Reaction #1256712

Reaction equation

aluminum

10

4-(3,5-dimethyl-pyridin-4-yl)-3,5-dimethyl-phenylamine

nitrosonium tetrafluoroborate

NaI

Na2S2O3

→

title compound

Yield 72.0%

4-(4-iodo-2,6-dimethyl-phenyl)-3,5-dimethyl-pyridine

Yield 72.0%

Solvents

acetonitrile

acetonitrile

acetonitrile

Conditions

Workup

1. 1
   Temperatureto gradually warm to room temperature
2. 2
   workup.STIRRINGstirred at room temperature overnight
3. 3
   Extractionextracted with chloroform (50 mL×3)
4. 4
   OtherThe organic layer was separated
5. 5
   Dryingdried over anhydrous Na2SO4
6. 6
   Filtrationfiltered
7. 7
   Concentrationconcentrated in vacuo
8. 8
   OtherThe crude product was purified by flash chromatography on silica gel
9. 9
   Washeluting with 8:1 chloroform

Procedure

To a stirring suspension of nitrosonium tetrafluoroborate (0.876 g, 7.50 mmol) in dry acetonitrile (10 mL) was added dropwise via syringe a solution of 10 (0.904 g, 4.00 mmol) in dry acetonitrile (15 mL) under N2 at −30° C. The reaction mixture was next stirred at −30° C. for 1 h. To the resulting yellow solution was then added dropwise in the dark a solution of anhydrous NaI (1.125 g, 7.50 mmol) in dry acetonitrile (10 mL) under N2 at −30° C. The reaction mixture was covered with aluminum foil, allowed to gradually warm to room temperature, and stirred at room temperature overnight. The resulting red solution was next decolorized using an aqueous solution of Na2S2O3 and extracted with chloroform (50 mL×3). The organic layer was separated, dried over anhydrous Na2SO4, filtered, and concentrated in vacuo. The crude product was purified by flash chromatography on silica gel, eluting with 8:1 chloroform: ethyl acetate, to give 0.96 g (72%) of the title compound as a yellow solid: mp 242-243° C.; 1H NMR (400 MHz, CDCl3): δ 8.397 (s, 2H), 7.520 (s, 2H), 1.908 (s, 6H), 1.838 (s, 6H); 13C NMR (100 MHz, CDCl3): δ 148.611, 147.520, 136.983, 136.774, 130.841, 93.681, 19.488, 16.758; MS(ESI): m/z 338.2[(M+H)+, 100]; Anal. Calcd. for C15H16IN: C, 53.43; H, 4.78; N, 4.15. Found; C, 52.91; H, 4.72; N, 4.07.

Source