4-bromo-N,N-dimethylaniline → HCID 20740831, compound

HRID 1883344Notes

Reaction equation

HRID 1883344 reaction equation
[O-]P([O-])([O-])=O.[K+].[K+].[K+].Br[C:10]1[CH:18]=[CH:17][C:13]([N:14]([CH3:16])[CH3:15])=[CH:12][CH:11]=1.[C@@H:19]1([NH2:26])[CH2:24][CH2:23][CH2:22][CH2:21][C@H:20]1[NH2:25]>[Cu]I.O1CCOCC1>[CH3:15][N:14]([CH3:16])[C:13]1[CH:17]=[CH:18][C:10]([NH:25][C@@H:20]2[CH2:21][CH2:22][CH2:23][CH2:24][C@H:19]2[NH2:26])=[CH:11][CH:12]=1

Participants

6

Reactant 3

HCID 114654-bromo-N,N-dimethylanilineHCID 438061,2-Diaminocyclohexane, trans-HCID 62657Potassium Phosphate, Tribasic

Product 1

HCID 20740831HCID 20740831, compoundYield 59.3%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

An oven-dried resealable Schlenk tube was charged with CuI (190 mg, 0.998 mmol), K3PO4 (2.10 g, 9.89 mmol), 4-bromo-N,N-dimethylaniline (1.00 g, 5.00 mmol), evacuated and backfilled with argon. trans-1,2-Cyclohexanediamine (0.60 L, 5.00 mmol) and dioxane (3.0 mL) were added under argon. The Schlenk tube was sealed and the reaction mixture was stirred magnetically at 110° C. for 70 h. The resulting dark brown suspension was cooled to room temperature and filtered through a 2×1 cm pad of Celite eluting with 50 mL of dichloromethane. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (2×20 cm; dichloromethane saturated with aq NH3-methanol 40:1; 20 mL fractions). Fractions 12-16 provided 692 mg (59% yield) of the product as a brown solid. 1H NMR (400 MHz, CDCl3): δ 6.75−6.63 (m, 4H), 3.00 (br s, 1H), 2.87−2.77 (m, 7H), 2.53−2.45 (m, 1H), 2.17−2.04 (m, 1H), 2.02−1.94 (m, 1H), 1.78−1.16 (m, 7H), 1.04−0.92 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 144.7, 140.9, 116.2, 116.1, 62.0, 56.5, 42.6, 35.7, 33.0, 25.8, 25.5.

Workup

  1. customevacuated
  2. customThe Schlenk tube was sealed
  3. temperatureThe resulting dark brown suspension was cooled to room temperature
  4. filtrationfiltered through a 2×1 cm pad of Celite
  5. washeluting with 50 mL of dichloromethane
  6. concentrationThe filtrate was concentrated
  7. customthe residue was purified by flash chromatography on silica gel (2×20 cm; dichloromethane saturated with aq NH3-methanol 40:1; 20 mL fractions)

Sources & evidence

ORD record
ord-7b8a4d52b6f0447f98fbace5ec40787e
Source dataset
uspto-grants-2004_07
Patent number
US06759554B2

Reaction notes

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