Research On Synthesis And Bioactivity Of Four Series Pyridine Derivative

Natural pyridine compounds and their structurally related compounds,with broad spectrum of biological activities and variety of structure,are naturally included in nicotianaspp plants,and its abstractions from nicotianaspp as pesticides have been investigated and used for long time.However,synthetic pyridines compounds as pesticides have flourished only for the recent decades.In recent years,some more effective pesticides, such as imidacloprid,hcetamiprid,thiadoprid,pyroxidechlor,pyridinthion and denment, have been synthesized through chemical modification of natural compounds of nicotianaspp.This discovery showed that synthesized pyridine compounds have been successfully developed in insecticide,fungicide and herbicide,and will play an important part in synthesis and biological activity of pesticide aspect.The synthesis and bioactivity study of pyridine compounds have became one of active studied fields to the chemicals and biological scholars.By adopting the connection method of active structure base in this dissertation,for example,connection of pyridine N-oxide pyridine,Nitro substituted pyridine and dicarborimide,four classes pyridine compounds(total 45) have been synthesized.The main result is followed.Series N-methyl-N-substituted methylpyridineamine compounds are synthesized firstly (labeled classâ… ).The 2-Chloro-5-aminemethylpyridine is important intermediate in the synthesis process of N-methyl-N-substituted methylpyridineamine.Its synthesis steps starts from Gabriel condensation reaction by 2-Chloro-5-Chloro methylpyridine and K₂CO₃,and reacted production was hydrolyzed in basicity solution in the same time,then hydrolytic production was distilled by vapor.By crystallizing the distilled production,we finally got intermediate 2-Chloro-5-aminomethylpyridine.Then,the reaction of N-methyl and N-substituted of 2-Chloro-5-aminomethylpyridine gave series N-methyl-N-substituted methylpyridine compounds,i.e.,the 11 target compounds.The Elemental analysis was carried on and spectra of IR,GC-MS,¹H NMR,¹³C NMR were presented.The structures of N-methyl-N-substituted methylpyridineamine agree with the IR,GC-MS,¹H NMR,¹³C NMR spectroscopic data.Then series N-(6-Chloro-3-Pyridinemethy)-diearborimide compounds have been synthesised(labeled classâ…¡).The dicarborimide salt of potassium is important intermediate in the synthesis process of N-(6-Chloro-3-Pyridinemethy)-dicarborimide.As the starting intermediate for the synthesis,diearborimide salt of potassium was generated through two step reactions.Firstly,reaction of raw diearboracid anhydride with carbamide produced intermediate diearborimide,then reactions of dicarborimide with KOH in methanol solution generated intermediate diearborimide salt of potassium in good yield.We researched a convenient synthesis method of target product of N-(6-Chloro-3-Pyridinemethy) -diearborimide be using the reaction of Nucleophilic substitution of diearborimide salt of potassium with 6-chloro-3-chloromethypyridine.The 7 compounds are synthesized.The Elemental analysis was carried out and spectra of IR, GC-MS,¹H NMR,¹³C NMR were presented.The structures of N-(6-chloro-3-pyridinemethy)-diearbonylimides(â…¡₁-â…¡₇) agree with the IR,GC-MS,¹H NMR,¹³C NMR spectroscopic data.Series N-(6-Chloro-1-oxide-3-methylpyridine) dicarborimide compounds are also synthesised(labeled classâ…¢).The N-oxidepyridine is important intermediate in the synthesis process of N-(6-Chloro-1-oxide-3-methylpyridine ) dicarborimide.Its synthesis method starts with N atom was oxidegenated by raw hydrogen peroxide in trifluoro acetic acid.Then series N-(6-Chloro-1-oxide-3-methylpyridine ) dicarborimide compounds were obtained by Gabriel condensation reaction of 6-Chloro-1-oxide-3-methylpyridine with diearborimide salt of potassium,i.e.,the 7 compounds are