CN102477045A - Bithiophene quinoid compound, its preparation method, intermediate thereof and its application - Google Patents
Bithiophene quinoid compound, its preparation method, intermediate thereof and its application Download PDFInfo
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Abstract
The invention discloses a bithiophene quinoid compound shown in a formula I, its preparation method, an intermediate thereof and an application of the compound taken as a semiconductor active layer in an organic film field effect transistor. The compound has the characteristics of low LUMO energy level, large conjugated system scope, good flatness, strong self assembly capability and good dissolvability, and is in favor of solution treatment. The prepared organic film field effect transistor device has the advantage of high mobility and strong air stability, wherein R is a n-alkyl of H, C1-C30 or a C3-C30 branched chain alkyl.
Description
Technical field
The present invention relates to one type of thiophthene quinoid compound, its preparation method, midbody and as the application of semiconductor active layer in organic film FET (OTFT).
Background technology
Organic field effect tube (Organic field-effect transistor is called for short OFET) is a kind of active part that utilizes electric field regulation and control organic semiconductor material conductivity, aspect RF identification trade mark and the flexible demonstration wide application prospect is being arranged.With the inorganic field effect transistor; That organic field effect tube has is with low cost, preparation technology is simple, snappiness good, light weight, advantage (Specialissue:Organic Electronics and Optoelectronics such as be easy to carry; Forrest, S.R.; Thompson, M.E.ed.Chem.Rev.2007,107,923-1386; Rogers, J.A.et al.Proc Natl AcadSci USA.2009,106,10875-10876.).
Realize these advantages of organic field effect tube, its core material organic semiconductor must satisfy the performance height, can carry out conditions such as solution processing and air stability be good.Organic semiconductor material can be divided into p-type organic semiconductor material (hole transport) and n-type organic semiconductor material (electric transmission) according to the kind of transmission current carrier.P-type organic semiconductor material development rapidly, a large amount of performances are high, can carry out the good small molecules of solution processing and air-stable and macromolecular material by report (Ong, B.S.et al.Chem.sEur.J.2008,14,4766-4778 in succession; McCulloch, I.et al.Nat.Mater.2006,5,328-333; Gao, P.et al.Adv.Mater.2009,21,213-216; Hamilton, R.et al.Adv.Mater.2009,21,1166-1171; Payne, M.M.et.al.J.Am.Chem.Soc.2005,127,4986-4987; Ebata, H.et al.J.Am.Chem.Soc.2007,129,15732-15733.).And n-type organic semiconductor material development relatively lags behind, and the material that can satisfy above-mentioned condition simultaneously is (Yan, H.et al.Nature 2009,457,679-686 seldom; Gao, X.et al.J.Am.Chem.Soc.2010,132,3697-3699.), although many n-type organic semiconductor material have high mobility, the air stability difference perhaps needs vacuum evaporation.In addition, construct organic p-n junction and logical complement circuit and also need adopt p-type and n-type organic semiconductor material (Meijer, E.J.et al.Nat.Mater.2003,2,678-682 simultaneously; Klauk, H.et al.Nature 2007,445,745-748.).Therefore, the n-type organic semiconductor material that has an excellent over-all properties is quite important for the development of OFET technology.
The substituted quinones of dintrile methylene radical is very strong electron acceptor(EA) and has lower lumo energy, these characteristics make its as n-type organic semiconductor material in the OFET field by broad research.Handa, people such as S. adopt the mode of solution processing to handle the substituted company of dintrile methylene radical three thiophene quinoid compounds, and the FET mobility that makes film reaches 0.16cm
2V
-1S
-1(Handa, S.et al.J.Am.Chem.Soc.2007,129,11684-11685.), yet this film placed for two weeks in air after, its mobility is sharply reduced to 0.01cm
2V
-1S
-1Takimiya etc. have reported compound (the Yuki Suzuki.Et al.J.Am.Chem.Soc.2010 of the quinoid structure of thiophthene TT, DTT and BDT; 132; 10453-10466), the BDT quinoid structural compounds film through solution-treated has high mobility 0.012cm
2V
-1S
-1
Summary of the invention
Technical problem to be solved by this invention is to have overcome that the FET device mobility that n-type organic semiconductor material makes in the prior art is low, the defective of air stability difference; One type of thiophthene quinoid compound, its preparation method, midbody are provided and as the application of semiconductor active layer in organic film FET (OTFT); This compound solution processibility is good, and the OTFT device that makes has very high mobility and air stability.
