N4-substited pyrazolyl [4,5-e][1,2,4] thiadiazine derivative and its preparation process and medicine composition
A technology of thiadiazine and derivatives, applied in the field of derivative drugs
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Embodiment 1
[0039] Example 1. Preparation of intermediate 7-methyl-1,1,3-trioxy-2,4-dihydropyrazol[4,5-e][1,2,4]thiadiazine (4)
[0040] Add 5.1g (22mmol) of 1-methyl-5-sulfonamido-4-pyrazolecarboxylic acid ethyl ester (1), 3.8g (66mmol) of 85% hydrazine hydrate and 25ml of ethanol in a 100ml flask, heat and stir to reflux for 10h , the solvent and unreacted hydrazine hydrate were distilled off under reduced pressure, and the residual oil was recrystallized from absolute ethanol to obtain a white solid (2). Dissolve 2.19g (10mmol) (2) in 50ml 2N HCl, slowly add 2ml of NaNO 2 (0.85g, 12mmol) aqueous solution, the temperature was kept below 10°C, the mixture was stirred at this temperature for about 2h, a white solid (3) was precipitated, filtered and washed with water. The product was not further purified due to its instability, but was pure enough for the next step. Add 8.8g (40mmol) (3) into 100ml of toluene, heat and stir to reflux for 7h, after the reaction is complete, filter the pr...
Embodiment 2
[0041] Example 2. 2-benzyl-7-methyl-1,1,3-trioxy-2,4-dihydropyrazol[4,5-e][1,2,4]thiadiazine (5a ) preparation
[0042] 1 equivalent of the intermediate 7-methyl-1,1,3-trioxo-2,4-dihydropyrazol[4,5-e][1,2,4]thiadiazine prepared in Example 1 , dissolved in dry dimethylformamide (DMF), under N 2 Under protection, slowly add 2 equivalents of sodium hydride containing 60% mineral oil, keep the temperature below 10°C, after the addition is complete, stir for 15-20min, then slowly add 1 equivalent of benzyl bromide. The reaction mixture was stirred for an additional 10 h at 28 °C. After cooling, the solvent was evaporated under reduced pressure. The residue was separated and purified by flash column chromatography. Eluent: dichloromethane:methanol (4:1), recrystallized from an organic solvent to obtain crystals. Yield 65%, white solid, mp 187°C (dec) (ethanol). The product spectrum data are as follows:
[0043] IR (KBr, cm -1 ): 3430 (NH), 3032 (Py-CH), 1594 (C=O), 1342, 114...
Embodiment 3
[0044] Example 3. 2-(p-cyanobenzyl)-7-methyl-1,1,3-trioxy-2,4-dihydropyrazol[4,5-e][1,2,4] The preparation of thiadiazine (5b), preparation method is as embodiment 2, difference is:
[0045] The 7-methyl-1,1,3-trioxy-2,4-dihydropyrazol[4,5-e][1,2,4]thiadiazine and p-cyanochloride prepared in Example 1 Benzyl was reacted at 30-40°C for 12h, eluent: dichloromethane:methanol (4:1), yield 55%, white solid, mp 244°C (dec) (ethanol). The product spectrum data are as follows:
[0046] IR (KBr, cm -1 ): 3461 (NH), 2236 (CN), 1598 (C=O); 1338, 1143 (SO 2 ). 1 H-NMR (DMSO-d 6 )δ: 7.74(d, 2H, J=8.0Hz, Ar-H); 7.41(d, 2H, J=8.0Hz, Ar-H); 7.12(s, 1H, Py-H); 4.97(s, 2H, CH 2 ); 3.84 (s, 3H, CH 3 ). 13 C-NMR (DMSO-d 6 )δ: 152(C 3 =O), 144(C-1'), 132(2C, C-3', 5'), 128(C-7a), 127(2C, C-2', 6'), 125(C-4a ), 123(C-5), 118(C-4'), 109(CN), 46(CH 2 ), 37 (CH 3 ). MS (EI) m / z 318 (M+1).
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