CH561226A5 - - Google Patents
Info
- Publication number
- CH561226A5 CH561226A5 CH248173A CH248173A CH561226A5 CH 561226 A5 CH561226 A5 CH 561226A5 CH 248173 A CH248173 A CH 248173A CH 248173 A CH248173 A CH 248173A CH 561226 A5 CH561226 A5 CH 561226A5
- Authority
- CH
- Switzerland
- Prior art keywords
- iron
- chelates
- formula
- solution
- compound
- Prior art date
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 48
- 229910052742 iron Inorganic materials 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 206010022971 Iron Deficiencies Diseases 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000013522 chelant Substances 0.000 claims description 6
- -1 phenolic amino acids Chemical class 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- CCVYRRGZDBSHFU-UHFFFAOYSA-N (2-hydroxyphenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1O CCVYRRGZDBSHFU-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910006069 SO3H Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000012470 diluted sample Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000000797 iron chelating agent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000002689 soil Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910017974 NH40H Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000001768 cations Chemical group 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
- 229960004887 ferric hydroxide Drugs 0.000 claims description 2
- VUWZPRWSIVNGKG-UHFFFAOYSA-N fluoromethane Chemical compound F[CH2] VUWZPRWSIVNGKG-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical group O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 2
- 208000006278 hypochromic anemia Diseases 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical class OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Fertilizers (AREA)
Description
L'invention a pour objet la synthèse de nouveaux chélates de
Fe ou de Fe t 3 d'acides hydroxyphénylacétiques substitués ayant la formule générale:
EMI1.1
Ces aminoacides phénoliques, dont l'obtention a été décrite dans la demande de brevet suisse N 019049/72 du 29 décembre 1972, de la même titulaire, sont caractérisés par leur grande stabilité à pH alcalin et ont une utilité dans l'agriculture pour la correction des déficiences en fer dans les végétaux, aussi bien que sur les sols acides qu'alcalins.
Dans la formule I, X est l'hydrogène ou un substituant choisi parmi COOH, -NO2, Cl, -CH3, H2 et -SO3H.
R est un radical -COOH, -CH2OH, -NH2, -SH ou -NHCH3.
La valeur n dans la chaîne -(CH2F est comprise entre 1 et 10 mais est préférablement 1 ou 2.
Les solutions aqueuses des chélates formés entre ces composés et les ions de Fe + 2 ou Fe + 3 sont fortement colorées en rouge ou violet à un pH compris entre 1 et 7 et d'une couleur orange à jaune à un pH de 7 à 14, sans précipiter le fer comme hydroxyde.
La formule précise des chélates n'est pas connue, cependant il a été possible de vérifier qu'on peut obtenir jusqu'à 3 classes de chélates avec le Fe + 3, ayant la relation molaire, respectivement atomique, anionjcation 1/1, 2/1 ou 3/1. La formation d'un de ces chélates dépend en particulier du pH du milieu et de la proportion de l'anion par rapport au cation, le fer dans ce cas.
En pratique, pour la préparation de ces chélates dans la forme pure, on traite le composé de formule I dissous dans la quantité minimale d'eau avec un excès d'hydroxyde ou de carbonate de fer en le chauffant à 60-70 C pendant 1-2 heures jusqu'à ce qu'un échantillon, dilué suffisamment, donne une transmission constante à B470 nm, et l'on neutralise la solution avec du carbonate ou bicarbonate de sodium jusqu'à pH = 7.
Le liquide épais résultant, d'une couleur violette, est concentré au vide jusqu'à la sécheresse. On broie le résidu jusqu'à une poudre impalpable. De cette façon on obtient une poudre d'une couleur marron foncé laquelle, lorsqu'on la dissout dans l'eau, produit une solution violet rougeâtre ayant un pH =6,5-7. Lorsqu'on y ajoute de la soude caustique jusqu'à un pH = 12, la couleur change de violet à jaune orange, la solution ne donnant aucun précipité même après 15 jours, ce qui indique que le fer est fortement séquestré.