Therefore, the present invention relates to one type suc as formula the thiophthene quinoid compound shown in the I;
Wherein, R is H, C
1～C
30Positive alkyl or C
3～C
30Branched-chain alkyl.
Wherein, described C
1～C
30Positive alkyl preferable be C
2～C
10Positive alkyl; That better is C
4～C
8Positive alkyl; Best is n-hexyl.
Wherein, described C
3～C
30Branched-chain alkyl preferable be C
10～C
25Branched-chain alkyl; That better is C
15～C
20Branched-chain alkyl; Best is 3-hexyl undecyl.
The invention further relates to the preparation method of formula I compound, it comprises the following step:
(1) compound I I and propane dinitrile negative ion are carried out linked reaction, make compound III;
(2) compound III is carried out oxidizing reaction, get final product;
Wherein, the definition of R group is ditto said.
Wherein, in the step (1), the method for described linked reaction and condition all can be the ordinary method and the condition of this type of reaction of this area.Preferred especially following method of the present invention and condition: in the organic solvent, compound I I is carried out linked reaction with the propane dinitrile negative ion under the catalysis of phosphine part coordinate zeroth order palladium reagent, get final product.
Wherein, described organic solvent can be the conventional solvent of this type of reaction of this area, and preferable is the alkyloxy-ethers kind solvent, and better is glycol dimethyl ether.What described phosphine part coordinate zeroth order palladium reagent was preferable is tetrakis triphenylphosphine palladium (0).What the mol ratio of described phosphine part coordinate zeroth order palladium reagent and compound I I was preferable is 0.01: 1～0.5: 1, and better is 0.2: 1.What the mol ratio of described propane dinitrile negative ion and compound I I was preferable is 2: 1～6: 1, and better is 4: 1.What the temperature of described reaction was preferable is 60～100 ℃, and better is 85 ℃.The time of described reaction is preferable accomplish with detection reaction till.
Wherein, in organic solvent, being reacted by propane dinitrile and highly basic that described propane dinitrile negative ion is preferable makes.Described organic solvent can be the conventional solvent of this type of reaction of this area, and preferable is glycol dimethyl ether.What described highly basic was preferable is active metal hydrogenate, and better is sodium hydride and/or potassium hydride KH.What the mol ratio of described highly basic and propane dinitrile was preferable is 2: 1～4: 1, and better is 2: 1.What the temperature of described reaction was preferable is-20～20 ℃, and better is 0 ℃.
Wherein, in the step (2), the method for described oxidizing reaction and condition all can be the ordinary method and the condition of this type of reaction of this area; Preferred especially following method of the present invention and condition:
Method (1) in organic solvent or under condition of no solvent, with compound III and bromine water reaction, gets final product;
Perhaps, method (2) with compound III and air reaction, gets final product.
Wherein, what the organic solvent described in the method (1) was preferable is the alkyloxy-ethers kind solvent, and better is glycol dimethyl ether.What described bromine water was preferable is saturated bromine water.Br in the described bromine water
2With the mol ratio of compound III preferable be 2: 1～10: 1.What the temperature of described reaction was preferable is 15～35 ℃.The time of described reaction is preferable accomplish with detection reaction till.
Wherein, compound III described in the method (2) and air reaction are preferable comprises following steps: in organic solvent or under condition of no solvent, be positioned over oxidation in the air with compound III is uncovered, get final product.Wherein, what described organic solvent was preferable is the alkyloxy-ethers kind solvent, and better is glycol dimethyl ether.What the temperature of described reaction was preferable is 15～35 ℃.The time of described reaction is preferable accomplish with detection reaction till.
Preferable, compound I can be made by following method: in the organic solvent, compound I I is carried out linked reaction with the propane dinitrile negative ion under the catalysis of phosphine part coordinate zeroth order palladium reagent, again with the gained reaction mixture directly and bromine water carry out oxidizing reaction, get final product; Wherein, what described organic solvent was preferable is the alkyloxy-ethers kind solvent, and better is glycol dimethyl ether, and what described phosphine part coordinate zeroth order palladium reagent was preferable is tetrakis triphenylphosphine palladium (0); What the mol ratio of described phosphine part coordinate zeroth order palladium reagent and compound I I was preferable is 0.01: 1～0.5: 1, and better is 0.2: 1; What the mol ratio of described propane dinitrile negative ion and compound I I was preferable is 2: 1～6: 1, and better is 4: 1; What the temperature of described linked reaction was preferable is 60～100 ℃, and better is 85 ℃; What described bromine water was preferable is saturated bromine water; Br in the described bromine water
2With the mol ratio of compound III preferable be 2: 1～10: 1; What the temperature of described oxidizing reaction was preferable is 15～35 ℃.
