CN103242225A - Picolinate amino pyridine compound and preparation method thereof - Google Patents
Picolinate amino pyridine compound and preparation method thereof Download PDFInfo
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- CN103242225A CN103242225A CN2012100318246A CN201210031824A CN103242225A CN 103242225 A CN103242225 A CN 103242225A CN 2012100318246 A CN2012100318246 A CN 2012100318246A CN 201210031824 A CN201210031824 A CN 201210031824A CN 103242225 A CN103242225 A CN 103242225A
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- ABZKBRNXRVEVQX-UHFFFAOYSA-N CCN(Cc(cn1)ccc1Cl)c(nc(cc1)Cl)c1[N+]([O-])=O Chemical compound CCN(Cc(cn1)ccc1Cl)c(nc(cc1)Cl)c1[N+]([O-])=O ABZKBRNXRVEVQX-UHFFFAOYSA-N 0.000 description 1
- ZILFZCOQMGGHOZ-UHFFFAOYSA-N CCN(Cc(cn1)ccc1Cl)c(nc(cc1)N(C)C)c1[N+]([O-])=O Chemical compound CCN(Cc(cn1)ccc1Cl)c(nc(cc1)N(C)C)c1[N+]([O-])=O ZILFZCOQMGGHOZ-UHFFFAOYSA-N 0.000 description 1
- FCJFHODOZJWXJW-UHFFFAOYSA-N CN(Cc(cc1)cnc1Cl)c(nc(cc1)Cl)c1[N+]([O-])=O Chemical compound CN(Cc(cc1)cnc1Cl)c(nc(cc1)Cl)c1[N+]([O-])=O FCJFHODOZJWXJW-UHFFFAOYSA-N 0.000 description 1
- SGRPXRMZAKPZRE-UHFFFAOYSA-N CN(Cc(cn1)ccc1Cl)c1nc(OC)ccc1[N+]([O-])=O Chemical compound CN(Cc(cn1)ccc1Cl)c1nc(OC)ccc1[N+]([O-])=O SGRPXRMZAKPZRE-UHFFFAOYSA-N 0.000 description 1
- XALCOJXGWJXWBL-UHFFFAOYSA-N CNCc(cc1)cnc1Cl Chemical compound CNCc(cc1)cnc1Cl XALCOJXGWJXWBL-UHFFFAOYSA-N 0.000 description 1
- SKCNYHLTRZIINA-UHFFFAOYSA-N ClCc(cn1)ccc1Cl Chemical compound ClCc(cn1)ccc1Cl SKCNYHLTRZIINA-UHFFFAOYSA-N 0.000 description 1
- MIOCBYZCVQVHIQ-UHFFFAOYSA-N [O-][N+](C(C(N1)Cl)=CC=C1Cl)=O Chemical compound [O-][N+](C(C(N1)Cl)=CC=C1Cl)=O MIOCBYZCVQVHIQ-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N c1ccncc1 Chemical compound c1ccncc1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a picolinate amino pyridine compound which is shown in the formula (I) and has sterilizing, insect/mite killing and weeding bioactivity as well as a preparation method thereof, a sterilizing, insect/mite killing and weeding herbicide composition containing the compound, and an application and method for controlling fungi, insects/mites and weeds by using the compound.
Description
Technical field
The present invention relates to have desinsection, sterilization, the bioactive pyridyl-methanamine yl pyridines of weeding compounds and preparation method thereof, the desinsection that contains described compound, sterilization, herbicidal composition and with purposes and the method for these compounds control insects, fungi, weeds.
Background technology
Heterogeneous ring compound particularly pyridine-heterocyclic compound is a class important compound in pharmaceutical chemistry, and they have the biological activity of wide spectrum.Although the relevant heterogeneous ring compound particularly report of pyridine-heterocyclic compound is a lot.But relevant pyridyl-methanamine yl pyridines compounds removes Shiokawa in the heterogeneous ring compound that EP 0398084A2 replaces about the nitro shown in the general formula (A), has reported outside four compounds shown in formula (B)～formula (E), fails to find other bibliographical information.And from EP 0398084A2, can not find any biologically active data about four compounds shown in formula (B)～formula (E).
The control of insect, germ, weeds is extremely important in the process that realizes high-efficiency agriculture.The control of insect, germ, weeds simultaneously woods, herd, also very important in secondary, fishing and the public health.Though existing a lot of insects, germ, control of weeds agent on the market, but because problem such as the continuous expansion in market and insect, germ, the resistance of weeds, the work-ing life of medicine and the economy of medicine and people are to the pay attention to day by day of environment, need scientists constantly to study, and then exploitation efficient, the safety, economy, the Environmental compatibility and the desinsection with different modes of action, sterilization, weedicide new variety that make new advances.
For obtaining to have efficient, the broad-spectrum biological activity material of unique effect mechanism, we have designed and synthesized the pyridyl-methanamine yl pyridines compounds with desinsection, sterilization, weeding activity, compare with four compounds shown in the formula of reporting among the EP 0398084A2 (B)～formula (E), not only has different constructional features, and have more excellent and the biological activity of wide spectrum more, some compound demonstrates the biological activity suitable with the commercialization pesticide imidacloprid as 08 grade.
