CN109734694B

CN109734694B - Sulfonyl sesamol derivative and its prepn process, agricultural pesticide and application in preventing and controlling agricultural pests

Info

Publication number: CN109734694B
Application number: CN201910111754.7A
Authority: CN
Inventors: 车志平; 田月娥; 刘圣明; 林晓民; 陈根强
Original assignee: Henan University of Science and Technology
Current assignee: Henan University of Science and Technology
Priority date: 2019-02-12
Filing date: 2019-02-12
Publication date: 2020-07-10
Anticipated expiration: 2039-02-12
Also published as: CN109734694A

Abstract

The invention belongs to the technical field of heterocyclic compound synthesis, and particularly relates to a sulfonyl sesamol derivative, a preparation method thereof, an agricultural pesticide and application in preventing and controlling agricultural pests. The structural formula of the sulfonyl sesamol derivative is as follows:

wherein R is selected from any one of alkyl with 1-5 carbon atoms, phenyl, alkyl substituted phenyl, methoxyphenyl, halogenated phenyl, nitrophenyl, 4-halogenated-3-nitrophenyl, thienyl, naphthyl and quinolyl. The sulfonyl sesamol derivative is prepared by the reaction of sesamol and substituted sulfonyl chloride. The sulfonyl sesamol derivative has obvious insecticidal activity and can be used for preparing novel insecticides.

Description

Sulfonyl sesamol derivative and its prepn process, agricultural pesticide and application in preventing and controlling agricultural pests

Technical Field

The invention belongs to the technical field of heterocyclic compound synthesis, and particularly relates to a sulfonyl sesamol derivative, a preparation method thereof, an agricultural pesticide and application in preventing and controlling agricultural pests.

Background

Sesamol (3, 4-methylenedioxyphenol) is a natural phenolic compound, is an important aroma component and a quality stabilizer of sesame oil, and has strong antioxidant and antibacterial activities. Sesamol is also a drug synthesis intermediate with wide application, can be used for synthesizing synergist of pyrethrin pesticides such as piperonyl butoxide (i.e. synergistic ether) in agriculture, and can be used for synthesizing paroxetine, antineoplastic drugs VP-16 and VM-26, and ACEI (cardiovascular disease-resistant drug) in medicine.

Sesamol derivatives have recently received much attention from researchers due to their high practical utility value, and have a broad spectrum of biological activities such as bacteriostatic activity, antioxidant activity, antitumor activity, etc. 1-alkoxysesamol derivatives have been reported as monoamine oxidase inhibitors, such as the Synthesis and evaluation of 1-alkoxysesamol derivatives as monoamine oxidase inhibitors (Idalet Engelrepeat, the Synthesis and evaluation of sesamol and benzodioxan derivatives as monoamine oxidase inhibitors) (International Engelrepeat, biological & Medicinal Chemistry L et, 2015: 1896. diaryl sesame derivatives have been reported as evaluation of antioxidant activity of DPPH radicals, such as rodrigz, 1335. et al, which report on arylsesamol derivatives as DPPH radicals (Synthesis and chemical reaction of DPPH radicals) (Synthesis and evaluation of antioxidant activity of Securiol derivatives of DPPH radicals) (Synthesis of chemical reaction of DPPH radicals, Synthesis of chemical reaction of chemical).

The patent document of the invention in China with the grant publication number of CN101193901B discloses a sesamol derivative and a preparation method thereof. The preparation method of the sesamol derivative comprises the following steps: sesamol and phosphoryl chloride are reacted in an organic solvent under the action of organic base such as triethylamine to obtain dichloro [3, 4-methylenedioxy phenol ] -phosphino-1-ketone, and then the dichloro [3, 4-methylenedioxy phenol ] -phosphino-1-ketone is sequentially reacted with 3-aminopropanol and an acid solution. The sesamol derivative has strong antioxidation effect. At present, almost no study on sulfonyl sesame phenol derivatives exists in the prior art, and the study on the performance of the sulfonyl sesame phenol derivatives is not reported.

Disclosure of Invention

The first object of the present invention is to provide a sulfonyl sesamol derivative having a good pesticidal effect.

The second object of the present invention is to provide a method for preparing sulfonyl sesamol derivatives, which has a high yield.

