CN102659752B - Tetracene derivative field effect transistor material and preparation method thereof - Google Patents
Tetracene derivative field effect transistor material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a tetracene derivative field effect transistor material and a preparation method thereof. The tetracene derivative field effect transistor material has a general structural formula I, wherein Ar represents aryl, substituted aryl, heterocyclic aryl or substituted heterocyclic aryl and R represents one of alkyl, alkoxy, alkyl sulphanyl and the like. The tetracene derivative field effect transistor material can be synthesized by a Sonogashira coupling reaction and a Bergman cyclization reaction. The tetracene derivative field effect transistor material has high stability and high dissolvability and can improve a mobility ratio of OFETs devices.
Description
Technical field
The present invention relates to a class condensed ring conjugation material, is class tetracene derivative field effect transistor tube material and preparation method thereof specifically.
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Background technology
Organic semiconductor material has that relating to property of structure is strong, solution processable and can processing in advantages such as flexible substrate, becomes the main body of electronic information material of new generation.Research and develop new and effective organic conjugate semiconductor material and will produce wide market outlook in electronic industry.Its neutral line acene class material (Acenes) is especially noticeable.And benzene material being widely used in photovoltaic cell (OPVs) and organic field effect tube (OFETs), in all OFET materials, one dimension or two-dimentional condensed ring (1D/2D Fusedaceneorheteroacene) material has all shown high device mobility.For example, pentacene (Pentacene), rubrene (Rubrene), tetracene (Tetracene) derivative (has exceeded 5 cm Ji perylene diimide (PDI) class material all has high mobility
2/ Vs).Anthony group obtains a large amount of conjugated polyene class materials with practical value, and these materials are mainly p-shaped materials, and n-type conjugated polyene material is still less.Especially air-stable, can solution method control film growth material few, this field also becomes worldwide Research Challenges.
Pentacene is to study at present a class p-type organic semiconductor material the most widely, and it deposits the thin-film device hole mobility of making up to 1.5 cm in the substrate of chemically modified
2/ Vs, but the intrinsic defect of pentacene makes to be restricted in the practical application of its being on the scene effect transistor device.For example: pentacene is insoluble in most of common organic solvents, cause pentacene almost only to prepare OFETs device by the mode of physical vapor deposition; There is lower highest occupied molecular orbital (HOMO) energy level, easily there is oxidation or free radical reaction and cause stability of material reduce; Arrange on the limit (Herringbone) of facing that presents " herringbone like " when condensed state, and the unfavorable dry pi-conjugated track of this mode is overlapping, thereby causes device mobility to be difficult to reach the limit that material itself can reach.Overcoming pentacene system defect has many methods, is included in acene system, to introduce long alkyl chain and improve its solvability, also can in acene system, introduce high electronegative atom or strong electron-withdrawing group group, reduces HOMO energy level, improves stability of molecule.Recently, continue to bring out containing heteroatoms acene analog derivative molecule as the novel of OFETs semiconductor active layer, as 3,4,9,10-perylene diimide (PTCDI) and four thieno-anthracenes, can interact to strengthen molecular interaction to introducing sulphur etc. in polycyclic aromatic hydrocarbons system by Van der Waals force, π rail interaction and S-S containing the heteroatoms of empty d track, make the molecular arrangement under solid-state tightr, thereby obtain the OFETs device of high mobility.The present invention has synthesized a class tetracene derivative field effect transistor tube material cleverly by Sonogashira coupling and Bergman cyclization, and introduce suitable flexible alkyl chains in one dimension member ring systems, improve stability and the solvability of material, obtained the acene material of excellent performance.And use raw material be pyrene, cheap and easy to get, be beneficial to industrialization produce.
Summary of the invention
technical problem:the object of the invention is to develop a class and there is the advantages such as high mobility, stability, film-forming properties, solvability, and prepare easy, with low cost tetracene derivative field effect transistor tube material.
technical scheme:the preparation method of a class tetracene derivative field effect transistor tube material of the present invention, its structure can be represented by logical formula I:
Wherein Ar represents the one in aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl; R is the one in the substituting groups such as alkyl, alkoxyl group, alkylthio.
