10.1002/cplu.201900243
ChemPlusChem
FULL PAPER
found 249.0041. Found (%): C 36.96, H 1.29, N 24.03. C7H3FN4O4. Calcd.
(%): C 37.18, H 1.34, N 24.78.
3-(4-Methoxy-3,5-dinitrophenyl)-1,2,3,4-oxatriazolium-5-olate (21). A
solution of appropriate azasidnones 20 (0.6 mmol) or 19 (8 mmol) in
H2SO4 (0.6 ml) was stirred at room temperature and treated by dropwise
addition of HNO3 (d = 1.5 г/см3, 0.5 ml, 12 mmol) and the mixture was
stirred for 2 h. The reaction mixture was poured by ice water (7 ml) the
precipitate that formed was filtered off, washed with water, and air-dried.
Yield 78% (А) or 89% (В), milky white needles, mp 99–101 ºC (EtOH).
IR: = 3101 (w), 1842 (s), 1788 (w), 1625 (w), 1542 (vs), 1494 (m), 1370
3-(4-Methyl-3-nitrophenyl)-1,2,3,4-oxatriazolium-5-olate (15). Yield
70%, grey solid, mp 103–105 ºC (EtOH). IR: = 1804 (vs), 1774 (m),
1540 (m), 1372 (w), 1345 (w), 1189 (w), 1135 (w), 749 (w) cm−1. 1H NMR
(300.1 MHz, [D6]DMSO): δ = 8.66 (s, 1H), 8.38 (d, 1H, J = 8.4 Hz), 7.92
(d, 1H, J = 8.4 Hz), 2.68 (s, 3H, Me) ppm. 13C NMR (75.5 MHz,
[D6]DMSO): δ = 164.99 (C-O), 149.04, 138.81, 134.85 (CH), 132.64,
125.37 (CH), 117.72 (CH), 19.55 (Me) ppm. 14N NMR (21.7 MHz,
[D6]DMSO): δ = –10.52 (NO2), –75.36 (N+) ppm. HRMS (ESI): m/z calcd.
for C8H6N4NaO4 [M+Na]+ 245.0281; found 245.0278. Found (%): C 42.91,
H 2.53, N 24.91. C8H6N4O4. Calcd. (%): C 43.25, H 2.72, N 25.22.
(m), 1352 (s), 1334 (m), 1274 (w), 1194 (w), 977 (w), 747 (w) cm−1 1H
.
NMR (300.1 MHz, [D6]DMSO): δ = 9.05 (s, 2H), 4.09 (s, 3H, ОСН3) ppm.
13C NMR (150.90 MHz, [D6]DMSO): δ = 160.04 (C-O), 144.94 (2СNO2),
139.94 (C-OMe), 123.76 (C-N+), 118.09 (2CH), 60.16 (ОМе) ppm. 14N
NMR (43.37 MHz, [D6]DMSO): δ = –18.77 (NO2), –78.47 (N+) ppm.
Found, m/z: 306.0071 [M+Na]+. HRMS (ESI): m/z calcd. for
C8H5N5NaO7. Calcd., m/z: 306.0081. Found (%): C 33.93, H 1.78, N
24.73. C8H5N5O7. Calcd. (%): C 40.35, H 2.54, N 23.53.
3-(4-Chloro-3-nitrophenyl)-1,2,3,4-oxatriazolium-5-olate (9). Yield
78%, white needles, mp 137–139 ºC (EtOH). IR: = 3089 (w), 1806 (vs),
1777 (m), 1547 (m), 1362 (s), 1187 (m), 1119 (w), 901 (w), 747 (m) cm−1
.
1H NMR (500.13 MHz, [D6]DMSO): δ = 8.85 (d, 1H, J = 2.4 Hz), 8.42 (dd,
1H, J = 8.8, 2.4 Hz), 7.92 (d, 1H, J = 8.8 Hz) ppm. 13C NMR (125.76 MHz,
[D6]DMSO): δ = 164.94 (C-O), 148.02, 133.78 (CH), 133.34, 130.24,
126.18 (CH), 119.13 (CH) ppm. 14N NMR (136.14 MHz, [D6]DMSO): δ = –
15.74 (NO2), –77.16 (N+) ppm. HRMS (ESI): m/z calcd. for
C7H3ClN4NaO4 [M(37Cl)+Na]+, [M(35Cl)+Na]+ 266.9706, 264.9735; found
266.9710, 264.9738. Found (%): C 34.25, H 1.13, N 22.87. C7H3ClN4O4.
Calcd. (%): C 34.66, H 1.25, N 23.09.
3-Phenyl-1,2,3,4-oxatriazolium-5-phenylaminide (22). Yield 83%, mp
110-112 ºC (CН2Cl2) (lit. mp 110-111 ºC [30]).
