反应详情

温度

70 °C

A solution of 3.60 g (34.0 mmol) of Na2CO3 in a mixture of 150 ml of water and 45 ml of methanol was purged with argon for 30 min. The obtained solution was added to a mixture of 5.00 g (14.0 mmol) of N-(2-methylphenyl)-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-tetrahydronaphthalen-1-amine, 4.85 g (14.0 mmol) of N-[(6-bromopyridin-2-yl)methyl]-2,6-diisopropylaniline, 0.80 g (0.70 mmol) of Pd(PPh3)4, and 180 ml of toluene in argon atmosphere. This mixture was stirred for 12 h at 70° C. and then cooled to room temperature. The organic layer was separated; the aqueous layer was extracted with 3×50 ml of ethyl acetate. The combined organic extract was washed with brine, dried over Na2SO4, and evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate-triethylamine=100:10:1, vol.). Yield 2.50 g (36%) of a yellow oil. Anal. Calc. for C35H41N3: C, 83.45; H, 8.20; N, 8.34. Found: C, 83.69; H, 8.08; N, 8.13. 1H NMR (CDCl3): δ 7.62-7.63 (m, 1H, 7-H in tetrahydronaphtalene); 7.55-7.58 (m, 1H, 4-H in Py); 7.52-7.54 (m, 1H, 3-H in Py); 7.41-7.44 (m, 1H, 6-H in tetrahydronaphtalene); 7.37-7.39 (m, 1H, 5-H in Py); 7.15-7.16 (m, 1H, 5-H in tetrahydronaphtalene); 7.03-7.10 (m, 4H, 3,4,5-H in 2,6-diisopropylphenyl and 5-H in 2-methylphenyl); 6.93 (m, 1H, 3-H in 2-methylphenyl); 6.70 (m, 1H, 6-H in 2-methylphenyl); 6.59 (m, 1H, 4-H in 2-methylphenyl); 5.35 (m, 1H, 1-H in tetrahydronaphtalene); 3.94-4.03 (m, 2H, CH2); 3.92-3.94 (m, 1H, 4- or 4′-H in tetrahydronaphtalene); 3.68-3.70 (m, 1H, 4′- or 4-H in tetrahydronaphtalene); 3.30 (sept, J=6.8 Hz, 2H, CH in 2,6-diisopropylphenyl); 3.16-3.24 (m, 1H, 3- or 3′-H in tetrahydronaphtalene); 2.92-3.00 (m, 1H, 3′- or 3-H in tetrahydronaphtalene); 2.38-2.47 (m, 1H, 2- or 2′-H in tetrahydronaphtalene); 2.14-2.22 (m, 1H, 2′- or 2-H in tetrahydronaphtalene); 1.75 (s, 3H, CH3 in 2-methylphenyl); 1.18-1.22 (m, 12H, CH3 in 2,6-diisopropylphenyl).

1. customwas purged with argon for 30 min
2. temperaturecooled to room temperature
3. customThe organic layer was separated
4. extractionthe aqueous layer was extracted with 3×50 ml of ethyl acetate
5. extractionThe combined organic extract
6. washwas washed with brine
7. dry with materialdried over Na2SO4
8. customevaporated to dryness
9. customThe residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate-triethylamine=100:10:1, vol.)