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(400 MHz, CD3CN): d=7.79 (d, J=9.4 Hz, 2H), 7.68 (d, J=9.2 Hz,
2H), 5.61 (m, 3H), 4.42 (d, J=6.3 Hz, 2H), 3.52 ppm (s, 6H).
ESI-MS: m/z calcd (%) for C11H16N+: 162.1280 [M+]; found:
162.1277 (100).
N-Allyl-N,N,4-trimethylbenzenaminium hexafluorophosphate
(1b-PF6).
N-Allyl-N,N-dimethylbenzenaminium iodide (1a-I)[30]
To a stirred solution of dimethylaniline (0.38 mL, 3.0 mmol) was
added allyl iodide (0.82 mL, 9.0 mmol), and the solution was
heated at 308C overnight. The solution became yellow as the reac-
tion went on. The solvent was removed by evaporation and dried
under vacuum for 3 h to obtain a dark brown solid (0.860 g, 99%
yield). M.p. 87–888C (Ref. [30]: 87–888C); 1H NMR (400 MHz,
CD3CN): d=7.75 (d, J=8.2 Hz, 2H), 7.61 (m, 3H), 5.59 (m, 3H), 4.44
(d, J=5.6, 2H), 3.53 ppm (s, 6H).
Prepared in 80% yield as a white solid by a route analogous to
that described for 1a-PF6. 1H NMR (400 MHz, CD3CN): d=7.55 (d,
J=8.6 Hz, 2H), 7.43 (d, J=8.4 Hz, 2H), 5.49–5.65 (m, 3H), 4.29 (d,
J=6.5 Hz, 2H), 3.45 (s, 6H), 2.40 ppm (s, 3H); 13C NMR (100 MHz,
CD3CN): d=20.9, 54.6, 72.5, 121.6, 126.0, 129.6, 131.8 ppm; HR-ESI-
MS: m/z calcd (%) for C12H18N+: 176.1441 [M+]; found: 176.1434
(100).
N,N,N-Triethylprop-2-en-1-aminium bromide (3a-Br)[32,33]
N-Allyl-N,N,4-trimethylbenzenaminium iodide (1b-I).
Prepared in 92% yield as a white hygroscopic solid by a route anal-
ogous to that described for 1a-Br. H NMR (400 MHz, CD3CN): d=
5.93 (m, 1H), 5.68 (d, J=12.1 Hz, 1H), 5.65 (d, J=5.4 Hz, 1H), 3.76
(d, J=7.0 Hz, 2H), 3.19 (q, J=7.2 Hz, 6H), 1.25 ppm (tt, J=1.2 Hz,
9H).
Prepared in 90% yield as an orange liquid by a route analogous to
1
that described for 1e-Br. M.p. not determined; liquid at room tem-
1
perature. H NMR (400 MHz, CDCl3): d=7.76 (d, J=7.4, 2H), 7.42 (d,
J=8.8 Hz, 2H), 5.87 (d, J=16 Hz, 1H), 5.58 (d, J=10 Hz, 1H), 5.49
(m, 1H), 5.07 (d, J=7.4 Hz, 2H), 3.93 (s, 6H), 2.44 ppm (s, 3H);
13C NMR (100 MHz, CDCl3): d=21.0, 54.6, 71.1, 120.8, 124.8, 129.9,
131.4, 141.3 ppm; ESI-MS: m/z calcd (%) for C12H18N+: 176.143 [M+
]; found 176.142 (100); HR-ESI-MS: m/z calcd (%) for C12H17IN+:
302.0400 [M+]; found: 302.0369 (100).
N,N-Diethyl-N-methylprop-2-en-1-aminium bromide (3b-Br)
Prepared in 73% yield as a yellow solid by a route analogous to
that described for 1a-Br. 1H NMR (400 MHz, CD3CN): d=5.97 (m,
1H), 5.69 (d, J=11.6 Hz, 1H), 5.66 (d, J=4.6 Hz, 1H), 3.85 (d, J=
7.5 Hz, 2H), 3.27 (q, J=7.24 Hz, 4H), 2.89 (s, 3H), 1.28 ppm (tt, J=
1.5 Hz, 6H); 13C NMR (100 MHz, CD3CN): d=8.2, 47.7, 57.1, 63.7,
N-Allyl-N,N-diethylbenzenaminium bromide (1e-Br)[31]
125.9, 129.0 ppm; ESI-MS: m/z calcd (%) for C8H18N+: 128.143 [M+];
Diethylaniline (0.48 mL, 3.0 mmol) and allyl bromide (0.78 mL,
9.0 mmol) were combined and kept stirring at 508C for 48 h. The
white solid was precipitated then washed with diethyl ether. The
product was dried under vacuum to obtain a white solid (0.702,
87% yield). M.p. 144–1468C; 1H NMR (400 MHz, CD3CN): d=7.72
(br, 2H), 7.63 (m, 3H), 5.69 (m, 3H), 4.38 (d, J=7.1 Hz, 2H), 3.81 (m,
4H), 1.10 ppm (t, J=7.1 Hz, 6H).
