Ammonium Chloride → HCID 21099418, compound

HRID 1351670Notes

Reaction equation

HRID 1351670 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([S:8]([C:11]2[CH:18]=[CH:17][CH:16]=[CH:15][C:12]=2[C:13]#[N:14])(=[O:10])=[O:9])=[CH:4][CH:3]=1.C(C1C=CC=CC=1S)#N.[F:28][C:29]1[CH:34]=[C:33]([F:35])[CH:32]=[CH:31][C:30]=1[C:36](=[O:38])[CH3:37].P([O-])([O-])([O-])=O.[K+].[K+].[K+].[Cl-].[NH4+]>O1CCCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>[F:28][C:29]1[CH:34]=[C:33]([F:35])[CH:32]=[CH:31][C:30]=1[C:36](=[O:38])[CH2:37][C:2]1[CH:7]=[CH:6][C:5]([S:8]([C:11]2[CH:18]=[CH:17][CH:16]=[CH:15][C:12]=2[C:13]#[N:14])(=[O:10])=[O:9])=[CH:4][CH:3]=1

Participants

9

Reactant 5

HCID 25517Ammonium ChlorideHCID 62657Potassium Phosphate, TribasicHCID 677702,4-DifluoroacetophenoneHCID 110189262-MercaptobenzonitrileHCID 21099421HCID 21099421, compound

Product 1

HCID 21099418HCID 21099418, compoundYield 56%

Reagents, catalysts & solvents 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 2-[(4-bromophenyl)sulfonyl]benzonitrile (prepared according to the methods of Example 1 Step 1 using 2-cyanobenzenethiol followed by Example 16 Step 1; 0.32 g, 0.993 mmol), 2′,4′-difluoroacetophenone (0.31 g, 1.99 mmol), potassium phosphate (0.48 g, 2.26 mmol), tris(dibenzylideneacetone)dipalladium(0) (9 mg, 0.0098 mmol) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (13 mg, 0.022 mmol) in tetrahydrofuran (1 mL) was degassed then heated at 80° C. under nitrogen for 14 hours. Saturated ammonium chloride solution was added and the products extracted into ethyl acetate. The organic layer was dried over MgSO4 and concentrated in vacuo while loading onto silica. Dry flash column chromatography eluting with 25–40% ethyl acetate/isohexane followed by recrystallisation from ethanol gave the title compound as a beige solid (0.22 g, 56%). δH (500 MHz, CDCl3): 8.33 (1H, d, J=8.0 Hz), 8.05 (2H, d, J=8.3 Hz), 7.95–7.89 (1H, m), 7.83–7.77 (2H, m), 7.70–7.68 (1H, m), 7.43 (2H, d, J=8.3 Hz), 7.00–6.96 (1H, m), 6.92–6.88 (1H, m), 4.33 (2H, d, J=2.7 Hz).

Workup

  1. customprepared
  2. extractionthe products extracted into ethyl acetate
  3. dry with materialThe organic layer was dried over MgSO4
  4. concentrationconcentrated in vacuo
  5. customDry flash column chromatography
  6. washeluting with 25–40% ethyl acetate/isohexane
  7. customfollowed by recrystallisation from ethanol

Sources & evidence

ORD record
ord-6030138600da426abc03244a8eabf890
Source dataset
uspto-grants-2007_05
Patent number
US07217740B2

Reaction notes

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