2-Methyl-3-butyn-2-ol → HCID 67000911, compound

HRID 269081Notes

Reaction equation

HRID 269081 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5](Br)=[CH:4][N:3]=1.[CH3:9][C:10]([OH:14])([C:12]#[CH:13])[CH3:11].CCN(CC)CC>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:1][C:2]1[N:3]=[CH:4][C:5]([C:13]#[C:12][C:10]([CH3:11])([OH:14])[CH3:9])=[CH:6][CH:7]=1

Participants

7

Reactant 3

HCID 82582-Methyl-3-butyn-2-olHCID 8471TriethylamineHCID 706222-Amino-5-bromopyridine

Product 1

HCID 67000911HCID 67000911, compoundYield 94.6%

Reagents, catalysts & solvents 3

HCID 11776TriphenylphosphineCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of commercially available 2-amino-5-bromopyridine (25 g, 144 mmol), 2-methyl-3-butyn-2-ol (21.2 mL, 217 mmol), Et3N (30.2 mL, 217 mmol), PdCl2(PPh3)2 (507 mg, 0.5 mol %) and PPh3 (95 mg, 0.25 mol %) in DMF (140 mL) was purged for 10 min with argon. Then Cul (83 mg, 0.3 mol %) was added and the reaction mixture was heated up to 90° C., stirring was continued at 90° C. for 16 h. Cooled to 23° C., the reaction mixture was concentrated in vacuum to remove all volatiles left a dark brown residue which was purified by flash chromatography with n-heptane and ethyl acetate to give the title compound as a brown solid (24 g, 94%, contains residual DMF). MS (ISP) 177.2 [(M+H)+].

Workup

  1. customwas purged for 10 min with argon
  2. additionThen Cul (83 mg, 0.3 mol %) was added
  3. temperatureCooled to 23° C.
  4. concentrationthe reaction mixture was concentrated in vacuum
  5. customto remove all volatiles
  6. waitleft a dark brown residue which
  7. customwas purified by flash chromatography with n-heptane and ethyl acetate

Sources & evidence

ORD record
ord-0c6967b9ac9e40f488e46332c5d8c4ac
Source dataset
uspto-grants-2008_11
Patent number
US07446113B2

Reaction notes

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