The Journal of Organic Chemistry
Article
4.82−4.75 (m, 1H), 4.66 (d, J = 6.3 Hz, 2H), 3.56−3.49 (m, 1H), 1.42
(d, J = 6.8 Hz, 6H), 1.24 (d, J = 6.7 Hz, 6H); 13C NMR (101 MHz,
CDCl3) δ 163.1, 162.8, 161.1 (d, JC−F = 245.0 Hz), 130.2 (d, JC−F = 5.0
Hz), 129.6 (d, JC−F = 8.1 Hz), 124.6 (d, JC−F = 15.0, Hz), 124.4 (d,
JC−F = 4.0 Hz), 115.6 (d, JC−F = 21.0 Hz), 49.7, 46.7, 37.4 (d, JC−F = 4.0
Hz), 21.0, 20.2; HRMS Calcd for C16H21F3N2NaO2 [M+Na+]:
353.1453; Found: 353.1459.
N1-(2,5-Dimethylbenzyl)-N2,N2-diisopropyloxalamide (1m). Puri-
fied by column chromatography on silica gel with petroleum ester/
ethyl acetate (9/1) as an eluent; yield 88% (5.10 g); white solid; mp =
95−97 °C; 1H NMR (400 MHz, CDCl3) δ 7.26 (br s, 1H), 7.06−7.04
(m, 2H), 7.01−6.99 (m, 1H), 4.75−4.67 (m, 1H), 4.40 (d, J = 5.7 Hz,
2H), 3.53−3.46 (m, 1H), 2.29−2.28 (m, 6H), 1.39 (d, J = 6.8 Hz,
6H), 1.23 (d, J = 6.7 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 163.2.
163.0, 135.7, 134.9, 133.2, 130.4, 129.3, 128.5, 49.7, 46.5, 41.4, 21.0,
20.9, 20.1, 18.6; HRMS Calcd for C17H26N2NaO2 [M+Na+]:
313.1892; Found: 313.1894.
N1-(2,4-Difluorobenzyl)-N2,N2-diisopropyloxalamide (1g). Purified
by column chromatography on silica gel with petroleum ester/ethyl
acetate (12/1) as an eluent; Yield 90% (5.36 g); white solid; mp =
N1,N1-Diisopropyl-N2-(1-phenylethyl)oxalamide (1n). Purified by
column chromatography on silica gel with petroleum ester/ethyl
acetate (10/1) as an eluent; yield 86% (4.75 g); white solid; mp =
1
105−106 °C; H NMR (400 MHz, CDCl3) δ 7.52 (br s, 1H), 7.31
(dd, J = 14.9, 8.3 Hz, 1H), 6.83−6.75 (m, 2H), 4.71−4.65 (m, 1H),
4.44 (d, J = 6.1 Hz, 2H), 3.52−3.45 (m, 1H), 1.37 (d, J = 6.8 Hz, 6H),
1.20 (d, J = 6.7 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 163.3, 163.1
(dd, JC−F = 154.0 Hz, 12.0 Hz), 163.0, 160.6 (dd, JC−F = 154.0 Hz, 12.0
Hz), 131.1 (dd, JC−F = 10.0 Hz, 6.0 Hz), 120.7 (dd, JC−F = 15.0 Hz, 4.0
Hz), 111.5 (dd, JC−F = 22.0 Hz, 4.0 Hz), 104.0 (t, JC−F = 26.0 Hz),
49.8, 46.7, 36.8, 36.7, 20.9, 20.1; HRMS Calcd for C15H20F2N2NaO2
[M+Na+]: 321.1391, Found: 321.1394.
