CN115304543B - Preparation method and product of aryl sulfonamide containing norbornenyl and application of aryl sulfonamide - Google Patents

Preparation method and product of aryl sulfonamide containing norbornenyl and application of aryl sulfonamide Download PDF

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CN115304543B
CN115304543B CN202210770634.XA CN202210770634A CN115304543B CN 115304543 B CN115304543 B CN 115304543B CN 202210770634 A CN202210770634 A CN 202210770634A CN 115304543 B CN115304543 B CN 115304543B
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norbornene
norbornenyl
chloride
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sulfonyl chloride
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CN115304543A (en
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谷文
杨子辉
孙雪宝
金道峻
邱遗贵
王石发
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Nanjing Forestry University
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Abstract

The invention discloses a preparation method and a product of norbornenyl-containing arylsulfonamide and application thereof, wherein the norbornenyl-containing arylsulfonamide has the structural formula shown as follows: The application of the norbornenyl-containing arylsulfonamide in preventing and controlling plant fungi in agriculture or forestry shows that the activity result shows that: the compound provided by the invention has better control effect on sclerotinia sclerotiorum, botrytis cinerea and phytophthora capsici leonian.

Description

Preparation method and product of aryl sulfonamide containing norbornenyl and application of aryl sulfonamide
Technical Field
The invention belongs to the technical field of pesticide synthesis, and particularly relates to a preparation method of aryl sulfonamide containing norbornenyl, a product and application thereof.
Background
Norbornene (Norbornene) is a bridged cyclic hydrocarbon of norbornene (norcamphene) and has the chemical formula C 7H10 as an important chemical intermediate. Is a white solid with a stimulating sour taste. The molecule consists of cyclohexene rings and methylene bridges (between C-3 and C-6). The presence of a double bond in the molecule causes a significant ring tension and a significant reaction. There are various methods for synthesizing norbornene, such as Diels-Alder reaction of cyclopentadiene and ethylene. Similar to bicylic, norbornadiene is also present, which has the same structure as norbornane without complete saturation of the double bonds, but which has two more double bonds. Norbornene undergoes acid-catalyzed hydration to form norbornyl alcohol with water.
At present, norbornene is mainly used for transition metal catalysis to affect the migration of electrophilic transition metals. For example, in the field of cycloolefin ROMP research, norbornene and its derivatives are the most studied and most widely used type of monomers because of their high reactivity, abundant sources, and inexpensive price. Except for researching and expanding the ROMP applicable monomer, researchers mainly try continuously from the aspects of steric hindrance, chemical configuration, side group polarity, copolymerization modification with other cycloolefins or norbornene-based monomers and the like of the norbornene-based monomers, fully exert the advantages of the cycloolefins ROMP, and are combined with other polymerization methods to continuously improve the performance of the obtained polymer and apply the polymer to different research fields. Norbornene and its derivative ROMP have achieved a series of research results in the fields of flame retardant materials, exchange membranes, nanomaterials, biological medicines, etc., among which the research in the field of flame retardant materials is the earliest and many products have been industrialized. In the field of exchange membranes, the research is mainly conducted on how to find application in fuel cells due to the fact that norbornene-based polymer membranes are good in thermal stability, acid and alkali resistance and conductivity. Nanomaterials are one of the most popular research fields in recent years, and norbornene-based nanometal polymer materials, nanomagnetic polymer materials and the like have been preliminarily applied. In the field of biological medicine, norbornene and derivatives thereof have great development prospect, the current research is mainly focused on drug delivery materials, and preliminary research results are available, but industrialization is yet to be further researched, but the application of the norbornene and derivatives thereof in medicine or pesticide is less reported.
The preparation method of the norbornenyl-containing arylsulfonamide and the application of the norbornenyl-containing arylsulfonamide in agricultural bactericides are not reported.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present invention has been made in view of the above and/or problems occurring in the prior art.
It is therefore an object of the present invention to overcome the deficiencies in the prior art and to provide aromatic sulfonamides containing norbornenyl groups.
