CN101830909A - Preparation method of tetrahydro-cyclopentyl[2,1-b;3,4-b'] bi-thiophene ketone - Google Patents
Preparation method of tetrahydro-cyclopentyl[2,1-b;3,4-b'] bi-thiophene ketone Download PDFInfo
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Abstract
The invention discloses a preparation method of tetrahydro-cyclopentyl[2,1-b;3,4-b'] bi-thiophene ketone, aiming to solve the problem of lower reaction yield. The invention comprises the following steps of: (1) carrying out a coupling reaction on 2-bromine-3-methyl thiophene and 3.84g of 2-thiophene boric acid to obtain 3-methyl2,2'-bithiophene; (2) carrying out an oxidation reaction on 3-methylbithiophene and potassium permanganate to obtain 2,2'-bithiophene3-formic acid; and (3) reacting the 3-methylbithiophene with concentrated sulfuric acid (98 percent) to obtain the tetrahydro-cyclopentyl[2,1-b;3,4-b'] bi-thiophene ketone. The invention is mainly used for preparing the tetrahydro-cyclopentyl[2,1-b;3,4-b'] bi-thiophene ketone.
Description
Technical field
The present invention relates to a kind of 4 hydrogen-ring penta [2,1-b; 3,4-b '] preparation method of two thienones.
Background technology
Since people such as Heeger in 1977 found the polyacetylene conduction, conjugated polymers had attracted numerous scientists to study with its outstanding photoelectric properties.Because the big pi-conjugated backbone structure of this class material, has the unidimensional charge transmission, thereby has an excellent photoelectric characteristic, be applied in numerous photoelectric devices field or have potential use, as polymer LED (PLED), organic photovoltaic battery (OPV), thin film transistor (TFT) etc.
Contain 4 hydrogen-ring penta that two alkyl replace [2,1-b; 3,4-b '] two thiophene D-A-D type polymkeric substance are the novel conjugated polymerss of a class, can serve as the efficient donor material in the body heterojunction photovoltaic cell.As 2007, people such as Heeger reported 4 hydrogen-ring penta of containing two iso-octyl and replacing [2,1-b; 3,4-b '] two thiophene and 4, two (the 5-bromothiophenes-2-yl)-2 of 7-, 1, the multipolymer of 3-diazosulfide (PCPDTBT, its structure is suc as formula shown in (I)), the electricity conversion of this polymkeric substance reaches 5.5% (Nature Materials.6 (2007) 497-500).By the design rhythmo structure,, obtained 6.5% efficiency of conversion based on the photovoltaic cell of PCPDTBT.This novel conjugated polymers is one of donor material of at present high-photoelectric transformation efficiency.
And 4 hydrogen-ring penta [2,1-b; 3,4-b '] two thienones are critical materials of this efficient donor material, its structure suc as formula shown in:
Present monomer 4 hydrogen-ring penta [2,1-b; 3,4-b '] preparation method of two thienones: Synthetic metals 92 (1998) 25-31 for example, and " expedient synthesis of symmetric aryl ketones and ofambient-temperature molten salts of imidazole ", Synthesis 9 (2000) 1253-1258 disclose a kind of 4 hydrogen-ring penta [2,1-b; 3,4-b '] preparation method of two thienones, this method is by 3 bromo thiophene and N, and the protection carbonyl goes blocking group to obtain the product synthetic method at last through iodide reaction, ring-closure reaction behind the N-dimethyl methyl acyl chloride reaction, and its synthetic route is as follows:
But this method adopts the low temperature lithium for approach, severe reaction conditions, and reactions steps is longer, and yield is lower, the 4 hydrogen-ring penta of this method [2,1-b; 3,4-b '] two thienone total recoverys are 42%.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art and defective, provide 4 hydrogen-ring penta that a kind of reactions steps is less, reaction yield is higher [2,1-b; 3,4-b '] preparation method of two thienones.
In order to solve the problems of the technologies described above, the present invention design three-step reaction prepare 4 hydrogen-ring penta [2,1-b; 3,4-b '] route of two thienones is as follows:
At first by the synthetic 3-methyl di-thiophene of linked reaction; Then it is oxidized to 3-formic acid di-thiophene; At last by intramolecular ring-closing reaction obtain purpose product 4 hydrogen-ring penta [2,1-b; 3,4-b '] two thienones.
