CN1035326C - Process for preparing derivates of 1,2,4-triazols - Google Patents
Process for preparing derivates of 1,2,4-triazols Download PDFInfo
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- CN1035326C CN1035326C CN91102410A CN91102410A CN1035326C CN 1035326 C CN1035326 C CN 1035326C CN 91102410 A CN91102410 A CN 91102410A CN 91102410 A CN91102410 A CN 91102410A CN 1035326 C CN1035326 C CN 1035326C
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Abstract
The invention relates to a method for preparing plant protectant, which contains triazole compound or the salt and inert carrier in formula I. Compound in formula I is applicable to protect crops from the side effect of poisoning plant of weedicide. Z in the formula indicates halogen, nitryl, cyano-group, trifluoromethyl, substitutable alkyl, alkoxyl, alkyl sulphide radical, naphthene base, phenyl, or substituted phenoxyl. Y indicates H, substitutable alkyl, alkenyl, alkynyl, or naphthene base. n indicates 0, 1, 2 or 3. X stands for oxhydryl, alkyl, naphthene alkoxy, phenoxyl, alkenoxy, alkynyl, substituted alkoxyl, alkylthio or the radicals in the following.
Description
The present invention has narrated the method for preparing plant protection product, and this plant protection product contains triazole compounds or its salt (when X=OH) of formula I, and the composition that they can be used as plant protection product is used for agricultural.
Wherein Z or identical is perhaps inequality, its expression fontanel element, nitro, cyano group, trifluoromethyl, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group or (C
1-C
4) the alkyl sulfenyl, alkyl wherein, alkoxyl group and alkylthio can be replaced by one or more fontanelle atoms, are particularly replaced by fluorine or chlorine, Z also represents can be by (C
1-C
4) (C that replaces of alkyl
3-C
6) cycloalkyl, or phenyl, phenoxy group, wherein phenyl and phenoxy group can be plain single or polysubstituted by fontanel, and/or replaced by the trifluoromethyl list;
Y represents hydrogen, can be by (the C of all or part of replacement of fontanelle atom
1-C
4) alkyl, and/or by (C
1-C
4) alkoxyl group or (C
1-C
4) (C that replaces of alkylthio
1-C
4) alkyl, or (C
2-C
6) alkenyl, (C
2-C
6) alkynyl, perhaps the expression can be by (C
1-C
4) alkyl and/or the (C that replaces of dichloroethylene
3-C
6) cycloalkyl;
X represents hydroxyl, (C
1-C
4) alkyl, (C
3-C
6) cycloalkyloxy, phenyl-(C
1-C
6) alkoxyl group, phenoxy group, (C
2-C
6) alkenyloxy, (C
2-C
6) alkynyloxy group, (C
1-C
6) alkoxyl group or (C
1-C
6) alkylthio, wherein alkoxyl group or alkylthio can be by (C
1-C
2) alkoxyl group, list-(C
1-C
4) alkyl amino-carbonyl, two-[(C
1-C
4) alkyl] aminocarboxyl, phenyl amino carbonyl, N-[(C
1-C
4) alkyl]-N-phenyl-aminocarboxyl, list-(C
1-C
6) alkylamino, two-(C
1-C
6) alkylamino, [(C
1-C
6) alkyl] the ketonic oxygen base, (C
1-C
2) alkylthio, cyano group or fontanel are plain to be replaced, X also can be the group that is expressed from the next:
Or
Wherein R represents hydrogen or (C
1-C
4) alkyl, perhaps the expression list-(C
1-C
4) alkylamino, two-(C
1-C
4) alkylamino, (C
5-C
6) cycloalkyl amino, piperidino-(1-position only), morpholino, 2,6-thebaine generation or have formula
Group, R wherein
1And R
2Can be identical or different, they represent (C
1-C
4) alkyl, R
1And R
2Also can form a five-ring alkyl jointly, six-ring alkyl or seven-membered ring alkyl; N represents numeral 0,1,2 or 3.
The example of suitable salt has metal-salt, as basic metal or alkaline earth salt, particularly sodium salt and sylvite, and ammonium salt, list-, two-, three-or four-(C
1-C
4) alkylammonium salt, single-, two-, three-or four (C
1-C
4) alkanol ammonium salts.
Formula I compound is that Y represents by F preferably, (the C of Cl or all or part of replacement of Br
1-C
2) alkyl; Z can be identical or different, and Z can represent fontanel element, (C
1-C
4) alkoxyl group, (C
1-C
4) alkyl or CF
3,
X represents the alkoxyl group or the hydroxyl of (C1-C6);
N represents 1,2, or 3.
Good especially representative is that wherein Y is CCl in these compounds
3, CHCl
2, CHF
2CF
2Or CH
3Compound.
Unexpectedly, these compounds of formula I can reduce or eliminate fully the toxic side effect of plant herbicide to crop effectively.Such compound is also referred to as toxicide or safener (safen-ers).From science publication [Chem.Ber.94 1868 (1961), Chem.Ber.963 (1963) and Chem.Ber.98642 (1965)] and German Patent 1,123,3, can recognize that segment bounds I compound is a known compound.But these documents all do not disclose the detoxification of these compounds.
Most of formula I compound is new, does not promptly report in the past.They are following formula I compound:
Wherein Z can be identical or different, its expression fontanel element, nitro, cyano group, trifluoromethyl, alkyl (C1-C4), alkoxyl group (C1-C4) or (C1-C4) alkylthio, alkyl wherein, alkoxyl group and alkylthio can be replaced by one or more fontanelle atoms (particularly fluorine or chlorine), and Z also can represent by the cycloalkyl of (C3-C6) of the alkyl of (C1-C4) replacement, phenyl or phenoxy group, wherein phenyl and phenoxy group can be undertaken singly or polysubstituted by the fontanel element, and/or are replaced by the trifluoromethyl list;
Y represents hydrogen, can be by all or part of replacement of fontanelle atom and/or by the alkoxyl group of (C1-C4) or the alkyl of alkylthio (C1-C4) mono-substituted (C1-C4) or alkenyl (C2-C6), (C2-C6) alkynyl, or expression can be by the cycloalkyl of (C3-C6) of the alkyl of (C1-C4) and/or dichloroethylene replacement;
X represents hydroxyl, (C1-C4) alkyl, (C3-C6) cycloalkyloxy, the alkoxyl group of phenyl-(C1-C6), phenoxy group, (C2-C6) alkenyloxy, (C2-C6) alkynyloxy group, alkoxyl group (C1-C6) or alkylthio (C1-C6), wherein alkoxyl group or alkylthio can be by the alkoxyl groups of (C1-C2), alkyl amino-carbonyl singly-(C1-C4), two [alkyl (C1-C4)] aminocarboxyl, phenyl amino carbonyl, alkyl N-[(C1-C4)]-N-phenyl-aminocarboxyl, alkylamino singly-(C1-C6), two-(C1-C6) alkylamino, [alkyl (C1-C6)] ketonic oxygen base, alkylthio (C1-C2), cyano group or fontanel are plain to be replaced, and perhaps X represents to have the group of following formula:
Or
Wherein R represents hydrogen, and alkyl (C1-C4) is or single-(C1-C4) alkylamino, two-(C1-C4) alkylamino, cycloalkyl amino (C5-C6), piperidino-(1-position only), morpholino, 2,6-thebaine generation or have formula
Group, R wherein
1And R
2Can be identical or different, the alkyl of their expressions (C1-C4), R
1And R
2Also can form the five-ring alkyl jointly, six-ring alkyl or seven-membered ring alkyl;
N represents numeral 0,1,2 or 3.If X=OH, the salt of formula I also can be used for agricultural so, if the alkyl of X=(C1-C4), Y is necessary for CCl so
3Or CHCl
2, except the following formula I compound, wherein
A) Y represents H, and (Z) n represents H, 4-Cl, 4-CH
3, 2-OCH
3, 4-OCH
3Or 4-OC
2H
5, X represents OH, OCH
3Or OC
2H
5
B) Y represents CH
3, (Z)
nExpression 4-NO
2, 4-OCH
3, 2-Cl, 4-Cl, 2-OCH
3-4-NO
2Or 2-CH
3-4-NO
2, X represents OH or OC
2H
5
C) Y represents C
2H
5Or CH (CH
3)
2, (Z) n represents H, X represents OCH
3
The method of preparation formula I new compound and salt thereof comprises:
A) with formula II compound:
(X wherein
1Identical with the implication of X, but can not be hydroxyl) with
Al) formula is the compound reaction of Y-CO-Cl; Or with
A2) formula is the anhydride reaction of Y-CO-O-CO-Y; Or with
A3) formula is Y-C (OR ')
3Ortho ester reaction, R wherein
1The alkyl of expression (C1-C4), perhaps
B) for the compound of preparation Y=H or alkyl (C1-C4), with the formula III compound:
With alkali reaction, Y wherein
1Expression H or alkyl (C1-C4), R
3The alkoxyl group or the CH of expression (C1-C4)
3
Heating is at a1) and the compound that a2) obtains under the situation, if suitable words heat in acetic acid.When needing,, the formula I compound that obtains is changed into other compound of formula I by generating the method for derivative.
