CN105440050B - A method of preparing the benzothiophene derivative with charge transport properties - Google Patents
A method of preparing the benzothiophene derivative with charge transport properties Download PDFInfo
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- CN105440050B CN105440050B CN201410340494.8A CN201410340494A CN105440050B CN 105440050 B CN105440050 B CN 105440050B CN 201410340494 A CN201410340494 A CN 201410340494A CN 105440050 B CN105440050 B CN 105440050B
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- 0 CC(C*)c(cc12)ccc1[s]c1c2[s]c2c1cccc2 Chemical compound CC(C*)c(cc12)ccc1[s]c1c2[s]c2c1cccc2 0.000 description 1
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Abstract
The present invention provides a kind of methods of the compound of formula I.The method of the present invention is divided into two steps：Using o-chlorobenzaldehyde as initial feed synthetic intermediate；Laggard single step reaction is simply purified to intermediate obtains the compound of formula I.The preparation method is easy to operate, yield stable, process efficient environmental protection.The final product impurity of preparation is few, and purity is high, can be used for the charge transport materials of OFETs.
Description
Technical field
The invention belongs to organic field effect tube fields, and in particular to a method of preparing benzothiophene derivative.
Background technology
Organic field effect tube (OFETs, organic field effect transistors) is using pi-conjugated
Organic compound be semi-conducting material, the potential organic photoelectric device of one kind of materials conductive ability is controlled by electric field
Part.In recent years, OFETs achieves great development in the key components of flexible organic opto-electronic device and circuit, and
The charge transport materials to play a crucial role in OFETs devices are with the rigidity and ring of p-type thiophenes especially sulfur heterocyclic ring
Molecule is widely used.Thiophene-based heterocycle has lower highest occupied molecular orbital(HOMO) (HOMO), good conjugacy
And higher thermal stability；Meanwhile it not only contributing to be formed with adjacent sulphur atom and symmetry molecular structure stronger
Intermolecular interaction effectively improves intermolecular charge transmission, and then improves the field effect behavior of material, can also make material
Material molecule is preferably accumulated in the film, is conducive to preparation and the stabilization of OFETs devices.
Simultaneously [3,2-b] [1] benzothiophene (hereinafter referred to as " BTBT ") and its derivative are a kind of functional to benzothiophene
P-type thiophene based charge transport materials, have many advantages, such as high mobility and to the good stability of air, document report
The derivative C8-BTBT mobilities of (J.Am.Chem.Soc., 2007,129,15732-15733) BTBT are up to 1.8cm2V-1S-1,
However existing synthetic method constrains the industrialized production and broader practice of BTBT and its derivative.
BTBT compound structures are as shown in formula I：
In the document patent reported, mostly there is high reaction temperature, post-processing complexity, product in the method for synthesizing BTBT
The problems such as purity is relatively low, yield is relatively low.
The synthetic route for preparing BTBT in the prior art mainly has following five kinds：
(1) using the adjacent halobenzene formaldehyde compounds of formula a as raw material, merely through single step reaction, final product BTBT is synthesized, in document
It is on the books in Tetrahedron Lett., 2011,52,285-288 and JP2010275192A.This method wants synthesis condition
It asks high, needs strict temperature control, and product purity is low, purifying technique is complicated；
(2) it using the acetylene compound of formula b as raw material, is reacted by 2 steps, synthesizes final product BTBT, such as document
Eur.J.Org.Chem., 2011,7331-7338 and J.Heterocyclic Chem., 1981,1729-1750.This method makes
Raw material is difficult to obtain, and on the high side and synthesis technology is complicated, and production cost is higher, is unfavorable for industrialized production；
(3) it is that raw material directly synthesizes final product BTBT by the thione compounds of formula c, such as document Phosphorrus,
Sulfur.and Silicon, 2011,186,2341-2349, Liebigs.Ann.Chem., 1981,1729-1750 and
CN102199142.The organic solvent CS that this method is more demanding to synthesis condition, post-processing is complicated, uses2To operating personnel pole
It is big for harmful and pollution, do not meet environmental requirement；
(4) using the benzyl chloride compound of formula d or benzyl dichloride as Material synthesis final product BTBT, such as document
Collect.Czech.Chem.Commun.,2002,67,645-664and J.Am.Chem.Soc.,2012,134,16548-
16550.The synthesis technology needs up to 250-260 DEG C or so of reaction temperature, and raw material benzyl dichloride is difficult to obtain, and is not easy industry
Metaplasia is produced；Simultaneously using benzyl chloride as the building-up process of raw material in need a large amount of diphenyl ether to make solvent, pollute larger and yield compared with
It is low；
(5) using the benzaldehyde compound of formula e as Material synthesis final product BTBT, such as document JP20080900963.The technique
Though method temperature is down to 220 DEG C, the reaction time is also shorter, needs to use a large amount of toluene in its reaction and last handling process,
Pollution is big, does not meet environmental requirement.
