576
D. Geffken – M. A. Ko¨llner · 3,6-Diaminosubstituierte 1,2,4-Triazin-5(2H)-one
CH2CH3), 2.89 (q, 2 H, J = 7.12 Hz, CH2CH3), 4.58 (d, Ethyl-6-amino-3-benzylamino-5-oxo-1,2,4-triazin-2(5H)-
2 H, J = 5.85 Hz, CH2NH), 6.41 (s, 2 H, NH2), 7.16 – 7.39 carboxylat (6f)
(m, 4 H, Ar-H), 9.68 (t, 1 H, J = 5.85 Hz, CH2NH). – 13C-
Ausb.: 57 %. – Schmp. 170 ◦C. – IR (KBr): ν =
NMR (100.61 MHz, [D6]DMSO): δ = 8.3 (CH2CH3), 28.8
2
3408, 3318 (NH), 1727, 1638 cm−1 (C=O). – 1H-NMR
(400.14 MHz, [D6]DMSO): δ = 1.31 (t, 3 H, J = 7.12 Hz,
CH2CH3), 4.35 (q, 2 H, J = 7.12 Hz, CH2CH3), 4.61 (d,
2 H, J = 5.85 Hz, CH2NH), 6.42 (s, 2 H, NH2), 7.24 – 7.35
(m, 5 H, Ar-H), 9.13 (t, 1 H, J = 5.85 Hz, CH2NH). –
13C-NMR (100.61 MHz, [D6]DMSO): δ = 14.0 (CH2CH3),
44.0 (CH2NH), 64.3 (CH2CH3), 127.0, 127.2, 128.3 (Ar-C,
tert.), 138.3 (Ar-C, quart.), 145.7 (C-6), 153.00, 153.4 (C-5
und CO2C2H5), 157.5 (C-3). – C13H15N5O3 (289.30): ber.
C 53.97, H 5.23, N 24.21; gef. C 53.72, H 5.40, N 24.12.
(CH2CH3), 43.0 (CH2NH), 115.0 (d, JC−F = 21.28 Hz,
3
Ar-C, tert.), 129.4 (d, JC−F = 8.07 Hz, Ar-C, tert.), 134.4
4
(d, JC−F = 3.67 Hz, Ar-C, quart.), 144.9 (C-6), 153.2
(C-5), 157.3 (C-3), 161.2 (d, 1JC−F = 242.83 Hz, CF), 178.4
(COCH2). – C13H14FN5O2 (291.29): ber. C 53.61, H 4.84,
N 24.04; gef. C 53.43, H 4.98, N 23.87.
Methyl-6-amino-3-(4-fluorbenzylamino)-5-oxo-1,2,4-tri-
azin-2(5H)-carboxylat Hydrat (6c)
Ausb.: 51 %. – Schmp. 168 ◦C. – IR (KBr): ν =
3411, 3321 (NH), 1734, 1673 cm−1 (C=O). – 1H-NMR
(400.14 MHz, [D6]DMSO): δ = 3.88 (s, 3 H, CH3), 4.58
(d, 2 H, J = 5.85 Hz, CH2NH), 6.43 (s, 2 H, NH2), 7.15 –
7.39 (m, 4 H, Ar-H), 9.12 (t, 1 H, J = 5.85 Hz, CH2NH). –
13C-NMR (100.61 MHz, [D6]DMSO): δ = 43.2 (CH2NH),
Benzyl-6-amino-3-benzylamino-5-oxo-1,2,4-triazin-2(5H)-
carboxylat (6g)
Ausb.: 62 %. – Schmp. 148 ◦C. – IR (KBr): ν =
3420, 3318 (NH), 1723, 1668 cm−1 (C=O). – 1H-NMR
(400.14 MHz, [D6]DMSO): δ = 4.62 (d, 2 H, J = 5.85 Hz,
CH2NH), 5.36 (s, 2 H, OCH2Ph), 6.42 (s, 2 H, NH2),
7.24 – 7.48 (m, 10 H, Ar-H), 9.13 (t, 1 H, J = 5.85 Hz,
CH2NH). – 13C-NMR (100.61 MHz, [D6]DMSO): δ =
44.0 (CH2NH), 69.3 (OCH2Ph), 127.0, 127.3, 128.3, 128.5,
128.6, 128.6 (Ar-C, tert.), 134.8 (CCH2O), 138.3 (CCH2N),
145.8 (C-6), 153.0, 153.4 (C-5 und CO2CH2), 157.4 (C-3). –
C18H17N5O3 (351.37): ber. C 61.53, H 4.88, N 19.93; gef.
C 61.52, H 5.06, N 19.81.