Unexpectedly, at a1) and a2) in two kinds of methods, be added to acyl chlorides or acid anhydrides on the free amino after, often can observe the direct ring formation of two steps reaction at once, obtain formula I compound.Unexpected also have, at a1) method in, reaction is to take place under the situation that does not add alkali.On the contrary, add alkali and then generate arborescens product (normally will add alkali in other cases).
Formula II compound and acid anhydrides, the reaction of acyl chlorides (YCOCl) or ortho ester is preferably in the organic solvent of inert, no proton and carries out.During with acid anhydrides or ortho ester reaction (method a2 or a3), agents useful for same itself also can be used as solvent.A3) method is particularly carried out in the presence of organic acid (for example right-toluenesulphonic acids) preferably at acid catalyst.
A1), a2) and a3) in the method, suitable inert solvent is best with aromatics especially, benzene for example, toluene, dimethylbenzene and chlorobenzene perhaps are cyclic ether compounds, for example tetrahydrofuran (THF) is with Er Evil, alkane, or ketone compounds, for example acetone, and dipolar, aprotonic solvent, for example dimethyl formamide.According to solvent, temperature of reaction can change between 10 ℃ and reaction mixture boiling point.If a1) use aromatic solvent in the method, then after adding acyl chlorides, the water of generation is removed by water separator under reflux temperature.At a1) or a2) in the method,, under several situations, at first generate intermediate product with formula IV according to (Z) n in the formula II compound and X group:
This product can be separated under certain condition.When using described solvent, if reaction stops at this stage, then subsequent reactions must carry out in acetic acid.About 50 ℃ between the reflux temperature, heating intermediate product IV can finish this reaction in acetic acid.This subsequent reactions can carry out in a retort, adds before the acetic acid, and the organic solvent distillation that will use the fs is shifted out.
The method b of preparation I compound), identical with Chem.Ber.96 3120 (1963) described methods substantially.The mineral alkali that adopts, preferably sodium hydroxide or potassium hydroxide.As described in above-mentioned document,, can make the compound of formula III with kharophen malonic ester or kharophen etheric acid ester cpds and diazonium salt reaction.
According to the reaction of generation derivative commonly used, the above-mentioned formula I compound that obtains can be changed the derivative of accepted way of doing sth I compound.Therefore, the ester of formula I compound is hydrolyzed with acid or alkali, can accesses the formula I compound of X=OH.Adopt usual method, the acid of formula I (X=OH) and suitable alkali reaction can access the salt of formula I compound.Adopt usual method, for example make the ester of formula I compound at first generate corresponding acyl chlorides, can obtain other ester class or amides of formula I.
The preparation method of formula II compound is known basically.α-chlorine hydrazone with formula V:
Can access formula II compound with ammonia react.And phenyl diazonium salt and α-fontanel are reacted for acetylacetic ester or alpha-halogen-beta-diketon, can preparation formula V compound.This two reactions have been described among J.Chem.Soc.87 1859 (1905) and the Ber.d.dt.Chem.Ges.50 1482 (1917).
Formula I compound is applicable to that mainly cover crop exempts from the toxic side effect of weedicide.
Formula I compound can use with other weedicide; simultaneously can resist or remove fully the harmful side effect of these weedicides; and not weakening the herbicide action of these weedicides to weeds, this just might further enlarge the use field of plant protection product commonly used.
From the european patent application of having announced 31,938, known safener (Safeners), but these safeners all there is unsuitable effect for phenoxy group phenoxy carboxylic acid ester herbicide.
Formula I compound can reduce the toxic side effect of following weedicide: amino formate; Thiolcarbamates; N-acetyl fontanel phenyl amines; The phenoxy carboxylic acid derivative, naphthyloxy carboxylic acid derivative and the phenoxy group phenoxy carboxylic acid derivative that replace, heteroaryloxy phenoxy carboxylic acid derivative, quinolyl oxygen base for example, quinoxalinyl oxygen base, pyridyl oxygen base benzoxazolyl oxygen base, benzothiazolyl oxygen base-phenoxy carboxylic acid ester class and methone 9 oxime derivate.In these compounds, phenoxy group phenoxy carboxylic acid ester class and heteroaryl oxygen phenoxyl carboxylic acid esters are better, and the ester class that is particularly suitable for this respect is low alkyl, alkenyl and alkynyl ester class.
Weedicide cited below is an example, does not plan to limit the kind of weedicide here.
A) alkyl (C1-C4), alkenyl (C2-C4) and (C3-C4) alkynyl phenoxy group phenoxy carboxylic acid ester class and heteroaryl oxygen phenoxyl carboxylic ester type weedicide, for example
2-(4-(2,4 dichloro benzene oxygen base)-phenoxy group)-methyl propionate,
2-(4-(4-bromo-2-chlorophenoxy)-phenoxy group)-methyl propionate,
2-(4-(4-4-trifluoromethylphenopendant)-phenoxy group)-methyl propionate,
2-(4-(2-chloro-4-4-trifluoromethylphenopendant)-phenoxy group)-methyl propionate,
2-(4-(2, the 4-dichloro benzyl)-phenoxy group)-methyl propionate,
4-(1-(4-4-trifluoromethylphenopendant)-phenoxy group)-amylene-[2]-ethyl ester,
2-(4-(3,5-dichloropyridine-2-base oxygen base)-phenoxy group)-ethyl propionate,
2-(4-(3,5-dichloropyridine-2-base oxygen base)-phenoxy group) propionic acid propargyl ester,
2-(4-(6-Lv benzoxazole-2-base oxygen base)-phenoxy group)-ethyl propionate,
2-(4-(6-chloro benzothiazole-2-base oxygen base)-phenoxy group) ethyl propionate,
2-(4-(3-chloro-5-trifluoromethyl-2-pyridyl oxygen base)-phenoxy group)-methyl propionate,
2-(4-(5-trifluoromethyl-2-pyridyl oxygen base)-phenoxy group)-butyl propionate,
2-(4-(6-chloro-2-quinoxalinyl oxygen base)-phenoxy group)-ethyl propionate,
2-(4-(6-fluoro-2-quinoxalinyl oxygen base)-phenoxy group)-ethyl propionate,
2-(4-(6-chloro-2-quinolyl oxygen base)-phenoxy group)-ethyl propionate,
B) acetochloroanilide weedicide, for example
N-methoxymethyl-2,6-diethyl-acetochloroanilide,
N-(3 '-methoxy-propyl-2 ')-methyl-6-ethyl-acetochloroanilide,
N-(3-methyl isophthalic acid, 2,4-oxadiazole-5-ylmethyl)-monochloroacetic acid 2, the 6-xylidine;
C) thiocarbamates, for example
N, N-dipropyl thiocarbamate S-ethyl ester or
N, N-diisobutyl thiocarbamate S-ethyl ester;
D) methone derivatives class, for example
2-(N-oxyethyl group butyryl imino-)-5-(2-ethylenebis dithiocarbamate propyl group)-3-hydroxyl-2-tetrahydrobenzene-1-ketone,
2-(N-oxyethyl group butyryl imino-)-5-(2-phenyl sulfo-propyl group)-3-hydroxyl-2-tetrahydrobenzene-1-ketone, perhaps
2-(1-allyloxy imino-butyl)-4-methoxycarbonyl-5,5-dimethyl-3-oxo cyclohexenol.