Summary of the invention
The invention provides pyridyl-methanamine yl pyridines compounds and the isomer thereof of the biologically active shown in the general formula (I):
Wherein:
I.R is hydrogen, halogen, nitro, cyano group, C
1～C
3Haloalkyl;
II.p is one 0 to 3 integer;
III.R
1And R
2Be identical or different, and representative
(a) hydrogen, halogen;
(b) alkyl, alkoxyl group, alkylthio, alkyl sulphonyl, alkyl sulphinyl, alkoxy carbonyl, alkenyl, alkenyl oxy, alkenyl thio, the alkenyl alkylsulfonyl, the alkenyl sulfinyl, alkynyl, the alkynyloxy base, the alkynyl sulfenyl, the alkynyl alkylsulfonyl, the alkynyl sulfinyl, cycloalkyl, cycloalkyl oxy, the cycloalkyl sulfenyl, the naphthene sulfamide base, the cycloalkyl sulfinyl, alkyl-carbonyl, aryl, aryloxy, artyl sulfo, the aryloxy carbonyl, aryl sulfonyl, aryl sulfonyl kia, heteroaryl, heteroaryl oxygen base, the heteroaryl sulfenyl, heteroaryl oxygen base carbonyl, heteroarylsulfonyl, the heteroaryl sulfinyl;
(c) NR
3R
4(R
3And R
4Be identical or different, and represent hydrogen, alkyl, alkoxyl group, alkylthio, alkyl sulphonyl, alkyl sulphinyl, alkoxy carbonyl, alkenyl, alkenyl oxy, alkenyl thio, the alkenyl alkylsulfonyl, the alkenyl sulfinyl, alkynyl, the alkynyloxy base, the alkynyl sulfenyl, the alkynyl alkylsulfonyl, the alkynyl sulfinyl, cycloalkyl, cycloalkyl oxy, the cycloalkyl sulfenyl, the naphthene sulfamide base, the cycloalkyl sulfinyl, alkyl-carbonyl, aryl, aryloxy, artyl sulfo, the aryloxy carbonyl, aryl sulfonyl, aryl sulfonyl kia, heteroaryl, heteroaryl oxygen base, the heteroaryl sulfenyl, heteroaryl oxygen base carbonyl, heteroarylsulfonyl, the heteroaryl sulfinyl);
(d) as determined implication, R in case of necessity in III. (a), III. (b) or III. (c)
1Or R
2In hydrogen atom can be partly or entirely be selected from following in identical or different substituting group replace:
Halogen, nitro, cyano group, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkoxyl group, alkylthio, amino, alkylamino, dialkyl amido, haloalkyl, alkenyl oxy, alkenyl thio, alkenyl amino, alkenyl alkyl, halogenated alkenyl, the alkynyloxy base, the alkynyl sulfenyl, alkynyl amino, the alkynyl alkyl, the halo alkynyl, cycloalkyl oxy, the cycloalkyl sulfenyl, cycloalkyl amino, cycloalkylalkyl, halogenated cycloalkyl, aryloxy, artyl sulfo, arylamino, arylalkyl, halogenated aryl, heteroaryl oxygen base, the heteroaryl sulfenyl, heteroaryl nitrogen base, heteroarylalkyl, the halo heteroaryl;
(e) as in III. (a), III. (b), III. (c) or III. (d), having determined aryl and the partly or entirely hydrogenation of heteroaryl of implication, wherein 1 or 2 CH
2Group can be replaced by CO;
IV.R
3Be halogen, C
1～C
3Alkyl, C
1～C
3Haloalkyl;
V.R=3-NO
2, R
2=CH
3The time, R
p 1≠ 6-Cl, 6-H;
VI.R=3-NO
2, R
2=CH (CH
3)
2The time, R
p 1≠ 6-H;
In the definition of the compound that provides above (I), no matter the separately use or be used in the compound word of used term represents following substituting group:
Halogen: refer to fluorine, chlorine, bromine and iodine;
Alkyl: the straight or branched alkyl that refers to have 1-6 carbon atom;
Alkoxyl group: refer to have the straight or branched alkoxyl group of 1-6 carbon atom, be connected on the structure through the Sauerstoffatom key;
Alkylthio: refer to have the straight or branched alkylthio of 1-6 carbon atom, be connected on the structure through the sulphur atom key;
Alkenyl: the straight or branched thiazolinyl that refers to have 2-6 carbon atom;
Alkynyl: the straight or branched alkynyl that refers to have 2-6 carbon atom;
Aryl: the naphthyl that refers to have the phenyl of 6 carbon atoms and have 12 carbon atoms;
Heteroaryl: the heteroaryl that refers to 10 carbon atoms of as many as;
Halo: refer to that 1, a plurality of or all hydrogen atoms are replaced by halogen, as 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.
Compound shown in (I) of the present invention, because the two keys of carbon-to-carbon double bond, carbon-to-carbon three key or carbon-nitrogen connect different substituents and can form geometrical isomer (representing different configurations with Z and E respectively), 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 relates to the mixture of geometrical isomer and any ratio of steric isomer.
The synthetic pyridyl-methanamine yl pyridines compounds shown in the general formula (I) that has of inventors of the present invention has broad spectrum activity: the compound that has can be used for preventing and treating the various harmful insects such as aphid etc.; The compound that has can be used for control 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 the various crops the various harmful insects such as aphid, also can be used for simultaneously preventing and treating on the various crops by multiple fungus-caused diseases such as Haplomycetes, Phycomycetes, Oomycete, Ascomycetes and deuteromycetes, and the compound that has has very high biological activity and makes just can obtain good effect under very low dosage.Specifically, part of compounds of the present invention has excellent activity to harmful insect such as aphid etc.
Can the present invention be described with the compound that following table 1～table 2 is listed, but not limit the present invention.Fusing point that the present invention gives is all not calibrated.The formula (B) reported among the EP 0398084A2 that the present invention synthesized and two compounds shown in the formula (C) have also been listed in table 1 and the table 2, the fusing point of the formula of reporting among the EP 0398084A2 (B) is 123～124 ℃, the fusing point of formula (C) is 71～74 ℃, the formula that the present invention synthesized (B) is liquid of vicidity, refrigerator is placed after fixing, and the fusing point of formula (C) is 71.4～72.7 ℃.
Table 1
Table 2
* Py H represents H on the pyridine ring
Compound shown in the formula of the present invention (I) can prepare by reaction formula 1, reaction formula 2 and the reaction formula 3 shown in following.All as preceding restriction, X ' and X are leavings group such as halogen (fluorine, chlorine, bromine), sulphonate etc. to substituting group wherein except specializing.
Reaction formula 1-1:
Reaction formula 1-2:
Reaction formula 2-1:
Reaction formula 2-2:
Reaction formula 3:
The compound of formula (I) can prepare (reaction formula 1-1) like this: at N, in dinethylformamide or benzene, toluene, the tetrahydrofuran (THF) equal solvent, in the presence of alkali such as sodium hydride or potassium hydroxide, salt of wormwood, in 25～80 ℃ or high to the solvent refluxing temperature, with the compound shown in the compound shown in the formula (II) and the formula (III) react the compound of formula (I).
The compound of formula (I) also can prepare (reaction formula 1-2) like this: at N, dinethylformamide or tetrahydrofuran (THF), water, methylene dichloride, benzene, in single solvents such as toluene or their mixed solvent, at sodium hydride or potassium hydroxide, alkali such as salt of wormwood exist down, in room temperature or high to the solvent refluxing temperature, with the compound of the compound shown in the formula (II) and formula (IV) react the compound of formula V, in alcohol or water equal solvent, add alkali metallic sodium or sodium alkoxide in case of necessity, sodium hydride etc., in room temperature or high to the solvent refluxing temperature, the compound of formula V and R
p 1H reacts, and gets the compound of formula (I).
The compound of formula (II) can prepare (reaction formula 2-1) like this: in the mixed solvent of single solvent such as trichloromethane or methylene dichloride, benzene, toluene or they and water or alcohol, in the presence of alkali such as sodium hydride or sodium hydroxide, salt of wormwood, in room temperature or high to the solvent refluxing temperature, compound shown in the formula (VI) and the reaction of compound (VII), get the compound of formula (II), but adding phase-transfer catalyst benzyltriethylammoinium chloride or Tetrabutyl amonium bromide etc. can impel reaction to carry out or accelerated reaction is carried out.
Formula (II:R
2=H) compound also can prepare (reaction formula 2-2) like this: at N, in dinethylformamide or the ethanol equal solvent, in room temperature or high to the solvent refluxing temperature, the compound reaction of the compound shown in the formula (VI) and formula (VIII) obtains the compound of formula (IX), in methyl alcohol or ethanol equal solvent, in room temperature or high to the solvent refluxing temperature, the compound of formula (IX) gets formula (II:R with reduction such as hydrazine or hydrazine hydrate, shortenings
2=H) compound.