Une méthode rapide de préparer ces chélates consiste à mélanger convenablement un sel de fer + 2 ou + 3 finement pulvérisé avec le composé de formule I sous la forme acide ou sodique, et à neutraliser le mélange avec du carbonate sodique, carbonate d'ammonium, ammoniac, etc. On obtient de cette façon un composé moins pur, lequel, lorsqu'on le dissout dans l'eau, est transformé en le chélate de fer correspondant.
Les chélates de fer de ces aminoacides phénoliques peuvent être appliqués seuls ou ensemble avec d'autres ingrédients, soit sur le sol ou moyennant aspersion sur les feuilles des végétaux, étant d'une grande utilité pour les plantes qui présentent des déficiences en fer, aussi bien dans des sols acides qu'alcalins.
Exemple 1:
On dissout 1000 p. d'acide a^(carboxyméthylaminofio- hydroxyphénylacétique dans 500 p. d'eau, et on y ajoute ensuite de l'hydroxyde ferrique récemment précipité et lavé (I'équivalent à 700 p. de Cl3Fe.6H2O). On chauffe jusqu'à la dissolution maximale du précipité, en vérifiant moyennant un petit échantillon suffisamment dilué, jusqu'à ce que la transmission à B470 nm soit constante. On neutralise ensuite la solution jusqu'au pH = 7 moyennant du bicarbonate de sodium et on la porte à sec à une température maximale de 70"C. On broie le résidu finement, et on le tamise. On obtient 1100 p. du chélate de fer sous forme d'une poudre marron foncé; la solution à 1% a une couleur violette et un pH de 6,7.
Le contenu en fer du produit varie entre 10,5 et 11%.
Exemple 2:
On prend 500 p. d'acide -(carboxyméthylamino)-o-hydroxy- phénylacétique finement pulvérisé et on fait le mélange avec 300 p. de SO4Fe-5H2O, on y ajoute ensuite 100 p. d'eau et on l'agite au maximum jusqu'à la formation d'une bouillie, puis on y ajoute 150 p. de NH40H 25% et on évapore l'ensemble à sec. Le solide restant est finement trituré, et l'on obtient 650 p. d'une poudre d'une couleur marron rougeâtre. Le pH de la solution à 1% est de 6,5 et le contenu en fer 8 à 8,5%. Le produit contient 80% environ de chélate de fer et 20% de sulfate d'ammonium.
Exemple 3:
On procéde de la même façon que dans l'exemple 1, mais en utilisant 1000 p. d'acide a-(2-hydroxyéthylamino)-o-hydroxyphé- nylacétique. On obtient un produit ayant des caractéristiques semblables mais plus résistant aux alcalis.
Exemple 4:
On procède de la même façon que dans l'exemple 2, mais en employant 450 p. d'acide -(2-hydroxyéthylamino)-o-hydroxy- phénylacétique. On obtient un produit d'une couleur marron rougeâtre avec une teneur en fer de 8,5 à 9%. Le pH de la solution à
1% est de 6,6.
Tous ces composés appliqués aux doses convenables ont un grand intérêt comme correcteurs des déficiences en fer dans la plupart des végétaux et spécialement des fruitiers.
REVENDICATION
Procédé de préparation de chélates de fer, correcteurs de la chlorosis ferrique dans les végétaux, caractérisé en ce que l'on fait réagir un composé de formule
EMI1.2
dans laquelle X représente de l'hydrogène ou un substituant choisi parmi COOH, -NO2, Cl, -CH3, -NH2 et -SO3H, R est un radical COOH, -CH2OH, -NH2, -SH ou -NHCH3, et n est un nombre compris entre 1 et 10, avec un hydroxyde ou un sel de
Fe(II) ou Fe(III), et l'on neutralise jusqu'à un pH de 7 et évapore à sec.
SOUS-REVENDICATIONS
1. Procédé selon la revendication, caractérisé en ce que le composé de formule I est l'acide -(carboxyméthylamino)-o- hydroxyphénylacétique (X = H, n = 1, R = COOH).
