tert-Butanol → HCID 66847104, compound

HRID 529749Notes

Reaction equation

HRID 529749 reaction equation
[Br:1][C:2]1[S:3][C:4](C(O)=O)=[C:5]([C:7]2[CH:12]=[C:11]([Cl:13])[CH:10]=[CH:9][C:8]=2[O:14][CH3:15])[N:6]=1.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:26])C=CC=CC=1.C([N:38]([CH2:41]C)CC)C.[C:43]([OH:47])([CH3:46])([CH3:45])[CH3:44]>>[Br:1][C:2]1[S:3][C:4]([NH:38][C:41](=[O:26])[O:47][C:43]([CH3:46])([CH3:45])[CH3:44])=[C:5]([C:7]2[CH:12]=[C:11]([Cl:13])[CH:10]=[CH:9][C:8]=2[O:14][CH3:15])[N:6]=1

Participants

5

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 66847284HCID 66847284, compound

Product 1

HCID 66847104HCID 66847104, compoundYield 66%

Procedure

2-bromo-4-(5-chloro-2-methoxyphenyl)thiazole-5-carboxylic acid (1.22 g, 3.50 mmol), diphenylphosphoryl azide (963 mg, 3.50 mmol) and triethylamine (354 mg, 3.50 mmol) in tert-butanol (30 mL) were stirred at 85° C. for 4 hours. After cooling, the reaction was partitioned between ethyl acetate and water, the organics separated then washed with brine, and evaporated to dryness. The resulting residues were purified by flash chromatography on silica gel (50 to 100% dichloromethane in cyclohexane) to yield tert-butyl 2-bromo-4-(5-chloro-2-methoxyphenyl)thiazol-5-ylcarbamate (970 mg, 66%). LCMS (method 1) [M+H-tBu]+=364.8, RT=4.61 min. 1H NMR (400 MHz, DMSO-d6): δ (ppm) 7.43 (dd, 1H), 7.30 (d, 1H), 7.11 (d, 1H), 3.77 (s, 3H), 1.45 (s, 9H).

Workup

  1. temperatureAfter cooling
  2. customthe reaction was partitioned between ethyl acetate and water
  3. customthe organics separated
  4. washthen washed with brine
  5. customevaporated to dryness
  6. customThe resulting residues were purified by flash chromatography on silica gel (50 to 100% dichloromethane in cyclohexane)

Sources & evidence

ORD record
ord-542793afeb394ef6bab8f5ef38df6272
Source dataset
uspto-grants-2016_05
Patent number
US09346815B2

Reaction notes

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