synthesized.The Elemental analysis was carried on and spectra of IR,¹H NMR,¹³C NMR,GC-MS were presented.The structures of series N-(6-Chloro-1-oxide-3-Pyridinemethy)-dicarborimide compounds agree with the IR,¹H NMR,¹³C NMR and GC-MS spectroscopic data.Series N-substituted-base-multi-substituted pyridine compounds are finally synthesised(labeled classâ…£).The 2-amino-3-nitro-5-bromide-pyridine is important intermediate in the synthesis process of N-substituted-base-multi-substituted pyridine compounds.Raw material 2-amino-5-bromide-pyridine was added carefully into a mixture of concentrate sulfuric acid and fuming nitric acid,and N-nitro-2-amino-5-bromide-pyridine was crystallized in hot water.Then, N-nitro-2-amino-5-bromide-pyridine was added carefully into a mixture of concentrate sulfuric acid and fuming nitric acid,and 2-amino-3-nitro-5-bromide-pyridine was crystallized also in hot water.Finally,the reaction of N-methyl and N-substitution of 2-amino-3-nitro-5-bromide-pyridine gave series N-substituted-base-multi-substituted pyridine compounds,i.e.,the 20 compounds are synthesized.The Elemental analysis was carded on and spectra of IR,¹H NMR,¹³C NMR,GC-MS were presented.The structures of N-methyl-N-formylamino-3-nitro-5-bromide- pyridine agree with the IR,GC-MS,¹H NMR, ¹³C NMR spectroscopic data.The experimental circumstance and the synthetic methods of the intermediate and target compounds have been investigated and optimized in the synthesis progress.The synthesis condition of reaction of nucleophilie substitution between classâ…¡compounds and classâ…¢compounds are analyzed under normal synthesis method and microwave-assisted synthesis method.The contrast result shows that the microwave-assisted synthesis method can be carded on with better reaction conditions and gives higher yield than the normal synthesis procedure.The microwave-assisted synthesis method possesses several advantages,i.e,faster reaction rates and higher yields rate.The reaction time of target compound N-(6-chloro-3-pyridinemethyl) phthalimide reduces from 9 h to 20 min and yields rate rises from 80%to 97%when we takepIace the normal synthesis procedure with the microwave-assisted synthesis method.The pesticide activity and bactericidal activity of all the target compounds have been evaluated.The pesticide activity is evaluated under 5 target insects,i.e.,diamondback moth, xylostella,bean aphid,crαccivura,spider mite,nilaparvata lugens.The experimental result is followed that with the medicament concentration 10 ug/mL,the mortality ratio to C.pipiens of compoundsâ…¢₁,â…¢₇,â…£₂,â…£₃ are respectively 92.6%,90.5%,94.6%,97.3 %and the mortality ratio to pipiens ofcompoundsâ… ₁,â…¡3,â…¡7,â…¢₆,â…£₆,â…£₈,â…£₁₀,â…£₁₁,â…£₁₄,â…£₁₅,â…£₁₆,â…£₁₉,â…£₂₀ are all 100%,i.e.,nearly equal mortality rate to the contrasted drug imidacloprid;with the medicament concentration 1 ug/mL,mortality rate to C.pipiens of the compoundâ…¡₃ andâ…¢₇ are 97.5%and 96.5%,and the mortality rate to C.pipiens of compoundsâ… ₁,â…¡₇,â…¢₁,â…¢₆,â…£₁₉,â…£₂₀ are also 100%,i.e,nearly equal mortality rate to the contrasted drug imidacloprid.With the medicament concentration 200 ug/mL,the mortality ratio to A.craccivura of compoundsâ… ₂,â…¢₁,â…¢₂ are 93.8%,96.3% and 90.5%,and the mortality rate to A.craccivura of compoundsâ… ₁,â…¡₇,â…¢₆,â…¢₇,â…£₂₀ are also 100%,With the medicament concentration 20 ug/mL,the mortality ratio to A.craccivura of compounds ofâ… ₁,â…¡₇,â…£₂₀ are also 100%.Mortality ratio shows that 17 compounds of total 45 compounds are A grade activation of suppressing insecticide activities.By using growing speed method,the bactericidal activity of all synthesized compounds have been evaluated under tested objection of botryris cinerea pers,fusarium qraminearum and pyricularia oryzae.The experimented result indicates that all the compounds don't present distinct activity of restraining bactericide.