4418 J . Org. Chem., Vol. 67, No. 13, 2002
Heller et al.
Alternatively, acetylene may simply be bubbled through the
solution. The mixture was irradiated by two 460 W lamps
(∼420 nm) for 4 h. The reaction was quenched by switching
off the lamps and simultaneously introducing air. The obtained
reaction mixture was filtered; the solvent was removed, and
the residue was either distilled under vacuum (boiling point
of the desired pyridine: 60-62 °C at 10-2 mbar) or chromato-
graphed on silica gel (5:1 toluene/ethyl acetate) to give 8.6 g
(44.5 mmol) of pure 2-(2,2-diethoxy-ethyl)-pyridine (yield 87%;
GLC result from crude product, 89%).
Rea ction w ith Solid Nitr ile a n d Alk yn e Com p ou n d s.
The same procedure was employed using solid nitriles and/or
alkynes. The nitrile (and/or alkyne) was dissolved in 10 mL of
an organic solvent like toluene or hexane.
Rea ction in Liqu id Nitr ile (With ou t Ad d ition a l Sol-
ven t). The same procedure was employed working without
additional solvent.
PY 120.7, 123.0, 135.5, 148.7, 158.9; MS m/z 234 (M+ - H, 1),
178 (2), 164 (2), 136 (2), 122 (100), 106 (21), 93 (22). Anal. Calcd
for C15H25NO (235.37): C, 76.55; H, 10.71; N, 5.95. Found: C,
76.53; H, 11.00; N, 5.96.
2-(2-Non yloxy-eth yl)-p yr id in e: yield 78%; 1H NMR (400
MHz, CDCl3) δ 0.80 (t, 3H, J ) 6.9 Hz, CH3), 1.17 (m, 12H, 6
× CH2), 1.46 (m, 2H, CH2), 2.98 (t, 2H, J ) 6.8 Hz, CH2), 3.35
(t, 2H, J ) 6.6 Hz, CH2O), 3.71 (t, 2H, J ) 6.9 Hz, CH2O), PY
7.02 (t, 1H, J ) 6.2 Hz), 7.12 (d, 1H, J ) 7.9 Hz), 7.45 (t, 1H,
J ) 7.7 Hz), 8.45 (d, 1H, J ) 4.9 Hz); 13C NMR (400 MHz,
CDCl3) δ 13.9, 22.5, 26.0, 29.1, 29.3, 29.4, 29.5, 31.7, 38.6, 69.9,
70.9, PY 121.0, 123.4, 136.0, 149.1, 159.2; MS m/z 250 (M+
+
H, 4), 248 (7), 136 (2), 122 (100), 106 (26), 93 (18). Anal. Calcd
for C16H27NO (249.39): C, 77.06; H, 10.91; N, 5.62. Found: C,
77.06; H, 10.92; N, 5.61.
Exa m p les.
2-(2-P r op oxy-eth yl)-p yr id in e: yield 77%; 1H NMR (400
MHz, CDCl3) δ 0.67 (t, 3H, J ) 7.4 Hz, CH3), 1.36 (m, 2H,
CH2), 2.87 (t, 2H, J ) 6.8 Hz, CH2), 3.19 (t, 2H, J ) 6.6 Hz,
CH2O), 3.60 (t, 2H, J ) 6.8 Hz, CH2O), PY 6.89 (t, 1H, J ) 6.2
Hz), 7.00 (d, 1H, J ) 7.7 Hz), 7.36 (t, 1H, J ) 7.6 Hz), 8.32 (d,
1H, J ) 5.0 Hz); 13C NMR (400 MHz, CDCl3) δ 10.1, 22.5, 38.4,
69.6, 72.2, PY 120.8, 123.1, 135.7, 148.8, 159.0; MS m/z 164
(M+ - H, 1), 150 (1), 136 (2), 122 (100), 106 (27), 93 (41). Anal.
Calcd for C10H15NO (165.23): C, 72.69; H, 9.15, N, 8.48.
