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CN104016985A - Pyrazolo pyrimidine compound and application thereof - Google Patents

Pyrazolo pyrimidine compound and application thereof Download PDF

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Publication number
CN104016985A
CN104016985A CN201310067016.XA CN201310067016A CN104016985A CN 104016985 A CN104016985 A CN 104016985A CN 201310067016 A CN201310067016 A CN 201310067016A CN 104016985 A CN104016985 A CN 104016985A
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compound
alkyl
composition
disease
plant
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CN104016985B (en
Inventor
徐玉芳
赵振江
朱维平
李洪林
李鹏飞
李宝聚
石延霞
钱旭红
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East China University of Science and Technology
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

The invention discloses a compound shown in general formula I and an application thereof as a plant disease-resistant activator, wherein R1 is independently selected from hydrogen, C1-C6 alkyl, C1-C6 halogenated alkyl, C3-C6 naphthenic base, halogen, nitro and hydroxyl; R2 is independently selected from C1-C6 alkyl, C1-C6 halogenated alkyl, hydroxyl, C1-C6 alkoxy, C1-C6 halogenated alkoxy, substituted or unsubstituted C6-C14 aryl, halogen, nitro, amino, C1-C6 alkoxy, carboxyl, C1-C3 alcoxyl formyl and pentabasic or hexahydric nitrogen and heterocyclic ring of oxygen or sulfur-containing; n is selected from 0-5. The compound is used for inhibiting the pathogens through inducing the plants to generate disease resistance, rather than directly killing or inhibiting the pathogens; the compound has the advantages of systematicness, long-lasting effect, broad spectrum and safety, so that the dosage of highly toxic pesticide can be reduced, and environment friendliness, great industrial/commercial prospect and market value are achieved.

Description

A kind of Pyrazolopyrimidine compound and uses thereof
Technical field
The present invention relates to agricultural cience and farming techniques field.Specifically, the present invention relates to heterogeneous ring compound shown in formula I and produce the application in anti-insect activity at inducing plant.
Background technology
Agricultural chemicals (Pesticides) mainly refers to for preventing the various diseases (insect, evil mite, nematode, pathogenic bacteria, weeds and muroid) of agriculture forest and husbandry in producing and the chemicals of coordinate plant growth.Before the eighties, " killing " of being mainly used in pest of agricultural chemicals, but since the eighties, the concept of agricultural chemicals has a very large change.Today, people do not focus on " killing ", but more pay attention to regulate.Therefore, the aim of modern is to insect pest germ high-efficiency prevention and control, should safety to non-target organism and environment.
Agricultural chemicals has had the history of very long development in about 150 years in the world, 70, the eighties, the scientific research of chemical pesticide, exploitation and produce unprecedentedly active, efficiently, the agricultural chemicals novel type of low toxicity, mechanism of action novelty, as pyrethroid, pyrazoles, pyridines, nicotinoids, pyroles, process for preparation of benzoylurea compounds; Amino formate, beta-methoxy acrylic ester, benzimidazoles, triazole bactericidal agent; Imidazolone type, sulfonylurea herbicide etc. emerge in an endless stream, the motorway that impels chemical pesticide to step into develop rapidly.Yet the negative impact that the extensive use of traditional agricultural chemicals brings to environment and cause pathogenic micro-organism and the resistance of insect is had a greatly reduced quality its application power, if few, with agricultural chemicals, harmful organism can not effectively preventing, usually cause the agriculture underproduction, directly have influence on the development of national economy, the agricultural chemicals of 21 century progressively develops to the new ideas of biological regulation.
China Shi Yige large agricultural country, after liberation, China's pesticide industry is flourish, and pesticide species and output are doubled and redoubled, and China's agricultural chemicals output can meet agriculture needs, and has the outlet of some amount, but kind is still not enough.China is used pesticide preparation to reach 65～700,000 tons every year, and effective constituent amount reaches 22～250,000 tons.Really can prevent harmful organism seldom, approximately have more than 90% agricultural chemicals to be dissipated in contaminate environment in farmland, particularly highly toxic pesticide contaminate environment is more serious.
Since Chester K. in 1933 delivers about " the acquisition physiologic immunity of plant " literary composition first, more existing authors summarize it.Wherein the system about tobacco obtains disease resistance most study, to it, antiviral, antimycotic and resistance to bacteria has all carried out systematic study to different researchers, as Resistance In Tobacco tobacco mosaic virus (TMV) (TMV), anti-eye spot (Cercospora nicotianae), anti-balck shank (Phytophthora parasitica), downy mildew resistance (Peronospora tabacina), antibacterium wildfire (Pseudomonas syrtngae pv.tabaci) etc., and find pathogenesis-related proteins and system to obtain disease resistence gene proteins encoded.Eighties of last century beginning of the sixties, Ross research tobacco mosaic virus (TMV) has proposed systemic acquired resistance in plant (systemic acquired resistance, SAR),, when the induction bacterium of necrotic type pathogen or screening is infected or after the induction of some chemicals processes, what some plant can be to pathogen subsequently infects generation resistance.And these biological and chemical agents that can inducing plant produce SAR are just called plant disease resistance inductor or activator.
Yet so far, the research and development of Plant activator launch based on 1,2,3-thiadiazoles mostly, this limitation causes and is difficult to produce initiative achievement in research.
Therefore, the Plant activator that development and application possesses new mother nucleus structure is badly in need of in this area.
Summary of the invention
The object of the present invention is to provide can inducing plant anti-disease activity but not direct killing or suppress the heterogeneous ring compound of phytopathogen and as the application of Plant activator.
