CN109694338A - A kind of methoxyacetophenone derivative and preparation method thereof, application - Google Patents

A kind of methoxyacetophenone derivative and preparation method thereof, application Download PDF

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CN109694338A
CN109694338A CN201710994239.9A CN201710994239A CN109694338A CN 109694338 A CN109694338 A CN 109694338A CN 201710994239 A CN201710994239 A CN 201710994239A CN 109694338 A CN109694338 A CN 109694338A
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methoxyacetophenone
derivative
chloride
preparation
bis
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CN109694338B (en
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车志平
田月娥
刘圣明
陈根强
肖涛
韩华民
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Henan University of Science and Technology
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Henan University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/73—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/75—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/76—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a kind of methoxyacetophenone derivatives and preparation method thereof, application, belong to plant pest management technical field.Methoxyacetophenone derivative of the invention has the structure as shown in formula (1), wherein R1Selected from H, CH3、CH2CH3、OCH3、F、Cl、Br、NO2、CH2One or more of Br；R2And R3It is each independently selected from one of F, Cl, Br.Methoxyacetophenone derivative of the invention has preferable antibacterial and insecticidal activity, can be used in preparing novel plant pathogenic fungi antibacterial agent and pests insecticide.

Description

A kind of methoxyacetophenone derivative and preparation method thereof, application
Technical field
The present invention relates to a kind of methoxyacetophenone derivatives and preparation method thereof, application, belong to plant pest management Technical field.
Background technique
Using and two or more active subunits group is gathered in same molecule can obtain more preferably with principle Reactive compound, this medicine and pesticide research field have special meaning.
Paeonol (Paeonolum) and paeonol derivative, because its with antibacterial anti-inflammatory, it is antitumor, Analgesia, it is antipyretic, inhibit allergy, antiatherosclerosis, the pharmacological activity such as anti-hepatic fibrosis and quite by the favor of researcher. As " synthesis, characterization and biology of [Asia (E) -1- (bis- chlorine-2-hydroxyl -4- methoxyphenyl of 3,5-) ethylamino] ethyl acetate are living Journal of Sex Research " (such as Ding Sheng, Du Qian, Bai Linshan Anhui University of Technology journal (from section version), 2015,32:330-7) disclose one kind The compound as made from Paeonol has certain antibacterial action, has to Escherichia coli and staphylococcus aureus preferable Bactericidal effect.In the prior art, the methoxyacetophenone class with stronger prevention and treatment plant pathogenic fungi and pest effect is derivative Object has not been reported.
Summary of the invention
The purpose of the present invention is to provide a kind of sterilization and the good methoxyacetophenone derivatives of insecticidal properties.
The object of the invention is also to provide the preparation method and applications of above-mentioned methoxyacetophenone derivative.
To achieve the above object, the technical solution of methoxyacetophenone derivative of the invention is:
A kind of methoxyacetophenone derivative has the structure as shown in formula (1):
Wherein, R1Selected from H, CH3、CH2CH3、OCH3、F、Cl、Br、NO2、CH2One or more of Br；R2And R3Respectively Independently selected from one of F, Cl, Br.
Methoxyacetophenone derivative of the invention has a stronger theoretical and application value, and using and and principle by two Kind or two or more active subunits groups are gathered in same molecule to obtain better reactive compound.In addition, of the invention Compound introduce halogen atom in specific position and be also beneficial to obtain the better derivative of activity.Methoxyacetophenone of the invention Derivative has preferable antibacterial and insecticidal activity, can be used in preparing novel plant pathogenic fungi antibacterial agent and pest desinsection Agent.
Above-mentioned R1Selected from H, CH3、CH2CH3、OCH3、F、Cl、Br、NO2、CH2Several in Br refer in above-mentioned group Two or more be connected to R1The different of corresponding phenyl ring replace on position.Such as R1For m-NO2,p-Cl.For choosing From the R of one of above-mentioned group1Group, it is generally preferable to be p-CH3、p-CH2CH3、p-OCH3、p-F、p-Cl、p-Br、o-NO2、 m-NO2、p-NO2Or p-CH2Br。
Preferably, R2And R3It is Cl, i.e., methoxyacetophenone derivative is the chloro- 2- of 3,5- bis- [(benzenesulfonyl) oxygen] -4- Methoxyacetophenone derivative.