The compound of formula (III) can prepare (reaction formula 3) like this: at solvent R
p 1Among the H, in subzero 15 ℃ or high to the solvent refluxing temperature, use R
p 1The compound of alkaline purification general formulas (IV) such as ONa or sodium hydride, sodium hydroxide, salt of wormwood gets the compound of formula (III).
The compound of formula (III) also can prepare (reaction formula 3) like this: at water or N, in the dinethylformamide equal solvent, in subzero 15 ℃ or high to the solvent refluxing temperature, use R
p 1The reaction of the compound of H and formula (IV) gets the compound of formula (III), can impel reaction to carry out or accelerated reaction is carried out but add suitable alkali such as triethylamine or sodium hydride, sodium hydroxide, salt of wormwood etc.
The compound of formula (III) can also prepare (reaction formula 3) like this: in benzene or toluene, sherwood oil equal solvent, in subzero 15 ℃ or high to the solvent refluxing temperature, in the presence of alkali such as sodium hydride or sodium hydroxide, salt of wormwood, use R
p 1The compound of H and formula (IV) react the compound of formula (III).
Pyridyl-methanamine yl pyridines compounds provided by the invention, biologically active and the compound that has have good biological activity. particularly aspect the preventing and treating of the diseases of agricultural, gardening and flowers, show high reactivity.Harmful organism described here include but not limited to this:
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 (Pyricularia oryzae); Stripe rust of wheat (Puccinia striformis), leaf rust (Puccinia recondita) and other rust; Big wheat yellow rust (Puccinia striformis), 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 (Gaeumannomyces graminis).The cercospora brown spot of peanut (Cercospora arachidicola) and the cercospora black spot of peanut (Cercosporidium personata); The mould genus of its tail spore on beet, soybean and the paddy is sick.Tomato, cucumber, grape grey mould (Botrytis cinerea).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 (Sclerotonia sclerotiorum); Wheat scab (Gibberella zeae); Phytophthora capsici disease (Phytophythora capsici).
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.
Injurious weed: monocotyledon weed lady's-grass, barnyard grass grass, Herba Setariae Viridis, hard Cao, Wang grass, bromegrass, amur foxtail, Triticum tauschii, alkali thatch, flower of Stinkgrass, wild avena sativa, rye grass; Broadleaf weed piemarker, chickweed, black nightshade, lamb's-quarters, recessed amaranth, Amaranthus retroflexus etc.
With pyridyl-methanamine yl pyridines compounds 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 the compound of general formula (I) 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 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 be conducive to store, 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 the carrier of mite and the pleasant to the ear usefulness of fungicidal composition.
Suitable solid carrier comprises natural and synthetic clay and silicate, for example diatomite, talcum, attapulgite, pure aluminium silicate (kaolin), montmorillonite and mica; Calcium 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.
Sterilization, desinsection/acaricidal composition are processed into the form of enriched material usually and are used for transportation with this, by the user it are diluted before using.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 tensio-active agent nonionic or ion.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 solid inert carrier, also contains 3-10% weight fraction powder, adds 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 mycocides, can have more broad spectrum activity than independent general formula (I) compound.In addition, but the Fungicidally active of other mycocide mutual-through type (I) compound has synergism.The example that can be included in the acaricide compound in the present composition has: methoxy acrylate series bactericidal agent, F-1991, derosal, m-tetrachlorophthalodinitrile, dimethomorph, triadimefon, cyanogen bacterium azoles, zinc manganese ethylenebisdithiocarbamate etc.
By in composition, adding other one or more sterilants, can have more broad spectrum activity than independent general formula (I) compound.In addition, but the insecticidal activity of other sterilant mutual-through type (I) compound has 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, chlorine insect amide, Flubendiamide etc.
Embodiment
The invention will be further described below in conjunction with embodiment, and the yield among the embodiment is all without optimization, and fusing point is not calibrated.
The preparation of compound (02) in the embodiment 1 present embodiment instruction card 1
In being furnished with the 250mL there-necked flask of magnetic stirring apparatus and drying tube, add 2-chloro-5-chloromethylpyridine (16.10g) and trichloromethane (60mL), behind the stirring at room 0.5-1.0hr, drip the ethylamine solution (18.0mL) of 60-70% and 20% the NaOH aqueous solution (40.0mL) respectively, after drip finishing, add benzyltriethylammoinium chloride (0.1g), the stirring at room reaction is spent the night.Regulate pH value to weakly alkaline, tell organic layer, water layer dichloromethane extraction secondary, after merging organic phase and washing twice with cryosel, anhydrous sodium sulfate drying.Concentrating under reduced pressure gets salmon liquid 2-chloro-5-ethamine picoline 15.9g, content 98.5%.GC-MS(M)(EI，70eV，m/z)(relative intensity％)calc：170；found：170.
In 100mL single port bottle, add 2-chloro-3-nitropyridine (1.60g) and 15mL N, dinethylformamide (DMF), salt of wormwood (2.63g), under the stirring at room, drip the 10.0mL DMF solution of 2-chloro-5-ethamine picoline (1.72g), drip and be warming up to 50-80 ℃ of reaction 3-5hr after finishing, after the cooling reaction solution is poured in the 100mL water, ethyl acetate extraction, washing, anhydrous sodium sulfate drying, concentrating under reduced pressure obtain the thick product of 2.62g.Be that eluent carries out column chromatography and gets yellow viscous liquid N-((2-chloropyridine-5-yl) methyl)-N-ethyl-3-nitropyridine-2-amine 1.49g, content 99.8%, yield 50.3% with 1: 5 ethyl acetate and sherwood oil mixed solution.GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：292；found：292；1HNMR(CDCl
3/TMS，300MHz)δ(ppm)：1.172(t，J＝6.9Hz，3H，CH
3)，3.252(q，J＝6.9Hz，2H，CH
2)，4.751(s，2H，CH
2)，6.776(m，1H，Py H)，7.259(d，J＝8.4Hz，1H，Py H)，7.680(d，J＝5.7Hz，1H，Py H)，8.058(d，J＝8.4Hz，1H，Py H)，8.299(d，J＝8，4Hz，1H，Py H)，8.364(s，1H，Py H).
The preparation of compound (08) in the embodiment 2 present embodiment instruction cards 1
Synthetic method with reference to 2-chloro-5-ethamine picoline among the embodiment 1 prepares 2-chloro-5-methylamine picoline.
In 100mL single port bottle, add 2,6-two chloro-3-nitropyridine (2.00g) and N, dinethylformamide (DMF 15mL), salt of wormwood (2.87g), under the stirring at room, drip DMF (8.0mL) solution of 2-chloro-5-methylamine picoline (1.60g), be warming up to 50-80 ℃ of reaction 3-5hr after drip finishing, after the cooling reaction solution is poured in the 100mL water, ethyl acetate extraction, anhydrous sodium sulfate drying, concentrating under reduced pressure obtain 6-chloro-N-((2-chloropyridine-5-yl) methyl)-N-methyl-3-nitro pyridine-2-amine brown viscous solid 3.07g, content 67.3%.GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：312；found：312。Without purification process, be directly used in next step and synthesize.
