CN102295633B - Preparation method of 5,5'-dibromo-2,2'-bithiophene - Google Patents

Preparation method of 5,5'-dibromo-2,2'-bithiophene Download PDF

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CN102295633B
CN102295633B CN2011101781796A CN201110178179A CN102295633B CN 102295633 B CN102295633 B CN 102295633B CN 2011101781796 A CN2011101781796 A CN 2011101781796A CN 201110178179 A CN201110178179 A CN 201110178179A CN 102295633 B CN102295633 B CN 102295633B
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bithiophene
preparation
dibromo
reaction
catalyst
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CN102295633A (en
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何建明
何甫长
周恭训
金望志
裴文
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LINHAI LIMIN CHEMICALS CO Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention relates to a preparation method of 5,5'-dibromo-2,2'-bithiophene. The invention belongs to the technical field of fine chemical synthesis. The method comprises steps that: 2-bromothiophene is adopted as a raw material; a tin-system solid super acid modified by a transition metal is adopted as a catalyst; in a solvent of an ionic liquid reaction system, the materials are subject to a reaction for 1 to 20 hours under a temperature of 30 to 150 DEG C; when the reaction is finished, the product is cooled to 25 DEG C, and is extracted 2 to 3 times by using toluene; the extracts are combined and condensed, and a product 5,5'-dibromo-2,2'-bithiophene is obtained. With the preparation method provided by the invention, the invention is advantaged in that: (1) solid acid is adopted as a catalyst; the product is obtained with a one-step reaction; the reaction condition is mild; and the operation is simple; (2) the cost of the adopted solid acid catalyst is low; the preparation of the catalyst is convenient; the catalyst resists high temperature; three-waste pollutions are not brought in; and the catalyst is easy to recycle and to reuse; (3) the technology is simple; post-treatment is convenient; the product structural formula is verified by nuclear magnetometer, mass spectrum and the like; the yield of the product is higher than 74%, and the purity of the product is high; and the method is suitable for industrialized productions.

