CN107082762A - The synthetic method of benzophenanthrene benzoyloxy alkynes benzyne benzene Qiao Lian perylene list imines dihexyls - Google Patents
The synthetic method of benzophenanthrene benzoyloxy alkynes benzyne benzene Qiao Lian perylene list imines dihexyls Download PDFInfo
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Abstract
It is an object of the invention to provide a kind of synthetic method of benzophenanthrene benzoyloxy alkynes benzyne benzene Qiao Lian perylene list imines dihexyls.Its synthetic route is：The hexyloxy benzophenanthrene of Part I synthesis acetylenylbenzene containing iodophenyl formyloxy five.Part II Shi synthesizes the Ji perylene diimide diester derivs of Ben containing alkynes using 3,4, 9, 10-perylenetetracarboxylic dianhydride as raw material.Part III is that the intermediate for obtaining above-mentioned two parts passes through Sonogashira cross-coupling reactions, synthesis benzophenanthrene oxygen carbonyl benzyne benzyne benzene Qiao Lian perylene list imines dihexyl binary compounds.Benzophenanthrene and its derivative are currently that perylene diimide derivative is a kind of excellent n-type organic semiconducting materials with most commonly used discotic mesogenic material , Er.The present invention designs and synthesizes the discotic mesogenic binary compound containing electron donor bridge receptor structure, and this kind of compound can be applicable in organic solar batteries, Organic Light Emitting Diode equimolecular device.
Description
Technical field
The present invention relates to a kind of synthetic method of benzophenanthrene benzoyloxy alkynes benzyne benzene Qiao Lian perylene list imines dihexyls.
Background technology
In discotic mesogenic, benzophenanthrene as a kind of common material, because its have good photochemistry and heat endurance,
Raw material is easy to get, product is easy to purification, structure-rich is changeable and has the advantages that higher charge transport rate in the longitudinal axis, therefore
It is preferred donor monomer；Er perylene diimide visible region have strong absorption, photochemistry and heat endurance is good and synthetic method into
It is ripe, with good liquid crystal property, therefore good receptor unit can be used as.The present invention by design and synthesize containing electronics to
The discotic mesogenic binary compound of body (D)-bridge (B)-acceptor (A) structure, this kind of compound can apply organic photovoltaic material,
Liquid crystal material, organic solar batteries, Organic Light Emitting Diode equimolecular device.
The content of the invention
It is an object of the invention to provide the synthesis side of benzophenanthrene benzoyloxy alkynes benzyne benzene Qiao Lian perylene list imines dihexyls
Method.
The synthetic route of the present invention can be divided into three below part：
Part I, using parabromobenzoic acid methyl esters as raw material, passes through palladium chtalyst Sonogashira cross-coupling reactions and water
Solution reaction, synthesizes to acetylenylbenzene formic acid；Adjacent two hexyloxies benzene and 2- hexyloxy-phenols are made in the oxidation of ferric trichloride again
With the lower generation coupling reaction generation hexyloxy benzophenanthrene of monohydroxy five；Sent out by 4- (acetenyl) benzoic acid and monohydroxy benzophenanthrene
Raw esterification is prepared for containing the hexyloxy triphenylene compound (compound 6) of alkynes dibenzoyl epoxide five, finally with
The hexyloxy benzophenanthrene (compound 7) of 1,4- diiodo-benzenes reaction generation acetenyl containing iodophenyl formyloxy five.
Part II, He Cheng perylene acid anhydrides diester is expected first by Yuan of perylene dicarboxylic anhydride；Ran Hou perylene acid anhydrides diester and 4- Iodoanilines
Carry out amidatioon get and obtain the Ji perylene diimides of Ben containing alkynes Dao perylene diimide diester (compound 10), then by trimethyl silicane ethyl-acetylene
Diester deriv (compound 12).
Part III is by containing the alkoxy triphenylene compound of alkynes dibenzoyl epoxide five and perylene diimide two
Ester intermediate coupling reaction obtains benzophenanthrene benzoyloxy alkynes benzyne benzene Qiao Lian perylene list imines dihexyl binary compound (chemical combination
Thing 13).
Benzophenanthrene and its derivative are currently that, with most commonly used discotic mesogenic material, they have photoelectricity well
Performance, easily forms columnar liquid crystalline phase.In the presence of Benzophenanthrene discotic mesogenic is with columnar phase, its one-dimensional square possesses higher current-carrying
Transport factor, can as photoelectric device hole transmission layer.Perylene diimide derivative is that a class has special condensed cyclic structure to Er
Compound, there are four electrophilic carbonyls, obtain that electronic capability is very strong, and with higher electron affinity, in visible ray
Area has very strong absorption to near-infrared, is a kind of excellent n-type organic semiconducting materials, is widely used in organic photovoltaic field.
