10.1002/cmdc.201800567
ChemMedChem
FULL PAPER
4-(2-Chlorophenyl)-N-(3,4,5-trimethoxyphenyl)sydnone (8). N-(3,4,5-
Trimethoxyphenyl)sydnone (101 mg, 0.399 mmol) and 1,2-
dichlorobenzene (88 mg, 0.60 mmol) were subjected to the general
conditions affording 8 as a colourless solid (105 mg, 73%). M.p.: 135-
136 °C; 1H NMR (400 MHz, CDCl3) δ 3.67 (6H, s), 3.85 (3H, s), 6.59 (2H,
s), 7.29-7.45 (4H, m); 13C NMR (101 MHz, CDCl3) δ 56.4, 61.2, 101.2,
105.7, 124.3, 127.6, 129.9, 130.3, 131.7, 132.9, 135.7, 140.6, 153.7,
167.0; FTIR: νmax 3058 (w), 2943 (w), 1757 (s), 1608 (m), 1234 (m), 1130
(s), 1049 (w), 988 (m); HRMS calculated for C17H16[35]ClN2O5 (ES+)(+H+):
363.0748. Found: 363.0736.
(101 MHz, CDCl3): δ 56.0, 56.1, 61.1, 104.2, 107.9, 115.3, 120.0, 126.6,
127.5, 138.5, 153.4, 162.3, 167.1. FTIR: νmax 3116 (w), 3091 (w), 2944
(w), 2841 (w), 1729 (s), 1578 (s), 1125 (s), 991 (m); HRMS calculated for
C18H19N2O6 (ES+)(+H+): 359.1243. Found: 359.1239.
3,4-Bis(4-methoxyphenyl)sydnone
(14).[30]
N-(4-
Methoxyphenyl)sydnone (1.00 g, 5.21 mmol) and 4-chloroanisole (0.99 g,
7.8 mmol) were subjected to the general conditions affording 14 as a tan
solid (1.51 g, 97%). M.p.: 136-137 °C (dec.) (Lit.[30] 136–137 °C); 1H NMR
(400 MHz, CDCl3) δ 3.78 (3H, s), 3.89 (3H, s), 6.79 – 6.86 (2H, m), 6.98
– 7.06 (2H, m), 7.20– 7.26 (2H, m), 7.35 – 7.43 (2H, m); 13C NMR (101
MHz, CDCl3) δ 55.4, 55.9, 108.0, 114.4, 115.2, 117.0, 126.3, 127.4,
129.0, 159.8, 162.1, 167.4.
4-(3-Amino-4-methoxyphenyl)-N-(3,4,5-trimethoxyphenyl)sydnone
(9). N-(3,4,5-Trimethoxyphenyl)sydnone (100 mg, 0.396 mmol) and 5-
bromo-2-methoxyaniline (120 mg, 0.595 mmol) were subjected to the
general conditions affording 9 as an orange solid (135 mg, 91%). M.p.:
173-174 °C; 1H NMR (400 MHz, CDCl3) δ 3.77 (6H, s), 3.80 (3H, s), 3.83
(2H, s), 3.90 (3H, s), 6.52 (1H, dd, J = 8.5, 2.0 Hz), 6.64 (1H, d, J = 8.5
Hz), 6.68 (2H, s), 6.85 (1H, d, J = 2.0 Hz); 13C NMR (101 MHz, CDCl3) δ
55.6, 56.6, 61.2, 102.5, 108.4, 110.2, 113.4, 117.1, 118.1, 130.1, 136.6,
140.5, 147.7, 154.0, 167.2; FTIR: νmax 3471 (w), 3367 (w), 2941 (w),
2838 (w), 1732 (s), 1606 (m), 1224 (s), 1127 (s); HRMS calculated for
C18H20N3O6 (ES+)(+H+): 374.1352. Found: 374.1353.
4-Phenyl-N-(4-methoxyphenyl)sydnone
(15).[30]
N-(4-
Methoxyphenyl)sydnone (105 mg, 0.547 mmol) and chlorobenzene (92
mg, 0.82 mmol) were subjected to the general conditions affording 14 as
a pink solid (122 mg, 83%). M.p.: 106-107 °C (dec) (Lit.[30] 106-
1H NMR (400 MHz, CDCl3) δ 3.89 (3H, s), 7.02 (2H, d, J = 9.0 Hz), 7.30
(5H, s), 7.39 (2H, d, J = 9.0 Hz); 13C NMR (101 MHz, CDCl3) δ 55.9,
107.8, 115.3, 124.8, 126.3, 127.4, 127.5, 128.7, 128.9, 162.2, 167.3.
