* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Monatshefte fuer Chemie, 1928, vol. 50, p. 92
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6
[ 110590-81-3 ]
[ 128-69-8 ]
[ 522647-62-7 ]
Reference：
[1] Chemistry - A European Journal, 2007, vol. 13, # 12, p. 3330 - 3345
Stage #1: at 20℃; for 2 h; Stage #2: at 80 - 100℃; for 4 - 6 h;
EXAMPLE 1; 1,7-dibromoperylene-3,4,9,10-tetracarboxyl dianhydride (2)(2) The 3,4,9, 10-perylenetetracarboxyl dianhydride (1) is dissolved in96percent H2SO4 and left under stirring for 2 hours at room temperature. Then, iodine (30-40 mmoles per mole of anhydride) is added and the composition is heated to 8O0C. When the purple vapours of iodine are given off, the bromide is added drop by drop (molar ratio with the anhydride 2-2.5:1) and the temperature is increased to about 100°C. After 4-6 hours, the reaction is extinguished by adding ice until cooling. The resulting precipitate is then filtered on Buchner filter and washed first in a 5percent solution of sodium metabisulfite to eliminate the residual bromine and then several times in water. The precipitate <n="21"/>is then dried first in an oven and then on a thimble for drying from solid form. A red solid is thus obtained, having a sufficient degree of purity to be used as such in the subsequent preparations.One of the preparations is reported below: 5 g 3,4,9, 10-perylenetetracarboxyl dianhydride (1)1.65 cc Br2 113 mg I2 100 cc 96percent H2SO46 g of 1 ,7-dibromoperylene-3,4,9,10-tetracarboxyl dianhydride (2) was obtained. The yield was 87percent.Note. Besides the 1 ,7 dibromurated isomer, the reaction also yields a small percentage of 1 ,6 disubstituted product, as can be seen from a careful examination of the 1H NMR spectra (see further on, for the complete characterisation). There is no way of separating the two isomers, neither here nor in the next steps. In the characterisations of the products obtained in the next synthesis steps, reference will exclusively be made - when not indicated otherwise - to the 1 ,7 isomer.Empirical formula: C24H6Br2Oe Molecular weight: 550 Solubility: in concentrated H2SO4 Elemental analysis:Theoretical data Experimental datapercent C = 52.36 percent C = 51.61percent H = 1.09 percent H = 1.081H NMR spectrum, 300 MHz: solvent D2SO4 The spectrum is composed of three signals present in the aromatic area: δ 10.71(d 2H J=8 Hz), 10.04(s 2H), 9.82(d 2H J=8 Hz). Some lower signals are also often present, with chemical shifts very close to the ones described above: in all likelihood, these signals are to be attributed to the small percentage of 1 ,6 isomer that is formed together with the main product.
Reference：
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16
[ 128-69-8 ]
[ 118129-60-5 ]
Yield
Reaction Conditions
Operation in experiment
90%
With sulfuric acid; bromine; iodine In water
Example 1 A mixture of 292.5 g (0.75 mol) of perylene-3,4,9,10-tetracarboxylic dianhydride (purity>98percent) and 4420 g of 100percent by weight sulfuric acid was stirred for 12 hours at room temperature, 7 g of iodine were then added, and it was heated to 85° C. Subsequently, 262.5 g (1.64 mol) of bromine were added dropwise over 8 hours. The reaction mixture was cooled to room temperature, the excess bromine was displaced by nitrogen and then the concentration of sulfuric acid was reduced to 86percent by weight by adding a total of 670 g of water, a little at a time, over 1 hour. During this addition the reaction mixture heats up to 85° C. again: it was cooled and the precipitated product was filtered off over a G4 glass frit, washed with 3 kg of 86percent by weight sulfuric acid and then stirred up in 5 l of water; the mixture was filtered again and the product was washed to neutrality and dried under reduced pressure at 120° C. 370 g of II were obtained in the form of a bright red finely crystalline powder with a melting point>360° C. and a purity of >98percent, corresponding to a yield of 90percent. Analytical data: Elemental analysis (percent by weight calc./found): C: 52.4/52.1; H: 1.1/1.1; O: 17.45/17.4; Br: 29.1/29.4; IR (KBr): ν=1782+1770 (s, C=O), 1735+1723 (s, C=O) cm-1; UV/VIS (H2 SO4): λmax (ε)=408 (10309), 520 (29410), 554 (43141) nm.
90%
With sulfuric acid; bromine; iodine In water
Example 1 A mixture of 292.5 g (0.75 mol) of perylene-3,4,9,10-tetracarboxylic dianhydride (purity >98percent) and 4420 g of 100percent by weight sulfuric acid was stirred for 12 hours at room temperature, 7 g of iodine were added, and the mixture was then heated to 85° C. 262.5 g (1.64 mol) of bromine were then added dropwise over 8 hours. The reaction mixture was cooled to room temperature, the excess bromine was displaced by nitrogen, and the concentration of sulfuric acid in the reaction mixture was reduced to 86percent by weight by adding, a little at a time, a total of 670 g of water over 1 hour. The reaction mixture, which heats up to 85° C. during this procedure, was cooled to room temperature and the precipitated product was filtered off over a G4 glass frit, washed with 3 kg of 85percent by weight sulfuric acid, then stirred up in 5 l of water, filtered off again, washed to neutrality and dried under reduced pressure at 120° C. 370 g of II were obtained in the form of a bright red, finely crystalline powder with a melting point >360° C. and a purity of >98percent, corresponding to a yield of 90percent.
81%
Stage #1: at 55℃; for 24 h; Stage #2: at 55℃; for 5 h; Stage #3: at 85℃; for 25 h;
In the first step a synthesis of 1 ,7-dibromoperylene-3,4:9,10-tetracarboxydianhydride represented by the general structural formula 30 was carried out: <n="35"/>1 (30)For this purpose 3,4:9,10-perylenetetracarboxylic dianhydride (28.52 g, 72.7 mmol) was added to 420 ml concentrated sulfuric acid and stirred at 55° C for 24 hours. Iodine (0.685 g, 2.70 mmol) was added to the reaction mixture and stirred for additional 5 hours, at 55° C. Bromine (8.3 ml, 162 mmol) was added dropwise to the reaction flask over 1 hour and stirred for 24 hours at 85° C. The excess bromine was then displaced with the nitrogen gas N2. Water (66 ml) was added dropwise to the cooled mixture and the precipitate was filtered off. The crude product was washed with 220 ml 86 percent H2SO4 followed by water and this procedure was repeated two times to produce the crude product (32.32 g, 81 percent). This product was used further without any purification. M.S.: 549.0 (calcd. 550.11 ).
81%
Stage #1: at 55℃; for 24 h; Stage #2: at 55℃; for 5 h; Stage #3: at 85℃; for 24 h; Inert atmosphere
For this purpose 3,4:9,10-perylenetetracarboxylic dianhydride (28.52 g, 72.7 mmol) was added to 420 ml concentrated sulfuric acid and stirred at 55° C for 24 hours. Iodine (0.685 g, 2.70 mmol) was added to the reaction mixture and stirred for additional 5 hours, at 55° C. Bromine (8.3 ml, 162 mmol) was added drop wise to the reaction flask over 1 hour and stirred for 24 hours at 85° C. The excess bromine was then displaced with the nitrogen gas N2. Water (66 ml) was added dropwise to the cooled mixture and the precipitate was filtered off. The crude product was washed with 220 ml 86 percent H2SO4 followed by water and this procedure was repeated two times to produce the crude product (32.32 g, 81 percent). This product was used further without any purification. M. S. : 549.0 (calcd. 550.11).
80%
Stage #1: at 55℃; for 30 h; Stage #2: at 85℃; for 32.5 h;
Into a 1000 mL four-necked flask equipped with an exhaust gas absorber, 450 mL of concentrated sulfuric acid and perylene anhydride (29 g, 74.0 mmol) were added,Heated to 55 ° C,Heat stirring 30h,JoinI2(0.7 g),The temperature was raised to 85 ° C,Bromine (8.2 mL,162.8 mmol) of sulfuric acid was added over 2.5 hours. Canada completed, insulation reaction 30h. After cooling to room temperature, water (100 mL) was added dropwise and the solid was precipitatedOut, sand core funnel filter. Filter cake with 80percent H2SO4 (250mL) washing, and then washed to the filtrate was neutral, dry, freshRed solid of the compound of formula IVa (32.4 g) in 80percent yield
64%
at 85℃;
Commercially available Perylene-3,4.9,10-tetracarboxylιc dianhydπde (100.0 g, 0.255 mol) was brominated with mixture of bromine (29 rmL) and Iodine (2.38 g) in 100percent sulfuric acid (845 mL) at.~ 85° C The yield of 1 ,7-dibromoperylene-3,4-9,10-tetracarboxylic dianhydride was 90 g (64percent)Analysis: calculated' C24H6Br2O6, C 52.40, H 1.10, Br 29 05, O 17.45 percent; found: C 52 29, H, 1.07, Br 28, 79 percent. Absorption spectrum (9.82x105 M solution in 93percent sulfuric acid)- 405 (9572), 516 (27892), 553 (37769).N.N'-Dicyclohexyl-i y-dibromopeiylene-SAψ.IO-tetracarboxydiimide was synthesized by reaction of 1 ,7-dιbromoperylene-3,4.9,10-tetracarboxylιc dianhydride (30.0 g) with cyclohexylamine (18.6 mL) in N-methylpyrrolidone (390 mL) at -85 ° C. The yield of N,N'-dιcyclohexyl-1 ,7- dibromoperylene-3,4:9,10-tetracarboxydiimide was 30 g (77percent).N.N'-Dicyclohexyl-I J-di^ct-i-ynyOperylene-S^ ψ.IO-tetracarboxydiimide by Sonogashira reaction: N.N'-dicyclohexyl-I J-dibromperylene-S^ ψ.IO-tetracarboxydiimide (24.7 g) and octyne-1 (15 2 g) in the presence of bis(triphenylphosphine)palladium(ll) chloride (2.42 g), triphenylphospine (0 9 g),and copper(l) iodide (0.66 g). The yield of N.N'-dicyclohexyl-i y-dKoct-i-ynyOperylene-SAψ.IO- tetracarboxydiimide was 15.7 g (60 percent).N,N'-Dicyclohexyl-5,11-dιhexylcoronene-2,3:8,9-tetracarboxydiimιde was synthesized by heating of N,N'-dicyclohexyl-1 ,7-dι(oct-1-ynyl)perylene-3,4.9,10-tetracarboxydιιmide (7.7 g) in toluene (400 mL) in the presence of 1 ,8-Diazabicyclo[5 4.0]undec-7-ene (0 6 ml) at 100-110° C for 20 hours.5,1 i-dihexylcoronene^S'δ.ψ-tetracarboxylic dianhydride was prepared by hydrolysis of N1N'- dicyclohexyl-5,11-dihexylcoronene-2,3:8,9-tetracarboxydiimide (6 4 g, 8 3 mmol) with Potassium <n="14"/>~ ~ hydroxide (7.0 g, 85percent) in the mixture of tert-butanol (400 mL) and water (0.4 mL) at 85-900C. The yield of 5,1 i-dihexylcoronene^.S.δ.ψ-tetracarboxyhc dianhydπde was 4.2 g (83percent).N,N'-(1-undecyl)dodecyl-5,11-dιhexylcoronene-2,3:8,9-tetracarboxydiimιde by the reaction of 5,11-di(hexyl)coronene-2,3:8,9-tetracarboxylic dianhydride with 12-tricosanamine5,11-di(hexyl)coronene-2,3l8,9-tetracarboxylic dianhydride (3 44 g), 12-tricosanamine (7.38 g), benzoic acid (45 mg) and 3-chlorophenol (15 mL) was evacuated and saturated with argon two times at room temperature and 2 times at 1000C The reaction mixture was agitated at ~140°C for 1 hour and 160-165°C for 20 hours in a flow of argon. After that the reaction mixture was agitated at ~100°C and was vacuumed at 10 mm Hg for half an hour. Then apparatus was filled with argon once again and heating was continued for the next 24 hours.A drop of reaction mixture was mixed with acetic acid (5 mL), centrifuged, solid was dissolved in chloroform (0 5 mL) which was washed with water and dried over sodium sulfate. Thin layer chromatography probe showed good formation of product with Rf 0 9 (eluent: Chloroform-Hexane- Ethylacetate-Methanol (100 50:0 3:0 1 by V)).The reaction mixture was added in small portions to acetic acid (500 mL) with simultaneous shaking. The orange-red suspension was kept for 3 hours with periodic shaking, then filtered off. The filter cake was washed with water (0.5 L), and then was shaken with water (0.5 L) and chloroform (250 mL) in a separator funnel. The organic layer was separated, washed with water (2x350 mL) and dried over sodium sulfate overnight. The evaporation resulted in 7.0 g of crude product.Column chromatography was carried out using exactly tuned eluent mixture1 chloroform (700 mL), petroleum ether (2 L), ethylacetate (0 6 mL) and methanol (0 2).Column chromatography was carried out using column1 I = 20, d = 7 cm Elution of orange fraction and evaporation resulted in orange soft solid material, which was dissolved in chloroform (25 mL) and added slowly to methanol (400 mL) with agitation. The soft precipitate was dried on air overnight, then in vacuum (15 mm Hg) at mild heating (35°) for 5 hours. The yield of preparation of N1N'- (1-undecyl)dodecyl-5,11-dιhexylcoronene-2,3:8,9-tetracarboxydiimιde was 5.0 g (70percent).
64%
at 85℃;
Commercially available Perylene-3,4.9,10-tetracarboxylιc dian hydride (100.0 g, 0.255 mol) was brominated with mixture of bromine (29 ml.) and Iodine (2.38 g) in 100percent sulfuric acid (845 ml.) at.~ 85° C. The yield of 1 ,7-dibromoperylene-3,4:9,10-tetracarboxylic dianhydride was 90 g (64percent). Analysis: calculated' C24H6Br2O6, C 52.40, H 1.10, Br 29 05, O 17.45 percent; found: C 52 29, H, 1 07, Br 28, 79 percent Absorption spectrum (9 82x105 M solution in 93percent sulfuric acid): 405 (9572), 516 (27892), 553 (37769).N.N'-Dicyclohexyl-I J-dibromoperylene-S^.ψ.IO-tetracarboxydiimide was synthesized by reaction of 1 ,7-dιbromoperylene-3,4.9,10-tetracarboxylιc dianhydride (30.0 g) with cyclohexylamine (18.6 mL) in N-methylpyrrolidone (390 mL) at -85 ° C. The yield of N,N'-dιcyclohexyl-1 ,7- dibromoperylene-3,4:9,10-tetracarboxydiimιde was 30 g (77percent). N.N'-Dicyclohexyl-I J-dKoct-i-ynyOperylene-S^ ψ.IO-tetracarboxydiimide by Sonogashira reaction: N.N'-dicyclohexyl-I J-dibromperylene-S^ ψ.IO-tetracarboxydiimide (24.7 g) and octyne-1 (15 2 g) in the presence of bis(triphenylphosphine)palladium(ll) chloride (2.42 g), triphenylphospine (0 9 g),and copper(l) iodide (0.66 g). The yield of N.N'-dicyclohexyl-I J-d^oct-i-ynyOperylene-Sλψ.IO- tetracarboxydiimide was 15.7 g (60 percent). N,N'-Dicyclohexyl-5,11-dιhexylcoronene-2,3:8,9-tetracarboxydiimιde was synthesized by heating of N,N'-dicyclohexyl-1 ,7-dι(oct-1-ynyl)perylene-3,4.9,10-tetracarboxydιιmide (7.7 g) in toluene (400 mL) in the presence of 1 ,8-Dιazabιcyclo[5.4.0]undec-7-ene (0.6 ml) at 100-110° C for 20 hours. 5,1 i-dihexylcoronene^.S'δ.ψ-tetracarboxylic dianhydride was prepared by hydrolysis of N1N'- dicyclohexyl-5,11-dihexylcoronene-2,3:8,9-tetracarboxydiimide (6 4 g, 8 3 mmol) with Potassium hydroxide (7 0 g, 85percent) in the mixture of tert-butanol (400 mL) and water (0.4 mL) at 85-90°C The yield of 5,1 i-dihexylcoronene^S'δ.ψ-tetracarboxylic dianhydride was 4 2 g (83percent). <n="20"/>N,N'-(1-undecyl)dodecyl-5,11-dιhexylcoronene-2,3:8,9-tetracarboxydiimιde by the reaction of 5,11-di(hexyl)coronene-2,3:8,9-tetracarboxylic dianhydride with 12-tπcosanamine. 5,11- di(hexyl)coronene-2,3.8,9-tetracarboxylιc dianhydride (3.44 g), 12-tπcosanamine (7.38 g), benzoic acid (45 mg) and 3-chlorophenol (15 mL) was evacuated and saturated with argon two times at room temperature and 2 times at 1000C The reaction mixture was agitated at ~140°C for 1 hour and 160- 165°C for 20 hours in a flow of argon After that the reaction mixture was agitated at ~100°C and was vacuumed at 10 mm Hg for half an hour. Then apparatus was filled with argon once again and heating was continued for the next 24 hours The yield of preparation of N,N'-(1-undecyl)dodecyl-5,11- dihexylcoronene-2,3.8,9-tetracarboxydιιmide was 5.0 g (70percent).