The present invention by designing and synthesizing the discotic mesogenic binary compound containing electron donor (D)-bridge (B)-acceptor (A) structure, this
Class compound can be applied in organic photovoltaic material, liquid crystal material, organic solar batteries, Organic Light Emitting Diode equimolecular device
Part.
Brief description of the drawings
Fig. 1 is the structural formula of benzophenanthrene benzoyloxy alkynes benzyne benzene Qiao Lian perylene list imines dihexyls of the present invention.
Fig. 2 is the chemical equation of synthetic route of the present invention.
Marked 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 8,9- compounds 9,10- compounds 10,11- compounds 11,12- compounds 12,13- compounds
13。
In figure：R=C6H13。
Embodiment
Embodiment：
Chemical reagent and solvent used in embodiment are that analysis is pure.
(1) synthesis of the synthesis (compound 1) of 4- (3- hydroxy-3-methyl -1- butynyls) methyl benzoate
Palladium (II) will be closed to 1g methyl-bromobenzoates, 0.088g cuprous iodides, 0.362g dichlorides two (triphenyl phosphorus),
0.122g triphenylphosphines are added in there-necked flask, add 0.5ml 3- hydroxy-3-methyl -1- butine, 24ml tetrahydrofurans and
8ml triethylamines, under nitrogen protection, are reacted at room temperature 3.5 hours.Reaction solution is that 5% ammonium chloride is molten with 80mL mass percent concentrations
Liquid/20mL dichloromethane extraction, collected organic layer, vacuum distillation obtains crude product.Crude product purified by silica gel chromatographic column is purified, and is washed
De- liquid proportional ethyl acetate：Petroleum ether volume ratio is 10:1, obtain compound 1,0.87g, yield 87%, Mp 67-68 DEG C, IR
(KBr)νmax(cm-1):3298,2106,1585,1543,1390,621；1H NMR(CDCl3,400MHz)δ:7.98 (dd, J=
6.7,1.8Hz, 2H), 7.48 (dd, J=6.7,1.8Hz, 2H), 3.92 (s, 3H), 2.03 (s, 1H), 1.64 (s, 6H)
(2) synthesis of 4- (acetenyl) benzoic acid (compound 2)
By 0.3g sodium hydroxides, the mixing of 10mL n-butanols is stirred at reflux at 110 DEG C, add 0.4g 4- (3- hydroxyls-
3- methyl isophthalic acids-butynyl) methyl benzoate, flows back 10 minutes at 110 DEG C.Room temperature is cooled to, 4- (acetenyl) benzene first is filtered to obtain
Sour sodium.4- (acetenyl) sodium benzoate is dissolved in water, watery hydrochloric acid acidifying has solid precipitation.Dissolved and extracted with ethyl acetate, nothing
Aqueous sodium persulfate is dried, and is concentrated to give 4- (acetenyl) benzoic acid.Mp.84-85℃,IR(KBr)νmax(cm-1):3298(C-H),
2106 (C ≡ C), 1585 (C=O), 1543,1390,621；1H NMR(400MHz,CDCl3)δ:12.72(s,1H),8.16(t,J
=6.9Hz, 2H), 7.76 (t, J=6.9Hz, 2H), 3.11 (s, 1H)
(3) synthesis of adjacent own alkoxy phenol (compound 3)
20g catechols, 89.9g1- bromos n-hexane, 73.5g Anhydrous potassium carbonates, 6.0g KIs and 250mL is anhydrous
Ethanol, the back flow reaction after 60 hours at 85 DEG C, suction filtration at room temperature, the rotated evaporimeter of filtrate is removed after solvent,
The cut of 84 DEG C of collection, obtains 48g colourless oil liquids i.e. compound 3, yield is in the case of 0.5mmHg vacuum distillation
96%.Bp:106±3℃,IR(KBr)νmax(cm-1):1260,930；1H NMR(400MHz,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).
(4) synthesis of adjacent two own alkoxy benzenes (compound 4)
Take 50g catechols, 75g 1- bromos n-hexane, 100g Anhydrous potassium carbonates, 3.8g KIs and 500mL anhydrous
Ethanol, 85 DEG C of back flow reactions are after 12 hours, at room temperature suction filtration, and the rotated evaporimeter of filtrate is removed after solvent, and 0.5mmHg's subtracts
The cut of 140-143 DEG C of collection, obtains 25.5 grams of colourless oil liquids i.e. compound 4, yield is 29% in the case of pressure distillation.Bp
255±3℃,IR(KBr)νmax(cm-1):1250,939；1H NMR(400MHz,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).
(5) synthesis of the hexyloxy of monohydroxy-five benzophenanthrene (compound 5)
It is molten that compound 4 obtained by taking compound 3 obtained by 4.44g steps (3) and 1.56g steps (4) is dissolved in 60mL dichloromethane
In liquid the dichloromethane solution that 80mL contains 12.96g anhydrous ferric trichlorides and 8mL nitromethanes is added dropwise to through constant pressure funnel
In, 30 minutes completion of dropping；Then after the temperature of reaction being maintained in the range of 0 DEG C -3 DEG C into isothermal reaction 3 hours, 50mL is added
Methanol and 25mL water terminating reactions, the mixture of reaction is respectively that 2mol/L watery hydrochloric acid is washed twice with 15mL concentration, and 15mL satisfies
With brine It once, organic layer is separated, is added after anhydrous sodium sulfate drying water removal, rotated evaporimeter removes solvent, obtains
To crude product purified by silica gel (200-300 mesh) column chromatography purification (leacheate be ethyl acetate/petroleum ether volume ratio be 1:30-1:
15) 2.14g brown yellow solids i.e. compound 5, is obtained, yield is 36%.Mp 47.7-50.1℃,IR(KBr)νmax(cm-1):
3040,1240,837；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).
(6) conjunction of 2- [4- (acetenyl) benzoyloxy] -3,6,7,10,11- five (alkoxy) benzophenanthrene (compound 6)
Into
By 0.28g monohydroxy benzophenanthrenes, 0.11g 4- (acetenyl) benzoic acid, 0.15g dicyclohexylcarbodiimides and
0.0092g 4-N, TMSDMA N dimethylamine yl pyridines are added in the dichloromethane that 12mL is dried.It is stirred at room temperature 24 hours, filters, will filter
Liquid is spin-dried for, and with the purification of silica gel (200-300 mesh) column chromatography, (leacheate is that ethyl acetate/petroleum ether volume ratio is 1:20-1:15),
Ethyl alcohol recrystallization, obtains white solid i.e. compound 6.Mp 151-152℃,IR(KBr)νmax(cm-1):3734,3444,2927,
2858,1723 (C=O), 1662,1591,1512,1433 (C=C), 1364,1262 (C-O-C), 1163 (C-O), 1029,
834,745,535；1H NMR(400MHz,CDCl3)δ8.32-8.26(m,2H),8.22(s,1H),7.93(s,1H),7.90(s,
1H), 7.85 (d, J=5Hz, 2H), 7.80 (d, J=6.5Hz, 1H), 7.72-7.67 (m, 2H), 4.29-4.21 (m, 11H),
3.33(s,1H),1.96(m,9H),1.82-1.75(m,2H),1.51-1.19(m,27H),1.04-0.91(m,14H),0.85
(m,3H).
