CN115838364A - Synthetic method of 3, 3-bithiophene - Google Patents
Synthetic method of 3, 3-bithiophene Download PDFInfo
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- CN115838364A CN115838364A CN202211636369.2A CN202211636369A CN115838364A CN 115838364 A CN115838364 A CN 115838364A CN 202211636369 A CN202211636369 A CN 202211636369A CN 115838364 A CN115838364 A CN 115838364A
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- bithiophene
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- cyclohexane
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- IAAQEGBHNXAHBF-UHFFFAOYSA-N 3-thiophen-3-ylthiophene Chemical compound S1C=CC(C2=CSC=C2)=C1 IAAQEGBHNXAHBF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000010189 synthetic method Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 150000003577 thiophenes Chemical class 0.000 claims abstract description 22
- -1 cyclohexyl magnesium halide Chemical class 0.000 claims abstract description 19
- 238000007259 addition reaction Methods 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 150000003624 transition metals Chemical class 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000001308 synthesis method Methods 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 27
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 24
- 229910052749 magnesium Inorganic materials 0.000 claims description 21
- 239000011777 magnesium Substances 0.000 claims description 21
- 239000012044 organic layer Substances 0.000 claims description 19
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 18
- 150000001934 cyclohexanes Chemical class 0.000 claims description 17
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical compound BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 claims description 8
- 238000003747 Grignard reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 5
- QUBJDMPBDURTJT-UHFFFAOYSA-N 3-chlorothiophene Chemical compound ClC=1C=CSC=1 QUBJDMPBDURTJT-UHFFFAOYSA-N 0.000 claims description 3
- WGKRMQIQXMJVFZ-UHFFFAOYSA-N 3-iodothiophene Chemical compound IC=1C=CSC=1 WGKRMQIQXMJVFZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- FUCOMWZKWIEKRK-UHFFFAOYSA-N iodocyclohexane Chemical compound IC1CCCCC1 FUCOMWZKWIEKRK-UHFFFAOYSA-N 0.000 claims description 3
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 claims description 3
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 claims description 3
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical class C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000002920 hazardous waste Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000012827 research and development Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000011259 mixed solution Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 238000002390 rotary evaporation Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
Abstract
The invention relates to the technical field of thiophene derivative synthesis, in particular to a method for synthesizing 3, 3-bithiophene. The invention mixes cyclohexyl magnesium halide, halogenated thiophene, transition metal catalyst and naphthenic hydrocarbon solvent, and then carries out addition reaction to obtain 3, 3-bithiophene. The invention utilizes cyclohexyl magnesium halide and halogenated thiophene to complete addition reaction to generate 3, 3-bithiophene. The synthesis method provided by the invention is simple and convenient to operate, simple in process and basically free of side reaction. Meanwhile, the 3, 3-bithiophene synthesized by the method has high purity, basically no hazardous waste is generated, and the method is suitable for large-scale production, so that the commercialization process of the 3, 3-bithiophene can be promoted, the 3, 3-bithiophene produced in batches can be used as an important drug intermediate, can also be used for research and development and production of organic photoelectric materials, powerfully drives the use scale of bithiophene derivative materials at home and abroad, and has remarkable social benefits.
Description
Technical Field
The invention relates to the technical field of thiophene derivative synthesis, in particular to a method for synthesizing 3, 3-bithiophene.
Background
The 3, 3-bithiophene has the characteristics of higher hole mobility and conductivity, good thermal stability and easiness in film formation, is one of the most potential photoelectric materials in the photoelectric field, is used as an excellent material intermediate, and has wide application value in the fields of photocatalytic degradation of organic pollutants, bioelectrochromic materials, cationic surfactant semiconductor packaging, electromagnetic shielding materials and the like.
