CN106588769A - Synthesis method of benzophenanthrene-alkyne-benzene-alkyne-benzene bridging perylene bisimide diester binary compound - Google Patents

Synthesis method of benzophenanthrene-alkyne-benzene-alkyne-benzene bridging perylene bisimide diester binary compound Download PDF

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CN106588769A
CN106588769A CN201610977146.0A CN201610977146A CN106588769A CN 106588769 A CN106588769 A CN 106588769A CN 201610977146 A CN201610977146 A CN 201610977146A CN 106588769 A CN106588769 A CN 106588769A
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benzene
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王桂霞
张洲洋
姚威
邓海
孔翔飞
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Guilin University of Technology
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    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
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    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/3444—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing one nitrogen atom, e.g. pyridine
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Abstract

The invention discloses a synthesis method of a benzophenanthrene-alkyne-benzene-alkyne-benzene bridging perylene bisimide diester binary compound. The synthetic route is as follows: (1) the synthesis of a benzophenanthrene derivative; (2) the synthesis of a perylene bisimide diester derivative; and (3) coupling reaction of the intermediates obtained by the step (1) and the step (2) to obtain the benzophenanthrene-alkyne-benzene-alkyne-benzene bridging perylene bisimide diester binary compound. The benzophenanthrene-alkyne-benzene-alkyne-benzene bridging perylene bisimide diester binary compound is a D-B-A structural binary compound with an alkoxy benzophenanthrene unit as an electron donor (Donor) and a perylene bisimide unit as an electron acceptor (Acceptor), the benzophenanthrene-alkyne-benzene-alkyne-benzene bridging perylene bisimide diester binary compound has intramolecular photoinduced electron transfer properties, and also has the properties of columnar phase discotic liquid crystals. The properties of enabling electrons and holes to respectively directionally migrating along a molecular column of a discotic liquid crystal receptor unit and a molecular column of a donor unit are expected to be obtained, current carrier loss can be reduced, and the properties of organic photovoltaic devices are promising to improve.

Description

Benzo phenanthryne benzyne benzeno connects the synthetic method of perylene diimide diester binary compound
Technical field
The present invention relates to a kind of benzo phenanthryne benzyne benzeno connects the synthetic method of perylene diimide binary compound.
Background technology
When columnar phase discotic mesogenic material is in liquid crystalline phase, because π stronger between disc-shaped core-pi-electron interacts, easily It is self-assembled into orderly molecular columns.So that there is higher carrier mobility along the axial direction of molecular columns, can be used as light The active layer and decorative layer of electronic device is used.
Benzophenanthrene liquid crystal material preparation method is simple, yield is higher, be easy to purification, and ultraviolet region has stronger absorption, root It is reported that it can be to study ground at present as the hole transmission layer of organic luminescent device, the centre of luminescence and hole transmission layer etc. Most commonly used discotic mesogenic material.Especially in optics, photoelectricity and electronics have wide application prospect.Er perylene diimides Class discotic mesogenic material is the compound that a class has special condensed cyclic structure, with good light, heat stability and non-oxidizability, Possess the excellent optical properties such as wider spectral absorption scope, and high-fluorescence quantum yield, low Stokes displacements simultaneously, and By being in electron deficiency system property in perylene core, with higher electron affinity energy, this make perylene diimide analog derivative becomes a kind of Typical N-shaped organic semiconducting materials, therefore obtained widely studied in organic photovoltaic field.
The content of the invention
It is an object of the invention to provide a kind of benzo phenanthryne benzyne benzeno connects the synthesis of perylene diimide diester binary compound Method.
Concretely comprise the following steps：
(1) adjacent two hexyloxy benzene and 2- hexyloxy-phenols into coupling reaction occur under the Oxidation of ferric chloride to generate The hexyloxy benzophenanthrene of monohydroxy five；Then the alkoxyl of alkynes benzyne base five is contained by Material synthesis of the hexyloxy benzophenanthrene of monohydroxy five Triphenylene (compound 8).
(2) expect He Cheng perylene anhydride diester by Yuan of perylene dicarboxylic anhydride；Ran Hou perylene anhydride diester carries out amidatioon with 4- Iodoanilines Get is Dao perylene diimide diester (compound 15).
(3) will obtain with perylene diimide diester intermediate coupling reaction containing the alkoxyl triphenylene of alkynes benzyne base five Benzo phenanthryne benzyne benzeno connects perylene diimide diester binary compound (compound 16).
The present invention has been designed and synthesized with alkoxyl benzophenanthrene unit as electron donor (Donor), and perylene diimide unit is The binary compound for having a D-B-A type structures of electron acceptor (Acceptor), this kind of compound has both had intramolecular photo-induction conductive The property of son transfer, the property may again with columnar phase discotic mesogenic.Expection obtains having makes electronics and hole respectively along disk The property of the molecular columns of shape liquid crystal receptor unit and the molecular columns directional migration of donor monomer, so as to reduce the loss of carrier, Pole is hopeful the performance for improving organic photovoltaic devices.
Description of the drawings
Fig. 1 is synthetic route chart of the present invention containing the alkoxyl triphenylene (compound 8) of alkynes benzyne base five.
