1644
O. I. KOLODIAZHNYI AND O. O. KOLODIAZHNA
1H). 13C NMR (125.74 MHz, CDCl3): d ¼ 24.5, 28.5, 28.8, 47.5, 53.0 (d, J ¼ 6.9),
59.0, 73.5 (d, J ¼ 158.8), 81.5, 159. 31P NMR (80.95 MHz, CDCl3): dP ¼ 26.9.
Diethyl Hydroxy[6-methyl-4-(4-methylpent-3-enyl)cyclohex-3-en-1-
yl]methyl-Phosphonate (4)
Yield 80%. The product was purified by column chromatography on silica gel
(EtOAc–hexane, 1:3) to afford the desired phosphonate. Colorless oil, bp 180 ꢁC
1
(0.08 mmHg). H NMR (500 MHz, CDCl3): d ¼ 0.99 (d, 3H, J ¼ 6 Hz), 1.33 (t, 6H
J ¼ 7 Hz), 1.6 (s, 3H), 1.87 (s 3H), 1.91–2.22 (m, 10H), 3.51 (br, 1H), 4.17 (m, 5H,
J ¼ 7 Hz, J ¼ 8 Hz), 6.28 (s, 1H), 5.32 (m, 2H). 13C NMR (125.74 MHz, CDCl3):
d ¼ 8.87, 16.28, 17.3, 25.4, 25.78, 27.01, 27.08, 29.96, 32.15, 33.69 (d, J ¼ 150 Hz),
42.8, 61.81 (d, J ¼ 6 Hz), 120.6, 123.9, 130.8, 135.59. 31P NMR (80.95 MHz, CDCl3:
dP ¼ 26.6. Anal. calcd. for C18H33O4P: C, 62.77; H, 9.66; P, 8.99. Found: C, 62.58; H,
9.55; P, 8.80.
Diethyl Hydroxy(3,8,8-trimethyl-1,2,3,4,5,6,7,8-octahydro-
naphthalene-2-yl) Methylphosphonate (5)
Yield 80%, colorless solid, bp 190 ꢁC (0.1 mmHg), mp 107–110 ꢁC (hexane).
1H NMR (500 MHz, CDCl3): d ¼ 0.957 (d, 3H, J 6), 0.975 (s, 6H), 1.34 (t, 6H,
J ¼ 7 Hz), 1.43 (m, 2H), 1.6 (m, 4H), 1.8 (m, 2H), 1.9 (m, 1H), 2.0 (m, 1H), 2.19
(m, 2H), 2.91 (br, 1H), 4.2 (m, 5H). 13C NMR (125.74 MHz, CDCl3): d ¼ 16.4,
19.27, 19.99, 24.87, 27.02, 27.07, 28.1, 28.97, 32.89, 33.73, 39.5, 48.9, 62.17 (d,
J ¼ 6 Hz), 62.17, 70.88 (d, J ¼ 160 Hz), 127.2, 133.61. 31P NMR (80.95 MHz,
CDCl3): d ¼ 25.63. Anal. calcd. for C18H33O4P: C, 62.77; H, 9.66; P, 8.99. Found:
C, 62.53; H, 9.54; P, 9.19.
Diethyl (2E)-1-Hydroxy-3,7-dimethyl-2,6-octadienyl-phosphonate (6)
1
Yield 80%, bp 135 ꢁC (0.08 mm Hg). H NMR (300 MHz, CDCl3): d ¼ 1.28
(t, JHH ¼ 7 Hz), 1.29 (t, JHH ¼ 7 Hz), 1.61 (s, 3H), 1.69 (s, 3H); 2.1 (br, 4H), 4.12
(m, 4H), 4.52 (dd, 1H, JHH ¼ 9 Hz, JHP ¼ 9 Hz), 5.12 (br, 1H), 5.36 (br, 1H). 13C
NMR (125.74 MHz, CDCl3): d ¼ 16.4, 17.0, 17.6, 25.60, 26.7, 37.90, 37.9, 61.7,
61.8, 65.1, 66.1, 119.1, 124.0, 131.7, 138.8. 31P NMR (80.95 MHz, CDCl3):
d ¼ 24.19. Anal. calcd. for C14H27O4P: C, 57.92; H, 9.37. Found: C, 57.99;
H, 9.49.
Diethyl (SP,R/RP,R)-(6E)-1-Hydroxy-3,7-dimethyl-2,6-octenyl-
phosphonate (7)
Yield 80%, bp 145–150 ꢁC (0.08 mmHg). Mixture of (SpR=RpR)-diastereomers.
1H NMR (300 MHz, CDCl3), d ¼ 0.96 (d, 3H, J ¼ 7 Hz), 1.29 (t, 3H, J ¼ 7 Hz), 1.30
(t, 3H, J ¼ 7 Hz), 1.58 (s, 3H), 1.65 (s, 3H), 1.83 (m, 2H), 1.96 (m, 2H), 3.82 (m, 1H),
4.09 (m, 4H), 5.07 (t, 1H, J ¼ 7 Hz), 5.7 (br, 1H). 13C NMR (125.74 MHz, CDCl3):
(SpR) d ¼ 16.45, 16.49, 17.6, 20.25, 25.19, 25.52, 25.65, 28.30 d (J ¼ 12 Hz), 35.75,
38.11, 62.51 d (J ¼ 7.5 Hz), 62.64 d (J ¼ 6 Hz), 65.59 d (J ¼ 158 Hz), 124.70, 131.09;