In first aspect, the invention provides the heterogeneous ring compound shown in general formula I,
In formula,
R 1independently be selected from: hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, halogen, nitro, hydroxyl;
R 2independently be selected from: the heterocycle of C1-C6 alkyl, C1-C6 haloalkyl, hydroxyl, C1-C6 alkoxyl group, C1-C6 halogenated alkoxy, replacement or unsubstituted C6-C14 aryl, halogen, nitro, amino, C1-C6 alkylamino, carboxyl, C1-C3 alkoxyl formyl, 5 yuan or 6 yuan of nitrogenous, oxygen or sulphur;
N is the integer that is selected from 0-5.
In a preferred embodiment, in general formula I, R 1it is methyl; R 2independently be selected from: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxyl group, C1-C3 halogenated alkoxy, halogen, nitro; N is the integer that is selected from 0-5.
In further preferred implementation, described compound is selected from lower group:
In second aspect, the invention provides the disease-resistant composition of a kind of inducing plant, comprise in Pesticide Science acceptable carrier and as the compound described in the first aspect present invention of inducing plant anti-disease activity composition.
In a preferred embodiment, described composition is for preventing and treating bacterium, fungi or the infringement of virus to plant.
In a preferred embodiment, described composition is for preventing and treating by muskmelon ball chamber bacterium (Mycosphaerella melonis), the withered bacterium of stem (Corynespora cassiicola), pseudomonas syringae angular leaf spot of cucumber pathotype (Pseudomonas syringae pv.Lachrymans), phytophthora infestans (Phytophthora infestans (Mont.) De Bary), thanatephorus cucumeris(frank) donk (Thanatephorus cucumeris (Frank) Donk.), the germ Plant diseases of Botrytis cinerea (Botrytis cinerea Pers.ex Fr.) or sharp Fusariumsp cucumber specialized form (Fusarium oxysporum (Schl.) F.sp cucumerinum Owen).
In a preferred embodiment, described plant includes but not limited to: cucumber, paddy rice, tomato, wax gourd, soybean tobacco, corn, wheat, various flowers etc.
In a preferred embodiment, described composition is used for preventing and treating the climing rot of cucumber, Cucumber Target Leaf Spot, cucumber bacterial angular leaf spot, tomato late blight, rice sheath blight disease, gray mold of cucumber or cucumber fusarium axysporum.
In the third aspect, the invention provides compound described in the first aspect present invention purposes in preparing the disease-resistant composition of inducing plant.
In a preferred embodiment, described composition is for preventing and treating bacterium, fungi or the infringement of virus to plant.
In a preferred embodiment, described plant includes but not limited to: cucumber, paddy rice, tomato, wax gourd, soybean tobacco.
In a preferred embodiment, described composition is for preventing and treating by muskmelon ball chamber bacterium (Mycosphaerella melonis), the withered bacterium of stem (Corynespora cassiicola), pseudomonas syringae angular leaf spot of cucumber pathotype (Pseudomonas syringae pv.Lachrymans), phytophthora infestans (Phytophthora infestans (Mont.) De Bary), thanatephorus cucumeris(frank) donk (Thanatephorus cucumeris (Frank) Donk.), the germ Plant diseases of Botrytis cinerea (Botrytis cinerea Pers.ex Fr.) or sharp Fusariumsp cucumber specialized form (Fusarium oxysporum (Schl.) F.sp cucumerinum Owen).
In a preferred embodiment, described composition is used for preventing and treating the climing rot of cucumber, Cucumber Target Leaf Spot, cucumber bacterial angular leaf spot, tomato late blight, rice sheath blight disease, gray mold of cucumber or cucumber fusarium axysporum.
In fourth aspect, the invention provides a kind of disease-resistant method of inducing plant, described method comprises: the composition described in the compound described in first aspect present invention or second aspect present invention is applied to described plant.
In fourth aspect, the invention provides the method for preparing compound shown in general formula I, described method comprises implements the reaction shown in following synthetic route:
Take 1-alkyl-4-carboxylicesters-5-amino-pyrazol and formyl ammonium is starting raw material, through reaction, obtaining intermediate A; Intermediate A is by POCl 3chloro, obtains intermediate B; Intermediate B hydrazinolysis obtains Compound C; Intermediate C and various aldehyde form corresponding hydrazone (methylene radical diazanyl) compound P.
R in formula 1and R 2as above limited.
In a preferred embodiment, described method comprises the reaction shown in the following synthetic route of enforcement:
R 1as above limited.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can combining mutually between specifically described each technical characterictic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, at this, tire out and state no longer one by one.
Embodiment
Contriver is through extensive and deep research, find unexpectedly to take that shown in formula I that pyrazolopyrimidine is parent nucleus, compound has the activity that outstanding inducing plant produces disease resistance, not only can alleviate pathogenic bacteria, for example fungi, bacterium or the threat of virus to plant, can also reduce traditional agricultural chemicals, particularly the consumption of highly toxic pesticide, environmentally friendly.This compounds has industrialization, commercialization prospect, international and domesticly there is huge marketable value, has a extensive future, and remarkable in economical benefits.Completed on this basis the present invention.
Group definition
Term used herein " alkyl " comprises side chain and straight chained alkyl, and it comprises 1-6 carbon atom conventionally, preferably 1-4 carbon atom, more preferably 1-3 carbon atom.The example of alkyl includes but not limited to: methyl, ethyl, propyl group, butyl, the tertiary butyl, isobutyl-etc.
