JOURNAL OF CHEMICAL RESEARCH 2011 697
+
1
09.5. HRMS (ESI): m/z [M + Na] calcd for C H BrN 253.9581;
11
6
found: 253.9580. Anal. Calcd for C H BrN: C, 56.93; H, 2.61; Br,
11
6
3
4.43; N, 6.04. Found: C, 56.89; H, 2.58; Br, 34.39; N, 6.10%.
-Iodonaphthalene-1-carbonitrile (3c): Colourless solid, 49%
8
4
−1
yield, m.p. 116–117 °C (lit. 113–115 °C). IR (CHCl , cm ): 3019,
3
1
2
216 (CN), 1497, 1261, 1215, 820, 768. H NMR (300 MHz, CDCl ):
3
δ 8.35 (dd, J = 7.5, 1.2 Hz, 1H), 8.11–8.05 (m, 2H), 7.92 (dd, J = 8.4,
13
1
,4 Hz, 1H), 7.55 (t, J = 7.2 Hz, 1H), 7.25 (t, J = 8.1 Hz, 1H).
C
NMR (75 MHz, CDCl ): δ 143.4, 138.7, 134.9, 134.5, 131.3, 130.2,
3
+
1
28.0, 125.2, 118.8 (CN), 112.4, 92.2. HRMS (ESI): m/z [M + Na]
calcd for C H IN: 301.9443, found 301.9438.
11
6
Naphthalene-1,8-dicarbonitrile (4): Bromide 3b (0.232 g, 1.00 mmol),
DMAC (5 mL), K [Fe(CN) ]·3H O (0.105 g, 0.250 mmol), sodium
4
6
2
carbonate (0.106 g, 1.00 mmol) and Pd(OAc) (0.0033 g, 0.010 mmol)
2
were placed in a 25-mL flask. The flask was evacuated, filled with
nitrogen, and heated at 120 °C for 3 h. Upon completion (TLC), the
mixture was cooled to room temperature and diluted with EtOAc
(
10 mL). The resulting slurry was filtered and the filtrate was washed
with water (2 × 15 mL) and 5% NH in water (10 mL). The organic
3
layer was dried over Na SO and the solvent was removed using a
2
4
rotating evaporator, giving a light yellow solid, which was purified by
column chromatography (silica gel, hexane-EtOAc, 7:3), giving 4
5
(
0.145 g, 81%) as a colourless solid; m.p. 231–232 °C (lit. 232 °C).
−1
1
IR (CHCl , cm ): 2283 (CN), 1586, 1360, 930, 743. H NMR
3
(
7
1
300 MHz, CDCl ) δ 8.20 (d, J = 7.5 Hz, 2H), 8.17 (d, J = 7.5 Hz, 2H),
3
13
.71 (t, J = 7.5 Hz, 2H). C NMR (75 MHz, CDCl ): δ 137.7, 134.4,
3
+
33.2, 126.6, 116.6 (CN), 108.6, 104.8. HRMS (ESI): m/z [M + Na]
calcd for C H N : 201.0429; found: 201.0425.
12
6
2
V.S.N. and D.B thank the Wayland E. Noland Research
Fellowship Fund of the University of Minnesota Foundation
for generous financial support of this project.
Received 11 October 2011; accepted 22 November 2011
Paper 1100925 doi: 10.3184/174751911X13222107572093
Published online: 27 December 2011
Fig. 5 Packing in 8-iodonaphthalene-1-carbonitrile. Top: view
along the a axis. Bottom: view along the b axis. Only one of the
two disordered orientations of the molecules is shown to
improve the clarity.
References
1
2
3
4
G.R. Desiraju and R.L. Harlow, J. Am. Chem. Soc., 1989, 111, 6757.
L. Kalb, Ber. Dtsch. Chem. Ges., 1914, 47, 1724.
P.H. Gore and I.M. Khan, J. Chem. Soc. Perkin Trans. 1, 1979, 2779.
G. Müller, G. Dürner, W.J. Bats and M.W. Göbel, Liebigs Ann. Chem.,
1
40.2, 136.6, 129.9, 126.7, 126.2, 122.5, 119.9, 112.6, 87.3. HRMS
+
(
ESI): m/z [M + Na] calcd for C H IN: 291.9599; found: 291.9594.
10 8
1
994, 1075.
Synthesis of compounds (3); general procedure
5
6
7
8
9
E.F. Bradbrook and R.P. Linstead, J. Chem. Soc., 1936, 1739.
A.J. Boulton and A.U. Rahman, Chem. Commun., 1968, 73.
A.J. Boulton and S.S. Mathur, J. Org. Chem., 1973, 38, 1054.
G. Ege and E. Beisiegel, Synthesis, 1974, 22.
J. Nakayama, T. Segiri, R. Ohya and M.J. Hoshino, Chem. Soc. Chem.
Comm., 1980, 791.
S.J. Chang, Syn. Comm., 1982, 12, 673.
