The Journal of Organic Chemistry
Note
2,6-Dichlorobenzonitrile (2k).22 White solid, yield 65% (67.0 mg).
Eluent: Petroleum ether/EtOAc = 30/1. 1H NMR (500 MHz,
CDCl3) δ 7.51−7.43 (m, 3H). 13C{1H} NMR (125.76 MHz, CDCl3)
δ 138.5, 133.9, 128.2, 114.4, 113.3. GC−MS (EI, 70 eV) m/z = 172
(M+). HRMS (ESI-TOF) m/z: [M]+ Calcd for C7H3Cl2N 170.9643,
found 170.9635.
CDCl3) δ 7.80 (d, J = 7.7 Hz, 2H), 7.58−7.55 (m, 1H), 7.45−7.42
(m, 2H), 6.89 (s, 2H), 2.33 (s, 3H), 2.08 (s, 6H). 13C{1H} NMR
(125.76 MHz, CDCl3) δ 200.8, 138.5, 137.4, 136.9, 134.2, 133.6,
129.4, 128.8, 128.4, 21.2, 19.4. GC−MS (EI, 70 eV) m/z = 224 (M+).
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C16H17O 225.1279,
found 225.1283.
2-Naphthonitrile (2l).17 White solid, yield 54% (49.6 mg). Eluent:
Petroleum ether/EtOAc = 30/1. 1H NMR (500 MHz, CDCl3) δ
8.22(s, 1H), 7.92−7.88 (m, 3H), 7.66−7.59 (m, 3H). 13C{1H} NMR
(125.76 MHz, CDCl3) δ 134.7, 134.2, 132.3, 129.2, 129.1, 128.4,
128.1, 127.7, 126.4, 119.3, 109.4. GC−MS (EI, 70 eV) m/z = 153 (M
+). HRMS (ESI-TOF) m/z: [M]+ Calcd for C11H7N 153.0578, found
153.0898.
Mesityl(p-toly)methanone (3b).27 Yellow oil, yield 83% (118.6
1
mg). Eluent: Petroleum ether/EtOAc = 50/1. H NMR (500 MHz,
CDCl3) δ 7.70 (d, J = 7.7 Hz, 2H), 7.24 (d, J = 7.9 Hz, 2H), 6.89 (s,
2H), 2.41 (s, 3H), 2.33 (s, 3H), 2.08 (s, 6H). 13C{1H} NMR (125.76
MHz, CDCl3) δ 200.4, 144.5, 138.3, 137.2, 135.0, 134.2, 129.6, 129.5,
128.3, 21.8, 21.2, 19.3. GC−MS (EI, 70 eV) m/z = 238 (M+). HRMS
(ESI-TOF) m/z: [M + H]+ Calcd for C17H19O 239.1436, found
239.1452.
Thiophene-2-carbonitrile (2m).17 Colorless oil, yield 42% (27.4
1
Mesityl(o-tolyl)methanone (3c).26 Yellow solid, yield 90% (128.6
mg). Eluent: Petroleum ether/EtOAc = 30/1. H NMR (500 MHz,
CDCl3) δ 7.63−7.61 (m, 2H), 7.14−7.12 (m, 1H). 13C{1H} NMR
(125.76 MHz, CDCl3) δ 137.5, 132.6, 127.7, 114.3, 109.9. GC−MS
(EI, 70 eV) m/z = 109 (M+). HRMS (ESI-TOF) m/z: [M + H]+
Calcd for C5H4NS 110.0064, found 110.0234.
1
mg). Eluent: Petroleum ether/EtOAc = 40/1. H NMR (500 MHz,
CDCl3) δ 7.41−7.35 (m, 2H), 7.32−7.30 (m, 1H), 7.16 (t, J = 7.4
Hz, 1H), 6.88 (s, 2H), 2.70 (s, 3H), 2.33 (s, 3H), 2.10 (s, 6H).
13C{1H} NMR (125.76 MHz, CDCl3) δ 202.7, 140.0, 138.5, 138.5,
137.0, 134.4, 132.2, 132.2, 131.9, 128.5, 125.9, 21.8, 21.2, 19.4. GC−
MS (EI, 70 eV) m/z = 238 (M+). HRMS (ESI-TOF) m/z: [M + H]+
Calcd for C17H19O 239.1436, found 239.1513.
