1
91.1545, HRMS (ESI, -ve) calc. for (CH
3
SO
2
)
2
N 279.9178,
1-(2-Ethoxy-2-oxoethyl)-3-(methoxymethyl)pyridinium octyl
sulfate (6). Yield 77%, brown liquid. H NMR: d 0.84–0.87
1
found 279.9174.
(
m, 3H), 1.21–1.29 (m, 13H), 1.45–1.47 (m, 2H), 3.42 (s, 3H),
.65–3.70 (t, J = 6.6 Hz, 2H), 4.23–4.28 (q, J = 4.8 Hz, 2H),
1
-(2-Hydroxyethyl)-3-(methoxymethyl)pyridinium bis(trifluo-
3
4
8
2
1
romethylsulfonyl)amide (8). Quantitative, light yellow liquid.
H NMR: d 3.41 (s, 3H), 3.84–3.89 (m, 2H), 4.66–4.68 (m, 4H),
.23–5.26 (t, J = 5.3 Hz, 1H), 8.12–8.16 (m, 1H), 8.52–8.55 (m,
H), 8.92–8.98 (m, 2H) ppm. C NMR: d 58.3, 60.1, 63.4, 69.6,
19.6 (CF ), 127.4, 139.1, 143.4, 143.9, 144.3 ppm. HRMS (ESI,
ve) calc. for C 168.1019, found 168.1018, HRMS (ESI,
ve) calc. for N(SO 279.9178, found 279.9192.
.69 (s, 2H), 5.68 (s, 2H) 8.21–8.26 (m, 1H), 8.62–8.65 (m, 1H),
1
13
.98–9.00 (m, 1H), 9.06 (s, 1H). C NMR: d 14.0, 15.0, 22.1,
5
1
1
+
-
5.6, 28.7, 28.8, 29.1, 31.3, 58.3, 60.4, 62.3, 65.6, 69.5, 127.5,
39.2, 144.4, 145.1, 145.4, 166.5 ppm. HRMS (ESI, +ve) calc.
13
3
for C11
calc. for C
H
16NO
210.1125, found 210.1119, HRMS (ESI, -ve)
209.0853, found 209.0851.
3
9
H
14NO
2
H
17OSO
8
3
2
CF
)
3 2
3
-(Methoxymethyl)-1-(2-oxo-2-(pentyloxy)ethyl)pyridinium
1
Synthesis of octyl sulfates 3, 4, 5a, 6 and 7. The heterocyclic
amine (4.07 mmol), alkyl bromide (4.88 mmol) and sodium
iodide (0.61 g, 4.07 mmol) were stirred at 110 C for 24 h. The
octyl sulfate (7). Yield 87%, light brown liquid. H NMR:
d 0.84–0.91 (m, 6H), 1.26–1.34 (m, 14H), 1.46–1.50 (m, 2H),
1.61–1.66 (m, 2H), 3.44 (s, 3H), 3.66–3.70 (t, J = 6.6 Hz,
2H), 4.16–4.21 (t, J = 6.6 Hz, 2H), 4.70 (s, 2H), 5.69 (s, 2H)
8.22–8.27 (m, 1H), 8.63–8.66 (m, 1H), 8.99–9.01(m, 1H), 9.08
(s, 1H). C NMR: d 13.8, 14.0, 21.7, 22.1, 25.6, 27.4, 27.6,
28.7, 28.8, 29.1, 31.3, 58.3, 60.4, 65.5, 66.2, 69.5, 127.5, 139.2,
144.4, 145.1, 145.3, 166.4 ppm. HRMS (ESI, +ve) calc. for
◦
reaction apparatus was moisture guarded and a reflux condenser
was used while the reaction mixture was heated. The quaternary
salt was extracted into water (50 mL) and its aqueous solution
was purified by extraction with diethyl ether (2 ¥ 20 mL). The
aqueous solution of quaternary halide was treated with aqueous
ammonium octyl sulfate (0.92 g, 4.07 mmol in 20 mL of water)
and the resultant was stirred for 10 min. The product was
isolated by solvent extraction with dichloromethane (3 ¥ 20 mL).
1
3
C
for C
14
H
22NO
3
252.1594, found 252.1603, HRMS (ESI, -ve) calc.
209.0853, found 209.0843.
8
H
17OSO
3
1
,1¢-(2,2¢-Methylenebis(oxy)bis(ethane-2,1-diyl))dipyridinium
The extracts were dried over anhydrous MgSO
under reduced pressure to yield a pure product.
4
and evaporated
dichloride (9a). Pyridine (1.9 mL, 23.49 mmol) was added to
bis(2-chloroethoxy)methane (1.7 g, 9.82 mmol) in one portion
24
and the resulting solution was stirred at room temperature for
1 h before being heated to 110 C for 24 h. The solution was
1
-Butyl-3-(methoxymethyl)pyridinium octyl sulfate (3).