J. Nakayama, E. Ohshima, A. Ishii and M. Hoshino, J. Org. Chem., 1983,
4
A. Cuprous cyanide solution was prepared by adding a solution of
sodium cyanide (0.826 g, 16.80 mmol) in water (6.0 mL) to a stirred
solution of cuprous chloride (0.668 g, 6.75 mmol) in water (10 mL)
at 0 °C.
B. H SO (0.242 mL) was added to a mixture of 2 (4.50 mmol) and
2
4
1
1
0
1
water (5 mL) at 0 °C, and the solution was stirred for 20 min. This
solution was kept at 0 °C while a solution of NaNO2 (0.345 g,
8, 60.
5
.00 mmol) in water (5 mL) was added. The solution turned orange
1
1
2
3
Z. Zhu, N.L. Colbry, M. Lovdahl, K.E. Mennen, A. Acciacca, V.G. Beylin,
J.D. Clark and D.T. Belmont, Org. Process Res. Dev., 2007, 11, 907.
H. Waldmann and S. Back, Justus Liebigs Ann. Chem., 1940, 545, 52.
and gas bubbles were evolved. The cooled cuprous cyanide solution
from part A was added and the mixture was stirred for 2 h at room
temperature and warmed to 50 °C with stirring for 2 h and then cooled
to room temperature. The solution was extracted with ethyl acetate
14 M.J. Perkins, J. Chem. Soc., 1964, 3005.
15 Obtained from the Aldrich Chemical Co., Milwauke, Wisconsin, USA.
16 S.F. Gait, M.E. Peek, C.W. Rees and R.C. Storr, J. Chem. Soc. Perkin Trans
I, 1974, 1248.
(
2 × 20 mL), washed with aqueous 5% NaHCO (20 mL) and dried
3
over Na SO . The solvent was removed using a rotating evaporator,
2
4
1
7
BASF, DE Patent 147852, 1903; Frdl. 1903, 7, 131; A.V. Schulthess,
Thesis, 1944, ETH, Zurich, Switzerland.
M.A. Nielsen, M.K. Nielsen and T. Pittelkow, Org. Process Res. Dev.,
giving a crude product which was purified by column chromatography
silica gel, hexane-EtOAc, 8:2), giving the desired compounds 3.
-Chloronaphthalene-1-carbonitrile (3a): Colourless solid, 56%
(
1
8
8
2
004, 8, 1059.
3
−1
yield, m.p. 144–145 °C (lit. 145 °C). IR (CHCl cm ): 3019, 2222
CN), 1506, 1215, 823, 763. H NMR (75 MHz, CDCl ): δ 8.12–8.06
m, 2H), 7.85 (d, J = 7.2 Hz, 1H), 7.72 (d, J = 7.5 Hz, 1H), 7.62–7.48
m, 2H). C NMR (75 MHz, CDCl ): δ 137.7, 134.9, 134.0, 130.3,
3
19 S.A. Weissman, D. Zewge and C. Chen, J. Org. Chem., 2005, 70, 1508.
20 M. Kuroda, J. Nakayama, M. Hoshino, N. Furusho, T. Kawata and S. Ohba,
Tetrahedron, 1993, 49, 3735.
21 Bruker, SMART and SAINT, 2003, Bruker AXS Inc., Madison, Wisconsin,
USA.
1
(
(
(
3
13
3
1
+
28.7, 128.4, 127.1, 125.4, 119.4 (CN), 108.0. HRMS (ESI): m/z [M
+
22 G.M. Sheldrick, Acta Crystallogr., 2008, A64, 112.
Na] calcd for C H ClN: 210.0086; found: 210.0079.
11 6
2
3
R.C. Haltiwagner, P.T. Reurskens, J.M.J. Vancan and W.S. Veeman,
J. Cryst. Spect. Res., 1984, 14, 589.
H. Bock, M. Sievert and Z. Havlas, Chem. Eur. J., 1998, 4, 677.
8
-Bromonaphthalene-1-carbonitrile (3b): Colourless solid, 53%
−1
yield, m.p. 133–135 °C. IR (CHCl , cm ): 2253 (CN), 1500, 1261,
203, 908, 736. H NMR (300 MHz, CDCl ): δ 8.10 (d, J = 7.8 Hz,
H), 7.96 (d, J = 7.5 Hz, 1H), 7.90 (d, J = 8.1 Hz, 1H), 7.57 (t, J =
.1 Hz, 1H), 7.43 (t, J = 7.8 Hz, 1H). C NMR (75 MHz, CDCl ):
3
2
4
1
1
2
8
3
25 C.C. Steele and R. Adams, J. Am. Chem. Soc., 1930, 52, 4528.
L.F. Fieser and A.M. Seligman, J. Am. Chem. Soc., 1939, 61, 136.
27 R. Scholl, C. Seer and R. Weitzenbock, Ber. Dtsch. Chem. Ges., 1910, 43,
2
6
13
3
δ 138.2, 134.9, 134.6, 134.3, 129.5, 129.1, 127.5, 125.3, 119.3 (CN),
2202.