Preferably, the methoxyacetophenone derivative is selected from:
The technical solution of the preparation method of methoxyacetophenone derivative of the invention is:
A kind of preparation method of above-mentioned methoxyacetophenone derivative, includes the following steps:
The chloro- Paeonolum of 3,5- bis-, triethylamine, benzene sulfonyl chloride or substituted phenylsulfonyl chloride are added molten Reacted in agent, extract, separation to get.
The preparation method of methoxyacetophenone derivative of the invention uses bis- chlorine-2-hydroxyl -4- methoxybenzene second of 3,5- Ketone is reacted with substituted phenylsulfonyl chloride is made the chloro- 2- of 3,5- of series bis- [(benzenesulfonyl) oxygen] -4- methoxyacetophenone analog derivative, This method is simple, easily operated.Wherein, the effect of triethylamine is mainly except the HCl that dereaction generates.The following institute of reaction formula Show:
The substituted phenylsulfonyl chloride be p-methyl benzene sulfonic chloride, to ethyl benzene sulfonyl chloride, to Methoxybenzenesulfonyl chloride, to fluorine Benzene sulfonyl chloride, parachloroben-zenesulfonyl chloride, p-bromobenzenesulfonyl chloride, ortho-nitrophenyl sulfonic acid chloride, m-nitrobenzene sulfonyl chloride, p-nitrophenyl sulphonyl Chlorine, to any one in chlorine m-nitrobenzene sulfonyl chloride, 4- Bromomethylbenzenesulfonyl chloride.
The chloro- Paeonolum of the 3,5- bis-, triethylamine, benzene sulfonyl chloride or substituted phenylsulfonyl chloride object The ratio of the amount of matter is 1:0.8-1.2:1.0-1.5.
The solvent is methylene chloride or acetone.
Water is added into reaction system after reaction, methylene chloride is then added and is extracted.The effect of water is washing The salt that excessive triethylamine and reaction generate.The additional amount general control of water is the one third of the volume of methylene chloride.
Organic phase saturated common salt water washing is taken after extraction, it is then dry with anhydrous sodium sulfate.It is dried, fills after washing Divide the purity for improving product.In order to further increase product purity, it is concentrated under reduced pressure after the drying.
It is described to be separated into thin-layer chromatography separation.
The chloro- Paeonolum of above-mentioned 3,5- bis- is made by the method included the following steps:
Paeonolum is uniform with mixed in hydrochloric acid, H is added at 50 DEG C2O2Reaction is separated by solid-liquid separation, i.e., ?.
The concentration of the hydrochloric acid is 4-6mol/L.Preferably 6mol/L.
The H2O2It is preferred that use concentration for 30% hydrogen peroxide.H2O2Effect be to make oxidant, can recycle chlorine from Son, regeneration chlorine continue chlorination.
H is added2O2It is cooled to room temperature after completion of the reaction.
The purity of product for amplitude peak is improved, described be separated by solid-liquid separation filters for decompression.It is carried out after separation of solid and liquid true Sky is dry.It is recrystallized after vacuum drying.
In reaction, Paeonolum, HCl, H2O2Molar ratio be 1.0:200.0:2.0.
The technical solution of the application of methoxyacetophenone derivative of the invention is:
A kind of application of above-mentioned methoxyacetophenone derivative in terms of sterilization or desinsection.Specifically, the application is Plant sterilization or plant murder the application in terms of worm.Further, sterilization is to kill mildew bacterium or wilt, particularly, It is to kill botrytis cinerea [Botrytis cinerea Pers.] or tobacco wilt [Fusarium oxysporum (Schlecht)f.sp.nicotianae(Johns.)Snyder et H ansen].Desinsection is to kill the moth pests.Particularly It is to kill double committee noctuids.Preferably, the application is the application in terms of preparing fungicide or insecticide.It the fungicide and kills It is bactericide and vegetable insecticide that worm agent, which is made,.When concrete application, it can be used methoxyacetophenone derivative and other Conventional auxiliary material such as solvent etc. is configured to liquid formulation or paste carries out sterilization or desinsection.
