Hydrochloric Acid → 4-Hydroxy-1,1-dioxo-N-phenyl-1,2-dihydro-1-benzothiopyran-3-carboxamide

HRID 597263Notes

Reaction equation

HRID 597263 reaction equation
[C:1](Cl)(Cl)=[O:2].N1([C:10]2[C:15]3[CH:16]=[CH:17][CH:18]=[CH:19][C:14]=3[S:13](=[O:21])(=[O:20])[CH2:12][CH:11]=2)CCCC1.[NH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.Cl.[OH2:30]>C1C=CC=CC=1.CO.O1CCCC1.C(N(CC)CC)C>[OH:30][C:10]1[C:15]2[CH:16]=[CH:17][CH:18]=[CH:19][C:14]=2[S:13](=[O:20])(=[O:21])[CH2:12][C:11]=1[C:1]([NH:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:2]

Participants

10

Reactant 5

HCID 313Hydrochloric AcidHCID 962WaterHCID 6115AnilineHCID 6371PhosgeneHCID 214134244-(Pyrrolidin-1-yl)-1-benzothiopyran-1,1(2H)-dione

Product 1

HCID 706325224-Hydroxy-1,1-dioxo-N-phenyl-1,2-dihydro-1-benzothiopyran-3-carboxamide

Reagents, catalysts & solvents 4

HCID 241BenzeneSolventHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent3×HCID 8471TriethylamineSolvent2×

Procedure

Preparation from the enamine-acid chloride. -- To 28.5 g. of a 12.5% solution of phosgene in benzene was added 30 ml. of tetrahydrofuran. The temperature of the solution was maintained at -10° to -15° and a solution of 7.5 g. (0.03 mole) of 4-(1-pyrrolidinyl)-2H-1-benzothiopyran 1,1-dioxide and 5 ml. (0.036 mole) of triethylamine in 125 ml. of tetrahydrofuran was added with stirring over a period of 20 minutes. After stirring at room temperature for 2 hr., a solution of 3.1 g. (0.033 mole) of aniline and 5 ml. of triethylamine in 25 ml. of tetrahydrofuran was added, the mixture was refluxed for 2 hr., and about a third of the solvent was distilled off. The remaining mixture was poured into ice-water and extracted with dichloromethane. The organic layer washed well with water, dried (MgSO4) and evaporated to give 12.3 g. of a dark syrup. This crude enamine-amide was dissolved in 100 ml. of methanol, treated successively with 10 ml. of water and 2 ml. of concentrated hydrochloric acid, and heated on a steam bath for 20 minutes. The mixture was cooled and filtered to yield 6 g. (64%) of product, m.p. 204°-208°.

Workup

  1. temperatureThe temperature of the solution was maintained at -10° to -15°
  2. stirringAfter stirring at room temperature for 2 hr
  3. temperaturethe mixture was refluxed for 2 hr
  4. distillation, and about a third of the solvent was distilled off
  5. additionThe remaining mixture was poured into ice-water
  6. extractionextracted with dichloromethane
  7. washThe organic layer washed well with water
  8. dry with materialdried (MgSO4)
  9. customevaporated
  10. customto give 12.3 g
  11. temperatureThe mixture was cooled
  12. filtrationfiltered
  13. customto yield 6 g

Sources & evidence

ORD record
ord-5a791761b09e43b499a93a75dc35b801
Source dataset
uspto-grants-1977_03
Patent number
US04013686

Reaction notes

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