萘酰亚胺、吡啶、苯基脲类化合物的研制及应用研究
发布时间：2018-08-08 15:31
【摘要】：萘酰亚胺和吡啶基团具有优异的生物活性,在有机合成及农药领域具有重要的价值。萘乙酸、肉桂酸等有机酸在植物生长发育中也起了重要的调控作用。为了开发高活性的化合物,利用生物电子等排原理和活性亚结构拼接的方法,分别将萘酰亚胺和吡啶基团作为良好的药效团引入有机酸中,设计合成了萘酰亚胺衍生物和吡啶衍生物两个系列共35个化合物。基于苯基脲类和嘌呤类细胞分裂素的优异活性,设计合成了5个苯基脲类化合物和1个嘌呤类化合物。对所有化合物采用NMR、MS进行了结构表征。系统地考察了三类化合物对作物种子萌发及幼苗生长的影响,对于高活性的化合物开发了适宜的制剂配方,继而进行盆栽土培试验考察化合物对苗期小麦、大豆、生菜生长发育的影响,通过田间药效试验探讨了筛选出的化合物在小麦、苹果及马铃薯上的应用效果,为新型高效化合物的研制及应用提供理论依据和数据支撑。主要内容和研究结论如下:1.以1,8-萘二甲酸酐和有机酸为起始原料,设计合成了21个萘酰亚胺衍生物,其中17个未见文献报道。采用浸种法考察了化合物对小麦种子萌发及幼苗生长的影响。结果显示:25oC下浸种7 h可有效保证小麦种子较高的发芽率和种子活力。在6.25~125 mg/L浓度范围内,除Ⅱ4q和Ⅱ4r外,其他化合物不同程度地促进了小麦种子的萌发和幼苗生长。随着浸种浓度的增大,促进作用呈现出先增加后降低的趋势。目标化合物通过提高种子的发芽势、发芽率和发芽指数来提高种子的萌发活力,通过促进主根、侧根和茎的生长和提高幼苗的鲜重来促进幼苗的生长。在12.5 mg/L浓度下,部分化合物对黄瓜子叶生根具有显著的促进作用。植物生长调节活性较高的化合物有:Ⅱ4a、Ⅱ4b、Ⅱ4d、Ⅱ4h、Ⅱ4i、Ⅱ4l、Ⅱ4m、Ⅱ4n和Ⅱ4u。在125 mg/L浓度下,Ⅱ4a、Ⅱ4b、Ⅱ4d、Ⅱ4h和Ⅱ4i表现出良好的杀菌活性。2.以2-乙醇吡啶或2-氨甲基吡啶和有机酸为起始原料,设计合成了14个吡啶类化合物,其中8个未见文献报道。参照调吡脲的合成方法,设计合成了5个苯基脲类化合物,其中3个未见文献报道;作为对照,以6-氯嘌呤为先导,合成了1个嘌呤类新化合物。采用14个吡啶类化合物在10~60 mg/L浓度范围内以及6个细胞分裂素类化合物在6.25~125 mg/L浓度范围内浸种处理,均不同程度地促进了小麦种子的萌发和幼苗生长。随着浸种浓度的增大,目标化合物对小麦种子的发芽势、发芽率、发芽指数、主根长、侧根长、茎高和鲜重均呈现出先增加后降低的趋势。在12.5 mg/L浓度下,Ⅳ3a、Ⅳ3b、Ⅳ3e和Ⅳ3f具有较高的细胞分裂素活性。植物生长调节活性较高的化合物有:Ⅲ3a、Ⅲ3b、Ⅲ3d、Ⅲ3g、Ⅲ3h、Ⅲ3i、Ⅲ3j、Ⅲ3l、Ⅳ3a、Ⅳ3b、Ⅳ3e和Ⅳ3f。在125 mg/L浓度下,化合物Ⅳ3e和Ⅳ3f表现出优异的杀菌活性,尤其对番茄早疫病菌的防效达91.4%和75.6%。3.开发了稳定的Ⅱ4a、Ⅱ4b、Ⅱ4d、Ⅱ4h、Ⅱ4i、Ⅱ4l、Ⅱ4m、Ⅱ4n、Ⅱ4u、Ⅳ3a、Ⅳ3b、Ⅳ3e和Ⅳ3f的50 g/L悬浮剂配方,Ⅲ3g、Ⅲ3i、Ⅲ3j和Ⅲ3l的60 g/L悬浮剂配方。获得了稳定的Ⅲ3a、Ⅲ3b、Ⅲ3d和Ⅲ3h的60 g/L水剂配方。初步探讨了50 g/L Ⅱ4a SC体系的稳定机理。复合分散剂SC-6吸附于Ⅱ4a颗粒表面,提供了静电斥力和空间位阻,保证体系有较小的粒度、较高的Zeta电位绝对值和适中的粘度,有效地阻止了颗粒间的相互聚结以及颗粒的沉降。4.盆栽土培试验结果显示:以Ⅱ4a(25 mg/L)、Ⅱ4b(25 mg/L)、Ⅱ4d(25 mg/L)、Ⅱ4u(25 mg/L)、Ⅲ3a(30 mg/L)、Ⅲ3b(30 mg/L)、Ⅲ3d(30 mg/L)、Ⅲ3g(30 mg/L)、Ⅲ3h(30 mg/L)、Ⅳ3a(12.5 mg/L)、Ⅳ3e(25 mg/L)和Ⅳ3f(25 mg/L)浸种及叶面喷雾处理,显著促进了苗期小麦、大豆的生长发育。生理生化指标方面,小麦和大豆的根系活力以及叶片中的叶绿素、可溶性糖、可溶性蛋白和游离氨基酸含量较空白有显著提高。应用于生菜上,以上新化合物处理显著促进了生菜生物量的积累,提升了生菜叶片中叶绿素含量、根系活力以及营养品质,其中Ⅲ3g处理后的叶片可溶性糖含量增幅达76.6%。5.首次将Ⅱ4a、Ⅱ4b、Ⅱ4d、Ⅱ4u、Ⅲ3a、Ⅲ3b、Ⅲ3d和Ⅲ3g应用于大田小麦上。新化合物通过增大小麦旗叶的SPAD值和净光合速率(Pn),有效地提高了叶绿素含量、促进光合作用,并不同程度地增大了亩穗数、穗粒数和千粒重,从而显著增加了小麦的产量,产量增幅为8.1%~18.6%,Ⅲ3b处理增幅最大。首次将新化合物Ⅱ4a、Ⅲ3a、Ⅲ3h、Ⅳ3a、Ⅳ3e和Ⅳ3f应用于苹果树上,苹果叶片的SPAD值和净光合速率显著增大;产量方面,单果重增幅为11.0%~24.8%,Ⅳ3f处理增幅最大;同时苹果品质得到改善,可溶性固形物和Vc含量增加,可滴定酸含量降低。首次将新化合物Ⅱ4b、Ⅲ3b、Ⅲ3g、Ⅳ3e和Ⅳ3f应用于大田马铃薯上,马铃薯叶片SPAD值和净光合速率显著增大,进而提高马铃薯产量,单株薯重增幅在18.9%~30.2%;品质方面,淀粉含量增幅为3.7%~16.4%,Vc含量增幅为10.3%~16.0%。
[Abstract]:Naphthalimide and pyridine group have excellent biological activity, and have important value in the field of organic synthesis and pesticides. The organic acids such as naphthacetic acid and cinnamic acid play an important role in the growth and development of plants. In order to develop highly active compounds, the principles of bioelectronic wait and the stitching of active substructures are used, respectively. Two series of 35 compounds were designed and synthesized by introducing naphthyl imide and pyridine group as good drug groups into organic acids. Based on the excellent activity of benzylureas and purine cytokinins, 5 phenyl urea