4 hydrogen of the present invention-ring penta [2,1-b; 3,4-b '] two thienone preparation methods, its structural formula is shown in (II):
Comprise the steps:
(1) with 2-bromo-3 methyl thiophene 3.54g (20mmol); 2-thienyl boric acid 3.84g (30mmol); triphenylphosphine; triphenylphosphine 52.4mg (0.2mmol); tetrahydrofuran (THF) 100ml; solution of potassium carbonate 100ml (2mol/L) joins in the reaction flask, stirs to add palladium 65mg, heat temperature raising to 65 ℃ back flow reaction 4h under argon shield.Be cooled to room temperature, through the toluene extraction, the saturated sodium-chloride water solution washing, anhydrous magnesium sulfate drying concentrates and the column chromatography aftertreatment gets 3-methyl 2,2 '-bithiophene;
(2) the 3-methyl di-thiophene 9g (0.05mol) that step (1) is obtained, pyridine 100ml, water 100ml, potassium permanganate 39.5g (0.25mol) joins in the reaction flask, under agitation heat temperature raising to 50 ℃ reaction 24h.The back separatory is left standstill in cooling, with saturated sodium-chloride water solution organic phase is washed till neutrality, uses the anhydrous magnesium sulfate drying organic phase, filtrate is concentrated with the column chromatography aftertreatment get 2,2 '-bithiophene 3-formic acid
(3) the 3-formic acid di-thiophene 2.1g (0.01mol) that step (2) is obtained, the vitriol oil (98%) 100ml joins in the reaction flask, react 4h under stirring at room, stopped reaction is through ethyl acetate extraction, with saturated sodium-chloride water solution organic phase is washed till neutrality, use the anhydrous magnesium sulfate drying organic phase, filter, filtrate is concentrated, the aftertreatment of post layer obtain 4 hydrogen-ring penta [2,1-b; 3,4-b '] two thienones.
Preparation method's reactions steps of the present invention is less, total three-step reaction just can obtain 4 hydrogen-ring penta [2,1-b; 3,4-b '] two thienones, and the synthetic method of documents need four-step reaction can obtain 4 hydrogen-ring penta [2,1-b; 3,4-b '] two thienones; Reaction yield of the present invention is higher, and the total recovery of three-step reaction is 58%, is higher than the disclosed total recovery of documents, and the total recovery of the four-step reaction of the synthetic method of documents is 42%.Preparation method's of the present invention reaction is all carried out under room temperature or a little higher than room temperature situation in addition, mild condition, is easy to realize, therefore is more suitable in industrialization and scale operation.
Utilize technology of the present invention preparation 4 hydrogen rings penta [2,1-b; 3,4-b '] two thienones can prepare the precursor of PCPDTBT easily by reduction and alkylation, and and then prepare PCPDTBT, be used for high-efficiency polymer body heterojunction photovoltaic cell.
Embodiment
Embodiment 1
(1) the 3-methyl 2, the preparation of 2 '-bithiophene
Add 3.54g (20mmol) 2-bromo-3 methyl thiophene in the 250ml there-necked flask; 3.84g (30mmol) 2-thienyl boric acid; 52.4mg (0.2mmol) triphenylphosphine; the 100ml tetrahydrofuran (THF); 100ml (2mol/L) solution of potassium carbonate; argon shield is stirred the back and is added the 65mg palladium, heats to 65 ℃ of backflow 4h.Stop heating, reduce to room temperature, divide the extractive reaction system 3 times with 200ml toluene, merge organic phase, with saturated sodium-chloride water solution organic phase is washed till neutrality, then with the organic phase anhydrous magnesium sulfate drying, organic phase is filtered, filtrate concentrates, and then the enriched material column chromatography is obtained colourless liquid 3.3g, yield: 92%.
Structure is identified:
1H?NMR(500MHz，CD
3COCD
3)：2.36(m，3H)，6.94(d，1H)，7.11(t，1H)，7.18(dd，1H)，7.30(d，2H)，7.46(dd，4H).
(2) 2, the preparation of 2 '-bithiophene 3-formic acid
Add 9g (0.05mol) 3-methyl di-thiophene in the 250ml there-necked flask, the 100ml pyridine, 100ml water, 39.5g (0.25mol) potassium permanganate stirs, heat temperature raising to 50 ℃ reaction 24h.Separatory is left standstill in cooling, divides aqueous phase extracted 3 times with the 200ml ethyl acetate, merges organic phase, with saturated sodium-chloride water solution organic phase is washed till neutrality, uses the anhydrous magnesium sulfate drying organic phase, filter, filtrate is concentrated, then the enriched material column chromatography is obtained the 8.5g product, yield 81%.
