Dimethylformamide → 4-[5-(4,4-Dimethyl-2-oxo-1,3-oxazolidin-3-yl)-1,2,4-thiadiazol-3-yl]benzonitrile

HRID 1436446Notes

Reaction equation

HRID 1436446 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:12]=[C:11]([N:13]3[C:17]([CH3:19])([CH3:18])[CH2:16][O:15][C:14]3=[O:20])[S:10][N:9]=2)=[CH:4][CH:3]=1.[CH3:21][N:22](C)C=O>C(OCC)(=O)C.[C-]#N.[Zn+2].[C-]#N.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:18][C:17]1([CH3:19])[CH2:16][O:15][C:14](=[O:20])[N:13]1[C:11]1[S:10][N:9]=[C:8]([C:5]2[CH:6]=[CH:7][C:2]([C:21]#[N:22])=[CH:3][CH:4]=2)[N:12]=1

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 250273683-[3-(4-Bromophenyl)-1,2,4-thiadiazol-5-yl]-4,4-dimethyl-1,3-oxazolidin-2-one

Product 1

HCID 250273694-[5-(4,4-Dimethyl-2-oxo-1,3-oxazolidin-3-yl)-1,2,4-thiadiazol-3-yl]benzonitrileYield 84%

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalyst2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

3-[3-(4-bromophenyl)-1,2,4-thiadiazol-5-yl]-4,4-dimethyl-1,3-oxazolidin-2-one (0.67 g, 1.9 mmol), prepared in step 4 of Example 93, was dissolved in dimethylformamide (19 mL). Zinc cyanide (0.132 g, 1.14 mmol) was added, the mixture was purged with nitrogen for 15 min, and then tetrakis(triphenylphosphine)palladium (0.11 g, 0.095 mmol) was added. The mixture was heated to 120° C. for 2 h, additional tetrakis(triphenylphosphine)palladium (0.11 g, 0.095 mmol) was added and stirring was continued for 45 min. The mixture was cooled, diluted with ethyl acetate, washed with water, brine, dried over anhydrous MgSO4, filtered and concentrated. Flash chromatography (10% acetone in hexane) afforded the title compound (0.48 g, 84%) as a white solid. Analytical HPLC: HPLC purity 100% at 210-370 nm, 9.7 min; 100% at 248 nm, 9.7 min; the Xterra® RP18 column, 3.5μ, 150×4.6 mm column, 1.2 mL/min, 85/15-5/95 (Ammon. Form. Buff. pH=3.5/ACN+MeOH) for 10 min, hold 4 min.

Workup

  1. customthe mixture was purged with nitrogen for 15 min
  2. temperatureThe mixture was cooled
  3. washwashed with water, brine
  4. dry with materialdried over anhydrous MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-70231db898ae47828db895f285cc7bf6
Source dataset
uspto-grants-2009_11
Patent number
US07618990B2

Reaction notes

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