Preparation And Application Of Naphthalimide,Pyridine,and Phenyl Urea Derivatives

1,8-naphthalimide and pyridine and their derivatives possess excellent biological activities,which have been widely applied in the field of organic synthesis and pesticide.Organic acids such as 1-naphthylacetic acid(NAA)and cinnamic acid play important role in regulating plant growth.In order to search for novel compounds with good bioactivities,the naphthalimide and pyridine groups were introduced into the organic acids as good pharmacophores,respectively.By following the principle of bioisosterism and combination of bioactive sub-structures,two series of thirty-five naphthalimide derivatives and pyridine derivatives were synthesized.Based on the excellent bioactivity of phenyl urea and adenine-type cytokinin,five phenylurea compounds and one purine compound were designed and synthesized.The chemical structures of the products were elucidated by NMR and MS techniques.The effects of all compounds on seed germination and early seedling growth were systematically evaluated.For the compounds with high bioactivities,appropriate formulations were developed.Subsequently,the effects of these compounds on growth and development of seedling stage of wheat,soybean,and lettuce were investigated by pot culture experiments.The field efficacies of new compounds on field wheat,apple,and potato were investigated by field trials,which provided theoretical basis and data support for the development and application of newly high-efficient compounds.The main contents are as follows:1.Twenty-one naphthalimide derivatives were designed and synthesized with 1,8-naphthalic anhydride and organic acids as starting material,of which seventeen compounds had not been reported in the literature.The effects of compounds on seed germination and early seedling growth of wheat were investigated by seed soaking method.The results showed that the germination rate and vigor of wheat seeds could be effectively improved by soaking for 7 h at 25oC.In the range of 6.25~125 mg/L,except ?4 q and ?4 r,other compounds showed promoting effects on seed germination and early seedling growth of wheat in varing degree.With the increase of soaking concentration,the promoting rates showed the trend of increasing first and then decreasing.The target compounds improved the germination vigor by increasing the germination potential,germination rate and germination index of the seeds,and promoted the growth of early seedlings by promoting the growth of the primary roots,lateral roots and stems and increasing the fresh weight of early seedlings.At the concentration of 12.5 mg/L,some compounds exhibited significant stimulating effect on radicle growth of cucumber cotyledons.The compounds with higher plant growth regulating activities were: ?4 a,?4b,?4 d,?4h,?4 i,?4l,?4 m,?4n,and ?4 u.At the concentration of 125 mg/L,?4 a,?4b,?4 d,?4h,and ?4 i showed good fungicidal activities.2.Fourteen pyridine compounds were designed and synthesized with 2-ethanol pyridine or 2-aminomethylpyridine and organic acids as the starting materials,of which eight compounds had not been reported in the literature.According to the synthesis method of forchlorfenuron,five phenyl urea compounds were synthesized,of which three compounds had not been reported.As a control,a new purine compound was synthesized using 6-chloropurine as the precursor.The seeds germination and early seedling growth of wheat were promoted by seed soaking with fourteen pyridine compounds in the range of 10~60 mg/L and six cytokinins in the range of 6.25~125 mg/L in varing degree.With the increase of soaking concentration,the germination potential,germination rate,germination index,primary root length,lateral root length,stem height and fresh weight of wheat showed the trend of increasing first and then decreasing.At the concentration of 12.5 mg/L,?3 a,?3b,?3 e,and ?3 f showed higher cytokinin activity.The compounds with higher plant growth regulating activities were: ?3 a,?3b,?3 d,?3g,?3 h,?3i,?3 j,?3l,?3 a,?3b,?3 e,and ?3 f.At the concentration of 125 mg/L,compound ?3 e and ?3 f showed excellent fungicidal activities,especially,they exhibited 91.4% and 75.6% fungicidal activities against Alternaria solani,respectively.3.The SC formulations of 50 g/L ?4 a,?4b,?4 d,?4h,?4 i,?4l,?4 m,?4n,?4 u,?3a,?3 b,?3e,and ?3 f were developed,and the SC formulations of 60 g/L ?3 g,?3i,?3 j,and ?3 l were also obtained.The stable AS formulations of 60 g/L ?3 a,?3b,?3 d,and ?3 h were developed.The stability mechanism of 50 g/L ?4 a SC was discussed preliminarily.The composite dispersing agent SC-6 adsorbed on the surface of ?4 a particles,providing electrostatic repulsion and steric hindrance to ensure that the system had smaller particle size,higher absolute value of Zeta potential and moderate viscosity,effectively prevented the mutual coalescence and sedimentation of particles.4.The pot culture experiments showed that the seedling growth and development of wheat and soybean were significantly promoted by seed soaking and foliar spraying with ?4a(25 mg/L),?4b(25 mg/L),?4d(25 mg/L),?4u(25 mg/L),?3a(30 mg/L),?3b(30 mg/L),?3d(30 mg/L),?3g(30 mg/L),?3h(30 mg/L),?3a(12.5 mg/L),?3e(25 mg/L),and ?3f(25 mg/L).In terms of physiological and biochemical indexes,the root vigor and the contents of chlorophyll,soluble sugar,soluble protein,and free amino acid in leaves of wheat and soybean were significantly higher than those in blank control.Meanwhile,the application of these compounds promoted the accumulation of lettuce biomass,increased the chlorophyll contents,improved root vigor and nutritive quality,and the soluble sugar content increased by 76.6% with ?3 g treatment.5.For the first time,?4 a,?4b,?4 d,?4u,?3 a,?3b,?3 d,and ?3 g were used in field wheat.By increasing the SPAD value and net photosynthetic rate(Pn)of wheat flag leaf,the new compounds effectively increased the contents of chlorophyll and promoted the photosynthesis.And spike number per mu,the grain number per spike,and 1000-grain weight were increased in varying degree,which significantly increased the yields of wheat.The yields increased by 8.1%~18.6%,and the ?3 b treatment contributed the maximum yield.For the first time,the new compounds ?4 a,?3a,?3 h,?3a,?3 e,and ?3 f were used in apple trees.The SPAD value and Pn of apple leaves were significantly increased.The yields of fruit increased by 11.0%~24.8%,and the ?3 f treatment contributed the maximum yield.Meanwhile,the quality of apples were improved,the contents of soluble solids and vitamin C increased,and the content of titratable acid decreased.For the first time,the new compounds ?4 b,?3b,?3 g,?3e,and ?3 f were used in field potato.The SPAD value and Pn of potato leaves were significantly increased,so as to further increase the yields of potato,the single yield increased by 18.9%~30.2%.In terms of quality,starch content increased by 3.7%~16.4%,vitamin C content increased by 10.3%~16.0%.