PAPER
Facile Synthesis of Alkynyl and Allyl Ketones
2393
1
H NMR (200 MHz, CDCl ): = 2.76 (s, 3 H), 7.28–7.78 (m, 7 H),
Anal. Calcd for C H ClO: C, 66.49; H, 5.02; Cl, 19.63. Found: C,
3
10
9
8
.10–8.20 (m, 2 H).
66.43; H, 5.08; Cl, 19.69.
EIMS: m/z (%) = 77 (100), 120 (60), 215 (32), 220 (22) (M+).
1
-[2-Chloro-3,3,3-trifluoro-(E)-1-propenyl]-2,2-dimethylcyclo-
propyl-3-buten-1-one (3l)
Liquid.
1
-(4-Methoxyphenyl)-2-heptyn-1-one (3g)
Liquid.
IR (KBr): 731, 767, 805, 954, 1052, 1137, 1291, 1382, 1407, 1656,
IR (KBr): 1257, 1314, 1457, 1510, 1601, 1643, 2201, 2867, 2957
cm .
1H NMR (200 MHz, CDCl3): = 0.98 (t, 3 H, J = 6.8 Hz), 1.5 (m,
–
1
–
1
1697, 1742, 2962, 3081 cm .
1H NMR (200 MHz, CDCl
): = 1.25 (s, 6 H), 1.90 (d, 1 H, J = 6.8
Hz), 2.25 (m, 1 H), 3.25 (d, 2 H, J = 6.7 Hz), 5.05–5.18 (m, 2 H),
.75–5.90 (m, 1 H), 6.92–7.05 (m, 1 H).
3
2
6
H), 1.7 (q, 2 H, J = 6.0 Hz), 2.48 (t, 2 H, J = 7.2 Hz), 3.90 (s, 3 H),
.92 (d, 2 H, J = 8.2Hz), 8.6 (d, 2 H, J = 8.2 Hz).
5
EIMS: m/z (%) = 41 (100), 68 (35), 137 (40), 192 (15), 225 (20),
266 (M ) (6).
EIMS: m/z (%) = 41 (100), 135 (40), 186 (32), 211 (24), 216 (16)
+
+
(
M ).
Anal. Calcd for C H ClF O: C, 54.04; H, 5.29; Cl, 13.29; F, 21.37.
1
2
14
3
1
-Phenyl-3-buten-1-one (3h)
Found: C, 54.10; H, 5.35; Cl, 13.37; F, 21.46.
Liquid.
1
-Octen-4-one (3m)
IR (KBr): 693, 759, 1220, 1296, 1446, 1624, 1672, 2934, 2972,
–
1
Liquid.
3
060 cm .
1H NMR (200 MHz, CDCl3): = 3.75 (d, 2 H, J = 6.5 Hz), 5.15–
.25 (m, 2 H), 6.0–6.2 (m, 1 H), 7.41–7.61 (m, 3 H), 7.90 (d, 2 H,
–
1
IR (KBr): 970, 1280, 1375,1462, 1640, 1886, 2850, 2920 cm .
5
1H NMR (200 MHz, CDCl3): = 0.9 (t, 3 H, J = 6.8 Hz), 1.24 (m,
2 H), 1.50 (m, 2 H), 2.35 (t, 2 H, J = 6.8 Hz), 3.12 (d, 2 H, J = 6.5
Hz), 5.02–5.16 (m, 2 H), 5.8–5.97 (m, 1 H).
J = 8.0 Hz).
13C NMR (50 MHz, proton decoupled, CDCl3): = 43.5, 118.8,
1
28.4, 131.2, 133.3, 136.7, 198.1.
EIMS: m/z (%) = 41(80), 57 (100), 85 (90), 111 (12), 126 (8) (M+).
EIMS: m/z (%) = 39 (55), 51 (50), 77 (90), 105 (100), 131 (10), 146
Anal. Calcd for C H O: C, 76.14; H, 11.18. Found: C, 76.21; H,
11.26.
8
14
+
(
25) (M ).
1
-(4-Methoxyphenyl)-3-buten-1-one (3i)
1-Heptadecen-4-one (3n)
Liquid.
Liquid.
–
1
IR (KBr): 664, 772, 922, 1031, 1260, 1421, 1575, 1601, 1677, 2841,
IR (KBr): 970,1288, 1375, 1462, 1634, 1876, 2854, 2925 cm .
–
1
2
966, 3078 cm .
