Catalytic Synthesis And Properties Of 1,3-dicyclopropyl-2-buten-1-one

As an important power source for aerospace vehicles,high-energy fuel is one of the key factors determining the speed and carrying capacity of aerospace vehicles.Traditional aerospace fuels have energy deficiencies,while there are multiple ring structures in the tension ring hydrocarbon fuel molecules,which can release additional energy during the combustion process,and have the advantages of high density and high volume calorific value.It can effectively improve the cruising range of aircraft by replacing traditional RP-3 fuel,and is an important direction of high-energy hydrocarbon fuel research.The preparation of strained ring hydrocarbon fuels from ketenes has the characteristics of low cost,high atom utilization and mild reaction conditions,and is expected to become the mainstream process of strained ring hydrocarbon fuels.In this subject,1,3-dicyclopropyl-2-buten-1-one was synthesized by using cyclopropyl methyl ketone as raw material under the action of basic catalyst.The main research progress is as follows:（1）A high-purity sample of 1,3-dicyclopropyl-2-buten-1-one was prepared.Starting from cyclopropyl methyl ketone,the crude product was synthesized under the catalysis of sodium tert-butoxide,and was separated and purified to obtain a 96%pure sample.The structure of 1,3-dicyclopropyl-2-buten-1-one was analyzed by GC-MS,FTIR,NMR and other methods,and the mass-to-charge ratio of the molecule was obtained as 149,in which there were C=C and C=O functional group,there are 8 kinds of carbon and 8 kinds of hydrogen,which is consistent with the structure of1,3-dicyclopropyl-2-buten-1-one.（2）The physicochemical properties of 1,3-dicyclopropyl-2-buten-1-one were determined.Through the optimization of structure and frequency,1,3-dicyclopropyl-2-buten-1-one has two isomers,among which E-type enone is more stable.Based on this,the enthalpy of formation of E-type enone in liquid state(-481.1k J·mol^-1),standard molar combustion enthalpy(5454.8 k J·mol^-1),maximum specific impulse（285.6 s）,and maximum electrostatic potential(17.44 kcal·mol^-1 and-44.60kcal·mol^-1)and other basic parameters;the density-viscosity fitting equation of1,3-dicyclopropyl-2-buten-1-one was measured(ρ=-8.417×10^-4T+0.992 andη=7.66e^-0.03T+0.134),boiling point（226.9℃）and surface tension（17.1 m N·m-1）and other basic parameters.（3）The optimized process conditions for the preparation of1,3-dicyclopropyl-2-buten-1-one were obtained.The effects of basicity,steric hindrance and configuration of basic catalysts on the conversion rate,selectivity and yield of the reaction were studied.It was found that under the experimental conditions,the weaker the basicity,the higher the selectivity;the greater the steric hindrance,the higher the selectivity.higher selectivity.At the same time,the process conditions were optimized in the condensation experiment using aluminum tert-butoxide as catalyst,and the optimum selectivity was obtained when the temperature was 120℃and the catalyst dosage was 10%.