Synthesis And Biological Activity Of 4-Aryl(Methyl) Imidazolinoquinoxalinones

Because imidazolines and quinoxalinones have broad-spectrum biological activities,they have become one of the hot spots in drug and pesticide research.Therefore,in this thesis,we designed and synthesized a series of 4-aryl（methyl）imidazolinoquinoxalinones I,and the structures of the target compounds were characterized by IR,¹H NMR and ¹³C NMR,and the single crystal structures of some compounds were determined by x-ray diffraction,and the fungicidal activity of the synthesized compounds was investigated.（1）A series of 2-bromoacetamide compounds VIII-1～VIII-27 were synthesized in yields of 73.0%～94.2%by reaction of bromoacetyl bromide with arylamine or benzylamine and their derivatives under ice-water bath with triethylamine as acid binding agent.（2）In the mixed solvent of DMF and THF（V:V=1:2）,bromoacetamides VIII reacted with o-phenylenediamine or o-aminoacetanilide at 65°C for 5 h under the action of K₂CO₃to produce a series of compounds N-aryl-2-（（2-substituted aminophenyl）amino）acetamides VI-1～VI-4 and VII-1～VII-27 in yields of 31.0%～92.4%.（3）Reduction of N-aryl-2-（（2-substituted aminophenyl）amino）acetamides VI and VII by Li Al H₄gave a series of N-（2-aminophenyl）-N′-（substituted amino）1,2-ethylenediamines V-1～V-31 in yields of 51.9%～93.6%.（4）N-（2-aminophenyl）-N′-（substituted amino）-1,2-ethylenediamines V reacted with ethyl glyoxylate or ethyl pyruvate under the catalyst to synthesize a series of4-aryl（methyl）imidazolinoquinoxalinone I-2～I-33.The reaction conditions are:n（compounds V-2～V-4）:n（ethyl glyoxylate）=1:2.0,or n（compounds V-5～V-31）:n（ethyl glyoxylate/ethyl pyruvate）=1:4.0,DABCO（30%mol）as catalyst,toluene as solvent,temperature 100°C,time5 h.The yields of the reactions are 28.6%～72.0%.When there is no ethyl group on the N atom,compound V reacted with ethyl glyoxylate giving only the target compound I in relatively higher yield,and no quinoxalinedione was found.When the N atom is connected to the ethyl group,and the substituent R is on the para or meta positions of the phenyl group,quinoxalinedione IX was also generated in the reaction in addition to the target compound I.But,when the substituent R is on the ortho position,the reaction gave only the quinoxalinedione compound IX without the target product I.（5）The fungicidal activity of the synthesized N-aryl-2-（（2-substituted aminophenyl）amino）acetamideVIandVII,N-（2-aminobenzyl）-N′-（substituted amino）-1,2-ethylenediamines V and 4-aryl（methyl）imidazolinoquinoxalinone I and1-ethyl-4-（2-（arylamino）ethyl）-1,4-quinoxaline-2,3-dione IX were tested.The inhibitory rates of amides VII-13,VII-20 and VII-26 against Magnaporthe grisea were 82.2%,87.8%and87.8%,respectively.The inhibition rates of amides VII-11 and VII-13 against Sclerotinia sclerotiorum were both 77.4%,which were higher than that of chlorothalonil.The inhibition rates of ethylenediamine V-24 against Magnaporthe grisea and Sclerotinia sclerotiorum were93.9%and 81.7%,respectively;The inhibition rates of ethylenediamine compounds V-26 and V-27 against Sclerotinia sclerotiorum were both 87.0%,which were higher than that of chlorothalonil.The inhibitory activities of imidazolinoquinoxalinones I-23 and I-29 against Magnaporthe grisea were 87.8%.The inhibitory activities of imidazolinoquinoxalinones I-15,and I-31 against Sclerotinia sclerotiorum were 83.9%and 80.5%,respectively,which were higher than that of chlorothalonil.The inhibitory activities of quinoxaline dione compounds IX-13 and IX-10 against Sclerotinia sclerotiorum were 88.7%and 82.1%,which were higher than that of chlorothalonil.