CN100430373C - Biological active compound of methoxy acrylic ester containing bis trifluoromethyl phenyl and preparing process thereof - Google Patents
Biological active compound of methoxy acrylic ester containing bis trifluoromethyl phenyl and preparing process thereof Download PDFInfo
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- CN100430373C CN100430373C CNB200510031418XA CN200510031418A CN100430373C CN 100430373 C CN100430373 C CN 100430373C CN B200510031418X A CNB200510031418X A CN B200510031418XA CN 200510031418 A CN200510031418 A CN 200510031418A CN 100430373 C CN100430373 C CN 100430373C
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Abstract
The present invention discloses a methoxyacrylate compound and a preparation method thereof. The methoxyacrylate compound is represented by general formulas I, II and III, has fungicidal, acaricidal and pesticidal biological activity and contains double trifluoromethylphenyl. The present invention also discloses a fungicidal, acaricidal and pesticidal composition containing the compound and a method for controlling fungi, acarids and pests by the compounds, wherein A, B, W, n, Y and K are defined in the specification.
Description
Technical field
The present invention relates to have fungicidal, kill mite, bioactive methoxy acrylate compound that contains bis trifluoromethyl phenyl of desinsection and preparation method thereof, contain the fungicidal of described compound, the purposes and the method for killing mite, insecticides and controlling fungies, mite, worm with these compounds.
Background technology
In world patent WO 96 16047, disclose by BASF AG development, the exploitation of Japanese Cao Da company contain pyrimidine structure first also be a unique commercial methoxy acrylate class miticide (test code number: NA83, common name: fluacrypyrim, trade name: Titaron), its structural formula is as follows.Fluacrypyrim has higher acaricidal activity, but it need just have fungicidal activity to the part disease under like this than higher dosage at 250mg/L, and as seen its sterilization effect is excellent not enough, and its insecticidal effect is also very not remarkable simultaneously.Equally, commercial methoxy acrylate series bactericidal agent (test code number a: CGA 279202 with single trifluoromethylbenzene based structures by the research and development of Switzerland Novartis Co.,Ltd is disclosed in EP 472300, common name: trifloxystrobin, trade name: Flint), its structural formula is as follows.It is of great use as sterilant that EP 472300 has described CGA 279202, but this compound does not have acaricidal activity.In addition, the methoxy acrylate compound of patent report only has Fungicidally active mostly, and the methoxy acrylate compound of relevant acaricidal activity and/or insecticidal activity, its report is very few.
In order to obtain to have the methoxy acrylate compound of higher acaricidal activity and/or insecticidal activity; In order to obtain just can control under more low dose of the methoxy acrylate compound of various fungal diseases; In order to obtain under more low dose of, just can to control various fungal diseases, also has the higher compound that kills mite and/or insecticidal activity simultaneously; Inventors of the present invention further investigate the methoxy acrylate compound that contains bis trifluoromethyl phenyl.
Summary of the invention
The invention provides general formula (I), (II) and (III) shown in the methoxy acrylate compound that contains bis trifluoromethyl phenyl and all geometrical isomer and steric isomers:
Wherein:
I.A is selected from following group:
U is CH or N;
G is 0 or 1;
V is O, S or NR
SR
V(when g=1), wherein R
SAnd R
VBe identical or different, and represent H or alkyl;
R ' is C
1～C
6Alkyl or H;
II.B is selected from following group:
XR R
1CHXR R
2
B-1 B-2 B-3
X is O, S, SO, SO
2Or NR
SR
V(R
SAnd R
VBe identical or different, and represent H or alkyl);
R is an alkyl, haloalkyl, alkenyl, halogenated alkenyl, alkynyl or halo alkynyl;
R
1Be hydrogen, alkyl, haloalkyl;
R
2Be hydrogen, haloalkyl, cyano group;
III.W is a hydrogen, cyano group, halogen, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy or phenyl;
IV.n is 0 or one from 1 to 2 a integer, and when n＞1, W can be identical or different;
V.Y is selected from following group:
Y-1 Y-2 Y-3 Y-4
B defines among B such as the II;
Z is O, S, SO, SO
2, NR
SR
V(R
SAnd R
VBe identical or different, and represent H or alkyl);
R
3Be alkylidene group, halo alkylidene group, cyano group alkylidene group, alkane sulphur alkylidene group, sulphonyl alkylidene group, sulfinyl alkylidene group, alcoxyl alkylidene group;
VI.K is selected from following group:
K-1 K-2 K-3 K-4 K-5
B defines among B such as the II;
Z defines among Z such as the V;
R
3As R among the V
3Define;
In the compound that provides above (I), (II) and the definition (III), no matter the separately use or be used in the compound word the following substituting group of general proxy of used term:
Halogen: refer to fluorine, chlorine, bromine and iodine;
Alkyl: refer to have the straight or branched alkyl of 1-6 carbon atom, for example methyl, ethyl, n-propyl, sec.-propyl or different butyl, amyl group, hexyl isomer;
Haloalkyl: refer to have the straight or branched alkyl of 1-6 carbon atom, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen atom, for example, and C
1Haloalkyl such as chloromethyl, brooethyl, methyl fluoride, dichloromethyl, two brooethyls, difluoromethyl, trichloromethyl, trisbromomethyl, trifluoromethyl, chlorine methyl fluoride;
Alkoxyl group: refer to have the straight or branched alkoxyl group of 1-6 carbon atom, be connected on the structure, as methoxyl group, oxyethyl group, positive propoxy, isopropoxy and different butoxy or pentyloxy isomers through the Sauerstoffatom key;
Halogenated alkoxy: refer to have the straight or branched alkoxyl group of 1-6 carbon atom, the hydrogen atom on these alkoxyl groups can partly or entirely be replaced by halogen atom, for example, and C
1Halogenated alkoxy such as chlorine methoxyl group, bromine methoxyl group, fluorine methoxyl group, dichloro methoxyl group, dibromo methoxyl group, difluoro-methoxy, trichlorine methoxyl group, tribromo methoxyl group, trifluoromethoxy, chlorine fluorine methoxyl group;
Aryl: the naphthyl that refers to have the phenyl of 6 carbon atoms and have 12 carbon atoms.
(I) of the present invention, (II) and (III) shown in compound, because carbon-to-carbon double bond is connected different substituting groups and can forms geometrical isomer (representing different configurations with Z and E respectively) with the two keys of carbon-nitrogen, the present invention includes the mixture of Z type isomer and E-isomer and their any ratios.
Compound of the present invention can form steric isomer (representing different configurations with R and S respectively) owing to connect different substituting groups on carbon or the nitrogen-atoms, the present invention includes the mixture of R type isomer and S type isomer and their any ratios.
Compound of the present invention not only relates to geometrical isomer (Z/E formula) and steric isomer R/S formula), also relate to the mixture of geometrical isomer and any ratio of steric isomer.
Inventors of the present invention synthesized have general formula (I), (II) and (III) shown in the methoxy acrylate compound that contains bis trifluoromethyl phenyl have broad spectrum of activity: the compound that has can be used for preventing and treating on various crops such as the various mite classes of cotton spider mites, tangerine Panonychus citri and/or such as the various harmful insects of leafhopper, aphid; The compound that has can be used for preventing and treating on various crops by multiple fungus-caused diseases such as Haplomycetes, Phycomycetes, Oomycete, Ascomycetes and deuteromycetes; The compound that has not only can be used for preventing and treating on various crops such as the various mite classes of cotton spider mites, tangerine Panonychus citri with such as the various harmful insects of leafhopper, aphid, also can be used for simultaneously preventing and treating on various crops by multiple fungus-caused diseases such as Haplomycetes, Phycomycetes, Oomycete, Ascomycetes and deuteromycetes.And since these compounds have very high biological activity and make it under very low dosage, just can obtain good effect.The compound that has also has good activity to gray mold, head blight, sclerotium disease, phytophthora root rot except Powdery Mildew, oidium, rice blast are shown the good active.Specifically, part of compounds of the present invention not only has excellent activity to pathogenic bacteria such as Powdery Mildew, rice blast, also mite such as acarina such as two-spotted spider mite and harmful insect such as aphid etc. is also had excellent activity simultaneously.
