CN103524441B - Containing compound and preparation method thereof and the application as weedicide of triazole structure - Google Patents

Containing compound and preparation method thereof and the application as weedicide of triazole structure Download PDF

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CN103524441B
CN103524441B CN201310451042.2A CN201310451042A CN103524441B CN 103524441 B CN103524441 B CN 103524441B CN 201310451042 A CN201310451042 A CN 201310451042A CN 103524441 B CN103524441 B CN 103524441B
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triazole
compound
herba
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preparation
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CN103524441A (en
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曹永松
丁光龙
耿倩倩
刘瑶
郭明程
段永恒
邓宇芳
张文兵
何顺
李健强
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China Agricultural 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
    • C07D249/14—Nitrogen 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
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
    • A01N57/32—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds containing heterocyclic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6518—Five-membered rings

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

Abstract

The invention discloses a kind of compound containing triazole structure and preparation method thereof and the application as weedicide.Containing the structural formula of the compound of triazole structure such as formula shown in I; in formula I; R represents that allyl group, carbonatoms are the alkyl acyl of 1 ~ 20, substituted or unsubstituted benzoyl, O; O-dimethyl thio phosphoryl, phenyl, benzene oxygen ethanoyl, 3-phenyl-2-acryl or 2,6-dinitrobenzene-4-trifluoromethyl.The preparation method of compound shown in formula I provided by the invention, comprises the steps: under the katalysis of alkali, 3-amino-1H-1, and 2,4-triazole and electrophilic reagent obtain compound shown in formula I through electrophilic substitution reaction.Weedicide provided by the invention can be used for management of weeds dog tail, lady's-grass, Herba Eleusines Indicae, black nightshade, three-coloured amaranth, piemarker, lamb's-quarters, humulus grass, summer cypress, Herba seu Flos Convolvuli arvensis, Herba Acalyphae, Herba Ixeritis chinensis and early keng rice.

Description

Containing compound and preparation method thereof and the application as weedicide of triazole structure
Technical field
The present invention relates to a kind of compound containing triazole structure and preparation method thereof and the application as weedicide, belong to field of pesticide chemistry.
Background technology
At present, the research and development emphasis of chemical pesticide is design containing aromatic ring, heterocycle and fused ring compound and screening.Having different bioactive group is combined in same molecule, can realize bioactive superposition or enhancing.Triazole class compounds has good biological activity, and it has the plurality of advantages such as active high and low poison, wide spectrum, Uptake and translocation be good as sterilant, sterilant, miticide.After the agriculture of U.S. FMC, Tao Shi benefit, Japanese Wu Yu chemistry and Japanese Chugai Deng Ji company develop triazole herbicide, structure of modification is carried out to triazole class compounds and the research that obtains novel herbicidal compound has become a new focus.Because traditional triazole herbicide herbicide spectrum is narrow, speed of action is slow, dosage is large; therefore other some active groups (as halogen-containing benzoyl, benzene oxygen ethanoyl etc.) are introduced in triazole class compounds, efficient, lasting novel herbicidal compound can be obtained.According to high flux screening principle, often a series of active group is introduced in triazole class compounds, to increasing the action target site of new compound, improving weeding activity and speed of action, reducing consumption.By literature search, US Patent No. 3144460 discloses a kind of synthesis and biological activity of 1,2, the 4-triazole derivative containing urea groups.The periodicals such as " Central China Normal University's journal (natural science edition) " the 33rd volume the 3rd phase 383-386, " organic chemistry " the 28th volume the 6th phase 1065-1070, " organic chemistry " the 29th volume second phase 245-251 in 2009 in 2008 in 1999 report 1, the synthesis of 2,4-triazole derivative and the research of weeding activity; Patent CN102775361, JPH0341072, JPH05163253, JPH05163254, JPS5998004 etc. all disclose synthesis and the weeding activity of 1,2,4-triazole derivative.Along with becoming increasingly conspicuous of Weed Resistance problem, the weedicide new variety of novel structure, mechanism of action uniqueness become the active demand in market, are therefore that parent is developed it and will be had good prospect containing herbicidal compound of several functions group with triazole class compounds.
Summary of the invention
The object of this invention is to provide a kind of compound containing triazole structure and preparation method thereof and the application as weedicide.
