CN103130804A - N,N'-dialkyl-14H-benzo[4,5]isoquinolino[2,1-a]perimidine-14-one-3,4,10,11-diimide compound and preparation method and application thereof - Google Patents
N,N'-dialkyl-14H-benzo[4,5]isoquinolino[2,1-a]perimidine-14-one-3,4,10,11-diimide compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a N,N'-dialkyl-14H-benzo[4,5]isoquinolino[2,1-a]perimidine-14-one-3,4,10,11-diimide (BIPOI) compound, and a preparation method and an application thereof. The compound has a structure as shown in formula I, wherein R and R' are alkyls or aryls. The invention also provides a preparation method of the compound in formula I. The synthetic route provided in the invention is simple and effective; raw materials are commercialized cheap products, which realizes low synthesis cost; the synthetic method has universality, and can be popularized and applied to synthesis of other BIPOI compounds. An OFET prepared by using the BIPOI of the invention as an organic semiconductor layer has higher electron mobility and on/off ratio ( the maximum of mu is 0.05 cm2/V.s, and the on/off ratio is larger than 108), and the BIPOI of the invention has good application prospects in OFET.
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
The molecule that much has a system conjugation due to it 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.Science 1998,280, and 1741), people have carried out a large amount of scientific researches to this quasi-molecule.And have in these application, OFET is due to its low cost, and snappiness is good, but the characteristics such as solution method processing, in Electronic Paper, storer, the fields such as senser element have a good application prospect.
Key components-organic semiconductor material of OFET is divided into p-type and n-shaped 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-shaped material also seldom, (Y.G.Wen and Y.Q.Liu, Adv.Mater.2010,22,133 1-1345 on their main Ju Xian Zai perylene diimides and naphthoyl imide compounds; R ü diger Schmidt.; Mang Mang Ling.; Frank W 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).Researcher is also rolled into a ball strong electron-withdrawing group and is introduced in other conjugated systems, reduces minimum unoccupied molecular orbital(MO) (LUMO) energy level of conjugated molecule system, obtains well behaved n-shaped material with prestige.But this method all has larger synthetic difficulty, and electron-withdrawing group easily causes the distortion on molecular skeleton plane and affects packing of molecules.Bibliographical information is arranged, and heteroatomic introducing can affect electronic structure and solid-state accumulation (Werz, the D.B. of compound simultaneously; Gleiter, R.; Rominger, F.J.Am.Chem.Soc.2002,124,10638) and n-type organic semiconductor material can build (Ando, S. based on the heterocyclic system with electrophilic; 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 have good planarity, electrophilic and functional heterocyclic conjugated molecule system are significant for the research of n-type OFET.
Summary of the invention
The purpose 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 shown in formula I provided by the invention, N '-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 suc as formula shown in I.
In described formula I, R and R ' all are selected from any one in alkyl and aryl.
Preferably, described alkyl is straight chained alkyl, branched-chain alkyl or carbon fluorine alkyl group; Described aryl is phenyl or contains substituent phenyl;
Preferred, described straight chained alkyl is that the total number of carbon atoms is the straight chained alkyl of 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-octyl group dodecyl 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 fluoropropyls;
Described containing in substituent phenyl, described substituting group is selected from least a 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: N-alkyl-4 shown in formula VI, 5-imide-1, N-alkyl-4 shown in 8-naphthalene acid anhydride compound and described formula V, 5-two amidos-1,8 naphthalimide compounds mixing in solvent carries out the condensation dehydration reaction, obtains compound shown in described formula I;
In described formula V and formula VI, R and R ' all are selected from any one in alkyl and aryl.
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-octyl group dodecyl 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 fluoropropyls; Described containing in substituent phenyl, described substituting group is selected from least a in aniline, benzylamine and p-trifluoromethylaniline, preferred benzylamine.
In aforesaid method, N-alkyl-4 shown in described formula VI, 5-imide-1, N-alkyl-4 shown in 8-naphthalene acid anhydride compound and formula V, the mole dosage ratio that feeds intake of 5-two amidos-1,8 naphthalimide compound is 1: 1-1.2, specifically can be 1: 1-1.1 or 1: 1.1-1.2, preferred 1: 1; In described condensation dehydration reaction step, temperature is 120-150 ℃, specifically can be 120-130 ℃, 120-140 ℃, 130-150 ℃ or 140-150 ℃, and preferred 150 ℃, the time is 8-12 hour, specifically can be 8-10 or 10-12 hour, preferred 12 hours; Described condensation dehydration reaction is carried out in inert atmosphere; Described inert atmosphere is nitrogen atmosphere; Described solvent is selected from least a in propyl carbinol, n-propyl alcohol and Pentyl alcohol, preferred propyl carbinol.
The present invention also provides compound shown in the intermediate formula V in the preparation I compound,
In described formula V, R is selected from any one in alkyl and aryl.
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-octyl group dodecyl 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 fluoropropyls; Described containing in substituent phenyl, described substituting group is selected from least a in aniline, benzylamine and p-trifluoromethylaniline, preferred benzylamine.
Shown in the described formula V of preparation provided by the invention, the method for compound, comprise the steps:
1) oxidizing reaction is carried out in 5-nitro acenaphthene, oxygenant and the backflow of solvent mixing, react the complete naphthalene of 4-nitro-1,8 shown in the formula II dicarboxylic anhydride that obtains;
2) with step 1) 4-nitro-1,8 naphthalene dicarboxylic anhydride shown in gained formula II carries out nitration reaction with the nitrating agent mixing in reaction solvent, and react complete and obtain shown in formula III 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydride;
3) with described step 2) shown in the gained formula III 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydride and alkylamine mixing in solvent react, and react complete N-alkyl-4 shown in formula IV that obtain, 5-dinitrobenzene-1,8 naphthalimide;
In described formula IV, R is selected from any one in alkyl and aryl;
4) with step 3) N-alkyl-4 shown in gained formula IV, 5-dinitrobenzene-1,8 naphthalimide, catalyzer and hydrogen carry out reduction reaction in solvent, react complete N-alkyl-4 shown in described formula V that obtain, 5-two amidos-1,8 naphthalimide.
The described step 1 of aforesaid method) in, described oxygenant is selected from least a 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, preferred 1: 5; In described oxidation step, the time is 8-10 hour, specifically can be 8-9 hour or 9-10 hour, preferred 10 hours;
Described step 2) in, described reaction solvent is selected from least a 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 a in nitrosonitric acid and concentrated nitric acid, preferred nitrosonitric acid; Described step 1) shown in gained formula II, the amount ratio of 4-nitro-1,8 naphthalene dicarboxylic anhydride 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 ℃, specifically can be 0-20 ℃ or 20-40 ℃, preferred 0 ℃; In described nitration reaction step, temperature is 50-70 ℃, specifically can be 50-60 ℃ or 60-70 ℃, and preferred 70 ℃, the time is 1-3 hour, specifically can be 1-2 hour or 2-3 hour, preferred 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-octyl group dodecyl 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 fluoropropyls; Described containing in substituent phenyl, described substituting group is selected from least a in aniline, benzylamine and p-trifluoromethylaniline, preferred benzylamine; Described solvent is selected from anhydrous N, N '-dimethyl formamide, N, at least a in N '-N,N-DIMETHYLACETAMIDE, preferred anhydrous N, N '-dimethyl formamide; Described alkylamine is selected from least a in n-octyl amine, 2-hexyl decyl amine, normal hexyl Amine and 2-hexyl amino dodecane, at least a in preferred n-octyl amine and 2-hexyl decyl amine; Described step 2) shown in the gained formula III 4, the amount ratio of 5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydride 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 ℃, specifically can be 100-110 ℃ or 110-120 ℃, and preferred 120 ℃, the time is 8-12 hour, specifically can be 8-10 hour or 10-12 hour, preferred 12 hours;
Described step 4) in, described catalyzer is 10% palladium-carbon catalyst for the mass percent that can purchase available palladium from open commercial sources, wherein; Described solvent is selected from least a in dehydrated alcohol, methyl alcohol and propyl alcohol, preferred dehydrated alcohol; Described step 3) N-alkyl-4 shown in gained formula IV, the mass ratio of 5-dinitrobenzene-1,8 naphthalimide and catalyzer is 1: 0.05-0.1, preferred 1: 0.1; In described reduction reaction step, temperature is 20-40 ℃, specifically can be 20-30 ℃ or 30-40 ℃, preferred 20 ℃, time is 5-9 hour, specifically can be 5-7 hour or 7-9 hour, preferred 9 hours, pressure is 1-2atm, specifically can be 1-1.5atm or 1.5-2atm, preferred 2atm.