The ratio of safener and weedicide can change in 1: 10 to 10: 1 wide region, and especially Chang Yong scope is between 2: 1 to 1: 10.In particular case, the optimum amount of weedicide and safener depends on the kind of used weedicide and safener, and the pending properties of doing, and can determine this amount according to various different situations by suitable test.
Safener is mainly used in cereal crop (wheat, rye, barley or oat), rice, corn, jowar, and cotton, beet, sugarcane and soybean.According to the character of safener, safener formula I can be used for the pre-treatment (seed dressing) of crop seed, perhaps before sowing safener is put into kind of a sub-trenches, perhaps uses with weedicide before crop germinates or after germinateing.Processing before germinateing comprises the processing of cultural area prior to seeding and has sowed but the plant processing of unerupted cultural area still.Safener preferably uses with weedicide.The preparation of barreled mixture (tank mixtures) or finished product all can be used for this purpose.
Therefore, the present invention has also narrated cover crop, makes its method that exempts from the side effect of weedicide poisonous plant, and this method is included in uses the formula I compound of using significant quantity before or after the weedicide, or the formula I compound of significant quantity is used with weedicide.
Formula I compound has also shown the effect of sterilant, therefore can be used for going out except that phytopathogen, wheat powdery mildew fungi for example, rust fungi and phytophthora (Phytopthora) fungi, Staphlosporonites (Botrytis) fungi, Coniosporium (Piricularia) fungi or venturia inaequalis belong to (Venturia inegualis) fungi.During use, formula I compound can be mixed with pulvis with formulation adjuvant commonly used, wettable powder, and dispersion agent, missible oil etc., these preparations or use as pulvis perhaps dissolve using before or are dispersed in the solvent (water).
In addition, segment bounds I compound also has the effect of coordinate plant growth.Therefore they can influence the regulative mode of plant metabolism, can be used for selectively contained material effect in the plant is improved output, and be used for impelling dry and suppress plant-growth.
Compound of the present invention can be used for conventional formulation, makes wettable powder, missible oil, spray solution, pulvis, Drug coating, granula or microgranules.
The connotation of wettable powder is, this powder can be evenly dispersed in the water when preparation, except active compound, it also contains thinner or inert substance, if need, can add wetting agent, for example the Fatty Alcohol(C12-C14 and C12-C18) of the alkylphenol of many ethoxylations (Polyoxethylated alkylphenols), many ethoxylations (Polyoxethylated fatty alcohols), alkyl sulfonic ester or benzene sulfonamide acid esters; Dispersion agent, wooden sodium sulfonate for example, 2,2 '-dinaphthyl methane-6,6 '-sodium disulfonate, sodium dibutyl naphthalene sulfonate or oleoyl methylamino second sulphonyl sodium (Sodium oleoylmethyltauride).Its preparation can be according to a conventional method, for example grinds and mix each component.
Also can prepare missible oil, for example active compound is dissolved in the inert organic solvents (as butanols, pimelinketone, dimethyl formamide, the aromatic series of dimethyl or higher or varsol), and add one or more emulsifying agents.If active compound is a liquid, can all or part of province desolvate.Exemplify out spendable emulsifying agent below: alkyl aryl sulphonic acid calcium class, for example calcium dodecylbenzene sulphonate; Perhaps nonionic emulsifier, the for example polyoxyethylene sorbitol acid anhydride ester of the sorbitan ester of the macrogol ester of lipid acid, alkylaryl polyglycol ether, fatty alcohol polyglycol ether, propylene oxide/oxirane condensation product, alkyl polyglycol ether, lipid acid, lipid acid, or polyoxyethylene sorbitol ester.
With the solid matter (for example talcum) of active compound and pulverizing, natural clay (as kaolin, wilkinite, pyrophyllite or diatomite) mixes, and can make pulvis.
The preparation of granula is to have on adsorbing, the lightweight granular inert material by active compound is atomised to, perhaps with the concentrate of active compound with tackiness agent (polyvinyl alcohol for example, sodium polyacrylate or mineral oil) be bonded to the surface of carrier (for example sand, kaolin or sticking shape inert material).When making the mixture with fertilizer if desired, suitable active compound also can be granulated according to the ordinary method of producing fertiliser granulates.
In wettable powder, the concentration of active compound is about 10～90% by weight; Remainder can be used conventional recipe ingredient polishing to 100% by weight.In missible oil, the concentration of active compound is about 10～80% by weight.As the prescription of pulvis, in most of the cases contain the active compound of 5% to 20% weight, and the solution that can spray contains the active compound of 1% to 20% weight approximately.For granula, it is liquid or solid that the content of active compound depends in part on active compound, also depends on the granulating assistant of use, weighting agent etc.
In addition, if desired, the prescription of above-mentioned active compound also should contain tackiness agent, wetting agent, and dispersion agent, emulsifying agent, permeate agent, solvent, weighting agent or carrier, these reagent are all used always in concrete prescription.
If desired, the commodity concentrate can be diluted according to a conventional method during use, dilute with water wettable powder for example, missible oil and dispersion agent also carry out the part dilution to minitype particle.For pulvis, granula and the prescription that can spray solution generally further diluted without other inert substance before using.
When formula I compound uses as safener.Desired applicating ratio will be according to the weedicide of specification sheets and use, and its variation range is very big, and per hectare is used 0.01 to 10 kilogram of active compound generally speaking.
With embodiment the present invention is described below,
A. prepare example
A) the formula I compound of 10 parts of weight and talcum or a kind of inert substance of 90 parts of weight are mixed, in taper pulverizer (beakermill), pulverize this mixture, obtain pulvis.
B) with the formula I compound of 25 parts of weight, 64 parts of weight contain kaolinic quartz (as inert substance), the oleoyl methylamino second sulphonyl sodium (Sodium oleoylmethyltauride) (as lubricant and dispersion agent) of the lignin sulfonic acid potassium of 10 parts of weight and 1 part of weight mixes, in pin type dry pan, grind this mixture, obtain dispersive wettable powder in water easily.
C) the easily preparation of dispersive dispersion concentrate in water: with the formula I compound of 20 parts of weight, the alkyl phenol polyoxyethylene glycol ether of 6 parts of weight (Triton * 207), the different tridecyl alcohol polyglycol ether (8EO) of 3 parts of weight and the paraffin mineral oil of 71 parts of weight (for example boiling range is about 255 ℃ to more than 377 ℃) mix, in ball formula pulverizer, grind this mixture, make granularity less than 5 microns.
D) preparation missible oil: with the formula I compound of 15 parts of weight, the nonyl phenol (as emulsifying agent) of the oxyethyl group of the pimelinketone of 75 parts of weight (as solvent) and 10 parts of weight mixes.
E) in water easily emulsive, by the concentrate that phenoxy carboxylic acid ester and toxicide (10: 1) constitute, prepare by following substances:
The 2-[4-of 12.00% weight (6-Lv benzoxazole-2-base-oxygen base)-phenoxy group) ethyl propionate,
The formula I compound of 1.20% weight,
The dimethylbenzene of 69.00% weight,
Ten DAADBSA calcium of 7.80% weight,
The nonyl phenol of the ethoxylation of 6.00% weight (10EO),
The Viscotrol C of the ethoxylation of 4.00% weight (40EO).
Above-mentioned prescription is pressed a) described method preparation of example.
F) by 2-[4-(6-Lv benzoxazole-2-base-oxygen base)-phenoxy group of 4.0% weight]-ethyl propionate,
The formula I compound of 40.0% weight,
The dimethyl of 30.0% weight,
The pimelinketone of 20.0% weight,
The calcium dodecylbenzene sulphonate of 4.0% weight and
The Viscotrol C of the ethoxylation of 2.0% weight (40EO) makes easy emulsive in water, contains the concentrate of phenoxy carboxylic acid ester and toxicide (1: 10).