The third object of the present invention is to provide an agricultural insecticide comprising the above sulfonyl sesamol derivative, which has a good insecticidal effect.

The fourth purpose of the invention is to provide the application of the sulfonyl sesamol derivative in the aspect of controlling agricultural pests, which can be used for controlling lepidoptera pests.

In order to achieve the purpose, the invention adopts the technical scheme that:

a sulfonyl sesamol derivative has a structure shown as a formula (1):

in the formula, R is selected from any one of alkyl, phenyl, alkyl substituted phenyl, methoxyphenyl, halogenated phenyl, nitrophenyl, 4-halogenated-3-nitrophenyl, thienyl, naphthyl and quinolyl with the carbon number of 1-5.

The invention provides a novel sesame phenol derivative, namely a sulfonyl sesame phenol derivative. The sulfonyl sesamol phenol derivative has good insecticidal activity and can be used for preparing novel insecticides.

Preferably, R is selected from any one of ethyl, phenyl, p-methylphenyl, p-methoxyphenyl, 4-tert-butylphenyl, 2,4, 6-trimethylphenyl, 2,4, 6-triisopropylphenyl, 4-fluorophenyl, 4-bromophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-chloro-3-nitrophenyl, 2-thienyl, 1-naphthyl and 8-quinolyl. The sulfonyl sesamol derivative with the substituent is easy to synthesize.

A preparation method of sulfonyl sesamol derivatives comprises the following steps: under the action of organic base, sesamol and substituted sulfonyl chloride shown as a formula (2) are mixed and reacted in an organic solvent to obtain the sesamol;

In the preparation process, the substituted sulfonyl chloride and sesamol are subjected to nucleophilic substitution reaction under an alkaline condition to generate the sulfonyl sesamol derivative. The preparation method of the sulfonyl sesamol derivative is simple and has mild reaction conditions. The yield of the sulfonyl sesamol derivatives prepared by the preparation method is high and is over 85 percent, and the preparation method is suitable for large-scale production.

The organic base is triethylamine. The organic base reacts with the sesamol to remove hydrogen on the hydroxyl of the sesamol, so that the sesamol and the substituted sulfonyl chloride have nucleophilic substitution reaction.

The molar ratio of the sesamol to the substituted sulfonyl chloride is (0.9-1.3): (1.0-1.5). To complete the sesamol reaction, an excess of substituted sulfonyl chloride was added.

An agricultural insecticide comprising the sulfonyl sesamol derivative. The sulfonyl sesamol derivative has good insecticidal property and can be used as an effective component of agricultural insecticide.

The agricultural insecticide is an agricultural insecticide for controlling lepidopteran pests, and the insecticide can kill or prevent the pests.

An application of the sulfonyl sesamol derivative in the aspect of preventing and controlling agricultural pests. The sulfonyl sesamol derivative has a good effect on the prevention and control of agricultural pests such as lepidoptera and the like.

The agricultural pests comprise lepidoptera pests, and the lepidoptera pests have great harm to crops.

Drawings

FIG. 1 is a hydrogen spectrum of compound 3a in the example of the sulfonyl sesamol derivative;

FIG. 2 is a hydrogen spectrum of Compound 3b in the example of the sulfonyl sesamol derivative;

FIG. 3 is a hydrogen spectrum of compound 3c in the example of the sulfonyl sesamol derivative;

FIG. 4 is a photograph of abnormal insects in larval armyworms in an example of the use of sulfonyl sesamol derivatives for controlling agricultural pests;

FIG. 5 is a photograph of an abnormal insect in a armyworm in a pupal stage in an example of the use of a sulfonyl sesamol derivative for controlling agricultural pests;

FIG. 6 is a photograph of an abnormal insect in a mythimna separata in an example of the use of a sulfonyl sesamol derivative for controlling agricultural pests.

Detailed Description

The sulfonyl sesamol derivative has the following structure:

The alkyl with 1-5 carbon atoms comprises straight-chain alkyl, branched-chain alkyl and cycloalkyl. Wherein the linear alkyl is selected from any one of methyl, ethyl, propyl, butyl and pentyl. The branched alkyl group is selected from any one of isopropyl and tert-butyl. The cycloalkyl group is selected from any one of cyclopropyl, methylcyclopropyl, cyclobutyl and cyclopentyl.

The alkyl group in the alkyl-substituted phenyl group is an alkyl group having 1 to 5 carbon atoms.

The halogenated phenyl is any one of fluorinated phenyl, brominated phenyl and chlorinated phenyl.

The 4-halogeno-3-nitrophenyl group is any one of 4-chloro-3-nitrophenyl group, 4-fluoro-3-nitrophenyl group and 4-bromo-3-nitrophenyl group.

The preparation method of the sulfonyl sesamol derivative comprises the following steps: under the action of organic base, sesamol and substituted sulfonyl chloride are mixed and reacted in an organic solvent to obtain the sesamol.

The substituted sulfonyl chloride is any one of ethyl sulfonyl chloride, benzene sulfonyl chloride, p-methylbenzene sulfonyl chloride, p-methoxybenzene sulfonyl chloride, 4-tert-butylbenzene sulfonyl chloride, mesitylene sulfonyl chloride, 2,4, 6-triisopropylbenzene sulfonyl chloride, 4-fluorobenzene sulfonyl chloride, 4-bromobenzene sulfonyl chloride, 2-nitrobenzene sulfonyl chloride, 3-nitrobenzene sulfonyl chloride, 4-chlorine-3-nitrobenzene sulfonyl chloride, thiophene-2-sulfonyl chloride, 1-naphthalene sulfonyl chloride and 8-quinoline sulfonyl chloride.

Preferably, the organic solvent is any one of dichloromethane and acetone.

Under the action of organic base, the sesamol and the substituted sulfonyl chloride are mixed in organic solvent to react, namely organic solution of the organic base is added into organic solution of the sesamol and the substituted sulfonyl chloride to react.

The molar ratio of the organic base to the sesamol to the substituted sulfonyl chloride is (1.1-1.6): (0.9-1.3): (1.0-1.5).

After mixing and reacting, extracting, washing and drying are carried out in sequence. The extraction is performed by adopting dichloromethane. The washing is performed by using saturated saline solution. The drying is anhydrous sodium sulfate drying.

Drying, concentrating, and separating. The separation is carried out by silica gel column chromatography.

The agricultural insecticide taking the sulfonyl sesamol derivative as an active ingredient is an insecticide for preventing and controlling lepidoptera pests, and the lepidoptera pests are at least one of armyworms, cabbage caterpillars and prodenia litura.

The sulfonyl sesamol derivative is mainly used for preventing and controlling lepidoptera pests when preventing and controlling agricultural pests, and the lepidoptera pests are at least one of armyworms, cabbage caterpillars and prodenia litura.

The invention is further described with reference to the following specific embodiments and the accompanying drawings.

The reagents involved in the following examples are commercially available conventional products.

Examples of sulfonylsesamol derivatives

The general structural formula of the sulfonyl sesamol derivatives (compounds 3a to 3p) of this example is:

sulfonyl sesamol derivatives (Compounds 3a to 3) of the present examplep) and its physicochemical properties are shown in table 1.

TABLE 1 physicochemical Properties of sulfonyl sesamol Compounds 3a to 3p

In other embodiments of the sulfonyl sesamol derivatives of the present invention, the R group can also be other groups such as methyl, propyl, and the like.

Examples of the preparation method of sulfonyl sesamol derivatives

The preparation method of the sulfonyl sesamol derivative of the embodiment comprises the following steps:

adding sesamol (3, 4-methylenedioxyphenol, 1mmol) to a 50m L flask to replace sulfonyl chloride (compounds 2 a-2 p, 1.1mmol), adding 10m L dichloromethane to completely dissolve the sesamol, slowly adding a dichloromethane solution of triethylamine (1.2mmol) dropwise, stirring at room temperature after the dropwise addition is finished, and carrying out T L C tracking monitoring until the reaction is finished, adding 30m L water, extracting with 80m L dichloromethane, repeating the extraction for 3 times, combining organic phases, washing with saturated common salt water, drying with anhydrous sodium sulfate, concentrating and evaporating the solvent, and separating by silica gel column chromatography to obtain target products 3 a-3 p, wherein the reaction formula is as follows:

wherein the substituted sulfonyl chlorides corresponding to 2a to 2p and the reaction yields are shown in Table 2.

