2218
M. Okimoto, Y. Takahashi
PAPER
3-Isopropyl-1,1,2,2-tetramethoxycarbonylcyclopropane (6c)
13C NMR (CDCl3): = 32.62 (CH), 44.10 (C), 53.06 (CH3), 53.59
(CH3), 110.56 (CH), 110.68 (CH), 142.40 (CH), 144.36 (C), 163.94
(C=O), 166.18 (C=O).
Bp 164–166 °C/5 Torr; mp 61–63 °C (Lit.5 bp 120 °C/0.03).
3-Phenyl-1,1,2,2-tetramethoxycarbonylcyclopropane (6d)
MS (EI): m/z (%) = 340 (M+, 31), 281 (100), 249 (90), 221 (56), 193
(37), 111 (65).
Mp 83–85 °C (Lit.5 mp 85–86 °C).
3-(4-Methoxyphenyl)-1,1,2,2-tetramethoxycarbonylcyclopro-
pane (6e)
Mp 103–106 °C.
1,1,2,2-Tetramethoxycarbonylcyclobutane (6j)
Mp 82–84 °C (Lit.5 mp 82–83 °C).
IR (KBr): 1745, 1732, 1275, 1260, 1235 cm–1.
1H NMR (CDCl3): = 3.68 (s, 6 H), 3.72 (s, 1 H), 3.77 (s, 3 H), 3.82
1,1,2,2-Tetramethoxycarbonylcyclopentane (6k)
Bp 155–157 °C/3Torr (Lit.5 bp not reported).
(s, 6 H), 6.81, 7.35 (2 d, 4 H, J = 8 Hz).
1,4-Diiodo-1,1,4,4-tetramethoxycarbonylbutane (7j)
Mp 138–140 °C.
IR (KBr): 2955, 1742, 1435, 1246, 1200 cm–1.
1H NMR (CDCl3): = 2.29 (s, 4 H), 3.82 (s, 12 H).
13C NMR (CDCl3): = 38.48 (CH2), 41.25 (C), 54.08 (CH3), 168.18
(C=O).
13C NMR (CDCl3): = 39.78 (CH), 45.00 (C), 52.82 (CH3), 53.47
(CH3), 55.18 (CH3), 113.45 (CH), 122.65 (C), 130.96 (CH), 159.10
(C), 164.72 (C=O), 167.04 (C=O).
MS (EI): m/z (%) = 380 (M+, 13), 321 (47), 320 (41), 261 (100), 233
(45), 151 (51).
3-(4-Chlorophenyl)-1,1,2,2-tetramethoxycarbonylcyclopro-
pane (6f)
MS (EI): m/z (%) = 256 (66), 223 (63), 184 (22), 112 (68), 59 (72).
Mp 92–94 °C.
IR (KBr): 1747, 1732, 1275, 1260, 1235 cm–1.
1,7-Dibromo-1,1,7,7-tetramethoxycarbonylheptane (7l)
Mp 82–83 °C.
1H NMR (CDCl3): = 3.68 (s, 6 H), 3.73 (s, 1 H), 3.82 (s, 6 H), 7.24,
IR (KBr): 2955, 1749, 1437, 1262, 1240 cm–1.
7.40 (2 d, 4 H, J = 9 Hz).
1H NMR (CDCl3): = 1.3–1.5 (br, 6 H), 2.1–2.4 (br, 4 H), 3.82 (s,
12 H).
13C NMR (CDCl3): = 25.00 (CH2), 28.63 (CH2), 38.12 (CH2),
53.03 (CH3), 62.55 (C), 167.36 (C=O).
13C NMR (CDCl3): = 39.42 (CH), 44.87 (C), 52.94 (CH3), 53.59
(CH3), 128.15 (CH), 129.45 (C), 131.24 (H), 133.65 (C), 164.55
(C=O), 166.75 (C=O).
MS (EI): m/z (%) = 384 (M+, 3), 327 (33), 325 (100), 265 (31), 237
(45), 155 (32).
MS (EI): m/z (%) = 235 (32), 210 (38), 145 (46), 113 (86), 59 (100)
31 (73).
3-(4-Nitrophenyl)-1,1,2,2-tetramethoxycarbonylcyclopropane
(6g)
Mp 133–135 °C.
