References
- Park , O. S. , Grillasca , Y. , García , G. A. and Maldonado , L. A. 1977 . Synth. Commun. , 7 : 345
- Aldehyde 1 was prepared in about 50% overall yield from diethyl malonate as follows: a: CH2=CH-CN, triton B (diox.); b: H3O+; c: EtOH, H+ (C6H6); d: Na (tol.); e: HOCH2CH2OH, H+ (C6H6); f: LiAlH4 (THF); g: Collins (CH2Cl2). It is a colorless oil: ir (film) v 2700, 1725 and 1100–1030 cm−1; pmr (CCl4, 60 MHz) δ 3.90 (s, OCH 2) and 9.57 (broad s, CH=O)
- Stork , G. , Kraus , G. A. and García , G. A. 1974 . J. Org. Chem. , 39 : 3459 The enolates 2a 2b were prepared from the corresponding methyl ketones according to:. Compound 3a, crystalline solid, mp 55–57[ddot]; ir (KBr) v 3300, 1700 and 1140–920 cm−1; pmr (CCl4, 60 MHz) δ 0.97 (d, J = 6 Hz, (CH 3)2CH), 3.33 (broad signal, OH, disappears with D2O) and 4.00 (s, OCH2 CH 2O). Compound 3b, colorless oil; ir (film) v 3400, 1700 and 1680 (enone s-cis and s-trans conformations), 1620 and 1100–1040 cm−1; pmr (CDCl3, 60 MHz) δ 1.93 and 2.20 (2s, (CH 3)2C=CH), 4.00 (s, OCH2 CH 2O), 5.40 (broad signal, OH, disappears with D2O) and 6.13 (broad s, C=CH-C=O)
- Compound 4a, colorless oil; uv (EtOH) γmax 228 nm (ε 10000); ir (film) v 1690 and 1655 (enone s-cis and s-trans conformations), 1620 and 1130–920 cm−1 pmr (CCl4, 60 MHz) δ 0.90 (d, J = 6 Hz, (CH 3)2CH), 3.93 (s, OCH 2 CH 2O), 6.00 (d, J = 16 Hz, CH-CH=CH-CO) and 6.70 (dd, J1 = 16 Hz, J2 = 6 Hz, CH-CH[dbnd]CH-C[dbnd]O); ms (70 eV, rel. intensity) z/e 252 (4%), 169 (2%), 99 (92%) and 28 (100%). Compound 4b, pale yellow oil; uv (EtOH) γmax 260 nm (ε 12800); ir (film) v 1675, 1650, 1620, 1600 and 1100–1030 cm−1; pmr (CCl4, 60 MHz) δ 1.97 and 2.15 (2s, (CH 3)2C[dbnd]CH), 3.95 (s, OCH 2 CH 2O), 6.07 (d, J = 16 Hz, CH-CH[dbnd]CH-C[dbnd]O), 6.22 (broad s, (CH3)2C[dbnd]CH-C[dbnd]O) and 6.73 (dd, J1 = 16 Hz, J2 = 6 Hz, CH-CH[dbnd]CH-C[dbnd]O); ms (70 eV, rel. intensity) z/e 250 (2%), 206 (1%), 167 (2%), 99 (100%), 88 (45%) and 28 (85%)
- Compound 5a, colorless oil; ir (film) v 1710 and 1100–920 cm−1; pmr (CCl4, 60 MHz) δ 0.86 (d, J = 6 Hz, CH3-CH), 0.92 (d, J = 6 Hz, (CH 3)2CH) and 3.90 (s, OCH 2 CH 2O); ms (70 eV, rel. intensity) z/e 268 (8%), 183 (8%), 99 (100%), 86 (11%) and 69 (6%). Compound 5b, colorless oil; uv (EtOH) γmax 237 nm (ε 11400); ir (film) v 1695, 1630 and 1100–1030 cm−1; pmr (CCl4, 60 MHz) δ 0.83 (d, J = 6 Hz, CH 3-CH), 1.83 and 2.09 (2s, (CH 3)2C[dbnd]CH), 3.80 (s, OCH 2 CH 2O) and 5.87 (broad s, C[dbnd]CH-C[dbnd]O)
- Birch , A. J. , Macdonald , P. L. and Powell , V. H. 1970 . J. Chem. Soc. , : 1469 . Compound 6a, colorless oil; ir (film) v 1710 cm−1 pmr (CCl4, 60 MHz) δ 0.89 (d, J = 6 Hz, CH3-CH) and 0.91 (d, J = 6 Hz, (CH3)2CH); ms (70 eV, rel. intensity) z/e 224 (6%), 127 (24%), 125 (56%), 85 (51%), 57 (100%), 55 (62%), 43 (52%) and 28 (79%)
- Compound 6b, colorless oil; uv (EtOH) γmax 238 nm (ε 10900); ir (film) v 1710, 1690 and 1620 cm−1 pmr (CCl4, 60 MHz) δ 0.85 (d, J = 6 Hz, CH3-CH), 1.82 and 2.08 (2s, (CH3)2C[dbnd]CH) and 5.83 (broad s, C[dbnd] CH-C[dbnd]O)
- 8 Compound was obtained as a pale yellow oil (crude). Spectroscopic data was recorded on this crude product: ir (film) v 3400, 2220, 1680 and 1605 cm−1; pmr (CCl4, 60 MHz) δ 0.85 (d, J = 6 Hz, CH3-CH), 1.86 and 2.10 (2s, (CH3)2C[dbnd]CH), 4.66 (broad signal, OH, disappears with D2O) and 5.90 (broad s, C[dbnd] CH-C[dbnd]O)
- 9 Compound, colorless oil; uv (EtOH) γmax 240 nm (ε 10000); ir (film) v 2200, 1690 and 1620 cm−1; pmr (CCl4, 60 MHz) δ 0.85 (d, J = 6 Hz, CH3-CH), 1.86 and 2.10 (2s, (CH3)2C[dbnd]CH), 5.85 (broad s, C[dbnd] CH-C[dbnd]O) and 6.42 (broad s, CH[dbnd]C-CN); ms (70 eV, rel. intensity) z/e 231 (2%), 148 (1%), 125 (17%) and 83 (100%)
- Base treatment was necessary in order to convert HCl addition compounds into dehydrojuvabione
- Mori , K. and Matsui , M. 1967 . Tetrahedron Lett. , : 4853