The present invention also provides N-alkyl-4 shown in the intermediate formula VI in the preparation I compound, 5-imide-1, and 8-naphthalene acid anhydride compound,
In described formula VI, R ' is selected from any one in alkyl and aryl.
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 that straight chained alkyl or the total number of carbon atoms of 1-7 are 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-octyl group dodecyl 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 fluoropropyls; Described containing in substituent phenyl, described substituting group is selected from least a 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 mixing in solvent reacts, and reacts the complete compound shown in described formula VI that obtains.
In aforesaid method, described alkylamine is selected from least a in 2-hexyl decyl amine, 2-hexyl amino dodecane, preferred 2-hexyl decyl amine; Described solvent is selected from anhydrous N, N '-dimethyl formamide, N, at least a in N '-N,N-DIMETHYLACETAMIDE, preferred anhydrous N, N '-dimethyl formamide; Described Isosorbide-5-Nitrae, the mass ratio of 5,8-naphthalenetetracarbacidic acidic acid anhydride and alkylamine are 2: 0.8-1.2 specifically can be 2: 0.8-1.0 or 2: 1.0-1.2, preferred 2: 0.8; In described reactions steps, temperature is 120-140 ℃, specifically can be 120-130 ℃ or 130-140 ℃, and preferred 140 ℃, the time is 3-7 hour, specifically can be 3-5 hour or 5-7 hour, preferred 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; application and the organic field effect tube take claim 1-3 arbitrary described compound as organic semiconductor layer of 11-imide compound in being prepared with field effect transistors 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 synthetic cost is low; Synthetic method has universality, can promote the use of the synthetic of BIPOI compound that other various substituting groups replace.
2, the BIPOI compound that replaces is linear pi-conjugated molecule, has the two dimensional structure of rigidity.
3, the BIPOI compound that replaces has lower lumo energy and (3.85eV), satisfies the n-type OFET device condition of preparation high mobility.
4. all higher (μ is up to 0.05cm to the BIPOI that replaces take the present invention as the mobility (μ) of the OFET of organic semiconductor layer preparation and on-off ratio
2/ Vs, on-off ratio is greater than 10
8), good application prospect is arranged in OFET.
Description of drawings
Fig. 1 is embodiment 7 compound Ns, N '-di-n-octyl-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone-3,4,10, the uv-visible absorption spectra of 11-imide (BIPOI-DO) solution.
Fig. 2 is the cyclic voltammetry curve of embodiment 7 compd B IPOI-DO.
Fig. 3 is the thermogravimetric 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 the structural representation take embodiment 7 compd B IPOI-DO as the organic field effect tube of the employing of organic layer.
Fig. 6 is the transfer characteristic curve figure take embodiment 7 compd B IPOI-DO as the organic field effect tube of organic layer.
Fig. 7 is the synthesis flow schematic diagram of compound shown in formula I provided by the invention.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described reactant all can get from open commercial sources if no special instructions.
Compound N-n-octyl shown in embodiment 1, preparation formula V-4,5-diaminostilbene, 8-naphthalimide
1) 4-nitro-1, synthetic (the formula II compound) of 8-naphthalene dicarboxylic anhydride
Add 150ml Glacial acetic acid and 44.8g (150mmol) sodium dichromate 99 in the 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 the 500ml frozen water, separate out yellow solid, suction filtration, filter cake is washed with water to neutrality, dries.Get 4-nitro-1,8 naphthalene dicarboxylic anhydride 4.2g.Yield 57%
The structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:243 (M
+).
Nucleus magnetic hydrogen spectrum:
1H NMR (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 spectrum:
13C NMR (d6-DMSO, 100MHz): δ 160.0,159.4,149.5,133.2, and 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) 4,5-dinitrobenzene-1, synthetic (the formula III compound) of 8-naphthalene dicarboxylic anhydride
Add the 20ml vitriol oil in the 50ml there-necked flask, 4.2g (17.3mmol) step 1) prepare compound 4-nitro-1,8 naphthalene dicarboxylic anhydride shown in gained formula II, drip nitrosonitric acid 8mL under 0 ℃, be warming up to 70 ℃ and stirred 2 hours.Reaction solution is chilled to room temperature, in the frozen water mixed solution of impouring 200ml, filters, and filter cake is washed with water to neutrality, dries.Get 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydride 2.5g.Yield 51%.This compound dissolution is very poor.