Description

A kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene
Technical field
The invention belongs to technical field of fine chemical synthesis, be specifically related to the preparation method of a kind of industrialization simple to operate, easy, 5_5'-two bromo-2_2'-bithiophenes that environmental pollution is little.
Background technology
5,5'-dibromo-2,2 '-bithiophene is widely used in the fields such as medicine, agricultural chemicals, dyestuff, chemical reagent, pluronic polymer as important organic raw material or functional organic material.The synthetic present bibliographical information of 5,5'-dibromo-2,2 '-bithiophene has following several preparation method: 1) make 2,2'-bithiophene by 2-bromothiophene process self coupling, make target product 5 by 2,2'-bithiophene bromination again, the 5'-dibromo-2,2 '-bithiophene.The method needs two-step reaction, and complex steps and ultimate yield are not high; 2) be raw material with 2,2-dibromo thiophene, at LiCl and ZnCl 2Effect under generate intermediate thiophene zinc chloride reagent, the low temperature linked reaction obtains target product in tetrachlorobenzoquinone again.This method agents useful for same is expensive, severe reaction conditions, the unfavorable suitability for industrialized production of using; 3) under the catalysis of Palladous chloride, take the 2-bromothiophene as raw material, AgF is additive, obtains target product by Ullman type oxidative coupling reaction.This method need be added the phosphine part of contaminate environment, and used divalence palladium catalyst is comparatively expensive, and can not recycle and reuse.
Solid super-strong acid is a kind of solid acid catalyst of Recent study and exploitation, is to compare 100%H 2SO 4Strength of acid strong solid acid also, its strength of acid represents known 100%H with special (Hammett) acidity function h0 of Harmer 2SO 4Special (Hammett) acidity function h0 of Harmer=-11.93, so the solid of every H0＜-11.93 all is called solid super-strong acid.SO 4 2-/ MxOy type solid super-strong acid is as a kind of novel heterogeneous catalyst, generally has not etching apparatus, pollution is little, high temperature resistant, aftertreatment is simple, the advantage such as easily separated, reusable, has obtained broad research in the acid catalysis field.Tin for transition metal and modification is that solid super-strong acid there is not yet report in the application of preparation 5,5'-dibromo-2,2 '-bithiophene.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide the preparation method of a kind of industrialization simple to operate, easy, 5_5'-two bromo-2_2'-bithiophenes that environmental pollution is little.
Described a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene, it is characterized in that comprising following synthesis step: take the 2-bromothiophene as raw material, adopting transition metal modified tin is that solid super-strong acid is as catalyzer, in the solvent of ionic liquid reaction system, at 30-150 ℃ of reaction 1-20h, cooling was 25 ℃ after reaction finished, extract 2-3 time combining extraction liquid, the concentrated product 5 that obtains with toluene, the 5'-dibromo-2,2 '-bithiophene.
Described a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene is characterized in that described solid super acid catalyst is: SO 4 2-/ SnO 2-Fe 2O 3, S 2O 8 2-/ SnO 2-Fe 2O 3, SO 4 2-/ SnO 2-ZnO, S 2O 8 2-/ SnO 2-ZnO, SO 4 2-/ SnO 2-TiO 2Or S 2O 8 2-/ SnO 2-TiO 2In any one.
Described a kind of 5,5'-two bromo-2, the preparation method of 2'-bithiophene is characterized in that described ionic liquid is a kind of in 1-alkyl-3-methyl imidazolium tetrafluoroborate or the 1-alkyl-3-Methylimidazole hexafluorophosphate, and wherein alkyl is that carbon atom quantity is the alkyl of 1-18;
Described a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene is characterized in that the consumption of described ionic liquid is the 10-60% of 2-bromothiophene quality, is preferably 30%.
Described a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene is characterized in that described temperature of reaction is 100-130 ℃, and the reaction times is 5-10h.
Described a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene, the each consumption that it is characterized in that described extraction agent toluene is 50ml.
Described a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene is characterized in that described catalyst levels is the 1-10% of 2-bromothiophene quality, is preferably 5%.
Described a kind of 5,5'-two bromo-2, the preparation method of 2'-bithiophene, it is characterized in that the described method for preparing solid super acid catalyst is co-precipitation-pickling process, detailed process is as follows: any corresponding soluble salt solution is dissolved in the distilled water in the soluble salt solution of tin and iron or zinc or the titanium, and transferring pH through strong aqua is 8, room temperature ageing 24h, after suction filtration, removal of impurities, oven dry, grinding, with the H of 0.2-5mol/L 2SO 4Or (the NH of 1-2mol/L 4) 2S 2O 8Solution carries out dip treating, after filtration, the drying, 500-600 ℃ of lower roasting, obtains solid super acid catalyst in air atmosphere.
Described a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene is characterized in that described solubility pink salt is SnCl 45H 2O; Described soluble ferric iron salt is FeCl 36H 2O, soluble zinc salt are ZnCl 2, the solubility titanium salt is TiCl 4, described SnCl 45H 2O and FeCl 36H 2O, ZnCl 2Or TiCl 4Mole proportioning that feeds intake be 1:2-9.
Described a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene is characterized in that described solid super acid catalyst expression formula is SO 4 2-/ SnO 2-Fe 2O 3Or S 2O 8 2-/ SnO 2-Fe 2O 3
By adopting above-mentioned technology, to tie mutually with prior art, beneficial effect of the present invention is as follows:
