CN103130804B - N, N '-dialkyl group-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone-3,4,10,11-imide compound and preparation method thereof and application - Google Patents
N, N '-dialkyl group-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone-3,4,10,11-imide compound and preparation method thereof and application Download PDFInfo
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Abstract
The invention discloses a kind of N, N '-dialkyl group-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone 3,4,10,11-imide (BIPOI) compound and preparation method thereof and application.Structure is such as formula shown in I, and wherein, R and R ' is alkyl or aryl.Present invention also offers the preparation method of formula I.Synthetic route provided by the invention is simple, effective; Raw material is business-like cheap products, and synthesis cost is low; Synthetic method has universality, can promote the use of the synthesis of other BIPOI compounds.The electronic mobility of the OFET prepared for organic semiconductor layer with BIPOI of the present invention and on-off ratio are all higher, and (μ is up to 0.05cm
2/ Vs, on-off ratio is greater than 10
8), in OFET, there is good application prospect.
Description
Technical field
The present invention relates to N, N '-dialkyl group-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone-3,4,10,11-imide compound and preparation method thereof and application.
Background technology
Much there is the molecule of system conjugation because it is at field widespread use (Barbarella, G. such as organic solar, organic field effect tube (OFET) and Organic Light Emitting Diodes; Melucci, M.; Sotgiu, G.Adv.Mater., 2005,17,1581; Katz, H.E.Chem.Mater.2004,16,4748; Sirringhaus, H.; Tessler, N.; Friend, H.R.Science1998,280,1741), people have carried out a large amount of scientific researches to this quasi-molecule.And having in these application, OFET is due to its low cost, and snappiness is good, can the characteristic such as solution method processing, and in Electronic Paper, storer, the fields such as senser element have a good application prospect.
Key components-the organic semiconductor material of OFET is divided into p-type and n-type material by transport-type.Outstanding p-type organic semiconductor material has a lot of bibliographical information (Takimiya, K.; Ebata, H.; Sakamoto, K.; Izawa, T.; Otsubo, T.; Kunugi, Y.J.Am.Chem.Soc., 2006,128,12604; Mas-Torrent, M.; Durkut, M.; Hadley.P.; Ribas, X.; Rovira, C.J.Am.Chem.Soc., 2004,126,984; Bao, Z.; Lovinger, A.J.; Dodabalapur, A.Appl.Phys.Lett., 1996,69,3066).And functional n-type material is also little, (Y.G.WenandY.Q.Liu, Adv.Mater.2010,22,1331-1345 on their primary limitation perylene diimides and naphthoyl imide compounds; R ü digerSchmidt.; MangMangLing.; FrankW ü rthner.Adv.Mater.2007,19,3692-3695; Oh, J.H.; Liu, S.; Bao, Z.; Schmidt, R.; Wu ¨ rthner, F.Appl.Phys.Lett.2007,91,212107).Strong electron-withdrawing group group also introduces in other conjugated systems by researcher, reduces minimum unoccupied molecular orbital(MO) (LUMO) energy level of conjugated molecule system, obtains n-type material of good performance to hope.But this method all has larger synthesis difficulty, and electron-withdrawing group easily causes the distortion of molecular skeleton plane and affects packing of molecules.Have bibliographical information, heteroatomic introducing can affect the electronic structure of compound and solid-state accumulation (Werz, D.B. simultaneously; Gleiter, R.; Rominger, F.J.Am.Chem.Soc.2002,124,10638) and n-type organic semiconductor material can build (Ando, S. based on having electron-withdrawing heterocyclic system; Nishida, J.; Tada, H.; Inoue, Y.; Tokito, S.; Yamashita, Y.J.Am.Chem.Soc.2005,127,5336; Naraso; Nishida, J.; Kumaki, D.; Tokito, S.; Yamashita, Y.J.Am.Chem.Soc.2006,128,9598; Wang, Z.; Kim, C.; Facchetti, A.; Marks, T.J.J.Am.Chem.Soc.2007,129,13362.). therefore synthesize from simple method and there is good planarity, electron-withdrawing and functional heterocyclic conjugated molecule system is significant for the research of n-type OFET.
Summary of the invention
The object of this invention is to provide N, N '-dialkyl group-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone-3,4,10,11-imide compound and preparation method thereof and application.
N, N shown in formula I provided by the invention '-dialkyl group-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone-3,4,10,11-imide compound (being called for short BIPOI), its general structure is such as formula shown in I.
In described formula I, R and R ' be all selected from alkyl and aryl any one.
Preferably, described alkyl is straight chained alkyl, branched-chain alkyl or carbon fluorine alkyl group; Described aryl is phenyl or contains substituent phenyl;
Preferred, the straight chained alkyl of described straight chained alkyl to be the total number of carbon atoms be 1-16, as n-octyl; Described branched-chain alkyl is 2-methyl-propyl, 2-butyl hexyl, 2-hexyl octyl group, 2-octyl-decyl, 2-hexyl decyl, 2-octyldodecyl or 2-decyl dodecyl; Described carbon fluorine alkyl group is 2,2,3,3,4,4,4-seven fluorine butyl or 2,2,3,3,3-five fluoropropyl;
Described containing in substituent phenyl, described substituting group is selected from least one in aniline, benzylamine and p-trifluoromethylaniline, preferred benzylamine.
The method of compound shown in the described formula I of preparation provided by the invention, comprise the steps: the alkyl of N-shown in formula VI-4,5-imide-1, N-alkyl-4 shown in 8-naphthalene acid anhydride compound and described formula V, 5-bis-amido-1,8 naphthalimide compounds mix and carry out condensation dehydration reaction in solvent, obtain compound shown in described formula I;
In described formula V and formula VI, R and R ' be all selected from alkyl and aryl any one.