The 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) N-n-octyl-4,5-dinitrobenzene-1, synthetic (the formula IV compound) of 8-naphthalimide
Under nitrogen protection, add the anhydrous DMF of 50ml in the there-necked flask of 100ml, 1g (3.47mmol) step 2) compound 4 shown in preparation gained formula III, 5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydride, 1mL n-octyl amine.120 ℃ of stirrings are spent the night, cooling after, pour in 200mL water, the 150mL dichloromethane extraction, organic phase after anhydrous sodium sulfate drying, is spin-dried for methylene dichloride with 100mL saturated nacl aqueous solution washing 5 times.Column chromatography is crossed out product than methylene dichloride=1: 1 (V/V) for washing the pouring agent with sherwood oil, gets 0.9g N-n-octyl-4,5-dinitrobenzene-1,8-naphthalimide.Yield 64%.
The structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:399 (M
+).
Nucleus magnetic hydrogen spectrum:
1H NMR (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 spectrum:
13C NMR: δ 14.07,22.62,27.03,27.94, and 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, synthetic (the formula V compound) of 8-naphthalimide
Add 50mL ethanol in 100mL single port bottle, 0.8g step 3) compound N-n-octyl-4 shown in preparation gained formula IV, 5-dinitrobenzene-1,8 naphthalimides, 0.1g the mass percent of palladium is 10% palladium-carbon catalyst, drains a bottle interior air, 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=(V/V) column chromatography went out product in 10: 1.Obtain N-n-octyl-4,5-two amidos-1,8-naphthalimide 0.5g.Yield 75%.
The structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:339 (M
+).
Nucleus magnetic hydrogen spectrum:
1H NMR (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 spectrum:
13C NMR: δ 14.09,22.64,27.24,28.21, and 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) 4-nitro-1, synthetic (the formula II compound) of 8-naphthalene dicarboxylic anhydride
Add 150ml Glacial acetic acid and 44.8g (150mmol) sodium dichromate 99 in the 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 the 500ml frozen water, separate out yellow solid, suction filtration, filter cake is washed with water to neutrality, dries.Get 4-nitro-1,8 naphthalene dicarboxylic anhydride 4.2g.Yield 57%
The structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:243 (M
+).
Nucleus magnetic hydrogen spectrum:
1H NMR (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 spectrum:
13C NMR (d6-DMSO, 100MHz): δ 160.0,159.4,149.5,133.2, and 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) 4,5-dinitrobenzene-1, synthetic (the formula III compound) of 8-naphthalene dicarboxylic anhydride
Add the 20ml vitriol oil in the 50ml there-necked flask, 4.2g (17.3mmol) step 1) prepare compound 4-nitro-1,8 naphthalene dicarboxylic anhydride shown in gained formula II, drip nitrosonitric acid 8mL under 0 ℃, be warming up to 70 ℃ and stirred 2 hours.Reaction solution is chilled to room temperature, in the frozen water mixed solution of impouring 200ml, filters, and filter cake is washed with water to neutrality, dries.Get 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydride 2.5g.Yield 51%.This compound dissolution is very poor.
The 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) N-(2-hexyl) decyl-4,5-dinitrobenzene-1, synthetic (the formula IV compound) of 8-naphthalimide
Under nitrogen protection, add the anhydrous DMF of 50ml in the there-necked flask of 100ml; 1g (3.47mmol) step 2) compound 4 shown in preparation gained formula III, 5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydride; 1.5mL 2-hexyl decyl amine; 120 ℃ of stirrings are spent the night, cooling after, pour in 200mL water; the 150mL dichloromethane extraction; organic phase after anhydrous sodium sulfate drying, is spin-dried for methylene dichloride with 100mL saturated nacl aqueous solution washing 5 times.Column chromatography is crossed out product than methylene dichloride=1: 1 (V/V) for washing the pouring agent with sherwood oil, gets 1.0gN-(2-hexyl) decyl-4,5-dinitrobenzene-1,8 naphthalimide.Yield 58%.
The structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:511 (M
+).
