CN104059027B - One class contains (E)-methoxyimino methyl phenylacetate compounds of 1,2,4-triazole and its production and use - Google Patents

One class contains (E)-methoxyimino methyl phenylacetate compounds of 1,2,4-triazole and its production and use Download PDF

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CN104059027B
CN104059027B CN201410309699.XA CN201410309699A CN104059027B CN 104059027 B CN104059027 B CN 104059027B CN 201410309699 A CN201410309699 A CN 201410309699A CN 104059027 B CN104059027 B CN 104059027B
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triazole
nitro
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fluorine
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CN104059027A (en
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王献友
贡东军
庞艳苹
陈培云
赵志磊
吴广臣
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Hebei University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

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

Abstract

The invention discloses a kind of newly, the compound with fungicidal activity, a kind of preparation method and purposes of this compound are provided simultaneously.This compound is (the E)-methoxyimino methyl phenylacetate compounds of a class containing 1,2,4-triazole, and the compound of its preparation method represented by general formula I I and the compound represented by general formula III carry out reaction and form; Compound provided by the present invention has good fungicidal activity, can be applied preparing in crop bactericide.

Description

One class contains (E)-methoxyimino methyl phenylacetate compounds of 1,2,4-triazole and its production and use
Technical field
The present invention relates to compound and its production and use, the class specifically relating to have fungicidal activity contains (E)-methoxyimino methyl phenylacetate compounds of 1,2,4-triazole and its production and use.
Background technology
Grain is significant to human survival, development and social stability, uses agricultural chemicals effectively can improve grain yield.Agricultural chemicals is while making tremendous contribution for human civilization, and high poison, the environment that the agricultural chemicals of high residue is also depended on for existence to the mankind bring negative impact.Along with the progress of society and the raising of civilization, require harmonious co-existence between man and nature, people it is also proposed higher requirement to agricultural chemicals, therefore, research and development are efficient, low toxicity, environment friendly agricultural that easily degraded, security and Environmental compatibility are good have become current pesticide research main flow and direction.
Sterilant, as one of large main flow kind of agricultural chemicals three, agricultural application and pesticide industry market occupies an important position.Sterilant comprises traditional multiaction site sterilant and modern selectivity sterilant, and in general the former action site is many, fungicidal spectrum wide, but security is low, and easily to environment, the action site of the latter has specificity, more single, safe and efficient.
Methoxy acrylic bactericide is a class Di Du ﹑ Gao Xiao ﹑ Guang Pu ﹑ systemic fungicide.Almost all there is good activity to diseases such as all Zhen Jun ﹑ Luan Jun Gang ﹑ algae Jun Gang ﹑ Ascomycetes and deuteromycetes.And effectively can prevent and treat the pathogenic bacteria series other sterilant being produced to resistance.BASF and ICI company are all investigators of methoxy acrylic bactericide the earliest, but the patent of ICI company first methoxy acrylate compound (Azoxystrobin) prior to BASF openly out, the BASF AG simultaneously studying this compounds is made to abandon its research, they change atom N into the C atom in compound, introduce an oxime ether group, thereby produce the kresoxim-methyl series bactericidal agent that sterilization effect is more excellent.
At present, in order to prevent farm crop to produce resistance to existing sterilant, researchist striving to find out more newly, there is bioactive sterilant.
Summary of the invention
The object of the present invention is to provide a kind of newly, the compound with fungicidal activity, a kind of preparation method and purposes of this compound are provided simultaneously.
Provided by the present invention newly, the compound with fungicidal activity is (the E)-methoxyimino methyl phenylacetate compounds of a class containing 1,2,4-triazole, the following I of its general structure
In formula I, substituent R 1, R 2for independently selected from one or more