Preferably, in described formula V and formula VI, described alkyl is straight chained alkyl, branched-chain alkyl or carbon fluorine alkyl group; Described aryl is phenyl or contains substituent phenyl; Wherein, described straight chained alkyl is preferably the straight chained alkyl that the total number of carbon atoms is 1-16, as n-octyl; Described branched-chain alkyl is preferably 2-methyl-propyl, 2-butyl hexyl, 2-hexyl octyl group, 2-octyl-decyl, 2-hexyl decyl, 2-octyldodecyl or 2-decyl dodecyl; Described carbon fluorine alkyl group is 2,2,3,3,4,4,4-seven fluorine butyl or 2,2,3,3,3-five fluoropropyl; Described containing in substituent phenyl, described substituting group is selected from least one in aniline, benzylamine and p-trifluoromethylaniline, preferred benzylamine.
In aforesaid method, the imide-1 of N-alkyl-4,5-shown in described formula VI, the mole dosage ratio that feeds intake of the amido-1,8 of N-alkyl-4,5-bis-shown in 8-naphthalene acid anhydride compound and formula V naphthalimide compound is 1: 1-1.2, specifically can be 1: 1-1.1 or 1: 1.1-1.2, preferably 1: 1; In described condensation dehydration reaction step, temperature is 120-150 DEG C, and specifically can be 120-130 DEG C, 120-140 DEG C, 130-150 DEG C or 140-150 DEG C, preferably 150 DEG C, the time is 8-12 hour, specifically can be 8-10 or 10-12 hour, preferably 12 hours; Described condensation dehydration reaction is carried out in an inert atmosphere; Described inert atmosphere is nitrogen atmosphere; Described solvent is selected from least one in propyl carbinol, n-propyl alcohol and Pentyl alcohol, preferred propyl carbinol.
Present invention also offers compound shown in the intermediate formula V in preparation I compound,
In described formula V, R be selected from alkyl and aryl any one.
Preferably, in described formula V, described alkyl is straight chained alkyl, branched-chain alkyl or carbon fluorine alkyl group; Described aryl is phenyl or contains substituent phenyl; Wherein, described straight chained alkyl is preferably the straight chained alkyl that the total number of carbon atoms is 1-16, as n-octyl; Described branched-chain alkyl is preferably 2-methyl-propyl, 2-butyl hexyl, 2-hexyl octyl group, 2-octyl-decyl, 2-hexyl decyl, 2-octyldodecyl or 2-decyl dodecyl; Described carbon fluorine alkyl group is 2,2,3,3,4,4,4-seven fluorine butyl or 2,2,3,3,3-five fluoropropyl; Described containing in substituent phenyl, described substituting group is selected from least one in aniline, benzylamine and p-trifluoromethylaniline, preferred benzylamine.
Shown in the described formula V of preparation provided by the invention, the method for compound, comprises the steps:
1) oxidizing reaction is carried out in 5-nitro acenaphthene, oxygenant and solvent mixing backflow, react complete and obtain the nitro-1,8 of 4-shown in formula II naphthalene dicarboxylic anhydride;
2) by step 1) 4-nitro-1,8 naphthalene dicarboxylic anhydride shown in gained formula II mixes with nitrating agent and carries out nitration reaction, react complete and obtain 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydrides shown in formula III in reaction solvent;
3) by described step 2) 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydrides shown in gained formula III and alkylamine mix and react, react complete and obtain the alkyl-4,5-of N-shown in formula IV dinitrobenzene-1,8 naphthalimide in solvent;
In described formula IV, R be selected from alkyl and aryl any one;
4) by step 3) N-alkyl-4,5-dinitrobenzene-1,8 naphthalimide, catalyzer and hydrogen shown in gained formula IV carries out reduction reaction in solvent, and react complete and obtain the amido-1,8 of N-alkyl-4,5-bis-shown in described formula V naphthalimide.
The described step 1 of aforesaid method) in, described oxygenant is selected from least one of sodium dichromate 99 and potassium bichromate, preferred sodium dichromate 99; Described solvent is selected from Glacial acetic acid; The molar ratio of described 5-nitro acenaphthene and oxygenant is 1: 4-6, specifically can be 1: 4-5 or 1: 5-6, preferably 1: 5; In described oxidation step, the time is 8-10 hour, specifically can be 8-9 hour or 9-10 hour, preferably 10 hours;
Described step 2) in, described reaction solvent is selected from least one in the vitriol oil and acetic acid, the preferred vitriol oil; The mass percentage concentration of the described vitriol oil is 98%; Described nitrating agent is selected from least one in nitrosonitric acid and concentrated nitric acid, preferred nitrosonitric acid; Described step 1) amount ratio of 4-nitro-1,8 naphthalene dicarboxylic anhydride shown in gained formula II and nitrating agent is 1mmol-17.3mmol: 1mL-8mL, specifically can be 1mmol-3mmol: 1mL-8mL, 3mmol-17.3mmol: 1mL-8mL, preferred 17.3mmol: 8mL; In described mixing step, temperature is 0-40 DEG C, specifically can be 0-20 DEG C or 20-40 DEG C, preferably 0 DEG C; In described nitration reaction step, temperature is 50-70 DEG C, specifically can be 50-60 DEG C or 60-70 DEG C, preferably 70 DEG C, and the time is 1-3 hour, specifically can be 1-2 hour or 2-3 hour, preferably 2 hours;
Described step 3) in described formula V, described alkyl is straight chained alkyl, branched-chain alkyl or carbon fluorine alkyl group; Described aryl is phenyl or contains substituent phenyl; Wherein, described straight chained alkyl is preferably the straight chained alkyl that the total number of carbon atoms is 1-16, as n-octyl; Described branched-chain alkyl is preferably 2-methyl-propyl, 2-butyl hexyl, 2-hexyl octyl group, 2-octyl-decyl, 2-hexyl decyl, 2-octyldodecyl or 2-decyl dodecyl; Described carbon fluorine alkyl group is 2,2,3,3,4,4,4-seven fluorine butyl or 2,2,3,3,3-five fluoropropyl; Described containing in substituent phenyl, described substituting group is selected from least one in aniline, benzylamine and p-trifluoromethylaniline, preferred benzylamine; Described solvent is selected from anhydrous N, N '-dimethyl methane amide, N, at least one in N '-dimethyl ethanamide, preferred anhydrous N, N '-dimethyl methane amide; Described alkylamine is selected from least one in n-octyl amine, 2-hexyl decyl amine, normal hexyl Amine and 2-hexyl amino dodecane, at least one in preferred n-octyl amine and 2-hexyl decyl amine; Described step 2) amount ratio of 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydrides shown in gained formula III and alkylamine is 2-4mmol: 1-1.5mL, specifically can be 2-3.47mmol: 1-1.5mL or 3.47-4mmol: 1-1.5mL, preferred 3.47mmol: 1-1.5mL; In described reactions steps, temperature is 100-120 DEG C, specifically can be 100-110 DEG C or 110-120 DEG C, preferably 120 DEG C, and the time is 8-12 hour, specifically can be 8-10 hour or 10-12 hour, preferably 12 hours;
Described step 4) in, described catalyzer is the mass percent can purchasing available palladium from open commercial sources is the palladium-carbon catalyst of 10%, wherein; Described solvent is selected from least one in dehydrated alcohol, methyl alcohol and propyl alcohol, preferred dehydrated alcohol; Described step 3) mass ratio of N-alkyl-4,5-dinitrobenzene-1,8 naphthalimide shown in gained formula IV and catalyzer is 1: 0.05-0.1, preferably 1: 0.1; In described reduction reaction step, temperature is 20-40 DEG C, specifically can be 20-30 DEG C or 30-40 DEG C, preferably 20 DEG C, time is 5-9 hour, specifically can be 5-7 hour or 7-9 hour, preferably 9 hours, pressure is 1-2atm, specifically can be 1-1.5atm or 1.5-2atm, preferred 2atm.
