Job/Unit: O42015
/KAP1
Date: 09-04-14 18:50:59
Pages: 10
Metal-Free One-Pot Oxidation of Methylarenes
7.35 (t, J = 7.6 Hz, 1 H), 7.47 (t, J = 7.6 Hz, 1 H), 7.79 (d, J = Method B 314.5 mg (85%). Colorless oil. 1H NMR (400 MHz,
7.8 Hz, 1 H), 10.26 (s, 1 H) ppm. 13C NMR (100 Hz, CDCl3): δ =
CDCl3): δ = 7.42–7.48 (m, 2 H), 7.65–7.67 (m, 1 H), 7.91–7.94 (m,
19.51, 126.25, 131.70, 131.98, 133.58, 134.08, 140.54, 192.74 ppm.
1 H), 10.38 (s, 1 H) ppm. 13C NMR (100 Hz, CDCl3): δ = 127.10,
IR (ATR): ν = 2863, 1692 cm–1.
127.88, 129.84, 133.48, 133.87, 135.32, 191.86 ppm. IR (ATR): ν =
˜
˜
2868, 1690 cm–1.
3-Methylbenzaldehyde (commercially available): Yield 192.2 mg
(80%, from 3-methylbenzyl chloride). Colorless oil. 1H NMR
(400 MHz, CDCl3): δ = 2.41 (s, 3 H), 7.41–7.46 (m, 2 H), 7.68–
7.70 (m, 2 H), 9.99 (s, 1 H) ppm. 13C NMR (100 Hz, CDCl3): δ =
21.02, 127.06, 128.74, 129.86, 135.14, 136.35, 138.76, 192.41 ppm.
3-Bromobenzaldehyde (commercially available): Yield Method A
236.8 mg (64%), Method B 259.0 mg (70%). Colorless oil. 1H
NMR (400 MHz, CDCl3): δ = 7.43 (t, J = 7.9 Hz, 1 H), 7.77 (ddd,
J = 7.9, 1.8, 1.4 Hz, 1 H), 7.82 (dt, J = 7.9, 1.6 Hz, 1 H), 8.02 (t,
J = 1.6 Hz, 1 H), 9.97 (s, 1 H) ppm. 13C NMR (100 Hz, CDCl3): δ
= 123.31, 128.33, 130.58, 132.29, 137.25, 137.93, 190.68 ppm. IR
IR (ATR): ν = 2820, 1700 cm–1.
˜
4-Methylbenzaldehyde (commercially available): Yield 235.5 mg
(98%, from 4-methylbenzyl bromide), 204.3 mg (85%, from 4-
methylbenzyl chloride). Method A 122.6 mg (51%), Method B
146.6 mg (61%). Colorless oil. 1H NMR (400 MHz, CDCl3): δ =
2.44 (s, 3 H), 7.33 (d, J = 7.9 Hz, 2 H), 7.77 (d, J = 7.9 Hz, 2 H),
9.96 (s, 1 H) ppm. 13C NMR (100 Hz, CDCl3): δ = 21.82, 129.65,
(ATR): ν = 2876, 1668 cm–1.
˜
4-Bromobenzaldehyde (commercially available): Yield 355.2 mg
(96%, from 4-bromobenzyl bromide), Method A 277.5 mg (75%),
1
Method B 266.4 mg (72%). White solid; m.p. 58–60 °C. H NMR
(400 MHz, CDCl3): δ = 7.69 (d, J = 8.6 Hz, 2 H), 7.75 (d, J =
129.79, 134.13, 145.49, 191.94 ppm. IR (ATR):
ν = 2824,
˜
8.6 Hz, 2 H), 9.98 (s, 1 H) ppm. 13C NMR (100 Hz, CDCl3): δ =
1701 cm–1.
129.8, 131.0, 132.4, 135.0, 191.0 ppm. IR (ATR): ν = 2859,
˜
4-tert-Butylbenzaldehyde (commercially available): Yield 314.7 mg
(97%, from 4-tert-butylbenzyl bromide), Method A 246.6 mg
(76%), Method B 227.1 mg (70%). Light yellow oil. 1H NMR
(400 MHz, CDCl3): δ = 1.36 (s, 9 H), 7.56 (d, J = 8.2 Hz, 2 H),
7.82 (d, J = 8.2 Hz, 2 H), 9.98 (s, 1 H) ppm. 13C NMR (100 Hz,
1685 cm–1.
