CH2N), 4.73 (2H, s, NCH2O); δC 17.6, 27.8, 31.4, 45.7, 66.7,
1-Cyclododecyloxymethylpyrrolidin-2-one 34
74.0, 174.9.
Recrystallised from dichloromethane–light petroleum (yield
85%), mp 50–52 ЊC; δH 1.35 (18 H, m, CH2), 1.43 (2 H, m, CH2),
1.61 (2 H, m, CH2), 2.04 (2 H, m, CH2 pyr), 2.41 (2 H, t, J 8.3,
CH2 pyr), 3.50 (2 H, t, J 8.3 CH2 pyr), 3.56 (1 H, m, OCH), 4.73
(2 H, s, OCH2N); δC 17.9, 20.9 (2 C), 23.2 (2 C), 23.4 (2 C), 24.1,
24.1 (2 C), 29.2 (2 C), 31.2, 45.9, 70.4, 74.3, 175.6 (Found:
C, 72.5; H, 11.2, N, 4.7. C17H31NO2 requires C, 72.5; H, 11.1;
N, 5.0%).
Methoxymethylcyclododecane28 28
Oil (yield 92%); δH 1.20–1.80 (22 H, m, CH2), 3.37 (3 H, s,
OMe), 3.57 (1 H, m, OCH), 4.64 (2H, s, OCH2O); δC 20.9, 23.2,
23.3, 24.5, 29.5, 55.3, 74.5, 94.7.
1,2:5,6-Di-O-isopropylidene-3-O-methoxymethyl-ꢀ-D-gluco-
furanose29 29
1,2:5,6-Di-O-isopropylidene-3-O-(2-oxopyrrolidin-1-ylmethyl)-
ꢀ-D-glucofuranose 35
Syrup (65%), [α]2D0 Ϫ20.5 (c 1.80, CHCl3) {lit.29 [α]2D0 Ϫ17.9 (c 2.2,
CHCl3)}; δH 1.32 (3 H, s, Me), 1.34 (3 H, s, Me), 1.42 (3 H, s,
Me), 1.50 (3 H, s, Me), 3.41 (3 H, s, OMe), 3.99 (1 H, dd, J 8.6
and 5.5, HA-6), 4.10 (1 H, dd, J 8.6 and 6.0, HB-6), 4.11(1 H, dd,
J 8.6 and 3.0, H-4), 4.21 (1 H, d, J 3.0, H-3), 4.28 (1 H, d[t],
J 8.5 and 5.9, H-5), 4.57 (1 H, d, J 3.6, H-2), 4.71 and 4.74 (2 H,
ABq, J 6.7, OCH2OMe), 5.88 (1 H, d, J 3.6, H-1); δC 25.4, 26.3,
26.8 (2C), 55.8, 67.5, 72.3, 79.1, 81.1, 83.3, 96.1, 105.2, 109.1,
111.9.
Syrup (yield 76%), [α]2D0 Ϫ25.2 (c 1.59, CHCl3); δH 1.30 (3 H, s,
Me), 1.33 (3 H, s, Me), 1.40 (3 H, s, Me), 1.47 (3 H, s, Me), 2.03
(2 H, m, CH2 pyr), 2.42 (2 H, m, CH2 pyr), 3.40 (1 H, m,
CHAHBN), 3.66 (1 H, m, CHAHBN), 3.98 (1 H, dd, J 8.6 and
5.2, HA-6), 4.04 (1 H, dd, J 8.7 and 3.0, H-4), 4.05 (1H, d, J 3.0,
H-3), 4.09 (1 H, dd, J 8.6 and 6.1, HB-6), 4.25 (1 H, ddd, J 8.7,
6.1 and 5.2, H-5), 4.57 (1 H, d, J 3.6, H-2), 4.61 (1 H, d, J 10.5,
OCHAHBN), 5.02 (1 H, d, J 10.5, OCHAHBN), 5.85 (1 H, d,
J 3.6, H-1); δC 18.0, 25.4, 26.2, 26.8, 26.9, 31.1, 45.9, 53.4, 67.7,
71.5, 72.2, 79.1, 80.9, 82.8, 105.3, 109.1, 112.0, 176.2 (Found:
C, 57.2; H, 7.8; N, 3.8. C17H27NO7 requires C, 57.1; H, 7.6;
N, 3.9%).
