Job/Unit: O42751
/KAP1
Date: 29-10-14 18:42:44
Pages: 12
ortho-Benzoyloxylation of N,N-Dialkylanilines
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Yield: 59% (165 mg); yellow liquid. H NMR (300 MHz, CDCl3): 1022, 706 cm–1. MS (ESI):m/z (%) = 346 (100) [M + H]+, 348 (100)
δ = 8.22–8.20 (m, 2 H), 7.64–7.61 (m, 1 H), 7.52–7.49 (m, 2 H), (M + 2 + H)+. HRMS (ESI): m/z calcd. for C17H17NO2Br [M +
7.02–6.97 (m, 2 H), 6.94–6.93 (m, 1 H), 5.71–5.63 (m, 1 H), 5.14–
5.10 (m, 1 H), 5.01–4.99 (m, 1 H), 3.58 (d, J = 6.10 Hz, 2 H), 2.67
(s, 3 H), 2.31 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
164.9, 143.8, 142.3, 135.1, 133.3, 132.1, 130.1, 129.8, 128.4, 127.0,
H]+ 346.04372; found 346.04376.
2-(Diallylamino)-5-methylphenyl Benzoate (18): Isolated by column
chromatography (ethyl acetate/hexane = 1:10; Rf = 0.4). Yield: 41%
(125 mg); yellowish liquid. 1H NMR (300 MHz, CDCl3): δ = 8.21–
8.19 (m, 2 H), 7.64–7.62 (m, 1 H), 7.52–7.49 (m, 2 H), 6.99–6.93
(m, 3 H), 5.72–5.64 (m, 2 H), 5.10 (dd, J = 1.53, 17.24 Hz, 2 H),
5.03–5.01 (m, 2 H), 3.63 (d, J = 5.95 Hz, 4 H), 2.31 (s, 3 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 164.8, 144.8, 140.6, 135.0, 133.2,
132.8, 130.1, 129.9, 128.4, 126.7, 123.8, 122.4, 117.0, 55.1,
123.8, 120.2, 116.9, 59.0, 39.6, 20.5 ppm. FTIR: ν = 2922, 2854,
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2795, 1739, 1601, 1510, 1450, 1420, 1353, 1313, 1262, 1242, 1177,
1155, 1083, 1061, 1024, 997, 921, 813, 706 cm–1. MS (ESI): m/z (%)
= 282 (40) [M + H]+, 355 (100) [M + 74]. HRMS (ESI): m/z calcd.
for C18H20NO2 [M + H]+ 282.14886; found 282.14854.
20.6 ppm. FTIR: ν = 3075, 3009, 2923, 2856, 1740, 1641, 1601,
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2-[Allyl(methyl)amino]-5-ethylphenyl Benzoate (14): Isolated by col-
umn chromatography (ethyl acetate/hexane = 1:10; Rf = 0.5). Yield:
58% (171 mg); yellowish liquid. H NMR (300 MHz, CDCl3): δ =
8.23–8.21 (m, 2 H), 7.66–7.61 (m, 1 H), 7.53–7.48 (m, 2 H), 7.06–
6.96 (m, 3 H), 5.72–5.61 (m, 1 H), 5.15–5.10 (m, 1 H), 5.02–4.99
(m, 1 H), 3.59 (d, J = 5.85 Hz, 2 H), 2.67 (s, 3 H), 2.63–2.58 (m, 2
H), 1.26–1.21 (m, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
164.9, 143.9, 142.6, 138.5, 135.2, 133.3, 130.1, 129.9, 128.5, 125.7,
1508, 1450, 1244, 1175, 1154, 1113, 1061, 921, 706 cm–1. MS (ESI):
m/z (%) = 308 (100) [M + H]+, 330 (10) [M + Na]+. HRMS (ESI):
m/z calcd. for C20H22NO2 [M + H]+ 308.16451; found 308.16262.
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2-(Diethylamino)-5-methylphenyl Benzoate (19): Isolated by column
chromatography (ethyl acetate/hexane = 1:10; Rf = 0.4). Yield: 40%
(113 mg); yellowish liquid. 1H NMR (300 MHz, CDCl3): δ = 8.22–
8.19 (m, 2 H), 7.65–7.60 (m, 1 H), 7.53–7.48 (m, 2 H), 7.02–6.94
(m, 3 H), 3.04–2.97 (m, 4 H), 2.32 (s, 3 H), 0.97–0.92 (m, 6 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 164.9, 146.1, 140.5, 133.1, 133.0,
122.7, 120.2, 116.9, 59.0, 39.7, 27.9, 15.3 ppm. FTIR: ν = 3071,
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2963, 2930, 2870, 2795, 1739, 1640, 1510, 1450, 1422, 1262, 1242,
1177, 1154, 1083, 1060, 1023, 706 cm–1. MS (ESI): m/z (%) = 296
(100) [M + H]+. HRMS (ESI) calcd. for C19H22NO2[M + H]+
296.16451; found 296.16406.