In order to solve the technical problems, the invention provides the following technical scheme: the structural formula of the norbornenyl-containing arylsulfonamide is shown as follows:
it is still another object of the present invention to provide a process for the preparation of aromatic sulfonamide compounds containing norbornenyl which overcomes the disadvantages of the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation method of the norbornenyl-containing arylsulfonamide comprises the steps of reacting an arylsulfonyl chloride intermediate with 5-norbornene-2-methylamine, triethylamine and 4-dimethylaminopyridine to synthesize the norbornenyl-containing arylsulfonamide I-1-I-8.
As a preferable embodiment of the process for producing an aromatic sulfonamide containing norbornene according to the present invention, wherein:
5-norbornene-2-methylamine (1.0 mmol), 4-dimethylaminopyridine (0.1 mmol), triethylamine (1.0 mmol) were dissolved in anhydrous dichloromethane, cooled to 0℃and then an arylsulfonyl chloride (1.0 mol) solution in 5mL of anhydrous dichloromethane was added in portions to react at 25℃for 1 to 5 hours. TLC monitored complete reaction of the starting material, washing the organic layer 3 times with water (8 ml x 3), washing 3 times with saturated brine (8 ml x 3), drying, suction filtration, concentrating to remove dichloromethane, and column chromatography (CH 2Cl2: meoh=20:1) of the crude product to give the target compounds I-1 to I-8.
As a preferable embodiment of the process for producing an aromatic sulfonamide containing norbornene according to the present invention, wherein: the molar ratio of the intermediate arylsulfonyl chloride to the 5-norbornene-2-methylamine is 1.1:0.
As a preferable embodiment of the process for producing an aromatic sulfonamide containing norbornene according to the present invention, wherein: the feeding mole ratio of the 5-norbornene-2-methylamine to the triethylamine is 1:1.0.
As a preferable embodiment of the process for producing an aromatic sulfonamide containing norbornene according to the present invention, wherein: the molar ratio of the arylsulfonyl chloride intermediate to 4-dimethylaminopyridine was 1.0:0.1.
As a preferable embodiment of the process for producing an aromatic sulfonamide containing norbornene according to the present invention, wherein: synthesizing the aryl sulfonamide I-1 to I-8 containing norbornenyl, wherein the synthesis reaction temperature is 25 ℃, and the reaction time is 1 to 5 hours.
It is another object of the present invention to overcome the deficiencies in the prior art and to provide the use of norbornenyl-containing arylsulfonamides for controlling plant fungi in agriculture or forestry, including Sclerotinia sclerotiorum, sclerotinia viticola and Phytophthora capsici.
The invention has the beneficial effects that:
(1) The norbornenyl-containing arylsulfonamide disclosed by the invention is novel in molecular structure and is a novel compound; the chemical structure has clear characteristics, and the structural formula contains norbornene, wherein various aromatic groups are connected with the norbornene through amide bonds; the preparation method of the compound is simple and convenient, the raw materials are easy to obtain, the reaction conditions are easy to control, and particularly, in the step of synthesizing the norbornenyl-containing arylsulfonamide, the product is obtained through column chromatography.
(2) The compound disclosed by the invention is a medicament for preventing and treating plant fungi in the field of agriculture or forestry, and has a good prevention and treatment effect on sclerotinia sclerotiorum, botrytis cinerea and phytophthora capsici.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a schematic diagram of the preparation method of the norbornenyl-containing arylsulfonamide I-1 to I-8 in the embodiment of the invention.
