Synthesis of o,p-EDDHA and Its Detection as the Main Impurity in o,o-EDDHA Commercial Iron Chelates

Gallego, Manuel Requena; Sierra, Miguel Á.; Alcázar, Roberto; Ramírez, Pedro José Rueda; Piñar, Carmen; Mancheño, María J.; García‐Marco, Sonia; Yunta, Felipe; Lucena, Juan J.

doi:10.1021/jf025727g

Cited by 30 publications

(40 citation statements)

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“…In the present work this process was studied and it could be observed that o,p-EDDHA was the fastest chelating agent solubilising Fe from several Fecontaining minerals and selected soils. This fact can be due to the coordination of the Fe 3+ inside the chelate; this chelating agent has five donor groups able to bind Fe instead of six and thus it could yield a faster solubilisation of Fe (Go´mez-Gallego et al, 2002). Nevertheless, the maximum amount of Fe that can be solubilised was high for o,o-EDDHA and low for EDTA.…”

Section: Fe Solubilisation From Soils and Fe Oxidesmentioning

confidence: 99%

“…However, due to its lower stability constant, o,p-EDDHA/ Fe 3+ is expected to disappear sooner than o,o-EDDHA/Fe 3+ from alkaline soil solutions. This behaviour may be related to the presence of only five bonds between the Fe and the ligand (Go´mez-Gallego et al, 2002). Thus, while o,p-EDDHA/Fe 3+ can be a good chelate to correct Fe chlorosis, it is likely to be active for only a short time due to its low stability in soils .…”

Section: Fe Solubilisation From Soils and Fe Oxidesmentioning

confidence: 99%

“…Nowadays, the industrial synthesis of commercial products (Petree et al, 1978) produces a mixture of three regioisomeric compounds, o,o-EDDHA, o,p-EDDHA and p,p-EDDHA ( Figure 1) in variable amounts (Cremonini et al, 2001;Herna´ndez-Apaolaza et al, 1997;Go´mez-Gallego et al, 2002). After addition of inorganic Fe salts the o,o-EDDHA/Fe 3+ and o,p-EDDHA/ Fe 3+ complexes are formed but p,p-EDDHA does not form the Fe 3+ complex because the two p-hydroxyphenyl groups are sterically impeded to bind Fe 3+ (Yunta et al, 2003a).…”

Section: Introductionmentioning

confidence: 99%

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Effectiveness of Ethylenediamine-N(o-hydroxyphenylacetic)-N′(p-hydroxyphenylacetic) acid (o,p-EDDHA) to Supply Iron to Plants

et al. 2006

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The Fe chelate o,p-EDDHA/Fe 3+ , in addition to o,o-EDDHA/Fe 3+ , was found recently to be a component of commercial EDDHA/Fe 3+ chelates. The European Regulation on fertilisers has included o,p-EDDHA as an authorized chelating agent. The efficacy of o,o-EDDHA/Fe 3+ , o,p-EDDHA/Fe 3+ and EDTA/Fe 3+ chelates as Fe sources in plant nutrition was studied. Iron-chelate reductase (FC-R) in young cucumber plants (Cucumis sativus L.) roots reduced o,p-EDDHA/Fe 3+ faster than o,o-EDDHA/ Fe 3+ , EDTA/Fe 3+ and a commercial source of EDDHA/Fe 3+ . The o,p-EDDHA/Fe 3+ chelate was also more effective than the o,o-EDDHA/Fe 3+ in decreasing the severity of Fe-deficiency chlorosis in leaves of young soybean (Glycine max L.) plants grown hydroponically. The o,p-EDDHA ligand was more effective in the short-term than the EDTA and o,o-EDDHA ligands at dissolving Fe from selected Fe minerals and soils. However, the ultimate quantity of dissolve Fe was greatest with the o,o-EDDHA ligand.Abbreviations: BPDS -Bathophenanthroline disulfonic acid or 4,7-diphenyl-1,10-phenantroline disulfonic acid; EDDA -ethylene diamine diacetic acid; EDTA -Ethylene diamine tetraacetic acid; FC-R -Iron chelate reductase; HEPES -4-(2-Hydroxyethyl)piperazine-1

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Section: Fe Solubilisation From Soils and Fe Oxidesmentioning

confidence: 99%

Section: Fe Solubilisation From Soils and Fe Oxidesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Effectiveness of Ethylenediamine-N(o-hydroxyphenylacetic)-N′(p-hydroxyphenylacetic) acid (o,p-EDDHA) to Supply Iron to Plants

et al. 2006

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“…EDDHA is industrially prepared by a Mannich-like reaction between phenol, ethylenediamine and glyoxylic acid (Petree et al 1978). This pathway is known to produce around 4-6% Fe chelated with o,o-EDDHA as the main component, together with a mixture of positional isomers that have been identified as o,p-EDDHA and p,p-EDDHA (Cremonini et al 2001;Gómez -Gallego et al 2002) accompanied by other unknown by-products that are also able to complex Fe 3+ . The o, oEDDHA positional isomer is found to form the most stable complexes with iron (Hernández- Apaolaza et al 1997;Yunta et al 2003a) and presents two regioisomers (meso and racemic) with different agronomic efficacy (Cerdán et al 2006); o,pEDDHA has now been included as an authorized chelating agent in the European Regulation on fertilizers (EC Regulation No.…”

