Alexander Wagner et al.
UPDATES
crude product mixture was separated by column chromatog-
raphy (SiO2, pentane/Et2O=30:1!15:1) to give 20b (yield:
62 mg, 27%) and 18b (yield: 117 mg, 62%), both as colorless
viscous liquids.
13C NMR (CDCl3, 75.5 MHz): d=55.8, 115.8, 115.9, 120.8,
127.8, 128.0, 129.0, 129.7, 137.0, 148.1; IR (neat/ATR probe):
n=3062, 3029, 2925, 2854, 1598, 1578, 1502, 1452, 1351,
1297, 1246, 1203, 1069, 1028, 990, 940, 909, 892, 812, 748,
20b: Known compound; the NMR and IR spectroscopic
726, 690 cmꢀ1
C15H12D2N2: 224.1277.
2-[Mesityl(methyl)amino]acetonitrile (22): Following
; HR-MS (EI): m/z=224.1275, calcd. for
data agree with those given in ref.[14c]
;
13C multiplicities are
1
based on gHSQC experiments; H NMR (CDCl3, 300 MHz):
d=0.93 (t, J=7.3 Hz, 3H), 0.99 (t, J=7.3 Hz, 3H), 1.33–
1.63 (m, 6H), 1.82–1.90 (m, 2H), 3.16–3.32 (m, 2H), 4.29 (t,
J=7.8 Hz, 1H), 6.95–7.01 (m, 3H), 7.27–7.34 (m, 2H);
13C NMR (CDCl3, 75.5 MHz): d=13.6 (q), 14.0 (q), 19.4 (t),
20.4 (t), 30.2 (t), 34.3 (t), 49.1 (t), 54.3 (d), 119.1 (s), 119.2
(d), 121.7 (d), 129.4 (d), 147.8 (s); IR (neat/ATR probe): n=
3061, 2958, 2932, 2872, 1597, 1498, 1465, 1377, 1281, 1257,
1219, 1179, 1134, 1112, 1037, 993, 931, 748, 692 cmꢀ1; HR-
MS (EI): m/z 230.1794, calcd. for C15H22N2: 230.1778.
ACHTUNGTRENNUNG
General Procedure B, N,N,2,4,6-pentamethylaniline 21
(184 mL, 1.00 mmol) was reacted with Me3SiCN (270 mL,
2.00 mmol) and FeCl2 (15 mol%) for 72 h under reflux to
furnish 22; yield: 135 mg (72%); 1H NMR (CDCl3,
400 MHz): d=2.29 (s, 3H), 2.32 (s, 6H), 2.97 (s, 3H), 3.95
(s, 2H), 6.88 (s, 2H); 13C NMR (CDCl3, 100.6 MHz): d=
18.9, 20.7, 40.3, 44.0, 117.6, 129.7, 135.9, 136.9, 144.2; IR
(neat/ATR probe): n=2919, 2860, 2802, 2237, 1486, 1451,
1376, 1201, 1106, 994, 928, 853, 732 cmꢀ1; HR-MS (EI): m/
z=188.1307, calcd. for C12H16N2: 188.1308.
1
18b: H NMR (CDCl3, 300 MHz): d=0.97 (t, J=7.3 Hz,
3H), 1.34–1.46 (m, 2H), 1.56–1.69 (m, 2H), 3.32–3.37 (m,
2H), 4.15 (s, 2H), 6.84–6.92 (m, 3H), 7.27–7.33 (m, 2H);
13C NMR (CDCl3, 75.5 MHz): d=14.1, 20.4, 29.4, 40.2, 52.0,
115.0, 116.4, 119.9, 129.6, 147.4 ppm; IR (neat/ATR probe):
n=3060, 3041, 2957, 2929, 2871, 1599, 1577, 1503, 1457,
1428, 1367, 1347, 1252, 1220, 1180, 1041, 924, 868, 747,
690 cmꢀ1; HR-MS (EI): m/z=188.1305, calcd. for C12H16N2:
188.1308.
2-[BenzylACTHNGUTRENNU(G methyl)amino]acetonitrile (24): Following Gen-
eral Procedure A, benzyldimethylamine 23 (152 mL,
1.00 mmol) was reacted with Me3SiCN (270 mL, 2.00 mmol)
for 24 h at 08C to furnish 24; yield: 129 mg (81%); known
compound; the NMR spectroscopic data agree with those
given in ref.[12a,53] 1H NMR (CDCl3, 400 MHz): d=2.44 (s,
3H), 3.45 (s, 2H), 3.61 (s, 2H), 7.26–7.37 (m, 5H); 13C NMR
(CDCl3, 100.6 MHz): d=42.5, 44.3, 60.3, 114.7, 127.9, 128.7,
129.1, 137.1; IR (neat/ATR probe): n=3064, 3031, 2983,
2949, 2842, 2231, 1496, 1454, 1416, 1371, 1327, 1125, 1037,
1027, 983, 840, 740, 698 cmꢀ1; HR-MS (EI): m/z=160.0996,
calcd, for C10H12N2: 160.0995.
2-(Dibenzylamino)-2-phenylacetonitrile (26): Analogous
to General Procedure A, tribenzylamine 25 (290 mg,
1.00 mmol) was reacted with Me3SiCN (270 mL, 2.00 mmol)
and FeCl2 (15 mol%) for 24 h to furnish 26; yield: 128 mg
(41%); known compound; the NMR spectroscopic data
agree with those given in ref.[12a,53] 1H NMR (CDCl3,
400 MHz): d=3.45 (d, 2J=13.6 Hz, 2H), 3.91 (d, 2J=
13.6 Hz, 2H), 4.94 (s, 1H), 7.28–7.44 (m, 13H), 7.60–7.62
(m, 2H); 13C NMR (CDCl3, 100.6 MHz): d=55.1, 57.4,
115.5, 127.77, 127.79, 128.7, 128.89, 128.93, 134.0, 137.8; IR
(neat/ATR probe): n=3061, 3033, 2925, 2803, 2235, 1493,
1452, 1372, 1113, 1076, 1027, 966, 924, 744, 694 cmꢀ1; HR-
MS (EI): m/z=312.1606, calcd. for C22H20N2: 312.1621.