The present invention is on the basis of said synthesis route research, by largely groping, works out new manufacturing technique method,
The relatively inexpensive raw material being easy to get is chosen, simultaneous reactions mild condition is easy to operate, post-processing is simple, reduces organic solvent uses, and produces
Product purity improves, yield increases, production cost substantially reduces.
Invention content
The purpose of the present invention is to provide it is a kind of it is simple to operation, be easily purified, yield is higher and production cost is relatively low
The method for preparing benzothiophene derivative being easily industrialized.
In order to solve the above technical problems, the present invention provides a kind of method preparing the compound BTBT such as Formulas I, reaction route
As follows：
The preparation method specifically includes following two steps：
Using the o-chlorobenzaldehyde of formula II as raw material in organic solvent, formula III is obtained by the reaction with NaHS in step 1
Thioketones intermediary；
Step 2, in the presence of catalyst and organic solvent, the chemical combination of the thioketones intermediary reaction production I of the formula III
Object.
In certain embodiments of the present invention, the organic solvent described in step 1 be selected from by N-Methyl pyrrolidone,
The group of naphthane, n,N-Dimethylformamide and combinations thereof composition, preferably N-Methyl pyrrolidone or N, N- dimethyl formyls
Amine.
In certain embodiments of the present invention, organic solvent described in step 2 is selected from by N-Methyl pyrrolidone, four
The group of hydrogen naphthalene, n,N-Dimethylformamide and combinations thereof composition, preferably naphthane or N-Methyl pyrrolidone.
In certain embodiments of the present invention, catalyst described in step 2 is selected from by palladium catalyst, copper catalyst, iron
The group of catalyst and combinations thereof composition.
In certain embodiments of the present invention, the palladium catalyst is selected from by palladium, palladium bichloride, four triphenylphosphines
The group of palladium, two triphenyl palladium chlorides and combinations thereof composition, preferably palladium.
In certain embodiments of the present invention, the copper catalyst is selected from by copper powder, copper chloride, cuprous iodide, oxidation
The group formed in copper and combinations thereof, preferably copper powder.
In certain embodiments of the present invention, the iron catalyst is selected from by iron powder, ferric trichloride, iron oxide, four oxygen
Change the group of three-iron and combinations thereof composition, preferably iron powder.
Preparation method of the present invention, wherein carried out at a temperature of 80-200 DEG C it is preferred that reacting, it is preferred to react
Condition is：The reaction temperature of step 1 is 80-150 DEG C, and the reaction temperature of step 2 is 120-200 DEG C.
Preparation method of the present invention, wherein reaction time are preferably within the scope of 0.5-10h, preferred reaction condition
For：The reaction time of step 1 is 0.5-3h, and the reaction time of step 2 is 3-10h.
Compared with prior art, the compound of the method formula I has the advantage that through the invention：
It is 1/5th of Similar types of materials o-bromobenzaldehye price, significantly 1. reaction raw materials o-chlorobenzaldehyde is cheap and easily-available
Reduce production cost；
2. reaction condition is mild, reaction temperature is less than 200 DEG C.Synthetic operation is simple, is suitable for industrialized production；
3. product purity is high, yield is good；Compared with existing synthetic method, the BTBT of this method synthesis is without a large amount of organic
Solvent and complicated post-processing can be obtained white solid.
Description of the drawings
Fig. 1 is the nuclear magnetic spectrogram of III compound of formula；
Fig. 2 is the DSC figures of III compound of formula；
Fig. 3 is the nuclear magnetic spectrogram of type I compound；
Fig. 4 is the high-efficient liquid phase chromatogram of type I compound.
Specific implementation mode
Illustrate the present invention below with reference to specific embodiment.It should be noted that the following examples are the present invention
Example, only be used for illustrate the present invention, be not intended to limit the present invention.
Embodiment 1
The preparation of the intermediate of formula III
20ml N-Methyl pyrrolidones are added in 10g o-chlorobenzaldehydes (as shown in formula II) and 11.4g NaHSs
(NMP) it in, is stirred evenly at 80 DEG C, to form a mixed solution.It heats up and maintains the temperature at 120 DEG C, reaction 3h.
After reaction, above-mentioned mixed solution is poured into 50ml ammonium chloride saturated solutions, is extracted with 25ml*3 ethyl acetate,
After the concentration of organic phase rotary evaporation, column chromatography (Rf=0.5) is carried out by eluant, eluent silica gel of petroleum ether, acquired solution utilizes rotation
Evaporimeter is spin-dried for, and obtains the intermediate that carrotiness solid is formula III.Yield：80%.
Embodiment 2
The preparation of the intermediate of formula III
20ml N,N-dimethylformamides are added in 10g o-chlorobenzaldehydes (as shown in formula II) and 11.4g NaHSs
(DMF) it in, is stirred evenly at 80 DEG C, to form a mixed solution.It heats up and maintains the temperature at 120 DEG C, reaction 3h.