Term used herein " alkoxyl group " refers to " alkyl-O-" group, and wherein, alkyl can be the straight or branched alkyl of C1-C6, preferably C1-C4 or C1-C3 straight or branched alkyl.Can be used for alkoxyl group of the present invention includes but not limited to: methoxyl group, oxyethyl group, propoxy-etc.
Term used herein " aryl " refers to monocycle, dicyclo or the three ring aromatic groups that contain 6-14 carbon atom.The present invention's aryl used includes but not limited to: phenyl, naphthyl, phenanthryl, anthryl, indenyl, Fluorene base, tetrahydro naphthyl, indanyl etc.Aryl optionally for example, is selected from following substituting group by 1-5 (, 1,2,3,4 or 5) and replaces: halogen (for example, F, Cl or Br), C 1-4aldehyde radical, C 1-6trifluoromethyl), the halogen alkoxyl group (including but not limited to trifluoromethoxy, bromine propoxy-etc.), carboxyl, the C that replace the alkyl that straight or branched alkyl, cyano group, nitro, amino, hydroxyl, methylol, halogen replace (includes but not limited to: 1-4alkoxyl group, ethoxycarbonyl, N (CH 3) and C 1-4acyl group.In concrete embodiment, aryl can be selected from following group by 1-5 and replace: halogen ,-OH, C 1-4alkoxyl group, C 1-4alkyl ,-NO 2,-NH 2,-N (CH 3) 2, carboxyl and ethoxycarbonyl etc.
" heterocycle " used herein is in finger ring, to contain 5-10 atom, and has 6, and 10 or 14 electronics share in member ring systems.And contained annular atoms is carbon atom and 1-3 the heteroatoms that is selected from oxygen, nitrogen or sulphur.
Useful heteroaryl comprises thienyl, furyl, pyranyl, pyrryl, imidazolyl, pyrazolyl, pyridyl, includes but not limited to: 2-pyridyl, 3-pyridyl and 4-pyridyl, pyrazinyl, pyrimidyl etc.
Heteroaryl can be optionally selected from following substituting group by 1-5 and replace: halogen, C 1-4aldehyde radical, C 1-6alkoxyl group (for example trifluoromethoxy), carboxyl, C that the alkyl (for example trifluoromethyl) that straight or branched alkyl, cyano group, nitro, amino, hydroxyl, methylol, halogen replace, halogen replace 1-4alkoxyl group, ethoxycarbonyl, N (CH 3) and C 1-4acyl group.Optionally, except containing fluoro substituents, on aryl, can also contain other substituting group mentioned above, for example Cl, Br ,-OH, C 1-4alkoxyl group, C 1-4alkyl chain ,-NO 2,-NH 2,-N (CH 3) 2, carboxyl, and ethoxycarbonyl etc.
Term used herein " halogen " refers to fluorine, chlorine, bromine or iodine.Term " halo " refers to the group being replaced by identical or different one or more above-mentioned halogen atom, for example trifluoromethyl, pentafluoroethyl group or similar group.
In addition, unless stated otherwise, group of the present invention is " replacement or unsubstituted ", otherwise group of the present invention all can be selected from the substituting group of lower group and be replaced: halogen, itrile group, nitro, hydroxyl, amino, C1-6 alkyl-amido, C1-6 alkyl, C2-6 thiazolinyl, C2-6 alkynyl, C1-6 alkoxyl group, halo C1-6 alkyl, halo C2-6 thiazolinyl, halo C2-6 alkynyl, halo C1-6 alkoxyl group, allyl group, benzyl, C6-12 aryl, C1-6 alkoxy-C 1-6 alkyl, C1-6 alkoxyl group-carbonyl, carbobenzoxy, C2-6 alkynyl-carbonyl, C2-6 thiazolinyl-carbonyl, C3-6 cycloalkyl-carbonyl, C1-6 alkyl-alkylsulfonyl, benzoyl, furans carbonyl or N, N-dimethyl amido carbonyl, or by one or more halogens that are selected from, C1-6 haloalkyl, C1-6 alkyl, the benzoyl that the substituting group of C1-6 alkoxyl group and C1-6 alkyl-carbonyl replaces, furans carbonyl or N, N-dimethyl amido carbonyl etc.
The compounds of this invention
In this article, term " compound of the present invention ", " Plant activator of the present invention " or " active ingredient in the disease-resistant composition of inducing plant of the present invention " have identical implication, can exchange use in this article, all refer to the compound shown in following general formula I
In formula,
R 1independently be selected from: hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, halogen, nitro, hydroxyl;
R 2independently be selected from: the heterocycle of C1-C6 alkyl, C1-C6 haloalkyl, hydroxyl, C1-C6 alkoxyl group, C1-C6 halogenated alkoxy, replacement or unsubstituted C6-C14 aryl, halogen, nitro, amino, C1-C6 alkylamino, carboxyl, C1-C3 alkoxyl formyl, 5 yuan or 6 yuan of nitrogenous, oxygen or sulphur;
N is the integer that is selected from 0-5.
In a preferred embodiment, R 1it is methyl; R 2independently be selected from: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxyl group, C1-C3 halogenated alkoxy, halogen, nitro; N is the integer that is selected from 0-5.
In further preferred embodiment, described compound is selected from lower group:
Compound shown in general formula I of the present invention can be prepared by implementing the reaction shown in following synthetic route:
Take 1-alkyl-4-carboxylicesters-5-amino-pyrazol and formyl ammonium is starting raw material, through reaction, obtaining intermediate A; Intermediate A is by POCl 3chloro, obtains intermediate B; Intermediate B hydrazinolysis obtains Compound C; Intermediate C and various aldehyde, the phenyl aldehyde for example replacing forms corresponding hydrazone (methylene radical diazanyl) compound P.
