Classifications

• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
  • C05D9/00—Other inorganic fertilisers
  • C05D9/02—Other inorganic fertilisers containing trace elements
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
  • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C229/34—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
  • C07C229/36—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings with at least one amino group and one carboxyl group bound to the same carbon atom of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
  • C07C229/76—Metal complexes of amino carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
  • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
  • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
  • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom

Definitions

• This invention relates to new non-symmetrical ethylene diamino hidroxyphenyl acetic acid derivatives. These products are useful for the treatment of iron chlorosis.
• Iron chlorosis is a nutritional plant disorder which results in a decrease in the amount of chlorophyll and in the yellowing or whitening of normally green plant tissue. It is a widespread problem in agriculture that affects the development of many crops provoking a decrease yield.
• ferric salts act to a certain extent by foliar penetration, but are substantially ineffectual when used for soil treatment. It is through the roots that the penetration of iron is at its most effective in controlling chlorosis.
• simple iron salts have been replaced by iron chelates which are hydrosoluble complexes consisting of an iron atom attached to several points of a single organic molecule known as chelates or co-ordinates.
• hexadentates such as complexes of iron with ethylene diamine tetracetic acid (EDTA) or with diethylene thamine pentacetic acid (DTPA) or with N,N'-ethylene-bis-(hydroxyphenyl)glycines (EDDHA), have been successfully used against chlorosis.
• EDTA ethylene diamine tetracetic acid
• DTPA diethylene thamine pentacetic acid
• ETDHA N,N'-ethylene-bis-(hydroxyphenyl)glycines
• N,N'-ethylene-bis(2-hydroxyphenyl)glycine (o,o-EDDHA) is often described as one of the most favorable compounds for complexing metals, and being most suitable for the use as a plant nutrient or fertilizer because the complexation affinity to iron is particularly strong.
• the ferric chelate of o,o-EDDHA shows a coordination number of 6 and is widely used for agrochemical purposes as a plant nutrient or plant fertilizer, and for the treatment of chlorosis in crop plants.
• the N,N'-ethylene-(2-hydroxyphenyl)-glycinyl-(4-hydroxyphenyl)glycine (o,p- EDDHA) is also known in the art. Contrary to o,o-EDDHA, in the o,p-EDDHA isomer one of the hydroxy groups is in the para- position of the benzene ring. For this reason, the ferric chelate of o,p-EDDHA shows a coordination number of 5 and its complexation affinity to iron is weaker than that of o,o- EDDHA. This compound has often being regarded as an undesired by- product being incurred by the manufacturing process of o,o-EDDHA.
• WO2005/095305 discloses isomeric mixtures comprising both (o,o-EDDHA) and (o,p-EDDHA) , wherein the molar ratio of (o,p-EDDHA) to (o,o-EDDHA) is higher than 0.8 : 1 , as nutrients for agricultural crop plants and agents for treatment of chlorosis in such plants.
• iron deficiency related plant diseases e.g. iron chlorosis
• EDDHA iron deficiency related plant diseases
• WO2005/095305 proposes to solve this problem by employing isomeric mixtures of o,o-EDDHA and o,p-EDDHA, as said above.
• o,p- EDDHAZFe 3+ shows lower stability than o, o-EDDHA/Fe 3+ .
• the problem to be solved by the present invention is to provide alternative products that may be useful for the treatment of iron deficiency related plant diseases. These products may have improved properties regarding the currently known treatments.
• the solution is based on the fact that the present inventors have identified that by eliminating one of the carboxylic groups of EDDHA and maintaining or modulating the hydroxyphenyl groups, the chelating affinity for polyvalent metals, particularly for iron, is retained, while some other properties may be improved, particularly those that make them useful for the treatment of iron chlorosis. See working examples 1 -7 herein for a further description.
• a first aspect of the invention relates to a compound of formula (I):
• X 1 is a C 6 or a Ci 0 aromatic system having a hydroxy group in the alpha position, being optionally substituted by up to four substituents independently selected from the group consisting of: phospho, sulfo, halo, carboxy, acetoxy, CrC 4 alkoxy or linear or branched d-C 4 alkyl.
