Reference and Notes
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The use of SPC as oxidant with water donor for oxidation of tertiary nitrogen compounds
to N-oxides has been reported:
<A NAME="RD08906ST-6A">6a</A>
Rosenau T.
Potthast A.
Kosma P.
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<A NAME="RD08906ST-7">7</A>
Typical Experimental Procedure: To a stirred solution of 4-picoline (10 mmol, 0.93 g), in MeCN (3 mL) were added
SPC (3.12 g, 20 mmol) and MTO (25 mg, 1 mol%) and the mixture was heated to 50 °C
under nitrogen atmosphere. AcOH (20 mol%) was added dropwise over a period of 15 min
at 50 °C to this vigorously stirred solution. A vibrant yellow color appeared in the
reaction mixture upon addition of AcOH. The progress of the reaction was monitored
by TLC (SiO2). After completion, the solvent was evaporated and the residue was dissolved in CH2Cl2. The organic layer was washed with water (2 ×) and dried over anhyd Na2SO4. The solvent was evaporated under reduced pressure and the residue thus obtained
was purified by passing through a short silica gel column using EtOAc-hexane (4:6)
as eluent. Evaporation of the solvent under reduced pressure yielded pure 4-picoline
N-oxide (1.02 g, 92%); mp 180-181 °C (Lit.
[9]
182 °C). IR: 3033, 1470, 1250, 1176 cm-1. 1H NMR: δ = 2.39 (s, 3 H), 7.10-7.22 (d, 2 H), 8.09-8.20 (d, 2 H).
<A NAME="RD08906ST-8">8</A>
Product Characterization Data.Pyridine N
-Oxide (Table
[2]
, entry 1): mp 60-61 °C (Lit.
[9]
62-63 °C). IR: 3076, 1388, 1265, 1176 cm-1. 1H NMR: δ = 7.42-7.45 (m, 3 H), 8.25-8.40 (m, 2 H).2-Picoline N
-Oxide (Table
[2]
, entry 4): Hygroscopic oil. IR: 3030, 1482, 1252, 1190 cm-1. 1H NMR: δ = 2.42 (s, 3 H), 7.10-7.19 (m, 3 H), 8.10-8.23 (m, 1 H).4-Cyanopyridine N
-Oxide (Table
[2]
, entry 5): mp 180-182 °C (Lit.
[9]
182-183 °C). IR: 3076, 2247, 1492, 1282, 1176 cm-1. 1H NMR: δ = 7.89-8.00 (d, 2 H), 8.42-8.46 (d, 2 H).Nicotinamide N
-Oxide (Table
[2]
, entry 6): mp 289-290 °C (decomp.). IR: 3350, 3060, 1694, 1450, 1140 cm-1. 1H NMR: δ = 7.37-7.45 (m, 2 H), 8.27-8.40 (m, 2 H).3-Picoline N
-Oxide (Table
[2]
, entry 7): Hygroscopic oil. IR: 3030, 1470, 1252, 1162 cm-1. 1H NMR: δ = 2.35 (s, 3 H), 7.11-7.21 (m, 2 H), 8.18-8.20 (m, 2 H).Quinoline N
-Oxide (Table
[2]
, entry 8): mp 50-52 °C (Lit.
[9]
52-53 °C). IR: 3030, 1484, 1298, 1176 cm-1. 1H NMR: δ = 7.21-7.35 (m, 4 H), 8.10-8.19 (m, 2 H), 8.40 (m, 1 H).N
,
N
-Diethylaniline N
-Oxide (Table
[2]
, entry 9): Hygroscopic solid. IR: 3013, 2941, 1369, 1219, 1190 cm-1. 1H NMR: δ = 1.2 (t, 6 H), 3.3 (q, 2 H), 6.9 (m, 3 H), 7.3 (m, 2 H).N
,
N
-Dimethylaniline N
-Oxide (Table
[2]
, entry 10): Hygroscopic solid. IR: 3010, 2941, 1367, 1219, 1175 cm-1. 1H NMR: δ = 3.32 (s, 6 H), 7.22-7.28 (m, 3 H), 7.49-7.55 (m, 2 H).Triethylamine N
-Oxide (Table
[2]
, entry 11): Hygroscopic solid. IR: 2940, 2870, 1470, 1250 cm-1. 1H NMR: δ = 1.12 (t, 9 H), 3.30 (q, 6 H).
<A NAME="RD08906ST-9">9</A>
Prasad MR.
Kamalkar G.
Madhavi G.
Kulkarni SJ.
Raghavan KV.
J. Mol. Catal. A: Chem.
2002,
186:
109