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Russ.Chem.Bull., Int.Ed., Vol. 56, No. 6, June, 2007
Panteleeva et al.
colorless oil, Rf 0.3 (hexane—Et2O, 6 : 1). IR (thin film), ν/cm–1
:
2227 (C≡N). 1H NMR (acetoneꢀd6), δ: 1.97—2.08 (m,
2 H, CH2); 2.75 (t, 4 H, 2 ArCH2, J = 8 Hz); 7.42 (d,
2 AA´BB´ systems, 4 H, H(2´), H(6´), H(2″), H(6″), J = 8 Hz);
7.68 (d, 2 AA´BB´ systems, 4 H, H(3´), H(5´), H(3″), H(5″),
J = 8 Hz). Highꢀresolution MS, found: m/z 246.1126 [M]+.
2228 (C≡N). 1H NMR (acetoneꢀd6), δ: 2.10—2.25 (m, 2 H,
CH2); 2.86 (t, 2 H, ArCH2, J = 9 Hz); 3.47 (t, 2 H, CH2Br, J =
9 Hz); 7.45 (d, AA´BB´ system, 2 H, H(3), H(5), J = 8 Hz); 7.68
(d, AA´BB´ system, 2 H, H(2), H(6), J = 8 Hz). Highꢀresoluꢀ
tion MS, found: m/z 222.9994 [M]+. C10H10NBr. Calculated:
M = 222.9997. Indane 11 (0.26 mmol) and nitrile 12 (0.24 mmol)
were detected in a fraction with Rf ~0.8. For this fraction,
1H NMR (CDCl3), δ: 2.10 (quint, 2 H, CH2, J = 9 Hz);
2.90—2.97 (m, 4 H, 2 CH2); 7.27 (d, 1 H, H(7), J = 9 Hz); 7.39
(dd, 1 H, H(6), J = 9 Hz, J = 1 Hz); 7.46 (d, 1 H, H(4), J =
1 Hz) (the signals relate to compound 11); 3.34 (d, 2 H, ArCH2,
J = 7 Hz); 5.10 (dd, 1 H, =CH2, J = 16.7 Hz, J = 2.0 Hz); 5.13
(dd, 1 H, =CH2, J = 10.2 Hz, J = 2.0 Hz); 5.93 (ddt, 1 H,
=CH—, J = 16.7 Hz, J = 10.2 Hz, J = 6.6 Hz); 7.28 (d,
AA´BB´ system, 2 H, H(3), H(5), J = 8.4 Hz); 7.56 (d,
AA´BB´ system, 2 H, H(2), H(6), J = 8.4 Hz) (the signals
relate to compound 12). GLCꢀMS revealed two peaks with
m/z 143 ([M]+).
C17H14N2. Calculated: M = 246.1157.
1,5ꢀBis(4ꢀcyanophenyl)pentane (7). A reaction of dianion
12– with 1,5ꢀdibromopentane (see Table 1, entry 14) gave a
mixture of products from which compound 7 (1.030 g, 75%) was
isolated as a white solid, Rf 0.3 (hexane—Et2O, 8 : 1), m.p.
117 °C. IR (KBr), ν/cm–1: 2226 (C≡N). 1H NMR (acetoneꢀd6),
δ: 1.31—1.45 (m, 2 H, CH2); 1.61—1.76 (m, 4 H, 2 CH2); 2.71
(t, 4 H, 2 ArCH2, J = 8 Hz); 7.41 (d, 2 AA´BB´ systems,
4 H, H(2´), H(6´), H(2″), H(6″), J = 8 Hz); 7.66 (d,
2 AA´BB´ systems, 4 H, H(3´), H(5´), H(3″), H(5″), J = 8 Hz).
Highꢀresolution MS, found: m/z 274.1468 [M]+. C19H18N22
.
Calculated: M = 274.1469.
4ꢀ{3ꢀ[4ꢀ(3ꢀBromopropyl)phenyl]propyl}benzonitrile (20).