TABLE 2 substituted sulfonyl chloride compounds corresponding to Compounds 2 a-2 p and product yields

Compound (I)	Substituted sulphonyl chlorides	Yield of the products (3a to 3p)
			Compound 2a	Ethanesulfonyl chloride	85％
Compound 2b	Benzenesulfonyl chlorides	88％
			Compound 2c	P-methylbenzenesulfonyl chloride	89％
Compound 2d	P-methoxybenzenesulfonyl chloride	89％
			Compound 2e	4-tert-butylbenzenesulfonyl chloride	92％
Compound 2f
		2,4, 6-trimethylbenzenesulfonyl chloride	95％
Compound 2g
		2,4, 6-triisopropylbenzenesulfonyl chloride	93％
Compound 2h				4-fluorobenzenesulfonyl chloride	97％
	Compound 2i	4-bromobenzenesulfonyl chloride	91％
Compound 2j				2-Nitrobenzenesulfonyl chlorides	88％
	Compound 2k	3-Nitrobenzenesulfonyl chlorides	94％
Compound 2l				4-Nitrobenzenesulfonyl chlorides	100％
	Compound 2m	4-chloro-3-nitrobenzenesulfonyl chloride	86％
Compound 2n				Thiophene-2-sulfonyl chlorides	92％
	Compound 2o	1-naphthalenesulfonyl chlorides	92％
Compound 2p				8-quinolinesulfonyl chlorides	90％

Test example 1

The compounds 3a to 3p in examples of the sulfonyl sesamol derivative were subjected to a 400MHz nuclear magnetic resonance test for hydrogen spectra and a High Resolution Mass Spectrometry (HRMS) test. In the nuclear magnetic resonance test, CDCl is used₃TMS is an internal standard substance. The hydrogen spectrum information and mass spectrum results of each compound are as follows:

compound 3 a: as shown in fig. 1, the chemical shifts of the peaks are: 6.796(d, J ═ 2.4Hz, 1H), 6.793(d, J ═ 8.4Hz, 1H), 6.73(dd, J ═ 8.4Hz, 2.4Hz, 1H), 6.01(s, 2H), 3.29(q, J ═ 7.2Hz, 2H), 1.54(t, J ═ 7.6Hz, 3H). HRMS (ESI ion source) for this compound: calcd for (theoretical value) C₉H₁₂O₅S([M+H]⁺) 231.0322; found (experimental value) 231.0320.

Compound 3 b: as shown in fig. 2, the chemical shifts of the peaks are: 7.82 ~ 7.86(m, 2H), 7.65 ~ 7.69(m, 1H), 7.51 ~ 7.56(m, 2H), 6.64(d, J ═ 8.4Hz, 1H), 6.52(d, J ═ 2.4Hz, 1H), 6.38(dd, J ═ 8.4Hz, 2.4Hz, 1H), 5.96(s, 2H). HRMS (ESI ion source) for this compound: calcd for C₁₃H₁₁O₅S([M+H]⁺)，279.0322；found，279.0322。

Compound 3 c: as shown in fig. 3, the chemical shifts of the peaks are: 7.69 to 7.72(m, 2H), 7.30 to 7.33(m, 2H), 6.65(d, J ═ 8.4Hz, 1H), 6.53(d, J ═ 2.4Hz, 1H), 6.39(dd, J ═ 8.4Hz, 2.4Hz, 1H), 5.96(s, 2H), 2.45(s, 3H). HRMS (ESI ion source) for this compound: calcd for C₁₄H₁₃O₅S([M+H]⁺)，293.0478；found，293.0480。

Compound 3 d: the chemical shifts of the peaks are respectively: 7.73 to 7.77(m, 2H), 6.95 to 6.99(m, 2H), 6.65(d, J ═ 8.4Hz, 1H), 6.53(d, J ═ 2.4Hz, 1H), 6.39(dd, J ═ 8.4Hz, 2.4Hz, 1H), 5.96(s, 2H), 3.88(s, 3H). Of the compoundHRMS (ESI ion source): calcd for C₁₄H₁₃O₆S([M+H]⁺)，309.0427；found，309.0428。

