Synthesis and Characterisation of New Nonracemic Quaternary Ammonium Salts
Letters in Organic Chemistry, 2012, Vol. 9, No. 6
433
21
= - 130 (c 0.15, CHCl3); IR (KBr): ꢀ (cm-1): 3419,
121.21 (C-Br), 128.67 (Cvinyl), 129.15 (2CH), 129.48 (2CH),
130.95 (2CH), 131.41 (Cvinyl), 131.76 (2CH), 134.26 (C),
136.77 (C), 137.60 (C).
ꢀ
[ ]D
1060, 745.
N-3-bromophenanthrylmethylquinine Hexafluorophos-
phate (12b)
3-bromo-6-methylphenanthrene (10)
The photolysis of alkenes 9, according to procedure B,
gave 3-bromo-6-methylphenanthrene 10 as a white solid in
87% yield; mp = 162-164 °C; 1H NMR (300MHz, CDCl3): ꢀ
(ppm): 2.64 (s, 3H, CH3), 7.47 (dd, J1 = 8.4 Hz, J2 = 1.5 Hz,
1H), 7.62 (d, J = 9 Hz, 1H), 7.66-7.75 (m, 3H), 7.80 (d, J =
8.1 Hz, 1H), 8.38 (s, 1H), 8.81 (d, J = 1.2 Hz, 1H); 13C NMR
(75 MHz, CDCl3): ꢀ (ppm): 22.48 (CH3), 120.96, 122.79,
125.68, 125.89, 127.61, 128.84, 129.34, 129.66, 129.93,
130.41, 130.56, 131.11, 131.91, 137.13.
It was prepared in 91 % yield by reacting 11 with 5
equivalents of potassium hexafluorophosphate, according to
procedure E; mp = 166-168 °C. This new compound showed
identical 1H and 13C NMR data to those of the corresponding
parent dibromide 11.
21
ꢀ
= - 120 (c 0.09, CHCl3); IR (KBr): ꢀ (cm-1): 3522,
[ ]D
839, 557.
O(9)-Allyl-N-3-bromophenanthrylmethylquinine
mide (13)
Bro-
3-bromo-6-bromomethylphenanthrene (8)
Compound
8
was prepared from 3-bromo-6-
It was prepared, in 88% yield as a light yellow solid,
from 11 (2 g, 3.36 mmol) and allyl bromide (1.7 mL, 19.75
methylphenanthrene 10 (2 g, 7.38 mmol) using N-
bromosuccinimide (1.3 g, 7.38 mmol) in the presence of
benzoylperoxide (0,003 g, 0,73 mmol), according to proce-
dure C. Purification on column chromatography using cy-
clohexane/ethyl acetate (98:2) as the eluent yielded 2.10 g
21
mmol) according to procedure F; mp = 200-202 °C;
ꢀ
=
[ ]D
- 190 (c 0.2, CHCl3); 1H NMR: (300 MHz, CDCl3): ꢀ (ppm):
1.28-1.35 (m, 1H), 1.90-2.26 (m, 5H), 2.80-2.89 (m, 1H),
3.65-3.77 (m, 3H), 3.91 (d, J = 11.4 Hz, 2H), 3.99 (s, 3H),
4.32-4.39 (m, 1H), 4.51-4.57 (m, 1H), 4.97 (d, J = 10.5 Hz,
1H), 5.15-5.22 (m, 2H), 5.68-5.72 (m, 3H), 6.29-6.35 (m,
1H), 6.67 (d, J = 3.9 Hz, 1H), 7.19-7.26 (m, 1H), 7.40-7.48
(m, 2H), 7.70 (d, J = 4.5, 1H), 7.80 -7.86 (m, 2H), 8.04-8.14
(m, 4H), 8.17-8.21 (m, 1H), 8.70-8.77 (m, 1H), 8.79 (d, J =
4.5 Hz, 1H); 13C NMR (75 MHz, CDCl3): ꢀ (ppm): 20.72,
24.94, 26.42, 37.68, 52.78, 56.07, 60.57, 62.68, 64.30, 66.36,
79.56, 102.27, 116.87, 118.44, 120.62, 121.90, 122.28,
124.71, 125.75, 126.04, 126.39, 126.60, 127.41, 128.92,
131.02, 131.11, 131.39, 131.48, 131.75, 131.93, 136.55,
138.27, 138.39, 143.93, 144.34, 145.01, 147.75, 157.82; IR
(KBr): ꢀ (cm-1): 1514, 1463, 457.