(7) 2- [4- (4 iodophenyl) acetenyl formyloxy] -3,6,7,10,11- five (hexyloxy) benzophenanthrene (compound
7) synthesis
Nitrogen protection under, by dried 0.2g compounds 6,0.1g Isosorbide-5-Nitrae-diiodo-benzene, 6.1mg triphenylphosphines,
2.2mg cuprous iodides and double (triphenylphosphine) palladium chlorides (II) of 16.1mg are added in dry there-necked flask, and the good device of frame is taken out very
Sky, inflated with nitrogen, in triplicate.Then under positive pressure protection, 12mL tetrahydrofurans and 4mL triethylamines are separately added into.80 DEG C of heating,
Lucifuge is stirred at reflux, and reaction is stayed overnight.Be cooled to room temperature, reaction solution with 80mL mass percent concentrations be 5% ammonium chloride solution/
20mL chloroform extractions three times, collected organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, revolving removes solvent.Slightly
Product is purified with silica gel chromatographic column, obtains compound 7 (0.18g, yield 78%).Mp 120-121℃.IR(KBr)νmax(cm-1):3734,3444,2927,2858,1723 (C=O), 1662,1591,1512,1433 (C=C), 1364,1262 (C-O-C),
1163(C-O),1029,834,745,535.1H NMR(400MHz,CDCl3)δ8.36-8.26(m,2H),8.24(s,1H),
7.92 (d, J=10Hz, 2H), 7.88-7.76 (m, 3H), 7.74-7.68 (m, 2H), 7.59-7.50 (m, 2H), 7.50-7.43
(m,2H),4.43-4.14(m,10H),2.07-1.89(m,8H),1.85-1.75(m,2H),1.66-1.50(m,12H),
(t, J=7.0Hz, the 3H) of 1.50-1.33 (m, 18H), 1.02-0.88 (m, 12H), 0.85
(the synthesis of the 8) own esters of perylene -3,4,9,10- tetracarboxylic acids (compound 8)
By 3.5g perylenes -3,4,9,10- tetracarboxylic acid dianhydrides are added to mass ratio in 2.5% potassium hydroxide aqueous solution 400mL,
70 DEG C are reacted 1.5 hours.It is cooled to room temperature, suction filtration, regulation filtrate pH=7, get Dao perylene tetracarboxylic acid potassium.By 14.72g 1- bromines oneself
Alkane, 1.45g TBABs are added in filtrate, are reacted 6 hours at 100 DEG C.Room temperature is cooled to, is 1 with volume ratio:3 water/
Dichloromethane is extracted, collected organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, and vacuum distillation removes solvent.Crude product
It is 1 with volume ratio:1 dichloromethane/ethyl alcohol recrystallization suction filtration, is filtered under diminished pressure and obtains yellow powder i.e. compound 8,6.51g, production
Rate 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(400MHz,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 the 9) perylene -3,4- own esters of dicarboxylic acid anhydride -9,10- dioctyl phthalate (compound 9)
After 6.51g compounds 8 are completely dissolved in 3.6ml toluene and 18.0ml normal heptanes, 1.54g is added to toluene sulphur
Acid, 95 DEG C are reacted 5 hours, and suction filtration after frozen water cooling, filter cake volume ratio is 1:4 methylene chloride/methanol recrystallization, ice water cooling
But suction filtration after, is repeated twice, obtains red solid 3.88g i.e. compound 9, 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(400MHz,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).
(10) N- (synthesis of 4- iodophenyl) perylene imines dioctyl phthalate dihexyls (compound 10)
Under nitrogen protection, dried 2.00g compounds 9 are added into flask, 3.03g 4- Iodoanilines, 0.32g is anhydrous
Zinc acetate and 20.00g imidazoles, vacuum nitrogen gas, in triplicate.150 DEG C of stirring heating, reaction is stayed overnight, and is cooled to room temperature.Instead
It is 1 to answer thing volume ratio: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/ethyl alcohol recrystallization, obtains Orange red solid 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)。
(11) N- (synthesis of 4- (3- methylsilyls acetylene)-phenyl) perylene imines dioctyl phthalate dihexyls (compound 11)
Under nitrogen protection, by 0.1g compounds 10 dried in advance, 3.4mg triphenylphosphines, 1.2mg cuprous iodides
Added with double (triphenylphosphine) palladium chlorides (II) of 9mg in dry there-necked flask, add 0.025g trimethyl silicane ethyl-acetylenes,
15mL tetrahydrofurans and 5mL triethylamines.40 DEG C of heating, lucifuge is stirred at reflux, and reaction is stayed overnight.Room temperature is cooled to, reaction solution is used
80mL mass percent concentrations are 5% ammonium chloride solution/20mL chloroform extractions three times, collected organic layer, saturated aqueous common salt
