Helvetica Chimica Acta – Vol. 90 (2007)
2409
1
1
3
H); 7.01 (d, J ¼ 8.3, 1 H); 6.59 (d, J ¼ 9.7, 1 H); 6.05 (d, J ¼ 9.7, 1 H). 13C-NMR: 148.2; 145.6; 135.1;
28.6; 128.1; 128.0; 127.8; 127.3; 126.8; 126.1; 125.1; 125.0; 124.3; 122.5; 121.0; 115.9; 83.6. HR-MS:
þ
þ
34.1358 (M , C H O ; calc. 334.1358).
25
18
2-Methyl-2-(4-methylpent-3-enyl)-2H-benzo[h]chromene (17). Reaction of 12 (144 mg, 1 mmol)
with citral (304mg, 2 mmol) in CHCl 3 (10 ml) afforded 17 (209 mg, 75%). Liquid. IR (neat): 3054, 2971,
1
2
924, 1645, 1618, 1568, 1508, 1449, 1383, 1338, 1271, 1188, 1098, 995, 924, 814, 754, 731. H-NMR: 8.27 –
8
.24( m, 1 H); 7.77 – 7.74( m, 1 H); 7.4 9 – 7.4 5 m( , 2 H); 7.44 (d, J ¼ 8.3, 1 H); 7.35 (d, J ¼ 8.3, 1 H); 6.49 (d,
J ¼ 9.8, 1 H); 5.62 (d, J ¼ 9.8, 1 H); 5.19 – 5.14( m, 1 H); 2.29 – 2.18 (m, 2 H); 1.91 – 1.77 (m, 2 H); 1.69 (s,
13
3
1
1
H); 1.60 (s, 3 H); 1.52 (s, 3 H). C-NMR: 148.8; 134.9; 132.2; 128.8; 128.0; 126.5; 125.6; 125.3; 125.0;
þ
24.6; 123.7; 122.4; 120.0; 115.5; 79.6; 41.6; 26.8; 26.1; 23.1; 18.0. EI-MS: 278 (M ), 263, 196, 195, 194,166,
65, 152, 69. HR-MS: 278.1673 (M , C H O ; calc. 278.1671).
þ
þ
20
22
2-(4,8-Dimethylnona-3,7-dienyl)-2-methyl-2H-benzo[h]chromene (18). Reaction of 12 (144 mg,
1
mmol) with (E,E)-farnesal (441 mg, 2 mmol) in CHCl (10 ml) afforded 18 (289 mg, 83%). Liquid. IR
3
(
neat): 3054, 2967, 2924, 1645, 1618, 1568, 1508, 1449, 1381, 1271, 1188, 1101, 995, 924, 814, 754, 731.
1
H-NMR: 8.30 – 8.27 (m, 1 H); 7.79 – 7.76 (m, 1 H); 7.51 – 7.45 (m, 2 H); 7.37 (d, J ¼ 8.3, 1 H); 7.18 (d, J ¼
8
(
.3, 1 H); 6.51 (d, J ¼ 9.8, 1 H); 5.63 (d, J ¼ 9.8, 1 H); 5.21 – 5.16 (m, 2 H); 2.33 – 2.26 (m, 2 H); 2.16 – 2.00
13
m, 4H); 1.97 – 1.82 ( m, 2 H); 1.75 (s, 3 H); 1.73 (s, 3 H); 1.66 (s, 3 H); 1.64 (s, 3 H). C-NMR: 148.9;
1
5
5
35.8; 135.0; 131.8; 128.8; 128.1; 126.5; 125.7; 125.4; 125.1; 124.9; 124.5; 123.7; 122.5; 120.1; 115.6; 79.6;
þ
4.0; 41.7; 40.2; 26.8; 26.2; 22.9; 18.2; 16.4. EI-MS: 346 (M ), 196, 195, 165, 137, 107, 95, 93, 81, 69, 68, 67,
þ
þ
5. HR-MS: 346.2298 (M , C H O ; calc. 346.2297).
25
30
(
8R,10R)-9,10,11,11a-Tetrahydro-9,9-dimethyl-8,10-methano-8H-benzo[c]xanthene (19). Reaction
of 12 (144 mg, 1 mmol) with (À)-(1R)-myrtenal (300 mg, 2 mmol) in CHCl (10 ml) afforded 19 (213 mg,
3
1
7
1
5
2
7%). Liquid: IR (neat): 2926, 1566, 1462, 1387, 1263, 1192, 1101, 804, 745. H-NMR: 8.09 – 8.04( m,
H); 7.62 – 7.57 (m, 1 H); 7.33 – 7.26 (m, 2 H); 7.22 (d, J ¼ 8.3, 1 H); 7.02 (d, J ¼ 8.3, 1 H); 6.01 (s, 1 H);
.07 – 5.01 (m, 1 H); 2.65 – 2.61 (m, 2 H); 2.27 – 1.91 (m, 5 H); 1.20 (s, 3 H); 0.85 (s, 3 H). HR-MS:
þ
þ
76.1515 (M , C H O ; calc. 276.1514).