60%
Stage #1: at 20℃; for 2 h; Stage #2: at 80℃; for 18 h;
Perylene-3 ,4,9,10-tetracarboxylic dianhydride (Perylene-3 ,4,9,10-tetracarboxylic dianhydride) 16g (0.0407mol), iodine (iodine) 0.39g (0.00152mol), 98percent sulfuric acid (sulfuric acid) 225ml at room temperature And stirred (stirring) at room temperature for 2 hours. Raising the temperature to 80° and slowly added bromine (bromine) 4.6ml (0.09mol) over 2 hours. After reaction for 16 hours while maintaining the temperature, it cooled to room temperature to remove the remaining bromine with nitrogen gas. The ice bath under reduced pressure, the resulting precipitate was slowly poured into distilled water 2000ml under (Ice-bath) and filtered. Distillation until pH = 7 Then washed with water several times and dried in a vacuum oven waterway. Material to be produced in the present synthesis process is a mixed state of bromine is substituted one or two substances and substituted material, so that little or no solubility was purified in the next step. The final product yield to 9.624g exhibited a 60percent
42%
Stage #1: at 20℃; for 2 h; Stage #2: at 80℃; for 20 h;
first,32 g of perylenetetracarboxylic anhydride and 1 g of iodine (I2) were placed in 450 ml of sulfuric acid and stirred at room temperature for 2 hours.to the next,The temperature of the reaction mixture was raised to 80°C and, using a dropping funnel,9.5 ml of bromine (Br2) was added dropwise over 3 hours and then reacted under reflux conditions for 17 hours.After completion of the reaction, nitrogen gas was blown to remove remaining bromine gas,The reaction mixture was cooled to room temperature,Slowly poured into 3 L of ice water to form a precipitate. after, The precipitate was filtered and washed several times with distilled water,The filtered material was oven dried, Compound 1-4a in which the bromine atom was substituted at the bay-position (1, 7-position of the perylene) was obtained in a yield of 42.8percent.
6 g
Stage #1: With iodine In sulfuric acid at 50℃; for 12 h; Stage #2: With bromine In sulfuric acid at 80℃; for 48 h;
A mixture of 5.0 g (13 mmol) of perylene-3,4:9,10-tetraboxylicacid bisanhydride (1) and sulfuric acid (100 mL) was stirred at 50 C for 12 h, and subsequently I2 (0.56 g) was added. The reaction mixture was heated to 80 C, and bromine 2.2 g (15 mmol) was added dropwise over a time period of 2 h. After bromine addition, the reaction mixture was heated for an additional 48 h, the excess bromine was removed by saturated aqueous solution of K2CO3, and water (100 mL) was added carefully. The precipitate was separated by filtration, washed with water (100 mL), and dried in a vacuum to give a red powder 6.0 g. Without further purification it was used to the next reaction.
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Yield
Reaction Conditions
Operation in experiment
92%
at 65℃; for 30 h;
A mixture of 3,4,9,10-perylenetetracarboxylic dianhydride(3.30 g, 8.41 mmol), chlorosulfonic acid (20 mL, 300 mmol) andiodine (0.56 g, 2.20 mmol) was stirred at 65 C for 30 h. Aftercooling to room temperature, the solution was added dropwise toan ice-water mixture. The precipitate was collected by filtration togive a red solid (4.14 g, 92percent). 1H NMR (d-DMSO, ppm): 8.75 (s, 4H,aromatic protons). 13C NMR (d-DMSO, ppm): 119.75, 125.29, 129.5,134.88, 136.22, 158.16, 168.53. Mass (EI): m/z 532.
74.4%
at 20 - 70℃; for 6.33333 h; Inert atmosphere
10253] (Compound (Id) Manufacturing Process)10254] Chlorosulfuric acid (500 g, 4.29 mol) was inserted into a 1000 ml three neck flask under an argon gas flow. 3,4,9,10-perylene tetracarboxylic acid dianhydride (50 g,0.127 mol) was added to the chlorosulfuric acid for 20 minutes at the room temperature and then iodine (8.5 g, 0.024 mol) was added. 10255] Then, the temperature of the reaction liquid was increased up to 70° C., and reaction was performed with stirring for 6 hours.10256] After the reaction was completed, the reaction liquidwas cooled such that the temperature became the room temperature, and quenching was performed with cool water(2000 ml). The reaction liquid was discolored from dark brown to scarlet and crystals were precipitated. These crystals were taken out, and subjected to slurry washing with water (1000 ml) three times. Then, slurry washing was performed three times with acetonitrile (500 ml), and taken crystals were dried. Thus, a compound (abbreviated to a “compound (1)- bid”) which was represented by the following formula (1)- bid, as the compound (Id) was obtained (collected amount:50.1 g, and yield: 74.4percent).10257] It was confirmed that the compound (1)-bid was obtained, by MS measurement, ion chromatography, and IR measurement. For example, a spectrum of a pro-ion peak mlz=530 was confirmed in the MS measurement. It was confirmed that a chlorine content was 25.1percent (ideal value: 26.8percent) by using an oxygen combustion method in the ion chromatography.
74.4%
Stage #1: at 20℃; for 0.333333 h; Inert atmosphere Stage #2: at 70℃; for 6 h;
First, a reaction represented by the reaction formula (1-11) was performed as a reaction process 1.500 g of chlorosulthric acid (4.29 mol) was added to 1000 mE of a three-necked flask through argon gas, and 50 g (0.127mol) of 3,4,9,10-perylenetetracarboxylic acid dianhydridewas added thereto at room temperature for 20 minutes. Next, 8.5 g (0.024 mol) of iodine was added thereto. The tempera- tare of the obtained reaction liquid was increased to 70° C., and the reaction liquid was reacted by stirring for 6 hours.After the reaction was terminated, the temperature of the reaction liquid was cooled to the room temperature, 2000 mE of ice water was added thereto, and then the reaction liquid was quenched. The color of the reaction liquid was changed from dark brown into vermilion and crystals were deposited. The crystals were collected by filtration to be slurry-washed using 1000 mE of water for three times. Subsequently, slurry washing was thrther performed using 500 mE of acetonitrile for three times. The collected crystals by filtration were dried. The wet weight of an obtained product was 102 g, the dry 25 weight thereof was 50.1 g, and the yield thereof was 74.4percent.
62.2%
at 70℃; for 5 h;
In a 100 ml three-necked flask equipped with a reflux condenser and two glass stoppers 3,4:9,10-perylene tetracarboxylic dianhydride (1 g, 2.55 mmol) and iodine (170 mg, 0.67 mmol) were dissolved in chlorosulfonic acid (10 ml). The mixture was heated to 70 °C for 5 h. Afterwards the reaction mixture was poured into an ice-water mixture and the insoluble product was collected by filtration. The crude product was purified by soxhlet extraction using dichloromethane as solvent. The solvent was evaporated by the rotary evaporator to yield a red solid. Yield 2.3 g (62.2percent) IR (ν(cm-1)): ν=1080 [C-Cl aromatic], 1475-1600 [aromatic stretch], 1700 [CO anhydride], 3000 [C-H aromatic], Elemental analysis for chlorine: calculated: 26.75percent measured: 23.4-23.93percent.
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2.2.1 Synthesis of N,N′-bis-(dodecyl)-3,4,9,10-perylenebis(dicarboximide) (3)
N,N′-bis(dodecyl)-3,4,9,10-perylenebis(dicarboximide) (3) was synthesized and purified according to our published work [1]. A mixture of perylene-3,4,9,10-tetracarboxylic acid dianhydride (1, 1 g, 2.55 mmol), dodecylamine (2, 2.04 g, 11 mmol), m-cresol (40 mL) and isoquinoline (4 mL) were stirred under argon atmosphere at 120 °C for 1 h, at 160 °C for 2 h and finally at 200 °C for 5 h. The warm solution was poured into 250 mL of acetone, and the precipitate was filtered out and dried at 100 °C under vacuum. The crude product was treated with acetone in a Soxhlet apparatus for 24 h, in order to remove unreacted amine and high boiling points solvents, m-cresol and isoquinoline. The crude product is further purified by sublimation at 350 °C on salt-ice cooled glass surface to obtain red color powder 3 (1.76 g, 95 %). M.p.:> 400 °C. FTIR (Fig. S1, KBr, thin film, cm-1): ν = 3073 (aromatic CH- stretch), 2960, 2920 and 2850 (aliphatic CH- stretch), 1697 and 1650 (imide C=O stretch), 1591 (aromatic C=C stretch), 1343 (imide C-N stretch), 1254 and 1089 (C-N stretch), 808 and 747 (CH- bend). 1H NMR (Fig. S2, 400 MHz, CDCl3): δH (ppm) = 8.70 - 8.62 (dd, J =8.0 Hz, 8Ar-H), 4.20 (t, J =6.5 Hz, 2CH2), 1.4-1.2 (m, 20CH2), 0.87 (t, J =5.6 Hz, 2CH3). 13C NMR (100.6 MHz, CDCl3): δC (ppm) = 163.31, 134.54, 126.35, 123.35, 123.00, 40.75, 31.90, 29.60, 29.55, 29.45, 29.30, 28.10, 27.10, 22.60, 14.10. UV/Vis (Fig. S3, CHCl3): λmax nm ε = 459 18,500, 490 51,300, 526 85,200. Fluorescence Fig. S3, CHCl3, λexc = 485 nm): λmax (nm) = 540, 576, 625. Fluorescence quantum yield (c = 1 × 10-6 M in ethanol, reference rhodamine 101 in ethanol with f = 100 %, λexc. = 485 nm) = 100 %. MS (Fig. S4, EI): m/z: 727 [M]+. Anal. Calcd. for C48H58N2O4, (Mw, 726.98); C, 79.30; H, 8.04; N, 3.85. Found: C, 79.19; H, 8.04; N, 3.81.
94%
In neat (no solvent) at 110℃; for 0.166667h; Green chemistry;
93.6%
Stage #1: n-Dodecylamine; perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With 1H-imidazole; zinc diacetate at 130℃; for 24h; Inert atmosphere;
Stage #2: With hydrogenchloride In ethanol; water at 20℃;
90%
In <i>tert</i>-butyl alcohol at 120℃; for 20h;
83%
78%
With 1H-imidazole at 160℃; for 4h;
43.2%
With 1H-imidazole In toluene at 180℃; for 24h;
1 Synthesis of N, N'-didodecyl-3,4,9,10-perylenetetracarboximide (1)
In a 100 mL single-necked flask, 3,4,9,10-perylenetetracarboxylic dianhydride (1.0 g, 2.55 mmol), dodecylamine(2.8 g, 15.31 mmol), 5 g imidazole and 5 mL toluene and reacted at 180 °C for 24 h. The reaction solution was poured into 100mL 2M hydrochloric acid,Suction filtration, the filter cake to CH2Cl2 as eluent, separated by column chromatography to give a dark red solid 0.8g, the yield was 43.2%.
Alkaline conditions;
With zinc acetate hydrate In quinoline Reflux;
With 1H-imidazole at 110℃; for 3h;
Stage #1: n-Dodecylamine; perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride In water at 20℃; for 0.333333h; Green chemistry;
Stage #2: In water at 200℃; for 24h; Autoclave; High pressure; Green chemistry;
With zinc diacetate In 1-methyl-pyrrolidin-2-one at 180℃; for 8h; Inert atmosphere;
2 Example 2
5g of perylene anhydride, 11.80 g n-dodecylamine,4.2g of zinc acetate was mixed with 100mL of N-methylpyrrolidone. Under the protection of argon,After refluxing at 180 ° C for 8 hours, the heating was stopped and the mixture was naturally cooled to room temperature.Then the obtained reaction solution was mixed with 1000 mL of absolute ethanol, and after ultrasonic treatment for 1 h,After freezing in a refrigerator at -18 ° C for 2 days,Suction filter through a 0.45 μm nylon filter and collect the filter cake,The obtained filter cake was dispersed in a 500 mL sodium hydroxide solution having a concentration of 1 mol / L.Sonicate for 30min, and then suction filter to obtain the crude product. Repeat the washing process 3 times.Then the filter cake was washed with distilled water to be neutral, and then placed in an oven at 80 ° C for 24 hours.To obtain a perylene diimide derivative
With 1H-imidazole; zinc diacetate; at 130℃; for 5h;Inert atmosphere;
0.4g perylene tetracarboxylic anhydride,0.77g <strong>[3241-20-1]9-aminoheptadecane</strong>,0.14g anhydrous zinc acetateAnd 4.0g imidazole are added sequentiallyIn a 50mL flask,Under the protection of nitrogen atmosphere,Heat until the imidazole is dissolved (130)And stir vigorously for 5 hours,After the reaction solution is cooled to room temperature, use 12 mLThe tetrahydrofuran dissolves,Then add to 300mL 2mol/L hydrochloric acidMixture with methanol (volume ratio is 2:1)Formation of a precipitate. filter,Wash the filter cake with water and methanol successively,Dry the filter cake,Take methylene chloride:N-hexane (volume ratio, 1:1)Column chromatographic separation for the eluent,Prepare compound P2c-1;
Example 1G: Preparation of trans -PDIS?lEPr and cz's-PDIS?lEPrPDM EPr frans-PDIS,1 EPr c/s-PDIS21 EPr[0146] A mixture of 1.5 g (3.8 mmol) of perylene-3,4,9,10-tetracarboxylic dianhydride (Aldrich), 1.0 g (11.4 mmol) of <strong>[616-24-0]3-aminopentane</strong> (Aldrich), and 20 g of imidazole was heated at 200 C in a sealed vessel for 2 h. The mixture was cooled slightly and treated with 100 mL of dioxane. The mixture was stirred at ambient temperature for 2 h then filtered. The filter cake was washed successively with methanol (100 mL), and diethyl ether (100 mL). The filter cake was dried to give 1.86 g (92% yield) of PDIlEPr as deep red needles.[0147] 1H NMR (CDCI3, 500 MHz): delta 8.69 (d, 4H, J= 7.8), 8.64 (d, 4H, J= 8.1), 5.09 (m, 2H), 2.29 (m, 4H), 1.97 (m, 4H), 0.95 (t, 12H, J= 7.5).[0148] A mixture of 0.374 g (0.705 mmol) of PDIlEPr, 0.40 g (1.41 mmol) of Davy Reagent, and 15 mL of o-dichlorobenzene was heated in an oil bath at 180 C for 7 min. The mixture was cooled immediately in a water bath and purified by flash chromatography (Si02, toluene?methylene chloride, 5.5 x 40 cm). The concentrated product fraction was sonicated with 25 mL of acetone, filtered, and dried to give 107 mg (27% yield) of frans-PDISilEPr as a deep purple solid.[0149] 1H NMR (CDCls, 500 MHz): delta 9.08 (d, 2H, J = 8.4), 8.67 (d, 2H, J = 8.1), 8.59 (d, 2H, J = 8.1), 8.52 (d, 2H, J = 8.5), 6.32 (m, 2H), 2.35 (m, 4H), 2.08 (m, 4H), 0.98 (t, 12H, J = 7.5). Anal. Calcd for C34H30N2O2S2: C, 72.57; H, 5.37; N, 4.98. Found: C, 72.65; H, 5.33; N, 5.06.[0150] c/s-PDIS2lEPr (104 mg, 26%> yield) was isolated as a deep purple solid.[0151] 1H NMR (CDCI3, 500 MHz): delta 9.09 (d, 2H, J = 8.3), 8.66 (d, 2H, J = 8.0), 8.62 (d, 2H, J = 8.1), 8.49 (d, 2H, J = 8.5), 6.32 (m, 2H), 2.35 (m, 4H), 2.08 (m, 4H), 0.98 (t, 12H, J = 7.5). Anal. Calcd for C34H30N2O2S2: C, 72.57; H, 5.37; N, 4.98. Found: C, 72.82; H, 5.42; N, 5.20.
