Reaktion #1256720

Reaktionsgleichung

19

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

sodium methoxide

→

title compound

Ausbeute 131.3%

2-[4-(2-{4-[3,5-dimethyl-1-(2-propyl-heptyl)-1 H-pyridin-4-ylidene]-3,5-dimethyl-cyclohexa-2,5-dienylidene}-ethylidene)-cyclohexa-2,5-dienylidene]-malononitrile

Ausbeute 131.3%

Lösungsmittel

CH2Cl2

methanol

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.STIRRINGAfter stirring at room temperature for 10 min
2. 2
   Sonstigethe solvent was removed under reduced pressure
3. 3
   SonstigeThe resulting purple solid was then partitioned between water (50 mL) and CH2Cl2 (50 mL)
4. 4
   SonstigeThe organic layer was separated
5. 5
   Trocknendried over anhydrous Na2SO4
6. 6
   Filtrationfiltered
7. 7
   Einengenconcentrated in vacuo
8. 8
   SonstigeThe crude product was purified by flash chromatography on silica gel eluting with 4:100 methnol

Vorschrift

To a solution of 2-propyl-1-heptanol (0.81 g, 5.1 mmol) in dry CH2Cl2 (15 mL) was added dropwise a solution of trifluoromethanesufonic anhydride (1.77 g, 6.10 mmol) in the same solvent (5 mL). After stirring at room temperature for 20 min, the reaction mixture was poured into ice (40 mL), and neutralized with saturated aqueous NaHCO3 solution. The organic layer was separated, washed with water, dried over anhydrous Na2SO4, filtered, and concentrated in vacuo to give nearly pure 2-propyl-1-heptyl triflate as purple liquid (1.40 g, 94.1%). Next, 2-propyl-1-heptyl friflate (0.319 g 1.10 mmol ) was added dropwise to a solution of 19 (0.377 g, 1.00 mmol) in dry CH2Cl2 (20 mL). The reaction mixture was stirred at room temperature for 4 h. A solution of sodium methoxide in methanol (2.4 mL, 0.5 M) was then added dropwise to the resulting solution of pyridinium salt 20. The color of the mixture immediately changed from yellow to red. After stirring at room temperature for 10 min, the solvent was removed under reduced pressure. The resulting purple solid was then partitioned between water (50 mL) and CH2Cl2 (50 mL). 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 4:100 methnol: CH2Cl2, to give 0.340 g (65.7%) of the title compound as purple solid: mp 161-162° C.; 1H NMR (400 MHz, DMSO-d6): δ 9.039 (s, 2H), 7.418 (s, 2H), 7.286 (d, 2H, J=8.0 Hz), 7.145 (d, 1H, J=16.4 Hz), 6.919 (d, 1H, J=16.4 Hz ), 6.739 (d, 2H, J=7.6 Hz), 4.453 (m, 2H, J=5.2Hz), 2.125 (m, 1H), 2.074 (s, 6H), 1.859 (s, 6H), 1.319-1.219 (m, 12H), 0.849 (m, 6H); 13C NMR (125 MHz, DMSO-d6): δ 157.523, 142.592, 141.882, 138.688, 136.859, 133.320, 131.364, 129.981, 126.942, 125.704, 125.468, 121.582, 118.070, 64.195, 38.546, 32.695, 31.366, 30.156, 29.419, 25.061, 21.894, 19.010, 18.855, 16.581, 14.215, 13.942; MS (high resolution, EI): m/z 517.3451 [M+]; calcd, 517.3457; Anal. Calcd. for C36H43N3·1/3 H2O: C, 82.56; H, 8.40; N, 8.02. Found; C, 82.59; H, 8.11;N, 8.36.

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