Compound shown in formula I provided by the present invention,
In formula I, R represents that allyl group, carbonatoms are the alkyl acyl of 1 ~ 20, substituted or unsubstituted benzoyl, O, O-dimethyl thio phosphoryl, phenyl, benzene oxygen ethanoyl, 3-phenyl-2-acryl or 2,6-dinitrobenzene-4-trifluoromethyl.
In above-mentioned compound, the carbonatoms of described alkyl acyl can be 3 ~ 18, as propionyl, butyryl radicals, pentanoyl, caproyl, lauroyl or stearoyl;
The benzoyl of described replacement can be single-substituted formyl radical or disubstituted benzene formyl radical; substituting group in the benzoyl of described replacement can be fluorine, chlorine, nitro or methyl; as 2-chlorobenzene formacyl, 4-chlorobenzene formacyl, 2; 6-dichloro-benzoyl base, 2-fluoro benzoyl, 4-fluoro benzoyl, 2,6-difluoro benzoyls, 4-nitro benzoyl or 4-methyl benzoyl.
Invention further provides the preparation method of compound shown in formula I, comprise the steps:
Under the katalysis of alkali, 3-amino-1H-1,2,4-triazole and electrophilic reagent obtain compound shown in formula I through electrophilic substitution reaction;
Described electrophilic reagent is chlorallylene, the alkyl acyl chloride that carbonatoms is 1 ~ 20, substituted or unsubstituted Benzoyl chloride, O, O-dimethyl thiophosphoryl chloride, phenyl isocyanate, phenoxyacetyl chloride, 3-phenyl-2-acrylate chloride or chloro-3, the 5-dinitro-p-trifluorotoluenes of 4-.
In above-mentioned preparation method, the carbonatoms of described alkyl acyl chloride can be 3 ~ 18, specifically can be propionyl chloride, butyryl chloride, valeryl chloride, caproyl chloride, lauroyl chloride or stearoyl chlorine;
The benzoyl of described replacement can be single-substituted formyl chloride or disubstituted benzene formyl chloride, substituting group in the Benzoyl chloride of described replacement can be fluorine, chlorine, nitro or methyl, specifically can be Benzoyl chloride, 2-chloro-benzoyl chloride, 4-chloro-benzoyl chloride, 2,6-dichlorobenzoyl chloride, 2-fluorobenzoyl chloride, 4-fluorobenzoyl chloride, 2,6-difluoro benzoyl chlorides, 4-nitrobenzoyl chloride or 4-methyl benzoyl chloride.
In above-mentioned preparation method, described alkali can be pyridine, triethylamine, Tri-n-Propylamine, tri-n-butylamine, N, N-diisopropylethylamine, DMAP, Tetramethyl Ethylene Diamine, 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU), 1,5-diazabicylo [4.3.0]-5-in ninth of the ten Heavenly Stems alkene (DBN), 1, at least one in 5,7-tri-azabicyclic [4.4.0]-5-in last of the ten Heavenly stems alkene (TBD);
The solvent of described electrophilic substitution reaction can be at least one in dimethyl formamide, pyridine, tetrahydrofuran (THF), acetone, butanone, pimelinketone, dioxane, methylnaphthalene, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, methylene dichloride, ethylene dichloride, chloroform, hexanaphthene, hexane, phenyl ether, tetracol phenixin, N-Methyl pyrrolidone, N-formyl morpholine and N-acetylmorpholine.
In above-mentioned preparation method, described electrophilic reagent is dissolved in the solvent of described electrophilic substitution reaction and obtains solution, described solution is added drop-wise to by described 3-amino-1H-1, in the system of 2,4-triazole, described solvent and described alkali composition;
Before the described solution of dropping, described system can be cooled to-5 ~ 15 DEG C, specifically can be-5 ~ 11 DEG C ,-5 DEG C ,-4 DEG C ,-3 DEG C, 0 DEG C, 1 DEG C, 3 DEG C, 6 DEG C, 7 DEG C, 8 DEG C, 10 DEG C, 11 DEG C or 15 DEG C.
