Study On Synthesis Technology Of Propamidine-intermediate Compounds

The novel systemic fungicide-propamidine achieved comprehensive treatment of antiseptic drug-fast and served for agriculture.Propamidine has a role of the prevention and treatment on the plant botrytiscirerea and other plant pathogeny and it is also a novel,low poison and non-pollution agriculture antiseptic.So this has economy and society significance.In the paper,p-fluorobenzonitrile,p-chlorobenzene-1-carboxi-midamide hydrochloride, p-fluorobenzene-1-carboxi-midamide hydrochloride and 1,3-bis(4-nitrile phenoxy) propane as four ropamidine-intermediate compounds were studied and measured.1.Using the KF as a fluridizer,Ph₄PBr as a PTC(phase transfer catalyzer), p-chlorphennitrile as raw material,p-fluorobenzonitrile was gained and measured by melting point and IR.After many single factor experiments,the optimum preparation conditions of fluorination were obtained as follows:n(KF):n(p-fluorobenzonitrile) =2.0:1.0,solvent is 100mL DMI,the reaction time:6h and the reaction temperature:210℃.n(p-fluorobenzonitrile):n(Ph₄PBr) =0.025:0.0025.2.Using p-chlorphenamidine,glycol as raw materials,the first step addition reaction catalyzer--------sodium ethylate produced from the sodamide and glycol,the second step amido reaction processed by adding the ammonium chloride,p-chlorobenzene-1-carboxi-midamide hydrochloride was gained by alkaline catalyze and measured by IR.The product can be easily obtained without pollution to the entironment.After many single factor experiments,the optimum preparation conditions of fluorination were obtained as follows: n(p-chlorphennitrile):n(sodamide):n(ammonium chloride) =1.0:1.1:1.1,the addition reaction time:22h and the reaction temperature:25℃,amido reaction time:2h,reaction temperature:40℃.3.Using N-acetylcysteine as addition catalyzer,adding the ammonirm acetate in the amido reaction,the time was short,laboratory manipulate easily and achieved the industrialization easily by this means and it was very innovative without register in domestic using p-fluorobenzonitrile as raw material,N-acetylcysteine as addition catalyzer,adding the ammonirm acetate in the amido reaction,the p-fluorobenzene-1-carboxi-midamide hydrochloride was gained and measured by IR.After many single factor experiments,the optimum preparation conditions of fluorination were obtained as follows:n(p-fluorobenzo- nitrile):n(N-acetylcysteine): n(ammonium acetate) =1.0:1.1:1.1,the addition reaction time:7h and the reaction temperature:25℃,amido reaction time:5h,reaction temperature:60℃.4.In the etherification reaction,using the p-fluorobenzonitrile as raw material,and the 1,3-propylene glycol potassium was gained by azeotropic removing water reaction of 1,3-propylene glycol,potassium hydroxide and toluene.The nucleophilic substitution reaction was occurred by the fluorobenzonitrile and 1,3- propylene glycol potassium and the etherification product 1,3-bis(4-nitrile phenoxy) propane was gained and measured by IR.After many single factor experiments,the optimum preparation conditions of etherification were obtained as follows:n(fluorobenzonitrile):n(1,3-propylene glycol):n(KOH) =1.0:1.1:1.1,the etherification reaction time:24h and the etherification reaction temperature:60℃.