Dimethylformamide → 5-[2-(Trimethylsilyl)ethynyl]-4-thiazolemethanol

HRID 1799761Notes

Reaction equation

HRID 1799761 reaction equation
Br[C:2]1[S:6][CH:5]=[N:4][C:3]=1[CH2:7][OH:8].C(N(CC)CC)C.[CH3:16][Si:17]([C:20]#[CH:21])([CH3:19])[CH3:18].CN(C=O)C>[Cu]I.[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O.C1(C)C=CC=CC=1>[CH3:16][Si:17]([CH3:19])([CH3:18])[C:20]#[C:21][C:2]1[S:6][CH:5]=[N:4][C:3]=1[CH2:7][OH:8]

Participants

9

Reactant 4

HCID 6228DimethylformamideHCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 592179555-Bromo-4-thiazolemethanol

Product 1

HCID 592179795-[2-(Trimethylsilyl)ethynyl]-4-thiazolemethanol

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

(5-Bromothiazol-4-yl)-methanol (6.15 g), 8.9 ml of triethylamine, 61 mg of copper(I) iodide, 5.4 ml of trimethylsilylacetylene, and 223 mg of bis(triphenylphosphine) palladium(II) dichloride were added in that order to 25 ml of DMF, the mixture was stirred, and the air in the system was replaced by argon. The reaction mixture was stirred with heating at 90° C. for 90 min and was then allowed to stand for cooling. Toluene (74 ml) and 25 ml of water were added to the reaction mixture, and the aqueous layer was separated. Water (25 ml) was added to the organic layer, and the mixture was adjusted to pH 2 by the addition of 5 N hydrochloric acid, followed by separation of the aqueous layer. The organic layer was washed with 25 ml of 5% sodium bicarbonate water and 25 ml of 10% brine in that order and was then treated with 1.4 g of activated carbon and anhydrous magnesium sulfate. The solvent was removed by distillation, and the solid was separated to give 5.35 g of [5-[2-(trimethylsilyl)ethynyl]thiazol-4-yl]-methanol.

Workup

  1. stirringThe reaction mixture was stirred
  2. temperaturefor cooling
  3. customthe aqueous layer was separated
  4. additionWater (25 ml) was added to the organic layer
  5. additionthe mixture was adjusted to pH 2 by the addition of 5 N hydrochloric acid
  6. customfollowed by separation of the aqueous layer
  7. washThe organic layer was washed with 25 ml of 5% sodium bicarbonate water and 25 ml of 10% brine in that order
  8. additionwas then treated with 1.4 g of activated carbon and anhydrous magnesium sulfate
  9. customThe solvent was removed by distillation
  10. customthe solid was separated

Sources & evidence

ORD record
ord-a7aa0684878943b9bdfef8b0f119ca89
Source dataset
uspto-grants-2013_01
Patent number
US08344154B2

Reaction notes

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