In above-mentioned preparation method, described 3-amino-1H-1, 2, 4-triazole, the mol ratio of described alkali and described electrophilic reagent can be 1.0:1.5 ~ 8:0.8 ~ 1.5, specifically can be 1.0:1.5 ~ 6:0.8 ~ 1.2, 1.0:1.5:0.8, 1.0:1.5:0.9, 1.0:1.5:1.1, 1.0:1.5:1.2, 1.0:2.0:0.8, 1.0:2.0:1.0, 1.0:2.0:1.1, 1.0:3.0:0.9, 1.0:3.0:1.0, 1.0:3.0:1.2, 1.0:4.0:1.1, 1.0:4.0:1.2, 1.0:4.0:1.5, 1.0:6.0:0.8, 1.0:6.0:1.3, 1.0:6.0:1.4, 1.0:6.0:1.5, 1.0:7.0:1.2, 1.0:7.0:1.5 or 1.0:8.0:1.1, 1:8:1,
Shown in the temperature of electrophilic substitution reaction be 20 DEG C ~ 30 DEG C, the time is 4 ~ 7 hours, specifically can be 4 ~ 7 hours, 4 hours, 5 hours, 6 hours or 7 hours.
Present invention also offers compound shown in formula I as the application in weedicide.
The present invention still further provides a kind of weedicide, and its activeconstituents is compound shown in formula I.
Weedicide provided by the invention can be used for management of weeds dog tail, lady's-grass, Herba Eleusines Indicae, black nightshade, three-coloured amaranth, piemarker, lamb's-quarters, humulus grass, summer cypress, Herba seu Flos Convolvuli arvensis, Herba Acalyphae, Herba Ixeritis chinensis and early keng rice.
Herbicidal compound containing triazole structure provided by the invention, its novel structure, has the plurality of advantages such as activity is high, broad weed-killing spectrum, has good weeding activity.Preparation method provided by the invention, technique is simple, and reaction mechanism is shorter.
Embodiment
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
The structural formula of the electrophilic reagent used by following embodiment is as shown in table 1.
The structural formula of table 1 electrophilic reagent
"--" representative is blank herein.
Embodiment 1, preparation Compound C 1(3-allyl amino-4H-1,2,4-triazole)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the triethylamine of 2,4-triazole, 50ml dimethyl formamide and 0.04mol, cooling and stirring to system temperature is 3 DEG C; The dimethyl formamide solution of 0.012mol chlorallylene is dropwise added in four-hole bottle, after dropping terminates, stirring at normal temperature reaction 7h, dissolve with methylene dichloride after underpressure distillation precipitation, separatory after washing, gets oil reservoir, revolve and steam recrystallizing methanol after precipitation, obtain Compound C 1, productive rate is 71.4%, and purity is 99.1%.
3-allyl amino-4H-1, the carbon modal data of 2,4-triazole 13cNMR(CDCl 3) δ ppm=54.5,114.9,134.3,148.1,158.3.
Through characterizing, it is target compound.
Embodiment 2, preparation Compound C 2(N-(4H-[1,2,4] triazole-3-base)-propionic acid amide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the tri-n-butylamine of 2,4-triazole, 50ml dimethyl sulfoxide (DMSO) and 0.06mol, cooling and stirring to system temperature is 10 DEG C; In four-hole bottle, dropwise add the acetonitrile solution of 0.014mol propionyl chloride, drip after terminating, stirring at normal temperature reaction 4h, dissolves with methylene dichloride after underpressure distillation precipitation, washing, separatory gets oil reservoir, revolves and steams recrystallizing methanol after precipitation, obtain Compound C 2, productive rate is 73.7%, and purity is 98.5%.
N-(4H-[1,2,4] triazole-3-base) the carbon modal data of-propionic acid amide 13cNMR(CDCl 3) δ ppm=9.7,26.7,148.0,158.4,172.7.
Through characterizing, it is target compound.
Embodiment 3, preparation Compound C 3(N-(4H-[1,2,4] triazole-3-base)-butyramide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the pyridine of 2,4-triazole, 50ml pimelinketone and 0.08mol, cooling and stirring to system temperature is 15 DEG C; In four-hole bottle, dropwise add the cyclohexanone solution of 0.011mol butyryl chloride, drip after terminating, stirring at normal temperature reaction 4h, dissolves with methylene dichloride after underpressure distillation precipitation, washing, separatory gets oil reservoir, revolves and steams recrystallizing methanol after precipitation, obtain Compound C 3, productive rate is 70.2%, and purity is 99.6%.
N-(4H-[1,2,4] triazole-3-base) the carbon modal data of-butyramide 13cNMR(CDCl 3) δ ppm=13.0,18.8,36.1,148.2,158.1,172.0.