It is labeled as in figure：1- compounds 1,2- compounds 2,3- compounds 3,4- compounds 4,5- compounds 5,6- compounds 6,7- compounds 7,8- compounds 8.
Fig. 2 is the synthetic route chart of perylene diimide diester (compound 15) of the present invention.
It is labeled as in figure：11- compounds 11,12- compounds 12,13- compounds 13,14- compounds 14,15- compounds 15。
Fig. 3 is the synthesis road that benzo phenanthryne benzyne benzeno of the present invention connects perylene diimide diester binary compound (compound 16) Line chart.
It is labeled as in figure：8- compounds 8,15- compounds 15,16- compounds 16.
Specific embodiment
Embodiment：
It is pure that chemical reagent and solvent used in embodiment is analysis.
(1) synthesis of adjacent hexyloxy-phenol (compound 1)
By catechol (20g, 0.1816mol), 1- bromo normal hexane (89.9g, 0.5448mol), Anhydrous potassium carbonate (73.5g, 0.5448mol), potassium iodide (6.0g) and dehydrated alcohol (250mL) mix, and mixeding liquid temperature is risen to into 85 DEG C of backflows After 60 hours, the mixture of reaction is cooled to into room temperature sucking filtration, with ethanol (150mL) filter cake is washed, sucking filtration is repeated twice.Filter After liquid revolving, then the fraction of 142-155 DEG C (0.5mmHg) is collected in vacuum distillation, obtains compound 1 for colourless oil liquid (48g), yield 96%；IR(KBr)νmax(cm-1):3540,3050,2930,2850,1800,1600,1500,1360, 1260.1H NMR(300MHz,CDCl3)δ:6.89 (s, 4H), 3.99 (t, J=6.9Hz, 4H), 1.83-1.76 (m, J= 6.9Hz, 4H), 1.49-1.31 (m, 12H), 0.9 (t, J=6.9Hz, 6H).
(2) synthesis of the hexyloxy benzene (compound 2) of 1,2- bis-
By catechol (50g, 0.45mol), 1- bromo normal hexane (75g, 0.45mol), Anhydrous potassium carbonate (100g, 0.725mol), potassium iodide (3.8g) and dehydrated alcohol (500mL) mix, after mixeding liquid temperature is risen to into 85 DEG C of backflows 12 hours, The mixture of reaction is cooled to into sucking filtration after room temperature, with ethanol (150mL) filter cake is washed, sucking filtration is repeated twice.Filtrate rotates Afterwards, the fraction of 140-143 DEG C (0.5mmHg) is collected in vacuum distillation, compound 2 is obtained for colourless oil liquid (25.5g), product Rate 29%；IR(KBr)νmax(cm-1):3060,2930,2860,1590,1470,1500,1390,1250.1H NMR(300MHz, CDCl3)δ:6.95-6.82 (m, 4H), 5.68 (s, 1H), 4.02 (t, J=6.9Hz, 2H), 1.83-1.76 (m, 2H), 1.48- 1.31 (m, 6H), 0.91 (t, J=6.9Hz, 3H).
(3) synthesis of the hexyloxy benzophenanthrenes (compound 3) of 2- hydroxyls -3,6,7,10,11- five
Anhydrous ferric trichloride (12.96g, 79.2mmol) is dissolved in dichloromethane (80mL) and nitromethane (8mL).Change Compound 1 (4.44g, 16mmol) and compound 2 (1.56g, 8mmol) are dissolved in dichloromethane (60mL), at 0 DEG C, by compound 1 In the dichloromethane and nitromethane solution that the mixed solution of compound 2 drops to above-mentioned anhydrous ferric trichloride, about 30 minutes Completion of dropping.The mixture of reaction is maintained in the range of 0 DEG C -3 DEG C after continuing to react 3 hours, adds 50mL methanol and 25mL Water terminating reaction.The mixture of reaction 15mL concentration is that 2mol/L dilute hydrochloric acid is washed twice, with 15mL saturated common salt water washings Once, collected organic layer, after adding anhydrous sodium sulfate drying eliminating water, vacuum rotary steam removes solvent, the crude product purified by silica gel color for obtaining (leacheate is the purification of spectrum post:Ethyl acetate/petroleum ether volume ratio is 1:30-1:15) 2.14g white solids i.e. compound, is obtained 3, yield is 36%, Mp:47.0-50.0℃；IR(KBr)νmax(cm-1):3734,3446,2957,2859,2360,2340, 1618,1518,1469,1265,1171,1105,860,727,650,516；1H NMR(400MHz,CDCl3)δ:7.96(s, 1H),7.83(s,3H),7.82(s,1H),7.77(s,1H),5.91(s,1H),4.31-4.19(m,10H),1.98-1.90(m, 10H),1.59-1.40(m,30H),0.96-0.92(m,15H)。
