Journal of Agricultural and Food Chemistry
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(ppm): −124.59; HRMS (ESI): calcd. for C13H14FN5 [M + H]+
260.13060, found: 260.13011.
260 °C; H NMR (400 MHz, DMSO-d6) δ (ppm): 2.34 (s, 3H,
CH3), 2.42 (s, 3H, CH3), 7.01 (d, J = 8.9 Hz, 2H, Ar H), 7.80 (s, 2H,
NH2), 8.14 (d, J = 9.1 Hz, 2H, Ar H), 8.43 (s, 1H, CHN), 11.26 (s,
1H, NH); 13C NMR (100 MHz, DMSO-d6) δ (ppm): 21.79, 25.80,
104.58, 111.27 (2C), 126.78 (2C), 138.76, 141.25, 150.22, 160.10,
164.55, 165.86; HRMS (ESI): calcd. for C13H14N6O2 [M + H]+
287.12510, found: 287.12477.
2.6.12. (E)-2,6-dimethyl-5-((2-(o-tolyl)hydrazineylidene)methyl)-
pyrimidin-4-amine (5l). Yellow solid; yield 84%; m.p. 239−241 °C;
1H NMR (400 MHz, DMSO-d6) δ (ppm): 2.25 (s, 3H, CH3), 2.55 (s,
3H, CH3), 2.60 (s, 3H, CH3), 6.80 (t, J = 7.3 Hz, 1H, Ar H), 7.15 (dt,
J = 12.3, 7.6 Hz, 3H, Ar H), 8.59 (s, 1H, CHN), 9.39 (d, J = 117.6
Hz, 2H, NH2), 10.08 (s, 1H, NH); 13C NMR (100 MHz, DMSO-d6)
δ (ppm): 16.49, 18.11, 21.47, 106.54, 111.70, 120.41, 121.97, 127.41,
131.14, 133.82, 142.32, 153.47, 159.14, 160.69; HRMS (ESI): calcd.
for C14H17N5 [M + H]+ 256.15567, found: 256.15610.
2.6.13. (E)-2,6-dimethyl-5-((2-(m-tolyl)hydrazineylidene)methyl)-
pyrimidin-4-amine (5m). Yellow solid; yield 75%; m.p. 178−180 °C;
1H NMR (400 MHz, DMSO-d6) δ (ppm): 2.26 (s, 3H, CH3), 2.32 (s,
3H, CH3), 2.39 (s, 3H, CH3), 6.59 (d, J = 7.4 Hz, 1H, Ar H), 6.71 (s,
2H, Ar H), 7.12 (t, J = 8.0 Hz, 1H, Ar H), 7.82 (s, 2H, NH2), 8.26 (s,
1H, CHN), 10.29 (s, 1H, NH); 13C NMR (100 MHz, DMSO-d6)
δ (ppm): 21.73, 21.85, 25.75, 105.42, 109.32, 112.52, 120.25, 129.65,
135.76, 138.93, 145.24, 159.90, 162.72, 164.64; HRMS (ESI): calcd.
for C14H17N5 [M + H]+ 256.15567, found: 256.15577.
2.6.14. (E)-2,6-dimethyl-5-((2-(p-tolyl)hydrazineylidene)methyl)-
pyrimidin-4-amine (5n). Yellow solid; yield 64%; m.p. 245−247 °C;
1H NMR (400 MHz, DMSO-d6) δ (ppm): 2.21 (s, 3H, CH3), 2.32 (s,
3H, CH3), 2.38 (s, 3H, CH3), 6.81 (d, J = 8.2 Hz, 2H, Ar H), 7.05 (d,
J = 8.1 Hz, 2H, Ar H), 7.86 (s, 2H, NH2), 8.23 (s, 1H, CHN),
10.25 (s, 1H, NH); 13C NMR (100 MHz, DMSO-d6) δ (ppm): 20.64,
21.68, 25.68, 105.41, 111.95 (2C), 127.87, 130.14 (2C), 135.19,
142.95, 159.80, 162.46, 164.44; HRMS (ESI): calcd. for C14H17N5
[M + H]+ 256.15567, found: 256.15540.
