Job/Unit: O30338
/KAP1
Date: 02-05-13 16:11:13
Pages: 11
C. V. Stevens et al.
FULL PAPER
CHaHb), 3.31 (s, 3 H, CH3-N+), 3.34–3.42 (m, 1 H, CHH-N+),
s, 26 H, 13 (CH2)octadec], 1.43 [br. s, 4 H, 2 (CH2)octadec], 1.78–1.82
H), 2.62–2.81 (m, 2 H), 3.28 (s, 3 H, CH3-N+), 3.33–3.43 (m, 1 H,
3.56–3.64 (m, 1 H, CHH-N+), 4.49 (t, J = 3.9 Hz, 1 H, CH- (m, 1 H), 1.94–2.15 (m, 3 H), 2.27–2.44 (m, 2 H), 2.49–2.59 (m, 2
N+) ppm. 13C NMR (CD3OD, 75.4 MHz, 25 °C): δ = 14.3 (CH3-
CH2), 23.5 [(CH2)hexyl], 25.3 (CH2-CH2-N+), 27.2 [(CH2)hexyl], 27.5 CHH-N+), 3.55 (ddd, J1 = 12.5, J2 = 12.5, J3 = 4.6 Hz, 1 H, CHH-
(CH2-CH), 27.9 (CH2-CH), 32.5 [(CH2)hexyl], 33.8 (CH2-Cq), 34.0 N+), 4.41 (t, J = 4.4 Hz, 1 H, CH-N+) ppm. 13C NMR (CD3OD,
(CH2-Cq), 42.1 (CH3-N+), 49.0 (CD3OD), 57.8 (CH2-N+), 72.0
75.4 MHz, 25 °C): δ = 14.5 (CH3-CH2), 23.8 (CH2), 25.3 (CH2),
(CH-N+), 73.3 (C -N+), 114.6 (C -CϵN) ppm. IR: ν = 1467 cm–1. 27.42 (CH2), 27.56 (CH2), 27.80 (CH2), 30.40 (CH2), 30.52 (CH2),
˜
q
q
MS (EGI, POS): m/z = 221.3 (100) [C14H25N2]+. MS (EGI, NEG):
127.0 (100) [I]–. C14H25IN2 (348.27): calcd. for C 48.28, H 7.24, N
8.04; found C 48.21, H 6.93, N 8.16.
30.61 (CH2), 30.70 (CH2), 30.84 (8 CH2), 33.1 (CH2), 33.7 (CH2),
33.9 (CH2), 41.6 (CH3-N+), 49.0 (CD3OD), 57.8 (CH2-N+), 71.9
(CH-N+), 73.4 (C -N+), 114.4 (C -CϵN) ppm. IR: ν = 291, 2850,
˜
q
q
1466 (νCϵN) cm–1. MS (EGI, POS): m/z (%) = 389.3 (100)
[C26H49N2]+. C26H49IN2 (516.59): calcd. for C 60.45, H 9.56, N
5.42; found C 60.28, H 9.73, N 5.39.
1-Cyano-7-cyclohexyl-7-methyl-7-azoniabicyclo[2.2.1]heptane Iodide
(12c): The same procedure as for 12a was used at reflux starting
from 11c (6.48 g, 31.72 mmol), yielding 12c as a yellow powder in
1
a yield of 93% (10.21 g), m.p. 162.8–163.0 °C. H NMR (CD3OD,
Syntheses of 7-Alkyl-1-cyano-7-methyl-7-azoniabicyclo[2.2.1]hept-
ane Tetrafluoroborates 13a–d: The synthesis of 1-cyano-7-methyl-7-
octyl-7-azoniabicyclo[2.2.1]heptane tetrafluoroborate (13a) was
chosen as an example of the synthesis of the 7-alkyl-1-cyano-7-
methyl-7-azoniabicyclo[2.2.1]heptane tetrafluoroborates.
300 MHz, 25 °C): δ = 1.21–1.34 (m, 1 H), 1.52–2.15 (m, 10 H),
2.32–2.88 (m, 7 H), 3.18 (s, 3 H, CH3-N+), 3.88 (tt, J1 = 11.6, J2
= 3.2 Hz, 1 H, CHCy-N+), 4.46 (t, J = 4.7 Hz, 1 H, CH-N+) ppm.
