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W. Krasodomski et al. / Tetrahedron 59 (2003) 5677–5683
(d, 1H, J¼7.8 Hz), 8.93 (d, 1H, J¼8.4 Hz); dC (CDCl3)
20.7, 96.4, 116.4, 117.8, 119.6, 124.4, 126.0, 126.7, 127.1,
129.2, 130.0, 130.2, 132.6, 136.4, 137.6, 149.8. Anal. found:
C 82.89, H 5.43, N 11.98%; calcd for C16H12N2: C 82.73, H
5.21, N 12.06% (Table 1).
with malonodinitrile was carried out according to the
general procedure described under Section 4.3. Orange oil,
after chromatography; yield 1.35 g (73%); IR (KBr) nmax
(cm21) 3052, 2979, 2884, 2226, 1634, 1592, 1504, 948, 898,
856, 823, 756; dH (CDCl3) 1.63 (d, 3H, J¼7.1 Hz), 2.02 (s,
3H), 4.62 (q, 1H, J¼7.1 Hz), 7.27 (d, 1H, J¼8.5 Hz), 7.48
(t, 1H, J¼6.8 Hz), 7.51 (t, 1H, J¼6.9 Hz), 7.70 (s, 1H),
7.81–7.84 (m, 3H); dC (CDCl3) 16.6, 18.3, 45.3, 85.4,
111.8, 111.9, 125.1, 125.8, 126.4, 126.6, 127.6, 127.8,
128.8, 132.7, 133.3, 135.9, 184.0. Anal. found: C 82.78, H
5.72, N 11.44%; calcd for C17H14N2: C 82.93, H 5.69, N
11.38%.
4.7.4. 4-Amino-2-methylphenanthrene (12). Elimination
of the nitrile group from 11 was performed as described in
the general procedure under Section 4.5. Light brown
prisms (from ethanol); yield 264 mg (85%); mp 110–
1128C; IR (KBr) nmax (cm21) 3449, 3376, 2935, 2845, 1613,
1599, 1338, 824, 745; dH (CDCl3) 2.45 (s, 3H), 4.34 (s, 2H),
6.82 (s, 1H), 7.16 (s, 1H), 7.49–7.63 (m, 4H), 7.85 (d, 1H,
J¼7.8 Hz), 9.16 (d, 1H, J¼8.4 Hz); dC (CDCl3) 21.2, 117.0,
117.6, 120.3, 125.0, 125.4, 125.9, 127.2, 127.5, 128.7, 130.9,
132.5, 134.6, 136.6, 144.9. Anal. found: C 86.65, H 6.64, N
6.59%; calcd for C15H13N: C 86.92, H 6.32, N 6.76%.
4.8.4. 4-Amino-1,2-dimethylphenanthrene-3-carbo-
nitrile (16). Cyclisation of dinitrile 15 (1.0 g, 4 mmol) to
aminonitrile 16 was carried out as described in Section 4.4.
Pale yellow needles (from ethanol); yield 0.74 g (74%); mp
135–1368C; IR (KBr) nmax (cm21) 3437, 3369, 3049, 2998,
2923, 2195, 1639, 1580, 814, 764, 664; dH (CDCl3) 2.53 (s,
3H), 2.63 (s, 3H), 5.18 (s, 2H), 7.58 (t, 1H, J¼7.0 Hz), 7.63
(t, 1H, J¼7.0 Hz), 7.80 (d, 1H, J¼9.1 Hz), 7.87 (d, 1H,
J¼9.2 Hz), 7.91 (d, 1H, J¼7.7 Hz), 9.09 (d, 1H, J¼8.7 Hz);
dC (CDCl3) 14.9, 19.2, 97.1, 117.2, 118.5, 122.8, 124.9,
126.0, 126.2, 126.8, 128.8, 129.9, 130.2, 132.0, 134.7,
135.3, 147.6. Anal. found: C 83.15, H 5.79, N 11.12%; calcd
for C17H14N2: C 82.93, H 5.69, N 11.38%.
4.7.5. 2-Methylphenanthrene (13). 2-Methylphenanthrene
was obtained from amine 12 according to the general
procedure given under Section 4.6. Yield 75 mg (41%); mp
55–578C (lit.15 mp 56–578C); IR (KBr) n max (cm21) 3046,
3026, 1598, 823, 806, 746; dH (CDCl3) 2.55 (s, 3H), 7.44–
7.50 (m, 1H), 7.53–7.67 (m, 4H), 7.70 (m, 1H), 7.86 (m,
1H) 8.56 (d, 1H, J¼8.4 Hz), 8.64 (d, 1H, J¼8.3 Hz); dC
(CDCl3) 19.9, 120.9, 122.8, 122.9, 126.1, 126.4, 126.5,
126.7, 127.8, 128.5, 130.0, 130.7, 130.8, 131.7, 134.9.
4.8.5. 4-Amino-1,2-dimethylphenanthrene (17). Elimin-
ation of the nitrile function from 0.40 g (1.6 mmol) of
aminonitrile 16 was performed as described in Section 4.5.