B. chemical case
Parent compound
1) α-chloro-α-(3-trifluoromethyl hydrazono-)-glyoxalic acid methylester
161.6 gram (1.0 moles) 3-5-trifluoromethylanilines are dissolved in the mixture of 400 ml waters and 326 milliliters of concentrated hydrochloric acids, and at violent stirring and 0 ℃ of following 70 gram Sodium Nitrites solution in 400 ml waters that drips.
The diazonium salt solution that generates is added drop-wise under violent stirring in 165.5 gram α-chloro methyl acetoacetates, 800 ml waters, 444 gram sodium-acetates and the 1000 milliliters of alcoholic acid mixtures, and keeping temperature during dropping is 10 ℃.Further stir after 3 hours, this mixture dilute with water, suction filtration is collected thick product, and extracts with the methyl alcohol boiling.Get 263.6 grams, productive rate: 94%, fusing point: 145 ℃.
2) alpha-amino group-α-(3-trifluoromethyl hydrazono-)-glyoxalic acid methylester
100 gram (0.356 mole) α-chloro-α-(3-trifluoromethyl hydrazono-)-glyoxalic acid methylesters are dissolved in 560 milliliters of tetrahydrofuran (THF)s, and drip 61 grams, 25% strong aqua down at+15 ℃ to+20 ℃.After at room temperature further stirring 5 hours, mixture is poured in the water, suction filtration is collected product, and thick product is with the methyl alcohol extraction of seething with excitement.Get 88.3 grams, productive rate: 95%, fusing point: 138 ℃.
The finished product
3) 1-(3-trifluoromethyl)-3-methoxycarbonyl-5-trichloromethyl-1,2, the 4-triazole
A) with toluene be solvent
At first 26.1 gram (0.1 mole) alpha-amino group-α-(3-trifluoromethyl hydrazono-)-glyoxalic acid methylesters are placed 150 milliliters of toluene, under agitation drip 0., 12 moles of trichoroacetic chlorides, make the mixture boiling then, reflux by a water separator, until there not being water to flow out (about 1 hour).
After the cooling, wash toluene solution with water, and under vacuum, steam toluene, remaining thick product recrystallization from methyl alcohol.Get 24 grams, productive rate: 61.7%, product is faint yellow crystallization, fusing point: 92～93 ℃.
B) with the tetrahydrofuran (THF) be solvent
182.8 gram (0.7 mole) alpha-amino group-α-(3-trifluoromethyl hydrazono-)-glyoxalic acid methylesters are dissolved in 1,200 milliliter of tetrahydrofuran (THF), under agitation,, in 10 minutes, splash into 191 gram (1.05 moles) trichoroacetic chlorides without cooling.Mixture at room temperature stirred 30 minutes, refluxed then 15 minutes, at room temperature stirred 5 hours again.Then mixture is put into water, suction filtration is collected the crystallization of separating out, and washes with water, obtains faint yellow crystallization 233.8 grams, productive rate: 86%, and fusing point: 90 ℃.
After the recrystallization, the fusing point of sample is 92～93 ℃ from methyl alcohol.
4) 1-(3-trifluoromethyl)-5-trichloromethyl-1,2,4-triazole-3-carboxylic acid
At first with 210 gram (0.54 mole) 1-(3-trifluoromethyl)-3-methoxycarbonyl-5-trichloromethyls-1,2, the 4-triazole places 540 ml methanol, adds 0.57 mole of (22.8 gram) sodium hydroxide again and is dissolved in the solution of 100 ml waters.After at room temperature stirring 5 hours, mixture is poured in 4000 ml waters, filtered and collect undissolved material, the pH value of regulating filtrate with hydrochloric acid is 1, at this moment is settled out clear crystal, and suction filtration is collected, and washes with water.With above-mentioned in water insoluble material (sodium salt of carboxylic acid) be dissolved in the mixed solution of 2,000 ml methanol and 1000 ml waters, with the pH value to 1 of hydrochloric acid conditioning solution, suction filtration is collected the colourless crystallization of separating out, and washes it with water.
The carboxylic acid of merge collecting, and with 1000 milliliters of toluene recrystallizations, 174 restrain productive rate: 84%, fusing point: 133～136 ℃.
5) 1-(3-trifluoromethyl)-3-isopropoxy carbonyl-5-trichloromethyl-1,2, the 4-triazole
With 20 gram (0.0534 mole) 1-(3-trifluoromethyl)-5-trichloromethyls-1,2, the vlil of 4-triazole-3-carboxylic acid in 70 milliliters of thionyl chloride 30 minutes removed excessive thionyl chloride then under the vacuum, and thick acyl chlorides was seethed with excitement 60 minutes in 120 milliliters of Virahols.After solution is cooled, inject frozen water, suction filtration is collected colourless crystallization.
Above-mentioned colourless coarse crystallization is ground under room temperature in the mixed solution of methanol-water=1: 2 (50 milliliters), and suction filtration is collected once more, and at air drying.Get 19.4 grams, productive rate: 87.3%, fusing point: 91 ℃.
6) 1-(3-trifluoromethyl)-5-trichloromethyl-1,2,4-triazole-3-carboxylic acid 3 '-5-trifluoromethylaniline
Similar approach according to example 5 changes into acyl chlorides with 0.0345 moles of carboxylic acids, it is dissolved in 80 milliliters of toluene, and under+5 ℃, drip the mixture that contains 0.0345 mole of (5.56 gram) 3-5-trifluoromethylaniline and 0.0345 mole of (3.5 gram) triethylamine in 20 minutes.Mixture washes with water after at room temperature stirring 5 hours, and removes toluene under vacuum.Resistates obtains 14.4 gram colourless crystallizations, fusing point with recrystallization in 40 ml methanol: 126 ℃, and productive rate: 81%.
7) 1-(3-trifluoromethyl)-3-methoxycarbonyl-5-dichloromethyl-1,2, the 4-triazole
0.1 mole of (26.1 gram) alpha-amino group-α-(3-trifluoromethyl hydrazono-)-glyoxalic acid methylester is dissolved in 150 milliliters of toluene, under stirring and room temperature, drips 0.105 mole of (15.5 gram) dichloroacetyl chloride.Mixture refluxed 60 minutes through water separator, after the cooling, washed mixture with water for several times, removed toluene under the vacuum.Resistates is shallow Honey color slurries, gets 28.2 grams, productive rate: 80%.n
D 30：1.5259。
NMR (Nuclear Magnetic Resonance) spectrum: at CDCl
3In, COOCH
3δ 4.05; CHCl
2δ 6.72; With toluene-ethyl acetate=2: 1 was developping agent, Rf value: 0.52.
8) 1-(2,6-diethyl phenyl)-3-methoxycarbonyl-5-trichloromethyl-1,2, the 4-triazole
0.15 mole of (37.4 gram) alpha-amino group-α-(2,6-diethyl phenyl hydrazono-)-glyoxalic acid methylester is dissolved in 165 milliliters of tetrahydrofuran (THF)s, and drips 0.194 mole of (35.4 gram) trichoroacetic chloride.Mixture fully stirs with methylene dichloride at room temperature stirring and falling back in 3 hours, washes organic phase then with water, removes under the vacuum and desolvates, and gets 51.7 grams, productive rate: 91.5%
According to nucleus magnetic resonance POP and ultimate analysis, the light brown slurries that obtain are the open chain compound of following formula:
18.9 gram (0.047 mole) above-claimed cpds are placed 120 milliliters of Glacial acetic acid, refluxed 1.5 hours; After the cooling, mixture is poured in the water and with ethylene dichloride and is fully stirred.The organic phase water is given a baby a bath on the third day after its birth time then, removes under the vacuum and desolvates.
Remaining faint yellow crystallization is ground with 20 ml methanol, and the suction filtration collection, gets 16.4 grams, productive rate: 91%, and molten point: 76～77 ℃.