compounds and 1 purine compounds were designed and synthesized. The structure was characterized by NMR and MS. The effects of three kinds of compounds on the seed germination and seedling growth were systematically investigated. A suitable formulation was developed for the highly active compounds. Then the effects of the compound on the growth and development of wheat, soybean and lettuce were investigated by pot culture test. The application of the selected compounds on wheat, apple and potato was used to provide theoretical basis and data support for the development and application of new high efficiency compounds. The main contents and conclusions were as follows: 1. the design and synthesis of 21 naphthalimide derivatives were made with 1,8- naphthalene two methanic anhydride and organic acids as starting materials, of which 17 had not been found. The effect of compounds on Seed Germination and seedling growth of wheat was investigated by soaking method. The results showed that 7 h seed soaking under 25oC could effectively guarantee the higher germination rate and seed vigor of wheat seeds. In the range of 6.25~125 mg/L concentration, except for II 4q and II 4R, other compounds promoted the germination and young of wheat seeds. The growth of seedlings. With the increase of seed soaking concentration, the promotion is increasing first and then decreasing. The target compound improves the germination vigor by raising the seed germination potential, germination rate and germination index, and promotes the growth of the seedlings by promoting the growth of the main root, the lateral root and the stem and the fresh weight of the seedlings. Under the concentration of 12.5 mg/L, Some compounds have significant promoting effect on Ye Shenggen. The compounds with high regulatory activity of plant growth are: II 4a, II 4b, II 4D, II 4h, II 4I, II 4L, II 4m, II 4N and II 4u. at the 125 mg/L concentration, II 4a, II 4b, II and II Acid was used as the starting material to design and synthesize 14 pyridine compounds, of which 8 were not reported. 5 phenyl urea compounds were designed and synthesized according to the synthesis of pyrerorea. 3 of them were not reported. As a control, 1 new purine compounds were synthesized with 6- chloropurine. 14 pyridine compounds were used in 10~60 m. The germination and seedling growth of wheat seeds were promoted in the concentration range of g/L and 6 cytokinins in the concentration range of 6.25~125 mg/L. The germination potential, germination rate, germinating index, length of main root, length of lateral root, stem height and fresh weight of the target compound were increased with the increase of seed soaking concentration. At the concentration of 12.5 mg/L, IV 3a, IV 3b, IV 3E and IV 3F have higher cytokinin activity. The compounds with higher regulatory activity of plant growth are: III 3a, III 3b, III 3D, III 3h, III 