FIG. 2 shows a plate test of Compound I-5 of the present invention on Phytophthora capsici (the concentration of the liquid medicine from left to right is 12.5mg/L,3.125mg/L,0.781mg/L,0.195mg/L,0.049mg/L and 0mg/L in this order)
FIG. 3 is a schematic diagram of the in vivo experiments (leaf blade method) of the compound I-1 on Sclerotinia sclerotiorum in the examples of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
5-Norbornene-2-methylamine (1.0 mmol), 4-dimethylaminopyridine (0.1 mmol), triethylamine (1.0 mmol) were dissolved in anhydrous dichloromethane, cooled to 0℃and then an arylsulfonyl chloride (1.0 mol) solution in 5mL of anhydrous dichloromethane was added in portions to react at 25℃for 1 to 5 hours. TLC monitored complete reaction of the starting material, washing the organic layer 3 times with water (8 ml x 3), washing 3 times with saturated brine (8 ml x 3), drying, suction filtration, concentrating to remove dichloromethane, and column chromatography (CH 2Cl2: meoh=20:1) of the crude product to give the target compounds I-1 to I-8. The preparation method of the norbornenyl-containing arylsulfonamide I-1 to I-8 is schematically shown in figure 1.
Various arylsulfonyl chlorides, 4-dimethylaminopyridine, triethylamine, sodium chloride and 5-norbornene-2-methylamine were purchased from Shanghai Bi de technology Co., ltd; methylene chloride and methanol were purchased from south Beijing late sunny Co., ltd; silica gel plates and silica gel powder were purchased from tobacco stand marine fine chemical company, inc.
Example 1
5-Norbornene-2-methylamine (1.0 mmol), 4-dimethylaminopyridine (0.1 mmol), triethylamine (1.0 mmol) were dissolved in anhydrous dichloromethane, cooled to 0℃and a solution of 8-quinoline sulfonyl chloride (1.0 mol) in 5mL of anhydrous dichloromethane was added in portions, and the mixture was reacted at 25℃for 1 hour. TLC monitored complete reaction of the starting material, washing the organic layer 3 times with water (8 ml x 3), washing 3 times with saturated brine (8 ml x 3), drying, suction filtration, concentrating to remove dichloromethane, and column chromatography (CH 2Cl2: meoh=20:1, volume ratio) of the crude product to give the target compound I-1.
I-1, white powder, yield 90％,m.p.125.8-126.4℃;1H NMR(600MHz,CDCl3)δ9.08–9.05(m,1H),8.46–8.42(m,1H),8.32(dd,J＝8.3,1.6Hz,1H),8.07(dd,J＝8.2,1.2Hz,1H),7.69–7.66(m,1H),7.61–7.59(m,1H),6.39(s,1H),5.98–5.50(m,2H),2.78(s,1H),2.70–2.67(m,2H),2.46–2.42(m,1H),2.22–2.17(m,1H),1.73–1.68(m,1H),1.36(dd,J＝8.3,1.9Hz,1H),1.17–1.09(m,1H),0.37–0.34(m,1H);13C NMR(150MHz,CDCl3)δ151.03,143.02,137.74,137.33,135.75,133.15,131.49,131.45,128.73,125.88,122.26,49.36,47.54,43.97,42.27,38.75,30.03.
Example 2
5-Norbornene-2-methylamine (1.0 mmol), 4-dimethylaminopyridine (0.1 mmol), triethylamine (1.0 mmol) were dissolved in anhydrous dichloromethane, cooled to 0℃and a solution of 6-methyl-8-quinolinesulfonyl chloride (1.0 mol) in 5mL of anhydrous dichloromethane was added in portions to react at 25℃for 1 hour. TLC monitored complete reaction of the starting material, washing the organic layer 3 times with water (8 ml x 3), washing 3 times with saturated brine (8 ml x 3), drying, suction filtration, concentrating to remove dichloromethane, and column chromatography (CH 2Cl2: meoh=20:1, volume ratio) of the crude product to give the target compound I-2.
I-2, white powder, yield 80％,m.p.133-135℃;1H NMR(600MHz,CDCl3)δ8.90(s,1H),8.36–8.32(m,1H),8.05(s,1H),7.98(d,J＝8.2Hz,1H),7.61(td,J＝7.7,1.8Hz,1H),6.34(t,J＝5.3Hz,1H),5.98–5.51(m,2H),2.78(s,1H),2.72-2.64(m,2H),2.58(s,3H),2.46–2.41(m,1H),2.21–2.18(m,1H),1.73–1.68(m,1H),1.36(d,J＝8.1Hz,1H),1.17–1.10(m,1H),0.37–0.34(m,1H);13C NMR(150MHz,CDCl3)δ153.01,141.43,137.70,136.07,135.65,132.51,132.05,131.53,130.25,128.62,125.75,49.35,47.54,43.98,42.27,38.77,30.04,18.75.