2.6.15. (E)-5-((2-(4-methoxyphenyl)hydrazineylidene)methyl)-
2,6-dimethylpyrimidin-4-amine (5o). Yellow solid; yield 75%; m.p.
199−201 °C; 1H NMR (400 MHz, DMSO-d6) δ (ppm): 2.54 (s, 3H,
CH3), 2.57 (s, 3H, CH3), 3.70 (s, 3H, OCH3), 6.92 (q, J = 9.0 Hz,
4H, Ar H), 8.12 (s, 1H, CHN), 9.33 (d, J = 107.9 Hz, 2H, NH2),
10.76 (s, 1H, NH); 13C NMR (100 MHz, DMSO-d6) δ (ppm): 16.41,
21.38, 55.73, 106.72, 113.62 (2C), 115.29 (2C), 130.48, 138.30,
152.40, 153.82, 158.72, 160.58; HRMS (ESI): calcd. for C14H17N5O
[M + H]+ 272.15059, found: 272.15107.
2.6.16. (E)-5-((2-(2,4-difluorophenyl)hydrazineylidene)methyl)-
2,6-dimethylpyrimidin-4-amine (5p). White solid; yield 54%; m.p.
232−233 °C; 1H NMR (400 MHz, DMSO-d6) δ (ppm): 2.31 (s, 3H,
CH3), 2.36 (s, 3H, CH3), 6.95−7.04 (m, 1H, Ar H), 7.10−7.26 (m,
2H, Ar H), 7.73 (s, 2H, NH2), 8.54 (s, 1H, CHN), 10.08 (s, 1H,
NH); 13C NMR (100 MHz, DMSO-d6) δ (ppm): 26.55, 30.58,
109.11 (t, J = 24.6 Hz), 109.70, 116.52 (d, J = 21.0 Hz), 118.16 (d, J
= 4.7 Hz), 135.02 (d, J = 7.3 Hz), 143.70, 153.38 (dd, J = 241.8, 12.3
Hz), 159.56 (dd, J = 236.6, 11.1 Hz), 164.43, 167.93, 169.53; 19F
NMR (376 MHz, DMSO-d6) δ (ppm): −129.35, −123.70; HRMS
(ESI): calcd. for C13H13F2N5 [M + H]+ 278.12118, found: 278.12115.
2.6.17. (E)-5-((2-(2,4-dichlorophenyl)hydrazineylidene)methyl)-
2,6-dimethylpyrimidin-4-amine (5q). White solid; yield 86%; m.p.
251−253 °C; 1H NMR (400 MHz, DMSO-d6) δ (ppm): 2.33 (s, 3H,
CH3), 2.40 (s, 3H, CH3), 7.22 (d, J = 8.8 Hz, 1H, Ar H), 7.34 (dd, J =
8.8, 2.3 Hz, 1H, Ar H), 7.50 (d, J = 2.3 Hz, 1H, Ar H), 7.76 (s, 2H,
NH2), 8.79 (s, 1H, CHN), 9.98 (s, 1H, NH); 13C NMR (100
MHz, DMSO-d6) δ (ppm): 21.85, 25.81, 104.93, 114.30, 117.15,
122.63, 128.73, 129.29, 140.50, 141.21, 160.10, 164.30, 165.51;
HRMS (ESI): calcd. for C13H13Cl2N5 [M + H]+ 310.06208, found:
310.06156.