Nucleus magnetic hydrogen spectrum:
1H NMR (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 spectrum:
13C NMR: δ 14.07,14.09,22.62,22.65, and 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, synthetic (the formula V compound) of 8-naphthalimide
Add 50mL ethanol in 100mL single port bottle, 1.0g step 3) compound N-2-hexyl decyl-4 shown in preparation gained formula IV, 5-dinitrobenzene-1,8 naphthalimides, 0.1g the mass percent of palladium is 10% palladium-carbon catalyst, drains a bottle interior air, 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=(V/V) column chromatography went out product in 10: 1.Obtain N-(2-hexyl) decyl-4,5-two amidos-1,8 naphthalimide 0.7g.Yield 80%.
The structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:451 (M
+).
Nucleus magnetic hydrogen spectrum:
1H NMR (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 spectrum:
13C NMR: δ 14.09,14.11,22.66,26.61, and 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.
Compound N shown in embodiment 3, preparation formula VI-(2-hexyl) decyl-4,5-imide-1,8-naphthalene acid anhydride synthetic
Under nitrogen protection, add the 2g Isosorbide-5-Nitrae in the 100mL there-necked flask, 5,8-naphthalenetetracarbacidic acidic acid anhydride, the anhydrous DMF of 50mL after being warming up to 140 ℃, drips the DMF solution of 1.8g 2-hexyl decyl amine.Rate of addition is slow, drips off in three hours.Continue to stir 5 hours in 140 ℃.Reaction solution is cooled to room temperature, pours in 200mL water, and the 150mL dichloromethane extraction, organic phase is washed 5 times with the 100mL saturated nacl aqueous solution.After anhydrous sodium sulfate drying, be spin-dried for.Column chromatography, with sherwood oil than methylene dichloride=1: 1 (V/V) for washing the pouring agent, cross product, obtain 1.4g N-(2-hexyl) decyl-4,5-imide-1,8-naphthalene acid anhydride.Productive rate 36%.
The structural characterization data are as follows:
Mass spectrum: [MS (EI)] m/z:491 (M
+).
Nucleus magnetic hydrogen spectrum:
1H NMR (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 spectrum:
13C NMR: δ 14.07,14.10,22.62,22.65, and 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 shown in embodiment 4, formula I, N '-di-n-octyl-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone-3,4,10,11-imide (BIPOI-DO) synthetic
Under nitrogen protection, add compound N-n-octyl-4 shown in 1g (2.94mmol) embodiment 1 preparation gained formula V in the 100mL there-necked flask, the 5-diaminostilbene; the 8-naphthalimide; 1.1g (2.94mmol) N-octyl group-4 shown in formula VI, 5-imide-1,8-naphthalene acid anhydride, propyl carbinol 50mL; be heated to 150 ℃ of stirrings and carried out the condensation dehydration reaction in 12 hours; be cooled to room temperature, add reaction solution and pour in the 250ml sherwood oil, have the purple solid to separate out; suction filtration, the filter cake column chromatography.With methylene dichloride than ethyl acetate=5: 1 (V/V) for washing the pouring agent, cross product.Obtain 910mg intense violet color solid.Productive rate 50%.
The structural characterization data are as follows:
Mass spectrum: [MALDI (TOF)] m/z:682 (M
+).
Nucleus magnetic hydrogen spectrum:
1H NMR (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 spectrum:
13C NMR: δ 14.90,23.38,27.86,27.97, and 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.
N-n-octyl-3 shown in embodiment 5, formula I, 4-imide-N '-(2-hexyl) Kui Ji-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone (BIPOI-O-2HD) synthetic
Under nitrogen protection; add compound N-n-octyl-4 shown in 1g (2.94mmol) embodiment 1 preparation gained formula V in the 100mL there-necked flask; the 5-diaminostilbene; the 8-naphthalimide; 1.45g (2.94mmol) compound N-(2-hexyl) decyl-4 shown in embodiment 3 preparation gained formula VI; 5-imide-1; the 8-naphthalene acid anhydride; propyl carbinol 50mL is heated to 150 ℃ of stirrings and carried out the condensation dehydration reaction in 12 hours, is cooled to room temperature; adding reaction solution pours in the 250ml sherwood oil; there is the purple solid to separate out, suction filtration, filter cake column chromatography.With methylene dichloride than ethyl acetate=5: 1 (V/V) for washing the pouring agent, cross product.Obtain 800mg intense violet color solid.Productive rate 34%.
The structural characterization data are as follows:
Mass spectrum: [MALDI (TOF)] m/z:794 (M
+).
