Dodecane → 3,5-Dimethyltriphenylamine

HRID 1883323Notes

Reaction equation

HRID 1883323 reaction equation
[C:1]1([NH:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.CC(C)([O-])C.[Na+].[C@@H]1(N)CCCC[C@H]1N.CCCCCCCCCCCC.I[C:41]1[CH:42]=[C:43]([CH3:48])[CH:44]=[C:45]([CH3:47])[CH:46]=1>[Cu]I.O1CCOCC1>[CH3:47][C:45]1[CH:46]=[C:41]([N:7]([C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH:42]=[C:43]([CH3:48])[CH:44]=1

Participants

8

Reactant 5

HCID 8182DodecaneHCID 11487DiphenylamineHCID 438061,2-Diaminocyclohexane, trans-HCID 1409241-Iodo-3,5-dimethylbenzeneHCID 23676156Sodium t-butoxide

Product 1

HCID 105164103,5-DimethyltriphenylamineYield 74.2%

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 (2.0 mg, 0.0105 mmol, 1.0 mol %), diphenylamine (210 mg, 1.24 mmol), sodium tert-butoxide (145 mg, 1.51 mmol), evacuated and backfilled with argon. trans-1,2-Cyclohexanediamine (13 μL, 0.108 mmol, 11 mol %), dodecane (235 μL), 5-iodo-m-xylene (150 μL, 1.04 mmol) and dioxane (1.0 mL) were added under argon. The Schlenk tube was sealed and the reaction mixture was stirred magnetically at 110° C. for 24 h. The resulting pale brown suspension was cooled to room temperature and filtered through a 0.5×1 cm pad of silica gel eluting with 10 mL of hexane-ethyl acetate 5:1. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (2×25 cm; hexane-ethyl acetate 40:1; 15 mL fractions). Fractions 9-13 provided 211 mg (74% yield) of the product as white crystals. The 1H NMR spectrum was in accord with that reported by Goodbrand et al. Goodbrand, H. B.; Hu, N. X. J. Org. Chem. 1999, 64, 670.

Workup

  1. customevacuated
  2. customThe Schlenk tube was sealed
  3. temperatureThe resulting pale brown suspension was cooled to room temperature
  4. filtrationfiltered through a 0.5×1 cm pad of silica gel eluting with 10 mL of hexane-ethyl acetate 5:1
  5. concentrationThe filtrate was concentrated
  6. customthe residue was purified by flash chromatography on silica gel (2×25 cm; hexane-ethyl acetate 40:1; 15 mL fractions)

Sources & evidence

ORD record
ord-09e2fcc8ce0e47b0955fb0154317cfe6
Source dataset
uspto-grants-2004_07
Patent number
US06759554B2

Reaction notes

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