SCHINK ET AL.
7
filtered, washed with 5 ml of demineralized water, and
dried under reduced pressure. Yields: 1.86-g (89%) 6a,
2.06-g (94%) 6b, and 1.98-g (89%) 6c.
4.5 | Synthesis and characterization of 6d
and 6e (modified after Marukawa et al.61)
In a 100-ml Schlenk tube was placed 1.75 mmol of the
respective α,ω-dihydroxyalkane (550-mg 5d and 600-mg
5e), which was dissolved in a mixture of 25 ml of
pyridine and 25 ml of chloroform. The solution was then
cooled to 0ꢀC–5ꢀC using a cryostat; 6.29-mmol (1.23 g)
p-toluenesulfonyl chloride is added in portions over a
period of 30 min. The resulting solution was stirred
under cooling for 18 h. Then 50 ml of demineralized
water was added to the reaction mixture, which was
then extracted three times with 50 ml of chloroform in a
separating funnel. The combined organic phases were
washed with diluted hydrochloric acid, saturated
NaHCO3 solution, and brine before they were dried over
Na2SO4 and filtered. Evaporation of the solvent yields
crude 6d and 6e, respectively as white solids. 6d was
purified by recrystallization from a mixture of acetone
and ethanol. After standing in the refrigerator overnight,
the crystalline material was filtered, washed with 5 ml of
demineralized water, and dried under reduced pressure.
Yield: 937-mg (86%) 6d. 6e was purified by column
chromatography using chloroform as the eluent. Yield:
946-mg (83%) 6e.
4.4.1 | Tetradecane-1,14-diyl bis
(4-methylbenzenesulfonate) (6a)
1
m.p. 77ꢀC–79ꢀC60; H-NMR (500 MHz, CDCl3, 298 K): δ
(ppm) = 1.19–1.24 (s, 16H), 1.25–1.32 (m, 4H), 1.58–1.68
3
(m, 4H), 2.45 (s, 6H), 4.02 (t, JCH2/CH2 = 6.59 Hz, 4H),
3
3
7.35 (d, JCH2/CH2 = 8.59 Hz, 4H), 7.79 (d, JCH2/
= 8.59 Hz, 4H); 13C-NMR (126 MHz, CDCl3, 298 K):
CH2
δ (ppm) = 21.59, 25.28, 28.77, 28.87, 29.32, 29.42, 29.45,
29.49, 70.68, 127.84, 129.76, 133.22, 144.59; IR (ATR): ~ν
(cm−1) = 3061 (w, CHarom.), 2976 (w, CH3), 2922
(m, CH2), 2850 (m, CH2), 1597 (w, C Carom.), 1473
(m, C Carom.), 1356 (s, SO2), 1173 (s, SO2), 947 (s), 835
(s, CHarom.), 723 (w, CH2), 665 (m), 553 (s).
4.4.2 | Hexadecane-1,16-diyl bis
(4-methylbenzenesulfonate) (6b)
1
m.p. 81ꢀC–83ꢀC56; H-NMR (500 MHz, CDCl3, 298 K): δ
(ppm) = 1.18–1.26 (m, 20H), 1.26–1.34 (m, 4H), 1.59–1.67
3
(m, 4H), 2.45 (s, 6H), 4.02 (t, JCH2/CH2 = 6.30 Hz, 4H),
3
3
7.35 (d, JCH2/CH2 = 8.59 Hz, 4H), 7.79 (d, JCH2/
4.5.1 | Icosane-1,20-diyl bis
(4-methylbenzenesulfonate) (6d)
= 8.59 Hz, 4H); 13C-NMR (126 MHz, CDCl3, 298 K):
CH2
δ (ppm) = 21.59, 25.28, 28.77, 28.88, 29.33, 29.44, 29.45,
29.54, 70.68, 127.84, 129.76, 133.23, 144.59; IR (ATR): ~ν
(cm−1) = 3053 (w, CHarom.), 2976 (w, CH3), 2920 (m,
CH2), 2849 (m, CH2), 1599 (w, C Carom.), 1474 (m,
C Carom.), 1356 (s, SO2), 1173 (s, SO2), 947 (s), 837 (s,
CHarom.), 721 (w, CH2), 665 (m), 553 (s).
1
m.p. 92ꢀC–93ꢀC; H-NMR (500 MHz, CDCl3, 298 K): δ
(ppm) = 1.18–1.34 (m, 32H), 1.60–1.67 (m, 4H), 2.45 (s,
6H), 4.02 (t, JCH2/CH2 = 6.59 Hz, 4H), 7.35 (d, JCH2/
3
3
3
= 8.02 Hz, 4H), 7.79 (d, JCH2/CH2 = 8.2 Hz, 4H);
CH2
13C-NMR (126 MHz, CDCl3, 298 K): δ (ppm) = 21.84,
25.54, 29.03, 29.14, 29.60, 29.72, 29.82, 29.87, 29.91, 70.94,
128.10, 130.02, 133.49, 144.84; IR (ATR): ~ν (cm−1) = 3049
(w, CHarom.), 2980 (w, CH3), 2918 (m, CH2), 2848 (m,
CH2), 1597 (w,. C Carom.), 1476 (m, C Carom.), 1356 (s,
SO2), 1175 (s, SO2), 947 (s), 837 (s, CHarom.), 719 (w,
CH2), 665 (m), 554 (s).
4.4.3 | Octadecane-1,18-diyl bis
(4-methylbenzenesulfonate) (6c)
1
m.p. 89ꢀC–91ꢀC; H-NMR (600 MHz, CDCl3, 298 K): δ
(ppm) = 1.13–1.45 (m, 28H), 1.58–1.78 (m, 4H), 2.45
3
(s, 6H), 4.02 (t, JCH2/CH2 = 6.72 Hz, 4H), 7.34 (d,
3
3JCH2/CH2 = 7.70 Hz, 4H), 7.79 (d, JCH2/CH2 = 7.70 Hz,
4.5.2 | Docosane-1,22-diyl bis
(4-methylbenzenesulfonate) (6e)
4H); 13C-NMR (151 MHz, CDCl3, 298 K):
δ
(ppm) = 21.58, 25.26, 28.75, 28.86, 29.33, 29.44, 29.55,
29.61, 70.67, 127.81, 129.75, 133.17, 144.58; IR (ATR): ~ν
(cm−1) = 3061 (w, CHarom.), 2976 (w, CH3), 2918 (m,
CH2), 2848 (m, CH2), 1599 (w, C Carom.), 1474 (m,
C Carom.), 1355 (s, SO2), 1172 (s, SO2), 947 (s), 837 (s,
CHarom.), 721 (w, CH2), 665 (m), 554 (s); elemental
analysis: calcd. C 64.61, H 8.47, S 10.78, found C 65.01, H
8.44, S 10.64.
1
m.p. 98ꢀC–99ꢀC; H-NMR (600 MHz, CDCl3, 298 K): δ
(ppm) = 1.15–1.35 (m, 36H), 1.59–1.67 (m, 4H), 2.45
3
(s, 6H), 4.02 (t, JCH2/CH2 = 6.51 Hz, 4H), 7.35 (d,
3JCH2/CH2 = 8.07 Hz, 4H), 7.79 (d, JCH2/CH2 = 8.25 Hz,
3
4H); 13C-NMR (151 MHz, CDCl3, 298 K):
(ppm) = 21.59, 25.27, 28.76, 28.88, 29.34, 29.46, 29.57,
29.61, 29.64, 29.66, 70.68, 127.84, 129.75, 133.18,
δ