On leave from Rostov State University, Russia.
8a All melting points were determined on a Büchi apparatus and are uncorrected. The 1H and 13C NMR spectra were recorded on a Bruker Avance 400 spectrometer in the solvent indicated with TMS as an internal standard. All coupling constants are given in Hz and chemical shifts are given in ppm. 1,3,5-Triazine (Fluka) and the alkylamines (Acros and Aldrich) were obtained from commercial sources and were used as such. AgPy2MnO4 can be easily prepared from relatively cheap AgNO3 [Aldrich catalogue: AgNO3 (³99%) (25 g, 58.5 Euro)], pyridine and KMnO4.
[8b]
Flash column chromatography was performed on Kieselgel 60 (ROCC, 0.040-0.063 mm).
2-Amino and 2-Alkylamino-1,3,5-triazines 4; General Procedure: To a stirred mixture of alkylamine (5 mL) and ethanol (5 mL) at -11 °C to -5 °C 1,3,5-triazine (1; 0.081 g, 1 mmol) was added. After dissolving of 1, AgPy2MnO4 (0.578 g, 1.5 mmol) was added in small portions over 40 min. Subsequently, alkylamine and ethanol were removed under reduced pressure. The residue was grinded with silica gel (3-4 g), brought onto a column with silica gel (3.5 × 25 cm) and chromatographed using CH2Cl2-MeOH (50:1) as the eluent, yielding 2-alkylamino-1,3,5-triazines 4. For the amination and methylamination a 7 N NH3 solution in MeOH (or 2 N NH3 in EtOH; 10 mL) and a 2 N methylamine solution in MeOH (15 mL) were used, respectively.
2-Amino-1,3,5-triazine (
4a): white solid; mp >206 °C (sublimation) (Lit.
[3a]
226 °C). 1H NMR (400 MHz, CDCl3): δ = 8.60 (s, 2 H, H-4, H-6), 5.34 (br s, 2 H, NH2). 1H NMR (400 MHz, DMSO-d
6): δ = 8.45 (s, 2 H, H-4, H-6), 7.52 (br s, 2 H, NH2). 13C NMR (100 MHz, CDCl3): δ = 165.9, 165.7. HRMS (ESI): m/z [M + H]+ calcd for C3H5N4: 97.0514; found: 97.0511.
2-Methylamino-1,3,5-triazine (
4b): white solid; mp 109-110 °C (Lit.
[3a]
109-110 °C). 1H NMR (400 MHz, CDCl3): δ = 8.61 (s, 1 H, H-4 or H-6), 8.48 (s, 1 H, H-6 or H-4), 5.65 (br s, 1 H, NH2), 3.04 (d, J = 5.1 Hz, 3 H, CH3). 13C NMR (100 MHz, CDCl3): δ = 166.3, 165.5, 165.1. HRMS (ESI): m/z [M + H]+ calcd for C4H7N4: 111.0671; found: 111.0667.
2-Isopropylamino-1,3,5-triazine (
4c): white solid; mp 73-74 °C. 1H NMR (400 MHz, CDCl3): δ = 8.57 (s, 1 H, H-4 or H-6), 8.47 (s, 1 H, H-6 or H-4), 5.51 (br s, 1 H, NH), 4.20 [m, 1 H, CH(CH3)2], 1.26 [d, J = 6.5 Hz, 6 H, CH(CH
3)2]. 13C NMR (100 MHz, CDCl3): δ = 166.3, 165.6, 163.8, 42.8, 22.5. HRMS (ESI): m/z [M + H]+ calcd for C6H11N4: 139.0984; found: 139.0990.
2-Butylamino-1,3,5-triazine (
4d): white solid; mp 61-63 °C (Lit.
[3a]
61-62 °C). 1H NMR (400 MHz, CDCl3): δ = 8.58 (s, 1 H, H-4 or H-6), 8.46 (s, 1 H, H-6 orH-4), 6.29 (br s, 1 H, NH), 3.44 (dt, J = 5.9, 7.1 Hz, 2 H, CH
2CH2CH2CH3), 1.60 (m, 2 H, CH2CH
2CH2CH3), 1.41 (m, 2 H, CH2CH2CH
2CH3), 0.95 (t, J = 7.3 Hz, 3 H, CH2CH2CH2CH
3). 1H NMR (400 MHz, DMSO-d
6): δ = 8.56 (d, J = 1.3 Hz, 1 H, H-4 or H-6), 8.47 (d, J = 1.3 Hz, 1 H, H-6 or H-4), 8.11 (br s, 1 H, NH), 3.33 (dt, J = 6.0, 7.1 Hz, 2 H, CH
2CH2CH2CH3), 1.55 (m, 2 H, CH2CH
2CH2CH3), 1.36 (m, 2 H, CH2CH2CH
2CH3), 0.94 (t, J = 7.3 Hz, 3 H, CH2CH2CH2CH
3). 13C NMR (100 MHz, CDCl3): δ = 166.3, 165.5, 164.6, 40.7, 31.3, 20.0, 13.7. HRMS (ESI): m/z [M + H]+ calcd for C7H13N4: 153.1140; found: 153.1140.
2-Amylamino-1,3,5-triazine (
4e): white solid; mp 47-49 °C. 1H NMR (400 MHz, CDCl3): δ = 8.58 (s, 1 H, H-4 or H-6), 8.48 (s, 1 H, H-6 or H-4), 6.25 (br s, 1 H, NH), 3.44 (dt, J = 5.9, 7.1 Hz, 2 H, CH
2CH2CH2CH2CH3), 1.62 (m, 2 H, CH2CH
2CH2CH2CH3), 1.36 (m, 4 H, CH2CH2CH
2CH
2CH3), 0.91 (t, J = 7.1 Hz, 3 H, CH2CH2CH2CH2CH
3). 13C NMR (100 MHz, CDCl3): δ = 166.3, 165.5, 164.6, 41.0, 29.0, 28.9, 22.4, 14.0. HRMS (ESI): m/z [M + H]+ calcd for C8H15N4: 167.1297; found: 167.1303.
2-(Piperidin-1-yl)-1,3,5-triazine (
4f): white solid; mp 43-44 °C (Lit.
[3a]
43-44 °C). 1H NMR (400 MHz, CDCl3): δ = 8.49 (s, 2 H, H-4, H-6), 3.81 (m, 4 H, α-CH2 of piperidinyl), 1.70 (m, 6 H, β-CH2 and γ-CH2 of piperidinyl). 13C NMR (100 MHz, CDCl3): δ = 165.6, 162.7, 44.3, 25.7, 24.6. HRMS (ESI): m/z [M + H]+ calcd for C8H13N4: 165.1140; found: 165.1134.
2-(Morpholin-1-yl)-1,3,5-triazine (
4g): white solid; mp 108-110 °C (Lit.
[3c]
106-108 °C). 1H NMR (400 MHz, CDCl3): δ = 8.54 (s, 2 H, H-4, H-6), 3.87 [m, 4 H, O(CH2)2], 3.75 [m, 4 H, N(CH2)2]. 13C NMR (100 MHz, CDCl3): δ = 165.7, 163.2, 66.6, 43.5. HRMS (ESI): m/z [M + H]+ calcd for C7H11N4O: 167.0933; found: 167.0931.