Through characterizing, it is target compound.
Embodiment 4, preparation Compound C 4(N-(4H-[1,2,4] triazole-3-base)-valeramide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the Tetramethyl Ethylene Diamine of 2,4-triazole, 50ml methylnaphthalene and 0.06mol, cooling and stirring to system temperature is 8 DEG C; In four-hole bottle, dropwise add the dichloromethane solution of 0.014mol valeryl chloride, drip after terminating, stirring at normal temperature reaction 6h, separatory after washing, get oil reservoir, recrystallizing methanol after underpressure distillation precipitation, obtain Compound C 4, productive rate is 66.3%, and purity is 99.2%.
N-(4H-[1,2,4] triazole-3-base) the carbon modal data of-valeramide 13cNMR(CDCl 3) δ ppm=13.322.128.233.6148.2158.5172.2.
Embodiment 5, preparation Compound C 5(N-(4H-[1,2,4] triazole-3-base)-hexanamide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the DMAP of 2,4-triazole, 50ml pyridine and 0.03mol, cooling and stirring is-3 DEG C to system temperature; In four-hole bottle, dropwise add the acetonitrile solution of 0.01mol caproyl chloride, drip after terminating, stirring at normal temperature reaction 5h, dissolves with methylene dichloride after decompression precipitation, washing, separatory gets oil reservoir, revolves and steams recrystallizing methanol after precipitation, obtain Compound C 5, productive rate is 70.5%, and purity is 99.8%.
N-(4H-[1,2,4] triazole-3-base) the carbon modal data of-hexanamide 13cNMR(CDCl 3) δ ppm=14.0,22.4,25.7,31.5,33.9,148.3,158.0,171.9.
Through characterizing, it is target compound.
Embodiment 6, preparation Compound C 6(N-(4H-[1,2,4] triazole-3-base)-lauramide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the Tri-n-Propylamine of 2,4-triazole, 50ml toluene and 0.06mol, cooling and stirring to system temperature is 8 DEG C; In four-hole bottle, dropwise add the toluene solution of 0.013mol lauroyl chloride, drip after terminating, stirring at normal temperature reaction 6h, separatory after washing, gets oil reservoir, and revolve and steam recrystallizing methanol after precipitation, obtain Compound C 6, productive rate is 68.6%, and purity is 99.4%.
N-(4H-[1,2,4] triazole-3-base) the carbon modal data of-lauramide 13cNMR(CDCl 3) δ ppm=14.0,23.1,26.0,29.3,29.6,30.0,30.1,30.2,30.3,32.5,33.9,148.2,158.4,170.1.
Through characterizing, it is target compound.
Embodiment 7, preparation Compound C 7(N-(4H-[1,2,4] triazole-3-base)-stearylamide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the TBD of 2,4-triazole, 50ml dimethylbenzene and 0.015mol, cooling and stirring is-5 DEG C to system temperature; In four-hole bottle, dropwise add the xylene solution of 0.009mol stearoyl chlorine, drip after terminating, stirring at normal temperature reaction 7h, separatory after washing, get oil reservoir, recrystallizing methanol after underpressure distillation precipitation, obtain Compound C 7, productive rate is 70.1%, and purity is 99.0%.
N-(4H-[1,2,4] triazole-3-base) the carbon modal data of-stearylamide 13cNMR(CDCl 3) δ ppm=14.1,23.2,26.0,29.2,29.5,30.0,30.1,30.2,30.3,30.3,30.3,30.3,30.3,30.3,30.3,30.3,33.9,148.1,158.4,172.0.
Through characterizing, it is target compound.
Embodiment 8, preparation Compound C 8(N-(4H-[1,2,4] triazole-3-base)-O, O '-dimethyl thiophosphoryl amide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the Tetramethyl Ethylene Diamine of 2,4-triazole, 50mlN-acetylmorpholine and 0.04mol, cooling and stirring is-4 DEG C to system temperature; Dropwise 0.011molO is added in four-hole bottle, the acetone soln of O-dimethyl thiophosphoryl chloride, after dropping terminates, stirring at normal temperature reaction 6h, dissolves with methylene dichloride after underpressure distillation precipitation, washing, separatory gets oil reservoir, revolves and steams recrystallizing methanol after precipitation, obtain chemical combination C8, productive rate is 69.5%, and purity is 99.6%.
