Dimethylformamide → HCID 86647429, compound

HRID 2071062Notes

Reaction equation

HRID 2071062 reaction equation
Br[C:2]1[CH:3]=[C:4]([S:9]([O:12][NH:13][CH3:14])(=[O:11])=[O:10])[CH:5]=[C:6]([Br:8])[CH:7]=1.[CH3:15][N:16](C=O)C.[NH4+].[OH-]>[C-]#N.[C-]#N.[Zn+2].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.[Pd].CCOC(C)=O>[Br:8][C:6]1[CH:7]=[C:2]([CH:3]=[C:4]([S:9]([O:12][NH:13][CH3:14])(=[O:11])=[O:10])[CH:5]=1)[C:15]#[N:16]

Participants

8

Reactant 3

HCID 6228DimethylformamideHCID 14923Ammonium HydroxideHCID 86647430HCID 86647430, compound

Product 1

HCID 86647429HCID 86647429, compoundYield 31%

Reagents, catalysts & solvents 4

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 23938PalladiumCatalystHCID 178418397HCID 178418397, compoundCatalyst2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 751 mg (2.29 mmol) of O-(3,5-dibromophenylsulfonyl)-N-methylhydroxylamine, 159 mg (1.35 mmol) of Zn(CN)2 and 164 mg (0.142 mmol) of Pd(PPh3)4, 8 mL of DMF (degassed) was stirred at 80° C. After 70 min., 334 mg of Pd((PPh3)4, was added and after 35 min. 414 mg of Pd(PPh3)4 was added. After 1 h, EtOAc and 20 mL of 10% NH4OH (aq) was added, and the layers were separated. The organic layer was washed with 20 mL of 10% NH4OH (aq) and 20 mL of brine. The combined aqueous layer was extracted with EtOAc. The combined extracts were dried over Na2SO4, filtered, and concentrated. Purification by flash silica gel chromatography provided 194 mg of 3-bromo-5-(methylaminooxysulfonyl)benzonitrile as a yellow solid in 31% yield.

Workup

  1. waitAfter 1 h
  2. customthe layers were separated
  3. washThe organic layer was washed with 20 mL of 10% NH4OH (aq) and 20 mL of brine
  4. extractionThe combined aqueous layer was extracted with EtOAc
  5. dry with materialThe combined extracts were dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customPurification by flash silica gel chromatography

Sources & evidence

ORD record
ord-705e43eab39c42d1b9a46d3c49f4b2df
Source dataset
uspto-grants-2012_10
Patent number
US08299267B2

Reaction notes

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