(4) synthesis of the hexyloxy benzophenanthrenes (compound 4) of 2- triflates -3,6,7,10,11- five
Under nitrogen protection, take compound 3 (0.65g, 0.87mmol) and be placed in and be dried there-necked flask, and add 6mL pyridines molten Solution, stirs 15 minutes under ice-water bath.Under nitrogen protection trifluoromethanesulfanhydride anhydride (0.30g, 1.05mmol) is added dropwise over there-necked flask, Ice bath is removed after being added dropwise to complete within 15 minutes.Nitrogen is protected, and is reacted 5 hours under room temperature.Reactant liquor 10mL mass percent concentrations Dilute hydrochloric acid and 20mL dichloromethane extraction for 5%, collected organic layer, vacuum distillation obtains crude product.Crude product volume ratio For 1:4 methylene chloride-methanol recrystallization, after being dried brown solid 0.67g is compound 4, yield 87.56%；Mp: 166.5-167℃；IR(KBr)νmax(cm-1):3734,3446,2957,2859,2360,2340,1618,1518,1469, 1265,1171,1105,860,727,650,516；1H NMR(500MHz,CDCl3)δ8.19(s,1H),7.87(s,1H),7.82 (s,1H),7.80(s,2H),7.71(s,1H),4.29-4.21(m,10H),1.99-1.91(m,10H),1.63-1.55(m, 10H),1.41(m,20H),0.96-0.92(m,15H)。
(5) conjunction of 2- (3- methyl -3- hydroxyls-ethyl acetylene base) the hexyloxy benzophenanthrenes (compound 5) of -3,6,7,10,11- five Into
Under nitrogen protection, compound 4 (0.67g, 0.76mmol), triphenylphosphine (0.0203g, 0.076mmol) iodate are taken Cuprous (0.0148g, 0.076mmol) and dichloride two (triphenyl phosphorus) are closed palladium (II) (0.0540g, 0.076mmol) and add three Mouth bottle, is subsequently adding 15mL tetrahydrofurans, 5mL triethylamine stirring and dissolving, is subsequently adding 2- methyl -3- butyne-2-alcohols (0.098g, 1.15mmol), 80 DEG C are stirred at reflux overnight.Reactant liquor with 80mL mass percent concentrations be 5% ammonium chloride solution/ 20mL dichloromethane is extracted, and collected organic layer, vacuum distillation obtains crude product.Crude product purified by silica gel chromatographic column is purified, eluting Liquid proportional ethyl acetate：Petroleum ether is 10:1, obtain 0.43g compounds 5, yield 87.56%；Mp:131-132℃；IR(KBr) νmax(cm-1):3735,3448,2928,2360,1615,1517,1434,1264,1175,959,837,750,616；1HNMR (400MHz,CDCl3) δ 8.46 (s, 1H), 7.86 (d, J=7.2Hz, 2H), 7.81 (s, 2H), 7.74 (s, 1H), 4.23 (m, 10H), 2.17 (s, 1H), 1.94 (t, J=5.2Hz, 10H), 1.72 (s, 6H), 1.63-1.55 (m, 10H), 1.41 (m, 20H), 0.94(m,15H)。
(6) synthesis of the hexyloxy benzophenanthrenes (compound 6) of 2- alkynyls -3,6,7,10,11- five
Under nitrogen protection, by compound 5 (0.43g, 0.53mmol), potassium hydroxide (0.27g, 4.77mmol) and 25ml first Benzene adds flask, and 110 DEG C are stirred at reflux 2 hours.Reactant liquor volume ratio is 1:3 water and dichloromethane are extracted, and are collected organic Layer, vacuum distillation obtains crude product.Crude product purified by silica gel chromatographic column is purified, eluting liquid proportional ethyl acetate：Petroleum ether volume Than for 1:30, obtain light yellow solid 0.25g i.e. compound 6, yield 61.4%；Mp:124-126℃；IR(KBr)νmax(cm-1): 3445,3315,2956,2858,2360,2101,1614,1516,1434,1263,1171,1041,929,834,727,636；1HNMR(400MHz,CDCl3) δ 8.46 (s, 1H), 7.86 (d, J=7.2Hz, 2H), 7.81 (s, 2H), 7.74 (s, 1H), 4.23 (m, 10H), 4.0 (s, 1H), 1.94 (t, J=5.2Hz, 10H), 1.63-1.55 (m, 10H), 1.41 (m, 20H), 0.94 (m, 15H)。
(7) 2- (3- methyl -3- hydroxyls-ethyl acetylene base benzene) hexyloxy benzophenanthrene (compounds of alkynyl -3,6,7,10,11- five 7) synthesis