Example 3
5-Norbornene-2-methylamine (1.0 mmol), 4-dimethylaminopyridine (0.1 mmol), triethylamine (1.0 mmol) were dissolved in anhydrous dichloromethane, cooled to 0℃and a solution of 1-naphthalenesulfonyl chloride (1.0 mol) in 5mL of anhydrous dichloromethane was added in portions and the mixture was reacted at 25℃for 3 hours. TLC monitored complete reaction of the starting material, washing the organic layer 3 times with water (8 ml x 3), washing 3 times with saturated brine (8 ml x 3), drying, suction filtration, concentrating to remove dichloromethane, and column chromatography (CH 2Cl2: meoh=20:1, volume ratio) of the crude product to give the target compound I-3.
I-3, white powder, yield 82％,m.p 99.1-100.0℃;1H NMR(600MHz,CDCl3)δ8.44(d,J＝13.1Hz,1H),7.98–7.91(m,3H),7.85–7.82(m,1H),7.66–7.60(m,2H),6.08–5.75(m,2H),4.57(s,1H),2.82–2.75(m,3H),2.66–2.59(m,1H),2.21–2.16(m,1H),1.80–1.76(m,1H),1.25–1.18(m,1H),0.46–0.43(m,1H);13C NMR(150MHz,CDCl3)δ137.97,132.14,131.56,129.47,129.22,128.74,128.44,127.91,127.53,122.30,47.20,43.96,42.30,38.96,30.00.
Example 4
5-Norbornene-2-methylamine (1.0 mmol), 4-dimethylaminopyridine (0.1 mmol), triethylamine (1.0 mmol) were dissolved in anhydrous dichloromethane, cooled to 0℃and a solution of 4-biphenylsulfonyl chloride (1.0 mol) in 5mL of anhydrous dichloromethane was added in portions, and the mixture was reacted at 25℃for 2 hours. TLC monitored complete reaction of the starting material, washing the organic layer 3 times with water (8 ml x 3), washing 3 times with saturated brine (8 ml x 3), drying, suction filtration, concentrating to remove dichloromethane, and column chromatography (CH 2Cl2: meoh=20:1, volume ratio) of the crude product to give the target compound I-4.
I-4, white solid, yield 92％,m.p 161.5-162.7℃;1H NMR(600MHz,CDCl3)δ7.94–7.91(m,2H),7.73–7.72(m,2H),7.62–7.60(m,2H),7.48(t,J＝7.7Hz,2H),7.42(t,J＝7.3Hz,1H),6.12–5.79(m,2H),4.58(s,1H),2.84(s,1H),2.80–2.75(m,2H),2.67–2.62(m,1H),2.23–2.17(m,1H),1.83–1.78(m,1H),1.43–1.41(m,1H),1.27–1.20(m,1H),0.49–0.47(m,1H);13C NMR(150MHz,CDCl3)δ145.48,139.31,138.48,137.98,131.59,129.04,128.45,127.68,126.57,127.29,49.44,47.20,43.97,42.33,38.96,30.03.
Example 5
5-Norbornene-2-methylamine (1.0 mmol), 4-dimethylaminopyridine (0.1 mmol), triethylamine (1.0 mmol) were dissolved in anhydrous dichloromethane, cooled to 0℃and a solution of 2-thiophenesulfonyl chloride (1.0 mol) in 5mL of anhydrous dichloromethane was added in portions, and the mixture was reacted at 25℃for 1 hour. TLC monitored complete reaction of the starting material, washing the organic layer 3 times with water (8 ml x 3), washing 3 times with saturated brine (8 ml x 3), drying, suction filtration, concentrating to remove dichloromethane, and column chromatography (CH 2Cl2: meoh=20:1, volume ratio) of the crude product to give the target compound I-5.
