(NO2); δH(CDCl3) 8.11 (s, 1H), 7.64 (s, 1H), 2.45 (s, 3H), 2.42 (s,
3H).
Acknowledgements
2,4-Dimethylbenzonitrile (23). Oil.25 νmax(KBr)/cmϪ1 2220
(CN); δH (CDCl3) 7.48 (d, 1H, J = 7.9), 7.12 (s, 1H), 7.07 (d, 1H,
J = 7.9), 2.50 (s, 3H), 2.37 (s, 3H).
This work was supported by a Grant-in-Aid (no. 12640576)
from the Ministry of Education, Culture, Sports, Science, and
Technology, Japan. The authors acknowledge the Catalytic
Society of Japan and Dr M. Nakano of TOSOH Corporation,
Ltd. for the generous gifts of zeolite samples. X. P. thanks the
Japan Society for the Promotion of Science for a Fellowship
(no. P99282).
2,4-Dimethyl-3-nitrobenzonitrile (24). Mp 122–123 ЊC;
(Found: C, 61.32; H, 4.75; N, 15.92. C9H8N2O2 requires C,
61.36; H, 4.58; N, 15.90%); νmax(KBr)/cmϪ1 2230 (CN), 1527
(NO2), 1373 (NO2); δH(CDCl3) 7.45 (d, 1H, J = 7.9), 7.41 (d, 1H,
J = 7.9), 2.61 (s, 3H), 2.41 (s, 3H).
2,4-Dimethyl-5-nitrobenzonitrile (25). Mp 109–110 ЊC (lit.21
108 ЊC); νmax(KBr)/cmϪ1 2230 (CN), 1521 (NO2), 1342 (NO2);
δH (CDCl3) 7.87 (s, 1H), 7.60 (s, 1H), 2.60 (s, 3H), 2.57 (s, 3H).
2,5-Dimethylbenzonitrile (26). Oil.25 νmax(KBr)/cmϪ1 2236
(CN), 1524 (NO2), 1352 (NO2); δH (CDCl3) 7.39 (s, 1H),
7.28 (d, 1H, J = 8.3), 7.19 (d, 1H, J = 8.3), 2.49 (s, 3H), 2.33 (s,
3H).
References
1 For a general survey of aromatic nitration, see: (a) L. F. Albright,
R. V. C. Carr and R. J. Schmitt, eds. Nitration, ACS Symposium
Series 623, American Chemical Society, Washington DC, 1996;
(b) G. A. Olah, R. Malhotra and S. C. Narang, Nitration: Methods
and Mechanisms, VCH Publishers Inc., New York, 1989;
(c) K. Schofield, Aromatic Nitration, Cambridge University Press,
London, 1980.
2 H. Suzuki, S. Yonezawa, N. Nonoyama and T. Mori, J. Chem. Soc.,
Perkin Trans. 1, 1996, 2385.
3 (a) K. Smith, S. Almeer and C. Peters, Chem. Commun., 2001, 2748;
(b) K. Smith, S. Almeer and S. J. Black, Chem. Commun., 2000,
1571; (c) K. Smith, T. Gibbins, R. W. Millar and R. P. Claridge,
J. Chem. Soc., Perkin Trans. 1, 2000, 2753.
2,5-Dimethyl-6-nitrobenzonitrile (27). Mp 76–77 ЊC (lit.34a
85 ЊC); νmax(KBr)/cmϪ1 2234 (CN), 1528 (NO2), 1356 (NO2);
δH (CDCl3) 7.45 (d, 1H, J = 8.3), 7.41 (d, 1H, J = 8.3), 2.60 (s,
3H), 2.41 (s, 3H).
2,5-Dimethyl-4-nitrobenzonitrile (28). Mp 117–118 ЊC;34b
νmax(KBr)/cmϪ1 2235(CN), 1531 (NO2), 1358 (NO2); δH (CDCl3)
7.87 (s, 1H), 7.60 (s, 1H), 2.60 (s, 3H), 2.57 (s, 3H).