Under nitrogen protection, by 4- (4- iodobenzenes) -2- methyl -3- butyne-2-alcohols (0.24g, 0.83mmol), compound 6 (0.55g, 0.73mmol), triphenylphosphine (0.03g, 0.22mmol), Hydro-Giene (Water Science). (0.04g, 0.22mmol), dichloride two (triphenyl phosphorus) close palladium (II) (0.15g, 0.22mmol) and in there-necked flask, then bromo-iodobenzene (0.31g, 1.1mmol) are added Add 16mL tetrahydrofurans, 4mL triethylamine stirring and dissolving, room temperature reaction 48 hours.Reactant liquor 80mL mass percent concentrations Extract for 5% ammonium chloride solution/20mL dichloromethane, collected organic layer, vacuum distillation obtains crude product.Crude product purified by silica gel chromatograph Post is purified, eluting liquid proportional dichloromethane：Petroleum ether volume ratio is 2:3, obtain light yellow solid 0.21g i.e. compound 7, yield 65%, Mp:81-82℃；IR(KBr)νmax(cm-1):3466,2982,2360,1651,1579,1481,1370,1272,1157, 1097,962,804,749,684,572.1H NMR(400MHz,CDCl3):δ 8.56 (s, 1H), 7.88 (d, J=12.8Hz, 2H), 7.79 (d, J=8.8Hz, 3H), 7.56 (d, J=8.0Hz, 2H), 7.43 (d, J=8.0Hz, 2H), 4.32-4.20 (m, 10H),2.05-1.91(m,11H),1.73-1.52(m,16H),1.41(ms,20H),0.95(m,15H)。
(8) synthesis of the hexyloxy benzophenanthrenes (compound 8) of 2- (4- acetylenylbenzenes) alkynyl -3,6,7,10,11- five
Under nitrogen protection, by dried compound 7 (0.90g, 0.99mmol) and potassium hydroxide (0.15g, 2.27mmol) dry flask is added, under positive pressure protection, add toluene (50mL), intensification to be stirred at reflux 2 hours.It is cooled to room Temperature, 20mL concentration is that 2mol/L hydrochloric acid/20mL dichloromethane is extracted three times, collected organic layer, saturated common salt water washing, anhydrous sulfur Sour sodium is dried, and revolving removes solvent, and crude product purified by silica gel chromatographic column purifies to obtain white solid i.e. compound 8 (0.70g, yield 78%)；Mp:161-162℃；IR(KBr)νmax(cm-1):3466,2982,2360,1651,1579,1481,1370,1272, 1157,1097,962,804,749,684,572；1H NMR(400MHz,CDCl3):δ 8.56 (s, 1H), 7.88 (d, J= 12.8Hz, 2H), 7.79 (d, J=8.8Hz, 3H), 7.56 (d, J=8.0Hz, 2H), 7.43 (d, J=8.0Hz, 2H), 4.32- 4.20(m,10H),2.05-1.91(m,11H),1.73-1.52(m,16H),1.41(ms,20H),0.95(m,15H)。
(the synthesis of the own ester (compound 13) of 9) perylene -3,4,9,10- tetracarboxylic acids four
Jiang perylene -3,4,9,10- tetracarboxylic acid dianhydrides (compound 11) (3.5g, 8.92mmol) are added to 400mL concentration for 2.5% Potassium hydroxide aqueous solution in, 70 DEG C react 1.5 hours.Room temperature is cooled to, sucking filtration adjusts filtrate pH=7, and get is Dao perylene tetramethyl The aqueous solution of sour potassium (compound 12).By hexyl bromide 1 bromohexane (14.72g, 89.2mmol) and tetrabutyl ammonium bromide (1.45g, 4.5mmol) it is added in filtrate, reacts 6 hours at 100 DEG C.Room temperature is cooled to, is 1 with volume ratio:3 water/dichloromethane extraction, Collected organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, vacuum distillation removes solvent.Crude product volume ratio is 1:1 Dichloromethane/ethyl alcohol recrystallization sucking filtration, filtration under diminished pressure obtains yellow powder compound 13 (6.51g, yield 95%)；Mp>300 ℃；IR(KBr)νmax(cm-1)：3430,2930 (C-H), 2850 (C-H), 1730 (C=O), 1630,1460,1400,1270 (C- O),1170,1000,747；1HNMR(500MHz,CDCl3)δ:8.15 (d, J=8.0Hz, 2H), 8.09 (d, J=8.0Hz, 2H), 7.98-7.93 (m, 4H), 4.35 (t, J=7.0Hz, 8H), 1.86-1.80 (m, 8H), 1.50-1.37 (m, 24H), 0.93 (t, J =7.0Hz, 12H).
(the synthesis of 10) perylenes -3,4- dicarboxylic acid anhydrides -9,10- dioctyl phthalate dihexyls (compound 14)
After during compound 13 (6.51g, 8.51mmol) is completely dissolved in into toluene (3.6ml) and normal heptane (18.0ml), plus Enter p-methyl benzenesulfonic acid (1.54g, 8.95mmol), 95 DEG C are reacted 5 hours, sucking filtration after frozen water cooling, filter cake volume ratio is 1:4 Methylene chloride/methanol recrystallization, sucking filtration after frozen water cooling, is repeated twice, and obtains red solid i.e. compound 14 (3.88g, yield 79%)；Mp>300℃；IR(KBr)νmax(cm-1):3430,2920 (C-H), 2850 (C-H), 1730 (C=O), 1630,1290 (C-O),1150,1010,857,805,737；1HNMR(500MHz,CDCl3)δ:8.15 (d, J=8.0Hz, 2H), 8.09 (d, J =8.0Hz, 2H), 7.98-7.93 (m, 4H), 4.35 (t, J=7.0Hz, 4H), 1.86-1.80 (m, 4H), 1.50-1.37 (m, 12H), 0.93 (t, J=7.0Hz, 6H).