I-5, colorless oil, yield 60％;1H NMR(600MHz,CDCl3)δ7.64–7.58(m,2H),7.10–7.08(m,1H),6.12–5.80(m,2H),5.17(s,1H),2.85–2.77(m,3H),2.68–2.63(m,1H),2.24–2.18(m,1H),1.83–1.79(m,1H),1.42(dd,J＝8.3,1.9Hz,1H),1.27–1.20(m,1H),0.49–0.46(m,1H);13C NMR(150MHz,CDCl3)δ140.79,137.79,136.78,136.03,131.94,131.61,127.29,49.34,47.29,43.89,42.25,38.58,29.96.
Example 6
5-Norbornene-2-methylamine (1.0 mmol), 4-dimethylaminopyridine (0.1 mmol), triethylamine (1.0 mmol) were dissolved in anhydrous dichloromethane, cooled to 0℃and 5mL of an anhydrous dichloromethane solution of 5-chloro-2-thiophenesulfonyl chloride (1.0 mol) was added in portions, and the mixture was reacted at 25℃for 3 hours. TLC monitored complete reaction of the starting material, washing the organic layer 3 times with water (8 ml x 3), washing 3 times with saturated brine (8 ml x 3), drying, suction filtration, concentrating to remove dichloromethane, and column chromatography (CH 2Cl2: meoh=20:1, volume ratio) of the crude product to give the target compound I-6.
I-6 white solid, yield 80％,m.p 116.3-118.2℃;1H NMR(600MHz,CDCl3)δ7.38(d,J＝4.0Hz,1H),6.92(d,J＝4.0Hz,1H),6.16–5.84(m,2H),4.69(t,J＝5.3Hz,1H),2.85–2.78(m,3H),2.72-2.67(m,1H),2.25–2.19(m,1H),1.86–1.82(m,1H),1.46–1.45(m,1H),1.30–1.23(m,1H),0.52-0.49(m,1H);13C NMR(150MHz,CDCl3)δ138.88,138.13,137.05,136.00,131.53,131.41,126.66,49.49,47.41,44.02,42.35,38.79,30.03.
Example 7
5-Norbornene-2-methylamine (1.0 mmol), 4-dimethylaminopyridine (0.1 mmol), triethylamine (1.0 mmol) were dissolved in anhydrous dichloromethane, cooled to 0℃and a 5mL solution of pyridine-3-sulfonyl chloride (1.0 mol) in anhydrous dichloromethane was added in portions, and the mixture was reacted at 25℃for 2 hours. TLC monitored complete reaction of the starting material, washing the organic layer 3 times with water (8 ml x 3), washing 3 times with saturated brine (8 ml x 3), drying, suction filtration, concentrating to remove dichloromethane, and column chromatography (CH 2Cl2: meoh=20:1, volume ratio) of the crude product to give the target compound I-7.
I-7, white solid, yield 66％,m.p 113-115℃;1H NMR(600MHz,CDCl3)δ9.11(d,J＝12.7Hz,1H),8.82(d,J＝4.1Hz,1H),8.19(t,J＝9.5Hz,1H),7.50(dd,J＝7.8,4.8Hz,1H),6.14–5.80(m,2H),4.79(d,J＝5.3Hz,1H),2.82–2.75(m,2H),2.70–2.60(m,1H),2.39(s,1H),2.23–2.17(m,1H),1.83–1.79(m,1H),1.44(d,J＝8.1Hz,1H),1.26–1.21(m,1H),0.49–0.46(m,1H);13C NMR(150MHz,CDCl3)δ152.89,147.80,138.12,136.85,134.86,131.48,123.82,49.45,47.18,43.93,42.31,38.94,30.01.