2
54.7 (OCH3), 114.9 (d, JC−F = 21.28 Hz, Ar-C, tert.),
3
4
129.3 (d, JC−F = 8.07 Hz, Ar-C, tert.), 134.5 (d, JC−F
=
2.93 Hz, Ar-C, quart.), 145.7 (C-6), 153.2, 153.4 (C-5
1
und CO2CH3), 157.4 (C-3), 161.2 (d, JC−F = 242.09 Hz,
CF). – C12H12FN5O3 · H2O (311.27): ber. C 46.30, H 4.52,
N 22.50; gef. C 46.76, H 4.23, N 22.65.
2-Acetyl-6-amino-3-(4-chlorbenzylamino)-1,2,4-triazin-
5(2H)-on (6d)
Ausb.: 72 %. – Schmp. 280 ◦C. – IR (KBr): ν =
3467, 3343 (NH), 1712, 1670 cm−1 (C=O). – 1H-NMR
(400.14 MHz, [D6]DMSO): δ = 2.46 (s, 3 H, CH3), 4.60
(d, 2 H, J = 6.02 Hz, CH2NH), 6.42 (s, 2 H, NH2), 7.37 –
7.40 (m, 4 H, Ar-H), 9.64 (t, 1 H, J = 6.02 Hz, CH2NH). –
13C-NMR (100.61 MHz, [D6]DMSO): δ = 24.9 (CH3), 43.5
(CH2NH), 128.6, 129.5 (Ar-C, tert.), 131.9 (CCl), 137.9
(Ar-C, quart.), 145.5 (C-6), 153.7 (C-5), 157.8 (C-3), 176.0
(COCH3). – C12H12ClN5O2 (293.71): ber. C 49.07, H 4.12,
N 23.84; gef. C 48.92, H 4.38, N 23.55.
2-Acetyl-6-amino-3-phenylamino-1,2,4-triazin-5(2H)-on
(6h)
Der Reaktionsansatz wird filtriert, das Lo¨semittel i. Vak.
eingedampft und der Ru¨ckstand aus Tetrahydrofuran um-
◦
kristallisiert. Ausb.: 85 %. – Schmp. > 300 C. – IR (KBr):
ν = 3466, 3347 (NH), 1720, 1659 cm−1 (C=O). – 1H-NMR
(400.14 MHz, [D6]DMSO): δ = 2.52 (s, 3 H, CH3), 6.57
(s, 2 H, NH2), 7.18 – 7.58 (m, 5 H, Ar-H), 11.10 (s, 1 H,
ArNH). – 13C-NMR (100.61 MHz, [D6]DMSO): δ = 24.6
(CH3), 123.1, 125.1, 128.8 (Ar-C, tert.), 136.4 (Ar-C- quart.),
145.4 (C-6), 151.5 (C-5), 157.2 (C-3), 176.3 (COCH3). –
C11H11N5O3 (245.24): ber. C 53.87, H 4.52, N 28.56; gef.
C 53.77, H 4.93, N 28.88.
Benzyl-6-amino-3-(4-chlorbenzylamino)-5-oxo-1,2,4-tri-
azin-2(5H)-carboxylat (6e)
Ausb.: 55 %. – Schmp. 174 ◦C. – IR (KBr): ν =
3510, 3396 (NH), 1722, 1708 cm−1 (C=O). – 1H-NMR
(400.14 MHz, [D6]DMSO): δ = 4.60 (d, 2 H, J = 6.10 Hz,
CH2NH), 5.36 (s, 2 H, OCH2Ph), 6.43 (s, 2 H, NH2), 7.38 –
7.48 (m, 9 H, Ar-H), 9.18 (t, 1 H, J = 6.10 Hz, CH2NH). –
13C-NMR (100.61 MHz, [D6]DMSO): δ = 43.4 (CH2NH),
Ethyl-6-amino-3-(naphthalen-1-ylamino)-5-oxo-1,2,4-tri-
azin-2(5H)-carboxylat (6i)
Das ausgefallene Reaktionsprodukt wird abgetrennt, mit
69.3 (OCH2Ph), 128.2, 128.5, 128.6, 128.6, 129.1 (Ar-C, Pyridin (2×2 mL) gewaschen und anschließend getrocknet.
◦
tert.), 131.5 (CCl), 134.8 (CCH2O), 137.5 (CCH2N), 145.8 Ausb.: 75 %. – Schmp. 178 C. – IR (KBr): ν = 3417, 3314
(C-6), 152.9, 153.4 (C-5 und CO2CH2), 157.4 (C-3). – (NH), 1718, 1667 cm−1 (C=O). – 1H-NMR (400.14 MHz,
C18H16ClN5O3 (385.81): ber. C 56.04, H 4.18, N 18.15; gef. [D6]DMSO): δ = 1.38 (t, 3 H, J = 7.08 Hz, CH2CH3),
C 56.02, H 4.50, N 18.04.
4.47 (q, 2 H, J = 7.08 Hz, CH2CH3), 6.52 (s, 2 H, NH2),
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Download Date | 9/19/15 8:34 PM