A reaction of dianion 12– with 1,3ꢀdibromopropane (see Table 1,
entry 6) gave a mixture of products from which compound 20
(0.034 g, 2%) was isolated as a white solid, Rf 0.15 (hexꢀ
ane—Et2O, 9 : 1). IR (KBr), ν/cm–1: 2227 (C≡N). 1H NMR
(acetoneꢀd6), δ: 1.85—2.18 (m, 4 H, 2 CH2); 2.56—2.79 (m,
6 H, 3 ArCH2); 3.45 (t, 2 H, CH2Br, J = 8 Hz); 7.14 (s, 4 H,
H(2´), H(3´), H(5´), H(6´)); 7.41 (d, AA´BB´ system, 2 H,
H(3), H(5), J = 8 Hz); 7.66 (d, AA´BB´ system, 2 H, H(2),
H(6), J = 8 Hz). Highꢀresolution MS, found: m/z 341.0779 [M]+.
4ꢀ(4ꢀBromobutyl)benzonitrile (3) and 2ꢀcyanoꢀ5,6,7,8ꢀtetraꢀ
hydronaphthalene (13). A reaction of radical anion 1•– with
1,4ꢀdibromobutane (see Table 1, entry 2) gave a mixture of
products from which nitrile 3 (0.091 g, 16%) was isolated as a
colorless oil, Rf 0.3 (hexane—Et2O, 6 : 1). IR (thin film), ν/cm–1
:
2227 (C≡N). 1H NMR (acetoneꢀd6), δ: 1.67—1.94 (m, 4 H,
2 CH2); 2.74 (t, 2 H, ArCH2, J = 9 Hz); 3.50 (t, 2 H, CH2Br, J =
9 Hz); 7.43 (d, AA´BB´ system, 2 H, H(3), H(5), J = 8.4 Hz);
7.67 (d, AA´BB´ system, 2 H, H(2), H(6), J = 8.4 Hz). Highꢀ
resolution MS, found: m/z 237.0150 [M]+. C11H12NBr. Calcuꢀ
lated: M = 237.0153. Tetrahydronaphthalene 13 (0.038 g, 10%)
was isolated as a viscous white solid, Rf 0.5 (hexane—Et2O,
6 : 1), m.p. 20 °C (cf. Ref. 38: m.p. 20—21 °C). IR (KBr),
ν/cm–1: 2230 (C≡N). 1H NMR (CDCl3), δ: 1.77—1.82 (m, 4 H,
2 CH2); 2.73—2.80 (m, 4 H, 2 ArCH2); 7.11 (d, 1 H, H(4),
J = 8 Hz); 7.31 (dd, 1 H, H(3), J = 8 Hz, J = 1.5 Hz); 7.32
(d, 1 H, H(1), J = 1.5 Hz). Highꢀresolution MS, found:
m/z 157.0893 [M]+. C11H11N. Calculated: M = 157.0891.
4ꢀ(5ꢀBromopentyl)benzonitrile (4) and 2ꢀ(5ꢀbromopentyl)ꢀ
1,4ꢀdicyanobenzene (14). A reaction of radical anion 1•– with
1,5ꢀdibromopentane (see Table 1, entry 4) gave a mixture of
products from which nitrile 4 (0.121 g, 20%) was isolated as a
C19H20NBr. Calculated: M = 341.0779.
1,4ꢀBis[3ꢀ(4ꢀcyanophenyl)propyl]benzene (22). A reaction of
dianion 12– with 1,3ꢀdibromopropane (see Table 1, entry 6)
gave a mixture of products from which compound 22 (0.145 g,
8%) was isolated as a white solid, Rf 0.4 (hexane—Et2O, 9 : 1),
m.p. 280 °C. Found (%): C, 84.71; H, 6.94; N, 8.32. C26H24N2.