13C NMR (CD3OD, 75.4 MHz, 25 °C): δ = 25.7 (CH2), 26.1 (CH2),
26.4 (CH2), 27.2 (CH2), 27.8 (CH2), 28.6 (CH2), 29.3 (CH2), 33.2
(CH2), 35.8 (CH2), 36.6 (CH3-N+), 49.0 (CD3OD), 69.0 (CHCy
-
1-Cyano-7-methyl-7-octyl-7-azoniabicyclo[2.2.1]heptane
Tetra-
N+), 71.2 (C -N+), 73.6 (CH-N+), 116.1 (C -CϵN) ppm. IR: ν =
fluoroborate (13a): Iodide 12a (1.87 g, 4.94 mmol) was dissolved in
distilled H2O (35 mL) in a 50 mL flask. AgBF4 (0.96 g, 4.94 mmol)
was added and the reaction mixture was shielded from light and
stirred for 1 h at room temperature. The resulting yellow suspension
of AgI was removed by filtration, the volatiles were evaporated and
13a was obtained as white crystals in a yield of 70% (1.16 g). If
necessary these salts were recrystallized from acetone/diethyl ether,
m.p. 131.9–132.8 °C. 1H NMR (CD3OD, 300 MHz, 25 °C): δ =
0.89–0.91 (m, 3 H, CH3-CH2), 1.32–1.41 [m, 10 H, 5 (CH2)octyl],
1.72–1.86 (m, 1 H, CH2-CHH-CH2-N+), 1.92–2.13 (m, 3 H, 2 CH-
CHexoHendo, CH2-CHH-CH2-N+), 2.25–2.45 (m, 2 H, 2 CH-
CHexoHendo), 2.48–2.79 (m, 4 H, 2 Cq-CHaHb, 2 Cq-CHaHb), 3.26
(s, 3 H, CH3-N+), 3.30–3.40 (m, 1 H, CHH-N+), 3.54 (ddd, J1 =
12.5, J2 = 12.5, J3 = 4.7 Hz, 1 H, CHH-N+), 4.40 (t, J = 4.4 Hz, 1
H, CH-N+) ppm. 13C NMR (CD3OD, 75.4 MHz, 25 °C): δ =
14.5 (CH3-CH2), 23.7 [(CH2)octyl], 25.1 (CH2-CH2-N+), 27.35
[(CH2)octyl], 27.43 (CH2-CH), 27.7 (CH2-CH), 30.2 [(CH2)octyl],
30.3 [(CH2)octyl], 32.9 [(CH2)octyl], 33.7 (CH2-Cq), 33.9 (CH2-Cq),
41.5 (CH3-N+), 49.1 (CD3OD), 57.8 (CH2-N+), 72.0 (CH-N+), 73.2
(Cq-N+), 114.7 (Cq-CϵN) ppm. 19F NMR (CD3OD, 284 MHz,
˜
q
q
1448 cm–1. MS (EGI, POS): m/z (%) = 219.0 (100) [C14H23N2]+.
MS (EGI, NEG): 127.0 (100) [I]–, m.p. 162.8–163.0 °C. C14H23IN2
(346.26): calcd. for C 48.56, H 6.70, N 8.09; found C 48.19, H 6.49,
N 8.02.
7-Butyl-1-cyano-7-methyl-7-azoniabicyclo[2.2.1]heptane
Iodide
(12d): The same procedure as for 12a was used starting from 11d
(7.05 g, 39.55 mmol), yielding 12d as a pale-yellow powder in a
yield of 86% (10.89 g), m.p. 173.8–174.2 °C. 1H NMR (CD3OD,
300 MHz, 25 °C): δ = 1.05 (t, J = 7.4 Hz, 3 H, CH3-CH2), 1.39–
1.62 (m, 2 H, CH3-CH2-CH2), 1.74–1.89 (m, 1 H, CH2-CHH-CH2-
N+), 1.92–2.18 (m, 3 H, 2 CH-CHexoHendo, CH2-CHH-CH2-N+),
2.30–2.48 (m, 2 H, 2 CH-CHexoHendo), 2.53–2.84 (m, 4 H, 2 Cq-
CHaHb, 2 Cq-CHaHb), 3.31 (s, 3 H, CH3-N+), 3.38 (ddd, J1 = 12.7,
J2 = 12.7, J3 = 5.0 Hz, 1 H, CHH-N+), 3.60 (ddd, J1 = 12.5, J2 =
12.5, J3 = 4.8 Hz, 1 H, CHH-N+), 4.48 (t, J = 4.7 Hz, 1 H, CH-
N+) ppm. 13C NMR (CD3OD, 75.4 MHz, 25 °C): δ = 14.1 (CH3-
CH2), 20.9 (CH3-CH2-CH2), 27.2 (CH2-CH2-N+), 27.5 (CH2-CH),
27.9 (CH2-CH), 33.8 (CH2-Cq), 34.0 (CH2-Cq), 42.0 (CH3-N+),
49.0 (CD3OD), 57.6 (CH2-N+), 72.0 (CH-N+), 73.3 (Cq-N+), 114.6
25 °C): δ = –151.82 (BF ) ppm. IR: ν = 1046 (νBF4), 1032
˜
4
(C -CϵN) ppm. IR: ν = 1463 cm–1. MS (EGI, POS): m/z (%) =
(νBF4) cm–1. MS (EGI, POS): m/z (%)
=
249.3 (100)
˜
q
193.0 (100) [C12H21N2]+. MS (EGI, NEG): 127.0 (100) [I]–.
