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Typical Procedure
for Conversion of
N
-Alkyl-
O
-benzoyl Hydroxylamines to Ketones: N-α-Methyl benzyl-O-benzoyl hydroxylamine (100 mg, 0.41
mmol) was dissolved in DMF (0.59 mL) at ambient temperature. Caesium carbonate
(135 mg, 0.41 mmol) was added and the resulting reaction mixture
was heated at 50 ˚C overnight. The resulting reaction mixture
was allowed to cool and purified directly by column chromatography,
eluting with 20% EtOAc-PE, to give acetophenone
(42 mg, 84%) as a clear colourless oil. IR (thin film):
1683, 1599, 1582, 1449, 1359, 1266, 1180, 1078, 1025, 955, 760,
690 cm-¹. ¹H NMR
(400 MHz, CDCl3): δ = 7.85 (d, J = 7.2 Hz, 2 H), 7.45 (t, J = 7.3 Hz, 1 H), 7.40-7.30
(m, 2 H), 2.50 (s, 3 H). ¹³C NMR (100 MHz,
CDCl3): δ = 198.1, 137.1, 133.1, 128.6,
128.3, 26.6. MS (EI): m/z = 120.06 [M]+.
Typical Procedure for the One-Pot Conversion
of Primary Amines to Ketones: Benzoyl peroxide (326 mg, 1.01
mmol, 75%) was dissolved in DMF (2.53 mL) and cooled to
0 ˚C. Caesium carbonate (493 mg, 1.51 mmol) was added with
stirring followed by cyclohexyl ethylamine (0.18 mL, 1.21 mmol).
The resulting reaction mixture was stirred at 0 ˚C for
2 h before warming to r.t. TLC was used to confirm complete consumption
of benzoyl peroxide before heating at 50 ˚C overnight.
The resulting reaction mixture was purified directly by column chromatography,
eluting with 20% EtOAc-PE, to give cyclohexyl
methyl ketone
(75 mg, 59%) as a clear colourless
oil. IR (thin film): 2931, 2854, 1706 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 2.3-2.1 (m,
1 H), 2.05 (s, 3 H), 1.80-1.85 (m, 2 H), 1.70-1.75
(m,
2 H), 1.55-1.65 (m, 1 H), 1.05-1.30
(m, 5 H). ¹³C NMR (100 MHz, CDCl3): δ = 212.2,
51.4, 28.4, 27.8, 25.8, 25.6. MS (EI): m/z = 126.22 [M]+.