CN1942417B - Plan nutrient based on o,p-ethylene(bis)hydroxyphenyl glycines - Google Patents

Abstract

The invention relates to novel mixtures of N,N'-ethylene-bis(hydroxyphenyl)glycines comprising a mixture of o,p- and o,o-isomers, wherein the ratio of o, pto o, o-isomer is higher than 0.8 : 1. The novel mixtures have improved characteristics for supplying crop plants with essential metal chelates required as plant nutrients. With the novel mixtures, in particular the short-term supply of metal chelates is improved, while the long term supply is maintained as for known chelating agents comprizing only the o,o-isomer of N,N'-ethylene-bis(hydroxyphenyl)glycine. The invention further refers to metal complexes of the isomer mixture, their use in the field of agriculture as plant nutrient or as component of fertilizers for plants and for treatment of chlorosis in crop plants.

Description

Based on o, the nutrient for plants of p-ethylidene (two) hydroxy phenyl glycine

The present invention relates to new N, N '-ethylidene-two (hydroxy phenyl)-glycine, its metal complex, contain its mixture as the pesticide composition of activeconstituents, its in agriculture field as component and the chlorotic application of treatment plant of nutrient for plants or plant with fertilizer.

The N of formula I, N '-ethylidene-two (hydroxy phenyl) glycine (EDDHA) is known.

The position of aromatic hydroxy on the different aromatic carbon atom on two isolating phenyl ring makes can form different isomer.Hydroxyl-substituent main positions is ortho position and the contraposition on its phenyl ring separately.

One of isomer is N, N '-ethylidene-two (4-hydroxy phenyl) glycine, wherein two phenyl ring all by the hydroxyl para-orientation (p, p-EDDHA).This compound is known in the art, it has been generally acknowledged that not to be suitable for complexing metal in the agricultural.Another isomer is N, N '-ethylidene-two (2-hydroxy phenyl) glycine, wherein two phenyl ring all replaced by the hydroxyl ortho position (o, o-EDDHA).This compound is known in the art, is described to the compound of suitable complexing metal usually, and is suitable as nutrient for plants or fertilizer most, because its complexing avidity to iron is strong especially.

O, the ligancy that the iron chelate of o-EDDHA shows is 6, is widely used in agricultural as nutrient for plants or vegetable fertilizer be used for the treatment of the verticillium of crop.For example showing o among the US-A-2921847, the sample picture of the iron chelate of o-EDDHA.

Another kind of isomer is the N of formula II, N '-ethylidene-(2-hydroxy phenyl)-glycine base-(4-hydroxy phenyl) glycine, one of them phenyl ring is replaced by the hydroxyl ortho position, and another phenyl ring by the hydroxyl para-orientation (o, p-EDDHA).

Because o, the ligancy that the iron chelate of p-EDDHA shows is 5, and its complexing avidity to iron is weaker than o, and o-EDDHA, this compound are regarded as usually at o, the undesirable by product that produces in the manufacturing processed of o-EDDHA.

Yet a spot of o, p-EDDHA be usually as o, the o-EDDHA product do not wish but unavoidable impurities and being accepted that it produces as by product in manufacturing processed.In fact a spot of o that the impurity of o-EDDHA exists, p-EDDHA, in most commercial EDDHA product, have all been found as o.

For pure products being provided and reaching the uniformity of product, the industrialized preparing process purposes of great majority expection are to avoid the o as by product, p-EDDHA, for example disclosed method in CH-A-633257.

In order to treat the plant verticillium, be applicable to that the sequestrant of iron should

A) iron there is fully stable avidity, competes mutually with other cationic complexing actions avoiding,

B) should with common soil material Fails To Respond,

C) avidity to iron (II) should be low,

D) in dicotyledons, should not stop iron reduction and

E) in monocotyledons, should not compete (competing with the plant siderophore is o, one of shortcoming of o-EDDHA) with natural sequestrant plant siderophore.In addition,

F) this sequestrant should be able to discharge iron very apace from solid phase of soil.

Based on o, the performance that the commercially available sequestrant of o-EDDHA is used for the treatment of the plant verticillium is not exclusively gratifying in this respect.Similarly, from the said products, obtain iron and be delayed to a certain extent, even be intended to promptly provide under the situation of plant nutrition plain sheet to the plant administration what expect.

An object of the present invention is to provide a kind of improved EDDHA sequestrant, this sequestrant not only discharges iron more quickly than known commercially available sequestrant, and does not change the profitable power spectrum of the sequestrant of description of the Prior Art.

Be surprised to find that the aforementioned undesirable by product o that uses higher amount in iron chelating agent EDDHA product, p-EDDHA has in fact improved the nutrient for plants and the fertilizer performance of described product.

According to the present invention, proposition is by containing N, the o of N '-ethylidene-two (hydroxy phenyl) glycine, o-and o, use the o of significant quantity in the p-mixture of isomers, p-EDDHA improves nutrient for plants and the verticillium curative properties of metal chelator EDDHA, it is characterized in that N, N '-ethylidene-(2-hydroxy phenyl)-glycine base-(4-hydroxy phenyl) glycine (o, p-EDDHA) and N, (o, mol ratio o-EDDHA) is greater than 0.8: 1, particularly 0.9: 1 to 100: 1 for N '-ethylidene-two (2-hydroxy phenyl) glycine.Preferably, o, p-EDDHA and o, the ratio of o-EDDHA is 1: 1 to 50: 1, or 2: 1 to 10: 1, or 0.9: 1 to 2: 1.

