Methyl 4-(chlorocarbonyl)benzoate

slight yellow to white solid

This example demonstrates the preparation of 4-chlorocarbonyl- benzoic acid methyl ester having the following structure. In a 4 L kettle with mechanical stirrer, reflux condenser, addition funnel, thermometer, water bath and hot plate, 438 g dimethyl terephthalate (DMT) and 2700 mL toluene were added. The kettle was heated to about 65 00 to dissolve all the DMT. After dissolution, a potassium hydroxide solution (144.54 g in 700 mL methanol) was added dropwise over 45 minutes. The reaction was stirred at 65 00 for three hours and then the reaction cooled to room temperature overnight. The solid was collected after filtration and washed with 3750 mL toluene at 80 00. The product was filtered again and dried in the oven at 110 00. The yield was 465.9 g(95.3percent).In a 2 Lthree neck round bottom flask with mechanical stirrer, addition funnel, water bath, thermometer, nitrogen sweep, and hot plate, 130.31 g of the product made in previous step and 1000 mL toluene were added. Then 48 mL of thionyl chloride was added dropwise. After the completion of addition, the mixture was heated to 67 00 for three hours. The reaction cooled to room temperature and was stirred overnight. The contents were filtered to collect the filtrate. The excess solvent was removed by vacuum and 86.52 g of product was obtained (73percent yield).This example demonstrates the preparation of 4-chlorocarbonyl-benzoic acid methyl ester having the following structure (0147) (0148) In a 4 L kettle with mechanical stirrer, reflux condenser, addition funnel, thermometer, water bath and hot plate, 438 g dimethyl terephthalate (DMT) and 2700 mL toluene were added. The kettle was heated to about 65° C. to dissolve all the DMT. After dissolution, a potassium hydroxide solution (144.54 g in 700 mL methanol) was added dropwise over 45 minutes. The reaction was stirred at 65° C. for three hours and then the reaction cooled to room temperature overnight. The solid was collected after filtration and washed with 3750 mL toluene at 80° C. The product was filtered again and dried in the oven at 110° C. The yield was 465.9 g (95.3percent). (0149) In a 2 L three neck round bottom flask with mechanical stirrer, addition funnel, water bath, thermometer, nitrogen sweep, and hot plate, 130.31 g of the product made in previous step and 1000 mL toluene were added. Then 48 mL of thionyl chloride was added dropwise. After the completion of addition, the mixture was heated to 67° C. for three hours. The reaction cooled to room temperature and was stirred overnight. The contents were filtered to collect the filtrate. The excess solvent was removed by vacuum and 86.52 g of product was obtained (73percent yield).4-Chlorocarbonyl-benzoic acid methyl ester (2).; To a mixture of Terephtalic acid monomethyl ester, compound 1 (lo.oog, 0.056 mol) and SOClReaction conditions to obtain compound 49 (4-Chlorocarbonyl-benzoic acid methyl ester): Terephthalic acid monomethyl ester (0.25 g, 1.4 mmol) was dissolved in thionyl chloride (5 ml) and refluxed for 1 hour. Excess thionyl chloride was removed in vacuo to give an off-white solid. The solid was dissolved in anhydrous benzene (7 ml), and the solvent was evaporated. The procedure was repeated 3 times, and the solid was dried at high temperatures to remove residual solvent. 273 mg was obtained at 93percent yield.[Example 1] 75percent methyl-4-formylbenzoate (methyl-4-formylbenzoate 16. 4g) was melted at 60°C, and 1.5 molar equivalent of chlorine gas (C12) was added thereto while bubbling for 10 hours to obtain methyl-4-chloroformylbenzoate with the yield of 90percent. 19.8g of methyl-4-chloroformylbenzoate dissolved in 80g of toluene at 60°C was dropwisely added into 10percent aqueous ammonia for 2 hours, which includes 10 molar equivalent of ammonia with respect to methyl-4- chloroformylbenzoate. In this reaction, the reaction temperature was maintained at 5 to 20°C. Then, cooling of the reactant was stopped to increase the temperature of the reactant to room temperature. The reactant was filtered to obtain white crystalline methyl-4-carbamoylbenzoate with the yield of 98percent and the purity of 95percent. 1N aqueous sodium hydroxide solution including 5 molar equivalent of sodium hydroxide with respect to methyl-4-carbamoylbenzoate is cooled to 0°C, and 17. 9g of methyl-4-carbamoylbenzoate was added thereto. While maintaining the temperature of the reactant at 0 to 10°C, 10percent aqueous NaOCI solution including 1.05 molar equivalent of NaOCI was added into the reactant for 30 minutes, and the reaction was continued for 2 hours. Then, the temperature of the reactant was increased to 50°C, and maintained for 1 hour. By adding aqueous NaOH, the pH of the reactant was adjusted to 4, and solid target compound was precipitated. By filtering the reactant, the target compound, p- aminobenzoic acid was obtained with the yield of 95percent.

Molecular Weight:198.60
XLogP3:2.9
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:3
Exact Mass:198.0083718
Monoisotopic Mass:198.0083718
Topological Polar Surface Area:43.4
Heavy Atom Count:13
Complexity:207
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes