The Journal of Organic Chemistry
Article
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differentiate all the signals corresponding to each isomer. H NMR
300 MHz, DMSO): δ (ppm) 9.99−10.33 (m, 1H), 8.74 (d, J = 11.1
(ν, cm , KBr): 2960, 2872, 2359, 1672, 1468, 1468, 1432, 1389. MS
(EI:) 157 (17), 114 (100), 102 (8), 86 (14), 72 (13).
(
Hz, 1H), 8.26−8.57 (m, 1H), 7.93−8.17 (m, 1H), 7.47−7.78 (m, 3H),
N,N-Dicyclohexylformamide (13j). The crude mixture was
purified by flash chromatography with DCM/AcOEt (1:1), and the
product was obtained as white crystals. Yield: 420 mg, 67%. Mp: 60−
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.12−7.50 (m, 2H), 4.41 (d, J = 7.1 Hz, 2H), 1.29 (t, J = 7.0 Hz, 3H).
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C{ H} NMR (75 MHz, DMSO): δ (ppm) 163.5, 159.6, 140.5,
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40.5, 137.2, 136.8, 130.8, 130.6, 126.5, 126.3, 123.0, 122.4, 122.4,
22.3, 121.0, 120.7, 119.0, 118.7, 111.6, 110.7, 110.2, 109.6, 37.4, 14.1.
IR (ν, cm , KBr): 3240, 3049, 2967, 2872, 1654, 1541, 1474. HRMS:
62 °C (lit. 61 °C). H NMR (300 MHz, CDCl ): δ (ppm) 8.34 (s,
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1H), 3.78−4.10 (m, 1H), 3.00−3.11 (m, 1H), 0.80−2.03 (m, 20H).
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C{ H} NMR (75 MHz, CDCl ): δ (ppm) 161.6, 54.9, 52.3, 34.6,
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calcd for C H N O, 239.1184; found, 239.1177.
30.4, 26.2, 25.8, 25.3, 25.2. IR (ν, cm , KBr): 2931, 2852, 2666, 1661,
1446, 1422, 1379, 1292, 1231. MS (EI): 209 (24), 166 (20), 128
(100).
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Benzothiazole (13c). The crude mixture was purified by flash
chromatography with DCM/cyclohexane (1:1), and the product was
obtained as a brown liquid. Yield: 336 mg, 83%. H NMR (300 MHz,
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N-(2-Hydroxyethyl)formamide (13k). The crude mixture was
CDCl ): δ (ppm) 9.00 (s, 1H), 8.15 (d, J = 8.2 Hz, 1H), 7.92−8.01
purified by flash chromatography with DCM/MeOH (9:1), and the
product was obtained as a pale yellow oil. Yield: 246 mg, 92%. H
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(
m, 1H), 7.30−7.60 (m, 2H). C{ H} NMR (75 MHz, CDCl ): δ
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(
ppm) 159.3, 153.2, 133.7, 126.1, 125.5, 123.6, 121.9. IR (ν, cm ,
NMR (300 MHz, DMSO): δ (ppm) 8.00 (s. 1H), 4.71 (t, J = 5.4 Hz,
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KBr): 3060, 1555, 1471, 1423, 1315, 1291, 1266, 873, 758, 728.
HRMS: calcd for C H NS, 136.0220; found, 136.0217.
1H), 3.36−3.43 (m, 2H), 3.09−3.17 (m, 2H). C{ H} NMR (75
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MHz, DMSO): δ (ppm) 161.6, 60.1, 40.5. IR (ν, cm , KBr) 3380,
2888, 1666, 1538, 1389. MS (EI) [M − OH]:71 (56), 58 (70),
43(52), 30 (100).
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N-Formyl-4-aminoantipyrine (13d). The crude mixture was
purified by flash chromatography with DCM, and the product was
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obtained as a beige solid. Yield: 644 mg, 93%. Mp: 188−190 °C (lit.
N-Formyl-(S)-phenylalanine Methyl Ester (13l). The crude
mixture was purified by flash chromatography with DCM/MeOH
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92−194 °C). The presence of two rotamers was observed in the
NMR spectra in an 0.85 (M):0.15 (m) ratio. H NMR (300 MHz,
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(9:1), and the product was obtained as a viscous oil. Yield: 590 mg,
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CDCl ): δ (ppm) 9.21 (s, 1H), 8.47 (m) (d, J = 11.4 Hz, 1H), 8.23
95%. H NMR (300 MHz, CDCl ): δ (ppm) 8.17 (s, 1H), 7.09−
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(
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M) (d, J = 1.2 Hz, 1H), 7.27−7.50 (m, 5H), 3.10 (s, 3H), 2.25 (s,
7.33(m, 5H), 6.11 (s, 1H), 4.94−5.01 (m, 1H), 3.75 (s, 3H), 3.16 (t, J
= 5.9 Hz, 2H). C NMR (75 MHz, CDCl
136.0, 129.8, 129.2, 127.8, 53.0, 52.3, 38.3. IR (ν, cm , KBr): 3301,
H). 13C{ H} NMR (75 MHz, CDCl ): δ (ppm) 160.5, 149.8, 134.2,
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): δ (ppm) 172.0, 161.3,
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29.3, 127.4, 127.1, 124.7, 124.2, 107.0, 36.1, 35.7, 12.1. IR (ν, cm ,
KBr): 3180, 3111, 3055, 2934, 2877, 1688, 1644, 1590. HRMS: calcd
for C H N O , 232.1086; found, 232.1085.