The invention still further relates to and comprise N, the metal complex of the isomer mixture of N '-ethylidene-two (hydroxy phenyl) glycine, N wherein, N '-ethylidene-(2-hydroxy phenyl)-glycine base-(4-hydroxy phenyl) glycine (o, p-EDDHA) and N, (o, mol ratio o-EDDHA) is greater than 0.8: 1, particularly 0.9: 1 to 100: 1 for N '-ethylidene-two (2-hydroxy phenyl) glycine.Preferably, o, p-EDDHA and o, the ratio of o-EDDHA is 1: 1 to 50: 1, or 2: 1 to 10: 1, or 0.9: 1 to 2: 1.

The agricultural that can be advantageously used for the metal complex of EDDHA-mixture of the present invention goes up the effective constituent in the acceptable composition, or as nutrient for plants as single activeconstituents, or as the part of nutrient for plants combination, or the component in the vegetable fertilizer in the agricultural.The EDDHA isomer mixture that is preferred for these purposes comprises the o according to the described ratio of specification sheets of the present invention, p-EDDHA and o, the iron chelate of o-EDDHA.Iron chelate can be used as the nutrient substance of agricultural crops especially and treats the medicament of the verticillium of described plant, use with suitable inert support material with acceptable composition form on the agricultural in the practice of agriculture, perhaps the active ingredient of as fertilizer sources is used for the crop of agricultural cultivation.

Preferably, described metallo-chelate is a ferric iron EDDHA inner complex.Described ferric chelate is not limited to only comprise iron as metal chelate, and it also can contain other metals, and preferred as alkali or alkaline-earth metal are as sodium, potassium, calcium or magnesium, particularly sodium.Preferably, ferric chelate is inner complex or its mixture of Na Fe (EDDHA), K Fe (EDDHA) type.

The iron level of ferric chelate is 0.5-10wt% normally, preferred 1-8wt%, particularly 1.5-7%, particularly 2-6wt% or 2-5.5wt%, especially 2.4-5.5wt%.

Differed widely with former analytical technology, utilize special research and development and analytical procedure that be fit to this purpose, promptly permanent (isocratic) ion pair high performance liquid chromatography, the now available quantitative and definite exactly o of qualitative parameter, p-EDDHA and o, the content of o-EDDHA, make and contain o, the beneficial effect of the mixture of p-EDDHA and contained o, p-EDDHA and o, the mol ratio of o-EDDHA is interrelated.

This analytical procedure is known basically, and public publication has been in Journal ofChromatography A, 1996,727, and 253-264 and Journal ofChromatography A, 1997,789,453-460.Be the object of the invention, the special adjustment of wherein said method is fit to measure the EDDHA isomer.

This inflation method has been described a kind of process, is used for chromatographic determination and contains o, and o-EDDHA and o, p-EDDHA describe in detail in the following embodiments as the amount of chelated iron total amount in the sample of sequestrant and its ferric chelate.

Analytical procedure by new research and development is to o in the commercially available product up to now, p-EDDHA and o, the ratio of o-EDDHA is measured under standard laboratory conditions, is presented at all o in the known product, p-EDDHA and o, the ratio of o-EDDHA all is lower than 0.7: 1.

EDDHA mixture of the present invention and the pesticide composition that contains these mixtures are used with the aq suspension form of the dilution that obtained by the common standard preparation of pesticide field usually, can be by conventional application process as spraying or dust and be applied to the plant of plan handling, or the plant zone of growing.When for operation is rationalized, plan other agriculturals of administration simultaneously when going up the activeconstituents that uses, the consecutive order that dispenser can any hope carries out, perhaps even the mixed thing form of the bucket dispenser to be made by the commercial preparation.Perhaps, under the situation through selecting, EDDHA mixture of the present invention can promptly be used as the form of pulvis or granule by solid preparation, and granule may need to sneak in the soil with machinery.

Other agriculturals go up the available activeconstituents and can be other fertilizer, trace nutrient donors or influence plant-growth and other preparations of growth.Equally, can also use plant protection products such as selective herbicide or sterilant, mycocide, bactericide, nematocides, invertebrate poison when needing simultaneously, or the mixture of some described preparations.

The agricultural that also can contain the composition of the isomer mixture of EDDHA of the present invention and preparation goes up in acceptable carrier, tensio-active agent or the preparation technique commonly used other and uses the promotion auxiliary agent.Suitable carrier and tensio-active agent can be solid or liquid, corresponding to material commonly used in the preparation technique, for example natural or regenerated mineral substance, solvent, dispersion agent, wetting agent, tackifier, thickening material, tackiness agent or fertilizer.Described carrier and additive are described in for example WO95/30651.

EDDHA mixture of the present invention uses with the commercially pure crude product form that the form of not changing promptly obtains in manufacturing processed, or preferred auxiliary agent commonly used in preparation technique uses, and for example advantageously is mixed with missible oil for this purpose in known manner, can applies paste, can directly sprays or dilutable solution, dilute emulsion, wettable powder, soluble powder, pulvis, granule and by for example being encapsulated in the polymkeric substance.

As the character of composition, application process as spray, atomize, dust, spreading, coating, soil soak into or cast is to select according to its intended purposes and main environment.

Preparation, the composition or the preparation that promptly contain mixture of the present invention, also can contain solid or liquid adjuvants such as carrier or solvent, and prepare in a manner known way, for example by mixing equably and/or grinding activeconstituents and weighting agent, for example solvent, solid carrier and the surface active cpd (tensio-active agent) suitably the time.

Other auxiliary components that are preferred for comprising the above-mentioned type in the composition of EDDHA-mixture of the present invention are sodium lignosulfonate, dextrin, isooctylphenol polyglycol ether, poly carboxylic acid sodium 2,5-furandione polymkeric substance and 2,4,4-2,4,4-Trimethyl-1-pentene, and pelopon A.Conventional other tensio-active agents that use are well known by persons skilled in the art in the preparation technique, perhaps can find in the correlation technique document.

