8138
O. Roy et al. / Tetrahedron 56 (2000) 8133±8140
1686, 1603, 1454; 1H NMR 1.31 (t, 3H, J7.2 Hz,
OCH2CH3), 4.22 (q, 2H, J7.2 Hz, OCH2CH3), 4.80 (s,
2H, OCH2CvCH2), 5.35 (s, 2H, OCH2Ph), 6.15 (s, 1H,
CvCHH), 6.33 (s, 1H, CvCHH), 7.0 (m, 2H), 7.40 (m,
6H), 7.87 (dd, 1H, J8.0 and 1.9 Hz); 13C NMR 14.0
(OCH2CH3), 60.7 (OCH2CH3), 66.5 (OCH2CvCH2,
OCH2Ph), 113.2, 120.0, 120.5, 126.3 (CvCH2), 128.0,
128.4, 133.6, 135.1, 135.9, 157.8 (CvCH2), 165.2 and
165.7 (CO2Et and CO2Bn); EIMS m/z 341 (M1, 16), 233
(58), 203 (13), 181 (8), 161 (15), 131 (15), 121 (100); Anal.
calcd for C20H20O5: C: 70.28%, H: 5.90%; found: C:
70.53%, H: 5.72%.
(CO2Et); EIMS m/z 236 (M1,85), 191 (27), 123 (100);
Anal. calcd for C13H16O4: C: 66.09%, H: 6.82%; found:
C: 66.10%, H: 6.83%.
Ethyl 3-(p-formylphenyl)-oxy-2-methylenepropanoate (3i).
Colorless oil; IR (cm21) 2990, 1692, 1645, 1603, 1580,
1
1510; H NMR 1.24 (t, 3H, J7.2 Hz, OCH2CH3), 4.18
(q, 2H, J7.2 Hz, OCH2CH3), 4.75 (s, 2H, OCH2CvCH2),
5.91 (s, 1H, CvCHH), 6.35 (s, 1H, CvCHH), 6.96 (d, 2H,
J8.8 Hz), 7.75 (d, 2H, J8.8 Hz), 9.79 (s, 1H, CHO); 13C
NMR 13.9 (OCH2CH3), 60.8 (OCH2CH3), 66.0
(OCH2CvCH2), 114.8 (2 CH), 126.4 (CvCH2), 130.0,
131.7, 135.0, 162.9 (CvCH2), 164.9 (CO2Et), 190.4
(CHO); EIMS m/z 234 (M1, 49), 205 (8), 188 (100), 161
(54), 131 (39), 121 (80); Anal. calcd for C13H14O4: C:
66.66%, H: 6.02%; found: C: 66.62%, H: 6.10%.
Ethyl 3-(o-cyanophenyl)-oxy-2-methylenepropanoate (3e).
Mp 41±428C; IR (cm21) 2991, 2222, 1707, 1599, 1493; 1H
NMR 1.33 (t, 3H, J7.2 Hz, OCH2CH3), 4.27 (q, 2H,
J7.2 Hz, OCH2CH3), 4.85 (s, 2H, OCH2CvCH2), 6.15
(bs, 1H, CvCHH), 6.45 (bs, 1H, CvCHH), 7.02 (m, 2H),
7.55 (m, 2H); 13C NMR 14.1 (OCH2CH3), 61.0 (OCH2CH3),
66.5 (OCH2CvCH2), 102.2, 112.5, 116.2, 121.2, 126.6
(CvCH2), 133.7, 134.3, 134.6, 159.8 (CvCH2), 165.0
(CO2Et); EIMS m/z 231 (M1, 69), 186 (55), 157 (11), 129
(18), 119 (93), 113 (100); Anal. calcd for C13H13O3N: C:
67.52%, H: 5.67%, N: 6.06%; found: C: 67.49%, H: 5.38%,
N: 5.76%.
Ethyl 3-(p-chlorophenyl)-oxy-2-methylenepropanoate (3j).
Colorless oil; IR (cm21) 2984, 1713, 1493; 1H NMR 1.31 (t,
3H, J7.1 Hz, OCH2CH3), 4.26 (q, 2H, J7.1 Hz,
OCH2CH3), 4.72 (t, 2H, J1.5 Hz, OCH2CvCH2), 5.96
(q, 1H, J1.5 Hz, CvCHH), 6.40 (q, 1H, J1.5 Hz,
CvCHH), 6.90 (m, 2H), 7.22 (m, 2H); 13C NMR 14.0
(OCH2CH3), 60.8 (OCH2CH3), 66.2 (OCH2CvCH2),
115.9, 125.8, 126.1 (CvCH2), 129.2, 135.6, 156.7
(CvCH2), 165.2 (CO2Et); EIMS m/z 240, 242 (M1,100,
33), 194 (54), 166 (23), 159 (72), 128 (87), 113 (92);
Anal. calcd for C12H14O3Cl: C: 59.88%, H: 5.44%; found:
C: 60.09%, H: 5.42%.