Perhaps; Preferable, compound I also can be made by following method: in the organic solvent, compound I I is carried out linked reaction with the propane dinitrile negative ion under the catalysis of phosphine part coordinate zeroth order palladium reagent; Again uncovered being positioned over of gained reaction mixture carried out oxidizing reaction in the air, get final product; Wherein, what described organic solvent was preferable is the alkyloxy-ethers kind solvent, and better is glycol dimethyl ether, and what described phosphine part coordinate zeroth order palladium reagent was preferable is tetrakis triphenylphosphine palladium (0); What the mol ratio of described phosphine part coordinate zeroth order palladium reagent and compound I I was preferable is 0.01: 1～0.5: 1, and better is 0.2: 1; What the mol ratio of described propane dinitrile negative ion and compound I I was preferable is 2: 1～6: 1, and better is 4: 1; What the temperature of described linked reaction was preferable is 60～100 ℃, and better is 85 ℃; What the temperature of described oxidizing reaction was preferable is 15～35 ℃.
Compound I I described in the present invention can be made by following method: compound IV is carried out bromo-reaction, get final product;
Wherein, the definition of R group is ditto said.
Wherein, the method for described bromo-reaction and condition all can be the ordinary method and the condition of this type of reaction of this area, preferred especially following method of the present invention and condition: in the organic solvent, with compound IV and N-bromo-succinimide (NBS) reaction, get final product.
Wherein, what described organic solvent was preferable is the substituted acid amides of N-alkyl, and better is N-Methyl pyrrolidone.What the mol ratio of described N-bromo-succinimide and compound IV was preferable is 2: 1～5: 1, and better is 3: 1.What the temperature of described reaction was preferable is 15～35 ℃.The time of described reaction is preferable accomplish with detection reaction till.
On the basis that meets this area general knowledge, but above-mentioned each preferred feature arbitrary combination among the present invention promptly gets each preferred embodiments of the present invention.
The invention still further relates to midbody compound suc as formula the preparation I compound shown in VIIa, VIa, Va, IVa, IIa, VIb, Vb, IVb, IIb or the III;
Wherein, the definition of R group is ditto said in the compound III.
The invention further relates to suc as formula the thiophthene quinoid compound shown in the I as the application of semiconductor active layer in organic film FET.
Raw material described in the present invention or reagent except that specifying, all commercially available getting.
Positive progressive effect of the present invention is: thiophthene quinoid compound of the present invention have lower lumo energy, conjugated system scope big and have good planarity, the self-assembly ability is strong, solvability good, help solution processing, not only mobility height but also air stability are strong as the organic film FET device of semiconductor active layer preparation with it.
Description of drawings
Fig. 1 is the structural representation of the OTFT device of compound I a preparation.
Fig. 2 is the curve of output of the OTFT device of compound I a preparation.
Fig. 3 is the transition curve of the OTFT device of compound I a preparation.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
Used raw material or reagent is except that specifying among the embodiment, all commercially available getting.
Room temperature described in the embodiment all refers to 15～35 ℃.
But preparing method's reference Mingqian He. of compound IV a, IVb; Feixia, Zhang.J.Org.Chem.2007,72,442-451.
Synthetic (compound I Ia is that R is the compound of 3-hexyl undecyl among the compound I I) of embodiment 1 compound I Ia
5mL N-Methyl pyrrolidone and 2.5mL water join in the 50mL there-necked flask; Stir down; In system, add 0.165g (0.2mmol) compound IV a (compound IV a is that R is the compound of 3-hexyl undecyl in the compound IV) and 0.11g (0.61mmol) NBS successively, stirred overnight under the room temperature.Add 10mL water termination reaction, ethyl acetate extraction (15mL * 2), anhydrous magnesium sulfate drying.Filter concentrating under reduced pressure, purification by silica gel column chromatography (eluent: sherwood oil), obtain 0.13g compound I Ia, productive rate 72%.
Its structure appraising datum is following:
Fusing point: 58～59 ℃;
Nucleus magnetic hydrogen spectrum:
1H NMR (300MHz, CDCl
3): δ 0.88 (t, J=6.0Hz, 12H), 1.27 (br, 50H), 1.61-1.68 (m, 4H), 2.70 (t, J=8.1Hz, 4H);
Nuclear-magnetism carbon spectrum:
13C NMR (100MHz, CDCl
3): δ 10.21,18.77, and 22.34,22.66,25.43,25.74,25.81,26.13,27.67,28.00,29.46,29.48,33.16,104.57,125.73,127.51,131.71,134.95;
Mass spectrum (MALDI-TOF): m/z=888.4 (M
++ H).
