CN106986801A - A kind of new methoxy acrylic ester compounds and its preparation method and application - Google Patents
A kind of new methoxy acrylic ester compounds and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/56—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
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- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
- C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
- C07C205/37—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/734—Ethers
- C07C69/736—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
Abstract
The invention provides a kind of new methoxy acrylic ester compounds and its preparation method and application, it is related to pesticide sterilizing technical field.A kind of new methoxy acrylic ester compounds, with novel structure, while having broad spectrum antibacterial activity, consumption is small and effect is notable, available for new type bactericide is prepared, the disease for preventing and treating crops.A kind of preparation method of new methoxy acrylic ester compounds, the preparation method is simple, and mild condition is easy to operate, and the Fungicidal substance with good bactericidal effect can be made.Above-mentioned new methoxy acrylic ester compounds have preferable bactericidal activity, can be applied in sterilization field.
Description
Technical field
The present invention relates to pesticide sterilizing technical field, and more particularly to a kind of new methoxy acrylic ester compounds and
Its preparation method and application.
Background technology
China's pesticide producing is quickly grown, it has also become second-biggest-in-the-world pesticide producing state, is also agricultural chemicals big export country, is agriculture
Medicine production provides important support.
Methoxy acrylic bactericide is the novel agricultural bactericide of the great development potentiality of a class and the market vitality.This
Series bactericidal agent mainly acts on the mitochondrial respiratory of fungi, i.e., by suppressing cytochrome b c1 electron transmission, so as to suppress line
The breathing of plastochondria, interference cell energy supply, makes cell death, plays bactericidal action.Methoxy acrylic bactericide is killed
Bacterium wide spectrum, good activity is all shown to nearly all fungus disease, is widely used in the preventing and treating of crop disease fungal pathogenses.
But, it is easy to it is the significant challenge that the series bactericidal agent is faced to produce resistance.Research shows, target gene point mutation
It is the combination that the difference on the one of the main reasons for causing the series bactericidal agent to produce resistance, inhibitor structure can make it in target
Environment is different, so as to cause it to produce Different resistance levels, therefore, the pesticide species of initiative novel structure are to reduce or subtract
Delay one of drug-fast fundamental way.
The content of the invention
It is an object of the invention to provide a kind of new methoxy acrylic ester compounds, it has novel structure,
There is broad spectrum antibacterial activity simultaneously, consumption is small and effect is notable, available for new type bactericide is prepared, the disease for preventing and treating crops
Evil.
Another object of the present invention is to provide a kind of preparation method of new methoxy acrylic ester compounds, the system
Preparation Method is easy to operate, mild condition, and the Fungicidal substance with good bactericidal effect can be made.
The present invention is solved its technical problem and realized using following technical scheme.
The present invention proposes a kind of new methoxy acrylic ester compounds, and its general formula of molecular structure is：
Wherein, X is oxygen atom or sulphur atom, RnN substituent is represented, n is 1 to 3 positive integer, n substituent difference
The uncombined site of phenyl ring is independently incorporated into, and n substituent is separately hydrogen-based, C1~C5Saturation or unsaturated lipid
Fat alkyl, ring-shaped fat alkyl, C1~C5Alkoxy, C1~C5Halohydrocarbyl, halogen, amino, nitro, cyano group, substitution do not take
The phenyl in generation, substituted or unsubstituted pyridine radicals, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substitution
Or any one in unsubstituted naphthyl, substituted or unsubstituted heterocycle containing N.
The present invention proposes a kind of preparation method of new methoxy acrylic ester compounds, including makes as shown in formula (I)
Reactant and 3- (2- bromomethyls) phenyl -3- methoxy-methyl acrylates react；
Wherein, X is oxygen atom or sulphur atom, RnN substituent is represented, n is 1 to 3 positive integer, n substituent difference
The uncombined site of phenyl ring is independently incorporated into, and n substituent is separately hydrogen-based, C1~C5Saturation or unsaturated lipid
Fat alkyl, ring-shaped fat alkyl, C1~C5Alkoxy, C1~C5Halohydrocarbyl, halogen, amino, nitro, cyano group, substitution do not take
The phenyl in generation, substituted or unsubstituted pyridine radicals, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substitution
Or any one in unsubstituted naphthyl, substituted or unsubstituted heterocycle containing N.
A kind of new methoxy acrylic ester compounds of the embodiment of the present invention and its preparation method and application it is beneficial
Effect is：The new methoxy acrylic ester compounds with novel structure are prepared, with broad spectrum antibacterial activity, consumption
Small and effect is notable, available for new type bactericide is prepared, the disease for preventing and treating crops.Preparation method is easy to operate, condition temperature
With the Fungicidal substance with good bactericidal effect can be made.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional production that can be obtained by commercially available purchase
Product.
Below to a kind of new methoxy acrylic ester compounds of the embodiment of the present invention and its preparation method and application
It is specifically described.
A kind of new methoxy acrylic ester compounds provided in an embodiment of the present invention, its general formula of molecular structure is：
Wherein, X is oxygen atom or sulphur atom, RnN substituent is represented, n is 1 to 3 positive integer, n substituent difference
The uncombined site of phenyl ring is independently incorporated into, and n substituent is separately hydrogen-based, C1~C5Saturation or unsaturated lipid
Fat alkyl, ring-shaped fat alkyl, C1~C5Alkoxy, C1~C5Halohydrocarbyl, halogen, amino, nitro, cyano group, substitution do not take
The phenyl in generation, substituted or unsubstituted pyridine radicals, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substitution
Or any one in unsubstituted naphthyl, substituted or unsubstituted heterocycle containing N.
Further, in present pre-ferred embodiments, X is oxygen atom or sulphur atom, RnN substituent is represented, n is 1
To 3 positive integer, n substituent is separately hydrogen-based, halogen, amino, C1~C5Alkoxy, C1~C5Saturation or insatiable hunger
With any one in aliphatic group, cyano group, substituted or unsubstituted phenyl.
Further, in present pre-ferred embodiments, new methoxy acrylic ester compounds are such as formula (1) to formula
It is (22) any shown in,
Further, in present pre-ferred embodiments, X is oxygen atom or sulphur atom, RnN substituent is represented, n is 1
To 3 positive integer, n substituent is separately the tert-butyl group, cyano group, trifluoromethoxy, trifluoromethyl, difluoromethyl, second
Alkenyl, hydrogen-based, it is fluorine-based in any one.
Further, in present pre-ferred embodiments, X is oxygen atom, and n is 1, R1For trifluoromethoxy.
Present invention also offers a kind of preparation method of above-mentioned new methoxy acrylic ester compounds, including make such as formula
(I) reactant shown in reacts with 3- (2- bromomethyls) phenyl -3- methoxy-methyl acrylates；
Wherein, X is oxygen atom or sulphur atom, RnN substituent is represented, n is 1 to 3 positive integer, n substituent difference
The uncombined site of phenyl ring is independently incorporated into, and n substituent is separately hydrogen-based, C1~C5Saturation or unsaturated lipid
Fat alkyl, ring-shaped fat alkyl, C1~C5Alkoxy, C1~C5Halohydrocarbyl, halogen, amino, nitro, cyano group, substitution do not take
The phenyl in generation, substituted or unsubstituted pyridine radicals, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substitution
Or any one in unsubstituted naphthyl, substituted or unsubstituted heterocycle containing N.
Further, in present pre-ferred embodiments, the conjunction of new methoxy acrylic ester compounds of the invention
It is into route：
In embodiments of the present invention, reactant can be by directly buying acquisition, and intermediate can be obtained by testing preparation
, to prepare end-product.When reactant is to trifluoro-methoxy-phenol, the method prepared is tested as follows：
Prepare 3- (2- methyl) phenyl propiolic acid methyl esters.
Diazol is typically that primary arylamine is made in the aqueous solution of excessive inorganic acid with natrium nitrosum effect, diazo-reaction
It is an exothermic reaction, while most of diazols are extremely unstable, is easily decomposed in room temperature, therefore General reactions condition is low temperature.
Specifically, o-toluidine is dissolved in 15% concentrated hydrochloric acid, stirred under cryogenic, until again without adjacent methyl
Anilinechloride crystallization is separated out.Preferably, the temperature of stirring is 0~5 DEG C., will be molten under conditions of stirring in order to be well mixed
The aqueous solution for having natrium nitrosum is added dropwise in above-mentioned solution and obtains diazonium salt solution.For the purposes of well mixed, in the bar of stirring
Tetrafluoro boric acid sodium water solution is added in diazonium salt solution under part, filtering, washing obtain intermediate product.Preferably, washing step
Including：Rinsed 2~3 times with tetrafluoro boric acid sodium solution, then be respectively washed 2~3 times with ethanol and ether.
Using acetonitrile as reaction dissolvent, by intermediate product, reactant Methyl propiolate, sodium carbonate, catalyst PdCl2Mixing
22~26h is reacted, filtrate mix, is extracted with ethyl acetate 2~3 times by filtering with water, after drying is concentrated, then with petroleum ether, second
Acetoacetic ester is purified as eluent by column chromatography, obtains 3- (2- methyl) phenyl propiolic acid methyl esters.Wherein, petroleum ether, acetic acid
The volume ratio of ethyl ester is 7~9:1.Preferably, petroleum ether, the volume ratio of ethyl acetate are 8:1.In the other embodiment of the present invention
In, solvent can be the organic solvents such as ethanol, and the present invention is not limited it.Wherein, o-toluidine, 15% concentrated hydrochloric acid,
Natrium nitrosum, sodium tetrafluoroborate, Methyl propiolate, sodium carbonate, PdCl2Amount ratio be 0.25mol:130mL:6~7mol:40
~50g:0.2~0.3mol:0.5mol:5%mol.
Prepare 3- (2- methyl) phenyl -3- methoxy-methyl acrylates.
Reactant 3- (2- methyl) phenyl propiolic acid methyl esters, methanol, catalyst potassium hydroxide are added into solvent dimethyl Asia
In sulfone, 16~20h is reacted under conditions of 110~130 DEG C.Target product is obtained after purification.Specifically, the step of purification is wrapped
Include：Reacted product is added to the water immediately, is extracted with ethyl acetate 2~3 times, merges after organic relevant dry concentration, uses stone
The mixture of oily ether and ethyl acetate is used as eluent, column chromatography purification.Wherein the volume ratio of petroleum ether and ethyl acetate be 8~
10:1.Preferably, the volume ratio of petroleum ether and ethyl acetate is 10:1.In other embodiments of the invention, solvent can be
The organic solvents such as carbon tetrachloride, the present invention is not limited it.
Wherein, 3- (2- methyl) phenyl propiolic acid methyl esters, methanol, potassium hydroxide, the amount ratio of solvent are 0.05mol:
0.05~0.06mol:0.05~0.06mol:100mL.
Prepare 3- (2- bromomethyls) phenyl -3- methoxy-methyl acrylates.
Reactant 3- (2- methyl) phenyl -3- methoxy-methyl acrylates and N-bromosuccinimide, initiator is even
Nitrogen bis-isobutyronitrile adds solvent C Cl4In, it is heated to after backflow, reacts 1~2h.Cold filtration, 3- (2- are obtained by filtrate purification
Bromomethyl) phenyl -3- methoxy-methyl acrylates.In other embodiments of the invention, solvent can be organic molten for ethanol etc.
Agent, the present invention is not limited it.
Specifically, the step of purification includes：Filtrate decompression is distilled, column chromatography, using volume ratio as 14~16:1 oil
Ether, ethyl acetate are used as eluent.Preferably, petroleum ether, the volume ratio of ethyl acetate are 15:1.
Wherein, 3- (2- methyl) phenyl -3- methoxy-methyl acrylates, N-bromosuccinimide, azodiisobutyronitrile,
The amount ratio of solvent is 0.05mol:0.05~0.06mol:0.1g:100mL.
Prepare 3- [2- (4- trifluoromethoxies) benzene Oxymethylene] phenyl -3- methoxy-methyl acrylates.
By reactant 3- (2- bromomethyls) phenyl -3- methoxy-methyl acrylates and to trifluoro-methoxy-phenol, acid binding agent
Potassium carbonate is added in solvent dimethylformamide, and 0.5~1.5h is reacted under conditions of 80~100 DEG C.Reaction solution is added to
In excessive water, stirring separates out solid, is filtrated to get crude product, and purification obtains new methoxy acrylic ester compounds.Tool
The step of body, purification, includes：Dried with after re-crystallizing in ethyl acetate.In other embodiments of the invention, solvent can be
The organic solvents such as ethanol, the present invention is not limited it.Wherein, 3- (2- bromomethyls) phenyl -3- methoxy-methyl acrylates, right
Trifluoro-methoxy-phenol, potassium carbonate, the amount ratio of solvent are 0.02mol:0.02~0.03mol:0.03mol:70~90mL.