130.0, 128.4, 126.8, 123.7, 123.1, 46.8, 20.6, 12.4 ppm. FTIR: ν =
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2972, 2928, 2867, 1739, 1603, 1508, 1451, 1381, 1256, 1223, 1171,
1107, 1061, 1024, 706 cm–1. MS (ESI): m/z (%) = 284 (100) [M +
H]+. HRMS (ESI): m/z calcd. for C18H22NO2 [M + H]+ 284.16451;
found 284.16256.
2-[Allyl(methyl)amino]-5-methoxyphenyl Benzoate (15): Isolated by
column chromatography (ethyl acetate/hexane = 1:10; Rf = 0.3).
Yield: 65% (193 mg); yellowish liquid. 1H NMR (300 MHz,
5-Methyl-2-(pyrrolidin-1-yl)phenyl Benzoate (20): Isolated by col-
CDCl3): δ = 8.22–8.21 (m, 2 H), 7.65–7.62 (m, 1 H), 7.53–7.49 (m, umn chromatography (ethyl acetate/hexane = 1:10; Rf = 0.5). Yield:
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2 H), 7.06–7.04 (m, 1 H), 6.79–6.76 (m, 1 H), 6.73–6.72 (m, 1 H),
5.70–5.62 (m, 1 H), 5.13–5.09 (m, 1 H), 5.01–4.99 (m, 1 H), 3.78
48% (134 mg); yellowish liquid. H NMR (300 MHz, CDCl3): δ =
8.23–8.21 (m, 2 H), 7.66–7.62 (m, 1 H), 7.54–7.49 (m, 2 H), 6.97–
(s, 3 H), 3.51 (d, J = 6.10 Hz, 2 H), 2.62 (m, 3 H) ppm. 13C NMR 6.94 (m, 1 H), 6.86 (br. s, 1 H), 6.75–6.73 (m, 1 H), 3.29–3.25 (m,
(100 MHz, CDCl3): δ = 164.7, 155.3, 145.4, 138.4, 135.2, 133.3, 4 H), 2.27 (s, 3 H), 1.85–1.81 (m, 4 H) ppm. 13C NMR (100 MHz,
130.0, 129.6, 128.4, 121.6, 116.9, 111.7, 109.2, 59.4, 55.5, 40.2 ppm.
CDCl3): δ = 165.4, 139.6, 138.6, 133.3, 130.2, 129.8, 128.5, 127.4,
FTIR: ν = 3071, 2950, 2837, 2793, 1739, 1618, 1580, 1507, 1449, 127.1, 124.2, 115.6, 50.1, 25.2, 20.1 ppm. FTIR: ν = 2962, 2923,
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1421, 1261, 1182, 1154, 1109, 1083, 1059, 1030, 922, 706 cm–1. MS 2862, 1735, 1623, 1515, 1453, 1355, 1261, 1226, 1142, 1061, 1023,
(ESI): m/z (%) = 257 (100) [M – 40], 298 (52) [M + H]+, 320 (15)
[M + Na]+. HRMS (ESI): m/z calcd. for C18H20NO3 [M + H]+
298.14377; found 298.14337.
800, 771, 707 cm–1. MS (ESI): m/z (%) = 282 (100) [M + H]+, 304
(7) [M + Na]+. HRMS (ESI): m/z calcd. for C18H20NO2 [M +
H]+ 282.14886; found 282.14711.
5-Chloro-2-(pyrrolidin-1-yl)phenyl Benzoate (21): Isolated by col-
umn chromatography (ethyl acetate/hexane = 1:10; Rf = 0.4). Yield:
51% (153 mg); yellow liquid. 1H NMR (300 MHz, CDCl3): δ =
8.21–8.19 (m, 2 H), 7.67–7.64 (m, 1 H), 7.54–7.51 (m, 2 H), 7.19–
7.17 (m, 1 H), 7.11–7.08 (m, 1 H), 7.02–7.01 (m, 1 H), 3.30–3.27
(m, 4 H), 1.86–1.83 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 165.0, 140.6, 138.3, 133.6, 130.2, 128.9, 128.5, 126.5, 124.0,
2-[Allyl(methyl)amino]-5-fluorophenyl Benzoate (16): Isolated by
column chromatography (ethyl acetate/hexane = 1:10; Rf = 0.4).