9) 1-(3-trifluoromethyl)-3-methoxycarbonyl-5-(2,2-dimethyl ethene-1-yl)-1,2, the 4-triazole
26.1 gram (0.1 mole) alpha-amino group-α-(3-trifluoromethyl hydrazono-) glyoxalic acid methylesters are dissolved in 150 milliliters of tetrahydrofuran (THF)s, need not cooling, splash into 15.4 gram (0.13 mole) β in 10 minutes, the beta-dimethyl-acrylate chloride.After reaction mixture under refluxad seethed with excitement 1 hour, distill out most of tetrahydrofuran (THF) under the normal pressure, add excessive water again, stirred reaction mixture.After the water decant gone out, the coarse crystallization recrystallizing methanol, 24 grams, productive rate: 73.7%, fusing point: 143～144 ℃.
10) 1-(4-fluorophenyl)-3-methoxycarbonyl)-and 5-methoxymethyl-1,2, the 4-triazole
21.1 gram (0.1 mole) alpha-amino group-α-(4-fluorophenyl hydrazono-)-glyoxalic acid methylesters are dissolved in 140 milliliters of toluene, need not cooling, drip 14.1 gram (0.13 mole) methoxyacetyl chlorides in 10 minutes.This toluene solution through water separator boiling 1.5 hours, is cooled off then, and washes secondary with water, use 200 milliliters at every turn.Steam toluene under the vacuum, resistates is recrystallization in methyl alcohol.Get 15.2 grams, productive rate: 57.4%, fusing point: 93～94 ℃.
11) 1-(2,4 dichloro benzene base)-3-ethoxy carbonyl-5-methyl isophthalic acid, 2, the 4-triazole
11a) α-(2,4 dichloro benzene base azo)-acetamino diethyl malonate
0.2 mole of (33.4 gram) 2,4 dichloro aniline short period of time in 60 ml waters and 75 milliliters of concentrated hydrochloric acids is boiled.Then this suspension is cooled to+5 ℃, and under this temperature, it is carried out diazotization with 0.2 mole of (13.8 gram) Sodium Nitrite solution in 25 ml waters.
With the diazonium salt solution that obtains in 15 minutes, in+5 to+7 ℃ be added drop-wise to by intensively stirred, contain 300 milliliters of ethanol, 200 milliliter water are in the mixture of 100 gram sodium-acetates and 0.2 mole of (43.3 gram) acetamino diethyl malonate.After at room temperature further stirring 1 hour, mixture is poured in the water, suction filtration is collected product, and crystallization washes with water.Behind ethanol water recrystallization, the crystalline melt point that obtains is 123～124 ℃, gets 71 grams, productive rate: 91%.
11b) 1-(2,4 dichloro benzene base)-5-methyl isophthalic acid, 2,4-triazole-3-carboxylic acid
With 39 gram (0.1 mole) example 11a) product that obtains refluxes in 165 ml waters and 24.2 gram potassium hydroxide mixtures and boiled 5 minutes.The solution that generates is cooled to 60 ℃, and uses the concentrated hydrochloric acid acidifying.Suction filtration is collected 1-(2,4 dichloro benzene base)-5-methyl isophthalic acid, and 2,4-triazole-3-carboxylic acid precipitation, and wash with water until being neutral, get 25.6 grams, productive rate: 94%, fusing point: 163～164 ℃.
11c) 1-(2,4-dioxy phenyl)-3-ethoxy carbonyl-5-methyl isophthalic acid, 2, the 4-triazole
With 0.01 mole of 11b) compound in 150 milliliters of thionyl chloride, reflux and boiled 2 hours, under vacuum, remove excessive thionyl chloride then, thick acyl chlorides heated and boiled 30 minutes in 500 milliliters of ethanol.Subsequently mixture is poured in the water, suction filtration is collected the crystallization of separating out, and is washed with water to neutrality.Get 24 grams, productive rate: 80%, fusing point: 131～132 ℃.
After recrystallizing methanol, crystalline melt point is 133～134 ℃.
12) 1-(2,4 dichloro benzene base)-3-ethoxy carbonyl-5-methyl isophthalic acid, 2, the 4-triazole
12a) 0.1 mole (27.6 gram) alpha-amino group-α-(2,4 dichloro benzene base hydrazono-) glyoxylic acid ethyl ester refluxed 2 hours in 150 milliliters of acetic anhydride, removed excessive acetic anhydride then under the vacuum, thick product ethyl alcohol recrystallization.Get 21.6 grams, productive rate: 72%, fusing point: 133～134 ℃.
121b) 0.1 mole of (27.6 gram) alpha-amino group-α-(2,4 dichloro benzene base hydrazono-) glyoxylic acid ethyl ester was refluxed 4 hours in 130 milliliters of former acetic acid triethyls, under vacuum, remove excessive ortho-acetate, product ethyl alcohol recrystallization then.Get 18.9 grams, productive rate: 63%, fusing point: 133～134 ℃.
13) 1-(2,4 dichloro benzene base)-3-ethoxy carbonyl-1,2, the 4-triazole
0.1 mole of (27.6 gram) alpha-amino group-α-(2,4 dichloro benzene base hydrazono-) glyoxylic acid ethyl ester was refluxed 5 hours in 120 milliliters of trimethyl orthoformates, remove excessive ortho-formiate then under the vacuum, the resistates ethyl alcohol recrystallization.Get 21.4 grams, productive rate: 75%, fusing point: 105～106 ℃.
14) 1-phenyl-3-ethanoyl-5-trichloromethyl-1,2, the 4-triazole
23.6 gram (0.13 mole) trichoroacetic chlorides are under agitation once added in 0.1 mole of (17.7 gram) alpha-amino group-α-phenyl hydrazono-methyl-glyoxal solution in 150 milliliters of tetrahydrofuran (THF)s.After boiling 1 hour under refluxing, mixture is poured in 1 premium on currency, decant goes out to precipitate the water on the thick product subsequently, and thick product is heavily tied product with methyl alcohol, gets 21.0 grams, productive rate: 66%, and fusing point: 139～140 ℃.