3030, 2953, 2960, 2870, 1744, 1668, 1543. MS (EI) [M − NHCOH]:
162 (17), 91 (20), 44 (18). [α]1
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= 89.14 (c = 1.1).
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D
N-(Pyridin-2-yl)formamide (13e). The crude mixture was
purified by flash chromatography with DCM/AcOEt (9:1), and the
product was obtained as a white solid. Yield: 307 mg, 84%. Mp: 75−76
Methyl Formylglycinate (13m). The crude mixture was purified
by flash chromatography with DCM/MeOH (9:1), and the product
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was obtained as a colorless oil. Yield: 351 mg, quantitative. H NMR
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C (lit. 75−76 °C). The presence of two rotamers was observed in
(300 MHz, CDCl ): δ (ppm) 7.28 (s, 1H), 4.11 (d, J = 5.3 Hz, 2H),
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the NMR spectra in a 0.6 (M):0.4 (m) ratio. H NMR (300 MHz,
3.79 (s, 3H). C{ H} NMR (75 MHz, CDCl ): δ (ppm) 170.0, 161.1,
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CDCl ): δ (ppm) 9.97 (m) (br s, 1H), 9.77 (M) (br s, 1H), 9.33 (m)
52.5, 39.8. IR (ν, cm , KBr): 3424, 2917, 2849, 1741, 1688, 1452,
1442, 1391, 1312, 1226, 1051. MS (EI) [M − CO]: 89 (22), 58 (65),
30 (100).
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(
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d, J = 10.5 Hz, 1H), 8.53(M) (s, 1H), 8.30 (dd, 6.6 Hz, 1H), 7.56−
.88 (m, 1H), 7.09 (td, 1H), 6.94(m) (d, J = 8.2 Hz, 1H). 13C{ H}
NMR (75 MHz, CDCl ): δ (ppm) 162.9, 159.5, 151.0, 150.9, 148.5,
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N-Phenylacetamide (14a). The crude mixture was purified by
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47.4, 138.8, 138.7, 120.2, 119.8, 115.1, 110.5. IR (ν, cm , KBr):
flash chromatography with DCM, the product was obtained as white
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189. 3081, 2987, 1711, 1596, 1551, 1499. MS (EI): 122 (30), 94
crystals. Yield: 377 mg, 93%. Mp: 112−113 °C (lit. 112−114 °C).
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(
100), 67 (90).
H NMR (300 MHz, CDCl ): δ (ppm) 7.51 (s, 1H), 7.49−7.50 (m,
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Pyrrolidine-1-carbaldehyde (13f). The crude mixture was
2H), 7.25−7.30 (m, 2H), 7.10 (m, 1H), 2.16 (s, 3H). C{ H} NMR
purified by flash chromatography with DCM/AcOEt (8:2), and the
(75 MHz, CDCl ): δ (ppm) 168.5, 137.9, 128.9, 124.3, 119.9, 24.5. IR
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product was obtained as a yellow oil. Yield: 297 mg, quantitative. H
(ν, cm , KBr): 3293, 3259, 3194, 3135, 3059, 1663, 1598, 1556, 1508.
NMR (300 MHz, CDCl ): δ (ppm) 8.27 (s, 1H), 3.43−3.51 (m, 4H),
MS (EI): 135 (26), 93(100), 43 (22).
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.91−1.93 (m, 4H). C{ H} NMR (75 MHz, CDCl ): δ (ppm)
N-Pyridin-2-ylacetamide (14b). The crude mixture was purified
by flash chromatography with DCM/AcOEt (7:3), and the product
was obtained as a beige crystals. Yield: 208 mg, 51%. Mp: 73−75 °C
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60.9, 46.0, 43.1, 24.9, 24.2. IR (ν, cm , KBr): 2974, 2881, 1656,
429, 1388, 1334. MS (EI): 99 (88), 71 (65), 56 (0,5), 43 (100).