• X 2 is a C 6 or a Ci 0 aromat ic system having a hydroxy group in the alpha position, or a five or six membered heterocycle having in the alpha position a heteroatom selected from the group consisting of N, O and S, optionally comprising other N, O or S atoms in their structure, and having from 0-3 double bonds, said aromatic, or heterocyclic system being optionally substituted by up to four substituents independently selected from the group consisting of: phospho, sulfo, halo, carboxy, acetoxy, d-C 4 alkoxy, linear or branched CrC 4 alkyl.
• Y is (CH 2 ) n or is a xylylene group of formula: n is an integer selected from 2, 3 and 4, R 1 , R 2 are independently selected from the group consisting of H, linear or branched CrC 4 alkyl, C 6 or Ci 0 aryl.
• the invention in a second aspect relates to a process for preparing a compound of formula (I) as defined in the first aspect of the invention and in its corresponding embodiments, which process comprises the step of reducing a compound of formula (II):
• X 1 , X 2 and Y are as defined above, in an appropriate solvent system, in the presence of a reducing agent.
• the invention relates to the use of a compound of formula (I), as defined in the first aspect of the invention and its corresponding embodiments, as a complex forming agent for polyvalent metals.
• the invention in a fourth aspect relates to a chelate of a compound of the formula (I), as defined in the first aspect of the invention and its corresponding embodiments, with one or more polyvalent metals.
• the invention in a fifth aspect relates to an agrochemical composition comprising a compound of formula (I), as defined in the first aspect of the invention and its corresponding embodiments, or a polivalent metal chelate thereof.
• the invention in a sixth aspect relates to the use of a compound, as defined in the first aspect of the invention and its corresponding embodiments, or a polyvalent metal chelate thereof, for the preparation of a composition for treating an iron deficiency related plant disease.
• the invention relates to the use of the intermediate of formula (II) as defined in the seventh aspect of the invention and its corresponding embodiments, for the preparation of a compound of formula (I), as defined in the first aspect of the invention and its corresponding embodiments.
• Figure 1 shows the SPAD index of the fourth level, represented versus the days of treatment, for plants grown on soil treated with each of the tested compounds and the control.
• Figure 2 shows the dry weight of shoots (expressed in grams) in the soil experiment, with the tested compounds and the control, at three sampling times.
• Figure 3 shows the iron concentration in leaves of the plants treated with the tested compounds and the control, at three sampling times.
• linear or branched d-C 4 alkyl is taken to mean herein a linear or branched alkyl group which contains up to 4 atoms of carbon. Thus it includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- butyl and tert-butyl.
• CrC 4 alkoxy it is meant herein the alkyl groups mentioned above bound through oxygen, examples of which include methoxy, ethoxy, isopropoxy, tert- butoxy, and the like.
• halo in this invention, refers to F, Cl, Br, I, preferably Cl.
• a C 6 or a Ci 0 aromatic system or a C 6 or a Ci 0 aryl group include phenyl and naphtyl.
• X 2 in the compounds of formula (I) is a C 6 or a Ci 0 aromatic system having a hydroxy group in the alpha position, or a five or six membered heterocycle having in the alpha position a heteroatom selected from the group consisting of N, O and S, optionally comprising other N, O or S atoms in their structure, and having from 0-3 double bonds, said aromatic, or heterocyclic system being optionally substituted by up to four substituents independently selected from the group consisting of: phospho, sulfo, halo, carboxy, acetoxy, d-C 4 alkoxy, linear or branched d-C 4 alkyl.
• Heterocycle as meant herein includes both non-aromatic heterocycles (e.g. 2-azetidinyl, 2- pyrrolidyl, 2-piperidinyl), and heteroaromatic rings.
• Preferably said heterocycle is heteroaromatic.
