2-氯-1,3-苯二酚

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Treatment of tetrachlorophthalic anhydride (5 g, 17.49 mmol) and 2-chlororesorcinol (7.58 g, 41.98 mmol) according to the procedure described in Example 1, Step 1, provided 9.3 g of the crude product. Suspension of 8 g of the crude 9.3 g in DMF:water (1:1), followed by filtration provided 8.65 g (16.05 mmol, 91.7% AUC yield) of 4,4′,5,5′,6,7-hexachloro-3′,6′-dihydroxy-3H-spiro[isobenzofuran-1,9′-xanthen]-3-one that was isolated as an orange solid. 1H NMR (300 MHz; DMSO d6) δ 11.09 (S, 2H), 7.03 (d, J=9 Hz, 2H), 6.81 (d, J=8.7 Hz, 2H). provided 9.3 g of the crude product followed by filtration

反应条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To an aqueous solution (100 mL) of potassium hydroxide (11.0 g) was added 2-chlorobenzene-1,3-diol (22.8 g). Then, dimethyl sulfate (19.9 g) was slowly added to the reaction mixture while keeping the reaction mixture at 10° C. to 20° C., and the mixture was stirred at 100° C. for 2 days. The reaction mixture was acidified with 2N hydrochloric acid, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/petroleum ether) to give the title compound (18.0 g). at 10° C. to 20° C. the mixture was extracted with dichloromethane The organic layer was dried over anhydrous sodium sulfate the solvent was evaporated under reduced pressure The residue was purified by silica gel column chromatography (ethyl acetate/petroleum ether)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To ethyl 4-chloro-3-oxobutanoate (4.91 mL) was added sulfuric acid (12.91 mL) at 0° C., then was added 2-chlorobenzene-1,3-diol (5.0 g) in several portions at 0° C. The mixture was warmed to room temperature and stirred at the same temperature for 2 h. The reaction mixture was poured into water under stirring at 0° C. The precipitate was collected by m filtration and washed with hexane to give the title compound (2.78 g). under stirring at 0° C The precipitate was collected by m filtration washed with hexane

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Treatment of tetrachlorophthalic anhydride (5 g, 17.49 mmol) and 2-chlororesorcinol (7.58 g, 41.98 mmol) according to the procedure described in Example 1, Step 1, provided 9.3 g of the crude product. Suspension of 8 g of the crude 9.3 g in DMF:water (1:1), followed by filtration provided 8.65 g (16.05 mmol, 91.7% AUC yield) of 4,4′,5,5′,6,7-hexachloro-3′,6′-dihydroxy-3H-spiro[isobenzofuran-1,9′-xanthen]-3-one that was isolated as an orange solid. 1H NMR (300 MHz; DMSO d6) δ 11.09 (S, 2H), 7.03 (d, J=9 Hz, 2H), 6.81 (d, J=8.7 Hz, 2H). provided 9.3 g of the crude product followed by filtration

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Treatment of tetrachlorophthalic anhydride (5 g, 17.49 mmol) and 2-chlororesorcinol (7.58 g, 41.98 mmol) according to the procedure described in Example 1, Step 1, provided 9.3 g of the crude product. Suspension of 8 g of the crude 9.3 g in DMF:water (1:1), followed by filtration provided 8.65 g (16.05 mmol, 91.7% AUC yield) of 4,4′,5,5′,6,7-hexachloro-3′,6′-dihydroxy-3H-spiro[isobenzofuran-1,9′-xanthen]-3-one that was isolated as an orange solid. 1H NMR (300 MHz; DMSO d6) δ 11.09 (S, 2H), 7.03 (d, J=9 Hz, 2H), 6.81 (d, J=8.7 Hz, 2H). provided 9.3 g of the crude product followed by filtration

反应条件: temp:210.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of 2-chloro-4,6-di-tert-butylresorcinol (25.7 g, 100 mmol, prepared as described in Example 1A) and p-toluenesulfonic acid monohydrate (0.2 g, 1 mmol) is added to a flask--which is equipped with a gas withdrawing port leading to a dry ice cooled trap--heated at 210° C. for 2 hours, then allowed to cool. Recrystallization from toluene affords pure 2-chlororesorcinol (13.2-13.9 g, 91-96% yield). The yield of recovered isobutylene is >95%. is added to a flask which is equipped with a gas withdrawing port leading to a dry ice cooled trap to cool Recrystallization from toluene