Example 8
5-Norbornene-2-methylamine (1.0 mmol), 4-dimethylaminopyridine (0.1 mmol), triethylamine (1.0 mmol) were dissolved in anhydrous dichloromethane, cooled to 0℃and a 5mL solution of 2-chloropyridine-5-sulfonyl chloride (1.0 mol) in anhydrous dichloromethane was added in portions to react at 25℃for 5 hours. TLC monitored complete reaction of the starting material, washing the organic layer 3 times with water (8 ml x 3), washing 3 times with saturated brine (8 ml x 3), drying, suction filtration, concentrating to remove dichloromethane, and column chromatography (CH 2Cl2:meoh=20:1, volume ratio) of the crude product to give the target compound I-8.
I-8, white solid, yield 63％,m.p 133.0-133.7℃;1H NMR(600MHz,CDCl3)δ8.84(d,J＝2.3Hz,1H),8.08(dd,J＝8.4,2.5Hz,1H),7.49(d,J＝8.4Hz,1H),6.16–5.82(m,2H),4.84(t,J＝5.7Hz,1H),2.83–2.74(m,3H),2.71–2.66(m,1H),2.23–2.17(m,1H),1.84–1.80(m,1H),1.46–1.44(m,1H),1.28–1.21(m,1H),0.49–0.46(m,1H);13C NMR(150MHz,CDCl3)δ155.32,148.30,138.23,137.23,135.69,131.38,124.71,77.21,77.00,76.79,49.46,48.45,47.21,44.91,43.93,42.31,41.66,38.93,30.85,30.00.
Example 9
Sterilization Activity (ex vivo) experiment
The plant fungi used in the experiment are strains preserved at the temperature of 4 ℃ in a laboratory, and are botrytis cinerea, gibberella wheat, phytophthora infestans, phytophthora capsici, botrytis cinerea, pineapple bacteria and sclerotium bacteria of sugarcane. The culture medium is potato agarose culture medium (PDA for short). PDA culture medium formula comprises potato (peeled) 200g, glucose 20g, agar 15g, distilled water 1000mL, and preparation method: cleaning potato, peeling, weighing 200g, cutting into small pieces, adding water, boiling for 20-30 min, tearing by a glass rod, filtering with eight layers of gauze, adding 20g agar according to experimental requirement, adding 20g glucose, stirring, cooling slightly after full dissolution, supplementing water to 1000mL, packaging, sterilizing at 121deg.C for 15 min, and cooling for use.
The experimental method comprises the following steps: the growth rate method is adopted.
(1) Firstly, 7 plant fungi are cultured on a PDA flat plate at 25 ℃ for about 3-6 days for standby;
(2) Heating PDA culture medium to dissolve, cooling to 45-50deg.C, adding 250 μl of compound to be tested with concentration of 10g/L to obtain culture medium containing 50mg/L of medicinal liquid, respectively pouring into culture dish, and cooling to obtain fluxapyroxad hydroxylamine as positive control;
(3) Taking circular fungus cakes (with the diameter of 0.50 cm) from the edge of hypha of each strain cultivated for 6d (the growth condition is as consistent as possible) by using a puncher in a sterile operation mode, picking the circular fungus cakes to the center of a medicine-containing flat plate by using an inoculating needle, and then inverting a culture dish into an incubator (28 ℃) for cultivation;
(4) Observing and measuring the growth condition of hyphae at different times after treatment, measuring the diameter by adopting a crisscross method, processing data, and calculating the inhibition rate;
(5) Inhibition ratio (%) = (control hypha diameter-treated hypha diameter)/(control hypha diameter-0.5 cm) ×100;
(6) Each treatment was repeated 3 times.
TABLE 1 test results of the inhibitory Activity of norbornenyl-containing arylsulfonamides against seven agricultural pathogenic fungi
Note a three replicates were set for each treatment in the test, and the data in the table are averages of the three replicates.