1) to adopt solid acid be catalyzer in the present invention, obtains product by single step reaction, and reaction conditions is gentle, simple to operate;
2) low, easy to prepare, not water funk, high temperature resistant, the three-waste free pollution of the solid acid catalyst cost that uses of the present invention and easily recycling;
3) technique of the present invention is simple, convenient post-treatment, and the product structure formula that obtains is by the checking of nuclear-magnetism, mass spectrum etc., and yield is up to more than 74%, and purity is high, is suitable for suitability for industrialized production.
Embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1: add 2-bromothiophene 163g in 250 mL round-bottomed flasks, after stirring, add S 2O 8 2-/ SnO 2-Fe 2O 3Catalyzer (Fe/ Sn mole proportioning is 1:9) 8.15g, 1-butyl-3-methyl imidazolium tetrafluoroborate 50g is heated to 130 ℃ of reaction 10h, end is cooled to room temperature with reaction solution, use the toluene extracting twice, use toluene 50 mL, combining extraction liquid at every turn, concentrated, obtain product 5,5'-dibromo-2,2 '-bithiophene 251g, yield 77.5%, 142～143 ℃ of fusing points. 1H?NMR?(400?MHz,?CDCl 3)?δppm:?6.85?(d,? J?=?3.9?Hz,?2H),?6.96?(d,? J?=?3.9?Hz,?2H； 13C?NMR?(CDCl 3)?δppm:?111.5,?124.1,?130.7,?137.8；?IR?(KBr)?ν：3100,?3069,?2921,?1507,?1417?cm -1；MS?(EI):?m/z?(%):?324?(100)?[M +],?322?(50),?164?(25)。
Embodiment 2: add 2-bromothiophene 163g in the 250mL round-bottomed flask, after stirring, add SO 4 2-/ SnO 2-Fe 2O 3Catalyzer (Fe/ Sn mole proportioning is 1:4) 16.3g, 1-octyl group-3-methyl imidazolium tetrafluoroborate 16g is heated to 100 ℃ of reaction 5h, end is cooled to room temperature with reaction solution, use the toluene extracting twice, use toluene 50mL, combining extraction liquid at every turn, concentrated, obtain product 5,5'-dibromo-2,2 '-bithiophene 243 g, yield 75%, 142～143 ℃ of fusing points.
Embodiment 3: add 2-bromothiophene 163g in the 250mL round-bottomed flask, after stirring, add S 2O 8 2-/ SnO 2-Fe 2O 3Catalyzer (Fe/ Sn mole proportioning is 1:6) 16.3g, 1-octyl group-3-Methylimidazole hexafluorophosphate 30g is at 60 ℃ of reaction 20h, end is cooled to room temperature with reaction solution, use the toluene extracting twice, use toluene 50mL, combining extraction liquid at every turn, concentrated, obtain product 5,5'-dibromo-2,2 '-bithiophene 244g, yield 75.5%, 142～143 ℃ of fusing points.
Embodiment 4: add 2-bromothiophene 163g in the 250mL round-bottomed flask, after stirring, add S 2O 8 2-/ SnO 2-Fe 2O 3Catalyzer (Fe/ Sn mole proportioning is 1:2) 1.63g, 1-butyl-3-methyl imidazolium tetrafluoroborate 55.2g is at 150 ℃ of reaction 1h, end is cooled to room temperature with reaction solution, use the toluene extracting twice, use toluene 50mL, combining extraction liquid at every turn, concentrated, obtain product 5,5'-dibromo-2,2 '-bithiophene 250.4g, yield 77.2%, 142～143 ℃ of fusing points.
Embodiment 5: add 2-bromothiophene 163g in the 250mL round-bottomed flask, after stirring, add S 2O 8 2-/ SnO 2-TiO 2Catalyzer (Ti/ Sn mole proportioning is 1:3) 8g, 1-butyl-3-Methylimidazole hexafluorophosphate 16.3g is at 110 ℃ of reaction 5h, end is cooled to room temperature with reaction solution, use the toluene extracting twice, use toluene 50mL, combining extraction liquid at every turn, concentrated, obtain product 5,5'-dibromo-2,2 '-bithiophene 240g, yield 74%, 142～143 ℃ of fusing points.
Embodiment 6: add 2-bromothiophene 163g in the 250mL round-bottomed flask, after stirring, add S 2O 8 2-/ SnO 2-ZnO catalyst (Ti/ Sn mole proportioning is 1:3) 8g, 1-dodecyl-3-Methylimidazole hexafluorophosphate 50g is at 110 ℃ of reaction 5h, end is cooled to room temperature with reaction solution, use the toluene extracting twice, use toluene 50mL, combining extraction liquid at every turn, concentrated, obtain product 5,5'-dibromo-2,2 '-bithiophene 246.5g, yield 76%, 142～143 ℃ of fusing points.
Embodiment 7: catalyst S 2O 8 2-/ SnO 2-Fe 2O 3Preparation
Get commercial 20gSnCl 45H 2O and 1.71gFeCl 36H 2O(Chemical Reagent Co., Ltd., Sinopharm Group produces) be dissolved in the 200 mL distilled water, stir lower 25 %(w/w of adding) to transfer pH be 8 to ammoniacal liquor, and ageing 24h under the room temperature, suction filtration is removed Cl through the washing of 2% Spirit of Mindererus -(with the AgNO of 0.1 mol/L 3Check), filter cake ground 100 orders at 100 ℃ of lower dry 24h, placed 1mol/L (NH 4) 2S 2O 8Flood in the solution (15 mL/g), then filter, oven dry, 550 ℃ of roasting 5h obtain described S 2O 8 2-/ SnO 2-Fe 2O 3Catalyzer (Fe/ Sn mole proportioning is 1:9).
Embodiment 8: catalyst S O 4 2-/ SnO 2-Fe 2O 3Preparation
Get commercial 20gSnCl 45H 2O and 3.86gFeCl 36H 2O(Chemical Reagent Co., Ltd., Sinopharm Group produces) be dissolved in the 200 mL distilled water, stir lower 25 %(w/w of adding) to transfer pH be 8 to ammoniacal liquor, and ageing 24h under the room temperature, suction filtration is removed Cl through the washing of 2% Spirit of Mindererus -(with the AgNO of 0.1 mol/L 3Check), filter cake ground 100 orders at 100 ℃ of lower dry 24h, placed 2 mol/L H 2SO 4Carry out dip treating in the solution (15 mL/g), then filter, oven dry, 600 ℃ of roasting 3h obtain described SO 4 2-/ SnO 2-Fe 2O 3Catalyzer (Fe/ Sn mole proportioning is 1:4).
Embodiment 9: catalyst S 2O 8 2-/ SnO 2-Fe 2O 3Preparation
Get commercial 20gSnCl 45H 2O and 2.51gFeCl 36H 2O(Chemical Reagent Co., Ltd., Sinopharm Group produces) be dissolved in 200 mL distillation and stir lower 25 %(w/w of adding) to transfer pH be 8 to ammoniacal liquor, ageing 24h under the room temperature, suction filtration is removed Cl through the washing of 2% Spirit of Mindererus -(with the AgNO of 0.1 mol/L 3Check), filter cake ground 100 orders at 100 ℃ of lower dry 24h, placed (the NH of 2mol/L 4) 2S 2O 8Dip treating in the solution (15 mL/g) is then filtered, oven dry, and 550 ℃ of roasting 8h obtain described S 2O 8 2-/ SnO 2-Fe 2O 3Catalyzer (Fe/ Sn mole proportioning is 1:6).

