Hydrochloric Acid → Sodium 2-carboxy-benzo[b]thiophene-3-sulfonate

HRID 128255Notes

Reaction equation

HRID 128255 reaction equation
Cl[C:2]1[C:3]2[CH:13]=[CH:12][CH:11]=[CH:10][C:4]=2[S:5][C:6]=1[C:7](Cl)=[O:8].[OH-:14].[Na+:15].[S:16]([O-:19])([OH:18])=[O:17].[Na+].Cl>O.[Cu]Cl>[C:7]([C:6]1[S:5][C:4]2[CH:10]=[CH:11][CH:12]=[CH:13][C:3]=2[C:2]=1[S:16]([O-:19])(=[O:18])=[O:17])([OH:14])=[O:8].[Na+:15]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 14798Sodium Hydroxide2×HCID 5198983-Chlorobenzo(b)thiophene-2-carbonyl chlorideHCID 23665763Sodium Bisulfite

Product 1

HCID 23714405Sodium 2-carboxy-benzo[b]thiophene-3-sulfonateYield 48%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 962WaterSolvent

Procedure

74.0 gm (0.32 mol) of 3-chloro-benzo[b]thiophene-2-carboxylic acid chloride (m.p. 112°-113° C.) were stirred with a solution of 25.6 gm (0.64 mol) of sodium hydroxide in 250 cc of water for 12 hours while keeping the reaction temperature at 50° C. Thereafter 66.6 gm (0.64 mol) of solid sodium hydrogen sulfite were added to the neutral-reacting solution. The reaction mixture was made slightly alkaline by addition of a 40% sodium hydroxide solution and heated for 16 hours to 143° C. in an autoclave after addition of 3.0 gm (0.03 mol) of copper(I)-chloride. After cooling, the mixture was adjusted to pH 4 by adding hydrochloric acid, filtered and extracted once with 200 cc of ethyl acetate to remove the residual unreacted starting material. After further acidification to pH 1 and by addition of 60 gm of sodium chloride a colorless precipitate was obtained from the aqueous phase, which was suction-filtered off, washed with 30 cc of saturated aqueous sodium chloride solution and suction-filtered. The reaction product was dissolved in warm methanol and separated from the insoluble excess sodium chloride. The solvent was evaporated in vacuo, and the residue was dried by azeotropic distillation with 50 cc of toluene. 43 gm (48% of theory) of colorless crude sodium 2-carboxy-benzo[b]thiophene-3-sulfonate were obtained, which were further processed without further purification.

Workup

  1. customat 50° C
  2. temperatureheated for 16 hours to 143° C. in an autoclave
  3. temperatureAfter cooling
  4. filtrationfiltered
  5. extractionextracted once with 200 cc of ethyl acetate
  6. customto remove the residual
  7. additionAfter further acidification to pH 1 and by addition of 60 gm of sodium chloride a colorless precipitate
  8. customwas obtained from the aqueous phase, which
  9. filtrationwas suction-filtered off
  10. washwashed with 30 cc of saturated aqueous sodium chloride solution
  11. filtrationsuction-filtered
  12. dissolutionThe reaction product was dissolved in warm methanol
  13. customseparated from the insoluble excess sodium chloride
  14. customThe solvent was evaporated in vacuo
  15. dry with materialthe residue was dried by azeotropic distillation with 50 cc of toluene

Sources & evidence

ORD record
ord-5b869c65d948469488ee3910faaec793
Source dataset
uspto-grants-1981_03
Patent number
US04259336

Reaction notes

Loading…