In formula I general formula, aryl or substituted aryl are the one in benzene, biphenyl, naphthalene, acenaphthene, anthracene, phenanthrene, Bi, perylene, fluorenes, spiral shell fluorenes; Heterocyclic aryl or substituted heterocycle aryl are the one in pyrroles, pyridine, thiophene, carbazole, silicon fluorenes, phosphorus fluorenes, quinoline, isoquinoline 99.9, phthalazines, pyrimidine, pyridazine, pyrazine, thiodiphenylamine, acridine, dihydroketoacridine, phenanthroline, indoles, thiazole, diazole, triazole, benzodiazole or benzothiazole; The substituting group of aryl or heterocyclic aryl is the one in halogen, alkyl, alkoxyl group, amino, hydroxyl, sulfydryl, ester group, boric acid ester group, acyl group, amide group, cyano group, aryloxy, aromatic base or heterocyclic substituent, and the number of substituted aryl or substituted heterocycle aryl is single or multiple.
Preparation method comprises following synthesis step:
1). the compound of Ar representative is dissolved in organic solvent, under the existence of catalyzer, reacts at 20～100 ℃ with halide reagent, and reaction 1h～2d, obtains class halo Ar as the formula (1);
2). halo Ar is dissolved in to organic solvent, adds palladium catalyst, cuprous iodide and trimethylsilyl acetylene, stir 6 h～5 d at 20～135 ℃, obtain the Ar compound that class trimethylsilyl acetylene as the formula (2) replaces;
3). the Ar compound that trimethylsilyl acetylene is replaced is dissolved in organic solvent, adds highly basic, stirs 1～48 h at 50～120 ℃, obtains the Ar compound that a class replaces suc as formula (3) represented class acetylene;
4). pyrene is dissolved in to organic solvent, adds aluminum chloride and halohydrocarbon, carry out Fu-Ke alkylated reaction at 10～50 ℃, reaction 5～12 h, obtain suc as formula (4) represented 2,7-dialkyl group pyrene;
5). 2,7-dialkyl group pyrene is dissolved in to organic solvent, drip halide reagent, carry out substitution reaction at 0～50 ℃, reaction 1 h～2 d, obtain suc as formula (5) represented 2,7-dialkyl group-4,5,9,10-, tetra-halo pyrenes;
6). by 2,7-dialkyl group-4,5,9,10-tetra-halo pyrenes and ethynyl are dissolved in organic solvent for Ar compound, add palladium catalyst and cuprous iodide, and 60～135 ℃ are carried out Sonogashira coupling and Bergman cyclization, reaction 8～24 h, obtain the tetracene derivative field effect transistor tube material as shown in logical formula I;
Step 1) compound of described Ar representative is aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl; Described aryl or substituted aryl are benzene, biphenyl, naphthalene, acenaphthene, anthracene, phenanthrene, Bi, perylene, fluorenes or spiral shell fluorenes; Substituted heterocycle aryl or substituted heterocycle aryl are pyrroles, pyridine, furans, thiophene, carbazole, silicon fluorenes, phosphorus fluorenes, quinoline, isoquinoline 99.9, phthalazines, pyrimidine, pyridazine, pyrazine, thiodiphenylamine, acridine, dihydroketoacridine, phenanthroline, indoles, thiazole, diazole, triazole, benzodiazole or benzothiazole; Described halide reagent is N-bromo-succinimide (NBS), N-chlorosuccinimide (NCS), N-N-iodosuccinimide (NIS), bromine, iodine+Periodic acid, potassiumiodide+Periodic acid etc.; Described organic solvent is methylene dichloride, trichloromethane, tetracol phenixin etc.; X in formula (1)
1the halogen atoms such as Cl, Br, I; Step 2) described palladium catalyst is tetrakis triphenylphosphine palladium, palladium, dichloro two triphenylphosphine palladiums etc.; Described organic solvent is tetrahydrofuran (THF), Diisopropylamine, toluene, benzene etc.; Step 3) described organic solvent is methyl alcohol, ethanol etc.; Described highly basic is potassium hydroxide, sodium hydroxide etc.; Step 4) described halohydrocarbon can be hydrochloric ether, hydrobromic ether and idohydrocarbon.Described organic solvent is methylene dichloride, trichloromethane etc.; In formula (4), R is alkyl, alkoxyl group, alkylthio etc.; Step 5) described halide reagent is N-bromo-succinimide (NBS), N-chlorosuccinimide (NCS), N-N-iodosuccinimide (NIS), bromine, iodine+Periodic acid, potassiumiodide+Periodic acid etc.; Described organic solvent is methylene dichloride, trichloromethane and tetracol phenixin etc.; R in formula (5) is alkyl, alkoxyl group, alkylthio etc.; X
2the halogen atoms such as Cl, Br, I; Step 6) described palladium catalyst is tetrakis triphenylphosphine palladium, palladium, dichloro two triphenylphosphine palladiums etc.; Described organic solvent is tetrahydrofuran (THF), Diisopropylamine, toluene etc.