Present invention also offers the naphthalene acid anhydride of N-alkyl-4,5-imide-1,8-shown in the intermediate formula VI in preparation I compound compound,
In described formula VI, R ' be selected from alkyl and aryl any one.
Preferably, in described formula VI, described alkyl is straight chained alkyl, branched-chain alkyl or carbon fluorine alkyl group; Described aryl is phenyl or contains substituent phenyl; Wherein, described straight chained alkyl is preferably the straight chained alkyl that the total number of carbon atoms is 1-16, and more preferably the total number of carbon atoms is the straight chained alkyl of 1-7 or the total number of carbon atoms is the straight chained alkyl of 9-16; Described branched-chain alkyl is preferably 2-methyl-propyl, 2-butyl hexyl, 2-hexyl octyl group, 2-octyl-decyl, 2-hexyl decyl, 2-octyldodecyl or 2-decyl dodecyl; Described carbon fluorine alkyl group is 2,2,3,3,4,4,4-seven fluorine butyl or 2,2,3,3,3-five fluoropropyl; Described containing in substituent phenyl, described substituting group is selected from least one in aniline, benzylamine and p-trifluoromethylaniline.
The method of compound shown in preparation formula VI provided by the invention, comprises the steps: Isosorbide-5-Nitrae, and 5,8-naphthalenetetracarbacidic acidic acid anhydride and alkylamine mix and react in solvent, react complete and obtain compound shown in described formula VI.
In aforesaid method, described alkylamine is selected from least one in 2-hexyl decyl amine, 2-hexyl amino dodecane, preferred 2-hexyl decyl amine; Described solvent is selected from anhydrous N, N '-dimethyl methane amide, N, at least one in N '-dimethyl ethanamide, preferred anhydrous N, N '-dimethyl methane amide; Described Isosorbide-5-Nitrae, the mass ratio of 5,8-naphthalenetetracarbacidic acidic acid anhydride and alkylamine is 2: 0.8-1.2, specifically can be 2: 0.8-1.0 or 2: 1.0-1.2, preferably 2: 0.8; In described reactions steps, temperature is 120-140 DEG C, specifically can be 120-130 DEG C or 130-140 DEG C, preferably 140 DEG C, and the time is 3-7 hour, specifically can be 3-5 hour or 5-7 hour, preferably 5 hours.
Above-mentioned reaction process schematic diagram as shown in Figure 7.
In addition; N shown in the formula I that the invention described above provides; N '-dialkyl group-14H-benzo [4; 5] isoquino [2; 1-a] perimidine-14-ketone-3,4,10; 11-imide compound, at the application prepared in organic field effect tube and the organic field effect tube being organic semiconductor layer with the arbitrary described compound of claim 1-3, also belongs to protection scope of the present invention.
The invention has the advantages that:
1, synthetic route is simple, effective; Raw material is business-like cheap products, and synthesis cost is low; Synthetic method has universality, can promote the use of the synthesis of the BIPOI compound that other various substituting groups replace.
2, the BIPOI compound replaced is linear pi-conjugated molecule, has the two dimensional structure of rigidity.
3, the BIPOI compound replaced has lower lumo energy (-3.85eV), meets the n-type OFET device conditions preparing high mobility.
4. all higher (μ is up to 0.05cm for the mobility (μ) of OFET that the BIPOI replaced with the present invention is prepared for organic semiconductor layer and on-off ratio
2/ Vs, on-off ratio is greater than 10
8), in OFET, there is good application prospect.
Accompanying drawing explanation
Fig. 1 is embodiment 7 compound N, the uv-visible absorption spectra of N '-di-n-octyl-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone-3,4,10,11-imide (BIPOI-DO) solution.
Fig. 2 is the cyclic voltammetry curve of embodiment 7 compd B IPOI-DO.
Fig. 3 is the thermal gravimetric analysis curve of embodiment 7 compd B IPOI-DO.
Fig. 4 is the differential thermal analysis curve of embodiment 7 compd B IPOI-DO.
Fig. 5 is with the structural representation of the organic field effect tube of the embodiment 7 compd B IPOI-DO employing that is organic layer.
Fig. 6 is with the transfer characteristic curve figure of the embodiment 7 compd B IPOI-DO organic field effect tube that is organic layer.
Fig. 7 is the synthesis flow schematic diagram of compound shown in formula I provided by the invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described reactant all can obtain from open commercial sources if no special instructions.