Table 2 EC 50 values for some of the compounds
The results of the bactericidal activity measurement of the test groups I-1 to I-8 and the reference drug fluxapyroxad hydroxylamine are shown in tables 1 and 2. As can be seen from the results in tables 1 and 2, at the concentration of 50mg/L, the compounds I-1 to I-8 show different degrees of bactericidal activity on 7 plant fungi, and part of the compounds have better inhibitory activity on Sclerotinia sclerotiorum, wherein the inhibition rate of the compound I-1 on the Sclerotinia sclerotiorum reaches 88.4% at the concentration of 50 mg/L; in addition, the inhibition rate of I-5 to the botrytis cinerea is 72.9%; the inhibition rate of I-6 to the grape vine cavity germ is 89.8%; the inhibition rate of I-5 to phytophthora capsici reaches 93.7%, which is equivalent to that of fluxapyroxad hydroxylamine. In addition, the series of compounds have moderate inhibitory activity on potato late blight bacteria and sugarcane pineapple bacteria. In view of the good bactericidal activity of I-5 on phytophthora capsici, EC 50 of the phytophthora capsici is tested to be 4.18mg/L. As can be seen from the plate experiment (figure 2), compared with the blank control (0 mg/L), the I-5 has a certain inhibition effect on the growth of phytophthora capsici hyphae at the concentration of 12.5mg/L, and has a better inhibition effect on the phytophthora capsici hyphae. The series of compounds have good inhibitory activity on phytophthora capsici and have the potential of developing bactericides.
Example 10
Measurement of laccase Activity (ex vivo)
In this experiment, the in vitro enzyme inhibition activity was determined using a Coriolus laccase produced by ChemeGen Kuma Limited (Shanghai). Cysteine was the positive control and DMSO was the negative control. In turn, 10. Mu.L of the test compound solution and 40. Mu.L of the purified laccase were added to a 96-well plate containing 120. Mu.L of citric acid-phosphate buffer (15 mmol of 2% trisodium citrate and 100mL of 150mmol of monophosphate, pH 4.5), 10mL of laccase substrate ABTS (2, 20-Azino-bis (3-ethylbenzothiazoline-6-sulfonic) diamine salt). Enzyme activity was detected by monitoring ABTS oxidation at 420 nm. Finally, the IC 50 value of absorbance slope (OD/h) was calculated using SPSS statistical software 23.0.
TABLE 3 laccase inhibitory Activity of Compound I-5
Compound I-5 has better inhibitory activity on laccase under in vitro conditions, IC 50 value is 5.409 μm, better than positive control cysteine (IC 50 = 35.501 μm).
Example 11
Sclerotinia sclerotiorum living experiment (leaf blade method)
Picking fresh rape leaves with uniform size from campus of Nanjing forestry university, washing with sterilized water, washing with 75% ethanol, and drying in shade at room temperature. An appropriate amount of compound I-1 and positive control was taken as fluxapyroxad hydroxylamine (pydiflumetofen), dissolved in DMSO and dissolved in 0.2% Tween-80 aqueous solution to prepare a concentration of 200 mg/L. Then spraying (the spraying amount is 5mL,1 concentration) on the surface of each rape leaf, uniformly spraying, and naturally drying in the shade. After the surface of the leaf is free from liquid, the epidermis of the leaf is penetrated by an inoculating needle, rape sclerotium bacterial cake (0.5 cm diameter) is inoculated, each leaf is inoculated with 2-4 bacterial cakes, and a blank control is a mixed aqueous solution of DMSO and 0.2% Tween-80 without medicament. The intra-group parallelism and the extra-group parallelism are set. Two parallel groups were incubated (25.+ -. 2 ℃ and 95% relative humidity) for 5 days. The lesion diameter was measured and the inhibition rate was calculated.
Calculation formula of protective activity inhibition (%): (control plaque diameter-plaque diameter of test compound)/control plaque diameter-0.5) x 100.
