Method for synthesizing tert-butyl acetylene which is intermediate of terbinafine medicines
A technology of terbinafine and synthesis method, which is applied in the field of synthesis of terbinafine pharmaceutical intermediate tert-butylacetylene, can solve the problems such as the reduction of terbinafine clearance rate, achieve reduction of reaction temperature and reaction time, increase Reaction yield, the effect of reducing intermediate links
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example 1
[0012] In the reaction vessel that stirrer, thermometer, dropping funnel, condenser are installed, add mass fraction and be 30% potassium bisulfite solution 310ml, mass fraction is 60% hexane 300ml, raise solution temperature to 90 ℃, control Stir at 150rpm, add 0.73mol of 1,1-diamino-3,3-dimethylbutane (2) dropwise, control the dropwise addition time at 3h, add 0.81mol of phenyl hypochlorite (3), and react for 90min , raise the temperature of the solution to 110°C, continue the reaction for 3h, lower the temperature of the solution to 10°C, precipitate solids, filter, wash with potassium iodide solution, wash with acetonitrile with a mass fraction of 80%, distill under reduced pressure at 1.1kPa, collect 100--108°C Fractions were recrystallized in 90% cyclohexane to obtain 41.30 g of crystalline tert-butylacetylene with a yield of 69%.
example 2
[0014] In the reaction vessel that stirrer, thermometer, dropping funnel, condenser are installed, add mass fraction and be 32% potassium bisulfite solution 310ml, mass fraction is 62% hexane 300ml, raise solution temperature to 92 ℃, control Stir at 160rpm, add 0.73mol of 1,1-diamino-3,3-dimethylbutane (2) dropwise, control the dropwise addition time at 4h, add 0.83mol of phenyl hypochlorite (3), and react for 110min , raise the solution temperature to 112°C, continue the reaction for 4h, lower the solution temperature to 12°C, precipitate solids, filter, wash with ammonium chloride solution, wash with acetonitrile with a mass fraction of 82%, distill under reduced pressure at 1.2kPa, collect 100--108 The fraction at ℃ was recrystallized in cyclohexane with a mass fraction of 92% to obtain 43.09 g of crystalline tert-butylacetylene, with a yield of 72%.
example 3
[0016] In the reaction vessel that stirrer, thermometer, dropping funnel, condenser are installed, add mass fraction and be 35% potassium bisulfite solution 310ml, mass fraction is 65% hexane 300ml, raise solution temperature to 95 ℃, control Stirring speed is 170rpm, 0.73mol of 1,1-diamino-3,3-dimethylbutane (2) is added dropwise, the dropping time is controlled at 5h, 0.84mol of phenyl hypochlorite (3) is added, and the reaction is 120min , raise the temperature of the solution to 115°C, continue the reaction for 5h, lower the temperature of the solution to 15°C, precipitate a solid, filter, wash with potassium iodide solution, wash with acetonitrile with a mass fraction of 85%, distill under reduced pressure, collect the fraction at 100--108°C, Recrystallized in 1.3 kPa cyclohexane to obtain 47.29 g of crystalline tert-butylacetylene with a yield of 79%.
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