(synthesis of the 11) perylene-N- to iodobenzene alkynes -3,4- dicarboximides -9,10- dioctyl phthalate dihexyls (compound 15)
Under nitrogen protection, dried compound 14 (2.00g, 3.46mmol), 4- Iodoanilines is added in flask (3.03g, 13.83mmol), Glacial acetic acid zinc (0.32g, 1.73mmol) and imidazoles (20.00g), vacuum nitrogen gas repeat Three times.Stirring heats up 150 DEG C, and reaction overnight, is cooled to room temperature.Reactant volume ratio is 1:3 water/dichloromethane extraction, Collected organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, revolving removes solvent.It is 1 with volume ratio:1 dichloromethane Alkane/ethyl alcohol recrystallization, obtains Orange red solid i.e. compound 15 (2.65g, yield 98%), Mp:254-255℃；IR(KBr) νmax(cm-1):3450,2956,2856,1709,1667,1596,1511,1469,1366,1274,1177,1067,1012, 961,809,778；1H NMR(400MHz,CDCl3) δ 8.57 (d, J=8.0Hz, 2H), 8.35 (dd, J=8.2,4.5Hz, 4H), 8.07 (d, J=8.0Hz, 2H), 7.90 (d, J=8.4Hz, 2H), 7.14 (d, J=8.4Hz, 2H), 4.35 (t, J=6.8Hz, 4H), 1.83 (q, J=7.2Hz, 4H), 1.46 (m, 4H), 1.36 (m, 8H), 0.97-0.88 (m, 6H).
(12) benzo phenanthryne benzyne benzeno connects the synthesis of perylene diimide binary compound (compound 16)
Under nitrogen protection, by advance dried compound 8 (0.70g, 0.82mmol), compound 15 (0.30g, 0.38mmol), triphenylphosphine (10.1mg, 0.04mmol), Hydro-Giene (Water Science). (3.7mg, 0.02mmol) and double (triphenylphosphines) two Palladous chloride. (II) (27.0mg, 0.04mmol) is added in dry there-necked flask, vacuum nitrogen gas, in triplicate.Then just Under pressure protection, it is separately added into tetrahydrofuran (15mL) and triethylamine (5mL) heats up 80 DEG C, lucifuge is stirred at reflux, and reaction is overnight.It is cold But to room temperature, reactant liquor 80mL mass percent concentrations are 5% ammonium chloride solution/20mL chloroform extractions three times, are received Collection organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, revolving removes solvent.Crude product purified by silica gel chromatographic column is purified, and is obtained It is compound 16 (0.53g, yield 92%) to white solid, Mp:226.6-227.4℃；IR(KBr)νmax(cm-1):3735, 3650,2953,2856,2361,1704,1612,1593,1467,1432,1360,1295,1263,1170,1063,836, 747,669,420；1H NMR(400MHz,CDCl3) δ 8.55 (d, J=8.0Hz, 2H), 8.22 (s, 3H), 8.13 (d, J= 8.0Hz, 2H), 7.99 (d, J=8.0Hz, 2H), 7.68-7.54 (m, 8H), 7.49-7.42 (m, 3H), 7.38 (d, J= 5.6Hz, 2H), 4.35 (t, J=6.8Hz, 4H), 4.27-4.09 (m, 10H), 1.98 (m, 10H), 1.84 (m, 4H), 1.53- 1.32(m,32H),1.04-0.88(m,21H)。

Claims (1)

1. a kind of benzo phenanthryne benzyne benzeno connects the synthetic method of perylene diimide diester binary compound, it is characterised in that concrete step Suddenly it is：
(1) adjacent hexyloxy-phenol is the synthesis of compound 1
By 20g catechols, 89.9g 1- bromo normal hexane, 73.5g Anhydrous potassium carbonates, 6.0g potassium iodide and the anhydrous second of 250mL Alcohol mix, by mixeding liquid temperature rise to 85 DEG C backflow 60 hours after, the mixture of reaction is cooled to into room temperature sucking filtration, use 150mL Washing with alcohol filter cake, sucking filtration is repeated twice；After filtrate revolving, then 142-155 DEG C, the fraction of 0.5mmHg are collected in vacuum distillation, 48g compounds 1 are obtained for colourless oil liquid, yield 96%；IR(KBr)νmax(cm-1):3540,3050,2930,2850, 1800,1600,1500,1360,1260.1H NMR(300MHz,CDCl3)δ:6.89 (s, 4H), 3.99 (t, J=6.9Hz, 4H), 1.83-1.76 (m, J=6.9Hz, 4H), 1.49-1.31 (m, 12H), 0.9 (t, J=6.9Hz, 6H)；
(2) the hexyloxy benzene of 1,2- bis- is the synthesis of compound 2
50g catechols, 75g 1- bromo normal hexane, 100g Anhydrous potassium carbonates, 3.8g potassium iodide and 500mL dehydrated alcohol are mixed Close, by mixeding liquid temperature rise to 85 DEG C backflow 12 hours after, the mixture of reaction is cooled to into sucking filtration after room temperature, use 150mL second Alcohol washs filter cake, and sucking filtration is repeated twice；After filtrate revolving, 140-143 DEG C, 0.5mmHg fractions are collected in vacuum distillation, obtained 25.5g compounds 2 be colourless oil liquid, yield 29%；IR(KBr)νmax(cm-1):3060,2930,2860,1590,1470, 1500,1390,1250.1H NMR(300MHz,CDCl3)δ:6.95-6.82 (m, 4H), 5.68 (s, 1H), 4.02 (t, J= 6.9Hz, 2H), 1.83-1.76 (m, 2H), 1.48-1.31 (m, 6H), 0.91 (t, J=6.9Hz, 3H)；
