10.1002/ejoc.202100647
European Journal of Organic Chemistry
FULL PAPER
141.8, 134.3, 119.6, 24.1, 13.7; HRMS (ESI): m/z calcd for C7H9N2O2S+:
185.0379 [M+H]+; found: 185.0385.
3-(((3-Nitropyridin-2-yl)thio)methyl)benzonitrile (2m). Yellow solid (450
mg, 83%); m.p. 150-152°C; 1H NMR (700 MHz, DMSO-d6) δ=8.86 (dd,
J=4.6, 1.6 Hz, 1H), 8.62 (dd, J=8.2, 1.6 Hz, 1H), 7.91 (brs, J=1.8 Hz, 1H),
7.80 (brd, J=7.9 Hz, 1H), 7.71 (brd, J=7.7 Hz, 1H), 7.52 (t, J=7.7 Hz, 1H),
7.48 (dd, J=8.3, 4.6 Hz, 1H), 4.54 (s, 2H); 13C NMR (75 MHz, DMSO-d6)
δ=155.2, 153.7, 141.5, 139.4, 134.5, 134.2, 132.7, 130.8, 129.5, 120.3,
118.6, 111.3, 33.2; HRMS (ESI): m/z calcd for C13H10N3O2S+: 272.0488
[M+H]+; found: 272.0489.
2-(Hexylthio)-3-nitropyridine (2d). Light yellowish oil (355 mg, 74%); 1H
NMR (700 MHz, DMSO-d6) δ=8.81 (dd, J=4.6, 1.5 Hz, 1H), 8.58 (dd, J=8.2,
1.5 Hz, 1H), 7.43 (dd, J=8.2, 4.6 Hz, 1H), 3.19 (t, J=7.4 Hz, 2H), 1.66-1.61
(m, 2H), 1.44-1.37 (m, 2H), 1.31-1.26 (m, 4H), 0.86 (t, J=7.1 Hz, 3H); 13
C
NMR (75 MHz, DMSO-d6) δ=156.3, 153.6, 141.8, 134.2, 119.5, 30.8, 29.7,
28.1, 21.9, 13.8; HRMS (ESI): m/z calcd for C11H17N2O2S+: 241.1005
[M+H]+; found: 241.1005.
2-(Allylthio)-3-nitropyridine (2n). Yellow solid (271 mg, 69%); m.p. 54-
56°C; 1H NMR (700 MHz, DMSO-d6) δ 8.83 (dd, J=4.6, 1.6 Hz, 1H), 8.60
(dd, J=8.2, 1.6 Hz, 1H), 7.45 (dd, J=8.3, 4.6 Hz, 1H), 5.95 (ddt, J=17.0,
10.0, 6.9 Hz, 1H), 5.34 (dq, J=17.0, 1.5 Hz, 1H), 5.15 – 5.11 (m, 1H), 3.90
(brd, J=6.9 Hz, 2H).13C NMR (75 MHz, DMSO-d6) δ=155.5, 153.6, 141.7,
134.3, 133.2, 119.9, 118.4, 32.6; HRMS (ESI): m/z calcd for C8H9N2O2S+:
197.0379 [M+H]+; found: 197.0381.
2-((4-Fluorobenzyl)thio)-3-nitropyridine (2e). Yellow solid (423 mg,
80%); m.p. 108-110°C; 1H NMR (700 MHz, DMSO-d6) δ=8.87 (dd, J=4.6,
1.5 Hz, 1H), 8.62 (dd, J=8.2, 1.5 Hz, 1H), 7.49-7.45 (m, 3H), 7.13 (t, J=8.8
Hz, 2H), 4.48 (s, 2H); 13C NMR (75 MHz, DMSO-d6) δ=161.3 (d, J=243.5
Hz), 155.7, 153.7, 141.4, 134.4, 133.2 (d, J=3.1 Hz), 131.2 (d, J=8.2 Hz),
120.1, 115.1 (d, J=21.5 Hz), 33.4; HRMS (ESI): m/z calcd for
C12H10FN2O2S+: 265.0442 [M+H]+; found: 265.0443.
2-((2-Methylallyl)thio)-3-nitropyridine (2o). Light yellow oil (231 mg,
55%); 1H NMR (700 MHz, DMSO-d6) δ=8.82 (dd, J=4.6, 1.6 Hz, 1H), 8.60
(dd, J=8.2, 1.6 Hz, 1H), 7.44 (dd, J=8.2, 4.6 Hz, 1H), 5.05 (brs, 1H), 4.89
(brs, 1H), 3.93 (s, 2H), 1.80 (s, 3H); 13C NMR (75 MHz, DMSO-d6) δ=155.7,
153.6, 141.9, 140.3, 134.3, 119.9, 114.4, 36.4, 21.5; HRMS (ESI): m/z
calcd for C9H11N2O2S+: 211.0536 [M+H]+; found: 211.0539.