1H NMR (200 MHz, CDCl3): = 0.9 (t, 3 H, J = 6.5 Hz), 1.24 (m,
20 H), 1.55 (m, 2 H), 2.38 (t, 2 H, J = 6.8 Hz), 3.10 (d, 2 H, J = 6.5
Hz), 5.02–5.16 (m, 2 H), 5.8–5.97 (m, 1 H).
1
H NMR (200 MHz, CDCl ): = 3.70 (d, 2 H, J = 6.5 Hz), 3.9 (s, 3
3
H), 5.10–5.25 (m, 2 H), 5.95–6.18 (m, 1 H), 6.92 (d, 2 H, J = 8.5
Hz), 7.92 (d, 2 H, J = 8.5 Hz).
EIMS: m/z (%) = 41(80), 69 (100), 84 (98), 97 (40), 125 (10),
+
+
EIMS: m/z (%) = 41 (2), 77 (18), 92 (15), 135 (100) (M – 41).
212(4), 237(15),252 (10) (M ), 254 (10).
Anal. Calcd for C H O : C, 74.98; H, 6.86. Found: C, 74.93; H,
Anal. Calcd for C H O (252.439): C, 80.89; H, 12.78. Found: C,
11
12
2
17 32
6
.93.
80.83; H, 12.89.
1
-(3,4-Dimethoxyphenyl)-3-buten-1-one (3j)
Acknowledgement
Liquid.
IR (KBr): 635, 764, 876, 1023, 1159, 1266, 1456, 1591, 1669, 2842,
BVS and MSR thank CSIR, New Delhi for the award of the fel-
lowships.
–
1
2
936, 3080 cm .
1
H NMR (200 MHz, CDCl ): = 3.64 (d, 2 H, J = 6.5 Hz), 3.9 (s, 6
3
H), 5.10–5.18 (m, 2 H), 5.95–6.10 (m, 1 H), 6.80 (d, 1 H, J = 2.0
Hz), 7.45–7.55 (m, 2 H).
References
(
1) (a) Thompson, C. F.; Jamison, T. F.; Jacobsen, E. N. J. Am.
Chem. Soc. 2001, 123, 9974. (b) Li, P.; Fong, W. M.; Chao,
L. C. F.; Fung, S. H. C.; Williams, I. D. J. Org. Chem. 2001,
66, 4087. (c) Adlington, R. M.; Baldwin, J. E.; Pritchard, G.
J.; Spencer, K. C. Tetrahedron Lett. 2000, 41, 575.
EIMS: m/z (%) = 39 (18), 41 (20), 51 (5), 79 (18), 165 (100), 175
+
(
8), 206 (20) (M ).
Anal. Calcd for C H O : C, 69.89; H, 6.84. Found: C, 69.96; H,
12
14
3
6
.91.
(
9
d) Kel’in, A. V.; Gevorgyan, V. J. Org. Chem. 2002, 67,
5. (e) Bagley, M. C.; Dale, J. W.; Bower, J. Chem.
Commun. 2002, 1682.
1
-(4-Chlorophenyl)-3-buten-1-one (3k)
Liquid.
IR (KBr): 693, 757, 831, 966, 1091, 1219, 1295, 1447, 1594, 1623,
(2) (a) Perollier, C.; Sorokin, A. B. Chem. Commun. 2002,
1548. (b) Basak, A.; Bdour, H. M.; Shain, J. C.; Mandal, S.;
Rudra, K. R.; Nag, S. Bioorg. Med. Chem. Lett. 2000, 10,
–
1
1
672, 2969 cm .
1H NMR (200 MHz, CDCl3): = 3.70 (d, 2 H, J = 6.5 Hz), 5.09–
.14 (m, 2 H), 5.95–6.15 (m, 1 H), 7.42 (d, 2 H, J = 8.0 Hz), 7.90
d, 2 H, J = 8.0 Hz).
EIMS: m/z (%) = 41 (100), 77 (25), 111 (2), 139 (3), 141 (2), 149
1321. (c) Baldwin, J. E.; Pritchard, G. J.; Rathmell, R. E. J.
5
(
Chem. Soc., Perkin Trans. 1 2001, 2906.
(3) (a) Davis, R. B.; Scheiber, D. H. J. Am. Chem. Soc. 1956, 78,
1675. (b) Normant, J. F. Synthesis 1972, 63.
+
(
30), 180 (2) (M ).
(c) Yamaguchi, M.; Shibato, K.; Fujuwara, S.; Hirao, I.
Synthesis 1986, 421. (d) Chowdhury, C.; Kundu, N.
Tetrahedron 1999, 55, 7011.
Synthesis 2003, No. 15, 2390–2394 © Thieme Stuttgart · New York