Can the present invention be described with the compound of listing in the following table 1.But do not limit the present invention.Among the present invention the fusing point of giving all not calibrated.In the table 1 in acrylate-based-CO
2CH
3With-OCH
3Group is the isomer (i.e. (E)-isomer configuration) that is positioned at two key both sides.
Table 1
Continuous table 1
Continuous table 1
Continuous table 1
Continuous table 1
Continuous table 1
Continuous table 1
Continuous table 1
Formula of the present invention (I), (II) and (III) shown in compound can prepare by reaction formula 1, reaction formula 2 and the reaction formula 3 shown in following.All as preceding qualification, L is leavings group such as halogen (chlorine, bromine) to substituting group wherein except that specializing.
Reaction formula 1:
Reaction formula 2:
Reaction formula 3:
The compound of the general formula of V ≠ NH (I) and formula (II) can prepare like this: at solvent N, in the dinethylformamide, handle logical formula V or compound (VI) with alkali sodium hydride, potassium hydroxide or salt of wormwood, the compound that adds formula (IV) then gets final product.
The preparation method of formula (III) compound: at solvent N, in the dinethylformamide, with the compound of alkali sodium hydride, potassium hydroxide or salt of wormwood processing formula (VII), the compound that adds formula (VIII) then gets final product.
Preferred solvent is N, dinethylformamide or tetrahydrofuran (THF).
Preferred alkali is potassium hydroxide, salt of wormwood, sodium hydroxide, sodium hydride or sodium methylate.
Formula (IV) compound can be prepared with reference to following pertinent literature:
Having narrated A among European patent EP 203606 and the EP254426 respectively is A-1, and wherein U=CH, L are that bromine and A are A-1, wherein U=N, when L is bromine, the preparation method of general formula (IV) compound.
Having narrated A in the U.S. Pat 5869517 is A-2, wherein during U=N, and the preparation method of general formula (IV) compound.
Having narrated A in the U.S. Pat 6103717 is A-3, wherein during U=N, and the preparation method of general formula (IV) compound.
When having narrated A among the world patent WO99/11129 and being A-5, the preparation method of general formula (IV) compound.
When A is A-4, when general formula (IV) compound synthetic can be A-5 with reference to A, the preparation method of general formula (IV) compound.
Narrated the preparation method of general formula (VII) compound among European patent EP 0382375 and the EP0415569.
Oxime shown in the logical formula V, when B is B-1, can be in appropriate solvent (as methyl alcohol, chloroform, bismethane or ethanol) by corresponding aldoxime, generate the alpha-chloro aldoxime with chlorine or t-butyl hypochlorate reaction, again in appropriate solvent (as methyl alcohol, ethanol or water), add an appropriate base (as sodium alkoxide, triethylamine or sodium hydroxide) in case of necessity, obtain with corresponding alcohol, mercaptan or amine reaction.
Oxime shown in the logical formula V when B is B-2, can add suitable alkali (as sodium hydroxide or salt of wormwood) reaction acquisition in case of necessity by corresponding ketone and oxammonium hydrochloride in appropriate solvent (as methyl alcohol or ethanol).
Oxime shown in the logical formula V, when B is B-3, can be by corresponding raw material such as benzyl cyanogen with Isopentyl nitrite or raw material aldehyde, ketone and oxammonium hydrochloride react acquisition in appropriate solvent accordingly.
Compound shown in the general formula (VI) when Y is Y-1, can generate acid amides by corresponding amine and corresponding acyl chloride reaction, obtains under the effect of thiophosphoric anhydride or phosphorus pentachloride then.
Compound shown in the general formula (VI) when Y is Y-2, can generate α by corresponding dual-trifluoromethyl benzaldehyde and corresponding aldehydes or ketones aldol condensation, beta-unsaturated aldehyde or alpha, beta-unsaturated ketone, and then the synthetic method of the logical formula V of reference is synthesized.
Compound shown in the general formula (VI) when Y is Y-3, can obtain with an appropriate reductant (as sodium borohydride) reaction by corresponding ketone or ketone in appropriate solvent (as water and/or ethanol).
When A was A-1 and V=NH, general formula (I), (II) and compound (III) can be that the methanol solution reaction of general formula (I), (II) and compound (III) and the methylamine of A-1 and V=O obtains by corresponding A.
As Z=SO or SO
2The time, general formula I), (II) and compound (III), in the time of can be by Z=S, corresponding general formula I), (II) and compound (III) and oxygenant such as Sodium peroxoborate or hydrogen peroxide react acquisition in appropriate solvent.
The methoxy acrylate compound that contains bis trifluoromethyl phenyl provided by the invention, biologically active and the compound that has have fabulous biological activity. particularly aspect the preventing and treating of agricultural, gardening, flowers and sanitary insect pest, show high reactivity.Harmful organism described here include but not limited to this:
Harmful insect: Orthoptera such as blattaria, Thysanoptera such as cotton thrips, rice thrips, melon thrips, Homoptera such as leafhopper, plant hopper, aphid, lepidopteran such as oriental armyworm, prodenia litura, small cabbage moth, cabbage caterpillar, Hymenoptera such as sawfly larva, Diptera such as yellow-fever mosquito, culex, fly, acarina such as tangerine Panonychus citri, cotton spider mites;
Harmful pathogenic bacteria: the phytophthora kind, white powder belongs to kind, the Gibberella kind, the Venturia kind, species of Monilinia fructicola, the Rhizoctonia kind, the Staphlosporonites kind, the Pyricularia Sacc. kind, the fusarium kind is as rice blast (Pyriculariaoryzae); Stripe rust of wheat (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust; Big wheat yellow rust (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust; Barley and wheat powdery mildew (Erysiphe graminis), powdery mildew of cucumber (Sphaerotheca fuligenea), apple mildew (Podosphaera leucotrichar) and uncinula necator (Podosphaera leucotrichar); Wheat hypochnus and glume blight (Septoria nodorum).Length on the cereal wriggle spore, the mouth spore is mould, Septoria is sick, caryosphere shell Pseudomonas disease, Pseudocercosporella herpotrichoides and take-all (Gaeumannomycesgraminis).The cercospora brown spot of peanut (Cercospora arachidicola) and the cercospora black spot of peanut (Cercosporidiumpersonata); The mould genus of its tail spore on beet, soybean and the paddy is sick.Tomato, cucumber, grape grey mould (Botrytiscinerea).Hinge spore on the vegetables (as cucumber) belongs to sick.Anthrax on the cucumber, scab of apple, cucumber downy mildew, downy mildew of garpe, the eqpidemic disease on potato and the tomato, other rhizoctonia on the list bacterium Thanatephorus cucumeris on the paddy and other hosts such as wheat and barley, the vegetables; Sclerotinia rot of colza (Sclerotoniasclerotiorum); Wheat scab (Gibberella zeae); Phytophthora capsici disease (Phytophythora capsici).
With the methoxy acrylate compound that contains bis trifluoromethyl phenyl provided by the invention, Agrotechnical formulation as effective ingredient, can make desirable any formulation such as missible oil, wettable powder, suspension agent, granula, suitable auxiliary agent comprises carrier (thinner) and other auxiliary such as spreader-sticker, emulsifying agent, wetting agent, dispersion agent, tackiness agent and decomposition agent.
The present invention also provides preparation of compositions method as defined above, and method is that general formula (I), (II) and compound (III) and at least a carrier are mixed.This composition can contain the mixture of simplification compound of the present invention or several compounds.
According to composition of the present invention, preferably contain from the activeconstituents of 1-99% weight.Carrier of the present invention is the material that satisfies following condition: be convenient to be applied to pending site after it and activeconstituents are prepared, as plant, seed or soil; Perhaps help storing, transport or operation.Carrier can be solid or liquid, comprise be generally gas but be compressed into the liquid bead material and can use any usually at the preparation desinsection, kill used carrier in mite and the fungicidal composition.
Suitable solid carrier comprises natural and synthetic clay and silicate, for example diatomite, talcum, attapulgite, pure aluminium silicate (kaolin), montmorillonite and mica; Lime carbonate; Calcium sulfate; Ammonium sulfate; Synthetic silica and synthetic calcium silicate or pure aluminium silicate; Element such as carbon and sulphur; Natural and synthetic resin such as coumarone resin, polyvinyl chloride and styrene polymer and multipolymer; Solid polystream phenol; Pitch; Wax such as beeswax, paraffin.
Suitable liquid vehicle comprises water; Pure as Virahol, ethanol; Ketone such as acetone, methyl ethyl ketone, cyclohexyl ketone; Ether; Aromatic hydrocarbons such as benzene, toluene and dimethylbenzene; Petroleum fractions such as kerosene and mineral oil; Hydrochloric ether such as tetracol phenixin, tetrachloroethylene also comprise these mixtures of liquids.
Desinsection, kill mite, fungicidal composition is processed into the form of enriched material usually and is used for transportation with this, before using, it is diluted by the user.Having of a spot of supporting surfactant helps dilution.Therefore, in composition of the present invention, has a kind of carrier preferred surfactant at least.Contain at least two kinds of carriers as composition, wherein at least a is tensio-active agent.
Tensio-active agent can be emulsifying agent, dispersion agent or wetting agent; It can be non-ionic or the ionic tensio-active agent.Sodium salt or calcium salt as polyacrylic acid and lignosulfonic acid; Contain the lipid acid of at least 12 carbon atoms or the condenses of aliphatic amide or acid amides and oxyethane and/or propylene oxide in the molecule; Glycol, sorbyl alcohol, the condenses of sucrose or pentaerythritol fatty ester and these esters and oxyethane and/or propylene oxide; The vitriol of these condensess or sulfonate; But the basic metal or the alkaline earth salt that in molecule, contain the sulfuric acid sulphonate of at least 10 carbon atoms.
The example of composition of the present invention is wettable powder, pulvis, granule and solution, emulsible enriching agent, emulsion, suspension enriching agent, aerosol and smoke substance.Wettable powder contains 15,25,50% weight activeconstituents usually, and usually except that solid inert carrier, also contains 3-10% weight fraction powder, can add 0-10% weight stablizer and/or other additive such as permeate agent and tackiness agent in case of necessity.Pulvis may be molded to the pulvis enriching agent that has the composition similar to wettable powder but do not have dispersion agent usually.Granula is made usually has 10-100 order (1.676-0.152mm) size, and available agglomerating or implantttion technique preparation.Usually, granula contains the activeconstituents of 0.5-50% weight and 0-10% weight additive such as stablizer, tensio-active agent, slowly-releasing modifying agent.Outside but emulsion concentrate desolventizes, can contain cosolvent in case of necessity, the 1-50%W/V activeconstituents, other additive of 2-20%W/V emulsifying agent and 0-20%W/V such as stablizer, permeate agent and corrosion inhibitor, suspension enriching agent contain the activeconstituents of 10-75% weight, the dispersion agent of 0.5-15% weight, other additive such as defoamer, corrosion inhibitor, stablizer, permeate agent and the tackiness agent of 0.1-10% weight usually.
Water dispersant and emulsion, for example by dilute with water according to the composition that wettable powder of the present invention or enriched material obtain, also list scope of the present invention in.Indication emulsion comprises two kinds of water-in-oil and oil-in-waters.
By in composition, adding other one or more miticides, make its can than independent general formula (I), (II) and/or (III) compound have more broad spectrum of activity.In addition, but other miticide mutual-through type (I), (II) and/or (III) acaricidal activity of compound have synergism.The example that can be included in the acaricide compound in the present composition has: aramite, propargite, methamidophos, azoles mite ester, hexythiazox and pyridaben etc.
By in composition, adding other one or more mycocides, make its can than independent general formula (I), (II) and/or (III) compound have more broad spectrum of activity.In addition, but other mycocide mutual-through type (I), (II) and/or (III) Fungicidally active of compound have synergism.The example that can be included in the acaricide compound in the present composition has: F-1991, derosal, m-tetrachlorophthalodinitrile, dimethomorph, triadimefon, cyanogen bacterium azoles, zinc manganese ethylenebisdithiocarbamate etc.
By in composition, adding other one or more sterilants, make its can than independent general formula (I), (II) and/or (III) compound have more broad spectrum of activity.In addition, but other sterilant mutual-through type (I), (II) and/or (III) insecticidal activity of compound have synergism.Can comprise organophosphorus insecticides such as acephatemet, Volaton, monocrotophos with the suitable sterilant of compound formation composition of the present invention, Provado, triaxamate, indenes worm prestige and pyrethroid insecticides such as fenvalerate, cyfloxylate, bifenthrin etc.
The invention will be further described below in conjunction with embodiment, and the yield among the embodiment is all without optimization.
Embodiment 1
The preparation method of compound 01 in this example instruction card 1.
3, synthesizing of 5-dual-trifluoromethyl benzaldehyde oxime: with 3,5-dual-trifluoromethyl benzaldehyde (24.2g=0.10mol) and oxammonium hydrochloride (7.30g=0.105mol) backflow 4-5hr in methyl alcohol (100ml), after the cooling, under agitation in the impouring trash ice (250g), filter 3,5-dual-trifluoromethyl benzaldehyde oxime white solid 23.4g, yield 91.0%, fusing point: 91.2-91.3 ℃.
GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：257；found：257(100)，238(45)，214(42)，213(40)，182(40)，163(35)，144(15).
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：7.885(s，1H)，8.032(s，2H)，8.221(s，1H)。
α-chloro-3, synthesizing of 5-dual-trifluoromethyl benzaldehyde oxime: with 3,5-dual-trifluoromethyl benzaldehyde oxime (12.85g=0.05mol) is dissolved in the methyl alcohol (200ml), under-5-0 ℃, slowly drip t-butyl hypochlorate (5.5g=0.05mol), behind about 0.5-1.0hr, decompression gets viscous liquid 13.08g after removing solvent, content 90.0% (GC-MS), yield 80.7%.
GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：291；found：291(15)，256(20)，255(100)，236(30)，213(25).
Alpha-methylmercapto-3, synthesizing of 5-dual-trifluoromethyl benzaldehyde oxime: with α-chloro-3,5-dual-trifluoromethyl benzaldehyde oxime (90%, 9.72g=0.03mol) be dissolved in the dehydrated alcohol (80ml), under stirring at room, be added drop-wise to the aqueous solution (20% of sodium methyl mercaptide, 14.7g=0.042mol) in, at 30-40 ℃ of reaction 2-3hr, cooling, ethyl acetate extraction, icy salt solution is washed till neutrality, anhydrous sodium sulfate drying, decompression removes solvent, gets alpha-methylmercapto-3,5-dual-trifluoromethyl benzaldehyde oxime 8.1g, content 90.0% (GC-MS) is yellow viscous solid, yield 80.2%.
GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：303；found：303(70)，286(25)，256(75)，240(40)，213(100)，170(25).
2-[2-[alpha-methylmercapto-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl]-3-methoxy-methyl acrylate (01 compound): with salt of wormwood (2.40g=17.4mmol) and N, dinethylformamide (15ml) adds in the exsiccant there-necked flask, after stirring 5-10min, under-5-0 ℃, drip above-mentioned oxime (90.0%, N 2.36g=7.0mmol), dinethylformamide solution (5ml).Behind the stirring reaction 0.5hr, with (E)-2-[2-(brooethyl) phenyl]-N of 3-methoxy-methyl acrylate (2.58g=9.0mmol), dinethylformamide solution (10ml) is added drop-wise in the above-mentioned reaction mixture, in 40-50 ℃ of insulation reaction 10-12hr.Mixture is poured in the trash ice, used ethyl acetate extraction 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 15) with ethyl acetate and sherwood oil gets title compound 1.08g for elutriant carries out column chromatography, and content 95.0% is white solid, yield 28.9%, fusing point: 79.6-80.1 ℃.
GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：507；found：507(1)，286(8)，257(12)，205(12)，189(30)，145(100).
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：2.170(s，3H，SCH
3)，3.680(s，3H，OCH
3)，3.815(s，3H，OCH
3)，5.210(s，2H，CH
2O)，7.155～7.591(m，5H，ph H+C＝C H)，7.901(s，1H，ph H)，7.976(s，2H，ph H).
Embodiment 2
The preparation method of compound 02 in this example instruction card 1.
α-methoxyl group-3, synthesizing of 5-dual-trifluoromethyl benzaldehyde oxime: in 10-25 ℃, will be by the α-chloro-3 of embodiment 1 preparation, 5-dual-trifluoromethyl benzaldehyde oxime (90.0%, 4.70g=14.5mmol) slowly be added drop-wise to the methanol solution (8% of sodium methylate, 30.5g=45.0mmol) in, insulation reaction 0.5-1.0hr.Mixture is poured in a large amount of frozen water, used ethyl acetate extraction 2 times, the extract of merging washs 2-3 time with icy salt solution, anhydrous Na
2SO
4Drying concentrates, and gets white viscous solid 4.08g, content 70.5% (GC), yield 69.1%.
GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：287；found：287(20)，286(40)，268(18)，255(15)，240(100)，213(40).
2-[2-[α-methoxyl group-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl]-3-methoxy-methyl acrylate (02 compound):
With potassium hydroxide (0.56g=10mmol) and N, dinethylformamide (15ml) adds in the exsiccant there-necked flask, stir 5-10min after, under-5-0 ℃, drip above-mentioned oxime (70.5%, N 2.85g=7.0mmol), dinethylformamide solution (3ml).After stirring 0.5hr, with (E)-2-[2-(brooethyl) phenyl]-N of 3-methoxy-methyl acrylate (2.58g=9.0mmol), dinethylformamide (10ml) drips of solution is added in the above-mentioned reaction mixture, in 15-25 ℃ of insulation reaction 10-12hr.Mixture is poured in the frozen water, used ethyl acetate extraction 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 10) with ethyl acetate and sherwood oil gets title compound 1.01g for elutriant carries out column chromatography, and 95.0% (GC-MS) is white solid, yield 27.9%, fusing point: 86.3-86.6 ℃.
GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：491；found：491(0.5)，460(1)，241(10)，205(12)，189(40)，145(100).
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：3.693(s，3H，OCH
3)，3.832(s，3H，OCH
3)，4.148(s，3H，OCH
3)，5.064(s，2H，OCH
2)，7.172-8.181(m，8H，PhH+CH＝).
Embodiment 3
The preparation method of compound 03 in this example instruction card 1.
2-bromo-3 ', synthesizing of 5 '-bis trifluoromethyl methyl phenyl ketone: to magnetic stir bar is housed, prolong, thermometer, constant pressure funnel and drying tube, in the 250ml there-necked flask of device for absorbing tail gas, add 3,5-bis trifluoromethyl methyl phenyl ketone (25.6g=0.1mol), anhydrous diethyl ether (100ml) and aluminum trichloride (anhydrous) (1g), after stirring, ice-water bath is chilled to 5-10 ℃, and dropping liquid bromine (17.6g=0.11mol) from dropping funnel drips 1-2 earlier and drips, after treating that color disappears, control speed drips, drip finish after, behind the insulation reaction 2-3hr, again in room temperature reaction 1-2hr, add frozen water (200g), extracted with diethyl ether is told organic layer, the saturated common salt water washing, anhydrous sodium sulfate drying, precipitation get thick product 26.6g, yield 79.4%.
GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：334；found：334.
2-methylthio group-3 ', synthesizing of 5 '-bis trifluoromethyl methyl phenyl ketone: with 2-bromo-3 ', 5 '-bis trifluoromethyl methyl phenyl ketone (8.38g=0.025mol), sodium methyl mercaptide (20%, 11.0g=0.03mol) and water (10g) behind 50-60 ℃ of stirring reaction 2-3hr, ethyl acetate extraction is washed to neutrality, anhydrous sodium sulfate drying, precipitation gets thick product 6.2g, content 92.0% (GC-MS), yield 75.6%.
LC-MS(APCI，Neg)(M
+-1)：calc：301 found：301。
2-methylthio group-3 ', synthesizing of 5 '-bis trifluoromethyl methyl phenyl ketone oxime: in 20-25 ℃, to 2-methylthio group-3 ', 5 '-bis trifluoromethyl methyl phenyl ketone (92.0%, 5.9g=18mmol), drip (30% in the mixture of oxammonium hydrochloride (1.72g=24.7mmol) and ethanol (15ml), 4.8g=36mmol) aqueous sodium hydroxide solution, after drip finishing, in 75-80 ℃ of reaction 4-5hr, cooling, 10% hydrochloric acid transfers to neutrality, ethyl acetate extraction is washed to neutrality, anhydrous sodium sulfate drying, decompression removes solvent, get 2-methylthio group-3 ', 5 '-bis trifluoromethyl methyl phenyl ketone oxime white solid 4.1g, total content 92.1% (GC), yield 65.9%, fusing point: 109.2-110.1 ℃.
GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：317；found：317(20)，298(15)，271(100)，270(30)，255(15)，240(30)，239(85)，219(25).
2-[2-[1-(3, the 5-bis trifluoromethyl phenyl)-2-methylthio group-ethyleneamines oxygen methyl]-phenyl]-3-methoxy-methyl acrylate (03 compound): with sodium hydride (60%, 1.0g=25mmol and N, dinethylformamide (15ml) adds in the exsiccant there-necked flask, after stirring 5-10min, under-5-0 ℃, drip above-mentioned oxime (92.1%, 4.1g=11.9mmol) N, dinethylformamide (10ml) solution.After stirring 0.5hr, will) (E)-2-[2-(brooethyl) phenyl]-(N of 3.6g=12.6mmol, dinethylformamide (10ml) drips of solution is added in the above-mentioned reaction mixture 3-methoxy-methyl acrylate, insulation reaction 0.5-1.0hr.Mixture is poured in the frozen water, used ethyl acetate extraction 2 times, the extract of merging washs 2-3 time with icy salt solution, anhydrous Na
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 20) with ethyl acetate and sherwood oil gets title compound 1.52g for elutriant carries out column chromatography, and content 90.2% (GC) is viscous liquid, yield 22.1%.
LC-MS(APCI，Pos)(M
++1)(relative intensity％)：calc：522，found：522.2.
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：2.037(s，3H，SCH
3)，3.829(s，2H，CH
2)，3.698(s，3H，OCH
3)，3.830(s，3H，OCH
3)，5.196(s，2H，CH
2)，7.180～7.608(m，5H，Ph H)，7.859(s，1H，Ph H)，8.174(s，2H，Ph H).
Embodiment 4
The preparation method of compound 05 in this example instruction card 1.
2-methoxy imino-2-[2-[α-methoxyl group-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl] methyl acetate (05 compound): with potassium hydroxide (0.56g=10mmol) and N, dinethylformamide (15ml) adds in the exsiccant there-necked flask, after stirring 5-10min, under-5-0 ℃, drip and press α-methoxyl group-3 that embodiment 2 methods prepare, 5-dual-trifluoromethyl benzaldehyde oxime (70.5%, 2.85g=7.0mmol) N, dinethylformamide solution (3ml).After stirring 0.5hr, with (E)-2-[2-(brooethyl) phenyl]-N of 2-methoxy imino methyl acetate (2.58g=9.0mmol), dinethylformamide (10ml) drips of solution is added in the above-mentioned reaction mixture insulation reaction 0.5-1.0hr.Mixture is poured in the frozen water, used ethyl acetate extraction 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 15) with ethyl acetate and sherwood oil gets title compound 1.12g for elutriant carries out column chromatography, and content 91.0% (GC) is white solid, yield 29.6%, fusing point 71.6-73.7 ℃.
GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：492；found：492(0)，461(8)，241(35)，222(40)，205(15)，190(30).146(25)，131(70)，116(100)，59(30).
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)3.836(s，3H，OCH
3)，4.042(s，3H，OCH
3)，4.114(s，3H，OCH
3)，5.020(s，2H，CH
2)，7.187～7.533(m，4H，ph H)，7.854(s，1H，ph H)，8.145(s，2H，ph H).
Embodiment 5
The preparation method of compound 06 in this example instruction card 1.
2-methoxy imino-2-[2-[alpha-methylmercapto-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl] methyl acetate (06 compound): with sodium hydride (60%, 0.36g=9.0mmol) and N, dinethylformamide (15ml) adds in the exsiccant there-necked flask, stir 5-10min after, under-5-0 ℃, drip alpha-methylmercapto-3,5-dual-trifluoromethyl benzaldehyde oxime (82%, N 2.59g=7.0mmol), dinethylformamide (5ml) solution.Behind the stirring reaction 0.5hr, with (E)-2-[2-(brooethyl) phenyl]-N of 2-methoxy imino methyl acetate (2.58g=9.0mmol), dinethylformamide (10ml) drips of solution is added in the above-mentioned reaction mixture insulation reaction 0.5-1.0hr.Mixture is poured in the frozen water, used ethyl acetate extraction 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 10) with ethyl acetate and sherwood oil gets title compound 1.06g for elutriant carries out column chromatography, is oily matter, content 92.0% (GC), yield 27.4%.
LC-MS(APCI，Pos)(M
++1)(relative intensity％)：calc：509，found：509.2.
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：2.146(s，3H，SCH
3)，3.821(s，3H，OCH
3)，4.043(s，3H，OCH
3)，5.167(s，2H，CH
2O)，7.184～7.493(m，4H，ph H)，7.901(s，1H，ph H)，7.949(s，2H，ph H).
Embodiment 6
The preparation method of compound 10 in this example instruction card 1.
2-methoxy imino-N-methyl-2-[2-[alpha-methylmercapto-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl] ethanamide (10 compound): with 2-methoxy imino-2-[2-[alpha-methylmercapto-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl] methyl acetate (92%, 0.61g=1.1mmol) with the methanol solution of the methylamine of 3-5 times of mol ratio, behind stirring at room reaction 15-20hr, mixture is poured in the frozen water, with ethyl acetate extraction 2 times, the extract that merges washes anhydrous Na with water 2-3 time
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 10) with ethyl acetate and sherwood oil gets title compound 0.38g for elutriant carries out column chromatography, is white solid, content 93.4%, yield 63.3%, fusing point: 132.1-133.9 ℃.
LC-MS(APCI，Pos)(M
++1)(relative intensity％)：calc：508，found：508.2.
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：2.150(s，3H，SCH
3)，2.870(d，3H，NCH
3)，3.945(s，3H，OCH
3)，5.178(s，2H，CH
2)，6.798(s，1H，NH)，7.194～7.517(m，4H，ph H)，7.900(s，1H，ph H)，7.953(s，2H，ph H).
Embodiment 7
The preparation method of compound 11 in this example instruction card 1.
2-methoxy imino-N-methyl-2-[2-[α-methoxyl group-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl] ethanamide (11 compound): with 2-methoxy imino-2-[2-[α-methoxyl group-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl] methyl acetate (91.0%, 0.61g=1.1mmol) with the methanol solution of the methylamine of 3-5 times of mol ratio, behind stirring at room reaction 15-20hr, mixture is poured in the frozen water, with ethyl acetate extraction 2 times, the extract that merges washes anhydrous Na with water 2-3 time
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 10) with ethyl acetate and sherwood oil gets title compound 0.32g for elutriant carries out column chromatography, is white solid, content 95.4%, yield 55.1%, fusing point: 156.5-157.4 ℃.
LC-MS(APCI，Pos)(M
++1)(relative intensity％)：calc：491，found：491.2.
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：2.865(d，3H，NCH
3)，3.950(s，3H，OCH
3)，4.118(s，3H，OCH
3)，5.169(s，2H，CH
2)，6.808(s，1H，NH)，7.214～7.521(m，4H，ph H)，7.900(s，1H，ph H)，7.948(s，2H，ph H).
Embodiment 8
The preparation method of compound 16 in this example instruction card 1.
α-ethylmercapto group-3, synthesizing of 5-dual-trifluoromethyl benzaldehyde oxime: with 3,5-dual-trifluoromethyl benzaldehyde oxime (12.85g=0.05mol) is dissolved in the methyl alcohol (200ml), under-5-0 ℃, slowly drips t-butyl hypochlorate (5.5g=0.05mol), behind about 0.5-1.0hr, drip equimolar triethylamine and sulfur alcohol successively, after drip finishing, continue reaction 1-2hr, reaction mixture is poured in the water, ethyl acetate extraction, icy salt solution is washed till neutrality, anhydrous sodium sulfate drying, decompression removes solvent, get alpha-methylmercapto-3,5-dual-trifluoromethyl benzaldehyde oxime 12.57g, content 95.2% (GC-MS), be yellow viscous liquid, yield 75.5%.
GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：317；found：317(30)，289(25)，257(100)，240(80)，239(85)，220(70)，213(62)，189(15)，170(60)，61(70).
2-[2-[α-ethylmercapto group-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl]-3-methoxy-methyl acrylate (16 compound): with potassium hydroxide (0.56g=10mmol) and N, dinethylformamide (15ml) adds in the exsiccant there-necked flask, after stirring 5-10min, under-5-0 ℃, drip above-mentioned oxime (95.2%, N 2.33g=7.0mmol), dinethylformamide solution (5ml).Behind the stirring reaction 0.5hr, with (E)-2-[2-(brooethyl) phenyl]-N of 3-methoxy-methyl acrylate (2.58g=9.0mmol), dinethylformamide solution (10ml) is added drop-wise in the above-mentioned reaction mixture, in 15-25 ℃ of insulation reaction 10-12hr.Mixture is poured in the trash ice, used ethyl acetate extraction 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 15) with ethyl acetate and sherwood oil gets title compound 1.08g for elutriant carries out column chromatography, and content 95.0% is white solid, yield 28.9%, fusing point: 79.6-80.1 ℃.
LC-MS(APCI，Pos)(M
++1)(relative intensity％)：calc：522，found：522.2.
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：1.138-1.187(t，3H，CH
3)，2.684-2.757(q，2H，SCH
2)，.700(s，3H，OCH
3)，3.819(s，3H，OCH
3)，5.222(s，2H，OCH
2)，7.161-7.169(d，1H，CH)，7.327-7.600(m，4H，oximePhH)，7.896-8.043(2s.2H，PhH).
Embodiment 9
The preparation method of compound 20 in this example instruction card 1.
α-oxyethyl group-3,5-dual-trifluoromethyl benzaldehyde oxime synthetic: with reference to embodiment 2 synthetic α-methoxyl groups-3, the method for 5-dual-trifluoromethyl benzaldehyde oxime is synthesized.
GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：301：found：301(5)，282(10)，241(100)，213(25)，170(10).
2-[2-[α-oxyethyl group-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl]-3-methoxy-methyl acrylate (20 compound): with potassium hydroxide (0.56g=10mmol) and N, dinethylformamide (15ml) adds in the exsiccant there-necked flask, after stirring 5-10min, under-5-0 ℃, drip above-mentioned oxime (85.5%, N 2.47g=7.0mmol), dinethylformamide solution (3ml).After stirring 0.5hr, with (E)-2-[2-(brooethyl) phenyl]-N of 3-methoxy-methyl acrylate (2.58g=9.0mmol), dinethylformamide (10ml) drips of solution is added in the above-mentioned reaction mixture, in 15-25 ℃ of insulation reaction 10-12hr.Mixture is poured in the frozen water, used ethyl acetate extraction 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 10) with ethyl acetate and sherwood oil gets thick shape title compound 1.17g, 95.4% (GC-MS), yield 31.58% for elutriant carries out column chromatography.
LC-MS(APCI，Pos)(M
++1)(relative intensity％)：calc：505，found：505.2.
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：1.239-1.278(t，3H，CH
3)，3.693(s，3H，OCH
3)，3.832(s，3H，OCH
3)，4.584-4.667(q，2H，OCH
2)，5.064(s，2H，OCH
2)，7.172-8.181(m，8H，PhH+CH＝).
Embodiment 10
The preparation method of compound 63 in this example instruction card 1.
N-methoxyl group-N-[2-[alpha-methylmercapto-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl] Urethylane (compound 63): with sodium hydride (60%, 0.36g=9.0mmol) and N, dinethylformamide (15ml) adds in the exsiccant there-necked flask, stir 5-10min after, under-5-0 ℃, drip alpha-methylmercapto-3,5-dual-trifluoromethyl benzaldehyde oxime (82%, N 2.59g=7.0mmol), dinethylformamide solution (5ml).Behind the stirring reaction 0.5hr, with the N of N-methoxyl group-N-(2-2-bromomethylphenyl) Urethylane (2.47g=9.0mmol), dinethylformamide solution (10ml) is added drop-wise in the above-mentioned reaction mixture, insulation reaction 0.5-1.0hr.Mixture is poured in the trash ice, used ethyl acetate extraction 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 10) with ethyl acetate and sherwood oil gets title compound 1.01g for elutriant carries out column chromatography, is viscous liquid, content 90.0%, yield 26.2%.
LC-MS(APCI，Pos)(M
++1)(relative intensity％)：calc：537，found：537.2.
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：2.190(s，3H，SCH
3)，3.745(s，3H，OCH
3)，3.784(s，3H，OCH
3)，5.344(s，2H，CH
2)，7.261～7.573(m，4H，ph H)，7.910(s，1H，ph H)，7.959(s，2H，ph H).
Embodiment 11
The preparation method of compound 73 in this example instruction card 1.
[2-[alpha-methylmercapto-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl] (5,6-dihydro-1,4,2-dioxazine-3-yl) ketone O-methyloxime (73 compound): (60%, 0.36g=9.0mmol) and N, dinethylformamide (15ml) adds in the exsiccant there-necked flask with sodium hydride, after stirring 5-10min, under-5-0 ℃, drip alpha-methylmercapto-3,5-dual-trifluoromethyl benzaldehyde oxime (82%, 2.59g=7.0mmol) N, dinethylformamide (5ml) solution.Behind the stirring reaction 0.5hr, with [2-(brooethyl) phenyl] (5,6-dihydro-1,4,2-dioxazine-3-yl) N of ketone O-methyloxime (2.58g=9.0mmol), dinethylformamide (10ml) drips of solution is added in the above-mentioned reaction mixture insulation reaction 0.5-1.0hr.Reactant is poured in the trash ice, used ethyl acetate extraction 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 10) with ethyl acetate and sherwood oil gets title compound 1.11g for elutriant carries out column chromatography, is viscous liquid, content 90%, yield 26.6%.
LC-MS(APCI，Pos)(M
++1)(relative intensity％)：calc：536，found：536.2.
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：2.174(s，3H，SCH
3)，3.977(s，3H，OCH
3)，4.146-4.147(t，2H，CH
2)，4.463-4.490(t，2H，CH
2)，5.222(s，2H，CH
2)，7.178～7.488(m，4H，ph H)，7.901(s，1H，ph H)，7.981(s，2H，ph H).
Embodiment 12
The preparation method of compound 117 in this example instruction card 1.
4-[2-[alpha-methylmercapto-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl]-2,4-dihydro-5-methoxyl group-2-methyl-3H-1,2,4-triazole-3-ketone (117 compound): with aqueous sodium hydroxide solution (20%, 1.8g=9.0mmol) and toluene (10ml) add in the there-necked flask, after stirring 5-10min,, drip alpha-methylmercapto-3 in room temperature, 5-dual-trifluoromethyl benzaldehyde oxime (82%, toluene 2.59g=7.0mmol) (5ml) solution.Behind the stirring reaction 0.5hr, with 4-(2-2-bromomethylphenyl)-2,4-dihydro-5-methoxyl group-2-methyl-3H-1,2, toluene (5ml) solution and the Tetrabutyl amonium bromide (0.8g) of 4-triazole-3-ketone (2.68g=9.0mmol) are added drop-wise in the above-mentioned reaction mixture, behind 50-60 ℃ of insulation reaction 4-5hr, mixture is poured in the trash ice, with ethyl acetate extraction 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 10) with ethyl acetate and sherwood oil gets title compound 1.03g for elutriant carries out column chromatography, content 90.0%, yield 25.5%.
LC-MS(APCI，Pos)(M
++1)(relative intensity％)：calc：521，found：521.0.
Embodiment 13
The preparation method of compound 120 in this example instruction card 1.
2-[2-(3,5-dual-trifluoromethyl benzene oxygen ylmethyl)-phenyl]-3-methoxy-methyl acrylate (51 compound): with sodium hydride (60%, 0.92g=23mmol) and N, dinethylformamide (8mL) adds in the exsiccant there-necked flask, after stirring 5-10min, under 15-20 ℃, drip 3, the N of 5-dual-trifluoromethyl phenol (3.0g=13mmol), dinethylformamide (8mL) solution.After stirring 0.5hr, with (E)-2-[2-(brooethyl) phenyl]-N of 3-methoxy-methyl acrylate (3.8g=13mmol), dinethylformamide (8ml) drips of solution is added in the above-mentioned reaction mixture insulation reaction 2-3hr.Mixture is poured in the frozen water, used ethyl acetate extraction 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 10) with ethyl acetate and sherwood oil gets thick title compound 3.22g, content 95.0% (GC), yield 54.2% for elutriant carries out column chromatography.
LC-MS(APCI，Pos)(M
++1)(relative intensity％)：calc：435，found：435.2.
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：3.723(s，3H，OCH
3)，3.836(s，3H，OCH
3)，5.050(s，2H，CH
2O)，7.182～7.617(m，8H，ph H+＝C H).
Embodiment 14
The preparation method of compound 124 in this example instruction card 1.
1-(3, the 5-bis trifluoromethyl phenyl)-2-methylthio group ethanol synthetic: in 10-20 ℃, to 2-methylthio group-3 ', 5 '-bis trifluoromethyl methyl phenyl ketone (88%, 4.5g=13mmol) and in the mixture of ethanol (5ml), drip by sodium borohydride 1.0g (26mmol), water (3g), the mixture that sodium hydroxide (0.1g) and ethanol (5g) are formed, drip finish after, continue insulation reaction to there not being raw material.Ethyl acetate extraction is washed to neutrality, and anhydrous sodium sulfate drying, precipitation get thick product 3.2g, content 92% (GC), yield 73.8%.
2-[[2-[1-(3, the 5-bis trifluoromethyl phenyl)-and the 2-methylthio group] ethoxymethyl] phenyl]-3-methoxy-methyl acrylate (124 compound): with sodium hydride (60%, 0.36g=9.0mmol) and tetrahydrofuran (THF) (15ml) add in the exsiccant there-necked flask, under the room temperature, drip above-mentioned alcohol (92%, first hydrogen furans (3ml) solution 2.32g=7.0mmol).0.5hr after, with (E)-2-[2-(brooethyl) phenyl]-tetrahydrofuran (THF) (10ml) drips of solution of 3-methoxy-methyl acrylate (2.58g=9.0mmol) is added in the above-mentioned reaction mixture insulation reaction 2-3hr.Mixture is poured in the frozen water, used ethyl acetate extraction 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 10) with ethyl acetate and sherwood oil gets title compound 0.80g for elutriant carries out column chromatography, and 90.0% (GC) is viscous liquid, yield 20.2%.
LC-MS(APCI，Pos)(M
++1)(relative intensity％)：calc：509，found：509.2.
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：2.036(s，3H，SCH
3)，2.660～2.939(m，2H，CH
2)，3.628(s，3H，OCH
3)，3.737(s，3H，OCH
3)，4.218-4.426(q，2H，CH
2)，4.537(t，1H，CH)，7.104～7.563(m，5H，Ph H+C＝CH)，7.819(s，1H，ph H)，7.842(s，2H，ph H)
Embodiment 15
The preparation method of compound 139 in this example instruction card 1.
N-chloracetyl-3; synthesizing of 5-bis trifluoromethyl aniline: to magnetic stir bar is housed; prolong; thermometer; constant pressure funnel and drying tube; in the dry there-necked flask of device for absorbing tail gas; add 3; 5-bis trifluoromethyl aniline (22.9g=0.10mol); triethylamine (11.6g=0.115mol) and toluene (60ml); after stirring; ice-water bath is chilled to 10-15 ℃, drips chloroacetyl chloride (12.5g=0.11mol) from dropping funnel, after drip finishing; in room temperature reaction 2-3hr; add frozen water (200g), ethyl acetate extraction is told organic layer; the saturated common salt water washing; anhydrous sodium sulfate drying, precipitation get the thick product 24.2g of white solid, yield 79.3%.
N-first sulphur ethanoyl-3,5-bis trifluoromethyl aniline synthetic: with N-chloracetyl-3, the aqueous solution (20% of 5-bis trifluoromethyl aniline (15.28g=0.05mol), sodium methyl mercaptide; 24.5g=0.07mol) and ethanol (50ml), under 50-60 ℃, stirring reaction 2-3hr; add frozen water (200g); ethyl acetate extraction 2 times is told organic layer, the saturated common salt water washing; anhydrous sodium sulfate drying; precipitation gets oily crude product 11.2g, content 92%, yield 65.0%.
N-first sulphur ethanethioyl-3,5-bis trifluoromethyl aniline synthetic: with N-first sulphur ethanoyl-3,5-bis trifluoromethyl aniline (92%; 11.2g=32.5mmol), thiophosphoric anhydride (7.22g=32.5mmol) and toluene (40ml), under 80-90 ℃, stirring reaction 3-4hr; add frozen water (200g); ethyl acetate extraction 2 times is told organic layer, the saturated common salt water washing; anhydrous sodium sulfate drying; precipitation gets oily crude product 6.5g, content 90%, yield 54.0%.
2-[2-[[1-(3; 5-bis trifluoromethyl phenyl imido grpup)-and the 2-methylthio group] ethyl] thiomethyl] phenyl]-3-methoxy-methyl acrylate (139 compound): with salt of wormwood (2.76g=0.02mol) and N; dinethylformamide (25ml) adds in the exsiccant there-necked flask; after stirring 5-10min; in room temperature, drip N-first sulphur ethanethioyl-3,5-bis trifluoromethyl aniline (90%; 3.7g=0.01mol) N, dinethylformamide (8ml) solution.Behind the stirring reaction 15min, drip (E)-2-[2-(brooethyl) phenyl]-N of 3-methoxy-methyl acrylate (2.85g=0.01mol), dinethylformamide (10ml) solution, drip finish after, continue reaction 3-4hr.Mixture is poured in the frozen water, used ethyl acetate extraction 2 times, the extract of merging washes with water 2-3 time, anhydrous Na
2SO
4Drying concentrates, and gets thick product.Mixed solution (1: 10) with ethyl acetate and sherwood oil gets title compound 1.48g for elutriant carries out column chromatography, content 93%, yield 25.6%.
LC-MS(APCI，Pos)(M
++1)(relative intensity％)：calc：537，found：537.2.
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：2.164(s，3H，SCH
3)，3.348(s，2H，SCH
2)，3.678(s，3H，OCH
3)，3.846(s，3H，OCH
3)，4.185(s，2H，CH
2S)，7.017～7.746(m，8H，ph H+C＝C H)
Embodiment 16
Preparation missible oil: with 20 parts of (weight meter) methoxy acrylate compounds that contain bis trifluoromethyl phenyl provided by the invention, 73 parts of thinners such as dimethylbenzene and 7 parts of suitable auxiliary agent uniform mixing can prepare missible oil, and dilute with water can be used (active compound content is 20%).
Embodiment 17
(01) compound 2-[2-[alpha-methylmercapto-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl]-preparation of 3-methoxy-methyl acrylate 20% missible oil: with 20 parts of compounds 01 (weight meter), 73 parts of thinners such as dimethylbenzene and 7 parts of suitable auxiliary agent uniform mixing can prepare missible oil, and dilute with water can be used (active compound content is 20%).
Embodiment 18
Preparation wettable powder: with the methoxy acrylate compound of 20 parts of (by weight) bis trifluoromethyl phenyls provided by the invention, 53 parts of clays, 20 parts of white carbon blacks, 5 parts of lignin silicate and 2 parts of polyoxy ethyl alkyl oxide mixing are worn into fine powder and can be made wettable powder (active compound content is 20%).
Give birth to and survey embodiment
Institute's synthetic compound is carried out sterilization, killed mite and insecticidal activity test, now listed the experimental result of part of compounds.
The fungicidal activity of 19 pairs of wheat powdery mildews of embodiment (Erysiphe graminis)
Method is as follows: testing compound is dissolved in suitable solvent such as the acetone, is diluted with water to desired concn again.This solution is sprayed onto treated to dry on the measuring plants 2 hours, carry out the germ inoculation after one day.Activity in per-cent, is divided into A, B, C, D level Four with respect to blank, and prevention effect 100%-90% is the A level, and prevention effect 90%-70% is the B level, and prevention effect 70%-50% is the C level, and prevention effect 0%-50% is the D level.
Dispenser was inoculated after one day.10-15 days " Invest, Then Investigate " results are placed in the inoculation back in the artificial climate greenhouse.Partial test the results are shown in Table 2 and table 3.
Table 2 part of compounds and oxime bacterium ester when test concentrations is 500mg/l to the fungicidal activity of wheat powdery mildew (Erysiphegraminis)
| Compound | Active rank | Compound | Active rank | Compound | Active rank | Compound | Active rank |
| 01 | A | 12 | A | 28 | A | 94 | A |
| 02 | A | 13 | B | 63 | A | 124 | D |
| 03 | D | 14 | B | 64 | A | 135 | A |
| 04 | A | 16 | A | 65 | A | 136 | A |
| 05 | A | 17 | A | 70 | A | 139 | A |
| 06 | A | 18 | A | 73 | A | 140 | A |
| 08 | A | 19 | A | 74 | A | 149 | A |
| 09 | A | 20 | A | 75 | A | 151 | A |
| 10 | A | 21 | A | 79 | A | 224 | A |
| 11 | A | 27 | A | 82 | A | Oxime bacterium ester | A |
Table 3 part of compounds and oxime bacterium ester when test concentrations is 25mg/l to the fungicidal activity of wheat powdery mildew (Erysiphegraminis)
| Compound | Active rank | Compound | Active rank | Compound | Active rank | Compound | Active rank |
| 01 | A | 06 | A | 12 | A | 73 | A |
| 02 | A | 09 | A | 16 | A | 75 | A |
| 04 | B | 10 | A | 63 | A | 224 | B |
| 05 | A | 11 | A | 65 | A | Oxime bacterium ester | A |
The fungicidal activity of 20 pairs of rice blast fungus of embodiment (Pyricularia oryzae)
Method is as follows: the mother liquor that test compounds is made into predetermined concentration with suitable thinner (as acetone), get 1 milliliter of soup in 50 milliliters of PDA substratum that dissolve with transfer pipet, after fully shaking up, pour into respectively in 3 culture dish and repeat as 3 times, cooling back is that 5 millimeters bacterium cake places culture dish central authorities with inoculating needle picking diameter, establishes thinner simultaneously for contrasting.Activity in per-cent, is divided into A, B, C, D level Four with respect to blank, and inverse amplification factor 100%-90% is the A level, and inverse amplification factor 90%-70% is the B level, and inverse amplification factor 70%-50% is the C level, and inverse amplification factor 0%-50% is the D level.
Put into the incubator of optimal temperature after inoculation finishes, measure the mycelial growth diameter after 3 days, calculate mycelial growth inhibition rate.Partial test the results are shown in Table 4.
