Synthesis And Insecticidal Activity Of Several Spinosad Derivatives

Spinosad is a macrolide compound pesticides,its safety and bio-pesticides chemical p esticides,spinosad has become a high-quality green bio-pesticides. At present,due to the biosynthesis of complex spinosad yield was also affected,and therefore looking for high-y ield,low toxicity and residue of the new active substance spinosad,the paper combined w ith spinosad mechanism based on the use trichloroacetylpyrrol Asia amine and click chemi stry,according to the relevant literature,to improve its lipophilic and reduce dipole mome nt,be reasonable chemical modification,is an important way to filter spinosad class of hi ghly active compounds. This article retain spinosad nucleus structure unchanged,synthesi s modification,synthesis of novel derivatives of spinosad its C-9 position rhamnose site an d C-17 amino sugars parts and preliminary bioassay new synthetic compounds insecticidal activity,and further study of the derivative structure-activity relationships and insecticidal activity, in order to get higher spinosad derivative activity.The main contents:1. Orthogonal design experiments to study the acid hydrolysis process raw spinosad,s pinosad optimal hydrolysis conditions for raw materials: trifluoroacetic acetic acid concent ration 2mol / L,hydrolysis time 9h,hydrolysis temperature is 90 ℃,the use of acid hydr olysis spinosad free C-9 and C-17-hydroxyl aglycone hydroxy leave as glycosylation reacti on glycosylation receptors.2.In three monosaccharide(D- glucose,D- galactose,L- rhamnose) as spinosyn deri vatives synthesized glycosyl donor to spinosad(liberated C-9 and C-17 hydroxyl hydroxy)for glycosyl acceptor,trichloroacetimidate method using glycosylation reaction and linkin g reaction,to establish and optimize spinosyn derivatives chemical synthesis method,diff erent glycosylated macrolides obtained by chemical synthesis and more Spinosad derivativ es,their derivatives structure through Nuclear magnetic resonance spectrum 1H-NMR,nu clear magnetic resonance spectrum13C-NMR,HPLC were characterized. Its ownership co nfirm nine kinds of spinosad derivatives are: 9-0-(β-D- glucopyranose)-17-0-(β-D- gluco pyranose)spinosad17-0-(β-D- glucopyranosyl)spinosad,9-0-(β-D- galactopyranosyl)-17-0-( β-D- galactopyranosyl) spinosad,17-0-(β-D- galactopyranosyl)spinosad,9-0-(β-L- r hamnopyranosyl)-17-0-(β-L- rhamnopyranosyl) spinosad17-0-(β-D--rhamnopyranosyl)s pinosad,2-(2’-amide-ethoxy)- ethyl-β-D- glucopyranose spinosad,2-(2’-amide-ethoxy)- ethyl-β-D- galactopyranose spinosad.3.Method trichloroacetyl total of five stride Reaction: Preparation pseudoaglycone,a ll benzoylated carbohydrate,selective free hydroxy,esterified,the glycosidic bond is formed to give a new novel compound. There are three big reaction link: preparing a glycosyl ated azide,preparation and amide bond spinosad acids. Esterification and glycoside bond f ormation anhydrous oxygen-free environment must be strictly controlled,three-dimension al configuration of the glycosidic bond can be controlled. Overall reaction conditions stabil ized,high yield and high efficiency. Spinosad synthesized derivatives at 20 mg / L dose Va lley Pirates are on the saw and Tribolium etc. showed some insecticidal activity,mortality at 41% to 69%. Spinosad synthetic derivative of the insecticidal activity of spinosad just co mplements the saw castaneum and Tribolium the insecticidal spectrum, but its onset time and with other types of insecticides virulence comparison remains to be turned. Although s pinosad derivatives Valley saw Pirates and Tribolium insecticidal activity somewhat less m ature product spinosad, but still its derivatives do further research and virulence insecticid e structural transformation to hope to get more quality spinosad derivatives.