The traditional 3, 3-bithiophene synthesis method comprises a metal catalytic coupling method and a chemical oxidative polymerization method, wherein the metal catalytic coupling method is completed by using monohalogenated thiophene as a raw material under the catalysis of transition metal palladium, but the method has low yield and low practical application value; the chemical oxidative polymerization method is usually to dissolve a monomer in an aqueous solution or an organic solution, and add a suitable oxidant under an acidic condition for reaction to obtain a target product, but the process conditions of the method are difficult to control, and small changes in the process parameters such as the type and concentration of the oxidant, the reaction time and temperature, the monomer concentration, the acidity and the like can significantly affect the reaction product, so that the method is complicated to operate.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a method for synthesizing 3, 3-bithiophene, which is simple in operation, suitable for large-scale production, and high in yield and purity of the obtained 3, 3-bithiophene.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for synthesizing 3, 3-bithiophene, which comprises the following steps:
mixing cyclohexyl magnesium halide, halogenated thiophene, transition metal catalyst and naphthenic hydrocarbon solvent to carry out addition reaction to obtain 3, 3-bithiophene.
Preferably, the preparation method of the cyclohexyl magnesium halide comprises the following steps: mixing metal magnesium, an ether solvent, a catalyst and halogenated cyclohexane to carry out Grignard reaction to obtain cyclohexyl magnesium halide.
Preferably, the metal magnesium is one or more of magnesium chips, magnesium strips and magnesium powder; the halogenated cyclohexane comprises one of bromocyclohexane, chlorocyclohexane and iodocyclohexane; the catalyst is one or more of iodine, methyl magnesium iodide and ethyl magnesium bromide; the ether solvent is one or more of tetrahydrofuran, diethyl ether and methyl tert-butyl ether.
Preferably, the transition metal catalyst comprises NiCl 2 、Ni(CO) 4 、SnCl 2 ·H 2 PtCl 6 And HCo (CO) 4 One or more of the above; the halogenated thiophene comprises one of 3-bromothiophene, 3-chlorothiophene and 3-iodothiophene.
Preferably, the naphthenic solvent is one or two of cyclohexane and cyclopentane.
Preferably, the molar ratio of the halogenated cyclohexane to the metal magnesium is 1.5 to 1; the molar ratio of the halogenated cyclohexane to the catalyst is 1.005 to 0.03.
Preferably, the molar ratio of the cyclohexyl magnesium halide to the halogenated thiophene is 1.5-1, and the molar ratio of the halogenated thiophene to the transition metal catalyst is 1: 0.005-0.05.
Preferably, the temperature of the Grignard reaction is-78 to 70 ℃, and the time is 4 to 6 hours.
Preferably, the temperature of the addition reaction is-78-70 ℃ and the time is 40-90 min.
Preferably, the method further comprises the following steps after the addition reaction is terminated: purifying the obtained reaction liquid; and the purification step comprises the steps of stirring and mixing the reaction solution and a purification solvent, standing for layering to obtain an organic layer containing the 3, 3-bithiophene, and sequentially washing, drying, desolventizing, concentrating and recrystallizing the organic layer containing the 3, 3-bithiophene to obtain the 3, 3-bithiophene.
The invention provides a method for synthesizing 3, 3-bithiophene, which comprises the following steps: mixing cyclohexyl magnesium halide, halogenated thiophene, transition metal catalyst and naphthenic hydrocarbon solvent to carry out addition reaction to obtain 3, 3-bithiophene. The invention utilizes cyclohexyl magnesium halide and halogenated thiophene to complete addition reaction to generate 3, 3-bithiophene. The synthesis method provided by the invention is simple and convenient to operate, simple in process and basically free of side reaction.
The synthesis method provided by the invention has the advantages of simple process and high reaction efficiency, simultaneously has high purity of target products, basically generates no hazardous wastes, and is suitable for large-scale production, so that the commercialization process of the 3, 3-bithiophene can be promoted, the 3, 3-bithiophene produced in batches can be used as an important drug intermediate, can be used for research and development and production of organic photoelectric materials, powerfully drives the use scale of bithiophene derivative materials at home and abroad, and has remarkable social benefits.
