萘酰亞胺、吡啶、苯基脲類化合物的研制及應(yīng)用研究
發(fā)布時間：2018-08-08 15:31
【摘要】：萘酰亞胺和吡啶基團(tuán)具有優(yōu)異的生物活性,在有機(jī)合成及農(nóng)藥領(lǐng)域具有重要的價(jià)值。萘乙酸、肉桂酸等有機(jī)酸在植物生長發(fā)育中也起了重要的調(diào)控作用。為了開發(fā)高活性的化合物,利用生物電子等排原理和活性亞結(jié)構(gòu)拼接的方法,分別將萘酰亞胺和吡啶基團(tuán)作為良好的藥效團(tuán)引入有機(jī)酸中,設(shè)計(jì)合成了萘酰亞胺衍生物和吡啶衍生物兩個系列共35個化合物�；诒交孱惡袜堰暑惣�(xì)胞分裂素的優(yōu)異活性,設(shè)計(jì)合成了5個苯基脲類化合物和1個嘌呤類化合物。對所有化合物采用NMR、MS進(jìn)行了結(jié)構(gòu)表征。系統(tǒng)地考察了三類化合物對作物種子萌發(fā)及幼苗生長的影響,對于高活性的化合物開發(fā)了適宜的制劑配方,繼而進(jìn)行盆栽土培試驗(yàn)考察化合物對苗期小麥、大豆、生菜生長發(fā)育的影響,通過田間藥效試驗(yàn)探討了篩選出的化合物在小麥、蘋果及馬鈴薯上的應(yīng)用效果,為新型高效化合物的研制及應(yīng)用提供理論依據(jù)和數(shù)據(jù)支撐。主要內(nèi)容和研究結(jié)論如下:1.以1,8-萘二甲酸酐和有機(jī)酸為起始原料,設(shè)計(jì)合成了21個萘酰亞胺衍生物,其中17個未見文獻(xiàn)報(bào)道。采用浸種法考察了化合物對小麥種子萌發(fā)及幼苗生長的影響。結(jié)果顯示:25oC下浸種7 h可有效保證小麥種子較高的發(fā)芽率和種子活力。在6.25~125 mg/L濃度范圍內(nèi),除Ⅱ4q和Ⅱ4r外,其他化合物不同程度地促進(jìn)了小麥種子的萌發(fā)和幼苗生長。隨著浸種濃度的增大,促進(jìn)作用呈現(xiàn)出先增加后降低的趨勢。目標(biāo)化合物通過提高種子的發(fā)芽勢、發(fā)芽率和發(fā)芽指數(shù)來提高種子的萌發(fā)活力,通過促進(jìn)主根、側(cè)根和莖的生長和提高幼苗的鮮重來促進(jìn)幼苗的生長。在12.5 mg/L濃度下,部分化合物對黃瓜子葉生根具有顯著的促進(jìn)作用。植物生長調(diào)節(jié)活性較高的化合物有:Ⅱ4a、Ⅱ4b、Ⅱ4d、Ⅱ4h、Ⅱ4i、Ⅱ4l、Ⅱ4m、Ⅱ4n和Ⅱ4u。在125 mg/L濃度下,Ⅱ4a、Ⅱ4b、Ⅱ4d、Ⅱ4h和Ⅱ4i表現(xiàn)出良好的殺菌活性。2.以2-乙醇吡啶或2-氨甲基吡啶和有機(jī)酸為起始原料,設(shè)計(jì)合成了14個吡啶類化合物,其中8個未見文獻(xiàn)報(bào)道。參照調(diào)吡脲的合成方法,設(shè)計(jì)合成了5個苯基脲類化合物,其中3個未見文獻(xiàn)報(bào)道;作為對照,以6-氯嘌呤為先導(dǎo),合成了1個嘌呤類新化合物。采用14個吡啶類化合物在10~60 mg/L濃度范圍內(nèi)以及6個細(xì)胞分裂素類化合物在6.25~125 mg/L濃度范圍內(nèi)浸種處理,均不同程度地促進(jìn)了小麥種子的萌發(fā)和幼苗生長。隨著浸種濃度的增大,目標(biāo)化合物對小麥種子的發(fā)芽勢、發(fā)芽率、發(fā)芽指數(shù)、主根長、側(cè)根長、莖高和鮮重均呈現(xiàn)出先增加后降低的趨勢。