反応 #1256716

反応方程式

HCl

NaH

malononitrile

11

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

→

title compound

収率 95.5%

2-[4-(3,5-dimethyl-pyridin-4-yl)-3,5-dimethyl-phenyl]-malononitrile

収率 95.5%

溶媒

1,2-dimethoxyethane

1,2-dimethoxyethane

反応条件

後処理

1. 1
   workup.STIRRINGThe reaction mixture was next stirred at 85° C. under N2 for 5 h
2. 2
   その他The solvent was then removed under reduced pressure
3. 3
   洗浄The resulting solid was washed with benzene (20 mL)
4. 4
   workup.DISSOLUTIONdissolved in water
5. 5
   ろ過filtered
6. 6
   その他to give a dark-yellow aqueous solution
7. 7
   ろ過the resulting yellow precipitate was collected by filtration
8. 8
   その他to give an orange solid
9. 9
   その他The crude product was purified by flash chromatography on silica gel eluting with 1:1 hexane

実験手順

To an ice-cooled suspension of NaH (0.12 g, 5.0 mmol) in anhydrous 1,2-dimethoxyethane (8 mL) was added dropwise via syringe a solution of malononitrile (0.165 g, 2.50 mmol) in anhydrous 1,2-dimethoxyethane (2 mL) under N2. The mixture was stirred for 1 h at room temperature under N2. Next, 11 (0.674 g, 2.00 mmol) and tetrakis(triphenyphophine)palladium(0) (0.232 g, 0.200 mmol) were added to the resulting pink suspension under an N2 flow. The reaction mixture was next stirred at 85° C. under N2 for 5 h. The solvent was then removed under reduced pressure. The resulting solid was washed with benzene (20 mL), dissolved in water, and filtered to give a dark-yellow aqueous solution. This solution was neutralized with 5% HCl to pH=7, and the resulting yellow precipitate was collected by filtration to give an orange solid. The crude product was purified by flash chromatography on silica gel eluting with 1:1 hexane: ethyl acetate, to give 0.525 g (95.5%) of the title compound as red solid: mp 58-60° C.; 1H NMR (400 MHz, CDCl3): δ 8.412 (s, 2H), 7.286 (s, 2H), 5.100 (s, 1H), 1.946 (s, 6H), 1.895 (s, 6H); 13C NMR (100 MHz, CDCl3): δ 149.066, 146.564, 139.513, 137.283, 130.441, 126.692, 125.518, 112.024,28.059, 19.988, 16.704; Anal. Calcd. for C18H17N3·H2O: C, 73.69; H, 6.53; N, 14.32. Found; C, 73.36; H, 6.35; N, 14.07.

出典