Compound 3 e: the chemical shifts of the peaks are respectively: 7.74 to 7.77(m, 2H), 7.51 to 7.55(m, 2H), 6.66(d, J ═ 8.8Hz, 1H), 6.54(d, J ═ 2.4Hz, 1H), 6.41(dd, J ═ 8.4Hz, 2.4Hz, 1H), 5.96(s, 2H), 1.35(s, 9H). HRMS (ESI ion source) for this compound: calcd for C₁₇H₁₉O₅S([M+H]⁺)，335.0948；found，335.0945。

Compound 3 f: the chemical shifts of the peaks are respectively: 6.97(q, J ═ 0.8Hz, 2H), 6.64(d, J ═ 8.4Hz, 1H), 6.51(d, J ═ 2.4Hz, 1H), 6.38(d, J ═ 8.8Hz, 2.4Hz, 1H), 5.95(s, 2H), 2.56(s, 6H), 2.32(s, 3H). HRMS (ESI ion source) for this compound: calcd for C₁₆H₁₇O₅S([M+H]⁺)，293.0478；found，293.0480。

Compound 3 g: the chemical shifts of the peaks are respectively: 7.19(s, 2H), 6.67(d, J ═ 8.8Hz, 1H), 6.54(d, J ═ 2.4Hz, 1H), 6.43(dd, J ═ 8.4Hz, 2.4Hz, 1H), 5.95(s, 2H), 4.01 to 4.08(m, 2H), 2.89 to 2.96(m, 1H), 1.28(s, 3H), 1.26(s, 3H), 1.20(s, 6H), 1.19(s, 6H). HRMS (ESI ion source) for this compound: calcd for C₂₂H₂₉O₅S([M+H]⁺)，405.1730；found，405.1731。

Compound 3 h: the chemical shifts of the peaks are respectively: 7.83 to 7.88(m, 2H), 7.18 to 7.24(m, 2H), 6.66(d, J ═ 8.8Hz, 1H), 6.54(d, J ═ 2.0Hz, 1H), 6.38(dd, J ═ 8.4Hz, 2.4Hz, 1H), 5.98(s, 2H). HRMS (ESI ion source) for this compound: calcd for C₁₃H₁₀FO₅S([M+H]⁺)，297.0027；found，297.0230。

Compound 3 i: the chemical shifts of the peaks are respectively: 7.66-7.71 (m, 4H), 6.67(d, J ═ 8.4Hz, 1H), 6.55(d, J ═ 2.4Hz, 1H), 6.39(dd, J ═ 8.4Hz, 2.4Hz, 1H), 5.98(s, 2H). HRMS (ESI ion source) for this compound: calcd for C₁₃H₁₀BrO₅S([M+H]⁺)，356.9427；found，356.9425。

Compound 3 j: the chemical shifts of the peaks are respectively: 7.94-7.97 (m, 1H), 7.80-7.85 (m, 2H), 7.67-7.72 (m, 1H), 6.73(d, J ═ 2.0Hz, 1H), 6.70(d, J ═ 8.4Hz, 1H), 6.65(dd, J ═ 8.4Hz, 2.4Hz, 1H), 5.99(s, 2H). HRMS (ESI ion source) for this compound: calcd for C₁₃H₁₀NO₇S([M+H]⁺)，324.0172；found，324.0172。

Compound 3 k: the chemical shifts of the peaks are respectively: 8.70(t, J ═ 2.5Hz, 1H), 8.52 to 8.55(m, 1H), 8.16 to 8.18(m, 1H), 7.81(t, J ═ 8.0Hz, 1H), 6.67(d, J ═ 8.4Hz, 1H), 6.57(d, J ═ 2.4Hz, 1H), 6.40(dd, J ═ 8.4Hz, 2.4Hz, 1H), 5.99(s, 2H). HRMS (ESI ion source) for this compound: calcd for C₁₃H₁₀NO₇S([M+H]⁺)，324.0172；found，324.0176。

Compound 3 l: the chemical shifts of the peaks are respectively: 8.37-8.40 (m, 2H), 8.03-8.06 (m, 2H), 6.67(d, J ═ 8.4Hz, 1H), 6.56(d, J ═ 2.4Hz, 1H), 6.39(dd, J ═ 8.4Hz, 2.4Hz, 1H), 5.99(s, 2H). HRMS (ESI ion source) for this compound: calcd for C₁₃H₁₀NO₇S([M+H]⁺)，324.0172；found，324.0175。

