Synthesis And Fungicidal Activity Of Cyclopentanedione And Indandione Derivatives Incorporating Substituted Ester And Phenylhydrazine Moiety

Cyclopentanedione was a common ?-dicarbonyl compound with excellent biological activity and widely used in synthesizing antibiotic and prostaglandin.Indandione was a bioactive compound and a kind of intermidate used to synthesize steride,insecticide and herbicide.In this article,substituted phenylhydrazine moiety and ester moiety were introduced to the structure of 1,3-cyclopentanedione and 1,3-indandione to synthesize novel cyclopentanedione and indandione derivatives.The antifungal activities of the compounds were aslo evaluated.Firstly,the intermediate 2-(1-hydroxyethylidene)-1,3-cyclopentanedione was prepared by the reaction of Fridel-Crafts acylation with butanedioic anhydride in catalytic condition of alchlor.Then,it was used to synthesize fourteen cyclopentanedione derivatives A and B containing substituted phenylhydrazine moiety and ester moiety.Meanwhile,the intermediate 2-(1-hydroxyethylidene)-1,3-indandione was prepared by the cyclization reaction with diethyl phthalate as the raw material.Then,it was used to synthesize eleven indandione derivatives 4 containing substituted phenylhydrazine moiety.Similarly,it was used to synthesize eleven indandione derivatives C-E containing substituted phenyl hydrazine moiety and ester moiety.The structures of the compounds were confirmed by FT-IR,1H NMR and MS.The antifungal activities of the title compounds against Fusarium graminearum,Botrytis cinereo,Rhizoctonia solani and Colletotrichum capsici were screened in vitro with mycelia growth rate method.The EC50 values were evaluated using the double broth dilution method.At the concentration of 10 ?g/mL,the cyclopentandione derivatives A and B exhibited remarekable fungicidal activities.The compounds As and A4 showed higher activities against F.graminearum and B.cinerea with EC50 values of 0.2816 ?g/mL and 0.2295 ?g/mL,lower than the value 0.4953 ?g/mL of carbendazim and the value 0.3579?g/mL of procymidone,respectively.The compound B5 showed highest activity against R.solani with EC50 value of 0.0157 ?g/mL,lower than the value 0.5417 ?g/mL of carbendazim.The compound As displayed good activity against C.capsici with EC50 value of 0.4668 pg/mL.The indandione derivatives C and D showed remarkable activity against B.cinerea.Among them,the compound Di gave EC50 value of 0.4112 ?g/mL.The preliminary structure-activity relationship analysis indicated that the cyclopentanedione derivatives A and B showed higher biological activity than the indandione derivatives C and D.Among the compounds A and B,the compounds with medium sized alkyl at the alcohol part of ester,such as i-C3H7 and n-C4H9,showed higher activity.When the strong electronegative 4-Cl or 4-Br group was introduced to benzene ring,the corresponding compounds also showed good bioactivity.Among the compounds C and D,the compounds wth small sized alkyl at the alcohol part of ester,sruch as C2H5,showed higher activity.When the group 2-F,4-F,4-Br or 4-CH3 was introduced to benzene ring,the corresponding compounds showed better activity.