2. Procédé selon la revendication, caractérisé en ce que le composé de formule I est l'acide a-(2-hydroxyéthylamino > o- hydroxyphénylacétique (X = H, n = 1, R = CH2OH).
**ATTENTION** fin du champ DESC peut contenir debut de CLMS **.
The subject of the invention is the synthesis of novel chelates of
Fe or Fe t 3 of substituted hydroxyphenylacetic acids having the general formula:
EMI1.1
These phenolic amino acids, the production of which was described in Swiss patent application N 019049/72 of December 29, 1972, of the same holder, are characterized by their high stability at alkaline pH and have utility in agriculture for correction of iron deficiencies in plants, as well as in acidic and alkaline soils.
In formula I, X is hydrogen or a substituent selected from COOH, -NO2, Cl, -CH3, H2 and -SO3H.
R is a -COOH, -CH2OH, -NH2, -SH or -NHCH3 radical.
The value n in the chain - (CH2F is between 1 and 10 but is preferably 1 or 2.
The aqueous solutions of the chelates formed between these compounds and the ions of Fe + 2 or Fe + 3 are strongly colored red or purple at a pH between 1 and 7 and an orange to yellow color at a pH of 7 to 14 , without precipitating iron as hydroxide.
The precise formula of the chelates is not known, however it was possible to verify that up to 3 classes of chelates can be obtained with Fe + 3, having the molar relation, respectively atomic, anionjcation 1/1, 2 / 1 or 3/1. The formation of one of these chelates depends in particular on the pH of the medium and on the proportion of the anion relative to the cation, iron in this case.
In practice, for the preparation of these chelates in the pure form, the compound of formula I dissolved in the minimum amount of water is treated with an excess of iron hydroxide or carbonate by heating it at 60-70 C for 1 -2 hours until a sufficiently diluted sample gives constant transmission at B470 nm, and the solution is neutralized with sodium carbonate or bicarbonate to pH = 7.
The resulting thick liquid, purple in color, is concentrated in a vacuum until dry. The residue is ground to an impalpable powder. In this way a powder of a dark brown color is obtained which, when dissolved in water, produces a reddish purple solution having a pH = 6.5-7. When caustic soda is added to it up to a pH = 12, the color changes from purple to orange yellow, the solution giving no precipitate even after 15 days, which indicates that the iron is strongly sequestered.
A rapid method of preparing these chelates is to properly mix a finely powdered + 2 or + 3 iron salt with the compound of formula I in acid or sodium form, and neutralize the mixture with sodium carbonate, ammonium carbonate, ammonia, etc. In this way, a less pure compound is obtained, which, when dissolved in water, is transformed into the corresponding iron chelate.
The iron chelates of these phenolic amino acids can be applied alone or together with other ingredients, either on the ground or by sprinkling on the leaves of plants, being of great utility for plants which have iron deficiencies, too. well in acidic and alkaline soils.
Example 1:
1000 p. of α 3 (carboxymethylaminofio-hydroxyphenylacetic acid in 500 p. of water, followed by addition of recently precipitated and washed ferric hydroxide (equivalent to 700 p. of Cl3Fe.6H2O). maximum dissolution of the precipitate, checking with a small sufficiently diluted sample, until the transmission at B470 nm is constant.The solution is then neutralized to pH = 7 using sodium bicarbonate and brought to dryness at a maximum temperature of 70 ° C. The residue is finely ground, and sieved. 1100 p. of the iron chelate is obtained as a dark brown powder; the 1% solution has a purple color and a pH of from 6.7.
The iron content of the product varies between 10.5 and 11%.
Example 2:
We take 500 p. finely powdered - (carboxymethylamino) -o-hydroxyphenylacetic acid and mixed with 300 p. of SO4Fe-5H2O, then added 100 p. of water and stirred as much as possible until a slurry forms, then 150 p. 25% NH40H and the whole is evaporated to dryness. The remaining solid is finely triturated, and 650 p is obtained. of a powder of a reddish brown color. The pH of the 1% solution is 6.5, and the iron content is 8-8.5%. The product contains approximately 80% iron chelate and 20% ammonium sulfate.