Methoxyacetophenone derivative of the invention has good sterilization and insecticidal effect, the suppression to frequently seen plants germ For rate processed up to 50% or more, the desinsection death rate has been more than the fungicide and insecticide of commercialization 30% or more.
Detailed description of the invention
Fig. 1 is that the methoxyacetophenone derivative and control group in embodiment 8,9,12 imitate the poisoning in double committee's noctuid pupa time Fruit figure；
Fig. 2 is that the methoxyacetophenone derivative and control group in embodiment 9,12 imitate the poisoning in double committee's noctuid adult stages Fruit figure；
Fig. 3 be embodiment 1,2,3,4,9,12 in methoxyacetophenone derivative and control group to botrytis cinerea Inhibitory effect figure；
Fig. 4 is the suppression of methoxyacetophenone derivative and control group to tobacco wilt in embodiment 2,3,4,9,12 Effect picture processed.
Specific embodiment
Technical solution of the present invention is described further combined with specific embodiments below.
Embodiment 1
The structural formula of the chloro- Paeonolum of 3,5- bis- of the present embodiment is as follows:
The preparation method of the chloro- Paeonolum of 3,5- bis- of the present embodiment includes the following steps:
It takes the Paeonol (Paeonolum) of 10mmol to be added in the flask of 500mL, concentration is then added For the hydrochloric acid solution of 6.0mol/L, it is completely dissolved Paeonol, is warming up to 50 DEG C, the mass fraction that 20mL is then added is 30% Hydrogen peroxide reaction 0.5h reaction solution is cooled to room temperature, a large amount of solids are generated in reaction solution after reaction；Decompression filters, Then vacuum drying obtains crude product；Crude product is recrystallized up to the chloro- Paeonolum of sterling 3,5- bis-.
The structural formula of the methoxyacetophenone derivative of the present embodiment is as follows:
The preparation method of the methoxyacetophenone derivative of the present embodiment includes the following steps:
The chloro- Paeonolum of 3,5- bis- of 1.0mmol is added in the flask of 50mL, dichloromethane is added Alkane makes it completely dissolved, and 1.0mmol triethylamine is then added thereto, the two of substituted phenylsulfonyl chloride is then slowly added dropwise thereto Chloromethanes solution, wherein the amount of the substance of substituted phenylsulfonyl chloride is 1.2mmol；It is reacted at room temperature, with TLC tracing detection To fully reacting, the water of 10mL is then added into reaction solution, is extracted with dichloromethane, merges organic phase, organic phase saturation Brine It, it is then dry with anhydrous sodium sulfate, it is concentrated under reduced pressure, is separated with thin-layer chromatography up to sterling.
The reaction equation of above-mentioned reaction is as follows:
The physicochemical property of the methoxyacetophenone derivative of the present embodiment is as follows:
1) compound is white solid, yield 87%, molecular formula C15H12Cl2O5S。
2) compound nuclear magnetic resonance map (1H NMR, 400MHz) feature:
With deuterated CDCl3For solvent, TMS is internal standard compound, wherein each peak belongs to are as follows: δ: 7.85 (d, J=8.0Hz, 2H), 7.67-7.69 (m, 2H), 7.52-7.55 (m, 2H), 6.53 (s, 3H), 2.55 (s, 3H).
3) source ES mass spectrum (MS) figure feature of compound: its [M]+Peak is 374.
Embodiment 2
Structure of the chloro- Paeonolum of 3,5- bis- of the present embodiment and preparation method thereof is the same as embodiment 1.
