Diketo acids with nucleobase scaffolds: anti-HIV replication inhibitors targeted at HIV integrase
An alkyl, benzyl technology, applied to diketoacids with nucleobase scaffolds: the target is in the field of anti-HIV replication inhibitors of HIV integrase, which can solve the problem that the 3′-processing step does not show inhibition
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Embodiment 1
[0543] 4-(1,3-Dibenzyl-1,2,3,4-tetrahydro-2,4-dioxopyrimidin-5-yl)-2-hydroxy-4-oxobut-2-enoic acid Methyl ester (3a).
[0544]
[0545] Step 1: Preparation of 5-acetyl-1,3-dibenzyluracil (2a).
[0546]
[0547] A suspension of 5-acetyluracil (3.1 g, 20 mmol) and potassium carbonate (6.9 g, 50 mmol) in DMF (75 mL) was stirred for 20 min. Then benzyl bromide (6.0 mL, 50 mmol) was added. The resulting mixture was stirred at room temperature for 8 h. DMF was evaporated in vacuum. The residue was purified by column chromatography (dichloromethane: methanol 40:1). The appropriate fraction was concentrated and crystallized from ethanol to obtain 5.34 g of white solid. The yield was 79.8%. Mp.92-93℃. 1 HNMR(CDCl 3 ): 8.23 (s, 1H), 7.29-7.49 (m, 10H), 5.17 (s, 2H), 5.01 (s, 2H), 2.62 (s, 3H). 13 CNMR(CDCl 3 ): 194.5, 160.7, 151.0, 148.4, 136.2, 134.4, 129.2, 129.0, 128.9, 128.5, 128.2, 127.8, 112.2, 53.4, 44.9, 30.7. FAB-HRMS: [M+H] + Calculated value C 20 H 19 N 2 O 3 335.1396, the ...
Embodiment 2
[0552] 4-(1,3-Dibenzyl-1,2,3,4-tetrahydro-2,4-dioxopyrimidin-5-yl)-2-hydroxy-4-oxobut-2-enoic acid (4a)
[0553]
[0554] The 4-(1,3-dibenzyl-1,2,3,4-tetrahydro-2,4-dioxopyrimidin-5-yl)-2-hydroxy-4-oxobut-2-ene A solution of methyl acid (3a) (757 mg, 1.8 mmol) in dioxane (100 mL) was refluxed with 1N HCl (60 mL) for 4 h. The solution was evaporated to dryness. The obtained solid was recrystallized with hexane and ethyl acetate (3:1) to obtain 617 mg of pale yellow solid. The yield was 84.2%. Mp.186-188℃. 1 HNMR(DMSO-d 6 ): 8.89 (s, 1H), 7.57 (s, 1H), 7.24-7.36 (m, 10H), 5.16 (s, 2H), 5.02 (s, 2H). 13 CNMR(DMSO-d 6 ): 186.1, 169.0, 163.2, 159.9, 151.1, 150.2, 136.5, 135.8, 128.7, 128.4, 128.0, 127.8, 127.6, 127.3, 107.7, 100.9, 52.8, 44.2. FAB-HRMS: [M+H] + Calculated value C 22 H 19 N 2 O 6 407.1243, the measured value is 407.1248.
Embodiment 3
[0556] 4-[1,3-bis(2-fluorobenzyl)-1,2,3,4-tetrahydro-2,4-dioxopyrimidin-5-yl]-2-hydroxy-4-oxobutane Methyl-2-enoate (3b).
[0557]
[0558] Step 1: Preparation of 1,3-bis(2-fluorobenzyl)-5-acetyluracil (2b)
[0559]
[0560] The title compound of this step was synthesized using a method similar to that described in Step 1 of Example 1, except that 2-fluorobenzyl bromide was used instead of benzyl bromide. The yield was 43.9%. Mp.149-150℃. 1 HNMR(CDCl 3 ): 8.35 (d, 1H, J = 1.0 Hz), 7.36-7.44 (m, 2H), 7.04-7.26 (m, 6H), 5.24 (s, 2H), 5.07 (s, 2H), 2.62 (s, 3H). 13 CNMR(CDCl 3 ): 194.3, 161.1 (d, J = 247.9 Hz), 160.7 (d, J = 247.9 Hz), 160.6, 150.8, 148.8 (d, J = 2.9 Hz), 131.3 (d, J = 3.4 Hz), 130.9 ( d, J = 8.2 Hz), 129.19 (d, J = 8.2 Hz), 129.17 (d, J = 2.9 Hz), 124.7 (d, J = 3.8 Hz), 124.1 (d, J = 3.8 Hz), 123.1 ( d, J = 14.5 Hz), 121.4 (d, J = 14.5 Hz), 115.9 (d, J = 21.6 Hz), 115.5 (d, J = 21.6 Hz), 112.2, 47.8, 38.8, 30.6.
[0561] FAB-HRMS: [M+H] + Calculated value C 20 H...
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