The diaminostilbene of compound N-n-octyl-4,5-shown in embodiment 1, preparation formula V, 8-naphthalimide
1) synthesis (formula II compound) of 4-nitro-1,8-naphthalene dicarboxylic anhydride
150ml Glacial acetic acid and 44.8g (150mmol) sodium dichromate 99 is added in 250ml there-necked flask, then add 6g (10mmol) 5-nitro acenaphthene in batches, this mixed solution is at return stirring after 10 hours, be cooled to room temperature, pour in 500ml frozen water, separate out yellow solid, suction filtration, filter cake is washed with water to neutrality, dries.Obtain 4-nitro-1,8 naphthalene dicarboxylic anhydride 4.2g.Yield 57%
Structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:243 (M
+).
Nucleus magnetic hydrogen spectrum:
1hNMR (d6-DMSO, 400MHz): δ 8.75 (d, J=8.8Hz, 1H), 8.66 (d, J=7.2Hz, 1H), 8.63 (d, J=8.4Hz, 1H), 8.56 (d, J=8.0Hz, 1H), 8.12 (t, J=8.0Hz, 1H).
Nuclear-magnetism carbon is composed:
13cNMR (d6-DMSO, 100MHz): δ 160.0,159.4,149.5,133.2,131.1,130.6,130.3,129.8,124.3,124.0,122.8,120.0.
As from the foregoing, this product structure is correct, is target product.
2) synthesis (formula III compound) of 4,5-dinitrobenzene-1,8-naphthalene dicarboxylic anhydrides
The 20ml vitriol oil is added, 4.2g (17.3mmol) step 1 in 50ml there-necked flask) prepare the nitro-1,8 of compound 4-shown in gained formula II naphthalene dicarboxylic anhydride, at 0 DEG C, drip nitrosonitric acid 8mL, be warming up to 70 DEG C and stir 2 hours.Reaction solution is chilled to room temperature, and in the frozen water mixed solution of impouring 200ml, filter, filter cake is washed with water to neutrality, dries.Obtain 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydride 2.5g.Yield 51%.This compound dissolution is very poor.
Structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:288 (M
+).
As from the foregoing, this product structure is correct, is target product.
3) synthesis (formula IV compound) of N-n-octyl-4,5-dinitrobenzene-1,8-naphthalimide
Under nitrogen protection, in the there-necked flask of 100ml, add the anhydrous DMF of 50ml, 1g (3.47mmol) step 2) prepare the dinitrobenzene-1,8 of compound 4,5-shown in gained formula III naphthalene dicarboxylic anhydride, 1mL n-octyl amine.120 DEG C of stirrings are spent the night, and after cooling, pour in 200mL water, 150mL dichloromethane extraction, organic phase 100mL saturated nacl aqueous solution washs 5 times, after anhydrous sodium sulfate drying, is spin-dried for methylene dichloride.Column chromatography, with sherwood oil than methylene dichloride=1: 1 (V/V) crosses out product for washing pouring agent, obtains 0.9gN-n-octyl-4,5-dinitrobenzene-1,8-naphthalimide.Yield 64%.
Structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:399 (M
+).
Nucleus magnetic hydrogen spectrum:
1hNMR (CDCl
3, 400MHz): δ 0.88 (t, J=6.6Hz, 3H), 1.28-1.30 (m, 10H), 1.76 (m, 2H), 4.20 (t, J=7.6Hz, 2H), 8.46 (d, J=7.9Hz, 2H), 8.82 (d, J=7.9Hz, 2H).
Nuclear-magnetism carbon is composed:
13cNMR: δ 14.07,22.62,27.03,27.94,29.15,29.22,31.77,41.30,115.64,126.46,129.90,131.67,148.58,161.57.
As from the foregoing, this product structure is correct, is target product.
4) N-n-octyl-4,5-diaminostilbene, the synthesis (formula V compound) of 8-naphthalimide
50mL ethanol is added in 100mL single port bottle, 0.8g step 3) prepare compound N-n-octyl-4 shown in gained formula IV, 5-dinitrobenzene-1,8 naphthalimides, the mass percent of 0.1g palladium is the palladium-carbon catalyst of 10%, drains air in bottle, accesses 2 atmospheric hydrogen balloons, stirred overnight at room temperature, green solution generates.Reacting liquid filtering, after filtrate is spin-dried for, with methylene dichloride than ethyl acetate=10: 1 (V/V) column chromatography goes out product.Obtain N-n-octyl-4,5-bis-amido-1,8-naphthalimide 0.5g.Yield 75%.
Structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:339 (M
+).
Nucleus magnetic hydrogen spectrum:
1hNMR (CDCl
3, 400MHz): δ 0.85 (t, J=6.8Hz, 3H), 1.26-1.40 (m, 10H), 1.68 (m, 2H), 4.11 (t, J=7.6Hz, 2H), 6.77 (d, J=8.0Hz, 2H), 8.37 (d, J=8.0Hz, 2H).
Nuclear-magnetism carbon is composed:
13cNMR: δ 14.09,22.64,27.24,28.21,29.26,29.42,31.84,40.12,111.99,112.10,113.58,132.29,133.62,151.39,164.37.
As from the foregoing, this product structure is correct, is target product.
Compound N shown in embodiment 2, preparation formula V-(2-hexyl) decyl-4,5-diaminostilbene, 8-naphthalimide
1) synthesis (formula II compound) of 4-nitro-1,8-naphthalene dicarboxylic anhydride
150ml Glacial acetic acid and 44.8g (150mmol) sodium dichromate 99 is added in 250ml there-necked flask, then add 6g (30mmol) 5-nitro acenaphthene in batches, this mixed solution is at return stirring after 10 hours, be cooled to room temperature, pour in 500ml frozen water, separate out yellow solid, suction filtration, filter cake is washed with water to neutrality, dries.Obtain 4-nitro-1,8 naphthalene dicarboxylic anhydride 4.2g.Yield 57%
Structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:243 (M
+).