beneficial effect:compared with prior art, tetracene derivative field effect transistor tube material of the present invention, synthetic by Sonogashira coupling and Bergman cyclization, simple to operate, by product is few, be easy to separate; Employing pyrene is raw material, not only cheap and easy to get, and strengthened pi-conjugated, be conducive to molecular assembly pile up; The introducing of alkyl chain, has improved stability, the solvability of material, thereby obtains the tetracene field effect transistor tube material of excellent performance.
The present invention has obtained a class tetracene derivative field effect transistor tube material, by nucleus magnetic resonance, mass spectrum etc., compound structure is characterized.Then utilize the optical physicss of method to them such as ultraviolet, fluorescence spectrum, cyclic voltammetric, thermogravimetric analysis, electrochemical properties and thermostability are studied.
The advantages such as tetracene derivative of the present invention has good stability, solvability is good, mobility is high, synthesis technique is simple, with low cost are a kind of OFET materials of excellent performance.
Accompanying drawing explanation
Fig. 1. tetracene derivative A-1, B-1, thermogravimetric analysis (DTG) curve of C-1.
Fig. 2. tetracene derivative A-1, B-1, uv-absorbing and the fluorescent emission curve of C-1 in chloroform soln.
Fig. 3. tetracene derivative A-1, B-1, cyclic voltammetric (CV) curve of C-1 in dichloromethane solution.
Embodiment
Following examples are to further illustrate of the present invention, are not limitations of the present invention.
Embodiment 1:
In single necked round bottom flask (250 mL), add pyrene (10 g, 49.5 mmol), aluminum trichloride (anhydrous) (0.65 g, 4.92 mmol) and methylene dichloride (100 mL), nitrogen protection, stirs under room temperature.Then, tertiary butyl chloride (10.05 g, 108.4 mmol) is dissolved in to dichloromethane solution (15 mL), joins slowly in reaction system.After dropwising, continue stirring at room temperature 6 h.With the aluminum chloride in cryosel acid (3 M) neutralization reaction system, dichloromethane extraction, organic phase water, saturated sodium bicarbonate, saturated nacl aqueous solution washing, anhydrous magnesium sulfate drying, concentrated, ethyl alcohol recrystallization obtains 9 g 2,7-di-t-butyl pyrene, productive rate 57.5%.
1H?NMR(400?MHz,?CDCl
3)δ?(ppm)：8.18(s,?4H)，8.02(s,?4H)，1.58(s,?18H).
In two mouthfuls of round-bottomed flasks (250 mL), add 2,7-di-t-butyl pyrene (7.32 g, 20 mmol), iron powder (2.5 g, 44.6 mmol) and chloroform (100 mL), stirring at room temperature.Then drip the chloroform soln (20 mL) of bromine (19.2 g, 120 mmol).Dropwise rear room temperature reaction 1.5 h, add sodium sulfite solution to extract the reaction of going out.Dichloromethane extraction, concentrated, sherwood oil resedimentation obtains 10g 4,5,9,10-tetrabromobisphenol, 7-di-t-butyl pyrene.Productive rate 79.1%.
1H?NMR?(400?MHz,?CDCl
3)δ(ppm):?8.86(s,?4H),?1.62(s,?18H).
