615
MOHAMMED., Orient. J. Chem., Vol. 35(2), 611-617 (2019)
over MgSO4, then evaporation the solvent in vacuo.
The purification through flash chromatography, gave
the expected products (17-19) as a white solid.
quietly to the mixture of the reaction mixture then
stirring for 6 hours at room temperature.The resultant
was concentrated and dissolved in EtOAc, followed
by washing with 1N HCl, 1N NaOH, saturated NaCl
solution.Theorganiclayerwasremovedbyvacuum.The
purifiecation through flash chromatography, produced
the expected products (21-23) as yellow solid
1-benzyl-1,2,3,4,5,6-hexahydroazocino
[2,3-b]quinolin-7-ol (17): (70%). (203-205)oC. IR
ν
max(cm-1) = 3340, 2975, 1620, 1386, 1499, 1473,
1090, 1050, 885, 742. 1H NMR: δ (ppm) = 7.82 (dd,
1H, J = 3 and 6 Hz, CHar), 7.71 (dd, 1H, J = 3 and
6 Hz, CHar), 7.37-7.15 (m, 7H, CHar), 4.62 (s, 2H,
CH2), 3.62 (t, 1H, J = 3 Hz, CHa), 3.34 (appearant
t, 1H, J = 3 and 6 Hz, CHb), 2.45 (t, 2H, J = 3 Hz,
CH2), 1.75-1.72 (m, 2H, CH2), 1.66-1.61 (m, 2H,
CH2), 1.42-1.37 (m, 3H, CH2). 13C NMR: δ (ppm) =
169.1, 163.8, 142.7, 138.2, 131.4, 129.0 (2), 128.8,
127.8, 127.9, 127.3, 125.2, 124.3, 122.6, 115.2,
53.3, 50.0, 29.3, 27.1, 26.1, 24.0.
1-benzyl-1,2,3,4,5,6-hexahydroazocino
[2,3-b]quinolin-7-yl 4-nitrobenzenesulfonate (21):
(79%). (182-184)oC. IR (ATR) νmax (cm-1) = 2962,
1615, 1258, 1084, 1014, 791, 745.1H NMR:δ (ppm)
= 7.46 (d, 2H, J = 6 Hz, CHar), 8.29 (d, 2H, J = 6
Hz, CHar), 7.77 (dd, 1H, J = 3 and 6 Hz, CHar), 7.75
(d, 1H, J = 6 Hz, CHar), 7.29-7.16 (m, 7H, CHar),
4.61 (s, 2H, CH2), 3.62 (t, 1H, J = 3 Hz, CHa), 3.33
(t, 1H, J = 3 Hz, CHb), 2.46 (t, 2H, J = 3 Hz, CH2),
1.75-1.71 (m, 2H, CH2), 1.60-1.55 (m, 2H, CH2),
1.40-1.35 (m, 2H, CH2). 13C NMR: δ (ppm) = 164.9,
159.0, 147.5, 146.1, 145.0, 138.1, 132.1, 131.2, 130.6
(2), 129.0, 128.8 (2), 128.7 (2), 127.6 (2), 124.5, 124.2
(2), 123.6, 53.0, 49.7, 29.2, 26.8, 25.8, 24.1.
1-benzyl-2,3,4,5,6,7-hexahydro-1H-
azonino[2,3-b]quinolin-8-ol (18):(74%).(215-217oC.
IR νmax(cm-1) = 3342, 2975, 1621, 1389, 1450, 1473,
1090, 1050, 885, 742. 1H NMR: δ (ppm) = 7.81 (dd,
1H, J = 3 and 6 Hz, CHar), 7.62 (dd, 1H, J = 3 and
9 Hz, CHar), 7.35-7.14 (m, 7H, CHar), 4.61 (s, 2H,
CH2), 3.52-3.49 (m, 2H, CH2), 2.53 (t, 2H, J = 3 Hz,
CHb), 1.87-1.83 (m, 2H, CH2), 1.76-1.71 (m, 2H,
CH2), 1.52-1.46 (m, 4H, 2CH2), 1.40 (s, 1H, OH).
13C NMR: δ (ppm) = 169.0, 167.1, 142.7, 138.3,
131.6, 129.1 (2), 129.0 (2), 128.1, 127.5, 125.3,
124.5, 122.7, 115.5, 53.3, 49.4, 30.3, 29.2, 28.1,
28.1, 23.7.