Nucleus magnetic hydrogen spectrum:
1hNMR (d6-DMSO, 400MHz): δ 8.75 (d, J=8.8Hz, 1H), 8.66 (d, J=7.2Hz, 1H), 8.63 (d, J=8.4Hz, 1H), 8.56 (d, J=8.0Hz, 1H), 8.12 (t, J=8.0Hz, 1H).
Nuclear-magnetism carbon is composed:
13cNMR (d6-DMSO, 100MHz): δ 160.0,159.4,149.5,133.2,131.1,130.6,130.3,129.8,124.3,124.0,122.8,120.0.
As from the foregoing, this product structure is correct, is target product.
2) synthesis (formula III compound) of 4,5-dinitrobenzene-1,8-naphthalene dicarboxylic anhydrides
The 20ml vitriol oil is added, 4.2g (17.3mmol) step 1 in 50ml there-necked flask) prepare the nitro-1,8 of compound 4-shown in gained formula II naphthalene dicarboxylic anhydride, at 0 DEG C, drip nitrosonitric acid 8mL, be warming up to 70 DEG C and stir 2 hours.Reaction solution is chilled to room temperature, and in the frozen water mixed solution of impouring 200ml, filter, filter cake is washed with water to neutrality, dries.Obtain 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydride 2.5g.Yield 51%.This compound dissolution is very poor.
Structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:288 (M
+).
As from the foregoing, this product structure is correct, is target product.
3) synthesis (formula IV compound) of N-(2-hexyl) decyl-4,5-dinitrobenzene-1,8-naphthalimide
Under nitrogen protection, in the there-necked flask of 100ml, add the anhydrous DMF of 50ml; 1g (3.47mmol) step 2) prepare the dinitrobenzene-1,8 of compound 4,5-shown in gained formula III naphthalene dicarboxylic anhydride; 1.5mL2-hexyl decyl amine; 120 DEG C of stirrings are spent the night, and after cooling, pour in 200mL water; 150mL dichloromethane extraction; organic phase 100mL saturated nacl aqueous solution washs 5 times, after anhydrous sodium sulfate drying, is spin-dried for methylene dichloride.Column chromatography, with sherwood oil than methylene dichloride=1: 1 (V/V) crosses out product for washing pouring agent, obtains 1.0gN-(2-hexyl) decyl-4,5-dinitrobenzene-1,8 naphthalimide.Yield 58%.
Structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:511 (M
+).
Nucleus magnetic hydrogen spectrum:
1hNMR (CDCl
3, 400MHz): δ 0.86 (m, 6H), 1.24-1.34 (m, 24H), 1.98 (m, 1H), 4.12 (t, J=7.3Hz, 2H), 8.46 (d, J=7.9Hz, 2H), 8.82 (d, J=7.9Hz, 2H).
Nuclear-magnetism carbon is composed:
13cNMR: δ 14.07,14.09,22.62,22.65,26.34,26.37,29.28,29.54,29.66,29.98,31.63,31.81,31.87,36.62,45.29,115.66,126.47,126.62,129.93,131.75,148.61,161.94.
As from the foregoing, this product structure is correct, is target product.
4) N-(2-hexyl) decyl-4,5-diaminostilbene, the synthesis (formula V compound) of 8-naphthalimide
50mL ethanol is added in 100mL single port bottle, 1.0g step 3) prepare the hexyl of compound N-2-shown in gained formula IV decyl-4,5-dinitrobenzene-1,8 naphthalimides, the mass percent of 0.1g palladium is the palladium-carbon catalyst of 10%, drains air in bottle, accesses 2 atmospheric hydrogen balloons, stirred overnight at room temperature, green solution generates.Reacting liquid filtering, after filtrate is spin-dried for, with methylene dichloride than ethyl acetate=10: 1 (V/V) column chromatography goes out product.Obtain N-(2-hexyl) decyl-4,5-bis-amido-1,8 naphthalimide 0.7g.Yield 80%.
Structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:451 (M
+).
Nucleus magnetic hydrogen spectrum:
1hNMR (CDCl
3, 400MHz): δ 0.85 (m, 6H), 1.21-1.40 (m, 24H), 1.97 (m, 1H), 4.06 (t, J=8.7Hz, 2H), 6.79 (d, J=8.0Hz, 2H), 8.37 (d, J=8.0Hz, 2H).
Nuclear-magnetism carbon is composed:
13cNMR: δ 14.09,14.11,22.66,26.61,29.30,29.58,29.78,30.08,31.78,31.82,31.87,31.90,36.61,45.30,112.07,112.21,113.68,132.32,133.68,151.22,164.73.
As from the foregoing, this product structure is correct, is target product.
The synthesis of compound N shown in embodiment 3, preparation formula VI-(2-hexyl) decyl-4,5-imide-1,8-naphthalene acid anhydride
Under nitrogen protection, in 100mL there-necked flask, add 2g1,4,5,8-naphthalenetetracarbacidic acidic acid anhydride, the anhydrous DMF of 50mL, after being warming up to 140 DEG C, drip the DMF solution of 1.8g2-hexyl decyl amine.Rate of addition is slow, within three hours, drips off.Stirring 5 hours is continued in 140 DEG C.Reaction solution is cooled to room temperature, and pour in 200mL water, 150mL dichloromethane extraction, organic phase 100mL saturated nacl aqueous solution washs 5 times.After anhydrous sodium sulfate drying, be spin-dried for.Column chromatography, with sherwood oil than methylene dichloride=1: 1 (V/V), for washing pouring agent, crosses product, obtain 1.4gN-(2-hexyl) decyl-4,5-imide-1,8-naphthalene acid anhydride.Productive rate 36%.
Structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:491 (M
+).
Nucleus magnetic hydrogen spectrum:
1hNMR (CDCl
3, 400MHz): δ 0.83-0.85 (m, 6H), 1.23-1.31 (m, 24H), 1.98 (m, 1H), 4.14 (t, J=7.3Hz, 2H), 8.82 (s, 4H).
