WO2002000604A1 - Nouveau procede de preparation d'acides bis(2-hydroxyaryl)aminoacetiques dans lequel sont utilises des agents de transfert de cyanure - Google Patents

Nouveau procede de preparation d'acides bis(2-hydroxyaryl)aminoacetiques dans lequel sont utilises des agents de transfert de cyanure Download PDF

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Publication number
WO2002000604A1
WO2002000604A1 PCT/ES2001/000243 ES0100243W WO0200604A1 WO 2002000604 A1 WO2002000604 A1 WO 2002000604A1 ES 0100243 W ES0100243 W ES 0100243W WO 0200604 A1 WO0200604 A1 WO 0200604A1
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WIPO (PCT)
Prior art keywords
cyanide
bis
amino
hydrolysis
nitrile
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Ceased
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PCT/ES2001/000243
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English (en)
Spanish (es)
Inventor
Miguel Angel Sierra Rodriguez
Mar Gomez Gallego
Roberto Alcazar Montero
Juan Jose Lucena Marotta
Ana Alvarez Fernandez
Felipe Yunta Mezquita
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Universidad Complutense de Madrid
Universidad Autonoma de Madrid
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Universidad Complutense de Madrid
Universidad Autonoma de Madrid
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Priority to AU74118/01A priority Critical patent/AU7411801A/en
Publication of WO2002000604A1 publication Critical patent/WO2002000604A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/26—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing carboxyl groups by reaction with HCN, or a salt thereof, and amines, or from aminonitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols

Definitions

  • the present invention falls within the field of agricultural chemistry, specifically within the area of metal chelating agents for the treatment of ferric chlorosis.
  • This invention relates to a general method of synthesis of bis (2-hydroxyaryl) aminoacetic acids that can be used as metal chelating agents and applied for the treatment of iron chlorosis.
  • Iron chlorosis is defined as any yellowing that occurs in young leaves due to the reduction of iron functionality in the synthesis of chlorophylls.
  • the correction of ferric chlorosis in crops is carried out through the use of synthetic chelates, so that the amount of chelates used in agriculture, in many cases reaches a percentage greater than 50% of the total fertilizers added to the crops [Sanz et al. , J. Plant Nutr. 1992, 15 (10), 1971].
  • products that are declared as iron chelates will be obtained by chemical combination of iron with an authorized chelating agent.
  • EDDHA ethylenediamine-N, N-bis-2-hydroxyphenyl acetic acid
  • the first procedure consists in the reaction, in alkaline medium, of a phenol, glyoxylic acid (or one of its salts, especially sodium glyoxalate) and a diamine, using a hydroalcoholic medium as solvent [U.S. Pat. No. 5,354,897].
  • a hydroalcoholic medium as solvent
  • EDDHA and its substituted aryl derivatives can be obtained, if one starts from functionalized phenols in position 4 [U.S. Pat. No. 3,903,119], [U.S. Pat. No. 3,981,712], [U.S. Pat No. 5,152,820], [U.S. Pat. No. 4,130,582].
  • the first stage of the reaction is an aromatic electrophilic substitution in the phenol that leads to mixtures of ortho and ⁇ -substituted products, which are very difficult to separate, and in which the isomer is sometimes the majority product.
  • ethylenediamine-N, N'-bis (4-hydroxyphenyl) acetic acid para- ⁇ DDIr has no interest as a chelating agent, since it cannot form stable chelates.
  • some modifications of the method have been described to increase the percentage of ortho-substituted product, such as the use of metal catalysts during the process [E.P. Pat. 0, 331, 556]. In spite of everything, the ortho isomer is obtained accompanied by the product to be substituted with percentages ranging between 20% and 50%.
  • Another alternative procedure consists in the reaction of phenol with glyoxylic acid in alkaline medium, to obtain a mixture of ortho acids and hydroxydandic acids [US Pat. .O. 5,248,816], [US Pat. .O. 5,354,897].
  • the ortho isomer can be used as a precursor to EDDHA, by oxidation to the corresponding ⁇ -keto acid, reaction with etiiendiamine and reduction [WO 94/14746].
  • the methods that are based on the use of HCN use diimines as precursors obtained from salicDaldehydes and diamines, which are transformed into the corresponding dinitriles by reaction with HCN, liquid or generated in situ from the treatment of cyanides at the appropriate pH [US Pat. No. 2,921,847].
  • the ligands are finally obtained by acid hydrolysis of the aminonitriles.
  • the high toxicity of HCN and the risks that its handling implies are the main drawbacks of this method.
  • the present invention consists of a new process that allows the synthesis of bis (2-hydroxyphenyl) aminoacetic acids (1), which have the amino groups linked by hydrocarbon chains of different length and structure, of etüendkmino- acids.
  • bis (2-hydroxy) phenylacetic (2) distinctly substituted in the aromatic ring and etuend mino-bis (2-suuanyl) phenylacetic acids (3).
  • the process described in this invention allows to obtain isomerically and chemically pure ligands, with different type and degree of substitution in the rings. benzene and with spacer chains between nitrogen atoms, of different length and structure.
  • the described method, object of the present invention competes for its versatility, simplicity and performance with those previously collected in the literature.
  • part of affordable products takes place in only three steps and the yields of the products obtained in all of them are high.
  • TMSCN trimethyl silyl cyanide
  • Example 2 As in Example 1, using salicylaldehyde and propylenediamine as the starting product. After hydrolysis, propylenediamino-bis (2-hydroxyphenylacetic acid) precipitates at pH 4.3 and is obtained in 41% yield from diimine.
  • Example 3 Butylenediamine-bis (2-hydroxyphenylacetic acid) As in Example 1, using salicylaldehyde and butylenediamine as the starting product. After hydrolysis, butylenediamine bis (2-hydroxyphenylacetic acid) precipitates at pH 4.4 and is obtained in 54% yield from diimine.
  • Example 2 As in Example 1, using salicylaldehyde and p-xylylenediamine as the starting product. After hydrolysis, the? -Xilylenendiamino-bis (2-hydroxyphenylacetic acid) is precipitated at pH 4.7 and is obtained in 73% yield from the diimine.
  • Example 5 n-xylylenediamino-bis (2-hydroxyphenylacetic acid) As in Example 1, using salicylaldehyde and m-xylylenediamine as the starting product. After hydrolysis, the / w-xylylenediamino-bis (2-hydroxyphenylacetic acid) precipitate at pH 4.5 and is obtained in 50% yield from the diimine.
  • Example 6 ethylenediamine bis (2-hydroxy-5-methylphenylacetic acid) As in Example 1, using 5-methyl salicyclic aldehyde and etiienediamine as the starting product. After hydrolysis ethenediamino-bis (2-hydroxy-5-methylphenylacetic acid) [US Pat. No. 5,152,820, US Pat. No. 4,130,582] is precipitated at pH 4.3 and is obtained in 63% yield from diimine.
  • Example 7 etUendiamino-bis (2-hydroxy-4-metuphenylacetic acid) As in Example 1, using 4-methyl salicylaldehyde and etiiendiamine as the starting product. After hydrolysis, ethylenediamine bis (2-hydroxy-4-methylphenylacetic acid) is precipitated at pH 3.7 and is obtained in 50% yield from diimine.
  • Example 8 ethylenediamine bis (2-hydroxy-5-carboxyphenylacetic acid)
  • Example 2 As in Example 1, using 5- carboxymethylsalicylaldehyde and etiiendiamine as the starting product. After hydrolysis, ethylenediamine-bis (2-hydroxy-5-carboxyphenylacetic acid) [U.S. Pat. No. 4,130,582]. Is obtained with 20% yield from the d ⁇ mina.
  • the titration of the samples by HPLC led to results similar to those obtained by photometric determination.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un nouveau procédé de synthèse d'acides bis(2-hydroxyaryl)aminoacétiques présentant un haut degré de pureté et un bon rendement. Ces composés peuvent être utilisés comme ligands pour l'obtention de chélates de fer de grand intérêt par leur application en agriculture comme fertilisants de micro-éléments nutritifs. Ce procédé est basé sur l'utilisation de cyanure de triméthylsilyle (TMSCN) dans une modification de la synthèse de Strecker. Grâce à leur haut degré de pureté, les ligands obtenus par ce procédé peuvent être utilisés comme patrons dans l'analyse et la quantification de chélates utilisés à des fins commerciales.
PCT/ES2001/000243 2000-06-28 2001-06-14 Nouveau procede de preparation d'acides bis(2-hydroxyaryl)aminoacetiques dans lequel sont utilises des agents de transfert de cyanure Ceased WO2002000604A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU74118/01A AU7411801A (en) 2000-06-28 2001-06-14 Novel method for preparing bis(2-hydroxyaryl)aminoacetic acids using cyanide transfer agents

