Triphenylphosphine → ethyl 1-[(2-bromo-5-methyl-1,3-thiazol-4-yl)methyl]-1H-pyrazole-4-carboxylate

HRID 1257386Notes

Reaction equation

HRID 1257386 reaction equation
[Br:1][C:2]1[S:3][C:4]([CH3:9])=[C:5]([CH2:7]O)[N:6]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[NH:29]1[CH:33]=[C:32]([C:34]([O:36][CH2:37][CH3:38])=[O:35])[CH:31]=[N:30]1.N(C(OC(C)C)=O)=NC(OC(C)C)=O.[Cl-].[NH4+]>O1CCCC1>[Br:1][C:2]1[S:3][C:4]([CH3:9])=[C:5]([CH2:7][N:29]2[CH:33]=[C:32]([C:34]([O:36][CH2:37][CH3:38])=[O:35])[CH:31]=[N:30]2)[N:6]=1

Participants

7

Reactant 5

HCID 11776TriphenylphosphineHCID 25517Ammonium ChlorideHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 142179ethyl 1H-pyrazole-4-carboxylateHCID 58127549(2-Bromo-5-methylthiazol-4-yl)methanol

Product 1

HCID 58127672ethyl 1-[(2-bromo-5-methyl-1,3-thiazol-4-yl)methyl]-1H-pyrazole-4-carboxylateYield 101.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Under a nitrogen atmosphere at 0° C., to a solution (10 mL) of the compound (590 mg, 2.8 mmol) obtained in Example 80d, triphenylphosphine (970 mg, 3.7 mmol) and ethyl 1H-pyrazole-4-carboxylate (480 mg, 3.4 mmol) in tetrahydrofuran was added diisopropyl azodicarboxylate (1.9 M toluene solution, 1.9 mL, 3.7 mmol), and the mixture was stirred at the same temperature for 2 hr. Saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure. The resulting crude title compound was purified by column chromatography (hexane-hexane/ethyl acetate=70/30) to give the title compound (940 mg, 100%) as a yellow oil.

Workup

  1. extractionthe mixture was extracted with ethyl acetate
  2. washThe obtained organic layer was washed with saturated brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. customThe solvent was evaporated under reduced pressure
  5. customThe resulting crude title compound was purified by column chromatography (hexane-hexane/ethyl acetate=70/30)

Sources & evidence

ORD record
ord-604857214f6c46e6a9e69bdb3ada76d6
Source dataset
uspto-grants-2013_06
Patent number
US08461348B2

Reaction notes

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