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EP0287885B1 - Procédé de préparation de la N,N-dicarboxyméthyl-sérine et de ses dérivés - Google Patents

Procédé de préparation de la N,N-dicarboxyméthyl-sérine et de ses dérivés Download PDF

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Publication number
EP0287885B1
EP0287885B1 EP88105376A EP88105376A EP0287885B1 EP 0287885 B1 EP0287885 B1 EP 0287885B1 EP 88105376 A EP88105376 A EP 88105376A EP 88105376 A EP88105376 A EP 88105376A EP 0287885 B1 EP0287885 B1 EP 0287885B1
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EP
European Patent Office
Prior art keywords
acid
serine
mol
salt
alkali metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88105376A
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German (de)
English (en)
Other versions
EP0287885A1 (fr
Inventor
Richard Dr. Baur
Felix Dr. Richter
Stefan Dr. Birnbach
Rolf Dr. Fikentscher
Alfred Dr. Oftring
Ekhard Dr. Winkler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to AT88105376T priority Critical patent/ATE72229T1/de
Publication of EP0287885A1 publication Critical patent/EP0287885A1/fr
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Publication of EP0287885B1 publication Critical patent/EP0287885B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic compounds

Definitions

  • the invention relates to a process for the preparation of serine-N, N-diacetic acid and derivatives and the intermediate product serine-N, N-diacetonitrile for the production of serine-N, N-diacetic acid and its salts.
  • the object of the present invention is to provide complexing agents for alkaline earth and heavy metal ions for a wide variety of technical fields, in particular for detergents, which, in addition to good complexing properties, are ecologically harmless, contain no phosphorus if possible and are readily biodegradable.
  • a technically advantageous manufacturing process is to be developed for these complexing agents.
  • serine-N, N-diacetic acid in the form of the free acid or in particular the sodium, potassium, ammonium or organic amine salts are excellent complexing agents for calcium, magnesium and iron, copper, nickel and manganese ions represent, while the acid derivatives, especially amides, esters and the nitriles are preferred intermediates for the preparation of the acid and its salts.
  • the invention therefore relates to a process for the preparation of compounds of the formula I.
  • Y represents the radical -COOH, which is optionally in the form of an alkali metal, ammonium or substituted ammonium salt, or represents the radical -CN and X is a hydroxyl group, the carboxylic acid group thereby present optionally being in the form of an alkali metal, ammonium or substituted ammonium salt, or a radical -NR3R4, in which R3 and R4 are identical or different and represent a hydrogen atom or an alkyl radical with 1 to 4 C.
  • -Atoms stand, means by 1 mol of serine (3-hydroxy-2-aminopropionic acid), optionally in the form of an alkali salt or acid amide, optionally substituted on the amide nitrogen atom by one or two alkyl radicals having 1 to 4 carbon atoms, in water, an organic solvent or their mixtures with 2.0 to 2.6 mol of formaldehyde and 2.0 to 2.3 mol of liquid hydrocyanic acid at temperatures from 0 to 45 ° C. or with 2.0 to 2.3 mol of alkali metal cyanide at temperatures from 40 to 100 ° C and, if appropriate, hydrolyze the amide and nitrile groups present in the presence of an acid or base and, if appropriate, isolate the free acid or a salt of the formula I.
  • the free serine N, N-diacetic acid and the sodium, potassium and ammonium salts in particular the trisodium, tripotassium and triammonium salt, and organic triamine salts with a tertiary nitrogen atom are to be mentioned in particular.
  • the bases on which the organic amine salts are based are, in particular, tertiary amines, such as trialkylamines having 1 to 4 carbon atoms in the alkyl, such as trimethyl and triethylamine, and trialkanolamines having 2 or 3 carbon atoms in the alkanol radical, preferably triethanolamine and tripropanolamine.
  • tertiary amines such as trialkylamines having 1 to 4 carbon atoms in the alkyl, such as trimethyl and triethylamine, and trialkanolamines having 2 or 3 carbon atoms in the alkanol radical, preferably triethanolamine and tripropanolamine.
  • the preferred starting compound is serine in the form of its racemic mixture and optionally in the form of the sodium, potassium or ammonium salt.
  • Water is preferably used as the solvent, or organic solvents which are miscible with water, such as methanol, ethanol, n-propanol, isopropanol, tertiary butanol, dioxane or tetrahydrofuran. Mixtures of these organic solvents with one another or their mixtures with water can also be used. In the case of aqueous mixtures, 10 to 70% by weight of organic solvent is expediently added to the weight of the water.
  • the concentration of the starting compounds in the respective solvent is advantageously 10 to 80% by weight, preferably 20 to 70% by weight.
  • the sodium or potassium salt of the serine in one of the abovementioned solvents or solvent mixtures with an aqueous solution being preferred, with the formaldehyde in the form of its aqueous, about 30% by weight solution and the liquid hydrocyanic acid the preferred temperatures of 15 to 25 ° C implemented.
  • reaction with akalicyanide in particular sodium or potassium cyanide, is preferably carried out at 70 to 100 ° C. instead of the liquid hydrocyanic acid.