(3) the hexyloxy benzophenanthrenes of 2- hydroxyls -3,6,7,10,11- five are the synthesis of compound 3
12.96g anhydrous ferric trichlorides are dissolved in 80mL dichloromethane and 8mL nitromethanes；4.44g compounds 1 and 1.56gization Compound 2 is dissolved in 60mL dichloromethane, at 0 DEG C, the mixed solution of compound 1 and compound 2 is dropped to into above-mentioned anhydrous trichlorine In changing the dichloromethane and nitromethane solution of ferrum, about 30 minutes completion of dropping；The mixture of reaction is maintained at into 0 DEG C of -3 DEG C of model After enclosing interior continuation reaction 3 hours, 50mL methanol and 25mL water terminating reactions are added；The mixture of reaction is with 15mL concentration 2mol/L dilute hydrochloric acid is washed twice, and be washed once with 15mL saturated aqueous common salts, collected organic layer, adds anhydrous sodium sulfate drying to remove After water, vacuum rotary steam removes solvent, the crude product purified by silica gel chromatographic column purification for obtaining, and leacheate is:Ethyl acetate/petroleum ether volume Than for 1:30-1:15,2.14g white solids i.e. compound 3 is obtained, yield is 36%, Mp:47.0-50.0℃；IR(KBr)νmax (cm-1):3734,3446,2957,2859,2360,2340,1618,1518,1469,1265,1171,1105,860,727, 650,516；1H NMR(400MHz,CDCl3)δ:7.96(s,1H),7.83(s,3H),7.82(s,1H),7.77(s,1H),5.91 (s,1H),4.31-4.19(m,10H),1.98-1.90(m,10H),1.59-1.40(m,30H),0.96-0.92(m,15H)；
(4) the hexyloxy benzophenanthrenes of 2- triflates -3,6,7,10,11- five are the synthesis of compound 4
Under nitrogen protection, 0.65g compounds 3 are taken it is placed in and be dried there-necked flask, and add 6mL pyridinium dissolutions, stirs under ice-water bath 15 minutes；Under nitrogen protection 0.30g trifluoromethanesulfanhydride anhydrides are added dropwise over there-necked flask, and ice bath is removed within 15 minutes after being added dropwise to complete； Nitrogen is protected, and is reacted 5 hours under room temperature；The reactant liquor dilute hydrochloric acid and 20mL dichloromethanes that 10mL mass percent concentrations are 5% Alkane is extracted, and collected organic layer, vacuum distillation obtains crude product；Crude product volume ratio is 1:4 methylene chloride-methanol is tied again Crystalline substance, after being dried 0.67g brown solids are compound 4, yield 87.56%；Mp:166.5-167℃；IR(KBr)νmax(cm-1):3734,3446,2957,2859,2360,2340,1618,1518,1469,1265,1171,1105,860,727,650, 516；1H NMR(500MHz,CDCl3)δ8.19(s,1H),7.87(s,1H),7.82(s,1H),7.80(s,2H),7.71(s, 1H),4.29-4.21(m,10H),1.99-1.91(m,10H),1.63-1.55(m,10H),1.41(m,20H),0.96-0.92 (m,15H)；
(5) 2- (3- methyl -3- hydroxyls-ethyl acetylene base) the hexyloxy benzophenanthrenes of -3,6,7,10,11- five are the synthetic nitrogen of compound 5 Under gas shielded, 0.67g compounds 4,0.0203g triphenylphosphines, 0.0148g Hydro-Giene (Water Science) .s and the (triphen of 0.0540g dichlorides two are taken Base phosphorus) palladium (II) addition 100mL there-necked flasks are closed, 15mL tetrahydrofurans, 5mL triethylamine stirring and dissolving are subsequently adding, it is subsequently adding 0.098g 2- methyl -3- butyne-2-alcohols, 80 DEG C are stirred at reflux overnight；Reactant liquor 80mL mass percent concentrations are 5% chlorine Change ammonium salt solution/20mL dichloromethane extraction, collected organic layer, vacuum distillation obtains crude product；Crude product purified by silica gel chromatographic column is carried out Purification, eluting liquid proportional ethyl acetate：Petroleum ether is 10:1, obtain 0.43g compounds 5, yield 87.56%；Mp:131-132 ℃；IR(KBr)νmax(cm-1):3735,3448,2928,2360,1615,1517,1434,1264,1175,959,837,750, 616；1HNMR(400MHz,CDCl3) δ 8.46 (s, 1H), 7.86 (d, J=7.2Hz, 2H), 7.81 (s, 2H), 7.74 (s, 1H), 4.23 (m, 10H), 2.17 (s, 1H), 1.94 (t, J=5.2Hz, 10H), 1.72 (s, 6H), 1.63-1.55 (m, 10H), 1.41 (m,20H),0.94(m,15H)；
