Synthesis Of Cvclopropyl Methvl Ketazine From Ketone And Hydrazine

Ketazines as a class of compounds with conjugated double bonds(-C=N-N=C-)show many special properties and high reactivities.Up to now,ketazines are extensively applied in many industrial fields,including pharmaceutical intermediates,photosensitive materials,polymerizable monomers,dyes,and aviation fuels.For the condensation reaction of cyclopropyl methyl ketone and hydrazine hydrate,we optimized the reaction conditions,measured the reaction enthalpy and kinetics,characterized the structure of cyclopropyl methyl ketazine,and obtained a series of its physicochemical properties.The main contents are summarized as follows:(1)Cyclopropyl methyl ketazine was prepared from cyclopropyl methyl ketone and hydrazine hydrate.A series of characterizations were performed after the product was purified through three times' distillation.The reaction heat was measured so that the enthalpy and Gibbs free energy were obtained.Under the atmospheric pressure,the reaction was studied at different rotation rates,mole ratios of cyclopropyl methyl ketone to hydrazine,reaction temperatures,and reaction times.With the optimized reaction conditions at 2/1,363.2 K and 7 h,the conversion rate of ketone was up to 96.8%and the yield of cyclopropyl methyl ketazine was up to 93.6%through the chromatograph measurements.The reaction kinetic model was established,and parameters such as reaction order and activation energy were calculated.(2)Physicochemical parameters of cyclopropyl methyl ketazine were measured and correlated in a temperature range(T,280?400 K).Properties were acquired including density(p,0.884?0.947 g·cm-3),dynamic viscosity(?,1.39?2.88 mPa·s),heat capacity(Cp,2.03?2.32 J·g-1·K-1),surface tension(22.1?25.0 mN·m-1),etc.The data of ?,?,and ? exhibit the positive correlations with temperature,while Vm,?,and Cp show the negative correlations,which all have a good fitting degree for equations.Considering the cyclopropyl methyl ketazine reaction systems,the vapor-liquid equilibria(VLE)of binary system(cyclopropyl methyl ketone+cyclopropyl methyl ketazine)were measured,and correlated with NRTL model to acquire the binary interaction parameters.In summary,a new ketazine(cyclopropyl methyl ketzaine)was prepared in this work.The reaction enthalpy and kinetics were measured,and a set of physicochemical parameters of cyclopropyl methyl ketazine were obtained.The above work provides a useful foundation for the industrial application of cyclopropyl methyl ketazine.