反应详情

This synthesis was adapted from Shoji Kajigaeshi, Takaaki Kakinami, Tsuyoshi Okamoto, Hiroko Nakamura, Masahiro Fujikawa, Bulletin of the Chemical Society of Japan, 1987, volume 60, pages 4187-4189. To a solution of resorcinol (5.00 grams, 45.4 millimoles, 1.0 equivalent), dissolved in 100 milliliters dichloromethane and 40 milliliters methanol, pyridinium tribromide (29.0 grams, 90.8 millimoles, 2.0 equivalent) was added in small portions over the course of 60-70 minutes. The reaction was stirred at room temperature overnight. The solvent was removed on the rotary evaporator, and the residue taken up in chloroform (1×50 milliliters) and reconcentrated. Addition of ethyl acetate resulted in precipitation of side product. The ethyl acetate phase was separated by decanting, and the precipitate was further washed several times (4×150 milliliters 1:1 ether/ethyl acetate, 1×150 milliliters ethyl acetate, solvent separated by decanting). The combined decanted solvents were concentrated, followed by purification via automated flash chromatography (methanol in chloroform, 0-15%). The product was obtained in the form of an off-white solid (10.9 grams, 40.7 millimoles, 90%). m.p.: 66.4° C.; 1H-NMR (400 MHz, CDCl3) δ 7.53 (s, 1H), 6.74 (s, 1H), 5.46 (s, 2H); 13C NMR (101 MHz, THF-d8) δ 155.60, 136.10, 105.13, 100.74, 67.57; FTIR: 569, 594, 659, 742, 837, 868, 993, 1053, 1138, 1193, 1282, 1326, 1440, 1462, 1494, 1577, 1598, 1711, 2918, 3089, 3379, 3451, 3504 cm−1; UV/Vis: 223, 236, 296 nm; ESI/MS/MS of m/z=267: 267 [M79Br/81Br-H]−, 188 [M81Br-HBr)]−, 186 [M79Br-HBr)]−, 160 [M81Br-HBr—CO)]−, 158 [M79Br-HBr—CO)]−, 81 [81Br]−, 79 [79Br]−; HRMS (ESI−): 374.95735 calc. for C6H3Br2O2− [M-H]−: 264.8505, found 264.8510.

1. customThe solvent was removed on the rotary evaporator
2. additionAddition of ethyl acetate
3. customresulted in precipitation of side product
4. customThe ethyl acetate phase was separated
5. customby decanting
6. customseveral times (4×150 milliliters 1:1 ether/ethyl acetate, 1×150 milliliters ethyl acetate, solvent separated by decanting)
7. customThe combined decanted solvents
8. concentrationwere concentrated
9. customfollowed by purification