Example 3:
The procedure is the same as in Example 1, but using 1000 p. a- (2-hydroxyethylamino) -o-hydroxyphenylacetic acid. A product is obtained having similar characteristics but more resistant to alkalis.
Example 4:
The procedure is the same as in Example 2, but using 450 p. - (2-Hydroxyethylamino) -o-hydroxy-phenylacetic acid. A product of a reddish brown color with an iron content of 8.5 to 9% is obtained. The pH of the solution at
1% is 6.6.
All these compounds applied at suitable doses are of great interest as correctors for iron deficiencies in most plants and especially fruit trees.
CLAIM
Process for preparing iron chelates, correctors for ferric chlorosis in plants, characterized in that a compound of formula is reacted
EMI1.2
where X represents hydrogen or a substituent selected from COOH, -NO2, Cl, -CH3, -NH2 and -SO3H, R is a COOH, -CH2OH, -NH2, -SH or -NHCH3 radical, and n is a number between 1 and 10, with a hydroxide or a salt of
Fe (II) or Fe (III), and neutralized to a pH of 7 and evaporated to dryness.
SUB-CLAIMS
1. Method according to claim, characterized in that the compound of formula I is - (carboxymethylamino) -o- hydroxyphenylacetic acid (X = H, n = 1, R = COOH).
2. Method according to claim, characterized in that the compound of formula I is a- (2-hydroxyethylamino> o-hydroxyphenylacetic acid (X = H, n = 1, R = CH2OH).
** ATTENTION ** end of DESC field can contain start of CLMS **.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES72400520A ES400520A1 (en) | 1972-02-22 | 1972-02-22 | Procedure for obtaining chelates from iron, correctors of ferrous chlorosis in vegetables. (Machine-translation by Google Translate, not legally binding) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH561226A5 true CH561226A5 (en) | 1975-04-30 |
Family
ID=8460525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH248173A CH561226A5 (en) | 1972-02-22 | 1973-02-21 |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS4896714A (en) |
| CH (1) | CH561226A5 (en) |
| ES (1) | ES400520A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3183967A1 (en) * | 2015-12-22 | 2017-06-28 | Trade Corporation International, S.A. Unipersonal | Process for the preparation of a quelating agent |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR055285A1 (en) * | 2005-11-11 | 2007-08-15 | Edgardo Adrian Hager | MINERAL SALTS OF MINERALS STABILIZED WITH AMINO ACIDS PRODUCTS AND FOOD SUPPLEMENT THAT UNDERSTAND AND OBTAINING PROCEDURES |
-
1972
- 1972-02-22 ES ES72400520A patent/ES400520A1/en not_active Expired
-
1973
- 1973-02-21 CH CH248173A patent/CH561226A5/fr not_active IP Right Cessation
- 1973-02-21 JP JP48021123A patent/JPS4896714A/ja active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3183967A1 (en) * | 2015-12-22 | 2017-06-28 | Trade Corporation International, S.A. Unipersonal | Process for the preparation of a quelating agent |
| WO2017108884A1 (en) * | 2015-12-22 | 2017-06-29 | Trade Corporation International, S.A. Unipersonal | Process for the preparation of a quelating agent |
| KR20180111784A (en) * | 2015-12-22 | 2018-10-11 | 트레이드 코포레이션 인터내셔널, 에스.에이. 유니퍼스널 | Methods for the preparation of chelating agents |
| RU2740577C2 (en) * | 2015-12-22 | 2021-01-15 | Трейд Корпорейшн Интернэшнл, С.А. Юниперсонал | Method of producing a chelating agent |
| US10934250B2 (en) | 2015-12-22 | 2021-03-02 | Trade Corporation International, S.A. Unipersonal | Process for the preparation of a chelating agent |
| AU2016376988B2 (en) * | 2015-12-22 | 2021-03-04 | Trade Corporation International, S.A. Unipersonal | Process for the preparation of a chelating agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS4896714A (en) | 1973-12-10 |
| ES400520A1 (en) | 1973-01-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased | ||
| PL | Patent ceased |