Synthesis And Catalytic Properties Of 1,4-diazabicyclo[2.2.2] Octane Quaternized Derivatives

Surfactant has many good properties such as low CMC value,surface tension of water or solution drop characteristics,good emulsification,foaming,wetting,solubilization,compound and resistance to calcium and magnesium ions.It has been widely used in fine chemical fields such as agriculture,medicine,cosmetics,washing,petroleum,mineral mining,paper making,etc.As a kind of phase transfer catalyst,surfactant is widely used in heterogeneous reaction to make the reaction faster,more thoroughly,higher yield and almost no by-products.In this paper,1,4-diazabicyclo[2.2.2]octane is used as raw material to react with bromoalkanes in order to obtain J series monoquaternary ammonium salt.Then the intermediate reacts with ethyl chloroacetate to obtain L series diquaternary ammonium salt.After alkaline hydrolysis and purification,JL series heterosurfactants are synthesized.Besides,the surface properties of JL series surfactants,J-16 acid functionalized ionic liquid and catalytic performance of L-14 are also studied.The main work of this paper is shown as follows:（1）After reaction of 1,4-diazabicyclo[2.2.2]octane with bromododecane,bromotetradecane and bromohexadecane,the monoquaternary ammonium salt surfactants J-12,J-14 and J-16 are obtained with the yields of 91.3%,93.3%and94.4%respectively（calculated as brominated alkanes）.Next,the products of the previous step reacted with ethyl chloroacetate respectively to obtain the ester-containing double quaternary L-12,L-14,and L-16 with the yields of 83.3%,84.6%,and 86.9%respectively（calculated as J series surfactants）.Then,after the hydrolysis process of L-12,L-14,L-16,the yields of heterosurfactants JL-12,JL-14,and JL-16 were 96.5%,97.1%,and 97.8%（calculated as L series surfactants）.And the structure was characterized by ¹H NMR,ESI-MS,FT-IR.（2）The Krafft points measured by using the cloud point method of JL-12,JL-14,JL-16 are 6,10,13℃respectively,and the CMC values measured by the conductivity method are 0.627,0.576,0.502 mmol respectively.Theγ_CMCvalue measured by the hanging drop method at 298.15 K are 38.23、37.83、36.65 m N/m respectively.The emulsification time measured by the measuring cylinder method was260,348,and 485 s respectively.The foaming performance of JL series surfactants is getting better and better with the increase of the hydrophobic carbon chain.The maximum concentration of CaCl₂and MgCl₂resistance of JL-12 are 20000 mg/L and30000 mg/L respectively,（it performs better than traditional surfactant SDS as 0.5mg/L and 2 mg/L）.Performance tests show that the synthesized JL series heterosurfactants have better surface properties and foam properties,and better resistance to Ca²⁺and Mg²⁺in water.Usingγ_CMCvalue to calculate the surface activity parameters of JL series surfactants,results show that the descending order of surface activity is JL-16,JL-14and JL-12 which means the longer hydrophobic chain leads to the stronger surface activity.The conductivity method is used to measure the influence of temperature on its CMC,and the thermodynamic parameters of micelle formation（i.e.,ΔG_m^θ,ΔH_m^θand TΔS_m^θ）are obtained.The results show that formation of micelles is an entropy-driven spontaneous heating process.（3）The CMC values of L-12,L-14,L-16 double quaternary ammonium salt surfactants at 298.15 K measured by the hanging drop method are 1.064,0.942,0.841mmol/L andγ_CMCvalues are respectively 38.23,37.83,36.65 m N/m respectively.Sulfuric acid and p-Toluenesulfonic acid are processed to obtain acid functionalized ionic liquids HSO₄-J-16 and Ts O-J-16.The esterification reaction of chloroacetic acid and n-dodecanol is taken as the research object,the catalytic effects of HSO₄-J-16 and Ts O-J-16 were studied.The results show that the catalytic effect of HSO₄-J-16 ionic liquid is better.The catalyst was recycled twice,with little change in catalytic activity.（4）Using L-14 as the solid-liquid phase transfer catalyst,the catalytic reaction kinetics of sodium benzoate and sodium phenoxyacetate with ethyl p-toluenesulfonate were studied respectively.The results show that the L-14 has no catalytic effect on the reaction of sodium benzoate and ethyl p-toluenesulfonate.However,it can accelerate the reaction speed of sodium phenoxyacetate and ethyl p-toluenesulfonate.When the concentration of L-14 is 0.01mol/L,the activation energy of the reaction drops by8.93k J/mol,which indicates that the catalyst has a good catalytic effect on the reaction.The apparent reaction rate constant is linearly positively correlated with the catalyst concentration.（5）A nucleophilic substitution reaction of sodium quinolinate with ethyl p-toluenesulfonic acid to synthesize the herbicide quizalofop-p-ethyl has been considered in this paper.In the presence of L-14 as a solid-liquid phase transfer catalyst,the kinetics of the catalytic reaction and the effect of the amount of catalyst on the reaction are studied.The effect of kinetics and catalyst dosage on the reaction can be shown as the fact that 0.01mol/L of the L-14 leads to an activation energy decrease of the reaction by 15.81k J/mol.The catalytic effect of L-14 is better compared with that using TTAB as a phase transfer catalyst.