2,5-Dimethyl-3-nitrobenzonitrile (29). Mp 117–118 ЊC
(Found: C, 60.96; H, 4.89; N, 15.71. C9H8N2O2 requires C,
61.36; H, 4.58; N, 15.90%); νmax(KBr)/cmϪ1 2235 (CN), 1533
(NO2), 1350 (NO2); δH (CDCl3) 7.92 (s, 1H,), 7.67 (s, 1H), 2.72
(s, 3H), 2.49 (s, 3H).
4 X. Peng and H. Suzuki, Org. Lett., 2001, 3, 3431.
5 E. R. Ward and J. G. Hawkins, J. Chem. Soc., 1954, 2975.
6 E. R. Ward, C. D. Johnson and L. A. Day, J. Chem. Soc., 1959,
487.
7 H. E. Fierz-David and R. Sponagel, Helv. Chem. Acta, 1943, 26, 98.
8 H. H. Hodgson and J. S. Whitehurst, J. Chem. Soc., 1945, 202.
9 An early claim10 that the reaction of naphthalene with excess NO2–
BF3 in nitromethane at 0 ЊC led to a 5 : 3 mixture of 2 and 3 was later
rectified; E. R. Ward and C. D. Johnson, J. Chem. Soc., 1961, 4314.
10 G. B. Bachman, H. Feuer, B. R. Bleustein and C. M. Vogt, J. Am.
Chem. Soc., 1955, 77, 6188.
11 N. Donaldson, The Chemistry and Technology of Naphthalene
Compounds; Edward Arnold, London, 1958, p. 151.
12 B. Gigante, A. O. Prezeres, M. J. Marcelo-Curto, A. Cornelis and
P. Laszlo, J. Org. Chem., 1995, 60, 3449.
13 (a) For a survey of the Kyodai-nitration, see: N. Nonoyama, T. Mori
and H. Suzuki, Zh. Org. Khim., 1998, 34, 1591 (Russ. J. Org. Chem.,
1998, 34, 1521); (b) T. Suzuki and R. Noyori, Chemtracts, 1997, 10,
813; (c) T. Mori and H. Suzuki, Synlett, 1995, 383.
14 (a) A. S. Paraskar, H. S. Jagtap and A. Sudalai, J. Chem. Res. (S),
2000, 39; (b) M. Makosza, W. Danikiewicz and K. Wojciechowski,
Liebigs Ann. Chem., 1987, 711.
15 (a) A. Rosowsky, R. A. Forsch, A. Null and R. G. Moran, J. Med.
Chem., 1999, 42, 3510; (b) D. L. Boger, M. J. Kochanny and
H. Cai et al., Bioorg. Med. Chem., 1998, 6, 643; (c) P. V. Divekar
and L. C. Vining, Can. J. Chem., 1964, 42, 63.
16 (a) E. S. Adams and K. L. Rinehart, J. Antibiot., 1994, 47, 1456;
(b) T. H. Fischer, S. M. Dershem and M. L. Prewitt, J. Org. Chem.,
1990, 55, 1040; (c) M. H. Gelb and R. H. Abeles, J. Med. Chem.,
1986, 29, 585.
17 (a) A. J. Bloom, M. Fleischmann and J. M. Mellor, Electrochim.
Acta, 1978, 32, 785; (b) S. J. Kuhn and G. A. Olah, J. Am. Chem.
Soc., 1961, 83, 4564.
18 I. I. Schuster, Magn. Reson. Chem., 1996, 34, 301.
19 H. Suzuki, J. Tomaru and T. Mori, J. Chem. Soc., Perkin Trans. 1,
1994, 2413.
20 (a) I. A. McCulloch, Macromolecules, 1994, 27, 1697; (b) C. Blooms-
field, R. B. Moodie and K. Schofield, J. Chem. Soc., Perkin Trans. 2,
1983, 1003; (c) W. O. Kermack, J. Chem. Soc., 1924, 125, 2285.
21 L. Chardonnens and W. J. Kramer, J. Am. Chem. Soc., 1957, 79,
4955.
22 R. D. George and A. W. Snow, J. Heterocycl. Chem., 1995, 32, 495.
23 J. G. Young and W. Onyebuagu, J. Org. Chem., 1990, 55, 2155.
24 J. Griffiths and B. Roozpeikar, J. Chem. Soc., Perkin Trans. 1, 1976,
42.
