Acetic Acid → 4-(5-Bromo-4-methylthiazol-2-yl)-3-methylbenzoic acid

HRID 531257Notes

Reaction equation

HRID 531257 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][C:10]=1[C:11]1[S:12][CH:13]=[C:14]([CH3:16])[N:15]=1)[C:5]([OH:7])=[O:6].C(O)(=O)C.[Br:21]Br.S(=O)(O)[O-].[Na+]>>[Br:21][C:13]1[S:12][C:11]([C:10]2[CH:9]=[CH:8][C:4]([C:5]([OH:7])=[O:6])=[CH:3][C:2]=2[CH3:1])=[N:15][C:14]=1[CH3:16]

Participants

5

Reactant 4

HCID 176Acetic AcidHCID 24408BromineHCID 23665763Sodium BisulfiteHCID 900091523-Methyl-4-(4-methyl-1,3-thiazol-2-yl)benzoic acid

Product 1

HCID 900090944-(5-Bromo-4-methylthiazol-2-yl)-3-methylbenzoic acidYield 87%

Procedure

3-Methyl-4-(4-methylthiazol-2-yl)benzoic acid (all recovered product from step A above) was dissolved in acetic acid (20 mL, 349 mmol), and bromine (1.774 mL, 34.4 mmol) was added. After sonicating for 5 minutes, LCMS showed complete conversion. Excess sodium bisulfite was added to the reaction solution until the red color disappeared. The suspension was filtered, and the filtrate was concentrated. The crude was purified on a silica gel column, eluting with 30% ethyl acetate, to give title compound as a white solid (6.2 g, 87% yield). LCMS (M+H)+: 313.9. 1H NMR (DMSO, 500 MHz): δ 7.90 (s, 1H), 7.85 (s, 2H), 2.56 (s, 3H), 2.40 (s, 3H).

Workup

  1. customAfter sonicating for 5 minutes
  2. filtrationThe suspension was filtered
  3. concentrationthe filtrate was concentrated
  4. customThe crude was purified on a silica gel column
  5. washeluting with 30% ethyl acetate

Sources & evidence

ORD record
ord-74836c9ba9a54d228f62881698670c11
Source dataset
uspto-grants-2016_05
Patent number
US09353101B2

Reaction notes

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