Claims (10)

1. one kind 5, the preparation method of 5'-dibromo-2,2 '-bithiophene, it is characterized in that comprising following synthesis step: take the 2-bromothiophene as raw material, adopting transition metal modified tin is that solid super-strong acid is as catalyzer, in the solvent of ionic liquid reaction system, at 30-150 ℃ of reaction 1-20h, reaction is cooled to 25 ℃ after finishing, and extracts 2-3 time combining extraction liquid with toluene, the concentrated product 5 that obtains, the 5'-dibromo-2,2 '-bithiophene, described solid super acid catalyst expression formula is SO 4 2-/ SnO 2-Fe 2O 3Or S 2O 8 2-/ SnO 2-Fe 2O 3
2. according to claim 1 a kind of 5,5'-two bromo-2, the preparation method of 2'-bithiophene, it is characterized in that described ionic liquid is a kind of in 1-alkyl-3-methyl imidazolium tetrafluoroborate or the 1-alkyl-3-Methylimidazole hexafluorophosphate, wherein alkyl is that carbon atom quantity is the alkyl of 1-18.
3. according to claim 1 a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene, the consumption that it is characterized in that described ionic liquid is 10 ~ 60% of 2-bromothiophene quality.
4. according to claim 1 a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene, the consumption that it is characterized in that described ionic liquid is 30% of 2-bromothiophene quality.
5. according to claim 1 a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene is characterized in that described temperature of reaction is 100-130 ℃, and the reaction times is 5-10h.
6. according to claim 1 a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene, the each consumption that it is characterized in that described extraction agent toluene is 50ml.
7. according to claim 1 a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene is characterized in that described catalyst levels is the 1-10% of 2-bromothiophene quality.
8. according to claim 1 a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene is characterized in that described catalyst levels is 5% of 2-bromothiophene quality.
9. according to claim 1 a kind of 5,5'-two bromo-2, the preparation method of 2'-bithiophene, the method that it is characterized in that preparing solid super acid catalyst is co-precipitation-pickling process, detailed process is as follows: the soluble salt solution of tin and the soluble salt solution of iron are dissolved in the distilled water, and transferring pH through strong aqua is 8, room temperature ageing 24h, after suction filtration, removal of impurities, oven dry, grinding, with the H of 0.2-5mol/L 2SO 4Or (the NH of 1-2mol/L 4) 2S 2O 8Solution carries out dip treating, after filtration, the drying, 500 ~ 600 ℃ of lower roastings, obtains solid super acid catalyst in air atmosphere.
10. according to claim 9 a kind of 5, the preparation method of 5'-dibromo-2,2 '-bithiophene is characterized in that described solubility pink salt is SnCl 45H 2O; Described soluble ferric iron salt is FeCl 36H 2O, described SnCl 45H 2O and FeCl 36H 2Mole proportioning that feeds intake of O is 1:2-9.
CN2011101781796A 2011-06-29 2011-06-29 Preparation method of 5,5'-dibromo-2,2'-bithiophene Expired - Fee Related CN102295633B (en)

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