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With phenylsilane; potassium hydroxide; In tetrahydrofuran; for 4h;Schlenk technique; Inert atmosphere; Reflux;
General procedure: Isobenzofuran-1(3H)-one (0.4 mmol), KOH (0.4 mmol), PhSiH3 (1.2 mmol), dried THF (2 mL) were charged in a Schlenk tube(15 mL) under N2 atmosphere. The mixture was refluxed for 4 h. After cooling to rt, the reaction was quenched with EtOH(0.5-1 mL). Solvent was removed under reduced pressure and the crude residue was purified by column chromatography on silica gel with petroleum ether-ethyl acetate as the eluent to afford the desired product.
A 45.85 g sample of an oxidation mixture in acetic acid from the oxidation of 3- and 4-chloroxylene in the presence of a catalyst composition comprising cobalt and manganese was treated with 0.143 g. of oxalic acid dihydrate and brought to reflux for 30 minutes (this process removed about 90% of the cobalt and >50% of the manganese by precipitation as the oxalate salts). The solution was then passed through a glass frit under vacuum. The remainder of the solvent was removed by evaporation (down to 16.2 g.) and distillation (down to 14.0 g. residue). The remaining light yellow solid was combined with 60 ml. of water and 40 ml. of toluene, and mixed. There was some emulsion layer which was treated in a second wash with an additional 15 ml. each of water and toluene. The solvent was removed by evaporation of each fraction to leave 10.6 g. in the water fraction and 2.7 g. in the toluene fraction. The fractions were analyzed by GC. The analytical results are shown in Table 7.
11
[ 615-60-1 ]
[ 608-23-1 ]
[ 54109-03-4 ]
[ 52010-22-7 ]
[ 89-20-3 ]
[ 27563-65-1 ]
Yield
Reaction Conditions
Operation in experiment
With oxygen; In acetic acid; xylene; at 35 - 40℃;Purification / work up;
Other experiments were carried out on actual oxidation mixtures from reactions of 3- and 4-chloroxylene with oxygen in acetic acid in the presence of a catalyst. In some cases the catalyst components were removed by precipitation, for example with oxalic acid, but the low levels of metals present in those samples still containing catalyst components did not affect the solubility characteristics of the organic species. At least a portion of oxidation reaction mixture was distilled in vacuo to remove acetic acid, leaving a solid residue which was dissolved in water. The extraction of a 30 wt. percent aqueous solution of 3- and 4-chloroxylene oxidation mixture was carried out with xylene. Six extractions were made starting with 130 kilograms (kg.) of solution extracting the aqueous phase with 155 kg. of xylene. At the beginning the temperature was approximately 35 C., and later was raised to 40 C. to present the crystallization of chlorophthalic acid. The results of extraction are shown Table 5. Unless noted, the values in the table represent relative percentages in the composition of the designated components (total percentage equals 100percent).
With N-Bromosuccinimide; azobisisobutyronitrile; In tetrachloromethane; for 2h;Heating; Reflux;
(a) 3-bromo-<strong>[52010-22-7]4-chloroisobenzofuran-1(3H)-one</strong> (100) <strong>[52010-22-7]4-chloroisobenzofuran-1(3H)-one</strong> (10 g, 59.32 mmol), (E)-2,2'-(diazene-1,2-diyl)bis(2-methylpropanenitrile) (0.974 g, 5.93 mmol) and 1-bromopyrrolidine-2,5-dione (11.61 g, 65.25 mmol) were dissolved CCl4 (100 mL) and heated at reflux for 2 hours. The reaction was cooled and filtered, the filtrate was evaporated to the desired compound as a yellow gum (14.20 g, 97% yield); 1H NMR (400.132 MHz, CDCl3) delta 7.32 (1H, s), 7.61 (1H, t), 7.73 (1H, d), 7.88 (1H, d); m/z (LC-MS, ESI+), RT=2.28 (M+H not detected).
With N-Bromosuccinimide; In tetrachloromethane; hexane; toluene;
EXAMPLE 18 3-Bromo-<strong>[52010-22-7]4-chloro-1-isobenzofuranone</strong> (XIII: R1 =4-Cl) A stirring refluxing mixture consisting of <strong>[52010-22-7]4-chloro-1-isobenzofuranone</strong> (2.35 g, 0.014 mol, described in Example 17) and N-bromosuccinimide (2.6 g, 0.014 mol) in 80 ml of carbon tetrachloride is irradiated with a 500 W photospot lamp for 1.5 hr. The reaction is cooled and filtered. The filtrate is evaporated to give 3.95 g of semi-solid. Chromatography on silica gel using 40% hexane in toluene afforded 2.4 g of off-white solid title compound: mp 70-72 C.; and nmr (CDCl3) delta 2.3 (s, 1H) and 7.7 (m, 3H).
With diisobutylaluminium hydride; In dichloromethane; at -78℃; for 3h;
To a solution of <strong>[52010-22-7]4-chloroisobenzofuran-1(3H)-one</strong> (7 g, 41.5 mmol) in DCM (120 mL) was cooled to -78 C., was added diisobutylaluminum hydride (7.66 g, 53.9 mmol). The mixture was stirred at -78 C. for 3 h and water (2.2 mL) was added. The mixture was warmed to 0 C. and 15% NaOH (2.2 mL) and then H2O (5.4 mL) was added. The mixture was stirred at RT for 1 h and was filtered. The filtrate was dried over sodium sulfate and concentrated to provide 4-chloro-1,3-dihydroisobenzofuran-1-ol (5.00 g) as a yellow oil.
With hydrogenchloride; In tetrahydrofuran; 1,4-dioxane; at 20℃; for 2h;
To a solution of 3-chloro-2-formylbenzoic acid (24 g, 91.0 mmol) in methanol (250 mL) was added NaBH4 (5.14 g, 136 mmol). The reaction was stirred at ambient temperature for 2 h. The mixture was concentrated to dryness to provide 3-chloro-2-(hydroxymethyl)benzoic acid as a yellow oil. To the oil in THF (80 mL) was added hydrogen chloride in dioxane (6N, 20 mL). The mixture was stirred at ambient temperature for 2 h and then extracted with EtOAc (3*50 mL). The combined organic phase was dried over sodium sulfate, filtered and the filtrate was concentrated in vacuo. The residue was purified by flash chromatography (PE/EtOAc=5/1) to provide 4-chloroisobenzofuran-1(3H)-one (12 g) as a yellow solid. MS (ESI) m/z=169 [M+H]+.
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