6
Tetrahedron
6.53 (d, J = 15.6 Hz, 1H), 6.53-6.40 (m, 1H), 5.39-5.25 (m,
(E)-1-(Buta-1,3-dienyl)-2,3-dimethoxybenzene and (Z)-1-
ACCEPTED MANUSCRIPT
1H), 5.13 (d, J = 9.8 Hz, 1H), 2.3 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 148.5, 137.3, 134.8, 132.8, 130.4, 129.0 (2C), 126.7,
126.4, 117.0, 23.9; NMR data for Z- isomer: 1H NMR (400 MHz,
CDCl3) δ 7.29 (d, J = 8.1 Hz, 1H), 7.21 (d, J = 9.1 Hz, 1H), 7.16-
7.09 (m, 2H), 6.95-6.83 (m, 1H), 6.54-6.46 (m, 1H), 6.22 (t, J =
11.3 Hz, 1H), 5.37 (d, J = 2.0 Hz, 1H), 5.20 (d, J = 10.3 Hz, 1H),
2.34 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 147.8, 134.9, 134.8,
133.4, 130.1, 128.8 (2C), 126.3 (2C), 119.2, 23.9; IR(neat) 3293,
3010, 2944, 2170, 160, 1498, 1488, 1259, 1102, 950 cm-1;
HRMS (ESI): m/zcalcd for C11H13 [M + H]+ 145.1017; found:
145.1013.
(Buta-1,3-dienyl)-2,3-dimethoxybenzene 5i: colorless liquid; E:Z
= 2:1; yield: 85%; Rf = 0.6 (5% EtOAc in hexane); NMR data for
E- isomer: H NMR (400 MHz, CDCl3) δ 7.14 (dd, J = 1.2, 8.1
1
Hz, 1H), 7.05-6.99 (m, 1H), 6.97-6.92 (m, 1H), 6.91-6.86 (m,
1H), 6.86-6.78 (m, 1H), 6.64-6.54 (m, 1H), 5.33 (d, J = 10.7 Hz,
1H), 5.19 (d, J = 10.3 Hz, 1H), 3.87 (s, 3H), 3.82 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ 153.1, 146.8, 137.7, 131.4, 130.9,
127.1, 124.0, 117.9, 117.6, 111.4, 61.0, 55.83; NMR data for Z-
1
isomer: H NMR (400 MHz, CDCl3) δ 7.03-6.99 (m, 1H), 6.87
(d, J = 1.5 Hz, 1H), 6.81-6.77 (m, 1H), 6.62-6.58 (m, 1H), 6.57
(d, J = 3.4 Hz, 1H), 6.32 (t, J = 11.3 Hz, 1H), 5.36 (dd, J = 17.1,
1.9 Hz, 1H), 5.20 (d, J = 10.3 Hz, 1H), 3.87 (s, 3H), 3.79 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 152.8, 147.1, 133.5, 131.6, 131.3,
125.9, 123.5, 122.7, 119.3, 111.6, 60.7, 55.8; HRMS (ESI): m/z
calcd for C12H15O2[M + H]+ 191.1078; found: 191.1063.
(E)-1-(Buta-1,3-dienyl)-4-ethylbenzene and (Z)-1-(Buta-1,3-
dienyl)-4-ethylbenzene 5f: colorless liquid; E:Z = 3:2; yield: 87%
Rf = 0.7 (hexane); NMR data for E- isomer: 1H NMR (400 MHz,
CDCl3) δ 7.34 (d, J = 8.1 Hz, 1H), 7.26 (s, 1H), 7.21-7.14 (m,
2H), 6.77 (dd, J = 15.6, 10.5 Hz, 1H), 6.54 (d, J = 15.7 Hz, 1H),
6.45 (dt, J = 16.8, 10.3 Hz, 1H), 5.32 (d, J = 17.2 Hz 1H), 5.15
(d, J = 10.3 Hz, 1H), 2.71-2.61 (m, 2H), 1.29-1.22 (m, 3H); 13C
NMR (100 MHz, CDCl3) δ 143.9, 137.3, 134.2, 132.8, 130.4,
128.1 (2C), 126.4 (2C), 117.1, 28.63, 15.56; NMR data for Z-
(E)-2-(Buta-1,3-dienyl)-1,4-dimethoxybenzene and (Z)-2-
(Buta-1,3-dienyl)-1,4-dimethoxybenzene 5j: colorless liquid; E:Z
= 3:2; yield: 90%; Rf = 0.55 (5% EtOAc in hexane); NMR data
for E- isomer: 1H NMR (400 MHz, CDCl3) δ 7.05 (d, J = 2.9 Hz,
1H), 6.91 (d, J = 2.9 Hz, 1H), 6.85-6.77 (m, 3H), 6.58 (d, J =
11.5 Hz, 1H), 6.52 (dt, J =16.9, 11.0 Hz, 1H), 5.36 (d, J = 16.6
1
isomer: H NMR (400 MHz, CDCl3) δ 7.34 (d, J = 8.1 Hz, 1H),
7.26 (s, 1H), 7.21-7.14 (m, 2H), 6.98-6.86 (m, 1H), 6.56-6.50 (m,
1H), 6.23 (t, J = 11.3 Hz, 1H), 5.41-5.34 (m, 1H), 5.22 (d, J = 9.8
Hz, 1H), 2.71-2.61 (m, 2H), 1.29-1.22 (m, 3H); 13C NMR (100
MHz, CDCl3) δ 143.2, 134.8, 134.6, 133.4, 130.2, 128.8 (2C),
127.8 (2C), 119.2, 28.65, 15.54; IR (neat): 3295, 3009, 2945,
2173, 1609, 1499, 1452, 1430, 1252, 1100, 1039 cm-1; HRMS
(ESI): m/z calcd for C12H15 [M + H]+ 159.1174; found: 159.1161.