R in formula 1and R 2as above limited.
In a preference, described method comprises implements the reaction shown in following synthetic route:
R 1and R 2as above limited.
Inducing plant anti-disease activity
Term used herein " inducing plant is disease-resistant " has identical meaning with " inducing plant anti-disease activity ", is used interchangeably in this article.The two all represents that certain compound itself and metabolite thereof there is no the activity of directly killing and wounding or suppressing pathogenic agent, but immunity system that can stimulating plant and make plant generation system obtain the material of disease-resistant performance.This type of disease resistance has following characteristics: systematicness, and SAR shows the non-inducible factor treatment sites of plant; Persistence, rear sustainable several weeks of SAR generation are some months even; Broad spectrum, SAR produces restraining effect to disease due to some fungies, bacterium, germ simultaneously; Security, these inductors itself do not produce toxic action to germ, but inducing plant body produces resistance, therefore environment is not had side effects.
In concrete embodiment, described " inducing plant is disease-resistant " represents to prevent and treat pathogenic agent, for example bacterium, fungi or the infringement of virus to plant.
In a preferred embodiment, described " inducing plant is disease-resistant " represents for control by muskmelon ball chamber bacterium (Mycosphaerella melonis), the withered bacterium of stem (Corynespora cassiicola), pseudomonas syringae angular leaf spot of cucumber pathotype (Pseudomonas syringae pv.Lachrymans), phytophthora infestans (Phytophthora infestans (Mont.) De Bary), thanatephorus cucumeris(frank) donk (Thanatephorus cucumeris (Frank) Donk.), the germ Plant diseases of Botrytis cinerea (Botrytis cinerea Pers.ex Fr.) or sharp Fusariumsp cucumber specialized form (Fusarium oxysporum (Schl.) F.sp cucumerinum Owen).
In a preferred embodiment, described plant includes but not limited to: cucumber, paddy rice, tomato, wax gourd, soybean, tobacco, corn, wheat, various flowers etc.
In a preferred embodiment, described " inducing plant is disease-resistant " composition is used for preventing and treating the climing rot of cucumber, Cucumber Target Leaf Spot, cucumber bacterial angular leaf spot, bacterial spot of tomato, tomato late blight, rice sheath blight disease, gray mold of cucumber or cucumber fusarium axysporum.
The composition that inducing plant is disease-resistant
The present invention also comprises the disease-resistant composition of inducing plant that contains the compounds of this invention.In concrete embodiment, in composition of the present invention, can contain the compounds of this invention of 0.01 (weight) %～95 (weight) % as activeconstituents.In concrete embodiment, the disease-resistant composition of inducing plant of the present invention comprises acceptable carrier in Pesticide Science.In described Pesticide Science, acceptable carrier comprises various solid carriers known in the art, liquid vehicle, carrier gas etc.
Described solid carrier can be that for example, clay material is as fine powder or the particle of kaolin, diatomite, synthetic hydrated silicon oxide, wilkinite, Fubasami clay and acid clay; All kinds of talcums, pottery and other inorganic materials are as the fine powder of sericite, quartz, sulphur, gac, calcium carbonate and hydrated SiO 2 or particle; And chemical fertilizer is as the fine powder of ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride or particle.
Described liquid vehicle for example can comprise, water; Alcohols is as methyl alcohol and ethanol; Ketone is as acetone and methyl ethyl ketone; Hydro carbons is as hexane, hexanaphthene, kerosene and light oil; Ester class is as vinyl acetic monomer and N-BUTYL ACETATE; Nitrile is as acetonitrile and isopropyl cyanide; Ethers as Di Iso Propyl Ether with diox; Amides is as DMF and N,N-dimethylacetamide; Halohydrocarbon is as methylene dichloride, trichloroethane and tetracol phenixin; Dimethyl sulfoxide (DMSO); And vegetables oil is as soya-bean oil and Oleum Gossypii semen.
Described carrier gas or propellent can include but not limited to, freonll-11, butane, LPG (liquefied petroleum gas (LPG)), dme and carbonic acid gas.
In composition of the present invention, also can contain tensio-active agent, as alkyl-sulphate, alkylsulfonate, alkylaryl sulphonate, alkyl aryl ether and their polyethylene oxide derivant, polyglycol ether, polyol ester and sugar alcohol derivant.
Composition of the present invention can also contain auxiliary, for example fixing agent or dispersion agent, for example, casein, gelatin, polysaccharide (as starch, Sudan Gum-arabic, derivatived cellulose and Lalgine), lignin derivative, wilkinite, sugar and as synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone and polyacrylic acid.
Composition of the present invention can also contain stablizer, for example, PAP (the acid phosphoric acid ester of sec.-propyl), BHT (2,6-, bis--tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetables oil, mineral oil, tensio-active agent, lipid acid and ester thereof.
Can be by various components be mixed with each other and make composition of the present invention.
Composition of the present invention can directly use or dilute with water after use.In addition, it can use with other sterilant, nematocides, miticide, sterilant, mould inhibitor, weedicide, plant-growth regulator, synergistic agent, fertilizer, soil redeposition and/or animal-feed blending or not blending but simultaneously use.
On the basis of the disease-resistant composition of inducing plant, the present invention also provides a kind of method of controlling plant diseases, method comprise by, such as spraying crop, impose in soil the means such as crop root composition of the present invention is applied to plant.While applying composition of the present invention, those skilled in the art can be according to comprising that number of times, place and the application process of preparation type, required dispenser, the concrete kind of pathogenic agent and degree of damage etc. determine suitable amount of application and concentration.