Synthetic (compound I Ib is that R is the compound of n-hexyl among the compound I I) of embodiment 2 compound I Ib
Compound method is with embodiment 1.
Productive rate 79%.
Its structure appraising datum is following:
Fusing point: 193～194 ℃;
Nucleus magnetic hydrogen spectrum:
1H NMR (300MHz, CDCl
3): δ 0.89 (t, J=6.9Hz, 6H), 1.30-1.38 (m, 12H), 1.69-1.74 (m, 4H), 2.74 (t, J=7.5Hz, 4H);
MS(EI)：m/z＝578(M
+)；
Ultimate analysis: molecular formula C
22H
26Br
2S
4Theoretical value: C 45.68, H 4.53%; Measured value: C 45.91, H 4.65%.
Synthetic (compound I a is that R is the compound of 3-hexyl undecyl in the compound I) of embodiment 3 compound I a (being called for short CMUT)
The 50mL there-necked flask finds time to irritate nitrogen three times; Add new glycol dimethyl ether and 58mg (2.4mmol) sodium hydride that steams of 15mL; Cryosel is bathed cooling down, adds 79mg (1.2mmol) propane dinitrile, recovers stirring at room half a hour; Add 0.27g (0.3mmol) compound I Ia and 0.069g (0.06mmol) four (triphenyl phosphorus) palladium (0) more successively, reflux three hours.Be chilled to room temperature, add the saturated bromine water of 20mL.Reaction finishes, and filters, and filtrating is used the saturated common salt water washing, concentrating under reduced pressure, purification by silica gel column chromatography (eluent: sherwood oil: methylene dichloride=1: 3 (v/v)), obtain compound I a 0.196g, productive rate 79%.
Its structure appraising datum is following:
Fusing point: 216～217 ℃;
Nucleus magnetic hydrogen spectrum:
1H NMR (300MHz, CDCl
3): δ 0.89 (t, J=6.0Hz, 12H), 1.27 (br, 50H), 1.61-1.66 (m, 4H), 2.91 (t, J=8.7Hz, 4H);
Nuclear-magnetism carbon spectrum:
13C NMR (100MHz.CDCl
3): δ 14.13,22.69, and 22.70,26.51,29.35,29.62,29.67,30.01,31.88,31.91,33.21,33.23,33.42,37.61,70.47,112.70,114.14,134.17,136.41,141.45,159.79,169.08;
Mass spectrum: (MALDI-TOF) m/z=855.6 (M
+);
Ultimate analysis: molecular formula C
28H
36O
4S
4Theoretical value: C 70.21, H 8.25, and N 6.55%; Measured value: C 69.97, H 8.26, and N 6.35%.
Synthetic (compounds ib is that R is the compound of n-hexyl in the compound I) of embodiment 4 compounds ibs (being called for short CMHT)
Compound method is with embodiment 3.
Productive rate: 73%.
The structure appraising datum is following:
Fusing point: 268～267 ℃;
Mass spectrum: (MALDI-TOF) m/z=547.44 (M
++ H);
Ultimate analysis: molecular formula C
28H
26N
4S
4Theoretical value: C 61.50, H 4.79, and N 10.25%; Measured value: C 61.74, H.4.62, N 10.17%.
Synthetic (compound I Ia is that R is the compound of 3-hexyl undecyl among the compound I I) of embodiment 5 compound I Ia
5mL N-Methyl pyrrolidone and 2.5mL water join in the 50mL there-necked flask; Stir down; In system, add 0.165g (0.2mmol) compound IV a (compound IV a is that R is the compound of 3-hexyl undecyl in the compound IV) and 0.07g (0.4mmol) NBS successively, stirred overnight under the room temperature.Add 10mL water termination reaction, ethyl acetate extraction (15mL * 2), anhydrous magnesium sulfate drying.Filter concentrating under reduced pressure, purification by silica gel column chromatography (eluent: sherwood oil), obtain 0.12g compound I Ia, productive rate 67%.
Its structure appraising datum is with embodiment 1.
