The Journal of Organic Chemistry
Article
flash column chromatography using a mixture of petroleum ether and
ethyl acetate afforded the desired product.
(t, J = 8.0 Hz, 2H), 2.12−1.98 (m, 4H); 13C NMR (100 MHz, CDCl3)
δ 49.8, 45.2, 23.9, 22.6; MS (ESI-quadrupole) calcd for C4H9N2O 101,
found 101 (M + H+); IR (KBr, cm−1) ν 1638, 1559, 1408.
1-Nitroso-4-phenylpiperazine (2l): yellow solid (57 mg, 60%
yield); mp 65−66 °C. 1H NMR (400 MHz, CDCl3) δ 7.34−7.26 (m,
2H), 6.99−6.90 (m, 3H), 4.40 (t, J = 6.0 Hz, 2H), 3.96 (t, J = 6.0 Hz,
2H), 3.39 (t, J = 6.0 Hz, 2H), 3.17 (t, J = 6.0 Hz, 2H); 13C NMR
(75 MHz, CDCl3) δ 150.2, 129.3, 121.0, 117.1, 50.2, 49.3, 48.6, 39.5;
MS (ESI-quadrupole) calcd for C10H14N3O 192, found 192 (M + H+);
IR (KBr, cm−1) ν 1647, 1570, 1409.
N,N-Dihexylnitrous amide (2a): pale yellow liquid (91 mg, 85%
1
yield); H NMR (400 MHz, CDCl3) δ 4.07 (t, J = 8.0 Hz, 2H), 3.53
(t, J = 8.0 Hz, 2H), 1.82−1.65 (m, 2H), 1.54−1.42 (m, 2H), 1.30−
1.24 (m, 12H), 0.95−0.85 (m, 6H); 13C NMR (75 MHz, CDCl3) δ
52.2, 43.6, 31.21, 31.17, 28.2, 26.7, 26.1, 25.9, 22.4, 13.9; MS (ESI-
quadrupole) calcd for C12H27N2O 215, found 215 (M + H+); IR (KBr,
cm−1) ν 1627, 1575, 1458.
N,N-Dibutylnitrous amide (2b): pale yellow liquid (73 mg, 92%
yield for 1b; 49 mg, 63% for 3c); 1H NMR (400 MHz, CDCl3) δ 4.08
(t, J = 8.0 Hz, 2H), 3.54 (t, J = 8.0 Hz, 2H), 1.80−1.67 (m, 2H), 1.53−
1.23 (m, 6H), 1.02−0.87 (m, 6H); 13C NMR (100 MHz, CDCl3) δ
51.7, 43.2, 30.1, 27.9, 20.2, 19.5, 13.3; MS (EI-ion trap) calcd for
C8H18N2O 158, found 158 (M+); IR (KBr, cm−1) ν 1640, 1571, 1458.
N-Butyl-N-methylnitrous amide (2c): pale yellow liquid (42 mg,
72% yield); 1H NMR (400 MHz, CDCl3) δ 4.14 (t, J = 8.0 Hz,
1.62H), 3.75 (s, 0.57H), 3.59 (t, J = 8.0 Hz, 0.38H), 3.05 (s, 2.43H),
1.76−1.69 (m, 1.62H), 1.53−1.44 (m, 0.38H), 1.42−1.34 (m, 1.62H),
1.32−1.25 (m, 0.38H), 0.97 (t, J = 8.0 Hz, 2.43H), 0.92 (t, J = 8.0 Hz,
0.57H); 13C NMR (100 MHz, CDCl3) δ 53.3, 44.5, 38.9, 31.2, 29.8,
27.6, 20.1, 19.4, 13.5, 13.4; MS (ESI-quadrupole) calcd for C5H13N2O
117, found 117 (M + H+); IR (KBr, cm−1) ν 1648, 1571, 1414.
N,N-Bis(2-hydroxyethyl)nitrous amide (2d): pale yellow liquid
1-Nitroso-4-(pyridin-2-yl)piperazine (2m): yellow solid (58 mg,
61% yield); mp 85−86 °C. 1H NMR (400 MHz, CDCl3) δ 8.20 (d, J =
4.0 Hz, 1H), 7.59−7.48 (m, 1H), 6.76−6.66 (m, 2H), 4.36 (t, J = 6.0
Hz, 2H), 3.89 (t, J = 6.0 Hz, 2H), 3.82 (t, J = 6.0 Hz, 2H), 3.62 (t, J =
6.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 158.0, 147.8, 137.6,
114.0, 107.2, 48.7, 45.6, 43.5, 39.6; MS (EI-ion trap) calcd for
C9H12N4O 192, found 192 (M+); IR (KBr, cm−1) ν 1637, 1566, 1409.
2-Nitroso-1,2,3,4-tetrahydroisoquinoline (2n): pale yellow liquid
1
(57 mg, 70% yield); H NMR (400 MHz, CDCl3) δ 7.34−7.09 (m,
4H), 5.40 (s, 0.60H), 4.84 (s, 1.40H), 4.55 (t, J = 6.0 Hz, 1.40H), 3.89
(t, J = 8.0 Hz, 0.60H), 3.11 (t, J = 6.0 Hz, 1.40H), 2.97 (t, J = 8.0 Hz,
0.60H); 13C NMR (100 MHz, CDCl3) δ 133.7, 129.8, 128.5, 127.9,
127.8, 127.1, 127.0, 126.0, 51.1, 47.5, 44.3, 40.6, 29.6, 27.2; MS (ESI-
quadrupole) calcd for C9H11N2O 163, found 163 (M + H+); IR (KBr,
cm−1) ν 1627, 1575, 1428.
1
(45 mg, 67% yield for 1d; 40 mg, 59% for 3e); H NMR (400 MHz,
d6-DMSO) δ 4.01−3.96 (m, 1H), 3.95−3.89 (m, 1H), 3.27−3.19 (m,
2H), 2.82−2.74 (m, 2H), 2.74−2.68 (m, 2H); 13C NMR (100 MHz,
d6-DMSO) δ 58.8, 56.9, 55.2, 46.6; MS (ESI-quadrupole) calcd for
C4H11N2O3 135, found 135 (M + H+); IR (KBr, cm−1) ν 3442, 1638,
1571, 1419.
tert-Butyl 4-nitrosopiperazine-1-carboxylate (2o): pale yellow
liquid (66 mg, 61% yield); H NMR (400 MHz, CDCl3) δ 4.26 (t,
1
J = 4.0 Hz, 2H), 3.81 (t, J = 4.0 Hz, 2H), 3.68 (t, J = 4.0 Hz, 2H), 3.46
(t, J = 4.0 Hz, 2H), 1.49 (s, 9H); 13C NMR (100 MHz, CDCl3) δ
154.0, 80.4, 49.0, 43.7, 42.0, 39.4, 28.0; MS (ESI-quadrupole) calcd for
C9H18N3O3 216, found 216 (M + H+); IR (KBr, cm−1) ν 1697, 1570,
1418.
(S)-Methyl 1-nitrosopyrrolidine-2-carboxylate (2p): pale yellow
liquid (43 mg, 55% yield);1H NMR (400 MHz, CDCl3) δ 5.33−5.28
(m, 1H), 4.58−4.35 (m, 5.12H), 3.81 (s, 3.22H), 3.73 (s, 3.64H),
3.72−3.61 (m, 1.83H), 2.45−2.18 (m, 3.89H),2.28−2.18 (m, 1.70H),
2.15−1.99 (m, 5.72H); 13C NMR (100 MHz, CDCl3) δ 170.7, 168.9,
61.7, 57.7, 52.6, 52.3, 49.7, 45.4, 28.7, 27.5, 23.0, 20.9; MS (EI-ion
trap) calcd for C6H10N2O3 158, found 158 (M+); IR (KBr, cm−1) ν
1648, 1560, 1409.
(S)-1-Nitrosopyrrolidine-2-carboxamide (2q): yellow solid (40 mg,
56% yield); mp 165−166 °C. 1H NMR (300 MHz, d6-DMSO) δ 7.75
(s, 1H), 7.48 (s, 1.20H), 7.33 (s, 1H), 7.03 (s, 1.20H), 5.07 (t, J =
3.0 Hz, 1H), 4.41−4.33 (m, 2.40H), 4.22 (t, J = 3.0 Hz, 1.20H), 3.53−
3.38 (m, 2H), 2.38−1.73 (m, 8.80H); 13C NMR (75 MHz, d6-DMSO)
δ 172.0, 170.2, 62.4, 59.2, 50.1, 46.0, 29.1, 28.2, 22.7, 20.9; MS (ESI-
quadrupole) calcd for C5H10N3O2 144, found 144 (M + H+); IR (KBr,
cm−1) ν 1681, 1613, 1403.
N,N-Bis(2-methoxyethyl)nitrous amide (2e): pale yellow liquid
(61 mg, 75% yield); 1H NMR (400 MHz, CDCl3) δ 4.37 (t, J = 6.0 Hz,
2H), 3.86 (t, J = 6.0 Hz, 2H), 3.73 (t, J = 6.0 Hz, 2H), 3.45 (t, J = 6.0
Hz, 2H), 3.37 (s, 3H), 3.30 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
70.4, 68.5, 58.5, 52.6, 44.2; MS (ESI-quadrupole) calcd for C6H15N2O3
163, found 163 (M + H+); IR (KBr, cm−1) ν 1638, 1571, 1452.
N-Benzyl-N-methylnitrous amide (2f): pale yellow liquid (58 mg,
1
77% yield); H NMR (300 MHz, CDCl3) δ 7.42−7.10 (m, 5H), 5.29
(s, 1.55H), 4.79 (s, 0.45H), 3.67 (s, 0.68H), 2.92 (s, 2.32H); 13C
NMR (75 MHz, CDCl3) δ 134.3, 133.6, 128.8, 128.6, 128.3, 128.0,
127.8, 127.7, 57.2, 47.4, 38.2, 30.7; HRMS (EI-TOF) calcd for
C8H10N2O 150.0793, found 150.0772 (M+); IR (KBr, cm−1) ν 1620,
1572, 1449.
N,N-Diallylnitrous amide (2g): pale yellow liquid (44 mg, 70%
yield); 1H NMR (400 MHz, CDCl3) δ 5.96−5.86 (m, 1H), 5.67−5.58
(m, 1H), 5.39−5.27 (m, 2H), 5.21−5.18 (m, 1H), 5.13−5.08 (m, 1H),
4.74−4.69 (m, 2H), 4.22−4.13 (m, 2H); 13C NMR (75 MHz, CDCl3)
δ 131.8, 129.1, 120.1, 119.1, 54.1, 45.1; MS (ESI-quadrupole) calcd for
C6H11N2O 127, found 127 (M + H+); IR (KBr, cm−1) ν 1637, 1572,
1420.
1-Nitrosopiperidine (2h): pale yellow liquid (47 mg, 83% yield);
1H NMR (400 MHz, CDCl3) δ 4.19 (t, J = 6.0 Hz, 2H), 3.78 (t, J =
6.0 Hz, 2H), 1.87−1.70 (m, 4H), 1.59−1.52 (m, 2H); 13C NMR
(100 MHz, CDCl3) δ 50.6, 39.5, 26.2, 24.5, 23.9; MS (ESI-
quadrupole) calcd for C5H11N2O 115, found 115 (M + H+); IR
(KBr, cm−1) ν 1638, 1571, 1419.
4-Nitrosomorpholine (2i): pale yellow liquid (45 mg, 78% yield);
1H NMR (300 MHz, CDCl3) δ 4.35−4.26 (t, J = 4.5 Hz, 2H), 3.95−
3.82 (m, 4H), 3.66 (t, J = 4.5 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ
67.2, 65.8, 49.9, 40.3; MS (ESI-quadrupole) calcd for C4H9N2O2 117,
found 117 (M + H+); IR (KBr, cm−1) ν 1672, 1561, 1431.
1-Nitrosopiperidin-4-ol (2j): pale yellow liquid (53 mg, 81% yield);
1H NMR (400 MHz, CDCl3) δ 4.48−4.38 (m, 1H), 4.20−4.08 (m,
2H), 4.03−3.92 (m, 1H), 3.86−3.74 (m, 1H), 3.45 (s, 1H), 2.10−2.00
(m, 1H), 1.91−1.74 (m, 2H), 1.68−1.53 (m, 1H); 13C NMR (100
MHz, CDCl3) δ 65.1, 46.6, 35.7, 33.6, 32.0; MS (ESI-quadrupole)
calcd for C5H11N2O2 131, found 131 (M + H+); IR (KBr, cm−1) ν
3411, 1638, 1560, 1421.
N,N-Dicyclohexylnitrous amide (2r): yellow solid (30 mg, 29%
1
yield); mp 104−105 °C. H NMR (400 MHz, CDCl3) δ 4.93−4.82
(m, 1H), 3.79−3.66 (m, 1H), 2.01−1.09 (m, 20H); 13C NMR
(75 MHz, CDCl3) δ 58.3, 52.0, 34.2, 29.2, 25.9, 25.3, 25.2; MS (EI-ion
trap) calcd for C12H22N2O 210, found 210 (M+); IR (KBr, cm−1) ν
1638, 1561, 1446.
N-Methyl-N-phenylnitrous amide (2s): pale yellow liquid (38 mg,
56% yield for 1s; 41 mg, 61% for 3a). 1H NMR (300 MHz, CDCl3) δ
7.60−7.31(m, 5H), 3.46 (s, 3H); 13C NMR (75 MHz, CDCl3) δ
142.2, 129.4, 127.3, 119.1, 31.4; MS (ESI-quadrupole) calcd for
C7H9N2O 137, found 137 (M + H+); IR (KBr, cm−1) ν 1631, 1515,
1468.
N-Ethyl-N-phenylnitrous amide (2t): pale yellow liquid (48 mg,
64% yield); 1H NMR (400 MHz, CDCl3) δ 7.56−7.50 (m, 2H), 7.50−
7.45 (m, 2H), 7.35 (t, J = 6.0 Hz, 1H), 4.07 (q, J = 8.0 Hz, 2H), 1.16
(t, J = 8.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 141.2, 129.3,
127.2, 119.4, 39.0, 11.6. MS (ESI-quadrupole) calcd for C8H11N2O
151, found 151 (M + H+); IR (KBr, cm−1) ν 1598, 1496, 1473.
N-Methyl-N-(p-tolyl)nitrous amide (2u): yellow solid (61 mg, 81%
1
yield); mp 50−51 °C; H NMR (400 MHz, CDCl3) δ 7.42 (d, J =
1-Nitrosopyrrolidine (2k): pale yellow liquid (37 mg, 74% yield);
8.0 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 3.45 (s, 3H), 2.40 (s, 3H);
1H NMR (400 MHz, CDCl3) δ 4.28 (t, J = 6.0 Hz, 2H), 3.59
13C NMR (75 MHz, CDCl3) δ 139.7, 137.1, 129.8, 119.1, 31.5, 20.8;
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dx.doi.org/10.1021/jo401915t | J. Org. Chem. XXXX, XXX, XXX−XXX