N-(4H-[1,2,4] triazole-3-base)-O, O ' the carbon modal data of-dimethyl thiophosphoryl amide 13cNMR(CDCl 3) δ ppm=40.2,40.3,148.2,158.4.
Through characterizing, it is target compound.
Embodiment 9, preparation Compound C 9(1-phenyl-3-(4H-[1,2,4] triazole-3-base)-urea)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the DBU of 2,4-triazole, 50ml butanone and 0.03mol, cooling and stirring to system temperature is 6 DEG C; In four-hole bottle, dropwise add the dichloroethane solution of 0.012mol phenyl isocyanate, drip after terminating, stirring at normal temperature reaction 5h, washing, separatory gets oil reservoir, and revolve and steam recrystallizing methanol after precipitation, obtain Compound C 9, productive rate is 68.8%, and content is 98.8%.
1-phenyl-3-(4H-[1,2,4] triazole-3-base) the carbon modal data of-urea 13cNMR(CDCl 3) δ ppm=120.3,120.4,124.1,128.6,128.7,138.2,148.3,152.2,158.4.
Through characterizing, it is target compound.
Embodiment 10, preparation Compound C 10(N-(4H-[1,2,4] triazole-3-base)-benzamide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the triethylamine of 2,4-triazole, 50ml dioxane and 0.06mol, cooling and stirring to system temperature is 0 DEG C; In four-hole bottle, dropwise add the tetrahydrofuran solution of 0.015mol Benzoyl chloride, drip after terminating, stirring at normal temperature reaction 6h, revolves after steaming precipitation and dissolves with methylene dichloride, washing, separatory gets oil reservoir, revolves and steams recrystallizing methanol after precipitation, obtain Compound C 10, productive rate is 71.9%, and purity is 99.4%.
N-(4H-[1,2,4] triazole-3-base) the carbon modal data of-benzamide 13cNMR(CDCl 3) δ ppm=127.3,127.4,128.5,128.6,131.9,133.5,148.1,158.2,165.2.
Through characterizing, it is target compound.
Embodiment 11, preparation Compound C 11(2-chloro-N-(4H-[1,2,4] triazole-3-base)-benzamide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the DBN of 2,4-triazole, 50ml pimelinketone and 0.02mol, cooling and stirring to system temperature is 11 DEG C; In four-hole bottle, dropwise add the acetone soln of 0.011mol2-chloro-benzoyl chloride, drip after terminating, stirring at normal temperature reaction 4h, dissolves with methylene dichloride after underpressure distillation precipitation, washing, separatory gets oil reservoir, revolves and steams recrystallizing methanol after precipitation, obtain Compound C 11, productive rate is 68.6%, and purity is 98.7%.
The chloro-N-(4H-of 2-[1,2,4] triazole-3-base) the carbon modal data of-benzamide 13cNMR(CDCl 3) δ ppm=126.7,128.7,129.0,132.6,133.3,133.9,148.2,158.5,165.3.
Embodiment 12, preparation Compound C 12(4-chloro-N-(4H-[1,2,4] triazole-3-base)-benzamide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the tri-n-butylamine of 2,4-triazole, 50ml hexanaphthene and 0.07mol, cooling and stirring to system temperature is 7 DEG C; In four-hole bottle, dropwise add the carbon tetrachloride solution of 0.015mol4-chloro-benzoyl chloride, drip after terminating, stirring at normal temperature reaction 4h, separatory after washing, get oil reservoir, recrystallizing methanol after underpressure distillation precipitation, obtain Compound C 12, productive rate is 66.5%, and purity is 99.6%.
The chloro-N-(4H-of 4-[1,2,4] triazole-3-base) the carbon modal data of-benzamide 13cNMR(CDCl 3) δ ppm=128.5,128.7,129.0,129.1,131.6,137.2,148.1,158.3,165.1.
Through characterizing, it is target compound.
Embodiment 13, preparation Compound C 13(2,6-bis-chloro-N-(4H-[1,2,4] triazole-3-base)-benzamide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the pyridine of 2,4-triazole, 50ml dimethyl formamide and 0.07mol, cooling and stirring to system temperature is 6 DEG C; Dropwise 0.012mol2 is added in four-hole bottle, the dimethyl formamide solution of 6-dichlorobenzoyl chloride, after dropping terminates, stirring at normal temperature reaction 6h, dissolves with methylene dichloride after underpressure distillation precipitation, washing, separatory gets oil reservoir, revolves and steams recrystallizing methanol after precipitation, obtain Compound C 13, productive rate is 72.8%, and purity is 99.7%.