1
(82% yield) of 8; mp = 173-175 °C; H NMR (300 MHz,
CDCl3): ꢀ (ppm): 4.77 (s, 3H, CH2Br), 7.64-7.77 (m, 5H),
8.57 (s, 1H), 8.78 (s, 1H); 13C NMR (75 MHz, CDCl3): ꢀ
(ppm): 34.41, 121.47, 123.50, 125.90, 127.33, 127.39,
128.45, 129.58, 129.76, 130.43, 130.55, 131.09, 131.79,
132.38, 136.67.
N-3-bromophenanthrylmethylquinine Bromide (11)
It was obtained in 96% yield, as a yellow solid, form 3-
bromo-6-bromomethylphenanthrene 8 (1 g, 2.85 mmol) and
quinine (0.95 g, 2.85 mmol) according to procedure D; mp =
21
1
205-207 °C;
ꢀ
= -200 (c 0.25, CHCl3); H NMR (300
[ ]D
MHz, CDCl3): ꢀ (ppm): 1.29-1.34 (m, 1H), 1.51-1.55 (m,
2H), 2.03-2.07 (m, 1H), 2.94-2.96 (m, 1H), 3.33-3.41 (m,
2H), 3.79 (s, 3H), 3.92-3.94 (m, 2H), 4.80-4.90 (m, 3H),
5.07 (d, J = 17.1 Hz, 1H), 5.41-5.50 (m, 2H), 6.15-6.23 (m,
2H), 6.53-6.57 (m, 1H), 6.93-6.99 (m, 2H), 7.29 (d, J = 8.5
Hz, 1H), 7.40-7.47 (m, 5H), 7.63 (d, J = 9.3 Hz, 1H), 7.88
(d, J = 9.3 Hz, 1H), 8.33 (d, J = 4.5 Hz, 1H), 8.80 (s, 1H),
9.19 (s, 1H); 13C NMR (75 MHz, CDCl3): ꢀ (ppm): 22.04,
25.37, 27.22, 38.33, 51.55, 56.76, 60.88, 63.06, 65.24, 69.31,
101.96, 118.32, 120.64, 120.96, 121.93, 122.77, 125.64,
125.93, 126.07, 126.52, 128.38, 129.28, 129.71, 130.56,
131.32, 131.76, 132.91, 136.65, 137.58, 142.81, 143.98,
144.26, 147.27, 158.04, 158.88; IR (KBr): ꢀ (cm-1): 3434,
1509, 458; Anal. Calcd. for C35H34Br2N2O2: C, 62.33; H,
5.08. Found: C, 62.28; H, 5.03.
O(9)-Allyl-N-3-bromophenanthrylmethylquinine Tetra-
fluoroborate (14a)
It was prepared in 90% yield as a yellow solid by react-
ing 13 with 5 equivalents of sodium tetrafluoroborate, ac-
cording to procedure E; mp = 144-146 °C. Compound 14a
showed identical 1H and 13C NMR data to those of the corre-
sponding parent dibromide 13.
21
ꢀ
= - 160 (c 0.15, CHCl3); IR (KBr): ꢀ (cm-1): 1460,
[ ]D
1066, 743.
O(9)-Allyl-N-3-bromophenanthrylmethylquinine hexa-
fluorophosphate (14b)
It was prepared in 93% yield as a light yellow by reacting
13 with 5 equivalents of potassium hexafluorophosphate,
according to procedure E; mp = 158-160 °C. Compound 14b
showed identical 1H and 13C NMR data to those of the corre-
sponding parent dibromide 13.
N-3-bromophenanthrylmethylquinine Tetrafluoroborate
(12a)
It was prepared in 94 % by reacting 11 with 5 equivalents
of sodium tetrafluoroborate, according to procedure E; mp =
1
194-196 °C. This new compound showed identical H and
21
= - 124 (c 0.1, CHCl3); IR (KBr): ꢀ (cm-1): 1466, 839,
13C NMR data to those of the corresponding parent dibro-
ꢀ
[ ]D
mide 11.
557.