Nuclear-magnetism carbon is composed:
13cNMR: δ 14.07,14.10,22.62,22.65,26.37,26.40,29.24,29.54,29.66,29.99,31.63,31.80,31.87,36.62,45.19,122.79,126.89,127.92,128.89,131.29,133.17,158.86,162.57.
As from the foregoing, this product structure is correct, is target product.
N, N shown in embodiment 4, formula I ' synthesis of-di-n-octyl-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone-3,4,10,11-imide (BIPOI-DO)
Under nitrogen protection, in 100mL there-necked flask, add 1g (2.94mmol) embodiment 1 prepare the diaminostilbene of compound N-n-octyl-4,5-shown in gained formula V; 8-naphthalimide; the naphthalene acid anhydride of N-octyl group-4,5-imide-1,8-shown in 1.1g (2.94mmol) formula VI, propyl carbinol 50mL; be heated to 150 DEG C of stirrings and carry out condensation dehydration reaction in 12 hours; be cooled to room temperature, add reaction solution and pour in 250ml sherwood oil, have violet solid to separate out; suction filtration, filter cake column chromatography.With methylene dichloride than ethyl acetate=5: 1 (V/V), for washing pouring agent, crosses product.Obtain 910mg intense violet color solid.Productive rate 50%.
Structural characterization data are as follows:
Mass spectrum: [MALDI (TOF)] m/z:682 (M
+).
Nucleus magnetic hydrogen spectrum:
1hNMR (CDCl
3, 400MHz): δ 0.87 (m, 6H), 1.28-1.43 (m, 20H), 1.75 (m, 4H), 4.20 (m, 4H), 7.65 (d, J=8.3Hz, 1H), 8.63 (d, J=8.3Hz, 2H), 8.80-8.83 (m, 3H), 9.05 (d, J=8.3Hz, 1H), 9.12 (d, J=8.3Hz, 1H).
Nuclear-magnetism carbon is composed:
13cNMR: δ 14.90,23.38,27.86,27.97,28.93,29.79,29.85,29.91,29.98,32.43,41.40,41.50,115.14,119.89,120.38,122.90,122.97,124.45,124.79,125.58,126.23,126.28,126.49,126.62,127.64,127.79,129.19,129.34,131.64,132.50,136.47,143.16,158.48,160.73,160.82,160.90,161.03.
As from the foregoing, this product structure is correct, is target product.
The synthesis of the imide of N-n-octyl-3,4-shown in embodiment 5, formula I-N '-(2-hexyl) Kui Ji-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone (BIPOI-O-2HD)
Under nitrogen protection; in 100mL there-necked flask, add 1g (2.94mmol) embodiment 1 prepare compound N-n-octyl-4 shown in gained formula V; 5-diaminostilbene; 8-naphthalimide; 1.45g (2.94mmol) embodiment 3 prepares compound N shown in gained formula VI-(2-hexyl) decyl-4; 5-imide-1; 8-naphthalene acid anhydride; propyl carbinol 50mL, is heated to 150 DEG C of stirrings and carries out condensation dehydration reaction in 12 hours, be cooled to room temperature; adding reaction solution pours in 250ml sherwood oil; violet solid is had to separate out, suction filtration, filter cake column chromatography.With methylene dichloride than ethyl acetate=5: 1 (V/V), for washing pouring agent, crosses product.Obtain 800mg intense violet color solid.Productive rate 34%.
Structural characterization data are as follows:
Mass spectrum: [MALDI (TOF)] m/z:794 (M
+).
Nucleus magnetic hydrogen spectrum:
1hNMR (CDCl
3, 400MHz): δ 0.86 (m, 9H), 1.28-1.45 (m, 34H), 1.75 (m, 2H), 1.99 (m, 1H), 4.17 (m, 4H), 7.62 (d, J=8.0Hz, 1H), 8.59 (m, 2H), 8.75-8.80 (m, 3H), 9.03 (d, J=10.4Hz, 1H), 9.14 (d, J=10.4Hz, 1H).
Nuclear-magnetism carbon is composed:
13cNMR: δ 14.13,22.68,26.44,26.45,27.23,28.03,29.29,29.34,29.39,29.61,29.75,30.07,31.70,31.88,31.91,36.73,40.61,45.04,115.90,118.46,118.55,118.99,121.35,125.26,125.85,126.53,126.58,126.95,127.68,128.47,129.33,130.78,131.02,132.90,133.43,137.63,142.70,146.90,161.06,162.84,162.93,162.99,163.23.
As from the foregoing, this product structure is correct, is target product.
The synthesis of N, N '-two shown in embodiment 6, formula I (2-hexyl) Kui Ji-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone-3,4,10,11-imide (BIPOI-D2HD)
Under nitrogen protection; in 100mL there-necked flask, add 1g (2.22mmol) embodiment 2 prepare compound N shown in gained formula V-(2-hexyl) decyl-4; 5-bis-amido-1; 8 naphthalimides; 1.1g (2.22mmol) embodiment 3 prepares compound N shown in gained formula VI-(2-hexyl) decyl-4; 5-imide-1; 8 naphthoyl dicarboxylic anhydrides; propyl carbinol 50mL, is heated to 150 DEG C of stirrings and carries out condensation dehydration reaction in 12 hours, be cooled to room temperature; adding reaction solution pours in 250ml sherwood oil; violet solid is had to separate out, suction filtration, filter cake column chromatography.With methylene dichloride than ethyl acetate=5: 1 (V/V), for washing pouring agent, crosses product.Obtain 710mg intense violet color solid.Productive rate 35%.
Structural characterization data are as follows:
Mass spectrum: [MALDI (TOF)] m/z:907 (M
+).
Nucleus magnetic hydrogen spectrum:
1hNMR (CDCl
3, 400MHz): δ 0.84 (m, 12H), 1.24-1.40 (m, 48H), 2.00 (m, 2H), 4.12 (m, 2H), 7.63 (d, J=8.0Hz, 1H), 8.59 (m, 2H), 8.77-8.81 (m, 3H), 9.03 (d, J=10.4Hz, 1H), 9.14 (d, J=10.4Hz, 1H).