1
142−144 °C; H NMR (400 MHz, CDCl3) δ 7.71 (br s, 1H), 7.35−
7.28 (m, 4H), 7.25−7.20 (m, 1H), 5.07−5.00 (m, 1H), 4.65−4.61 (m,
1H), 3.51−3.44 (m, 1H), 1.48 (d, J = 7.0 Hz, 3H), 1.40 (dd, J = 9.7,
6.8 Hz, 6H), 1.18 (dd, J = 9.9, 6.7 Hz, 6H); 13C NMR (101 MHz,
CDCl3) δ 163.3, 162.4, 143.0, 128.7, 127.3, 126.1, 49.7, 49.1, 46.5,
22.0, 20.8, 20.1; HRMS Calcd for C16H24N2NaO2 [M+Na+]:
299.1735; Found: 299.1734.
N1-(2,4-Dichlorobenzyl)-N2,N2-diisopropyloxalamide (1h). Puri-
fied by column chromatography on silica gel with petroleum ester/
ethyl acetate (10/1) as an eluent; yield 78% (5.15 g); white solid; mp
2-(2-(Diisopropylamino)-2-oxoacetamido)-2-phenylethyl Acetate
(1o). Purified by column chromatography on silica gel with petroleum
ester/ethyl acetate (7/1) as an eluent; yield 82% (5.48 g); white solid;
1
= 114−115 °C; H NMR (400 MHz, CDCl3) δ 7.44 (br s, 1H), 7.38
1
mp = 114−116 °C; H NMR (400 MHz, CDCl3) δ 7.71 (d, J = 8.2
(d, J = 2.1 Hz, 1H), 7.33 (d, J = 8.3 Hz, 1H), 7.21 (dd, J = 8.3, 2.1 Hz,
1H), 4.76−4.69 (m, 1H), 4.50 (d, J = 6.3 Hz, 2H), 3.54−3.48 (m,
1H), 1.40 (d, J = 6.8 Hz, 6H), 1.22 (d, J = 6.7 Hz, 6H); 13C NMR
(101 MHz, CDCl3) δ 163.4, 163.0, 134.3, 134.0 133.8, 130.7, 129.4,
127.4, 49.8, 46.6, 40.6, 20.9, 20.1; HRMS Calcd for C15H20Cl2N2NaO2
[M+Na+]: 353.0800, Found: 353.0776.
Hz, 1H), 7.33−7.27 (m, 5H), 5.26−5.21 (m, 1H), 4.74−4.67 (m, 1H),
4.35 (d, J = 5.8 Hz, 2H), 3.55−3.48 (m, 1H), 2.03 (s, 3H), 1.42 (dd, J
= 9.7, 6.8 Hz, 6H), 1.21 (dd, J = 6.6, 4.2 Hz, 6H); 13C NMR (101
MHz, CDCl3) δ 170.9, 162.8, 137.8, 128.9, 128.1, 126.8, 66.2, 52.4,
49.7, 46.7, 20.9, 20.8, 20.2, 20.1; HRMS Calcd for C18H26N2NaO4 [M
+Na+]: 357.1790; Found: 357.1791.
N1-(2-Chloro-4-fluorobenzyl)-N2,N2-diisopropyloxalamide (1i).
Purified by column chromatography on silica gel with petroleum
ester/ethyl acetate (12/1) as an eluent; yield 83% (5.21 g); white
N1-Benzyl-N2,N2-diisopropyloxalamide (1p). Purified by column
chromatography on silica gel with petroleum ester/ethyl acetate (6/1)
1
as an eluent; yield 91% (4.77 g); white solid; mp = 102−103 °C; H
1
solid; mp = 98−100 °C; H NMR (400 MHz, CDCl3) δ 7.62 (br s,
NMR (400 MHz, CDCl3) δ 7.36−7.27 (m, 5H), 7.20 (br s, 1H),
4.87−4.80 (m, 1H), 4.46 (d, J = 6.0 Hz, 2H), 3.56−3.49 (m, 1H), 1.42
(d, J = 6.8 Hz, 6H), 1.24 (d, J = 6.7 Hz, 6H); 13C NMR (101 MHz,
CDCl3) δ 163.2, 163.0, 137.5, 128.8, 127.9, 127.7, 49.7, 46.7, 43.4,
21.0, 20.1; HRMS Calcd for C15H22N2NaO2 [M+Na+]: 285.1579;
Found: 285.1579.
