1,10-Phenanthroline → N-(3,5-Dimethylphenyl)-4-cyanoaniline

HRID 1242987

Reaction equation

HRID 1242987 reaction equation
N1C2C(=CC=C3C=2N=CC=C3)C=CC=1.[C:15]([C:17]1[CH:23]=[CH:22][C:20]([NH2:21])=[CH:19][CH:18]=1)#[N:16].CC(C)([O-])C.[Na+].CCCCCCCCCCCC.I[C:43]1[CH:44]=[C:45]([CH3:50])[CH:46]=[C:47]([CH3:49])[CH:48]=1>[Cu]I.O1CCOCC1>[CH3:50][C:45]1[CH:44]=[C:43]([NH:21][C:20]2[CH:22]=[CH:23][C:17]([C:15]#[N:16])=[CH:18][CH:19]=2)[CH:48]=[C:47]([CH3:49])[CH:46]=1

Participants

8

Reactant 5

HCID 13181,10-PhenanthrolineHCID 8182DodecaneHCID 133964-AminobenzonitrileHCID 1409241-Iodo-3,5-dimethylbenzeneHCID 23676156Sodium t-butoxide

Product 1

HCID 21940688N-(3,5-Dimethylphenyl)-4-cyanoanilineYield 69%

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 (10 mg, 0.0525 mmol, 5.0 mol %), 1,10-phenanthroline (20 mg, 0.111 mmol), 4-cyanoaniline (146 mg, 1.24 mg), sodium tert-butoxide (145 mg, 1.51 mmol), evacuated and backfilled with argon. 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 23 h. The resulting brown suspension was cooled to room temperature and filtered through a 0.5×1 cm pad of silica gel eluting with 10 mL of ethyl acetate. The filtrate was concentrated and the residue was purified by flash chromatography on silica gel (2×15 cm; hexane-ethyl acetate 5:1; 10 mL fractions). Fractions 7–16 provided 159 mg (69% yield) of the product as white crystals. 1H NMR (400 MHz, CDCl3): δ 7.51–7.47 (m, 2H), 6.91–6.95 (m, 2H), 6.83–6.80 (m, 2H), 6.80–6.78 (m, 1H), 6.02 (br s, 1H), 2.33 (q, J=0.5 Hz, 6H).

Workup

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

Sources & evidence

ORD record
ord-7f214110d3fe4c68bc99562a5d3c7f16
Source dataset
uspto-grants-2006_10
Patent number
US07115784B2

Linked notes

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