The structural formula of the methoxyacetophenone derivative of the present embodiment is as follows:
Method in the preparation method reference implementation example 1 of the methoxyacetophenone derivative of the present embodiment, reaction equation are as follows:
The physicochemical property of the methoxyacetophenone derivative of the present embodiment is as follows:
1) compound is white solid, yield 85%, molecular formula C16H14Cl2O5S。
2) compound nuclear magnetic resonance map (1H NMR, 400MHz) feature:
With deuterated CDCl3For solvent, TMS is internal standard compound, wherein each peak belongs to are as follows: δ: 7.65 (d, J=7.2Hz, 2H), 7.43-7.46 (m, 3H), 6.50 (s, 3H), 2.43 (s, 3H), 2.39 (s, 3H).
3) source ES mass spectrum (MS) figure feature of compound: its [M]+Peak is 388.
Embodiment 3
Structure of the chloro- Paeonolum of 3,5- bis- of the present embodiment and preparation method thereof is the same as embodiment 1.
The structural formula of the methoxyacetophenone derivative of the present embodiment is as follows:
Method in the preparation method reference implementation example 1 of the methoxyacetophenone derivative of the present embodiment, reaction equation are as follows:
The physicochemical property of the methoxyacetophenone derivative of the present embodiment is as follows:
1) compound is white solid, yield 89%, molecular formula C17H16Cl2O5S。
2) compound nuclear magnetic resonance map (1H NMR, 400MHz) feature:
With deuterated CDCl3For solvent, TMS is internal standard compound, wherein each peak belongs to are as follows: δ: 7.73 (d, J=7.2Hz, 2H), 7.41-7.45 (m, 3H), 6.50 (s, 3H), 2.63-2.65 (m, 2H), 2.41 (s, 3H), 1.23 (t, J=2.8Hz, 3H).
3) source ES mass spectrum (MS) figure feature of compound: its [M]+Peak is 402.
Embodiment 4
Structure of the chloro- Paeonolum of 3,5- bis- of the present embodiment and preparation method thereof is the same as embodiment 1.
The structural formula of the methoxyacetophenone derivative of the present embodiment is as follows:
Method in the preparation method reference implementation example 1 of the methoxyacetophenone derivative of the present embodiment, reaction equation are as follows:
The physicochemical property of the methoxyacetophenone derivative of the present embodiment is as follows:
1) compound is white solid, yield 82%, molecular formula C16H14Cl2O6S。
2) compound nuclear magnetic resonance map (1H NMR, 400MHz) feature:
With deuterated CDCl3For solvent, TMS is internal standard compound, wherein each peak belongs to are as follows: δ: 7.68 (d, J=7.2Hz, 2H), 7.46 (s, 1H), 6.91-9.94 (m, 2H), 6.51 (s, 3H), 3.75 (s, 3H), 2.42 (s, 3H).
3) source ES mass spectrum (MS) figure feature of compound: its [M]+Peak is 404.
Embodiment 5
Structure of the chloro- Paeonolum of 3,5- bis- of the present embodiment and preparation method thereof is the same as embodiment 1.
The structural formula of the methoxyacetophenone derivative of the present embodiment is as follows:
Method in the preparation method reference implementation example 1 of the methoxyacetophenone derivative of the present embodiment, reaction equation are as follows:
The physicochemical property of the methoxyacetophenone derivative of the present embodiment is as follows:
1) compound is white solid, yield 85%, molecular formula C15H11Cl2FO5S。
2) compound nuclear magnetic resonance map (1H NMR, 400MHz) feature:
With deuterated CDCl3For solvent, TMS is internal standard compound, wherein each peak belongs to are as follows: δ: 7.86 (d, J=7.2Hz, 2H), 7.67-7.69 (m, 3H), 6.53 (s, 3H), 2.55 (s, 3H).
3) source ES mass spectrum (MS) figure feature of compound: its [M]+Peak is 392.
Embodiment 6
Structure of the chloro- Paeonolum of 3,5- bis- of the present embodiment and preparation method thereof is the same as embodiment 1.
