Acetic Acid → Methyl 2-aminobenzene-1-sulfonate

HRID 571578Notes

Reaction equation

HRID 571578 reaction equation
[CH3:1][O:2][S:3]([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[N+:12]([O-])=O)(=[O:5])=[O:4].C(O)(=O)C.Cl.[OH-].[Na+]>O.C(Cl)(Cl)Cl>[CH3:1][O:2][S:3]([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[NH2:12])(=[O:4])=[O:5]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 169151Benzenesulfonic acid, 2-nitro-, methyl ester

Product 1

HCID 13225915Methyl 2-aminobenzene-1-sulfonate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6212ChloroformSolvent

Procedure

688 g of 2-nitrobenzenesulfonic acid methyl ester, 4.7 L of acetic acid, and 2.18 kg of SnCl.H2O are placed in a reaction container having a stirrer, a thermometer, and a nitrogen introducing pipe attached thereto, and cooled to a temperature of not more than 10° C. Hydrochloric acid gas is blown into the reaction mixture under stirring for 4 hours. Next, the reaction mixture is stirred at not more than 10° C. for 10 hours. 8.4 L of chloroform is added to the reaction mixture, and neutralized by a 20% NaOH aqueous solution while the temperature is kept at not more than 10° C. Further, 56 L of water is added, and the reaction mixture is separated. An aqueous phase is extracted by 4 L of chloroform, washed with a chloroform layer with 4 L of water twice, and separated. The separated product is dried by anhydrous magnesium sulfate, and filtered to obtain a chloroform solution of 2-aminobenzenesulfonic acid methyl ester. The obtained solution and 950 g of diethylaniline are placed in a reaction container having a stirrer, a thermometer, and a nitrogen introducing pipe attached thereto, and 287 g of acrylic acid chloride is dropped at a temperature of not more than 5° C. over 15 minutes. The temperature is kept at not more than 5° C., and the solution is stirred for 6 hours. 800 mL of concentrated hydrochloric acid and 12.8 L of water are added to the reaction mixture, and the reaction mixture is separated. An organic layer is washed with 6.4 L of 2% hydrochloric acid, 6.4 L of water, 6.4 L of a 3% sodium hydrogen carbonate aqueous solution, and 6.4 L of water in this order. The organic layer is dried with anhydrous magnesium sulfate, filtered, and dried under reduced pressure at 30° C. to obtain 796 g of crystals. The crystals are refined by column chromatography (5 kg of silica gel, mobile phase of hexane/ethyl acetate=2/1) to obtain 406 g of Monomer 6B represented by the formula (6B):

Workup

  1. temperaturecooled to a temperature of not more than 10° C
  2. stirringNext, the reaction mixture is stirred at not more than 10° C. for 10 hours
  3. customis kept at not more than 10° C
  4. customthe reaction mixture is separated
  5. extractionAn aqueous phase is extracted by 4 L of chloroform
  6. washwashed with a chloroform layer with 4 L of water twice
  7. customseparated
  8. dry with materialThe separated product is dried by anhydrous magnesium sulfate
  9. filtrationfiltered

Sources & evidence

ORD record
ord-11fd5ea7e4ea4ecab1d09a2b043c852e
Source dataset
uspto-grants-2015_05
Patent number
US09029056B2

Reaction notes

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