3ꢁ-(Methoxymethoxy)cholestane30 30
Recrystallised from light petroleum (88%), mp 64–65 ЊC (lit.30b
64–64 ЊC); [α]2D2 ϩ18.4 (c 1.51, CHCl3) {lit.30b [α]2D2 ϩ18.5
(CHCl3)}; δH 0.64 (3 H, s, Me-11), 0.80 (3 H, s, Me-19), 0.85
(3 H, d, J 6.5, Me-26 or -27), 0.86 (3 H, d, J 6.5, Me-27 or -26),
0.89 (3 H, d, J 6.5, Me-21), 0.90–2.00 (31 H, complex), 3.36 (3
H, s, OMe), 3.49 (1 H, m, H-3), 4.67 and 4.68 (2 H, ABq, J 7.0,
OCH2O); δC 12.0, 12.2, 18.6, 21.2, 22.5, 22.8, 23.8, 24.2, 28.0,
28.2, 28.7, 28.8, 32.1, 35.2, 35.5, 35.6, 35.8, 36.1, 37.0, 39.5,
40.0, 42.6, 44.8, 54.3, 55.1, 56.2, 56.4, 76.3, 94.5.
1-(Cholestan-3ꢁ-yloxymethyl)pyrrolidin-2-one 36
Recrystallised from light petroleum (yield 81%), mp 108–109
ЊC, [α]2D0 ϩ10.6 (c 1.06, CHCl3); δH 0.63 (3 H, s, Me-11), 0.78
(3 H, s, Me-19), 0.85 (3 H, d, J 6.6, Me-26 or -27), 0.86 (3 H, d,
J 6.6, Me-27 or -26), 0.89 (3 H, d, J 6.6, Me-21), 0.90–2.00
(31 H, complex), 2.05 (2 H, m, CH2 pyr), 2.41 (2 H, t, J 7.9, CH2
pyr), 3.31 (1 H, m, H-3), 3.48 (2 H, t, J 7.1, CH2N), 4.75 and
4.79 (2 H, ABq, J 7.9, OCH2N); δC 11.9, 12.2, 17.9, 18.6, 21.1,
22.5, 22.8, 23.7, 24.1, 27.9, 28.2, 28.3, 28.7, 31.2, 31.9, 34.8,
35.4, 35.5, 35.7, 36.1, 36.8, 39.4, 39.9, 42.5, 44.6, 45.7, 54.2,
56.1, 56.4, 70.3, 76.3, 175.5 (Found: C, 79.2; H, 11.3; N, 3.0.
C32H55NO2 requires C, 79.1; H, 11.4; N, 2.9%).
(4-Methoxybenzyloxy)cyclododecane 31
Viscous oil (yield 89%); δH 1.30 (18 H, m, CH2), 1.52 (2 H, m,
CH2), 1.64 (2 H, m, CH2), 3.51 (1 H, m, OCH), 3.80 (3 H, s,
OMe), 4.44 (2 H, s, OCH2Ph), 6.87 (2 H, d, J 8.4, Ph), 7.27 (2 H,
d, J 8.4, Ph); δC 20.8 (2 C), 23.1 (2 C), 23.3 (2 C), 24.1, 24.6
(2 C), 28.9 (2 C), 55.3, 69.9, 75.9, 113.7 (2 C), 129.2 (2 C), 131.4,
159.0 (Found: C, 78.7; H, 10.8. C20H32O2 requires C, 78.9; H,
10.6%).
3-Cyclododecyloxymethyloxazolidin-2-one 37
Recrystallised from light petroleum (yield 89%), mp 72–74 ЊC;
δH 1.30–1.60 (22 H, complex), 1.45 (2 H, m, CH2), 1.63 (2 H, m,
CH2), 3.62 (1 H, m, OCH), 3.72 (2 H, m, CH2 oxa), 4.35 (2 H,
m, CH2 oxa), 4.75 (2 H, s, OCH2N); δC 20.8 (2 C), 23.1 (2 C),
23.3 (2 C), 23.9, 24.5 (2 C), 29.1 (2 C), 43.1, 62.0, 72.6, 74.8,
158.1 (Found: C, 67.6; H, 10.4, N, 4.9. C16H29NO3 requires C,
67.8; H, 10.3; N, 4.9%).