2.6.4. (E)-5-((2-(2-chlorophenyl)hydrazineylidene)methyl)-2,6-di-
methylpyrimidin-4-amine (5d). Yellow solid; yield 61%; m.p. 255−
1
257 °C; H NMR (400 MHz, DMSO-d6) δ (ppm): 2.38 (s, 3H,
CH3), 2.45 (s, 3H, CH3), 6.79−6.86 (m, 1H, Ar H), 7.22−7.31 (m,
2H, Ar H), 7.37 (dd, J = 7.9, 1.1 Hz, 1H, Ar H), 8.08 (s, 2H, NH2),
8.79 (s, 1H, CHN), 9.96 (s, 1H, NH); 13C NMR (100 MHz,
DMSO-d6) δ (ppm): 20.92, 25.06, 105.30, 113.39, 116.78, 120.31,
128.72, 130.07, 139.65, 141.19, 160.20, 162.34, 164.30; HRMS (ESI):
calcd. for C13H14ClN5 [M + H]+ 276.10105, found: 276.10117.
2.6.5. (E)-5-((2-(3-chlorophenyl)hydrazineylidene)methyl)-2,6-di-
methylpyrimidin-4-amine (5e). Yellow solid; yield 58%; m.p. 231−
1
233 °C; H NMR (400 MHz, DMSO-d6) δ (ppm): 2.36 (s, 3H,
CH3), 2.42 (s, 3H, CH3), 6.79 (dd, J = 7.8, 1.2 Hz, 1H, Ar H), 6.86
(dd, J = 8.3, 1.2 Hz, 1H, Ar H), 6.91 (t, J = 1.9 Hz, 1H, Ar H), 7.25 (t,
J = 8.0 Hz, 1H, Ar H), 7.97 (s, 2H, NH2), 8.30 (s, 1H, CHN),
10.65 (s, 1H, NH); 13C NMR (100 MHz, DMSO-d6) δ (ppm): 21.13,
25.26, 105.22, 110.84, 111.27, 118.82, 131.42, 134.42, 136.97, 146.55,
160.05, 162.16, 164.36; HRMS (ESI): calcd. for C13H14ClN5 [M +
H]+ 276.10105, found: 276.10067.
2.6.6. (E)-5-((2-(4-chlorophenyl)hydrazineylidene)methyl)-2,6-di-
methylpyrimidin-4-amine (5f). Yellow solid; yield 86%; m.p. 235−
1
236 °C; H NMR (400 MHz, DMSO-d6) δ (ppm): 2.34 (s, 3H,
CH3), 2.40 (s, 3H, CH3), 6.89 (d, J = 8.5 Hz, 2H, Ar H), 7.25 (d, J =
8.6 Hz, 2H, Ar H), 7.92 (s, 2H, NH2), 8.23 (s, 1H, CHN), 10.48
(s, 1H, NH); 13C NMR (100 MHz, DMSO-d6) δ (ppm): 25.94,
30.04, 109.94, 118.04 (2C), 127.17, 134.09 (2C), 140.79, 148.50,
164.44, 166.26, 168.55; HRMS (ESI): calcd. for C13H14ClN5 [M +
H]+ 276.10105, found: 276.10153.
2.6.7. (E)-5-((2-(2-bromophenyl)hydrazineylidene)methyl)-2,6-
dimethylpyrimidin-4-amine (5g). Yellow solid; yield 63%; m.p.
231−233 °C; 1H NMR (400 MHz, DMSO-d6) δ (ppm): 2.32 (s, 3H,
CH3), 2.40 (s, 3H, CH3), 6.73 (td, J = 7.6, 1.5 Hz, 1H, Ar H), 7.17
(dd, J = 8.1, 1.3 Hz, 1H, Ar H), 7.29 (t, J = 7.7 Hz, 1H, Ar H), 7.49
(dd, J = 7.9, 1.3 Hz, 1H, Ar H), 7.78 (s, 2H, NH2), 8.77 (s, 1H, CH
N), 9.63 (s, 1H, NH); 13C NMR (100 MHz, DMSO-d6) δ (ppm):
26.71, 30.63, 109.73, 111.15, 118.27, 125.33, 133.76, 137.79, 144.97,
146.86, 164.53, 168.48, 169.72; HRMS (ESI): calcd. for C13H14BrN5
[M + H]+ 320.05053, found: 320.05048.