Substituent R 1for independently selected from one or more hydrogen, C 1~ C 4alkyl, alkoxyl group, benzyloxy, hydroxyl, nitro, halogen atom;
Substituent R 2for independently selected from one or more expression hydrogen, C 1~ C 4alkyl, alkoxyl group, hydroxyl, itrile group, nitro, halogen atom.
In view of economy and the biological activity of compound, the preferred compound of the present invention is:
R in formula I 1h, methyl, methoxyl group;
R 24-nitro, 4-chlorine, 4-methyl, 4-bromine, 4-fluorine, 4-hydroxyl, 4-hydrogen, 4-methoxyl group, 4-dimethylamino, 2-nitro, 2-chlorine, 2-bromine, 2-fluorine, 2-hydroxyl, 2-methoxyl group, 3-nitro, 3-bromine, 3-fluorine, 2,4-dichloro, 3, the chloro-6-fluorine of 4-dimethoxy, 2-, 3,4-dichloros.
The preparation method of above-claimed cpd provided by the present invention is that the compound represented by general formula I I and the compound represented by general formula III react,
R in formula II, III 1be independently selected from one or more hydrogen, C 1~ C 4alkyl, alkoxyl group, benzyloxy, hydroxyl, nitro, halogen atom;
R 2be independently selected from one or more expression hydrogen, C 1~ C 4alkyl, alkoxyl group, hydroxyl, itrile group, nitro, halogen atom;
X is chlorine, bromine atoms.
More preferably
R 1it is the one in H, methyl, methoxyl group; R 24-nitro, 4-chlorine, 4-methyl, 4-bromine, 4-fluorine, 4-hydroxyl, 4-hydrogen, 4-methoxyl group, 4-dimethylamino, 2-nitro, 2-chlorine, 2-bromine, 2-fluorine, 2-hydroxyl, 2-methoxyl group, 3-nitro, 3-bromine, 3-fluorine, 2,4-dichloro, 3, one in the chloro-6-fluorine of 4-dimethoxy, 2-, 3,4-dichloros.
In above-mentioned reaction, its reaction conditions is DMF//K 2cO 3, temperature of reaction is normal temperature, stirs.
Compound represented by above-mentioned general formula I I, can buy from market, also can obtain in such a way.
Reaction formula 2:
Compound shown in formula I more specifically obtains preparation process: at suitable solvent as in DMF, in 80 DEG C of reactions, with the compound of suitable alkali as sodium carbonate, salt of wormwood process formula II, then add the compound of formula III.
Formula I provided by the invention, has certain fungicidal activity, can be used for controlling the germ harmful to farm crop.Therefore it is being prepared in crop bactericide and can be applied.This completes the purposes invention of compound of the present invention.
Harmful levels of pathogens described here comprises by multiple fungus-caused diseases such as Ascomycetes, Basidiomycetes, Oomycete, deuteromycetes, Phycomycetes, Haplomyceteses.
Embodiment
Following embodiment and raw test-results of surveying can be used to further illustrate the present invention, but do not mean that restriction the present invention.
The synthesis of embodiment 1.3-aryl-4-amino-5-sulfydryl-1,2,4-triazole
(1) synthesis of benzoyl hydrazine
In 50mL round-bottomed flask, add ethyl benzoate 15g, add ethanol, add 85% hydrazine hydrate of 10mL after solid stirring and dissolving (when just adding hydrazine hydrate, system is changeable is brown color, turns green gradually, along with heating, finally become colorless transparent liquid), reflux 4h, steams unnecessary alcohol after cooling, has a large amount of solid to separate out, filter, with ethyl alcohol recrystallization, obtain white needles, dry product 12.6g.Yield: 92.6%.
(2) synthesis of benzoyl hydrazine dithiocarbonic acid sylvite
Add in 100mL there-necked flask benzoyl hydrazine 8g, dehydrated alcohol 30mL, with benzoyl hydrazine 1:1.2 KOH doubly, after stirring and dissolving, under ice bath, drip 1:1 CS doubly 2, temperature rising reflux 2h, after reaction terminates, cool to room temperature, separate out faint yellow solid, suction filtration, obtains white powdery solids 1.2g, yield with ethanol alcohol recrystallization: 81.6%.
(3) synthesis of 3-aryl-4-amino-5-sulfydryl-1,2,4-triazole
5.0g (0.02mol) benzoyl hydrazine dithiocarbonic acid sylvite is joined in 25mL dehydrated alcohol, is yellow emulsion after stirring, adds 3.12g (0.05mol) 80% hydrazine hydrate, reflux 6h; Add 100mL water after cooling, obtain yellow-green soln, be acidified to pH=2 ~ 3 with concentrated hydrochloric acid, have a large amount of white solid to separate out, hold over night, suction filtration also washes with water to neutrality, dry 2.4g target compound, yield: 63.1%, m.p.:201-202 DEG C; IR:(KBr, cm -1): 3412,3070,2667,1640; 1h NMR (600MHz, DMSO-d6) δ: 13.90 (s, 1H, triazole-NH), 7.52-8.01 (m, 5H, Ar-H), 5.81 (s, 2H, NH 2).
Embodiment 2.3-sulfydryl-4-substituted-phenyl imido grpup-5-phenyl-4H-1, the preparation of 2,4-triazole (II)