The formula I compound that exemplifies out in the Table I is to prepare according to the method that is similar to example 3 to 14.Table I instance number (Z) n Y X fusing point (℃) preparation method
n
D 30By instance number
15 3-Cl CCl
3 -OC
2H
5 76-77 3a
16 3-Cl CCl
3 -OH 124-127 4
17 3-C1 CHCl
2 -OCC
2H
5 Slrup 3a
18 2-Cl CCl
3 -CC
2H
5 99-100 3a
19 2-Cl CCl
3 -OH 204-205 4
20 2-Cl CCl
2 -OCH
3 114-115 3b
21 2-Cl CCl
3 -OCH
2CH
2CH
3 90-92 5
22 4-Cl CHCl
3 -CCH
3 152-153 3a
23 3，5-Cl
3 CHCl
2 -OCH
3 1,5809 3a
24 4-NO
2CHCl
2-OCH
3149-150 3a Table I instance number (Z) n Y X fusing point (℃) preparation method
n
D 30By instance number 25 3,5-Cl
2CCl
3-OCH
3143-145 3b 26 3,5-Cl
2CCl
3-OH 194-195 4 27 2-Cl CHCl
2-OC
2H
5135-136 3a 28 3-Cl CHCl
2-OH 114 4 29 2-Cl CHCl
2-OCH
3158 3a, 30 4-NO
2CCl
3-OCH
3201-203 3b 31 H CCl
3-OCH
3103-104 3b 32 H CCl
3-OH 154-156 4 33 4-F CHCl
2-OCH
3168 3a, 34 3-CN CCl
3-OH 155 4 35 4-Cl-C
6H
4-O-CCl
3-OH 142 4 36 2,4-Cl
2CCl
3-OC
2H
5111-112 8 37 2,4-Cl
2CCl
3-OH 156 4 38 4-Cl-C
6H
4-O-CCl
3-OCH
31,5925 3b 39 2,4-Cl
2CHCl
2-OCH
3147 3a, 40 2-Cl CHCl
2-OH 188-189 4 41
CCl
3-OCH
3Slurry 3b 42
CCl
3-OH 141 4 43 2,4-Cl
2CCl
3-NH-C
6H
5215-217 6 Table I instance number (Z) n Y X fusing points (℃) preparation method
n
D 30By instance number 44 2,4-Cl
2CCl
3-NH-C
6H
4-3-CF
3166-167 645 3,5-Cl
2CCl
3" 160-161 646 2,4-Cl
2, CCl
3" 173 6
5-OCH
347 2,4-Cl
2CCl
3-OCH
3162-163 3,b48 2,4-Cl
2CCl
3-OCH
2CH
2CH
2CH
366-67 549 2-CH
3, 4-Cl CCl
3 
166 650 2-CH
3, 4-Cl CCl
3 
167-168 651 2,4-Cl
2CCl
3 187-188 5
*52 3-CF
3CCl
3-OC
2H
564 3,a53 3,5-Cl
2CCl
3 203 5
*54 2-CH
3, 4-Cl CCl
3 
203 6 Table I instance number (Z) n Y X fusing points (℃) preparation method
n
D 30By instance number 55 2,4-Cl
2CCl
3 193-194 656 2,4-Cl
2CCl
3 
68-72 657 2,4-Cl
2CCl
3 205-207 658 4-Cl CCl
3-OCH
3136-137 3b59 4-Cl CCl
3-CH 145-147 460 3-Cl, 4-F CCl
3 
131-132 561 3-Cl, 4-F CCl
3-OCH
2CH (CH
3)
2122-123 562 2,4-Cl
2CCl
3 
160-163 663 2,4-Cl
2CCl
3-N (C
2H
5)
2Glass-like 664 4-CH
3CCl
3-OH 146 465 4-CH
3CCl
3-OCH
3132-134 3b66 4-F CCl
3-OCH
3113-114 3b67 2-CH
3, 4-Cl CCl
3-OC
2H
5117-118 868 2-CH
3, 4-Cl CCl
3-OCH
3125-126 3b69 3-CN CCl
3-CCH
3125-126 3,b70 2,4-Cl
2CCl
3-OCH (CH
3)
2154-155 571 2,4-Cl
2CCl
3-OCH
2CH
2C
3129-130 5 Table I instance number (Z) n Y X fusing points (℃) preparation method
n
D 30By instance number 72 4-F CCl
3-OH 131-132 473 4-F CCl
3-OCH
2CH
2CH
3120-121 574 3-Cl, 4-F CCl
3-OCH
3114-115 3,b75 2,6-(C
2H
5)
2CCl
3-OH 193-195 476 2,4-Cl
2CCl
3-OCH
2CH (CH
3)
2119-121 577 2-Cl CCl
3-OCH (CH
3)
2131-132 578 2,4-Cl
2, CCl
3-OCH
3155 3b
5-OCH
379 2，4-Cl
2， CCl
3 -OH 215 4
5-OCH
380 2-CH
3, 4-Cl CCl
3-OH 112 481 2-Cl CCl
3-OCH
2CH (CH
3)
279-80 582 2-CGH
3, 4-Cl CCl
3 
153 5
*83 3-Cl, 4-F CCl
3-OC
2H
5118-119 884 3-Cl, 4-F CCl
3-OH
2H
5174 485 4-F CCl
3-OCH
2CH (CH
3)
2103-104 586 2-CH
3, 4-Cl CCl
3-OCH
2CH
2CH
2CH
3112 587 4-Cl CCl
3-OC
2H
5161-162 888 4-CH
3CCl
3-OCH (CH
3)
2154-155 589 H CHCl
2-OH 185 490 2,4-Cl
2CF
3-OCH
3131 3b91 4-CH
3CCl
3-OC
2H
5104-105 892 4-CH
3CCl
3-OCH
2CH (CH
3)
2125-126 593
CCl
3-OC
2H
5147 894 " CCl
3-OCH
2CH
2CH
399 5 Table I instance number (Z) n Y X fusing points (℃) preparation method
n
D 30By instance number
95 4-F CF
3 -OCH
3 87-88 3b
96 4-Cl CCl
3 -OCH
2CH(CH
3)
2 138-139 5
97 2，6-(C
2H
5)
2 CCl
3 -OC
2H
5 96-97 8
98 3，4-Cl
2 CCl
3 -OCH
3 133 3b
99 2，6(C
2H
5)
2 CCl
3 -ONa 233-234 4
100 2，6(C
2H
5)
2 CCl
3 -OCH
2CH
2CH
3 1.5390 5
101 2，6(C
2H
5)
2 CCl
3 -OCH(CH
3)
2 83-84 5
102 2，6(C
2H
5)
2 CCl
3 -OCH
2CH(CH
3)
2 1,5147 5
103 3，4-Cl
2 CCl
3 OH 167-168 4
104 2-CF
3，4-Cl CCl
3 OCH
3 110 3a
105 2-CF
3，4-Cl CCl
3 OH 143-145 4
106 2-F，4-Cl-5-OCH
3 CCl
3 OCH
3 177-178 3a
107 2-F，4-Cl，5-OCH
3 CCl
3 OH 176 4
108 2-CHF
2CF
2O- CCl
3 OCH
3 116-117 3a
109 3-CHClF-CF
2O- CCl
3 OCH
3 syrup 3a
110 2-CH
3，3-Cl CCl
3 OCH
3 144-145 3a
111 2，6-Cl
2 CCl
3 OCH
3 143-144 3a
112 2，5-(OCH
3)
2，4-Cl CCl
3 OCH
3 149 3a
113 2，5-(OCH
3)
2，4-Cl CCl
3 OH 223-224 4
114 3，5-Cl
2，4-OCH
3 CCl
3 OCH
3 148-149 3a
115 3，5-Cl
2-4-OCH
3 CCl
3 OH 150 4
116 2-Cl，4-Br CCl
3 OC
2H
5 113-114 3a
117 2-Cl，4-Br CCl
3 OH 220 4
118 2-Br CCl
3 OCH
3 126-127 3a
119 2-Br CCl
3 OH 195-196 4
120 2，-Cl
2 CCl
3 OCH
2CH
2Cl 88-89 5
121 3-CHClF-CF
2O- CCl
3 OH 128-130 4
122 2-CH
3，4-Cl CCl
3 CH
3 141 14
123 3-CH
3, 4-CHF
2CF
2O CCl
3CH
3119-120 14 Table I instance number (Z) n Y X fusing points (℃) preparation method
n
D 30By instance number 124 2,4-Cl
2CCl
3CH
3120-121 14 125 3-OCF
3CCl
3CH
392-93 14 126 3-CHCl
2CF
2O CCl
3CH
3114-115 14 127 H CCl
3CH
3139-140 14 128 2-Cl CCl
3CH
3121-122 14 l29 3-CF
2Cl CCl
3CH
3Syrup 14 130 4-Cl (CH
3)
2C=CH-OCH
3118-119 9 131 2-CH
3, 4-Cl (CH
3)
2C=CH-OCH
3142-143 9 132 2-Cl CH
2Cl OCH
3112-113 10 133 2-CH
3, 4-Cl CH
3OCH
373 10 134 3-Cl, 4-F (CH
3)
2C=CH-OCH
3185-186 9 135 2,4-Cl
2, 5-OCH
3(CH
3)
2C=CH-OCH
3200-201 9 136 3,4-Cl
2CHCl
2-CF
2-OC
2H
5ND30:1.5458 9 137 2-CH, 4-Cl CHCl
2-CF
2-OC
2H
5ND30:1.5272 9 138 2-CH
3, 4-Cl CHF
2-CF
2-OC
2H
5ND30:1.4991 9 139 4-F CHF
2-CF
2-OCH
366-67 9 140 2-Cl (CH
3)
2C=CH-OH 194 4 141 3,4-Cl
2CF
2H-CF
2-OC
2H
5ND30:1.5198 9 142 2,4-Cl
2, 5-OCH
3CF
2H-CF
2-OCH
3112-113 9 143 2-CH
3, 4-Cl CH
3CH=CH-OCH
3175-176 9 144 4-F
OCH
3149-160 9 145 3-CF
2HCF
2-CR
2-OCH
2Gather 9 146 2,4-Cl
2HCF
2-CF
2-OC
2H
5Starch 9 Table I instance number (Z) n Y X fusing points (℃) preparation method
n
D 30By instance number 147 2,4-Cl
2HCF
2-(CF
2)
3-OC
2H
5115-116 9,148 2,4-Cl
2BrCF
2-CF
2-OC
2H
5100-101 9,149 2,4-Cl
2HCF
2-CF
2-OH 123-124 9150 2-Cl CH
3OH 190 11b151 2-Cl CH
3OC
2H
5110-111 11c152 4-Cl CH
3OH 172 11b153 4-Cl CH
3OC
2H
5115 11c154 3-Cl, 4-F CH
3OH 183 11b155 4-F CH
3OH 177 11b156 2-CH
3, 4-Cl CH
3OH 177-178 11b,157 2,4-Cl
2, 5-OCH
3CH
3OH 193-194 11b,158 2,4-Cl
2CH
3OCH
3180-181 11c159 3-Cl, 4-F CH
3OCH
3140-142 11c160 3-Cl, 4-F CH
3OC
2H
5114-115 11c,161 2,6-(C
2H
5)
2CHF
2-CF
2-OH 222-223 4162 4-F CH
3OC
2H
5105-106 11c163 2-CH
3, 4-Cl CH
3OC
2H
5153-154 11c,164 2,4-Cl
2H OH 185-186 4,165 2,4-Cl
2H OC
2H
5105-106 13166 4-CH
3CH
3OC
2H
51,5466 11c167 4-CH
3CH
3OH 183 11b168 2-Cl, 4-Br CH
3OC
2H
5142-143 11c169 2-Cl, 4-Br CH
3OH 132-173 11b170 3-CF
3CH
3OH 164-165 11b,171 2,4-Cl
2CH
3OC
2H
5133-134 11c,172 2,4-Cl
2CH
3OH 163-164 11b6) in toluene, the alcohol of gram molecular weight such as use, triethylamine is as acid binding agent.