Dodecanenitrile (2n).22 Colorless oil, yield 78% (84.4 mg). Eluent:
Petroleum ether/EtOAc = 30/1. 1H NMR (500 MHz, CDCl3) δ 2.33
(t, J = 7.1 Hz, 2H), 1.68−1.62 (m, 2H), 1.47−1.41 (m, 2H), 1.31−
1.26 (m, 14H), 0.88 (t, J = 7.1 Hz, 3H). 13C{1H} NMR (125.76
MHz, CDCl3) δ 119.9, 31.9, 29.6, 29.5, 29.3, 28.8, 28.7, 25.4, 22.7,
17.1, 14.1. GC−MS (EI, 70 eV) m/z = 181 (M+). HRMS (ESI-TOF)
m/z: [M + H]+ Calcd for C12H24N 182.1909, found 182.1959.
Cyclohexanecarbonitrile (2o).23 Colorless oil, yield 74% (48.4
(4-(tert-Butyl)phenyl)(mesityl)methanone (3d).28 Yellow oil, yield
1
94% (158.0 mg). Eluent: Petroleum ether/EtOAc = 40/1. H NMR
(500 MHz, CDCl3) δ 7.74 (d, J = 8.0 Hz, 2H), 7.45 (d, J = 8.4 Hz,
2H), 6.89 (s, 2H), 2.33 (s, 3H), 2.09 (s, 6H), 1.34 (s, 9H). 13C{1H}
NMR (125.76 MHz, CDCl3) δ 200.5, 157.4, 138.3, 137.2, 134.8,
134.2, 129.4, 128.3, 125.7, 35.2, 31.1, 21.2, 19.4. GC−MS (EI, 70 eV)
m/z = 280 (M+). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
C20H25O 281.1905, found 281.1907.
1
mg). Eluent: Petroleum ether/EtOAc = 50/1. H NMR (500 MHz,
CDCl3) δ 2.65−2.61 (m, 1H), 1.88−1.83 (m, 2H), 1.76−1.66 (m,
4H), 1.54−1.41 (m, 4H). 13C{1H} NMR (125.76 MHz, CDCl3) δ
122.7, 29.5, 28.0, 25.2, 24.1. GC−MS (EI, 70 eV) m/z = 109 (M+).
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C7H12N 110.0970,
found 110.0929.
Mesityl(4-methoxyphenyl)methanone (3e).26 Yellow oil, yield
1
76% (115.8 mg). Eluent: Petroleum ether/EtOAc = 30/1. H NMR
(500 MHz, CDCl3) δ 7.66−7.61 (m, 2H), 6.78−6.71 (m, 4H), 3.70
(s, 3H), 2.19 (s, 3H), 1.96 (s, 6H). 13C{1H} NMR (125.76 MHz,
CDCl3) δ 199.2, 164.0, 138.2, 137.2, 134.1, 131.8, 130.5, 128.3, 114.0,
55.5, 21.2, 19.3. GC−MS (EI, 70 eV) m/z = 254 (M+). HRMS (ESI-
TOF) m/z: [M + H]+ Calcd for C17H19O2 225.1385, found 225.1390.
Fluorophenyl)(mesityl)methanone (3f).29 Yellow oil, yield 82%
2-Phenylacetonitrile (2p).24 Colorless oil, yield 47% (33.0 mg).
Eluent: Petroleum ether/EtOAc = 30/1. 1H NMR (500 MHz,
CDCl3) δ 7.38−7.35 (m, 2H), 7.33−7.30 (m, 3H), 3.72 (s, 2H).
13C{1H} NMR (125.76 MHz, CDCl3) δ 130.0, 129.2, 128.1, 128.0,
118.0, 23.6. GC−MS (EI, 70 eV) m/z = 117 (M+). HRMS (ESI-
TOF) m/z: [M + H]+ Calcd for C8H8N 118.0657, found 118.0700.
2-Phenylpropanenitrile (2q).25 Yellow oil, yield 44% (34.6 mg).
Eluent: Petroleum ether/EtOAc = 30/1. 1H NMR (500 MHz,
CDCl3) δ 7.40−7.31 (m, 5H), 3.90 (q, J = 7.3 Hz, 1H), 1.64 (d, J =
7.3 Hz, 3H). 13C{1H} NMR (125.76 MHz, CDCl3) δ 137.1, 129.2,
128.1, 126.7, 121.6, 31.3, 21.5. GC−MS (EI, 70 eV) m/z = 131 (M+).
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C9H10N 132.0813,
found 132.0799.
Typical Procedure for Conversion of Methyl Esters to
Ketones. Under air, a mixture of aryl ester 1 (0.3 mmol), arene (0.6
mL), I2 (38.1 mg, 0.15 mmol), and PCl3 (27 μL, 0.3 mmol) was
stirred in a 25 mL closed sealed tube in an oil bath at 160 °C for the
indicated time. After the mixture was cooled down to the room
temperature, the mixture was quenched with Na2S2O3 aqueous
solution and was extracted with EtOAc three times. Then the
combined organic layer was dried over MgSO4 and filtrated. The
filtrate was concentrated, and the residue was further purified by
column chromatography on silica gel to give the product 3.