IR (KBr): 1759, 1743, 1354, 1267, 1234 cm–1.
1H NMR (CDCl3): = 3.70 (s, 6 H), 3.82 (s, 1 H), 3.86 (s, 6 H), 7.66,
8.16 (2d, 4 H, J = 9 Hz).
13C NMR (CDCl3): = 39.21 (CH), 44.92 (C), 53.18 (CH3), 53.79
(CH3), 123.10 (CH), 130.96 (CH), 138.53 (C), 147.41 (C), 164.43
(C=O), 166.39 (C=O).
1,8-Dichloro-1,1,8,8-tetramethoxycarbonyloctane (7m)
Mp 88–90 °C.
IR (KBr): 2955, 1753, 1437, 1259, 1159 cm–1.
1H NMR (CDCl3): = 1.1–1.5 (br, 8 H), 2.1–2.2 (br, 4 H), 3.83 (s,
12 H).
13C NMR (CDCl3): = 23.78 (CH2), 28.71 (CH2), 37.54 (CH2),
53.75 (CH3), 70.77 (C), 167.32 (C=O).
MS (EI): m/z (%) = 249 (23), 168 (29), 166 (100), 135 (24), 113
(54), 59 (59).
MS (EI): m/z (%) = 395 (M+, 2), 337 (17), 336 (100), 248 (29), 166
(23), 59 (19).
1,8-Diiodo-1,1,8,8-tetramethoxycarbonyloctane (7n)
Mp 133–135 °C.
IR (KBr): 2955, 1744, 1435, 1246, 1043 cm–1.
3-(2-Pyridyl)-1,1,2,2-tetramethoxycarbonylcyclopropane (6h)
Mp 104–106 °C.
1H NMR (CDCl3): = 1.2–1.5 (br, 8 H), 2.0–2.2 (br, 4 H), 3.8 (s, 12
H).
13C NMR (CDCl3): = 27.49 (CH2), 28.55 (CH2), 40.03 (CH2),
43.82 (C), 53.87 (CH3), 168.67 (C=O).
IR (KBr): 1760, 1735, 1437, 1260, 1245 cm–1.
1H NMR (CDCl3): = 3.70 (s, 6 H), 3.82 (s, 6 H), 3.84 (s, 1 H), 7.1–
7.3 (m, 1 H), 7.5–7.8 (m, 2 H), 8.4–8.5 (m, 1 H).
13C NMR (CDCl3): = 40.11 (CH), 44.30 (C), 52.82 (CH3), 53.51
(CH3), 122.57 (CH), 125.87 (CH), 135.80 (CH), 148.67 (CH),
151.07 (C), 164.67 (C=O), 166.71 (C=O).
MS (EI): m/z (%) = 285 (24), 252 (34), 215 (89), 150 (51), 133 (31),
80 (100).
MS (EI): m/z (%) = 351 (M+, 3), 320(40) 292 (100), 260 (46), 233
(60), 202 (34).
References
(1) (a) Fichter, F.; Ruegg, R. Helv. Chim. Acta 1937, 20, 1578.
(b) Szper, J. Bull. Soc. Chim. Fr. 1932, 51, 653.
(2) (a) Okubo, T.; Tsutusmi, S. Bull. Chem. Soc. Jpn. 1964, 37,
1794. (b) Osa, T.; Ohkatsu, Y.; Tezuka, M. 149th
3-(2-Furyl)-1,1,2,2-tetramethoxycarbonylcyclopropane (6i)
Mp 84–86 °C.
IR (KBr): 1759, 1739, 1337, 1261, 1217 cm–1.
1H NMR (CDCl3): = 3.62 (s, 1 H), 3.73 (s, 6 H), 3.80 (s, 6 H), 6.3–
6.5 (m, 2 H), 7.4 (br s, 1 H).
Electrochemical Society Meeting, Ext. Abst. P.764;
American Chemical Society: Washington D.C., 1976.
(c) White, D. A. J. Electrochem. Soc. 1977, 124, 1177.
(d) Brettle, R.; Parkin, J. G. J. Chem. Soc. C 1967, 1352.
Synthesis 2002, No. 15, 2215–2219 ISSN 0039-7881 © Thieme Stuttgart · New York