In being furnished with the 100mL there-necked flask of magnetic stirring apparatus and drying tube, add sodium Metal 99.5 (0.23g) and methyl alcohol (30mL), reaction does not produce to there being gas under the water-bath, drip methyl alcohol (10mL) solution of 6-chloro-N-((2-chloropyridine-5-yl) methyl)-N-methyl-3-nitro pyridine-2-amine (3.07g), drip and finish back normal-temperature reaction 3-5hr, reaction solution is poured in the 100mL water, ethyl acetate extraction, washing, anhydrous sodium sulfate drying, concentrating under reduced pressure obtain thick product 2.57g.Be that eluent carries out column chromatography and gets golden yellow solid 6-methoxyl group-N-((2-chloropyridine-5-yl) methyl)-N-methyl-3-nitro pyridine-2-amine 1.18g with 1: 10 ethyl acetate and sherwood oil mixed solution, content 99.0%, fusing point: 87.9-89.0 ℃, two step total recoverys 38.9%.GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：308；found：308；
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：2.876(s，3H，NCH
3)，3.827(s，3H，OCH
3)，4.895(s，2H，CH
2)，6.174(d，J＝9.0Hz，1H，Py H)，7.315(d，J＝8.4Hz，1H，Py H)，7.628-7.663(m，1H，Py H)，8.175(d，J＝9.0Hz，1H，Py H)，8.359(d，J＝2.4Hz，1H，Py H).
The preparation of compound (11) in the embodiment 3 present embodiment instruction cards 1
In the there-necked flask of the 250mL that is furnished with magnetic agitation, constant pressure funnel and drying tube, add 2,6-two chloro-3-nitropyridines (9.6g) and ethanol (60mL), behind the stirring at room 15-30min, drip ethanol (30mL) solution of sodium ethylate (3.4g), 30-45min drips off, during reaction 2-3h falls back under the room temperature, filter, dry faint yellow solid 2-chloro-6-oxyethyl group-3-nitropyridine 9.7g, content 80.0%, the GC-MS (M of getting
+) (EI, 70eV, m/z) (relative intensity%) calc:202; Found:202.
In 100mL single port bottle, add above-mentioned 2-chloro-6-oxyethyl group-3-nitropyridine (2.10g) and 15mLN, dinethylformamide (DMF), salt of wormwood (2.87g), under the stirring at room, drip DMF (10.0mL) solution of 2-chloro-5-methylamine picoline (1.60g), drip and be warming up to 50-80 ℃ of reaction 3-5hr after finishing, after the cooling reaction solution is poured in the 100mL water, ethyl acetate extraction, washing, anhydrous sodium sulfate drying, concentrating under reduced pressure obtain thick product 2.89g.Be that eluent carries out column chromatography and gets yellow viscous solid 6-oxyethyl group-N-((2-chloropyridine-5-yl) methyl)-N-methyl-3-nitro pyridine-2-amine 1.41g, content 97.0%, yield 51.1% with the mixed solution of 1: 10 ethyl acetate and sherwood oil.GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：322；found：322；
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：1.289(t，J＝7.2，3H，CH
3)，2.863(s，3H，CH
3)，4.198(q，J＝7.2Hz，2H，CH
2)，4.862(s，2H，CH
2)，6.148(d，J＝8.7Hz，1H，Py H)，7.301(d，J＝8.7Hz，1H，Py H)，7.609(d，J＝8.7Hz，1H，Py H)，8.169(d，J＝8.7Hz，1H，Py H)，8.341(s，1H，Py H).
The preparation of compound (33) in the embodiment 4 present embodiment instruction cards 1
In 100mL single port bottle, add 6-chloro-N-((2-chloropyridine-5-yl) methyl)-N-ethyl-3-nitropyridine-2-amine (2.50g) and N, dinethylformamide (DMF15mL), salt of wormwood (1.60g), under the stirring at room, drip 33% dimethylamine agueous solution (10.0mL), reaction 3-5hr, reaction solution is poured in the 100mL water, ethyl acetate extraction, anhydrous sodium sulfate drying, concentrating under reduced pressure obtain thick product 2.31g.Be that eluent carries out column chromatography and gets golden yellow solid 2-[N-((2-chloropyridine-5-yl) methyl)-N-ethyl with the mixed solution of 1: 10 ethyl acetate and sherwood oil]-6-dimethylin-3-nitropyridine-2-amine 0.91g, content 92.0%, fusing point: 93.7-95.1 ℃, yield 32.6%.GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：335；found：335；
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：(CDCl
3)：1.200(t，J＝7.2Hz，3H，CH
3)，3.074(s，6H，2CH
3)，3.296(q，J＝7.2Hz，2H，CH
2)，4.487(s，2H，CH
2)，5.980(d，J＝9.0Hz，1H，Py H)，7.266(d，J＝6.6Hz，1H，Py H)，7.076(d，J＝10.8Hz，1H，Py H)，8.149(d，J＝9.0Hz，1H，Py H)，8.531(s，1H，Py H).
The preparation of compound (44) in the embodiment 5 present embodiment instruction cards 1
In being furnished with the 250mL there-necked flask of magnetic stirring apparatus and drying tube, add O-phthalic acid imide sylvite (18.50g) and N, N-methylformamide (DMF100mL), behind the stirring at room 10-15min, drip DMF (40.0mL) solution of 2-chloro-5-chloromethylpyridine (16.20g), after drip finishing, stirring at room reaction 6-8hr.Reaction solution is poured in the water, filtered, dry N-(2-chloro-5-pyridyl) methylphthalic acid imines 19.05g, the content 97.5% of getting.GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：272；found：272.
Above-mentioned gained solid is dissolved in the ethanol (150mL), behind the mechanical stirring 15-30min, drip the 8-10mL hydrazine hydrate, backflow 2-6hr filters, and the aqueous sodium hydroxide solution with 20% is regulated pH value to alkalescence, dichloromethane extraction, washing, anhydrous sodium sulfate drying, decompression precipitation get weak yellow liquid 2-chloro-5-aminomethyl-pyridine 9.50g, content 99.0%, GC-MS (M
+) (EI, 70eV, m/z) (relative intensity%) calc:142; Found:142.
In 100mL single port bottle, add 2,3-two chloro-5-5-flumethiazine (1.22g) and N, dinethylformamide (DMF15mL), salt of wormwood (1.80g) is under the stirring at room, drip DMF (8.0mL) solution of 2-chloro-5-aminomethyl-pyridine (0.85g), be warming up to 50-80 ℃ of reaction 3-5hr after drip finishing, after the cooling reaction solution poured in the 100mL water into ethyl acetate extraction, washing, anhydrous sodium sulfate drying, concentrating under reduced pressure get thick product 1.67g.Be that eluent carries out column chromatography and gets faint yellow solid N-((2-chloropyridine-5-yl) methyl)-3-chloro-5-5-flumethiazine-2-amine 0.66g, content 98.1%, fusing point: 99.2-100.5 with 1: 10 ethyl acetate and sherwood oil mixed solution.Yield 35.6%.GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：321；found：321；
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：4.738(d，J＝5.7Hz，2H，CH
2)，7.290(d，J＝8.4Hz，1H，Py H)，7.657-7.692(m，2H，Py H)，8.279-8.289(m，1H，Py H)，8.404(d，J＝2.4Hz，1H，PyH).