Table 4 part of compounds and oxime bacterium ester when test concentrations is 25mg/l to the fungicidal activity of rice blast fungus (Pyriculariaoryzae)
| Compound | Active rank | Compound | Active rank | Compound | Active rank | Compound | Active rank |
| 01 | A | 10 | A | 19 | A | 75 | A |
| 02 | A | 11 | A | 20 | A | 119 | A |
| 03 | D | 12 | A | 21 | A | 120 | A |
| 04 | A | 13 | B | 27 | A | 139 | A |
| 05 | A | 14 | A | 63 | A | 140 | A |
| 06 | A | 16 | A | 64 | B | 157 | A |
| 07 | A | 17 | A | 65 | A | Oxime bacterium ester | A |
| 09 | A | 18 | A | 73 | A |
The acaricidal activity of 21 pairs of two-spotted spider mites of embodiment (Tetranychus urticae)
Method is as follows: the bean seedlings of selecting to grow fine are inoculated red spider, after treating that red spider grows surely, flooded 10 seconds being with the mite bean seedlings to cut in the soup for preparing, taking-up is inhaled with filter paper and is removed unnecessary soup, insert in the beaker that is filled with water, in observing indoor cultivation, checking after 24 hours survival and dead mite number has 100-200 mite on every strain bean seedlings.Experiment repeats 3 times.Results averaged.Activity in per-cent, is divided into A, B, C, D level Four with respect to blank, and mortality ratio 100%-90% is the A level, and mortality ratio 90%-70% is the B level, and mortality ratio 70%-50% is the C level, and mortality ratio 0%-50% is the D level.Partial test the results are shown in Table 5.
Table 5 part of compounds and oxime bacterium ester are to the acaricidal activity of two-spotted spider mite (Tetranychus urticae)
| Compound | Active (500mg/L) | Active (100mg/L) | Compound | Active (500mg/L) | Active (100mg/L) |
| 01 | A | A | 17 | A | A |
| 02 | A | A | 18 | A | A |
| 03 | A | B | 19 | A | C |
| 08 | B | D | 63 | A | -* |
| 09 | A | A | 65 | A | - |
| 10 | A | A | 120 | A | A |
| 11 | A | A | Oxime bacterium ester | D | D |
| 16 | A | A |
*No test
The insecticidal test of 22 pairs of rice green leafhoppers of embodiment (Nephotettix cincticeps)
Will be by the missible oil or the wettable powder that contains the methoxy acrylate compound of bis trifluoromethyl phenyl provided by the invention of above-mentioned Agrotechnical formulation embodiment method preparation, dilute with water is made into the pesticidal solutions of predetermined concentration, choosing two core rice seedlings immerses in the soup, take out after 5 seconds and dry, place Boiling tube, 20 or above rice green leafhopper nymph in 5 age are introduced in every pipe 20 strains then, the mouth of pipe is placed under the greenhouse experiment with white gauze wrapping, checks survival and dead borer population after 24 hours.Experiment repeats 3 times.Results averaged.Activity in per-cent, is divided into A, B, C, D level Four with respect to blank, and mortality ratio 100%-90% is the A level, and mortality ratio 90%-70% is the B level, and mortality ratio 70%-50% is the C level, and mortality ratio 0%-50% is the D level.Partial results sees Table 6.
Table 6 part of compounds and oxime bacterium ester are to the insecticidal activity of rice green leafhopper (Nephotettix cincticeps)
| Compound | Mortality ratio (500mg/L) | Active rank (500mg/L) |
| 01 | 20 | D |
| 02 | 100 | A |
| 03 | 25 | D |
| 09 | 60 | C |
| Oxime bacterium ester | 90 | A |
The activity experiment of 23 pairs of bean aphids of embodiment (Aphis fabae)
Will be by the missible oil or the wettable powder that contains the methoxy acrylate compound of bis trifluoromethyl phenyl provided by the invention of above-mentioned Agrotechnical formulation embodiment method preparation, dilute with water is made into the pesticidal solutions of predetermined concentration, bean aphid is connected on the bean seedlings that just have been unearthed, every strain connects more than 20, then bean seedlings is dipped in the soup together with the examination worm, takes out after 5 seconds, unnecessary soup is removed in suction, insert in the sponge of suction, cover, check survival and dead borer population after 24 hours with glass-tube.Repeat results averaged 3 times.Activity in per-cent, is divided into A, B, C, D level Four with respect to blank, and mortality ratio 100%-90% is the A level, and mortality ratio 90%-70% is the B level, and mortality ratio 70%-50% is the C level, and mortality ratio 0%-50% is the D level.Partial test the results are shown in Table 7.
Table 7 part of compounds and oxime bacterium ester are to the insecticidal activity of bean aphid (Aphis fabae)
| Compound | Active rank (500mg/L) | Active rank (100mg/L) | Compound | Active rank (500mg/L) | Active rank (100mg/L) |
| 01 | B | D | 05 | A | C |
| 02 | A | A | Oxime bacterium ester | A | - |
| 03 | A | C |
*No test
Claims (4)
1. have fungicidal, kill mite, the bioactive methoxy acrylate compound that contains bis trifluoromethyl phenyl of desinsection, it is characterized in that representing with general formula (I), (II) with (III):
Wherein:
I.A is selected from following group:
U is CH or N;
V is O, S or NH;
R ' is C
1～C
6Alkyl or H;
II.B is selected from following group:
XR R
1CHXR
B-1 B-2
X is O, S, SO, SO
2Or NH;
R is an alkyl;
R
1It is hydrogen or alkyl;
V.Y is selected from following group:
R
3Z Z
Y-1 Y-2 Y-3 Y-4
B defines among B such as the II;
Z is O, S, SO, SO
2Or NH;
R
3It is alkylidene group;
VI.K is selected from following group:
R
3Z Z
K-1 K-2 K-3 K-4
B defines among B such as the II;
Z defines among Z such as the V;
R
3As R among the V
3Define;
In the compound that provides above (I), (II) and the definition (III), no matter the separately use or be used in the compound word of used term, alkyl is meant the straight or branched alkyl with 1-6 carbon atom.
2. the methoxy acrylate compound that contains bis trifluoromethyl phenyl according to claim 1, it is characterized in that general formula (I), (II) and (III) shown in compound be:
2-[2-[α-methoxyl group-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl]-the 3-methoxy-methyl acrylate;
2-methoxy imino-2-[2-[α-methoxyl group-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl] methyl acetate;
2-[2-[alpha-methylmercapto-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl]-the 3-methoxy-methyl acrylate;
2-[2-[α-ethylmercapto group-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl]-the 3-methoxy-methyl acrylate;
2-[2-[α-oxyethyl group-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl]-the 3-methoxy-methyl acrylate;
2-[2-[1-(3, the 5-bis trifluoromethyl phenyl)-2-methylthio group-ethyleneamines oxygen methyl]-phenyl]-the 3-methoxy-methyl acrylate;
2-methoxy imino-2-[2-[alpha-methylmercapto-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl] methyl acetate;
2-methoxy imino-N-methyl-2-[2-[alpha-methylmercapto-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl] ethanamide;
2-methoxy imino-N-methyl-2-[2-[α-methoxyl group-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl] ethanamide;
[2-[alpha-methylmercapto-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl] (5,6-dihydro-1,4,2-dioxazine-3-yl) ketone O-methyloxime;
[2-[α-methoxyl group-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl] (5,6-dihydro-1,4,2-dioxazine-3-yl) ketone O-methyloxime;
2-[2-(3,5-dual-trifluoromethyl benzene oxygen ylmethyl)-phenyl]-the 3-methoxy-methyl acrylate;
2-[2-[α-(N-methylamino)-(3,5-bis trifluoromethyl Ben Yajiaji) amine oxygen methyl] phenyl]-the 3-methoxy-methyl acrylate.
3. the preparation method who contains the methoxy acrylate compound of bis trifluoromethyl phenyl according to claim 1 and 2, it is characterized in that at alkali potassium hydroxide, sodium hydride or salt of wormwood exist down, react general formula (I) or the compound (II) that promptly gets V ≠ NH with the compound of formula (IV) and the compound of formula V or formula (VI)
Y＝O，S
A, B, Y have the above-mentioned definition of giving in the formula, and L is leavings group Br.
4. the purposes that contains the methoxy acrylate compound of bis trifluoromethyl phenyl according to claim 1 and 2 is characterized in that having fungicidal under 18.75～375 gram effective constituent/hectare consumptions, killing mite, desinsection biological activity.
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