CN106588768A - Synthetic method for benzophenanthrene benzyne bridging perylene bisimide diester binary compound - Google Patents
Synthetic method for benzophenanthrene benzyne bridging perylene bisimide diester binary compound Download PDFInfo
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Abstract
The invention discloses a synthetic method for a benzophenanthrene benzyne bridging perylene bisimide diester binary compound. The synthetic method includes the synthetic routes of (1) synthesis of a benzophenanthrene derivative containing alkynyl, (2) synthesis of a perylene bisimide diester compound, and (3) obtaining of the benzophenanthrene benzyne bridging perylene bisimide diester binary compound through a coupled reaction of intermediates, namely the benzophenanthrene derivative containing alkynyl and the perylene bisimide diester compound. The benzophenanthrene benzyne bridging perylene bisimide diester binary compound is of the D-B-A type structure with an alkoxy benzophenanthrene unit as an electronic donor and a perylene bisimide diester unit as an electronic acceptor, and the benzophenanthrene benzyne bridging perylene bisimide diester binary compound has the property of photoinduced electron transfer in molecules and also has the property of columnar phase discotic liquid crystals. The property that electrons and holes are made to be directionally transferred along molecular columns of acceptor units and molecular columns of donor units of the discotic liquid crystals is expected to be achieved, and thus carrier loss is reduced, and the performance of organic photovoltaic devices can be improved prospectively.
Description
Technical field
The present invention relates to a kind of benzo phenanthryne benzeno connects the synthetic method of perylene diimide diester 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 benzeno connects the synthetic method of perylene diimide diester binary compound.
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 alkoxy benzene of alkynyl five is contained by Material synthesis of the hexyloxy benzophenanthrene of monohydroxy five
And phenanthrene derivative (compound 6).
(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) benzo will be obtained containing the alkoxyl triphenylene of alkynyl five and perylene diimide diester intermediate coupling reaction
Phenanthryne benzeno Lian perylene diimides diester binary compound (compound 16).
The present invention has been designed and synthesized with alkoxyl benzophenanthrene unit as electron donor (Donor), perylene diimide diester list
Unit for electron acceptor (Acceptor) the binary compound for having a D-B-A type structures, this kind of compound both had intramolecular photo-induction
The property of electron transfer is led, there may be the property of columnar phase discotic mesogenic again.Expection obtains having makes electronics and hole difference
Along the property of the molecular columns directional migration of the molecular columns and donor monomer of discotic mesogenic receptor unit, so as to reduce the damage of carrier
Lose, 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 6) of alkynyl 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。
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 synthetic route that benzo phenanthryne benzeno of the present invention connects perylene diimide diester binary compound (compound 16)
Figure.
It is labeled as in figure：6- compounds 6,15- 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, 79.2mol) is dissolved in dichloromethane (80mL) and nitromethane (8mL).Chemical combination
Thing 1 (4.44g, 16mmol) and compound 2 (1.56g, 8mmol) are dissolved in dichloromethane (60mL), at 0 DEG C, by the He of compound 1
The mixed solution of compound 2 is dropped in the dichloromethane and nitromethane solution of above-mentioned anhydrous ferric trichloride, 30 minutes Deca
Finish.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 ends
Only react.The mixture of reaction is washed twice with the dilute hydrochloric acid that 15mL concentration is 2mol/L, with 15mL saturated common salts water washing one
It is secondary.Organic layer is separated, after adding anhydrous sodium sulfate drying eliminating water, vacuum rotary steam removes solvent, the crude product purified by silica gel chromatograph for obtaining
(leacheate is for post purification:Ethyl acetate/petroleum ether volume ratio is 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；1HNMR(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 three mouthfuls
Bottle, ice bath is removed in 15 minutes after dripping.Nitrogen is protected, and is reacted 5 hours under room temperature.Reactant liquor 10mL is that mass percent is dense
The dilute hydrochloric acid for 5% and the extraction of 10mL dichloromethane are spent, collected organic layer, vacuum distillation obtains crude product.Crude product volume