The preparation of compound (46 and 47) in the embodiment 6 present embodiment instruction cards 1
Embodiment 1 is seen in the preparation of 2-chloro-5-ethamine picoline.
In 100mL single port bottle, add 2,6-two chloro-3-cyanopyridine (1.72g) and N, dinethylformamide (DMF 15mL), salt of wormwood (2.00g) is under the stirring at room, drip DMF (10.0mL) solution of 2-chloro-5-ethamine picoline (1.70g), be warming up to 60-80 ℃ of reaction 3-5hr after drip finishing, after the cooling reaction solution poured in the 100mL water into ethyl acetate extraction, washing, anhydrous sodium sulfate drying, concentrating under reduced pressure obtain the thick product of 2.54g.Be that eluent carries out column chromatography and gets beige solid N-((2-chloropyridine-5-yl) methyl)-N-ethyl-5-cyanopyridine-2-amine 0.59g, content 98.0%, fusing point: 87.3-87.7, yield 18.9% with 1: 10 ethyl acetate and sherwood oil mixed solution.GC-MS(M
+)(EI，70eV，m/z)(relative intensity％)calc：306；found：306；
1H NMR(CDCl
3/TMS，300MHz)δ(ppm)：1.194(t，J＝7.2Hz，3H，CH
3)，3.515(q，J＝7.2Hz，2H，CH
2)，4.795(s，2H，CH
2)，6.413(d，J＝8.7Hz，1H，Py H)，7.296(d，J＝8.7Hz，1H，Py H)，7.591(m，2H，Py H)，8.324(d，J＝2.4Hz，1H，Py H)。
Also obtain off-white color solid N-((2-chloropyridine-5-yl) methyl)-N-ethyl-3-cyanopyridine-2-amine 0.26g simultaneously, content 98.0%, yield 8.5%.GC-MS(M
+)(EI，70eV，m/z)(relative intensity ％)calc：306；found：306；
1HNMR(CDCl
3/TMS，300MHz)δ(ppm)：1.353(t，J＝7.2Hz，3H，CH
3)，3.763(t，J＝7.2Hz，2H，CH
2)，4.821(s，2H，CH
2)，6.676(d，J＝8.1Hz，1H，Py H)，7.305(d，J＝8.4Hz，1H，Py H)，7.696-7.734(m，2H，Py H)，8.375(d，J＝2.4Hz，1H，Py H).
Embodiment 7 preparation missible oil: with 20 parts (weight meter) the pyridyl-methanamine yl pyridines compounds that contains provided by the invention, 73 parts of thinners such as dimethylbenzene and 7 parts of even mixing of suitable auxiliary agent can prepare missible oil, and dilute with water can be used (active compound content is 20%).
The preparation of embodiment 8 compounds 08 (6-methoxyl group-N-((2-chloropyridine-5-yl) methyl)-N-methyl-3-nitro pyridine-2-amine) 20% missible oil: with 20 parts of compounds 05 (weight meter), 73 parts of thinners such as dimethylbenzene and 7 parts of even mixing of suitable auxiliary agent can prepare missible oil, and dilute with water can be used (active compound content is 20%).
Embodiment 9 preparation wettable powders: with 20 parts of (by weight) pyridyl-methanamine yl pyridines provided by the invention compounds, 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, desinsection, killed mite and weeding activity test, listed the experimental result of part of compounds below.
The insecticidal activity evaluation of 10 pairs of bean aphids of embodiment (Aphis fabae)
Method is as follows: take by weighing an amount of formula provided by the invention (I) compound, with suitable solvent such as N, the dinethylformamide dissolving adds a small amount of tween 80 emulsifying agent again, stirs, and adds quantitative clear water, is mixed with desired concn, establishes clear water and is contrast.Bean aphid is connected on the bean seedlings that just have been unearthed, and every strain connects more than 20, then bean seedlings is dipped in formula provided by the invention (I) the soup soup together with the examination worm, take out after 5 seconds, inhale and remove unnecessary soup, insert in the sponge of suction, cover with glass-tube, check 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 such as following table 3～table 4.
Table 3 part of compounds and Compound C under 500mg/L concentration to the activity (%) of aphid
| Compound | 02 | 03 | 04 | 08 | 10 | 11 | 12 | 13 | 14 | 16 | 17 |
| Active rank | A | A | C | A | A | A | B | A | A | A | B |
| Compound | 18 | 19 | 20 | 21 | 23 | 33 | 39 | 40 | 43 | 44 | Compound C |
| Active rank | B | A | B | A | C | B | C | C | B | C | D |
Table 4 part of compounds and compd B, C and Provado under 500～6.25mg/L concentration to the activity (%) of aphid
| Compound | 500mg/L | 100mg/L | 25mg/L | 6.25mg/L |
| 02 | 100 | 98.7 | 46.2 | 21.1 |
| 08 | 100 | 100 | 100 | 96.0 |
| 11 | 100 | 87.5 | 46.5 | 12.7 |
| 13 | 91.5 | 68.1 | 63.5 | 29.8 |
| 14 | 99.3 | 88.0 | 77.0 | 12.3 |
| 21 | 94.1 | 43.3 | 43.0 | 13.6 |
| Compd B | 100 | 96.8 | 57.0 | 5.10 |
| Compound C | 19.6 | / | / | / |
| Provado | 100 | 100 | 100 | 94.5 |
/: the expression undetermined
The insecticidal activity evaluation of 11 pairs of Nilaparvata lugen (brown planthopper)s of embodiment (Nilaparvata lugens)
Take by weighing an amount of formula provided by the invention (I) compound, with suitable solvent such as N, the dinethylformamide dissolving adds a small amount of tween 80 emulsifying agent again, stirs, and adds quantitative clear water, is mixed with desired concn, establishes clear water and is contrast.Choose two core rice seedlings and immerse in the soup, take out after 5 seconds and dry, place Boiling tube, every pipe 20 strains, introduce 20 or above Nilaparvata lugen (brown planthopper) nymph in 3～5 age then, the mouth of pipe is placed under the greenhouse experiment with white gauze wrapping, checks survival and dead borer population after 72 hours.Experiment repeats 3 times.Results averaged.Active with respect to blank in per-cent, the result shows that formula (I) compound has insecticidal activity to Nilaparvata lugen (brown planthopper): under 40mg/L concentration, the activity that compound 08 kills Nilaparvata lugen (brown planthopper) reaches more than 80%, and the activity that compound 11 kills Nilaparvata lugen (brown planthopper) reaches more than 60%.