4-(Thiophen-2-yl)-N-(4-methoxyphenyl)sydnone
Methoxyphenyl)sydnone (101 mg, 0.526 mmol) and 2-chlorothiophene
(16).[30]
N-(4-
4-(3-Hydroxy-4-methoxyphenyl)-N-(3,4,5-trimethoxyphenyl)sydnone
(10). N-(3,4,5-Trimethoxyphenyl)sydnone (500 mg, 1.98 mmol) and 5-
bromo-2-methoxyphenol (604 mg, 2.97 mmol) were subjected to the
general conditions. Flash silica chromatography (eluting solvent 10%-
30% ethyl acetate in dichloromethane) afforded 10 as a yellow solid (599
mg, 81%). M.p.: 237-239 °C (dec.); 1H NMR (400 MHz, DMSO): δ 3.73
(9H, s), 3.76 (3H, s), 6.71 (1H, dd, J = 8.5, 2.0 Hz), 6.88 (1H, d, J = 2.0
Hz), 6.91 (1H, d, J = 8.5 Hz), 7.13 (2H, s), 9.28 (1H,s); 13C NMR (101
MHz, DMSO): δ 55.5, 56.5, 60.4, 103.9, 108.1, 112.0, 114.1, 117.0,
118.5, 129.9, 139.8, 146.3, 148.1, 153.5, 166.2; FTIR: νmax 3415 (br),
3062 (w), 2947 (w), 1718 (s), 1605 (m), 1243 (s), 1125 (s), 1014 (s), 949
(m); HRMS calculated for C18H19N2O7 (ES+)(+H+): 375.1192. Found:
375.1192.
(93 mg, 0.78 mmol) were subjected to the general conditions affording 16
as orange crystals (128 mg, 89%). M.p.: 129 °C (Lit.[30]
1H NMR
(400 MHz, CDCl3) δ 3.93 (3H, s), 6.98 (1H, dt, J = 5.0, 4.0 Hz), 7.11 (2H,
d, J = 9.0 Hz), 7.23 (1H, dd, J = 5.0, 1.0 Hz), 7.33 (1H, dd, J = 4.0, 1.0
Hz), 7.46 (2H, d, J = 9.0 Hz); 13C NMR (101 MHz, CDCl3) δ 57.0, 106.6,
115.4, 125.8, 126.1, 126.2, 126.4, 127.3, 127.5, 162.8, 165.9; FTIR: νmax
3080 (w), 2941 (w), 2840 (w), 1756 (s), 1735 (s), 1176 (m), 1017 (s), 991
(m); HRMS calculated for C13H10N2O3S (TOF ES+)(+H+): 275.0490.
Found: 275.0503.
4-(2-Chlorophenyl)-N-(4-methoxyphenyl)sydnone
(17).[30]
N-(4-
Methoxyphenyl)sydnone (102 mg, 0.531 mmol) and 1,2-dichlorobenzene
(117 mg, 0.796 mmol) were subjected to the general conditions affording
17 as an orange oil (151 mg, 94%). 1H NMR (400 MHz, CDCl3) δ 3.82
(3H, s), 6.91 (2H, d, J = 9.0 Hz), 7.27-7.40 (6H, m); 13C NMR (101 MHz,
CDCl3) δ 55.8, 105.8, 115.0, 120.4, 124.0, 125.2, 127.5, 130.4, 131.5,
133.0, 135.4, 162.0, 167.2; FTIR: νmax 3066 (w), 2936 (w), 2843 (w),
1757 (s), 1743 (s), 1028 (m), 1002 (m); HRMS calculated for
C15H12N2O335Cl (TOF ES+)(+H+): 303.0536. Found: 303.0524.
4-(3,4,5-Trimethoxyphenyl)-N-(3-hydroxy-4-
methoxyphenyl)sydnone
(11).[36]
N-(3-Hydroxy-4-
methoxyphenyl)sydnone (473 mg, 2.27 mmol) and 5-bromo-1,2,3-
trimethoxybenzene (842 mg, 3.41 mmol) were subjected to the general
conditions affording 11 as a colourless solid (402 mg, 47%). M.p.: 196-
197 °C (Lit.[36] 196–197 °C); 1H NMR (400 MHz, CDCl3) δ 3.67 (6H, s),
3.83 (3H, s), 4.00 (3H, s), 5.94 (1H, s), 6.59 (2H, s), 6.92-7.05 (2H, m),
7.09 (1H, s); 13C NMR (101 MHz, CDCl3) δ 56.1, 56.5, 61.0, 104.7, 108.0,
111.0, 111.7, 117.2, 119.9, 127.8, 138.5, 147.0, 149.5, 153.3, 167.2;
FTIR: νmax 3295 (br), 3082 (w), 2940 (w), 2836 (w), 1710 (s), 1600 (w),
1581 (m), 1509 (s), 1229 (s), 1125 (s) 1014 (m), 998 (m); HRMS
calculated for C18H19N2O7 (ES+)(+H+): 375.1192. Found: 375.1181.
