Dimethylformamide → HCID 57809214, compound

HRID 2105849Notes

Reaction equation

HRID 2105849 reaction equation
[CH3:1][N:2]([CH3:21])[S:3]([C:6]1[C:7](I)=[CH:8][C:9]([O:17][CH2:18][CH3:19])=[C:10]([CH:16]=1)[C:11]([O:13][CH2:14][CH3:15])=[O:12])(=[O:5])=[O:4].[CH3:22][N:23](C)C=O>[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.O>[C:22]([C:7]1[C:6]([S:3](=[O:5])(=[O:4])[N:2]([CH3:21])[CH3:1])=[CH:16][C:10]([C:11]([O:13][CH2:14][CH3:15])=[O:12])=[C:9]([O:17][CH2:18][CH3:19])[CH:8]=1)#[N:23]

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 68873821HCID 68873821, compound

Product 1

HCID 57809214HCID 57809214, compoundYield 92%

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

Ethyl 5-dimethylsulfamoyl-2-ethoxy-4-iodobenzoate (1.01 g, 2.36 mmol), zinc cyanide (0.167 g, 1.42 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.191 g, 0.165 mmol) were combined under nitrogen in a flame-dried Schlenk tube. Dimethylformamide (9 mL) was added and the reaction mixture was put through three freeze-pump-thaw cycles and then put under a nitrogen atmosphere and heated at 80° C. for 16 h. After cooling to room temperature, water (50 mL) was added and the resulting mixture was extracted with diethyl ether (100 mL, 2×50 mL). The combined organic phases were washed with brine (3×50 mL) and then dried over magnesium sulfate and concentrated. Purification of the crude residue by flash column chromatography (silica gel, eluting with 33% ethyl acetate in hexanes) gave ethyl 4-cyano-5-dimethylsulfamoyl-2-ethoxybenzoate as an off-white solid (0.708 g, 92%). LC-MS: 327.1 [(M+H)+].

Workup

  1. temperatureAfter cooling to room temperature
  2. extractionthe resulting mixture was extracted with diethyl ether (100 mL, 2×50 mL)
  3. washThe combined organic phases were washed with brine (3×50 mL)
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated
  6. customPurification of the crude residue
  7. washby flash column chromatography (silica gel, eluting with 33% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-3c333aa656bc46a5aac1864983cd5980
Source dataset
uspto-grants-2009_08
Patent number
US07579368B2

Reaction notes

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