-b ] benzofuran.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to solve the technical problems of high reaction temperature, long reaction steps, low total yield, harsh reaction conditions, outstanding environmental protection problem and high energy consumption in the prior art, and provides a preparation method of 9-chloronaphtho [2,3-b ] benzofuran, which has mild reaction conditions, high efficiency and high economy.
The first aspect of the invention provides a process for the preparation of 9-chloronaphtho [2,3-b ] benzofuran comprising: 2-chloro-6-naphthol and o-dibromobenzene are used as raw materials to react under the action of a nickel salt catalyst, a ligand and alkali to prepare 9-chloronaphtho [2,3-b ] benzofuran; the reaction formula is as follows:
wherein the catalyst is nickel salt;
the ligand has a structure of formula I:
wherein R is alkyl or hydrogen. The preparation method synthesizes the 9-chloronaphtho [2,3-b ] benzofuran by a one-pot method through a series reaction of C-O coupling and C-C coupling, and no additional solvent is needed in the whole reaction system.
In one embodiment of the present invention, the nickel salt is at least one selected from the group consisting of nickel chloride, nickel triflate, nickel acetylacetonate, and nickel acetate.
In one embodiment of the present invention, the alkyl group in the ligand is t-butyl, isopropyl, methyl or hydrogen. When R is tert-butyl, the ligand is Salen ligand L1; when R is isopropyl, the ligand is Salen ligand L2; when R is methyl, the ligand is Salen ligand L3; when R is hydrogen, the ligand is Salen ligand L4.
In one embodiment of the present invention, the base is an organic base or an inorganic base.
In one embodiment of the present invention, the organic base is at least one selected from 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), sodium tert-butoxide, potassium tert-butoxide, and lithium tert-butoxide.
In one embodiment of the present invention, the inorganic base is at least one selected from the group consisting of sodium hydroxide, potassium carbonate and potassium phosphate.
In one embodiment of the present invention, the molar ratio of the 2-chloro-6-naphthol to the o-dibromobenzene is 1 (3 to 10).
In one embodiment of the present invention, the molar ratio of the catalyst to 2-chloro-6-naphthol is (0.05 to 0.2): 1;
in one embodiment of the present invention, the molar ratio of the ligand to 2-chloro-6-naphthol is (0.05 to 0.2): 1.
In one embodiment of the present invention, the molar ratio of the base to 2-chloro-6-naphthol is (1 to 4): 1.
In one embodiment of the invention, the above reaction is carried out under inert gas.
In an embodiment of the present invention, the inert gas is at least one selected from nitrogen, argon, helium and neon.
In one embodiment of the present invention, the reaction temperature of the above reaction is 110 to 140 ℃.
In one embodiment of the present invention, the reaction time of the above reaction is 12 to 36 hours.
In an embodiment of the present invention, the preparation method further includes the following steps: recovering o-dibromobenzene by reduced pressure distillation, adding water and an organic solvent for extraction, and obtaining 9-chloronaphtho [2,3-b ] benzofuran by column chromatography, desolventizing and recrystallizing an organic layer.
In an embodiment of the present invention, the organic solvent is at least one selected from butyl acetate, ethyl acetate, dichloromethane, tetrahydrofuran, and 1, 2-dichloroethane.
In one embodiment of the present invention, the solvent used for the recrystallization is at least one selected from ethyl acetate, methylene chloride, o-xylene, methanol, ethanol, petroleum ether, n-hexane, tetrahydrofuran, and acetonitrile.
Compared with the prior art, the invention has the following technical effects:
(1) The invention adopts cheap and easily obtained 2-chloro-6-naphthol and o-dibromobenzene as raw materials, the 2-chloro-6-naphthol is directly reacted with o-dibromobenzene in series by one pot method for one step without further modification, thus avoiding the phenolic hydroxyl demethylation reaction and intermediate separation process, shortening the reaction steps and having convenient operation.
(2) In the reaction process, the o-dibromobenzene is used as a reactant and a reaction solvent, and excessive o-dibromobenzene can be recycled, so that the use of an additional solvent is avoided, and the method is economical and environment-friendly.
(3) The preparation method can react at a lower temperature (110-150 ℃), has mild reaction conditions, simple post-treatment and purification, high total yield, low production cost and the like.
(4) The preparation method has the advantages of simple preparation steps, low production cost, mild reaction conditions, high total yield, environment friendliness and the like, and is favorable for large-scale industrial production.