Advantage of the present invention:
1. the compounds of this invention provides a kind of brand-new thinking for controlling plant diseases;
2. the compounds of this invention energy inducing plant produces the disease resistance of resisting fungi, bacterium or virus;
3. application the compounds of this invention can reduce the consumption of traditional agricultural chemicals, particularly highly toxic pesticide, environmentally friendly; With
4. the compounds of this invention has great industrialization, commercialization prospect and marketable value, remarkable in economical benefits.
Below in conjunction with concrete case study on implementation, technical scheme of the present invention is further described, but following case study on implementation is not construed as limiting the invention, the various application processes of all foundations principle of the present invention and technique means employing, all belong to the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition, or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise per-cent and umber calculate by weight.
Embodiment
Synthesizing of embodiment 1.4-α-tolylene diazanyl-1-methyl-pyrazoles [3,4-d] pyrimidine (P-1)
(1) 1-methyl-pyrazoles [3,4-d] pyrimidin-4-one is synthetic
Weigh 5-amino-1-methylpyrazole-4-carboxylic acid, ethyl ester (2g, 11.8mmol) in 25mL single port flask, measure 15mL methane amide and add, be heated to 180 ° of C stirring reaction 5h, be then cooled to room temperature, filter, ethanol (2 * 8mL) washing, without purifying.
(2) the chloro-1-methyl isophthalic acid-hydrogen-pyrazoles of 4-[3,4-d] pyrimidine is synthetic
Weigh 1-methyl isophthalic acid-hydrogen-pyrazoles [3,4-d] and pyrimidin-4-one (500mg, 3.3mmol) in 25mL there-necked flask, measuring the phosphorus oxychloride that 5mL heavily steamed adds, heating reflux reaction 5h, be cooled to room temperature, pressure reducing and steaming solvent, adds remaining solid in frozen water, saturated sodium bicarbonate neutralization, ethyl acetate (25mL) extraction, first by saturated sodium bicarbonate solution and water washing organic phase, anhydrous sodium sulfate drying, rotation solvent evaporated, obtain faint yellow solid 450mg, productive rate 80%, GC/MS:168.
(3) 4-diazanyl-1-methyl-pyrazoles [3,4-d] pyrimidine is synthetic
Weigh the chloro-1-methyl isophthalic acid-hydrogen-pyrazoles of 4-[3,4-d] pyrimidine (200mg, 1.1mmol) in 25mL single port flask, add 5mL dehydrated alcohol, be stirred to substrate and all dissolve, slowly drip 5mL hydrazine hydrate, be heated to 70oC back flow reaction 3h, be then cooled to room temperature, separate out white solid, filter, the cold absolute ethanol washing of filter cake, dry, obtain white solid 150mg, productive rate 77%, ESI:164.1.
(4) 4-α-tolylene diazanyl-1-methyl-pyrazoles [3,4-d] pyrimidine (P-1) is synthetic
Weigh 4-diazanyl-1-methyl isophthalic acid-hydrogen-pyrazoles [3,4-d] and pyrimidine (100mg, 609 μ mol) in 25mL single port flask, measure the dehydrated alcohol of 10mL, drip 50mg acetic acid, heated and stirred to raw material dissolves completely, take phenyl aldehyde (129mg, 1.2mmol) and add above-mentioned reaction system, continue heating reflux reaction 2.5h, then be cooled to room temperature, filter, filter cake absolute ethanol washing, dehydrated alcohol recrystallization obtains white solid 130mg, productive rate 84%, fusing point 238.0-240.3 ° C. 1H?NMR(400MHz,DMSO-d 6)δ12.09(s,1H),8.38(d,J=2.4Hz,2H),8.28(s,1H),7.80(d,J=7.2Hz,2H),7.53-7.43(m,3H),3.97(s,3H)。 13C?NMR(100MHz,DMSO-d 6)δ156.5,155.4,154.0,145.9,134.6,130.3,129.5,127.3,99.7,33.9。HRMS (EI/[M +]): C 13h 12n 6calculated value: 252.1123; Experimental value: 252.1127.
Synthesizing of embodiment 2.4-(3-oil of mirbane methylene radical)-diazanyl-1-methyl-pyrazoles [3,4-d] pyrimidine (P-2)
Weigh 4-diazanyl-1-methyl isophthalic acid-hydrogen-pyrazoles [3,4-d] and pyrimidine (100mg, 609 μ mol) in 25mL single port flask, measure the dehydrated alcohol of 10mL, drip 50mg acetic acid, heated and stirred to raw material dissolves completely, take 3-nitrobenzaldehyde (184mg, 1.2mmol) and add above-mentioned reaction system, continue heating reflux reaction 2.5h, then be cooled to room temperature, filter, filter cake absolute ethanol washing, dehydrated alcohol recrystallization obtains white solid 153mg, productive rate 84%, fusing point 306.3-308.7 ° C. 1H?NMR(400MHz,DMSO-d 6)δ12.32(s,1H),8.51(s,1H),8.40-8.36(m,3H),8.26(dd,J 1=8.0Hz,J 2=8.4Hz,2H),7.77(dd,J 1=8.0Hz,J 2=7.6Hz,1H),3.97(s,3H)。HRMS (EI/[M +]): C 13h 11n 7o 2calculated value: 297.0974; Experimental value: 297.0978.
