CN104725276B - Heptafluoroisopropyl-containing carbonyl oxime ether compound, preparation method and applications thereof - Google Patents
Heptafluoroisopropyl-containing carbonyl oxime ether compound, preparation method and applications thereof Download PDFInfo
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- 0 *c1cc(C(C(F)(F)F)(C(F)(F)F)F)ccc1NC(C(c1cccc(Cl)c1)=C)=NO Chemical compound *c1cc(C(C(F)(F)F)(C(F)(F)F)F)ccc1NC(C(c1cccc(Cl)c1)=C)=NO 0.000 description 2
- QVAUOEHPYOFAQA-UHFFFAOYSA-N Cc1cc(C(C(F)(F)F)(C(F)(F)F)F)ccc1N Chemical compound Cc1cc(C(C(F)(F)F)(C(F)(F)F)F)ccc1N QVAUOEHPYOFAQA-UHFFFAOYSA-N 0.000 description 1
- OWTBICFGRAHSBW-XFXZXTDPSA-N Cc1cccc(Cl)c1C(/C(/Cl)=N/O)=O Chemical compound Cc1cccc(Cl)c1C(/C(/Cl)=N/O)=O OWTBICFGRAHSBW-XFXZXTDPSA-N 0.000 description 1
- ONTXHZNZIXWXJS-MKFZHGHUSA-N O/N=C(/C(c1cc(Cl)ccc1)=[U])\Cl Chemical compound O/N=C(/C(c1cc(Cl)ccc1)=[U])\Cl ONTXHZNZIXWXJS-MKFZHGHUSA-N 0.000 description 1
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Abstract
The present invention discloses a heptafluoroisopropyl-containing carbonyl oxime ether compound, which has the following structural general formula (I), wherein each substituent is defined in the instruction. The present invention further provides a preparation method and applications of the compound. The compound of the present invention is particularly suitable for prevention and control of Mythimna separate, AphiscraccivoraKoch, Tetranychus cinnabarinus, cucumber downy mildew bacteria and rice sheath blight disease bacteria.
Description
Technical field
The invention belongs to parasite killing, antibacterial field, are related to a kind of carbonyl oximido ether compound for containing seven fluorine isopropyls, its system
Preparation Method and application.
Background technology
Oxime compound has excellent parasite killing, sterilization, weeding, an anti-phytoviral activity, many kinds also have low toxicity,
The advantages of low-residual.The nineties in 20th century, oximes Agrochemicals are rapid, develop large quantities of antibacterial and herbicide.Current oxime
The MOLECULE DESIGN of class compound, synthesis remain one of focus of pesticides discovery with bioactivity research.
Fluorine atom has physics and chemistry of the introducing of special chemistry and biological characteristicses, fluoro-containing group or fluorine atom to compound
Property, physiologically active etc. produce significant impact.It has been found that fluorine atom and fluoro-containing group are incorporated into biological living
In the organic compound of property, its biological activity can be greatly improved, and carcinogenic, teratogenesis will not be caused to mammal.Entirely
Fluorine isopropyl has low polarity, highly lipophilic, electronegativity and biological stability, has extensively in pesticide, medicine and Material Field
Application.
The present invention is conscientiously studied for the novel agricultural of exploitation with horticultural chemistry medicine, is drawn in oxime and oxime ether structure
Enter seven fluorine isopropyls, be as a result found that by formula of the present invention（I）The carbonyl oximido ether compound containing seven fluorine isopropyls for representing.Text
Offer（Journal of Enzyme Inhibition and Medicinal Chemistry,2009,24(5),1141-
1147.）Report and be similar to the oxime compound of the present invention, but only have studied such compound with oxidation resistance and remove free radical
Activity, not describing it is used for the purposes of cultural control insect pest, disease.
In the prior art, formula of the present invention（I）The preparation of the carbonyl oximido ether compound containing seven fluorine isopropyls for representing
And its parasite killing, bactericidal activity are not disclosed.
The content of the invention
It is an object of the invention to provide provide a kind of structure the novel carbonyl oximido ether compound containing seven fluorine isopropyls,
It can be applicable to agriculturally with the insect pest of preventing and treating crop and disease.
It is to reach goal of the invention the technical solution used in the present invention：
A kind of carbonyl oximido ether compound for containing seven fluorine isopropyls, with following general structure（I）：
In formula：
G contains at least one in phenyl ring, naphthalene nucleus, fragrant 6 yuan of rings or 5 yuan of heteroaromatics, and the ring of 5 yuan of heteroaromatics
Selected from the hetero atom of oxygen atom, sulphur atom or nitrogen-atoms；
X is independently selected from hydrogen, C1-C6Alkyl, C3-C6Cycloalkyl, C2-C6Alkenyl, C2-C6Alkynyl, C1-C6Alkoxyl, halogen
For C1-C6Alkyl, halo C1-C6Alkoxyl, halogen, cyano group, nitro or hydroxyl；
Y is independently selected from hydrogen, C1-C6Alkyl, C3-C6Cycloalkyl, C2-C6Alkenyl, C2-C6Alkynyl, C1-C6Alkoxyl, halogen
For C1-C6Alkyl, halo C1-C6Alkoxyl, phenyl, halogen, cyano group, nitro or hydroxyl；
R is selected from hydrogen, C1-C6Alkyl, halo C1-C6Alkyl, C3-C6Cycloalkyl, C2-C6Alkenyl, C2-C6Alkynyl or-A-Q
Group the, in-A-Q groups：
A is selected from C1-C6Alkylidene, C2-C6Alkenylene or C2-C6Alkynylene；
Q selected from hydrogen, phenyl ring, naphthalene nucleus, fragrant 6 yuan of rings, 5 yuan of heteroaromatics, by 1-5 independently selected from halogen, nitro, cyanogen
Base, C1-C6Alkyl, C1-C6Alkoxyl, halo C1-C6Alkyl or halo C1-C6The phenyl ring of the substituent group of alkoxyl, naphthalene nucleus, virtue
Fragrant 6 yuan of rings or 5 yuan of heteroaromatics；
M is 0～5 integer；
N is 0～4 integer.