76%
With 1H-imidazole; In 1,3,5-trimethyl-benzene; at 140℃; for 24h;
5 gr of perylene dianhydride (1), 18 gr imidazole, 4.5 mL ethylpropylamine (3- aminopentane) and 20 mL mesitylene (as additional solvent beside imidazole) were mixed and heated in oil bath to 140 C deg for 24 h. 200 mL HCl 1M was added and stirred for 20 min. The solution was filtered and washed with EtOH. A red solid was obtained (2) and dried in high vacuum overnight. Yield: 76%.
With 1H-imidazole; at 160℃; for 3h;Inert atmosphere;
In the test tube with the branch pipe, the perylene glycosides, imidazole and 2-amino-pentane molar ratio of 1: 3: 3 were mixed, under a nitrogen atmosphere and heated to 160 , reaction for 3 hours, and then extracted with dichloromethane, filtration, column chromatography, column chromatography with a developing solvent of CH2Cl2(Column chromatographic run are the steps involved in the case), to give perylene diimide.
Perylene-3,4,9,l0-tetracarboxylic acid dianhydride (5.00 g, 12.7 mmol, 1 equiv.) was suspended in cone sulfuric acid (150 mL) and stirred 1 h at room temperature. Iodine (0.26 g, 1.0 mmol, 0.08 equiv.) was added, and the mixture was warmed up to 85 C over 45 min. Finally, bromine (3.92 mL, 12.2 g, 76.5 mmol, 6 equiv.) was added, and the mixture was stirred overnight at 95 C. After cooling, the intensive red raw product was precipitated by the addition of water. The residue was washed with water until the wash solution had a neutral pH value and then dried to obtain a rust-colored 6.91 g product (Yield, 99%)
90%
With sulfuric acid; bromine; iodine; In water;
Example 1 A mixture of 292.5 g (0.75 mol) of perylene-3,4,9,10-tetracarboxylic dianhydride (purity>98%) and 4420 g of 100% by weight sulfuric acid was stirred for 12 hours at room temperature, 7 g of iodine were then added, and it was heated to 85 C. Subsequently, 262.5 g (1.64 mol) of bromine were added dropwise over 8 hours. The reaction mixture was cooled to room temperature, the excess bromine was displaced by nitrogen and then the concentration of sulfuric acid was reduced to 86% by weight by adding a total of 670 g of water, a little at a time, over 1 hour. During this addition the reaction mixture heats up to 85 C. again: it was cooled and the precipitated product was filtered off over a G4 glass frit, washed with 3 kg of 86% by weight sulfuric acid and then stirred up in 5 l of water; the mixture was filtered again and the product was washed to neutrality and dried under reduced pressure at 120 C. 370 g of II were obtained in the form of a bright red finely crystalline powder with a melting point>360 C. and a purity of >98%, corresponding to a yield of 90%. Analytical data: Elemental analysis (% by weight calc./found): C: 52.4/52.1; H: 1.1/1.1; O: 17.45/17.4; Br: 29.1/29.4; IR (KBr): nu=1782+1770 (s, C=O), 1735+1723 (s, C=O) cm-1; UV/VIS (H2 SO4): lambdamax (epsilon)=408 (10309), 520 (29410), 554 (43141) nm.
90%
With sulfuric acid; bromine; iodine; In water;
Example 1 A mixture of 292.5 g (0.75 mol) of perylene-3,4,9,10-tetracarboxylic dianhydride (purity >98%) and 4420 g of 100% by weight sulfuric acid was stirred for 12 hours at room temperature, 7 g of iodine were added, and the mixture was then heated to 85 C. 262.5 g (1.64 mol) of bromine were then added dropwise over 8 hours. The reaction mixture was cooled to room temperature, the excess bromine was displaced by nitrogen, and the concentration of sulfuric acid in the reaction mixture was reduced to 86% by weight by adding, a little at a time, a total of 670 g of water over 1 hour. The reaction mixture, which heats up to 85 C. during this procedure, was cooled to room temperature and the precipitated product was filtered off over a G4 glass frit, washed with 3 kg of 85% by weight sulfuric acid, then stirred up in 5 l of water, filtered off again, washed to neutrality and dried under reduced pressure at 120 C. 370 g of II were obtained in the form of a bright red, finely crystalline powder with a melting point >360 C. and a purity of >98%, corresponding to a yield of 90%.
81%
In the first step a synthesis of 1 ,7-dibromoperylene-3,4:9,10-tetracarboxydianhydride represented by the general structural formula 30 was carried out: <n="35"/>1 (30)For this purpose 3,4:9,10-perylenetetracarboxylic dianhydride (28.52 g, 72.7 mmol) was added to 420 ml concentrated sulfuric acid and stirred at 55 C for 24 hours. Iodine (0.685 g, 2.70 mmol) was added to the reaction mixture and stirred for additional 5 hours, at 55 C. Bromine (8.3 ml, 162 mmol) was added dropwise to the reaction flask over 1 hour and stirred for 24 hours at 85 C. The excess bromine was then displaced with the nitrogen gas N2. Water (66 ml) was added dropwise to the cooled mixture and the precipitate was filtered off. The crude product was washed with 220 ml 86 % H2SO4 followed by water and this procedure was repeated two times to produce the crude product (32.32 g, 81 %). This product was used further without any purification. M.S.: 549.0 (calcd. 550.11 ).
81%
For this purpose 3,4:9,10-perylenetetracarboxylic dianhydride (28.52 g, 72.7 mmol) was added to 420 ml concentrated sulfuric acid and stirred at 55 C for 24 hours. Iodine (0.685 g, 2.70 mmol) was added to the reaction mixture and stirred for additional 5 hours, at 55 C. Bromine (8.3 ml, 162 mmol) was added drop wise to the reaction flask over 1 hour and stirred for 24 hours at 85 C. The excess bromine was then displaced with the nitrogen gas N2. Water (66 ml) was added dropwise to the cooled mixture and the precipitate was filtered off. The crude product was washed with 220 ml 86 % H2SO4 followed by water and this procedure was repeated two times to produce the crude product (32.32 g, 81 %). This product was used further without any purification. M. S. : 549.0 (calcd. 550.11).
80%
Into a 1000 mL four-necked flask equipped with an exhaust gas absorber, 450 mL of concentrated sulfuric acid and perylene anhydride (29 g, 74.0 mmol) were added,Heated to 55 C,Heat stirring 30h,JoinI2(0.7 g),The temperature was raised to 85 C,Bromine (8.2 mL,162.8 mmol) of sulfuric acid was added over 2.5 hours. Canada completed, insulation reaction 30h. After cooling to room temperature, water (100 mL) was added dropwise and the solid was precipitatedOut, sand core funnel filter. Filter cake with 80% H2SO4 (250mL) washing, and then washed to the filtrate was neutral, dry, freshRed solid of the compound of formula IVa (32.4 g) in 80% yield
64%
With sulfuric acid; bromine; iodine; at 85℃;
Commercially available Perylene-3,4.9,10-tetracarboxyliotac dianhyd?de (100.0 g, 0.255 mol) was brominated with mixture of bromine (29 rmL) and Iodine (2.38 g) in 100% sulfuric acid (845 mL) at.~ 85 C The yield of 1 ,7-dibromoperylene-3,4-9,10-tetracarboxylic dianhydride was 90 g (64%)Analysis: calculated' C24H6Br2O6, C 52.40, H 1.10, Br 29 05, O 17.45 %; found: C 52 29, H, 1.07, Br 28, 79 %. Absorption spectrum (9.82x105 M solution in 93% sulfuric acid)- 405 (9572), 516 (27892), 553 (37769).N.N'-Dicyclohexyl-i y-dibromopeiylene-SAtheta.IO-tetracarboxydiimide was synthesized by reaction of 1 ,7-diotabromoperylene-3,4.9,10-tetracarboxyliotac dianhydride (30.0 g) with cyclohexylamine (18.6 mL) in N-methylpyrrolidone (390 mL) at -85 C. The yield of N,N'-diotacyclohexyl-1 ,7- dibromoperylene-3,4:9,10-tetracarboxydiimide was 30 g (77%).N.N'-Dicyclohexyl-I J-di^ct-i-ynyOperylene-S^ theta.IO-tetracarboxydiimide by Sonogashira reaction: N.N'-dicyclohexyl-I J-dibromperylene-S^ theta.IO-tetracarboxydiimide (24.7 g) and octyne-1 (15 2 g) in the presence of bis(triphenylphosphine)palladium(ll) chloride (2.42 g), triphenylphospine (0 9 g),and copper(l) iodide (0.66 g). The yield of N.N'-dicyclohexyl-i y-dKoct-i-ynyOperylene-SAtheta.IO- tetracarboxydiimide was 15.7 g (60 %).N,N'-Dicyclohexyl-5,11-diotahexylcoronene-2,3:8,9-tetracarboxydiimiotade was synthesized by heating of N,N'-dicyclohexyl-1 ,7-diota(oct-1-ynyl)perylene-3,4.9,10-tetracarboxydiotaiotamide (7.7 g) in toluene (400 mL) in the presence of 1 ,8-Diazabicyclo[5 4.0]undec-7-ene (0 6 ml) at 100-110 C for 20 hours.5,1 i-dihexylcoronene^S'delta.theta-tetracarboxylic dianhydride was prepared by hydrolysis of N1N'- dicyclohexyl-5,11-dihexylcoronene-2,3:8,9-tetracarboxydiimide (6 4 g, 8 3 mmol) with Potassium <n="14"/>~ ~ hydroxide (7.0 g, 85%) in the mixture of tert-butanol (400 mL) and water (0.4 mL) at 85-900C. The yield of 5,1 i-dihexylcoronene^.S.delta.theta-tetracarboxyhc dianhyd?de was 4.2 g (83%).N,N'-(1-undecyl)dodecyl-5,11-diotahexylcoronene-2,3:8,9-tetracarboxydiimiotade by the reaction of 5,11-di(hexyl)coronene-2,3:8,9-tetracarboxylic dianhydride with 12-tricosanamine5,11-di(hexyl)coronene-2,3l8,9-tetracarboxylic dianhydride (3 44 g), 12-tricosanamine (7.38 g), benzoic acid (45 mg) and 3-chlorophenol (15 mL) was evacuated and saturated with argon two times at room temperature and 2 times at 1000C The reaction mixture was agitated at ~140C for 1 hour and 160-165C for 20 hours in a flow of argon. After that the reaction mixture was agitated at ~100C and was vacuumed at 10 mm Hg for half an hour. Then apparatus was filled with argon once again and heating was continued for the next 24 hours.A drop of reaction mixture was mixed with acetic acid (5 mL), centrifuged, solid was dissolved in chloroform (0 5 mL) which was washed with water and dried over sodium sulfate. Thin layer chromatography probe showed good formation of product with Rf 0 9 (eluent: Chloroform-Hexane- Ethylacetate-Methanol (100 50:0 3:0 1 by V)).The reaction mixture was added in small portions to acetic acid (500 mL) with simultaneous shaking. The orange-red suspension was kept for 3 hours with periodic shaking, then filtered off. The filter cake was washed with water (0.5 L), and then was shaken with water (0.5 L) and chloroform (250 mL) in a separator funnel. The organic layer was separated, washed with water (2x350 mL) and dried over sodium sulfate overnight. The evaporation resulted in 7.0 g of crude product.Column chromatography was carried out using exactly tuned eluent mixture1 chloroform (700 mL), petroleum ether (2 L), ethylacetate (0 6 mL) and methanol (0 2).Column chromatography was carried out using column1 I = 20, d = 7 cm Elution of orange fraction and evaporation resulted in orange soft solid material, which was dissolved in chloroform (25 mL) and added slowly to methanol (400 mL) with agitation. The soft precipitate was dried on air overnight, then in vacuum (15 mm Hg) at mild heating (35) for 5 hours. The yield of preparation of N1N'- (1-undecyl)dodecyl-5,11-diotahexylcoronene-2,3:8,9-tetracarboxydiimiotade was 5.0 g (70%).
64%
With sulfuric acid; bromine; iodine; at 85℃;
Commercially available Perylene-3,4.9,10-tetracarboxyliotac dian hydride (100.0 g, 0.255 mol) was brominated with mixture of bromine (29 ml.) and Iodine (2.38 g) in 100% sulfuric acid (845 ml.) at.~ 85 C. The yield of 1 ,7-dibromoperylene-3,4:9,10-tetracarboxylic dianhydride was 90 g (64%). Analysis: calculated' C24H6Br2O6, C 52.40, H 1.10, Br 29 05, O 17.45 %; found: C 52 29, H, 1 07, Br 28, 79 % Absorption spectrum (9 82x105 M solution in 93% sulfuric acid): 405 (9572), 516 (27892), 553 (37769).N.N'-Dicyclohexyl-I J-dibromoperylene-S^.theta.IO-tetracarboxydiimide was synthesized by reaction of 1 ,7-diotabromoperylene-3,4.9,10-tetracarboxyliotac dianhydride (30.0 g) with cyclohexylamine (18.6 mL) in N-methylpyrrolidone (390 mL) at -85 C. The yield of N,N'-diotacyclohexyl-1 ,7- dibromoperylene-3,4:9,10-tetracarboxydiimiotade was 30 g (77%). N.N'-Dicyclohexyl-I J-dKoct-i-ynyOperylene-S^ theta.IO-tetracarboxydiimide by Sonogashira reaction: N.N'-dicyclohexyl-I J-dibromperylene-S^ theta.IO-tetracarboxydiimide (24.7 g) and octyne-1 (15 2 g) in the presence of bis(triphenylphosphine)palladium(ll) chloride (2.42 g), triphenylphospine (0 9 g),and copper(l) iodide (0.66 g). The yield of N.N'-dicyclohexyl-I J-d^oct-i-ynyOperylene-Slambdatheta.IO- tetracarboxydiimide was 15.7 g (60 %). N,N'-Dicyclohexyl-5,11-diotahexylcoronene-2,3:8,9-tetracarboxydiimiotade was synthesized by heating of N,N'-dicyclohexyl-1 ,7-diota(oct-1-ynyl)perylene-3,4.9,10-tetracarboxydiotaiotamide (7.7 g) in toluene (400 mL) in the presence of 1 ,8-Diotaazabiotacyclo[5.4.0]undec-7-ene (0.6 ml) at 100-110 C for 20 hours. 5,1 i-dihexylcoronene^.S'delta.theta-tetracarboxylic dianhydride was prepared by hydrolysis of N1N'- dicyclohexyl-5,11-dihexylcoronene-2,3:8,9-tetracarboxydiimide (6 4 g, 8 3 mmol) with Potassium hydroxide (7 0 g, 85%) in the mixture of tert-butanol (400 mL) and water (0.4 mL) at 85-90C The yield of 5,1 i-dihexylcoronene^S'delta.theta-tetracarboxylic dianhydride was 4 2 g (83%). <n="20"/>N,N'-(1-undecyl)dodecyl-5,11-diotahexylcoronene-2,3:8,9-tetracarboxydiimiotade by the reaction of 5,11-di(hexyl)coronene-2,3:8,9-tetracarboxylic dianhydride with 12-t?cosanamine. 5,11- di(hexyl)coronene-2,3.8,9-tetracarboxyliotac dianhydride (3.44 g), 12-t?cosanamine (7.38 g), benzoic acid (45 mg) and 3-chlorophenol (15 mL) was evacuated and saturated with argon two times at room temperature and 2 times at 1000C The reaction mixture was agitated at ~140C for 1 hour and 160- 165C for 20 hours in a flow of argon After that the reaction mixture was agitated at ~100C and was vacuumed at 10 mm Hg for half an hour. Then apparatus was filled with argon once again and heating was continued for the next 24 hours The yield of preparation of N,N'-(1-undecyl)dodecyl-5,11- dihexylcoronene-2,3.8,9-tetracarboxydiotaiotamide was 5.0 g (70%).