4-Chlorobenzaldehyde (commercially available): Yield 253.02 mg
(90%, from 4-chlorobenzyl bromide), 261.5 mg (93%, from 4-chlo-
robenzyl chloride), Method A 185.5 mg (66%), Method B 185.5 mg
1
(66%). White solid; m.p. 48–49 °C. H NMR (400 MHz, CDCl3):
CDCl3):
δ = 31.00, 35.25, 125.90, 129.61, 133.99, 158.35,
δ = 7.52 (d, J = 8.6 Hz, 2 H), 7.83 (d, J = 8.6 Hz, 2 H), 9.99 (s, 1
191.98 ppm. IR (ATR): ν = 2963, 1697 cm–1.
˜
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 129.44, 130.88, 134.69,
140.94, 190.82 ppm. IR (Nujol): ν = 2727, 1710 cm–1.
2-Methoxybenzaldehyde (commercially available): Yield Method A
0 mg (0%), Method B 198.8 mg (73%). White solid; m.p. 36–38 °C.
1H NMR (400 MHz, CDCl3): δ = 3.92 (s, 3 H), 6.98–7.04 (m, 2
H), 7.55 (t, J = 7.9 Hz, 1 H), 7.83 (d, J = 7.9 Hz, 1 H), 10.48 (s, 1
H) ppm. 13C NMR (100 Hz, CDCl3): δ = 55.51, 111.54, 120.53,
˜
4-Fluorobenzaldehyde (commercially available): Yield 188.6 mg
(76%, from 4-fluorobenzyl bromide). Colorless oil. 1H NMR
(400 MHz, CDCl3): δ = 7.22 (t, J = 8.8 Hz, 2 H), 7.92 (dd, J = 5.5,
8.8 Hz, 2 H), 9.97 (s, 1 H) ppm. 13C NMR (100 Hz, CDCl3): δ =
116.30 (d, JC,F = 22.9 Hz), 132.18 (d, JC,F = 9.5 Hz), 132.91. 166.48
124.69, 128.37, 135.87, 161.73, 189.70 ppm. IR (ATR): ν = 2845,
˜
1685 cm–1.
(d, JC,F = 256.5 Hz), 190.46 ppm. IR (ATR): ν = 2828, 1693, 1595,
˜
5-Bromo-2-methoxybenzaldehyde (commercially available): Yield
Method B 118.27 mg (55%). White solid; m.p. 115–116 °C. 1H
NMR (400 MHz, CDCl3): δ = 3.93 (s, 3 H), 6.90 (d, J = 8.0 Hz, 1
H), 7.63 (dd, J = 2.6, 8.0 Hz, 1 H), 7.92 (d, J = 2.6 Hz, 1 H), 10.39
(s, 1 H) ppm. 13C NMR (100 Hz, CDCl3): δ = 55.95, 113.45,
1226, 1148, 831 cm–1.
4-(Hydroxymethyl)benzaldehyde (commercially available): Yield
253.2 mg [93%, from 4-(hydroxymethyl)benzyl chloride]. White so-
1
lid; m.p. 39–43 °C. H NMR (400 MHz, CDCl3): δ = 1.90 (br., 1
H), 4.81 (s, 2 H), 7.54 (d, J = 8.1 Hz, 2 H), 7.89 (d, J = 8.1 Hz, 2
113.68, 126.06, 131.05, 138.27, 160.71, 188.35 ppm. IR (ATR): ν =
˜
H), 10.01 (s, 1 H) ppm. 13C NMR (100 Hz, CDCl3): δ = 64.14,
2830, 1683, 1567, 1416, 1259, 1191 cm–1.