3I, III 3j, IV, IV, IV, IV, IV, IV, IV, IV, IV, IV, IV, IV and IV are excellent. The fungicidal activity, especially for tomato early pestilence pathogens, was 91.4% and 75.6%.3., which developed stable II 4a, II 4b, II 4D, II 4h, 4h, II 4I, II 4L, II 4m, II 4U, IV 3a, IV 3b, IV, IV, III, III, III and III suspending agent formulation, and obtained a stable III, III, III, III and III 60 water agent. The stabilization mechanism of 50 g/L II 4A SC system was preliminarily discussed. The composite dispersing agent SC-6 was adsorbed on the surface of II 4A particles, providing electrostatic repulsion and space steric resistance, which ensured that the system had smaller granularity, higher Zeta potential absolute value and moderate viscosity, which effectively prevented the interaction between particles and the settlement of particles in.4. potted soil culture. The experimental results showed that the growth and development of wheat and soybean at seedling stage were significantly promoted by II 4a (25 mg/L), II 4B (25 mg/L), II 4D (25 mg/L), II 4U (25 mg/L), III 3A (30 mg/L), 30 mg/L, III 30 (30), III. The root activity of wheat and soybean and the content of chlorophyll, soluble sugar, soluble protein and free amino acid in the leaves were significantly higher than that in the blank. The application of the new compounds to lettuce significantly promoted the accumulation of the biomass of lettuce, increased the content of chlorophyll, root activity and nutritional quality in the leaves of lettuce. The increase of soluble sugar content of leaves after treatment with III 3G reached 76.6%.5. for the first time by applying II 4a, II 4b, II 4D, II 4U, III 3a, III 3b, III 3D and III 3G on the field wheat. By increasing the SPAD value and net photosynthetic rate (Pn), the new compound effectively increased the content of leaf green and promoted photosynthesis, and increased acre in varying degrees. The number of spikes, grain number per spike and 1000 grain weight significantly increased the yield of wheat, the increase of yield was 8.1%~18.6%, and the growth of the third 3B was the largest. The new compound II 4a, III 3a, III 3h, IV 3a, IV 3E and IV 3F were applied to apple trees for the first time, and the SPAD value and net photosynthetic rate of apple leaves increased significantly, and the yield increase was 11.0%~24.8%, IV 3F. At the same time, the quality of the apple was improved, the content of the soluble solids and Vc increased, the content of titratable acid decreased. The new compound II 4b, III 3b, III 3G, IV 3E and IV 3F were applied to potato in the field for the first time. The SPAD value and net photosynthetic rate of potato leaves increased significantly, and then the potato yield was increased and the weight per plant increased in 18.9%~. 30.2%, in terms of quality, starch content increased by 3.7%~16.4% and Vc content increased by 10.3%~16.0%.
