6
Tetrahedron
1712, 1363; MS (70 eV): m/z 169 (M+., 100%), 171 (91 %), 90
1H), 4.02 (t, J=7.1 Hz, 1H), 3.36 (d, J=7.1 Hz, 1H). 13C NMR
ACCEPTED MANUSCRIPT
(33 %), 233 (18 %), 235 (18 %).
(100 MHz, CDCl3, ppm): δ 146.2, 143.5, 111.8, 110.9, 109.9,
29.8, 22.6; IR (KBr, cm-1): 3414, 3025, 1743, 1521, 1356, 1003;
MS (70 eV): m/z 77 (M+., 100 %), 107 (52 %), 89 (41 %), 78 (36
%), 153 (23 %).
4.6.5. 2-(4-nitrobenzyl)malononitrile (3e)17: Orange solid; mp
153-154 oC; yield 11 mg (0.22 mmol, 22%); 1H NMR (400 MHz,
CDCl3, ppm): 8.30 (d, J=8 Hz, 2H), 7.55 (d, J=8 Hz, 2H), 4.04
(t= 6.8 Hz, 1H), 3.41 (d, J = 6.8 Hz, 2H); 13C NMR (100 MHz,
CDCl3, ppm): 148.49, 139.75, 130.54, 124.65, 111.59, 36.25,
24.56; IR (KBr, cm-1): 3104, 2929, 2256, 1602, 1517, 1346; MS
(70 eV): m/z 136 (M+., 100%), 106 (70 %), 89 (41 %), 78 (48 %),
89 (36 %), 201 (21 %).
4.6.13. 2-cyano-3-(furan-2-yl)propanamide (4k)19: Brown oil;
yield 15 mg (0.30 mmol, 30%); 1H NMR (500 MHz, CDCl3,
ppm): δ 7.38-7.35 (m, 1H), 6.32 (dd, J=3.1, 1.9 Hz, 1H), 6.25 (d,
J=3.1 Hz, 1H), 3.70 (dd, J=8.0, 5.4 Hz, 1H), 3.40-3.23 (m, 1H);
13C NMR (125 MHz, CDCl3): δ 165.29, 149.13, 142.57, 117.32,
110.61, 108.47, 37.51, 28.41; IR (KBr, cm-1): 3454, 3361, 3240,
2216, 1647, 1546, 1517 1352, 1174; MS (70 eV): m/z 81(M+.,
100 %), 53 (18 %), 164 (15 %), 65 (11 %), 120 (8 %).
4.6.6. 2-(4-hydroxybenzyl)malononitrile (3f)17: White solid; mp
173-176 oC; yield 6 mg (0.12 mmol, 12%); H NMR (500 MHz,
1
MeOD, ppm): δ 7.19 (d, J=8.0 Hz, 2H), 6.81-6.78 (d, J=8 Hz,
2H), 3.18 (sl, 1H); 13C NMR (125 MHz, MeOD, ppm): δ 158.54,
131.58, 131.21, 126.25, 116.59, 116.41, 114.62, 36.35 ; IR (KBr,
cm-1): 3414, 2920, 2530, 2270, 1608, 1516, 1259; MS (70 eV):
m/z 121 (M+., 100 %), 122(90 %), 93 (47 %), 65 (41 %).
Acknowledgments
DEQJ thanks to Coordenação de Aperfeiçoamento de Pessoal de
Nível Superior (CAPES), IMF and WGB thank to Conselho
Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
for scholarships, respectively. The authors thank to CNPq and
Fundação de Amparo a Pesquisa do Estado de São Paulo
(FAPESP) for financial support. ALMP thanks to Núcleo de
Pesquisa em Ciência e Tecnologia de BioRecursos (CITECBio)
of the University of São Paulo for financial and structural
support. ALMP and LJFP thank to CNPq (Programa Ciência sem
4.6.7. 2-(4-methoxybenzyl)malononitrile (3g)17: White solid; mp
o
1
80-81 C; yield 42 mg (0.84 mmol, 84%); H NMR (500 MHz,
MeOD, ppm): δ 7.30-7.28 (d, J=8 Hz, 2H), 6.94-6.92 (d, J=8 Hz,
2H), 3.79 (s, 3H). 3.23 (sl, 2H); 13C NMR (125 MHz, MeOD,
ppm): δ 161.11, 131.60, 127.51, 115.25, 114.59, 55.73, 36.28; IR
(KBr, cm-1): 2933, 2918, 2837, 2256, 1610, 1508, 1249; MS (70
eV): m/z 121 (M+., 100 %), 77 (11 %), 186 (9 %).18
Fronteiras
- Pequisador Visitante Especial (PVE, Proc.
400202/2014-0).
4.6.8.
2-(4-hydroxy-3-methoxybenzyl)malononitrile
(3h)17:
1
Colorless oil; yield 33 mg (0.66 mmol, 66%); H NMR (400
MHz, MeOD, ppm): δ 6.89 (d, J=8.1 Hz, 1H), 6.81 (dd, J=2.2,
0.4 Hz, 1H), 6.78 (ddt, J=8.1, 2.2, 0.5 Hz, 1H), 3.83 (s, 3H), 3.14
(s, 2H); 13C NMR (100 MHz, MeOD, ppm): δ 147.66, 146.40,
126.88, 120.33, 115.79, 113.19, 111.43, 54.97, 35.14. IR (KBr,
cm-1): 3394, 2229, 1585, 1564, 1514, 1280; MS (70 eV): m/z 137
(M+., 100 %), 202 (19 %), 122 (17 %), 94 (11 %).