Nuclear-magnetism carbon is composed:
13cNMR: δ 14.30,22.69,26.44,26.47,26.54,27.44,29.34,29.58,29.61,29.71,29.74,29.78,30.02,30.07,31.71,31.91,36.66,116.03,118.54,118.80,119.09,126.04,126.74,127.03,127.96,128.69,130.99,131.16,133.07,142.91,161.21,163.13,163.16,163.49,163.78
Embodiment 7, embodiment 4 prepare N shown in gained formula I, N '-di-n-octyl-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone-3,4, the spectral quality of 10,11-imide (BIPOI-DO), electrochemical properties, thermodynamic property and field-effect transistor character
1) spectral quality of compd B IPOI-DO
Fig. 1 is the ultra-violet absorption spectrum of compd B IPOI-DO dichloromethane solution.As shown in Figure 1, the ultraviolet maximum absorption peak position of compd B IPOI-DO in methylene dichloride is about 575nm, and calculating optical band gap is that (optical band gap is according to formula E for 1.77eV
g=1240/ λ calculates, wherein E
gfor optical band gap, λ is the cut off value of ultraviolet absorption curve).
2) electrochemical properties of compd B IPOI-DO
Fig. 2 is the cyclic voltammetry curve of compd B IPOI-DO.Electrolyzer adopts three-electrode system, and platinum is working electrode, and platinum filament is to electrode, and Ag/AgCl is reference electrode, Bu
4nPF
6as supporting electrolyte.The condition of cyclic voltammetric is: sweep limit is 0 ~ 1.5V (vs.Ag/AgCl), and scanning speed is 50mV/s.
Electro-chemical test shows its initial reduction current potential about-0.55V, and LUMO (the minimum non-occupied orbital energy level) energy level calculated thus is-3.85eV, shows that compound is suitable as N-shaped organic effect semiconductor material.
3) thermodynamic property of compd B IPOI-DO
Fig. 3 is the TGA curve of compd B IPOI-DO, and as seen from the figure, compd B IPOI-DO demonstrates excellent thermostability, and decomposition temperature is at about 380 DEG C.This compound of DSC (see Fig. 4) test display has two transformation temperatures, and its fusing point is at about 268 DEG C.
4) the field-effect transistor character of compd B IPOI
Fig. 5 is the structural representation of organic field effect tube, adopts lower electrode arrangement.As shown in the figure, adopt highly doped silicon chip as gate electrode (gateelectrode), the thick silicon-dioxide of 300nm is as insulation layer (dielectriclayer), its surface octadecyl trichlorosilane alkane (OTS) is modified, source electrode S (source) and drain electrode D (drain) all uses gold (Au) as electrode, compd B IPOI in vacuum tightness close to 10
-4under Pa, evaporation is on silicon-dioxide, and the organic layer thickness of evaporation is 30nm.Compound before evaporation all in 10
-4under Pa, to carry out purification once minimum in vacuum-sublimation.
Under condition of nitrogen gas, the electrical property of prepared organic field effect tube (OFET) is at room temperature measured with Keithley4200SCS semi-conductor test instrument.Determine that two key parameters of the performance of OFET are: the mobility (μ) of current carrier and the on-off ratio (I of device
on/ I
off).Mobility refers to: under unit electric field, and (unit is cm to the average drift velocity of current carrier
2/ Vs), it reflects hole or electronics transfer ability in the semiconductors under the electric field.On-off ratio is defined as: under certain grid voltage, and the ratio of the electric current of transistor under "On" state and "Off" state, it reflects the quality of devices switch performance.For a high performance field-effect transistor, its mobility and on-off ratio should be high as much as possible.
Fig. 6 is that prepared field-effect transistor is 25 DEG C at underlayer temperature, transfer characteristic curve when drain-source voltage is 60V.The mobility that can be calculated field-effect transistor by the data in figure is 0.05cm
2/ Vs and on-off ratio are 10
8.
Carrier mobility can be drawn by Equation for Calculating:
I
dS=(W/2L) C
iμ (V
g-V
t)
2(saturation region, V
dS=V
g-V
t)
Wherein, I
dSfor drain current, μ is carrier mobility, V
gfor grid voltage, V
tfor threshold voltage, W is channel width (W=1.4mm), L is channel length (L=0.04mm), C
ifor isolator electric capacity (C
i=7.5 × 10
-9f/cm
2).Utilize (I
dS, sat)
1/2to V
gmapping, and does linear regression, the slope of the tropic thus can extrapolate carrier mobility (μ), try to achieve V by the section of the tropic and axle
t.Mobility can calculate according to the slope of formula from transition curve.I
DS＝(W/2L)C
iμ(V
G-V
T)
2。On-off ratio can be drawn by the ratio of the maxima and minima of figure right side source-drain current.We are with three BIPOI compounds of synthesis for organic layer has prepared a lot of organic field effect tube devices, and in these devices, wherein the highest mobility is 0.05cm
2/ Vs, on-off ratio is greater than 10
8.
The silicon-dioxide that table 1, OTS modify is the performance perameter based on compd B IPOI organic field effect tube of insulation layer
| Compound | Mobility (cm 2/V·s) | On-off ratio | Threshold voltage (volt) |
| BIPOI-DO | 5×10 -2 | 10 8 | 36 |
| BIPOI-O-2HD | 9.4×10 -5 | 5×10 4 | 13 |
| BIPOI-D2HD | 4.6×10 -3 | 10 7 | 17 |
The physicals of table 2, compd B IPOI
All experimental results show, BIPOI compound shown in formula I provided by the invention is excellent organic semiconductor material.Good device performance depends on this material reasonable plane skeleton and solid-state accumulation closely.The present invention is not limited to these reported three materials, changes different substituted radicals and can obtain a series of heterocyclic compound, and the synthetic method that the present invention provides is simple, effective.This relation be-tween structure and properties for research organic semiconductor material is very helpful, can instruct the Design and synthesis of high performance material further.