2-[Benzyl
ACHTUNGTRENNUNG(phenyl)amino]-2-phenylacetonitrile (20c) and
2-[benzyl(phenyl)amino]acetonitrile (18c): Following Gener-
ACHTUNGTRENNUNG
al Procedure A, N,N-dibenzylaniline 19c (273 mg,
1.00 mmol) was reacted with Me3SiCN (270 mL, 2.00 mmol)
for 50 h. The crude product mixture was separated by
column chromatography (SiO2, pentane/Et2O=8:1) to give
18c (yield: 104 mg, 47%) as a colorless viscous liquid and
a mixed fraction of 19c and 20c.
Pure 20c (yield: 101 mg, 34%) could then be crystallized
from pentane/Et2O=5:1; mp 133.0–133.58C (ref.[51] mp
1
1348C, from EtOH); H NMR (CDCl3, 300 MHz): d=4.28–
4.40 (m, 2H), 5.65 (s, 1H), 6.86–6.96 (m, 3H), 7.13–7.23 (m,
7H), 7.28–7.33 (m, 3H), 7.46–7.49 (m, 2H); 13C NMR
(CDCl3, 75.5 MHz): d=54.0, 58.7, 116.8, 119.9, 122.5, 127.5,
127.7, 127.8, 128.7, 129.1, 129.2, 129.3, 133.5, 137.6, 147.4; IR
(neat/ATR probe): n=3061, 3025, 2922, 2852, 1597, 1581,
1494, 1465, 1452, 1379, 1337, 1264, 1253, 1219, 1121, 1070,
1027, 938, 921, 909, 761, 746, 724, 692 cmꢀ1; HR-MS (EI):
m/z=298.1459, calcd. for C21H18N2: 298.1465.
2-[MethylACTHNUTRGENUG(N octyl)amino]acetonitrile (28): Following Gener-
al Procedure A, dimethyloctylamine 27 (205 mL, 1.00 mmol)
was reacted with Me3SiCN (270 mL, 2.00 mmol) for 26 h.
The crude product was purified by column chromatography
(SiO2, pentane/Et2O=2:1) to give 28 as a colorless viscous
liquid; yield: 84 mg (46%); known compound; the NMR
spectroscopic data agree with those given in ref.[54] 1H NMR
(CDCl3, 300 MHz): d=0.85–0.89 (m, 3H), 1.25–1.29 (m,
10H), 1.42–1.48 (m, 2H), 2.36 (s, 3H), 2.43–2.47 (m, 2H),
3.54 (s, 2H); 13C NMR (CDCl3, 75.5 MHz): d=14.2, 22.8,
27.2, 27.4, 29.3, 29.5, 31.9, 42.1, 45.1, 56.0, 114.7; IR (neat/
ATR probe): n=2924, 2854, 2803, 1681, 1458, 1378, 1321,
1159, 1105, 1043, 950, 860, 834, 723 cmꢀ1; HR-MS (EI): m/
z=182.1786, calcd. for C11H22N2: 182.1778.
2-[Methyl(tetradecyl)amino]acetonitrile (30): Following
General Procedure A, dimethyltetradecylamine 29 (305 mL,
1.00 mmol) was reacted with Me3SiCN (270 mL, 2.00 mmol)
for 26 h. The crude product was purified by column chroma-
tography (SiO2, pentane/Et2O=2:1) to give 30 as a colorless
viscous liquid; yield: 125 mg (47%); 1H NMR (CDCl3,
1
18c: Known compound; the H NMR spectroscopic data
agree with those given in ref.[52] 1H NMR (CDCl3,
400 MHz): d=4.08 (s, 2H), 4.53 (s, 2H), 6.95–7.00 (m, 3H),
7.32–7.39 (m, 7H); 13C NMR (CDCl3, 100.6 MHz): d=39.7,
55.9, 115.8, 115.9, 120.8, 127.8, 128.0, 129.0, 129.7, 136.9,
148.1; IR (neat/ATR probe): n=3062, 3029, 2925, 2852,
1598, 1579, 1503, 1495, 1452, 1426, 1357, 1221, 1199, 1168,
1027, 960, 937, 869, 749, 729, 690 cmꢀ1; HR-MS (EI): m/z=
222.1156, calcd. for C15H14N2: 222.1151.
2-[BenzylACHTUNGTRENNUNG(phenyl)amino]-2,2-dideuterioacetonitrile (18c’):
Following General Procedure A, N,N-dibenzylaniline 19c
(273 mg, 1.00 mmol) was reacted with Me3SiCN (270 mL,
2.00 mmol) for 50 h in CD3OH (2 mL). The crude product
was purified by column chromatography (SiO2, pentane/
Et2O=8:1) to give 18c’ as a colorless viscous liquid; yield:
103 mg (46%); 1H NMR (CDCl3, 300 MHz): d=4.08 (s,
0.03H), 4.53 (s, 2H), 6.95–7.00 (m, 3H), 7.31–7.40 ppm (m,
7H); 2H NMR (CCl4/CDCl3, 46.1 MHz): d=4.07 (s);
3066
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 3058 – 3070