Detailed Description
The invention provides a method for synthesizing 3, 3-bithiophene, which comprises the following steps:
mixing cyclohexyl magnesium halide, halogenated thiophene, transition metal catalyst and naphthenic hydrocarbon solvent to carry out addition reaction to obtain 3, 3-bithiophene.
In the present invention, unless otherwise specified, each of the substances is a commercially available product well known to those skilled in the art.
In the present invention, the cyclohexyl magnesium halide (RMgX, R is cyclohexyl) is preferably prepared by the following method: mixing metal magnesium, an ether solvent, a catalyst and halogenated cyclohexane to carry out Grignard reaction to obtain cyclohexyl magnesium halide. In the invention, the metal magnesium is preferably one or more of magnesium chips, magnesium strips and magnesium powder, and more preferably magnesium chips; the halogenated cyclohexane preferably comprises one of bromocyclohexane, chlorocyclohexane and iodocyclohexane, and is more preferably bromocyclohexane; the catalyst is preferably one or more of iodine, methyl magnesium iodide and ethyl magnesium bromide, and more preferably iodine; the ether solvent is preferably one or more of tetrahydrofuran, diethyl ether and methyl tert-butyl ether, and more preferably one or more of anhydrous tetrahydrofuran, anhydrous diethyl ether and anhydrous methyl tert-butyl ether; the molar ratio of the halogenated cyclohexane to the metal magnesium is preferably 1.5 to 1; the molar ratio of the halogenated cyclohexane to the catalyst is preferably 1.005 to 0.03.
In the present invention, the mixing is preferably: firstly mixing metal magnesium, an ether solvent and a catalyst at normal temperature and normal pressure to obtain a first mixture, slowly heating the first mixture to 30-70 ℃ under the condition of stirring, secondly mixing the first mixture and part of halogenated cyclohexane to obtain a second mixture, and dropwise adding the rest halogenated cyclohexane into the second mixture after reaction initiation; the halogenated cyclohexane is preferably mixed in the form of a mixed solution of the halogenated cyclohexane and an ether solvent; the ether solvent is preferably one or more of tetrahydrofuran, diethyl ether and methyl tert-butyl ether, and more preferably tetrahydrofuran; the temperature of the Grignard reaction is preferably-78 to 70 ℃, more preferably-50 to 50 ℃, even more preferably 30 to 40 ℃, and the time is preferably 4 to 6 hours, and the time of the Grignard reaction is calculated from the time when the residual halogenated cyclohexane is dripped. In the specific embodiment of the invention, the obtained reaction liquid containing the cyclohexyl magnesium halide is directly subjected to the next addition reaction without being processed.
In the present invention, the transition metal catalyst preferably comprises NiCl 2 、Ni(CO) 4 、SnCl 2 ·H 2 PtCl 6 And HCo (CO) 4 More preferably NiCl 2 (ii) a The halogenated thiophene comprises one of 3-bromothiophene, 3-chlorothiophene and 3-iodothiophene, and is more preferably 3-bromothiophene; the naphthenic solvent is preferably one or two of cyclohexane and cyclopentane; the molar ratio of the cyclohexyl magnesium halide to the halogenated thiophene is preferably 1.5 to 1, and the molar ratio of the halogenated thiophene to the transition metal catalyst is preferably 1: 0.005-0.05; the mixing is preferably: firstly, performing third mixing on the cyclohexyl magnesium halide and a transition metal catalyst to obtain a third mixed solution, and then dropwise adding a mixed solution of halogenated thiophene and a naphthenic solvent into the third mixed solution; the temperature of the addition reaction is preferably-78-70 ℃, more preferably-50 ℃, further preferably 30-40 ℃, and the time is preferably 40-90 min, more preferably 50-80 min, further preferably 50-60 min; the time of the addition reaction is calculated from the time when the mixed solution of the halogenated thiophene and the naphthenic solvent begins to drop.