Table 4 biological Activity of Compound I-1 on the living organism of Sclerotinia sclerotiorum
a The experiment was repeated 9 times per concentration
At a concentration of 200mg/L, the inhibition rate of the compound I-1 to the sclerotinia sclerotiorum is 75.8 percent and is close to the inhibition rate (90.3 percent) of the fluxapyroxad hydroxylamine. The living body protection activity of the compound on rape leaves is equivalent to that of positive control fluxapyroxad hydroxylamine. As can be seen from FIG. 3, the rape leaves treated by the I-1 liquid medicine has a certain inhibition on the growth of sclerotium hyphae, and the diameter of the disease spots is close to that of the leaves treated by the fluxapyroxad hydroxylamine liquid medicine, which shows that the compound I-1 has a stronger inhibition effect on sclerotium bacteria.
The norbornenyl-containing arylsulfonamide compound has obvious structural distinction and clear chemical structural characteristics, and has better effect on preventing and controlling sclerotinia sclerotiorum, botrytis cinerea and phytophthora capsici. Can be used for preventing and treating plant fungal diseases in agriculture or forestry. The preparation method of the compound is simple and convenient, the yield is higher, and the product property is stable.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.

Claims (9)

1. The norbornenyl-containing arylsulfonamides is characterized in that: the structural formula of the norbornenyl-containing arylsulfonamide is shown in formula I below:
Wherein Ar is selected from one of the following groups:
2. The method for preparing the norbornenyl-containing arylsulfonamides according to claim 1, characterized in that: comprises the steps of reacting arylsulfonyl chloride with 5-norbornene-2-methylamine, triethylamine and 4-dimethylaminopyridine to synthesize the aryl sulfonamide compound containing norbornenyl.
3. The process for producing an aromatic sulfonamide containing norbornene according to claim 2, wherein:
Dissolving 5-norbornene-2-methylamine, 4-dimethylaminopyridine and triethylamine in anhydrous dichloromethane, cooling to 0 ℃, adding an anhydrous dichloromethane solution of arylsulfonyl chloride in batches, and heating for reaction;
TLC monitors that the raw materials are completely reacted, the organic layer is washed 3 times with water, saturated saline water is washed 3 times, the organic layer is dried, suction filtered, dichloromethane is removed by concentration, and the crude product is subjected to column chromatography to obtain the target compound.
4. The process for producing an aromatic sulfonamide containing norbornene according to claim 2, wherein: the molar ratio of the intermediate arylsulfonyl chloride to the 5-norbornene-2-methylamine is 1.0:1.
5. The process for producing an aromatic sulfonamide containing norbornene according to claim 2, wherein: the feeding mole ratio of the 5-norbornene-2-methylamine to the triethylamine is 1:1.0.
6. The process for producing an aromatic sulfonamide containing norbornene according to claim 2, wherein: the molar ratio of the arylsulfonyl chloride intermediate to 4-dimethylaminopyridine was 1.0:0.1.
7. The process for producing an aromatic sulfonamide containing norbornene according to claim 2, wherein: synthesizing the norbornenyl-containing arylsulfonamide, wherein the synthesis reaction temperature is 25 ℃ and the reaction time is 1-5 h.
8. The process for producing an aromatic sulfonamide containing norbornene according to claim 2, wherein: the arylsulfonyl chloride comprises 8-quinoline sulfonyl chloride, 6-methyl-8-quinoline sulfonyl chloride, 1-naphthalene sulfonyl chloride, 2-thiophene sulfonyl chloride, 5-chloro-2-thiophene sulfonyl chloride, pyridine-3-sulfonyl chloride and 2-chloropyridine-5-sulfonyl chloride.
9. Use of the norbornenyl-containing arylsulfonamides according to claim 1 for combating plant fungi in agriculture or forestry, characterized in that: the plant fungi are Sclerotinia sclerotiorum, phytophthora capsici and Phytophthora capsici.
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Citations (1)

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US3052703A (en) * 1957-12-30 1962-09-04 Shell Oil Co N-acylated-amino derivatives of halogenated bicyclo (2, 2, 1) hept-5-en-2-yl compounds

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US3052703A (en) * 1957-12-30 1962-09-04 Shell Oil Co N-acylated-amino derivatives of halogenated bicyclo (2, 2, 1) hept-5-en-2-yl compounds

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