(1) 3-sulfydryl-4-phenyl imine base-5-phenyl-4H-1, the preparation of 2,4-triazole (II-a)
In the mono-neck round-bottomed flask of 50mL, add 3-aryl-4-amino-5-sulfydryl-1,2,4-triazole 1.39g (l0mmol), phenyl aldehyde 1.06g (10mmol), 30mL dehydrated alcohol and 3 Glacial acetic acid, heating, backflow, TLC monitors.After reacting completely, be cooled to room temperature, suction filtration, with ethyl alcohol recrystallization, obtain white rhabdolith.
(2) 3-sulfydryl-4-p-methoxyphenyl imido grpup-5-phenyl-4H-1,2, in the mono-neck round-bottomed flask of preparation 50mL of 4-triazole (II-b), add 3-aryl-4-amino-5-sulfydryl-1,2,4-triazole 1.39g (l0mmol), 4-methoxybenzaldehyde 1.36g (10mmol), 30mL dehydrated alcohol and 3 Glacial acetic acid, heating, backflow, TLC monitors.After reacting completely, be cooled to room temperature, suction filtration, with ethyl alcohol recrystallization, obtain white rhabdolith.
(3) synthesize other this type of intermediate (IIc ~ IIv) by same procedure, its physical properties and yield in table 1, 1h NMR data are in table 2
The physical properties of table 1 Compound II per a ~ IIv and yield
Table 2 Compound II per a ~ IIv's 1h NMR data
Embodiment 3. target compound (E)-2-(3-(4-(E)-2-substituted benzene methene amido-5-phenyl-4H-1,2,4-triazole-3-sulfydryl)-methylene radical)-phenyl) preparation of-3-methoxyimino methyl acetate (Ia-Iv)
(1) (E)-2-(3-(4-(E)-2-benzylideneamino-5-phenyl-4H-1,2,4-triazole-3-sulfydryl)-methylene radical)-phenyl) preparation of preparation of-3-methoxyimino methyl acetate (I-a)
Take 0.490g (1.75mmol) 3-sulfydryl-4-phenyl imine base-5-phenyl-4H-1,2,4-triazole 0.474g (1.75mmol) (E)-2-(2-brooethyl) phenyl-3-methoxyimino methyl acetate, 0.24g (1.75mmol) K 2cO 3, be dissolved in 15ml DMF, 80 DEG C of reaction 1h.Be cooled to room temperature, add 30mL water, separate out solid, suction filtration, adds hot recrystallization with ethanol (on a small quantity), and suction filtration obtains white shape solid.
(1) ((4-(E)-2-is to methoxybenzylidene amino-5-phenyl-4H-1 for 3-for (E)-2-, 2,4-triazole-3-sulfydryl)-methylene radical)-phenyl) preparation of preparation of-3-methoxyimino methyl acetate (I-b)
Take 0.542g (1.75mmol) 3-sulfydryl-4-p-methoxyphenyl imido grpup-5-phenyl-4H-1,2,4-triazole 0.474g (1.75mmol) (E)-2-(2-brooethyl) phenyl-3-methoxyimino methyl acetate, 0.24g (1.75mmol) K 2cO 3, be dissolved in 15ml DMF, 80 DEG C of reaction 1h.Be cooled to room temperature, add 30mL water, separate out solid, suction filtration, adds hot recrystallization with ethanol (on a small quantity), and suction filtration obtains white shape solid.
(3) synthesize other target compound (Ic ~ Iv) by same procedure, its physical properties and yield in table 3, 1h NMR data (TMS is interior mark) and HRMS (ESI) m/z [M+H] +in table 4
Table 3 target compound physical properties and yield
Table 4 target compound 1h NMR data (TMS is interior mark) and HRMS (ESI) m/z [M+H] +
The in vitro fungicidal activity of compound shown in embodiment 4. formula I to phytopathogen measures
(1) with fusarium graminearum, cotton seedling blight, gray mold of cucumber, rice sheath blight disease and wheat powdery mildew for determination object, adopt growth rate method measure.
Operating process: all compounds shown in formula I are formulated as 50 μ g/mL.Aseptically, picking test strain cake is placed in the PDA culture medium flat plate central authorities containing different agents concentration, with blank PDA substratum for contrast, is placed in 25 DEG C of constant incubators and cultivates, often kind of gradient parallel testing 3 times.
According to the growing state investigation pathogenic bacteria mycelial growth situation of bacterium colony in blank culture dish, after bacterium colony fully grows in blank, measure the colony diameter of each process with right-angled intersection method.Mycelial growth inhibition rate calculation formula is as follows:
Sterilization test result is in table 5.
(2) be 50 μ g/mL at drug concentration, Compound I s, Im, Ii are to rice sheath blight disease, and gray mold of cucumber, wheat scab shows certain bacteriostatic activity.Ic, Id, Ie, If have excellent fungicidal activity to wheat powdery mildew.
Compound shown in table 5 formula I is to the in vitro fungicidal activity measurement result (50 μ g/mL, inhibiting rate/%) of pathogenic
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all do within technical spirit of the present invention any amendment, equivalent to replace and improvement etc., all should be included within protection scope of the present invention.