Though the commercially available prod preferably is mixed with enriched material, the end user generally can use the sequestrant mixture of the dilute dispersion form of commercial preparation.

Preparation of the present invention contains the N that exists with ratio of mixture of the present invention usually, the ferric chelate of N '-ethylidene-two (hydroxy phenyl) glycine, and its content is 1-95wt%, or 30-88wt%, or 35-73wt%, or 35-79wt%.

If the preparation design contains other nutrient for plants or vegetable fertilizer, these materials are preferably selected from and comprise calcium sulfate, nitrocalcite Ca (NO so ₃) ₂* 4H ₂O, lime carbonate, saltpetre, sal epsom, potassium hydrogen phosphate KH ₂PO ₄, manganous sulfate, copper sulfate, zinc sulfate, nickelous chloride, rose vitriol, potassium hydroxide, sodium-chlor, boric acid and metal-salt thereof, Na ₂MoO ₄Group.The content separately of preferred other nutrient substance is 5-50wt%, preferred 10-25wt%, or 15-20wt%.

Preferred other nutrient substance is urea, melamine, potassium oxide and inorganic nitrate.Most preferred other nutrient for plants is a potassium oxide.

When preferred other nutrient substance was urea, its content was 1-20wt%, preferred 2-10wt%, or 3-7wt%.

The preferred independent preparation of the present invention is the composition that contains following ingredients: 1-99wt%N, the ferric chelate of N '-ethylidene-two (hydroxy phenyl) glycine,

O wherein, p-EDDHA and o, the ratio of o-EDDHA is higher than 0.8: 1;

1-20wt% urea,

The 0-50wt% potassium oxide; Or

30-88wt%N, the ferric chelate of N '-ethylidene-two (hydroxy phenyl) glycine,

O wherein, p-EDDHA and o, the ratio of o-EDDHA are 1: 1 to 50: 1;

2-10wt% urea,

The 10-25wt% potassium oxide; Or

35-73wt%N, the ferric chelate of N '-ethylidene-two (hydroxy phenyl) glycine,

O wherein, p-EDDHA and o, the ratio of o-EDDHA are 2: 1 to 10: 1 or 0.9: 1 to 2: 1;

3-7wt% urea,

The 15-20wt% potassium oxide.

Mixture of the present invention can contain the mixture of plant protection mycocide combination, can produce the synergistic activity that can't expect sometimes.Described mixture is not limited to two kinds of activeconstituentss (in the tabulation of a kind of and plant protection mycocide of formula I a kind of), and on the contrary, many mixtures comprise more than a kind of mycocide.The mixing element that is specially adapted to this purpose comprises, for example: azole, as oxygen azoles ring, bitertanol, chaff rhzomorph, SN-108266, the phonetic difenoconazole of benzene, alkene azoles alcohol, fluorine ring azoles, RH-7592, fluquinconazole, fluzilazol, flutriafol, own azoles alcohol, press down mould azoles, S-presses down mould azoles, imibenconazole, kind bacterium azoles, metconazole, nitrile bacterium azoles, dislikes imidazoles, pefurazoate, Topaze, pyrifenox, prochloraz, Wocosin 50TK, prothioconazoles, simeconazoles, tebuconazole, tertraconazole, triazolone, triadimenol, fluorine bacterium azoles and triticonazole; The rubigan class is as ancymidol, fenarimol and nuarimol; 2-amino-miazines is as the phonetic bacterium spirit of sulphur, dimethirimol and the phonetic phenol of second; The morpholine class is disliked luxuriant amine and tridemorph as dodemorph, fenpropimorph, spiral shell; The aniline pyridines is as cyprodinil, mepanipyrim and phonetic mould amine; Pyroles is as fenpiclonil and fludioxonil; Phenylamide is as M 9834, furalaxyl, metaxanin, mefenoxam (M-metaxanin), ofurace and Wakil; Benzimidazoles is as F-1991, derosal, debacarb, fuberidazole and thiabendazole; The dicarboximide class is as chlozolinate, dichlozolin, RP-26019, myclozolin, procymidone and Vinclozoline; Carboxyl acylamide is as carboxin, fenfuram, fultolanil, the spirit of furan pyrazoles, mebenil, oxycarboxin and thiophene fluorine bacterium amine; The guanidine class is as Guanoctine, dodine and biguanides suffering; Methoxy acrylic is as Azoxystrobin, ether bacterium amine (SSF-129), fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, Strobilurin and oxime bacterium ester; Dithiocarbamate is as Karbam Black, zinc manganese ethylenebisdithiocarbamate, maneb, Carbatene, zinc 1,2-propylene bisdithiocarbamate, thiram, zineb and ziram; N-halo methylthio group tetrahydric phthalimide class is as Difolatan, Vancide 89, dichlofluanid, fluoromide, Phaltan and Tolylfluanid; Copper compound is as Bordeaux mixture, copper hydroxide, COPPER OXYCHLORIDE 37,5, copper sulfate, Red copper oxide, mancopper and oxinecopper; The nitrophenol derivative disappears as dinitro ester and different third; Derivative of organic phosphorus is as Hinosan, iprobenfos, isoprothiolane, phosdiphen, pyrazophos and tolclofosmethyl; Other kinds are as Acibenzolar, anilazine, the benzene metsulfovax, miewensu, boscalid amine, chinomethionate, chloroneb, m-tetrachlorophthalodinitrile, IKF-916 (suggestion name cyanogen frost azoles), cyflufenamid, frost urea cyanogen, dichlone, diclomezin, dicloran, the mould prestige of second, dimethomorph, Guardian, zarilamid, SYP-LI90 (suggestion name: flumorph), the dicyan naphthoquinones, etridiazole, Famoxate, fenamidone, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl, dislike mould spirit, iprovalicarb, kasugamycin, methasulfocarb, metrafenone, pencycuron, phthalide, picobenzamid, Polyoxin, thiabendazole, Propamocarb, pyroquilon, proquinazid, benzene oxygen quinoline, quintozene, the silicon metsulfovax, sulphur, triazoxide, triadinil, tricyclazole, triforine, validamycin or zoxamide.

