Materiais moleculares funcionais contendo n-heterociclos - capes

LSYC146630 LSYC_036_007 Techset Composition Ltd, Salisbury, U.K. 1/20/2006[1,2,3]-Triazole Liquid Crystals 955sample was homogeneous, as confirmed by TLC performed on silica gel(Kieselgel 60 F 254-Merck) plates, which were visualized with UV light.Flash chromatography was performed with Merck silica gel 60 (230–400mesh).1 H NMR spectra were determined on a Varian Mercury Plus400-MHz instrument, with tetramethylsilane (TMS) as the internal standard.13 C NMR spectra were recorded on a Varian Mercury Plus 100-MHz spectrometer.Elemental analyses were within +0.4% of theoretical values andwere determined on a Perkin-Elmer 2400 instrument.1-Azido-4-decyloxy-benzene (2)4-N-decyloxyaniline 8.03 g (32.14 mmol) was dissolved in H 2 O (20 mL) andHCl conc. (20 mL). NaNO 2 (2.37 g, 34.33 mmol) dissolved in H 2 O (5 mL)was added dropwise to the mixture cooled at 0 8C. The mixture was stirredfor 10 min, then NaN 3 (2.09 g, 32.25 mmol) dissolved in H 2 O (5 mL) wasadded slowly, keeping the temperature under 2 8C. The resultant suspensionwas stirred for 20 more min, and then the phases were separated. Theaqueous phase was extracted with diethyl ether (3 50 mL). The combinedorganic phases were dried under Na 2 SO 4 and the solvents evaporated. Theresidue was purified by column chromatography (silica gel, hexane), furnishingthe product as yellow oil.Yield: 6.51 g (73%). IR (KBr): n max /cm 21 : 2926, 2855, 2111, 1503,1464, 1283, 1244, 825 cm 21 .General Procedure for Synthesis of Compounds 3a–eA mixture of respective terminal arylacetylene (0.677 mmol), CuI (6 mg,0.067 mmol), and triethylamine (9 mL, 0.067 mmol) in 20 mL of ethanol/water1:1 was stirred vigorously for 30 min. Then, 1-azido-4-decyloxy-benzene(2) (0.186 g, 0.677 mmol) dissolved in 5 mL of ethanol/water 1:1 was addeddropwise, and the resultant heterogenic mixture kept at 60 8C for 48 h. Aftercooling, the suspension was poured into water (30 mL). The solid wasfiltered, washed with water, and purified by recrystallization from heptane toafford a white powder.Phenyl 4-[1-(4-Decyloxyphenyl)-1H-[1,2,3]-triazol-4-yl]-4-decyloxybenzoate (3a)Yield: 0.247 g (56%). IR (KBr): 3100, 2953, 2919, 2849, 1733, 1607, 1522,1494, 1288, 1256, 1170, 1024, 815 cm 21 .1 H NMR (CDCl 3 ): d ¼ 0.88(t, J ¼ 6.4 Hz, 6 H), 1.28 (m, 24 H), 1.48 (m, 4 H), 1.82 (q, J ¼ 6.8 Hz, 4 H),4.03 (m, 4 H), 6.97 (d, J ¼ 8.4 Hz, 2 H), 7.03 (d, J ¼ 8.8 Hz, 2 H), 7.30(d, J ¼ 8.4 Hz, 2 H), 7.67 (d, J ¼ 8.8 Hz, 2 H), 7.95 (d, J ¼ 8.4 Hz, 2 H),