60%
Perylene-3 ,4,9,10-tetracarboxylic dianhydride (Perylene-3 ,4,9,10-tetracarboxylic dianhydride) 16g (0.0407mol), iodine (iodine) 0.39g (0.00152mol), 98% sulfuric acid (sulfuric acid) 225ml at room temperature And stirred (stirring) at room temperature for 2 hours. Raising the temperature to 80 and slowly added bromine (bromine) 4.6ml (0.09mol) over 2 hours. After reaction for 16 hours while maintaining the temperature, it cooled to room temperature to remove the remaining bromine with nitrogen gas. The ice bath under reduced pressure, the resulting precipitate was slowly poured into distilled water 2000ml under (Ice-bath) and filtered. Distillation until pH = 7 Then washed with water several times and dried in a vacuum oven waterway. Material to be produced in the present synthesis process is a mixed state of bromine is substituted one or two substances and substituted material, so that little or no solubility was purified in the next step. The final product yield to 9.624g exhibited a 60%
42%
first,32 g of perylenetetracarboxylic anhydride and 1 g of iodine (I2) were placed in 450 ml of sulfuric acid and stirred at room temperature for 2 hours.to the next,The temperature of the reaction mixture was raised to 80C and, using a dropping funnel,9.5 ml of bromine (Br2) was added dropwise over 3 hours and then reacted under reflux conditions for 17 hours.After completion of the reaction, nitrogen gas was blown to remove remaining bromine gas,The reaction mixture was cooled to room temperature,Slowly poured into 3 L of ice water to form a precipitate. after, The precipitate was filtered and washed several times with distilled water,The filtered material was oven dried, Compound 1-4a in which the bromine atom was substituted at the bay-position (1, 7-position of the perylene) was obtained in a yield of 42.8%.
Perylene-3,4,9,10-tetra-carboxylic dianhydride (32 g, 81.4 mmol) was dissolved in 450 mL of 98% H2SO4 and then 0.77 g (3.03 mmol) of iodine was added in the reaction mixture and stirred at room temperature (RT) for 2 h. The reaction temperature was set at 8O0C and then 9.2 mL (180 mmol) of bromine was added dropwise over 2 h. The reaction was conducted at the same temperature for 16 h. The reaction mixture was cooled to RT, and the excess Br2 was displaced by purging with N2. The product was precipitated by an addition of ice water and collected by suction filtration. The precipitate was washed with water several times until the aqueous layer became neutral to yield dibromo- dianhydride as a crude product. The crude product was dried under reduced pressure at 12O0C.
Example 3Preparation of a Perylene Poly(Oxyalkylene) Bisimide Compound; As outlined in scheme I above (described in German Patent DE 195 47 209 A1), the starting material (14.6 g, 37.2 mmol) was suspended in concentrated Sulfuric acid (221 g) and stirred overnight at room temperature. To the suspension was added 12 (350 mg, 1.38 mmol), and the mixture heated to 85 C. Bromine (4.22 ml, 82.6 mmol) was added dropwise over 30 min. The mixture was allowed to stir for 20 hours at 85 C. After cooling, the excess bromine was removed by a stream of nitrogen. Water (35 ml) was added dropwise to the reaction mixture, and the suspension heated to 85 C. for one hour. After cooling, the reaction mixture was filtered (M porosity glass frit) and washed repeatedly with water until the filtrate registered neutral to litmus. The red solid thus obtained was dried at 65-70 C for 4 days. The yield was a red powder (18.75 g).
6 g
A mixture of 5.0 g (13 mmol) of perylene-3,4:9,10-tetraboxylicacid bisanhydride (1) and sulfuric acid (100 mL) was stirred at 50 C for 12 h, and subsequently I2 (0.56 g) was added. The reaction mixture was heated to 80 C, and bromine 2.2 g (15 mmol) was added dropwise over a time period of 2 h. After bromine addition, the reaction mixture was heated for an additional 48 h, the excess bromine was removed by saturated aqueous solution of K2CO3, and water (100 mL) was added carefully. The precipitate was separated by filtration, washed with water (100 mL), and dried in a vacuum to give a red powder 6.0 g. Without further purification it was used to the next reaction.
Perylene-3,4,9,10-tetracarboxylic dianhydride (32.00 g, 81.40 mmol), iodine (0.78 g, 3.04 mmol) and sulfuric acid (98%, 450 ml) were mixed and stirred for 2 h at room temperature. The temperature of the mixture was raised to 80 C and bromine (8.33 ml, 162.80 mmol) was added dropwise over 1 h. The resulting mixture allowed to react for 16 h, upon which time, it was cooled to room temperature and the remaining bromine gas was displaced by nitrogen gas. The mixture was slowly poured into 3 L of ice water and the crude precipitate formed was collected by suction filtration followed by washing several times with distilled water. The crude product was dried at 80 C under reduced pressure and used in the next step without further purification. The crude product containing both mono- and di-bromoperylene derivatives was separated by column chromatography in next step, after introducing bulky substituents in the terminal-position to increase their solubilities.
Compound 3 was synthesized using literature procedure[23,36]. 2.5 g of PTCDA was added into a round bottom flask containing35 mL of H2SO4 (Conc.) and stirred for a period of 30 h at55 C. 0.061 g of iodine (I2) was added to the reaction mixture andfurther stirred for 5 h at same temperature. 0.7 mL of bromine (Br2)was added drop wise within 30 min. Reaction mixture was stirred for 24 h at 85 C. Excess bromine was removed by using N2 stream.20 mL of water was added to cool the mixture and filtered. Washedwith 85% H2SO4 followed by washing with distilled water severaltimes. 3.39 g of dark red compound (96%) was obtained that wasdried in oven at 100 C for 12 h. The obtained brominated compound(3) was used for further reactions without characterization.
1,6-dibromo perylene-3,4,9,10-tetracarboxylic dianhydride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
87%
EXAMPLE 1; 1,7-dibromoperylene-3,4,9,10-tetracarboxyl dianhydride (2)(2) The 3,4,9, 10-perylenetetracarboxyl dianhydride (1) is dissolved in96% H2SO4 and left under stirring for 2 hours at room temperature. Then, iodine (30-40 mmoles per mole of anhydride) is added and the composition is heated to 8O0C. When the purple vapours of iodine are given off, the bromide is added drop by drop (molar ratio with the anhydride 2-2.5:1) and the temperature is increased to about 100C. After 4-6 hours, the reaction is extinguished by adding ice until cooling. The resulting precipitate is then filtered on Buchner filter and washed first in a 5% solution of sodium metabisulfite to eliminate the residual bromine and then several times in water. The precipitate <n="21"/>is then dried first in an oven and then on a thimble for drying from solid form. A red solid is thus obtained, having a sufficient degree of purity to be used as such in the subsequent preparations.One of the preparations is reported below: 5 g 3,4,9, 10-perylenetetracarboxyl dianhydride (1)1.65 cc Br2 113 mg I2 100 cc 96% H2SO46 g of 1 ,7-dibromoperylene-3,4,9,10-tetracarboxyl dianhydride (2) was obtained. The yield was 87%.Note. Besides the 1 ,7 dibromurated isomer, the reaction also yields a small percentage of 1 ,6 disubstituted product, as can be seen from a careful examination of the 1H NMR spectra (see further on, for the complete characterisation). There is no way of separating the two isomers, neither here nor in the next steps. In the characterisations of the products obtained in the next synthesis steps, reference will exclusively be made - when not indicated otherwise - to the 1 ,7 isomer.Empirical formula: C24H6Br2Oe Molecular weight: 550 Solubility: in concentrated H2SO4 Elemental analysis:Theoretical data Experimental data% C = 52.36 % C = 51.61% H = 1.09 % H = 1.081H NMR spectrum, 300 MHz: solvent D2SO4 The spectrum is composed of three signals present in the aromatic area: delta 10.71(d 2H J=8 Hz), 10.04(s 2H), 9.82(d 2H J=8 Hz). Some lower signals are also often present, with chemical shifts very close to the ones described above: in all likelihood, these signals are to be attributed to the small percentage of 1 ,6 isomer that is formed together with the main product.
With sulfuric acid; bromine; iodine; at 80 - 100℃;
The commercially available 3,4:9, 10-perylenetetracarboxyl diahydride (1) (5 g) was initially dissolved in 96% sulfuric acid (100 ml) and stirred for 2 hours at room temperature. 113 g of elemental iodine were then added and the mixture was heated. When a temperature of 80C was attained, elemental bromine was added dropwise (1.65 ml). The reaction mixture was left stirring for 4-6 hours at 100C. At the end of cooling, it was added dropwise to ice and was then filtered and washed with a 5% sodium metabilsulfite solution to give a red solid (6 g), which was brought to dryness and characterized (yield 87%). In addition to the more important isomer (1,7) (2a), a small quantity of the l,6-dibromoperylene-3,4:9,10-tetracarboxyl dianhydride (2b) was obtained. The two isomers could not be separated, thus the mixture was used in the next steps without further purification. NMR (200MHz, D2S04): delta 10.71 (d, J = 8Hz, 2H, H aromatic), 10.04 (s, 2H, H aromatic), 9.82 (d, J = 8Hz, 2H, H aromatic) ppm. The signals from the lesser isomer (1,6) are mostly superimposed to the ones for (2a). Elemental analysis: C^eOeB calc C 52.4 %, H 1.1 %; found C 51.6 %, H 1.1 %.
Perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA)(39.4 g, 100 mmol) was dissolved in Conc. H2SO4 (350 mL).The solution was stirred at room temperature under nitrogenatmosphere for 16 h. During this time catalytic amount of iodine(504 mg, 2 mmol) granules was added in a definite interval.To this reaction mixture, bromine (10.3 mL, 200 mmol)was added drop wise for a period of 12 h. The reaction mixturewas stirred at 85 C for 10 h, then, the reaction mixturewas cooled to room temperature, washed with wateruntil the pH of the solution was reached to about 7and the crude was filtered off, afforded dark red precipitate.It is a mixture of 1, 7- and 1, 6, dibromo isomers.M. F: C24H8Br2O6, Yield: 84%, m. p 300 C. Thecrude was used for the further imidification reactions.FT-IR (KBr, cm-1 ): 3157 (aromatic nu C-H), 1768, 1745 (nuC=O), 1504 (aromatic nu C=C ), 1296, 1282, 1238, 1130, 1053,1507, 1406, 1301 (nu C-o) and 860, 733 (nu C-Br).
Compound 2 was synthesized according to the literature procedure [8]. 31 Perylene-3,4,9,10-tetracarboxylic dianhydride (5.70g, 14.53mmol) was added to 90ml 32 concentrated sulfuric acid and stirred at 50C for 24h. 33 Iodine (0.137g, 0.54mmol) was added to the reaction mixture and stirred for an additional 6h at 50C. 34 Bromine (1.67ml, 32.4mmol) was added dropwise to the reaction mixture over 2h. and stirred for 24h at 85C. Excess bromine was then displaced with N2 gas. The mixture was poured into cold water (50ml) and the precipitate filtered off. The crude product was washed two times with 45ml 85% H2SO4 followed by 35 water to afford 36 2 (6.36g, 79%). Product 2 has brown-red color and used without further purification. FT-IR (KBr, cm-1): nu=3058 (C-H phenyl), 1771 and 1725 (C=O anhydride), 1595 and 1497 (C=C) 1374 (C-O-C), 803 and 733 (C-H bend), 692 (C-Br). UV/Vis (DMF): lambdamax (nm) (epsilon)=425, 488, 517. Fluorescence (DMF): lambdamax (nm)=552, 584, 621. Anal. Calcd. for C24H10Br2O6 (Mw, 554.14.0); C, 52.02; H, 1.82; Br, 28.84. Found: C, 51.55; H, 2.05.
[0160] A mixture of 1,7 & 1,6 dibromoperylene-3,4:9,10-tetracarboxylic acidbisanhydride (Scheme 1), was generated by bromination of perylene 3,4:9,10tetracarboxylic his anhydride according to a literature procedure (J. Org. Chem. 2004,69, 7933-7939).[0161] A mixture of 100 g of perylene-3,4:9,10-tetracarboxylic acid bisanhydride (Compound 1) and 1.5kg of 100 wt % sulfuric acid was stirred for 12 hours at room temperature, and subsequently ?2 (2.5 g) was added. The reaction mixture was heated to 85 C, and 90 g of bromine was added dropwise over a time period of 8 hours down a large, water-cooled condenser. After bromine addition, the reaction mixture was heated for an additional 10 hours at 85 C. HBr gas formed during the reaction was vented from the top of the condenser by a gentle stream of N2 gas into a 500 mL aqueous quenching solution of w/w 5% NaOH,0.05% Na2S2O5. The reaction was cooled to room temperature and excess bromine was removed by bubbling the reaction with N2 gas into the quenching solution. 65 mL of water was added carefully to precipitate the product. The resulting precipitate was separated by filtration through a G4 funnel, washed with 3 x 300 g of 86% sulfuric acid followed by a large amount of water. The product was dried in a vacuum to give 135g (96%) of an isomeric mixture of 1,7 & 1,6 dibromoperylene-3,4:9,10-tetracarboxylic acid bisanhydride as a red powder. The crude product could not be purified since it is insoluble in organic solvents and was used without further purification.
With triethylamine; In dimethyl sulfoxide; at 150℃; for 4h;Product distribution / selectivity;
Example 4 This example describes two methods for the preparation of bis-N,N'-(2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)ethyl)perylenetetracarboxylic diimide. Method A: 2-[2-[2-(2-Aminoethoxy)ethoxy]ethoxy]ethanol (2.6 g, 13.5 mmol), perylenetetracarboxylic dianhydride (2.2 g, 5.6 mmol), and triethylamine (25 mL, 180 mmol) were mixed with 50 mL of dry DMSO (4A activated MS, 3 days) in a 250-mL flask under argon. After the reaction mixture was stirred for 4 h at 150 C., the reaction solution was cooled to 80 C. and transferred to a 1000-mL flask. A mixture of 600 mL 10% aqueous HCl and 300 mL methanol was added to the reaction solution, then the solution was stirred for additional 2 hours at 60 C. After the mixture was cooled to RT overnight, the precipitate was collected using paper filter. The resulting collection was washed with 400 mL water, and the water layer was re-extracted with 50 mL chloroform. The filtrate could be extracted with chloroform to gain more products, but these products were contaminated and needed column purification. The combined organic layer was concentrated to give the crude title product; further purification was carried out on a silica-gel column eluted with CH2Cl2/CH3OH (5:1). Detection of the products on TLC plates was accomplished using UV light or sulfuiric acid solution (5% conc. sulfuric acid in EtOH). The title compound was obtained as dark-red solid (3.6 g, 86% yield): Rf0.4 (CH2Cl2/CH3OH, 10:1). 1H-NMR (60-70 mg/0.5 ml; CDCl3/CD3OD/100/5) delta7.96 (d, 4H, J=8.1 Hz, aromatic ring), 7.61 (d, 4H, J=8.1 Hz, aromatic ring), 4.32 (t, 4H, J=5.7 Hz, CH2N), 3.65-3.29 (m, 28H, CH2OCH2, HOCH2); 13C-NMR (60-70 mg/0.5 ml; CDCl3/CD3OD/100/5) delta162.7, 133.1, 130.4, 128.1, 124.7, 122.5, 122.4, 72.9, 70.79, 70.76, 70.4, 70.2, 68.0, 61.6, 39.5. 1H-NMR (DMSO-d6) delta7.13 (bd, 4H, aromatic ring), 6.92 (bd, 4H, aromatic ring), 4.59 (t, 4H, J=5.7 Hz, CH2N), 3.65-3.29 (m, 28H, CH2OCH2, HOCH2); 13C-NMR (DMSO-d6) delta161.2, 131.4, 128.8, 125.9, 122.6, 120.2, 72.3, 69.8, 69.7, 69.6, 66.5, 60.2, 45.67. MS (MALDI): m/z 765.82 [M+Na]+. Anal. Calcd. for C40H42N2O12 (742.77): C, 64.68; H, 5.70; N, 3.77. Found: C, 64.24; H, 5.52; N, 3.83.