Detailed Description
The following detailed description of specific embodiments of the invention is, but it should be understood that the invention is not limited to specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
Example 1: preparation method of 9-chloronaphtho [2,3-b ] benzofuran
353.9g of o-dibromobenzene (99%, 1.5 mol), 53.6g of 2-chloro-6-naphthol (99%, 0.3 mol), 3.9g of nickel chloride (99%, 0.03 mol), 20.6g of Salen ligand L1 (99%, 0.03 mol), 57.7g of sodium tert-butoxide (99%, 0.6 mol) are added into a 500mL reaction flask under the protection of nitrogen, the temperature is raised to 130 ℃ after charging, the stirring speed is 550rpm, and the reaction is kept for 24 hours; after the reaction is finished, the unreacted o-dibromobenzene is recovered by reduced pressure distillation, the mixture is cooled to room temperature, water and butyl acetate are added into the residue to extract, the organic layer is subjected to silica gel column chromatography and desolventizing to obtain a crude product, and 57.8g of 9-chloronaphtho [2,3-b ] benzofuran is obtained by crystallization of a petroleum ether/ethyl acetate mixed solvent, and the yield is 76.2%.
Example 2: preparation method of 9-chloronaphtho [2,3-b ] benzofuran
707.8g of o-dibromobenzene (99%, 3.0 mol), 53.6g of 2-chloro-6-naphthol (99%, 0.3 mol), 3.2g of nickel triflate (99%, 0.015 mol), 10.3g of Salen ligand L1 (99%, 0.015 mol) and 101.0g of potassium tert-butoxide (99%, 0.9 mol) are added into a 1000mL reaction flask under the protection of argon, and after charging, the temperature is raised to 110 ℃, the stirring rotation speed is 550rpm, and the reaction is carried out for 36h; after the reaction is finished, the unreacted o-dibromobenzene is recovered by reduced pressure distillation, the mixture is cooled to room temperature, water and butyl acetate are added into the residue to extract, the organic layer is subjected to silica gel column chromatography and desolventizing to obtain a crude product, and 62.6g of 9-chloronaphtho [2,3-b ] benzofuran is obtained by crystallization of a petroleum ether/ethyl acetate mixed solvent, wherein the yield is 82.6%.
Example 3: preparation method of 9-chloronaphtho [2,3-b ] benzofuran
212.3g of o-dibromobenzene (99%, 0.9 mol), 53.6g of 2-chloro-6-naphthol (99%, 0.3 mol), 15.4g of nickel acetylacetonate (99%, 0.06 mol), 27.8g of Salen ligand L4 (99%, 0.06 mol), 24.0g of lithium tert-butoxide (99%, 0.3 mol) are added into a 500mL reaction flask under the protection of helium, and after charging, the temperature is raised to 120 ℃, the stirring speed is 550rpm, and the reaction is kept for 12 hours; after the reaction is finished, the unreacted o-dibromobenzene is recovered by reduced pressure distillation, the mixture is cooled to room temperature, water and butyl acetate are added into the residue to extract, the organic layer is subjected to silica gel column chromatography and desolventizing to obtain a crude product, and 29.3g of 9-chloronaphtho [2,3-b ] benzofuran is obtained by crystallization of a petroleum ether/ethyl acetate mixed solvent, wherein the yield is 38.6%.
Example 4: preparation method of 9-chloronaphtho [2,3-b ] benzofuran
Under the protection of neon, 707.8g of o-dibromobenzene (99%, 3.0 mol), 53.6g of 2-chloro-6-naphthol (99%, 0.3 mol), 7.95g of nickel acetate (99%, 0.045 mol), 20.6g of Salen ligand L1 (99%, 0.03 mol), 48g of sodium hydroxide (99%, 1.2 mol) are added into a 1000mL reaction bottle, after charging, the temperature is raised to 140 ℃, the stirring speed is 550rpm, and the reaction is carried out for 36 hours under heat preservation; after the reaction, the unreacted o-dibromobenzene is recovered by reduced pressure distillation, the mixture is cooled to room temperature, water and butyl acetate are added into the residue to extract, the organic layer is subjected to silica gel column chromatography and desolventizing to obtain a crude product, and the crude product is crystallized by using a petroleum ether/ethyl acetate mixed solvent to obtain 63.9g of 9-chloronaphtho [2,3-b ] benzofuran, wherein the yield is 84.3%.