The new methoxy acrylic ester compounds of the present invention have preferable bactericidal activity, can be applied in sterilization,
It can be applied to make bactericide.
Further, in present pre-ferred embodiments, bactericide also includes excipient.
Further, in present pre-ferred embodiments, excipient includes liquid-carrier or solid carrier.
Further, in present pre-ferred embodiments, new methoxy acrylic ester compounds are in bactericide
Effective dose is 0.1~99wt%.
Further, in present pre-ferred embodiments, bactericide is wettable powder, oil suspending agent, aqueous suspension, water and milk
Any of agent, aqua and missible oil.
The feature and performance to the present invention are described in further detail with reference to embodiments.
Embodiment 1
The preparation method of 3- (2- methyl) phenyl propiolic acid methyl esters is present embodiments provided, is comprised the following steps：
0.25mol o-toluidine is dissolved in 130mL 15% concentrated hydrochloric acid, 0 DEG C is cooled to, in the condition of stirring
Under, the aqueous solution dissolved with 6.3mol natrium nitrosums is added dropwise in above-mentioned solution and obtains diazonium salt solution.Under conditions of stirring
40g tetrafluoro boric acids sodium water solution is added in diazonium salt solution, filtering, washing obtain intermediate product.
By obtained intermediate product, 0.25mol Methyl propiolate, 0.5mol sodium carbonate, 5%mol PdCl2Mixing
24h is reacted, filtrate is mixed, is extracted with ethyl acetate 3 times by filtering with water, is 8 with volume ratio:1 petroleum ether, ethyl acetate
As eluent, purified by column chromatography, obtain 3- (2- methyl) phenyl propiolic acid methyl esters.
It is computed, yield is 45%.Nuclear magnetic resonance test result is as follows：
1H NMR (400MHz, CDCl3) δ 7.58 (d, J=8.3Hz, 2H), 7.45 (t, J=7.5Hz, 1H), 7.37 (t, J
=7.9Hz, 2H), 3.84 (s, 3H), 2.94 (s, 3H)；
13C NMR (100MHz, CDCl3) δ 154.44,132.97,130.65,128.55,119.50,86.47,80.33,
55.62,52.77.
Embodiment 2
Present embodiments provide the preparation method of 3- (2- methyl) phenyl -3- methoxy-methyl acrylates, including following step
Suddenly：
By 3- made from 0.05mol embodiment 1 (2- methyl) phenyl propiolic acid methyl esters, 0.06mol methanol,
0.06mol potassium hydroxide is added in 100mL solvent dimethyl sulfoxide (DMSO), and 18h is reacted under conditions of 120 DEG C.After reacting
Product be added to the water immediately, be extracted with ethyl acetate 3 times, merge it is organic be concerned with dry concentration after, with volume ratio be 10:1 stone
The mixture of oily ether and ethyl acetate carries out column chromatography purification as eluent.
It is computed, yield is 52%.Nuclear magnetic resonance test result is as follows：
1H NMR(400MHz,CDCl3) δ 7.50 (s, 1H), 7.38 (s, 1H), 7.22 (s, 1H), 7.22-7.19 (m, 1H),
5.18 (s, 1H), 3.77 (s, 3H), 3.51 (s, 3H), 2.22 (s, 3H)；
13C NMR(100MHz,CDCl3) δ 170.86,168.10,136.51,136.24,129.68,129.64,
128.51,125.57,88.43,56.47,52.01,20.27.
Embodiment 3
The preparation method of 3- (2- bromomethyls) phenyl -3- methoxy-methyl acrylates is present embodiments provided, including it is following
Step：
By (2- methyl) phenyl -3- methoxy-methyl acrylates of 3- made from 0.05mol embodiment 2 and 0.05mol
N-bromosuccinimide, 0.1g azodiisobutyronitrile add 100mL solvent C Cl4In, it is heated to after backflow, reacts
1.5h, cold filtration distills filtrate decompression, is 15 with volume ratio:1 petroleum ether and the mixture of ethyl acetate are used as elution
Agent carries out column chromatography purification.
It is computed, yield is 67%.Nuclear magnetic resonance test result is as follows：
1H NMR(400MHz,CDCl3) δ 7.58 (s, 1H), 7.47 (d, J=25.0Hz, 3H), 5.13 (s, 1H), 5.10
(s, 2H), 3.77 (s, 3H), 3.51 (s, 3H)；
13C NMR(100MHz,CDCl3) δ 170.18,168.10,140.59,134.57,129.07,128.55,
127.49,123.47,94.08,56.47,52.02,30.25.