2.6.8. (E)-5-((2-(3-bromophenyl)hydrazineylidene)methyl)-2,6-
dimethylpyrimidin-4-amine (5h). Yellow solid; yield 71%; m.p.
249−250 °C; 1H NMR (400 MHz, DMSO-d6) δ (ppm): 2.40 (s, 3H,
CH3), 2.46 (s, 3H, CH3), 6.94 (t, J = 8.4 Hz, 2H, Ar H), 7.07 (s, 1H,
Ar H), 7.20 (t, J = 8.0 Hz, 1H, Ar H), 8.26 (s, 1H, CHN), 8.36 (s,
2H, NH2), 10.77 (s, 1H, NH); 13C NMR (100 MHz, DMSO-d6) δ
(ppm): 21.76, 25.76, 105.04, 111.08, 114.01, 121.54, 123.00, 131.68,
137.45, 146.70, 159.92, 163.34, 165.05; HRMS (ESI): calcd. for
C13H14BrN5 [M + H]+ 320.05053, found: 320.04983.
2.6.9. (E)-5-((2-(4-bromophenyl)hydrazineylidene)methyl)-2,6-
dimethylpyrimidin-4-amine (5i). Yellow solid; yield 78%; m.p.
1
244−246 °C; H NMR (400 MHz, DMSO-d6) δ (ppm): 2.31 (s,
3H, CH3), 2.38 (s, 3H, CH3), 6.84 (d, J = 8.8 Hz, 2H, Ar H), 7.36 (d,
J = 8.8 Hz, 2H, Ar H), 7.74 (s, 2H, NH2), 8.24 (s, 1H, CHN),
10.43 (s, 1H, NH); 13C NMR (100 MHz, DMSO-d6) δ (ppm): 26.54,
30.52, 109.70, 114.55, 118.40 (2C), 136.85 (2C), 141.34, 148.86,
164.27, 167.49, 169.26; HRMS (ESI): calcd. for C13H14BrN5 [M +
H]+ 320.05053, found: 320.05022.
2.6.10. (E)-2,6-dimethyl-5-((2-(4-(trifluoromethyl)phenyl)-
hydrazineylidene)methyl)pyrimidin -4-amine (5j). Yellow solid;
yield 82%; m.p. > 260 °C; 1H NMR (400 MHz, DMSO-d6) δ
(ppm): 2.32 (s, 3H, CH3), 2.40 (s, 3H, CH3), 7.01 (d, J = 8.5 Hz, 2H,
Ar H), 7.54 (d, J = 8.6 Hz, 2H, Ar H), 7.78 (s, 2H, NH2), 8.32 (s, 1H,
CHN), 10.74 (s, 1H, NH); 13C NMR (100 MHz, DMSO-d6) δ
(ppm): 21.75, 25.74, 104.94, 111.63 (2C), 118.91 (q, J = 32.1 Hz),
125.43 (q, J = 270.4 Hz), 127.12 (d, J = 3.7 Hz, 2C), 138.44, 148.04,
160.01, 163.67, 165.27; 19F NMR (376 MHz, DMSO-d6) δ (ppm):
−59.27; HRMS (ESI): calcd. for C14H14F3N5 [M + H]+ 310.12741,
found: 310.12701.
2.7. Crystallographic Study. A colorless single crystal of 5i
suitable for X-ray analysis was crystallized from methanol at room
temperature. Unit cell determination and data collection were
performed using Mo Kα radiation (λ = 0.71073 Å) on a Bruker
AEPEX DUO CCD diffractometer in π−ω scan mode at 296(2) K.
The structure was solved directly using the SHELXS program of the
2.6.11. (E)-2,6-dimethyl-5-((2-(4-nitrophenyl)hydrazineylidene)-
methyl)pyrimidin-4-amine (5k). Brown solid; yield 65%; m.p. >
5807
J. Agric. Food Chem. 2021, 69, 5804−5817