Ethyl 3-(m-acetamidophenyl)-oxy-2-methylenepropano-
ate (3f). Mp 87±888C; IR (cm21) 3267, 3150, 2978, 1720,
1
1666, 1614, 1564, 1495; H NMR 1.30 (t, 3H, J7.2 Hz,
OCH2CH3), 2.13 (s, 3H, OvCCH3), 4.24 (q, 2H, J7.2 Hz,
OCH2CH3), 4.71 (s, 2H, OCH2CvCH2), 5.95 (d, 1H,
J1.1 Hz, CvCHH), 6.37 (d, 1H, J1.1 Hz, CvCHH),
6.63 (d, 1H, J8.3 Hz), 7.01 (d, 1H, J8.3 Hz), 7.18 (t,
1H, J8.3 Hz), 7.3 (bs, 1H), 8.0 (bs, 1H, NH); 13C NMR
14.0 (OCH2CH3), 24.3 (OvCCH3), 60.8 (OCH2CH3), 66.0
(OCH2CvCH2), 106.7, 110.3, 112.6, 126.4 (CvCH2),
129.5, 135.7, 139.3, 158.6 (CvCH2), 165.4 (CO2Et),
168.9 (OvCCH3); EIMS m/z 263 (M1, 32), 217 (20), 190
(15), 175 (100), 147 (66), 131 (10), 122 (32), 109 (41); Anal.
calcd for C14H17O4N: C: 63.87%, H: 6.51%, N: 5.32%;
found: C: 63.44%, H: 6.41%, N: 5.10%.
Ethyl 2-phenoxymethylhex-2-enoate (5). Colorless oil; IR
(cm21) 2961, 2874, 1713, 1599, 1497; 1H NMR 0.95 (t, 3H,
J7.4 Hz, CH3CH2CH3), 1.39 (t, 3H, J7.2 Hz,
OCH2CH3), 1.51 (sext, 2H, J7.4 Hz, CH2CH2CH3), 2.40
(q, 2H, J7.4 Hz, CH2CH2CH3), 4.23 (q, 2H, J7.4 Hz,
OCH2CH3), 4.77 (s, 2H, CH2OPh), 6.95 (m, 3H), 7.12 (t,
1H, J7.4 Hz, CvCH), 7.29 (m, 2H); 13C NMR 13.8
(CH2CH2CH3), 14.1 (OCH2CH3), 21.9 (CH2CH2CH3),
30.9 (CH2CH2CH3), 60.8 (OCH2CH3), 61.8 (CH2OPh),
114.9, 120.9, 128.1, 129.4, 149.4 (CvCHCH2), 158.8
(CvCHCH2), 166.7 (CO2Et); EIMS m/z 248 (M1, 83),
203 (68), 155 (93), 139 (19), 127 (49), 109 (100); Anal.
calcd for C15H20O3: C: 72.55%, H: 8.12%; found:
C:72.77%, H: 8.42%.
Ethyl 3-(m-methoxyphenyl)-oxy-2-methylenepropanoate
1
(3g). Colorless oil; IR (cm21) 2937, 1715, 1595, 1493; H
NMR 1.33 (t, 3H, J7.2 Hz, OCH2CH3), 3.79 (s, 3H,
OCH3), 4.27 (q, 2H, J7.2 Hz, OCH2CH3), 4.75 (s, 2H,
OCH2CvCH2), 6.00 (s, 1H, CvCHH), 6.40 (s, 1H,
CvCHH), 6.52±6.57 (m, 3H), 7.20 (t, 1H, J8.0 Hz); 13C
NMR 14.1 (OCH2CH3), 55.2 (OCH3), 60.9 (OCH2CH3),
66.0 (OCH2CvCH2), 101.2, 106.6, 106.8, 126.2
(CvCH2), 129.9, 135.9, 159.5 (CvCH2), 160.8, 165.4
(CO2Et); EIMS m/z 236 (M1, 70), 190 (100), 162 (60),
147 (34); Anal. calcd for C13H16O4: C:66.09%, H: 6.82%;
found: C: 66.09%, H: 6.82%.
The E-stereochemistry of the double bond of 5 was deter-
mined by NOE experiments (Scheme 4).
Ethyl 3-(p-methoxyphenyl)-oxy-2-methylenepropanoate
Scheme 4.
1
(3h). Colorless oil; IR (cm21) 2909, 1714, 1510; H NMR
1.33 (t, 3H, J7.2 Hz, OCH2CH3), 3.78 (s, 3H, OCH3), 4.27
(q, 2H, J7.2 Hz, OCH2CH3), 4.71 (s, 2H, OCH2CvCH2),
5.99 (s, 1H, CvCHH), 6.40 (s, 1H, CvCHH), 6.80±6.92
(m, 4H); 13C NMR 14.1 (OCH2CH3), 55.6 (OCH3), 60.8
(OCH2CH3), 66.8 (OCH2CvCH2), 114.5 (2 CH), 115.7 (2
CH), 126.0 (CvCH2), 136.2, 152.4, 154.0 (CvCH2), 165.0
Ethyl 2-methylene-3-phenoxyhexanoate (6). Colorless
1
oil; IR (cm21) 2961, 2874, 1713, 1599, 1495; H NMR
0.94 (t, 3H, J7.4 Hz, CH2CH2CH3), 1.33 (t, 3H,
J7.2 Hz, OCH2CH3), 1.48 (m, 2H, CH2CH2CH3), 1.76
(m, 2H, CH2CH2CH3), 4.27 (q, 2H, J7.2 Hz, OCH2CH3),