After reaction, above-mentioned mixed solution is poured into 50ml ammonium chloride saturated solutions, is extracted with 25ml*3 ethyl acetate,
After the concentration of organic phase rotary evaporation, column chromatography (Rf=0.5) is carried out by eluant, eluent silica gel of petroleum ether, acquired solution utilizes rotation
Evaporimeter is spin-dried for, and obtains the intermediate that carrotiness solid is formula III.Yield：72%.
Embodiment 3
The preparation of the compound of formula I
The intermediate of 10g formulas III is added in 10ml naphthane solvents, 10g iron powders are added as catalyst, are warming up to
170-180 DEG C, keep temperature-resistant reaction 5h.
After reaction, reaction solution is filtered, recycling iron powder.50ml methanol is added in filtrate, white precipitate, mistake is precipitated
Filter, drying is to get to white solid, being the compound of formula I, yield：81%.HPLC detections purity is up to 99.6%.
Embodiment 4
The preparation of the compound of formula I
The intermediate of 10g formulas III is added in 10ml N-Methyl pyrrolidones (NMP), 10g copper powders are added as catalysis
Agent is warming up to 180 DEG C, keeps temperature-resistant, reacts 6h.
After reaction, reaction solution is filtered, recycles copper powder.50ml methanol is added in filtrate, white precipitate, mistake is precipitated
Filter, drying is to get to white solid, being the compound of formula I.Yield：79%.
Embodiment 5
The preparation of the compound of formula I
The intermediate of 10g formulas III is added in 10mlN- methyl pyrrolidones (NMP), 10g palladiums are added as catalysis
Agent is warming up to 170 DEG C, keeps temperature-resistant, reacts 6h.
After reaction, 50ml methanol is added in reaction solution, precipitation, filtering is precipitated.With n-hexane do eluant, eluent silica gel into
Row column chromatography, acquired solution are spin-dried for using Rotary Evaporators, obtain white solid, are the compound of formula I.Yield：82%.
It will be understood by those skilled in the art that above-mentioned reaction condition, is not the unique side for realizing technical solution of the present invention
Formula, those skilled in the art can on the basis of not departing from present inventive concept, according to actual needs to the reaction condition into
Row is changed and realizes technical scheme of the present invention.
Claims (4)
1. a kind of method of the compound of formula I,
It is characterized in that, the preparation method includes：
Step 1, using the o-chlorobenzaldehyde of formula II as raw material,
In organic solvent, the thioketones intermediary of formula III is obtained by the reaction with NaHS
Step 2, in the presence of catalyst and organic solvent, the compound of the thioketones intermediary reaction production I of the formula III,
The wherein described catalyst is selected from the group being made of palladium, copper powder, iron powder and combinations thereof.
2. according to the method described in claim 1, it is characterized in that, the organic solvent is selected from by N-Methyl pyrrolidone, four
The group of hydrogen naphthalene, N,N-dimethylformamide and combinations thereof composition.
3. according to the method described in claim 1, it is characterized in that, the reaction temperature of step 1 be 80-150 DEG C, step 2
Reaction temperature is 120-200 DEG C.
4. according to the method described in claim 1, it is characterized in that, the reaction time of step 1 be 0.5-3h, step 2 it is anti-
It is 3-10h between seasonable.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102199142A (en) * | 2011-03-29 | 2011-09-28 | 浙江工业大学 | Preparation method for 3H-1,2-benzodithiol-3-thione and derivatives thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199142A (en) * | 2011-03-29 | 2011-09-28 | 浙江工业大学 | Preparation method for 3H-1,2-benzodithiol-3-thione and derivatives thereof |
Non-Patent Citations (3)
| Title |
|---|
| A facile synthesis of 3H-benzo[1,2]dithiole-3-thiones and their condensation with active methylene compounds;Hongwei Jin et al.;《Phosphorus, Sulfur and Silicon and the Related Elements》;20111231;第186卷(第12期);第2341-2349页，摘要，第2342-2343页结果与讨论部分 * |
| A New Mode of Formation of Sulfur-Containing Heterocycles;M. G. Voronkov et al.;《Angewandte Chemie》;19690430;第8卷(第4期);第272-273页，第272页倒数第1段至第273页第2段 * |
| Syntheses and structures of novel fused-ring systems containing six or seven sulfur atoms: 2,3:5,6-bis(ethylenedithio)thieno[3,2-b] thiophene and 3,4:6,7-bis(ethylenedithio)thieno[3,2-c][1,2]dithiin;Motoko Tanaka et al.;《Bulletin of the Chemical Society of Japan》;19951231;第68卷(第4期);第1193-1199页，第1193页右栏倒数第2段，1194页Scheme 1 * |
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