CN104045651A - Preparation method of cyclopentyldithiophene with side chain comprising biquaternary ammonium salt group and conjugated polyelectrolyte of cyclopentyldithiophene - Google Patents

Preparation method of cyclopentyldithiophene with side chain comprising biquaternary ammonium salt group and conjugated polyelectrolyte of cyclopentyldithiophene Download PDF

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CN104045651A
CN104045651A CN201410184616.9A CN201410184616A CN104045651A CN 104045651 A CN104045651 A CN 104045651A CN 201410184616 A CN201410184616 A CN 201410184616A CN 104045651 A CN104045651 A CN 104045651A
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thiophene
cyclopentano
reaction
preparation
cyclopentyldithiophene
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CN104045651B (en
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郭文娟
朱祥伟
裴梅山
丁峰
刘俊芝
王小超
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University of Jinan
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/143—Side-chains containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/18—Definition of the polymer structure conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
    • C08G2261/3342—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms derived from cycloolefins containing heteroatoms

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

The present invention relates a preparation method of cyclopentyldithiophene with a side chain comprising a biquaternary ammonium salt group and a conjugated polyelectrolyte of the cyclopentyldithiophene. The preparation method is as follows: using 4H-cyclopentyl [2,1-B: 3,4-B'] dithiophene as a starting material for bromination reaction with dibromopropane, then amino reaction with dimethylamine and then quaternary ammonium salinization reaction with methyl bromide to prepare a water soluble cyclopentyldithiophene derivative, then using ferric chloride to cause the occurrence of polymerization reaction. Product purity is over 96%. The preparation method has the advantages of simple reaction process, easy operation, easily obtained raw materials, low production cost, high product yield, high product purity and the like.