The chloro-N-(4H-of 2,6-bis-[1,2,4] triazole-3-base) the carbon modal data of-benzamide 13cNMR(CDCl 3) δ ppm=127.1,127.2,134.1,134.2,134.3,134.7,148.5,158.3,165.2.
Through characterizing, it is target compound.
Embodiment 14, preparation Compound C 14(4-fluoro-N-(4H-[1,2,4] triazole-3-base)-benzamide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the DBU of 2,4-triazole, 50ml chloroform and 0.04mol, cooling and stirring is-3 DEG C to system temperature; In four-hole bottle, dropwise add the chloroformic solution of 0.015mol4-fluorobenzoyl chloride, drip after terminating, stirring at normal temperature reaction 5h, separatory after washing, gets oil reservoir, and revolve and steam recrystallizing methanol after precipitation, obtain Compound C 14, productive rate is 74.4%, and purity is 99.3%.
The fluoro-N-(4H-of 4-[1,2,4] triazole-3-base) the carbon modal data of-benzamide 13cNMR(CDCl 3) δ ppm=115.6,115.7,128.8,128.9,129.1,148.2,158.3,165.1,165.5.
Through characterizing, it is target compound.
Embodiment 15, preparation Compound C 15(2-fluoro-N-(4H-[1,2,4] triazole-3-base)-benzamide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the pyridine of 2,4-triazole, 50ml phenyl ether and 0.06mol, cooling and stirring to system temperature is 3 DEG C; In four-hole bottle, dropwise add the hexane solution of 0.012mol2-fluorobenzoyl chloride, drip after terminating, stirring at normal temperature reaction 4h, separatory after washing, get oil reservoir, recrystallizing methanol after underpressure distillation precipitation, obtain Compound C 15, productive rate is 69.6%, and purity is 99.3%.
The fluoro-N-(4H-of 2-[1,2,4] triazole-3-base) the carbon modal data of-benzamide 13cNMR(CDCl 3) δ ppm=115.6,120.5,124.2,128.9,133.5,148.1,158.2,160.9,165.2.
Embodiment 16, preparation Compound C 16(2,6-bis-fluoro-N-(4H-[1,2,4] triazole-3-base)-benzamide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the TBD of 2,4-triazole, 50mlN-methyl-2-pyrrolidone and 0.015mol, cooling and stirring is-3 DEG C to system temperature; Dropwise 0.012mol2 is added in four-hole bottle, the acetonitrile solution of 6-difluoro benzoyl chloride, after dropping terminates, stirring at normal temperature reaction 4h, dissolves with methylene dichloride after underpressure distillation precipitation, washing, separatory gets oil reservoir, revolves and steams recrystallizing methanol after precipitation, obtain Compound C 16, productive rate is 66.9%, and purity is 99.3%.
The fluoro-N-(4H-of 2,6-bis-[1,2,4] triazole-3-base) the carbon modal data of-benzamide 13cNMR(CDCl 3) δ ppm=107.5,111.1,111.2,135.1,148.1,158.3,162.4,162.5,165.2.
Through characterizing, it is target compound.
Embodiment 17, preparation Compound C 17(4-nitro-N-(4H-[1,2,4] triazole-3-base)-benzamide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, 2, the DIPEA of 4-triazole, 50mlN-acetylmorpholine and 0.06mol, cooling and stirring to system temperature is 10 DEG C; The acetone soln of 0.008mol4-nitrobenzoyl chloride is dropwise added in four-hole bottle, after dropping terminates, stirring at normal temperature reaction 5h, dissolve with methylene dichloride after underpressure distillation precipitation, washing, separatory gets oil reservoir, revolve and steam recrystallizing methanol after precipitation, obtain Compound C 17, productive rate is 69.4%, and purity is 99.7%.
4-nitro-N-(4H-[1,2,4] triazole-3-base) the carbon modal data of-benzamide 13cNMR(CDCl 3) δ ppm=123.6,123.7,128.1,128.2,139.6,148.2,151.8,158.4,165.2.