In the present invention, after the reaction time is reached, the reaction is preferably terminated in the present invention, and then the obtained reaction solution is purified; the solution for terminating the reaction is preferably saturated ammonium chloride aqueous solution; the volume ratio of the saturated aqueous solution of ammonium chloride to the reaction solution is preferably 0.5 to 1.5; the purification is preferably to stir and mix the reaction solution and a purification solvent, then to stand and layer the reaction solution to obtain an organic layer containing 3, 3-bithiophene, and to sequentially perform water washing, drying, desolventizing, concentrating and recrystallizing on the organic layer containing 3, 3-bithiophene to obtain 3, 3-bithiophene; the solvent for purification is preferably one or more of ethyl acetate, methyl acetate and dichloromethane; the water consumption for washing is preferably 500-1000 mL; the number of washing times is preferably 2; the drying reagent is preferably anhydrous sodium sulfate; the desolventizing concentration is preferably to carry out rotary evaporation on the dried organic layer containing the 3, 3-bithiophene until no solvent is evaporated; the temperature of the rotary evaporation is preferably 40 ℃; the invention has no special requirements on the recrystallization, and the method is selected from the common methods of the technical personnel in the field.
The reaction route for synthesizing 3, 3-bithiophene is as follows:
the invention firstly utilizes the characteristics of high efficiency and mild Grignard reaction, introduces Grignard reagent in the reaction to generate cyclohexyl magnesium halide, and then completes addition reaction with halogenated thiophene to generate 3, 3-bithiophene.
The synthetic method of the 3, 3-bithiophene provided by the invention has simple process, the purity of the synthesized 3, 3-bithiophene is up to more than 98%, and the yield is up to more than 61%.
In order to further illustrate the present invention, the following examples are provided to describe the synthesis method of 3, 3-bithiophene provided by the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Under normal temperature and normal pressure, sequentially and uniformly mixing 30.7g of magnesium chips, 50mL of anhydrous tetrahydrofuran and 0.13g of iodine in a reaction container, slowly heating to 70 ℃ under the stirring condition, dropwise adding 10mL of mixed solution of bromocyclohexane and anhydrous tetrahydrofuran, wherein the mixed solution consists of 167g of bromocyclohexane and 500mL of anhydrous tetrahydrofuran, keeping the system temperature at 70 ℃ after the reaction starts to initiate, continuously dropwise adding the rest of mixed solution of bromocyclohexane and anhydrous tetrahydrofuran, keeping the system temperature at 70 ℃ after the reaction is carried out for 4 hours, and adding 2g of NiCl 2 (dppp), a mixed solution of 163.3g of 3-bromothiophene and 300mL of cyclohexane was added dropwise thereto, and the mixture was reacted for 70min to obtain a reaction solutionAdding 1L of saturated ammonium chloride aqueous solution and 1L of ethyl acetate into the reaction solution in sequence, continuing stirring for 30s, standing for layering, washing the obtained organic layer twice with 500mL of water each time, drying the organic layer with anhydrous sodium sulfate, filtering to remove the anhydrous sodium sulfate, performing rotary evaporation on the organic layer after water removal until no ethyl acetate exists, wherein the rotary evaporation temperature is 40 ℃, and recrystallizing the obtained residue to obtain 50.8g of white flaky crystal 3, 3-bithiophene with the purity of 98% and the yield of 61%.