2-((4-Сhlorobenzyl)thio)-3-nitropyridine (2f). Yellow solid (471 mg,
84%); m.p. 95-97°C; 1H NMR (700 MHz, DMSO-d6) δ=8.85 (dd, J=4.6, 1.5
Hz, 1H), 8.61 (dd, J=8.4, 1.5 Hz, 1H), 7.49-7.42 (m, 3H), 7.36 (d, J=8.6 Hz,
2H), 4.48 (s, 2H); 13C NMR (75 MHz, DMSO-d6) δ=155.5, 153.7, 141.5,
136.3, 134.4, 131.7, 131.0, 128.3, 120.2, 33.3; HRMS (ESI): m/z calcd for
C
12H10ClN2O2S+: 281.0146 [M+H]+; found: 281.0144.
2-((3-Nitropyridin-2-yl)thio)acetonitrile (2q). Brown solid (152 mg,
39%); m.p. 104-106°C; 1H NMR (700 MHz, DMSO-d6) δ=8.94 (dd, J=4.6,
1.5 Hz, 1H), 8.72 (dd, J=8.3, 1.6 Hz, 1H), 7.59 (dd, J=8.3, 4.6 Hz, 1H),
4.28 (s, 2H); 13C NMR (75 MHz, DMSO-d6) δ=154.0, 153.1, 141.6, 134.8,
121.2, 118.0, 16.1; HRMS (ESI): m/z calcd for C7H6N3O2S+: 196.0175
[M+H]+; found: 196.0180.
2-((4-Bromobenzyl)thio)-3-nitropyridine (2g). Yellow solid (461 mg,
71%); m.p. 97-99°C; 1H NMR (700 MHz, DMSO-d6) δ=8.85 (dd, J=4.6, 1.5
Hz, 1H), 8.62 (dd, J=8.4, 1.5 Hz, 1H), 7.50 (d, J=8.4 Hz, 2H), 7.46 (dd,
J=8.4, 4.6 Hz, 1H), 7.40 (d, J=8.4 Hz, 2H), 4.48 (s, 2H); 13C NMR (75 MHz,
DMSO-d6) δ=155.5, 153.7, 141.4, 136.7, 134.4, 131.4, 131.2, 120.2, 120.1,
33.4; HRMS (ESI): m/z calcd for C12H10BrN2O2S+: 324.9641 [M+H]+;
found: 324.9644.
Methyl 2-((3-nitropyridin-2-yl)thio)acetate (2r). Orange solid (224 mg,
49%); m.p. 59-61°C; 1H NMR (700 MHz, DMSO-d6) δ=8.77 (dd, J=4.6, 1.6
Hz, 1H), 8.64 (dd, J=8.3, 1.6 Hz, 1H), 7.46 (dd, J=8.3, 4.6 Hz, 1H), 4.08 (s,
2H), 3.64 (s, 3H); 13C NMR (75 MHz, DMSO-d6) δ=169.3, 155.0, 153.7,
141.5, 134.5, 120.3, 52.2, 32.6; HRMS (ESI): m/z calcd for C8H9N2O4S+:
229.0278 [M+H]+; found: 229.0281.
2-((3-Methoxybenzyl)thio)-3-nitropyridine (2h). Yellow solid (425 mg,
77%); m.p. 82-84°C; 1H NMR (700 MHz, DMSO-d6) δ=8.87 (dd, J = 4.6,
1.6 Hz, 1H), 8.62 (dd, J = 8.3, 1.6 Hz, 1H), 7.47 (dd, J = 8.3, 4.6 Hz, 1H),
7.23 (t, J = 7.8 Hz, 1H), 7.03 – 6.98 (m, 2H), 6.83 (dd, J = 8.3, 2.5 Hz, 1H),
4.46 (s, 2H), 3.73 (s, 3H); 13C NMR (75 MHz, DMSO-d6) δ=159.2, 155.9,
153.7, 141.4, 138.3, 134.3, 129.5, 121.4, 120.0, 114.9, 112.6, 54.9, 34.3;
HRMS (ESI): m/z calcd for C13H13N2O3S+: 277.0641 [M+H]+; found:
277.0641.
2-(Benzylthio)-6-methoxy-3-nitropyridine (4a). Yellow solid (348 mg,
63%); m.p. 103-105°C; 1H NMR (700 MHz, DMSO-d6) δ=8.51 (d, J=9.0 Hz,
1H), 7.44 (brd, J=7.2 Hz, 2H), 7.35 (brt, J=7.6 Hz, 2H), 7.28 (brt, J=7.4 Hz,
1H), 6.78 (d, J=9.0 Hz, 1H), 4.53 (s, 2H), 4.02 (s, 3H); 13C NMR (75 MHz,
DMSO-d6) δ=164.2, 157.6, 137.3, 136.4, 135.5, 129.0, 128.5, 127.2, 106.9,
54.9, 34.8; HRMS (ESI): m/z calcd for C13H13N2O3S+: 277.0641 [M+H]+;
found: 277.0644.
