تفاعل #663636

معادلة التفاعل

2-(2,6-dimethyl-4H-pyran-4-ylidene) malononitrile

aldehyde

tert-butyl 4-(((tert-butyloxycarbonyl)(4-formyl-2-methoxyphenyl)amino)methyl)phenylcarbamate

Piperidine

→

(E)-2-(2-(4-(4-aminobenzylamino)-3-methoxystyryl)-6-methyl-4H-pyran-4-ylidene)malononitrile

المذيبات

EtOH

ظروف التفاعل

المعالجة

1. 1
   أخرىThe solvent was removed with a stream of N2
2. 2
   أخرىthe crude mixture was purified by reverse phase
3. 3
   workup.ADDITIONThe purified product (8.1 mg) was treated with a 4N HCl solution in dioxane (4 N, 0.65 ml) for 3 hrs
4. 4
   workup.ADDITIONThe mixture was diluted with hexanes
5. 5
   غسيلwashed with hexanes
6. 6
   أخرىdried under vacuum

الإجراء التجريبي

A mixture of 2-(2,6-dimethyl-4H-pyran-4-ylidene) malononitrile (1, 16.5 mg, 96 μmol) and aldehyde 2d (34.9 mg, 76.5 μmol) were dissolved in anhydrous EtOH (0.5 ml) at 65 C. Piperidine (1 μl) was added and the mixture was stirred at 80° C. for 6 hrs. The solvent was removed with a stream of N2 and the crude mixture was purified by reverse phase HPLC using water/acetonitrile 40-100% gradient. Yield: 8.1 mg (17.4%). LCMS: m/z 611 (M+H+), 623 (M+Na+). H-NMR (400 MHz, CD2Cl2): 7.45 (1H, d, J=16 Hz) 7.29 (2H, d, J=12 Hz) 7.17 (2H, d, J=8 Hz) 7.03-7.12 (2H, m) 6.69-6.79 (2H, m) 6.52-6.61 (2H, m) 4.76 (2H, brs) 3.89 (3H, s) 2.43 (3H, s) 1.52, (9H, s) 1.41 (9H, brs). C-NMR (400 MHz, CD2Cl2): 162.54, 159.01, 156.35, 152.56, 137.61, 137.21, 134.39, 133.06, 132.89, 128.82, 120.38, 118.39, 117.99, 115.03, 114.99, 107.37, 106.31, 80.21, 58.97, 55.49, 29.68, 28.00, 27.93, 19.75. The purified product (8.1 mg) was treated with a 4N HCl solution in dioxane (4 N, 0.65 ml) for 3 hrs. The mixture was diluted with hexanes, the precipitate centrifuged, re-suspended and washed with hexanes, then dried under vacuum. LCMS ESI+ m/z: 411 (M+H+). H-NMR (400 MHz, DMSO-D6) 7.22-7.28 (5H, m) 6.83-6.89 (2H, m) 6.65 (1H, d, J=16 Hz) 6.54 (1H, d, J=16 Hz) 5.54 91H, s) 5.32 (1H, s) 4.22-4.38 (2H, brs) 3.92 (3H, s) 2.39 (3H, s).

المصدر