In single port bottle (50 mL), add 1-dodecyl thiophene (1.262 g, 5 mmol), I
2(0.544 g, 2.14 mmol), HIO
4(0.137 g, 0.72 mmol) and 80% acetic acid (12 mL).65
oc stirs 8h.Dichloromethane extraction, NaOH and hypo solution washing for organic phase.Concentrated, silica gel chromatographic column separates to obtain the iodo-thiophene of 1 g 1-dodecyl-4-, productive rate 53%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?7.03-7.04(d,?1H),?6.47-6.48(d,?1H),?2.77-2.81(t,?2H),?1.60-1.67(m,?2H),?1.27-1.45(m,?18H),?0.87-0.91(t,?3H).?GC-MS(m/z):?387(M
+).
In two-mouth bottle (50 mL), add Pd (PPh
3)
4(28.99 mg; 0.025 mmol) and CuI(10 mg; 0.025 mmol); nitrogen protection; then iodo-1-dodecyl-4-thiophene (398 mg, 1 mmol) and trimethylsilyl acetylene (120 mg, 1.1 mmol) are dissolved in Diisopropylamine and tetrahydrofuran (THF) mixing solutions (v/v=1/1); splash in reaction system, then continue reaction 8 h.Be cooled to room temperature, filter, concentrated filtrate, silica gel chromatographic column separating-purifying obtains 243 mg 1-dodecyl-4-trimethylsilyl acetylene base thiophene, productive rate 70%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?7.04-7.05(d,?1H),?6.60-6.61(d,?1H),?2.74-2.77(t,?2H),?1.60-1.67(m,?2H),?1.26(s,?18H),?0.86-0.90(t,?3H),?0.23(s,?9H).
In single port bottle (50 mL), add 1-dodecyl-4-trimethylsilyl acetylene base thiophene (1.5 g, 4.5 mmol), KOH(336 mg, 6 mmol) and methyl alcohol (15 mL), 80
ounder C, react 1h, be cooled to room temperature, dichloromethane extraction, concentrated, silica gel chromatographic column separating-purifying obtains 1 g 1-dodecyl-4-thiophene acetylene, productive rate 83.3%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?7.09-7.10(d,?1H),?6.63-6.64(d,?1H),?3.29(s,?1H),?2.75-2.79(t,?2H),?1.62-1.69(m,?2H),?1.27(s,?18H),?0.88-0.91(t,3H).
In two-mouth bottle (50 mL), add 4,5,9,10-tetrabromobisphenol, 7-di-t-butyl pyrene (500 mg, 0.79 mmol), Pd (PPh
3)
4(120 mg, 0.1 mmol) and CuI(20 mg, 0.1 mmol), under nitrogen protection, drip Diisopropylamine and the tetrahydrofuran (THF) mixing solutions (v/v=1/1) of 1-dodecyl-4-thiophene acetylene (1.1 g, 3.9 mmol), after dropwising, 80
oc reacts 8 h.Be cooled to room temperature, filter, concentrated filtrate obtains, and obtains 200 mg tetracene derivative A-1, productive rate 18% through silica gel chromatographic column separating-purifying.
1H?NMR?(400?MHz,?CDCl
3)δ(ppm):?8.85(s,?4H),?8.79(s,?4H),?7.36(d,?4H),?6.80(d,?4H),?2.86-2.90(t,?8H),?1.70-1.78(m,?8H),?1.64(s,?18H),?1.27(s,?72H),?0.86-0.89(t,?12H).
Embodiment 2:
In two-mouth bottle (250 mL), add Pd (PPh
3)
4(1.2 g; 1 mmol) and CuI(189 mg; 1 mmol); under nitrogen protection, drip Isosorbide-5-Nitrae-dimethyl-4-bromobenzene (7.4 g, 40 mmol) and trimethylsilyl acetylene (4.32 mg; 44 mmol) Diisopropylamine and tetrahydrofuran (THF) mixing solutions (150 mL; v/v=1/1), dropwise 80
oc reacts 12 h.Cooling, filter, concentrated filtrate, silica gel chromatography column separating purification obtains 5 g 1,2-dimethyl-4-trimethylsilyl acetylene base benzene, productive rate 61.9%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?7.26(s,?1H),?7.20-7.22(d,?1H),?7.05-7.07(d,?1H),?2.23-2.25(t,?3H),?0.25(s,?9H).
