PAPER
Symmetrical and Unsymmetrical Hydroxystilbenes via McMurry Coupling
2045
(E)-13,14-Dimethyl-1,6-dioxa(6.2)[20]orthocyclophan-13-ene
Anal. Calcd for C16H14O2: C, 80.65; H, 5.92. Found: C, 80.79; H,
(3b)
5.88.
IR: 3022, 2930, 1585, 1493, 720 cm–1.
(Z)-8,11,12-Trimethyl-1,4-dioxa(4.2)[18]orthocyclophan-11-
ene (7a)
1H NMR: d = 7.29–6.98 (m, 8 H), 4.20–4.04 (m, 4 H), 1.78 (s, 6 H),
1.80–1.78 (m, 4 H).
IR: 3052, 2962, 16126, 1545, 1402, 787 cm–1.
13C NMR: d = 156.6, 136.2, 130.0, 129.5, 127.8, 122.2, 117.6, 72.6,
26.8, 21.7.
1H NMR: d = 6.80–6.68 (m, 7 H), 4.52–4.23 (m, 2 H), 3.97–3.72 (m,
2 H), 2.13 (s, 3 H), 2.07 (s, 6 H).
13C NMR: d = 158.3, 156.8, 136.7, 136.2, 133.3, 131.2, 131.0,
129.8, 129.3, 128.6, 128.0, 123.9, 121.9, 121.6, 76.0, 23.5, 20.9.
Anal. Calcd for C20H22O2: C, 81.60; H, 7.53. Found: C, 81.74; H,
7.68.
(Z)-11,12-Diethyl-1,4-dioxa(4.2)[18]orthocyclophan-11-ene(3c)
Anal. Calcd for C19H20O2: C, 81.40; H, 7.19. Found: C, 81.22; H,
7.33.
IR: 2964, 1930, 1597, 1477, 755 cm–1.
1H NMR: d = 6.98–6.74 (m, 8 H), 4.45–4.33 (m, 2 H), 3.92–3.81 (m,
2 H), 2.55–2.43 (m, 4 H), 0.98 (t, J = 7.6 Hz, 6 H).
13C NMR: d = 155.8, 136.2, 135.8, 130.8, 127.0, 122.1, 119.6, 69.9,
26.6, 12.9.
(E)-8,11,12-Trimethyl-1,4-dioxa(4.2)[18]orthocyclophan-11-
ene (7a)
IR: 3060, 1599, 1567, 1484, 1436, 758 cm–1.
1H NMR: d = 7.32–6.95 (m, 7 H), 4.46–4.37 (m, 2 H), 3.88–3.76 (m,
2 H), 2.34 (s, 3 H), 1.88 (s, 6 H).
13C NMR: d = 159.2, 158.1, 135.7, 137.5, 133.9, 132.0, 130.6,
130.1, 129.9, 129.3, 129.3, 125.0, 123.2, 122.9, 79.7, 24.7, 21.5.
Anal. Calcd for C20H22O2: C, 81.60; H, 7.53. Found: C, 81.45; H,
7.41.
(E)-11,12-Diethyl-1,4-dioxa(4.2)[18]orthocyclophan-11-ene(3c)
IR: 3054, 1597, 1574, 796 cm–1.
Anal. Calcd for C19H20O2: C, 81.40; H, 7.19. Found: C, 81.26; H,
7.28.
1H NMR: d = 7.29–7.05 (m, 8 H), 4.39–4.27 (m, 2 H), 4.10–3.97 (m,
2 H), 2.32–1.96 (m, 4 H), 0.92 (t, J = 7.5 Hz, 6 H).
13C NMR: d = 157.0, 137.3, 136.1, 129.7, 127.8, 123.5, 122.2, 74.7,
29.1, 13.7.
(Z)-11,12-Dimethyl-7-ethoxy-1,4-dioxa(4.2)[18]orthocyclo-
phan-11-ene (7b)
IR: 3019, 1607, 1504, 1499, 786 cm–1.
1H NMR: d = 7.08–6.74 (m, 5 H), 6.37–6.32 (m, 2 H), 4.43–4.33 (m,
2 H), 3.91–3.78 (m, 4 H), 2.05 (s, 6 H), 1.31 (t, J = 7.0 Hz, 3 H).
Anal. Calcd for C20H22O2: C, 81.60; H, 7.53. Found: C, 81.42; H,
7.38.
13C NMR: d = 157.9, 156.0, 155.3, 137.8, 130.3, 130.1, 130.0,
129.8, 126.9, 122.5, 118.7, 108.2, 105.6, 69.7, 63.2, 20.7, 20.5,
14.7.