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES200001602A ES2174712B2 (es) 2000-06-28 2000-06-28 Nuevo procedimiento para la preparacion de acidos bis (2-hidroxiaril) aminoaceticos utilizando agentes de transferencia de cianuro.
ESP200001602 2000-06-28

Publications (1)

Publication Number Publication Date
WO2002000604A1 true WO2002000604A1 (fr) 2002-01-03

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PCT/ES2001/000243 Ceased WO2002000604A1 (fr) 2000-06-28 2001-06-14 Nouveau procede de preparation d'acides bis(2-hydroxyaryl)aminoacetiques dans lequel sont utilises des agents de transfert de cyanure

Country Status (3)

Country Link
AU (1) AU7411801A (fr)
ES (1) ES2174712B2 (fr)
WO (1) WO2002000604A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2824128A (en) * 1956-02-03 1958-02-18 Geigy Chem Corp Preparation of phenolic ethylenediaminepolycarboxylic acids
US2921847A (en) * 1955-10-10 1960-01-19 Geigy Chem Corp Iron chelates of ethylene bis(alphaimino-ortho-hydroxyphenylacetic acid) and method of overcoming iron deficiencies in growing plants therewith
US4130582A (en) * 1977-04-19 1978-12-19 Ciba-Geigy Corporation Preparation of phenolic ethylenediaminepolycarboxylic acids
US4730066A (en) * 1986-05-06 1988-03-08 Mallinckrodt, Inc. Complex for enhancing magnetic resonance imaging
EP0331556A2 (fr) * 1988-02-29 1989-09-06 Manufacture De Produits Chimiques Protex Nouveau procédé de préparation de l'acide éthylène-diamine-N-N'-bis (ortho-hydroxyphénylacétique) et de dérivés de celui-ci

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2921847A (en) * 1955-10-10 1960-01-19 Geigy Chem Corp Iron chelates of ethylene bis(alphaimino-ortho-hydroxyphenylacetic acid) and method of overcoming iron deficiencies in growing plants therewith
US2824128A (en) * 1956-02-03 1958-02-18 Geigy Chem Corp Preparation of phenolic ethylenediaminepolycarboxylic acids
US4130582A (en) * 1977-04-19 1978-12-19 Ciba-Geigy Corporation Preparation of phenolic ethylenediaminepolycarboxylic acids
US4730066A (en) * 1986-05-06 1988-03-08 Mallinckrodt, Inc. Complex for enhancing magnetic resonance imaging
EP0331556A2 (fr) * 1988-02-29 1989-09-06 Manufacture De Produits Chimiques Protex Nouveau procédé de préparation de l'acide éthylène-diamine-N-N'-bis (ortho-hydroxyphénylacétique) et de dérivés de celui-ci

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
AUSTRALIAN JOURNAL CHEMISTRY, vol. 40, no. 10, 1987, pages 1695 - 1704 *
CHEMICAL ABSTRACTS, vol. 54, 1960, Columbus, Ohio, US; abstract no. 10909D, A. FROST ET AL.: "Addition of hydrogen cyanide to aromatic schiff bases" *
DATABASE CAPLUS [online] G. WILSON: "Phenolic analogs of amino carboxylic acid ligands. I. Synthesis and characterization of N,N'-ethylen-bis(2-(o-hydroxyphenyl)glycines)(EHPG)", accession no. STN Database accession no. 1988:423334 *
DATABASE CAPLUS [online] J. LEBLANC ET AL.: "Synthesis of alpha-aminonitriles by self-catalyzed, stoichiometric reaction of primery amines, aldehydes and trimethylsilyl cyanide", accession no. STN Database accession no. 1993:21997 *
JOURNAL ORGANIC CHEMISTRY, vol. 24, 1959, pages 1905 - 1907 *
TETRAHEDRON LETTERS, vol. 33, no. 42, 1992, pages 6295 - 6298 *

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Publication number Publication date
ES2174712A1 (es) 2002-11-01
AU7411801A (en) 2002-01-08
ES2174712B2 (es) 2003-09-16

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