Furo[3,2-d]pyrimidine HIV-1 inhibitor as well as preparation method and application thereof
A HIV-1, 2-d technology, applied in pharmaceutical formulations, antiviral agents, medical preparations containing active ingredients, etc., can solve problems such as toxic and side effects, pharmacokinetic properties, etc., and achieve high application value.
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Embodiment 1
[0033] Example 1: Preparation of 4-((2-chlorofuro[3,2-d]pyrimidin-4-yl)oxy)-3,5-dimethylbenzonitrile (5)
[0034]
[0035] Weigh 4-hydroxy-3,5-dimethylbenzonitrile (1.5g, 10mmol) and potassium carbonate (1.7g, 12mmol) in 30mL of DMF, stir at room temperature for 15 minutes, then add 2,4-dichlorofuran And[3,2-d]pyrimidine 1 (1.9g, 10mmol) continued to stir at room temperature for 2h (TLC detected that the reaction was complete). After a large amount of white solid was formed, 100 mL of ice water was slowly added thereto, filtered, dried in vacuo, and recrystallized from ethanol to obtain Intermediate 5. White solid, yield 96%, melting point 225-228°C. 1 H NMR (400MHz, DMSO-d 6 )δ8.66 (d, J=2.2Hz, 1H, C 6 -furopyrimidine-H),7.78(s,2H,C 3 ,C 5 -Ph-H), 7.32(d,J=2.2Hz,1H,C 7 -furopyrimidine-H),2.14(s,6H).HRMS: m / z 300.1111[M+1] + .C 15 h 10 ClN 3 o 2 (299.0462).
Embodiment 2
[0036]Example 2: 3,5-Dimethyl-4-((2-(piperidin-4-ylamino)furo[3,2-d]pyrimidin-4-yl)oxy)benzonitrile (7) preparation of
[0037]
[0038] 5 (0.95g, 3.17mmol), N-Boc-4-aminopiperidine (0.83g, 3.80mmol) and potassium carbonate (0.87g, 6.33mmol) were added to 5mL of DMF in turn, then heated to reflux for 10h (TLC detection). After the reaction was cooled to room temperature, the reaction solution was slowly added dropwise to 50 mL of water, and a large amount of yellow solid was formed. After standing for 30min, filter and vacuum dry to obtain the crude product. Weigh the crude product (1.26g, 2.53mmol) and dissolve it in 4mL of dichloromethane, add 2.22mL of trifluoroacetic acid (30mmol), and stir at room temperature for 3-5h (TLC detection). Then the pH of the reaction solution was adjusted to 9 with saturated sodium bicarbonate solution, extracted with dichloromethane (3×5 mL), washed with saturated sodium chloride solution, and the organic layer was dried over anhydrous ...
Embodiment 3
[0039] Embodiment 3: the preparation of target compound A1-A6
[0040] Weigh compound 7 (0.5mmol) in 5mL DMF, then add potassium carbonate (0.14g, 1.0mmol) and substituted benzyl chloride or benzyl bromide (0.6mmol) in sequence, and stir at room temperature for 6-8h (TLC detection). Add 20 mL of saturated sodium chloride solution to the reaction solution, wash with ethyl acetate (3×10 mL), separate the organic layer, and dry over anhydrous sodium sulfate. Then, the crude product of the target compound was separated by flash column chromatography, and then recrystallized in the ethyl acetate-petroleum ether system to obtain the target compound A1-A6.
[0041] 4-((4-((4-(4-cyano-2,6-dimethylphenoxy)furo[3,2-d]pyrimidin-2-yl)amino)piperidin-1-yl )Methyl)benzenesulfonamide (A1)
[0042]
[0043] White solid, yield 66%, melting point 206-208°C. 1 H NMR (400MHz, DMSO-d 6 )δ8.23(d,J=2.1Hz, 1H,C 6 -furopyrimidine-H), 7.78 (d, J=8.0Hz, 2H, C 3 ,C 5 -Ph'-H),7.72(s,2H,C 3 ,C ...
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