In single port bottle (500 mL), add 1,2-dimethyl-4-trimethylsilyl acetylene base benzene (5 g, 25 mmol), KOH(6.72 g, 120 mmol) and methyl alcohol (300 mL), 80
oc reacts 1 h, cooling, dichloromethane extraction, and concentrated, silica gel chromatography column separating purification obtains 2.4 g 1,2-dimethyl-4-acetylenylbenzene, productive rate 74.5%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?7.29(s,?1H),?7.23-7.26(d,?1H),?7.08-7.09(d,?1H),?3.02(s,?1H),?2.27(s,?3H),?2.24(s,?3H).
In two-mouth bottle (250 mL), add 4,5,9,10-tetrabromobisphenol, 7-di-t-butyl pyrene (1.264 g, 2 mmol), Pd (PPh
3)
4(240 mg, 0.2 mmol) and CuI(40 mg, 0.2 mmol); under nitrogen protection, drip Diisopropylamine and tetrahydrofuran (THF) mixing solutions (80 mL of 1,2-dimethyl-4-acetylenylbenzene (1.04 g, 8 mmol); v/v=1/1), then 80
oc reacts 8 h.Cooling, filter, concentrated filtrate, silica gel chromatographic column separating-purifying obtains 210 mg tetracene derivative B-1, productive rate 12%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?8.97(s,?4H),?8.80(s,?4H),?7.53-7.54(d,?4H),?7.21-7.23(d,?4H),?2.35(s,?12H),?2.33(s,?12H),?1.66(s,?18H).
Embodiment 3:
In two-mouth bottle (250 mL), add 1,2-bis-octyloxy benzene (6.68 g, 20 mmol) and acetic acid (100 mL), stirring and dissolving, divide and add N-bromo-succinimide (NBS) (3.6 g for six times, 20 mmol), add NBS(0.5 g), room temperature reaction 1 h after at room temperature reacting 1h.After finishing, reaction uses NaHCO
3the aqueous solution regulates PH to neutral, dichloromethane extraction, and concentrated, acetone recrystallization obtains 7 g 1,2-bis-octyloxies-4-bromobenzene, productive rate 84.6%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?6.97-6.99（d,?1H）,?6.97(s,?1H),?6.72-6.74(d,?1H),?3.94-3.96(t,?4H),?1.77-1.82(m,?4H),?1.45(s,?4H),1.28-1.30(d,16H),?0.87-0.88(t,?6H).
In two-mouth bottle (100 mL), add Isosorbide-5-Nitrae-bis-octyloxy-4-bromobenzene (4.13 g, 10 mmol), Pd (PPh
3)
4(300 mg, 0.25 mmol) and CuI(48 mg, 0.25 mmol), under nitrogen protection, drip Diisopropylamine and the tetrahydrofuran (THF) mixing solutions (40 mL, v/v=1/1) of trimethylsilyl acetylene (4.32 mg, 44 mmol), dropwise 80
oc stirs 12 h.Cooling, filter, concentrated filtrate, directly drops into next step reaction without purifying.
In single port flask (250 mL), put into upper step and react the product, the KOH(2.8 g that obtain, 50 mmol) and methyl alcohol (120 mL), stirs and makes it to dissolve, then 80
oc reacts 2 h, cooling, dichloromethane extraction, and concentrated, silica gel chromatographic column separating-purifying obtains 1.25g 1,2-bis-octyloxies-4-acetylenylbenzene, productive rate 35%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?7.05-7.07(d,?1H),?7.00(s,?1H),?6.78-6.80(d,?1H),?3.96-4.00(m,?4H),?2.99(s,?1H),1.78-1.85(m,?4H),1.43-1.48(m,4H),?1.29(s,?16H),?0.87-0.91(t,?6H).
In two-mouth bottle (250mL), add 4,5,9,10-tetrabromobisphenol, 7-di-t-butyl pyrene (550 mg, 0.87 mmol), Pd (PPh
3)
4(150 mg, 0.125 mmol) and CuI(30 mg, 0.15 mmol); under nitrogen protection, drip Diisopropylamine and tetrahydrofuran (THF) mixing solutions (80 mL of 1,2-, bis-octyloxies-4-acetylenylbenzene (1.25 g, 3.49 mmol); v/v=1/1), after dropwising, 80
oc reacts 8 h.Cooling, filter, concentrated filtrate, silica gel chromatographic column separating-purifying obtains 180 mg tetracene derivative C-1, productive rate 11.8%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?8.94(s,?4H),?8.80(s,?4H),?7.33-7.35(d,?4H),?7.26(s,?4H),?6.90-6.93(d,?4H),?4.04-4.07(t,?8H),?3.97-4.00(t,?8H),?1.81-1.88(m,?16H),?1.65(s,?18H),?1.44-1.50(m,?16H),?1.25-1.31(d,?64H),?0.89-0.90(d,?24H).