Through characterizing, it is target compound.
Embodiment 18, preparation Compound C 18(4-methyl-N-(4H-[1,2,4] triazole-3-base)-benzamide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the DBU of 2,4-triazole, 50mlN-formyl morpholine and 0.03mol, cooling and stirring to system temperature is 1 DEG C; The tetrahydrofuran solution of 0.012mol4-methyl benzoyl chloride is dropwise added in four-hole bottle, after dropping terminates, stirring at normal temperature reaction 7h, dissolve with methylene dichloride after underpressure distillation precipitation, washing, separatory gets oil reservoir, revolve and steam recrystallizing methanol after precipitation, obtain Compound C 18, productive rate is 65.6%, and purity is 99.4%.
4-methyl-N-(4H-[1,2,4] triazole-3-base) the carbon modal data of-benzamide 13cNMR(CDCl 3) δ ppm=20.9,127.1,127.2,129.3,129.4,130.5,141.1,148.1,158.4,165.1.
Through characterizing, it is target compound.
Embodiment 19, preparation Compound C 19(2-phenoxy group-N-(4H-[1,2,4] triazole-3-base)-ethanamide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the tri-n-butylamine of 2,4-triazole, 50ml dimethyl sulfoxide (DMSO) and 0.08mol, cooling and stirring to system temperature is 7 DEG C; The dichloromethane solution of 0.011mol phenoxyacetyl chloride is dropwise added in four-hole bottle, after dropping terminates, stirring at normal temperature reaction 5h, dissolve with methylene dichloride after underpressure distillation precipitation, washing, separatory gets oil reservoir, revolve and steam recrystallizing methanol after precipitation, obtain Compound C 19, productive rate is 73.3%, and purity is 99.1%.
2-phenoxy group-N-(4H-[1,2,4] triazole-3-base) the carbon modal data of-ethanamide 13cNMR(CDCl 3) δ ppm=75.9,114.0,114.1,120.8,129.5,129.6,148.1,158.3,162.0,168.2.
Through characterizing, it is target compound.
Embodiment 20, preparation Compound C 20(3-phenyl-N-(4H-[1,2,4] triazole-3-base)-acrylamide)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the triethylamine of 2,4-triazole, 50ml pyridine and 0.02mol, cooling and stirring to system temperature is 3 DEG C; The acetonitrile solution of 0.01mol3-phenyl-2-acrylate chloride is dropwise added in four-hole bottle, after dropping terminates, stirring at normal temperature reaction 5h, dissolve with methylene dichloride after underpressure distillation precipitation, washing, separatory gets oil reservoir, revolve and steam recrystallizing methanol after precipitation, obtain Compound C 20, productive rate is 74.4%, and purity is 99.8%.
3-phenyl-N-(4H-[1,2,4] triazole-3-base) the carbon modal data of-acrylamide 13cNMR(CDCl 3) δ ppm=119.8,126.1,126.2,127.7,128.3,128.4,134.9,141.6,148.3,158.4,163.8.
Embodiment 21, preparation Compound C 21((2,6-dinitrobenzene-4-trifluoromethyl-phenyl)-(4H-[1,2,4] triazole-3-base)-amine)
To with the 3-amino-1H-1 adding 0.01mol in the 250ml four-hole bottle of magnetic agitation, cooling, thermometer, nitrogen protection, the pyridine of 2,4-triazole, 50ml dimethyl formamide and 0.08mol, cooling and stirring to system temperature is 15 DEG C; 0.01mol4-chloro-3 is dropwise added in four-hole bottle, the tetrahydrofuran solution of 5-dinitro-p-trifluorotoluene, after dropping terminates, stirring at normal temperature reaction 7h, dissolves with methylene dichloride after underpressure distillation precipitation, washing, separatory gets oil reservoir, revolves and steams recrystallizing methanol after precipitation, obtain Compound C 21, productive rate is 71.6%, and purity is 99.5%.
The carbon modal data of (2,6-dinitrobenzene-4-trifluoromethyl-phenyl)-(4H-[1,2,4] triazole-3-base)-amine 13cNMR(CDCl 3) δ ppm=117.3,122.8,127.3,127.4,136.1,136.2,140.2,148.1,158.4.
Through characterizing, it is target compound.