1,2:5,6-Di-O-isopropylidene-3-O-(4-methoxybenzyl)-ꢀ-D-gluco-
furanose 32
Viscous oil (yield 71%); [α]2D0 Ϫ22.2 (c 2.34, CHCl3); δH 1.31
(3 H, s, Me), 1.38 (3 H, s, Me), 1.43 (3 H, s, Me), 1.49 (3 H, s,
Me), 3.81 (3 H, s, OMe), 3.99 (1 H, dd, J 8.3 and 6.3, HA-6),
4.00 (1 H, d, J 3.1, H-3), 4.10 (1 H, dd, J 8.3 and 6.3, HB-6), 4.13
(1 H, dd, J 7.6 and 3.1, H-4), 4.34 (1 H, ddd, J 7.6, 6.3 and 5.7,
H-5), 4.56 (1 H, d, J 3.7, H-2), 4.58 (2 H, ABq, J 11.4,
OCH2Ph), 5.88 (1 H, d, J 3.7, H-1), 6.87 (2 H, d, J 8.7, Ph), 7.27
(2 H, d, J 8.7, Ph); δC 25.5, 26.3, 26.7(7), 26.8(4), 55.3, 67.4,
72.1, 73.0, 81.3(1), 81.3(3), 82.7, 105.3, 108.9, 111.8, 113.8,
129.3, 129.7, 159.4 (Found: C, 63.3; H, 7.2. C20H28O7 requires
C, 63.1; H, 7.4%).
1,2:5,6-Di-O-isopropylidene-3-O-(2-oxooxazolidin-3-ylmethyl)-
ꢀ-D-glucofuranose 38
Syrup (yield 64%), [α]2D0 Ϫ29.3 (c 2.48, CHCl3); δH 1.31 (3 H, s,
Me), 1.33 (3 H, s, Me), 1.42 (3 H, s, Me), 1.48 (3 H, s, Me), 3.63
(1 H, m, CHAHBCO), 3.88 (1, H, m CHAHBCO), 4.01 (1 H, dd,
J 8.8 and 4.6, HA-6), 4.05 (1 H, dd, J 8.9 and 3.0, H-4), 4.10
(1 H, dd, J 8.8 and 6.2, HB-6), 4.17 (1H, d, J 3.0, H-3), 4.25
1,2:5,6-Di-O-isopropylidene-3-O-benzyl-ꢀ-D-glucofuranose31 33
(1 H, ddd, J 8.9, 6.2 and 4.6, H-5), 4.36 [2 H, m, CH OC(᎐O)],
᎐
2
4.56 (1 H, d, J 3.7, H-2), 4.71 (1 H, d, J 11.0, OCHAHBN), 4.98
(1 H, d, J 11.0, O CHAHBN), 5.86 (1 H, d, J 3.7, H-1); δC 25.4,
26.2, 26.8, 27.0, 43.0, 62.2, 67.7, 72.3, 73.8, 80.0, 80.9, 82.9,
105.3, 109.2, 112.1, 158.3 (Found: C, 53.8; H, 7.0; N, 3.6.
C16H25NO8 requires C, 53.5; H, 7.0; N, 3.9%).
Viscous oil (yield 71%); bp 130–132 ЊC/0.02 mmHg (lit.,31 150–
155 ЊC/0.5 mmHg); [α]2D0 Ϫ25.2, (c 2.87, CHCl3)], [α]2D0 Ϫ28.6
(c 2.22, EtOH) {lit.,31 [α]2D0 Ϫ25 (c 2, EtOH)}; δH 1.31 (3 H, s,
Me), 1.38 (3 H, s, Me), 1.43 (3 H, s, Me), 1.49 (3 H, s, Me), 4.00
(1 H, dd, J 8.7 and 5.7, HA-6), 4.02 (1 H, d, J 3.1, H-3), 4.11
(1 H, dd, J 8.7 and 6.2, HB-6), 4.15 (1 H, dd, J 7.7 and 3.1, H-4),
4.37 (1 H, ddd, J 7.7, 6.2 and 5.7, H-5), 4.58 (1 H, d, J 3.7, H-2),
4.64 and 4.67 (2 H, ABq, J 7.4, OCH2Ph), 5.90 (1 H, d, J 3.7,
H-1), 7.28–7.36 (5 H, m, Ph); δC 25.4, 26.2, 26.7(8), 26.8(4),
67.4, 72.4, 72.5, 81.3, 81.7, 82.7, 105.3, 109.0, 111.8, 127.6,
127.8, 128.4, 137.7.
4-Cyclododecyloxymethylmorpholine 43
This was obtained by a modification of a literature method for
the preparation of aminol ethers.15 A mixture of morpholine
(4.40 g, 50.0 mmol), cyclododecanol (9.20 g, 50.0 mmol)
and anhydrous potassium carbonate (6.90 g, 50.0 mmol) in
1168
J. Chem. Soc., Perkin Trans. 1, 2002, 1161–1170