Helvetica Chimica Acta – Vol. 96 (2013)
2017
7.27 (m, HꢀC(2), HꢀC(18)); 7.37 (dd, 3J ¼ 8.2, 4J ¼ 1.6, HꢀC(12), HꢀC(30)); 7.68 – 7.78 (m, HꢀC(4),
HꢀC(11), HꢀC(16), HꢀC(29)); 8.01 (d, 3J ¼ 16.5, HꢀC(6), HꢀC(14)); 8.29 (s, HꢀC(8), HꢀC(28)).
13C-NMR (CDCl3): 28.0 (g-CH2); 31.0 (b-CH2); 69.7 (OCH2); 113.5 (C(1), C(19)); 121.1 (C(3), C(17));
123.9 (C(8), C(28)); 124.7 (C(5), C(15)); 125.2 (C(4), C(16)); 125.9 (C(12), C(30)); 126.6 (C(11),
C(29)); 126.6 (C(4a), C(15a)); 127.3 (C(6), C(14)); 128.8 (C(2), C(18)); 132.3 (C(9)); 133.9 (C(10));
136.5 (C(7), C(13)); 156.9 (C(19a), C(27a)). EI-MS: 446 (100, Mþ), 447 (35). Anal. calc. for C32H30O2
(446.6): C 86.06, H 6.77; found: C 86.27, H 6.98.
(5E,14E)-12,30-Bis(dodecyloxy)-21,22,23,24,25,26-hexahydro-7,10-etheno-9,13-(metheno)diben-
zo[i,v][1,8]dioxacyclotricosine (12a’). Yield: 305 mg (34%). Yellow solid. M.p. 190 – 1918. 1H-NMR
(CDCl3): 0.80 – 0.90 (m, 2 Me); 120 – 1.44 (m, 16 CH2); 1.44 – 1.58 (m, 2 CH2); 1.80 – 2.08 (m, 6 CH2);
4.00 – 4.15 (m, 4 CH2O); 6.89 (d, 3J ¼ 8.0, HꢀC(1), HꢀC(19)); 6.95 (s, HꢀC(11), HꢀC(29)); 6.99 (t, 3J ¼
8.0, HꢀC(3), HꢀC(17)); 7.18 (t, 3J ¼ 7.9, HꢀC(2), HꢀC(18)); 7.46 (d, 3J ¼ 16.7, HꢀC(6), HꢀC(14)); 7.73
(d, 3J ¼ 7.6, HꢀC(4), HꢀC(16)); 7.86 (d, 3J ¼ 16.7, HꢀC(5), HꢀC(15)); 8.11 (s, HꢀC(8), HꢀC(28)).
13C-NMR (CDCl3): 14.1 (Me); 22.7, 26.2, 28.0, 29.2, 29.5, 29.7, 30.9, 31.9 (CH2, partly superimposed); 68.3,
69.5 (OCH2); 104.6 (C(11), C(29)); 113.3 (C(1), C(19)); 121.1, 121.3, 123.6, 124.8, 125.5, 127.9 (remaining
arom. and olefin. CH); 124.0 (C(9)); 127.0, 127.2 (C(4a), C(7), C(13), C(15a)); 134.7 (C(10)); 155.5,
156.6 (C(12), C(19a), C(27a), C(30)). FD-MS: 815 (100, Mþ). Anal. calc. for C56H78O4 (815.2): C 82.51,
H 9.64; found: C 82.35, H 9.70.
6,7,8,9,10,11,12,13-Octahydro-21,24-etheno-23,27-(metheno)dibenzo[k,x][1,10]dioxacyclopentaco-
1
sine (12b). Yield: 330 mg (63%). Light yellow solid. M.p. 2668. The H-NMR spectrum of the product
1
revealed an (E,E)/(E,Z)-ratio of 4 :1. Recrystallization from acetone gave pure (E,E)-12b. H-NMR
3
(CDCl3): 1.55 – 1.70 (m, 2 d-CH2); 1.70 – 1.83 (m, 2 g-CH2); 1.83 – 1.99 (m, 2 b-CH2); 4.03 (t, J ¼ 5.2, 2
CH2O); 6.86 (d, 3J ¼ 8.3, HꢀC(1), HꢀC(19)); 6.96 (t, 3J ¼ 7.3, HꢀC(3), HꢀC(17)); 7.22 (t, 3J ¼ 7.3,
HꢀC(2), HꢀC(18)); 7.33 (d, 3J ¼ 16.6, HꢀC(6), HꢀC(14)); 7.45 (d, 3J ¼ 8.5, HꢀC(12), HꢀC(32)); 7.64 (d,
3J ¼ 7.6, HꢀC(4), HꢀC(16)); 7.74 (d, 3J ¼ 16.6, HꢀC(5), HꢀC(15)); 7.74 (d, 3J ¼ 8.5, HꢀC(11), HꢀC(31));
8.08 (s, HꢀC(8), HꢀC(30)). 13C-NMR (CDCl3): 27.9, 30.3, 31.0 (b-CH2, g-CH2, d-CH2); 68.5 (CH2O);
112.1 (C(1), C(19)); 120.6 (C(3), C(17)); 123.6 (C(8), C(30)); 124.2 (C(5), C(15)); 126.1 (C(4a),
C(15a)); 126.2 (C(4), C(16)); 126.3 (C(12), C(32)); 127.6 (C(11), C(31)); 128.2 (C(6), C(14)); 128.7
(C(2), C(18)); 132.5 (C(9)); 134.0 (C(10)); 136.1 (C(7), C(13)); 156.9 (C(19a), C(29a)). EI-MS: 474
(100, Mþ). Anal. calc. for C34H34O2 (474.7): C 86.04, H 7.22; found: C 86.29, H 7.13.