C. biological example
Example 1
Wheat up to growing three to four leaf stages, is used weedicide and compound treatment of the present invention in cultivation in the greenhouse then in diameter is 9 centimetres basin.Weedicide and formula I compound are used with the form of aqueous suspension or emulsion, and institute's water consumption is equivalent to 800 liters/hectare.Handle after three weeks, estimate the various infringements that the weedicide use causes plant, will consider the degree of long term inhibition plant-growth especially.
Presentation of results in Table I compound of the present invention can very effective reduction weedicide grievous injury.
Even quite excessive use weedicide H, i.e. 2.0 kilograms of active substance/hectares, the sign of weedicide infringement also can significantly reduce, and only exists slight permanent lesion.This has illustrated the good action of safener.Certainly, the slight infringement of weedicide is (the seeing example 2) that can eliminate fully.Therefore, the effect of the mixture of compound of the present invention and weedicide is suitable for removing selectively the weeds in the cereal crop. table 1 compound amount herbicide; ％ H+ α.i./ TA H-2,0 75 H+ 17 2.0+2.5 20 H+ 22 " 30 H+ 7 " 30 H+ 27 " 25 H+ 15 " 11 H+ 16 " 24 H+ 36 " 13 H+ 67 " 10 H+ 25 " 25 H+ 78 " 18 H+ 31 " 20 H+ 69 " 28 H+ 3 " 26 H+ 79 " 30 H+ 80 " 30 H+ 32 " 24 H+ 37 " 24 H+ 19 " 25 H+ 43 " 30 H+ 63 " 20 H+ 18 " 13 H+ 29 " 20 H+ 33 " 20 H+ 39 " 20 H+ 41 " 20 H+ 64 " 20 H+ 66 " 15 H+ 73 " 25 H+ 85 " 20 H+ 74 " 25 H+ 127 2.0+1.0 30 H+ 89 2.0+2.5 30 H+ 90 " 50 H+ 146 " 30 H+ 9 " 40 H+ 160 " 60 H+ 163 " 30 H+ 20 " 13 H+ 21 " 22 H+ 47 " 22 H+ 48 " 7 H+ 70 " 10 H+ 71 " 50 H+ 76 " 20 H+ 68 " 10 H+ 72 " 22 H+ 73 " 40 H+ 84 " 35 H+ 8 " 30 H+ 75 " 50 H+ 59 " 20 H+ 83 " 28 H+ 52 " 60 H+ 5 " 22 H+ 77 " 20 H+ 81 " 30 H+ 92 " 40 H+ 91 " 40 H+ 88 " 50 H+ 86 " 40 H+ 87 " 20 H+ 96 " 40 H+ 100 " 40 H+ 103 " 30 H+ 102 " 40 H+ 104 2.0+2.5 50 H+ 106 " 50 H+ 107 " 50 H+ 110 " 48 H+ 111 " 50 H+ 116 " 20 H+ 116 " 30 H+ 113 " 60 H+ 115 " 40 H+ 117 " 18 H+ 119 " 50 H+ 120 " 20 H+ 137 " 25 H+ 138 " 25 H+ 139 " 25 H+ 141 " 40 H+ 142 " 30 H+ 143 " 40 H+ 133 " 50 H+ 134 " 50 H+ 135 " 50 H+ 148 " 20 H+ 149 " 55 H+ 11c " 40 H+ 11b " 25 H+ 150 " 35 H+ 151 " 30 H+ 152 " 50 H+ 153 " 27 H+ 154 " 27 H+ 155 " 50 H+ 156 " 25 H+ 157 " 43 H+ 158 " 20 H+ 171 " 20
Abbreviation in the table 1
TA=summer wheat (Trilicum aestiyum)
The a.i.=active princlple
The H=fenoxaprop-ethyl
=2-(4-(6-chlorobenzene thiazole-2-base oxygen base)-phenoxy group)-ethyl propionate
Example 2
Sowing wheat and two kinds of weeds gramineous-Alopecurus wyosuroides and wild avena sativa (AYena fatua) in the fertile sandy soil in the basin of 9 cm diameters, and in the greenhouse, cultivate it under the nice and cool condition, up to the beginning packing, use compound treatment of the present invention then, form with aqueous suspension or emulsion is used, use (bucket mixes) with weedicide, water consumption is 300 liters/hectare.
After around the dispenser, estimate the variation and the damage of the plant-growth that is put to the test.
The result of table 2 shows that compound of the present invention has superior safety, can prevent the infringement of weedicide to crop (for example cereal crop) effectively, and don't influence is to the actual herbicide effect of gramineous weeds.
Therefore, the mixture of The compounds of this invention and weedicide can be used for removing selectively weeds.
Table 2 consumption to herbicide effect (%) the herbicidal compounds active principle kilogram/public affairs of wheat incline the infringement % for
H+ (instance number) H+ compound (instance number) (TA) ALM AVF weedicide A-0.8 52--
0.4 40 100 100
0.2 18 93 103H + 7 0.8 +0.4 2 - -
0.4 +0.2 0 100 100
0.2 +0.1 0 98 100H + 27 ″ 2 - -
0 100 100
0 99 99H + 15 ″ 2 - -
0 100 100
0 100 -H + 16 ″ 1 - -
0 100 100
0 98 98H + 18 ″ 3 - -
0 100 100
0 100 97H + 37 ″ 2 - -
0 100 100
0 99 100H + 36 ″ 2 - -
0 100 100
0 97 100
Table 2 consumption to herbicide effect (%) the herbicidal compounds active principle kilogram/public affairs of wheat incline the infringement % for H+(instance number) H+ compound (instance number) (TA) ALM AVF H+78 0.8+0.4 2--
0.4 +0.2 0 100 100
0.2 +0.1 0 100 100 H + 67 ″ 2 - -
0 100 100
0 100 100 H + 22 ″ 2 - -
0 100 100
0 100 99 H + 79 ″ 3 - -
2 100 100
0 98 98 H + 80 ″ 4 - -
2 100 100
0 98 100
0 - - H + 63 0 100 100
0 99 97 H + 19 ″ 2 - -
0 100 100
0 100 97ALM=Alopecurus myocuroidesAVF=wild avena sativa (Avena fatua) H=see Table 1
Example 3
In the basin of 13 cm diameters, sow barley (Variety Oriol) in the fertile sandy soil, and under outdoor climate conditions, cultivate, tiller until beginning, use the mixture (bucket mixes) of The compounds of this invention and weedicide to handle then, form with aqueous suspension or emulsion is used, and water consumption is 300 liters/hectare.