1H), 7.35 (dd, J = 8.5, 6.0 Hz, 1H), 7.09 (dd, J = 8.4, 2.6 Hz, 1H),
6.94−6.90 (m, 1H), 4.67−4.60 (m, 1H), 4.48 (d, J = 6.2 Hz, 2H),
3.51−3.44 (m, 1H), 1.36 (d, J = 6.8 Hz, 6H), 1.19 (d, J = 6.7 Hz, 6H);
13C NMR (101 MHz, CDCl3) δ 163.3, 163.0, 162.0 (d, JC−F = 248.0
Hz), 134.3 (d, JC−F = 5.0 Hz), 131.14, 131.10, 131.05, 117.0 (d, JC−F
=
25.0 Hz), 114.3 (d, JC−F = 21.0 Hz), 49.8, 46.6, 40.6, 20.9, 20.1; HRMS
Calcd for C15H20ClFN2NaO2 [M+Na+]: 337.1095, Found 337.1091.
N1-(2,3-Dimethylbenzyl)-N2,N2-diisopropyloxalamide (1j). Puri-
fied by column chromatography on silica gel with petroleum ester/
ethyl acetate (10/1) as an eluent; yield 91% (5.28 g); white solid; mp
= 93−95 °C; 1H NMR (400 MHz, CDCl3) δ 7.12−7.07 (m, 3H), 6.96
(br s, 1H), 4.82−4.75 (m, 1H), 4.47 (d, J = 5.6 Hz, 2H), 3.54−3.48
(m, 1H), 2.29 (s, 3H), 2.22 (s, 3H), 1.41 (d, J = 6.8 Hz, 6H), 1.24 (d, J
= 6.7 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 163.0, 162.9, 137.5,
135.2, 135.0, 129.8, 126.8, 125.8, 49.8, 46.6, 42.3, 21.0, 20.5, 20.1, 14.9;
HRMS Calcd for C17H26N2NaO2 [M+Na+]: 313.1892; Found:
313.1887.
N1-(3-Bromobenzyl)-N2,N2-diisopropyloxalamide (1q). Purified by
column chromatography on silica gel with petroleum ester/ethyl
acetate (9/1) as an eluent; yield 84% (5.71 g); white solid; mp = 103−
1
105 °C; H NMR (400 MHz, CDCl3) δ 7.44 (br s, 1H), 7.41−7.39
(m, 2H), 7.24−7.18 (m, 2H), 4.82−4.75 (m, 1H), 4.42 (d, J = 6.1 Hz,
2H), 3.56−3.49 (m, 1H), 1.41 (d, J = 6.8 Hz, 6H), 1.24 (d, J = 6.7 Hz,
6H); 13C NMR (101 MHz, CDCl3) δ 163.2, 163.0, 140.0, 130.8,
130.7, 130.3, 126.4, 122.8, 49.8, 46.7, 42.7, 20.9, 20.1; HRMS Calcd for
C15H21BrN2NaO2 [M+Na+]: 363.0684; Found: 363.0677.