Found: C, 72.67; H, 9.10; N, 8.47.
2-(2-Cycloh exyloxy-eth yl)-p yr id in e: yield 70%; 1H NMR
(400 MHz, CDCl3) δ 1.05-1.25 (m, 5H, 5 × CH2 a), 1.44 (m,
1H, CH2 e), 1.61 (m, 2H, 2 × CH2 e), 1.78 (m, 2H, 2 × CH2 e),
2.98 (t, 2H, J ) 6.9 Hz, CH2), 3.17 (m, 1H, CHO), 3.75 (t, 2H,
J ) 6.9 Hz, CH2O), PY 7.03 (t, 1H, J ) 6.1 Hz), 7.15 (d, 1H, J
) 7.7 Hz), 7.51 (t, 1H, J ) 7.6 Hz), 8.45 (d, 1H, J ) 4.6 Hz);
13C NMR (400 MHz, CDCl3) δ 23.9 (2C), 25.7, 32.1 (2C), 39.1,
67.1, 77.4, PY 121.0, 123,5, 136.0, 149.0, 159.4; MS m/z 204
(M+ - H, 1), 122 (100), 106 (39), 93 (34). Anal. Calcd for C13H19
-
NO (205.30): C, 76.06; H, 9.33; N, 6.82. Found: C, 76.07; H,
9.39; N, 6.88.
2-(2-Bu toxy-eth yl)-p yr id in e: yield 75%; 1H NMR (400
MHz, CDCl3) δ 0.77 (t, 3H, J ) 7.4 Hz, CH3), 1.21 (m, 2H,
CH2), 1.42 (m, 2H, CH2), 2.95 (s, 2H, J ) 6.8 Hz, CH2), 3.33 (t,
2H, J ) 6.5 Hz, CH2O), 3.68 (t, 2H, J ) 6.9 Hz, CH2O), PY
6.99 (t, 1H, J ) 6.2 Hz), 7.10 (d, 1H, J ) 8.0 Hz), 7.46 (t, 1H,
J ) 7.7 Hz), 8.42 (d, 1H, J ) 4.9 Hz); 13C NMR (400 MHz,
CDCl3) δ 13.7, 19.1, 31.5, 38.5, 69.8, 70.5, PY 121.0, 123.3,
135.9, 149.0, 159.2; MS m/z 180 (M+ + H, 1), 164 (2), 150 (1),
136 (2), 122 (100), 106 (21), 93 (22). Anal. Calcd for C11H17NO
(179.26): C, 73.70; H, 9.56; N, 7.81. Found: C, 73.71; H, 9.50;
N, 7.83.
ter t-Bu tyl-(p yr id in -2-yl)-a ceta te: yield 81%; 1H NMR
(400 MHz, CDCl3) δ 1.42 (s, 9H, 3 × CH3), 3.74 (s, 2H, CH2-
CdO), PY 7.15 (t, 1H, J ) 7.2 Hz), 7.25 (d, 1H, J ) 7.7 Hz),
7.62 (t, 1H, J ) 7.7 Hz), 8.53 (d, 1H, J ) 4.9 Hz); 13C NMR
(400 MHz, CDCl3) δ 28.0 (3C), 45.1, 81.1, 169.9, PY 121.8,
123.7, 136.4, 149.4, 154.9; MS m/z 193 (2), 138 (4), 120 (17),
92 (22), 57 (100). Anal. Calcd for C11H15NO2 (193.24): C, 68.37;
H, 7.82; N, 7.25. Found: C, 68.10; H, 7.95; N, 7.26.