In the above-mentioned composition that contains Fungicidal mixtures, the selection of the ratio of mixture of activeconstituents should make it reach the effect of the plant pathogenic microorganism on the optional control host plant, and this makes plant can make full use of the benefit that obtains the metal of magnitude of recruitment from EDDHA-inner complex mixture conversely again.With respect to the ratio of mixture of second kind of mycocide normally 100: 1 to 1: 100, more preferably 10: 1 to 1: 10.This mixture not only comprises one of listed Fungicidal active ingredient capable of being combined, and can comprise more than a kind of other activeconstituents that is selected from particular group, thereby forms for example ternary or or even quaternary mixture.

Preparation of the present invention also can contain weedicide, particularly the sulfonylurea described in for example EP-A-837632.

In order to make mixture of the present invention, can adopt several method.These methods are applicable to usually makes pure o, o-EDDHA and o, p-EDDHA.Pure products can be mixed afterwards, produce the mixture of wishing ratio.Preferred method is a direct production mixture of the present invention.For example, can adopt the method among the DE-1032748, this method is shown in scheme 1.

Scheme 1

In this method, the first step, two normal o-hydroxy benzaldehydes or p-hydroxy benzaldehyde or preferred its mixture with the 1 condensation of monovalent, remove and anhydrate, and produce aldimine.This reaction can be carried out under known standard reaction condition.The water that produces as product in the reaction process preferably is removed or captures.Usually this can realize as adding siccative such as sal epsom or sodium sulfate by the standard laboratory method, or by component distillation and with the Dean-Stark separator except that anhydrating.Under the situation of back, preferably use dry-out benzene or toluene as solvent.In second step, the product of the first step and prussic acid reaction.This step can be by in the presence of small amounts of inorganic acid example hydrochloric acid, and under about 20-25 ℃ of temperature, the aldimine product of handling the first step with the aqueous solution of prussic acid carries out.As selection, the acidic aqueous solution that can use alkali metal cyanide such as sodium cyanide is as cyanide source.

For making pure o, p-EDDHA only needs to change the details that the first step is reacted.In the case, use and 1, equimolar o-hydroxy benzaldehyde of 2-diaminoethanes or p-hydroxy benzaldehyde, be enough to one of two amino of condensation, after the reaction for the treatment of these compounds is finished, add the second normal another kind of hydroxy benzaldehyde isomer respectively, reaction mixture further reacts until finishing.

Hydroxy benzaldehyde and prussic acid reaction can also be produced corresponding cyanalcohol, in second step, this cyanalcohol and 1 reaction.

In the 3rd step, gained quadrol-N, N '-two (hydroxy phenyl) acetonitrile can pass through the currently known methods hydrolysis, for example by reacting hydrolysis with concentrated hydrochloric acid under 80-100 ℃ of temperature.Adding alkali then in reaction mixture, is 2-4 until the pH value, preferred 3-3.5.The collecting precipitation thing heats in concentrated hydrochloric acid then, produces gained N, the dihydrochloride of N '-ethylidene-two (hydroxy phenyl) glycine.By dihydrochloride being dissolved in the excessive sodium hydroxide solution and regulating pH value to 4, finally can obtain free acid itself.

Another kind method is described in J.Agric.Food Chem.2002,50,6395-6399.Can obtain pure o with this method, o-EDDHA and pure o, p-EDDHA.The ratio that these pure isomer can be wished mixes, to obtain mixture of the present invention.

The another kind of o that obtains in single container reaction (single-vessel reaction), the method for o-EDDHA is described in US4130582.The method of this EDDHA of preparation is intended to by suppressing p, and the formation of p-EDDHA produces highly purified o, o-EDDHA, otherwise main that form is p, p-EDDHA.It is included under the existence of alkali, excessive phenol and quadrol, glyoxalic acid reaction.When the content of water in the reactor keeps low, gained o, the purity of o-EDDHA surpasses 95%, but when allowing higher water-content, its purity drop.

Be unexpectedly, have now found that, mixture of the present invention can be synthetic in single container reaction, be fit to expand in proportion the reactor size of simple industrial scale, this method comprises uses the doubly excessive phenol initiator of 2-to 5-, with when phenol and quadrol and oxoethanoic acid react in the presence of alkali, the content of water is in the 15-30% of reaction mixture weight scope in the conditioned reaction mixture.

Using under the situation of a spot of especially phenol, just can not react in the phenol of fusing, the perhaps operating device of control response device suitably may a certain amount of inert organic solvents of interpolation, makes temperature of reaction be adjusted to 40-80 ℃.

O in sequestrant of the present invention, o-EDDHA and o, the embodiment that the ratio of mixture of p-EDDHA can be wished according to the present invention is regulated by changing described reaction conditions.

Particularly, this method that is used to prepare EDDHA mixture of the present invention is included under about 45-80 ℃ temperature, with phenol and quadrol, oxoethanoic acid and alkali reaction.Phenol, quadrol, acetaldehyde bronsted lowry acids and bases bronsted lowry are preferably with 4-10: the mol ratio of 0.5-0.55: 0.95-1.10: 0.75-1.25 exists, preferred alkali is alkali metal hydroxide, particularly sodium hydroxide.