Synthesizing of embodiment 3.4-(the fluoro-4-trifluoromethyl of 2-α-tolylene)-diazanyl-1-methyl-pyrazoles [3,4-d] pyrimidine (P-3)
Weigh 4-diazanyl-1-methyl isophthalic acid-hydrogen-pyrazoles [3,4-d] and pyrimidine (100mg, 609 μ mol) in 25mL single port flask, measure the dehydrated alcohol of 10mL, drip 50mg acetic acid, heated and stirred to raw material dissolves completely, take the fluoro-4-trifluoromethylated benzaldehyde of 2-(234mg, 1.22mmol) and add above-mentioned reaction system, continue heating reflux reaction 2.5h, then be cooled to room temperature, filter, filter cake absolute ethanol washing, dehydrated alcohol recrystallization obtains white solid 181mg, productive rate 87%, fusing point 247.2-249.0 ° C. 1H?NMR(400MHz,DMSO-d 6)δ12.34(s,1H),8.45-8.37(m,3H),8.24(dd,J 1=7.6Hz,J 2=7.6Hz,1H),7.79(d,J=10.8Hz,1H),7.69(d,J=8.4Hz,1H),3.97(s,3H)。 13C?NMR(100MHz,DMSO-d 6)δ161.4,158.9,156.3,155.2,154.0,137.3,134.4,128.3,126.4,125.0,122.3,114.299.7,33.9。 19F?NMR(376MHz,DMSO-d 6)δ-61.28,-117.94。HRMS (EI/[M +]): C 14h 10f 4n 6calculated value: 338.0903; Experimental value: 338.0907.
Synthesizing of embodiment 4.4-(2,3-difluorobenzene methylene radical)-diazanyl-1-methyl-pyrazoles [3,4-d] pyrimidine (P-4)
Weigh 4-diazanyl-1-methyl isophthalic acid-hydrogen-pyrazoles [3,4-d] and pyrimidine (100mg, 609 μ mol) in 25mL single port flask, measure the dehydrated alcohol of 10mL, drip 50mg acetic acid, heated and stirred to raw material dissolves completely, takes 2,3-difluorobenzaldehyde (173mg, 1.2mmol) add above-mentioned reaction system, continue heating reflux reaction 2.5h, be then cooled to room temperature, filter, filter cake absolute ethanol washing, dehydrated alcohol recrystallization obtains white solid 150mg, productive rate 85%, fusing point 290.2-292.5 ° C. 1H?NMR(400MHz,DMSO-d 6)δ12.21(s,1H),8.39(s,1H),8.37(s,1H),8.30(s,1H),7.77(dd,J 1=6.4Hz,J 2=6.4Hz,1H),7.46(d,J=8.8Hz,1H),7.31(d,J=5.6Hz,1H),3.95(s,3H)。 13CNMR(100MHz,DMSO-d 6)δ156.3,155.3,154.0,138.0,134.4,125.8,125.7,124.5,122.5,118.6,118.4,99.7,33.9。 19F?NMR(376MHz,DMSO-d 6)δ-138.82,-145.96。HRMS (EI/[M +]): C 13h 10f 2n 6calculated value: 288.0935; Experimental value: 288.0934.
Synthesizing of embodiment 5.4-(2,3,6-trifluoro-benzene methylene radical)-diazanyl-1-methyl-pyrazoles [3,4-d] pyrimidine (P-5)
Weigh 4-diazanyl-1-methyl isophthalic acid-hydrogen-pyrazoles [3,4-d] and pyrimidine (100mg, 609 μ mol) in 25mL single port flask, measure the dehydrated alcohol of 10mL, drip 50mg acetic acid, heated and stirred to raw material dissolves completely, takes 2,3,6-trifluro benzaldehyde (195mg, 1.2mmol) adds above-mentioned reaction system, continues heating reflux reaction 2.5h, then be cooled to room temperature, filter, filter cake absolute ethanol washing, dehydrated alcohol recrystallization obtains white solid 160mg, productive rate 85%, fusing point 284.6-286.0 ° C. 1H?NMR(400MHz,DMSO-d 6)δ12.27(s,1H),8.40(s,1H),8.35(s,1H),8.29(s,1H),7.56(d,J=4.8Hz,1H),7.26(s,1H),3.95(s,3H)。 19F?NMR(376MHz,DMSO-d 6)δ-118.29,-137.70,-142.13。HRMS (EI/[M +]): C 13h 9f 3n 6calculated value: 306.0841; Experimental value: 306.0844.
Embodiment 6.4-[(2,3,4,5-tetra fluoro benzene methylene radical)-diazanyl]-1-methyl-pyrazoles [3,4-d] pyrimidine (P-6) synthetic
Weigh 4-diazanyl-1-methyl isophthalic acid-hydrogen-pyrazoles [3,4-d] and pyrimidine (100mg, 609 μ mol) in 25mL single port flask, measure the dehydrated alcohol of 10mL, drip 50mg acetic acid, heated and stirred to raw material dissolves completely, take 2,3,4,5-tetrafluorobenzene carbaldehyde (216mg, 1.2mmol) add above-mentioned reaction system, continue heating reflux reaction 2.5h, be then cooled to room temperature, filter, filter cake absolute ethanol washing, dehydrated alcohol recrystallization obtains white solid 175mg, productive rate 88%, fusing point 313.2-314.1 ° C. 1H?NMR(400MHz,DMSO-d 6)δ12.31(s,1H),8.41(s,1H),8.39(s,1H),8.34(s,1H),7.89-7.87(m,1H),3.95(s,3H)。 19F?NMR(376MHz,DMSO-d 6)δ-138.59,-145.40,-154.61,-156.13。HRMS (EI/[M +]): C 13h 8f 4n 6calculated value: 324.0747; Experimental value: 324.0745.