2-(2,2-Dieth oxy-eth yl)-p yr id in e: yield 85%; 1H NMR (400
MHz, CDCl3) δ 0.85 (t, 6H, J ) 7.1 Hz, 2 × CH3), 2.82 (d, 2H,
J ) 5.8 Hz, CH2), 3.14-3.25 (m, 2H, CH2O), 3.36-3.46 (m,
2H, CH2O), 4.64 (t, 1H, J ) 5.8 Hz, CH), PY 6.82 (t, 1H, J )
6.2 Hz), 6.94 (d, 1H, J ) 7.8 Hz), 7.29 (t, 1H, J ) 7.7 Hz), 8.25
(d, 1H, J ) 4.4 Hz); 13C NMR 14.9 (2C), 43.1, 61.7 (2C), 102.6,
PY 121.1, 124.0, 135.8, 148.8, 157.4; MS m/z 195 (M+, 1), 166
(14), 150 (40), 122 (46), 103 (100). Anal. Calcd for C11H17NO2
(195.26): C, 67.66; H, 8.78; N, 7.17. Found: C, 67.81; H, 8.99;
N, 6.81.
2-(2-Hep tyloxy-eth yl)-p yr id in e: yield 77%; 1H NMR (400
MHz, CDCl3) δ 0.82 (t, 3H, J ) 6.9 Hz, CH3), 1.21 (m, 8H, 4 ×
CH2), 1.49 (m, 2H, CH2), 3.01 (t, 2H, J ) 6.9 Hz, CH2), 3.38 (t,
2H, J ) 6.6 Hz, CH2O), 3.74 (t, 2H, J ) 6.8 Hz, CH2O), PY
7.06 (t, 1H, J ) 6.1 Hz), 7.16 (d, 1H, J ) 7.9 Hz), 7.53 (t, 1H,
J ) 7.6 Hz), 8.48 (d, 1H, J ) 4.9 Hz); 13C NMR (400 MHz,
CDCl3) δ 14.0, 22.5, 26.0, 29.0, 29.5, 31.7, 38.7, 69.9, 71.0, PY
121.1, 123.5, 136.1, 149.1, 159.3; MS m/z 221 (M+, 2), 206 (2),
164 (2), 136 (3), 122 (100), 106 (35), 93 (36). Anal. Calcd for
C
14H23NO (221.34): C, 75.97; H, 10.47; N, 6.33. Found: C,
76.01; H, 10.62; N, 6.47.
2-(3,3-Dieth oxy-p r op yl)-p yr id in e: yield 81%; 1H NMR
(400 MHz, CDCl3) δ 1.11 (t, 6H, J ) 7.1 Hz, 2 × CH3), 1.96-
2.01 (m, 2H, CH2), 2.78 (t, 2H, J ) 7.9 Hz, CH2), 3.37-3.61
(m, 4H, 2 × CH2O), 4.44 (t, 1H, J ) 5.7 Hz, CH), PY 7.00 (t,
J ) 6.1 Hz), 7.06 (d, J ) 7.7 Hz), 7.48 (t, J ) 7.7 Hz), 8.43 (d,
J ) 4.5 Hz); 13C NMR (400 MHz, CDCl3) δ 15.2 (2C), 33.2,
33.3, 61.0 (2C), 102.2, PY 120.8, 122.6, 136.1, 149.1, 161.4; MS
m/z 209 (M+, 1), 180 (16), 164 (74), 136 (37), 118 (57), 103 (100),
1
2-(2-Octyloxy-eth yl)-p yr id in e: yield 80%; H NMR (400
MHz, CDCl3) δ 0.65 (t, 3H, J ) 6.8 Hz, CH3), 1.03 (m, 10H, 5
× CH2), 1.31 (m, 2H, CH2), 2.83 (t, 2H, J ) 6.8 Hz, CH2), 3.19
(t, 2H, J ) 6.6 Hz, CH2O), 3.56 (t, 2H, J ) 6.8 Hz, CH2O), PY
6.84 (t, 1H, J ) 6.2 Hz), 6.97 (d, 1H, J ) 7.9 Hz), 7.32 (t, 1H,
J ) 7.6 Hz), 8.28 (d, 1H, J ) 4.4 Hz); 13C NMR (400 MHz,
CDCl3) δ 13.6, 22.2, 25.7, 28.8, 28.9, 29.2, 31.4, 38.3, 69.5, 70.5,