Stannous chloride dihydrate → Methyl 2-aminobenzene-1-sulfonate

A reaction vessel equipped with a stirrer, a thermometer, and a nitrogen inlet tube was charged with 688 g of 2-nitrobenzene sulfonic acid methyl ester, 4.7 L of acetic acid, and 2.18 kg of SnCl2.2H2O, and the resultant mixture was cooled to 10° C. or less. Hydrochloric acid gas was bubbled through the mixture for 4 hours under stirring. Then, the mixture was stirred for 10 hours at 10° C. or less. Subsequently, 8.4 L of chloroform was added into the reaction mixture, and then while maintaining the temperature at 10° C. or less, the mixture was neutralized with aqueous 20% NaOH. The mixture was separated by further adding 56 L of water. The aqueous phase was extracted with 4 L of chloroform, and then the mixture including the chloroform layer was washed twice with 4 L of water, and separated. The mixture was dried by anhydrous magnesium sulfate, and then filtered to obtain 2-aminobenzene sulfonic acid methyl ester in chloroform solution. The obtained solution was charged along with 950 g of diethylaniline into a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen inlet tube, and then 287 g of acrylic acid chloride was dropped for 15 minutes at a temperature of 5° C. or less. The mixture was stirred for 6 hours while maintaining the temperature at 5° C. or less. Then, 800 ml of concentrated hydrochloric acid and 12.8 L of water were added into the reaction mixture to separate the mixture. The organic layer was washed with, in order, 6.4 L of 2% hydrochloric acid, 6.4 L of water, 6.4 L of aqueous 3% sodium hydrogen carbonate, and 6.4 L of water. The product was dried by anhydrous magnesium sulfate, then filtered, and dried under reduced pressure at 30° C. to obtain 796 g of crystals. These were purified by column chromatography (5 kg silica gel, mobile phase hexane:ethyl acetate=2/1), to obtain 406 g of the monomer 4B represented by Formula (4B).

1. customA reaction vessel equipped with a stirrer
2. customHydrochloric acid gas was bubbled through the mixture for 4 hours
3. stirringThen, the mixture was stirred for 10 hours at 10° C. or less
4. additionSubsequently, 8.4 L of chloroform was added into the reaction mixture
5. temperaturewhile maintaining the temperature at 10° C. or less
6. customThe mixture was separated
7. additionby further adding 56 L of water
8. extractionThe aqueous phase was extracted with 4 L of chloroform
9. washwas washed twice with 4 L of water
10. customseparated
11. dry with materialThe mixture was dried by anhydrous magnesium sulfate
12. filtrationfiltered

ORD record

ord-87809c0bfe374116b6a8f30e6b6c1af4

Source dataset

uspto-grants-2014_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08828633B2