With chlorosulfonic acid; iodine; at 65℃; for 30h;
A mixture of 3,4,9,10-perylenetetracarboxylic dianhydride(3.30 g, 8.41 mmol), chlorosulfonic acid (20 mL, 300 mmol) andiodine (0.56 g, 2.20 mmol) was stirred at 65 C for 30 h. Aftercooling to room temperature, the solution was added dropwise toan ice-water mixture. The precipitate was collected by filtration togive a red solid (4.14 g, 92%). 1H NMR (d-DMSO, ppm): 8.75 (s, 4H,aromatic protons). 13C NMR (d-DMSO, ppm): 119.75, 125.29, 129.5,134.88, 136.22, 158.16, 168.53. Mass (EI): m/z 532.
74.4%
With chlorosulfonic acid; iodine; at 20 - 70℃; for 6.33333h;Inert atmosphere;
10253] (Compound (Id) Manufacturing Process)10254] Chlorosulfuric acid (500 g, 4.29 mol) was inserted into a 1000 ml three neck flask under an argon gas flow. 3,4,9,10-perylene tetracarboxylic acid dianhydride (50 g,0.127 mol) was added to the chlorosulfuric acid for 20 minutes at the room temperature and then iodine (8.5 g, 0.024 mol) was added. 10255] Then, the temperature of the reaction liquid was increased up to 70 C., and reaction was performed with stirring for 6 hours.10256] After the reaction was completed, the reaction liquidwas cooled such that the temperature became the room temperature, and quenching was performed with cool water(2000 ml). The reaction liquid was discolored from dark brown to scarlet and crystals were precipitated. These crystals were taken out, and subjected to slurry washing with water (1000 ml) three times. Then, slurry washing was performed three times with acetonitrile (500 ml), and taken crystals were dried. Thus, a compound (abbreviated to a ?compound (1)- bid?) which was represented by the following formula (1)- bid, as the compound (Id) was obtained (collected amount:50.1 g, and yield: 74.4%).10257] It was confirmed that the compound (1)-bid was obtained, by MS measurement, ion chromatography, and IR measurement. For example, a spectrum of a pro-ion peak mlz=530 was confirmed in the MS measurement. It was confirmed that a chlorine content was 25.1% (ideal value: 26.8%) by using an oxygen combustion method in the ion chromatography.
74.4%
First, a reaction represented by the reaction formula (1-11) was performed as a reaction process 1.500 g of chlorosulthric acid (4.29 mol) was added to 1000 mE of a three-necked flask through argon gas, and 50 g (0.127mol) of 3,4,9,10-perylenetetracarboxylic acid dianhydridewas added thereto at room temperature for 20 minutes. Next, 8.5 g (0.024 mol) of iodine was added thereto. The tempera- tare of the obtained reaction liquid was increased to 70 C., and the reaction liquid was reacted by stirring for 6 hours.After the reaction was terminated, the temperature of the reaction liquid was cooled to the room temperature, 2000 mE of ice water was added thereto, and then the reaction liquid was quenched. The color of the reaction liquid was changed from dark brown into vermilion and crystals were deposited. The crystals were collected by filtration to be slurry-washed using 1000 mE of water for three times. Subsequently, slurry washing was thrther performed using 500 mE of acetonitrile for three times. The collected crystals by filtration were dried. The wet weight of an obtained product was 102 g, the dry 25 weight thereof was 50.1 g, and the yield thereof was 74.4%.
62.2%
With chlorosulfonic acid; iodine; at 70℃; for 5h;
In a 100 ml three-necked flask equipped with a reflux condenser and two glass stoppers 3,4:9,10-perylene tetracarboxylic dianhydride (1 g, 2.55 mmol) and iodine (170 mg, 0.67 mmol) were dissolved in chlorosulfonic acid (10 ml). The mixture was heated to 70 C for 5 h. Afterwards the reaction mixture was poured into an ice-water mixture and the insoluble product was collected by filtration. The crude product was purified by soxhlet extraction using dichloromethane as solvent. The solvent was evaporated by the rotary evaporator to yield a red solid. Yield 2.3 g (62.2%) IR (nu(cm-1)): nu=1080 [C-Cl aromatic], 1475-1600 [aromatic stretch], 1700 [CO anhydride], 3000 [C-H aromatic], Elemental analysis for chlorine: calculated: 26.75% measured: 23.4-23.93%.
With chlorosulfonic acid; iodine;
In the first step of the chlorinated dyes synthesis tetra-potassium salt of 1,6,7,12 tetrachloroperylene-3,4,9,10 tetracarboxylic acid was obtained using procedure reported by Gupta et al. [S1]. Iodine was added to 3,4,9,10-tetracarboxylic dianhydride in chlorosulphonic acid. The filtered out and dried product was dissolved in water using potassium hydroxide, following with potassium carbonate, finally filtered and dried to get tetrapotassium salt of 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic acid (PP1).
With chlorosulfonic acid; iodine; at 20 - 70℃; for 18h;
Perylene-3,4,9,10-tetracarboxylic dianhydride (39.2 g, 0.10 mmol),iodine (0.474 g, 3.73 mmol), and 450 mL of chlorosulfuric acid weremixed and stirred for 2 h at room temperature. The reaction temperaturewas increased to 70 C and the mixture was heated for 16 h. Themixture was slowly transferred to a litre of ice-water and red precipitatewas obtained. The precipitate was collected by suction filtration andwas washed with distilled water several times until the aqueous layerbecame neutral to yield crude product. The product was dried in avacuum oven at 80 C and used in the next step without further purification.
With chlorosulfonic acid; iodine;
Perylene-3,4,9,10-tetracarboxylic dianhydride (20 g, 0.051 mol),iodine (0.241 g, 1.90 mol), and 250 mL of chlorosulfuric acid were mixed and stirred for 2 h at room temperature. The reaction temperature was increased to 70 C and the mixture was heated for 16 h. The mixture was slowly transferred to a litre of ice-water and red precipitate was obtained. The precipitate was collected by suction filtration andwas washed with distilled water several times until the aqueous layer became neutral to yield crude product. The product was dried in avacuum oven at 80 C and used in the next step without further purification.
N,N'-bis((S)-1-carboxy-3-methylbutyl)-3,4:9,10-perylenetetracarboxylic diimide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
100%
With 1H-imidazole at 100℃; for 1h; Inert atmosphere;
97%
With 1H-imidazole at 120℃; for 0.5h;
2.2. Synthesis of PDIs derived from amino acid with aryl side groups andLeucine
General procedure: Asmentioned in the introduction perylene diimide derivatives PDIF,PDIW, PDIY, and PDIL, which were derived from aryl amino acids Phe,Trp, and Tyr, and isobutyl amino acid Leu, respectively, were preparedusing a modified procedure reported for the preparation of PDI analogues[20].Each amino acid (2.2 Eq)was added to perylene tetracarboxylic aciddianhydride (250mg)with imidazole (1 g) and the mixturewasmeltedand stirred at 120 °C for 30 min. After cooling to room temperature, themixture was dissolved in water and filtered. The filtrate was acidified(6 M HCl) and washed with EtOH (5-10 washes) to remove residualimidazole, as detected in 1H NMR spectra. The samples were driedunder high vacuum to obtain products in modest to excellent yields(36-97%). The products appeared as reddish/burgundy colored amorphoussolids. Upon examination by 1H NMR spectroscopy (DMSO-d6),each product exhibited a characteristic methine proton at 5.4-6.1 ppm, in addition to other signals expected for the PDI analogues.Thus, PDIF exhibited the appropriate 1H NMR signals, but those of theperylene corewere broadened, concealing the expected spin-spin splitting(Supplemental Material Figure S1A). PDIY exhibited the expectedaryl signals, but the methylene proton signals of the side chain wereapparently hidden under the solvent signal at 3.9 ppm. Addition oftwo drops of D2O to the sample induced shifting of the methylene protonsignals to 3.3 and 3.5 ppm, and eliminated the phenolic OH signal at9.6 ppm (Supplemental material Fig. S1B). PDIW exhibited highlybroadened perylene 1H NMR signals and they were shifted upfield ofthe typical positions, presumably due to stacking-induced aggregateformation. The perylene signals of this sample emerged upon warmingto 65 °C (Supplemental material Fig. S1C). PDIL exhibited the expected1H NMR signals including the downfield doublets for the perylenecore (8.4 and 8.7) ppm. These latter signals also exhibited adjoiningshoulders, probably also a consequence of aggregation in the sample(Supplemental material Fig. S1A).
95.4%
With 1H-imidazole at 120℃;
92%
With 1H-imidazole for 3h; Heating;
74%
Stage #1: L-leucine; perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With potassium hydroxide In water; dimethyl sulfoxide at 100℃; for 3h;
Stage #2: With hydrogenchloride In water
With 1H-imidazole at 120℃; for 5h; Schlenk technique; Inert atmosphere;
With 1H-imidazole; zinc diacetate; In water; at 190℃; for 18h;
Following the procedure described by Langhals et [AL.,] (Feiler, L. et [AL.,] Liebigs Ann. 1995,1229-1244), samples of 3, 4,9, 10-perylenetetracarboxylic dianhydride (4.50 g, 11.5 mmol), <strong>[80058-84-0]2,6-diisopropyl-4-bromoaniline</strong> (1.61 g, 6.28 mmol), Zn (OAc) [2APOS;2H20] (1.64 g, 7.47 mmol), imidazole (23 g), and distilled water (9.8 mL) were placed into a heavy-walled reaction vessel. The vessel was sealed tightly with a Teflon screw cap and the flask was placed into a [190 °C] oil bath and stirred for 18 h. After cooling, the crude material was passed through a plug of alumina column using chloroform. The filtrate was washed with water, dried, and concentrated. Column chromatography (silica, CHC13, 8 x 30 cm) afforded a red solid (1.63 g, 46percent): mp [GT;300 °C ; LH] NMR 8 1.17 (d, [J=] 6.9 Hz, 12H), 2.73 (m, 2H), 7.45 (s, 2H), 7.67 (t, [J=] 7.8 Hz, 2H), 7.94 (d, J= 8.1 Hz, 2H), 8.49 (m, 4H), 8.66 (d, J= [8.] 1Hz, 2H); FAB-MS obsd 559.1133, calcd, 559.1147 [(C34H26BRNO2)] ; [? LAB,] 356,482, 509 nm ; rem (ex = 509 nm) 539,577 [NM.]
In neat (no solvent) at 110℃; for 0.133333h; Green chemistry;
90%
With 1H-imidazole In toluene for 24h; Reflux; Inert atmosphere;
87%
In N,N-dimethyl-formamide at 200℃; for 0.966667h; Microwave irradiation;
82%
With 1-methyl-pyrrolidin-2-one; acetic acid at 80℃; for 12h;
80%
With 1H-imidazole In toluene for 24h; Inert atmosphere; Reflux;
79%
With 1H-imidazole In toluene at 180℃; for 4h;
75%
With 1H-imidazole at 140℃; for 3h;
Synthesis of N,N′-di(Octyl)-Perylene-3,4,9,10-Tetracarboxylicbisimide (PDI-4)
In a 50 mL round bottom flask, perylene-3,4,9,10-tetracarboxylic dianhydride, (0.784 g, 2 mmol), 1-octylamine (0.516 g, 4 mmol) and imidazole (4 g) were addedand refluxed at 140 °C for 3 h. The reaction mixture wascooled to room temperature and dispersed in 100 ml of ethanolfollowed by addition of 300 ml of 2 M HCl. The mixture wasstirred overnight. The resulting dark-red solid was filtered offand washed thoroughly with distilled water followed by methanol.The collected solid was dried under vacuum. The yieldwas 75 %. IR: ν (cm-1)=3017, 2959, 1671, 1650, 1591, 1575,1502, 1271.
With acetic acid In 1-methyl-pyrrolidin-2-one
With 1H-imidazole In toluene at 180℃;
4
Perylene tetracarboxylic diimide is first formed by reaction in imidazole at 180° C. with n-octylamine, and bromination thereof is then performed in refluxing dichloromethane.At this stage, the 1,7 isomer may be isolated by chromatography optionally followed by successive recrystallizations from a dichloromethane/methanol mixture.
With acetic acid In 1-methyl-pyrrolidin-2-one
With zinc acetate hydrate In quinoline Reflux;
3.82 g
In propan-1-ol; water at 70℃; for 12h;
2-2 Synthesis Example 2-2
3.92 g (10 mmol) of 3,4,9,10-perylenetetracarboxylic dianhydride is added to a mixed solvent of 100 ml of H20 and 100 ml of propanol. The mixture is agitated. Then, 2.93 g (40 mmol) of octylamine is added to the agitated mixture drop by drop. The resulting mixture is agitated at 70° C. for 12 hours. The agitated mixture is filtered at room temperature, cleaned with H2O and methanol, and dried, obtaining 3.82 g (7.6 mmol) of N,N′-dioctyl-3,4,9,10-perylenetetracarboxylic acid diimide.
Stage #1: n-Octylamine; perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With N-ethyl-N,N-diisopropylamine In water at 20℃; for 0.333333h; Green chemistry;
Stage #2: In water at 200℃; for 4h; Autoclave; High pressure; Green chemistry;
N,N'-bis(2-octyldodecyl)-perylene-3,4,9,10-bis(dicarboxiamide)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
93%
With 1H-imidazole; In o-xylene; at 180℃; for 4h;Inert atmosphere;
A mixture of 0.67 g (1.71 mmol) of perylene-3,4,9,10-tetracarboxylic dianhydride (Aldrich), 1.52 g (5.11 mmol) of <strong>[62281-06-5]2-octyldodecylamine</strong>, 3 mL of o-xylene, and 0.92 g (13.5 mmol) of imidazole was stirred under nitrogen atmosphere at 180 C for 4 h. The reaction mixture was cooled to room temperature, treated with methanol (20 mL), and the resulting mixture was sonicated for 10 min. The solid product was collected by filtration and then purified by column chromatography on silica gel with chloroform as eluent, affording 1.51 g (93% yield) of PDI20D as a red solid.[0157] 1H NMR (CDC13, 500 MHz): delta 8.56 (d, 4H, J= 8.0), 8.44 (d, 4H, J= 8.0), 4.13 (d, 4H, J= 7.0), 2.00 (m, 2H), 1.49-1.18 (m, 64H), 0.88-0.82 (t, 12H, J= 6.5). Anal. Calcd for C64H90N2O4: C, 80.79; H, 9.53; N, 2.94. Found: C, 80.76; H, 9.34; N, 3.08.[0158] A mixture of 0.17 g (0.19 mmol) of PDI20D, 0.15 g (0.37 mmol) of Lawesson's Reagent, and 20 mL of toluene was refluxed for 18 h. The mixture was concentrated in vacuo and purified by flash chromatography (Si02, chloroform, 3.5 x 40 cm) to give 45 mg (25% yield) of frans-PDIS220D as a deep purple solid.[0159] 1H NMR (CDCls, 500 MHz): delta 8.60 (d, 2H, J = 8.2), 8.38 (d, 2H, J= 7.9), 8.08 (d, 2H, J = 8.1), 7.98 (d, 2H, J= 8.4), 4.60 (d, 4H, J = 6.6), 2.25 (m, 2H), 1.60-1.10 (m, 64H), 0.87 (m, 12H). Anal. Calcd for C64H90N2O2S2: C, 78.15; H, 9.22; N, 2.85. Found: C, 77.98; H, 8.97; N, 3.01.
In 1,4-dioxane; N,N-dimethyl acetamide for 12h; Inert atmosphere; Reflux;
Preparation of (N-bis-pyridin-2-ylmethylethane-1,2-diamino)perylene-3,4,9,10-tetracarboxdiimide (2).
N,N-Bis(2-pyridylmethyl)ethane-1,2-diamine (6) (200 mg, 0.83 mmol) in dioxane (10 mL) was added dropwise over 30 min to a solution of perylene-3,4,9,10 -tetracarboxylic dianhydride (156 mg, 0.4 mmol) in 10 mL of DMA. The reaction mixture was refluxed for 12 h. The reaction product was separated by filtration and then recrystallization from CHCl3 to afford 2 as a red solid (292.5 mg, 87%). m.p.: > 300 °C; 1H NMR (400 MHz, CDCl3): δ 2.79 (b, 4H), 4.20 (b, 8H), 4.51 (b, 4H), 7.00 (m, 4H), 7.34 (m, 8H), 8.41 (d, J = 4.8 Hz, 4H), 8.60 (s, 8H) ppm. 13C NMR (150 MHz, CDCl3): δ 51.7, 60.4, 67.8, 121.8, 122.8, 123.1, 123.4, 129.5, 131.4, 134.6, 136.1, 148.9, 157.0, 159.7, 163.2 ppm. MS (ESI-TOF) calcd for [C52H40N8O4]+: 840.3; found: 840.9; Anal. calcd for C52H40N8O4: C, 74.27; H, 4.79; N, 13.33; found: C,74.21; H, 4.82; N 13.27.