Structure is identified:
1H?NMR(500MHz，CDCl
3)：6.95(t，1H)，7.38(d，1H)，7.52(d，1H)，7.60(m，2H).
(3) 4 hydrogen-ring penta [2,1-b; 3,4-b '] preparation of two thienones
Add 2.1g (0.01mol) 3-formic acid di-thiophene in the 250ml there-necked flask, the 100ml vitriol oil (98%) stirs down for 25 ℃ in room temperature, and stopped reaction behind the reaction 4h divides the extractive reaction system 3 times with ethyl acetate 200ml, merges organic phase; With saturated sodium-chloride water solution organic phase is washed till neutrality, uses the anhydrous magnesium sulfate drying organic phase, filter, filtrate is concentrated, column chromatography obtains product 1.5g, yield 78%.Three step overall yield 58%.
Structure is identified:
1H?NMR(500MHz，CDCl
3)：7.40(d，2H)，7.62(d，2H).
Data consistent among above-mentioned analytical data and Synthetic metals 92 (1998) 25-31, confirm material that this method obtains be really 4 hydrogen-ring penta [2,1-b; 3,4-b '] two thienones.
Claims (1)
- Hydrogen-ring penta [2,1-b; 3,4-b '] preparation method of two thienones, structure is suc as formula shown in (I):
Comprise the steps:(1) with 2-bromo-3 methyl thiophene 3.54g (20mmol); 2-thienyl boric acid 3.84g (30mmol); triphenylphosphine; triphenylphosphine 52.4mg (0.2mmol); tetrahydrofuran (THF) 100ml; solution of potassium carbonate 100ml (2mol/L) joins in the reaction flask, stirs to add palladium 65mg, heat temperature raising to 65 ℃ back flow reaction 4h under argon shield.Be cooled to room temperature, through the toluene extraction, the saturated sodium-chloride water solution washing, anhydrous magnesium sulfate drying concentrates and the column chromatography aftertreatment gets 3-methyl 2,2 '-bithiophene;(2) the 3-methyl di-thiophene 9g (0.05mol) that step (1) is obtained, pyridine 100ml, water 100ml, potassium permanganate 39.5g (0.25mol) joins in the reaction flask, under agitation heat temperature raising to 50 ℃ reaction 24h.The back separatory is left standstill in cooling, with saturated sodium-chloride water solution organic phase is washed till neutrality, uses the anhydrous magnesium sulfate drying organic phase, filtrate is concentrated with the column chromatography aftertreatment get 2,2 '-bithiophene 3-formic acid(3) the 3-formic acid di-thiophene 2.1g (0.01mol) that step (2) is obtained, the vitriol oil (98%) 100ml joins in the reaction flask, react 4h under stirring at room, stopped reaction is through ethyl acetate extraction, with saturated sodium-chloride water solution organic phase is washed till neutrality, use the anhydrous magnesium sulfate drying organic phase, filter, filtrate is concentrated, the aftertreatment of post layer obtain 4 hydrogen-ring penta [2,1-b; 3,4-b '] two thienones.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999064415A1 (en) * | 1998-06-11 | 1999-12-16 | Pfizer Pharmaceuticals Inc. | Sulfonylbenzene compounds as anti-inflammatory/analgesic agents |
| CN101142217A (en) * | 2005-03-21 | 2008-03-12 | 伊莱利利公司 | Imidazopyridazine compounds |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999064415A1 (en) * | 1998-06-11 | 1999-12-16 | Pfizer Pharmaceuticals Inc. | Sulfonylbenzene compounds as anti-inflammatory/analgesic agents |
| CN101142217A (en) * | 2005-03-21 | 2008-03-12 | 伊莱利利公司 | Imidazopyridazine compounds |
Non-Patent Citations (2)
| Title |
|---|
| NELSON, TODD D. ET AL.: "Cu, Ni, and Pd mediated homocoupling reactions in biaryl syntheses: The Ullmann reaction", 《ORGANIC REACTIONS》 * |
| WEI-CHE YEN ET AL.: "Synthesis and Characteri zation of Low Bandgap Copolymers Based on Indenofluorene and Thiophene Derivative", 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》 * |
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Application publication date: 20100915 |