The structural formula of the methoxyacetophenone derivative of the present embodiment is as follows:
Method in the preparation method reference implementation example 1 of the methoxyacetophenone derivative of the present embodiment, reaction equation are as follows:
The physicochemical property of the methoxyacetophenone derivative of the present embodiment is as follows:
1) compound is white solid, yield 83%, molecular formula C15H11Cl3O5S。
2) compound nuclear magnetic resonance map (1H NMR, 400MHz) feature:
With deuterated CDCl3For solvent, TMS is internal standard compound, wherein each peak belongs to are as follows: δ: 7.77 (d, J=8.0Hz, 2H), 7.66-7.69 (m, 2H), 7.49 (s, 1H), 6.51 (s, 3H), 2.53 (s, 3H).
3) source ES mass spectrum (MS) figure feature of compound: its [M]+Peak is 408.
Embodiment 7
Structure of the chloro- Paeonolum of 3,5- bis- of the present embodiment and preparation method thereof is the same as embodiment 1.
The structural formula of the methoxyacetophenone derivative of the present embodiment is as follows:
Method in the preparation method reference implementation example 1 of the methoxyacetophenone derivative of the present embodiment, reaction equation are as follows:
The physicochemical property of the methoxyacetophenone derivative of the present embodiment is as follows:
1) compound is white solid, yield 75%, molecular formula C15H11BrCl2O5S。
2) compound nuclear magnetic resonance map (1H NMR, 400MHz) feature:
With deuterated CDCl3For solvent, TMS is internal standard compound, wherein each peak belongs to are as follows: δ: 7.76-7.80 (m, 4H), 7.51 (s, 1H), 6.53 (s, 3H), 2.55 (s, 3H).
3) source ES mass spectrum (MS) figure feature of compound: its [M]+Peak is 452.
Embodiment 8
Structure of the chloro- Paeonolum of 3,5- bis- of the present embodiment and preparation method thereof is the same as embodiment 1.
The structural formula of the methoxyacetophenone derivative of the present embodiment is as follows:
Method in the preparation method reference implementation example 1 of the methoxyacetophenone derivative of the present embodiment, reaction equation are as follows:
The physicochemical property of the methoxyacetophenone derivative of the present embodiment is as follows:
1) compound is yellow solid, yield 74%, molecular formula C15H11Cl2NO7S。
2) compound nuclear magnetic resonance map (1H NMR, 400MHz) feature:
With deuterated CDCl3For solvent, TMS is internal standard compound, wherein each peak belongs to are as follows: δ: 8.34 (d, J=5.6Hz, 1H), 8.08-8.12 (m, 2H), 7.69-7.71 (m, 1H), 7.47 (s, 1H), 6.52 (s, 3H), 2.54 (s, 3H).
3) source ES mass spectrum (MS) figure feature of compound: its [M]+Peak is 419.
Embodiment 9
Structure of the chloro- Paeonolum of 3,5- bis- of the present embodiment and preparation method thereof is the same as embodiment 1.
The structural formula of the methoxyacetophenone derivative of the present embodiment is as follows:
Method in the preparation method reference implementation example 1 of the methoxyacetophenone derivative of the present embodiment, reaction equation are as follows:
The physicochemical property of the methoxyacetophenone derivative of the present embodiment is as follows:
1) compound is yellow solid, yield 78%, molecular formula C15H11Cl2NO7S。
2) compound nuclear magnetic resonance map (1H NMR, 400MHz) feature:
With deuterated CDCl3For solvent, TMS is internal standard compound, wherein each peak belongs to are as follows: δ: 8.57 (s, 1H), 8.36 (d, J= 5.6Hz, 1H), 8.05-8.09 (m, 2H), 7.47 (s, 1H), 6.53 (s, 3H), 2.50 (s, 3H).
3) source ES mass spectrum (MS) figure feature of compound: its [M]+Peak is 419.
Embodiment 10
Structure of the chloro- Paeonolum of 3,5- bis- of the present embodiment and preparation method thereof is the same as embodiment 1.
The structural formula of the methoxyacetophenone derivative of the present embodiment is as follows:
Method in the preparation method reference implementation example 1 of the methoxyacetophenone derivative of the present embodiment, reaction equation are as follows:
The physicochemical property of the methoxyacetophenone derivative of the present embodiment is as follows:
1) compound is yellow solid, yield 82%, molecular formula C15H11Cl2NO7S。
2) compound nuclear magnetic resonance map (1H NMR, 400MHz) feature:
With deuterated CDCl3For solvent, TMS is internal standard compound, wherein each peak belongs to are as follows: δ: 8.36 (d, J=5.6Hz, 2H), 8.10 (d, J=5.6Hz, 2H), 7.48 (s, 1H), 6.52 (s, 3H), 2.53 (s, 3H).