With benzoic acid In 2-monochlorophenol at 150℃; for 40h;
6.B
4-Octylaniline (2 1 O g, 11 mmol), perylene-3,4,9,10-tetracarboxylic acid dianhydride (2 20 g, 3 70 mmol), and benzoic acid (0.020 g, 0.16 mmol) were mixed with m-CIPhOH was added (9 rmL). The mixture was heated for 40 h at 150° C upon stirring. Solvent was removed in vacuo, residue was purified using column chromatography on silica gel using toluene-petroleum. ether mixture as eluent. Yield. 2.6 g (74%).
With 1H-imidazole at 120℃; for 6h; Inert atmosphere;
2.1 Synthesis of N,N'-diglycine-3,4,9,10-perylene tetracarboxylic acid diethylamide (GP)
0.3912 g (1 mmol) of perylene-3,4,9,10-tetracarboxylic dianhydride, 0.178 g (2 mmol) glyine and 2.0 g of imidazole were heated at 120 oC for 6 h under nitrogen atmosphere. Then 100 mL of ethanol was poured into the hot mixture, refluxed for 6 h, and kept for overnight to precipitate out. Followed it was acidified with dilute HCl. The resulting light yellow precipitate was concentrated by decompression filters, then washed with deionized water to neutral, filtrated and dried at 80 oC under vacuum oven to get 0.457 g orange-red powder (Yield: 88%). IR (KBr, cm-1): 436.8, 499.3, 631.1, 690.6, 750.0, 804.0, 855.2, 935.5, 1021.4, 1127.2, 1299.1, 1434.7, 1507.2, 1572.4, 1648.4, 2359.6, 2613.7; 1H NMR (DMSO-d6, 400MHz, ppm): 8.57-8.91 (d, 4H), 7.70(d, 4H), 4.77 (s, 4H)
82%
Stage #1: perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride; glycine With potassium hydroxide In water monomer; dimethyl sulfoxide at 100℃; for 3h;
Stage #2: With hydrogenchloride In water monomer; dimethyl sulfoxide at 20℃;
81%
With 1H-imidazole at 180℃; for 16h;
69.1%
In N,N-dimethyl-formamide at 90℃; for 8h;
42%
With triethylamine In N,N-dimethyl-formamide at 200℃; for 0.966667h; Microwave irradiation;
With Zinc acetate at 140℃; for 24h; Inert atmosphere;
2.2. Synthesis of dilithium salt of N,N'-bis (glycinyl) perylene diimide(Li2-PDI)
Li2-PDI was synthesized in two steps. Thefirst step involves thesynthesis of N,N'-bis (glycinyl) perylene diimide (H2PDI) by thereaction of PTCDA with glycine. The experimental details are asfollows. A mixture of 0.25 g (0.635 mmol) of PTCDA, 0.113 g(1.5 mmol) of glycine and 0.05 g of zinc acetate were stirred at140 °C for 24 h under argon atmosphere. Zinc acetate was used asthe catalyst for opening the anhydride ring of PTCDA [12]. Thismixture was cooled to room temperature and acidified with100 mL of 2 N HCl. The orange-red precipitate of H2PDI obtainedwas centrifuged, washed several times with deionized waterfollowed by ethanol and dried overnight in an air oven at 70 °C.In the second step, 50 mg of H2PDI and 8 mg of Li2CO3 wereadded to 18 mL of 5:1 (v/v) ethanol and water mixture and stirredat 50 °C for 24 h (Scheme 1) to obtain Li2-PDI. The obtained Li2-PDIsuspension was centrifuged several times and washed thoroughlywith absolute ethanol followed by drying at 100 °C overnight in anair oven. Brick red crystalline powder of Li2-PDI was obtained in92% yield with respect to H2PDI. 1H NMR (D2O, 500 MHz): δ 7.98(br, 8H, ArH), d 4.63 (s, 4H,CH2). 13C MAS solid state NMR(100 MHz): δ 43.91 (-CH2-), d 122.20 (Ar-C), d 128.24 (Ar-C), d132.70 (Ar-C), d 162.30 (NCO), d 173.72 (-COOLi). HRMS:calculated for C28H12O8N2Li2 + K: 557.0551, observed: 557.0529.
With 1H-imidazole at 110℃; for 4h; Inert atmosphere;
1,6-dibromo perylene-3,4,9,10-tetracarboxylic dianhydride[ No CAS ]
1,6,7-tribromoperylene-3,4:9,10-tetracarboxylic bisanhydride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sulfuric acid; bromine; iodine at 85℃; for 18h;
Stage #1: perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With sulfuric acid at 55℃; for 24h;
Stage #2: With iodine at 55℃; for 5h;
Stage #3: With bromine at 85℃; for 24h; Overall yield = 89 %;
With sulfuric acid; bromine; iodine at 85℃; for 24h;
Stage #1: perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With sulfuric acid at 20℃; for 6h; Sonication;
Stage #2: With bromine; iodine for 24h; Reflux;
1 Example 1
2.14g of the carboxylic acid 3,4,9,10-perylene tetracarboxylic dianhydride (PTDA) (M = 392) was added to the containing 18mL of concentrated (98%) H2SO4(M = 98,1.836g / mL) three-necked flask, the 35Hz ultrasonic vibration 10min, then placed on the collector and add thermostat magnetic stirrer condensing device, stirring at room temperature for 6h, the temperature was raised to 80 , reflux, during which added 0.053gI2(M = 127) as a catalyst and with pressure-equalizing dropping funnel was slowly added dropwise thereto within the liquid bromine (M = 160) about 0.577mL (3.12g / mL).After 24h of the reaction, the reaction was diluted with distilled water to concentrated sulfuric acid was 60% after suction filtration to obtain a cake, the cake was placed in a vacuum oven at 90 24h.The filter cake containing mainly the foregoing a, b, c three compounds wherein a: b: c = 7: 2: 1.
Stage #1: perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With sulfuric acid at 55℃; for 19h;
Stage #2: With iodine for 6h;
Stage #3: With bromine at 85℃; for 16h; Overall yield = 18.4 g;
Stage #1: perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With oleum, fuming sulfuric acid, 20% SO3; sulfuric acid
Stage #2: With bromine; iodine at 20 - 85℃; for 22h;
With 1H-imidazole; at 120℃; for 4h;Schlenk technique;
General procedure: 3,4,9,10-Perylene tetracarboxylic acid dianhydride (0.5mmol), L-aminoacid (1.05mmol) and 1 g of imidazole were added into a Schlenk and heated at 120 C for 4 h. The reaction mixture was cooled and poured into water and filtered. The filtrate was acidified with 2.0 M HCl and the precipitate was filtered and washed with water several times, then with methanol, dried under vacuum to give the final products. Yields: PDI-Thr 89%; PDI-Asp 85%; PDI-Met 87%; PDI-Cys 71%.
Example IB: Preparation of tra/iy-PDIS?lMHex and cz's-PDIS?lMHex (mixture of racemic and meso forms)Lawesson'sReagentPDM MHex(S,S)-trans- (R,R)-trans- (S,R)-trans- (R,S)-trans- PDIS21 MHex PDIS21 MHex PDIS21 MHex PDIS21 MHex[0125] A mixture of 4.2 g (10.7 mmol) of perylene-3,4,9, 10-tetracarboxylic dianhydride (Aldrich), 4.1 g (35.6 mmol) of (+/-)-2-aminoheptane (Aldrich), and 40 g of imidazole was heated in a sealed vessel at 200 C for 2 h. The mixture was cooled slightly and triturated with 70 mL of 1 ,4-dioxane. The mixture was cooled to room temperature and filtered. The filter cake was refluxed with 180 mL of 1 ,4-dioxane for 10 min., cooled to room temperature, filtered, and washed successively with 100 mL of methanol and twice with 80 mL of diethyl ether. The filter cake was dried to give 4.8 g (76% yield) of PDIlMHex as a bright red powder. [0126] 1H NMR (CDCI3, 500 MHz): delta 8.68 (d, 4H, J= 8.0), 8.63 (d, 4H, J= 8.0), 5.30 (m, 2H), 2.23 (m, 2H), 1.94 (m, 2H), 1.61 (d, 6H, J= 7.5), 1.42-1.20 (m, 12H), 0.85 (t, 6H, J = 8.0). Anal. Calcd for C38H38N2O4: C, 77.79; H, 6.53; N, 4.77. Found: C, 77.69; H, 6.46; N, 4.85.[0127] A mixture of 1.24 g (2.1 mmol) of PDIlMHex, 2.3 g (5.7 mmol) of Lawesson's Reagent, and 25 mL of 1-methylnaphthalene was heated in an oil bath at 180 C for 8 min. The mixture was cooled immediately in a water bath and purified by flash chromatography (S1O2, toluene, 5.5 x 40 cm). The concentrated product fraction was sonicated with 20 mL of acetone, filtered, and dried to give 180 mg (14% yield) of frans-PDISilMHex (mixture of racemic and meso forms) as a deep purple solid.[0128] 1H NMR (CDCI3, 500 MHz): delta 8.97 (m, 2H), 8.59 (m, 2H), 8.45 (m, 2H), 8.36 (m, 2H), 6.30 (m, 2H), 2.27 (m, 2H), 2.07 (m, 2H), 1.68 (m, 6H), 1.47-1.23 (m, 12H), 0.86 (m, 6H). Anal. Calcd for C38H38N2O2S2: C, 73.75; H, 6.19; N, 4.53. Found: C, 74.05; H, 6.16; N, 4.60.[0129] c/s-PDIS2lMHex (mixture of racemic and meso forms) (180 mg, 14% yield) was isolated as a deep purple solid. 1H NMR (CDC13, 500 MHz): delta 8.89 (m, 2H), 8.50 (m, 2H), 8.33 (m, 2H), 8.19 (m, 2H), 6.29 (m, 2H), 2.26 (m, 2H), 2.08 (m, 2H), 1.69 (m, 6H), 1.46- 1.24 (m, 12H), 0.87 (m, 6H). Anal. Calcd for C38H38N2O2S2: C, 73.75; H, 6.19; N, 4.53. Found: C, 74.01; H, 6.00; N, 4.62.
Stage #1: perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With sulfuric acid; iodine at 20℃; for 2h;
Stage #2: With bromine at 80℃; for 18h;
Stage #1: perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With sulfuric acid; iodine at 20℃; for 2h;
Stage #2: With bromine at 80℃; for 17h;
1,(7)-Dibromoperylene-3,4,9,10-tetracarboxydiimide (1,2):bromination
Perylene-3,4,9,10-tetracarboxylic dianhydride (32.0 g,81.4 mmol), iodine (0.78 g, 3.04 mmol) and sulfuric acid(98 %, 450 ml) were mixed and stirred 2 h at room temperature. The temperature of the mixture was raised to 80 °C, bromine (7.5 ml, 146.65 mmol) was added dropwise over 1 h. In this condition, the mixture was reacted for 16 h.After, cooled to room temperature and excess bromine gas was displaced by nitrogen gas. The mixture was poured in3 l of ice-water slowly, to obtain precipitate and the precipitate collected by suction filtration in crude product form.The crude produce was washed with distilled water several times. Then, crude product was dried at 100 C under reduced pressure and used for the next step without further purification. The crude contain both 1 and 2, there were separated in next step, after importing derivatives in terminal-position to get more solubility that able to purifying by column chromatography (Fig. 1; Scheme 1).
Stage #1: perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With sulfuric acid; iodine at 20℃; for 2h;
Stage #2: With bromine at 20 - 80℃; for 17h;
2.2.1. 1,(7)-(di)bromoperylene-3,4,9,10-tetracarboxydiimide (1,2);bromination
Perylene-3,4,9,10-tetracarboxylic dianhydride (32.0 g, 81.4 mmol), iodine (0.78 g, 3.04 mmol), and sulfuric acid (98%, 450 ml) were mixed and stirred for 2 h at room temperature. The temperature of the mixture was raised to 80 °C, bromine (7.5 ml, 146.65 mmol) was added dropwisely for 1 h. The mixture was reacted for 16 h. Then, it was cooled to room temperature and bromine gas was displaced by nitrogen gas. The mixturewas slowly poured into 3L of ice-water, producing precipitate collected by suction filtration in crude product form. The crude product was washed with distilled water several times. Then, the crude product was dried at 100 °C under reduced pressure and used in the next step without further purification. The crude containing both 1 and 2 was separated by column chromatography in next step, after importing derivatives in terminal-position to increase solubility.
Stage #1: perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With sulfuric acid at 20℃; for 12h;
Stage #2: With bromine at 85℃; for 10h;
Stage #1: perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With sulfuric acid; iodine at 85℃; for 2h;
Stage #2: With bromine at 85℃; for 18h; Overall yield = 16 g;
1 [Preparation Example 1] Preparation of Intermediates 1 and 2
11 g (0.028 mol) of perylenediamine hydrate, 0.265 g (0.001 mol) of iodine and 150 ml of 98% sulfuric acid were placed in a 500 ml three-necked round bottom flask, and the mixture was stirred at room temperature for 2 hours. The mixture was warmed to 85 [deg.] C and 3.16 ml (0.062 mol) of bromine was slowly added to the above mixture for 2 hours. The mixture was refluxed at 85 ° C for 16 hours, then cooled to room temperature and poured into 1.2 L of ice water. The resulting red precipitate was filtered with a vacuum filter and washed with water until neutralized with distilled water. And dried in an oven at 80 for one day to obtain 16 g of a red powder. The following reaction was carried out without purification.
Stage #1: perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With sulfuric acid; iodine at 20℃; for 2h;
Stage #2: With bromine at 80℃; for 17h; Sealed tube;
2.1 2.2.1 1,7-Dibromoperylene-3,4,9,10-tetracarboxydiimide: bromination
Perylene-3,4,9,10-tetracarboxylic dianhydride (32.00g, 81.40mmol), iodine (0.78g, 3.04mmol) and sulfuric acid (98%, 450mL) were mixed and stirred for 2hat room temperature. The temperature of the mixture was raised to 80°C and bromine (8.33mL, 162.80mmol) was added dropwise over 1h. The resulting mixture allowed to react for 16h as sealed, upon which time, it was cooled to room temperature and the remaining bromine gas was displaced by nitrogen gas. The mixture was slowly poured into 3L of ice water and the crude precipitate formed was collected by suction filtration followed by washing several times with distilled water. The crude product was dried at 80°C under reduced pressure and used in the next step without further purification. The crude product containing both mono- and di-bromoperylene derivatives was separated by column chromatography in next step, after introducing bulky substituents in the terminal-position to increase their solubilities.
Stage #1: perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With sulfuric acid; iodine at 20℃; for 2h;
Stage #2: With bromine at 80℃; for 16h;
1.1 (1) Bromination reaction
Perylene-3,4,9,10-tetracarboxylic dianhydride16 g (0.0407 mol), iodine 0.39 g (0.00152 mol), 225 ml of 98% sulfuric acid was stirred for 2 hours at room temperature.The temperature was raised to 80 ° C, and 4.6 ml (0.09 mol) of bromine was slowly added for 2 hours.After maintaining the temperature for 16 hours, the mixture was cooled to room temperature, and bromine remaining with nitrogen gas was removed.The resulting precipitate was slowly poured into 2000 ml of distilled water in a cold water bath and filtered under reduced pressure. Washed several times with distilled water until the pH was 7, and dried in a vacuum oven.Substances produced during this synthesis process are substituted with one bromine 1-bromoperylene-3,4,9,10-tetracarboxy dianhydride and Two bromines substituted 1,7-dibromoperylene-3,4,9,10-tetracarboxy dianhydride is in a mixed state.The bromination reaction is carried out as follows.