Hz, 1H), 5.18 (d, J = 10.2 Hz, 1H), 3.83 (s, 3H), 3.81 (s, 3H); 13
C
NMR (100 MHz, CDCl3) δ 153.7, 151.4, 137.8, 130.4, 127.4,
127.1, 117.3, 113.8, 112.3, 111.6, 56.2, 55.7; NMR data for Z-
isomer: H NMR (400 MHz, CDCl3) δ 6.94-6.88 (m, 1H), 6.86-
1
6.76 (m, 2H), 6.55-6.50 (m, 1H), 6.37-6.29 (m, 1H), 6.32 (t, J =
11.3 Hz, 1H), 5.41-5.31 (m, 1H), 5.21 (d, J = 10.3 Hz, 1H), 3.80
(s, 3H), 3.79 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 153.1,
151.5, 133.4, 130.9, 126.9, 126.0, 119.3, 116.6, 113.0, 111.0,
56.1, 55.8; IR (neat) 2924, 2838, 1733, 1674, 1610, 1584, 1495,
1460, 1426, 1281, 1218, 1173, 1124, 1044 cm-1; HRMS (ESI):
m/z calcd for C12H15O2[M + H]+ 191.1072; found: 191.1063.
(E)-1-(Buta-1,3-dienyl)-4-isopropylbenzene and (Z)-1-(Buta-
1,3-dienyl)-4-isopropylbenzene 5g: colorless liquid; E:Z = 3:2;
yield: 85%; Rf = 0.65 (hexane); NMR data for E- isomer: H
NMR (400 MHz, CDCl3) δ 7.33 (d, J = 8.1 Hz, 1H), 7.26-7.23
(m, 1H), 7.22-7.15 (m, 2H), 6.75 (dd, J = 15.5, 10.3 Hz, 1H),
6.58-6.51 (m, 1H), 6.45-6.40 (m, 1H), 5.34-5.27 (m, 1H), 5.14 (d,
J = 10.3 Hz, 1H), 2.95-2.84 (m, 1H), 1.28-1.21 (m, 6H); 13C
NMR (100 MHz, CDCl3) δ 148.5, 137.3, 132.8, 130.4, 129.0,
126.7 (2C), 126.4 (2C), 117.0, 33.9, 23.95 (2C); NMR data for Z-
1
(E)-1-(Buta-1,3-dienyl)-2-ethoxy-3-methoxybenzene and (Z)-
1-(Buta-1,3-dienyl)-2-ethoxy-3-methoxybenzene 5k: colorless
liquid; E:Z = 2:1; yield: 88%; Rf = 0.55 (5% EtOAc in hexane);
NMR data for E- isomer: 1H NMR (400 MHz, CDCl3) δ 7.15 (dd,
J = 1.2, 8.6 Hz, 1H), 7.05-7.01 (m, 1H), 6.97-6.91 (m, 1H), 6.87-
6.78 (m, 2H), 6.67-6.56 (m, 1H), 5.33 (d, J = 17.1 Hz, 1H), 5.18
(d, J = 10.3 Hz, 1H), 4.07-3.98 (m, 2H), 3.86 (s, 3H), 1.40 (t, J =
7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 153.2, 145.9, 137.7,
132.0, 131.6, 126.4, 123.3, 122.6, 119.1, 111.5, 69.0, 55.80,
1
isomer: H NMR (400 MHz, CDCl3) δ 7.33 (d, J = 8.1 Hz, 1H),
7.26-7.23 (m, 1H), 7.22-7.15 (m, 2H), 6.91 (d, J = 16.6 Hz, 1H),
6.55-6.48 (m, 1H), 6.22 (t, J = 11.3 Hz, 1H), 5.39-5.32 (m, 1H),
5.20 (d, J = 9.8 Hz, 1H), 2.95-2.84 (m, 1H), 1.28-1.21 (m, 6H);
13C NMR (100 MHz, CDCl3) δ 147.8, 134.9, 134.8, 133.4, 130.2,
128.8 (2C), 126.3 (2C), 119.2, 33.88, 23.91 (2C); IR(neat): 3296,
3019, 2178, 1601, 1495, 1457, 1433, 1250, 1102 cm-1; HRMS
(ESI): m/z calcd for C13H20N [M + NH4]+ 190.1596; found:
190.1564.