The fungicidal activity of 12 pairs of Sclerotinia sclerotiorums of embodiment (Sclerotonia sclerotiorum)
Method is as follows: testing compound is dissolved in suitable solvent such as N, in the dinethylformamide (DMF), is diluted to desired concn with the sterilized water that contains the 0.1%Tween80 emulsifying agent again; Get in the potato agar substratum (PDA) that the 3mL soup adds the 27mL be cooled to 45 ℃ and after fully shaking up with transfer pipet and to pour culture dish into; The cooling back is got 6mm diameter mycelia piece with inoculating needle from the germ colony edge of cultivating 7 days, moves to culture dish central authorities, and mycelia faces down, and establishes thinner simultaneously and is contrast, and every processing repeats for 4 times; Place 28 ℃ the biochemical incubator of constant temperature to cultivate in culture dish after disposing, measure the mycelial growth diameter after 4 days, adopt the EXCEL statistical software to analyze and calculate mycelial growth inhibition rate (%).Activity in per-cent, is divided into A, B, C, D level Four with respect to blank, and 90＜inhibiting rate≤100 are the A level, and 70＜inhibiting rate≤90 are the B level, and 50＜inhibiting rate≤70 are the C level, and inhibiting rate 0＜inhibiting rate≤50 are the D level.Partial test the results are shown in Table 5.
Table 5 part of compounds and compd B, C and Provado under 25mg/L concentration to the activity (%) of Sclerotinia sclerotiorum
| Compound | 17 | 18 | 27 | 33 | Compd B | Compound C | Provado |
| Active (%) | 76.9 | 54.7 | 41.2 | 90.8 | 0 | 0 | 0 |
| Active rank | B | C | C | A | D | D | D |
The fungicidal activity of 13 pairs of botrytis cinerea pers of embodiment (Botrytis cinerea)
Adopt the measuring method of the fungicidal activity of 12 pairs of Sclerotinia sclerotiorums of embodiment, measured the fungicidal activity to botrytis cinerea pers of synthetic chemical combination.Partial test the results are shown in Table 6.
Table 6 part of compounds and compd B, C, Provado under 25mg/L concentration to the activity (%) of botrytis cinerea pers
| Compound | 28 | 30 | 33 | 40 | 44 | 47 | Compd B | Compound C | Provado |
| Active (%) | 43.8 | 43.8 | 72.0 | 51.0 | 43.8 | 50.3 | 0 | 0 | 10 |
| Active rank | D | D | B | C | D | C | D | D | D |
Embodiment 14 weeding activity evaluations
Method is as follows: (1) is at sectional area 64cm
2The plastic tub alms bowl in quantitatively the dress soil pressure is flat, place Stainless steel basin, choose full seed, seed of the same size, divide monocotyledon weed (lady's-grass Digitaria sanguinalis, barnyard grass grass Echinochloa crus-galli, Herba Setariae Viridis Setaria viridis) and broadleaf weed (piemarker Abutilon theaphrasti (or chickweed Stelleria media or black nightshade Solanum nigrum), lamb's-quarters Chenopodium album, recessed amaranth Amaranthus ascedense or Amaranthus retroflexus Amaranthus retraflexus) divide the alms bowl sowing, respectively account for 1/3 of alms bowl area, cover the thick fine earth of 1cm, adding water to upper layer of soil from plastic tub alms bowl bottom soaks into, place hot-house culture, material to be tried grows to required leaf age and tests processing; (2) take by weighing an amount of have weeding, the bioactive N-oxygen of desinsection base virtue phenoxy carboxylic acid amide compounds provided by the invention, with N, the dinethylformamide dissolving, add a small amount of tween 80 emulsifying agent again, stir, add quantitative clear water, be mixed with desired concn, establish coordinative solvent and clear water and be contrast; (3) processing mode: soil treatment before the seedling is carried out in the sowing of examination material next day, unifacial leaf examination material grow to 1 heart stage of 1 leaf, dicotyledonous examination material grow to 2 leaf periods and carry out seedling after cauline leaf handle; (4) pipetting quantitatively by dosage is set that soup carries out cauline leaf spraying or the soil spraying is handled, is contrast with spraying solvent and clear water respectively, is standard control with the clodinafop-propargyl shown in the formula (P-i) simultaneously; (5) handle the examination material and place hot-house culture; (6) handle range estimation overground part growing state after 15-25 days, according to investigation result, calculate each compound as follows to the preventive effect of weeds: preventive effect (%)=(contrast plant height-processings plant height)/contrast plant height.Partial results sees Table 7.
The weeding activity (%) of table 7 part of compounds and compd B, C, Provado cauline leaf/soil treatment under 150g a.i./mu dosage
Claims (8)
1. a pyridyl-methanamine yl pyridines compounds and isomer thereof is characterized in that with general formula (I) expression:
Wherein:
I.R is hydrogen, halogen, nitro, cyano group, C
1～C
3Haloalkyl;
II.p is one 0 to 3 integer;
III.R
1And R
2Be identical or different, and representative
(a) hydrogen, halogen;
(b) alkyl, alkoxyl group, alkylthio, alkyl sulphonyl, alkyl sulphinyl, alkoxy carbonyl, alkenyl, alkenyl oxy, alkenyl thio, the alkenyl alkylsulfonyl, the alkenyl sulfinyl, alkynyl, the alkynyloxy base, the alkynyl sulfenyl, the alkynyl alkylsulfonyl, the alkynyl sulfinyl, cycloalkyl, cycloalkyl oxy, the cycloalkyl sulfenyl, the naphthene sulfamide base, the cycloalkyl sulfinyl, alkyl-carbonyl, aryl, aryloxy, artyl sulfo, the aryloxy carbonyl, aryl sulfonyl, aryl sulfonyl kia, heteroaryl, heteroaryl oxygen base, the heteroaryl sulfenyl, heteroaryl oxygen base carbonyl, heteroarylsulfonyl, the heteroaryl sulfinyl;
(c) NR
3R
4(R
3And R
4Be identical or different, and represent hydrogen, alkyl, alkoxyl group, alkylthio, alkyl sulphonyl, alkyl sulphinyl, alkoxy carbonyl, alkenyl, alkenyl oxy, alkenyl thio, the alkenyl alkylsulfonyl, the alkenyl sulfinyl, alkynyl, the alkynyloxy base, the alkynyl sulfenyl, the alkynyl alkylsulfonyl, the alkynyl sulfinyl, cycloalkyl, cycloalkyl oxy, the cycloalkyl sulfenyl, the naphthene sulfamide base, the cycloalkyl sulfinyl, alkyl-carbonyl, aryl, aryloxy, artyl sulfo, the aryloxy carbonyl, aryl sulfonyl, aryl sulfonyl kia, heteroaryl, heteroaryl oxygen base, the heteroaryl sulfenyl, heteroaryl oxygen base carbonyl, heteroarylsulfonyl, the heteroaryl sulfinyl);
(d) as determined implication, R in case of necessity in III. (a), III. (b) or III. (c)
1Or R
2In hydrogen atom can be partly or entirely be selected from following in identical or different substituting group replace:
Halogen, nitro, cyano group, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkoxyl group, alkylthio, amino, alkylamino, dialkyl amido, haloalkyl, alkenyl oxy, alkenyl thio, alkenyl amino, alkenyl alkyl, halogenated alkenyl, the alkynyloxy base, the alkynyl sulfenyl, alkynyl amino, the alkynyl alkyl, the halo alkynyl, cycloalkyl oxy, the cycloalkyl sulfenyl, cycloalkyl amino, cycloalkylalkyl, halogenated cycloalkyl, aryloxy, artyl sulfo, arylamino, arylalkyl, halogenated aryl, heteroaryl oxygen base, the heteroaryl sulfenyl, heteroaryl amino, heteroarylalkyl, the halo heteroaryl;
(e) as in III. (a), III. (b), III. (c) or III. (d), having determined aryl and the partly or entirely hydrogenation of heteroaryl of implication, wherein 1 or 2 CH
2Group can be replaced by CO;
IV.R
3Be halogen, C
1～C
3Alkyl, C
1～C
3Haloalkyl;
V.R=3-NO
2, R
2=CH
3The time, R
p 1≠ 6-Cl, 6-H;
VI.R=3-NO
2, R
2=CH (CH
3)
2The time, R
p 1≠ 6-H;
In the definition of the compound that provides above (I), no matter the separately use or be used in the compound word of used term represents following substituting group:
Halogen: refer to fluorine, chlorine, bromine and iodine;
Alkyl: the straight or branched alkyl that refers to have 1-6 carbon atom;
Alkoxyl group: refer to have the straight or branched alkoxyl group of 1-6 carbon atom, be connected on the structure through the Sauerstoffatom key;
Alkylthio: refer to have the straight or branched alkylthio of 1-6 carbon atom, be connected on the structure through the sulphur atom key;
Alkenyl: the straight or branched thiazolinyl that refers to have 2-6 carbon atom;
Alkynyl: the straight or branched alkynyl that refers to have 2-6 carbon atom;
Aryl: the naphthyl that refers to have the phenyl of 6 carbon atoms and have 12 carbon atoms;
Heteroaryl: the heteroaryl that refers to 10 carbon atoms of as many as;
Halo: refer to that 1, a plurality of or all hydrogen atoms are replaced by halogen, as 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.
