Substituted pyrazolo[1,5-a]pyrimidine compounds as trk inhibitors
A compound and drug technology, applied in the field of chemical medicine, can solve the problems of low total yield and achieve the effects of low synthesis cost, good metabolic stability, and convenient synthesis method
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[0104]
[0105] The present invention also provides the preparation method of the compound described in general formula (I), it comprises:
[0106] Preparation of intermediate (formula (II)):
[0107]
[0108] In some specific embodiments of the present invention, the intermediates include the following three types: compound (A), compound (B) and compound (C), and the respective preparation processes are as follows:
[0109] The preparation process of compound (A) (reaction formula 1):
[0110]
[0111] Reaction 1
[0112] As shown in reaction formula 1, the raw materials 2,5-difluorobenzaldehyde and methylamine are reductively aminated to obtain intermediate 1; intermediate 1 and 5-chloropyrazolo[1,5-a]pyrimidine are generated at high temperature Nucleophilic substitution gives intermediate 2; intermediate 2 is nitrated with nitric acid to give intermediate 3; intermediate 3 is reduced by zinc powder to give compound (A).
[0113] The preparation scheme of compound...
Embodiment 1
[0195] (S)-3-((5-((2,5-difluorobenzyl)(methyl)amino)pyrazolo[1,5-a]pyrimidin-3-yl)amino)-4- (3-Hydroxypyrrolidin-1-yl)cyclobut-3-ene-1,2-dione
[0196] Structural formula:
[0197]
[0198] Intermediate A (60 mg, 0.21 mmol, 1 eq), (S)-3-ethoxy-4-(3-hydroxypyrrolidin-1-yl)but-3-ene-1,2-dione (purchased (53 mg, 0.25 mmol, 1.2 eq) from Yancheng Zhengchi Biotechnology Co., Ltd. was dissolved in 5 mL of ethanol, refluxed at 80 °C for 12 hours, cooled to room temperature, and the reaction solution was concentrated to obtain a solid. The crude product was purified by column chromatography to give a brown color Solid (S)-3-((5-((2,5-difluorobenzyl)(methyl)amino)pyrazolo[1,5-a]pyrimidin-3-yl)amino)-4 -(3-Hydroxypyrrolidin-1-yl)cyclobut-3-ene-1,2-dione (30 mg, 32% yield). 1 H-NMR (400MHz, DMSO-d 6 )δ: 9.07(s,1H),8.64(d,J=8.0Hz,1H),7.87(s,1H),7.30–7.00(m,3H),6.66(d,J=8.0Hz,1H), 5.06(s,1H), 4.85(s,2H), 4.26(s,1H), 4.02-3.33(m,4H), 3.17(s,3H), 2.04-1.73(m,2H).MS(ESI) m / z 455.2[M+1...
Embodiment 1A
[0200] (S)-3-((5-((2,5-difluorobenzyl)(methyl)amino)pyrazolo[1,5-a]pyrimidin-3-yl)amino)-4- (3-Hydroxypyrrolidin-1-yl)cyclobut-3-ene-1,2-dione sulfate
[0201] Structural formula:
[0202]
[0203] To (S)-3-(((5-((2,5-difluorobenzyl)(methyl)amino)pyrazolo[1,5-a]pyrimidin-3-yl)amine at room temperature yl)-4-(3-hydroxypyrrolidin-1-yl)cyclobut-3-ene-1,2-dione (0.46 g, 1.0 mmol, 1 eq) in methanol (15 mL) was added Sulfuric acid (5 mL, 1 mmol, 1 eq). The resulting solution was stirred for 2 hours and then concentrated to give (S)-3-(((5-((2,5-difluorobenzyl)(methyl)amino)pyrazolo[1,5-a]pyrimidine as a yellow solid -3-yl)amino)-4-(3-hydroxypyrrolidin-1-yl)cyclobut-3-ene-1,2-dione sulfate (0.41 g, 72% yield).
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