• Preferred compounds of formula (I) are those wherein X 2 is selected from the group consisting of 2-hydroxyphenyl, 2-hydroxy-naphthyl, 2-furyl, 2-thienyl, 2- pyrrolyl, 2-pyridyl, 4-pyridimidinyl, 2-pyrazinyl optionally substituted by 2 or 1 substituents independently selected from the group consisting of: phospho, sulfo, halogen, CrC 4 alkoxy, carboxy, acetoxy, linear or branched CrC 4 alkyl.
• Preferred optional substituents include methyl, phenyl, phospho, sulfo, carboxy, acetyl.
• More preferred compounds of formula (I) are those wherein X 1 is 2- hydroxyphenyl or 2-hydroxynaphthyl, optionally substituted by 2 or 1 substituents independently selected from the group consisting of methyl or methoxy. Yet more preferred are those wherein X 1 is 2-hydroxyphenyl.
• Y is (CH 2 ) n , and more preferably n is 2.
• R 1 and R 2 are H.
• compounds of formula (I) are those wherein Y is (CH 2 ) n , and more preferably n is 2, X 1 is 2-hydroxyphenyl, X 2 is selected from the group consisting of 2-hydroxyphenyl, 2-hydroxynaphthyl, 2-furyl, 2-thienyl, 2-pyrrolyl, 2-pyridyl, 4-pyridmidinyl, 2-pyrazinyl, optionally substituted by 2 or 1 substituents independently selected from the group consisting of: d-C 4 5 alkyl, Ci-C 4 alkoxy, carboxy, sulfo, acetoxy .
• the most particularly preferred compounds are selected from the group consisting of:
• Preferred methods include, but are not limited to, those described below.
• the reactions are carried out in the solvents appropriate for the reagents and materials used and suited for the transformations carried out.
• An expert in organic synthesis will understand that the functional groups present in the
• the compounds of formula (I) as defined above can be prepared by a process which comprises the step of reducing a compound of formula (II):
• the reaction may be carried out in different solvent systems. Suitable solvent systems include d-C 4 alcohols such as methanol and ethanol, acetic acid, water and mixtures thereof. Preferably the reaction is carried out in methanol.
• Suitable reducing agents are hydrides and hydrogen with a metal catalyst.
• the reducing agent is selected from the group consisting of borohydrides, such as sodium cyanoborohydhde, sodium triacetoxyborohydhde, sodium borohydride. Better results are obtained when the reducing agent used is sodium borohydride or Pd hydrogenation.
• the reaction is preferably carried out at temperature ranging from 15 0 C to 4O 0 C. Better results are obtained when carried out from 18 0 C to 25 0 C.
• the process for preparing a compound of formula (I) according to the second aspect of the invention further previously comprises the step of preparing said compound of formula (II) by reacting a compound of formula (III) with a compound of formula (IV):
• the reaction between a compound of formula (III) with a compound of formula (IV) may be carried out in different solvent systems.
• Suitable solvent systems include CrC 4 alcohols such as methanol and ethanol;water; nitriles such as acetonitrile; ketones such as 2-butanone; and mixtures thereof.
• the reaction is carried out in methanol, ethanol, water or mixtures thereof.
• reaction between a compound of formula (III) with a compound of formula (IV), and the subsequent reduction of the compound of formula (II) obtained to prepare a compound of formula (I) is carried out as a one pot reaction.
• a compound of formula (I) as defined above may be used as a complex forming agent for polyvalent metals.
• said polyvalent metal is at least one polyvalent metal selected from the group consisting of iron, nickel, zinc, manganese, yterbium, gadolinium, cobalt and copper. More preferably, said metal is iron.
• a compound of the formula (I) as defined above may form chelates with one or more polyvalent metals.
• said polyvalent metal is at least one polyvalent metal selected from the group consisting of iron, nickel, zinc, manganese, yterbium, gadolinium, cobalt, copper, palladium, platinum and, gold. More preferably, said metal is iron.
• Such iron chelates may further contain e.g. an alkali-or alkaline earth metal, like sodium, potassium, calcium or magnesium, particularly sodium.