2. pyridyl-methanamine yl pyridines compounds according to claim 1 and isomer thereof is characterized in that the compound shown in the general formula (I) comprises geometrical isomer E formula and Z formula, and the mixture of E formula and Z formula; Comprise steric isomer R formula and S formula, and the mixture of R formula and S formula; The mixture that comprises geometrical isomer (Z/E formula) and steric isomer (R/S formula).
3. according to claim 1 or 2 tins of pyridyl-methanamine yl pyridines compounds and isomer thereof of stating, it is characterized in that in the compound shown in the general formula (I): R is nitro; P is 1; R
1, R
2And R
3Be identical or different, and represent hydrogen, halogen, C
1～C
3Alkyl, C
1～C
3Alkoxyl group, C
1～C
3Alkylthio, C
2～C
6Alkenyl, C
2～C
6Alkenyl oxy, C
2～C
6Alkenyl thio, C
2～C
6Alkynyl, C
2～C
6Alkynyloxy base, C
2～C
6Alkynyl sulfenyl, C
3～C
6Cycloalkyl, C
3～C
6Cycloalkyl oxy, C
3～C
6Cycloalkyl sulfenyl, aryl, aryloxy, artyl sulfo, heteroaryl, heteroaryl oxygen base, heteroaryl sulfenyl, NR
4R
5(R
4And R
5Be identical or different, and represent C
1～C
3Alkyl), R in case of necessity
1, R
2Or R
3In hydrogen atom partly or entirely be selected from substituting group identical or different in following and replaced: halogen, C
1～C
3Alkyl, C
2～C
6Alkenyl, C
2～C
6Alkynyl, C
3～C
6Cycloalkyl, aryl, heteroaryl, C
1～C
3Alkoxyl group, C
1～C
3Alkylthio, amino, C
1～C
3Alkylamino, C
1～C
3Dialkyl amido.
4. pyridyl-methanamine yl pyridines compounds according to claim 1 and 2 and isomer thereof, it is characterized in that in the compound shown in the general formula (I): R is nitro; P is 1; R
1Be C
1～C
3Alkoxyl group, C
3～C
6Alkenyl oxy, C
3～C
6Alkynyloxy base, NR
4R
5(R
4And R
5Be identical or different, and represent C
1～C
3Alkyl); R
2Be C
1～C
3Alkyl, C
1～C
3Haloalkyl; R
3Be halogen, C
1～C
3Alkyl, C
1～C
3Haloalkyl.
5. according to claim 1 or 2 tins of pyridyl-methanamine yl pyridines compounds and isomer thereof of stating, it is characterized in that in the compound shown in the general formula (I): R is nitro; P is 1; R
1Be methoxyl group, oxyethyl group, propoxy-, N (CH
3)
2R
2Be methyl, ethyl; R
3Be chlorine, trifluoromethyl.
6. pyridyl-methanamine yl pyridines compounds according to claim 1 and 2 and isomer thereof is characterized in that the compound shown in the general formula (I) is:
N-((2-chloropyridine-5-yl) methyl)-N-ethyl-3-nitropyridine-2-amine;
N-((2-chloropyridine-5-yl) methyl)-N-butyl-3-nitropyridine-2-amine;
6-chloro-N-((2-chloropyridine-5-yl) methyl)-3-nitropyridine-2-amine;
6-methoxyl group-N-((2-chloropyridine-5-yl) methyl)-N-methyl-3-nitro pyridine-2-amine;
6-oxyethyl group-N-((2-chloropyridine-5-yl) methyl)-N-ethyl-3-nitropyridine-2-amine;
6-oxyethyl group-N-((2-chloropyridine-5-yl) methyl)-N-methyl-3-nitro pyridine-2-amine;
6-methoxyl group-N-((2-chloropyridine-5-yl) methyl)-N-ethyl-3-nitropyridine-2-amine;
6-propoxy--N-((2-chloropyridine-5-yl) methyl)-N-ethyl-3-nitropyridine-2-amine;
6-propoxy--N-((2-chloropyridine-5-yl) methyl)-N-methyl-3-nitro pyridine-2-amine;
6-methoxyl group-N-((2-chloropyridine-5-yl) methyl)-N-butyl-3-nitropyridine-2-amine;
6-phenoxy group-N-((2-chloropyridine-5-yl) methyl)-N-ethyl-3-nitropyridine-2-amine;
6-phenoxy group-N-((2-chloropyridine-5-yl) methyl)-N-methyl-3-nitro pyridine-2-amine;
6-oxyethyl group-N-((2-chloropyridine-5-yl) methyl)-N-propyl group-3-nitropyridine-2-amine;
6-methoxyl group-N-((2-chloropyridine-5-yl) methyl)-N-propyl group-3-nitropyridine-2-amine;
6-propoxy--N-((2-chloropyridine-5-yl) methyl)-N-propyl group-3-nitropyridine-2-amine;
6-phenoxy group-N-((2-chloropyridine-5-yl) methyl)-N-sec.-propyl-3-nitropyridine-2-amine;
6-methylamino-N-((2-chloropyridine-5-yl) methyl)-N-methyl-3-nitro pyridine-2-amine;
6-ethylamino--N-((2-chloropyridine-5-yl) methyl)-N-methyl-3-nitro pyridine-2-amine;
6-(Pyrrolidine-1-yl)-N-((2-chloropyridine-5-yl) methyl)-N-methyl-3-nitro pyridine-2-amine;
6-dimethylin-N-((2-chloropyridine-5-yl) methyl)-N-ethyl-3-nitropyridine-2-amine;
6-dimethylin-N-((2-chloropyridine-5-yl) methyl)-N-methyl-3-nitro pyridine-2-amine;
6-methylthio group-N-((2-chloropyridine-5-yl) methyl)-N-methyl-3-nitro pyridine-2-amine;
N-((2-chloropyridine-5-yl) methyl)-5-5-flumethiazine-2-amine;
N-((2-chloropyridine-5-yl) methyl)-3-chloro-5-5-flumethiazine-2-amine;
6-chloro-N-((2-chloropyridine-5-yl) methyl)-N-ethyl-5-cyanopyridine-2-amine;
6-chloro-N-((2-chloropyridine-5-yl) methyl)-N-ethyl-3-cyanopyridine-2-amine.