Section: Introductionmentioning

confidence: 99%

Effectiveness of N,N′-Bis(2-hydroxy-5-methylbenzyl) ethylenediamine-N,N′-diacetic acid (HJB) to supply iron to dicot plants

2009

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Iron chlorosis is commonly corrected by the application of EDDHA chelates, whose industrial synthesis produces o,oEDDHA together with a mixture of regioisomers and other unknown byproducts. HJB, an o,oEDDHA analogous, is a new chelating agent with a purer synthesis pathway than EDDHA. The HJB/Fe 3+ stability constant is intermediate between the racemic and meso o,oEDDHA/Fe 3+ stereoisomers. This work studied the efficacy of HJB as a Fe source in plant nutrition. No significant differences between o,oEDDHA/Fe 3+ , HJB/Fe 3+ and HBED/Fe 3+ were observed when they are used as substrates of the iron-chelate reductase of mild chlorotic cucumber plants. Chelates prepared with the stable isotope 57 Fe were used in both soil and hydroponic experiments. In the hydroponic experiment, nutrient solutions with low doses of chelates were renewed weekly. Soybean plants treated with o, oEDDHA/ 57 Fe 3+ recorded the highest results in biomass, SPAD index and Fe nutrition. In the soil experiment, chelates were added once at a rate of 2.5 mg Fe per kg of a calcareous soil. Soybean plants treated with HJB/ 57 Fe 3+ recorded a higher biomass and SPAD index in young leaves than the plants treated with o,oEDDHA/ 57 Fe 3+ ; however, 57 Fe and total Fe concentrations in leaves were lower. The results of both pot experiments are associated with a faster ability by o,oEDDHA to provide Fe to the plants and with a more continuous supply of Fe from HJB/Fe 3+ . HJB/ 57 Fe 3+ effectively alleviated the Fedeficiency chlorosis of soybean with a longer lasting effect than o,oEDDHA/ 57 Fe 3+ .

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“…A novel method using cyanide transfer agents instead of HCN has been developed, although it has not yet been scaled up for industrial applications 16. Current industrial synthesis processes17, 18 lead to products which often contain starting chemicals as well as reaction byproducts 15, 19–26. For this reason, a common characteristic of these fertilizers is the occurrence of a significant water‐soluble Fe fraction not bound to the authorized chelating agents 20–22.…”

mentioning

confidence: 99%

Electrospray ionization collision‐induced dissociation mass spectrometry: a tool to characterize synthetic polyaminocarboxylate ferric chelates used as fertilizers

Orera¹,

Orduna²,

Abadı́a³

et al. 2009

Rapid Comm Mass Spectrometry

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Fertilizers based on synthetic polyaminocarboxylate ferric chelates have been known since the 1950s to be successful in supplying Fe to plants. In commercial Fe(III)‐chelate fertilizers, a significant part of the water‐soluble Fe‐fraction consists of still uncharacterized Fe byproducts, whose agronomical value is unknown. Although collision‐induced dissociation (CID) tandem mass spectrometry (MS/MS) is a valuable tool for the identification of such compounds, no fragmentation data have been reported for most Fe(III)‐chelate fertilizers. The aim of this study was to characterize the CID‐MS2 fragmentation patterns of the major synthetic Fe(III)‐chelates used as Fe‐fertilizers, and subsequently use this technique for the characterization of commercial fertilizers. Quadrupole‐time‐of‐flight (QTOF) and spherical ion trap mass analyzers equipped with an electrospray ionization (ESI) source were used. ESI‐CID‐MS2 spectra obtained were richer when using the QTOF device. Specific differences were found among Fe(III)‐chelate fragmentation patterns, even in the case of positional isomers. The analysis of a commercial Fe(III)‐chelate fertilizer by high‐performance liquid chromatography (HPLC) coupled to ESI‐MS(QTOF) revealed two previously unknown, Fe‐containing compounds, that were successfully identified by a comprehensive comparison of the ESI‐CID‐MS2(QTOF) spectra with those of pure chelates. This shows that HPLC/ESI‐CID‐MS2(QTOF), along with the Fe(III)‐chelate fragmentation patterns, could be a highly valuable tool to directly characterize the water‐soluble Fe fraction in Fe(III)‐chelate fertilizers. This could be of great importance in issues related to crop Fe‐fertilization, both from an agricultural and an environmental point of view. Copyright © 2009 John Wiley & Sons, Ltd.

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Synthesis of o,p-EDDHA and Its Detection as the Main Impurity in o,o-EDDHA Commercial Iron Chelates

Cited by 30 publications

References 20 publications

Effectiveness of Ethylenediamine-N(o-hydroxyphenylacetic)-N′(p-hydroxyphenylacetic) acid (o,p-EDDHA) to Supply Iron to Plants

Effectiveness of Ethylenediamine-N(o-hydroxyphenylacetic)-N′(p-hydroxyphenylacetic) acid (o,p-EDDHA) to Supply Iron to Plants

Effectiveness of N,N′-Bis(2-hydroxy-5-methylbenzyl) ethylenediamine-N,N′-diacetic acid (HJB) to supply iron to dicot plants

Electrospray ionization collision‐induced dissociation mass spectrometry: a tool to characterize synthetic polyaminocarboxylate ferric chelates used as fertilizers

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