Washing, anhydrous sodium sulfate drying, revolving removes solvent.Crude product purified by silica gel chromatographic column is purified, and obtains red solid i.e. compound
11 (0.09g, yields 90%).Mp>300℃；IR(KBr)νmax(cm-1):3450,2956,2856,1717,1667,1595,
1511,1469,1367,1276,1167,1062,1012,961,809,778；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),0.08(m,9H)。
(12) N- (synthesis of 4- ethynyl phenyl) perylene imines dioctyl phthalate dihexyls (compound 12)
Under nitrogen protection, 0.1g compounds 11,0.15g potassium carbonate are added into flask, 10mL methanol and 10mL bis- is added
Chloromethanes, is stirred at room temperature 4 hours.Reaction solution is extracted with 40mL water and 10mL dichloromethane, and collected organic layer, vacuum distillation is obtained slightly
Product.Crude product purified by silica gel chromatographic column is purified, and elutes liquid proportional ethyl acetate：Petroleum ether volume ratio is 1:30, obtain red solid
Body 0.09g, yield 91%；Mp>300℃；IR(KBr)νmax(cm-1):3450,2956,2856,1712,1661,1596,1511,
1471,1366,1274,1168,1067,1012,961,809,778；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), 3.45 (s, 1H), 1.83 (q, J=7.2Hz, 4H), 1.46
(m,4H),1.36(m,8H),0.97-0.88(m,6H)。
(13) synthesis of benzophenanthrene benzoyloxy alkynes benzyne benzene Qiao Lian perylene list imines dihexyls (compound 13)
Under nitrogen protection, by dried 0.7g compounds 7 in advance, 0.3g compounds 12,10.1mg triphenylphosphines,
3.4mg cuprous iodides and double (triphenylphosphine) palladium chlorides (II) of 27mg are added in dry there-necked flask, and the good device of frame is vacuumized,
Inflated with nitrogen, in triplicate.Then under positive pressure protection, 15mL tetrahydrofurans and 5mL triethylamines are separately added into.80 DEG C of heating, keeps away
Light is stirred at reflux, and reaction is stayed overnight.Room temperature is cooled to, reaction solution is 5% ammonium chloride solution/20mL with 80mL mass percent concentrations
Chloroform extraction three times, collected organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, revolving removes solvent.Crude product
Purified with silica gel chromatographic column, obtain red solid i.e. compound 13 (0.53g, yield 82%).Mp:251.8-252.6℃,IR
(KBr)νmax(cm-1):3734,3445,2928 (C-H), 2858,1716 (C=O), 1662,1591,1512,1433 (C=C),
1364,1262(C-O-C),1163(C-O),1029,834,746,535.1H NMR(400MHz,CDCl3)δ8.47(s,2H),
8.24 (t, J=7.5Hz, 2H), 8.16-7.99 (m, 4H), 7.94 (d, J=7.0Hz, 2H), 7.71-7.64 (m, 4H), 7.62
(d, J=8.0 Hz, 2H), 7.54 (m, 4H), 7.49-7.43 (m, 4H), 7.35-7.28 (m, 2H), 4.35 (t, J=7.0 Hz,
4H), 4.15 (m, 11H), 1.94 (d, J=6.0 Hz, 10H), 1.83 (m, 5H), 1.62-1.53 (m, 12H), 1.44 (m,
40H),1.31-1.18(m,10H).
Claims (1)
1. a kind of synthetic method of benzophenanthrene benzoyloxy alkynes benzyne benzene Qiao Lian perylene list imines dihexyls, it is characterised in that specific
Step is：
(1) synthesis of 4- (3- hydroxy-3-methyl -1- butynyls) methyl benzoate (compound 1)
Palladium (II), 0.122g will be closed to 1g methyl-bromobenzoates, 0.088g cuprous iodides, 0.362g dichlorides two (triphenyl phosphorus)
Triphenylphosphine is added in there-necked flask, adds 0.5ml 3- hydroxy-3-methyl -1- butine, 24ml tetrahydrofurans and the second of 8ml tri-
Amine, under nitrogen protection, is reacted at room temperature 3.5 hours.Reaction solution is 5% ammonium chloride solution/20mL with 80mL mass percent concentrations
Dichloromethane is extracted, and collected organic layer, vacuum distillation obtains crude product.Crude product purified by silica gel chromatographic column is purified, eluent ratio
Example ethyl acetate：Petroleum ether volume ratio is 10:1, obtain compound 1,0.87g, yield 87%, Mp 67-68 DEG C, IR (KBr)
νmax(cm-1):3298,2106,1585,1543,1390,621；1H NMR(CDCl3,400MHz)δ:7.98 (dd, J=6.7,
1.8Hz, 2H), 7.48 (dd, J=6.7,1.8Hz, 2H), 3.92 (s, 3H), 2.03 (s, 1H), 1.64 (s, 6H)
(2) synthesis of 4- (acetenyl) benzoic acid (compound 2)
By 0.3g sodium hydroxides, 10mL n-butanols are mixed, and are stirred at reflux at 110 DEG C, are added 0.4g 4- (3- hydroxyl -3- first
Base -1- butynyls) methyl benzoate, flows back 10 minutes at 110 DEG C.Room temperature is cooled to, 4- (acetenyl) sodium benzoate is filtered to obtain.