Synthesizing of embodiment 7.4-(the chloro-4-trifluoromethoxy of 3-α-tolylene)-diazanyl-1-methyl-pyrazoles [3,4-d] pyrimidine (P-7)
Weigh 4-diazanyl-1-methyl isophthalic acid-hydrogen-pyrazoles [3,4-d] and pyrimidine (100mg, 609 μ mol) in 25mL single port flask, measure the dehydrated alcohol of 10mL, drip 50mg acetic acid, heated and stirred to raw material dissolves completely, take the chloro-4-trifluoro-methoxybenzaldehyde of 3-(273mg, 1.2mmol) and add above-mentioned reaction system, continue heating reflux reaction 2.5h, then be cooled to room temperature, filter, filter cake absolute ethanol washing, dehydrated alcohol recrystallization obtains white solid 192mg, productive rate 85%, fusing point 219.8-221.6 ° C. 1H?NMR(400MHz,DMSO-d 6)δ12.10(s,1H),8.36(s,1H),8.30(s,1H),8.21(s,1H),7.96-7.89(m,2H),7.62(d,J=7.6Hz,1H),3.95(s,3H)。 13C?NMR(100MHz,DMSO-d 6)δ155.8,154.7,153.4,144.3,142.4,135.0,134.0,128.9,126.6,123.3,121.2,118.6,99.1,33.4。 19F?NMR(376MHz,DMSO-d 6)δ-56.95。HRMS (EI/[M +]): C 14h 10clF 3n 6o calculated value: 370.0557; Experimental value: 370.0558.
Synthesizing of embodiment 8.4-(the chloro-4-trifluoromethyl of 3-α-tolylene)-diazanyl-1-methyl-pyrazoles [3,4-d] pyrimidine (P-8)
Weigh 4-diazanyl-1-methyl isophthalic acid-hydrogen-pyrazoles [3,4-d] and pyrimidine (100mg, 609 μ mol) in 25mL single port flask, measure the dehydrated alcohol of 10mL, drip 50mg acetic acid, heated and stirred to raw material dissolves completely, take the chloro-4-trifluoromethylated benzaldehyde of 3-(254mg, 1.2mmol) and add above-mentioned reaction system, continue heating reflux reaction 2.5h, then be cooled to room temperature, filter, filter cake absolute ethanol washing, dehydrated alcohol recrystallization obtains white solid 200mg, productive rate 92%, fusing point 282.8-282.9 ° C is too accurate. 1H?NMR(400MHz,DMSO-d 6)δ12.32(s,1H),8.38(s,1H),8.27(s,1H),8.22(s,1H),7.92-7.86(m,3H),3.95(s,3H)。 13C?NMR(100MHz,DMSO-d 6)δ156.3,155.1,153.9,142.5,140.3,134.3,131.7,129.7,128.9,127.0,125.5,124.6,121.8,99.7,33.9。 19F?NMR(376MHz,DMSO-d 6)δ-61.11。HRMS (EI/[M +]): C 14h 10clF 3n 6calculated value: 354.0608; Experimental value: 354.0600.
Synthesizing of embodiment 9.4-(the bromo-5-trifluoromethyl of 2-α-tolylene)-diazanyl-1-methyl-pyrazoles [3,4-d] pyrimidine (P-9)
Weigh 4-diazanyl-1-methyl isophthalic acid-hydrogen-pyrazoles [3,4-d] and pyrimidine (100mg, 609 μ mol) in 25mL single port flask, measure the dehydrated alcohol of 10mL, drip 50mg acetic acid, heated and stirred to raw material dissolves completely, take the bromo-5-trifluoromethylated benzaldehyde of 2-(308mg, 1.2mmol) and add above-mentioned reaction system, continue heating reflux reaction 2.5h, then be cooled to room temperature, filter, filter cake absolute ethanol washing, dehydrated alcohol recrystallization obtains white solid 212mg, productive rate 87%, fusing point 293.0-295.4 ° C. 1H?NMR(400MHz,DMSO-d 6)δ12.40(s,1H),8.60(s,1H),8.40(s,1H),8.20(s,1H),8.16(s,1H),7.94(d,J=8.8Hz,1H),7.70-7.68(m,1H),3.95(s,3H)。 19F?NMR(376MHz,DMSO-d 6)δ-61.79。HRMS (EI/[M +]): C 14h 10brF 3n 6calculated value: 398.0102; Experimental value: 398.0106.
Embodiment 10.4-[(3-methyl-6-trifluoromethyl α-tolylene)-diazanyl]-1-methyl-pyrazoles [3,4-d] pyrimidine (P-10) synthetic
Weigh 4-diazanyl-1-methyl isophthalic acid-hydrogen-pyrazoles [3,4-d] and pyrimidine (100mg, 609 μ mol) in 25mL single port flask, measure the dehydrated alcohol of 10mL, drip 50mg acetic acid, heated and stirred to raw material dissolves completely, take 3-methyl-6-trifluoromethylated benzaldehyde (229mg, 1.2mmol) and add above-mentioned reaction system, continue heating reflux reaction 2.5h, then be cooled to room temperature, filter, filter cake absolute ethanol washing, dehydrated alcohol recrystallization obtains white solid 190mg, productive rate 93%, fusing point 270.5-272.3 ° C. 1H?NMR(400MHz,Acetone-d 6)δ11.19-11.17(m,1H),8.68(s,1H),8.40(d,J=8.0Hz,2H),8.24(s,1H),7.72(d,J=8.0Hz,1H),7.49(d,J=8.0Hz,1H),4.02(s,3H),2.57(s,3H)。 19F?NMR(376MHz,DMSO-d 6)δ-56.39。HRMS (EI/[M +]): C 15h 13f 3n 6calculated value: 334.1154; Experimental value: 334.1157.