+
found: 128.145 (100); HR-ESI-MS: m/z calcd (%) for C16H36BrN2
335.2056 [M+]; found: 335.2053 (100).
:
N-Benzyl-N,N-dimethylprop-2-en-1-aminium bromide (3c-Br)[31]
Prepared in 30% yield as a white hygroscopic solid by a route anal-
1
ogous to that described for 1a-Br. H NMR (400 MHz, CD3CN): d=
7.54 (m, 5H), 6.08 (m, 1H), 5.72 (d, J=9.8 Hz, 1H), 5.70 (d, J=
16.9 Hz, 1H), 4.51 (s, 2H), 3.97 (d, J=7.4 Hz, 2H), 2.94 ppm (s, 6H).
N-Allyl-N,N-diethylbenzenaminium iodide (1e-I)
Prepared in 98% yield as a white solid by a route analogous to
that described for 1e-Br. M.p. 105–1068C; 1H NMR (400 MHz,
CDCl3): d=7.96 (d, J=8.5, 2H), 7.65 (t, J=7.8 Hz, 2H), 7.54 (t, J=
7.4 Hz, 1H), 5.62–5.79 (m, 3H), 4.65 (d, J=5.9 Hz, 2H), 4.20 (dt, J=
7.3, 2H), 4.07 (dt, J=7.2 Hz, 2H), 1.22 ppm (t, J=7.0 Hz, 6H);
13C NMR (100 MHz, CDCl3): d=8.8, 58.0, 63.3, 122.7, 124.2, 129.4,
130.8, 131.3, 141.4 ppm; ESI-MS: m/z calcd (%) for C13H20N+:
190.159 [M+]; found: 190.158 (100); HR-ESI-MS: m/z calcd (%) for
C13H19IN+: 302.0557 [M+]; found: 316.0529 (100).
N,N-Diethyl-N-(2-hydroxyethyl)prop-2-en-1-aminium bromide
(3d-Br)[34]
Prepared in 72% yield as a white solid by a route analogous to
that described for 1a-Br. 1H NMR (400 MHz, CD3CN): d=6.04 (m,
1H), 5.7 (d, J=6.2 Hz, 1H), 5.67 (br, 1H), 4.03 (d, J=7.7 Hz, 2H),
3.97 (m, 2H), 3.41 (t, J=4.9 Hz, 2H), 3.08 ppm (s, 6H).
N,N,N-Triethylprop-2-en-1-aminium iodide (3a-I)[32,33]
Prepared in 92% yield as a yellow solid by a route analogous to
that described for 1a-Br. 1H NMR (400 MHz, CD3CN): d=5.93 (m,
1H), 5.68 (d, J=12.8 Hz, 1H), 5.65 (d, J=6.8 Hz, 1H), 3.76 (d, J=
7.3 Hz, 2H), 3.19 (q, J=7.5, 6H), 1.25 ppm (tt, J=1.96 Hz, 9H).
N-Allyl-N,N-dimethylbenzenaminium hexafluorophosphate
(1a-PF6).
N-Allyl-N,N-dimethylbenzenaminium bromide (1a-Br) (0.072 g,
0.3 mmol) was dissolved in water (1 mL) and combined with a satu-
rated solution of potassium hexafluorophosphate in water. A white
solid immediately precipitated. The compound was extracted with
dichloromethane and dried with magnesium sulfate. The solvent
was removed by evaporation to afford a pink solid and was then
recrystallized by dichloromethane/diethyl ether to afford 1a-PF6
(0.08 g, 87% yield; m.p. 88–908C). The compound was tested with
silver nitrate (AgNO3) to demonstrate the absence of bromide ions.
1H NMR (400 MHz, CD3CN): d=7.57–7.70 (m, 5H), 5.49–5.65 (m,
3H), 4.32 (d, J=6.1, 2H), 3.48 ppm (s, 6H); 13C NMR (100 MHz,
CD3CN): d=54.6, 72.6, 121.9, 125.9, 129.7, 131.5, 131.7 ppm; HR-
4-Methoxy-N,N-dimethylaniline (4c)[35]
A 50 mL round-bottomed flask equipped with a reflux condenser
was charged with 4-methoxyaniline (1.51 g, 12.26 mmol), TBAI
(0.316 g, 0.856 mmol), potassium hydroxide (1.644 g, 29.2 mmol),
benzene (14 mL), and water (2 mL). After 10 min, iodomethane
(0.78 mL, 12.58 mmol) was added dropwise over 2 min and stirred
at room temperature for 7 h. Then, additional TBAI (0.156 g,
0.42 mmol), potassium hydroxide (0.726 g, 12.92 mmol) and iodo-
methane (0.14 mL) were added and stirred at room temperature
Chem. Asian J. 2015, 10, 2484 – 2496
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