Embodiment 4
A kind of preparation method of new methoxy acrylic ester compounds is present embodiments provided, is comprised the following steps：
By 3- (2- methyl) phenyl -3- methoxyl group propylene made from 0.02mol reactant A, 0.02mol embodiment 3
Sour methyl esters, 0.03mol potassium carbonate are added in 80mL solvent dimethylformamides, and 1h is reacted under conditions of 90 DEG C.Will reaction
Solution is added in excessive water, and stirring separates out solid, is filtrated to get crude product, is dried with after re-crystallizing in ethyl acetate.
In the present embodiment, reactant A is to trifluoro-methoxy-phenol.
It is computed, yield is 72%.Nuclear magnetic resonance test result is as follows：
1H NMR(400MHz,CDCl3) δ 64~7.54 (m, 3H), 7.45 (s, 1H), 7.00 (d, J=10.0Hz, 4H),
5.25 (s, 1H), 5.16 (s, 2H), 3.77 (s, 3H), 3.51 (s, 3H)；
13C NMR(100MHz,CDCl3) δ 168.10,156.45,146.31,146.21,130.46,128.06,
127.73,124.58,120.29,115.78,94.08,69.20,56.47,52.01.
The preparation method for the new methoxy acrylic ester compounds that embodiment 5~25 is provided and the preparation of embodiment 4
Method is identical, and difference part is reactant A.Specific reactant A such as following table：
The reactant A of table 1
Comparative example 1
This comparative example provides the Fluoxastrobin bought on the market.
Test example 1
Choose new methoxy acrylic ester compounds, the Fluoxastrobin progressive of comparative example 1 prepared by embodiment 4~25
It can detect, method is as follows：
By embodiment 4~25 prepare new methoxy acrylic ester compounds, comparative example 1 Fluoxastrobin respectively with third
Ketone dissolves the mother liquor for being prepared into 10000 μ g/mL.Under aseptic technique, the 10000 μ g/mL mother liquors prepared are cultivated
Base is diluted to 50 μ g/mL toxic culture medium, and this experiment sets the blank control without chemicals treatment.
According to People's Republic of China's agricultural industry criteria (NY/T 1156.2-2006), entered using mycelial growth rate method
Row is determined.By cultured various pathogens, under aseptic technique with diameter 7mm sterilization punchers, from colony edge
Bacteria cake is cut, with inoculator by pure culture biscuits involvng inoculation in the flat board center containing various culture mediums, mycelia downwards, covers ware lid, is placed in
Cultivated in 25 DEG C of incubators.
Pathogen mycelial growth situation is investigated according to the growing state of bacterium colony in blank control culture dish, treated in blank control
Bacterium colony fully grow after, the colony diameter of each processing is measured with crossing method, calculating bacterium colony using formula below increases straight
Footpath, takes its average value.
Bacterium colony increases diameter=colony diameter-bacteria cake diameter.
Measurement result is calculated with following method, is increased with the bacterium colony that blank control bacterium colony increases diameter and each medium treatment
Diameter calculates mycelial growth inhibition rate of each medium treatment to various pathogens (referring to formula below).
Mycelial growth inhibition rate (%)=[(control bacterium colony increases diameter-chemicals treatment bacterium colony and increases diameter)/control bacterium colony
Increase diameter] × 100.
Test result is as follows：
The mycelial growth inhibition rate of table 2
As shown in Table 2, the compound that prepared by embodiment 4~25 is stood to rice banded sclerotial blight, rape sclerotium, apple wheel line, cotton
Withered, watermelon anthrax, several diseases of cucumber grey mold have the effect of suppression, i.e., with broad spectrum of activity.Wherein, embodiment 4, embodiment
12nd, compound prepared by embodiment 16, embodiment 20, embodiment 23 is higher than comparison medicine Fluoxastrobin to the inhibiting rate of a variety of diseases.
Illustrate that the drug effect of bactericide prepared by this several compound is better than Fluoxastrobin.
Accurate activity is carried out to compound prepared by active relatively good embodiment 4, embodiment 20, embodiment 23 to survey
Examination, it is as a result as shown in the table：
The accurate active testing result of table 3
As shown in Table 3, the effect of compound prepared by embodiment 4 is better than the Fluoxastrobin in comparative example 1, illustrates that its wide spectrum is lived
Property highest.
