Dicyclohexylamine → HCID 67215642, compound

HRID 2421451Notes

Reaction equation

HRID 2421451 reaction equation
[CH:1]1([NH:7][CH:8]2[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9]2)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.C[Mg]Br.[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.C(OCC)C>[CH:8]1([N:7]([CH:1]2[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6]2)[C:20](=[NH:21])[C:19]2[C:18]([F:17])=[CH:25][CH:24]=[CH:23][C:22]=2[F:26])[CH2:9][CH2:10][CH2:11][CH2:12][CH2:13]1

Participants

6

Reactant 3

HCID 7582DicyclohexylamineHCID 746952,6-DifluorobenzonitrileHCID 178418573HCID 178418573, compound

Product 1

HCID 67215642HCID 67215642, compoundYield 90.6%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
50 °C

Procedure

Dicyclohexylamine (9.06 g, 50.1 mmol) was dissolved in toluene (125 mL). The solution was warmed to 50° C. and a solution of methylmagnesiumbromide was added (16.7 mL, 3.0 M in diethylether, 50.1 mmol) and the reaction mixture was stirred for 2 hours at 50° C. The mixture was cooled to 0° C. and 2,6-difluorobenzonitrile (6.80 g, 48.9 mmol). After 45 hours, the reaction mixture was quenched with a solution of ammoniumchloride in water (3.0 g in 80 mL). The water and organic phases were separated and the water layer was extracted 3 times with diethylether (40 mL). The combined organic solutions were dried over sodium sulphate. The sodium sulphate was filtered off and the filtrate was evaporated to dryness yielding 14.2 g (89%) of the product. The product was characterized by 1H NMR (300 MHz) (CDCl3) δ (ppm): 7.2 (pent, 1H), 6.8 (dd, 2H), 5.9 (bs, 1H), 3.5-2.3 (bm, 3H), 1.9-0.6 (bm, 19H), by 13C NMR (75 MHz) (CDCl3) δ (ppm): 158.9 (dd, J=248 Hz, J=8 Hz) 156.4, 130.1, 130.0, 129.8, 118.8, 118.4, 118.1, 12.1, 111.7, 61.3 (bs), 56.9 (bs), 32.0 (bs), 30.1 (bs), 26.8 (bs), 25.8 and by 19F NMR (282 MHz) (CDCl3) δ (ppm): −114.3 (s).

Workup

  1. temperatureThe mixture was cooled to 0° C.
  2. waitAfter 45 hours
  3. customthe reaction mixture was quenched with a solution of ammoniumchloride in water (3.0 g in 80 mL)
  4. customThe water and organic phases were separated
  5. extractionthe water layer was extracted 3 times with diethylether (40 mL)
  6. dry with materialThe combined organic solutions were dried over sodium sulphate
  7. filtrationThe sodium sulphate was filtered off
  8. customthe filtrate was evaporated to dryness

Sources & evidence

ORD record
ord-68209f36cbba4428b1659ec15a8b2849
Source dataset
uspto-grants-2011_06
Patent number
US07956140B2

Reaction notes

Loading…