3) source ES mass spectrum (MS) figure feature of compound: its [M]+Peak is 419.
Embodiment 11
Structure of the chloro- Paeonolum of 3,5- bis- of the present embodiment and preparation method thereof is the same as embodiment 1.
The structural formula of the methoxyacetophenone derivative of the present embodiment is as follows:
Method in the preparation method reference implementation example 1 of the methoxyacetophenone derivative of the present embodiment, reaction equation are as follows:
The physicochemical property of the methoxyacetophenone derivative of the present embodiment is as follows:
1) compound is yellow solid, yield 76%, molecular formula C15H10Cl3NO7S。
2) compound nuclear magnetic resonance map (1H NMR, 400MHz) feature:
With deuterated CDCl3For solvent, TMS is internal standard compound, wherein each peak belongs to are as follows: δ: 8.53 (s, 1H), 8.08 (d, J= 5.6Hz, 1H), 7.99 (d, J=5.6Hz, 1H), 7.41 (s, 1H), 6.50 (s, 3H), 2.48 (s, 3H).
3) source ES mass spectrum (MS) figure feature of compound: its [M]+Peak is 453.
Embodiment 12
Structure of the chloro- Paeonolum of 3,5- bis- of the present embodiment and preparation method thereof is the same as embodiment 1.
The structural formula of the methoxyacetophenone derivative of the present embodiment is as follows:
Method in the preparation method reference implementation example 1 of the methoxyacetophenone derivative of the present embodiment, reaction equation are as follows:
The physicochemical property of the methoxyacetophenone derivative of the present embodiment is as follows:
1) compound is white solid, yield 89%, molecular formula C16H13BrCl2O5S。
2) compound nuclear magnetic resonance map (1H NMR, 400MHz) feature:
With deuterated CDCl3For solvent, TMS is internal standard compound, wherein each peak belongs to are as follows: δ: 7.69 (d, J=8.0Hz, 2H), 7.46 (d, J=7.2Hz, 2H), 7.42 (s, 1H), 6.48 (s, 3H), 4.51 (s, 2H), 2.53 (s, 3H).
3) source ES mass spectrum (MS) figure feature of compound: its [M]+Peak is 466.
Test example
(1) insecticidal activity is tested
1) for trying insect
3 ages double committees noctuid (Athetis dissimilis Hampson), by plant protection system, forestry institute, University Of Science and Technology Of He'nan Entomology laboratory provides.
2) test sample and reagent
Test sample
Methoxyacetophenone in toosendanin, the chloro- Paeonolum of 3,5- bis- and embodiment 1-12 is derivative Object (i.e. the chloro- 2- of 3,5- bis- [(benzenesulfonyl) oxygen] -4- methoxyacetophenone class compound).Solvent is acetone, Chengdu section dragon Chemical reagent factory analyzes pure.
3) measuring method
Poison is fed using leaflet dish additive process, normal blade is changed after 48h and is fed until sprouting wings, method detailed is as follows:
A. test worm is 3 ages double committee noctuids, and using leaflet dish additive process, using toosendanin as positive control, acetone is blank Control, institute's sample concentration are 1mg/mL.
B. every a sample sets three repeating groups, and each repeating groups select 10 stalwartnesses, uniform 3 age at double committee's nights Moth is raised in the culture dish that diameter is 9cm, and culture dish bottom spreads one layer of filter paper so as to moisturizing.
C. fresh maize leaf is cut into 1 × 1cm2Leaflet dish, in the sample medical fluid and control medical fluid prepared in advance Leaching 3 seconds, feeds test worm after natural drying, after test worm eats up leaflet dish, adds leaflet dish in time, feeds after raising 48h normal Blade is until sprout wings.