As preferred mode, in above-mentioned substituent group：
G is selected from naphthalene nucleus, fragrant 6 yuan of rings or 5 yuan of heteroaromatics, and the ring of 5 yuan of heteroaromatics containing at least one
The hetero atom of oxygen atom, sulphur atom or nitrogen-atoms；
X is independently selected from hydrogen, C1-C4Alkyl, C3-C6Cycloalkyl, C2-C3Alkenyl, C2-C3Alkynyl, C1-C3Alkoxyl, halogen
For C1-C3Alkyl, halo C1-C3Alkoxyl, halogen, cyano group, nitro or hydroxyl；
Y is independently selected from hydrogen, C1-C4Alkyl, C3-C6Cycloalkyl, C2-C3Alkenyl, C2-C3Alkynyl, C1-C3Alkoxyl, halogen
For C1-C3Alkyl, halo C1-C3Alkoxyl, phenyl, halogen, cyano group, nitro or hydroxyl；
R is selected from hydrogen, C1-C3Alkyl, halo C1-C3Alkyl, C3-C6Cycloalkyl, C2-C6Alkenyl, C2-C6Alkynyl or-A-Q
Group the, in-A-Q groups：
A is C1-C3Alkylidene；
Q selected from hydrogen, phenyl ring, naphthalene nucleus, fragrant 6 yuan of rings, 5 yuan of heteroaromatics, by 1-4 independently selected from halogen, nitro, cyanogen
Base, C1-C3Alkyl, C1-C3Alkoxyl, halo C1-C3Alkyl or halo C1-C3The phenyl ring of the substituent group of alkoxyl, naphthalene nucleus, virtue
Fragrant 6 yuan of rings or 5 yuan of heteroaromatics；
M is 0～4 integer；
N is 0～3 integer.
As further preferred mode, in above-mentioned substituent group：
G is selected from the yuan of rings of fragrance 6 or 5 yuan of heteroaromatics shown in G-4, G-5 or G-6 shown in naphthalene nucleus, G-1, G-2 or G-3；
X is independently selected from hydrogen, C1-C4Alkyl, C1-C3Alkoxyl, halo C1-C3Alkyl, halo C1-C3Alkoxyl, nitro or
Halogen；
Y is independently selected from hydrogen, C1-C4Alkyl, C1-C3Alkoxyl, halo C1-C3Alkyl, halo C1-C3Alkoxyl, halogen or
Hydroxyl；
R is selected from hydrogen, C1-C3Alkyl, halo C1-C3Alkyl or formula-A-Q groups, in-A-Q the groups：
A is C1-C3Alkylidene；
Q selected from hydrogen, phenyl ring, pyridine ring, thiazole ring, by 1-3 independently selected from halogen or C1-C3What alkyl group replaced
Phenyl ring, pyridine ring or thiazole ring；
M is 0～3 integer；
N is 0～2 integer.
As mode still further preferably, in above-mentioned substituent group：
G is selected from phenyl ring, the 5 yuan of heteroaromatics shown in G-4 or G-5 shown in naphthalene nucleus, G-1；
X is independently selected from hydrogen, methyl, methoxyl group, the tert-butyl group, trifluoromethyl, trifluoromethoxy, nitro, fluorine or chlorine；
Y is independently selected from hydrogen, methyl, ethyl, methoxyl group, fluorine, chlorine or hydroxyl；
R is selected from hydrogen or formula-A-Q groups, in-A-Q the groups：
A is methylene；
Q is selected from hydrogen, the phenyl ring, pyridine ring or the thiazole ring that are replaced independently selected from fluorine, chlorine, methyl group by 1-2.As
Most preferred mode, said structure formula（I）The shown carbonyl oximido ether compound for containing seven fluorine isopropyls has one of following knot
Structure formula：
In above-mentioned substituted radical：Alkyl refers to straight or branched form, for example methyl, ethyl, n-pro-pyl, isopropyl,
Normal-butyl, isobutyl group, sec-butyl, tertiary butyl, n-pentyl, isopentyl, n-hexyl etc.；Cycloalkyl refers to closed chain form,
Such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl etc.；Alkenyl refers to straight or branched form, such as vinyl, 1- propylene
Base, pi-allyl, isopropenyl, 1-butylene base, 1,3-butadiene base, 1- hexenyls etc.；Alkynyl refers to straight or branched form, example
Such as acetenyl, 1- propinyls, propargyl, 2-butyne base, valerylene base, 3- hexin bases；Haloalkyl refers to alkyl by one
Or the group that multiple halogen atoms replace；Alkoxyl refers to that alkyl end is connected with the group of oxygen atom, for example methoxyl group, ethyoxyl,
Positive propoxy, isopropoxy, tert-butoxy etc.；Halogenated alkoxy refers to that alkyl is optionally substituted with one or more halogen atoms, and end connects
There is the group of oxygen atom；Halogen refers to fluorine, chlorine, bromine, iodine.
Said structure formula of the present invention（I）The shown carbonyl oximido ether compound containing seven fluorine isopropyls includes appointing
Z the and/or E cis-trans-isomers of meaning ratio, or R the and/or S optical isomers of arbitrary proportion.In addition, the change that the present invention is included
Compound contains one or more asymmetric centers in its structural formula in some cases, with two or more optical isomers and
Diastereomer, present invention additionally comprises all single optical isomers and the mixing being made up of these isomers at any proportions
Thing.
The present invention also provides a kind of said structure formula（I）The system of the shown carbonyl oximido ether compound for containing seven fluorine isopropyls
Preparation Method, as an example, synthetic route is as follows：
The definition of the substituent group and preferably as previously mentioned.
Above-mentioned reaction is preferably carried out in the presence of an organic, the organic solvent be preferably ethyl acetate, dehydrated alcohol,
Tetrahydrofuran, acetonitrile, N,N-dimethylformamide, dichloromethane or toluene.The alkali for using is preferably sodium hydroxide, bicarbonate
Sodium, potassium carbonate, sodium carbonate, triethylamine or pyridine.Reaction is preferably carried out under 20～150 DEG C of reaction temperatures.Response time is general
For 1～12 hour.
Structure above（The synthesis of the Chlorocarbonyl oxime compound shown in II) refers to document（J Org Chem,
1942,7:408;Org.Synth,1955,3:191;Helvetica Chimica Acta,1999,82:1289. wait）Side
Method.
Formula（I）The carbonyl oximido ether compound containing seven fluorine isopropyls for representing is listed in concordance list 1, following institute
Show.
Concordance list 1
Table 2 below is the nuclear magnetic data of part of compounds described in concordance list 1.
Note：Compound number described in table 2 is corresponding with compound number described in table 1.Wherein s is unimodal, and brs is width
Unimodal, d is bimodal, and dd is double doublet, and t is triplet, and q is quartet, and m is multiplet.
The compound nuclear magnetic data of table 2
General structure of the present invention（I）The shown carbonyl oximido ether compound containing seven fluorine isopropyls is particularly suitable for using
In preventing and treating mythimna separata, aphis craccivora, Tetranychus cinnabarinus, lepidoptera pest, bacterium of downy mildew of cucumber and Rhizoctonia solani Kuhn.Specifically, it is right
In preventing and treating diamondback moth, lopper worm, Prodenia litura, beet armyworm, Spodopterafrugiperda, bollworm, oriental armyworm, tobacco budworm, cigarette
The little solid moth of acute tonsillitis, cnaphalocrocis medinalls guenee, rice Adoxophyes spp, codling moth, Fructus Persicae, oriental fruit months, black cutworm, Cinnabaris leaf
The agricultural pests classes such as demodicid mite, Tetranychus urticae, Phytophthira, aleyrodid class, thrips class, locustamigratoria, liriomyza bryoniae class are effective.The part of the present invention
Compound also has bactericidal activity, can be used for preventing and treating rice sheath blight disease, gray mold of cucumber, cucumber downy mildew, powdery mildew of cucumber
Deng.
General structure of the present invention（I）The shown carbonyl oximido ether compound containing seven fluorine isopropyls can be formulated
Into chemistry of pesticide insecticide or antibacterial.When chemistry of pesticide insecticide or antibacterial is formulated into, the chemistry of pesticide parasite killing
Contain 0.001%-99.99% in agent or antibacterial（Weight）General structure（I）The shown carbonyl oxime ether containing seven fluorine isopropyls
Class compound, remaining is agriculturally acceptable carrier.
Carrier can be solid or liquid.Suitable solid carrier includes natural or synthesis clay and silicate, example
Such as natural silica and kieselguhr；Magnesium silicate such as Talcum；Magnesiumaluminumsilicate such as kaolinite, Kaolin, montmorillonite and Muscovitum；White carbon
Black, Calcium Carbonate, precipitated calcium carbonate；Calcium sulfate；Limestone；Sodium sulfate；Amine salt such as ammonium sulfate, hexamethylene diamine.Liquid-carrier bag
Water and organic solvent are included, when solvent or diluent is done with water, organic solvent can also be used as adjuvant or antifreeze additive.Properly
Organic solvent include aromatic hydrocarbons such as benzene, dimethylbenzene, toluene etc.；Chlorohydrocarbon, such as chlorobenzene, vinyl chloride, chloroform, dichloro
Methane etc.；Aliphatic hydrocarbon, such as petroleum distillate, hexamethylene, light mineral oil；Alcohols, such as isopropanol, butanol, ethylene glycol, the third three
Alcohol and Hexalin etc.；And their ether and ester；Also ketone, such as acetone, Ketohexamethylene and dimethylformamide and N- first
Base-ketopyrrolidine.
Carrier can also be surfactant.Suitable surfactant can be emulsifying agent, dispersant or wetting agent；Can
Being ion-type or nonionic.Nonionic emulsifier for example polyoxyethylene fatty acid fat, polyoxyethylene aliphatic alcohol ether,
Polyoxyethylene fatty ammonia, and commercially available emulsifying agent：Agriculture breast 2201B, agriculture breast 0203B, agriculture breast 100#, agriculture breast 500#, agriculture breast
600#, agriculture breast 600-2#, agriculture breast 1601, agriculture breast 2201, agriculture breast NP-10, agriculture breast NP-15, agriculture breast 507#, agriculture breast OX-635, agriculture breast
OX-622, agriculture breast OX-653, agriculture breast OX-667, peaceful breast 36#.Dispersant includes sodium lignin sulfonate, pull open powder, lignin sulfonic acid
Calcium, condensation compound of methyl naphthalene sulfonic acid and formaldehyde etc..Wetting agent is：Sodium laurylsulfate, dodecylbenzene sodium sulfonate, Negel
Deng.
Above-mentioned chemistry of pesticide insecticide or antibacterial can be prepared by general method.For example, it is active substance is molten with liquid
Agent and/or solid carrier mix, while adding surfactant such as emulsifying agent, dispersant, stabilizer, wetting agent, can also add
Enter other auxiliary agents such as：Binding agent, defoamer, oxidant etc..
Above-mentioned chemistry of pesticide insecticide or antibacterial can be liquor, cream, suspending agent, aqueous suspension, microemulsion, Emulsion,
Powder, wettable powder, soluble powder, granule or capsule, the Emulsion can be aqueous emulsion, and the granule can be with
It is water-dispersible granules.
Meanwhile, formula of the present invention（I）The carbonyl oximido ether compound containing seven fluorine isopropyls for representing is to many beneficial
Insecticide and acarid, mammal, fish, bird there is hypotoxicity, and without phytotoxicity.
When harmful organism is prevented and treated, when the harmful organism that pesticidal preparations of the present invention are imposed on needs control or its life
On long medium, wherein active component is formula（I）The effective dose of the carbonyl oximido ether compound containing seven fluorine isopropyls for representing is
10 grams to 1000 grams of per hectare.
Formula of the present invention（I）The carbonyl oximido ether compound containing seven fluorine isopropyls for representing has compared to existing technology
Advantages below：
（1）Present invention synthesis first contains the carbonyl oximido ether compound of seven fluorine isopropyls, and compound structure has novelty；
（2）The compound and its preparation of the present invention has parasite killing and bactericidal activity concurrently, can be used to control insect pest and disease；
（3）The present invention compound and its preparation there is good safety, to part crop for example Semen Tritici aestivi, Semen sojae atricolor, Cotton Gossypii,
The safeties such as Semen Maydiss, Oryza sativa L. are good.
（4）The compound and its preparation of the present invention has rational toxicity, eco-toxicity and Environmental compatibility.
Specific embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses being potentially included in Claims scope
All alternatives, improvement project and equivalents.
First, compound synthesis embodiment
Embodiment 1
The system of N- hydroxyl -2- (3- chlorphenyls)-N '-[the fluorine isopropyl-phenyls of 2- methoxyl groups -4- seven] -2- oXo-acetamides
It is standby（Compound 60）
Step 1：Between chlorobenzene-alpha-chloro-alpha-carbonyl oxime synthesis
Weigh 0.1mol m chloroacetophenones, 150.0g and be dried dioxane and be dried ice bath in there-necked flask in 250mL.Instead
Answer bottle top plus drying tube.During 0 DEG C or so of temperature of reaction system, hydrogen chloride gas are passed through, adjust air velocity stably to per second
2～3 bubbles of clock.After steady air current, slowly instill 0.3mol amyl nitrite, it is ensured that temperature of reaction system 5 DEG C with
Under.Drop finishes, and continues body of ventilating, it is found that reactant liquor color is shown to have dissolved saturation in reactant liquor by colourless change laking
Hydrogen chloride gas.Stop ventilation body, allow reactant liquor to continue to react 1h or so at 0～5 DEG C, reactant liquor color is become by peony
It is faint yellow.Now TLC detections, raw material disappears, and reaction is finished.Reactant liquor is poured in frozen water, with dichloromethane (150mL × 2)
Extraction, 150mL saturated common salt water washings.Anhydrous magnesium sulfate is dried organic faciess, precipitation.Column chromatography for separation（Petroleum ether:Ethyl acetate
=7:1）Obtain faint yellow solid.Yield：71.5%, m.p.120～122 DEG C；1H NMR(400MHz,DMSO-d6), δ：7.57(t,
1H,J=8.00Hz,Ar-H),7.73(d,1H,J=8.00Hz,Ar-H),7.82(d,1H,J=8.00Hz,Ar-H),7.96(s,
1H,Ar-H),13.78(s,1H,OH)。
Step 2：The synthesis of target compound
Chlorobenzene-alpha-chloro-alpha-carbonyl oxime between 5mmol is dissolved in 6mL dehydrated alcohol, thereto Deca 5mmol2- methoxy
Base -4- sevoflurane isopropyl amine is dissolved in the solution of 6mL dehydrated alcohol, and drop finishes, and 0.42g sodium bicarbonate, room are added in reactant liquor
Lower stirring reaction 1h of temperature.Reactant liquor is poured in 10mL water, is stood, separate out solid, filtered, be dried, obtain faint yellow solid product,
Yield 85.7%.