After two weeks of dispenser, estimate growth change and other damage of being tried plant.
The result of table 3 shows that compound of the present invention has extraordinary security, can prevent the infringement of weedicide to crop (for example barley) effectively, and not weaken the practical function that it removes gramineous weeds.
Table 3
The compound amount herbicide effect, %
H1+ instance number (a.i. kilogram/hectare) HV
H1 3.0 30
1.5 13
H1+36 3.0+0.3 15
1.5+1.5 3
Abbreviation: HV=vulgare (Hordeum vulgare)
H=Diclofop-methyl [(2-(4-(2,4 dichloro benzene oxygen base)-phenoxy group)-third
Acid methyl esters]
Claims (3)
1. the method for preparing compound of Formula I,
Wherein Z can be identical or different, and it represents halogen, nitro, cyano group, trifluoromethyl, (C
1-C
4) alkyl, (C
1-C
4) alkoxyl group or (C
1-C
4) alkylthio, wherein alkyl, alkoxyl group and alkylthio can be replaced by one or more halogen atoms, and Z or expression can be by (C
1-C
4) (the C that replaces of alkyl
3-C
6) cycloalkyl, and phenyl or phenoxy group, wherein phenyl and phenoxy group can be replaced by the halogen list or be polysubstituted and/or replaced by the trifluoromethyl list,
Y represents can all or part of replaced by halogen atom and/or quilt (C
1-C
4) alkoxyl group or (C
1-C
4) mono-substituted (C of alkylthio
1-C
4) alkyl, (C
2-C
6) alkenyl or (C
2-C
6) alkynyl group, perhaps expression can be by (C
1-C
4) (the C that replaces of alkyl and/or dichloroethylene
3-C
6) cycloalkyl,
X represents hydroxyl, (C
1-C
4) alkyl, (C
3-C
6) cycloalkyloxy, phenyl-(C
1-C
6) alkoxyl group, phenoxy group, (C
2-C
6) alkenyloxy, (C
2-C
6) alkynyloxy group, (C
1-C
6) alkoxyl group or (C
1-C
5) alkylthio, wherein alkoxyl group or alkylthio can be replaced by following radicals: (C
1-C
2) alkoxyl group, list-(C
1-C
4) alkyl amino-carbonyl, two-((C
1-C
4) alkyl) aminocarboxyl, phenyl amino carbonyl, N-[(C
2-C
4) alkyl]-N-phenyl-aminocarboxyl, list-(C
1-C
6) alkylamino, two-(C
1-C
6) alkylamino, (C
1-C
6) the alkyl-carbonyl oxygen base, (C
1-C
2) alkylthio, cyano group or halogen or X represent to have the group of following formula:
Or
Wherein R represents hydrogen or (C
1-C
4) alkyl, or expression list-(C
1-C
4) alkylamino, two-(C
1-C
4) alkylamino, (C
5-C
6) cycloalkyl amino, pyridine subbase, morpholino or 2,6-thebaine generation or have formula
Group, R wherein
1And R
2Can be identical or different, they represent (C
1-C
4) alkyl, R
1And R
2Also can form the five-ring alkyl, six-ring alkyl or seven-membered ring alkyl,
N represents numeral 0,1,2 or 3,
Perhaps when X is OH, the method for the agricultural salt of preparation general formula (I) compound, still, except following general formula (I) compound:
(a) Y represents H, and Z represents that H and X represent OH, OCH
3, OC
2H
5Or NHC
6H
5,
(b) Y represents H, and Z represents 4-OCH
3And X represents OH, OCH
3Or NHC
6H
5,
(c) Y represents H, and Z represents 3-OCH
3, 4-Cl, 4-CH
3And X represents OCH
3,
(d) Y represents H, and Z represents that 3-Cl and X represent OH,
(e) Y represents CH
3, Z represents H or OCH
3And X represents OH,
(f) Y represents CH
3, Z represents 4-NO
2And X represents OH, OCH
3Or OC
2H
5,
(g) Y represents CH
3, Z represents 2-Cl, 4-NO
2-2-CH
3Or 4-NO
2-2-OCH
3And X represents OC
2H
5,
(h) Y represents C
2H
5, Z represents that H and X represent OH,
(i) Y represents n-propyl or sec.-propyl, and Z represents that H and X represent OH, OCH
3Or OC
2H
5,
(k) X represents CH
3, Y represents H or C
2H
5, Z represents H, 4-Cl or 4-OC
2H
5,
(l) X represents CH
3, Y represents CH
3And Z represents H, 4-Cl, 4-OCH
3, 4-OC
2H
5Or 4-NO
2,
This preparation method comprises:
A) with formula II compound:
X wherein
1Identical with the connotation of X, but can not be hydroxyl,
A1) with general formula be the compound reaction of Y-CO-C1, perhaps
A2) be the anhydride reaction of Y-CO-O-CO-Y with general formula, perhaps
A3) be Y-C (OR with general formula
1)
3Ortho ester reaction, R wherein
1Expression (C
1-C
4) alkyl, perhaps
B) if Y is H or (C in the compound
1-C
4) alkyl, then with formula III compound and alkali reaction,
Y wherein
1Expression hydrogen or (C
1-C
4) alkyl, R
3Expression (C
1-C
4) alkoxyl group or CH
3,
If desired, will be at a1) and the compound that a2) obtains under the situation in acetic acid, heat, and the formula I compound that obtains is changed into other compound or its salt with formula I by the method for preparing derivative.
2. method according to claim 1, wherein in formula I compound, Y represents can be all or part of by F, (the C that Cl or Br replace
1-C
2) alkyl,
Z can be identical or different, and it represents halogen, (C
1-C
4) alkoxyl group, (C
1-C
4) alkyl or CF
3,
X represents (C
1-C
6) alkoxyl group or hydroxyl,
N represents 1,2 or 3.
3. method according to claim 2, wherein in formula I compound, Y represents CCl
3, CHCl
3, CHF
2CF
2Or CH
3
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3525205.7 | 1985-07-15 | ||
| DE19853525205 DE3525205A1 (en) | 1984-09-11 | 1985-07-15 | PLANT PROTECTIVE AGENTS BASED ON 1,2,4-TRIAZOLE DERIVATIVES AND NEW DERIVATIVES OF 1,2,4-TRIAZOLE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1054595A CN1054595A (en) | 1991-09-18 |
| CN1035326C true CN1035326C (en) | 1997-07-02 |
Family
ID=6275800
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91102410A Expired - Lifetime CN1035326C (en) | 1985-07-15 | 1985-09-30 | Process for preparing derivates of 1,2,4-triazols |
| CN 85107316 Expired - Lifetime CN1021789C (en) | 1985-07-15 | 1985-09-30 | Compound containing 1,2,4-triazole derivatives, its preparation and its application used as plant protective agent |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85107316 Expired - Lifetime CN1021789C (en) | 1985-07-15 | 1985-09-30 | Compound containing 1,2,4-triazole derivatives, its preparation and its application used as plant protective agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1035326C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060650C (en) * | 1994-06-07 | 2001-01-17 | 张贵发 | Brain marrow source |
| TW201418242A (en) * | 2012-10-26 | 2014-05-16 | Du Pont | Substituted triazoles as herbicides |
| CN103420931B (en) * | 2013-05-02 | 2015-07-08 | 范国煌 | Pentacyclic compound capable of adjusting polarization of macrophages and resisting diabetes and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5188968A (en) * | 1975-02-04 | 1976-08-04 | Toriazoorujudotaino shinkiseiho |
-
1985
- 1985-09-30 CN CN91102410A patent/CN1035326C/en not_active Expired - Lifetime
- 1985-09-30 CN CN 85107316 patent/CN1021789C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5188968A (en) * | 1975-02-04 | 1976-08-04 | Toriazoorujudotaino shinkiseiho |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1021789C (en) | 1993-08-18 |
| CN85107316A (en) | 1987-01-14 |
| CN1054595A (en) | 1991-09-18 |
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