Synthesis
[Example 8]; [0397] In this embodiment, the method for the synthesis of 2-{N-(1-naphthalenyl)-N-[9-(1-naphthalenyl)carbazol-3-yl]amino}-9,10-diphenylanthracene (abbreviation: 2NCNPA) is specifically described by the anthracene derivative of the present invention represented by structural formula (220). ; [Step 1] Synthesis of N,N-diethylnaphthalenyl-H-carbazol-S-amine (abbreviation: NCN) (i) Synthesis of 9-(1-naphthalenyl)carbazole. the scheme for the synthesis of 9-(1-naphthalenyl)carbazole is illustrated in (C-18). 21 g (0.1 mol) of 1-bromonaphthalene, 17 g (0.1 mol) of carbazole, 950 mg (5 mmol) of copper (I) iodide, 33 g (240 mmol) of potassium carbonate, and 660 mg (2.5 mmol) of 18-crown-6-ether were added to a 500 mL three-necked flask with nitrogen displacement. To this mixture was added 80 mL of 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (abbreviation: DMPU), which was then stirred at 170 °C for 6 h under nitrogen protection. To this reaction mixture was added a further 10 g (50 mmol) of 1-bromonaphthalene, 2.0 g (10 mmol) of copper (I) iodide and 2.6 g (10 mmol) of 18-crown-6-ether and stirring was continued at 170 °C for 7.5 hours. Further 10 g (50 mmol) of 1-bromonaphthalene was added to this reaction mixture and stirring was continued at 180 °C for 6 hours. Upon completion of the reaction, about 200 mL of toluene and about 100 mL of 1 mol/L hydrochloric acid were added to this reaction mixture, and then the mixture was filtered through diatomaceous earth. The resulting filtrate was sequentially filtered through Florisil and diatomaceous earth. The organic and aqueous layers of the resulting filtrate were separated, and the organic layer was washed with 1 mol/L hydrochloric acid, then with water, and finally dried with magnesium sulfate. The suspension was filtered through Florisil and diatomaceous earth. The filtrate was concentrated to give an oil to which methanol was added and sonicated to precipitate solids. The precipitated solid was collected by filtration to give 22 g of 9-(1-naphthyl)carbazole as a white powder (75% yield).The Rf values (SiO2, eluent; hexane:ethyl acetate=10:1) for 9-(1-naphthyl)carbazole, 1-bromonaphthalene, and carbazole were 0.61, 0.74, and 0.24, respectively.
References
[1] Patent: WO2007/125934, 2007, A1. Location in patent: Page/Page column 168-169
[2] Patent: WO2009/72587, 2009, A1. Location in patent: Page/Page column 237-238
[3] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2006, vol. 63, # 1, p. 15 - 20
[4] Journal of Organic Chemistry, 2009, vol. 74, # 9, p. 3341 - 3349