4- (acetenyl) sodium benzoate is dissolved in water, watery hydrochloric acid acidifying has solid precipitation.Dissolved and extracted with ethyl acetate, anhydrous sulphur
Sour sodium is dried, and is concentrated to give 4- (acetenyl) benzoic acid.Mp.84-85℃,IR(KBr)νmax(cm-1):3298(C-H),2106(C
≡ C), 1585 (C=O), 1543,1390,621；1H NMR(400MHz,CDCl3)δ:12.72 (s, 1H), 8.16 (t, J=
6.9Hz, 2H), 7.76 (t, J=6.9Hz, 2H), 3.11 (s, 1H)
(3) synthesis of adjacent own alkoxy phenol (compound 3)
By 20g catechols, 89.9g1- bromos n-hexane, 73.5g Anhydrous potassium carbonates, 6.0g KIs and the anhydrous second of 250mL
Alcohol, the back flow reaction after 60 hours at 85 DEG C, suction filtration at room temperature, the rotated evaporimeter of filtrate is removed after solvent, in 0.5mmHg
Vacuum distillation in the case of collect 84 DEG C of cut, obtain 48g colourless oil liquids i.e. compound 3, yield is 96%.Bp:106
±3℃,IR(KBr)νmax(cm-1):1260,930；1H NMR(400MHz,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)
(4) synthesis of adjacent two own alkoxy benzenes (compound 4)
50g catechols, 75g 1- bromos n-hexane, 100g Anhydrous potassium carbonates, 3.8g KIs and 500mL absolute ethyl alcohols are taken,
85 DEG C of back flow reactions are after 12 hours, at room temperature suction filtration, and the rotated evaporimeter of filtrate is removed after solvent, and 0.5mmHg decompression is steamed
The cut of 140-143 DEG C of collection, obtains 25.5 grams of colourless oil liquids i.e. compound 4, yield is 29% in the case of evaporating.Bp 255
±3℃,IR(KBr)νmax(cm-1):1250,939；1H NMR(400MHz,CDCl3)δ:6.95-6.82(m,4H),5.68(s,
1H), (t, J=6.9Hz, the 3H) of 4.02 (t, J=6.9Hz, 2H), 1.83-1.76 (m, 2H), 1.48-1.31 (m, 6H), 0.91
(5) synthesis of the hexyloxy of monohydroxy-five benzophenanthrene (compound 5)
Compound 4 obtained by taking compound 3 obtained by 4.44g steps (3) and 1.56g steps (4) is dissolved in 60mL dichloromethane solutions
It is added dropwise to through constant pressure funnel in the dichloromethane solution that 80mL contains 12.96g anhydrous ferric trichlorides and 8mL nitromethanes,
30 minutes completion of dropping；Then after the temperature of reaction being maintained in the range of 0 DEG C -3 DEG C into isothermal reaction 3 hours, 50mL first is added
Alcohol and 25mL water terminating reactions, the mixture of reaction is respectively that 2mol/L watery hydrochloric acid is washed twice with 15mL concentration, 15mL saturations
Brine It once, separates organic layer, adds after anhydrous sodium sulfate drying water removal, rotated evaporimeter removes solvent, obtains
Crude product purified by silica gel (200-300 mesh) column chromatography purification (leacheate be ethyl acetate/petroleum ether volume ratio be 1:30-1:
15) 2.14g brown yellow solids i.e. compound 5, is obtained, yield is 36%.Mp 47.7-50.1℃,IR(KBr)νmax(cm-1):
3040,1240,837；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).
(6) synthesis of 2- [4- (acetenyl) benzoyloxy] -3,6,7,10,11- five (alkoxy) benzophenanthrene (compound 6)
By 0.28g monohydroxy benzophenanthrenes, 0.11g 4- (acetenyl) benzoic acid, 0.15g dicyclohexylcarbodiimides and
0.0092g 4-N, TMSDMA N dimethylamine yl pyridines are added in the dichloromethane that 12mL is dried.It is stirred at room temperature 24 hours, filters, will filter
Liquid is spin-dried for, and with the purification of silica gel (200-300 mesh) column chromatography, (leacheate is that ethyl acetate/petroleum ether volume ratio is 1:20-1:15),
Ethyl alcohol recrystallization, obtains white solid i.e. compound 6.Mp 151-152℃,IR(KBr)νmax(cm-1):3734,3444,2927,
2858,1723 (C=O), 1662,1591,1512,1433 (C=C), 1364,1262 (C-O-C), 1163 (C-O), 1029,
834,745,535；1H NMR(400MHz,CDCl3)δ8.32-8.26(m,2H),8.22(s,1H),7.93(s,1H),7.90(s,
1H), 7.85 (d, J=5Hz, 2H), 7.80 (d, J=6.5Hz, 1H), 7.72-7.67 (m, 2H), 4.29-4.21 (m, 11H),
3.33(s,1H),1.96(m,9H),1.82-1.75(m,2H),1.51-1.19(m,27H),1.04-0.91(m,14H),0.85
(m,3H).
(7) 2- [4- (4 iodophenyl) acetenyl formyloxy] -3,6,7,10,11- five (hexyloxy) benzophenanthrene (compound 7)
Synthesis
Under nitrogen protection, by dried 0.2g compounds 6,0.1g Isosorbide-5-Nitrae-diiodo-benzene, 6.1mg triphenylphosphines, 2.2mg
Cuprous iodide and double (triphenylphosphine) palladium chlorides (II) of 16.1mg are added in dry there-necked flask, and the good device of frame is vacuumized, and is filled
Nitrogen, in triplicate.Then under positive pressure protection, 12mL tetrahydrofurans and 4mL triethylamines are separately added into.80 DEG C of heating, lucifuge
It is stirred at reflux, reaction is stayed overnight.Room temperature is cooled to, reaction solution is 5% ammonium chloride solution/20mL tri- with 80mL mass percent concentrations
Chloromethanes is extracted three times, collected organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, and revolving removes solvent.Crude product is used
Silica gel chromatographic column is purified, and obtains compound 7 (0.18g, yield 78%).Mp 120-121℃.IR(KBr)νmax(cm-1):3734,
3444,2927,2858,1723 (C=O), 1662,1591,1512,1433 (C=C), 1364,1262 (C-O-C), 1163 (C-
O),1029,834,745,535.1H NMR(400MHz,CDCl3) δ 8.36-8.26 (m, 2H), 8.24 (s, 1H), 7.92 (d, J=
10Hz,2H),7.88-7.76(m,3H),7.74-7.68(m,2H),7.59-7.50(m,2H),7.50-7.43(m,2H),
4.43-4.14(m,10H),2.07-1.89(m,8H),1.85-1.75(m,2H),1.66-1.50(m,12H),1.50-1.33
(m, 18H), 1.02-0.88 (m, 12H), 0.85 (t, J=7.0Hz, 3H)
(the synthesis of the 8) own esters of perylene -3,4,9,10- tetracarboxylic acids (compound 8)
By 3.5g perylenes -3,4,9,10- tetracarboxylic acid dianhydrides are added to mass ratio in 2.5% potassium hydroxide aqueous solution 400mL, at 70 DEG C
Reaction 1.5 hours.It is cooled to room temperature, suction filtration, regulation filtrate pH=7, get Dao perylene tetracarboxylic acid potassium.By 14.72g hexyl bromide 1 bromohexanes,
1.45g TBABs are added in filtrate, are reacted 6 hours at 100 DEG C.Room temperature is cooled to, is 1 with volume ratio:3 water/bis-
Chloromethanes is extracted, collected organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, and vacuum distillation removes solvent.Crude product is used
Volume ratio is 1:1 dichloromethane/ethyl alcohol recrystallization suction filtration, is filtered under diminished pressure and obtains yellow powder i.e. compound 8,6.51g, 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(400MHz,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 the 9) perylene -3,4- own esters of dicarboxylic acid anhydride -9,10- dioctyl phthalate (compound 9)
After 6.51g compounds 8 are completely dissolved in 3.6ml toluene and 18.0ml normal heptanes, 1.54g p-methyl benzenesulfonic acid, 95 are added
DEG C reaction 5 hours, frozen water cooling after suction filtration, filter cake volume ratio be 1:4 methylene chloride/methanol recrystallization, after frozen water cooling
Suction filtration, is repeated twice, and obtains red solid 3.88g i.e. compound 9, 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(400MHz,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).
(10) N- (synthesis of 4- iodophenyl) perylene imines dioctyl phthalate dihexyls (compound 10)
Under nitrogen protection, dried 2.00g compounds 9,3.03g 4- Iodoanilines, 0.32g acetic anhydrides are added into flask
Zinc and 20.00g imidazoles, vacuum nitrogen gas, in triplicate.150 DEG C of stirring heating, reaction is stayed overnight, and 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 Orange red solid 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)。
(11) N- (synthesis of 4- (3- methylsilyls acetylene)-phenyl) perylene imines dioctyl phthalate dihexyls (compound 11)
Under nitrogen protection, by dried 0.1g compounds 10 in advance, 3.4mg triphenylphosphines, 1.2mg cuprous iodides and
Double (triphenylphosphine) palladium chlorides (II) of 9mg are added in dry there-necked flask, add 0.025g trimethyl silicane ethyl-acetylenes, 15mL
Tetrahydrofuran and 5mL triethylamines.40 DEG C of heating, lucifuge is stirred at reflux, and reaction is stayed overnight.It is cooled to room temperature, reaction solution 80mL matter
Amount percent concentration is 5% ammonium chloride solution/20mL chloroform extractions three times, collected organic layer, saturated common salt water washing, nothing
Aqueous sodium persulfate is dried, and revolving removes solvent.Crude product purified by silica gel chromatographic column is purified, and obtains red solid i.e. compound 11
(0.09g, yield 90%).Mp>300℃；IR(KBr)νmax(cm-1):3450,2956,2856,1717,1667,1595,1511,
1469,1367,1276,1167,1062,1012,961,809,778；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),0.08(m,9H)。
(12) N- (synthesis of 4- ethynyl phenyl) perylene imines dioctyl phthalate dihexyls (compound 12)
Under nitrogen protection, 0.1g compounds 11,0.15g potassium carbonate are added into flask, 10mL methanol and 10mL dichloromethanes is added
Alkane, is stirred at room temperature 4 hours.Reaction solution is extracted with 40mL water and 10mL dichloromethane, collected organic layer, and vacuum distillation, which is obtained, slightly produces
Thing.Crude product purified by silica gel chromatographic column is purified, and elutes liquid proportional ethyl acetate：Petroleum ether volume ratio is 1:30, obtain red solid
0.09g, yield 91%；Mp>300℃；IR(KBr)νmax(cm-1):3450,2956,2856,1712,1661,1596,1511,
1471,1366,1274,1168,1067,1012,961,809,778；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), 3.45 (s, 1H), 1.83 (q, J=7.2Hz, 4H), 1.46
(m,4H),1.36(m,8H),0.97-0.88(m,6H)。
(13) synthesis of benzophenanthrene benzoyloxy alkynes benzyne benzene Qiao Lian perylene list imines dihexyls (compound 13)
Under nitrogen protection, by dried 0.7g compounds 7 in advance, 0.3g compounds 12,10.1mg triphenylphosphines,
3.4mg cuprous iodides and double (triphenylphosphine) palladium chlorides (II) of 27mg are added in dry there-necked flask, and the good device of frame is vacuumized,
Inflated with nitrogen, in triplicate.Then under positive pressure protection, 15mL tetrahydrofurans and 5mL triethylamines are separately added into.80 DEG C of heating, keeps away
Light is stirred at reflux, and reaction is stayed overnight.Room temperature is cooled to, reaction solution is 5% ammonium chloride solution/20mL with 80mL mass percent concentrations
Chloroform extraction three times, collected organic layer, saturated common salt water washing, anhydrous sodium sulfate drying, revolving removes solvent.Crude product
Purified with silica gel chromatographic column, obtain red solid i.e. compound 13 (0.53g, yield 82%).Mp:251.8-252.6℃,IR
(KBr)νmax(cm-1):3734,3445,2928 (C-H), 2858,1716 (C=O), 1662,1591,1512,1433 (C=C),
1364,1262(C-O-C),1163(C-O),1029,834,746,535.1H NMR(400MHz,CDCl3)δ8.47(s,2H),
8.24 (t, J=7.5Hz, 2H), 8.16-7.99 (m, 4H), 7.94 (d, J=7.0Hz, 2H), 7.71-7.64 (m, 4H), 7.62
(d, J=8.0Hz, 2H), 7.54 (m, 4H), 7.49-7.43 (m, 4H), 7.35-7.28 (m, 2H), 4.35 (t, J=7.0Hz,
4H), 4.15 (m, 11H), 1.94 (d, J=6.0Hz, 10H), 1.83 (m, 5H), 1.62-1.53 (m, 12H), 1.44 (m, 40H),
1.31-1.18(m,10H).
The chemical reagent and solvent are that analysis is pure.
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| CN108047221B (en) * | 2017-12-19 | 2023-08-01 | 山东省医学科学院药物研究所 | Perylene diimide compound, synthesis method thereof and application thereof in H 2 O 2 Application in detection |
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