4-(3-Nitrophenyl)-N-(4-methoxyphenyl)sydnone
(18).[30]
N-(4-
Methoxyphenyl)sydnone (104 mg, 0.542 mmol) and 1-chloro-3-
nitrobenzene (128 mg, 0.812 mmol) were subjected to the general
conditions affording 18 as a yellow solid (144 mg, 85%). M.p.: 152-
153 °C (dec.) (Lit.[30] 152-
1H NMR (400 MHz, CDCl3) δ 3.92 (3H,
s), 7.09 (2H, d, J = 9.0 Hz), 7.43 (2H, d, J = 9.0 Hz), 7.50 (1H, t, J = 8.0
Hz), 7.75 (1H, d, J = 8.0 Hz), 8.02-8.12 (2H, m); 13C NMR (101 MHz, d6-
DMSO) δ 56.9, 106.5, 115.4, 121.2, 122.8, 126.5, 126.6, 127.1, 130.2,
132.8, 147.6, 161.9, 166.2.
4-(3,4,5-Trimethoxyphenyl)-N-(4-ethoxyphenyl)sydnone (12). N-(4-
Ethoxyphenyl)sydnone (102 mg, 0.494 mmol) and 5-bromo-1,2,3-
trimethoxybenzene (149 mg, 0.741 mmol) were subjected to the general
conditions affording 12 as colourless crystals (140 mg, 76%). M.p.: 129-
130 °C (dec.); 1H NMR (400 MHz, CDCl3) δ 1.45 (3H, t, J = 7.0 Hz), 3.63
(6H, s), 3.80 (3H, s), 4.09 (2H, q, J = 7.0 Hz), 6.54 (2H, s), 6.98-7.08 (2H,
m), 7.37-7.45 (2H, m); 13C NMR (101 MHz, CDCl3) δ 14.7, 56.0, 60.8,
64.4, 104.6, 107.8, 115.7, 120.0, 126.2, 127.1, 138.4, 153.3, 161.6,
166.8; FTIR: νmax 2984 (w), 2937 (w), 2834 (w), 1743 (s), 1583 (m), 1250
(m), 1126 (s), 1046 (w), 1002 (w); HRMS calculated for C19H21N2O6
(ES+)(+H+): 373.1400. Found: 373.1411.
4-(4-Tolyl)-N-(4-ethoxyphenyl)sydnone
(19).[30]
N-(4-
Ethoxyphenyl)sydnone (127 mg, 0.616 mmol) and 4-chlorotoluene (117
mg, 0.924 mmol) were subjected to the general conditions affording 19
as a tan solid (140 mg, 77%). M.p.: 123-124 °C (dec.) (Lit.[30] 123-124
1H NMR (400 MHz, CDCl3) δ 1.45 (3H, t, J = 7.0 Hz), 2.29 (3H, s,),
4.09 (2H, q, J = 7.0 Hz), 6.94-7.02 (2H, m), 7.08 (2H, d, J = 8.0 Hz), 7.18
(2H, d, J = 8.0 Hz), 7.30-7.39 (2H, m); 13C NMR (101 MHz, CDCl3) δ 14.7,
21.4, 64.3, 108.0, 115.6, 121.9, 126.2, 127.2, 127.3 129.5, 138.8, 161.5,
167.3; FTIR: νmax 2981 (w), 2934 (w), 1737 (s), 1115 (m), 1041 (m), 1002
(m); HRMS calculated for C17H16N2O3 (TOF ES+)(+H+): 297.1239. Found:
297.1249.
4-(3,4,5-Trimethoxyphenyl)-N-(4-methoxyphenyl)sydnone (13). N-(4-
Methoxyphenyl)sydnone (100 mg, 0.521 mmol) and 5-bromo-1,2,3-
trimethoxybenzene (193 mg, 0.781 mmol) were subjected to the general
conditions affording 13 as an yellow solid (132 mg, 71%). M.p.: 155-
157 °C (dec.); 1H NMR (400 MHz, CDCl3): δ 3.65 (6H, s), 3.82 (3H, s),
3.89 (3H, s), 6.55 (2H, s), 7.03-7.10 (2H, m), 7.41-7.47 (2H, m). 13C NMR
4-(4-Tolyl)-N-phenylsydnone (20).[30] N-Phenylsydnone (102 mg, 0.629
mmol) and 4-chlorotoluene (119 mg, 0.940 mmol) were subjected to the
7
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