Synthetic (compound I Ia is that R is the compound of 3-hexyl undecyl among the compound I I) of embodiment 6 compound I Ia
5mL N-Methyl pyrrolidone and 2.5mL water join in the 50mL there-necked flask; Stir down; In system, add 0.165g (0.2mmol) compound IV a (compound IV a is that R is the compound of 3-hexyl undecyl in the compound IV) and 0.18g (1.0mmol) NBS successively, stirred overnight under the room temperature.Add 10mL water termination reaction, ethyl acetate extraction (15mL * 2), anhydrous magnesium sulfate drying.Filter concentrating under reduced pressure, purification by silica gel column chromatography (eluent: sherwood oil), obtain 0.134g compound I Ia, productive rate 74%.
Its structure appraising datum is with embodiment 1.
Synthetic (compound I a is that R is the compound of 3-hexyl undecyl in the compound I) of embodiment 7 compound I a (being called for short CMUT)
The 250mL there-necked flask finds time to irritate nitrogen three times; Add new glycol dimethyl ether and 30mg (1.2mmol) sodium hydride that steams of 15mL, cryosel is bathed cooling down, adds 40mg (0.6mmol) propane dinitrile; Recover stirring at room half a hour; Add 0.27g (0.3mmol) compound I Ia and 0.0035g (0.003mmol) four (triphenyl phosphorus) palladium (0) more successively, be heated to 60 ℃, reacted 5 hours.Be chilled to room temperature, add the saturated bromine water of 100mL.Reaction finishes, and filters, and filtrating is used the saturated common salt water washing, concentrating under reduced pressure, purification by silica gel column chromatography (eluent: sherwood oil: methylene dichloride=1: 3 (v/v)), obtain compound I a 0.189g, productive rate 76%.
Its structure appraising datum is with embodiment 3.
Synthetic (compound I a is that R is the compound of 3-hexyl undecyl in the compound I) of embodiment 8 compound I a (being called for short CMUT)
The 150mL there-necked flask finds time to irritate nitrogen three times; Add new glycol dimethyl ether and 90mg (3.6mmol) sodium hydride that steams of 15mL; Cryosel is bathed cooling down, adds 120mg (1.8mmol) propane dinitrile, recovers stirring at room half a hour; Add 0.27g (0.3mmol) compound I Ia and 0.17g (0.15mmol) four (triphenyl phosphorus) palladium (0) more successively, reflux three hours.Be chilled to room temperature, add the saturated bromine water of 50mL.Reaction finishes, and filters, and filtrating is used the saturated common salt water washing, concentrating under reduced pressure, purification by silica gel column chromatography (eluent: sherwood oil: methylene dichloride=1: 3 (v/v)), obtain compound I a 0.192g, productive rate 77%.
Its structure appraising datum is with embodiment 3.
Synthetic (compound I a is that R is the compound of 3-hexyl undecyl in the compound I) of embodiment 9 compound I a (being called for short CMUT)
The 50mL there-necked flask finds time to irritate nitrogen three times; Add new glycol dimethyl ether and 58mg (2.4mmol) sodium hydride that steams of 15mL; Cryosel is bathed cooling down, adds 79mg (1.2mmol) propane dinitrile, recovers stirring at room half a hour; Add 0.27g (0.3mmol) compound I Ia and 0.069g (0.06mmol) four (triphenyl phosphorus) palladium (0) more successively, reflux three hours.Be chilled to room temperature, uncoveredly be positioned over oxidation in the air.Filter, filtrating is used the saturated common salt water washing, concentrating under reduced pressure, purification by silica gel column chromatography (eluent: sherwood oil: methylene dichloride=1: 3 (v/v)), obtain compound I a 0.184g, productive rate 74%.
Its structure appraising datum is with embodiment 3.
The preparation of embodiment 10 compound IV a (compound IV a is that R is the compound of 3-hexyl undecyl in the compound IV)
The 100ml there-necked flask finds time to irritate nitrogen three times, adds the new THF that steams of 2.25g (5mmol) tetrabromo and two thiophene and 50ml, is chilled to-78 ℃, and (-78 ℃ were stirred two hours down for 11mmol, 2.5M/THF) n-butyllithium solution slowly to drip 4.2ml.Add 2.95g (11mmol) 4-n-hexyl dodecanal fast, recover stirred overnight at room temperature.Add 30ml water termination reaction, ethyl acetate extraction (20ml * 3) merges organic phase, anhydrous sodium sulfate drying.Filter concentrating under reduced pressure, purification by silica gel column chromatography (eluent: sherwood oil: ETHYLE ACETATE=20: 1 (v/v)), separate obtaining compound VI Ia 2.53g (comprising compd A 1.22g and compd B 1.31g), productive rate 69%.Compd A and B are diastereomers, directly are used for step reaction down.