(Z)-8,15-Dimethoxy-11,12-dimethyl-1,4-dioxa(4.2)[18]orthocy-
clophan-11-ene (3d)
IR: 3000, 2834, 1577, 1494, 758 cm–1..
Anal. Calcd for C20H22O3: C, 77.39; H, 7.14. Found: C, 77.56; H,
7.19.
1H NMR: d = 6.74–6.46 (m, 6 H), 4.39–4.30 (m, 2 H), 3.82–3.69 (m,
2 H), 3.64 (s, 6 H), 2.07 (s, 6 H).
13C NMR: d = 154.5, 149.0, 138.4, 130.1, 119.5, 114.8, 112.3, 70.2,
(E)-11,12-Dimethyl-7-ethoxy-1,4-dioxa(4.2)[18]orthocyclo-
phan-11-ene (7b)
55.3, 20.5.
IR: 3018, 2922, 1607, 1513, 1503, 716 cm–1.
Anal. Calcd for C20H22O4: C, 73.60; H, 6.79. Found: C, 73.48; H,
6.62.
1H NMR: d = 7.28–6.99 (m, 5 H), 6.71–6.58 (m, 2 H), 4.50–4.30 (m,
2 H), 4.01 (q, J = 7.0 Hz, 2 H), 3.87–3.76 (m, 2 H), 1.86 (br s, 3 H),
1.82 (br s, 3 H), 1.40 (t, J = 7.0 Hz, 3 H).
13C NMR: d = 159.2, 158.8, 158.3, 136.7, 130.9, 130.8, 129.6,
129.3, 128.4, 127.9, 123.9, 121.8, 110.2, 107.9, 76.0, 75.9, 63.5,
23.5, 14.8.
(E)-8,15-Dimethoxy-11,12-dimethyl-1,4-dioxa(4.2)[18]orthocy-
clophan-11-ene (3d)
IR: 3064, 2834, 1604, 1568, 1485, 758 cm–1..
1H NMR: d = 7.00–6.71 (m, 6 H), 4.35 (d, J = 11.4 Hz, 2 H), 3.81–
3.73 (m, 8 H), 1.88 (s, 6 H).
13C NMR: d = 155.8, 151.8, 137.7, 131.1, 122.7, 114.3, 112.8, 76.1,
55.6, 23.5.
Anal. Calcd for C20H22O3: C, 77.39; H, 7.14. Found: C, 77.51; H,
7.26.
(Z)-11-Ethyl-12-methyl-1,4-dioxa(4.2)[18]orthocyclophan-11-
ene (7c)
Anal. Calcd for C20H22O4: C, 73.60; H, 6.79. Found: C, 73.69; H,
6.61.
IR: 3020, 2964, 1596, 1514, 1441, 751 cm–1.
1H NMR: d = 6.99–6.76 (m, 8 H), 4.48–4.35 (m, 2 H), 3.94–3.82 (m,
2 H), 2.57–2.46 (m, 2 H), 2.09 (s, 3 H), 0.99 (t, J = 7.5 Hz, 3 H).
(Z)-1,4-Dioxa(4.2)[18]orthocyclophan-11-ene (3e)
IR: 3053, 2919, 1597, 1573, 1426, 757 cm–1.
1H NMR: d = 7.15–6.76 (m, 8 H), 6.77 (s, 2 H), 4.19 (s, 4 H).
13C NMR: d = 154.9, 131.8, 128.8, 129.7, 122.3, 118.4, 70.8.
13C NMR: d = 156.0, 155.3, 137.8, 136.4, 136.3, 130.7, 130.0,
129.8, 127.0, 122.5, 122.2, 118.6, 70.0, 27.1, 19.9, 12.5.
Anal. Calcd for C19H20O2: C, 81.40; H, 7.19. Found: C, 81.54; H,
7.33.
Anal. Calcd for C16H14O2: C, 80.65; H, 5.92. Found: C, 80.86; H,
6.06.
(E)-11-Ethyl-12-methyl-1,4-dioxa(4.2)[18]orthocyclophan-11-
ene (7c)
(E)-1,4-Dioxa(4.2)[18]orthocyclophan-11-ene (3e)
IR: 3085, 2933, 1609, 1492, 772 cm–1.
IR: 2927, 1673, 1597, 1485, 755 cm–1.
1H NMR: d = 7.38–6.89 (m, 10 H), 4.17 (s, 4 H).
13C NMR: d = 156.1, 131.4, 130.0, 128.2, 123.1, 120.2, 71.7.
1H NMR: d = 7.28–6.99 (m, 8 H), 4.31–3.96 (m, 4 H), 2.42–2.16 (m,
2 H), 1.82 (s, 3 H), 0.91 (t, J = 7.6 Hz, 3 H).
Synthesis 2003, No. 13, 2041–2046 © Thieme Stuttgart · New York