2-Methyl-2-butene → 3-Methyl-5-phenylthiophene-2-carboxylic acid

HRID 1157146Notes

Reaction equation

HRID 1157146 reaction equation
[CH3:1][C:2]1[CH:6]=[C:5]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)[S:4][C:3]=1[CH:13]=[O:14].CC(=CC)C.[O-:20]Cl=O.[Na+]>CN(C)C=O.O>[CH3:1][C:2]1[CH:6]=[C:5]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)[S:4][C:3]=1[C:13]([OH:20])=[O:14]

Participants

6

Reactant 3

HCID 105532-Methyl-2-buteneHCID 19430383HCID 19430383, compoundHCID 23668197Sodium Chlorite

Product 1

HCID 141138883-Methyl-5-phenylthiophene-2-carboxylic acidYield 69%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a stirred solution of 3-methyl-5-phenyl-thiophene-2-carbaldehyde (0.200 g, 0.99 mmol) and 2-methyl-2-butene (2.77 g, 0.040 mol) in dimethylformamide (4 ml) at 0° C. was added NaClO2 (0.894 g, 9.89 mmol) and NaH2PO4 (1.09 g, 7.91 mmol) in water (5 ml). The solution was allowed to warm to room temperature and stirred for 18 hours. The solvent was removed at reduced pressure and the residue partitioned between dichloromethane (10 ml) and 1N HCl solution (10 ml). The organic was separated, the aqueous layer extracted with dichloromethane (2×5 ml). The combined organic layers were dried (MgSO4) and the solvent removed at reduced pressure to give a yellow oil. Purification by flash column chromatography 50% ethyl acetate/petrol 40-60° C.) gave the sub-title compound as a white solid (0.14 g, 69% yield): 1H NMR (400 MHz, CDCl3) δH 2.65 (3H, s), 7.25 (1H, s) 7.35-7.80 (5H, s).

Workup

  1. customThe solvent was removed at reduced pressure
  2. customthe residue partitioned between dichloromethane (10 ml) and 1N HCl solution (10 ml)
  3. customThe organic was separated
  4. extractionthe aqueous layer extracted with dichloromethane (2×5 ml)
  5. dry with materialThe combined organic layers were dried (MgSO4)
  6. customthe solvent removed at reduced pressure
  7. customto give a yellow oil
  8. customPurification by flash column chromatography 50% ethyl acetate/petrol 40-60° C.)

Sources & evidence

ORD record
ord-1a3a6e943bec46d8bcaee6caabedb814
Source dataset
uspto-grants-2010_10
Patent number
US07807659B2

Reaction notes

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