Another is applicable to that the method for preparing mixture of the present invention is by at high temperature changing change pH values with o, and o-EDDHA changes into o, p-EDDHA.The pH value of this kind conversion is pH1-14, or from greater than 7, particularly 8, and to 14, or 9-13, temperature is 50-120 ℃, or 70-100 ℃, or 80-90 ℃, the time is about 5-15 hour, or 6-12 hour, or 7-10 hour.

Under these conditions, in order to obtain mixture of the present invention, reaction must be carried out under selected condition, stops when obtaining the mixture that needs then.Usually, by quenching reaction mixture in water with stopped reaction.As selection, contain the o that is hopeful ratio, o-EDDHA and o, the solution of p-EDDHA can be used in the further reactions steps to produce metal complex, as producing iron chelate by adding iron(ic) chloride (III).This handles step and can carry out in accordance with known methods.

According to the definite reactions steps of selecting, how much reaction times the technician need to determine to obtain to wish the o of ratio, o-EDDHA and o, p-EDDHA on the basis of various routine tests.Reaction mixture can pass through Journal of Agriculture ﹠amp; Food Chemistry, (2001) 49(8) method 3527-32) is analyzed.

By with o, o-EDDHA places under these conditions, will change into o, p-EDDHA, thus can prepare the o with ratio of the present invention, o-EDDHA and o, the mixture of p-EDDHA easily.Two kinds of EDDHA mixture of isomers be can also use and o, the content of p-isomer improved by this method.The metal-salt of EDDHA such as molysite also are suitable as the educt of this method and can similarly use.

The method of US4130582 and reference wherein is that the technician knows and needs same initiator although for example be known in, and wherein is not taught in the disclosed technological process to the technician and can obtain o, p-EDDHA.

Within the scope of the present invention, need iron chelate to comprise with the agricultural crops of suffering from the plant verticillium in the agricultural practice, for example descend the plant of dependent of dead military hero: cereal (wheat, barley, rye, oat, rice, corn, jowar, millet and relevant kind) as the target plant of other nutrient for plants; Beet (sugar beet and fodder beet); The operatic circle, drupe and fruitlet (apple, pears, plum, peach, apricot, cherry, strawberry, raspberry and blackberry, blueberry); Leguminous plants (Kidney bean, French beans, pea, soybean); Oilseed plant (rape, leaf mustard, opium poppy, olive, Sunflower Receptacle, coconut, Viscotrol C plant, cocoa beans, peanut); Curcurbitaceae (cucurbit, cucumber, muskmelon); Textile plant (cotton, flax, hemp, jute); Citrus fruit (tangerine, lemon, natsudaidai, tangerine); Vegetables (spinach, lettuce, asparagus, Caulis et Folium Brassicae capitatae, Radix Dauci Sativae, onion, tomato, potato, pepper); Bay section (avocado, Chinese cassia tree, camphor); With plant such as tobacco, nut, coffee, sugarcane, tea, pepper, vine, hops, banana and natural rubber plant and ornamental plant.

Mixture of the present invention or the preferred application process that contains the pesticide composition of described mixture are aqeous suspension to be applied to soil (soil application as in the over top spraying or be administered in kind of the furrow) or as the soil pouring, and the frequency of dispenser and formulation rate can consider that character, weather, the crop of plantation, the level that influences of verticillium and the stage of maturity of processed plant of soil select.Mixture of the present invention also can be administered to blade (blade is used); the frequency of dispenser and consumption are also selected according to the crop etap under crop, verticillium level, the described situation, perhaps by with the liquid preparation dipping seed grain of activeconstituents or with solid preparation its dressing being applied to seed grain (dressing).

Favourable formulation rate is 1kg-50kg o normally, o-and o, the ferric chelate/ha of the isomer mixture of p-EDDHA, preferred 2.5kg-20kg effective constituent/ha, particularly 5kg-10kg effective constituent/ha.

When as seed dressing, favourable consumption is every kilogram of seed 0.001kg-1.0kg o, o-and o, the isomer mixture of p-EDDHA, particularly o, o-and o, the mixture of p-EDDHA ferric chelate.

The reference that this paper quotes is quoted for useful purpose reference.

The following example only is for foregoing invention is described, rather than limits its scope by any way.Institute is degree centigrade being unit to temperature.

Embodiment

Analytical procedure

By linear gradient ion pair high-performance liquid chromatogram determination iron chelate.When iron chelate (negatively charged ion) being added in the polar fluid (elutriant) that contains macrocation (ion pair reagent), formed ion pair.This ion pair is retained in the nonpolar solid phase (stationary phase).Strength retention depends on molecular size and acidity thereof.Then, every kind of iron chelate shows by the distinctive retention time of sequestrant decision and characteristic spectrum, with other separating substances that exist in itself and the sample.Be separated on the reverse phase silica gel post and carry out TBA ⁺The aqueous solution of (tetrabutylammonium) and acetonitrile are as elutriant.

Detection is based on photometry or the diode display detector of 480nm.For Fe ³⁺/ EDDHA can use gradient method or constant density method.Fe ³⁺/ EDDHA standardized solution (Fe) concentration=100mg/L.

Illustrate: with 0.1613g * 100/R N, N '-ethylidene-(2-hydroxy phenyl)-glycine base-(4-hydroxyl-phenyl) glycine (o, p-EDDHA) be dissolved in 150ml water and 2.7ml NaOH (in the concentration=0.1mol/l), wherein R is marked in the permanent pH system with Fe (III) and obtains by photometric titration, with per-cent is the sour form o of the standard of unit, the complexometric titration purity of p-EDDHA.After the dissolving, add 0.1271g ferric chloride hexahydrate (FeCl fully ₃6H ₂O), stir about 5 minutes.With sodium hydroxide solution (4.3) solution is adjusted to pH7.0.With solution standing over night in dark, make excessive iron as oxide precipitation, quantitatively filter by cellulose filter, water is supplied volume (250ml).