D. rearing conditions: temperature is 25 ± 2 DEG C, and relative humidity is 65%~80%, light application time 12h, interlunation For 12h.
E. survivor of a murder attempt's number of periodic logging test worm and performance symptom etc., the death rate (%) of test worm different times and correction are dead Rate (%) is calculated according to following equation:
Measurement result is shown in Table 1, and test result is as depicted in figs. 1 and 2.(Ι group includes upper and lower two to Ι group in Fig. 1 in Fig. 1 A sample) be embodiment 8 in sample insecticidal effect, the IIIth group (the IIIth group includes upper and lower two samples in Fig. 1) for implement The insecticidal effect of sample in example 9, the Vth group (the Vth group includes upper and lower two samples in Fig. 1) is the sample in embodiment 12 Insecticidal effect；CK is the insecticidal effect of control group (toosendanin).
Ι group (Ι group includes upper and lower two samples in Fig. 1) is the insecticidal effect of the sample in embodiment 9 in Fig. 2, the IV group (the IVth group includes upper and lower two samples in Fig. 1) insecticidal effect for the sample in embodiment 12；CK is control group (melia toosendan Element) insecticidal effect.
The insecticidal activity assay result of methoxyacetophenone derivative and control sample in 1 embodiment 1-12 of table
4) conclusion
Above-mentioned test result shows the chloro- 2- of 3,5- bis- [(benzenesulfonyl) oxygen] -4- methoxyacetophenone class of the invention Closing object has preferable insecticidal activity, and part of compound is higher than the plant source being commercialized to the insecticidal activity of double committee noctuids Insecticide toosendanin.
(2) Antibacterial Activity is tested
1) test sample and reagent
Positive control hymexazol (antibacterial agent has been commercialized), the chloro- Paeonolum of 3,5- bis-, embodiment Methoxyacetophenone derivative in 1-12, acetone (analysis is pure).
2) test plant disease fungus (totally 2 kinds)
Botrytis cinerea [Botrytis cinerea Pers.] and tobacco wilt [Fusarium oxysporum (Schlecht) f.sp.nicotianae (Johns.) Snyder et H ansen], it is planted by forestry institute, University Of Science and Technology Of He'nan Guarantor is that Plant Pathology laboratory provides.
3) sod cultivation (using mycelial growth rate method)
Culture medium: (it is matched PDA culture medium are as follows: peeled potatoes 200g, glucose 20g, agar 20g, distilled water constant volume To 1000mL).
Determine the chloro- Paeonolum of 3,5- bis- and embodiment 1- respectively using mycelial growth rate method Methoxyacetophenone derivative (the chloro- 2- of 3,5- bis- [(benzenesulfonyl) oxygen] -4- methoxyacetophenone class compound) in 12 is to 2 The indoor virulence of kind frequently seen plants disease fungus, using hymexazol as positive control.
By in the chloro- Paeonolum of 3,5- bis-, embodiment 1-12 methoxyacetophenone derivative (3, The chloro- 2- of 5- bis- [(benzenesulfonyl) oxygen] -4- methoxyacetophenone class compound) and hymexazol it is stand-by with acetone solution respectively, to When culture medium after sterilizing is cooled to 60-70 DEG C respectively with the chloro- Paeonolum of 3,5- bis-, embodiment 1-12 In methoxyacetophenone derivative (the chloro- 2- of 3,5- bis- [(benzenesulfonyl) oxygen] -4- methoxyacetophenone class compound) and dislike Mould spirit mixing is made containing 100mg/L band medicine culture medium after mixing well, is blank control with not adding medicine, each processing If three repeating groups.
After culture medium is fully cooled, inoculation growth vigor is consistent, diameter 5mm for trying pathogen bacteria cake, and in 28 ± 1 DEG C constant temperature incubation, when CK bacterium colony it is long to 7-8cm when measure.When investigation, colony diameter is measured using crossing method, and with following Formula calculates each sample to the growth inhibition ratio of surveyed pathogen.
