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CAS No. : | 848398-41-4 | MDL No. : | MFCD13250060 |
Formula : | C6H4Cl2N2O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | WRAAHQVXMZLMQR-UHFFFAOYSA-N |
M.W : | 191.02 | Pubchem ID : | 23125094 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
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* 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 sodium hydrogencarbonate; triethylamine; In tetrahydrofuran; at 0 - 20℃; for 4h; | Example 3 2-chloro-4-N,N-di-n-propylamino-5,7-dihydrofuro[3,4-d]pyrimidine: Under argon gas atmosphere, tetrahydrofuran (4 mL) was added to the compound prepared in Example 2 (757 mg), and then the mixture was stirred in an ice-bath. To the mixture, triethylamine (1.4 mL) and di-n-propylamine (1.3 mL) were dropped. The mixture was stirred for 4 hours at room temperature. The reaction mixture was poured into cooled 10% aqueous solution of citric acid, and then the mixture was extracted by ethyl acetate. The extract was washed with a saturated aqueous solution of sodium bicarbonate, and a saturated aqueous solution of sodium chloride, successively, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was purified by column chromatography on silica gel (hexane : ethyl acetate = 9 : 1) to give the title compound (784 mg) having the following physical data. TLC: Rf 0.71 (n-hexane : ethyl acetate =1:1); 1H-NMR (300MHz, CDCl3): delta 5.19, 4.86, 3.32, 1.62, 0.94. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With N,N-dimethyl-aniline; trichlorophosphate; at 0℃; for 12h;Reflux; | To a 0C solution of the aforementioned 3 (500 mg, 3.25 mmol) in phosphorus oxychloride (30 mL) was added dimethyl aniline (500 mg, 4.13 mmol). The resulting solution was refluxed for 12 hours. The solvents were removed under reduced pressure. The resulting residue was poured into ice (lOOg) and extracted with dichloromethane (50 mL x 3). The combined organic layers were washed with brine, dried over sodium sulfate. The Na2S04 was removed by filtration, and the volatiles were removed under reduced pressure. The resulting residue was purified by flash chromatography using a mixture of hexane and ethyl acetate to to provide the final product 4 (300 mg, 49%). LRMS (M + H+) m/z: calcd 192.01; found 192.10. |
Example 2 2,4-dichloro-5,7-dihydrofuro[3,4-d]pyrimidine: Under argon gas atmosphere, phenylphosphonic dichloride (16.1 mL) was added to the compound prepared in Example 1 (15.7 g). The mixture was stirred for 6 hours at 135 C, and then for 30 minutes at 165C. After the reaction mixture was cooled, it was dropped into ice-water (100 mL). Ethyl acetate (100 mL) was added to the mixture solution. An insoluble matter was removed by filtration under reduced pressure, and was washed with ethyl acetate. The filtrate and the washings were combined, and then the mixture was shaken and separated. The organic layer was washed with a saturated sodium bicarbonate and a saturated sodium chloride, successively, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and then dried under vacuum to give the title compound (3.66 g) having the following physical data. TLC: Rf 0.60 (hexane : ethyl acetate =1:1); 1H-NMR (300MHz, CDCl3): delta 5.17, 5.09. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With triethylamine; In dichloromethane; at 0 - 20℃; for 12h; | To a 0C solution of the aforementioned intermediate 4 (300 mg, 1.58 mmol) in DCM (50 mL) were added phenylmethanamine (300 mg, 3 mmol) and TEA (500 mg, 3.88 mmol). Then the reaction solution was stirred at room temperature for 12 hours. The resulting mixture was concentrated under reduces pressure. The resulting residue was purified by flash chromatography using a mixture of hexane and ethyl acetate to provide the desired 5 (300 mg, 73%). LRMS (M + H+) m/z: calcd 262.71; found 262.85. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide; at 100℃; for 5h; | [0139] A mixture of <strong>[848398-41-4]2,4-dichloro-5,7-dihydrofuro[3,4-d]pyrimidine</strong> (90 mg, 0.47 mmol), lH-indazol-5-amine (62.7 mg, 0.47 mmol), and diisopropylethylamine (0.16 mL, 0.94 mmol) in DMF (0.94 mL) was heated at 100 C for 5 h. TLC showed the reaction was complete. The mixture was then diluted with water. The resulted yellow precipitate was filtered and washed with water and dried in vacuo to provide 120 mg (89%) title compound which was used directly for next step reaction without further purification. |
