The Journal of Physical Chemistry A
ARTICLE
’ EXPERIMENTAL SECTION
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Synthesis of 2-(2,6-Dimethyl-4H-pyran-4-ylidene)-malo-
nonitrile (1). In a three-neck flask, 2,6-dimethylpyran-4-one
(1.2 g, 10 mmol) and malononitrile (1 g, 15 mmol) were
dissolved in acetic anhydride while stirring the mixture at
120 ꢀC. The reaction mixture was heated on a steam bath for
2 h and poured into a slurry of crushed ice and water (250 mL).
The precipitate was washed with water and extracted with
CHCl3. Viscous liquid product was obtained by column chro-
matography (CHCl3) (yield = 70%). 1H NMR (DMSO, ppm): δ
6.68 (s, 2H, ArH), δ 2.35 (s, 6H, 2(CH3)).
Synthesis of Cyano-(2,6-dimethyl-4H-pyran-4-ylidene)-
acetic Acid Methyl Ester (2). A solution of 1 equiv (5 g, 40
mmol) of 2,6-dimethylpyran-4-one and 1 equiv of methyl cyano
acetate (5.6 g, 57 mmol) in acetic anhydride was refluxed for 2-5 h.
The mixture was then poured into a mixture of water. The crude
product was extracted with ethyl ether (5 ꢀ 30 mL). The extracts
were washed with water and dried over MgSO4. Removal of the
solvent left residue, which was subjected to column chromatography,
EtOAc-petroleum ether (1:1, v/v) as a dark orange solid (yield =
28%). 1H NMR (DMSO, ppm): δ 7.80 (s, 1H, ArH), δ 6.59(s, 1H,
ArH), δ 3.67 (s, 3H, CH3), δ 2.34 (s, 6H, 2(CH3)).
(10) Schleyer, P. v. R.; Maerker, C.; Dransfeld, A.; Jiao, H.; van
Eikema Hommes, N. J. R. J. Am. Chem. Soc. 1996, 118, 6317.
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Jiao, H. Angew. Chem., Int. Ed. Engl. 1996, 35, 2638. (c) Jiao, H.; Schleyer,
P. v. R.; Mo, Y.; McAllister, M. A.; Tidwell, T. T. J. Am. Chem. Soc. 1997,
119, 7075. (d) Jiao, H.; Schleyer, P. v. R.; Beno, B. R.; Houk, K. N.;
Warmuth, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 2761. (e) Zywietz,
T. K.; Jiao, H.; Schleyer, P. v. R.; de Meijere, A. J. Org. Chem. 1998,
63, 3417. (f) Fokin, A. A.; Jiao, H.; Schleyer, P. v. R. J. Am. Chem. Soc.
1998, 120, 9364. (g) Mauksch, M.; Gogonea, V.; Jiao, H.; Schleyer,
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P. v. R. J. Phys. Org. Chem. 1998, 11, 655. (i) Schleyer, P. v. R.; Jiao, H.;
van Eikema Hommes, N. J. R.; Malkin, V. G.; Malkina, O. L. J. Am. Chem.
Soc. 1997, 119, 12669. (j) Cyranski, M. K.; Krygowski, T. M.;
Wisiorowski, M.; van Eikema Hommes, N. J. R.; Schleyer, P. v. R. Angew.
Chem., Int. Ed. 1998, 37, 177. (k) Cossio, F. P.; Morao, I.; Jiao, H.;
Schleyer, P. v. R. J. Am. Chem. Soc. 1999, 121, 6737. (l) Nyulaszi, L.;
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Fischer, T.; Schwerdtfeger, P. J. Org. Chem. 1997, 62, 8063. (n) West, R.;
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Lett. 1998, 39, 6791. (q) Nishinaga, T.; Izukawa, Y.; Komatsu, K. J. Phys.
Org. Chem. 1999, 11, 475. (r) Wannere, C. S.; Schleyer, P. v. R. Org. Lett.
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Synthesis of 2-(2,6-Bis(4-(dimethylamino)styryl)-4H-pyr-
an-4-ylidene) Malononitrile (3). A solution of 1 (1 g, 6.0
mmol), 4-dimethylamino benzaldehyde (1.9 g, 12.8 mmol),
and piperidine (0.45 mL) in acetonitrile (30 mL) was refluxed
for 8 h. The reaction solution was cooled to room temperature,
and the solid product was isolated and washed well with
acetonitrile and dried. The crude product was recrystallized from
methanol several times (yield = 23%). 1H NMR (DMSO, ppm):
δ 7.68-7.65 (d, 2H, J = 16.2 Hz), δ 7.66-7.65 (d, 4H, ArH), δ
7.07-7.04 (d, 2H, J = 16.2 Hz), δ 6.78-6.77 (d, 4H, ArH), δ
6.69 (s, 2H), δ 3.02 (s, 12H, 4(CH3)).
Synthesis of Methyl 2-(2,6-Bis(4-(dimethylamino)styryl)-
4H-pyran-4-ylidene)-2-cyanoacetate (4). A solution of 2 (1 g,
5 mmol), 4-dimethylamino benzaldehyde (1.6 g, 11 mmol), and
piperidine (0.45 mL) in acetonitrile (30 mL) was refluxed for 8 h.
The reaction solution was cooled to room temperature, and the
solid product was isolated and washed well with acetonitrile and
dried. The crude product was recrystallized from methanol
1
several times (yield = 47%). H NMR (DMSO, ppm): δ 7.90
(s, 1H), δ 7.69-7.67 (d, 1H, ArH), δ 7.67-7.65 (d, 1H, ArH), δ
7.62-7.59 (d, 1H, J = 18 Hz), δ 7.61-7.58 (d, 1H, J = 18 Hz), δ
7.06-7.03 (d, 1H, J = 18 Hz), δ 6.95-6.93 (d, 1H, J = 18 Hz), δ
6.77-6.75 (d, 1H, ArH), δ 6.76-6.74 (d, 1H, ArH), δ 6.66 (s, 1H),
δ 3.69 (s, 1H, CH3), δ 3.01 (s, 12H, 4(CH3)).
’ ASSOCIATED CONTENT
Supporting Information. 1H NMR chemical shift data
S
b
and optimized geometries of the species. This material is avail-
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’ AUTHOR INFORMATION
Corresponding Author
*E-mail: sung.s.park@samsung.com.
’ REFERENCES
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dx.doi.org/10.1021/jp110176c |J. Phys. Chem. A 2011, 115, 2830–2836