25 L. Friedman and H. Schechter, J. Org. Chem., 1961, 26, 2522.
26 Detailed information is available from Dr Masao Nakano, Research
Institute, TOSOH Corporation, Ltd., 4560 Kaisei-cho, Shinnanyo
746–8501, Japan.
27 Elseviers Encyclopedia of Organic Chemistry, vol. 12B, Elsevier,
Amsterdam, 1953, 4164, taken from ref. 14b.
Kyodai-nitration of benzenedicarbonitriles. Typical procedure.
Benzene-1,3-dicarbonitrile 33 (60 mg, 0.5 mmol), liquid NO2
(3.0 mL, 90 mmol), methanesulfonic acid (52 mg), FeCl3
(26 mg), and acetonitrile (30 mL) were placed in a two-necked
flask fitted with an inlet tube and a vent which permits waste
gas to escape. The mixture was cooled to Ϫ10 ЊC in an ice–salt
bath, while a stream of ozonized oxygen was introduced under
vigorous stirring through the gas inlet tube, which should dip
just below the surface of the liquid in the flask. The progress of
reaction was intermittently monitored by TLC. After 4 h, the
cooling bath was removed, and the mixture was further stirred
for 24 h at room temperature. Then, dry air was bubbled into
the mixture to expel and recover unchanged nitrogen dioxide by
cold trap. The mixture was evaporated under reduced pressure
to leave a solid residue, which was extracted three times with
dichloromethane. The combined extracts were washed with
brine, dried, and evaporated. Chromatography of the resulting
solid on silica gel using hexane–EtOAc as the solvent, followed
by recrystallization from ethanol gave 5-nitrobenzene-1,3-di-
carbonitrile 34 as colourless needles (35 mg, 41%). Unchanged
dinitrile 33 was recovered in 55% yield.
3-Nitrobenzene-1,2-dicarbonitrile (31). Mp 165–166 ЊC (lit.
14135 and 160 ЊC22); νmax(KBr)/cmϪ1 2240 (CN), 1541 (NO2),
1354 (NO2); δH (CDCl3) 8.57 (dd, 1H, J = 4.4, 1.2), 8.15 (dd, 1H,
J = 8.0, 0.8), 7.99 (t, 1H, J = 8.4); m/z 173 (84), 143 (84), 127
(68), 116 (49), 101 (51), 100 (100).
4-Nitrobenzene-1,2-dicarbonitrile (32). Mp 145–146 ЊC (lit.23
141 ЊC); νmax(KBr)/cmϪ1 2240 (CN), 1535 (NO2), 1356 (NO2);
δH (CDCl3) 8.69 (dd, 1H, J = 0.4, 2.0), 8.59 (dd, 1H, J = 8.4,
2.0), 8.07 (dd, 1H, J = 0.4, 8.4); m/z 173 (65), 127 (100), 101 (12).
5-Nitrobenzene-1,3-dicarbonitrile (34). Mp 214–215 ЊC (lit.
209–21036a and 204–205 ЊC36b); νmax(KBr)/cmϪ1 2245 (CN),
1543 (NO2), 1385, 1354 (NO2); δH (CDCl3) 8.75 (d, 2H, J = 1.5),
8.27 (t, 1H, J = 1.5); m/z 173 (64), 128 (11), 127 (100), 101 (10),
100 (77).
2-Nitrobenzene-1,4-dicarbonitrile (36). Mp 124–125 ЊC
(Found: C, 55.59; H, 2.16; N, 24.33. C9H8N2O2 requires C,
55.50; H, 1.75; N, 24.27%); νmax(KBr)/cmϪ1 2240 (CN), 1543
(NO2), 1356 (NO2); δH (CDCl3) 8.63 (d, 1H, J = 1.2), 8.10 (m,
2H); m/z 173 (53), 127 (74), 100 (100).
28 (a) G. S. Ponticello and J. J. Baldwin, J. Org. Chem., 1979, 44, 4003;
(b) E. Sorkin, W. Kraehenbuehl and H. Erlenmeyer, Helv. Chim.
Acta, 1948, 31, 65.
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 2 3 2 6 – 2 3 3 5
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