(6) the hexyloxy benzophenanthrenes of 2- alkynyls -3,6,7,10,11- five are the synthesis of compound 6
Under nitrogen protection, 0.43g compounds 5,0.27g potassium hydroxide and 25ml toluene are added into flask, 110 DEG C are stirred at reflux 2 Hour；Reactant liquor volume ratio is 1:3 water and dichloromethane are extracted, and collected organic layer, vacuum distillation obtains crude product；Crude product Purified with silica gel chromatographic column, eluting liquid proportional ethyl acetate：Petroleum ether volume ratio is 1:30, obtain 0.25g light yellow solids That is compound 6, yield 61.4%；Mp:124-126℃；IR(KBr)νmax(cm-1):3445,3315,2956,2858,2360, 2101,1614,1516,1434,1263,1171,1041,929,834,727,636；1HNMR(400MHz,CDCl3)δ8.46(s, 1H), 7.86 (d, J=7.2Hz, 2H), 7.81 (s, 2H), 7.74 (s, 1H), 4.23 (m, 10H), 4.0 (s, 1H), 1.94 (t, J =5.2Hz, 10H), 1.63-1.55 (m, 10H), 1.41 (m, 20H), 0.94 (m, 15H)；
(7) 2- (3- methyl -3- hydroxyls-ethyl acetylene base benzene) the hexyloxy benzophenanthrenes of alkynyl -3,6,7,10,11- five are compound 7 Synthesis
Under nitrogen protection, by 0.24g 4- (4- iodobenzenes) -2- methyl -3- butyne-2-alcohols, 0.55g compounds 6,0.03g triphenyls Phosphine, 0.04g Hydro-Giene (Water Science) .s, 0.15g dichlorides two (triphenyl phosphorus) are closed palladium (II) and 0.31g and bromo-iodobenzene are added in there-necked flask, It is subsequently adding 16mL tetrahydrofurans, 4mL triethylamine stirring and dissolving, room temperature reaction 48 hours；Reactant liquor 80mL mass percents Concentration is 5% ammonium chloride solution/20mL dichloromethane extraction, and collected organic layer, vacuum distillation obtains crude product；Crude product purified by silica gel Chromatographic column is purified, eluting liquid proportional dichloromethane：Petroleum ether volume ratio is 2:3,0.21g light yellow solids i.e. compound 7 is obtained, produce Rate 65%, Mp:81-82℃；IR(KBr)νmax(cm-1):3466,2982,2360,1651,1579,1481,1370,1272, 1157,1097,962,804,749,684,572.1H NMR(400MHz,CDCl3):δ 8.56 (s, 1H), 7.88 (d, J= 12.8Hz, 2H), 7.79 (d, J=8.8Hz, 3H), 7.56 (d, J=8.0Hz, 2H), 7.43 (d, J=8.0Hz, 2H), 4.32- 4.20(m,10H),2.05-1.91(m,11H),1.73-1.52(m,16H),1.41(ms,20H),0.95(m,15H)；
(8) the hexyloxy benzophenanthrenes of 2- (4- acetylenylbenzenes) alkynyl -3,6,7,10,11- five are the synthesis of compound 8
Under nitrogen protection, dried 0.90g compounds 7 and 0.15g potassium hydroxide are added in dry flask, malleation Under protection, 50mL toluene, intensification is added to be stirred at reflux 2 hours；Room temperature is cooled to, 20mL concentration is 2mol/L hydrochloric acid/20mL bis- Chloromethanes are extracted three times, collected organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, and revolving removes solvent, and crude product is used Silica gel chromatographic column purifies to obtain 0.70g white solids i.e. compound 8, yield 78%；Mp:161-162℃；IR(KBr)νmax(cm-1): 3466,2982,2360,1651,1579,1481,1370,1272,1157,1097,962,804,749,684,572；1H NMR (400MHz,CDCl3):δ 8.56 (s, 1H), 7.88 (d, J=12.8Hz, 2H), 7.79 (d, J=8.8Hz, 3H), 7.56 (d, J =8.0Hz, 2H), 7.43 (d, J=8.0Hz, 2H), 4.32-4.20 (m, 10H), 2.05-1.91 (m, 11H), 1.73-1.52 (m,16H),1.41(ms,20H),0.95(m,15H)；
(the own ester of 9) perylene -3,4,9,10- tetracarboxylic acids four is the synthesis of compound 13