1
15.62; NMR data for Z- isomer: H NMR (400 MHz, CDCl3) δ
7.05-6.99 (m, 1H), 6.96-6.94 (m, 1H), 6.88-6.78 (m, 2H), 6.58-
6.52 (m, 1H), 6.32 (t, J = 11.4 Hz, 1H), 5.36 (dd, J = 17.1, 2.4
Hz, 1H), 5.20 (d, J = 10.3 Hz, 1H), 4.07-3.96 (m, 2H), 3.86 (s,
3H), 1.35 (t, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ
153.0, 146.2, 133.7, 132.0, 131.6, 126.4, 123.3, 122.6, 119.1,
111.5, 69.0, 55.82, 15.65; IR (neat): 2975, 2930, 1678, 1578,
1475, 1459, 1441, 1386, 1263, 1211, 1180, 1069, 1029 cm-1;
HRMS (ESI): m/z calcd for C13H17O2 [M + H]+ 205.1129; found:
205.1223.
(E)-1-(Buta-1,3-dienyl)-2-methylbenzene and (Z)-1-(Buta-
1,3-dienyl)-2-methylbenzene 5h: colorless liquid; E:Z = 3:1;
yield: 82%; Rf = 0.7 (hexane); NMR data for E- isomer: 1H NMR
(400 MHz, CDCl3) δ 7.55-7.47 (m, 1H), 7.22-7.14 (m, 3H), 6.85-
6.78 (m, 1H), 6.76-6.66 (m, 1H), 6.61-6.50 (m, 1H), 5.35 (d, J =
16.6 Hz, 1H), 5.18 (d, J = 10.2 Hz, 1H), 2.38 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 137.5, 133.5, 130.8, 130.5, 130.4, 129.6,
(E)-5-(Buta-1,3-dienyl)-1,2,3-trimethoxybenzene and (Z)-5-
(Buta-1,3-dienyl)-1,2,3-trimethoxybenzene 5l: colorless liquid;
E:Z = 1:1; yield: 80%; Rf = 0.65 (10% EtOAc in hexane); NMR
1
127.5, 126.1, 125.2, 117.5, 19.8; NMR data for Z- isomer: H
1
NMR (400 MHz, CDCl3) δ 7.55-7.47 (m, 1H), 7.22-7.14 (m,
3H), 6.71-6.63 (m, 1H), 6.57-6.50 (m, 1H), 6.32 (t, J = 11.3 Hz,
1H), 5.36 (d, J = 17.1 Hz, 1H), 5.17 (d, J = 9.8 Hz, 1H), 2.28 (s,
3H); 13C NMR (100 MHz, CDCl3) δ 136.4, 136.0, 135.6, 130.9,
130.2, 129.9, 129.8, 127.3, 125.2, 119.0, 19.8; IR (neat): 3293,
3019, 2949, 2171, 1604, 1492, 1458, 1431, 1255, 1109, 1050 cm-
1; HRMS (ESI): m/z calcd for C11H12 [M ]+ 144.0939; found:
144.0885.
data for E- isomer: H NMR (400 MHz, CDCl3) δ 6.96-6.84 (m,
1H), 6.64 (s, 2H), 6.50-6.37 (m, 2H), 5.35 (d, J= 17.1 Hz, 1H),
5.16 (dd, J = 9.6, 1.5 Hz, 1H), 3.87 (s, 6H), 3.86 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ 153.3 (2C), 137.0, 133.1, 132.8,
130.5, 129.1, 117.5, 103.4 (2C), 60.95, 56.12 (2C); NMR data for
Z- isomer: 1H NMR (400 MHz, CDCl3) δ 6.73-6.66 (m, 1H), 6.54
(s, 2H), 6.51-6.46 (m, 1H), 6.23 (t, J = 11.3, 1H), 5.43-5.30 (m,
1H), 5.23 (d, J = 10.2 Hz, 1H), 3.89 (s, 3H), 3.87 (s, 6H), 13C
NMR (100 MHz, CDCl3) δ 153.0 (2C), 137.9, 137.3, 133.0,