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of new methoxy acrylic ester compounds, it is characterised in that its general formula of molecular structure is：
Wherein, X is oxygen atom or sulphur atom, RnN substituent is represented, the n is 1 to 3 positive integer, the n substituent point
It is not incorporated into the uncombined site of phenyl ring independently, and the n substituent is separately hydrogen-based, C1~C5Saturation or not
Saturated fat alkyl, ring-shaped fat alkyl, C1~C5Alkoxy, C1~C5Halohydrocarbyl, halogen, amino, nitro, cyano group, substitution
Or unsubstituted phenyl, substituted or unsubstituted pyridine radicals, substituted or unsubstituted thienyl, substituted or unsubstituted furans
Any one in base, substituted or unsubstituted naphthyl, substituted or unsubstituted heterocycle containing N.
2. new methoxy acrylic ester compounds according to claim 1, it is characterised in that the n substituent
It is separately hydrogen-based, halogen, amino, C1~C5Alkoxy, C1~C5Saturation or unsaturated aliphatic hydrocarbyl moiety, cyano group, substitution or
Any one in unsubstituted phenyl.
3. new methoxy acrylic ester compounds according to claim 1, it is characterised in that the new methoxyl group
Acrylic ester compound to be any as shown in formula (1) to formula (22),
4. new methoxy acrylic ester compounds according to claim 1, it is characterised in that the n substituent
Separately for the tert-butyl group, cyano group, trifluoromethoxy, trifluoromethyl, difluoromethyl, vinyl, hydrogen-based, it is fluorine-based in it is any
It is a kind of.
5. new methoxy acrylic ester compounds according to claim 1, it is characterised in that the X is oxygen atom,
The n is 1, the R1For trifluoromethoxy.
6. a kind of preparation method of new methoxy acrylic ester compounds as claimed in claim 1, it is characterised in that bag
Including makes the reactant as shown in formula (I) be reacted with 3- (2- bromomethyls) phenyl -3- methoxy-methyl acrylates；
Wherein, X is oxygen atom or sulphur atom, RnN substituent is represented, the n is 1 to 3 positive integer, the n substituent point
It is not incorporated into the uncombined site of phenyl ring independently, and the n substituent is separately hydrogen-based, C1~C5Saturation or not
Saturated fat alkyl, ring-shaped fat alkyl, C1~C5Alkoxy, C1~C5Halohydrocarbyl, halogen, amino, nitro, cyano group, substitution
Or unsubstituted phenyl, substituted or unsubstituted pyridine radicals, substituted or unsubstituted thienyl, substituted or unsubstituted furans
Any one in base, substituted or unsubstituted naphthyl, substituted or unsubstituted heterocycle containing N.
7. the preparation method of new methoxy acrylic ester compounds according to claim 6, it is characterised in that described
Reactant is to trifluoro-methoxy-phenol.
8. the preparation method of new methoxy acrylic ester compounds according to claim 7, it is characterised in that described
The step of being reacted with the 3- (2- bromomethyls) phenyl -3- methoxy-methyl acrylates trifluoro-methoxy-phenol includes：It will use
Amount is than being 0.02~0.03mol:0.02mol's is described to trifluoro-methoxy-phenol and the 3- (2- bromomethyls) phenyl -3- first
Epoxide methyl acrylate reacts under conditions of 80~100 DEG C.
9. the preparation method of new methoxy acrylic ester compounds according to claim 8, it is characterised in that described
The preparation method of 3- (2- bromomethyls) phenyl -3- methoxy-methyl acrylates includes：, will using azo-bis-isobutyl cyanide as initiator
3- (2- methyl) phenyl -3- methoxy-methyl acrylates react with N-bromosuccinimide.
10. application of the new methoxy acrylic ester compounds according to any one of claims 1 to 9 in sterilization.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113646295A (en) * | 2019-03-22 | 2021-11-12 | 先正达农作物保护股份公司 | Fungicidal compounds |
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| CN114634456A (en) * | 2022-03-22 | 2022-06-17 | 赣南师范大学 | 5-nitroimino-4H-1, 2, 4-triazole compound and preparation method and application thereof |
| CN114634456B (en) * | 2022-03-22 | 2024-02-20 | 赣南师范大学 | 5-nitroimino-4H-1, 2, 4-triazole compound and preparation method and application thereof |
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