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Two-Phase Oxidations with Aqueous Hydrogen Peroxide
111.7, 63.8, 32.1, 18.8, 12.6; 19F NMR (282 MHz, CDCl3): d=
À78.29; anal. calcd. for C12H12F3N3O3S: C 42.98, H 3.61, F
17.00, N 12.53; S 9.56; found: C 42.62, H 3.43, F 16.69, N
12.05, S 9.84.
C12H12F3N3O3S: C 57.24, H 7.20, F 11.32, N 8.34, S 6.37;
found: C 56.90, H 7.12, F 10.91, N 7.98, S 6.59.
1-Hexyl-3,5-dicyanopyridinium triflate (2b): Pyridine-3,5-
dicarbonitrile (150 mg, 1.16 mmol) and n-hexyl triflate (7b)
(299 mg, 1.29 mmol) were treated according to the general
procedure to give 2b; yield: 180 mg (43%); mp 201–2058C.
1H NMR (500 MHz, CD3CN): d=9.47 (d, J=1.2 Hz, 2H),
9.19 (s, 1H), 4.69 (t, J=7.7 Hz, 2H), 2.10–2.00 (m, 2H),
1.49–1.30 (m, 6H), 0.93 (t, J=7.0 Hz, 3H); 13C NMR
(126 MHz, CD3CN): d=151.7, 151.5, 120.9 (q, J=320.5 Hz),
114.8, 111.8, 64.0, 30.7, 30.2, 25.1, 22.0, 13.2; 19F NMR
Synthesis of 1-Alkyl-3,5-dinitropyridinium Triflates 3;
General Procedure
3,5-Dinitropyridine (1 equiv., usually 100–200 mg) was dis-
solved in anhydrous dichloromethane (3 mL) under an
argon atmosphere. Then the corresponding n-alkyl triflate 7
(1.5 equiv.) was added dropwise. The solution was stirred at
room temperature for 3 days. The solvent was evaporated
and residual material was dissolved in anhydrous acetoni-
trile (0.5 mL) followed by addition of anhydrous diethyl
ether (10 mL). A white precipitate formed. It was filtered
off and dried under vacuum. Further purification was per-
formed by dissolving the precipitate in anhydrous acetoni-
trile, followed by addition of anhydrous diethyl ether. The
precipitate was collected and dried under vacuum.
1-Butyl-3,5-dinitropyridinium triflate (3a): 3,5-Dinitropyri-
dine (100 mg, 0.591 mmol) and n-butyl triflate (7a) (183 mg,
0.887 mmol) were treated according to the general proce-
dure to give 3a; yield: 60 mg (24%); mp 153–1568C.
1H NMR (500 MHz, acetonitrile-d3): d=9.94 (d, J=2.1 Hz,
2H), 9.77 (t, J=2.1 Hz, 1H), 4.83 (t, J=7.8 Hz, 2H), 2.07
(ddt, J=9.6, 7.6, 3.7 Hz, 2H), 1.46 (h, J=7.5 Hz, 2H), 1.00
(t, J=7.4 Hz, 3H); 13C NMR (101 MHz, CD3CN): d=147.9,
147.5, 135.9, 121.9 (q, J=320.7 Hz), 65.2, 33.7, 19.8, 13.6;
19F NMR (282 MHz, CDCl3): d= À78.19; HR-MS (ESI+):
m/z=226.08217, calcd. for C9H12N3O4 [M]+: 226.08223.
1-Hexyl-3,5-dinitropyridinium triflate (3b): 3,5-Dinitropyr-
idine (100 mg, 0.591 mmol) and n-hexyl triflate (7b)
(208 mg, 0.887 mmol) were treated according to the general
procedure to give 3b; yield: 57 mg (24%); mp 192–1958C.
1H NMR (500 MHz, acetonitrile-d3): d=9.94 (d, J=1.9 Hz,
2H), 9.77 (t, J=2.0 Hz, 1H), 4.82 (t, J=7.8 Hz, 2H), 2.08
(tt, J=9.5, 6.9 Hz, 2H), 1.49–1.29 (m, 6H), 0.91 (t, 3H);
13C NMR (101 MHz, CD3CN): d=147.9, 147.5, 135.9, 121.9
(q, J=320.8 Hz), 65.4, 31.8, 31.7, 26.0, 23.0, 14.1; 19F NMR
(282 MHz, CDCl3): d= À78.17; HR-MS (ESI+): m/z=
254.11345, calcd. for C11H16N3O4 [M]+: 254.11353.
1-Octyl-3,5-dinitropyridinium triflate (3c): 3,5-Dinitropyri-
dine (100 mg, 0.591 mmol) and n-octyl triflate (7c) (233 mg,
0.887 mmol) were treated according to the general proce-
dure to give 3c; yield: 87 mg (32%); mp 177–1808C.
1H NMR (500 MHz, acetonitrile-d3): d=9.93 (d, J=2.0 Hz,
2H), 9.77 (t, J=2.1 Hz, 1H), 4.81 (t, J=7.9 Hz, 2H), 2.12–
2.02 (m, 2H), 1.51–1.22 (m, 10H), 0.89 (t, J=6.6 Hz, 3H);
13C NMR (101 MHz, CD3CN): d=147.9, 147.5, 135.9, 121.9
(q, J=320.4 Hz), 65.4, 32.3, 31.8, 29.6, 29.5, 26.3, 23.3, 14.3;
19F NMR (282 MHz, CDCl3): d= À78.16; HR-MS (ESI+):
m/z=282.14490, calcd. for C13H20N3O4 [M]+: 282.14483.
