Structure of 219715-62-5
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CAS No. : | 219715-62-5 |
Formula : | C7H9N5O2 |
M.W : | 195.18 |
SMILES Code : | NC1=NN2C(OC)=NC=C(OC)C2=N1 |
MDL No. : | MFCD17168561 |
InChI Key : | DBJPBHJHAPAUQU-UHFFFAOYSA-N |
Pubchem ID : | 11446888 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H332-H335 |
Precautionary Statements: | P261-P280-P305+P351+P338 |
* 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 |
---|---|---|
91.2% | With hydroxylamine hydrochloride; sodium methylate; triethylamine In 1,4-dioxane; methanol at 20 - 30℃; | To a 100 mL three-necked flask was added 1.5 g of ethyl 4- [4- (2,5-dimethoxypyrimidinyl)] - 3-thiourea,Hydrochloric acid hydroxylamine 0.5g,10 mL of 1,4-dioxane was added,Then, triethylamine (1.2 g)A solution of 0.5 g of sodium methoxide in methanol was further added,The reaction is carried out at 20 ° C to 30 ° C for 10 to 12 hours,HPLC tracking,After completion of the reaction,filter,To give 0.9 g of 2-amino-5,8-dimethoxy [1,2,4] triazolo [1,5-c] pyrimidine as a white solid,Content of 98.5percent,Yield 91.2percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70.4% | Stage #1: at 27 - 87℃; Stage #2: at 40℃; Stage #3: With hydroxylamine In water; toluene at 68 - 81℃; |
Example 4 Preparation of 2-amino-5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidine (Ia) To a 700 mL jacketed vessel equipped with a mechanical stirrer, a dual pH/temperature probe, a nitrogen inlet, and a reflux condenser was added sequentially 27.9 g (0.180 mol) of 4-amino-2,5-dimethoxypyrimidine followed by 165.4 g (0.207 mol) of 16.4 wt percent ethoxy carbonylisothiocyanate solution in toluene. The reaction mixture was heated to gentle reflux (87 ° C.) for 7 h at which time liquid chromatographic (LC) analysis indicated ˜95percent conversion of starting 4-amino-2,5-dimethoxypyrimidine. The reaction mixture was cooled to 27 ° C. and allowed to stand overnight. The mixture was heated to 40° C. and then 114.2 g (6.34 mol) of deionized water was added to the mixture. After heating to reflux (˜68° C.). , 14.3 g (0.217 mol) of a 50 wt percent aqueous hydroxylamine solution was continuously added over a 2 h 15 min period via a peristaltic pump. During the course of the amine addition, the reaction pH rose from 4.44 to 6.95. After complete addition of hydroxylamine, the pump line was flushed with 4.8 g (0.266 mol) of deionized water, the reaction mixture was heated to 81° C., and then stirred an additional 3 h during which time the reaction pH naturally raised to 7.40. The reaction mixture was cooled to ambient temperature (26° C.). The reaction mixture was then suction transferred into a temporary holding vessel. The reactor was washed with two 30 g portions of water. These water washes were combined with the reaction mixture. The combined mixture was suctioned filtered through a coarse Buchner funnel (filtration time about 30 seconds), and the filtrate was collected and filtered a second time through the cake. A final displacement cake wash with ˜40 g of methanol was performed and the product was dried at 60° C. under vacuum (˜<10 mm Hg; 1333 Pa) to afford 25.37 g of 2-amino-5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidine as a light cream colored solid. NMR analysis (using benzyl acetate as an internal standard) indicated an 97.3percent purity of 2-amino-5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidine active which corresponds to a 70.4percent yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52.8% | Stage #1: With hydroxylamine hydrochloride; triethylamine In acetonitrile at 45℃; for 2 h; Stage #2: With triethylamine; methyl chloroformate In acetonitrile at 5.8 - 76℃; for 4 h; |
Example 4 Preparation of 2-amino-5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidine (I) Step (b+c)' To a 25 mL three-neck round bottom flask were added 1.11 g (5.55 mmol) of 90 wt percent 2,5-dimethoxy-4-cyanoaminopyrimidine (2), 463 mg (6.66 mmol) of hydroxylamine hydrochloride, and 9.8 g of acetonitrile. To this mixture was added 681 mg (6.72 mmol) of triethylamine in one portion. The reaction mixture was heated to a gentle reflux (˜45° C.) for 2 h. The reaction mixture was cooled in an ice water bath to about 5.8° C. at which time an additional 716 mg (7.08 mmol) of triethylamine was added in one portion. To this mixture was added 662 mg (7.01 mmol) of methyl chloroformate in one portion at which time the internal reaction temperature rose from 5.8° C. to 12.1° C. The ice water bath was removed and the mixture was stirred at ambient temperature for 1 h and then at reflux (˜76° C.) for about 3 h. The reaction mixture was cooled to ambient temperature and an additional 100 μL of triethylamine was added to adjust the reaction pH to about 7-8. To this mixture was added 11.3 g of water; the mixture was transferred to a 100 mL round bottom flask; and the acetonitrile was removed in vacuo at 60 mm Hg and 30° C. The aqueous slurry was then suction filtered over a medium glass frit and the residue from the flask was transferred with 2 g of water. After the cake de-liquored, another 1 g displacement water wash was passed through the cake. After suction air drying the cake for 30 min, the mixture was allowed to dry over a nitrogen pad overnight. This afforded 588 mg (˜97percent pure by liquid chromatography (LC) analysis) of 2-amino-5,8-dimethoxy-[1,2,4]-triazolo[1,5-c]pyrimidine (I) as a light yellow solid in 52.8percent yield from starting 2,5-dimethoxy-4-cyanoaminopyrimidine (2). 1H NMR (DMSO-d6, 400 MHz) δ 3.90 (s, 3H), 4.06 (s, 3H), 6.28 (br s, 2H), 7.48 (s, 1H); 13C NMR (DMSO-d6, 100 MHz) δ 55.37, 57.04, 123.07, 138.60, 143.73, 148.50, 166.02. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | at 20℃; for 1.5 h; | Example 5Preparation of 5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidin-2-amine (5) 5-Chloro-8-methoxy[1,2,4]triazolo[1,5-c]pyrimidin-2-amine (4; 100 mg, 0.50 mmol) was suspended in acetonitrile (5 mL) at room temperature and treated with 25percent sodium methoxide in methanol (200 mg, 2 eq). The resulting slurry was stirred at room temperature for 1.5 hours and then filtered. The solids were washed with water and dried to afford the title compound as a chalk-colored solid (87 mg, 88percent) that was identical in HPLC retention to authentic 5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidin-2-amine (5): mp 185-186° C.; 1H NMR (DMSO-d6) δ 7.48 (s, 1H), 6.38 (br s, 2H), 4.04 (s, 3H), 3.88 (s, 3H); EIMS m/z 195. |
Tags: 219715-62-5 synthesis path| 219715-62-5 SDS| 219715-62-5 COA| 219715-62-5 purity| 219715-62-5 application| 219715-62-5 NMR| 219715-62-5 COA| 219715-62-5 structure
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