3.5g perylene -3,4,9,10- tetracarboxylic acid dianhydrides are that compound 11 is added to the potassium hydroxide that 400mL concentration is 2.5% water-soluble In liquid, react 1.5 hours at 70 DEG C；Room temperature is cooled to, sucking filtration adjusts filtrate pH=7, and get Dao perylene tetracarboxylic acid potassium is compound 12 Aqueous solution；14.72g hexyl bromide 1 bromohexanes and 1.45g tetrabutyl ammonium bromide are added in filtrate, are reacted 6 hours at 100 DEG C；Cooling It is 1 with volume ratio to room temperature:3 water/dichloromethane extraction, collected organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, Vacuum distillation removes solvent；Crude product volume ratio is 1:1 dichloromethane/ethyl alcohol recrystallization sucking filtration, filtration under diminished pressure is obtained 6.51g yellow powders are compound 13, yield 95%；Mp>300℃；IR(KBr)νmax(cm-1)：3430,2930(C-H),2850 (C-H), 1730 (C=O), 1630,1460,1400,1270 (C-O), 1170,1000,747；1HNMR(500MHz,CDCl3)δ: 8.15 (d, J=8.0Hz, 2H), 8.09 (d, J=8.0Hz, 2H), 7.98-7.93 (m, 4H), 4.35 (t, J=7.0Hz, 8H), 1.86-1.80 (m, 8H), 1.50-1.37 (m, 24H), 0.93 (t, J=7.0Hz, 12H)；
(10) perylene -3,4- dicarboxylic acid anhydride -9,10- dioctyl phthalate dihexyls are the synthesis of compound 14
After during 6.51g compounds 13 are completely dissolved in into 3.6mL toluene and 18.0mL normal heptane, addition 1.54g p-methyl benzenesulfonic acid, 95 DEG C reaction 5 hours, frozen water cooling after sucking filtration, filter cake volume ratio be 1:4 methylene chloride/methanol recrystallization, after frozen water cooling Sucking filtration, is repeated twice, and obtains 3.88g red solids i.e. compound 14, yield 79%；Mp>300℃；IR(KBr)νmax(cm-1): 3430,2920 (C-H), 2850 (C-H), 1730 (C=O), 1630,1290 (C-O), 1150,1010,857,805,737；1HNMR(500MHz,CDCl3)δ:8.15 (d, J=8.0Hz, 2H), 8.09 (d, J=8.0Hz, 2H), 7.98-7.93 (m, 4H), 4.35 (t, J=7.0Hz, 4H), 1.86-1.80 (m, 4H), 1.50-1.37 (m, 12H), 0.93 (t, J=7.0Hz, 6H)；
(11) perylene-N- are the synthesis of compound 15 to iodobenzene alkynes -3,4- dicarboximide -9,10- dioctyl phthalate dihexyls
Under nitrogen protection, 2.00g dried compound 14,3.03g 4- Iodoanilines, 0.32g Glacial acetic acids are added in flask Zinc and 20.00g imidazoles, vacuum nitrogen gas, in triplicate；Stirring heats up 150 DEG C, and reaction overnight, is cooled to room temperature；Reactant It is 1 with volume ratio:3 water/dichloromethane extraction, collected organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, revolving Remove solvent；It is 1 with volume ratio:1 dichloromethane/ethyl alcohol recrystallization, obtains 2.65g Orange red solids i.e. compound 15, produces Rate 98%, Mp:254-255℃；IR(KBr)νmax(cm-1):3450,2956,2856,1709,1667,1596,1511,1469, 1366,1274,1177,1067,1012,961,809,778；1H NMR(400MHz,CDCl3) δ 8.57 (d, J=8.0Hz, 2H), 8.35 (dd, J=8.2,4.5Hz, 4H), 8.07 (d, J=8.0Hz, 2H), 7.90 (d, J=8.4Hz, 2H), 7.14 (d, J= 8.4Hz, 2H), 4.35 (t, J=6.8Hz, 4H), 1.83 (q, J=7.2Hz, 4H), 1.46 (m, 4H), 1.36 (m, 8H), 0.97- 0.88(m,6H)；
(12) benzo phenanthryne benzyne benzeno connects the perylene diimide binary compound i.e. synthesis of compound 16
Under nitrogen protection, by advance dried 0.70g compounds 8,0.30g compounds 15,10.1mg triphenylphosphines, 3.7mg Hydro-Giene (Water Science) .s and double (triphenylphosphine) palladium chlorides (II) of 27.0mg are added in dry there-necked flask, vacuum nitrogen gas, In triplicate；Then under positive pressure protection, 15mL tetrahydrofurans are separately added into and 5mL triethylamines heats up 80 DEG C, lucifuge is stirred back Stream, reaction is overnight；Room temperature is cooled to, reactant liquor 80mL mass percent concentrations are 5% chloromethanes of ammonium chloride solution/20mL tri- Alkane is extracted three times, collected organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, and revolving removes solvent；Crude product purified by silica gel Chromatographic column is purified, and obtains 0.53g white solids i.e. compound 16, yield 92%, Mp:226.6-227.4℃；IR(KBr)νmax (cm-1):3735,3650,2953,2856,2361,1704,1612,1593,1467,1432,1360,1295,1263,1170, 1063,836,747,669,420；1H NMR(400MHz,CDCl3) δ 8.55 (d, J=8.0Hz, 2H), 8.22 (s, 3H), 8.13 (d, J=8.0Hz, 2H), 7.99 (d, J=8.0Hz, 2H), 7.68-7.54 (m, 8H), 7.49-7.42 (m, 3H), 7.38 (d, J =5.6Hz, 2H), 4.35 (t, J=6.8Hz, 4H), 4.27-4.09 (m, 10H), 1.98 (m, 10H), 1.84 (m, 4H), 1.53- 1.32(m,32H),1.04-0.88(m,21H)；
It is pure that the chemical reagent and solvent are analysis.
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