Nucleus magnetic hydrogen spectrum:
1H NMR (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 spectrum:
13C NMR: δ 14.13,22.68,26.44,26.45, and 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.
N shown in embodiment 6, formula I, N '-two (2-hexyl) Kui Ji-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone-3,4,10,11-imide (BIPOI-D2HD) synthetic
Under nitrogen protection; add compound N-(2-hexyl) decyl-4 shown in 1g (2.22mmol) embodiment 2 preparation gained formula V in the 100mL there-necked flask; 5-two amidos-1; 8 naphthalimides; 1.1g (2.22mmol) compound N-(2-hexyl) decyl-4 shown in embodiment 3 preparation gained formula VI; 5-imide-1; 8 naphthoyl dicarboxylic anhydrides; propyl carbinol 50mL is heated to 150 ℃ of stirrings and carried out the condensation dehydration reaction in 12 hours, is cooled to room temperature; adding reaction solution pours in the 250ml sherwood oil; there is the purple solid to separate out, suction filtration, filter cake column chromatography.With methylene dichloride than ethyl acetate=5: 1 (V/V) for washing the pouring agent, cross product.Obtain 710mg intense violet color solid.Productive rate 35%.
The structural characterization data are as follows:
Mass spectrum: [MALDI (TOF)] m/z:907 (M
+).
Nucleus magnetic hydrogen spectrum:
1H NMR (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 spectrum:
13C NMR: δ 14.30,22.69,26.44,26.47, and 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
N shown in embodiment 7, embodiment 4 preparation 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 the 575nm left and right, and calculating optical band gap is that (optical band gap is according to formula E for 1.77eV
g=1240/ λ calculates, wherein E
gBe 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 potential in-0.55V left and right, and LUMO (the minimum not occupied orbital energy level) energy level that calculates thus is-3.85eV to show 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 good thermostability, and decomposition temperature is 380 ℃ of left and right.DSC (seeing Fig. 4) test shows that this compound has two transformation temperatures, and its fusing point is 268 ℃ of left and right.
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 (gate electrode), the thick silicon-dioxide of 300nm is as insulation layer (dielectric layer), its surface is modified with octadecyl trichlorosilane alkane (OTS), source electrode S (source) and drain electrode D (drain) all use gold (Au) as electrode, compd B IPOI in vacuum tightness near 10
-4Under Pa, evaporation is to silicon-dioxide, and the organic layer thickness of evaporation is 30nm.Compound before evaporation all in 10
-4Under Pa, vacuum-sublimation is purified once minimum.
At room temperature measured the electrical property of prepared organic field effect tube (OFET) under condition of nitrogen gas with Keithley 4200SCS semi-conductor test instrument.Two key parameters that determine the performance of OFET are: the on-off ratio (I of the mobility of current carrier (μ) and device
on/ I
off).Mobility refers to: under unit electric field, (unit is cm to the average drift velocity of current carrier
2/ Vs), it has reflected hole or the transfer ability of electronics in semi-conductor under 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 has reflected 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 ℃ at underlayer temperature, the 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
DSBe drain current, μ is carrier mobility, V
GBe grid voltage, V
TBe threshold voltage, W is channel width (W=1.4mm), and L is channel length (L=0.04mm), C
iBe isolator electric capacity (C
i=7.5 * 10
-9F/cm
2).Utilize (I
DS, sat)
1/2To V
GMapping, and do linear regression, the slope of the tropic is extrapolated carrier mobility (μ) thus, tries to achieve V by the section of the tropic and axle
TMobility 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 maximum value of the figure right side source-drain current ratio with minimum value.We have prepared a lot of organic field effect tube devices take three synthetic BIPOI compounds as organic layer, 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 good organic semiconductor material.Good device performance depends on this material reasonable plane skeleton and solid-state accumulation closely.These three materials that the present invention is not limited to report change different substituted radicals and can obtain a series of heterocyclic compound, and the synthetic method that the present invention provides is simple, effective.This is very helpful for the structure of research organic semiconductor material and the relation of performance, can further instruct the design of high performance material with synthetic.
Claims (12)
1. N shown in formula I, N '-dialkyl group-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone-3,4,10, the 11-imide compound,
In described formula I, R and R ' all are selected from any one in alkyl and aryl.
