Synthesis And Biological Activities Of Novel (THIO)Phosphoryl Hydrazide Derivatives Incorporating A Moiety Of Tetramic Acid

The organic phosphates, used in preventing and controlling the plant disease, insect and weed, play very important role in the agricultural chemical domain. Because the organophosphate compounds show remarkable herbicidal, fungicidal and insecticidal activities and the phosphorus atom’s substituting group has many kinds of transformations, they become a class of compounds with good prospects in developing new pesticides with low toxicity and good environmental compatibility, particularly in introducing heterocyclic to the structure of them. Furthermore, natural pyrrolidine-2,4-dione(tetramic acid) compounds have diversified structures and excellent biological activities including antitumour, fungicidal and herbicidal activities, and some of artificial derivatives have been found to exhibit marked biological activities. In this article, the organic phosphate and phosphorothioate were modified by introducing the structure of pyrrolidine dione through hydrazine group to design and synthesize four series of novel phosphoryl hydrazide derivatives containing the group of tetramic acid. The herbicidal, fungicidal and insecticidal activities of all the title compounds were evaluated.Firstly, five3-(1-hydroxylylidene)tetramic acid analogs were synthesized through four steps with natural amino acids as raw materials. Phosphoryl hydrazides with the same alkoxy were synthesized with phosphorus thiochloride, methanol or ethanol, then they were reacted with tetramic acid analogs respectively to obtain nine O,O-dialkyl-(2-(1-(2,4-dioxopyrrolidin-3-ylidene)ethyl)hydrazinyl)phosphonothioates. In a similar way, other three series of thiophosphate were reacted with tetramic acid analogs respectively to obtain five0-methyl/phenyl-O-ethyl-(2-(1-(2,4-dioxopyrrolidin-3-ylidene)-ethyl)hydrazinyl)phosphonothioate, four0,0-diphenyl-(2-(1-(2,4-dioxopyrrolidin-3-ylidene)ethyl)-hydrazinyl)phosphonothioate and two N,N’-diphenyl-(2-(1-(2,4-dioxopyrrolidin-3-ylidene)ethyl)hydrazinyl)Phosphoricamide. Finally, the structures of all the title compounds were characterized by IR,’H NMR, MS, and elemental analysis.The herbicidal activities were evaluated at a concentration of100μg/mL. The results revealed that all the compounds exhibited herbicidal activities against Brassica campestris and Echinochloa crusgalli. The inhibitory rates of the title compounds is7.3%-69.8%in variety against the root of B. campestris. The compound11d showed highest inhibitory rates of69.8%. The inhibitory rates of the compounds is17.5%-67.6%in variety against the root of E. crusgalli and9.2%-30.5%stem of E. crusgalli, The highest inhibitory rates against the root of E. crusgalli is9c with67.6%.At the same time, fungicidal activities were evaluated at a concentration of100μg/mL. Some title compounds exhibited certain fungicidal activity against B. cinera and R. cerealis. Thereinto, the compound11d exhibited the best antifungal activities, its inhibitory rates against F. graminearum, B. cinera and R. cerealis were25.7%、49.9%and61.2%respectively. The compounds10c and11d showed highest inhibitory rates of52.9%against B. cinera and61.2%against R. cerealis respectively.The insecticidal activities were evaluated against Plutella xylostella(L.) at a concentration of100μg/mL. But all the title compounds did not exhibit obvious insecticidal activity.