在12.5 mg/L濃度下,Ⅳ3a、Ⅳ3b、Ⅳ3e和Ⅳ3f具有較高的細(xì)胞分裂素活性。植物生長調(diào)節(jié)活性較高的化合物有:Ⅲ3a、Ⅲ3b、Ⅲ3d、Ⅲ3g、Ⅲ3h、Ⅲ3i、Ⅲ3j、Ⅲ3l、Ⅳ3a、Ⅳ3b、Ⅳ3e和Ⅳ3f。在125 mg/L濃度下,化合物Ⅳ3e和Ⅳ3f表現(xiàn)出優(yōu)異的殺菌活性,尤其對番茄早疫病菌的防效達(dá)91.4%和75.6%。3.開發(fā)了穩(wěn)定的Ⅱ4a、Ⅱ4b、Ⅱ4d、Ⅱ4h、Ⅱ4i、Ⅱ4l、Ⅱ4m、Ⅱ4n、Ⅱ4u、Ⅳ3a、Ⅳ3b、Ⅳ3e和Ⅳ3f的50 g/L懸浮劑配方,Ⅲ3g、Ⅲ3i、Ⅲ3j和Ⅲ3l的60 g/L懸浮劑配方。獲得了穩(wěn)定的Ⅲ3a、Ⅲ3b、Ⅲ3d和Ⅲ3h的60 g/L水劑配方。初步探討了50 g/L Ⅱ4a SC體系的穩(wěn)定機(jī)理。復(fù)合分散劑SC-6吸附于Ⅱ4a顆粒表面,提供了靜電斥力和空間位阻,保證體系有較小的粒度、較高的Zeta電位絕對值和適中的粘度,有效地阻止了顆粒間的相互聚結(jié)以及顆粒的沉降。4.盆栽土培試驗(yàn)結(jié)果顯示: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)浸種及葉面噴霧處理,顯著促進(jìn)了苗期小麥、大豆的生長發(fā)育。生理生化指標(biāo)方面,小麥和大豆的根系活力以及葉片中的葉綠素、可溶性糖、可溶性蛋白和游離氨基酸含量較空白有顯著提高。應(yīng)用于生菜上,以上新化合物處理顯著促進(jìn)了生菜生物量的積累,提升了生菜葉片中葉綠素含量、根系活力以及營養(yǎng)品質(zhì),其中Ⅲ3g處理后的葉片可溶性糖含量增幅達(dá)76.6%。5.首次將Ⅱ4a、Ⅱ4b、Ⅱ4d、Ⅱ4u、Ⅲ3a、Ⅲ3b、Ⅲ3d和Ⅲ3g應(yīng)用于大田小麥上。新化合物通過增大小麥旗葉的SPAD值和凈光合速率(Pn),有效地提高了葉綠素含量、促進(jìn)光合作用,并不同程度地增大了畝穗數(shù)、穗粒數(shù)和千粒重,從而顯著增加了小麥的產(chǎn)量,產(chǎn)量增幅為8.1%~18.6%,Ⅲ3b處理增幅最大。首次將新化合物Ⅱ4a、Ⅲ3a、Ⅲ3h、Ⅳ3a、Ⅳ3e和Ⅳ3f應(yīng)用于蘋果樹上,蘋果葉片的SPAD值和凈光合速率顯著增大;產(chǎn)量方面,單果重增幅為11.0%~24.8%,Ⅳ3f處理增幅最大;同時蘋果品質(zhì)得到改善,可溶性固形物和Vc含量增加,可滴定酸含量降低。首次將新化合物Ⅱ4b、Ⅲ3b、Ⅲ3g、Ⅳ3e和Ⅳ3f應(yīng)用于大田馬鈴薯上,馬鈴薯葉片SPAD值和凈光合速率顯著增大,進(jìn)而提高馬鈴薯產(chǎn)量,單株薯重增幅在18.9%~30.2%;品質(zhì)方面,淀粉含量增幅為3.7%~16.4%,Vc含量增幅為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%.
【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TQ452
，
本文編號：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%.
【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TQ452
，
本文編號：2172222
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