Preparation method of drug sitagliptin for treating diabetes
A technology of sitagliptin and compounds, applied in the field of western medicine synthesis, can solve the problems of cumbersome reaction routes of sitagliptin, expensive raw materials, harsh reaction conditions, etc., achieve high yield, easy operation of the reaction process, and reduction of by-products Effect
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[0027] The invention discloses a preparation method of sitagliptin, which can be realized by those skilled in the art by referring to the contents of this article and appropriately improving process parameters. It should be pointed out that all similar replacements and modifications will be obvious to those skilled in the art, and they are all considered to be included in the present invention, and relevant persons can obviously make changes without departing from the content, spirit and scope of the present invention. Changes or appropriate changes and combinations are made to the content described herein to realize and apply the technology of the present invention.
[0028] In the present invention, unless otherwise specified, the scientific and technical terms used herein have the meanings commonly understood by those skilled in the art.
Embodiment 1
[0030] Embodiment 1: the preparation of formula II compound
[0031]
[0032] In 100mL tetrahydrofuran, under the protection of nitrogen, add compound I 5.92g (24mmol) and 4.44g (36mmol) NH 2 -OBn, stirred at room temperature for 1 hour, then added 0.11g (0.18mmol) [(p-cymene)RuCl 2 ] 2 And 0.049g (0.09mmol) (R,S)-t-Butyl Josiphos, continue to stir for 0.5 hours, finally add 6.81g (50mmol) ZnCl 2 and 5.88g (94mmol) NaBH 3 CN, continue to stir for 20 minutes, heat to reflux, TLC monitors the reaction process, after the reaction is completed, the excess reducing agent is quenched with a saturated ammonium chloride solution, filtered, washed with water, the organic phase is concentrated under reduced pressure, and 6.25g of compound II is obtained by column chromatography (17.7 mmol), yield 74%, e.e. >99.9%.
[0033] 1 H NMR (CHCl 3 -d,400M)δ: 7.32-7.45(m,5H),6.69(s,1H),6.65(s,1H),5.45(s,3H),4.77(s,2H),4.35(d,2H) ,3.44(m,1H),2.69(d,2H); 13 C NMR (CHCl 3-d,400M)δ: 173.1...
Embodiment 2
[0034] Embodiment 2: the preparation of formula III compound
[0035]
[0036] In a high-pressure reactor, 5.31g (15mmol) of compound II in 100mL of chloroform was subjected to hydrogenation reduction reaction on palladium carbon for 6 hours, filtered, washed with an appropriate amount of chloroform, and the filtrate was transferred to a round-bottomed flask, adjusted to pH 4 with hydrochloric acid, and refluxed. After 6 hours, adjust the pH to 6.8 with sodium hydroxide solution, separate layers, add anhydrous magnesium sulfate to the organic phase and dry overnight, and remove the solvent under reduced pressure to obtain 2.71 g (11.6 mmol) of compound III with a yield of 77%.
[0037] 1 H NMR (CHCl 3 -d,400M)δ: 6.81(s,1H),6.65(s,1H),3.34(m,1H),2.92(d,2H),2.34(d,2H); 13 C NMR (CHCl 3 -d,400M)δ:177.1,157.8,147.4,145.2,122.9,118.5, 106.8,48.3,46.6,37.1; MS-ESI(m / z):234.04[M+H] + .
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