Hydrochloric Acid → Psoromic Acid

HRID 1692624Notes

Reaction equation

HRID 1692624 reaction equation
C[O:2][C:3]([C:5]1[C:15]2[O:14][C:13]3[C:16]([CH:22]=[O:23])=[C:17]([OH:21])[CH:18]=[C:19]([CH3:20])[C:12]=3[C:11](=[O:24])[O:10][C:9]=2[C:8]([CH3:25])=[C:7]([O:26][CH3:27])[CH:6]=1)=[O:4].[I-].[Li+].Cl>CN(C)P(=O)(N(C)C)N(C)C>[CH3:20][C:19]1[C:12]2[C:11]([O:10][C:9]3[C:8]([CH3:25])=[C:7]([O:26][CH3:27])[CH:6]=[C:5]([C:3]([OH:4])=[O:2])[C:15]=3[O:14][C:13]=2[C:16]([CH:22]=[O:23])=[C:17]([OH:21])[CH:18]=1)=[O:24]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 66321Lithium iodide2×HCID 148259704-formyl-3-hydroxy-8-methoxy-1,9-dimethyl-11-oxo-11H-dibenzo[b,e][1,4]dioxepine-6-carboxylic acid methyl ester

Product 1

HCID 23725Psoromic Acid

Reagents, catalysts & solvents 1

HCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
90 °C

Procedure

4-Formyl-3-hydroxy-8-methoxy-1,9-dimethyl-11-oxo-11H-dibenzo[b,e][1,4]dioxepine-6-carboxylic acid methyl ester (42.0 mg) and lithium iodide (250 mg) were taken in hexamethylphosphoric triamide (5 ml). The mixture was stirred at 90° C. for 5 h and then lithium iodide (250 mg) was added again. The mixture was heated at 90° C. for 21 h. When the reaction was completed, the mixture was cooled and poured into hydrochloric acid cooled by an ice bath. The mixture was extracted with ethyl acetate. The organic extract was washed in turn with water, saturated aqueous sodium thiosulphate, and finally saturated brine, and was dried over anhydrous magnesium sulfate. The crude product was crystallized from dimethyl sulphoxide to afford psoromic acid, m.p. 264-265° C., 1HNMR (300 MHz, d6-DMSO): δ 2.20 (s, 3H), 2.46 (s, 3H), 3.83 (s, 3H), 6.83 (s, 1H), 7.08 (s, 1H), 10.46 (s, 1H).

Workup

  1. temperatureThe mixture was heated at 90° C. for 21 h
  2. temperaturethe mixture was cooled
  3. temperaturecooled by an ice bath
  4. extractionThe mixture was extracted with ethyl acetate
  5. extractionThe organic extract
  6. washwas washed in turn with water, saturated aqueous sodium thiosulphate, and finally saturated brine
  7. dry with materialwas dried over anhydrous magnesium sulfate
  8. customThe crude product was crystallized from dimethyl sulphoxide

Sources & evidence

ORD record
ord-1c45e4a62a41404595c2787af4902002
Source dataset
uspto-grants-2012_04
Patent number
US08158623B2

Reaction notes

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