3-(4-Methoxyphenyl-1,2,3,4-oxatriazolium-5-phenylaminide
(23).
Yield 72%, mp 95–98 ºC (CCl4) (lit. mp 99–100 ºC [10]). 1H NMR (200.1
MHz, [D6]DMSO): δ = 3.91 (s, 3H), 7.03 (t, 1 H, H4 (N−-Ar), J = 7.1 Hz),
7.21-7.32 (м, 6 H), 8.08 (d, 2 H, J = 8.9 Hz).
Nitration of 3-Aryl-1,2,3,4-oxatriazolium-5-arylaminides (General
method). A solution of appropriate compound 22 or 23 (0.4 mmol) in
H2SO4 (0.6 ml) was stirred at room temperature and treated by dropwise
addition of HNO3 (d = 1.5 г/см3, 0.5 ml, 12 mmol) and the mixture was
stirred for 2 h. Method I. The reaction mixture was poured by ice water (7
ml) the precipitate that formed was filtered off, washed with water, and
air-dried. The product was an appropriate compound 24 or 26. Method II.
The reaction mixture was warmed slowly to 80 оС and was stirred for 4 h.
The reaction mixture was cooled and poured by ice water (7 ml). The
precipitate that formed was filtered off, washed with water, and air-dried.
The product was an appropriate compound 25 or 27.
3-(5-Chloro-2-nitrophenyl)-1,2,3,4-oxatriazolium-5-olate (10). Yield
67%, white needles, mp 104–106 ºC (EtOH). IR: = 3114 (w), 3095 (w),
1789 (vs), 1585 (m), 1542 (m), 1346 (s), 1330 (s), 1182 (w), 973 (w), 746
(m) cm−1. 1H NMR (300.1 MHz, [D6]DMSO): δ = 8.54 (d, 1H, J = 8.9 Hz),
8.46 (d, 1H, J = 1.8 Hz), 8.27 (dd, 1H, J = 8.8, 1.8 Hz) ppm. 13C NMR
(150.90 MHz, [D6]DMSO): δ = 165.06 (C-O), 141.36, 140.46, 135.70
(CH), 129.16 (CH), 128.51 (CH), 128.03 ppm. 14N NMR (21.7 MHz,
[D6]DMSO): δ = –20.00 (NO2), –83.30 (N+) ppm. 15N NMR (30.4 MHz,
[D6]DMSO): δ = –9.04 (N2), –20.52 (NO2), –81.54 (N+), –144.38 (N4) ppm.
HRMS (ESI): m/z calcd. for C7H3ClN4NaO4 [M(37Cl)+Na]+, [M(35Cl)+Na]+
266.9706, 264.9735; found 266.9715, 264.9742. Found (%): C 34.50, H
1.13, N 22.82. C7H3ClN4O4. Calcd. (%): C 34.66, H 1.25, N 23.09.
3-Phenyl-1,2,3,4-oxatriazolium-5-(2,4-dinitrophenyl)aminide
(24).
Yield 0.084 g (64%), orange laminar crystals, mp 196–198 ºC (EtOH). IR:
= 3103 (w), 1663 (vs), 1587 (vs), 1515 (m), 1325 (s), 1282 (m), 974 (m),
906 (m), 680 (m) cm−1. 1H NMR (300.1 MHz, [D6]DMSO): δ = 8.69 (d, 1H
(N−-Ar), J = 2.7 Hz), 8.43 (dd, 1H (N−-Ar), J = 9 Hz, 2.7 Hz), 8.20 (d, 2H
(N+-Ar), J = 8.0 Hz), 7.88 (t, 1H (N+-Ar), J = 7.5 Hz), 7.88 (t, 1H (N−-Ar), J
= 7.5 Hz), 7.79 (t, 2H (N+-Ar), J = 8.0 Hz) ppm. 13C NMR (75.5 MHz,
[D6]DMSO): δ = 167.35 (C-N−), 145.60 (N−-Ar), 144.55 (N−-Ar), 141.01
(N−-Ar), 134.93 (2CH, (N+-Ar)), 134.20 (N+-Ar), 130.96 (CH, (N+-Ar)),
127.77 (CH, (N−-Ar)), 123.96 (CH, (N−-Ar)), 122.40 (2CH, (N+-Ar)),
120.08 (CH, (N−-Ar)) ppm. 14N NMR (21.7 MHz, [D6]DMSO): δ = –9.99, –
70.94 (N+) ppm. Found, m/z: 329.0632 [M+H]+. HRMS (ESI): m/z calcd.
