Preparation method of alogliptin benzoate
A technology for hydrolysis of benzoic acid and acid, applied in the preparation of carboxylate, organic chemistry, etc., can solve the problems of low yield and low purity of compound 4, and achieve the effects of high reaction yield, easy operation and low price
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Embodiment 1
[0031] Preparation of Formula 5:
[0032]
[0033] Dissolve (R)-3-amino-piperidine (43g) in 300mL of toluene, add benzaldehyde (45g) dropwise to the above solution at room temperature, continue to stir for 3 hours, distill toluene under reduced pressure to obtain 78g of oil, directly for the next reaction.
[0034] Preparation of Formula 4:
[0035]
[0036] at 0°C, N 2 Under protective conditions, add 6-methyl-3-chlorouracil (200g) into a 10L three-necked flask, dissolve it with DMF / DMSO (4.5L, 5 / 1) solution, add 60% NaH (54.8 g, 1.36mol), stirred for 30 minutes, then added LiBr (87g, 1mol), after continuing to stir for 20 minutes, to which o-cyanobenzyl bromide (244g, 1.25mol) was added dropwise, after reacting for 1 hour, moved to room temperature to continue Reaction, TLC tracked until the raw material reacted completely, and the solvent was evaporated under reduced pressure, and the residue was added with 1.2L water, and the 2 Cl 2 Extraction (1L × 3 times), co...
Embodiment 2
[0053] Preparation of Formula 5:
[0054]
[0055] Dissolve (R)-3-amino-piperidine (50g) in 300mL toluene, add p-tolualdehyde (66g) dropwise to the above solution at room temperature, continue to stir for 3 hours, distill toluene under reduced pressure to obtain 81g oily were used directly in the next reaction.
[0056] Preparation of formula 6 and formula 7:
[0057]
[0058] 2-(6-chloro-3-methyl-2,4-dioxo-3,4-dihydro-2-H-pyrimidin-1-ylmethyl)-benzylcyanide (100g), compound of formula 5 ( 80.7g) and sodium bicarbonate (193g) and 34g activated molecular sieve (4A) in anhydrous MeOH (2L), reflux at 100°C, stir for 3h, spot the plate until the reaction is complete, cool to room temperature (25°C), add 1L HCl (3mol / L) and stirred for 2 hours until the compound of formula 6 disappeared, evaporated methanol under reduced pressure, washed the water phase with 300ml of dichloromethane, removed the organic layer, adjusted the pH of the water phase to 9 with saturated sodium ca...
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