【学位授予单位】：青岛科技大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ452
，
本文编号：2172222
[Abstract]:Naphthalimide and pyridine group have excellent biological activity, and have important value in the field of organic synthesis and pesticides. The organic acids such as naphthacetic acid and cinnamic acid play an important role in the growth and development of plants. In order to develop highly active compounds, the principles of bioelectronic wait and the stitching of active substructures are used, respectively. Two series of 35 compounds were designed and synthesized by introducing naphthyl imide and pyridine group as good drug groups into organic acids. Based on the excellent activity of benzylureas and purine cytokinins, 5 phenyl urea compounds and 1 purine compounds were designed and synthesized. The structure was characterized by NMR and MS. The effects of three kinds of compounds on the seed germination and seedling growth were systematically investigated. A suitable formulation was developed for the highly active compounds. Then the effects of the compound on the growth and development of wheat, soybean and lettuce were investigated by pot culture test. The application of the selected compounds on wheat, apple and potato was used to provide theoretical basis and data support for the development and application of new high efficiency compounds. The main contents and conclusions were as follows: 1. the design and synthesis of 21 naphthalimide derivatives were made with 1,8- naphthalene two methanic anhydride and organic acids as starting materials, of which 17 had not been found. The effect of compounds on Seed Germination and seedling growth of wheat was investigated by soaking method. The results showed that 7 h seed soaking under 25oC could effectively guarantee the higher germination rate and seed vigor of wheat seeds. In the range of 6.25~125 mg/L concentration, except for II 4q and II 4R, other compounds promoted the germination and young of wheat seeds. The growth of seedlings. With the increase of seed soaking concentration, the promotion is increasing first and then decreasing. The target compound improves the germination vigor by raising the seed germination potential, germination rate and germination index, and promotes the growth of the seedlings by promoting the growth of the main root, the lateral root and the stem and the fresh weight of the seedlings. Under the concentration of 12.5 mg/L, Some compounds have significant promoting effect on Ye Shenggen. The compounds with high regulatory activity of plant growth are: II 4a, II 4b, II 4D, II 4h, II 4I, II 4L, II 4m, II 4N and II 4u. at the 125 mg/L concentration, II 4a, II 4b, II and II Acid was used as the starting material to design and synthesize 14 pyridine compounds, of which 8 were not reported. 5 phenyl urea compounds were designed and synthesized according to the synthesis of pyrerorea. 3 of them were not reported. As a control, 1 new purine compounds were synthesized with 6- chloropurine. 14 pyridine compounds were used in 10~60 m. The germination and seedling growth of wheat seeds were promoted in the concentration range of g/L and 6 cytokinins in the concentration range of 6.25~125 mg/L. The germination potential, germination rate, germinating index, length of main root, length of lateral root, stem height and fresh weight of the target compound were increased with the increase of seed soaking concentration. At the concentration of 12.5 mg/L, IV 3a, IV 3b, IV 3E and IV 3F have higher cytokinin activity. The compounds with higher regulatory activity of plant growth are: III 3a, III 3b, III 3D, III 3h, III 3I, III 3j, IV, IV, IV, IV, IV, IV, IV, IV, IV, IV, IV, IV and IV are excellent. The fungicidal activity, especially for tomato early pestilence pathogens, was 91.4% and 75.6%.3., which developed stable II 4a, II 4b, II 4D, II 4h, 4h, II 4I, II 4L, II 4m, II 4U, IV 3a, IV 3b, IV, IV, III, III, III and III suspending agent formulation, and obtained a stable III, III, III, III and III 60 water agent. The stabilization mechanism of 50 g/L II 4A SC system was preliminarily discussed. The composite dispersing agent SC-6 was adsorbed on the surface of II 4A particles, providing electrostatic repulsion and space steric resistance, which ensured that the system had smaller granularity, higher Zeta potential absolute value and moderate viscosity, which effectively prevented the interaction between particles and the settlement of particles in.4. potted soil culture. The experimental results showed that the growth and development of wheat and soybean at seedling stage were significantly promoted by II 4a (25 mg/L), II 4B (25 mg/L), II 4D (25 mg/L), II 4U (25 mg/L), III 3A (30 mg/L), 30 mg/L, III 30 (30), III. The root activity of wheat and soybean and the content of chlorophyll, soluble sugar, soluble protein and free amino acid in the leaves were significantly higher than that in the blank. The application of the new compounds to lettuce significantly promoted the accumulation of the biomass of lettuce, increased the content of chlorophyll, root activity and nutritional quality in the leaves of lettuce. The increase of soluble sugar content of leaves after treatment with III 3G reached 76.6%.5. for the first time by applying II 4a, II 4b, II 4D, II 4U, III 3a, III 3b, III 3D and III 3G on the field wheat. By increasing the SPAD value and net photosynthetic rate (Pn), the new compound effectively increased the content of leaf green and promoted photosynthesis, and increased acre in varying degrees. The number of spikes, grain number per spike and 1000 grain weight significantly increased the yield of wheat, the increase of yield was 8.1%~18.6%, and the growth of the third 3B was the largest. The new compound II 4a, III 3a, III 3h, IV 3a, IV 3E and IV 3F were applied to apple trees for the first time, and the SPAD value and net photosynthetic rate of apple leaves increased significantly, and the yield increase was 11.0%~24.8%, IV 3F. At the same time, the quality of the apple was improved, the content of the soluble solids and Vc increased, the content of titratable acid decreased. The new compound II 4b, III 3b, III 3G, IV 3E and IV 3F were applied to potato in the field for the first time. The SPAD value and net photosynthetic rate of potato leaves increased significantly, and then the potato yield was increased and the weight per plant increased in 18.9%~. 30.2%, in terms of quality, starch content increased by 3.7%~16.4% and Vc content increased by 10.3%~16.0%.
【学位授予单位】：青岛科技大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ452
，
本文编号：2172222
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