for C13H9N6O5. Calcd., m/z: 329.0629. Found (%): C 47.49, H 2.34, N
25.47. C13H8N6O5. Calcd. (%): C 47.57, H 2.46, N 25.60.
3-(2-Chloro-5-nitrophenyl)-1,2,3,4-oxatriazolium-5-olate (8). Yield
70%, light beige needles, mp 120–122 ºC (EtOH). IR: = 3116 (w), 1810
(vs), 1542 (m), 1351 (s), 1335 (m), 1183 (w), 1151 (w), 983 (w), 738 (w)
cm−1. 1H NMR (300.1 MHz, [D6]DMSO): δ = 9.01 (d, 1H, J = 2.0 Hz), 8.66
(dd, 1H, J = 8.9, 2.2 Hz), 8.24 (d, 1H, J = 9.0 Hz) ppm. 13C NMR (75.5
MHz, [D6]DMSO): δ = 164.89 (C-O), 146.73 (СNO2), 134.63 (CCl),
132.99 (CH), 132.29 (C-N+), 129.43 (CH), 123.65 (CH) ppm. 14N NMR
(21.7 MHz, [D6]DMSO): δ = –17.06 (NO2), –81.75 (N+) ppm. HRMS (ESI):
m/z calcd. for C7H3ClN4NaO4 [M(37Cl)+Na]+, [M(35Cl)+Na]+ 266.9706,
264.9735; found 266.9712, 264.9738. Found (%): C 34.50, H 1.13, N
22.88. C7H3ClN4O4. Calcd. (%): C 34.66, H 1.25, N 23.09.
3-(4-Methoxy-3-nitrophenyl)-1,2,3,4-oxatriazolium-5-olate (20). Yield
96%, beige needles, mp 155–157 ºC (EtOH). IR: = 3076 (w), 1796 (vs),
1614 (m), 1534 (m), 1363 (w), 1331 (m), 1282 (m), 1187 (w), 1002 (w),
733 (m) cm−1. 1H NMR (300.1 MHz, [D6]DMSO): δ = 8.66 (d, 1H, J = 2.2
Hz), 8.40 (dd, 1H, J = 9.3 Hz, J = 2.3 Hz), 7.72 (d, 1H, J = 9.3 Hz), 4.10
(s, 3H, ОСН3) ppm. 13C NMR (75.5 MHz, [D6]DMSO): δ = 165.04 (C-O),
155.34 (C-OMe), 139.00 (СNO2), 127.10 (CH), 126.27 (C-N+), 118.75
(CH), 116.08 (CH), 57.80 (ОМе) ppm. 14N NMR (21.7 MHz, [D6]DMSO):
δ = –14.14 (NO2), –74.36 (N+) ppm. Found, m/z: 239.0414 [M+Н]+.
HRMS (ESI): m/z calcd. for C8H7N4O5. Calcd., m/z: 239.0411. Found
(%): C 40.21, H 2.41, N 23.39. C8H6N4O5. Calcd. (%): C 40.35, H 2.54, N
23.53.
3-(4-Methoxy-3-nitrophenyl)-1,2,3,4-oxatriazolium-5-(2,4-
dinitrophenyl)aminide (26). Yield 0.121 mg (75%), orange laminar
crystals, mp 192–194 ºC (EtOH–MeCN). IR: = 3093 (w), 1686 (s), 1591
(s), 1532 (s), 1335 (s), 1295 (m), 1136 (w), 978 (w), 826 (w), 715 (s) cm−1
1H NMR (300.1 MHz, [D6]DMSO): δ = 8.74 (s, 1H (N+-Ar)), 8.68 (s, 1H
(N−-Ar)), 8.47 (d, 1H (N+-Ar), J = 8.5 Hz), 8.43 (d, 1H (N−-Ar), J = 7.9 Hz),
7.96 (d, 1H (N−-Ar), J = 8.6 Hz), 7.73 (d, 1H (N+-Ar), J = 8.9 Hz), 4.11 (s,
3H, OCH3 (N+-Ar)) ppm. 13C NMR (75.5 MHz, [D6]DMSO): δ = 166.54 (C-
N−), 155.75 (COMe, (N+-Ar)), 144.97 (N−-Ar), 144.13 (N−-Ar), 140.72 (N−-
Ar), 139.17 (N+-Ar), 127.57 (CH, (N+-Ar)), 127.38 (CH (N−-Ar)), 125.52
(N+-Ar), 123.62 (CH (N−-Ar)), 119.64 (CH (N−-Ar)), 119.26 (CH (N+-Ar)),
116.25 (CH (N+-Ar)), 57.95 (OCH3) ppm. 14N NMR (21.7 MHz,
.
This article is protected by copyright. All rights reserved.