Stage #1: perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With sulfuric acid; iodine at 20℃; for 2h;
Stage #2: With bromine at 80℃; for 18h;
4.4-1 N, N'-bis(2,6-diisopropylphenyl) -l-bromoperylene-3,4,9,10-tetrahydrocarboxydiimide(N, N' -Bis(2, 6-diisopropylphenyl)-1-bromoperylene-3,4,9,10-tetracarboxydiimide) (2a)
Perylene-3,4,9,10-tetracarboxylic dianhydride (16.0 g, 40.7 mmol), iodine (0.39 g, 1.52 mmol) and sulfuric acid ( 98%, 225ml) were mixed and stirred at room temperature for 2 hours.The reaction temperature was set to 80° C., and bromine (3.58 ml, 70 mmol) was added dropwise over 2 hours.The mixture was further reacted at 80° C. for 16 hours, cooled to room temperature, and the excess bromine gas was replaced with nitrogen gas.The precipitate obtained after adding ice water to the mixture was collected by suction filtration.The precipitate was washed several times with water until the aqueous layer became neutral to give dibromo dianhydride as a crude product.The crude product was then dried at 100° C. under reduced pressure and used in the next step without further purification.
N,N'-bis-(L-glutamicacid)-3,4,9,10-perylene tetracarboxylic diimide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
With 1H-imidazole at 110℃; for 8h; Inert atmosphere;
According to a particularly preferred embodiment, the method for preparing the PDI-Glu includes:
Add a mixture of perylene-3,4,9,10-tetracarboxylic dianhydride (1.0mmol) and L-glutamic acid (3.0mmol) to imidazole (5g) that has been dissolved at 110°C, and place it under nitrogen. The reaction was terminated after 8 hours of reaction in the pressure tube under the atmosphere. The mixture was cooled to room temperature and transferred, poured into the reaction mixture with 50 mL of water to dissolve and filtered. The filtrate was acidified with 2M HCl, and then allowed to stand overnight at room temperature to allow precipitation. The precipitate obtained by filtration is subjected to centrifugal washing treatment, first washing with ethanol, and then washing with water until it is neutral. After the product was dried at room temperature, a reddish brown powder was finally obtained (80% yield).
73%
With potassium hydroxide In water; dimethyl sulfoxide at 100℃; for 3h;
PDIB-Dimethylethoxysilane
PDIB-dimethylethoxysilane” refers to perylenediimide bridged dimethylethoxysilane. To a three-necked round bottom flask, 3,4,9,10-tetracarboxydianhydrideperylene (0.49 g, 1.12 mmol) and anhydrous ethanol (50.0 mL) were added and heated to reflux under argon atmosphere. Then excess 3-aminopropyldimethylethoxysilane (2.0 g, 12.4 mmol) was added and continued refluxing for 24 hours. The resulted dark red solid was washed with hexane and ethanol to remove excess 3-aminopropyldimethylethoxysilane. The dark red solid was dissolved in chloroform (50 mL) and insoluble solid was removed by centrifugation and gravity filtration. The filtrate was concentrated in vacuum to yield a dark red solid (500 mg, yield=59%). As shown in FIG. 7, 1H-NMR in CDCl3 {δ, ppm}: NMR, 8.49-8.47 (2H, d), 8.33-8.31 (2H, d), 4.17-4.14 (2H, t), 3.70-3.65 (2H, q), 1.82-1.76 (2H, m), 1.20-1.17 (3H, t), 0.76-0.73 (2H, t), 0.14 (16H, s). As shown in FIG. 8, FTIR stretchings (cm-1): 2955-2886 (C-H stretching of alkyl chains), 1692 (diimide carbonyl stretching), 1593-1577 (aromatic C-C stretching), 1439 (N-C stretching from perylenediimide), 1378-1248 (Si-C stretching), 1103-1072 (Si-O-). Elemental analysis (%): experimental-C, 66.8, H, 6.26, N, 4.04. Calculated-C, 67.2, H, 6.2, N, 4.1.
Stage #1: 3-(2-(2-(2-aminoethoxy)ethoxy)ethoxy)propen-1-ene; 2-(2-(2-(prop-2-yn-1-yloxy)ethoxy)ethoxy)ethanamine; perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With N,N-dimethyl acetamide In 1,4-dioxane at 120℃; for 12h; Inert atmosphere;
Stage #2: 2-azidoethyl 2,3,4,6-tetra-O-acetyl-β-lactopyranoside With copper(ll) sulfate pentahydrate; sodium L-ascorbate In tetrahydrofuran; water at 55℃; for 10h;
N, N'-di (l-glutamic amine)-perylene-3,4,9,10-tetracarboxylic diimide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
72%
Stage #1: L-glutamic acid; perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With 1H-imidazole at 165℃; for 7h; Inert atmosphere;
Stage #2: With ammonium hydroxide In water for 0.25h;
3.2. Synthesis of GAPTCD
L-glutamic acid (4.0 g, 24 mM), 1 (0.6 g, 1.6 mM), and 8.0 g of imidazole were mixed and heated to 165°C for 7 h with stirring under N2 atmosphere. After being cooled to room temperature, 100.0 mL of hot water was poured into the reaction ask, and then insoluble precipitate was filtered and discarded. To the aqueous solution was added 200 mL of 2.0 M diluted hydrochloric acid; then the precipitate was separated out and washed with water and ethanol, consecutively. The crude product was dissolved in 100.0 mL of DMF, and then diluted hydrochloric acid was added to adjust pH to 1. It was then dissolved in 100.0 mL of 0.1 MKOH solution and precipitated by adding diluted hydrochloric acid to pH 1. The precipitate was filtered and washed with diluted hydrochloric acid and ethanol. Compound 2 was then neutralized with 15 mL of 15%NH3*H2O and stirred for 15 min. The precipitate was filtered off as solvent being evaporated and then dried under vacuum at 100°C to give the reddish-brown product of GAPTCD (0.7 g, 72%).
2.2. Synthesis of PDIs derived from amino acid with aryl side groups andLeucine
General procedure: Asmentioned in the introduction perylene diimide derivatives PDIF,PDIW, PDIY, and PDIL, which were derived from aryl amino acids Phe,Trp, and Tyr, and isobutyl amino acid Leu, respectively, were preparedusing a modified procedure reported for the preparation of PDI analogues[20].Each amino acid (2.2 Eq)was added to perylene tetracarboxylic aciddianhydride (250mg)with imidazole (1 g) and the mixturewasmeltedand stirred at 120 °C for 30 min. After cooling to room temperature, themixture was dissolved in water and filtered. The filtrate was acidified(6 M HCl) and washed with EtOH (5-10 washes) to remove residualimidazole, as detected in 1H NMR spectra. The samples were driedunder high vacuum to obtain products in modest to excellent yields(36-97%). The products appeared as reddish/burgundy colored amorphoussolids. Upon examination by 1H NMR spectroscopy (DMSO-d6),each product exhibited a characteristic methine proton at 5.4-6.1 ppm, in addition to other signals expected for the PDI analogues.Thus, PDIF exhibited the appropriate 1H NMR signals, but those of theperylene corewere broadened, concealing the expected spin-spin splitting(Supplemental Material Figure S1A). PDIY exhibited the expectedaryl signals, but the methylene proton signals of the side chain wereapparently hidden under the solvent signal at 3.9 ppm. Addition oftwo drops of D2O to the sample induced shifting of the methylene protonsignals to 3.3 and 3.5 ppm, and eliminated the phenolic OH signal at9.6 ppm (Supplemental material Fig. S1B). PDIW exhibited highlybroadened perylene 1H NMR signals and they were shifted upfield ofthe typical positions, presumably due to stacking-induced aggregateformation. The perylene signals of this sample emerged upon warmingto 65 °C (Supplemental material Fig. S1C). PDIL exhibited the expected1H NMR signals including the downfield doublets for the perylenecore (8.4 and 8.7) ppm. These latter signals also exhibited adjoiningshoulders, probably also a consequence of aggregation in the sample(Supplemental material Fig. S1A).
With 1H-imidazole at 120℃; for 24h;
Synthesis of PDI/Trp
Tryptophan containing perylene bisanhydride derivative (PDI/Trp) was synthesized according to method in literature. 3,4,9,10-perylenetetracarboxylic acid bisanhydride(250 mg, 0.64 mmol), tryptophan (391.1 mg, 1.915 mmol)was stirred in imidazole (1 g) heated at 120 °C for 24 h. The reaction mixture was cooled to 90 °C than water was added to the solution and filterated. Then, 2M HCl was poured into the solution, the formed precipitate was filtrated and washed with excess distilled water than dried at 100 °C obtained to thePDI/Trp The procedure is shown in Scheme 1. 1H NMR(600 MHz, DMSO-d6): δ = 7.81 (4H), 7.64 (4H), 7.16 (4H),6.92 (2H), 6.03 (2H), 3.62 (4H). 13C NMR (DMSO-d6): δ =171.5, 162.5, 136.4, 133.3, 130, 128.2, 127.8, 124.2, 122.0,121.4, 118.9, 111.8, 110.7, 54.0. IR (cm-1): 3382, 3235, 1726,1691, 1651, 1590, 1572, 1451, 1433. MS-ESI (m/z) calcd forC46H28N4O8 [M-H+] - 765.641.
N,N'-bis-(L-methionine)-3,4,9,10-perylene tetracarboxylic diimide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
87%
With 1H-imidazole at 120℃; for 4h; Schlenk technique;
2.2 General procedure for PDI-AAs
General procedure: 3,4,9,10-Perylene tetracarboxylic acid dianhydride (0.5mmol), L-aminoacid (1.05mmol) and 1 g of imidazole were added into a Schlenk and heated at 120 °C for 4 h. The reaction mixture was cooled and poured into water and filtered. The filtrate was acidified with 2.0 M HCl and the precipitate was filtered and washed with water several times, then with methanol, dried under vacuum to give the final products. Yields: PDI-Thr 89%; PDI-Asp 85%; PDI-Met 87%; PDI-Cys 71%.
N-(1-butylpentyl)perylene-3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-imide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
at 130℃; for 3h;
50 mg of -3,4,9,10-tetracarboxylic dianhydride and 8 g of imidazole were mixed and heated to 130 C to dissolve the mixture. After the slow injection of the mixture relative to _3,4,9,10 - tetracarboxylic dianhydride in a molar excess of 5-aminononanamine solutionThe mixture was stirred for 3 hours to obtain a reaction solution, and then 10 ml of ethanol and 15 ml of concentrated hydrochloric acid (mass concentration: 36%) were added to the reaction solution. The mixture was stirred overnight, and the product was removed, washed with water until pH was neutral, and dried.
(1) A perylimide-containing perylimide derivative monomer having one end of the following formula substituted with <strong>[2198-45-0]5-aminononane</strong> was prepared.1.1) 100 mg of perylene-3,4,9,10-tetracarboxylic dianhydride,10 grams of imidazole and 110 mg of <strong>[2198-45-0]5-aminononane</strong>,Mixed and heated to 130 C for 3 hours to obtain a reaction solution,Then, 15 ml of ethanol and 15 ml of conc. Hydrochloric acid (mass concentration: 36%) were added to the reaction mixture and stirred overnight. The product was removed and rinsed with water until the pH was neutral and then dried.1.2) Take step 1.1) 100 mg of the product obtained after drying and 50 mg of potassium hydroxide, 10 ml of t-butanol was added as an organic solvent, and the reaction was carried out by heating at 90 C., and the reaction time was 1 hour to obtain a reaction solution. To the reaction mixture was added 40 mlHydrochloric acid (mass concentration of 10%), the precipitate was filtered after stirring for two hours. The product was removed, purified by column chromatography, and dried to give a peryleneimide-containing perylimide derivative substituted with unilateral alkyl chain.
With 1H-imidazole; at 130℃; for 1h;
100 mg of 3,4,9,10-decyltetracarboxylic diimide molecule A and 10 g of imidazole were heated to 130 C,Then add 80mg <strong>[2198-45-0]5-aminononane</strong>,Reaction 1h,Add 500mL of ethanol and 10mL of concentrated hydrochloric acid with a mass fraction of 36%.After stirring overnight, a solid precipitated, and the product was collected by suction filtration, and the solid was washed with water until neutral, and finally, the intermediate compound B was obtained by rotary distillation under reduced pressure.
N-N'-bis-(DL-aspartic acid)-3,4,9,10-perylenetetracarboxylic diimide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
83.1%
With 1H-imidazole; zinc diacetate; In ethanol; at 120℃;Inert atmosphere;
1.00 g (2.55 mmol) of perylene-3,4,9,10-tetracarboxylic dianhydride, 0.849 g (6.37 mmol) DL-aspartic acid, 0.200 g(0.912 mmol) zinc acetate and 18 g imidazole were heated at 120 C for 6 h under nitrogen atmosphere. Then 50 mL of ethanol was poured into the hot mixture, refluxed for 6 h and kept for overnight to precipitate out. The precipitate was filtered and washed with ethanol. The product was dried at 70 C under vacuum oven to get 1.32 g deep red powder, named as PDIC, with a yield of 83.1%. 1H NMR (D2O, 400 MHz,d ppm): 7.46 and 8.67 (each d, 8H, perylene),5.77 (t, 2H, CH), 2.91-3.35 (m, 4H, CH2). IR (KBr pellet) vmax in cm-1 3141 (perylene C-H stretching vibration), 2959 (DL-aspartic acid aliphatic chain CeH stretching vibration), 2849 (asymmetric CH2 stretching vibration), 1699 (perylene imde C=O), 1657 (peryleneimide C=O), 1592 (perylene C=C), 1353 (C-N), 1260 (carboxylic acid C-O), 1021 (carboxylic acid C-O), 858 (perylene C-H out-of-plane bending), 808 (C-H), 751 (CeH).
With 1H-imidazole; at 150℃; for 6h;Inert atmosphere;
PASP was prepared by an improved method from the literature. [46,47] Briefly, 3,4,9,10-perylenetetracarboxylic acid bisanhydride (392.8 mg, 1.0 mmol), aspartic acid (273.4 mg, 2.05 mmol), and 5.000 g of imidazole were added into a round bottom flask under mechanical stirring for 6 h under N2 atmosphere at 150 C. The reaction mixture was cooled to 90 C, and then 100.0 mL of water was poured into the reactor. After the insoluble impurities were removed, 250.0 mL of 2.0 M HCl was added to the aqueous solution. The fresh precipitate was washed twice with water and ethanol, and then dried under vacuum at 80 C to give the crude product. The crude product was further purified by dissolving it in 50.0 mL of dimethylformamide (DMF), using 2.0 M HCl to adjust to pH 1, and then the obtained precipitate was dissolved in 50.0 mL of a KOH solution (4.5 mmol, 252.5 mg), and 0.12 M HCl added dropwise to adjust the pH to 1. The final precipitate was washed twice with ethanol and then dried under vacuum at 80 C to give the product of PASPH*2O.
With 1H-imidazole;Inert atmosphere; Reflux;
(1) Weigh perylene dianhydride (PTCD, 196.4mg, 0.50mmol), aspartic acid (ASP, 136.7mg, 1mmol), imidazole (2.0g) and 100mL single-necked round bottom flask, stir under N2 protection, Heated to 150-180 , refluxed for 6-10h to obtain a dark red solution. The reaction liquid was cooled to room temperature, the liquid solidified, and 50 mL of hot water was added to the reactor. The product was dissolved in hot water and centrifuged to remove insoluble impurities; the aqueous solution was acidified with HCl (120 mL, 1-2 M) to obtain a red precipitate, centrifuged, and washed with water 2. Wash twice with ethanol to obtain a red precipitate, and vacuum dry at 80 C to obtain a crude red product. Dissolve the crude product in 25mL N,N-dimethylformamide (DMF), dropwise add 1-2M HCl to pH = 1 (the solution is close to colorless, the maximum amount of red precipitate), centrifuge; dissolve the precipitate in KOH aqueous solution In the solution, add 1-2M HCl dropwise to pH = 1, centrifuge, wash with water and wash with ethanol twice, and vacuum dry at 80 . The crude product was repeatedly dissolved with KOH and acidified with 1-2M HCl 2-3 times to obtain the red product PASP.
With acetic acid In N,N-dimethyl-formamide at 80℃; for 5h; Inert atmosphere;
2.2.1. Synthesis of N,N0-didodecyl-1,7-dibromoperylene-diimide 3
A mixture of 1,7-dibromoperylene-3,4,9,10-tertracarboxylic aciddiimide 2 (0.2 g, 0.36 mmol), dodecylamine (0.14 g, 0.76 mmol) anda drop of glacial acetic acid in anhydrous dimethyl formamide(DMF, 20 mL), was stirred for 5 h at 80 °C under N2 atmosphere.After being cooled to room temperature, 20 mL of distilled waterwas added into the reaction system. The precipitate was formedand filtered. The obtained solid was separated by column chromatographyon silica 100e200 mesh using CH2Cl2/petroleum ether(3:1, V/V) as eluent to afford crineous powder in yield of 84%.1HNMR (400 MHz, CDCl3) d: 9.46(d, J 8.0 Hz, 2H, Per-H), 8.90(s,2H, Per-H), 8.68 (d, J 8.0 Hz, 2H, Per-H), 4.20 (t, J 8.0 Hz, 4H,NCH2),1.75 (bs, 4H, CH2),1.24e1.49 (m, 36H, CH2), 0.88 (t, J 8.0 Hz,6H, CH3).