The mensuration elutriant

Two kinds of solution are used to prepare linear gradient elution liquid:

Solution A: in 3.33ml TBAOH (aqueous solution of 40wt% tetrabutylammonium), add 500ml water.Regulate pH to 6.0 with HCl.Add 350ml acetonitrile (HPLC level), water is supplied volume in the flask of 1L capacity, and filters by 0.2 μ m membrane filter.

Solution B: in 3.33ml TBAOH (aqueous solution of 40wt% tetrabutylammonium), add 150ml water.Regulate pH to 6.0 with HCl, add 750ml acetonitrile (HPLC level), water is supplied volume with solution in the flask of 1L capacity, and filters by 0.2 μ m membrane filter.Also can use TBACl or TBABr, as long as regulate pH to 6.0 with NaOH.For Fe ³⁺/ o, p-EDDHA measures, and also can adopt and only use permanent concentration (isocratic) method of solution A as elutriant.

Chromatographic instrument has been equipped with the gradient pump of carrying elutriant with the 1.5ml/min flow velocity.Table 1 has provided gradient table.

Table 1 gradient table

Time (min)	Flow velocity (ml/min)	％A	％B	Curve type
					0	1.5	100	0	Linear
5	1.5	100	0	Linear
					6	1.5	0	100	Linear
11	1.5	0	100	Linear
					12	1.5	100	0	Linear
20	1.5	100	0	Linear

For Fe ³⁺/ o, p-EDDHA measures, the permanent concentration wash-out that also can use 100%A to carry out 7 minutes.Chromatographic instrument has been equipped with the introduction valve with 20 μ l injection rings (loop).Used post is the C-18 post; 3.9 * 150mm ID; Dp=5 μ m (for example: C18 is from WATERS) and have the UV/VIS-detector of 480nm filter or diode array and integrator.

Sample is according to Directive 77/535/EEC, OJ № L213, method 1 preparation of 22.8.1977.

The preparation of sample solution

The 125mg that weighs, error (within) 0.1mg adds in the 100ml beaker and (for having the sample that surpasses 4% chelated iron, uses 80mg, for having the sample that is lower than 2% chelated iron, use 250mg).Adding 80ml water also stirred 30 minutes.After waiting to stir evenly, water with solution dilution to scale.

The preparation of calibration solution

Move in the flask of 4 100ml capacity with the inner complex standardized solution of transfer pipet, and water is supplied volume, homogenizing V1ml amount (seeing Table 2).

The preparation of table 2 working curve

Stratographic analysis

Before sample introduction, immediately all solution are filtered by 0.45 μ m membrane filter.Standardized solution (table 2) is injected chromatographic system.Determine the retention time of all solution and measure inner complex (Fe ³⁺/ o, p-EDDHA) area of chromatographic peak.

Draw calibration graph with the corresponding relatively sequestrant concentration (mg Fe/L or mmol/l) of the peak area value of standardized solution.

Injecting sample solution is identified sequestrant by the retention time at gained peak, if use diode-array detector, confirms with the UV-visible spectrum.Measure the peak area of sequestrant.Use working curve to determine the ionic concentration (mg Fe/L) of chelating or the concentration (mmol/L) of sequestrant.

Under the situation of iron chelate, in the fertilizer as Fe ³⁺/ o, the weight percent (Fe (%)) of the iron that p-EDDHA exists equals:

Fe (%)=C/m*0.01-is wherein:

C be with working curve determine by o, the concentration of the iron of p-EDDHA chelating (mg/L), m is to be the quality of the analysis of unit with sampling with the gram.

Preparation embodiment:

N, the preparation of N '-ethylidene-two [(hydroxy phenyl) acetonitrile]

Mixture in the 600ml dry toluene is cooled to 0 ℃ with 109.8g o-hydroxy benzaldehyde and 134.2g p-hydroxy benzaldehyde, adds the solution of 80g quadrol in the 300ml dry toluene, so that temperature is no more than 70 ℃.After adding amine and finishing, come out until no longer including water sepn with the Dean-Stark separator that connects reflux exchanger this mixture that refluxes.Underpressure distillation removes desolvates and excessive amine.Productive rate: 90%.

Under 0 ℃, in 268.1 weight part reaction product, add 700 parts by volume liquid hydrogen cyanic acid, 180 weight parts waters and 1.5 parts by volume hydrochloric acid.Reaction mixture was stirred above three hours.In the reaction times, form reaction product, it is leached.Fusing point: 113-115 ℃.

N, the preparation of N '-ethylidene-two (hydroxy phenyl) glycine

With 100 weight part N, N '-ethylidene-two [(hydroxy phenyl) acetonitrile] in 1000 parts by volume concentrated hydrochloric acids, be heated to 80-100 ℃ 3 hours.Educt slowly dissolves, and approximately after 1/2-1 hour, another kind of compound begins precipitation.With the reaction mixture cooling, throw out leaches, and uses washed with isopropyl alcohol.Water absorbs 100 weight part throw outs, and be heated to 100 ℃ 4 hours.Half water is steamed, add sodium hydroxide solution and reach 3.5 until the pH value.Form precipitation, it leached, be dissolved in the concentrated hydrochloric acid again, and be heated to 100 ℃ 1 hour.Resolution of precipitate in aqueous sodium hydroxide solution, and is adjusted to 4.0 with the pH value.Reaction product precipitation is filtered and with 0 ℃ washed with isopropyl alcohol, drying.Fusing point: 218-220 ℃, productive rate: 31%.

