Potassium Carbonate → HCID 59472661, compound

HRID 885140Notes

Reaction equation

HRID 885140 reaction equation
F[C:2]1[CH:9]=[CH:8][C:5]([CH:6]=O)=[CH:4][C:3]=1[C:10]#[N:11].[CH3:12][C:13]1[N:14]=[CH:15][NH:16][CH:17]=1.[C:18]([O-])([O-])=O.[K+].[K+].[N+](=C(P(=O)(OC)OC)C(=O)C)=[N-]>CN(C=O)C.CCOC(C)=O.CO.C(Cl)Cl>[C:6]([C:5]1[CH:8]=[CH:9][C:2]([N:16]2[CH:17]=[C:13]([CH3:12])[N:14]=[CH:15]2)=[C:3]([CH:4]=1)[C:10]#[N:11])#[CH:18]

Participants

9

Reactant 4

HCID 11430Potassium CarbonateHCID 27695822-Fluoro-5-formylbenzonitrileHCID 136023029(1E)-1-diazo-1-dimethoxyphosphorylpropan-2-oneHCID 178418800HCID 178418800, compound

Product 1

HCID 59472661HCID 59472661, compoundYield 29.2%

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 4-fluoro-3-cyanobenzaldehyde (3.0 g, 20 mmol) in 20 mL of DMF was treated with 4-methylimidazole (3.0 g, 37 mmol) and warmed to 100° C. Stirred overnight. Diluted with EtOAc, washed with sat'd NaHCO3, dried (Na2SO4), concentrated. Triturated with MeOH and filtered to give a single regioisomer (1.3 g, 6.1 mmol; 31%). Suspended in 20 mL of MeOH, treated with K2CO3 (1.4 g, 10 mmol) and dimethyl (1-diazo-2-oxopropyl)phosphonate (1.4 g, 7.3 mmol) and stirred overnight. Diluted with DCM and washed with water. Dried (Na2SO4), conc. Chromatography on silica (0-20% MeOH/DCM) gave the desired alkyne (606 mg; 15% overall yield):

Workup

  1. washwashed with sat'd NaHCO3
  2. dry with materialdried (Na2SO4)
  3. concentrationconcentrated
  4. customTriturated with MeOH
  5. filtrationfiltered
  6. customto give a single regioisomer (1.3 g, 6.1 mmol; 31%)
  7. stirringstirred overnight
  8. washwashed with water
  9. dry with materialDried (Na2SO4), conc. Chromatography on silica (0-20% MeOH/DCM)

Sources & evidence

ORD record
ord-2068d4ebd8c24282be79530cbfbcb9cf
Source dataset
uspto-grants-2012_08
Patent number
US08242150B2

Reaction notes

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