Study On The Synthesis, Characteristition And Activity Of Optically Active Herbicide Safeners Of R-(-)-BAS145138

The synthesis , Characteristition and Activity of Optically active Herbicide Safener s of R-(-)5-dichloroacetyl-3,3,6-trimethyl-9-oxo-l,5-diaza-bicyclo[4.3.0] nonane was desc ribed in this paper. The raw material (R,S)-3,3,6-trimethyl-9-oxo-l,5-diaza-bicyclo[4.3.0]nonane, the intermediate product (R,S)-3,3,6-trimethyl-9-oxo-l,5-diaza-bicyclo[4.3.0] non ane,and the end-product R-(-)5-dichloroacetyl-3,3,6-trimethyl-9-oxo-l,5-diaza-bicyclo[4.3.0]nonane were synthetized respectively.the optimum condition was presented by designin g orthogonal experiment scheme. The structural isomerism of intermediate product and end-product was also charactized. The biological active effect of R-(-)-BAS-145138 waspreliminarily determined.The exhaustive studys as follows.The raw material (R,S)-3,3,6-trimethyl-9-oxo-l,5-diaza-bicyclo[4.3.0] nonane was pr eparated by three step by utilizing propanone,nitromethane,KIP chlorhyaric acid and lev ulic acid .the yields were 63.4%,84.5%,81.8% respectively,the optimum methods of the three product was presented.(R,S)-3,3,6-trimethyl-9-oxo-l,5-diaza-bicyclo[4.3.0] nonane D-(-)-tartaric was syntheti zed form (R,S)-3,3,6-trimethyl-9-oxo-l,5-diaza-bicyclo[4.3.0] nonane and D-(-)-tartaric asa chiral reagent.the optimum experiment condition as follows, the mixture ratio was 1: 1,temperature was 20~25 and the string time was 2hr. R-(-) -3,3,6-trimethyl-9-oxo-l, 5-diaza-bicyclo[4.3.0] nonane D-(-)-tartaric was crystallized from (R,S)-3,3,6-trimethyl-9-oxo-l,5-diaza-bicyclo[4.3.0] nonane?D-(-)-tartaric. the optimum experiment condition as follows, the ratio of ethanol and propanol was 1:2 crystallizing point was 25 2 andcrystallizing time was 96 hr. S-(+)-3,3,6-trimethyl-9-oxo-l,5-diaza-bicyclo[4.3.0] nonanewas preparated by the ion exchange reaction from R-(-) -3,3,6-trimethyl-9-oxo-l,5-diaz a-bicyclo[4.3.0] nonane D-(-)-tartaric. the optimum experiment condition as follows, the effluent volume of water was 80ml,flow speed of elution was 30ml-cm-2-min-1 and the eluting temperature was 25 ,the yield was 96.3%,the SPR was 33.8% and the optical purity was 98.8%. The end-product R-(-)- BAS-145138 was synthized from S-(+)-3,3, 6-trimethyl-9-oxo-l,5-diaza-bicyclo[4.3.0] nonane and dichloracetyl chloride, the optimum experiment condition as follows, 25%sodium hydrate as catalyst, methyl-benzene as solvent, and temperature was 30~35 , the yield was 77.7%.The SPR was 48.5(2g/10 Oml,CHCl3) and the optical purity was 99.0%.The structure of the intermediate product and end-product were confirmed by TLC, UV,1HNMR, 13CNMR and elementary analysis.The influence of R-(-)-BAS-145138 on plant height and fresh weight in maize wa s reported by bioassay method. The main researching works concluded as follows, und er 0.5~5ug/kg chlorsulfuron herbicide safener concentrations were correlated with the height fresh weight in maize seedling. When the concentrations of the safener was 1, 2 mg/kg, the protect rates in maize from chlorsulfuron injury were 105.35---196.28%.With the increasing of concentration of chlorsulfuron, the content of GSH decrease d obviously. When the concentration of chlorsulfuron were 0.5~5ug/kg, the treatment which immerged concentration of R-(-)-BAS-145138 were 0.5~2.0mg/kg made the cont ent of GSH reaching 110.4~ 136.6% of comparing sample.The safener of R-(-)-BAS-145138 had biological activity, and could protect maize from herbicide chlorsulfuron injury.