Embodiment 2
N- hydroxyl -2- (4- methoxyl groups-phenyl)-N'- [the fluorine isopropyl-phenyls of 2- methoxyl groups -4- seven] -2- oxos-acetyl
The preparation of amine（Compound 26）
Step 1：Synthesis to methoxybenzene-alpha-chloro-alpha-carbonyl oxime
With acetanisole as raw material, experimental procedure with the middle chlorobenzene-alpha-chloro-alpha-carbonyl oxime of embodiment 1 conjunction
Into obtaining white solid, yield：84.8%, m.p.116～118 DEG C；1H NMR(400MHz,DMSO-d6), δ：3.85(s,3H,
OCH3),6.99(d,2H,J=8.80Hz,Ar-H),7.90(d,2H,J=8.80Hz,Ar-H),13.64(s,1H,OH)。
Step 2：The synthesis of target compound
So that to methoxybenzene-alpha-chloro-alpha-carbonyl oxime and 2- methoxyl group -4- sevoflurane isopropyl amine, as raw material, experiment is walked
The rapid synthesis with compound 60 in the step 2 of embodiment 1, obtains faint yellow solid, yield 84.3%.
Embodiment 3
N- (4- benzyl chloride epoxides)-N '-(the fluorine isopropyl-phenyls of 2,6- dimethyl -4- seven) -2- furan -2- base -2- oxos -
The preparation of acetamide（Compound 103）
Step 1：The synthesis of 2- furyl-alpha-chloro-alpha-carbonyl oximes
With 2- furan 1-Phenylethanone .s as raw material, experimental procedure with the middle chlorobenzene-alpha-chloro-alpha-carbonyl oxime of embodiment 1 synthesis,
Obtain black solid, yield：81.8%, m.p.124～126 DEG C；1H NMR(400MHz,DMSO-d6), δ：6.78(m,1H,Ar-H),
7.57(d,1H,Ar-H),8.13(d,1H,Ar-H),13.62(s,1H,OH)。
Step 2：N- (the fluorine isopropyl-phenyls of 2,6- dimethyl -4- seven) -2- furan -2- base-N '-hydroxyl -2- oxos-second
The synthesis of amide
With 2- furyls-alpha-chloro-alpha-carbonyl oxime and 2,6- dimethyl -4- sevoflurane isopropyls amine for raw material, experiment step
The rapid synthesis with compound 60 in the step 2 of embodiment 1, obtains faint yellow solid, yield 82.1%.
Step 3：The synthesis of target compound
By 2mmol N- (the fluorine isopropyl-phenyls of 2,6- dimethyl -4- seven) -2- furan -2- base-N '-hydroxyl -2- oxos -
Acetamide is dissolved in 15mL acetonitriles, is added thereto to 0.8g potassium carbonate, after stirring reaction 30min, Deca 2.4mmol in solution
The solution of 10mL acetonitriles is dissolved in benzyl chloride chlorine, drop finishes, stirring reaction 12h under room temperature.Filtration, filtrate pillar layer separation（Petroleum ether:
Ethyl acetate=8:1）, obtain yellow oily liquid, yield 81.6%.
Embodiment 4
N- (the chloro- pyridine -2- methoxyl groups of 5-) -2- (2,6- Dichloro-phenyls)-N '-(the fluorine isopropyls of 2- methyl -4- seven-benzene
Base) -2- oXo-acetamides preparation（Compound 154）
Step 1：The synthesis of 2,6- dichloro-benzenes-alpha-chloro-alpha-carbonyl oximes
With 2,6- dichloroacetophenones be raw material, experimental procedure with the middle chlorobenzene-alpha-chloro-alpha-carbonyl oxime of embodiment 1 conjunction
Into obtaining white solid, yield：81.3%, m.p.117～119 DEG C；1H NMR(400MHz,DMSO-d6), δ：7.70-8.09(m,
3H,Ar-H),13.65(s,1H,OH)。
Step 2：2- (2,6- Dichlorobenzene base)-N- hydroxy-ns '-(the fluorine isopropyl-phenyls of 2- methyl -4- seven) -2- oxos-second
The synthesis of amide
It is real with the synthesis of 2,6- dichloro-benzenes-alpha-chloro-alpha-carbonyl oximes and 2- methyl -4- sevoflurane isopropyls amine for raw material
Synthesis of the step with compound 60 in the step 2 of embodiment 1 is tested, faint yellow solid, yield 82.7% is obtained.
Step 3：The synthesis of target compound
With 2- (2,6- Dichlorobenzene base)-N- hydroxy-ns '-(the fluorine isopropyl-phenyls of 2- methyl -4- seven) -2- oXo-acetamides
It is raw material with 2-vhloro-5-chloromethylpyridine, experimental procedure obtains yellow oil with the synthesis of compound 103 in the step 3 of embodiment 3
Shape liquid, yield 80.6%.
The present configuration formula enumerated in concordance list 1 and concordance list 2（I）The shown carbonyl oxime ether containing seven fluorine isopropyls
Class compound, can be synthesized according to the preparation method described in above-mentioned synthetic example 1-4.
2nd, pharmaceutical formulation
Example 5 below to embodiment 9 is given with the general structure of the present invention（I）The shown carbonyl containing seven fluorine isopropyls
Oximido ether compound prepares the concrete instance of several pesticides or antibacterial dosage form as active substance component, processing, needs to refer to
What is gone out is that the present invention is not limited in the range of following examples.In these formulation examples, all of " % " refers both to weight
Percentage ratio.
The wettable powder agent prescription of embodiment 5
By 15% compound（I）（Compound 26 in table 1）, 5% lignosulfonates（Mq）, 1% lauryl alcohol polyoxy second
Alkene ether（JFC）, 40% kieselguhr and 44% precipitated calcium carbonate equably mix, crush, obtain final product wettable powder.
The emulsifiable concentrate formulation of embodiment 6
By 10% compound（I）（Compound 26 in table 1）, 5% agriculture breast 500（Calcium salt）, 5% agriculture breast 602,5%
METHYLPYRROLIDONE and 75% dimethylbenzene heated and stirred it is uniform, obtain final product cream.
The granule formulations of embodiment 7
By 5% compound（I）（Compound 26 in table 1）, 1% polyvinyl alcohol（PVA）, 4% naphthalene sulfonate formaldehyde condensation
Thing（NMO）Equably mix with 90% clay, crush, then add 20 parts of water to this 100 parts of mixture, mediate, use extruding granulating
Machine, makes the granule of 14-32 mesh, is dried, and obtains final product granule.
The water-dispersible granules formula of embodiment 8
By 20% compound（I）（Compound 26 in table 1）, naphthalenesulfonate formaldehyde condensation compound 4%, naphthalene sulfonate 1%, Linesless charcoal
Black 2% and 73% Kaolin carries out co-grinding, after adding water kneading, adds and is made in the comminutor equipped with certain specification screen cloth
Grain.Then again drying, screening obtain final product granular product (by screen cloth scope).
The aqueous suspension agent formula of embodiment 9
By 20% compound（I）（Compound 26 in table 1）, fatty alcohol-polyoxyethylene ether 1%, rosin segmented polyoxyethylene ether
Polyoxypropylene ether sulfonate 3%, aluminium-magnesium silicate 1%, organic silicon defoamer 0.4%, Propylene Glycol 5% and deionized water（69.5%）Carry out
It is pre-mixed uniformly, adds sand milling in sand mill, suspension mother solution is obtained after filtration, adds the xanthan gum for having configured（0.1%）Water
Solution shear mix homogeneously.
3rd, biological activity determination
Being given below carries out the example of biological activity determination using the compound of the present invention, it is pointed out that the present invention is simultaneously
It is not solely restricted in the range of following examples.
Note：Numbering described in biological activity determination embodiment is relative with the compound number described in concordance list 1 and concordance list 2
Should.
The insecticidal activity assay of embodiment 10
The following method of Insecticidal Activity experimental evidence is carried out：
Certain mass preparation is weighed, plus distilled water diluting is configured to determine desired concn medicinal liquid.Screening concentration is from 500mg/
L, 100mg/L, 20mg/L to 4mg/L, chemicals treatment amount of liquid medicine 10mL.Experiment target is designated as mythimna separata, aphis craccivora and Tetranychus cinnabarinus.
Leaf dipping method：It is mythimna separata for trying target, leaf of Semen Maydis will dries in the shade naturally after fully infiltrating in the medicinal liquid for preparing in right amount,
In being put into the culture dish for being lined with filter paper, mythimna separata 3 age mid-term larva, 10/ware is connect, be placed in 24～27 DEG C of observation indoor cultivation, 48h
Survey result afterwards.Polypide is touched with brush pen, it is reactionless to be considered as dead worm.General sieve experimental concentration 500mg/L, Primary Screening Test concentration 100,
20、4mg/L。
Infusion process：It is Tetranychus cinnabarinus, aphis craccivora for trying target, i.e., will be connected to the Folium Viciae fabae of Tetranychus cinnabarinus and aphis craccivora respectively
Piece dries in the shade naturally after fully infiltrating in the medicinal liquid for preparing, and Tetranychus cinnabarinus are placed in 24～27 DEG C of observation indoor cultivation, and aphis craccivora is put
Indoor cultivation, survey result after 48h are observed in 20～22 DEG C.Polypide is touched with brush pen, it is reactionless to be considered as dead worm.General sieve test is dense
Degree 500mg/L, Primary Screening Test concentration 100,20,4mg/L.
Test statistics：The dead borer population and borer population living of each process are counted, mortality rate is calculated.
CK compares mortality rate<20%, result of the test is credible, and result of the test is corrected, CK control mortality rates<Can not when 5%
Correction.
Raw test result shows：Majority of compounds of the present invention has preferable insecticidal activity, small part to aphis craccivora
Compound has insecticidal activity to Tetranychus cinnabarinus and mythimna separata." mg/L " refer both to every milligram of active matter/liter.
Under 500mg/L concentration：
Compound 9,10,13,15,23,32,35,36,59,60,97,98,105,113,114,115,116,138,142,
153rd, the mortality rate of 165,188 and 200 pairs of aphis craccivoras is more than 80%；
The mortality rate of 20,113 pairs of Tetranychus cinnabarinus of compound is more than 80%；
Compound 19,23,26,60,76,126,138,142,153,165,188,189,199,204,211 and 215 pairs glues
Worm mortality rate is more than 80%.
The bactericidal activity of embodiment 11 is determined
Bactericidal activity evaluation test is carried out according to following method：
Certain medicine is weighed, is dissolved with DMF, be diluted with water to 200mg/L concentration standby.
Trial crops are Fructus Cucumidis sativi, by potted plant cucumber seedling culture to the heart stage of 2 leaf 1, are for experiment.Trial crops are placed in into spraying
Foliar spray process is carried out on machine, the crop after chemicals treatment places shady place, pathogen spore is inoculated with after 24h, if 3 weights
It is multiple, separately set blank.Postvaccinal crop is placed in phjytotron and cultivates, and above disease is cultivated respectively after 7d and 10d
Investigation preventive effect.Live body bactericidal activity evaluation has been carried out to 4 kinds of targets.Measure target is Rhizoctonia solani Kuhn (Rhizoctonia
Solani), bacterium of downy mildew of cucumber (Bremia lactucae), cucumber powdery mildew's pathogen (Erysiphaceae) and gray mold of cucumber
Bacterium (Botrytis cinerea).Investigation method, disease scale and computational methods are with reference to National Standard of the People's Republic of China《Agriculture
Medicine field control effectiveness test criterion》, prevention effect is calculated with disease index.
Live body bactericidal activity evaluation result shows：The compounds of this invention has certain bactericidal activity, particularly to Fructus Cucumidis sativi
Pseudoperonospora cubensis and Rhizoctonia solani Kuhn have preferable bactericidal activity, " mg/L " refer both to every milligram of active matter/liter.
Under 200mg/L concentration：
The suppression ratio of 88,202 pairs of Rhizoctonia solani Kuhns of compound is more than 80%；
Compound 20,26,29,34,40,50,83,84,86,87,103,118,130,147,155,157,167,175,
191st, the suppression ratio of 206,209,213,227 and 235 pairs of bacterium of downy mildew of cucumber is more than 60%.
Claims (10)
1. a kind of carbonyl oximido ether compound for containing seven fluorine isopropyls, with following general structure (I)：
In formula：
G is former selected from oxygen containing at least one in naphthalene nucleus, fragrant 6 yuan of rings or 5 yuan of heteroaromatics, and the ring of 5 yuan of heteroaromatics
The hetero atom of son, sulphur atom or nitrogen-atoms；
X is independently selected from hydrogen, C1-C6Alkyl, C3-C6Cycloalkyl, C2-C6Alkenyl, C2-C6Alkynyl, C1-C6Alkoxyl, halo C1-
C6Alkyl, halo C1-C6Alkoxyl, halogen, cyano group, nitro or hydroxyl；
Y is independently selected from hydrogen, C1-C6Alkyl, C3-C6Cycloalkyl, C2-C6Alkenyl, C2-C6Alkynyl, C1-C6Alkoxyl, halo C1-
C6Alkyl, halo C1-C6Alkoxyl, phenyl, halogen, cyano group, nitro or hydroxyl；
R is selected from hydrogen, C1-C6Alkyl, halo C1-C6Alkyl, C3-C6Cycloalkyl, C2-C6Alkenyl, C2-C6Alkynyl or-A-Q groups,
In-A-Q the groups：
A is selected from C1-C6Alkylidene, C2-C6Alkenylene or C2-C6Alkynylene；
Q selected from hydrogen, naphthalene nucleus, fragrant 6 yuan of rings, 5 yuan of heteroaromatics, by 1-5 independently selected from halogen, nitro, cyano group, C1-C6Alkane
Base, C1-C6Alkoxyl, halo C1-C6Alkyl or halo C1-C6The naphthalene nucleus of the substituent group of alkoxyl, fragrant 6 yuan of rings or 5 yuan of virtues
Heterocycle；
M is 0～5 integer；
N is 0～4 integer.
2. according to the carbonyl oximido ether compound containing seven fluorine isopropyls described in claim 1, it is characterised in that：
G is former selected from oxygen containing at least one in naphthalene nucleus, fragrant 6 yuan of rings or 5 yuan of heteroaromatics, and the ring of 5 yuan of heteroaromatics
The hetero atom of son, sulphur atom or nitrogen-atoms；
X is independently selected from hydrogen, C1-C4Alkyl, C3-C6Cycloalkyl, C2-C3Alkenyl, C2-C3Alkynyl, C1-C3Alkoxyl, halo C1-
C3Alkyl, halo C1-C3Alkoxyl, halogen, cyano group, nitro or hydroxyl；
Y is independently selected from hydrogen, C1-C4Alkyl, C3-C6Cycloalkyl, C2-C3Alkenyl, C2-C3Alkynyl, C1-C3Alkoxyl, halo C1-
C3Alkyl, halo C1-C3Alkoxyl, phenyl, halogen, cyano group, nitro or hydroxyl；
R is selected from hydrogen, C1-C3Alkyl, halo C1-C3Alkyl, C3-C6Cycloalkyl, C2-C6Alkenyl, C2-C6Alkynyl or-A-Q groups,
In-A-Q the groups：
A is C1-C3Alkylidene；
Q selected from hydrogen, phenyl ring, naphthalene nucleus, fragrant 6 yuan of rings, 5 yuan of heteroaromatics, by 1-4 independently selected from halogen, nitro, cyano group, C1-
C3Alkyl, C1-C3Alkoxyl, halo C1-C3Alkyl or halo C1-C3The naphthalene nucleus of the substituent group of alkoxyl, fragrant 6 yuan of rings or 5
First heteroaromatic；
M is 0～4 integer；
N is 0～3 integer.
3. according to the carbonyl oximido ether compound containing seven fluorine isopropyls described in claim 2, it is characterised in that：
G-(X)mSelected from 5 yuan of heteroaromatics shown in the yuan of rings of fragrance 6 or G-4, G-5 or G-6 shown in naphthalene nucleus, G-1, G-2 or G-3；
X is independently selected from hydrogen, C1-C4Alkyl, C1-C3Alkoxyl, halo C1-C3Alkyl, halo C1-C3Alkoxyl, nitro or halogen
Element；
Y is independently selected from hydrogen, C1-C4Alkyl, C1-C3Alkoxyl, halo C1-C3Alkyl, halo C1-C3Alkoxyl, halogen or hydroxyl
Base；
R is selected from hydrogen, C1-C3Alkyl, halo C1-C3Alkyl or formula-A-Q groups, in-A-Q the groups：
A is C1-C3Alkylidene；
Q selected from hydrogen, phenyl ring, pyridine ring, thiazole ring, by 1-3 independently selected from halogen or C1-C3The phenyl ring of alkyl group replacement,
Pyridine ring or thiazole ring；
M is 0～3 integer；
N is 0～2 integer.
4. according to the carbonyl oximido ether compound containing seven fluorine isopropyls described in claim 3, it is characterised in that：
G is selected from phenyl ring, the 5 yuan of heteroaromatics shown in G-4 or G-5 shown in naphthalene nucleus, G-1；
X is independently selected from hydrogen, methyl, methoxyl group, the tert-butyl group, trifluoromethyl, trifluoromethoxy, nitro, fluorine or chlorine；
Y is independently selected from hydrogen, methyl, ethyl, methoxyl group, fluorine, chlorine or hydroxyl；
R is selected from hydrogen or formula-A-Q groups, in-A-Q the groups：
A is methylene；
Q is selected from hydrogen, the phenyl ring, pyridine ring or the thiazole ring that are replaced independently selected from fluorine, chlorine, methyl group by 1-2.
5. according to the carbonyl oximido ether compound containing seven fluorine isopropyls described in claim 3, it is characterised in that described to contain seven fluorine
The carbonyl oximido ether compound of isopropyl has one of following structural formula：
6. according to the carbonyl oximido ether compound containing seven fluorine isopropyls described in one of claim 1 to 5, it is characterised in that described
Carbonyl oximido ether compound containing seven fluorine isopropyls is prepared in accordance with the following methods：
7., according to the application of the carbonyl oximido ether compound containing seven fluorine isopropyls described in one of claim 1-5, its feature exists
It is used to prevent and treat aphis craccivora, Tetranychus cinnabarinus, lepidoptera pest, Cucumis satiuus L. in the carbonyl oximido ether compound for containing seven fluorine isopropyls
Mildew bacterium, cucumber powdery mildew's pathogen and Rhizoctonia solani Kuhn.
8. according to the application of the carbonyl oximido ether compound containing seven fluorine isopropyls described in claim 7, it is characterised in that described
Lepidoptera pest is mythimna separata.
9., according to the application of the carbonyl oximido ether compound containing seven fluorine isopropyls described in one of claim 1-5, its feature exists
In by the carbonyl oximido ether compound for containing seven fluorine isopropyls be used for prepare chemistry of pesticide insecticide or antibacterial, the pesticide
The carbonyl oxime ethers containing seven fluorine isopropyls containing 0.001%-99.99% percentage by weights in chemical insecticide or antibacterial
Compound, the chemistry of pesticide insecticide or antibacterial are liquor, cream, suspending agent, microemulsion, Emulsion, powder, wettable powder
Agent, soluble powder, granule or capsule.
10. according to the application of the carbonyl oximido ether compound containing seven fluorine isopropyls described in claim 9, it is characterised in that by institute
State chemistry of pesticide insecticide or antibacterial is applied on the medium of insect pest or its growth for needing control, the active component contains seven
The amount of application of the carbonyl oximido ether compound of fluorine isopropyl is 10 grams to 1000 grams of per hectare.
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| 含七氟异丙基的氯虫酰胺类似物的设计合成及生物活性;冯启等;《高等学校化学学报》;20110131;第32卷(第1期);第74-78页 * |
| 含七氟异丙基的苯胺类化合物的合成;唐秀红等;《化工生产与技术》;20081231;第15卷(第6期);第5-7页 * |
| 曹敏等.含全氟异丙基的呋喃酰基硫脲类化合物的合成及生物活性.《农药》.2012,第51卷(第7期),第488-493页. * |
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Effective date of registration: 20200429 Address after: 310023 No. 926, Xixi Road, Hangzhou, Zhejiang, Xihu District Co-patentee after: SINOCHEM LANTIAN Co.,Ltd. Patentee after: ZHEJIANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Ltd. Co-patentee after: SINOCHEM Corp. Address before: 310023 No. 926, Xixi Road, Hangzhou, Zhejiang, Xihu District Co-patentee before: SINOCHEM LANTIAN Co.,Ltd. Patentee before: ZHEJIANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Ltd. |