Hydrochloric Acid → HCID 68487354, compound

HRID 1874994Notes

Reaction equation

HRID 1874994 reaction equation
[CH:1]([C:3]1[NH:7][C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[CH:5][C:4]=1[CH3:13])=[O:2].CC(CC)=C.[OH2:19].P([O-])(O)(O)=O.[Na+].Cl([O-])=O.[Na+].[ClH:30]>CC(O)(C)C.O>[Cl:30][C:5]1[C:4]([CH3:13])=[C:3]([C:1]([OH:19])=[O:2])[NH:7][C:6]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 112402-Methyl-1-buteneHCID 516949Sodium Phosphate, Monobasic, Monohydrate2×HCID 9855648Ethyl 5-formyl-4-methyl-1H-pyrrole-2-carboxylateHCID 23668197Sodium Chlorite2×

Product 1

HCID 68487354HCID 68487354, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6386tert-ButanolSolvent

Procedure

To a solution of ethyl 5-formyl-4-methyl-1H-pyrrole-2-carboxylate (0.40 g, 2.21 mmol) in t-BuOH (25 mL) was added 2-methylbutene as a 2M solution (38 mL, 76.0 mmol). In a separate flask sodium dihydrogen phosphate monohydrate (2.1 g, 15.2 mmol) and sodium chlorite (1.8 g, 19.9 mmol) were dissolved in water (25 mL). The aqueous solution was added to the alcoholic reaction mixture dropwise and stirred for 3 h. Additional sodium dihydrogen phosphate monohydrate (1.05 g, 7.73 mmol) and sodium chlorite (0.9 g, 9.95 mmol) dissolved in water (10 mL) were added and the reaction mixture stirred an additional 2 h. The solution was acidified with aqueous 5% HCl to a pH ˜4 and extracted with EtOAc (3×25 mL). The organic layers combined, dried over sodium sulfate, filtered and the solvent evaporated. Purification by column chromatography twice afforded 4-chloro-5-[(ethyloxy)carbonyl]-3-methyl-1H-pyrrole-2-carboxylic acid (0.10 g, 20%) as a white solid. 1H NMR (400 MHz, DMSO-d6): δ ppm 12.32 (br. s., 1H) 4.24 (q, 2H) 2.19 (s, 3H) 1.28 (t, 3H). MS: m/z 232.1 (M+1).

Workup

  1. additionThe aqueous solution was added to the alcoholic reaction mixture dropwise
  2. additionwere added
  3. stirringthe reaction mixture stirred an additional 2 h
  4. extractionextracted with EtOAc (3×25 mL)
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. customthe solvent evaporated
  8. customPurification by column chromatography twice afforded 4-chloro-5-[(ethyloxy)carbonyl]-3-methyl-1H-pyrrole-2-carboxylic acid (0.10 g, 20%) as a white solid

Sources & evidence

ORD record
ord-773658a162bf4c02bd0d9af39481fb75
Source dataset
uspto-grants-2012_11
Patent number
US08304419B2

Reaction notes

Loading…