Diethyl Ether → 2,6-Difluoro-N,N-di(propan-2-yl)benzene-1-carboximidamide

HRID 646653Notes

Reaction equation

HRID 646653 reaction equation
CC[Mg+].[Br-].CCOCC.[CH:10]([NH:13][CH:14]([CH3:16])[CH3:15])([CH3:12])[CH3:11].[F:17][C:18]1[CH:25]=[CH:24][CH:23]=[C:22]([F:26])[C:19]=1[C:20]#[N:21]>C1(C)C=CC=CC=1>[CH:10]([N:13]([CH:14]([CH3:16])[CH3:15])[C:20](=[NH:21])[C:19]1[C:18]([F:17])=[CH:25][CH:24]=[CH:23][C:22]=1[F:26])([CH3:12])[CH3:11]

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 7912DiisopropylamineHCID 746952,6-DifluorobenzonitrileHCID 178461630HCID 178461630, compound

Product 1

HCID 237265252,6-Difluoro-N,N-di(propan-2-yl)benzene-1-carboximidamideYield 95.9%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of EtMgBr in ether (8.0 ml, 3.0 M, 23 mmol) was added to a solution of diisopropylamine (2.5 g, 23.8 mmol) in toluene (60 ml) at 50° C. The mixture was stirred for 1 h and a white precipitate formed. The mixture was cooled to 0° C. and 2,6-difluorobenzonitrile (3.33 g, 23 mmol) was added. The mixture was allowed to warm to room temperature and stirred for 16 hours subsequently. The conversion, determined by GC, appeared to be 98%. The mixture was quenched with an aqueous solution of ammonium chloride (10%, 100 ml). The organic phase was separated from the aqueous phase and the latter was extracted twice with diethylether (200 ml). The combined organic phases were dried over sodium sulphate, filtered and the solvent was removed under reduced pressure giving 5.30 g (91%) of pure product. The ligand was characterized by 1H NMR 300 MHz (CDCl3) δ (ppm): 7.2 (m, 1H), 6.8 (m. 2H), 5.5 (bs, 1H), 3.7 (bs, 1H), 1.5 (bs, 6H), 1.0 (bs 6H), by 13C NMR 75 MHz (CDCl3) δ (ppm): 158.9 dd, J=238 Hz, J=8 Hz), 155.7, 130.1, v130.0, 129.8, 112.1, 112.0, 111.9, 111.8, 52.0 (bs), 36.2 (bs), 21.3, 20.5 and by 19F NMR 282 MHz (CDCl3) δ (ppm): −113.5

Workup

  1. customa white precipitate formed
  2. temperatureto warm to room temperature
  3. stirringstirred for 16 hours subsequently
  4. customThe mixture was quenched with an aqueous solution of ammonium chloride (10%, 100 ml)
  5. customThe organic phase was separated from the aqueous phase
  6. extractionthe latter was extracted twice with diethylether (200 ml)
  7. dry with materialThe combined organic phases were dried over sodium sulphate
  8. filtrationfiltered
  9. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-7e21529159244a83a1aca719812bd350
Source dataset
uspto-grants-2010_04
Patent number
US07705172B2

Reaction notes

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