◦
◦
1
Yield 92%, bright yellow liquid (solidifies at 4 C). H NMR:
d 0.83–0.93 (m, 6H), 1.24–1.33 (m, 12H), 1.45–1.47 (m, 2H),
.88–1.95 (m, 2H), 3.40 (s, 3H) 3.65–3.70 (t, J = 6.6 Hz, 2H),
.60–4.65 (m, 4H), 8.13–8.18 (m, 1H), 8.52–8.55 (m, 1H)
.04–9.09 (m, 2H). C NMR: d 13.3, 14.0, 18.8, 22.1, 25.5, 28.7,
8.8, 29.1, 31.3, 32.8, 58.3, 60.6, 65.5, 69.5, 127.7, 139.4, 143.1,
43.8 ppm. HRMS (ESI, +ve) calc. for C11
found 180.1385, HRMS (ESI, -ve) calc. for C
09.0853, found 209.0843.
cooled and the volatiles removed in vacuo to give the desired
1
product as a light brown solid. H NMR: d 3.83 (t, J =
1
4
9
2
1
5
.1 Hz, 4H), 4.57 (s, 2H), 4.83 (t, J = 5.1 Hz, 2H), 8.19 (dt,
1
3
J = 6.9, 0.9 Hz, 4H), 8.65 (tt, J = 7.8, 1.5 Hz, 2H), 9.12 (m,
1
3
4
(
2
H). C NMR: d 60.2, 65.7, 94.1, 127.8, 145.3, 145.9. HRMS
2+ +
-
ESI, +ve) [M - Cl ] calc. for C15
95.1210.
H
20ClN
2
O 295.1208, found
2
H
18NO 180.1383,
17OSO
8
H
3
2
1,1¢-(2,2¢-Methylenebis(oxy)bis(ethane-2,1-diyl))dipyridinium
bis(trifluoromethylsulfonyl)amide (9b). To 9a (0.61 g, 1.83
mmol) in 10 mL distilled water was added lithium bistri-
fluoromethanesulfonimidate (1.15 g, 4.00 mmol), the resulting
solution was stirred at room temperature for 30 min. EtOAc
1
-Octyl-3-(Methoxymethyl)pyridinium octyl sulfate (4).
Yield 97%, yellow waxy solid (tends to solidify at room
temperature). H NMR: d 0.82–0.87 (m, 6H), 1.23–1.27 (m,
0H), 1.44–1.49 (m, 2H), 1.91–1.93 (m, 2H), 3.39 (s, 3H)
.65–3.69 (t, J = 6.6 Hz, 2H), 4.58–4.65 (m, 4H), 8.12–8.17
m, 1H), 8.52–8.54 (m, 1H) 9.03–9.08 (m, 2H). C NMR: d
3.9, 13.9, 22.1, 22.1, 25.4, 25.6, 28.4, 28.5, 28.7, 28.8, 29.1,
0.8, 31.2, 31.3, 58.3, 60.8, 65.5, 69.5, 127.7, 139.4, 143.1,
43.8 ppm. HRMS (ESI, +ve) calc. for C15
1
2
3
(
1
3
1
(
20 mL) was added to the reaction mixture and stirring was
continued for 10 min. The aqueous phase was washed with
a further 2 ¥ 20 mL EtOAc, combined organic phases were
1
3
washed with distilled water until AgNO test gave a negative
3
result, then dried (MgSO
4
), concentrated in vacuo then placed
H
26NO 236.2009,
17OSO
◦
under high vacuum at 40 C to give a clear oil (1.44 g, 97%).
found 236.2005, HRMS (ESI, -ve) calc. for C
09.0853, found 209.0835.
8
H
3
1
H NMR: d 3.81 (t, J = 4.8, 4H), 4.56 (s, 2H), 4.76 (t, J =
2
4
4
1
.8 Hz, 4H), 8.17 (m, 4H), 8.64 (tt, J = 7.8, 1.2 Hz, 2H), 8.99 (m,
13
H). C NMR: d 60.4, 65.7, 94.2, 119.5 (q, JC–F = 320.1 Hz),
1
-Butyl-3-(ethoxymethyl)pyridinium octyl sulfate (5a). Yield
2
+
- +
27.9, 145.2, 146.0. HRMS (ESI, +ve) [M - NTf
540.0692 found 540.0672, HRMS (ESI, -ve)
CF 279.9178, found 279.9178.
2
] calc. for
1
6
6
1
2
2
6
2
1
7%, light yellow liquid. H NMR: d 9.10 (s, 1H), 9.07 (d, J =
.1 Hz, 1H), 8.55 (d, J = 8.0 Hz, 1H), 8.15 (dd, J = 7.9, 6.1 Hz,
H), 4.70 (s, 2H), 4.65 (t, J = 7.4 Hz, 2H), 3.70 (t, J = 6.7 Hz,
H), 3.59 (q, J = 7.0 Hz, 2H), 1.96–1.86 (m, 2H), 1.49–1.43 (m,
H), 1.37–1.17 (m, 15H), 0.91 (t, J = 7.4 Hz, 3H), 0.84 (t, J =
.7 Hz, 3H). C NMR (150.8 MHz): d 13.1, 13.7, 14.7, 18.6,
1.9, 25.4, 28.5, 28.6, 28.9, 31.1, 32.6, 60.4, 65.4, 65.7, 67.4,
27.6, 139.6, 142.9, 143.5, 143.6. HRMS (ESI, +ve) calc. for
C
17
H
20
F
6
N
3
O
6
S
2
calc. for N(SO
2
)
3 2
1,1¢-(2,2¢-Methylenebis(oxy)bis(ethane-2,1-diyl))dipyridinium
hexafluorophosphate (9c). To dichloride salt 9a (0.53 g,
1.59 mmol) in 2 mL distilled water (sonication required) was
1
3
added KPF (0.64 g, 3.49 mmol) in 1.5 mL distilled water,
6
washing with 1 mL distilled water. The solution became viscous
and was sonicated for 15 min then stirred at room temperature
for 4 h. Solution filtered and residue washed with cold distilled
C
12
H
20NO 194.1539, found 194.1535. HRMS (ESI, -ve) calc.
for C 209.0853, found 209.0848.
8
H
17OSO
3
This journal is © The Royal Society of Chemistry 2010
Green Chem., 2010, 12, 1783–1789 | 1787