N1,N1-Diisopropyl-N2-(4-methylbenzyl)oxalamide (1r). Purified by
column chromatography on silica gel with petroleum ester/ethyl
acetate (12/1) as an eluent; yield 80% (4.42 g); white solid; mp =
N1-(3,4-Dimethylbenzyl)-N2,N2-diisopropyloxalamide (1k). Puri-
fied by column chromatography on silica gel with petroleum ester/
ethyl acetate (12/1) as an eluent; yield 92% (5.33 g); white solid; mp
= 113−115 °C; 1H NMR (400 MHz, CDCl3) δ 7.29 (br s, 1H), 7.09−
7.01 (m, 3H), 4.80−4.74 (m, 1H), 4.37 (d, J = 5.7 Hz, 2H), 3.53−3.47
(m, 1H), 2.23 (s, 6H), 1.40 (d, J = 6.8 Hz, 6H), 1.23 (d, J = 6.6 Hz,
6H); 13C NMR (151 MHz, CDCl3) δ 163.0, 137.0, 136.0, 134.8,
130.0, 129.26, 125.3, 49.7, 46.6, 43.2, 20.9, 20.1, 19.8, 19.5; HRMS
Calcd for C17H26N2NaO2 [M+Na+]: 313.1892; Found: 313.1877.
N1-(2,4-Dimethoxybenzyl)-N2,N2-diisopropyloxalamide (1l). Puri-
fied by column chromatography on silica gel with petroleum ester/
ethyl acetate (8/1) as an eluent; yield 76% (4.89 g); white solid; mp =
1
112−113 °C; H NMR (400 MHz, CDCl3) δ 7.26 (br s, 1H), 7.19−
7.12 (m, 4H), 4.83−4.77 (m, 1H), 4.40 (d, J = 5.9 Hz, 2H), 3.54−3.47
(m, 1H), 2.32 (s, 3H), 1.40 (d, J = 6.8 Hz, 6H), 1.23 (d, J = 6.7 Hz,
6H); 13C NMR (101 MHz, CDCl3) δ 162.1, 136.4, 133.5, 128.5,
126.9, 48.7, 45.7, 42.2, 20.2, 20.0, 19.2; HRMS Calcd for
C16H24N2NaO2 [M+Na+]: 299.1735; Found: 299.1734.
N1,N1-Diisopropyl-N2-(2-methylallyl)oxalamide (1s). Purified by
column chromatography on silica gel with petroleum ester/ethyl
acetate (8/1) as an eluent; yield 82% (3.71 g); white solid; mp = 60−
1
61 °C; H NMR (400 MHz, CDCl3) δ 7.10 (br s, 1H), 4.86 (d, J =
10.1 Hz, 2H), 4.74−4.67 (m, 1H), 3.81 (d, J = 6.2 Hz, 2H), 3.53−3.47
(m, 1H), 1.74 (s, 3H), 1.41 (dd, J = 6.8, 2.2 Hz, 6H), 1.22−1.21 (m,
6H); 13C NMR (101 MHz, CDCl3) δ 163.4, 163.3, 141.2, 111.4, 49.8,
46.6, 44.8, 20.9, 20.4, 20.1; HRMS Calcd for C12H22N2NaO2 [M
+Na+]: 249.1579; Found: 249.1573.
1
137−139 °C; H NMR (400 MHz, CDCl3) δ 7.19−7.17 (m, 2H),
6.44−6.40 (m, 2H), 4.80−4.73 (m, 1H), 4.38 (d, J = 6.0 Hz, 2H), 3.82
(s, 3H), 3.79 (s, 3H), 3.52−3.45 (m, 1H), 1.40 (d, J = 6.8 Hz, 6H),
1.21 (d, J = 6.7 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 163.2, 162.8,
160.7, 158.7, 130.5, 118.1, 103.9, 98.6, 55.44, 55.42, 49.6, 46.5, 38.8,
20.9, 20.1; HRMS Calcd for C17H26N2NaO4 [M+Na+]: 345.1790;
Found: 345.1783.
N1-(3,3-Dimethylbutan-2-yl)-N2,N2-diisopropyloxalamide (1t).
Purified by column chromatography on silica gel with petroleum
ester/ethyl acetate (9/1) as an eluent; yield 82% (3.71 g); white solid;
1
mp = 111−112 °C; H NMR (400 MHz, CDCl3) δ 6.94 (br s, 1H),
E
J. Org. Chem. XXXX, XXX, XXX−XXX