The structure appraising datum of compd A is following:
1H?NMR(300MHz，CDCl
3)：δ0.88(t，J＝6.0Hz，12H)，1.25(br，54H)，1.45(br，2H)，1.81-1.88(m，4H)，5.07(t，J＝6.6Hz，2H)；
MS(MALDI-TOF)：m/z＝817.5(M
+-OH)；
13C?NMR(300MHz，CDCl
3)：δ0.88(t，J＝6.0Hz，12H)，1.25(br，54H)，1.81-1.89(m，4H)，2.50(br，2H)，5.06(t，J＝6.6Hz，2H)；
MS(MALDI-TOF)：m/z＝817.1(M
+-OH)。
In the 100ml there-necked flask, add 2.5g (3mmol) compound VI Ia and 15ml acetone, slowly drip the saturated sulphuric acid soln of 15ml SRM 935a, stirred overnight under the room temperature.After removing acetone under reduced pressure, with ethyl acetate extraction (20ml * 2), organic phase is used saturated aqueous common salt washed twice, anhydrous magnesium sulfate drying.Filter concentrating under reduced pressure, purification by silica gel column chromatography (eluent: sherwood oil: ETHYLE ACETATE=50: 1 (v/v)), separate obtaining compound VI a 1.53g, yield 61%.
Its structure appraising datum is following:
mp：54～55℃；
1H?NMR(300MHz，CDCl
3)：δ0.88(t，J＝6.3Hz，12H)，1.28(br，50H)，1.69-1.76(m，4H)，3.07(t，J＝7.5Hz，4H)；
13C?NMR(100MHz，CDCl
3)：δ13.14，21.71，25.59，25.62，26.83，28.37，28.65，28.74，29.08，29.21，30.94，32.52，36.07，38.09，91.76，105.53，142.29，148.22；
MS(MALDI-TOF)m/z＝830.5(M
+)。
The 50ml there-necked flask finds time to irritate nitrogen three times, adds 1.38g (1.66mmol) compound VI a, 0.92g (6.64mmol) salt of wormwood and 15ml DMF successively, is heated to 60 ℃, drips 0.44g (3.65mmol) ethyl thioglycolate, and 60 ℃ were stirred 48 hours down.Add 30ml water termination reaction, generate a large amount of depositions in the system, filter, must precipitate, use ethyl alcohol recrystallization, obtain compound Va 0.82g, yield 56%.
Its structure appraising datum is following:
mp：102～103℃；
1H?NMR(300MHz，CDCl
3)：δ0.89(t，J＝6.0Hz，12H)，1.28(br，50H)，1.41(t，J＝7.2Hz，6H)，1.65-1.71(m，4H)，3.15(t，J＝8.1Hz，4H)，4.39(q，J＝8.1Hz，4H)：
13C?NMR(100MHz，CDCl
3)：δ13.16，13.4021.73，25.58，25.69，28.41，28.72，28.78，29.12，30.97，32.10，32.45，32.48，36.70，60.13，126.35，132.75，133.60，142.36，143.60，148.20，161.52；
MS(MALDI-TOF)：m/z＝873.7(M
++H)。
In the 50ml there-necked flask, add the tetrabutylammonium iodide of 15ml THF, 3ml methyl alcohol, 1.5ml water, 1.2g Lithium Hydroxide MonoHydrate, 0.82g compound Va and catalytic amount successively, reflux is spent the night.Remove most of organic solvent under reduced pressure, add 10ml water, be acidified to pH=2, have a large amount of solids to separate out, filter, must precipitate, use ethyl alcohol recrystallization, obtain compound IV a 0.75g, yield 99% with Hydrogen chloride.
Its structure appraising datum is following:
mp：301～302℃；
The solvability of compound IV a is relatively poor, can't obtain its NMR data;
MS(MALDI-TOF)：m/z＝817.1(M
++H)。
The preparation of embodiment 11 compound IV b (compound IV b is that R is the compound of n-hexyl in the compound IV)
The 100ml there-necked flask finds time to irritate nitrogen three times; Add the new THF that steams of 2.25g (5mmol) tetrabromo and two thiophene and 50ml, be chilled to-78 ℃, slowly drip 4.2ml (11mmol; 2.5M) n-butyllithium solution;-78 ℃ were stirred two hours down, and disposable adding 1.89g (10mmol) CuI continues to stir two hours down in-23 ℃.Be chilled to-78 ℃, add the positive oenanthyl chloro of 1.49g (10mmol) rapidly, recover room temperature, stirred overnight.Add the 30ml shrend reaction of going out, use ethyl acetate extraction (20ml * 2) again, organic phase is used anhydrous magnesium sulfate drying.Filter, the pressure reducing and steaming solvent, thick product recrystallization in ethanol obtains compound VI b 1.49g, yield 57%.