The weeding activity of embodiment 22, Compound C 1-Compound C 21
Choose wild grassland and carry out the test of pesticide effectiveness, evaluate the drug effect containing triazole structure herbicidal compound C1-C21 of above-mentioned preparation.
The spraying medicine concentration of often kind of compound is respectively 500mg/L and 1000mg/L, and each concentration establishes 3 process, averages, and each processing area is 10m 2, and the contrast of corresponding clear water is set.Within after dispenser 14 days, investigate its fresh weight preventive effect to weeds.
Fresh weight preventive effect (G 0for certain weeds fresh weight of clear water check plot, G is certain weeds fresh weight of chemicals treatment district).
Statistics is as shown in table 2.
Table 2 Compound C 1-C21 is to the fresh weight preventive effect of different sorts weeds
This grass is not had in the set hillslope processes of "--" representative.
Can be learnt by the data in table 2, triazole class compounds provided by the invention has certain inhibit activities to weeds dog tail, lady's-grass, Herba Eleusines Indicae, black nightshade, three-coloured amaranth, piemarker, lamb's-quarters, humulus grass, summer cypress, Herba seu Flos Convolvuli arvensis, Herba Acalyphae, Herba Ixeritis chinensis and early keng rice.

Claims (9)

1. compound shown in formula I,
In formula I, R represents O, O-dimethyl thio phosphoryl or 2,6-dinitrobenzene-4-trifluoromethyl.
2. the preparation method of compound shown in formula I described in claim 1, comprises the steps:
Under the katalysis of alkali, 3-amino-1H-1,2,4-triazole and electrophilic reagent obtain compound shown in formula I through electrophilic substitution reaction;
Described electrophilic reagent is chloro-3, the 5-dinitro-p-trifluorotoluenes of O, O-dimethyl thiophosphoryl chloride or 4-.
3. preparation method according to claim 2, is characterized in that:
Described alkali is pyridine, triethylamine, Tri-n-Propylamine, tri-n-butylamine, N, N-diisopropylethylamine, DMAP, Tetramethyl Ethylene Diamine, 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene, 1,5-diazabicylo [4.3.0]-5-in ninth of the ten Heavenly Stems alkene and 1, at least one in 5,7-tri-azabicyclic [4.4.0]-5-in last of the ten Heavenly stems alkene;
The solvent of described electrophilic substitution reaction is at least one in dimethyl formamide, pyridine, tetrahydrofuran (THF), acetone, butanone, pimelinketone, dioxane, methylnaphthalene, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, methylene dichloride, ethylene dichloride, chloroform, hexanaphthene, hexane, phenyl ether, tetracol phenixin, N-Methyl pyrrolidone, N-formyl morpholine and N-acetylmorpholine.
4. preparation method according to claim 3, it is characterized in that: described electrophilic reagent is dissolved in the solvent of described electrophilic substitution reaction and obtains solution, described solution is added drop-wise to by described 3-amino-1H-1, in the system of 2,4-triazole, described solvent and described alkali composition;
Before the described solution of dropping, described system is cooled to-5 ~ 15 DEG C.
5. preparation method according to claim 2, is characterized in that: described 3-amino-1H-1, and the mol ratio of 2,4-triazole, described alkali and described electrophilic reagent is 1.0:1.5 ~ 8:0.8 ~ 1.5;
The temperature of shown electrophilic substitution reaction is 20 DEG C ~ 30 DEG C, and the time is 4 ~ 7 hours.
6. compound is as the application in weedicide, it is characterized in that, described compound is compound described in claim 1 Chinese style I.
7. application according to claim 6, is characterized in that: described weedicide management of weeds dog tail, lady's-grass, Herba Eleusines Indicae, black nightshade, three-coloured amaranth, piemarker, lamb's-quarters, humulus grass, summer cypress, Herba seu Flos Convolvuli arvensis, Herba Acalyphae, Herba Ixeritis chinensis and early keng rice.
8. a weedicide, its activeconstituents is compound shown in formula described in claim 1 I.
9. weedicide according to claim 8, is characterized in that: described weedicide management of weeds dog tail, lady's-grass, Herba Eleusines Indicae, black nightshade, three-coloured amaranth, piemarker, lamb's-quarters, humulus grass, summer cypress, Herba seu Flos Convolvuli arvensis, Herba Acalyphae, Herba Ixeritis chinensis and early keng rice.
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