Yield: 42% (119 mg); yellowish liquid. 1H NMR (300 MHz,
CDCl3): δ = 8.21–8.19 (m, 2 H), 7.66–7.63 (m, 1 H), 7.54–7.50 (m,
2 H), 7.06–7.03 (m, 1 H), 6.95–6.89 (m, 2 H), 5.69–5.61 (m, 1 H),
5.14–5.10 (m, 1 H), 5.03–5.01 (m, 1 H), 3.55–3.54 (m, 2 H), 2.65
(s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 164.4, 157.8 (d, J
= 242.98 Hz), 144.7 (d, J = 10.89 Hz), 141.4, 134.8, 133.5, 130.1,
129.3, 128.5, 121.2 (d, J = 9.08 Hz), 117.2, 112.9, 112.7, 111.3,
121.3, 116.0, 113.6, 50.0, 25.3 ppm. FTIR: ν = 3066, 2963, 2866,
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1737, 1598, 1496, 1353, 1251, 1187, 1057, 1022, 882, 801, 707 cm–1.
MS (ESI): m/z (%) = 302 (100) [M + H]+. HRMS (ESI): m/z calcd.
for C17H16NO2Cl [M + H]+ 302.09423; found 302.09241.
111.1, 59.1, 39.9 ppm. FTIR: ν = 3075, 2953, 2852, 2797, 1743,
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1642, 1599, 1504, 1451, 1421, 1354, 1313, 1247, 1177, 1145, 1097,
1056, 1023, 956, 923, 838, 705 cm–1. MS (ESI): m/z (%) = 286 (100)
[M + H]+. HRMS (ESI): m/z calcd. for C17H17NO2F [M + H]+
286.12378; found 286.12350.
2-(Piperidin-1-yl)phenyl Benzoate (22): Isolated by column
chromatography (ethyl acetate/hexane = 1:10; Rf = 0.5). Yield: 52%
(146 mg); yellowish liquid. 1H NMR (300 MHz, CDCl3): δ = 8.24–
8.22 (m, 2 H), 7.67–7.62 (m, 1 H), 7.55–7.49 (m, 2 H), 7.24–7.19
(m, 1 H), 7.15–7.03 (m, 3 H), 2.95–2.93 (m, 4 H), 1.49–1.46 (m, 4
H), 1.28–1.24 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
164.8, 144.7, 133.3, 129.9, 128.4, 126.6, 123.0, 122.6, 120.1, 52.6,
2-[Allyl(methyl)amino]-5-bromophenyl Benzoate (17): Isolated by
column chromatography (ethyl acetate/hexane = 1:10; Rf = 0.7).
Yield: 45% (156 mg); yellowish liquid. 1H NMR (300 MHz,
CDCl3): δ = 8.13–8.11 (m, 2 H), 7.58 (tt, J = 7.32, 1.22 Hz, 1 H),
7.47–7.43 (m, 2 H), 7.25 (dd, J = 8.69, 2.44 Hz, 1 H), 7.20–7.19
(m, 1 H), 6.89 (br. s, 1 H), 5.63–5.55 (m, 1 H), 5.09–5.05 (m, 1 H),
4.98–4.96 (m, 1 H), 3.56 (d, J = 5.95 Hz, 1 H), 2.64 (s, 3 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 164.4, 143.8, 134.3, 133.6, 131.8,
26.3, 24.1 ppm. FTIR: ν = 3064, 2932, 2852, 2804, 1740, 1602,
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1493, 1448, 1260, 1182, 1059, 1023, 926 cm–1. MS (ESI): m/z (%)
= 282 (100) [M + H]+. HRMS (ESI): m/z calcd. for C18H20NO2
[M + H]+ 282.14886; found 282.14856.
130.1, 129.4, 129.2, 126.6, 121.2, 117.4, 58.4, 39.3 ppm. FTIR: ν =
3072, 2854, 1742, 1641, 1596, 1492, 1450, 1255, 1197, 1176, 1056,
5-Methyl-2-(piperidin-1-yl)phenyl Benzoate (23): Isolated by column
chromatography (ethyl acetate/hexane = 1:10; Rf = 0.6). Yield: 58%
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Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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