2-((2-Methoxybenzyl)thio)-3-nitropyridine (2i). Yellow solid (453 mg,
82%); m.p. 126-128°C; 1H NMR (700 MHz, DMSO-d6) δ=8.88 (dd, J=4.6,
1.6 Hz, 1H), 8.60 (dd, J=8.3, 1.6 Hz, 1H), 7.45 (dd, J=8.3, 4.6 Hz, 1H),
7.40 (dd, J=7.4, 1.7 Hz, 1H), 7.30 – 7.25 (m, 1H), 7.02 (d, J=8.2 Hz, 1H),
6.89 (t, J=7.4 Hz, 1H), 4.45 (s, 2H), 3.82 (s, 3H); 13C NMR (75 MHz,
DMSO-d6) δ=157.4, 156.5, 153.7, 141.4, 134.3, 130.7, 128.9, 124.0, 120.2,
119.7, 110.9, 55.5, 29.4; HRMS (ESI): m/z calcd for C13H13N2O3S+:
277.0641 [M+H]+; found: 277.0644.
6-Methoxy-2-(methylthio)-3-nitropyridine (4b). Yellow solid (348 mg,
87%); m.p. 134-136°C; 1H NMR (700 MHz, DMSO-d6) δ=8.50 (d, J=9.0 Hz,
1H), 6.75 (d, J=9.0 Hz, 1H), 4.06 (s, 3H), 2.57 (s, 3H); 13C NMR (75 MHz,
DMSO-d6) δ=164.2, 158.7, 137.3, 135.9, 106.4, 54.8, 14.0; HRMS (ESI):
m/z calcd for C7H9N2O3S+: 201.0328 [M+H]+; found: 201.0332.
3,5-Dimethyl-4-(((3-nitropyridin-2-yl)thio)methyl)isoxazole (2j). Yellow
solid (392 mg, 74%); m.p. 123-125°C; 1H NMR (700 MHz, DMSO-d6)
δ=8.88 (dd, J=4.6, 1.6 Hz, 1H), 8.61 (dd, J=8.3, 1.6 Hz, 1H), 7.47 (dd,
J=8.3, 4.6 Hz, 1H), 4.26 (s, 2H), 2.44 (s, 3H), 2.24 (s, 3H); 13C NMR (75
MHz, DMSO-d6) δ=166.7, 159.3, 155.5, 153.5, 141.7, 134.5, 120.1, 109.5,
22.3, 10.9, 9.8; HRMS (ESI): m/z calcd for C11H12N3O3S+: 266.0594
[M+H]+; found: 266.0593.
2-(2-Methylallyl)-6-methoxy-3-nitropyridine (4o). Yellow solid (249 mg,
52%); m.p. 76-78°C; 1H NMR (700 MHz, DMSO-d6) δ=8.49 (d, J=9.0 Hz,
1H), 6.76 (d, J=9.0 Hz, 1H), 5.05 (brs, 1H), 4.93 (brs, 1H), 4.04 (s, 3H),
3.95 (brs, 2H), 1.83 (s, 3H). 13C NMR (75 MHz, DMSO-d6) δ=164.1, 157.5,
140.2, 137.4, 135.9, 114.2, 106.8, 54.8, 36.8, 21.6; HRMS (ESI): m/z calcd
for C10H13N2O3S+: 241.0641 [M+H]+; found: 241.0645.
2-((6-Methoxy-3-nitropyridin-2-yl)thio)acetonitrile (4q). Yellow solid
(426 mg, 95%); m.p. 149-151°C; 1H NMR (700 MHz, DMSO-d6) δ=8.56 (d,
J=9.0 Hz, 1H), 6.89 (d, J=9.0 Hz, 1H), 4.31 (s, 2H), 4.16 (s, 3H). 13C NMR
(75 MHz, DMSO-d6) δ=164.6, 154.9, 137.5, 135.8, 118.2, 108.0, 55.2,
16.5; HRMS (ESI): m/z calcd for C8H8N3O3S+: 226.0281 [M+H]+; found:
226.0280.
Methyl 3-(((3-nitropyridin-2-yl)thio)methyl)benzoate (2l). Yellow solid
(407 mg, 67%); m.p. 96-98°C; 1H NMR (700 MHz, DMSO-d6) δ=8.85 (dd,
J=4.6, 1.6 Hz, 1H), 8.61 (dd, J=8.3, 1.6 Hz, 1H), 8.05 (brs, 1H), 7.83 (brd,
J=7.8 Hz, 1H), 7.73 (brd, J=7.7 Hz, 1H), 7.49 – 7.45 (m, 2H), 4.57 (s, 2H),
3.85 (s, 3H); 13C NMR (75 MHz, DMSO-d6) δ=166.0, 155.5, 153.7, 141.5,
138.1, 134.4, 134.1, 129.8, 129.7, 128.8, 127.8, 120.2, 52.1, 33.7; HRMS
(ESI): m/z calcd for C14H13N2O4S+: 305.0591 [M+H]+; found: 305.0594.
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