反应条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Into a 500 mL flask containing 156 mL of 96% (w/w) sulfuric acid are added 52.5 g of resorcinol. Before the resorcinol completely dissolves, another 156 mL of 96% (w/w) sulfuric acid and another 52.5 g of resorcinol are added. The resulting exotherm causes the temperature of the mixture to increase to as much as 90° C. When this the temperature is reached, or when the temperature of the mixture no longer increases, the mixture is heated to 110° C. for two hours. Then, the mixture is cooled to 15° C., after which time 120 g of chlorine are added at such a rate to maintain a temperature of 15° C. The mixture is then poured into a 2 liter flask containing 450 g of ice and 400 mL of water. To the resulting aqueous phase is added aqueous sodium hydroxide (prepared by dissolving 76 g of sodium hydroxide into 150 mL of water) followed by a 24-hour reflux of the mixture. The temperature of the solution is reduced to room temperature, and after extraction by ethyl ether and ether evaporation, the residual mixture, which contains resorcinol and 2-chlororesorcinol, is subjected to flash column chromatography, using CH2Cl2 as eluent. This affords 29 g (21% yield) of the pure 2-chlororesorcinol (M.P. 97° C.). The resulting exotherm causes the temperature of the mixture to increase to as much as 90° C when the temperature of the mixture no longer increases Then, the mixture is cooled to 15° C. to maintain a temperature of 15° C The mixture is then poured into a 2 liter flask followed by a 24-hour reflux of the mixture is reduced to room temperature after extraction by ethyl ether and ether evaporation

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Treatment of tetrachlorophthalic anhydride (5 g, 17.49 mmol) and 2-chlororesorcinol (7.58 g, 41.98 mmol) according to the procedure described in Example 1, Step 1, provided 9.3 g of the crude product. Suspension of 8 g of the crude 9.3 g in DMF:water (1:1), followed by filtration provided 8.65 g (16.05 mmol, 91.7% AUC yield) of 4,4′,5,5′,6,7-hexachloro-3′,6′-dihydroxy-3H-spiro[isobenzofuran-1,9′-xanthen]-3-one that was isolated as an orange solid. 1H NMR (300 MHz; DMSO d6) δ 11.09 (S, 2H), 7.03 (d, J=9 Hz, 2H), 6.81 (d, J=8.7 Hz, 2H). provided 9.3 g of the crude product followed by filtration

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: This compounds was synthesised in the same manner as described above. Chlororesorcinol (0.87 g, 6 mmol), phenylacetic acid (0.82 g, 6 mmol), BF3Et2O (4 ml), PCl5 (1.9 g, 9.1 mmol), DMF (5 ml and 10 ml). The pink precipitate formed was filtered and re-crystallized from methanol to give 6-Chloro-7-hydroxy-3-phenyl-chromen-4-one as fine light pink crystals (1.4 g, 85%); Rf 0.6 ethyl acetate/hexane (75/25). This compounds was synthesised in the same manner The pink precipitate formed was filtered re-crystallized from methanol

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Treatment of tetrachlorophthalic anhydride (5 g, 17.49 mmol) and 2-chlororesorcinol (7.58 g, 41.98 mmol) according to the procedure described in Example 1, Step 1, provided 9.3 g of the crude product. Suspension of 8 g of the crude 9.3 g in DMF:water (1:1), followed by filtration provided 8.65 g (16.05 mmol, 91.7% AUC yield) of 4,4′,5,5′,6,7-hexachloro-3′,6′-dihydroxy-3H-spiro[isobenzofuran-1,9′-xanthen]-3-one that was isolated as an orange solid. 1H NMR (300 MHz; DMSO d6) δ 11.09 (S, 2H), 7.03 (d, J=9 Hz, 2H), 6.81 (d, J=8.7 Hz, 2H). provided 9.3 g of the crude product followed by filtration

反应条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To an aqueous solution (100 mL) of potassium hydroxide (11.0 g) was added 2-chlorobenzene-1,3-diol (22.8 g). Then, dimethyl sulfate (19.9 g) was slowly added to the reaction mixture while keeping the reaction mixture at 10° C. to 20° C., and the mixture was stirred at 100° C. for 2 days. The reaction mixture was acidified with 2N hydrochloric acid, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/petroleum ether) to give the title compound (18.0 g). at 10° C. to 20° C. the mixture was extracted with dichloromethane The organic layer was dried over anhydrous sodium sulfate the solvent was evaporated under reduced pressure The residue was purified by silica gel column chromatography (ethyl acetate/petroleum ether)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To ethyl 4-chloro-3-oxobutanoate (4.91 mL) was added sulfuric acid (12.91 mL) at 0° C., then was added 2-chlorobenzene-1,3-diol (5.0 g) in several portions at 0° C. The mixture was warmed to room temperature and stirred at the same temperature for 2 h. The reaction mixture was poured into water under stirring at 0° C. The precipitate was collected by m filtration and washed with hexane to give the title compound (2.78 g). under stirring at 0° C The precipitate was collected by m filtration washed with hexane