Compound 3 m: the chemical shifts of the peaks are respectively: 8.31(d, J ═ 2.0Hz, 1H), 7.97(dd, J ═ 8.4Hz, 2.4Hz, 1H), 7.77(d, J ═ 8.4Hz, 1H), 6.70(d, J ═ 8.4Hz, 1H), 6.59(d, J ═ 2.4Hz, 1H), 6.41(dd, J ═ 8.4Hz, 2.4Hz, 1H), 6.01(s, 2H). HRMS (ESI ion source) for this compound: calcd for C₁₃H₉ClNO₇S([M+H]⁺)，357.9783；found，357.9787。

Compound 3 n: the chemical shifts of the peaks are respectively: 7.74(dd, J ═ 5.2Hz, 1.6Hz, 1H), 7.61(dd, J ═ 4.0Hz, 1.6Hz, 1H), 7.13(dd, J ═ 5.2Hz, 4.0Hz, 1H), 6.68(d, J ═ 8.4Hz, 1H), 6.58(d, J ═ 2.4Hz, 1H), 6.46(dd, J ═ 8.4Hz, 2.4Hz, 1H), 5.98(s, 2H). HRMS (ESI ion source) for this compound: calcd for C₁₁H₉O₅S₂([M+H]⁺)，284.9886；found，284.9886。

Compound 3 o: the chemical shifts of the peaks are respectively: 8.77 ~ 8.80(m, 1H), 8.12 ~ 8.14(m, 1H), 8.11(dd, J ═ 7.2Hz, 1.2Hz, 1H), 7.97 ~ 8.00(m, 1H), 7.76 ~ 7.80(m, 1H), 7.65 ~ 7.69(m, 1H), 7.50(dd, J ═ 8.4Hz, 7.2Hz, 1H), 6.53(d, J ═ 8.8Hz, 1H), 6.42(d, J ═ 2.4Hz, 1H), 6.25(dd, J ═ 8.4Hz, 2.4Hz, 1H), 5.90(s, 2H). HRMS (ESI ion source) for this compound: calcd for C₁₇H₁₃O₅S([M+H]⁺)，329.0478；found，329.0481。

Compound 3 p: the chemical shifts of the peaks are respectively: 9.27(dd, J ═ 4.4Hz, 2.0Hz, 1H), 8.40(dd, J ═ 7.2Hz, 1.6Hz, 1H), 8.31(dd, J ═ 8.4Hz, 1.6Hz, 1H), 8.15(dd, J ═ 8.4Hz, 1.6Hz, 1H), 7.58 to 7.64(m, 2H), 6.59(d, J ═ 2.4Hz, 1H), 6.57(d, J ═ 8.4Hz, 1H), 6.46(dd, J ═ 8.4Hz, 2.4Hz, 1H), 5.90(s, 2H). HRMS (ESI ion source) for this compound: calcd for C₁₆H₁₂NO₅S([M+H]⁺)，330.0431；found，330.0435。

Examples of agricultural insecticides

The active ingredient in the agricultural insecticide of this example was a sulfonyl sesamol derivative, and the remaining ingredients were formulated with reference to commercially available conventional agricultural insecticide ingredients. The sulfonyl sesamol derivative is one of sulfonyl sesamol derivatives 3a to 3p in the examples of the sulfonyl sesamol derivative.

Examples of the use of sulfonyl sesamol derivatives for controlling agricultural pests

The compounds 3a to 3p and sesamol in the examples of the sulfonyl sesamol derivative were subjected to a lepidopteran pest armyworm killing activity test by a leaflet disc addition method, respectively. The test insects are three-year-old early myxozoa, and commercial botanical insecticide Toosendanin (Toosendanin) is used as a positive treatment group. The specific test process is as follows:

1) respectively preparing the compounds 3 a-3 p, sesamol and toosendanin into acetone solution with the concentration of 1mg/m L to obtain 3 a-3 p liquid medicine, sesamol liquid medicine and toosendanin liquid medicine, cutting fresh corn leaves into small-leaf disks with the length of 1cm × 1cm, soaking the small-leaf disks in the 3 a-3 p liquid medicine, sesamol liquid medicine, toosendanin liquid medicine and acetone for 3s, and naturally drying.

