4-Bromotoluene → HCID 10420469, compound

HRID 984583Notes

Reaction equation

HRID 984583 reaction equation
[O-]P([O-])([O-])=O.[K+].[K+].[K+].[C@@H:9]1([NH2:16])[CH2:14][CH2:13][CH2:12][CH2:11][C@H:10]1[NH2:15].Br[C:18]1[CH:23]=[CH:22][C:21]([CH3:24])=[CH:20][CH:19]=1>[Cu]I.O1CCOCC1>[CH3:24][C:21]1[CH:22]=[CH:23][C:18]([NH:15][C@@H:10]2[CH2:11][CH2:12][CH2:13][CH2:14][C@H:9]2[NH2:16])=[CH:19][CH:20]=1

Participants

6

Reactant 3

HCID 78054-BromotolueneHCID 438061,2-Diaminocyclohexane, trans-HCID 62657Potassium Phosphate, Tribasic

Product 1

HCID 10420469HCID 10420469, compoundYield 64%

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), evacuated and backfilled with argon. trans-1,2-Cyclohexanediamine (0.60 mL, 5.00 mmol), 4-bromotoluene (0.70 mL, 5.69 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 black filtrate was concentrated and the residue was purified by flash chromatography on silica gel (2×20 cm; dichloromethane saturated with aq NH3-methanol 50:1; 15 mL fractions). Fractions 9-11 provided 650 mg (64% yield) of the product as a brown solid. 1H NMR (400 MHz, CDCl3): δ 7.00-6.95 (m, 2H), 6.62-6.57 (m, 2H), 3.30 (br s, 1H), 2.96-2.86 (br m, 1H), 2.49 (td, J=10.4, 3.6, 1H), 2.23 (s, 3H), 2.17-2.08 (m, 1H), 2.02-1.94 (m, 1H), 1.79-1.66 (m, 2H), 1.44 (br s, 2H), 1.38-1.17 (m, 3H), 1.07-0.95 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 145.9, 129.7, 126.6, 113.9, 60.5, 56.1, 35.2, 32.4, 25.3, 25.0, 20.3.

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 black filtrate was concentrated
  7. customthe residue was purified by flash chromatography on silica gel (2×20 cm; dichloromethane saturated with aq NH3-methanol 50:1; 15 mL fractions)

Sources & evidence

ORD record
ord-ce63f739cc1d46f4ad0e7d5529a99824
Source dataset
uspto-grants-2005_03
Patent number
US06867298B2

Reaction notes

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