Claims (4)

1. a class is containing (E)-methoxyimino methyl phenylacetate compounds of 1,2,4-triazole, it is characterized in that having the structure that following general formula I represents:
In formula I, substituent R 1for independently selected from one or more hydrogen;
Substituent R 2for independently selected from one or more expression hydrogen, C 1~ C 4alkyl, 4 ?methoxyl group, 2 ?methoxyl group, 3,4 ?dimethoxy, hydroxyl, itrile group, nitro, halogen atom.
2. compound according to claim 1, is characterized in that R in formula I 1be selected from H; R 2be selected from 4-nitro, 4-chlorine, 4-methyl, 4-bromine, 4-fluorine, 4-hydroxyl, 4-hydrogen, 4-methoxyl group, 2-nitro, 2-chlorine, 2-bromine, 2-fluorine, 2-hydroxyl, 2-methoxyl group, 3-nitro, 3-bromine, 3-fluorine, 2,4-dichloro, 3, any one in the chloro-6-fluorine of 4-dimethoxy, 2-, 3,4-dichloros.
3. the preparation method of compound described in claim 1, is characterized in that, its compound represented by general formula I I and the compound represented by general formula III react,
R in formula II, III 1, R 2definition identical with the definition in claim 1, wherein X is chlorine, bromine atoms;
Its reaction conditions is DMF//K 2cO 3, temperature of reaction is normal temperature, stirs.
4. compound described in claim 1 is preparing the application in crop bactericide.
CN201410309699.XA 2014-07-01 2014-07-01 One class contains (E)-methoxyimino methyl phenylacetate compounds of 1,2,4-triazole and its production and use Expired - Fee Related CN104059027B (en)

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CN107935950B (en) * 2017-12-21 2021-03-05 天津瑞岭化工有限公司 Triazole Schiff base compound and preparation method and application thereof
CN109053607B (en) * 2018-09-03 2021-10-15 湖南大学 4- (4-hydroxyphenylmethyleneamino) -1,2, 4-triazole-5-thione and medical application thereof
CN111087354B (en) * 2020-01-10 2022-04-15 河北大学 Preparation method and application of N- (2-isoxazole-3-methylphenyl) acetamide containing nitrogen heterocycle
CN113735842B (en) * 2020-05-27 2023-01-31 河北农业大学 1,2, 4-triazole Schiff base thioether derivatives, and preparation method and application thereof
CN111499587B (en) * 2020-06-01 2023-08-04 河北大学 Methoxy acrylic ester compound containing 1,2, 4-triazole Schiff base and preparation method and application thereof
CN114634456B (en) * 2022-03-22 2024-02-20 赣南师范大学 5-nitroimino-4H-1, 2, 4-triazole compound and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1434808A (en) * 1999-12-17 2003-08-06 圣诺菲-合成实验室公司 Novel branched substituted amino derivatives of 3-amino-1-phemyl-1H[1,2,4]triazo, methods for producing them and pharmaceutica compositions containing them
CN1436177A (en) * 2000-06-16 2003-08-13 拜尔农作物科学股份公司 Method for preparing substd.5-amino-N-pheny1-1,2,4, -triazole-3-sulfonamides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1434808A (en) * 1999-12-17 2003-08-06 圣诺菲-合成实验室公司 Novel branched substituted amino derivatives of 3-amino-1-phemyl-1H[1,2,4]triazo, methods for producing them and pharmaceutica compositions containing them
CN1436177A (en) * 2000-06-16 2003-08-13 拜尔农作物科学股份公司 Method for preparing substd.5-amino-N-pheny1-1,2,4, -triazole-3-sulfonamides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Combinatorial approach: identification of potential antifungals from triazole minilibraries;Manish Sudesh Bhatia, et al.;《Med. Chem. Res.》;20111231;第20卷;116-120 *

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