Supplementary Material
Supplementary data (1H NMR, 13C NMR spectra, FTIR, GC-MS)
associated with this article can be found, in the online version, at
References and notes
4.6.9. 2-(pyridin-3-ylmethyl)malononitrile (3i)18: Red oil; yield
46.5 mg (0.93 mmol, 93%); 1H NMR (400 MHz, MeOD, ppm): δ
8.58 (dd, J=2.3, 0.8 Hz, 1H), 8.53 (dd, J=4.9, 1.6 Hz, 1H), 7.89
(dt, J=7.9, 1.9 Hz, 1H), 7.46 (ddd, J=7.9, 4.9, 0.9 Hz, 1H), 3.38
(s, 2H); 13C NMR (100 MHz, MeOD, ppm): δ 150.97, 150.95,
149.94, 139.30, 132.28, 125.43, 125.37, 114.18, 111.96, 33.88;
IR (KBr, cm-1): 2264, 2931, 2272, 1712, 1394; MS (70 eV): m/z
92 (M+., 100 %), 65 (27 %), 157 (26 %).
1. Ranu, B.; Samanta, S. J. Org. Chem. 2003, 68, 7130.
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Org. Process Res. Dev. 2012, 16, 262. (b) Durchschein, K.; Wallner,
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Yang, Y.-Q.; Lu, Z. Chinese J. Chem. 2014, 32, 650. (b) Li, P.; Yu,
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Tetrahedron 2012, 68, 4609.
4.6.10. 2-(thiophen-2-ylmethyl)malononitrile (3j)19: Colorless oil;
yield 49.5 mg (0.99 mmol, 99%); 1H NMR (400 MHz, CDCl3): δ
7.31 (dd, J=5.1, 1.1 Hz, 1H), 7.10 (d, J=3.1 Hz, 1H), 7.02 (dd,
J=5.1, 3.5 Hz, 1H), 3.93 (t, J= 6.8 Hz, 1H), 3.53 (d, J=6.8 Hz,
2H); 13C NMR (100 MHz, CDCl3): δ 128.4, 127.7, 126.5, 114.0,
111.8, 25.5, 22.7; IR (KBr, cm-1): 2954, 2924, 2882, 1735, 1465.
MS (70 eV): m/z 97 (M+., 100 %), 162 (17 %), 45 (14 %), 53 (11
%).
5. (a) Birolli, W. G.; Ferreira, I. M.; Alvarenga, N.; Santos, D. d. A.;
de Matos, I. L.; Comasseto, J. V.; Porto, A. L. M. Biotechnol. Adv.
2015, 33, 481. (b) Muller, A.; Hauer, B.; Rosche, B. J. Mol. Catal.
B: Enzym. 2006, 38, 126.
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Sacchetti, A. J. Org. Chem. 2013, 78, 4811.
4.6.11. 2-(furan-2-ylmethyl)malononitrile (3k)18: Yellowish oil;
yield 35 mg (0.70 mmol, 70%); 1H NMR (400 MHz, CDCl3,
ppm): δ 7.41 (d, J=0.9 Hz, 1H), 6.37 (dd, J=4.8, 2.5 Hz, 1H),
4.02 (t, J=7.1 Hz, 1H), 3.36 (d, J=7.1 Hz, 1H); 13C NMR (100
MHz, CDCl3, ppm): δ 146.2, 143.5, 111.8, 110.9, 109.9, 29.8,
22.6; IR (KBr, cm-1): 3124, 3041, 2231, 1606, 1456, 1394; MS
(70 eV): m/z 81 (M+., 100 %), 164 (12 %), 53 (21 %), 65 (12 %).
7. (a) Korpak, M.; Pietruszka, J. Adv. Synth. Catal. 2011, 353, 1420;
Silva, V.; Stambuk, B.; Nascimento, M., J. Mol. Catal. B: Enzym.
2010, 63, 157-163. (b) Zampieri, D.; de Paula, B.; Zampieri, L.;
Vale, J.; Rodrigues, J.; Moran, P. J. Mol. Catal. B: Enzym.2013, 85,
61.
8. Iqbal, N.; Rudroff, F.; Brige, A.; Van Beeumen, J.; Mihovilovic,
M. Tetrahedron 2012, 68, 7619.
9. (a) Ferreira, I.; Meira, E.; Rosset, I.; Porto, A. J. Mol. Catal. B:
Enzym. 2015, 115, 59. (b) Ferreira, I. M.; de Vasconcellos, S. P.; da
Cruz, J. B.; Comasseto, J. V.; Porto, A. L. M.; Rocha, L. C. Biocat.
4.6.12. (4-nitrophenyl)methanol (3e1)19: Yellow crystal; mp 92-
o
95 C; yield 30 mg (0.60 mmol, 60%); 1H NMR (400 MHz,
CDCl3, ppm): δ 7.41 (d, J = 0.9 Hz, 1H), 6.37 (dd, J=4.8, 2.5 Hz,