2) Feeding the dried small leaf discs with test insects respectively, adding the small leaf discs in time after the test insects eat the small leaf discs, and feeding for 48h, and then changing and feeding normal leaves until eclosion; three repetitions are set for each liquid medicine, 10 healthy and uniform-sized three-year-old early armyworms are repeatedly selected and raised in a culture dish with the diameter of 9cm, and a layer of filter paper is laid at the bottom of the culture dish for moisture preservation. During the feeding process, a control group for feeding the small leaf dish without soaking the liquid medicine is arranged. The breeding conditions are as follows: the temperature is 25 +/-2 ℃, the relative humidity is 65-80%, the illumination time is 12h, the dark time is 12h, and the illumination and the dark are sequentially carried out at intervals.

3) During the raising period, the mortality (%) of the test insects at different periods was recorded and calculated according to the following formula: and (3) correcting the mortality rate (%) (treatment group mortality rate-control group mortality rate) by 100/(1-control group mortality rate), wherein the control group mortality rate is the natural mortality rate of the test insects. The calculation results are shown in table 3.

Table 3 results of activity test

As is clear from Table 3, the sulfonyl sesamol derivatives of the present invention all had insecticidal activity. In the first 10 days of the test, the insecticidal activity of the

sulfonyl sesamol derivatives

3b, 3d, 3e, 3f, 3g, 3h and 3i is higher than that of toosendanin, wherein the insecticidal activity of the

sulfonyl sesamol derivatives

3b, 3d, 3f and 3h is particularly remarkable; in the first 20 days of the test, the insecticidal activity of the

sulfonyl sesamol derivatives

3b, 3d, 3e, 3f, 3g, 3h, 3i, 3m and 3p is higher than that of toosendanin, wherein the activity of 3b, 3e, 3g and 3p is particularly remarkable. In the first 30 days of the test, the insecticidal activity of the

sulfonyl sesamol derivatives

3b, 3g, 3h and 3p is higher than that of toosendanin, wherein the activity of 3b is particularly obvious.

During the test period, mythimna separata in the larval stage, the pupal stage and the moth stage were picked and photographed as shown in FIGS. 4 to 6 (CK in the figure is the abnormal test insect in the control group). As can be seen from fig. 4 to 6, the sulfonyl sesamol derivatives of the present invention act on armyworm at different times.

Claims

1. A sulfonyl sesamol derivative is characterized by having a structure shown as a formula (1):

in the formula, R is selected from any one of ethyl, p-methoxyphenyl, 2,4, 6-trimethylphenyl, 2,4, 6-triisopropylphenyl, 4-fluorophenyl, 4-bromophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-chloro-3-nitrophenyl, 2-thienyl and 8-quinolyl.

2. The preparation method of the sulfonyl sesamol derivative is characterized by comprising the following steps: under the action of organic base, sesamol and substituted sulfonyl chloride shown as a formula (2) are mixed and reacted in an organic solvent to obtain the sesamol;

3. The method for producing a sulfonyl sesamol derivative according to claim 2, wherein the organic base is triethylamine.

4. The method for producing a sulfonyl sesamol derivative according to claim 2 or 3, wherein the molar ratio of sesamol to substituted sulfonyl chloride is (0.9 to 1.3): (1.0-1.5).

5. An agricultural insecticide, comprising a sulfonyl sesamol derivative; the sulfonyl sesamol derivative has a structure shown in a formula (1):

6. An agricultural insecticide according to claim 5, wherein said agricultural insecticide is an agricultural insecticide for controlling lepidopteran pests.

7. The application of the sulfonyl sesamol derivative in the aspect of controlling agricultural pests is characterized in that the agricultural pests are armyworms; the sulfonyl sesamol derivative has a structure shown in a formula (1):

in the formula, R is selected from any one of alkyl, phenyl, alkyl substituted phenyl, methoxyphenyl, halogenated phenyl, nitrophenyl, 4-halogenated-3-nitrophenyl, thienyl, naphthyl and quinolyl with the carbon number of 1-5; the number of carbon atoms in the alkyl group in the alkyl substituted phenyl is 1-5.