6,7,8,9,10,11,12,13,14,15-Decahydro-23,26-etheno-25,29-(metheno)dibenzo[m,z][1,12]dioxacyclo-
heptacosine (12c). Yield: 210 mg (38%). Nearly colorless solid. M.p. 2118. The 1H-NMR spectrum of the
product revealed an (E,E)/(E,Z)-ratio of 2 :1. Data of (E,E)-12c. 1H-NMR (CDCl3): 1.50 – 1.64 (m, 2 d-
CH2, 2 e-CH2); 1.70 – 1.84 (m, 2 g-CH2); 1.84 – 2.00 (m, 2 b-CH2); 4.07 (t, 3J ¼ 5.3, 2 CH2O); 6.90 (d, 3J ¼
8.0, HꢀC(1), HꢀC(19)); 6.95 (t, 3J ¼ 7.7, HꢀC(3), HꢀC(17)); 7.15 – 7.28 (m, HꢀC(2), HꢀC(18)); 7.39 – 7.60
(m, HꢀC(4), HꢀC(6), HꢀC(12), HꢀC(14), HꢀC(16), HꢀC(34)); 7.67 (d, 3J ¼ 16.5, HꢀC(5), HꢀC(15));
7.77 (d, HꢀC(11), HꢀC(33)); 7.88 (s, HꢀC(8), HꢀC(32)). 13C-NMR (CDCl3): 27.2, 29.8, 30.2, 30.2 (b-
CH2, g-CH2, d-CH2, e-CH2); 68.1 (OCH2); 111.7 (C(1), C(19)); 120.5 (C(3), C(17)); 124.6, 125.2, 125.4,
126.0, 127.9, 128.5, 128.8, 130.2 (arom. and olefin. CH); 132.5 (C(9)); 134.0 (C(10)); 136.1 (C(7), C(13));
156.9 (C(19a), C(31a)). EI-MS: 502 (100, Mþ). Anal. calc. for C36H38O2 (502.7): C 86.02, H 7.60; found: C
85.87, H 7.61.
9,16-(Epoxyoctanooxy)phenanthro[3,4-c]phenanthrene (¼4,13-(Epoxyoctanooxy)hexahelicene;
13b). The soln. of 12b (100 mg, 0.21 mmol) and I2 (107 mg, 0.42 mmol) in 2 l benzene was purged
with O2-free N2 for 30 min. Methyloxiran (1.5 ml, 21 mmol) was added, and the irradiation was started
with a Hanovia-450-W medium-pressure lamp, equipped with a Pyrex filter. The flow of N2 was reduced
but maintained until the reaction was complete, which became visible by the disappearance of the red
color (I2). The soln. was then treated with an aq. soln. of NaHSO3, dried (MgSO4), concentrated, and
filtered. CC (3 ꢁ 30 cm, alkaline Al2O3/Et2O) gave the desired 13b. The chromatography was repeated
with toluene/PE. Yield: 32 mg (32%). Pale yellow-crystals. M.p. 2438. FD-MS: 470 (100, Mþ). Anal. calc.
for C34H30O2 (470.6): C 86.78, H 6.43; found: C 86.83, H 6.55.
9,16-(Epoxydecanooxy)phenanthro[3,4-c]phenanthrene (¼4,13-(Epoxydecanooxy)hexahelicene;
13c). Prepared as described for 12b ! 13b. Yield: 38 mg (37%). Pale-yellow crystals. M.p. 2528. FD-
MS: 498 (100, Mþ). Anal. calc. for C36H34O2 (498.7): C 86.71, H 6.87; found: C 86.58, H 6.90.