1-benzyl-2,3,4,5,6,7-hexahydro-1H-
azonino[2,3-b]quinolin-8-yl 4-nitrobenzenesulfonate
(22): (86%). (197-199) oC. IR (ATR) νmax(cm-1)
= 2961, 1617, 1259, 1085, 1015, 794, 744.1H NMR:
δ (ppm) = 8.50 (d, 2H, J = 3 Hz, CHar), 8.24 (d, 2H,
J = 6 Hz, CHar), 7.85 (d, 1H, J = 3 Hz, CHar), 7.57
(d, 1H, J = 6 Hz, CHar), 7.32-7.30 (m, 6H, CHar),
7.15-7.12 (m, 1H, CHar), 4.62 (s, 2H, CH2), 3.56-3.51
(m, 2H, CH2), 2.57 (t, 2H, J = 3 Hz, CH2), 1.88-1.84
(m, 2H, CH2), 1.77-1.72 (m, 2H, CH2), 1.53-1.48
(m, 4H, 2CH2). 13C NMR: δ (ppm) = 167.9, 159.0,
147.5, 145.1, 138.0, 132.1, 131.3, 130.6 (2), 129.1,
128.8 (2), 128.6 (2), 128.0, 127.8 (2), 124.5, 124.2,
123.5, 53.1, 49.2, 30.1, 29.1, 27.8 (2), 27.7, 23.7.
1-benzyl-1,2,3,4,5,6,7,8,9,10-decahydro-
[1]azacyclododecino[2,3-b]quinolin-11-ol (19):
(73%). (235-237)oC. IR νmax(cm-1) = 3340, 2975,
1620, 1386, 1499, 1479, 1095, 1047, 885, 742.
1H NMR: δ (ppm) = 7.86 (d, 1H, J = 6 Hz, CHar),
7.66 (s, 1H, CHar), 7.28-7.14 (m, 7H, CHar), 4.58 (s,
2H, CH2), 3.51-3.46 (m, 2H, CH2), 2.51 (appearant
t, 2H, J = 3 and 6 Hz, CH2), 1.86-1.79 (m, 2H, CH2),
1.74-1.69 (m, 2H, CH2), 1.51-1.44 (m, 10H, 5CH2).
13C NMR:δ (ppm) = 168.7, 166.3, 142.2, 137.8, 128.6
(2), 128.3 (2), 127.5, 124.7, 123.9, 122.3, 115.5,
52.9, 49.9, 29.7, 29.1, 28.8 (4), 27.5 (3), 23.2.
1-benzyl-1,2,3,4,5,6,7,8,9,10-decahydro-
[1]azacyclododecino[2,3-b]quinolin-11-yl
4-nitrobenzenesulfonate (23): (89%). (210-212)oC.
IR (ATR) νmax (cm-1) = 2959, 1619, 1259, 1084, 1012,
1
794, 735. H NMR: δ (ppm) = 8.49 (d, 2H, J = 6 Hz,
CHar), 8.23 (d, 2H, J = 6 Hz, CHar), 7.85 (dd, 2H,
J = 3 and 6 Hz, CHar), 7.30-7.19 (m, 7H, CHar), 4.61
(s, 2H, CH2), 3.53-3.50 (m, 2H, CH2), 2.58 (appearant
t, 2H, J = 3 and 9 Hz, CH2), 1.87-1.82 (m, 2H, CH2),
1.77-1.71 (m, 2H, CH2), 1.52-1.46 (m, 10H, 3CH2).
13C NMR: δ (ppm) = 167.9, 159.1, 147.5, 146.1,
145.2, 138.1, 132.0, 131.4 (2), 130.6, 129.1, 128.9
(2), 128.7 (2), 128.1, 127.7, 124.2 (2), 123.5, 53.1,
49.2, 30.1, 29.2 (3), 29.0 (2), 27.7, 27.7, 23.6.
General Procedure of Nosylations: To a
solution of phenols (17-19) (0.2 mmol, 1 eq.) in
freshly distillated DCM (2.2 mL), was added triethyl
amine (20 µmL, 0.2 mmol, 1 eq.) with stirring 30
min at 0oC. Then p-nitrobenzene sulfonyl chloride
20 (44 mg, 0.2 mmol, 1 eq.) in DCM was added