Molecules 2014, 19
6317
Dimethyl 3-methyl-1-(tetrahydro-2H-pyran-2-yloxymethyl)-penta-1,2-dienephosphonate (7a). Yellow
1
oil, yield: 78%. Rf 0.58; IR (neat, cm−1): 1119 (C-O-C), 1250 (P=O), 1958 (C=C=C). H-NMR
(600.1 MHz): δ 1.07 (t, J = 7.4 Hz, 3H, Me-CH2), 1.53, 1.60, 1.71, 3.53, 4.32 (overlapping multiplets,
9H, OTHP), 1.80 (d, J = 6.7 Hz, 3H, Me-C=), 2.07 (m, 2H, Me-CH2), 3.76 (d, J = 11.2 Hz, 3H, MeO),
4.14 (m, 2H, CH2O). 13C-NMR (150.9 MHz) δ = 12.0 (J = 7.6 Hz), 18.1 (J = 6.6 Hz), 19.2, 25.5, 26.5
(J = 4.2 Hz), 30.4, 52.8 (J = 6.2 Hz), 61.9, 64.9 (J = 10.1 Hz), 90.7 (J = 191.2 Hz), 97.2, 104.6
(J = 15.6 Hz), 208.6 (J = 5.5 Hz). 31P-NMR (242.9 MHz): δ 20.3. Anal. Calcd for C14H25O5P
(304.32): C 55.25; H 8.28. Found: C 55.33; H 8.19.
Dimethyl 3-methyl-1-(tetrahydro-2H-pyran-2-yloxymethyl)-hepta-1,2-dienephosphonate (7b). Yellow
1
oil, yield: 75%. Rf 0.59; IR (neat, cm−1): 1121 (C-O-C), 1251 (P=O), 1956 (C=C=C). H-NMR
(600.1 MHz): δ 0.90 (t, J = 7.2 Hz, 3H, Me-(CH2)3), 1.44, 1.53, 1.60, 3.53, 4.36 (overlapping
multiplets, 9H, OTHP), 1.78 (d, J = 6.5 Hz, 3H, Me-C=), 1.36, 1.82, 2.05 (overlapping multiplets, 6H,
13
Me-(CH2)3), 3.75 (d, J = 11.2 Hz, 3H, MeO), 4.09 (m, 2H, CH2O). C-NMR (150.9 MHz) δ = 13.9,
18.0 (J = 6.7 Hz), 19.2, 22.2, 25.5, 29.4, 30.3, 32.9, 52.7 (J = 6.3 Hz), 61.8, 64.9 (J = 10.1 Hz), 90.3
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(J = 191.7 Hz), 97.3, 102.8 (J = 16.2 Hz), 208.8 (J = 5.4 Hz). P-NMR (242.9 MHz): δ 20.4. Anal.
Calcd for C16H29O5P (332.37): C 57.82, H 8.79. Found: C 57.90, H 8.72.
Dimethyl 2-cyclohexylidene-1-(tetrahydro-2H-pyran-2-yloxymethyl)-ethenephosphonate (7c). Yellow
1
oil, yield: 73%. Rf 0.57; IR (neat, cm−1): 1118 (C-O-C), 1252 (P=O), 1953 (C=C=C). H-NMR
(600.1 MHz): δ 1.25–2.23, 3.55, 3.86, 4.31 (overlapping multiplets, 19H, (CH2)5 + OTHP), 3.74 (d,
J = 11.1 Hz, 3H, MeO), 4.15 (m, 2H, CH2O). 13C-NMR (150.9 MHz) δ = 19.1, 25.5, 25.7, 26.5, 30.3
(J = 5.9 Hz), 30.4, 52.9 (J = 6.2 Hz), 62.0, 64.7 (J = 10.8 Hz), 88.6 (J = 190.7 Hz), 97.2, 105.1
(J = 15.6 Hz), 205.6 (J = 5.1 Hz). 31P-NMR (242.9 MHz): δ 21.2. Anal. Calcd for C16H27O5P
(330.36): C 58.17, H 8.24. Found: C 58.24, H 8.18.
Dimethyl 3-methyl-1-[1-(tetrahydro-2H-pyran-2-yloxy)-ethyl]-penta-1,2-dienephosphonate (7d). Orange
1
oil, yield: 74%. Rf 0.44; IR (neat, cm−1): 1122 (C-O-C), 1259 (P=O), 1951 (C=C=C). H-NMR
(600.1 MHz): δ 0.95 (t, J = 7.3 Hz, 3H, Me-CH2), 1.41 (dd, J = 6.4 Hz, J = 10.2 Hz, 3H, Me-CHO),
1.51, 1.58, 1.68, 3.63, 4.38 (overlapping multiplets, 9H, OTHP), 1.74 (d, J = 6.6 Hz, 3H, Me-C=), 2.04
(m, 2H, Me-CH2), 3.77 (d, J = 11.2 Hz, 3H, MeO), 4.67 (m, 1H, CHO). 13C-NMR (150.9 MHz)
δ = 12.3 (J = 7.5 Hz), 18.5 (J = 6.3 Hz), 19.4, 23.4 (J = 7.6 Hz), 25.5, 27.7 (J = 4.6 Hz), 30.5, 52.5
(J = 6.3 Hz), 62.4, 67.4 (J = 10.3 Hz), 95.8, 96.4 (J = 192.0 Hz), 104.4 (J = 15.9 Hz), 209.2
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(J = 5.1 Hz). P-NMR (242.9 MHz): δ 20.4. Anal. Calcd for C15H27O5P (318.35): C 56.59, H 8.55.
Found: C 56.64, H 8.63.
Dimethyl 3-methyl-1-[1-(tetrahydro-2H-pyran-2-yloxy)-ethyl]-hepta-1,2-dienephosphonate (7e). Orange
1
oil, yield: 72%. Rf 0.43; IR (neat, cm−1): 1120 (C-O-C), 1254 (P=O), 1956 (C=C=C). H-NMR
(600.1 MHz): δ 0.93 (t, J = 7.1 Hz, 3H, Me-(CH2)3), 1.43 (dd, J = 6.3 Hz, J = 10.0 Hz, 3H, Me-CHO),
1.48, 1.55, 1.64, 3.62, 4.38 (overlapping multiplets, 9H, OTHP), 1.77 (d, J = 6.6 Hz, 3H, Me-C=),
1.41, 1.74, 2.11 (overlapping multiplets, 6H, Me-(CH2)3), 3.76 (d, J = 11.2 Hz, 3H, MeO), 4.64
13
(m, 1H, CHO). C-NMR (150.9 MHz) δ = 13.8, 18.8 (J = 6.5 Hz), 19.5, 22.7, 23.5 (J = 7.5 Hz),
25.7, 29.6, 30.4, 32.8, 52.3 (J = 6.2 Hz), 62.3, 68.6 (J = 10.2 Hz), 91.4 (J = 191.7 Hz), 95.6, 103.4
(J = 16.2 Hz), 209.0 (J = 5.3 Hz). 31P-NMR (242.9 MHz): δ 20.5. Anal. Calcd for C17H31O5P
(346.40): C 58.94, H 9.02. Found: C 59.01, H 8.96.