C12H21IN2 (320.21): calcd. for C 45.01, H 6.61, N 8.75; found C
45.00, H 6.43, N 8.63.
[C16H29N2]+. MS (EGI, NEG): m/z (%) = 87.3 (100) [BF4]–.
C16H29BF4N2 (336.22): calcd. for C 57.16, H 8.69, N 8.33; found
C 56.81, H 8.58, N 8.22.
1-Cyano-7,7-dimethyl-7-azoniabicyclo[2.2.1]heptane Iodide (12e):
The same procedure as for 12a was used starting from 11e (2.63 g,
19.31 mmol), yielding 12e as a white powder in a yield of 83%
(4.46 g), m.p. 222.5 °C (decomp.). 1H NMR (CD3OD, 300 MHz,
25 °C): δ = 2.07–2.16 (m, 2 H, 2 CH-CHexoHendo), 2.39–2.72 (m, 6
H, 2 Cq-CHaHb, 2 Cq-CHaHb, 2 CH-CHexoHendo), 3.33 (s, 6 H, 2
CH3-N+), 4.43 (t, J = 4.7 Hz, 1 H, CH-N+) ppm. 13C NMR
(CD3OD, 75.4 MHz, 25 °C): δ = 27.9 (2 CH2-Cq), 33.6 (2 CH2-
CH), 45.1 (2 CH3-N+), 49.0 (CD3OD), 72.9 (Cq-N+), 75.2 (CH-
1-Cyano-7-hexyl-7-methyl-7-azoniabicyclo[2.2.1]heptane
Tetra-
fluoroborate (13b): The same procedure as for 13a was used starting
from 12b (2.43 g, 6.98 mmol), yielding 13b as a beige powder in
1
a yield of 54% (1.16 g), m.p. 118.0–118.4 °C. H NMR (CD3OD,
300 MHz, 25 °C): δ = 0.94 (t, J = 6.9 Hz, 3 H, CH3-CH2), 1.35–
1.47 [m, 6 H, 3 (CH2)hexyl], 1.72–1.86 (m, 1 H, CH2-CHH-CH2-
N+), 1.92–2.14 (m, 3 H, 2 CH-CHexoHendo, CH2-CHH-CH2-N+),
2.25–2.45 (m, 2 H, 2 CH-CHexoHendo), 2.48–2.79 (m, 4 H, 2 Cq-
CHaHb, 2 Cq-CHaHb), 3.26 (s, 3 H, CH3-N+), 3.30–3.40 (m, 1 H,
CHH-N+), 3.54 (ddd, J1 = 12.5, J2 = 12.5, J3 = 4.8 Hz, 1 H, CHH-
N+), 4.40 (t, J = 4.4 Hz, 1 H, CH-N+) ppm. 13C NMR (CD3OD,
75.4 MHz, 25 °C): δ = 14.3 (CH3-CH2), 23.4 [(CH2)hexyl], 25.0
(CH2-CH2-N+), 27.0 [(CH2)hexyl], 27.3 (CH2-CH), 27.6 (CH2-CH),
32.4 [(CH2)hexyl], 33.6 (CH2-Cq), 33.8 (CH2-Cq), 41.4 (CH3-N+),
49.0 (CD3OD), 57.7 (CH2-N+), 71.9 (CH-N+), 73.1 (Cq-N+), 114.6
N+), 114.3 (C -CϵN) ppm. IR: ν = 1463, 1238 cm–1. MS (EGI,
˜
q
POS): m/z (%) = 151.3 (100) [C8H12N2]+. MS (EGI, NEG): 127.0
(100) [I]–. C9H15IN2 (278.13): calcd. for C 38.86, H 5.44, N 10.07;
found C 38.73, H 5.67, N 9.94.
1-Cyano-7-methyl-7-octadecyl-7-azoniabicyclo[2.2.1]heptane Iodide
(12f): The same procedure as for 12a was used at reflux starting
from 11f (4.61 g, 12.30 mmol), yielding 12f as yellow crystals in (Cq-CϵN) ppm. 19F NMR (CD3OD, 284 MHz, 25 °C): δ =
1
a yield of 78% (4.96 g), m.p. 163.4–163.8 °C. H NMR (CD3OD, –151.82 (BF ) ppm. IR: ν = 1032 (νBF4) cm–1. MS (EGI, POS): m/z
˜
4
300 MHz, 25 °C): δ = 0.90 (t, J = 6.6 Hz, 3 H, CH3-CH2), 1.29 [br.
(%) = 221.0 (100) [C14H25N2]+. MS (EGI, NEG): m/z (%) = 87.3
8
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