2-amino-7,8-dihydro-6h-pyrido[4,3-d]pyrimidin-5-ones
A pyridine and pyrimidine technology applied in the field of 2-amino-7,8-dihydro-6H-pyrido[4,3-d]pyrimidin-5-one
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[0413] Referring to the examples below, the compounds of the invention can be synthesized using the methods described herein or other methods well known in the art.
[0414] The compounds and / or intermediates were characterized by high performance liquid chromatography (HPLC) using a Waters Millenium Chromatography System (Milford, MA) with a 2690 Separation Module. The analytical column was an Alltima C-18 reverse phase, 4.6 x 250 mm, purchased from Alltech (Deerfield, IL). Gradient elution was used, typically starting with 5% acetonitrile / 95% water and proceeding to 100% acetonitrile over 40 minutes. All solvents contained 0.1% trifluoroacetic acid (TFA). Compounds were detected by ultraviolet (UV) absorption at 220 or 254 nm. HPLC solvents were purchased from Burdick and Jackson (Muskegan, MI) or Fisher Scientific (Pittsburgh, PA). In some cases, purity is assessed by thin layer chromatography (TLC) using glass or plastic backed silica gel plates (eg, Baker-Flex Silica G...
example 1
[0456] Representative Procedures for Compounds of the Invention
[0457] Step A: α,β-Unsaturated Esters
[0458]
[0459] at -78°C, N 2 Next, to a stirred solution of triethylphosphonoacetate (88 mmol) in dry THF (176 mL) was added n-butyllithium (84 mmol) dropwise. The solution was stirred for 30 min keeping the internal temperature below -70 °C. at -78°C and N 2 Next, the phosphate ester solution was transferred via cannula to a solution of 2-bromo-4-fluorobenzaldehyde 1-1 (80 mmol) in THF (160 mL). The resulting solution was warmed to room temperature for 2 hours. By adding aqueous NH 4 The reaction mixture was quenched with Cl and then extracted with EtOAc (x3). The organic fractions were combined and washed with H 2 O (×3), washed with saturated brine (×3), then dried (Na 2 SO 4 ), filtered and evaporated under low pressure to yield a pale yellow oil. White crystals formed after cooling in the refrigerator. The crystals were filtered and washed with methanol...
example 2
[0479] Synthesis of Representative N-Alkylated Compounds of the Invention
[0480] Step A: Reductive Amination Reaction
[0481]
[0482] To a stirred solution of the free amine 1-5 (1 eq.), aldehyde 2-1 (1 eq.) in DCM was added sodium triacetoxyborohydride (1.1 eq.) at room temperature. The reaction was stirred at room temperature until complete as judged by LCMS. The mixture was subsequently made in DCM with aqueous NaHCO 3 The layers were separated, extracted with DCM (×3) and the combined organic fractions were subsequently washed with H 2 O (×3), washed with saturated brine (×3), then dried (Na 2 SO 4 ), filtered and evaporated under low pressure to give crude product compound 2-2, which was directly used in the next reaction.
[0483] Steps B-E: Acylation reaction, cyclization reaction, amino-pyrimidine-lactam formation reaction, Suzuki coupling reaction
[0484]
[0485] Steps B to E are the same as Steps E to G in Example 1.
[0486] Step F: Deprotect
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