1-Decyl-3,5-dinitropyridinium triflate (3d): 3,5-Dinitropyr-
idine (100 mg, 0.591 mmol) and n-decyl triflate (7d)
(258 mg, 0.887 mmol) were treated according to the general
procedure to give 3d; yield: 71 mg (26%); mp 192–1958C.
1H NMR (400 MHz, acetonitrile-d3): d=9.97 (d, J=1.9 Hz,
2H), 9.79 (t, J=2.0 Hz, 1H), 4.93–4.71 (m, 2H), 2.15–2.05
(m, 2H), 1.51–1.24 (m, 14H), 0.90 (t, J=7.0 Hz, 3H);
13C NMR (101 MHz, acetonitrile-d3): d=146.9, 146.5, 135.0,
121.0 (q, J=320.7 Hz), 64.4, 31.6, 30.9, 29.2, 28.6, 25.4, 22.4,
13.4; 19F NMR (282 MHz, CDCl3): d= À78.16; HR-MS
(282 MHz,
CDCl3):
d=À78.25;
anal.
calcd.
for
C14H16F3N3O3S: C 46.28, H 4.44, F 15.69, N 11.56, S 8.82;
found: C 45.95, H 4.21, F 15.32, N 11.27, S 8.44.
1-Octyl-3,5-dicyanopyridinium triflate (2c): Pyridine-3,5-
dicarbonitrile (150 mg, 1.16 mmol) and n-octyl triflate (7c)
(335 mg, 1.29 mmol) were treated according to the general
procedure to give 2c; yield: 200 mg (44%); mp 209–2118C.
1H NMR (500 MHz, CD3CN): d=9.49–9.44 (m, 2H), 9.19 (s,
1H), 4.68 (t, J=7.6 Hz, 2H), 2.10–2.01 (m, 2H), 1.37 (m,
10H), 0.91 (t, J=6.7 Hz, 3H); 13C NMR (126 MHz,
CD3CN): d=151.7, 151.5, 120.8 (q, J=320.4 Hz), 114.8,
111.7, 31.4, 30.3, 28.6, 28.5, 25.4, 22.3, 13.3; 19F NMR
(282 MHz,
CDCl3):
d=À78.24;
anal.
calcd.
for
C16H20F3N3O3S: C 49.10, H 5.15, F 14.56, N 10.74, S 8.19;
found: C 48.75, H 4.95, F 14.30, N 11.07, S 8.17.
1-Decyl-3,5-dicyanopyridinum triflate (2d): Pyridine-3,5-
dicarbonitrile (150 mg, 1.16 mmol) and n-decyl triflate (7d)
(371 mg, 1.29 mmol) were treated according to the general
procedure to give 7d; yield: 237 mg (49%); mp 218–2218C.
1H NMR (500 MHz, CD3CN): d=9.44 (s, 2H), 9.18 (s, 1H),
4.68 (t, J=7.7 Hz, 2H), 2.11–1.99 (m, 2H), 1.48–1.22 (m,
14H), 0.91 (t, J=6.6 Hz, 3H); 13C NMR (126 MHz,
CD3CN): d=151.7, 151.5, 120.9 (q, J=320.6 Hz), 114.8,
111.7, 64.0, 31.6, 30.2, 29.1, 29.0, 28.9, 28.5, 25.4, 22.3, 13.4;
19F NMR (282 MHz, CDCl3): d= À78.20; anal. calcd. for
C18H24F3N3O3S: C 51.54, H 5.77, F 13.59, N 10.02, S 7.64;
found: C 51.15, H 5.55, F 13.23, N 9.64, S 8.03.
1-Dodecyl-3,5-dicyanopyridinium triflate (2e): Pyridine-
3,5-dicarbonitrile (150 mg, 1.16 mmol) and n-dodecyl triflate
(7e) (407 mg, 1.29 mmol) were treated according to the gen-
eral procedure to give 2e; yield: 215 mg (42%); mp 222–
1
2258C. H NMR (500 MHz, CD3CN): d=9.42 (t, J=7.9 Hz,
2H), 9.18 (s, 1H), 4.66 (d, J=7.9 Hz, 2H), 2.08–2.00 (m,
2H), 1.46–1.26 (m, 18H), 0.91 (t, J=6.8 Hz, 3H); 13C NMR
(126 MHz, CD3CN): d=151.8, 151.4, 114.8, 111.6, 64.0, 31.6,
30.2, 29.3, 29.2–28.9 (m), 28.5, 25.3, 22.3, 13.3; 19F NMR
(282 MHz, CDCl3): d= À78.19; anal. calcd. for
C20H16F3N3O3S: C 53.68, H 6.31, F 12.74, N 9.39, S 7.17;
found: C 53.76, H 6.17, F 12.28, N 9.04 S 7.40.
1-Hexadecyl-3,5-dicyanopyridinium triflate (2f): Pyridine-
3,5-dicarbonitrile (150 mg, 1.16 mmol) and n-hexydecyl tri-
flate (7f) (479 mg, 1.29 mmol) were treated according to the
general procedure to give 2f; yield: 260 mg (45%); mp 230–
1
2338C. H NMR (500 MHz, CD3CN): d=9.40 (d, J=0.7 Hz,
2H), 9.18 (s, 1H), 4.65 (t, J=7.7 Hz, 2H), 2.08–1.99 (m,
2H), 1.35 (d, J=40.2 Hz, 26H), 0.91 (t, J=6.8 Hz, 3H);
13C NMR (101 MHz, CD3CN): d=151.7, 151.5, 114.9, 111.7,
64.0, 30.8, 30.2, 29.3, 29.2–29.0 (m), 28.5, 25.5, 22.4, 13.4;
19F NMR (282 MHz, CDCl3): d= À78.17; anal. calcd. for
Adv. Synth. Catal. 2015, 357, 3573 – 3586
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3581