Its structure appraising datum is following:
mp：160～161℃；
1H?NMR(300MHz，CDCl
3)：δ0.91(t，J＝6.6Hz，6H)，1.29-1.46(m，12H)，1.72-1.82(m，4H)，3.08(t，J＝7.2Hz，4H)；
13C?NMR(100MHz，CDCl
3)：δ14.2，22.6，24.1，29.0，31.7，41.7，106.7，143.3，143.4，193.0；
MS(EI)：m/z＝382(M
+-2C
5H
10)。
The compound method of compound Vb is with compound Va, yield 63%.
Its structure appraising datum is following:
mp：173～174℃；
1H?NMR(300MHz，CDCl
3)：δ0.89(t，J＝6.9Hz，6H)，1.31-1.44(m，18H)，1.71-1.76(m，4H)，3.14(t，J＝7.8Hz，4H)，4.38(q，J＝7.2Hz，4H)；
13C?NMR(100MHz，CDCl
3)：δ14.1，14.3，22.6，29.2，29.3.29.4，31.6，61.1，127.3，133.6，134.5，143.4，144.2，162.5；
MS(EI)：m/z＝564(M
+)。
The compound method of compound IV b is with compound IVa, productive rate 98%.
Its structure appraising datum is following:
mp：320～321℃；
1H?NMR(300MHz，CDCl
3)：δ0.85(t，J＝6.6Hz，6H)，1.26-1.36(m，12H)，1.63-1.70(m，4H)，3.11(t，J＝7.2Hz，4H)，13.38(b，1H)；
MS(MALDI-TOF)：m/z＝509(M
++H)。
Uv absorption spectrum and the electrochemical properties of effect embodiment 1 compound I a
The maximum absorption peak position is about 700nm in the uv absorption spectrum of compound I a, and optical band gap is 1.8eV.The cyclic voltammetry test is carried out on computer-controlled CHI610D electrochemical analyser, adopts three traditional electrode test systems, and platinum electrode is a working electrode, and SCE (SCE) is as reference electrode, and platinum filament is as counter electrode; Sample is dissolved in the methylene dichloride of new steaming, and (volumetric molar concentration is 1 * 10
-3M), Bu
4NPF
6(0.1M) as supporting electrolyte; Sweep velocity is 50mV/s, is reference with the ferrocene, and the energy level of ferrocene is 4.8eV under the vacuum condition.Because of the initial oxidation current potential of the relative SCE reference electrode of ferrocene in the methylene dichloride is 0.4eV, the lumo energy of material can be calculated by the formula of following energy level:
E
LUMO＝-(E
red onset-0.4+4.8)eV≈-(E
red onset+4.4)eV
Electro-chemical test shows their initial reduction potential about 0.1V, and the lumo energy that calculates thus is-4.3eV.
It is the structural representation of the organic film FET (OTFT) of semiconductor layer that Fig. 1 has provided with compound I a.As shown in Figure 1, OTFT preparation of devices method is following among the present invention: compound I a is dissolved in the solution that chlorobenzene is made into 5mg/ml, drops in the SiO that OTS modifies
2(as grid, the thickness of thermooxidizing silicon dioxide insulating layer is 300nm with highly doped silicon substrate, and electric capacity is 10nFcm in the/Si substrate
-2), process organic semiconductor thin film, on this film, to utilize mask plate deposited gold source-drain electrode, thereby make the OTFT device of upper electrode arrangement, the semiconductor channel length of this device is 31 μ m, channel width is 273 μ m.Among the present invention, the electrical property of OTFT device is measured in air, under the room temperature with Keithley 4200 semi-conductor test instruments.
Fig. 2 and Fig. 3 have provided curve of output and the transition curve with an OTFT device of compound I a preparation respectively.The present invention has prepared a plurality of OTFT devices with compound I a as organic semiconductor layer, and the mobility of these devices reaches as high as 0.48cm
2V
-1s
-1, on-off ratio is greater than 10
4, threshold voltage is lower than 30 volts.
Claims (13)
1. one type suc as formula the thiophthene quinoid compound shown in the I;
Wherein, R is H, C
1～C
30Positive alkyl or C
3～C
30Branched-chain alkyl.
2. thiophthene quinoid compound as claimed in claim 1 is characterized in that described C
1～C
30Positive alkyl be C
2～C
10Positive alkyl; Described C
3～C
30Branched-chain alkyl be C
10～C
25Branched-chain alkyl.
