Synthesis technology for continuously preparing azilsartan in micro-channel reactor
A technology of microchannel reactor and synthesis process, applied in chemistry/physics/physicochemical reactor, organic chemistry, chemical instruments and methods, etc., can solve the problem of low degree of automation and the acquisition of 2-ethylhexyl chloroformate raw materials Difficult, complex steps of the ring-forming reaction, etc., to achieve the effect of shortening the reaction time, lowering the reaction temperature, and reducing the reaction steps
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Embodiment 1
[0051]
[0052] 2-Ethoxy-1-[(2'-cyano[1,1'-biphenyl]-4-yl)methyl]-1H-benzimidazole-7-carboxylic acid methyl ester (SM- 1) Add 150g, 240g of 50% aqueous solution of hydroxylamine and 38g of triethylamine to 1500mL of absolute ethanol, heat to 80°C, reflux for 20h, monitor the progress of the reaction by TLC, developer: petroleum ether / ethyl acetate=1:2( Volume ratio). After reacting for 20 hours, stop the reaction, cool and crystallize, suction filter, wash, and air-dry at 50°C to obtain intermediate TAK1, a white solid of 95.2g, with a yield of 70%. The mass spectrum and NMR spectrum are shown in image 3 , Figure 5 .
Embodiment 2
[0053] Example 2: This scheme mainly undergoes two-step reactions, namely the addition reaction of SM-1 and hydroxylamine to synthesize intermediate TAK3, and the hydrolysis reaction of intermediate TAK3 to prepare the target compound azilsartan.
[0054]
[0055] Configure the dioxane solution of intermediate TAK1 and triethylamine in the first raw material storage tank, the molar volume ratio of TAK1, triethylamine and dioxane is 100mmol: 120mmol: 250mL, in the second raw material storage tank A dioxane solution of solid phosgene was configured in the mixture, and the molar volume ratio of solid phosgene and dioxane was 100mmol: 250mL. The solution in the storage tank waits to be pumped into the microstructure mixer and enters the microstructure reactor for reaction. The first reactor is a 1 / 4 stainless steel pipe with a length of 6 meters and a total volume of 100mL.
[0056] The first raw material storage tank (TAK1 and triethylamine dioxane solution) and the second raw...
Embodiment 3
[0061] The dioxane solution of intermediate TAK1 and diethylamine is configured in the first raw material storage tank, and the molar volume ratio of TAK1, diethylamine and dioxane is 100mmol: 120mmol: 250mL; in the second raw material storage tank Configure the dioxane solution of solid phosgene in the middle, the molar volume ratio of solid phosgene and dioxane is 100mmol: 250mL; The molar volume ratio is 0.4mol: 1000mL, the solution in the storage tank is waiting to be pumped into the microstructure mixer, and enters the microstructure reactor for reaction. The second reactor is a 1 / 4 stainless steel pipe with a length of 2 meters, which removes the epitaxial volume and effectively The total volume is 30 mL.
[0062] The first raw material storage tank (TAK1 and triethylamine dioxane solution) and the second raw material storage tank (solid phosgene dioxane solution) are pumped into the microstructure reactor according to the volume flow ratio of 1:1 , at 5°C, keep for 20m...
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