First 3,4,9,10 perylene tetracarboxylic dianhydride was dissolved in the KOH solution, followed by heating up to 198 deg.] C, at a pressure of 2MPa for 36h and then the reaction was kept cooled under pressure, until the pressure was decreased to atmospheric, the temperature drop to 85 C after hot filtration, the filtrate was finally adjusted to pH 4 with hydrochloric acid, filtered, and the filter was washed with water, and drying, to obtain a mixture of 3,9-perylenedicarboxylic acid and 3,10-perylenedicarboxylic acid. 1) Esterification: First, the mixture of 3,9-perylenedicarboxylic acid and 3,10-perylenedicarboxylic acid obtained in step (a) is dissolved in an organic solvent, After the temperature was raised to 42 to 45 C, the acylating agent was added dropwise,After the addition of the acylating agent, Adjust the pH to 6 ~ 7, and add acid and esterification catalyst, Then heated to 65 ~ 70 C, Insulation reaction 2 ~ 2. 5h after the temperature to reflux,Reflux reaction 2 ~ 3h,Cooling to 30 ~ 35 C,Then add isobutanol and then heated to reflux,Reflux 3 ~ 4h after vacuum distillation,A solid residue was obtained. The important parameters for the acylation reaction are PH,temperature,Time and catalyst, The invention adopts the optimization design of the above process parameters, The conversion of the reactants is high, And to achieve the two isomers are generated simultaneously, The yield of the desired product is high and the purity is good. (2) impurity removal: the solid residue dissolved in organic solvents, heated to 120 ~ 130 C after the addition of activated carbon hot filter, the filtrate. Add activated charcoal to remove the coking impurities. (3) recrystallization: The filtrate was cooled to 35 C recrystallized diisobutyl 3,9-perylene carboxylate and diisobutyl 3,10-perylene carboxylate mixtures thereof. (4) Separation: Ethanol was added to the mixture of diisobutyl 3,9-perylene carboxylate and diisobutyl 3,10-perylene carboxylate obtained in step (3) and heated to reflux, filtered and the filtrate was reduced Pressure distillation, drying, That isdiisobutyl 3,9-perylene carboxylate After the filtrate is dried, diisobutyl 3,10-perylene carboxylate.
With potassium hydroxide; at 198℃; under 15001.5 Torr; for 36h;
First 3,4,9,10 perylene tetracarboxylic dianhydride was dissolved in the KOH solution, followed by heating up to 198 deg.] C, at a pressure of 2MPa for 36h and then the reaction was kept cooled under pressure, until the pressure was decreased to atmospheric, the temperature drop to 85 C after hot filtration, the filtrate was finally adjusted to pH 4 with hydrochloric acid, filtered, and the filter was washed with water, and drying, to obtain a mixture of 3,9-perylenedicarboxylic acid and perylene-3,10-dicarboxylic acid.
With 1H-imidazole; zinc diacetate; at 160℃; for 4h;Inert atmosphere;
A solution of imidazole (20 g; 293 mmol)3,4,9,10-perylene tetracarboxylic dianhydride (1 g; 2.55 mmol)Anhydrous zinc acetate (0.44 g; 2.40 mmol)And 3- (di-n-butylamino) propylamine (1.24 ml; 6.38 mmol)The mixture was mixed and the mixture was stirred in an argon atmosphere at 160 C for 4 hours.After completion of the reaction,The mixture was extracted with water and chloroform using Soxhlet (Soxhlet)And then the extract is followedDried under vacuum to give compound B as a dark red powder in a yield of 80%. [Chemical Formula 5-A](Hereinafter referred to as compound B) has a concentration of about -0.5 V as measured by cyclic voltammetry (CV)(Relative to Ag / AgCl).
10 g of perylene-3,4,9,10-tetracarboxylic dianhydride, 16.67 g of <strong>[80058-84-0]4-bromo-2,6-diisopropylaniline</strong> and 250 mL of quinoline were heated to 210 DEG C under argon, and stayed for 17 hours. 10 g of the dried powder was mixed with 100 g of methanol and 10 g of K2CO3, and the mixture was heated to 80 DEG C and stirred for 12 hours. After cooling to room temperature, the crystals were precipitated using methanol. After the reaction was cooled to room temperature, crystals were precipitated with water, Filtered and dried to obtain an orange light-emitting fluorescent dye having a structure represented by the following formula (2a).
Perylene-3,4,9,10-tetracarboxylic acid dianhydride, 16.67 g of <strong>[80058-84-0]4-bromo-2,6-diisopropylaniline</strong> and 250 mL of quinoline were heated to 210 DEG C under argon, and 17 I stayed for hours.After cooling to room temperature, crystals were precipitated with methanol, filtered and dried.10 g of the dried powder wasmixed with 100 g of methanol together with 10g of K2CO3,and then the mixture was heated to 80 ° C and stirred for 12 hours.After the reaction was cooled to room temperature, crystals were precipitated with water, filtered and dried.10 g of the dried powder was mixed with 0.72 g of acryloyl chloride and 30 g of dioxane, followed by heating at 100 DEG C for 3 hours.The reaction product was cooled to room temperature, and crystals were precipitated by using water. The crystals were filtered and dried to obtain an orange fluorescent substance having a structure represented by the following formula (1a).
With water; potassium hydroxide; at 90 - 200℃; under 1500.15 - 2250.23 Torr; for 23h;Autoclave;
In the reaction bottle 3,4,9,10-perylenetetracarboxylic dianhydride40g Adding 200 mL of an aqueous solution containing 40 g of potassium hydroxide, Stir well and heat to 90 C. Then moving the reaction solution into the autoclave, Closed autoclave, Slowly warm to 200 C, It takes about 3 hours, At this time, the pressure in the kettle is 0.2 to 0.3 MPa. After the heat preservation reaction for 20 hours, the temperature was lowered to room temperature. Adjust the pH of the reaction solution to 8-9 with a 10% hydrochloric acid solution. Filter the reaction solution, Continue to adjust the pH of the filtrate to 2~3 with 10% hydrochloric acid solution. At this point, a large amount of solids precipitated. Filter the reaction solution, The filter cake was washed twice with 200 mL of saturated sodium chloride solution. Dry the filter cake to obtain 3,9-perylenedicarboxylic acid 31g
31 g
With water; potassium hydroxide; at 120℃; for 5h;Microwave irradiation;
In a microwave reactor,40 g of 3,4,9,10-tetradecanoic anhydride was added to 200 mL of an aqueous solution containing 33.5 g of potassium hydroxide.After stirring evenly, the microwave reaction was heated to 120 C.After the heat preservation reaction for 5 hours, the temperature was lowered to room temperature.The pH of the reaction solution was adjusted to 8-9 with a 10% hydrochloric acid solution, and the reaction solution was filtered.Continue to adjust the pH of the filtrate to 2 to 3 with a 10% hydrochloric acid solution, at which time a large amount of solid precipitates.The reaction solution was filtered, and the filter cake was washed twice with a saturated sodium chloride solution (200 mL).Dry the filter cake to obtain 3,9-nonanedicarboxylic acid 31g
31 g
With water; potassium hydroxide; at 90 - 200℃; under 1500.15 - 2250.23 Torr; for 23h;Autoclave;
40 g of 3,4,9,10-tetradecanoic anhydride was added to 200 mL of an aqueous solution containing 40 g of potassium hydroxide in a reaction flask, and the mixture was stirred and heated to 90 C.Then moving the reaction solution into the autoclave,The autoclave was sealed and slowly heated to 200 C for about 3 h. At this time, the pressure in the autoclave was 0.2-0.3 MPa. After the reaction for 20 h, the temperature was lowered to room temperature. The pH of the reaction solution was adjusted to 8-9 with 10% hydrochloric acid solution. The liquid was continuously adjusted to pH 2 to 3 with a 10% hydrochloric acid solution. At this time, a large amount of solid was precipitated, and the reaction solution was filtered. The filter cake was washed twice with a saturated sodium chloride solution (200 mL), and the filter cake was dried to obtain 3,9- Azelaic acid 31g
With 1H-imidazole; zinc(II) acetate dihydrate; In water; at 200℃; for 24.0h;Autoclave;
5.5 g (14 mmol) of Perylene-3,4,9,10-tetracarboxylic acid dianhydride (Compound 1), 1.57 g (7.6 mmol) of 2,5-di-tert-butyl aniline, 1.98 g (9.0 mmol) of zinc acetate dihydrate, 14 g (205.6 mmol) of imidazole and 12 mL of water were placed in a metal autoclave, well mixed with a spatula and reacted at 200 C. for 24 hours. After the reaction, contents were transferred to a 500 mL beaker and a residue was washed with about 200 mL of EtOH and poured into the beaker. To the mixture, 1 mL of concentrated hydrochloric acid was added dropwise, stirred for 1 hour at room temperature and EtOH was distilled off. CHCl3 was added to the residue, the mixture was transferred to a separation funnel and washed with water 3 times. The CHCl3 layer was dried over Na2SO3 and concentrated to dryness. The product was purified with column chromatography using chloroform/ethyl acetate 9:1 as an eluent (T, Dentani; et al., Dyes Pigments., 2007, 72(3), 303-307.). 1H-NMR (400 MHz, CDCl3) delta:1.30 (s, 9H), 1.33 (s, 9H), 7.03 (s, 1H), 7.45 (d, 1H, J=8.4 Hz), 7.58-7.65 (m, 3H), 7.90 (d, 2H, J=7.9 Hz), 8.44 (m, 3H), 8.64 (d, 2H, J=7.8 Hz).
N,N'-bis((1S)-1-naphthyleth-1-yl)perylene-3,4,9,10-tetracarboxylic diimide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
71%
With zinc(II) acetate dihydrate In quinoline Inert atmosphere;
Syntheses of (R,R)-1-BNP and (S,S)-1-BNP
General procedure: 3,4,9,10-Perylenetetracarboxylic dianhydride (202.5mg, 0.52mmol), (R)-(+)-1-(1-naphthyl)ethylamine (0.2 mL, 1.2 mmol), and zinc acetate dihydrate (124.7 mg, 0.57 mmol) were mixed in quinoline (20 mL) and were heated with stirring at 180 °C under nitrogen for 4 h. After cooling to room temperature, the reaction mixture was treated with 2 N HCl and stirred overnight at room temperature. The resulting dark red precipitate was collected by filtration, washed thoroughly with water and methanol (MeOH) and dried in vacuo. The crude product was purified by silica-gel column chromatography using CHCl3/EtOAc (20:1, v/v) as the eluent, to give 265.3mg (73% yield) of (R,R)-1-BNP as a dark red solid.
N,N'-bis((1R)-2-naphthyleth-1-yl)perylene-3,4,9,10-tetracarboxylic diimide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
63%
With zinc(II) acetate dihydrate; In quinoline;Inert atmosphere;
General procedure: 3,4,9,10-Perylenetetracarboxylic dianhydride (207.0mg, 0.53mmol), (R)-1-(2-naphthyl)ethylamine (181.5mg, 1.1mmol), and zinc acetate dihydrate (127.2mg, 0.58mmol) were mixed in quinoline (20mL) and were heated with stirring at 180C under nitrogen for 4h. After cooling to room temperature, the reaction mixture was treated with 2N HCl and stirred overnight at room temperature. The resulting dark red precipitate was collected by filtration, washed thoroughly with water and methanol (MeOH) and dried in vacuo. The crude product was purified by silica-gel column chromatography using CHCl3/EtOAc (20:1, v/v) as the eluent, to give 228.9 mg (63% yield) of (R,R)-2-BNP as a dark red solid. 1H NMR (500MHz, CDCl3): delta 2.14 (d, J=7.5Hz, 6H), 6.72 (q, J=7.0Hz, 2H), 7.41-7.46 (m, 4H), 7.65 (dd, J=2.0Hz, J=8.5Hz, 2H), 7.79 (dd, J=3.5Hz, J=6.0Hz, 2H), 7.80 (d, J=8.5Hz, 2H), 7.85 (dd, J=2.3Hz, J=6.8Hz, 2H), 8.03 (s, 2H), 8.46 (d, J=8.0Hz, 4H), 8.58 (d, J=8.0Hz, 4H). 13C NMR (125MHz, CDCl3): delta 16.37, 50.67, 123.00, 123.58, 125.60, 125.81, 126.02, 126.24, 126.28, 127.56, 127.77, 128.12, 129.41, 131.49, 132.62, 133.26, 134.44, 137.99, 163.38. MS (MALDI-TOF) m/z: 225.4 (M- + 1).
With dmap; N-ethyl-N,N-diisopropylamine; In chloroform; at 80℃; for 8.33h;Inert atmosphere;
Step 1. In a (200mL) round-bottomed flask, add methanetetraanhydride (3.92g, 0.01mol). Under nitrogen protection, add 100ml of chloroform, heat to 80 C, stir to dissolve; then add 0.2g of N. N-diisopropylethylamine (DIPEA) and 0.15g of 4-dimethylaminopyridine (DMAP), and 10 mL of chloroform dissolved in aza-15-crown ether-5 (4.38g, 0.02mol) was added dropwise. After about 20 minutes, the reaction was maintained for 8 hours after the dropwise addition was completed. After the reaction was completed, the solvent was distilled off under reduced pressure, 0.1 mol / L hydrochloric acid was added to adjust the pH to 5; petroleum ether was added for three extractions; and a "competitive" fluoride ion Fluorescent probe precursor compound, yield: 76%; FIG. 5 shows a synthetic roadmap of a competitive fluoride ion fluorescent probe precursor compound in this example;
With 1H-imidazole at 120℃; for 6h; Inert atmosphere;
2.2 Synthesis of N,N'-dialanine-3,4,9,10-perylene tetracarboxylic acid diethylamide (AP)
0.3912 g (1 mmol) of perylene-3,4,9,10-tetracarboxylic dianhydride, 0.178 g (2 mmol) alanine and 2.0 g of imidazole were heated at 120 oC for 6 h under nitrogen atmosphere. Then 100 mL of ethanol was poured into the hot mixture, refluxed for 6 h, and kept for overnight to precipitate out. Followed it was acidified with dilute HCl. The resulting light yellow precipitate was concentrated by decompression filters, then washed with deionized water to neutral, filtrated and dried at 80 oC under vacuum oven to get 0.481 g orange-red powder (Yield: 90%). IR (KBr, cm-1): 1255.4, 1401.6, 1590.2 cm-1, 1365.5, 1436.5, 1655.3, 1696.7,1742.3, 2940.5, 3443.3; 1H NMR (DMSO-d6, 400MHz, ppm): 8.01-8.03 (d, 8H), 5.52-5.56 (m, 2H), 1.66-1.68 (d, 6H); MALDI-TOF-MS: calcd for C30H18N2O8, 534.0
With 1H-imidazole at 120℃; for 6h; Inert atmosphere;
2.4 Synthesis of N,N'-dileucine-3,4,9,10-perylene tetracarboxylic acid diethylamide (LP)
0.3912 g (1 mmol) of perylene-3,4,9,10-tetracarboxylic dianhydride, 0.262 g (2 mmol) leucine and 2.0 g of imidazole were heated at 120 oC for 6 hrs under nitrogen atmosphere. The following experiment processing steps were similar to the above. The resulting get 0.593 g dark red powder (Yield: 96%). IR (KBr, cm-1): 1251.1, 1399.8, 1509.3, 1357.9, 1435.3, 1699.0, 1754.5, 2958.9, 3192.3; 1H NMR (DMSO-d6, 400 MHz, ppm): 8.60 (s, 4H), 8.39 (s, 4H), 5.58-5.61 (q, 2H), 3.40-3.46 (q, 2H), 2.06-2.14 (m, 4H), 1.63 (s, 2H), 0.93-1.06 (m, 12H); MALDI-TOF-MS: calcd. for C36H30N2O8, 617.9
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