• Chelates according to the invention may be used as active component in agriculturally acceptable compositions, as sole active component or in combination with other agriculturally active components, such as plant nutrients or plant fertilizers.
• agrochemical compositions according to the invention comprise a compound of formula (I) as defined above, or a metal chelate thereof.
• Said compositions may further comprise agriculturally acceptable carriers.
• the composition is preferably applied in the form of a solution or suspension by injecting into the soil.
• the other agriculturally acceptable active ingredients may be additional fertilizers, micronutrient donors or other preparations that influence plant growth and development or plant protection products like selective herbicides or insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures of several of such preparations, if desired.
• Agriculturally acceptable active ingredients also include other chelating agents.
• Said chelating agents include ethylene diamine tetracetic acid (EDTA), diethylene triamine pentacetic acid (DTPA), o,o-EDDHA and o,p- EDDHA.
• EDTA ethylene diamine tetracetic acid
• DTPA diethylene triamine pentacetic acid
• o,o-EDDHA o,p- EDDHA
• the agrochemical compositions of the invention also comprise o,o-EDDHA.
• Agriculturally acceptable carriers may be natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners or binders. Such carriers and additives are described, for example, in WO 95/30651.
• the compounds of formula (I) according to the invention are useful for treating an iron deficiency related plant disease.
• said disease is iron chlorosis.
• Preferred intermediates of formula (II) are those wherein X 1 is 2- hydroxyphenyl.
• Step 2 2-(2-((2-hydroxybenzyl)amino)ethylamino)-2-(2-hydroxyphenyl)acetic acid
• 1 H-NMR (500 MHz, D 2 O, 4.8(HDO), ppm): ⁇ 7.20-7 (m, 4H, Ar), 6.79-6.66 (m, 4H, Ar), 4.36 (s, CH), 3.87 (s, 2H, CH 2 ), 2.84-2.69 (m, 4H, CH 2 ).
• Example 2 2-(2-((2-hydroxy-1-naphtyl)methylamino)ethylamino)-2-(2- hydroxyphenyl)acetic acid.
• Example 1 The procedure of Example 1 is followed, but starting from equimolar amounts of 2-(2-aminoethylamino)-2-(2-hydroxyphenyl)acetic acid hydrochloride and 2-pyridinecarboxaldehyde at pH 7. After 20 h at room temperature the solvent was removed and the title Schiff base was obtained as yellow solid in 90% yield.
• Step 2 2-(2-((pyridin-2-yl)methylamino)ethylamino)-2-(2-hydroxyphenyl)acetic acid A mixture of equimolar amounts of the Schiff base obtained in Step 1 and
• the general procedure used for preparing the ferric chelates of the invention is the following:
• Example 12 Determination of Titrimetric purity of the chelating agent
• Chelating agent solution was prepared by dissolving an amount of chelating agent in the necessary amount of NaOH solution. Then pH is adjusted to 6 by the addition of MES biological buffer [2-(N-morpholino) ethanesulfonic acid] and maintaining at this pH with NaOH solution during the titration. Ionic strength is fixed at 0.1 M with NaCI and upper atmosphere was N 2 free of CO 2
• test solution was placed in a thermostated jacketed reaction vessel (i.e.100 ml or 150 ml capacity) with an airtight cap fitted with gas inlet and outlet tubes, the combined pH glass electrode, the photometric detector and two piston burettes, tip extending below the surface of the solution, and a magnetic stirrer.
• the photometric titration consisted of the addition of a Fe(III) standard solution, previously standardized by Atomic Absorption Spectroscopy, to the chelating agent until the absorbance at 480 nm presents no changes. End-point titration could be calculated for two linear segments' intersection and also using smoothed second derivative method.
• the chelating agent purities could also be determined by potentiometric titrations with a Cu 2+ ion selective electrode in the same conditions as before.
• the chelating agent solution is titrated with Cu(II) solution using selective Cu(II) electrode and reference electrode, Cu 2+ free cation is measured with the selective electrode.