Calculated (%): C, 85.68; H, 6.64; N, 7.69. IR (KBr), ν/cm–1
:
2226 (C≡N). 1H NMR (acetoneꢀd6), δ: 1.68—1.72 (m, 4 H,
2 CH2); 2.27—2.35, 2.98—3.04 (both m, 4 H each, 4 ArCH2);
7.08—7.12 (m, 4 H, H(2), H(3), H(5), H(6)); 7.44 (d,
2 AA´BB´ systems, 4 H, 2 H(2´), 2 H(6´), J = 8 Hz); 7.67 (d,
2 AA´BB´ systems, 4 H, 2 H(3´), 2 H(5´), J = 8 Hz).
Reaction of dianion 12– with 1,4ꢀdibromobutane in THF.
Dinitrile 1 (0.64 g, 5 mmol) was placed in a threeꢀneck flask
fitted with a stirrer, a bubbler, and a gas outlet. Tetrahydrofuran
(50 mL) was distilled under argon to the flask. Ammonia (30 mL)
was condensed with continuous stirring at –70 °C and then
metallic Na (0.24 g, 10.25 mmol) was added. The ammonia was
evaporated in an argon flow (~30 min). 1,4ꢀDibromobutane
(1.2 mL, 10 mmol) was added under argon with continuous
stirring at 10 °C to the resulting dark brown suspension of the
disodium salt of dianion 12– in NH3ꢀsaturated THF. The reacꢀ
tion mixture was stirred in an inert atmosphere for 40 min and
then treated and analyzed as described above. A mixture
of products obtained (2.01 g) mainly contained 1,4ꢀbis(4ꢀ
cyanophenyl)butane (6) (70%) (for the complete composition
of the products, see Table 1, entry 12).
Reaction of dianion 12– with 1,4ꢀdibromobutane under inꢀ
verse quenching. Dinitrile 1 (0.64 g, 5 mmol) was placed in a
twoꢀneck dropping funnel fitted with a pressure equalization
arm, a stirrer, and a gas outlet. Liquid NH3 (50 mL) was conꢀ
densed with continuous stirring at –70 °C into the funnel. Meꢀ
tallic Na (0.24 g, 10.2 mmol) was added with stirring in an
atmosphere of evaporating NH3. The resulting suspension of the
colorless oil, Rf 0.5 (hexane—Et2O, 6 : 1). IR (thin film), ν/cm–1
:
1
2227 (C≡N). H NMR (acetoneꢀd6), δ: 1.38—1.56, 1.58—1.68,
1.81—1.95 (all m, 2 H each, CH2); 2.73 (t, 2 H, ArCH2, J =
8 Hz); 3.48 (t, 2 H, CH2Br, J = 8 Hz); 7.45 (d, AA´BB´ system,
2 H, H(3), H(5), J = 8 Hz); 7.76 (d, AA´BB´ system, 2 H, H(2),
H(6), J = 8 Hz). Highꢀresolution MS, found: m/z 252.1531 [M]+.
C12H14NBr. Calculated: M = 252.1533. Bromopentyldicyanoꢀ
benzene 14 (0.05 mmol) was detected in a fraction with Rf ~0.2
with the starting dinitrile 1 (0.03 mmol). For compound 14,
1H NMR (CDCl3), δ: 1.43—1.59 (m, 2 H, CH2); 1.60—1.78,
1.82—1.97 (both m, 4 H each, 4 CH2); 2.88 (t, 2 H, ArCH2, J =
8 Hz); 3.40 (t, 2 H, CH2Br, J = 7 Hz); 7.55 (dd, 1 H, H(5), J =
8.6 Hz, J = 1.5 Hz); 7.60 (d, 1 H, H(3), J = 1.5 Hz); 7.70 (d,
1 H, H(6), J = 8.6 Hz). GLCꢀMS revealed a peak with
m/z 276 ([M]+).
1,3ꢀBis(4ꢀcyanophenyl)propane (5). A reaction of dianion
12– with 1,3ꢀdibromopropane (see Table 1, entry 5) gave a mixꢀ
ture of products from which compound 5 (0.266 g, 45%) was
isolated as a white solid, Rf 0.2 (hexane—Et2O, 8 : 1), m.p.
94—95 °C (cf. Ref. 25: m.p. 94—95 °C). IR (KBr), ν/cm–1
: