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CAS No. : | 29097-00-5 | MDL No. : | MFCD02936636 |
Formula : | C5H7N3O2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | KGQFAPZUQKYADG-UHFFFAOYSA-N |
M.W : | 141.13 | Pubchem ID : | 272904 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H319-H332-H335 | Packing Group: | |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With PPA; In water; | a) A mixture of 11.5 g of <strong>[29097-00-5]methyl 5-aminopyrazole-4-carboxylate</strong>, 16 ml of ethyl omega, omega, omega-trifluoroacetoacetate and 150 g of polyphosphoric acid was heated to 100 while stirring for 16 hours. After cooling to 20, cold water was added and the mixture was extracted with ethyl acetate. The organic phase was washed with 1N aqueous hydrochloric acid and aqueous saturated sodium chloride solution and then dried over Na2 SO4. The solvent was evaporated in a vacuum and the residue was taken up in ether. The solid product was filtered off under suction and recrystallized from 2-propanol. There was obtained an isomer of the product, namely methyl 7-hydroxy-5-(trifluoromethyl)pyrazolo-[1,5-a]pyrimidine-3-carboxylate of m.p. 216-217. The product enriched in the mother liquors was crystallized from ethyl acetate. There was obtained methyl 5-hydroxy-7-(trifluoromethyl)pyrazolo[1,5-a]pyrimidine-3-carboxylate of m.p. 149-150. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | 1.0 g of compound (2') is added to 10 ml of phosphoric acid to dissolve. This solution is ice-cooled to keep the temperature to -5 to 0C, and 0.54 g of sodium nitrite is added thereto, followed by stirring for 1 hour to obtain a diazonium salt solution. Separately, 20 ml of NMP (N- methylpyrrolidone) is added to 1.60 g of compound (3') and, under stirring, the aforesaid diazonium salt solution is added thereto at 8C or lower. Simultaneously with completion of the addition, the ice bath is removed, and stirring is continued for further 1 hour. 40 ml of methanol is added to the reaction solution, and the resulting mixture is stirred for 30 minutes. Crystals precipitated are collected by filtration, and spray-washed with 30 ml of methanol. The thus- obtained crystals are added, without drying, to 100 ml of water, followed by stirring at 20 to 25C for 30 minutes. Crystals precipitated are collected by filtration, and sufficiently spray-washed with water. The thus-obtained crystals are added, without drying, to 20 ml of NMP and 10 ml of water, followed by stirring for 30 minutes under heating at 100C. After stirring for 30 minutes at room temperature, crystals precipitated are collected by filtration, and spray-washed with 20 ml of NMP/water=2/l and 20 ml of water. The thus-obtained crystals are dried to obtain 2.0 g of compound D-228 of the invention. Yield: 80%.Infrared absorption chart is shown in Fig. 6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | In ethanol; at 25℃; for 1.5h;Sonication; | General procedure: A mixture of aminoazole 1c-e (1 mmol), acetoacetamide 2a,b,d (1 mmol), and aromatic aldehyde 3b,d-g (1 mmol) in 10 mL of ethanol was ultrasonicated at room temperature for 90 min in a round-bottom flask equipped with a condenser. The reaction mixture was allowed to stand up to 12 h at room temperature and then was filtered out to give the solid compounds 6a-e, which were washed with ethanol and air dried. Reaction products were obtained in high purity and did not require further purification by recrystallization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | In N,N-dimethyl-formamide; for 0.166667h;Reflux; | General procedure: A mixture of aminoazole 1c-e (1 mmol), acetoacetamide 2a,b,d (1 mmol), and aromatic aldehyde 3b,d-g (1 mmol) in 0.1 mL of DMF was heated to reflux for 10 min. After cooling acetone (10 mL) was added. The precipitate formed was filtered out to give the solid dihydropyrimidines 7a-e, which were washed with acetone and air dried. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrazine hydrate; In ethanol; at 20 - 75℃; | 100 g (645 mmol) of methyl (2E/Z)-2-cyano-3-ethoxyacrylate were initially charged in 481 ml of ethanol. 31 ml (645 mmol) of an 85% strength hydrazine hydrate solution were then added dropwise at room temperature with cooling (exothermal temperature.) over a period of 45 minutes. The mixture was stirred at 75 C. for another 12 hours. The hot mixture was filtered and the organic phase was concentrated under reduced pressure. This gave 64 g of methyl 5-amino-1H-pyrazole-4-carboxylate (log P =-0.07; HPLC content: 86%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.4 g | With acetic acid; for 24h;Reflux; | Diethylamine (2.8 mL, 27 mmol) was added to a cold solution of 1 (1.8 mL, 20 mmol) in dichloromethane (60 mL) at 0 C and the so formed solution was stirred at 0 C for 5 h and the volatile components were evaporated in vacuo (30 C, 20 mbar). The crude enamino ester 2, which was obtained as yellow oil, was dissolved in acetic acid (45 mL), aminopyrazole 3 (2.8 g, 20 mmol) was added and the mixture was heated under reflux for 24 h. Volatile components were evaporated in vacuo (40 C, 7 mbar) and the residue was triturated with warm water (60 C, 50 mL). The precipitate was collected by filtration and washed with ethanol (15 mL) to give a 1:3 mixture of 4 and 5 (?2 g). Subsequent crystallization from ethanol afforded the title compound 5 0.40 g (10%) as a pale yellow solid; mp 280-287 C; [Found: C, 49.67; H, 3.40; N, 21.64. C8H7N3O3 requires: C, 49.74; H, 3.65; N, 21.75%]; numax (ATR) 3068, 2963, 1699, 1624, 1575, 1504, 1468, 1433, 1411, 1391, 1249, 1209, 1150, 1123, 1069, 1017, 944, 904, 876, 800, 772, 719, 631 cm-1; deltaH (500 MHz, DMSO-d6) 3.83 (3H, s, OMe), 5.95 (1H, d, J=7.5 Hz, 6-H), 7.85 (1H, d, J=7.5 Hz, 5-H), 8.25 (1H, s, 2-H), 12.24 (1H, br s, 4-H); deltaC (126 MHz, DMSO-d6) 51.5, 96.7, 99.1, 140.6, 142.9, 143.5, 155.8; HRMS (ESI): MH+, found 194.0557. C8H8N3O3 requires 194.0566. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.04 g | With acetic acid; for 5h;Reflux; | General procedure: A mixture of dialkyl malonate (10 mmol), anhyd toluene (25 mL), and N,N-dimethylformamide dimethylacetal (DMFDMA) (1.6 mL, 12 mmol) was heated under reflux for 2 h, cooled, and volatile components were evaporated in vacuo. The crude enamino ester 6 was dissolved in acetic acid (30 mL), aminopyrazole 3 (1.4 g, 10 mmol) was added and the mixture was heated under reflux for 5 h. The reaction mixture was cooled to rt and the precipitate was collected by filtration and washed with ethanol (2×10 mL) to give the title compound 7. The following compounds were prepared in this manner. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.3 g | With acetic acid; for 5h;Reflux; | General procedure: A mixture of dialkyl malonate (10 mmol), anhyd toluene (25 mL), and N,N-dimethylformamide dimethylacetal (DMFDMA) (1.6 mL, 12 mmol) was heated under reflux for 2 h, cooled, and volatile components were evaporated in vacuo. The crude enamino ester 6 was dissolved in acetic acid (30 mL), aminopyrazole 3 (1.4 g, 10 mmol) was added and the mixture was heated under reflux for 5 h. The reaction mixture was cooled to rt and the precipitate was collected by filtration and washed with ethanol (2×10 mL) to give the title compound 7. The following compounds were prepared in this manner. |
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