Helvetica Chimica Acta ± Vol. 83 (2000)
3119
Experimental Part
General. Unless stated otherwise, all reagents and chemicals were obtained from commercial sources and
1
used without further purification. All reactions were conducted under an inert atmosphere of N
Spectra were obtained in a deuterated solvent (CDCl or D
2
. H-NMR
3
2
O) at 200 or 400 MHz; chemical shifts (d) in ppm
, 4.72 ppm for H O). The
relative to the residual non-deuterated solvent absorption (7.24 ppm for CHCl
3
2
13
C-NMR Spectra were recorded at 75 MHz; chemical shifts were referenced to the 13C resonance of CHCl
3
(
77.0 ppm).
H
2
O Determination. A blank sample of D
reference was recorded, and the H O signal was integrated (A). A sample of product was introduced in the same
tube and was recorded under the same conditions. The H O signal was integrated (B), after which subtraction of
B from A gave the integration (C) corresponding to the amount of H O from the product.
2
O with a known concentration of fumaronitrile as an internal
2
2
2
Bis(tetrahydrothiophenium) Salt 2 of 1-[2,5-bis(chloromethyl)-4-methoxyphenoxy]-3,7-dimethyloctane
BCDM; 1). Compound 1 (10 g, 27.7 mmol) and 12.4 g of tetrahydrothiophene (141 mmol) in 20 ml of MeOH
(
were stirred for 70 h at 308. The excess tetrahydrothiophene was distilled off, the crude product was dissolved in
a minimum amount of MeOH and precipitated in 100 ml of ice-cold acetone. The precipitate was washed with
4
3
0
4
0 ml of hexane and dried under vacuum for 4 h to give 11 g (75%) of 2. M.p. 81 ± 838 [11]. IR (NaCl): 3353,
1
016, 2926, 2462, 1633, 1514, 1463, 1417, 1317, 1226, 920, 875, 786, 739, 699, 662. H-NMR (D
2
O, 400 MHz):
O);
O, 75 MHz): 19.10 (C(9')); 22.07, 22.16 (C(8')); 24.13
.71 ± 1.80 (m, 19 H, alkyl side chain); 2.24 (m, 4SCH
2
CH
2 2 2
); 3.43 (m, 4 SCH ); 3.82 (s, MeO); 4.11 (m, CH
1
3
.33 (s, 2 ArCH
2
S); 7.12 (s, 2 arom. H). C-NMR (D
2
(C(5')); 27.41 (C(7')); 28.50, 28.55 (C(3')); 29.06 (C(11)); 35.37 (C(2')); 36.43 (C(4')); 38.64 (C(6')); 41.68 (C(7));
4
1
3.22 (C(8)); 48.99 (C(10)); 56.37 (C(9)); 67.75 (C(1')); 116.38, 115.55 (C(3), C(6)); 119.91, 119.86 (C(2), C(5));
51.41, 152.03 (C(1), C(4)).
1
-{2-[(Butylsulfanyl)methyl]-5-(chloromethyl)-4-methoxyphenoxy}-3,7-dimethyloctane (3) and 1-{5-[(Bu-
tylsulfanyl)methyl]-2-(chloromethyl)-4-methoxyphenoxy}-3,7-dimethyloctane (4). A mixture of 0.1342 g
1 equiv.) of t-BuONa and 0.1234 g (0.98 equiv.) of BuSH in 10 ml of MeOH was stirred for 30 min at 208.
(
The clear soln. was added dropwise to a stirred soln. of 0.834 g of 2 in 40 ml of MeOH at 108. After 40 min, the
soln. was neutralized with 1m aq. HCl and evaporated on a rotary evaporator. The crude product was diluted
with 20 ml of CHCl , and the precipitate was filtered off. The filtrate was concentrated in vacuo. The oil thus
3
obtained was diluted with 20 ml of octane and concentrated to remove tetrahydrothiophene. This sequence was
repeated three times to afford a mixture of 1 (18%), 3 and 4 (74%, in a 51:49 ratio), and the disubstituted
1
product (7%) as a light yellow viscous oil (39.5 g), calculated from H-NMR integral curve. IR (NaCl): 2954,
1
2
4
927, 2869, 1507, 1465, 1409, 1212, 1036, 865, 739, 696. H-NMR (CDCl
3
, 200 MHz): 6.92 ± 6.78 (br., 2 arom. H);
); 2.45
, 75 MHz): 13.56 (C(12)); 19.55 (C(9')); 21.91
C(11)); 22.45, 22.55 (C(8')); 24.53 (C(5')); 27.81 (C(7')); 29.64, 29.69 (C(3'), C(8)); 30.01 (C(9)); 31.39 (C(10));
2 2 2
.61 (s, CH Cl); 4.20 ± 3.75 (br., CH O); 3.84 ± 3.77 (4s, MeO, four compounds); 4.61 (m, BuSCH
S); 0.8 ± 2.0 (br., 19 H, alkyl side chain). 13C-NMR (CDCl
3
(
(
t, CH
2
3
1
1
6.10, 36.17, 36.25 (C(2')); 37.09, 37.14 (C(6')); 41.12, 41.44 (C(7)); 55.94, 56.04 (C(13)); 67.09, 67.19 (C(1'));
12.89, 113.12, 113.98, 114.24 (C(3), C(6)); 124.53, 124.86, 126.16, 126.58, 126.88, 128.46, 128.89 (C(2), C(5));
50.47, 150.87 (C(1), C(4)).
Compounds 3 and 4 (cf. Entry 3 in Table 1). A mixture of t-BuONa (0.86 g, 9 mmol) and BuSH (0.81 g,
mmol) in MeOH (20 g) was stirred for 30 min at 208. The clear soln. was added dropwise to a stirred soln. of 1
9
(
(
3.25 g, 9 mmol) in MeOH (70 g). After 1 h, the mixture was neutralized with 1m aq. HCl, diluted with CHCl
3
250 ml), washed with H
2
O (2Â 100 ml), dried (MgSO
4
), and concentrated in vacuo to give 3.70 g of a yellow oil,
which consists of a mixture of 1 (21%), 3 and 4 (56%, ratio 43 :57), and disubstituted product (23%), calculated
from H-NMR integral curve. IR (NaCl): 2954, 2927, 2869, 1507, 1465, 1409, 1212, 1036, 865, 739, 696. H-NMR
1
1