Trimethylsilylacetylene → HCID 19365967, compound

HRID 850094Notes

Reaction equation

HRID 850094 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[C:9]([OH:25])([C:16]([C:18]1[CH:23]=[CH:22][C:21](I)=[CH:20][CH:19]=1)=[CH2:17])[CH2:10][N:11]1[CH:15]=[N:14][CH:13]=[N:12]1.[CH3:26][Si:27]([C:30]#[CH:31])([CH3:29])[CH3:28]>[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.C(N(CC)CC)C>[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[C:9]([OH:25])([C:16]([C:18]1[CH:23]=[CH:22][C:21]([C:31]#[C:30][Si:27]([CH3:29])([CH3:28])[CH3:26])=[CH:20][CH:19]=1)=[CH2:17])[CH2:10][N:11]1[CH:15]=[N:14][CH:13]=[N:12]1

Participants

5

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 17892901HCID 17892901, compound

Product 1

HCID 19365967HCID 19365967, compoundYield 98%

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8471TriethylamineSolvent

Procedure

A mixture of 2-(2,4-difluorophenyl)-3-(4-iodophenyl)-1-(1,2,4-triazol-1-yl)-3-buten-2-ol (7.0 g, 15.5 mmol-see Preparation 20), trimethylsilylacetylene (2.6 ml, 18.5 mmol), cuprous iodide (0.015 g, 0.15 mmol), bis(triphenylphosphine) palladium (II) dichloride (0.21 g, 0.3 mmol) and triethylamine (80 ml) was stirred at room temperature under a nitrogen atmosphere for 24 hours. Volatile materials were removed under reduced pressure and the residue was partitioned between dichloromethane (200 ml) and a solution of ethylenediaminetetraacetic acid (2 g) in water (100 ml). The organic phase was dried (MgSO4) and evaporated under reduced pressure. The crude product was chromatographed on silica by elution with dichloromethanelmethanol (95:5). Fractions containing the desired product were combined and evaporated under reduced pressure to give 2-(2,4-difluorophenyl)-3-(4-[trimethylsilylethynyl]phenyl)-1-(1,2,4-triazol-1-yl)-3-buten-2-ol (6.4 g, 98%) as a yellow foam which was characterised by 1H-N.M.R. spectroscopy, (300 MHz, CDCl3): δ=0.22 (s,9H), 4.57 (d,1H), 4.89 (d,1H), 5.16 (s,1H), 5.26 (d,2H), 6.60-6.80 (m,2H), 7.21 (d,2H), 7.38 (d,2H), 7.42 (m,1H), 7.80 (s,2H) ppm.

Workup

  1. customVolatile materials were removed under reduced pressure
  2. customthe residue was partitioned between dichloromethane (200 ml)
  3. dry with materialThe organic phase was dried (MgSO4)
  4. customevaporated under reduced pressure
  5. customThe crude product was chromatographed on silica by elution with dichloromethanelmethanol (95:5)
  6. additionFractions containing the desired product
  7. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-236364b6b9e849b69c2edad08f4d3577
Source dataset
uspto-grants-2000_01
Patent number
US06015825

Reaction notes

Loading…