Procedure for the Preparation of 3a on Gram Scale. Under
air, a mixture of aryl ester 1a (0.75 mL, 6.0 mmol), mesitylene (12
mL), I2 (761.4 mg, 3.0 mmol), and PCl3 (0.525 mL, 6.0 mmol) was
stirred in a 50 mL closed sealed tube in oil bath at 160 °C for 70 h.
After the mixture was cooled down to the room temperature, the
mixture was quenched with Na2S2O3 aqueous solution and was
extracted with EtOAc three times. Then the combined organic layer
was dried over MgSO4 and filtrated. The filtrate was concentrated,
and the residue was further purified by column chromatography on
silica gel to give the product 3a in 1.29 g.
1
(119.0 mg). Eluent: Petroleum ether/EtOAc = 50/1. H NMR (500
MHz, CDCl3) δ 7.84−7.81 (m, 2H), 7.13−7.09 (m, 2H), 6.90 (s,
2H), 2.33 (s, 3H), 2.08 (s, 6H). 13C{1H} NMR (125.76 MHz,
CDCl3) δ 199.2, 166.1 (d, 1JC‑F = 255.3 Hz), 138.7, 136.5, 134.1,
133.1 (d, 4JC‑F = 2.7 Hz), 132.1 (d, 3JC‑F = 9.5 Hz), 128.4, 116.0 (d,
2JC‑F = 22.0 Hz), 21.2, 19.4. GC−MS (EI, 70 eV) m/z = 242 (M+).
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C16H16FO 243.1185,
found 243.1259.
Chlorophenyl)(mesityl)methanone (3g).30 Yellow oil, yield 81%
1
(125.8 mg). Eluent: Petroleum ether/EtOAc = 50/1. H NMR (500
MHz, CDCl3) δ 7.63 (d, J = 10.0 Hz, 2H), 7.29 (d, J = 10.0 Hz, 2H),
6.78 (s, 2H), 2.21 (s, 3H), 1.96 (s, 6H). 13C{1H} NMR (125.76
MHz, CDCl3) δ 198.3, 139.0, 137.7, 135.3, 134.7, 133.1, 129.7, 128.1,
127.4, 20.1, 18.3. GC−MS (EI, 70 eV) m/z = 259 (M+). HRMS
(ESI-TOF) m/z: [M + H]+ Calcd for C16H16ClO 259.0890, found
259.0907.
Bromophenyl)(mesityl)methanone (3h).31 Yellow oil, yield 90%
1
(163.6 mg). Eluent: Petroleum ether/EtOAc = 50/1. H NMR (500
MHz, CDCl3) δ 7.57 (d, J = 8.4 Hz, 2H), 7.49 (d, J = 8.8 Hz, 2H),
6.80 (s, 2H), 2.23 (s, 3H), 1.98 (s, 6H). 13C{1H} NMR (125.76
MHz, CDCl3) δ 199.7, 138.8, 136.3, 136.1, 134.2, 132.2, 130.9, 129.0,
128.5, 21.2, 19.4. GC−MS (EI, 70 eV) m/z = 303 (M+). HRMS
(ESI-TOF) m/z: [M + H]+ Calcd for C16H14BrO 303.0385, found
303.0379.
Mesityl(4-(trifluoromethyl)phenyl)methanone (3i).26 Yellow
solid, yield 63% (110.4 mg). Eluent: Petroleum ether/EtOAc = 50/
1. 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.1 Hz, 2H), 7.71 (d, J
= 8.2 Hz, 2H), 6.92 (s, 2H), 2.35 (s, 3H), 2.07 (s, 6H). 13C{1H}
NMR (125.76 MHz, CDCl3) δ 199.7, 139.9, 139.1, 136.0, 134.8 (d,
2JC‑F = 32.7 Hz), 134.3, 129.7, 128.6, 125.9 (q, 3JC‑F = 3.8 Hz), 123.6
(d, 1JC‑F = 272.9 Hz), 21.2, 19.4. GC−MS (EI, 70 eV) m/z = 292 (M
Yields were based on two parallel reactions, and the mass of the
product is the total mass of two parallel reactions!
Mesityl(phenyl)methanone (3a).26 Yellow oil, yield 98% (131.8
1
mg). Eluent: Petroleum ether/EtOAc = 50/1. H NMR (500 MHz,
2032
J. Org. Chem. 2021, 86, 2028−2035