38.3% | With sodium carbonate; In ethanol; at 15℃; for 12h; | To a solution of compound 2,4-dichloro-5 ,7- dihydro furo [3,4- d]pyrimidine (1.00 g, 5.30 mmol) in EtOH (30 mL) were addedNa2CO3(1.70g, 15.8 mmol) and compound 1H-indazol-5-amine (711 mg, 5.3 mmol). The resulting mixture was stirred for 12 h at 15C. After LCMS showed the reaction was completed, the solvent was removed under reduced pressure and the residue was dissolved in EtOAc (100 mL), washed by water (2 x 50 mL). The organic phase was dried over Na2 SO4, filtered and concentrated under reduced pressure to give compound the title compound as a solid (800 mg, yield: 38.3%). |
38.3% | With sodium carbonate; In ethanol; at 15℃; for 12h; | 2-chloro-N-(lH-indazol-5-yl)-5,7-dihydromro[3,4-d]pyrimidin-4-amine To a solution of compound <strong>[848398-41-4]2,4-dichloro-5,7-dihydrofuro[3,4-d]pyrimidine</strong> (1.00 g, 5.30 mmol) in EtOH (30 mL) were added Na2C03 (1.70 g, 15.8 mmol) and compound 1H- indazol-5 -amine (711 mg, 5.3 mmol). The resulting mixture was stirred for 12 h at 15C. After LCMS showed the reaction was completed, the solvent was removed under reduced pressure and the residue was dissolved in EtOAc (100 mL), washed by water (2 x 50 mL). The organic phase was dried over Na2S04, filtered and concentrated under reduced pressure to give compound the title compound as a solid (800 mg, yield: 38.3%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | In a 20 mL vial, INT-6 (0.05 g, 0.167 mmol) was added to 3 mL of dry DMF and sonicated briefly. To this, K2CO3 (0.231 g, 1.670 mmol) was added and the reaction was warmed to 90 C. for 10 min. The reaction was then cooled to room temperature and <strong>[848398-41-4]2,4-dichloro-5,7-dihydrofuro[3,4-d]pyrimidine</strong> (0.055 g, 0.288 mmol) was added and subsequently warmed to 90 C. for 2 h. Upon completion, the reaction was cooled, filtered to remove any undissolved potassium carbonate and the crude reaction mixture was directly purified by reverse phase prep-HPLC (10-95% MeCN/Water, 0.1% TFA) to yield I-86 (0.052 g, 0.114 mmol, 68% yield) as a yellow solid after lyophilization. 1H NMR (400 MHz, DMSO-d6): delta 9.31 (d, J=9.2 Hz, 1H), 8.13 (d, J=8.7 Hz, 1H), 8.10 (d, J=4.6 Hz, 1H), 7.79 (d, J=8.7 Hz, 1H), 7.58 (d, J=9.2 Hz, 1H), 7.11 (br, 1H), 4.98 (s, 4H), 3.55 (m, 1H), 3.39 (m, 2H), 1.12 (d, J=6.9 Hz, 3H) MS m/z (M+H): 453.8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With N-ethyl-N,N-diisopropylamine; In isopropyl alcohol; for 48h;Reflux; | General procedure: Procedure B: A mixture of substituted 2,4-dichloropyrimidine (1.0 equiv.), and substituted aniline (1.0-1.05 equiv.), and DIPEA (1.2 equiv.) in isopropanol (0.1 M) was stirred and heated at reflux. The reaction time, work-up, and product isolation procedure are described below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With N-ethyl-N,N-diisopropylamine; In isopropyl alcohol; at 100℃; for 18h; | General procedure: Procedure B: A mixture of substituted 2,4-dichloropyrimidine (1.0 equiv.), and substituted aniline (1.0-1.05 equiv.), and DIPEA (1.2 equiv.) in isopropanol (0.1 M) was stirred and heated at reflux. The reaction time, work-up, and product isolation procedure are described below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69.87% | With acetic acid; zinc; In methanol; at 70℃; for 4h; | CompoundII-29 (19.10g, 0.1mol, 1.0eq.), Acetic acid (34.3mL, 0.6mol, 6.0eq.) Andmethanol(150mL) placed in a reaction flask was added portionwise at 25 to zinc dust (26.16g, 0.4mol, 4.0eq.), The addition was completed temperaturewas raised to 70 Reactionfor 4 hours, TLC the reaction was complete. Cooling, filtration and the filtercake was washed twice with methanol, and the filtrate sand columnchromatography to obtain compoundI-29 was 10.94g,69.87% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide; at 100℃; for 5h; | A mixture of <strong>[848398-41-4]2,4-dichloro-5,7-dihydrofuro[3,4-d]pyrimidine</strong> (300 mg, 1.57 mmol), 4-(1H-pyrazol-4-yl)aniline (250 mg, 1.57 mmol), and diisopropylethylamine (0.55 mL, 3.14 mmol) in DIVIF (3.14 mL) was heated at 100 C for 5 h. TLC showed the reaction was complete. The mixture was then diluted with water. The resulted yellow precipitate was filtered and washed with water and dried in vacuo to provide 480 mg (97%) title compound which was used directly for next step reaction without further purification. |
97% | With N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide; at 100℃; for 5h; | [0100] A mixture of <strong>[848398-41-4]2,4-dichloro-5,7-dihydrofuro[3,4-d]pyrimidine</strong> (300 mg, 1.57 mmol), 4-(lH-pyrazol-4-yl)aniline (250 mg, 1.57 mmol), and diisopropylethylamine (0.55 mL, 3.14 mmol) in DMF (3.14 mL) was heated at 100 C for 5 h. TLC showed the reaction was complete. The mixture was then diluted with water. The resulted yellow precipitate was filtered and washed with water and dried in vacuo to provide 480 mg (97%) title compound which was used directly for next step reaction without further purification. |
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