Than for 1:4 methylene chloride-methanol recrystallization, 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) 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), 0.0203g triphenylphosphines (0.076mmol) iodate Asia are taken
Copper (0.0148g, 0.076mmol), dichloride two (triphenyl phosphorus) are closed palladium (II) (0.0540g, 0.076mmol) and add three mouthfuls
Bottle, be subsequently adding 15mL tetrahydrofurans, 5mL triethylamine stirring and dissolving, be subsequently adding 2- methyl -3- butyne-2-alcohols (0.098g,
1.15mmol), 80 DEG C are stirred at reflux overnight.Reactant liquor 80mL mass percent concentrations are 5% ammonium chloride solution/20mL dichloros
Methane is extracted, and collected organic layer, vacuum distillation obtains crude product.Crude product purified by silica gel chromatographic column is purified, eluting liquid proportional second
Acetoacetic ester：Petroleum ether volume ratio 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 0.25g light yellow solids 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)。
(the synthesis of the own ester (compound 13) of 7) perylene -3,4,9,10- tetracarboxylic acids four
Perylene -3, it is dense that 4,9,10- tetracarboxylic acid dianhydrides (compound 11) (3.5g, 8.92mmol) are added to 400mL mass percents
In spending the potassium hydroxide aqueous solution for 2.5%, react 1.5 hours at 70 DEG C.Room temperature is cooled to, sucking filtration adjusts filtrate pH to 7,
Aqueous solutions of the get Dao perylene tetracarboxylic acid potassium (compound 12).By hexyl bromide 1 bromohexane (14.72g, 89.2mmol), tetrabutyl ammonium bromide
During (1.45g, 4.5mmol) is added to filtrate, react 6 hours at 100 DEG C.Room temperature is cooled to, is 1 with volume ratio:3 water/dichloro
Methane is extracted, collected organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, and vacuum distillation removes solvent.Crude product body
Product is than being 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 8) perylenes -3,4- dicarboxylic acid anhydrides -9,10- dioctyl phthalate dihexyls (compound 14)
After compound 13 (6.51g, 8.51mmol) is completely dissolved in toluene (3.6ml) and normal heptane (18.0ml), add
P-methyl benzenesulfonic acid (1.54g, 8.95mmol), 95 DEG C are reacted 5 hours, and sucking filtration after frozen water cooling, filter cake volume ratio is 1:The two of 4
Chloromethanes/recrystallizing methanol, sucking filtration after frozen water cooling, are repeated twice, and obtain red solid (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 9) 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).
(10) benzo phenanthryne benzeno connects the synthesis of perylene diimide diester binary compound (compound 16)
Nitrogen protection under, by dried compound 6 (0.45g, 0.60mmol), compound 15 (0.49g,
0.63mmol), triphenylphosphine (15.7mg, 0.06mmol), Hydro-Giene (Water Science). (11.4mg, 0.06mmol) and double (triphenylphosphines) two
Palladous chloride. (II) (41.9mg, 0.06mmol) is added in dry there-necked flask, vacuum nitrogen gas, in triplicate.Then just
Under pressure protection, tetrahydrofuran (14mL) and triethylamine (3.5mL) are separately added into.The 80 DEG C of lucifuges that heat up are stirred at reflux, and reaction is overnight.
Room temperature is cooled to, 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 to 0.69g white solids, yield 82%；Mp:218.3-218.8℃；IR(KBr)νmax(cm-1):3446,
2953,2928,2857,2360,2340,1705,1668,1593,1511,1468,1432,1360,1296,1263,1171,
1064,1036,879,839,806,748,726,669,599.1H NMR(500MHz,CDCl3) δ 8.61 (d, J=8.0Hz,
2H), 8.45 (s, 1H), 8.37 (d, J=8.0Hz, 2H), 8.31 (d, J=8.0Hz, 2H), 8.06 (d, J=8.0Hz, 2H),
7.82-7.77 (m, 3H), 7.76 (s, 1H), 7.65 (s, 2H), 7.62 (s, 1H), 7.47-7.43 (m, 2H), 4.35 (t, J=
6.8Hz,4H),4.30-4.16(m,10H),2.07-1.89(m,10H),1.87-1.78(m,4H),1.69(m,2H),1.52-
1.33(m,30H),1.00-0.90(m,21H)。
Claims (1)
1. a kind of benzo phenanthryne benzeno connects the synthetic method of perylene diimide diester binary compound, it is characterised in that concrete steps
For：
(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,
Obtain compound 1, 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) 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, the fraction of 0.5mmHg are collected in vacuum distillation, are obtained
Compound 2,25.5g colourless oil liquids, 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 the mixture of 80mL dichloromethane and 8mL nitromethanes；4.44g compound 1
It is dissolved in 60mL dichloromethane with 1.56g compounds 2, at 0 DEG C, the mixed solution of compound 1 and compound 2 is dropped to
In stating the dichloromethane and nitromethane solution of anhydrous ferric trichloride, 30 minutes completion of dropping；The mixture of reaction is maintained at into 0
After continuing to react 3 hours in the range of DEG C -3 DEG C, 50mL methanol and 25mL water terminating reactions are added；The mixture of reaction is dense with 15mL
Spend the dilute hydrochloric acid for 2mol/L to wash twice, washed once with 15mL saturated aqueous common salts；Organic layer is separated, anhydrous sodium sulfate is added