Claims (10)
1. compd B IPOI-DO, BIPOI-O-2HD or BIPOI-D2HD:
2. prepare the method for compound described in claim 1 for one kind, comprise the steps: the alkyl of N-shown in formula VI-4,5-imide-1, N-alkyl-4 shown in 8 naphthalene acid anhydride compounds and formula V, 5-bis-amido-1,8 naphthalimide compounds mix and carry out condensation dehydration reaction in solvent, obtain described compound;
In described formula V and formula VI, R and R ' be all selected from n-octyl and 2-hexyl decyl any one.
3. method according to claim 2, is characterized in that: the mole dosage ratio that feeds intake of the naphthalimide compound of N-alkyl-4,5-bis-amido-1,8 shown in imide-1, the 8 naphthalene acid anhydride compound of N-alkyl-4,5-shown in described formula VI and formula V is 1:1-1.2; In described condensation dehydration reaction step, temperature is 120-150 DEG C, and the time is 8-12 hour; Described condensation dehydration reaction is carried out in an inert atmosphere; Described inert atmosphere is nitrogen atmosphere; Described solvent is selected from least one in propyl carbinol, n-propyl alcohol and Pentyl alcohol.
4. method according to claim 3, is characterized in that: the mole dosage ratio that feeds intake of the naphthalimide compound of N-alkyl-4,5-bis-amido-1,8 shown in imide-1, the 8 naphthalene acid anhydride compound of N-alkyl-4,5-shown in described formula VI and formula V is 1:1; In described condensation dehydration reaction step, temperature is 150 DEG C, and the time is 12 hours; Described solvent is propyl carbinol.
5. compound shown in formula V,
In described formula V, R be selected from n-octyl and 2-hexyl decyl any one.
6. prepare a method for compound shown in formula V described in claim 5, comprise the steps:
1) oxidizing reaction is carried out in 5-nitro acenaphthene, oxygenant and solvent mixing backflow, react complete and obtain the nitro-1,8 of 4-shown in formula II naphthalene dicarboxylic anhydride;
2) by step 1) 4-nitro-1,8 naphthalene dicarboxylic anhydride shown in gained formula II mixes with nitrating agent and carries out nitration reaction, react complete and obtain 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydrides shown in formula III in reaction solvent;
3) by described step 2) 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydrides shown in gained formula III and alkylamine mix and react, react complete and obtain the alkyl-4,5-of N-shown in formula IV dinitrobenzene-1,8 naphthalimide in solvent;
In described formula IV, R be selected from n-octyl and 2-hexyl decyl any one;
4) by step 3) N-alkyl-4,5-dinitrobenzene-1,8 naphthalimide, catalyzer and hydrogen shown in gained formula IV carries out reduction reaction in solvent, and react complete and obtain the amido-1,8 of N-alkyl-4,5-bis-shown in described formula V naphthalimide.
7. method according to claim 6, is characterized in that: described step 1) in, described oxygenant is selected from least one in sodium dichromate 99 and potassium bichromate; Described solvent is Glacial acetic acid; The molar ratio of described 5-nitro acenaphthene and oxygenant is 1:3-5; In described oxidation step, the time is 8-10 hour;
Described step 2) in, described reaction solvent is selected from least one in the vitriol oil and acetic acid; The mass percentage concentration of the described vitriol oil is 98%; Described nitrating agent is selected from least one in nitrosonitric acid and concentrated nitric acid; Described step 1) amount ratio of 4-nitro-1,8 naphthalene dicarboxylic anhydride shown in gained formula II and nitrating agent is 1mmol-17.3mmol:1mL-8mL; In described mixing step, temperature is 0-40 DEG C; In described nitration reaction step, temperature is 50-70 DEG C, and the time is 1-3 hour;
Described step 3) in, described solvent is selected from anhydrous N, N '-dimethyl methane amide, N, at least one in N '-dimethyl ethanamide; Described alkylamine be selected from n-octyl amine, 2-hexyl decyl amine, at least one; Described step 2) amount ratio of 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydrides shown in gained formula III and alkylamine is 2-4mmol:1mL; In described reactions steps, temperature is 100-120 DEG C, and the time is 8-12 hour;
Described step 4) in, described catalyzer is the mass percent of palladium is the palladium-carbon catalyst of 10%; Described solvent is selected from least one in dehydrated alcohol, methyl alcohol and n-propyl alcohol; Described step 3) mass ratio of N-alkyl-4,5-dinitrobenzene-1,8 naphthalimide shown in gained formula IV and reductive agent is 1:0.05-0.1; In described reduction reaction step, temperature is 20-40 DEG C, and the time is 5-9 hour, and pressure is 1-2atm.
8. method according to claim 7, is characterized in that: described step 1) in, described oxygenant is sodium dichromate 99; The molar ratio of described 5-nitro acenaphthene and oxygenant is 1:5; In described oxidation step, the time is 10 hours;
Described step 2) in, described reaction solvent is the vitriol oil; Described nitrating agent is nitrosonitric acid; Described step 1) amount ratio of 4-nitro-1,8 naphthalene dicarboxylic anhydride shown in gained formula II and nitrating agent is 17.3mmol:8mL; In described mixing step, temperature is 0 DEG C; In described nitration reaction step, temperature is 70 DEG C, and the time is 2 hours;
Described step 3) in, described solvent is anhydrous N, N '-dimethyl methane amide; Described alkylamine is selected from least one in n-octyl amine and 2-hexyl decyl amine; Described step 2) amount ratio of 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydrides shown in gained formula III and alkylamine is 3.47mmol:1-1.5mL; In described reactions steps, temperature is 120 DEG C, and the time is 12 hours;
Described step 4) in, described solvent is dehydrated alcohol; Described step 3) mass ratio of N-alkyl-4,5-dinitrobenzene-1,8 naphthalimide shown in gained formula IV and reductive agent is 1.0:0.1; In described reduction reaction step, temperature is 20 DEG C, and the time is 9 hours, and pressure is 2atm.
9. compound described in claim 1 is preparing the application in organic field effect tube.
10. with the organic field effect tube that compound described in claim 1 is organic semiconductor layer.
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