3. thiophthene quinoid compound as claimed in claim 2 is characterized in that described C
2～C
10Positive alkyl be C
4～C
8Positive alkyl; Described C
10～C
25Branched-chain alkyl be C
15～C
20Branched-chain alkyl.
4. thiophthene quinoid compound as claimed in claim 3 is characterized in that described C
4～C
8Positive alkyl be n-hexyl; Described C
15～C
20Branched-chain alkyl be 3-hexyl undecyl.
5. like the preparation method of each described formula I compound of claim 1～4, it is characterized in that comprising the following step:
(1) compound I I and propane dinitrile negative ion are carried out linked reaction, make compound III;
(2) compound III is carried out oxidizing reaction, get final product;
Wherein, each is said for the definition of R group such as claim 1～4.
6. preparation method as claimed in claim 5 is characterized in that, the linked reaction described in the step (1) comprises the following step: in the organic solvent, compound I I is reacted with the propane dinitrile negative ion under the catalysis of phosphine part coordinate zeroth order palladium reagent, get final product; Wherein, described organic solvent is the alkyloxy-ethers kind solvent; Described phosphine part coordinate zeroth order palladium reagent is tetrakis triphenylphosphine palladium (0); The mol ratio of described phosphine part coordinate zeroth order palladium reagent and compound I I is 0.01: 1～0.5: 1; The mol ratio of described propane dinitrile negative ion and compound I I is 2: 1～6: 1; The temperature of described reaction is 60～100 ℃; Till the time of described reaction accomplishes with detection reaction.
7. preparation method as claimed in claim 5 is characterized in that, the propane dinitrile negative ion described in the step (1) is reacted in organic solvent by propane dinitrile and highly basic and makes; Wherein, described organic solvent is the alkyloxy-ethers kind solvent; Described highly basic is active metal hydrogenate; The mol ratio of described highly basic and propane dinitrile is 2: 1～4: 1; The temperature of described reaction is-20～20 ℃.
8. preparation method as claimed in claim 5 is characterized in that, the oxidizing reaction described in the step (2) comprises the following step:
Method (1) in organic solvent or under condition of no solvent, with compound III and bromine water reaction, gets final product; Wherein, described organic solvent is the alkyloxy-ethers kind solvent; Described bromine water is saturated bromine water; Br in the described bromine water
2With the mol ratio of compound III be 2: 1～10: 1; The temperature of described reaction is 15～35 ℃; Till the time of described reaction accomplishes with detection reaction;
Perhaps, method (2) with compound III and air reaction, gets final product.
9. preparation method as claimed in claim 5; It is characterized in that; Described compound I is made by following method: in the organic solvent; Compound I I is carried out linked reaction with the propane dinitrile negative ion under the catalysis of phosphine part coordinate zeroth order palladium reagent, again with the gained reaction mixture directly and bromine water carry out oxidizing reaction, get final product; Wherein, described organic solvent is the alkyloxy-ethers kind solvent, and described phosphine part coordinate zeroth order palladium reagent is tetrakis triphenylphosphine palladium (0); The mol ratio of described phosphine part coordinate zeroth order palladium reagent and compound I I is 0.01: 1～0.5: 1; The mol ratio of described propane dinitrile negative ion and compound I I is 2: 1～6: 1; The temperature of described linked reaction is 60～100 ℃; Described bromine water is saturated bromine water; Br in the described bromine water
2With the mol ratio of compound III be 2: 1～10: 1; The temperature of described oxidizing reaction is 15～35 ℃.
10. preparation method as claimed in claim 5 is characterized in that, described formula II compound is made by following method: compound IV is carried out bromo-reaction, get final product;
Wherein, each is said for the definition of R group such as claim 1～4.
11. preparation method as claimed in claim 10 is characterized in that, described formula II compound is made by following method: in the organic solvent, with compound IV and the reaction of N-bromo-succinimide, get final product; Wherein, described organic solvent is the substituted acid amides of N-alkyl; The mol ratio of described N-bromo-succinimide and compound IV is 2: 1～5: 1; The temperature of described reaction is 15～35 ℃; Till the time of described reaction accomplishes with detection reaction.
12. midbody compound suc as formula the preparation I compound shown in VIIa, VIa, Va, IVa, IIa, VIb, Vb, IVb, IIb or the III;
Wherein, in the compound III definition of R group such as claim 1～4 each is said.
13. like each described formula I compound of claim 1～4 as the application of semiconductor active layer in organic film FET.
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