1,7-dibromo-N,N'-dicyclohexyl-perylene-3,4,9,10-tetracarboxylic acid diimide synthesis

Yield:191997-95-2 77%

Reaction Conditions:

in 1-methyl-pyrrolidin-2-one at 85;

Steps:

1

Commercially available Perylene-3,4.9,10-tetracarboxylιc 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-SAθ.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 (77%).N.N'-Dicyclohexyl-I J-di^ct-i-ynyOperylene-S^ θ.IO-tetracarboxydiimide by Sonogashira reaction: N.N'-dicyclohexyl-I J-dibromperylene-S^ θ.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-SAθ.IO- tetracarboxydiimide was 15.7 g (60 %).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.θ-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 85-90⁰C. The yield of 5,1 i-dihexylcoronene^.S.δ.θ-tetracarboxyhc dianhyd?de was 4.2 g (83%).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-2,3^l8,9-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 (70%).

References:

WO2009/109782,2009,A2 Location in patent:Page/Page column 12-13