Example 5: preparation method of 9-chloronaphtho [2,3-b ] benzofuran
Under the protection of nitrogen, 707.8g of o-dibromobenzene (99%, 3.0 mol), 53.6g of 2-chloro-6-naphthol (99%, 0.3 mol), 3.9g of nickel chloride (99%, 0.03 mol), 18.9g of Salen ligand L2 (99%, 0.03 mol) and 127.4g of potassium phosphate (99%, 0.6 mol) are added into a 1000mL reaction flask, the temperature is raised to 150 ℃ after charging, the stirring speed is 550rpm, and the reaction is carried out for 24 hours; after the reaction is finished, the unreacted o-dibromobenzene is recovered by reduced pressure distillation, the mixture is cooled to room temperature, water and butyl acetate are added into the residue to extract, the organic layer is subjected to silica gel column chromatography and desolventizing to obtain a crude product, and the crude product is crystallized by using a petroleum ether/ethyl acetate mixed solvent to obtain 54.8g of 9-chloronaphtho [2,3-b ] benzofuran, wherein the yield is 72.3%.
Example 6: preparation method of 9-chloronaphtho [2,3-b ] benzofuran
Under the protection of nitrogen, 707.8g of o-dibromobenzene (99%, 3.0 mol), 53.6g of 2-chloro-6-naphthol (99%, 0.3 mol), 7.7g of nickel acetylacetonate (99%, 0.03 mol), 20.6g of Salen ligand L1 (99%, 0.03 mol) and 48.0g of lithium tert-butoxide (99%, 0.6 mol) are added into a 1000mL reaction flask, after charging, the temperature is raised to 130 ℃, the stirring speed is 550rpm, and the reaction is kept for 18 hours; after the reaction, the unreacted o-dibromobenzene is recovered by reduced pressure distillation, the mixture is cooled to room temperature, water and butyl acetate are added into the residue to extract, the organic layer is subjected to silica gel column chromatography and desolventizing to obtain a crude product, and the crude product is crystallized by using a petroleum ether/ethyl acetate mixed solvent to obtain 63.4g of 9-chloronaphtho [2,3-b ] benzofuran, wherein the yield is 83.6%.
Example 7: preparation method of 9-chloronaphtho [2,3-b ] benzofuran
Under the protection of nitrogen, 353.9g of o-dibromobenzene (99%, 1.5 mol), 53.6g of 2-chloro-6-naphthol (99%, 0.3 mol), 7.7g of nickel acetylacetonate (99%, 0.03 mol), 15.6g of Salen ligand L3 (99%, 0.03 mol) and 48.0g of lithium tert-butoxide (99%, 0.6 mol) are added into a 500mL reaction bottle, after charging, the temperature is raised to 130 ℃, the stirring speed is 550rpm, and the reaction is kept for 24 hours; after the reaction is finished, the unreacted o-dibromobenzene is recovered by reduced pressure distillation, the mixture is cooled to room temperature, water and butyl acetate are added into the residue to extract, the organic layer is subjected to silica gel column chromatography and desolventizing to obtain a crude product, and the crude product is crystallized by using a petroleum ether/ethyl acetate mixed solvent to obtain 52.9g of 9-chloronaphtho [2,3-b ] benzofuran, wherein the yield is 69.8%.
Example 8: preparation method of 9-chloronaphtho [2,3-b ] benzofuran
Under the protection of nitrogen, 707.8g of o-dibromobenzene (99%, 3.0 mol), 53.6g of 2-chloro-6-naphthol (99%, 0.3 mol), 7.7g of nickel acetylacetonate (99%, 0.03 mol), 20.6g of Salen ligand L1 (99%, 0.03 mol), 165.9g of potassium carbonate (99%, 1.2 mol) are added into a 1000mL reaction flask, the temperature is raised to 150 ℃ after charging, the stirring speed is 550rpm, and the reaction is kept for 18 hours; after the reaction is finished, the unreacted o-dibromobenzene is recovered by reduced pressure distillation, the mixture is cooled to room temperature, water and butyl acetate are added into the residue to extract, the organic layer is subjected to silica gel column chromatography and desolventizing to obtain a crude product, and 53.4g of 9-chloronaphtho [2,3-b ] benzofuran is obtained by crystallizing by using a petroleum ether/ethyl acetate mixed solvent, wherein the yield is 70.4%.
Example 9: preparation method of 9-chloronaphtho [2,3-b ] benzofuran
707.8g of o-dibromobenzene (99%, 3.0 mol), 53.6g of 2-chloro-6-naphthol (99%, 0.3 mol), 6.4g of nickel triflate (99%, 0.03 mol), 18.9g of Salen ligand L2 (99%, 0.03 mol), 91.4g of 1, 8-diazabicyclo [5.4.0] undec-7-ene (99%, 0.6 mol) are added into a 1000mL reaction flask under the protection of nitrogen, the mixture is heated to 140 ℃, the stirring speed is 550rpm, and the reaction is carried out for 36 hours; after the reaction is finished, the unreacted o-dibromobenzene is recovered by reduced pressure distillation, the mixture is cooled to room temperature, water and butyl acetate are added into the residue to extract, the organic layer is subjected to silica gel column chromatography and desolventizing to obtain a crude product, and 58.9g of 9-chloronaphtho [2,3-b ] benzofuran is obtained by crystallization of a petroleum ether/ethyl acetate mixed solvent, and the yield is 77.7%.
Comparative example 1: the difference from example 1 is that the reaction system comprises 300g of o-xylene as solvent
Under the protection of nitrogen, 353.9g of o-dibromobenzene (99%, 1.5 mol), 53.6g of 2-chloro-6-naphthol (99%, 0.3 mol), 300g of o-xylene, 3.9g of nickel chloride (99%, 0.03 mol), 20.6g of Salen ligand L1 (99%, 0.03 mol) and 57.7g of sodium tert-butoxide (99%, 0.6 mol) are added into a 1000mL reaction bottle, and after charging, the temperature is raised to 130 ℃, the stirring speed is 550rpm, and the reaction is kept for 24 hours; after the reaction, the unreacted o-dibromobenzene is recovered by reduced pressure distillation, the mixture is cooled to room temperature, water and butyl acetate are added into the residue to extract, and the yield of 9-chloronaphtho [2,3-b ] benzofuran is less than 1% by GC-MS analysis of an organic layer.
Comparative example 2: the difference from example 1 is that the reaction system comprises 300g of N, N-dimethylformamide as solvent
Under the protection of nitrogen, 353.9g of o-dibromobenzene (99%, 1.5 mol), 53.6g of 2-chloro-6-naphthol (99%, 0.3 mol), 300g of N, N-dimethylformamide, 3.9g of nickel chloride (99%, 0.03 mol), 20.6g of Salen ligand L1 (99%, 0.03 mol), 57.7g of sodium tert-butoxide (99%, 0.6 mol) are added into a 1000mL reaction bottle, the mixture is heated to 130 ℃, the stirring speed is 550rpm, and the reaction is carried out for 24 hours; after the reaction, the unreacted o-dibromobenzene is recovered by reduced pressure distillation, the mixture is cooled to room temperature, water and butyl acetate are added into the residue to extract, and the yield of 9-chloronaphtho [2,3-b ] benzofuran is less than 1% by GC-MS analysis of an organic layer.
Comparative example 3: the difference from the examples is that the reaction system employs a palladium acetate/triphenylphosphine catalytic system
353.9g of o-dibromobenzene (99%, 1.5 mol), 53.6g of 2-chloro-6-naphthol (99%, 0.3 mol), 5.0g of palladium acetate (99%, 0.03 mol), 7.9g of triphenylphosphine (99%, 0.03 mol) and 57.7g of sodium tert-butoxide (99%, 0.6 mol) are added into a 500mL reaction flask under the protection of nitrogen, and after charging, the temperature is raised to 130 ℃, the stirring speed is 550rpm, and the reaction is carried out for 24 hours; after the reaction, the unreacted o-dibromobenzene is recovered by reduced pressure distillation, the mixture is cooled to room temperature, water and butyl acetate are added into the residue to extract, and the yield of 9-chloronaphtho [2,3-b ] benzofuran is less than 1% by GC-MS analysis of an organic layer.
Comparative example 4: the difference from the examples is that the reaction system adopts a catalytic system of cuprous iodide/phenanthroline
353.9g of o-dibromobenzene (99%, 1.5 mol), 53.6g of 2-chloro-6-naphthol (99%, 0.3 mol), 5.7g of copper iodide (99%, 0.03 mol), 5.4g of phenanthroline (99%, 0.03 mol) and 57.7g of sodium tert-butoxide (99%, 0.6 mol) are added into a 500mL reaction flask under the protection of nitrogen, and after charging, the temperature is raised to 130 ℃, the stirring speed is 550rpm, and the reaction is carried out for 24 hours; after the reaction, the unreacted o-dibromobenzene is recovered by reduced pressure distillation, the mixture is cooled to room temperature, water and butyl acetate are added into the residue to extract, and the yield of 9-chloronaphtho [2,3-b ] benzofuran is less than 1% by GC-MS analysis of an organic layer.
As is clear from the above examples and comparative examples, the 2-chloro-6-naphthol and the o-dibromobenzene react well under the condition of no solvent, and the addition of the solvent (o-xylene, N-dimethylformamide) reduces the concentration of the o-dibromobenzene, so that the reaction is difficult to carry out; in addition, adding a solvent into the reaction system, wherein the boiling point of the solvent is required to be higher than the reaction temperature, otherwise, the reaction system cannot be raised to the reaction temperature in the reaction process, so that the reaction cannot be carried out; the boiling point of the o-dibromobenzene is 224 ℃, which is higher than the highest reaction temperature (150 ℃), and the solvent and the o-dibromobenzene are compatible and difficult to separate when the o-dibromobenzene is recovered by reduced pressure distillation, which is not beneficial to the recovery treatment in the later period and the cost reduction of industrial mass production.
In addition, the nickel catalyst and the Salen ligand are specific catalyst and ligand combinations which are specifically selected for the reaction, other types of catalyst and ligand combinations (palladium acetate/triphenylphosphine or cuprous iodide/phenanthroline) are added in the reaction process, and the reaction cannot be carried out. Under the reaction condition, the palladium acetate/triphenylphosphine catalysis system can realize side reactions such as self-coupling and the like of the 2-chloro-6-naphthol and the o-dibromobenzene, and intermolecular reactions of the 2-chloro-6-naphthol and the o-dibromobenzene, but the side reactions are mainly reactions under the reaction system, and the target reaction intermediate products are few and can not further generate 9-chloronaphtho [2,3-b ] benzofuran; the cuprous iodide/phenanthroline catalysis system can realize intermolecular reaction of 2-chloro-6-naphthol and o-dibromobenzene, is not influenced by side reactions such as self-coupling of a substrate, but cannot realize intramolecular cyclization reaction to further generate 9-chloronaphtho [2,3-b ] benzofuran products.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (7)
1. A process for the preparation of 9-chloronaphtho [2,3-b ] benzofuran, said process comprising: 2-chloro-6-naphthol and o-dibromobenzene are used as raw materials, and react under the action of a catalyst, a ligand and alkali to prepare 9-chloronaphtho [2,3-b ] benzofuran; the reaction formula is as follows:
；
wherein the catalyst is nickel salt, and the nickel salt is at least one selected from nickel chloride, nickel triflate, nickel acetylacetonate and nickel acetate;
the ligand has the structure of formula I:
the compound of the formula I,
wherein R is tert-butyl, isopropyl or methyl;
the alkali is organic alkali or inorganic alkali, the organic alkali is selected from at least one of 1, 8-diazabicyclo [5.4.0] undec-7-ene, sodium tert-butoxide, potassium tert-butoxide and lithium tert-butoxide, and the inorganic alkali is selected from at least one of sodium hydroxide, potassium carbonate and potassium phosphate.
2. The preparation method according to claim 1, wherein the molar ratio of the 2-chloro-6-naphthol to the o-dibromobenzene is 1 (3-10);
and/or the mol ratio of the catalyst to the 2-chloro-6-naphthol is (0.05-0.2): 1;
and/or the molar ratio of the ligand to the 2-chloro-6-naphthol is (0.05-0.2): 1;
and/or the molar ratio of the alkali to the 2-chloro-6-naphthol is (1-4): 1.
3. The process according to claim 1, wherein the reaction is carried out under inert gas.
4. The method according to claim 3, wherein the inert gas is at least one selected from the group consisting of nitrogen, argon, helium, and neon.
5. The preparation method according to claim 1, wherein the reaction temperature of the reaction is 110-140 ℃; and/or the reaction time of the reaction is 12-36 h.
6. The method of manufacturing according to claim 1, further comprising the steps of:
recovering o-dibromobenzene by reduced pressure distillation, adding water and an organic solvent for extraction, and obtaining 9-chloronaphtho [2,3-b ] benzofuran by column chromatography, desolventizing and recrystallizing an organic layer.
7. The method according to claim 6, wherein the organic solvent is at least one selected from butyl acetate, ethyl acetate, methylene chloride, tetrahydrofuran, and 1, 2-dichloroethane;
and/or the solvent used for recrystallization is at least one selected from ethyl acetate, dichloromethane, o-xylene, methanol, ethanol, petroleum ether, n-hexane, tetrahydrofuran and acetonitrile.
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