3-(Chlorosulfonyl)benzoic acid

white to light beige crystalline powder

1.22 g (10 mmol) of benzoic acid were weighed into a 50 mL pear-shaped flask and then slowly added10 mL of chlorosulfonic acid was added and stirred at 100 & lt; 0 & gt; C for 45 min. After completion of the reaction, the reaction solution was added dropwise to ice brine, Then vacuum filtration, washing, vacuum drying, in a white solid, yield 88.7percent.Chlorosulfonation of benzoic acid derivatives. A mixture of 1 (5 g, 40.94 mmol) or 2 (5 g, 32.86mmol) in chlorosulfonic acid (20 mL) was heated to 65 °C in an oil bath for 4 h, after which time TLC indicated complete conversion of the starting material to the intermediates, 3-(chlorosulfonyl)benzoic acid (3) and 3-(chlorosulfonyl)-4- methoxybenzoic acid (4), respectively. The reaction mixture was slowly poured over ice and filtered. The solid was dried in vacuo to yield intermediates 3 (7.90 g, 87percent) and 4 (6.40 g, 86percent), which were carried forward without further purification.Benzoic acid (250 g, 2.05 mol) was placed in a 1-L round-bottom flask, and chlorosulfonic acid (1 L, 1760 g, 15.1 mol) was added. The mixture was heated with stirring at 120-125° C. for 2 h, allowed to cool to 40-50° C., and added dropwise to an excess of crushed ice. The precipitated product was collected by filtration and dissolved in 1 L of ethyl acetate; then the aqueous layer that formed was separated, and the organic layer was washed with 100 mL of water, dried over sodium sulfate, and concentrated by evaporation to near dryness. After trituration with 300 mL of hexane, the product was collected by filtration, washed on the filter with 200 mL of hexane, and dried in air to give 384.1 g (85percent) of 3-chlorosulfonylbenzoic acid, mp 134-135° C. (lit. mp 134-135° C.); 1H NMR (400 MHz, in CDCl3w/TMS, ppm) 11.43 (broad s, CO2H, 7.81 (t, J=8.0 Hz, H-5), 8.32 and 8.50 (2d, J=8.0 Hz, H4 and H-6), 8.79 (t, J=1.6 Hz, H-2); {1H}13C NMR (100 MHz, in CDCl3w/TMS, ppm) 170.00 (CO), 145.06 (C-3), 136.71 (C-6), 131.92 (C-4), 131.31 (C-1), 130.63 (C-5), 128.91 (C-2).20 mL of Chlorosulfonic acid (300.4 mmol, 7.34 eq) was added to 5.0 g of benzoic acid, S3, (40.9 mmol 1.0 eq) and the mixture was stirred at 120 - 125 °C. After 2 hours the mixture was added dropwise to 200 mL of ice. The resulting precipitate was collected, dissolved in 150 mL of ethyl acetate, washed with water (3 x 25 mL), driedover NaChlorosulfonic acid (2 mL, 300.4 mmol, ) was added to125, (500 mg, 40.9 mmol) and the mixture was stirred at 120 °C for 2 h.. After this time the mixture was added dropwise to a mxture of EtOAc (200 mL) and crushed ice. The resulting precipitate was collected, dissolved in ethyl acetate, washed with water (3 x 25 mL) and Brine, dried over Na2SO4, and the solvent was removed under reduced pressure. 1H-NMR (400 MHz, DMSO-d6): (5 = 8.80 (t, J = 1.4 Hz, 1H), 8.40 (m 1H), 8.19 (m, 1H), 7.69 (t, J = 7.5 Hz, 1H).ppm.Solid benzoic acid [(50] g, 0.41 mol) in portions was added to [CHLOROSULFONIC] acid (348.7 g, 200 mL, 3 mol) at room temperature. The reaction mixture was heated to [125-130 C] for 2 hr and was then poured into vigorously stirred crushed-ice (1000 g). After 30 min, the white solid was collected, washed with water [(1] L) and air dried to give 72.5 g (80percent) of the title compound. 1H NMR [(CDCL3] : d4-MeOH 4: 1, 60 MHz) 8 5.0 (s, 1H), 8.0-9. 1 (m, 4H).Benzoic acid (5 g, 40.9 mmol) was added in portions to chlorosulfonic acid (14.3 g, 122.9 mmol) under stirring at 5–10 C and then stirred at 110 C for 2 h. The reaction mixture was cooled to room temperature, poured on to crushed ice (∼100 g) under stirring during which solids precipitated. These solids were filtered, extracted with ethyl acetate (150 mL), dried over anhydrous NaThe benzoic acid 1 (12.20g, 10mmol) was added to chlorosulfonic acid (20mL, 30mmol) with stirring. The mixture was heated at 120°C for 4h. After cooling to rt, the mixture was poured into ice-water (100mL), the formed precipitate was collected by filtration and washed with ice-water. The separated solid was dissolved with ethyl acetate (50mL×3). The combined organic extracts were washed with saturated brine (50mL×2) and dried over anhydrous sodium sulfate overnight. After removal of the solvent, the residue was loaded onto a silica gel column and eluted with PE/EA (1:1, v/v) to afford compound 2 (11.93g) in 54percent yield as white solid. H NMR (400MHz, DMSO-d6) δ 12.27 (s, 1H), 8.20 (s, 1H), 7.89 (d, J=7.7Hz, 1H), 7.83 (d, J=7.7Hz, 1H), 7.47 (t, J=7.7Hz, 1H). 500g of benzoic acid, 763 g of chlorosulfonic acid was placed in a reactor with a micro-negative pressure alkali absorbing device.Turn on the stirring and add 7.5 g of fuming sulfuric acid.The closed reactor begins to heat up, The temperature was started at 90 ° C, and the GC gas spectrometer was followed. After 11 h, the amount of benzoic acid was ≤ 0.05percent, and the reaction was completed.Reduce the system temperature to 8 ° C, Start adding water while stirring.At first the temperature rose slightly, After the 45g water drop is added, The temperature does not change anymore, Then you can add 45g of water at a time.Stir for a while, let stand, layer, Approximately 862 g of the sulfonated liquid in the lower layer was transferred to another reactor.And adding 86g of anhydrous sodium sulfate and stirring for 1h, After filtration, 851 g of the obtained sulfonated solution was used.The upper aqueous layer is neutralized with alkali and poured into a wastewater tank.General procedure: A mixture of 1 (5g, 40.94mmol) or 2 (5g, 32.86mmol) in chlorosulfonic acid (20mL) was heated to 65°C in an oil bath for 4h, after which time TLC indicated complete conversion of the starting material to the intermediates, 3-(chlorosulfonyl)benzoic acid (3) and 3-(chlorosulfonyl)-4-methoxybenzoic acid (4), respectively. The reaction mixture was slowly poured over ice and filtered. The solid was dried in vacuo to yield intermediates 3 (7.90g, 87percent) and 4 (6.40g, 86percent), which were carried forward without further purification.

Molecular Weight:220.63
XLogP3:1.4
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:2
Exact Mass:219.9597075
Monoisotopic Mass:219.9597075
Topological Polar Surface Area:79.8
Heavy Atom Count:13
Complexity:292
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes