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Helvetica Chimica Acta – Vol.90 (2007)
(2E)-4-(3,4-Dimethoxy-2,5-bis(methoxymethoxy)-6-methylphenyl)-2-methylbut-2-en-1-ol (5).
Bu4NF · H2O (0.39 g, 1.5 mmol) in THF (5 ml) was quickly added to a soln. of 4 (0.47 g, 1 mmol) in
THF (20 ml) at 08.After stirring at 0 8 for 40 min, the reaction was quenched with an sat.aq.NH 4Cl soln.
(15 ml).The aq.phase was extracted with Et 2O (3 ꢀ 15 ml), the combined org.phase washed with brine
(4 ꢀ 10 ml), dried (Na2SO4), and concentrated, and the crude product purified by CC (SiO2, petroleum
ether/AcOEt 4 :1): pure 5 (0.344 g, 96.6%). Colorless oil. IR (film): 3431, 2924, 1467, 1427, 1393, 1158,
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1055, 975. H-NMR (400 MHz, CDCl3): 1.63 (s, OH); 1.83 (s, MeÀC(2)); 2.18 (s, MeÀC(6’)); 3.42 (d,
3J ¼ 6.4, CH2(4)); 3.58, 3.60 (2s, 2 MeOCH2); 3.86 (s, MeOÀ(3’), MeOÀC(4’)); 4.00 (s, CH2(1)); 5.05,
5.08 (2s, 2 OCH2O); 5.35 (t, 3J ¼ 5.1, HÀC(3)).EI-MS: 356 (27, Mþ), 294 (86), 249 (100), 235 (26), 217
(83), 189 (32), 83 (43), 45 (91).HR-EI-MS: 3561. 851 ( Mþ, C18H28O7þ ; calc.3561. 835).
1-[(2E)-4-Chloro-3-methylbut-2-enyl]-3,4-dimethoxy-2,5-bis(methoxymethoxy)-6-methylbenzene
(6). MsCl (0.2 ml, 2.63 mmol) was added dropwise to a stirred suspension of 5 (0.36 g, 1.01 mmol), 2,6-
dimethylpyridine (0.32 ml, 2.73 mmol) and LiCl (0.107 g, 2.53 mmol) in DMF (20 ml) at À 58.After
stirring at À 58 for 4 h, H2O (30 ml) was added, the resulting mixture extracted with petroleum ether/
Et2O 1:1 (3 ꢀ 40 ml), the combined org.phase washed with H 2O (4 ꢀ 30 ml), dried (Na2SO4), and
concentrated, and the crude product purified by CC (SiO2, petroleum ether/AcOEt 10 :1): pure 6
(0.365 g, 96.8%). Colorless oil. IR (film): 2991, 1159, 1103, 1025, 974, 666. 1H-NMR (400 MHz, CDCl3):
1.89 (s, MeÀC(3)’)); 2.17 (s, MeÀC(6)); 3.44 (d, 3J ¼ 6.4, CH2(1’)); 3.56, 3.59 (2s, 2 MeOCH2); 3.85, 3.86
(2s, MeOÀC(3), MeOÀC(4)); 4.00 (s, ClCH2 (4’)); 5.05, 5.06 (2s, 2 OCH2O); 5.48 (t, 3J ¼ 6.6, HÀC(2’)).
13C-NMR (100 MHz, CDCl3): 12.4 (MeÀC(6)); 14.3 (MeÀC(3’)); 26.2 (CH2(1’)); 52.2 (C(4’)); 57.4
(2 MeOCH2); 60.9 (MeOÀC(3), MeOÀ(4)); 99.3, 99.5 (2 OCH2O); 125.9 (C(6)); 128.0 (C(2’)); 129.1
(C(1)); 131.6 (C(3’)); 144.34 (C(3)); 144.9 (C(4)); 145.0 (C(5)); 145.3 (C(2)). EI-MS: 376 (1, M(37Cl)þ),
374 (3, M(35Cl)þ), 294 (44), 249 (100), 217 (38), 91 (14). HR-EI-MS: 376.1452/374.1480 (Mþ,
C18H27ClOþ6 ; calc. 376.1467/374.1496).
1-Chloro-4-[(2E,6E,10E,14E,18E,22E,26E,30E)-3,7,11,15,19,23,27,31,35-nonamethylhexatriaconta-
2,6,10,14,18,22,26,30,34-nonaenylsulfonyl]benzene (7).Sodium 4-chlorobenzenesulfinate (29.8 g,
15 mmol) and solanesyl bromide, prepared from solanesol (6.3 g, 10 mmol) and phosphorous tribromide
(0.5 ml, 5 mmol), were dissolved in DMF (80 ml). After stirring for 24 h at r.t., the mixture was poured
into H2O (50 ml) and Et2O (50 ml), the aq.phase extracted with Et O (3 ꢀ 80 ml), the combined org.
2
phase washed with H2O (3 ꢀ 80 ml), dried (Na2SO4), and concentrated, and the crude product
recrystallized from EtOH: pure 7 (6.7 g, 85%). White solid. M.p. 49.1 – 49.68.IR (KBr): 3087, 3053, 2919,
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1664, 1582, 1152, 1089, 767. H-NMR (400 MHz, CDCl3): 1.36, 1.60, 1.68 (3s, 10 MeC¼CH); 1.98 – 2.10
(m, 8 (CH2)2C¼C); 3.80 (d, 3J ¼ 7.2, SO2CH2); 5.05 – 5.19 (m, 9 C¼CH); 7.50 (d, 3J ¼ 8.8, 2 arom. H); 7.50
(d, 3J ¼ 8.8, 2 arom. H). 13C-NMR (100 MHz, CDCl3): 16.0, 16.3 (8 MeC¼C); 17.6 (1 MeÀC(35’)); 25.6
(1 MeÀC(35’)); 26.1, 26.6 – 26.7 (8 CH2CH¼C); 39.6 – 39.7 (8 CH2C(Me)¼C); 56.1 (SO2CH2(1’)); 110.0
(C(2’)); 123.1 – 124.4 (8 CH¼C); 129.2 – 131.1 (8 C(Me)¼C); 134.8 – 135.8 (C(3’), C(2), C(3), C(5),
C(6)); 137.2 (C(1)); 145.3 (C(4)); 140.3 (C(1)). ESI-MS: 813.9 (20, [M(37Cl) þ Na]þ), 812.9 (24), 811.9
(37, [M(35Cl) þ Na]þ) 475.5 (53), 301.3 (100). HR-MALDI-MS: 813.5353 and 811.5385 ([M þ Na]þ,
C51H77ClNaO2Sþ; calc. 813.5303 and 811.5333).
1-[(2E,6E,10E,14E,18E,22E,26E,30E,34E)-5-(4-Chlorophenylsulfonyl)-3,7,11,15,19,23,27,31,35,39-
decamethyltetraconta-2,6,10,14,18,22,26,30,34,38-decaenyl]-3,4-dimethoxy-2,5-bis(methoxymethoxy)-6-
methylbenzene (8).At À 708, 2.89m BuLi in hexane (0.5 ml) was added dropwise under stirring to a soln.
of 7 (0.95 g, 1.2 mmol) in THF/HMPA 8 :1 (25 ml), within 30 min under N2.After stirring at À 708 for
30 min, a soln.of 6 (0.258 g, 0.69 mmol) in THF (2 ml) was added dropwise, and the resulting mixture
was allowed to warm to r.t. over 2 h. After stirring for 1 h at r.t., H2O (20 ml) was added, the mixture
extracted with Et2O (3 ꢀ 50 ml), the combined org.phase washed with 1 n aq.HCl (50 ml) and H O
2
(50 ml), dried (Na2SO4), and concentrated, and the crude product purified by CC (SiO2, petroleum
ether/AcOEt 8 :1): pure 8 (0.59 g, 75.8%). Yellow oil. IR (film): 3050, 2958, 2922, 1664, 1597, 1056, 978,
665. 1H-NMR (400 MHz, CDCl3): 1.23 (s, MeC¼C); 1.60 (s, 8 MeC¼C); 1.68, 1.70 (2s, 2 MeC¼C); 1.85 –
2.10 (m, 8 (CH2)2CH¼C, MeÀC(6)); 2.22 (t, 2J ¼ À12.4, 3J ¼ 12.4, 1 H, CH2(4’)); 2.88 (d, 2J ¼ À12.4, 1 H,
CH2(4’)); 3.28 (dd, 2J ¼ À15.2, 3J ¼ 6.4, 1 H, CH2(1’)); 3.35 (dd, 2J ¼ À15.2, 3J ¼ 6.4, 1 H, CH2(1’)); 3.54,
3.57 (2s, 2 MeOCH2O); 3.84 (s, MeOÀC(3), MeOÀC(4)); 3.89 (m, HÀC(5’)); 4.84 (d, 3J ¼ 10.4,
HÀC(6’)); 5.00, 5.02 (2s, 2 OCH2O); 5.07 – 5.13 (m, 9 C¼CH); 7.46 (d, 3J ¼ 8.4, 2 arom. H (ArSO2)); 7.75