2. compound according to claim 1, it is characterized in that: 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; Described branched-chain alkyl is 2-methyl-propyl, 2-butyl hexyl, 2-hexyl octyl group, 2-octyl-decyl, 2-hexyl decyl, 2-octyl group dodecyl 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 fluoropropyls; Described containing in substituent phenyl, described substituting group is selected from least a in aniline, benzylamine and p-trifluoromethylaniline, preferred benzylamine.
3. method for preparing compound shown in the arbitrary described formula I of claim 1-2, comprise the steps: N-alkyl-4 shown in the described formula VI of claim 9 or 10,5-imide-1, N-alkyl-4 shown in 8 naphthalene acid anhydride compounds and the described formula V of claim 5 or 6,5-two amidos-1,8 naphthalimide compounds mixing in solvent carries out the condensation dehydration reaction, obtains compound shown in described formula I;
In described formula V and formula VI, R and R ' all are selected from any one in alkyl and aryl.
4. method according to claim 3, it is characterized in that: 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 that the total number of carbon atoms is the straight chained alkyl of 1-16; Described branched-chain alkyl is 2-methyl-propyl, 2-butyl hexyl, 2-hexyl octyl group, 2-octyl-decyl, 2-hexyl decyl, 2-octyl group dodecyl 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 fluoropropyls; Described containing in substituent phenyl, described substituting group is selected from least a in aniline, benzylamine and p-trifluoromethylaniline, preferred benzylamine;
N-alkyl-4 shown in described formula VI, N-alkyl-4 shown in 5-imide-1,8 naphthalene acid anhydride compound and formula V, the mole dosage ratio that feeds intake of 5-two amidos-1,8 naphthalimide compound is 1: 1-1.2, preferred 1: 1; In described condensation dehydration reaction step, temperature is 120-150 ℃, and preferred 150 ℃, the time is 8-12 hour, preferred 12 hours; Described condensation dehydration reaction is carried out in inert atmosphere; Described inert atmosphere is nitrogen atmosphere; Described solvent is selected from least a in propyl carbinol, n-propyl alcohol and Pentyl alcohol, preferred propyl carbinol.
5. compound shown in formula V,
In described formula V, R is selected from any one in alkyl and aryl.
6. compound according to claim 5, it is characterized in that: 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; Described branched-chain alkyl is 2-methyl-propyl, 2-butyl hexyl, 2-hexyl octyl group, 2-octyl-decyl, 2-hexyl decyl, 2-octyl group dodecyl 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 fluoropropyls; Described containing in substituent phenyl, described substituting group is selected from least a in aniline, benzylamine and p-trifluoromethylaniline, preferred benzylamine.
7. a method for preparing compound shown in the described formula V of claim 5 or 6, comprise the steps:
1) oxidizing reaction is carried out in 5-nitro acenaphthene, oxygenant and the backflow of solvent mixing, react the complete naphthalene of 4-nitro-1,8 shown in the formula II dicarboxylic anhydride that obtains;
2) with step 1) 4-nitro-1,8 naphthalene dicarboxylic anhydride shown in gained formula II carries out nitration reaction with the nitrating agent mixing in reaction solvent, and react complete and obtain shown in formula III 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydride;
3) with described step 2) shown in the gained formula III 4,5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydride and alkylamine mixing in solvent react, and react complete N-alkyl-4 shown in formula IV that obtain, 5-dinitrobenzene-1,8 naphthalimide;
In described formula IV, R is selected from any one in alkyl and aryl;
4) with step 3) N-alkyl-4 shown in gained formula IV, 5-dinitrobenzene-1,8 naphthalimide, catalyzer and hydrogen carry out reduction reaction in solvent, react complete N-alkyl-4 shown in described formula V that obtain, 5-two amidos-1,8 naphthalimide.