• the end-point of the potentiometric titrations could be determined by Gran equation method or using the first derivative method.
• Example 13 Determination of agrochemical activity
• Soybean seeds (Glycine max L. cv. Stine 0480) were germinated at 30 0 C and 60% RH on paper moistened with 1 M CaSO 4 in dark for 2 days.
• seedlings were placed in 10 L containers (50 seedlings per container) filled with a 1/5 diluted EDTA buffered nutrient solution
• Chelates used in the treatments were 0,0- EDDHA/Fe 3+ , o,p-EDDHA/Fe 3+ , EDTA/Fe 3+ and Example 1/Fe 3+ .
• the last one is the Fe chelate of the compound of the example 1 : 2-(2-((2- hydroxybenzyl)amino)ethylamino)-2-(2-hydroxyphenyl)acetic acid (DCHA).
• Nutrient solution contained macronutrients and anionic micronutrients as for the seedling period and the following cationic micronutrients composition: ( ⁇ M) 1.0 MnSO 4 , 0.5 CuSO 4 , 0.5 ZnSO 4 , 0.1 NiCI 2 and 0.1 CoSO 4 .
• 1g l_ " 1 of CaCO 3 was added to the nutrient solution to buffer pH at 7.5 and to simulate conditions of a calcareous soil. Plants were grown for 21 days in this nutrient solution in a growth chamber provided with fluorescent and sodium vapour lamps with a 16 h/30 0 C and 50% humidity day and 8 h/25 0 C and 70% humidity night regime. Water was added every 2 days and the nutrient solution was renewed every 7 days. Treatments were replicated four times in a completely randomised design. Plants were harvested after 7, 14 and 21 days.
• Example 1 presents a fast action to correct iron chlorosis, similar to o,p-EDDHA, but higher than o,o-EDDHA.
• Root and shoot were separated and washed using Tween 80 (Merck) and HCI solution and fresh and dry (after oven dry procedure) weights were determined. Samples were ground and after dry digestion in a muffle furnace (480 0 C), ashes are dissolved in HCI. Fe, Mn, Cu and Zn were analysed by atomic absorption spectrometry.
• Example 1/Fe 3+ is able to provide significantly higher amounts of iron and faster in this experimental conditions than the other treatments, even more than o,p-EDDHA in the third sampling time.
• Table 3 the Fe content in the plants in each sampling time for the treatments with the lower Fe application is presented.
• Soybean seeds (Glycine max L. cv. Stine 0480) were germinated at 30 0 C and 60% RH on paper moistened with 1 M CaSO 4 in dark for 2 days. Afterwards, seedlings were placed in 10 L containers (50 seedlings per container) filled with a 1/5 diluted EDTA buffered nutrient solution (macronuthents (mM)- 1.0 Ca(NO 3 ) 2 , 0.9 KNO 3 , 0.3 MgSO 4 , 0.1 KH 2 PO 4 ; cationic micronuthents ( ⁇ M)- 5.0 EDTA/Fe 3+ , 2.5 MnSO 4 , 1.0 CuSO 4 , 10 ZnSO 4 , 1.0 CoSO 4 , 1.0 NiCI 2 , 115.5 Na 2 EDTA; anionic micronutrients ( ⁇ M)- 35 NaCI, 10 H 3 BO 3 , 0.05 Na 2 MoO 4 ; 0.1 mM HEPES) for 4 days.
• the last one is the Fe chelate of the compound of the example 1 : 2-(2-((2-hydroxybenzyl)amino)ethylamino)-2-(2- hydroxyphenyl)acetic acid.
• Plants were grown for 21 days in this soil conditions in a growth chamber provided with fluorescent and sodium vapour lamps with a 16 h/30 0 C and 50% humidity day and 8 h/25 0 C and 70% humidity night regime. Treatments were replicated five times in a completely randomised design. Single plants were harvested after 2, 7 and 21 days.
• Example 1 is efficient to solve iron chlorosis in highly calcareous conditions. Its efficacy is related with its fast action mechanism.

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