20
20
(
10S)-9,10,11,11a-Tetrahydro-10-(1-methylethenyl)-8H-benzo[c]xanthene (20). Reaction of 12
(
(
1
144 mg, 1 mmol) with (S)-(À)-perillaldehyde (300 mg, 2 mmol) in CHCl3 (10 ml) afforded 20
193 mg, 70%). Liquid. IR (neat): 3054, 2938, 1644, 1570, 1510, 1435, 1395, 1335, 1262, 1248, 1196,
1
092, 1017, 889, 862, 804, 744. H-NMR: 8.18 – 8.15 (m, 1 H); 7.73 – 7.70 (m, 1 H); 7.45 – 7.38 (m, 2 H); 7.32
(
d, J ¼ 8.3, 1 H); 7.06 (d, J ¼ 8.3, 1 H); 6.15 (s, 1 H); 5.35 – 5.32 (m, 1 H); 4 .98 (s , 1 H); 4 .93 (s , 1 H); 2.69 –
2
3
1
2
.56 (m, 2 H); 2.35 – 2.31 (m, 2 H); 2.25 – 2.16 (m, 1 H); 2.05 – 1.95 (m, 1 H); 1.88 – 1.68 (m, 1 H); 1.84 (s,
13
H). C-NMR: 148.6; 146.7; 136.9; 134.4; 128.1; 126.1; 125.6; 124.8; 124.6; 122.1; 120.4; 117.8; 116.9;
þ
11.7; 74.7; 39.5; 36.5; 32.2; 28.4; 22.8. EI-MS: 276 (M ), 275, 261, 248, 247, 234, 233, 221, 220, 219, 208,
þ
þ
07, 195, 194, 181, 178, 165, 152. HR-MS: 276.1512 (M , C H O ; calc. 276.1514)
20
20
6
-Chloro-2,2-dimethyl-2H-benzo[h]chromene (21). Reaction of 4-chloronaphthalen-1-ol (14;
1
6
1
1
1
2
79 mg, 1 mmol) with 3-methylbut-2-enal (168 mg, 2 mmol) in CHCl3 (10 ml) afforded 21 (151 mg,
2%). Liquid. IR (neat): 3046, 2976, 2926, 1644, 1616, 1593, 1564, 1505, 1453, 1426, 1373, 1318, 1273, 1202,
1
165, 1125, 957, 889, 760. H-NMR: 8.24– 8.21 ( m, 1 H); 8.15 – 8.12 (m, 1 H); 7.57 – 7.46 (m, 2 H); 7.25 (s,
13
H); 6.36 (d, J ¼ 9.7, 1 H); 5.63 (d, J ¼ 9.7, 1 H); 1.55 (s, 6 H). C-NMR: 147.7; 131.5; 130.5; 127.6; 126.5;
þ
þ
26.4; 124.7; 123.1; 122.8; 122.3; 116.1; 77.6; 28.3; 28.2. HR-MS: 244.0652 (M , C H ClO ; calc.
15
13
44.0655).
-Chloro-2,2-diphenyl-2H-benzo[h]chromene (22). Reaction of 14 (179 mg, 1 mmol) with 3,3-
6
diphenylprop-2-enal (417 mg, 2 mmol) in CHCl (10 ml) afforded 22 (221 mg, 60%). Solid. M.p. 147 –
3
1
1
488. IR (KBr) 2924, 1449, 1373, 1265, 1213, 1113, 978, 932, 760. H-NMR: 8.36 – 8.35 (m, 1 H); 8.13 –
.10 (m, 1 H); 7.54– 7.47 ( m, 6 H); 7.34– 7.21 ( m, 7 H); 6.67 (d, J ¼ 9.7, 1 H); 6.21 (d, J ¼ 9.7, 1 H).
C-NMR: 147.2; 145.1; 143.9; 131.7; 128.6; 128.1; 127.8; 127.3; 126.8; 126.3; 124.9; 124.7; 123.5; 122.8;
8
13
þ
þ
8
3.6. EI-MS: 368 (M ), 333, 302, 293, 292, 291, 228, 226, 191, 178, 165. HR-MS: 268.0966 (M ,
þ
C H ClO ; calc. 368.0968).
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17
6-Chloro-2-methyl-2-(4-methylpent-3-enyl)-2H-benzo[h]chromene (23). Reaction of 14 (179 mg,
1
2
1
mmol) with citral (304mg, 2 mmol) in CHCl 3 (10 ml) afforded 23 (172 mg, 55%). Liquid. IR (neat):
971, 2924, 1644, 1564, 1505, 1451, 1375, 1271, 1196, 1113, 995, 901, 877, 760. H-NMR: 8.24– 8.21 ( m,
H); 8.15 – 8.12 (m, 1 H); 7.57 – 7.43 (m, 2 H); 7.24( s, 1 H); 6.4 0 (d , J ¼ 9.8, 1 H); 5.62 (d, J ¼ 9.8, 1 H);
1