7. according to claim 1 or 2 tins of thiazole methylamine yl pyridines compounds of stating and the preparation method of isomer thereof, it is characterized in that the compound shown in the formula (I) obtains by the prepared in reaction shown in following,
Reaction formula 1-1:
Reaction formula 1-2:
Reaction formula 2-1:
Reaction formula 2-2:
Reaction formula 3:
Reaction formula 1-1: at solvent N, in dinethylformamide or benzene, toluene, the tetrahydrofuran (THF), in the presence of alkali sodium hydride or potassium hydroxide, salt of wormwood, in 25～80 ℃ or high to the solvent refluxing temperature, with the compound shown in the compound shown in the formula (II) and the formula (III) react the compound of formula (I);
Reaction formula 1-2: at N, in dinethylformamide or tetrahydrofuran (THF), water, methylene dichloride, benzene, toluene single solvent or their mixed solvent, in the presence of alkali sodium hydride or potassium hydroxide, salt of wormwood, in room temperature or high to the solvent refluxing temperature, with formula (II) listen the compound of the compound show and formula (IV) react the compound of formula V, in alcohol or water solvent, add alkali metallic sodium or sodium alkoxide, sodium hydride in case of necessity, in room temperature or high to the solvent refluxing temperature, the compound of formula V and R
p 1H reacts, and gets the compound of formula (I);
Reaction formula 2-1: in the mixed solvent of trichloromethane or methylene dichloride, benzene, toluene single solvent or they and water or alcohol, in the presence of alkali sodium hydride or sodium hydroxide, salt of wormwood, in room temperature or high to the solvent refluxing temperature, compound shown in the formula (VI) and the reaction of compound (VII), get the compound of formula (II), but adding phase-transfer catalyst benzyltriethylammoinium chloride or Tetrabutyl amonium bromide can impel reaction to carry out or accelerated reaction is carried out;
Reaction formula 2-2: at solvent N, in dinethylformamide or the ethanol, in room temperature or high to the solvent refluxing temperature, the compound reaction of the compound shown in the formula (VI) and formula (VIII) obtains the compound of formula (IX), in solvent methanol or ethanol, in room temperature or high to the solvent refluxing temperature, the compound of formula (IX) gets formula (II:R with hydrazine or hydrazine hydrate, catalytic hydrogenating reduction
2=H) compound;
Reaction formula 3: at solvent R
p 1Among the H, in subzero 15 ℃ or high to the solvent refluxing temperature, use alkali R
p 1ONa or sodium hydride, sodium hydroxide, salt of wormwood are handled the compound of general formula (IV), get the compound of formula (III);
Reaction formula 3: at aqueous solvent or N, in the dinethylformamide, in subzero 15 ℃ or high to the solvent refluxing temperature, use R
p 1The reaction of the compound of H and formula (IV) gets the compound of formula (III), adds suitable alkali triethylamine or sodium hydride, sodium hydroxide, salt of wormwood and can impel to react and carry out or accelerated reaction is carried out;
Reaction formula 3: in solvent benzol or toluene, sherwood oil, in subzero 15 ℃ or high to the solvent refluxing temperature, in the presence of alkali sodium hydride or sodium hydroxide, salt of wormwood, use R
p 1The compound of H and formula (IV) react the compound of formula (III);
R, p, R in the formula
1, R
2And R
3Have and give definition in the claim 1, X ' and X are leavings group such as fluorine, chlorine, bromine, sulphonate.
8. germ or insect, evil mite, weeds there is purposes in the medicine of prevention effect according to each described pyridyl-methanamine yl pyridines compounds and isomer thereof in the claim 1～6 in preparation.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753779A (en) * | 2014-12-18 | 2016-07-13 | 湖南化工研究院有限公司 | 2-pyridylamine compounds, preparing method thereof and applications of the compounds |
| CN105777741A (en) * | 2014-12-18 | 2016-07-20 | 湖南化工研究院有限公司 | Thiazole alkyl pyridylamine compound and preparation method and application thereof |
| JP2017507989A (en) * | 2014-03-21 | 2017-03-23 | バイエル・クロップサイエンス・アクチェンゲゼルシャフト | Process for preparing N-[(6-chloropyridino-3-yl) methyl] -2,2-difluoroethan-1-amine by alkylating 2,2-difluoroethylamine |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5081132A (en) * | 1989-05-17 | 1992-01-14 | Nihon Tokushu Noyaku Seizo K.K. | Nitro-substituted heterocyclic compounds |
| WO2008063888A2 (en) * | 2006-11-22 | 2008-05-29 | Plexxikon, Inc. | Compounds modulating c-fms and/or c-kit activity and uses therefor |
| WO2010105960A1 (en) * | 2009-03-17 | 2010-09-23 | Neurosearch A/S | Substituted pyridine derivatives and their medical use |
| WO2011057022A1 (en) * | 2009-11-06 | 2011-05-12 | Plexxikon, Inc. | Compounds and methods for kinase modulation, and indications therefor |
-
2012
- 2012-02-13 CN CN201210031824.6A patent/CN103242225B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5081132A (en) * | 1989-05-17 | 1992-01-14 | Nihon Tokushu Noyaku Seizo K.K. | Nitro-substituted heterocyclic compounds |
| WO2008063888A2 (en) * | 2006-11-22 | 2008-05-29 | Plexxikon, Inc. | Compounds modulating c-fms and/or c-kit activity and uses therefor |
| WO2010105960A1 (en) * | 2009-03-17 | 2010-09-23 | Neurosearch A/S | Substituted pyridine derivatives and their medical use |
| WO2011057022A1 (en) * | 2009-11-06 | 2011-05-12 | Plexxikon, Inc. | Compounds and methods for kinase modulation, and indications therefor |
Non-Patent Citations (2)
| Title |
|---|
| 冯丽娟: "吡啶甲胺类化合物的合成及杀虫活性研究进展", 《济宁学院学报》, vol. 30, no. 3, 20 June 2009 (2009-06-20), pages 19 - 21 * |
| 吕兆萍: "四类吡啶化合物的合成与生物活性研究", 《中国博士学位论文全文数据库 工程科技I辑》, no. 1, 15 January 2009 (2009-01-15), pages 016 - 7 * |
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