Embodiment 11. plant disease-resistant Activation Activity tests
The present embodiment checked the compounds of this invention as Plant activator the prevention effect to phytopathogen:
1. experimental subjects: the climing rot of anti-yellowing melon, anti-Cucumber Target Leaf Spot, anti-cucumber bacterial angular leaf spot, anti-tomato late blight, rice sheath blight disease, gray mold of cucumber, cucumber fusarium axysporum.
2. test concentrations: this test all adopts 100mg/L test concentrations.
3. testing method: the good various crops of sowing in advance, and quantitatively take sample, and with DMF, dissolve and add proper amount of surfactant, be diluted with water to setting concentration.Adopt roll-back method inoculation first 7 days, 5 days, 3 days, 1 day, minute carry out drug treating four times, then disposablely inoculate pathogenic bacteria simultaneously.Experiment adopts pot-culture method to carry out, and repeats 3 times.The account form of disease index and protection effect is as follows: disease index=[∑ (the sick number of sheets * relative level numerical value at different levels) * 100]/(investigating the total number of sheets * highest level numerical value that represents of falling ill), prevention effect (%)=[(disease index-treatment zone, check plot disease index) * 100]/check plot disease index.
4. experimental result
The present invention has adopted method mentioned above to test the inducing anti-disease activity of five kinds of diseases to 10 imidazo thiazine derivatives, shown in the following list 1 of compound test activity data in early stage:
The disease-resistant Activation Activity test result of table 1. the compounds of this invention
N/A: do not record
The active testing of embodiment 12. the compounds of this invention Suppressing phytopathogens
In in vitro bacteriostatic experiment, it is active to the inhibition of described pathogenic bacteria or lethal effect that contriver has further tested the compounds of this invention.
Found that: the phytopathogen equal unrestraint effect of the compounds of this invention to test.Thereby further prove that the compounds of this invention does not possess and directly kills and wounds or restraining effect phytopathogen, but by the disease resistance of activated plant, resist the infringement of pathogenic bacteria.
Discuss:
From embodiment 12, can find out, the compounds of this invention possesses the activity of controlling plant diseases, 12 result further proves that compound of the present invention is not direct killing or suppresses phytopathogen in conjunction with the embodiments, but produce by inducing plant the effect that the disease resistance of resisting each row pathogenic agent realizes controlling plant diseases, this and traditional agricultural chemicals, for example jingganmycin is very different.In addition, from embodiment 11, it can also be seen that, the compounds of this invention all has preventive and therapeutic effect for plurality of plant diseases, therefore has the broad spectrum that traditional agricultural chemicals does not often possess.Those skilled in the art are also not difficult to understand, although traditional agricultural chemicals, for example jingganmycin also has good preventive and therapeutic effect to Plant diseases, they often single, the agricultural chemicals of existence effect have the open defects such as residual, contaminate environment.Compare with traditional agricultural chemicals, the compounds of this invention possesses that broad spectrum, toxicity are low, advantages of environment protection, and then possesses high economic worth and application prospect.
All documents of mentioning in the present invention are all quoted as a reference in this application, just as each piece of document, are quoted as a reference separately.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.

Claims (9)

1. the heterogeneous ring compound shown in general formula I,
In formula,
R 1independently be selected from: hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, halogen, nitro, hydroxyl;
R 2independently be selected from: the heterocycle of C1-C6 alkyl, C1-C6 haloalkyl, hydroxyl, C1-C6 alkoxyl group, C1-C6 halogenated alkoxy, replacement or unsubstituted C6-C14 aryl, halogen, nitro, amino, C1-C6 alkylamino, carboxyl, C1-C3 alkoxyl formyl, 5 yuan or 6 yuan of nitrogenous, oxygen or sulphur;
N is the integer that is selected from 0-5.
2. compound as claimed in claim 1, is characterized in that, in general formula I,
R 1it is methyl;
R 2independently be selected from: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxyl group, C1-C3 halogenated alkoxy, halogen, nitro;
N is the integer that is selected from 0-5.
3. the compound as described in any one in claim 1-2, is characterized in that, described compound is selected from lower group:
4. the disease-resistant composition of inducing plant, comprises in Pesticide Science acceptable carrier and as the compound described in any one in the claim 1-3 of inducing plant anti-disease activity composition.
5. composition as claimed in claim 4, is characterized in that, described composition is for preventing and treating bacterium, fungi or the infringement of virus to plant.
6. the composition as described in claim 4 or 5, is characterized in that, described composition is used for preventing and treating the climing rot of cucumber, Cucumber Target Leaf Spot, cucumber bacterial angular leaf spot, tomato late blight, rice sheath blight disease, gray mold of cucumber or cucumber fusarium axysporum.
7. the purposes of the compound described in any one in preparing the disease-resistant composition of inducing plant in claim 1-3.
8. the disease-resistant method of inducing plant, is characterized in that, described method comprises: the composition described in any one in the compound described in any one in claim 1-3 or claim 4-6 is applied to described plant.
9. the method for preparing compound shown in general formula I, described method comprises implements the reaction shown in following synthetic route:
Take 1-alkyl-4-carboxylicesters-5-amino-pyrazol and formyl ammonium is starting raw material, through reaction, obtaining intermediate A; Intermediate A is by POCl 3chloro, obtains intermediate B; Intermediate B hydrazinolysis obtains Compound C; Intermediate C and various aldehyde form corresponding hydrazone (methylene radical diazanyl) compound P.
R in formula 1and R 2as claim 1 limits.
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