After being dried eliminating water, vacuum rotary steam removes solvent, the crude product purified by silica gel chromatographic column purification for obtaining, and leacheate is:Ethyl acetate/oil
Ether volume ratio is 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；1HNMR(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 into there-necked flask, ice bath is removed within 15 minutes after dripping；
Nitrogen is protected, and is reacted 5 hours under room temperature；Reactant liquor 10mL is the dilute hydrochloric acid and 20mL dichloros that mass percent concentration is 5%
Methane 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, the i.e. synthesis of compound 5
Under nitrogen protection, 0.67g compounds 4,0.0203g triphenylphosphines, 0.0148g Hydro-Giene (Water Science) .s and 0.0540g dichlorides are taken
Two (triphenyl phosphorus) close palladium (II) and add there-necked flask, are subsequently adding 15mL tetrahydrofurans and 5mL triethylamine stirring and dissolving, Ran Houjia
Enter 0.098g 2- methyl -3- butyne-2-alcohols, 80 DEG C are stirred at reflux overnight；Reactant liquor 80mL mass percent concentrations are 5%
Ammonium chloride solution/20mL dichloromethane extraction, collected organic layer, vacuum distillation obtains crude product；Crude product purified by silica gel chromatographic column is entered
Row purification, eluting liquid proportional ethyl acetate：Petroleum ether volume ratio 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)；
(the own ester of 7) perylene -3,4,9,10- tetracarboxylic acids four is the synthesis of compound 13
It is the hydrogen that compound 11 is added to that 400mL mass percent concentrations are 2.5% by 3.5g perylene -3,4,9,10- tetracarboxylic acid dianhydrides
In oxidation aqueous solutions of potassium, react 1.5 hours at 70 DEG C；Room temperature is cooled to, sucking filtration adjusts filtrate pH to 7, get Dao perylene tetracarboxylic acid potassium
That is the aqueous solution of compound 12；14.72g hexyl bromide 1 bromohexanes, 1.45g tetrabutyl ammonium bromide are added in filtrate, at 100 DEG C 6 are reacted
Hour；Room temperature is cooled to, is 1 with volume ratio:3 water/dichloromethane extraction, collected organic layer, saturated common salt water washing is anhydrous
Sodium sulfate is dried, and vacuum distillation removes solvent；Crude product volume ratio is 1:1 dichloromethane/ethyl alcohol recrystallization sucking filtration, decompression
It is filtrated to get yellow powder i.e. 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)；
(8) 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)；
(9) perylene-N- are the synthesis of compound 15 to iodobenzene alkynes -3,4- dicarboximide -9,10- dioctyl phthalate dihexyls
Under nitrogen protection, dried 2.00g compounds 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)；
(10) benzo phenanthryne benzeno connects the perylene diimide diester binary compound i.e. synthesis of compound 16
Under nitrogen protection, by 0.45g dried compound 6,0.49g compounds 15,15.7mg triphenylphosphines, 11.4mg
Hydro-Giene (Water Science). and double (triphenylphosphine) palladium chlorides (II) of 41.9mg are added in dry there-necked flask, and vacuum nitrogen gas repeat
Three times；Then under positive pressure protection, 14mL tetrahydrofurans and 3.5mL triethylamines are separately added into；The 80 DEG C of lucifuges that heat up are stirred at reflux,
Reaction is overnight；Room temperature is cooled to, reactant liquor 80mL mass percent concentrations are 5% ammonium chloride solution/20mL chloroform extraction
Take three times, collected organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, revolving removes solvent；Crude product purified by silica gel chromatograph
Post is purified, and obtains white solid 0.69g, yield 82%；Mp:218.3-218.8℃；IR(KBr)νmax(cm-1):3446,2953,
2928,2857,2360,2340,1705,1668,1593,1511,1468,1432,1360,1296,1263,1171,1064,
1036,879,839,806,748,726,669,599.1H NMR(500MHz,CDCl3) δ 8.61 (d, J=8.0Hz, 2H), 8.45
(s, 1H), 8.37 (d, J=8.0Hz, 2H), 8.31 (d, J=8.0Hz, 2H), 8.06 (d, J=8.0Hz, 2H), 7.82-7.77
(m, 3H), 7.76 (s, 1H), 7.65 (s, 2H), 7.62 (s, 1H), 7.47-7.43 (m, 2H), 4.35 (t, J=6.8Hz, 4H),
4.30-4.16(m,10H),2.07-1.89(m,10H),1.87-1.78(m,4H),1.69(m,2H),1.52-1.33(m,
30H),1.00-0.90(m,21H)；
It is pure that the chemical reagent and solvent are analysis.
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| CN105541616A (en) * | 2015-12-05 | 2016-05-04 | 桂林理工大学 | Hexaalkoxytriphenylene-flexible bridge-perylenetetracarboxylic acid tetraester binary compound and preparation method thereof |
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| CN105541616A (en) * | 2015-12-05 | 2016-05-04 | 桂林理工大学 | Hexaalkoxytriphenylene-flexible bridge-perylenetetracarboxylic acid tetraester binary compound and preparation method thereof |
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