8. method according to claim 7 is characterized in that: described step 1), described oxygenant is selected from least a in sodium dichromate 99 and potassium bichromate, preferred sodium dichromate 99; Described solvent is Glacial acetic acid; The molar ratio of described 5-nitro acenaphthene and oxygenant is 1: 3-5, preferred 1: 5; In described oxidation step, the time is 8-10 hour, preferred 10 hours;
Described step 2) in, described reaction solvent is selected from least a 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 a in nitrosonitric acid and concentrated nitric acid, preferred nitrosonitric acid; Described step 1) shown in gained formula II, the amount ratio of 4-nitro-1,8 naphthalene dicarboxylic anhydride and nitrating agent is 1mmol-17.3mmol: 1mL-8mL, preferred 17.3mmol: 8mL; In described mixing step, temperature is 0-40 ℃, preferred 0 ℃; In described nitration reaction step, temperature is 50-70 ℃, and preferred 70 ℃, the time is 1-3 hour, preferred 2 hours;
Described step 3) in described formula IV, 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; Described branched-chain alkyl is preferably 2-methyl-propyl, 2-butyl hexyl, 2-hexyl octyl group, 2-octyl-decyl, 2-hexyl decyl, 2-octyl group dodecyl 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 fluoropropyls; Described containing in substituent phenyl, described substituting group is selected from least a in aniline, benzylamine and p-trifluoromethylaniline, preferred benzylamine; Described solvent is selected from anhydrous N, N '-dimethyl formamide,, at least a in N '-N,N-DIMETHYLACETAMIDE, preferred anhydrous N, N '-dimethyl formamide; Described alkylamine is selected from least a in n-octyl amine, 2-hexyl decyl amine, normal hexyl Amine and 2-hexyl amino dodecane, at least a in preferred n-octyl amine and 2-hexyl decyl amine; Described step 2) shown in the gained formula III 4, the amount ratio of 5-dinitrobenzene-1,8 naphthalene dicarboxylic anhydride and alkylamine is 2-4mmol: 1mL, preferred 3.47mmol: 1-1.5mL; In described reactions steps, temperature is 100-120 ℃, and preferred 120 ℃, the time is 8-12 hour, preferred 12 hours;
Described step 4) in, described catalyzer is that the mass percent of palladium is 10% palladium-carbon catalyst; Described solvent is selected from least a in dehydrated alcohol, methyl alcohol and n-propyl alcohol, preferred dehydrated alcohol; Described step 3) N-alkyl-4 shown in gained formula IV, the mass ratio of 5-dinitrobenzene-1,8 naphthalimide and reductive agent is 1: 0.05-0.1, preferred 1.0: 0.1; In described reduction reaction step, temperature is 20-40 ℃, and preferred 20 ℃, the time is 5-9 hour, and preferred 9 hours, pressure was 1-2atm, preferred 2atm.
9. N-alkyl-4 shown in formula VI, 5-imide-1,8 naphthalene anhydride compounds,
In described formula VI, R ' is selected from any one in alkyl and aryl.
10. compound according to claim 9, it is characterized in that: 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 that straight chained alkyl or the total number of carbon atoms of 1-7 are 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-octyl group dodecyl 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 fluoropropyls; Described containing in substituent phenyl, described substituting group is selected from least a in aniline, benzylamine and p-trifluoromethylaniline.
11. a method for preparing compound shown in the described formula VI of claim 9 or 10 comprises the steps: that with Isosorbide-5-Nitrae 5,8-naphthalenetetracarbacidic acidic acid anhydride and alkylamine mixing in solvent reacts, and reacts the complete compound shown in described formula VI that obtains; Described alkylamine is selected from least a in 2-hexyl decyl amine, 2-hexyl amino dodecane, preferred 2-hexyl decyl amine; Described solvent is selected from anhydrous N, N '-dimethyl formamide and N, at least a in N '-N,N-DIMETHYLACETAMIDE, preferred anhydrous N, N '-dimethyl formamide; Described Isosorbide-5-Nitrae, the mass ratio of 5,8-naphthalenetetracarbacidic acidic acid anhydride and alkylamine are 2: 0.8-1.2, preferred 2: 0.8; In described reactions steps, temperature is 120-140 ℃, and preferred 140 ℃, the time is 3-7 hour, preferred 5 hours.
12. N shown in the arbitrary described formula I of claim 1-2, N '-dialkyl group-14H-benzo [4,5] isoquino [2,1-a] perimidine-14-ketone-3,4, application or the organic field effect tube take claim 1-2 arbitrary described compound as organic semiconductor layer of 10,11-imide compound in being prepared with field effect transistors.
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| Title |
|---|
| ACS: "52671-86-0/RN，203915-43-9/RN", 《STN REGISTRY》 * |
| O.CHRISTMANN: "Synthesen in der Perimidin-Reihe,II", 《LIEBIGS ANN.CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440543A (en) * | 2017-02-16 | 2018-08-24 | 北京鼎材科技有限公司 | Perimidine derivative |
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| CN103130804B (en) | 2016-03-16 |
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