Description

A kind of side chain is containing the preparation method of bi-quaternary ammonium salt group cyclopentano two thiophene and conjugated polyelectrolytes thereof
Technical field
A kind of side chain is containing the preparation method of bi-quaternary ammonium salt group cyclopentano two thiophene and conjugated polyelectrolytes thereof.This synthetic method is with 4H-cyclopentano [2,1-B:3,4-B'] two thiophene are starting raw material, pass through successively and dibromopropane bromination reaction, react with dimethylamine is aminated, and react preparation with the salinization of monobromethane quaternary ammonium and there are good water miscible cyclopentano two thiophene derivant monomers, and cause the polyreaction of this monomer with iron trichloride.
Background technology
Water-Soluble Conjugated Polyelectrolytes, because it is by good water-soluble being combined as a whole of the excellent photoelectric property of traditional conjugated polymers and polyelectrolyte, obtains a large amount of application in the preparation of material for optoelectronic devices of new generation and chemical-biological fluorescent optical sensor at present.This compounds low toxic and environment-friendly, and due to side chain have with hydrophilic and ionic groups good water-soluble, workable in Application Areass such as photoelectric material processing, biological detection, represented than the better practical value of traditional conductive polymers.Current widely used Water-Soluble Conjugated Polyelectrolytes mainly contains poly-fluorenes class, polythiophene class, polyaniline compound etc. by its polymkeric substance conjugated backbone classification, and the synthetic and application of cyclopentano two thiophene-based conjugated polyelectrolytes is still in the blank phase.
Cyclopentano two thiophene and derivatives are a kind of emerging organic photoelectrical materials.Due to the molecule condensed ring symmetrical configuration of this type of organic compound, planarity is good, there is lower energy gap, this compounds, as an analog derivative of thiophene, has represented important using value at aspects such as organic solar batteries, OTFT, Organic Light Emitting Diode and conductive polymerss.
Derivative after cyclopentano two thiophene and the modification thereof of widespread use is at present mainly non-water-soluble, comprise cyclopentano [2,1-B:3,4-B'] two thiophene-4-ketone and analog, cyclopentano [2,1-B:3,4-B'] two thiophene and the analog thereof of 4 upper grafting alkyl group side chains, several compounds, because it is water-soluble poor, have limited such application of photoelectricity compound aspect biological detection above.Water-soluble cyclopentano two thiophene-based conjugated polyelectrolytes are because the plane symmetry of its condensed ring skeleton is good, and conjugated degree is high, can eliminate because main chain rotates the disadvantageous effect of bringing, thereby demonstrated good using value in solution.
Summary of the invention
The object of the invention is synthesizing water-solubility cyclopentano two thiophene monomers 4, two (3-trimethylammonium bromide base the propyl group)-4H-cyclopentanos [2 of 4'-, 1-B:3,4-B'] two thieno-s cause its polymerization, realize preparation and the application of water-soluble cyclopentano two thiophene conjugated polyelectrolytes.
Feature of the present invention is: with 4H-cyclopentano [2,1-B:3,4-B'] two thiophene are starting raw material, through reacting bromination with dibromopropane, aminated after reacting with dimethylamine, and after reacting with monobromethane, quaternary ammonium salinization makes 4, two (3-trimethylammonium bromide base the propyl group)-4H-cyclopentanos [2 of 4'-, 1-B:3,4-B'] two thiophene, and taking iron trichloride as initiator polymerization single polymerization monomer, synthetic subject polymer gathers [two (3-trimethyl ammonium chloride base propyl group)-4H-cyclopentanos [2 of 4,4'-by chemical oxidization method, 1-B:3,4-B'] two thiophene].
The main contents of this synthetic method are described below: 4, two (3-the bromopropyl)-4H-cyclopentanos [2 of 4'-, 1-B:3,4-B'] two thiophene (1) synthetic: using potassiumiodide as catalyzer, 4H-cyclopentano [2 under nitrogen atmosphere, 1-B:3,4-B'] two thiophene, dibromopropane stir substitution reaction occur in the dimethyl sulphoxide solution that contains potassium hydroxide under darkroom.Molar ratio is: 4H-cyclopentano [2,1-B:3,4-B'] two thiophene: dibromopropane: potassium hydroxide: potassiumiodide=1:2.5:5:0.06, and temperature of reaction is 25 DEG C, the reaction times is 12 ~ 14 h, is that developping agent column chromatography obtains faint yellow oily product with normal hexane.
Two (3-dimethylamino-propyl)-4H-cyclopentano [2, the 1-B:3 of 4,4'-, 4-B'] two thiophene (2) synthetic: under nitrogen atmosphere 4, two (3-bromopropyl)-4H-cyclopentano [2,1-B:3,4-B'] two thiophene of 4'-, dimethylamine carry out aminated reaction in methanol solution.Molar ratio is: 4, two (3-the bromopropyl)-4H-cyclopentanos [2 of 4'-, 1-B:3,4-B'] two thiophene: dimethylamine=1:2.3, temperature of reaction is 25 DEG C, reaction times is 48 ~ 72 h, with normal hexane: the solution of ethyl acetate: methyl alcohol: triethylamine=30:6:5:1 is that developping agent column chromatography obtains faint yellow oily product.
4, two (3-trimethylammonium bromide base the propyl group)-4H-cyclopentanos [2 of 4'-, 1-B:3,4-B'] two thiophene (3) synthetic: under nitrogen atmosphere 4, two (3-the dimethylamino-propyl)-4H-cyclopentanos [2 of 4'-, 1-B:3,4-B'] two thiophene, monobromethane carry out quaterisation in acetonitrile solution.Molar ratio is: two (3-dimethylamino-propyl)-4H-cyclopentano [2,1-B:3,4-B'] two thiophene: the monobromethane=1:8 of 4,4'-.Temperature of reaction is 25 DEG C, and the reaction times is 48 ~ 72 h, separates out product as white needles from acetonitrile solution.
Poly-[4; two (3-trimethyl ammonium chloride base the propyl group)-4H-cyclopentanos [2 of 4'-; 1-B:3; 4-B'] two thiophene] (4) synthetic: under nitrogen protection using iron trichloride as initiator in anhydrous chloroform trigger monomer 4; two (3-trimethylammonium bromide base the propyl group)-4H-cyclopentanos [2 of 4'-; 1-B:3,4-B'] two thiophene polymerizations.Molar ratio is: two (3-trimethylammonium bromide base propyl group)-4H-cyclopentano [2,1-B:3,4-B'] two thiophene: the iron trichloride=1:5 of 4,4'-, and temperature of reaction is 5 DEG C, the reaction times is 12 ~ 24 h.Reaction finishes after product and goes doping, carries out ion-exchange with tetrabutylammonium chloride, and Soxhlet extraction obtains atropurpureus powder after removing small molecules.
The present invention compared with prior art, has the following advantages:
(1) synthetic route of the present invention is carried out at normal temperatures, without processing such as heating, has reduced the difficulty of reaction, thereby can improve to a certain extent the yield of target compound, has reduced reaction cost.
(2) the each step reaction in synthetic route is easy to operate, respectively walks the easily separated purification of reactor product and yield high.
(3) in synthetic route of the present invention, raw material used is easy to get, and production cost is low.
Brief description of the drawings
Fig. 1 is the synthetic route chart of poly-[two (3-trimethyl ammonium chloride base propyl group)-4H-cyclopentano [2,1-B:3,4-B'] two thiophene of 4,4'-].
embodiment:
Understand the present invention for ease of further, the following example has been set forth more specific details.
Embodiment 1
Synthesizing of two (3-bromopropyl)-4H-cyclopentano [2,1-B:3,4-B'] two thiophene (1) of 4,4'-
By 0.2g 4H-cyclopentano [2; 1-B:3; 4-B'] potassiumiodide of two thiophene, 0.68g dibromopropane and 6mg is dissolved in the dimethyl sulphoxide solution of 3mL; above mixed solution is slowly dropped to 3mL under nitrogen protection containing in the dimethyl sulphoxide solution of 0.25g potassium hydroxide, by reaction unit stirring reaction 14 hours under darkroom.Add 30mL distilled water cancellation reaction, use dichloromethane solution extraction product, and with saturated nacl aqueous solution cleaning product 2 to 3 times, using separating funnel separatory, get upper strata anhydrous magnesium sulfate drying, filtration for purplish red solution, is that developping agent column chromatography obtains faint yellow oily product 4 with normal hexane after concentrated by rotary evaporation solution, two (3-the bromopropyl)-4H-cyclopentanos [2 of 4'-, 1-B:3,4-B'] two thiophene (534mg, productive rate: 53%).
Synthesizing of two (3-dimethylamino-propyl)-4H-cyclopentano [2,1-B:3,4-B'] two thiophene (2) of 4,4'-
Compound concentration is the dimethylamine methanol solution of 12mol/L, by two 4,4'-(3-bromopropyl)-4H-cyclopentanos [2,1-B:3,4-B'] two thiophene (534mg) revolve boil off desolventize after and vacuum-drying, add 5mL dimethylamine methanol solution, after ultrasonic 30 minutes, under normal temperature, react 24h.After reaction finishes, revolve and steam except desolventizing, add chloroform extraction product, and the sodium hydrogen carbonate solution cleaning product that is 5% with massfraction 2 to 3 times, use separating funnel separatory, get upper strata anhydrous magnesium sulfate drying, filtration for yellow solution, after concentrated by rotary evaporation solution with normal hexane: the solution of ethyl acetate: methyl alcohol: triethylamine=30:6:5:1 is that developping agent column chromatography obtains faint yellow oily product.With isopyknic normal hexane and ethyl acetate solution washed product, dry revolve to steam obtain light yellow product 4, two (3-dimethylamino-propyl)-4H-cyclopentano [2,1-B:3,4-B'] two thiophene (338mg, 76%) of 4'-.
Synthesizing of two (3-trimethylammonium bromide base propyl group)-4H-cyclopentano [2,1-B:3,4-B'] two thiophene (3) of 4,4'-
Compound concentration is the monobromethane acetonitrile solution of 4mol/L, by two 4,4'-(3-dimethylamino-propyl)-4H-cyclopentano [2,1-B:3,4-B'] two thiophene (338 mg) revolve boil off desolventize after and vacuum-drying, add the monobromethane acetonitrile solution of 4mL preparation, under normal temperature, after stirring reaction 24h, in solution, separate out white, needle-shaped crystals, after revolving and boiling off and desolventize, with normal hexane cleaning product 3 times, dry filter obtains white solid product (443 mg, 85%).
Synthesizing of poly-[two (3-trimethyl ammonium chloride base propyl group)-4H-cyclopentano [2,1-B:3,4-B'] two thiophene of 4,4'-] (4)
Monomer 4, two (3-trimethylammonium bromide base the propyl group)-4H-cyclopentanos [2 of 4'-, 1-B:3, 4-B'] ultrasonic being scattered in anhydrous chloroform of two thiophene (400 mg), add rapidly 660mg FERRIC CHLORIDE ANHYDROUS, under nitrogen atmosphere at 5 DEG C of temperature initiated polymerization 24h, after finishing, reaction adds a small amount of methyl alcohol cancellation reaction, reactant is leached, get filter residue and add hydrazine hydrate/dissolve with methanol solution, add tetrabutylammonium chloride to carry out ion-exchange four times to remove bromide anion, remove low-molecular(weight)polymer with acetone/methanol solution soxhlet extraction, finally obtain atropurpureus powder polymer (169mg, 42%).