Pale yellow prisms after sublimation; yield 0.33 g (92%);
mp 88–908C; IR (KBr) nmax (cm21) 3393, 3325, 3061,
2923, 2860, 1618, 814, 751, 626; dH (CDCl3) 2.44 (s, 3H),
2.54 (s, 3H), 4.24 (s, 2H), 6.85 (s, 1H), 7.51 (t, 1H,
J¼7.9 Hz), 7.57 (t, 1H, J¼6.9 Hz), 7.67 (d, 1H, J¼9.2 Hz),
7.86 (d, 1H, J¼7.7 Hz), 7.91 (d, 1H, J¼9.2 Hz), 9.25 (d, 1H,
J¼8.4 Hz); dC (CDCl3) 14.7, 20.8, 117.7, 117.9, 118.4,
123.3, 123.5, 125.1, 125.7, 126.9, 128.3, 131.2, 131.9,
132.8, 134.7, 142.4. Anal. found: C 86.67, H 6.91, N 6.27%;
calcd for C16H15N: C 86.84, H 6.83, N 6.33%.
4.8. Synthesis of 1,2-dimethylphenanthrene (18) from
1-(2-naphthyl)propan-2-one (9)
4.8.1. General procedure for alkylation of 1-(2-
naphthyl)propan-2-one (9) with methyl or ethyl iodide.
Synthesis of 3-(2-naphthyl)butan-2-one (14) and 3-(2-
naphthyl)pentan-2-one (19). In a 50 ml, three-necked flask
equipped with magnetic stirrer, a dropping funnel and a
thermometer were placed 50% sodium hydroxide solution
(15 ml) and TEBA (0.20 g, 0.90 mmol). The mixture was
preheated to 408C and a solution of 1-(2-naphthyl)propan-2-
one (9) (4.7 g, 25 mmol) in toluene (10 ml) was added. The
mixture was stirred vigorously and methyl or ethyl iodide
(33 mmol) was slowly added in the course of 45 min while
the temperature of the reaction mixture was maintained at
40–458C. After the addition of alkyl iodide had been
complete, the stirring was continued for additional 2 h. The
mixture was diluted with water (100 ml) and the product
was extracted with toluene (3£50 ml). The combined
extracts were dried over anhydrous magnesium sulfate.
Toluene was distilled off and oily ketones were distilled
under reduced pressure.
4.8.6. 1,2-Dimethylphenanthrene (18). Elimination of the
amino group from 270 mg (1.22 mmol) of 17 was carried
out as described in Section 4.6. Yield 130 mg (53%); mp
144–1458C; (lit.23 mp 142–1438C); IR (KBr) nmax (cm21
)
3048, 2997, 2922, 1636, 1575, 808, 745, 682; dH (CDCl3)
2.51 (s, 3H), 2.63 (s, 3H), 7.44 (d, 1H, J¼8.4 Hz), 7.55 (t,
1H, J¼8.0 Hz), 7.60 (t, 1H, J¼7.0 Hz), 7.73 (dd, 1H, J¼9.2,
6.1 Hz), 7.85 (d, 1H, J¼7.3 Hz), 8.01 (d, 1H, J¼8.7 Hz),
8.46 (d, 1H, J¼8.5 Hz), 8.65 (d, 1H, J¼8.3 Hz). dC (CDCl3)
15.1, 21.0, 122.7, 122.9, 126.1, 126.4, 126.6, 128.3, 128.7,
129.1, 130.7, 130.9, 131.1, 132.3, 134.4.
4.8.2. 3-(2-Naphthyl)butan-2-one (14). Colourless oil;
yield 2.98 g (59%); bp 95–1008C/20 Pa; (lit.22 no bp is
given); IR (neat) nmax (cm21) 3052, 2979, 1709, 1634, 1601,
1504, 952, 898, 856, 823, 751; dH (CDCl3) 1.47 (d, 3H,
J¼7.0 Hz), 2.05 (s, 3H), 3.88 (q, 1H, J¼6.9 Hz), 7.30 (d,
1H, J¼8.5 Hz), 7.44 (t, 1H, J¼6.8 Hz), 7.47 (t, 1H,
J¼6.7 Hz), 7.67 (s, 1H), 7.77–7.81 (m, 3H); dC (CDCl3)
17.2, 25.5, 53.7, 125.7, 125.8, 126.2, 126.5, 127.6, 128.6,
132.5, 133.6, 138.0, 208.5.
4.9. Synthesis of 4-amino-1-ethyl-2-methylnaphthalene-
3-carbonitrile (21) from 1-naphthylpropan-2-one (9)
4.9.1. 3-(2-Naphthyl)pentan-2-one (19). Ketone 9 (3.68 g,
20 mmol) was alkylated with ethyl iodide as described in
Section 4.8.1. Light brown oil; yield 1.15 g (30%); bp 105–
1068C/10 Pa; IR (neat) nmax (cm21) 3052, 2958, 1714, 1634,
1597, 1504, 818, 747; dH (CDCl3) 0.86 (t, 3H, J¼7.4 Hz),
1.78–1.84 (m, 2H), 2.07 (s, 3H), 3.70 (t, 1H, J¼7.4 Hz),
7.32 (d, 1H, J¼8.3 Hz), 7.45 (t, 1H, J¼6.8 Hz), 7.48 (t, 1H,
4.8.3. 3-(2-Naphthyl)-2-methylbut-1-ene-1,1-dicarbo-
nitrile (15). Condensation of ketone 14 (1.50 g, 7.5 mmol)