Example 2
Under normal temperature and normal pressure, 31.2g of magnesium chips, 50mL of anhydrous ether and 0.1g of iodine are sequentially put into a reaction container to be uniformly mixed, the temperature is slowly raised to 40 ℃ under the stirring condition, 10mL of mixed solution of bromocyclohexane and anhydrous ether is dropwise added, wherein the mixed solution consists of 163g of bromocyclohexane and 500mL of anhydrous ether, after the reaction is started to be initiated, the temperature of the system is kept at 40 ℃, the rest of mixed solution of bromocyclohexane and anhydrous ether is continuously dropwise added, after the reaction is carried out for 4 hours, the temperature of the system is kept at 40 ℃, and 2g of NiCl is added 2 (dppp), adding 163g of a mixed solution of 3-bromothiophene and 300mL of cyclopentane dropwise, reacting for 60min to obtain a reaction solution, sequentially adding 1L of ammonium chloride saturated aqueous solution and 1L of ethyl acetate into the obtained reaction solution, continuing stirring for 30s, standing for layering, washing the obtained organic layer twice with 500mL of water each time, drying the organic layer with anhydrous sodium sulfate, filtering to remove the anhydrous sodium sulfate, carrying out rotary evaporation on the organic layer after water removal until no ethyl acetate exists, wherein the rotary evaporation temperature is 40 ℃, and recrystallizing the obtained residue to obtain 52.5g of white flaky crystal 3, 3-bithiophene with the purity of 98% and the yield of 63%.
Example 3
Under normal temperature and normal pressure, 31.2g of magnesium chips, 50mL of anhydrous tetrahydrofuran and 0.15g of iodine are sequentially put into a reaction container to be uniformly mixed, the temperature is slowly raised to 35 ℃ under the stirring condition, 10mL of mixed solution of bromocyclohexane and anhydrous tetrahydrofuran is dropwise added, wherein the mixed solution consists of 164.5g of bromocyclohexane and 500mL of anhydrous tetrahydrofuran, the temperature of the system is kept at 35 ℃ after the reaction is initiated, the rest of mixed solution of bromocyclohexane and anhydrous tetrahydrofuran is continuously dropwise added, and after the reaction is carried out for 4 hours, the reaction is carried out for 4 hoursThe temperature of the holding system is 35 ℃, 2g of NiCl is added 2 (dppp), adding 163g of a mixed solution of 3-bromothiophene and 300mL of cyclopentane dropwise, reacting for 60min to obtain a reaction solution, sequentially adding 1L of ammonium chloride saturated aqueous solution and 1L of ethyl acetate into the obtained reaction solution, continuing stirring for 30s, standing for layering, washing the obtained organic layer twice with 500mL of water each time, drying the organic layer with anhydrous sodium sulfate, filtering to remove the anhydrous sodium sulfate, carrying out rotary evaporation on the organic layer after water removal until no ethyl acetate exists, wherein the rotary evaporation temperature is 40 ℃, and recrystallizing the obtained residue to obtain 51.5g of white flaky crystal 3, 3-bithiophene with the purity of 98.2% and the yield of 62%.
Example 4
Under normal temperature and normal pressure, sequentially and uniformly mixing 30.2g of magnesium chips, 50mL of anhydrous methyl tert-butyl ether and 0.09g of iodine in a reaction container, slowly heating to 35 ℃ under the stirring condition, dropwise adding 10mL of mixed solution of bromocyclohexane and anhydrous methyl tert-butyl ether, wherein the mixed solution consists of 163g of bromocyclohexane and 500mL of anhydrous methyl tert-butyl ether, keeping the temperature of the system at 35 ℃ after the reaction starts to initiate, continuously dropwise adding the rest of mixed solution of bromocyclohexane and anhydrous methyl tert-butyl ether, keeping the temperature of the system at 35 ℃ after the reaction is carried out for 4 hours, and adding 2g of NiCl 2 (dppp), adding 163g of a mixed solution of 3-bromothiophene and 300mL of cyclohexane dropwise, reacting for 40min to obtain a reaction solution, sequentially adding 1L of ammonium chloride saturated aqueous solution and 1L of ethyl acetate into the obtained reaction solution, continuing stirring for 30s, standing for layering, washing the obtained organic layer twice with 500mL of water each time, drying the organic layer with anhydrous sodium sulfate, filtering to remove the anhydrous sodium sulfate, carrying out rotary evaporation on the organic layer after water removal until no ethyl acetate exists, wherein the rotary evaporation temperature is 40 ℃, and recrystallizing the obtained residue to obtain 52.4g of white flaky crystal 3, 3-bithiophene, the purity is 98%, and the yield is 63%.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. A method for synthesizing 3, 3-bithiophene is characterized by comprising the following steps:
mixing cyclohexyl magnesium halide, halogenated thiophene, transition metal catalyst and naphthenic hydrocarbon solvent to carry out addition reaction to obtain 3, 3-bithiophene.
2. The synthesis method according to claim 1, wherein the cyclohexyl magnesium halide is prepared by the following steps: mixing metal magnesium, an ether solvent, a catalyst and halogenated cyclohexane to carry out Grignard reaction to obtain cyclohexyl magnesium halide.
3. The synthesis method according to claim 2, wherein the metal magnesium is one or more of magnesium chips, magnesium strips and magnesium powder; the halogenated cyclohexane comprises one of bromocyclohexane, chlorocyclohexane and iodocyclohexane; the catalyst is one or more of iodine, methyl magnesium iodide and ethyl magnesium bromide; the ether solvent is one or more of tetrahydrofuran, diethyl ether and methyl tert-butyl ether.
4. The method of synthesis of claim 1, wherein the transition metal catalyst comprises NiCl 2 、Ni(CO) 4 、SnCl 2 ·H 2 PtCl 6 And HCo (CO) 4 One or more of the above; the halogenated thiophene comprises one of 3-bromothiophene, 3-chlorothiophene and 3-iodothiophene.
5. The synthesis method of claim 1, wherein the naphthenic solvent is one or both of cyclohexane and cyclopentane.
6. The synthesis process according to any one of claims 2 to 3, wherein the molar ratio of the halogenated cyclohexane to the metallic magnesium is from 1.5 to 1; the molar ratio of the halogenated cyclohexane to the catalyst is 1.005 to 0.03.
7. The synthesis process according to any one of claims 1 to 4, wherein the molar ratio of the cyclohexyl magnesium halide to the halogenated thiophene is 1.5 to 1, and the molar ratio of the halogenated thiophene to the transition metal catalyst is 1: 0.005-0.05.
8. The synthesis method according to claim 1, wherein the temperature of the Grignard reaction is-78 to 70 ℃ and the time is 4 to 6 hours.
9. The synthesis method according to claim 1, characterized in that the temperature of the addition reaction is-78-70 ℃ and the time is 40-90 min.
10. The method of claim 1 or 9, further comprising, after the termination of the addition reaction: purifying the obtained reaction liquid; and the purification step comprises the steps of stirring and mixing the reaction solution and a purification solvent, standing for layering to obtain an organic layer containing the 3, 3-bithiophene, and sequentially washing, drying, desolventizing, concentrating and recrystallizing the organic layer containing the 3, 3-bithiophene to obtain the 3, 3-bithiophene.
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| CN102010399A (en) * | 2010-11-11 | 2011-04-13 | 华东理工大学 | Multiple thiophene group-containing photochromic compound |
| CN103483559A (en) * | 2013-09-17 | 2014-01-01 | 武汉工程大学 | Conjugated polymer based on 2,1,3-diazosulfide 2'-bithiophene derivative and synthesis method thereof |
| CN105358561A (en) * | 2013-03-13 | 2016-02-24 | 艾伯维德国有限责任两合公司 | Novel inhibitor compounds of phosphodiesterase type 10a |
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| CN102010399A (en) * | 2010-11-11 | 2011-04-13 | 华东理工大学 | Multiple thiophene group-containing photochromic compound |
| CN105358561A (en) * | 2013-03-13 | 2016-02-24 | 艾伯维德国有限责任两合公司 | Novel inhibitor compounds of phosphodiesterase type 10a |
| CN103483559A (en) * | 2013-09-17 | 2014-01-01 | 武汉工程大学 | Conjugated polymer based on 2,1,3-diazosulfide 2'-bithiophene derivative and synthesis method thereof |
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