Embodiment 4:
In two-mouth bottle (250 mL), add Pd (PPh
3)
4(1.2 g, 1 mmol) and CuI(189 mg, 1 mmol); under nitrogen protection, drip Diisopropylamine and tetrahydrofuran (THF) mixing solutions (150 mL of bromobenzene (6.28 g, 40 mmol) and trimethylsilyl acetylene (4.32 mg, 44 mmol); v/v=1/1), dropwise 80
oc reacts 12 h.Cooling, filter, concentrated filtrate, silica gel chromatography column separating purification obtains 4 g trimethylsilyl acetylene base benzene, productive rate 57.5%.
In single port bottle (500 mL), add trimethylsilyl acetylene base benzene (4 g, 23 mmol), KOH(6.72 g, 120 mmol) and methyl alcohol (300 mL), 80
oc reacts 1 h, cooling, dichloromethane extraction, and concentrated, silica gel chromatography column separating purification obtains 1.7 g acetylenylbenzenes, productive rate 74 %.
In two-mouth bottle (250 mL), add 4,5,9,10-tetrabromobisphenol, 7-dimethoxy pyrene (1.156 g, 2 mmol), Pd (PPh
3)
4(240 mg, 0.2 mmol) and CuI(40 mg, 0.2 mmol), under nitrogen protection, drip Diisopropylamine and the tetrahydrofuran (THF) mixing solutions (80 mL, v/v=1/1) of acetylenylbenzene (0.816 g, 8 mmol), then 80
oc reacts 8 h.Cooling, filter, concentrated filtrate, silica gel chromatographic column separating-purifying obtains 200 mg tetracene derivative D-1, productive rate 15%.
Embodiment 5:
In two-mouth bottle (250 mL), add Pd (PPh
3)
4(1.2 g, 1 mmol) and CuI(189 mg, 1 mmol); under nitrogen protection, drip Diisopropylamine and tetrahydrofuran (THF) mixing solutions (150 mL of 2-bromothiophene (6.52 g, 40 mmol) and trimethylsilyl acetylene (4.32 mg, 44 mmol); v/v=1/1), dropwise 80
oc reacts 12 h.Cooling, filter, concentrated filtrate, silica gel chromatography column separating purification obtains 4.4 g 2-trimethylsilyl acetylene base thiophene, productive rate 61.11%.
In single port bottle (500 mL), add 2-trimethylsilyl acetylene base thiophene (4.4 g, 24.44 mmol), KOH(5.6 g, 100 mmol) and methyl alcohol (290 mL), 80
oc reacts 1 h, cooling, dichloromethane extraction, and concentrated, silica gel chromatography column separating purification obtains 2 g 2-thiophene acetylenes, productive rate 75.76 %.
In two-mouth bottle (250 mL), add 4,5,9,10-tetrabromobisphenol, 7-dimethyl sulphur-based pyrene (1.22 g, 2 mmol), Pd (PPh
3)
4(240 mg, 0.2 mmol) and CuI(40 mg, 0.2 mmol), under nitrogen protection, drip Diisopropylamine and the tetrahydrofuran (THF) mixing solutions (80 mL, v/v=1/1) of 2-thiophene acetylene (0.864 g, 8 mmol), then 80
oc reacts 8 h.Cooling, filter, concentrated filtrate, silica gel chromatographic column separating-purifying obtains 190 mg tetracene derivative F-1, productive rate 13.1%.
Claims (9)
1. a class tetracene derivative field effect transistor tube material, is characterized in that this material is the compound of following formula I general formula:
Wherein Ar represents aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl, and the substituting group of described substituted aryl and substituted heterocycle aryl is alkyl or alkoxyl group; R is alkyl;
Described aryl is the one in phenyl, naphthyl, anthryl, phenanthryl; Described heterocyclic aryl is the one in furyl, thienyl.