N, the o of N '-ethylidene-two (hydroxy phenyl) glycine, o-and o, the preparation of p-mixture

With described in the US-A-4130582 and above-mentioned method, preparation o, o-EDDHA.With identical method, o-hydroxy benzaldehyde and reacting ethylenediamine by equimolar amount prepare o, p-EDDHA.After reaction is finished, add the p-hydroxy benzaldehyde of equimolar amount,, produce o, p-EDDHA as further reaction as described in the US-A-4130582.With 10g o, o-EDDHA and 10g o, p-EDDHA places mortar, fully grinds.

In single container reaction, prepare N, the o of N '-ethylidene-two (hydroxy phenyl) glycine, o-and o, p-mixture

In the reaction vessel that has been equipped with condenser, dropping funnel and mechanical stirring device, add the phenol of 17 moles of fusings, maintain the temperature at 40-45 ℃.Add 1 moles of ethylene diamine and 50% aqueous sodium hydroxide solution that contains 1.6 molar sodium hydroxides and 10 mole of water (10mol) then.After once more reaction mixture being cooled to 40-45 ℃, add the 50% aqueous acetaldehyde acid contain 2 mole of acetaldehyde acid, with reaction mixture be heated to 70 ℃ 3 hours.Then reaction mixture is poured in the excessive water, with the excessive phenol of dichloromethane extraction.Water detects by 1H-NMR, finds to contain about 1: 1 o, o-EDDHA and o, p-EDDHA.

The preparation of ferric chelate

To N, add sodium hydroxide solution in N '-ethylidene-two (hydroxy phenyl) glycine until obtaining clear solution.Consumption with excessive 27% slowly adds 40% technical grade iron(ic) chloride (III) solution, keeps the pH value at 7-8 by adding sodium hydroxide solution in addition simultaneously.Evaporating solns, the EDDHA Na Fe type ferric chelate of generation iron level 5.3%.

1.o o-EDDHA changes into o, p-EDDHA

Will be according to the 2g o of US4130582 preparation, o-EDDHA is dissolved in the water, and produces the 10ml20% aqueous solution.With o, o-EDDHA solution is adjusted to pH13 with 50% aqueous sodium hydroxide solution.Reaction mixture is heated to 80-90 ℃, and under this temperature, stirred 7 hours.With sample quenching in heavy water of reaction mixture, with 98% sulfuric acid with pH regulator to 0-1.According to Journal ofAgriculture ﹠amp; Food Chemistry, (2001) 49(8) 3527-32 is by proton-NMR analyzing samples.Find that mixture contains 1: 1 o, o-EDDHA and o, p-EDDHA.

Biological Examples

In biological test, use soybean (Cultivar Oshumi) plant.Plant is obtained under the standard seed growth procedure, the soybean seeds that germinates in the aseptic tray of sealing.Seed is placed on the cellulose paper that has soaked into 50ml distilled water in the tray, covers on it with other a piece of paper.The CaSO that adds 30ml distilled water and 20ml 1mM ₄Tray is placed in the constant temperature oven, unglazed, placed 3 days at 28 ℃.Afterwards, seedling like the developmental phase is placed on the porose flat board on the container that floats on the nutrient solution that is full of dilution and EDTA 7 days.Nutrient solution (iron-free) is the mixture of following ingredients: macronutrient: 1mM Ca (NO ₃) ₂4H ₂O, 0.9mM KNO ₃, 0.3mMMgSO ₄, 0.1mM KH ₂PO ₄Positively charged ion trace nutrient substance: 2.5 μ M MnSO ₄, 1 μ M CuSO ₄, 10 μ M ZnSO ₄, 1 μ M NiCl ₂, 1 μ M CoSO ₄, 115.5 μ M EDTANa ₂(surpassing the active 100 μ M of buffering micro-nutrients), 231 μ M KOH; Negatively charged ion micro-nutrients: 35 μ M NaCl, 10 μ M H ₃BO ₃, 0.05 μ M Na ₂MoO ₄Every jar with 0.1mM HEPES (N-2-hydroxyethyl piperazine-N '-2 ethane sulfonic aicd), 0.05mM KOH and 2g CaCO ₃PH is buffered to 7.5.Afterwards, plant is carried out stress step, is about to it and is placed in 5 buckets, and every bucket contains the nutrient solution that 10L does not have iron chelate.The eclipsed expression of blade iron verticillium.After 6 days, the stem of two strain plants is wound into together with foam materials, is positioned in the 2L polythene container (3 holes of each lid, every jar 2 strain plant).Jar is covered with lucifuge fully with black plastic.Container contains the nutrient solution that 2L continues the iron content processing of inflation.Nutrient solution is by foregoing macronutrient and negatively charged ion micro-nutrients and positively charged ion trace nutrient substance: MnSO ₄(1 μ M), CuSO ₄(0.5 μ M), ZnSO ₄(0.5 μ M), NiCl ₂(0.1 μ M) and CoSO ₄(0.1 μ M) forms.Add water every three days, weekly new soln more.After 14 days plant is taken a sample.Separate root and blade, use among the 0.1M HCl earlier 80 (polyoxyethylene sorbitanic monoleates) were washed 30 seconds, with a large amount of distillation washings, weighed afterwards and drying then.Determine the micro-nutrients in blade and the root behind dried digestion step and the atomic absorption method.In test, use Minolta SPAD 502 chlorophyl-meters to read the SPAD reading to all blades regularly.

Use 7 kinds of different processing:

Comparing embodiment 1: do not add iron.

Comparing embodiment 2:Fe-o, o-EDDHA 5 μ M.

Comparing embodiment 3:Fe-o, o-EDDHA 5 μ M+Fe-o, p-EDDHA 1 μ M.

Comparing embodiment 4:Fe-o, o-EDDHA 5 μ M+Fe-o, p-EDDHA 2.5 μ M.