Piperidine-1-carbaldehyde (13g). The crude mixture was
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(lit. 73−74 °C). H NMR (300 MHz, CDCl ): δ (ppm) 8.91 (br s,
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purified by flash chromatography with DCM/AcOEt (9:1), and the
1H), 8.10−8.36 (m, 2H), 7.65−7.77 (m, 1H), 7.05 (m, 1H), 2.21 (s,
3H). 13C{ H}NMR (75 MHz, CDCl ): δ (ppm) 168.9, 151.6, 147.5,
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product was obtained as a pale yellow oil. Yield: 339 mg, quantitative.
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H NMR (300 MHz, CDCl ): δ (ppm) 8.00 (s, 1H), 3.48 (t, J = 9 Hz,
138.5, 119.7, 114.2, 24.6. IR (ν, cm , KBr): 3191, 3112, 3007, 1692,
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H), 3.31 (t, J = 12 Hz, 2H), 1.51−1.73 (m, 6H). C{ H} NMR (75
1600, 1579, 1535. MS (EI): 136 (17), 94 (100), 78 (7), 67 (71), 43
(36), 39 (14).
N-Acetylpiperidine (14c). The crude mixture was purified by
flash chromatography with DCM/AcOEt (1:1), and the product was
obtained as a pale yellow liquid. Yield: 290 mg, 76%. H NMR (300
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MHz, CDCl ): δ (ppm) 160.8, 46.8, 40.6, 26.5, 25.0, 24.6. IR (ν, cm ,
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KBr): 2941, 2861, 1738, 1675, 1444, 1373, 1242. MS (EI): 113 (100),
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8 (35), 84 (53) 70 (32), 56 (77), 42 (62).
Morpholine-4-carbaldehyde (13h). The crude mixture was
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purified by flash chromatography with DCM/AcOEt (1:1), and the
MHz, CDCl ): δ (ppm) 3.53−3.56 (m, 2H), 3.37−3.41 (m, 2H), 2.08
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product was obtained as a yellow oil. Yield: 345 mg, quantitative. H
(s, 3H), 1.25−1.64 (m, 6H). C{ H} NMR (75 MHz, CDCl ): δ
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NMR (300 MHz, CDCl ): δ (ppm) 8.07 (s, 1H), 3.64−3.72 (m, 4H),
(ppm) 168.8, 47.4, 42.5, 26.4, 25.5, 24.4, 21.4. IR (ν, cm , KBr) 3458,
2935, 2856, 1625, 1445, 1268. MS (EI) 127 (50), 84 (75), 70 (35), 56
(47), 43 (68), 32 (100).
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.58 (t, J = 9 Hz, 2H), 3.40 (t, J = 9 Hz, 2H). C{ H} NMR (75
MHz, CDCl ): δ (ppm) 160.8, 67.2, 66.4, 45.8, 40.6. IR (ν, cm ,
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KBr): 2979, 2924, 2863, 1655, 1442,1399, 1363, 1301, 1272, 1232,
N-Acetylpyrrolidine (14d). The crude mixture was purified by
flash chromatography with AcOEt. and the product was obtained as a
yellow oil. Yield: 339 mg, quantitative. H NMR (300 MHz, CDCl
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188, 1111, 1069, 1006, 855, 811. MS (EI): 115 (99), 100 (74), 86
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(
46), 72 (33), 56 (92), 42 (100).
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):
N,N-Diisobutylformamide (13i). The crude mixture was purified
δ (ppm) 3.40−3.48 (m, 4H), 2.05 (s, 3H), 1.84−1.97 (m, 4H).
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by flash chromatography with DCM, and the product was obtained as
C{ H} NMR (75 MHz, CDCl
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): δ (ppm) 172.9, 47.3, 45.5, 26.0,
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a yellow oil. Yield: 471 mg, quantitative. H NMR (300 MHz, CDCl ):
24.5, 22.4. IR (ν, cm , KBr): 3421, 1663, 1609, 1476. MS (EI): 113
(13), 70 (22), 43 (40), 32 (100).
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δ (ppm) 8.07 (s, 1H), 3.13 (d, J = 7.6 Hz, 2H), 2.99 (d, J = 7.4 Hz,
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(
H), 1.64−2.19 (m, 2H), 0.89 (d, J = 6.7 Hz, 12H). C{ H} NMR
N-(2-Hydroxyethyl)acetamide (14e). The crude mixture was
purified by flash chromatography with DCM/AcOEt (1:1), and the
75 MHz, CDCl ): δ (ppm) 163.3, 55.4, 49.4, 26.4, 26.1, 20.0, 19.8. IR
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550
dx.doi.org/10.1021/jo500562w | J. Org. Chem. 2014, 79, 4544−4552