2. a class tetracene derivative field effect transistor tube material according to claim 1, it is characterized in that in formula I general formula, described aryl is phenyl or naphthyl, and described heterocyclic aryl is thienyl, and the substituting group number of substituted aryl or substituted heterocycle aryl is single or multiple.
3. a preparation method for tetracene derivative field effect transistor tube material as claimed in claim 1, is characterized in that the preparation method of this class material comprises following synthesis step:
X in formula (1)
1cl, Br or I atom; R in formula (4), formula (5) is alkyl; X in formula (5)
2cl, Br, I atom
The compound of a.Ar representative is dissolved in organic solvent, under the existence of catalyzer, reacts at 20～100 ℃ with halide reagent, and reaction 1h～48h, obtains class halo Ar as the formula (1);
B. halo Ar is dissolved in to organic solvent, adds palladium catalyst, cuprous iodide and trimethylsilyl acetylene, stir 6h～5 day at 20～135 ℃, obtain the Ar compound that class trimethylsilyl acetylene as the formula (2) replaces;
C. Ar compound trimethylsilyl acetylene being replaced is dissolved in organic solvent, adds highly basic, stirs 1～48h at 50～120 ℃, obtains the Ar compound that a class replaces suc as formula (3) represented class acetylene;
D. pyrene is dissolved in to organic solvent, adds aluminum chloride and halohydrocarbon, carry out Fu-Ke alkylated reaction at 10～50 ℃, reaction 5～12h, obtain suc as formula (4) represented 2,7-dialkyl group pyrene;
E. 2,7-dialkyl group pyrene is dissolved in to organic solvent, drip halide reagent, carry out substitution reaction at 0～50 ℃, reaction 1h～48h, obtain suc as formula (5) represented 2,7-dialkyl group-4,5,9,10-, tetra-halo pyrenes;
F. by 2,7-dialkyl group-4,5,9, the Ar compound that 10-tetra-halo pyrenes and acetylene replace is dissolved in organic solvent, adds palladium catalyst and cuprous iodide, and 60～135 ℃ are carried out Sonogashira coupling and Bergman cyclization, reaction 8～24h, obtains the tetracene derivative field effect transistor tube material as shown in logical formula I.
4. the preparation method of a class tetracene derivative field effect transistor tube material according to claim 3, is characterized in that described aryl is phenyl or naphthyl, and described heterocyclic aryl is thienyl; Described halide reagent is N-bromo-succinimide (NBS), N-chlorosuccinimide (NCS), N-N-iodosuccinimide (NIS), bromine, iodine+Periodic acid or potassiumiodide+Periodic acid; Described organic solvent is methylene dichloride, trichloromethane or tetracol phenixin.
5. the preparation method of a class tetracene derivative field effect transistor tube material according to claim 3, is characterized in that described in step b that palladium catalyst is tetrakis triphenylphosphine palladium, palladium or dichloro two triphenylphosphine palladiums; Described organic solvent is tetrahydrofuran (THF), Diisopropylamine, toluene or benzene.
6. the preparation method of a class tetracene derivative field effect transistor tube material according to claim 3, is characterized in that described in step c that organic solvent is methyl alcohol or ethanol; Described highly basic is potassium hydroxide or sodium hydroxide.
7. the preparation method of a class tetracene derivative field effect transistor tube material according to claim 3, is characterized in that the halohydrocarbon described in steps d is hydrochloric ether, hydrobromic ether or idohydrocarbon; Described organic solvent is methylene dichloride or trichloromethane.
8. the preparation method of a class tetracene derivative field effect transistor tube material according to claim 3, is characterized in that described in step e that halide reagent is N-bromo-succinimide (NBS), N-chlorosuccinimide (NCS), N-N-iodosuccinimide (NIS), bromine, iodine+Periodic acid or potassiumiodide+Periodic acid; Described organic solvent is methylene dichloride, trichloromethane or tetracol phenixin.
9. the preparation method of a class tetracene derivative field effect transistor tube material according to claim 3, is characterized in that the palladium catalyst described in step f is tetrakis triphenylphosphine palladium, palladium or dichloro two triphenylphosphine palladiums; Described organic solvent is tetrahydrofuran (THF), Diisopropylamine or toluene.
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