Comparing embodiment 5:Fe-o, o-EDDHA 10 μ M.

Embodiment 1:Fe-o, p-EDDHA 5 μ M.

Embodiment 2:Fe-o, o-EDDHA 5 μ M+Fe-o, p-EDDHA 5 μ M.

Handling four times for every kind repeats.

Table 3. the weight of fresh plant, fresh and dry blade and fresh and dry root.(numeral is 4 multiple mean values)

Handle	Plant fresh weight (g)	Root fresh weight (g)	Leaf fresh weight (g)	Leaf dry weight (g)	Root dry weight (g)
						Comparing embodiment 1	?5.133	2.859	?1.116	?0.339	?0.264
Comparing embodiment 2	?6.781	3.818	?1.257	?0.321	?0.282
						Comparing embodiment 3	?12.383	5.245	?3.877	?0.602	?0.364
Comparing embodiment 4	?20.344	9.660	?5.979	?0.895	?0.556
						Comparing embodiment 5	?15.862	7.316	?4.736	?0.781	?0.425
Embodiment 1	?21.186	8.933	?6.282	?1.136	?0.595
						Embodiment 2	?22.001	10.089	?6.499	?1.092	?0.643

Iron level in the table 4. plant each several part.(numeral is four multiple mean values)

?	The dried root of μ g Fe/g	μ g Fe/g cured leaf	The g μ Fe/ number of blade
				Comparing embodiment 1	26.51	31.35	10.92
Comparing embodiment 2	90.32	62.30	19.82
				Comparing embodiment 3	102.36	68.39	52.21
Comparing embodiment 4	98.46	74.12	64.06
				Comparing embodiment 5	77.22	74.87	55.15
Embodiment 1	128.48	80.98	91.91
				Embodiment 2	101.95	73.59	78.60

Table 5. the Spad index that obtains by plant in the process of the test (value of second leaf).Four multiple mean values.

Time/sky	C1	C2	C3	C4	C5	E1	E2
								0	20.8	12.7	16.8	18.1	16.6	14.7	17.2
2	19.2	10.1	15.5	17.6	15.7	14.0	16.9
								4	17.2	9.1	16.2	19.8	15.0	18.0	23.8
7	14.4	9.5	18.0	22.0	18.2	21.4	27.7
								9	13.6	9.2	18.1	24.1	19.7	23.9	30.6
11	12.8	8.2	18.2	22.7	19.0	24.9	30.5

Biological Examples shows, use o, and the ferric chelate of p-EDDHA is handled the remarkable increase that plant causes plant weight, sees Table embodiment 1 in 3 and the contrast of comparing embodiment 1-3.Contain 1: 1 o, p-EDDHA and o, the mixture of the ferric chelate of o-EDDHA show that also plant weight increases, and see Table the contrast of embodiment 2 and comparing embodiment 4 and 5 in 3.Under the test conditions in the plant each several part increase of iron level can see Table 4, the value of the value of comparing embodiment 1 and comparing embodiment 1-3 and embodiment 2 and comparing embodiment 4 and 5.

Also have the SPAD value of measuring as chlorophyll content in leaf blades in embodiment 1 than in comparing embodiment 1-3, or in embodiment 2, significantly raise than distinguishing more sharp in comparing embodiment 4 and 5.SPAD value after 11 days among the embodiment also is higher than comparing embodiment.These results are presented at o, and under the existence of the ferric chelate of p-EDDHA, plant is faster to the response of iron.

Claims (10)

1. mixture, the N that comprises isomery, N '-ethylidene-two (hydroxy phenyl) glycine, N wherein, N '-ethylidene-(2-hydroxy phenyl)-glycine base-(4-hydroxy phenyl) glycine " o; p-EDDHA " and N, the mol ratio of N '-ethylidene-two (2-hydroxy phenyl) glycine " o, o-EDDHA " was greater than 0.8: 1.

2. the N that contains isomery, the ferric chelate of the mixture of N '-ethylidene-two (hydroxy phenyl) glycine, N wherein, N '-ethylidene-(2-hydroxy phenyl)-glycine base-(4-hydroxy phenyl) glycine " o; p-EDDHA " and N, the mol ratio of N '-ethylidene-two (2-hydroxy phenyl) glycine " o, o-EDDHA " was greater than 0.8: 1.

3. according to the mixture of claim 1, the o of isomery wherein, p-and o, the ratio of o-EDDHA are 0.9: 1 to 100: 1.

4. the described preparation process of mixture of claim 1 comprises by change the pH value from pH 1 to pH14 under 50-120 ℃ temperature, and make o, o-EDDHA changes into o, p-EDDHA, and the time is 5-15 hour.

5. a pesticide composition contains ferric chelate according to claim 2.

6. composition according to claim 5 also contains other other nutrient for plants or vegetable fertilizer, weedicide, sterilant, mycocide, bactericide, nematocides, invertebrate poison or its mixture.

7. composition according to claim 6 contains urea, potassium oxide, inorganic nitrate, sulfonylurea or its mixture as other activeconstituents.

8. according to each described composition among the claim 5-7, contain 1-99wt%N, the ferric chelate of N '-ethylidene-two (hydroxy phenyl) glycine, o wherein, p-EDDHA and o, the ratio of o-EDDHA was greater than 0.8: 1; 1-20wt% urea and 0-50wt% potassium oxide.

9. ferric chelate according to claim 2 or according to the purposes of each described composition of claim 5-8 as nutrient for plants or fertilizer, or be used for the treatment of the purposes of plant verticillium.

10. the method for the plant verticillium of treatment in the cultivated plant comprises to plant or its planting area is used the described ferric chelate of claim 2 of significant quantity or according to each described composition of claim 5-8.