A kind of chemical synthesis method of carbitinib
A technology of chemical synthesis and carbitinib, applied in organic chemistry methods, organic chemistry, etc., can solve the problems of long synthesis steps, difficult separation, environmental pollution, etc., and achieve mild synthesis conditions, easy control of reactions, and safety high effect
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Embodiment 1
[0044] Synthesis of Example 1 Compound 2
[0045]
[0046] Compound 1 (26.6g, 0.1mol, 1.0eq) was dissolved in DMF (200ml), stirred to dissolve, and 2-fluoro-4-iodoaniline (26.07g, 0.11mol, 1.1eq) was added, and placed in 0 o Under the condition of C, N, N-diisopropylethylamine (69.3ml, 0.5mol, 5.0eq) was added dropwise under stirring. After the addition, the reaction solution was placed in 60 o Under the condition of C, react for 6h, add 1000ml of 0.5mol / L HCl solution to the reaction solution, stir for 10min, then add 500ml of ethyl acetate to the reaction solution, extract, collect the organic layer, and extract the aqueous layer with ethyl acetate (500ml×3 ), combined organic layers, dried over anhydrous magnesium sulfate for 2h, filtered, and removed ethyl acetate by distillation under reduced pressure to obtain a yellow oily liquid, which was purified by column chromatography (200-300 mesh silica gel was the stationary phase, dichloromethane : Methanol=4:1 is the elue...
Embodiment 2
[0050] Synthesis of Example 2 Compound 3
[0051]
[0052] A glass autoclave was charged with 10% Pd / C (11.7g, 4.4mmol, 0.05eq, 60.2%ww water, 10%ww palladium on carbon) and compound 2 (42.7g, 0.088mol, 1.0eq) under argon. Dissolve in 200ml absolute ethanol, room temperature H 2 Pressurize (20~60psi) to react overnight, remove 10% Pd / C by diatomaceous earth filtration, collect the filtrate, and remove the solvent under reduced pressure to obtain 34.20 g of compound 3 (yellow oil) with a yield of 98.8%. The magnetic resonance spectrum and mass spectrometry data of compound 3 are as follows:
[0053] 1 H NMR (500Hz, CDCl 3 ): δ7.704-7.695(m, 1H), 7.198-7.185(m, 1H), 7.064-7.054(m, 1H), 6.815-6.802(m, 1H), 6.556-6.545(m, 1H).
[0054] 13 C NMR (500Hz, CDCl 3 ): δ 169.743, 160.221, 154.859, 147.094, 138.428, 136.272, 130.569, 127.149, 125.144, 123.296, 112.885, 107.493, 94.195.
[0055] MS(EI): 393.98(MH + ).
Embodiment 3
[0056] Synthesis of Example 3 Compound 4
[0057]
[0058] Weigh compound 3 (33.07g, 0.08mmol, 1.0eq), 3-oxoazetidine hydrochloride (10.36g, 0.088mmol, 1.1eq), EDCI (18.41g, 0.096mol, 1.2eq) In DCM (300ml), then add DMAP (0.49g, 4mmol, 0.05eq), stir the reaction at room temperature for 9h, add 200ml of water to quench the reaction, extract the aqueous layer with DCM (200ml×2), collect the organic layer, and wash with saturated brine Then dried over anhydrous sodium sulfate. Filtration, the filtrate was concentrated to obtain a yellow solid, which was dissolved in 20ml of dichloromethane and dropped into 300ml of n-heptane. After the dropwise addition, stirred for 2h, a solid precipitated, collected by filtration, and dried to obtain compound 4 (white Solid matter) 32.85g, yield 91.9%. The magnetic resonance spectrum and mass spectrometry data of compound 4 are as follows:
[0059] 1 H NMR (500Hz, CDCl 3 ):δ 7.628-7.614(m, 1H), 7.245-7.231(m, 1H), 7.151-7.139(m, 1H), 6....
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