126.80, 129.87, 135.26, 148.04, 192.29 ppm. IR (ATR): ν = 3343,
˜
4-Methoxybenzaldehyde (commercially available): Yield 250.5 mg
(92%, from 4-methoxybenzyl chloride), Method A 0 mg (0%),
Method B 212.4 mg (78%). Colorless oil. 1H NMR (CDCl3,
400 MHz): δ = 3.90 (s, 3 H), 7.01 (d, J = 8.7 Hz, 2 H), 7.85 (d, J
= 8.7 Hz, 2 H), 9.89 (s, 1 H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 55.52, 114.25, 129.88, 131.92, 164.55, 190.78 ppm. IR (ATR):
2849, 1687 cm–1.
Ethyl 4-Formylbenzoate (commercially available): Yield 335.0 mg
(94%) [from 4-(ethoxycarbonyl)benzyl chloride], Method A
217.4 mg (61%), Method B 213.8 mg (60%). White solid; m.p. 154–
158 °C. 1H NMR (400 MHz, CDCl3): δ = 1.43 (t, J = 5.7 Hz, 3 H),
4.42 (q, J = 5.7 Hz, 2 H), 7.96 (d, J = 6.8 Hz, 2 H), 8.20 (d, J =
6.8 Hz, 2 H), 10.11 (s, 1 H) ppm. 13C NMR (100 Hz, CDCl3): δ =
14.18, 61.52, 129.39, 130.06, 135.37, 139.00, 165.47, 191.60 ppm.
ν = 2840, 2739, 1683 cm–1.
˜
Piperonyl Aldehyde (commercially available): Yield 252.2 mg (84%,
from piperonyl chloride). White solid; m.p. 37–39 °C. 1H NMR
(CDCl3, 400 MHz): δ = 6.08 (s, 2 H), 6.94 (d, J = 8.0 Hz, 1 H),
7.34 (d, J = 1.6 Hz, 1 H), 7.42 (dd, J = 8.0, 1.6 Hz, 1 H), 9.82 (s, 1
H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 102.09, 106.90, 108.34,
IR (ATR): ν = 2981, 1705 cm–1.
˜
4-Formylbenzamide (commercially available): Yield 134.2 mg (45%)
[from 4-(aminocarbonyl)benzyl chloride]. White solid; m.p. 165–
173 °C. 1H NMR (400 MHz, CDCl3): δ = 5.77 (br., 1 H), 6.11 (br.,
1 H), 7.98 (m, 4 H), 10.10 (s, 1 H) ppm. 13C NMR (100 Hz, [D6]-
DMSO): δ = 128.17, 129.34, 137.82, 139.34, 167.06, 192.89 ppm.
128.66, 131.87, 148.70, 153.09, 190.28 ppm. IR (Nujol): ν = 2725,
˜
1685 cm–1.
4-Iodobenzaldehyde (commercially available): Yield Method A
306.3 mg (66%), Method B 292.3 mg (63%). White solid; m.p. 73–
75 °C. 1H NMR (400 MHz, CDCl3): δ = 7.60 (d, J = 8.2 Hz, 2 H),
7.92 (d, J = 8.2 Hz, 2 H), 9.96 (s, 1 H) ppm. 13C NMR (100 Hz,
CDCl3): δ = 102.81, 130.79, 135.55, 138.40, 191.41 ppm. IR (ATR):
IR (ATR): ν = 3359, 3179, 2832, 1658 cm–1.
˜
4-Formylbenzophenone (commercially available): Yield Method A
214.4 mg (51%), Method B 252.3 mg (60%). White solid; m.p. 65–
1
67 °C. H NMR (400 MHz, CDCl3): δ = 7.52 (t, J = 7.2 Hz, 2 H),
ν = 2825, 1683 cm–1.
˜
7.64 (t, J = 7.2 Hz, 1 H), 7.82 (d, J = 7.2 Hz, 2 H), 7.93 (d, J =
8.5 Hz, 2 H), 8.01 (d, J = 8.5 Hz, 2 H), 10.14 (s, 1 H) ppm. 13C
NMR (100 Hz, CDCl3): δ = 128.53, 129.49, 130.11, 130.32, 133.13,
2-Bromobenzaldehyde (commercially available): Yield 303.4 mg
(82%, from 2-bromobenzyl bromide), Method A 270.1 mg (73%),
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7