Claims (6)

1. a side chain is containing the preparation method of bi-quaternary ammonium salt group cyclopentano two thiophene and conjugated polyelectrolytes thereof.
2. this synthetic method is with 4H-cyclopentano [2,1-B:3,4-B'] two thiophene are starting raw material, through reacting bromination with dibromopropane, aminated after reacting with dimethylamine, and quaternary ammonium salinization preparation has cyclopentano two thiophene derivants of good aqueous solubility after reacting with monobromethane, and cause its polymerization with iron trichloride.
3. bromination reaction is using potassiumiodide as catalyzer as described in claim 1, and 4H-cyclopentano under nitrogen atmosphere [2,1-B:3,4-B'] two thiophene, dibromopropane react in the dimethyl sulphoxide solution that contains potassium hydroxide under darkroom.
4. aminated reaction is under nitrogen atmosphere 4 as described in claim 1, and two (3-bromopropyl)-4H-cyclopentano [2,1-B:3,4-B'] two thiophene of 4'-, dimethylamine react in methanol solution.
5. quaternary ammonium salinization reaction is under nitrogen atmosphere 4 as described in claim 2, and two (3-dimethylamino-propyl)-4H-cyclopentano [2,1-B:3,4-B'] two thiophene of 4'-, monobromethane carry out quaterisation in acetonitrile solution.
6. polyreaction is to utilize iron trichloride by the monomer 4 of preparation as described in claim 2, two (3-trimethylammonium bromide base the propyl group)-4H-cyclopentanos [2 of 4'-, 1-B:3,4-B'] two thiophene initiated polymerization in anhydrous chloroform, go doping by product, utilize tetrabutylammonium chloride to carry out ion-exchange, Soxhlet extraction aftertreatment makes.
CN201410184616.9A 2014-05-05 2014-05-05 Preparation method of cyclopentyldithiophene with side chain comprising biquaternary ammonium salt group and conjugated polyelectrolyte of cyclopentyldithiophene Expired - Fee Related CN104045651B (en)

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