Test result is as shown in table 2 and Fig. 3,4, wherein in Fig. 3 a, b, c, d, e, g be respectively embodiment 1,2,3,4,9, 12 bactericidal effect figure, f are the bactericidal effect figure of control group (hymexazol).In Fig. 4 a, b, c, e, f be respectively embodiment 2,3,4, 9,12 bactericidal effect figure, d are the bactericidal effect figure of control group (hymexazol).
The fungistatic effect of methoxyacetophenone derivative and control sample in 2 embodiment 1-12 of table to strains tested
4) conclusion
The result shows that the chloro- 2- of 3,5- bis- [(benzenesulfonyl) oxygen] -4- methoxyacetophenone class compound of the invention is to institute It surveys 2 kinds of plant pathogenic fungis and shows preferable bacteriostatic activity, bacteriostatic activity of part of compound to 2 kinds of strains testeds All it is higher than the antibacterial agent hymexazol being commercialized.

Claims (10)

1. a kind of methoxyacetophenone derivative, which is characterized in that have the structure as shown in formula (1):
Wherein, R1Selected from H, CH3、CH2CH3、OCH3、F、Cl、Br、NO2、CH2One or more of Br；R2And R3It is respectively independent Ground is selected from one of F, Cl, Br.
2. methoxyacetophenone derivative according to claim 1, it is characterised in that: the methoxyacetophenone derivative It is selected from:
3. a kind of preparation method of methoxyacetophenone derivative as described in claim 1, which is characterized in that including walking as follows It is rapid:
The chloro- Paeonolum of 3,5- bis-, triethylamine, benzene sulfonyl chloride or substituted phenylsulfonyl chloride are added in solvent Reacted, extract, separation to get.
4. the preparation method of methoxyacetophenone derivative as claimed in claim 3, which is characterized in that the substitution benzene sulfonyl Chlorine be p-methyl benzene sulfonic chloride, to ethyl benzene sulfonyl chloride, to Methoxybenzenesulfonyl chloride, to fluorophenylsulfonyl chloride, parachloroben-zenesulfonyl chloride, P-bromobenzenesulfonyl chloride, ortho-nitrophenyl sulfonic acid chloride, m-nitrobenzene sulfonyl chloride, 4-Nitrobenzenesulfonyl chloride, to chlorine m-nitrobenzene sulfonyl chloride, Any one in 4- Bromomethylbenzenesulfonyl chloride.
5. the preparation method of methoxyacetophenone derivative as claimed in claim 3, which is characterized in that 3, the 5- bis- is chloro- Paeonolum, triethylamine, benzene sulfonyl chloride or substituted phenylsulfonyl chloride the ratio of amount of substance be 1:0.8-1.2: 1.0-1.5。
6. the preparation method of methoxyacetophenone derivative as claimed in claim 3, which is characterized in that the solvent is dichloro Methane or acetone.
7. the preparation method of methoxyacetophenone derivative as claimed in claim 3, which is characterized in that after reaction to anti- It answers and water is added in system, methylene chloride is then added and is extracted.
8. the preparation method of methoxyacetophenone derivative as claimed in claim 7, which is characterized in that take organic phase after extraction It is then dry with anhydrous sodium sulfate with saturated common salt water washing.
9. the preparation method of the methoxyacetophenone derivative as described in claim 3-8 any one, which is characterized in that described The chloro- Paeonolum of 3,5- bis- is made by the method included the following steps: by 2- hydroxyl -4- methoxybenzene second Ketone is uniform with mixed in hydrochloric acid, and H is added at 50 DEG C2O2Reaction, be separated by solid-liquid separation to get.
10. a kind of application of methoxyacetophenone derivative as described in claim 1 in terms of sterilization or desinsection.
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CN112321455A (en) * 2020-11-06 2021-02-05 河南科技大学 Paeonol acylhydrazone derivative, preparation method and application thereof, and pesticide

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CN112321455A (en) * 2020-11-06 2021-02-05 河南科技大学 Paeonol acylhydrazone derivative, preparation method and application thereof, and pesticide
CN112321455B (en) * 2020-11-06 2023-05-09 河南科技大学 Paeonol acylhydrazone derivative, preparation method and application thereof, and pesticide

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