  • hydrolysis or saponification to give the carboxylic acid is carried out in a conventional manner in an aqueous reaction mixture, if appropriate after adding water in the presence of alkalis, such as sodium or potassium hydroxide, or of acid such as sulfuric or hydrochloric acid.
  • This hydrolysis is expediently carried out at temperatures from 20 to 110 ° C., preferably 40 to 100 ° C., with a slight excess of base or acid, if necessary.
  • the serine-N, N-diacetic acid or an alkali salt is preferably obtained. Then salts with another cation can be prepared without further notice.
  • an acid derivative can also be produced in the usual way from the acid obtained.
  • the compounds of formula I can be isolated in pure form without difficulty. Spray or freeze drying, crystallization or precipitation are particularly suitable for the free acid and the salts. It can be advantageous to use the resulting solution directly for technical use.
  • the production process according to the invention has the advantage over known processes, in particular for the production of serine-N, N-diacetic acid and its salts, that there is practically no inorganic salt load. Due to the easy availability of the starting compounds, extremely inexpensive large-scale processes are made available.
  • the serine-N, N-diacetic acid and its salts produced by the invention are outstandingly suitable for complexing alkaline earth and heavy metal ions, in particular calcium, magnesium as well as iron, copper, nickel and manganese ions. Because of this ability, they have one Variety of technical applications. Since they are biodegradable compounds, they can be used in large quantities wherever the waste water has to be clarified and phosphorus-containing compounds should also be avoided.
  • the complexing agents mentioned can be used in washing and cleaning agents in order to control the content of free heavy metal ions in the washing agents themselves and in the washing solutions.
  • the amount used as a complexing agent is advantageously 0.1 to 2% based on the total weight of the detergent components.
  • bleach stabilization for example for sodium perborate
  • detergents and in the bleaching of textiles, cellulose or paper raw materials Traces of heavy metals such as iron, copper and manganese occur in the washing powder itself, in the water and in the textile goods and catalyze the decomposition of the sodium perborate.
  • the complexing agents mentioned bind these metal ions and prevent the undesired decomposition of the bleaching system during storage and in the wash liquor. This increases the efficiency of the bleaching system and fiber damage is suppressed.
  • the complexing agents mentioned can be used as so-called preservatives, advantageously in an amount of 0.05 to 1% by weight, based on the total weight of the detergent formulation.
  • the complexing agents mentioned prevent metal-catalyzed oxidative decomposition.
  • They can be used to stabilize phosphates in alkaline degreasing baths and prevent the precipitation of lime soaps, thereby preventing "tarnishing" of non-ferrous surfaces and extending the service life of alkaline cleaning baths.
  • the cooling water treatment with the complex images mentioned prevents deposits or dissolves existing ones. Use in an alkaline medium and thus the elimination of corrosion problems is an advantage.
  • the complexing agents mentioned can be used in developer / fixing baths which are prepared with hard water in order to prevent the precipitation of poorly soluble calcium and magnesium salts.
  • the precipitations lead to gray haze on films and images, as well as deposits in the tanks, which can thus advantageously be avoided.
  • Iron III complexing agent solutions can advantageously be used in bleach-fix baths, where they can replace the hexacyanoferrate solutions, which are of ecological concern.
  • applications in pharmaceuticals, cosmetics and foodstuffs are considered as various applications in order to prevent the metal-catalyzed oxidation of olefinic double bonds and thus the rancidity of the products.
  • Cu, Fe, Mn, Zn complexes are used to remedy heavy metal deficits.
  • the heavy metals are added as chelates to prevent precipitation as biologically inactive, insoluble salts.
  • flue gas scrubbing namely the removal of NO x from flue gases
  • H2S oxidation namely the removal of NO x from flue gases
  • metal extraction namely the removal of metal oxides
  • catalysts for org Use as catalysts for org.
  • Syntheses e.g. air oxidation of paraffins, hydroformylation of olefins to alcohols.
  • the complexing agents mentioned for alkaline earth and heavy metal ions are used as complexing agents in general and very particularly in detergents and cleaning agents and dishwashing detergents, in particular as complexing agents for heavy metal and / or alkaline earth metal ions, as bleach stabilizers and as builders.
  • the compounds mentioned are generally used in washing and cleaning formulations in an amount of 0.01 to 20% by weight, preferably 0.05 to 10% by weight, based on the total weight of the washing-agent formulation.
  • amounts from 1 to 10% by weight are preferred, when used as a bleach stabilizer for perborates, amounts from 0.05 to 1% by weight are particularly preferred.
  • amounts of 0.1 to 2% by weight are preferred.
  • Detergent and cleaning agent formulations which, based on the total weight, contain 0.01 to 20, preferably 0.05 to 10% by weight of the compound mentioned, as a rule contain, as additional constituents, 6 to 25% by weight, based on the total weight.
  • % Surfactants 15 to 50% by weight builder and optionally co-builder, 5 to 35% by weight bleach and optionally bleach activators, 3 to 30% by weight auxiliaries such as enzymes, foam regulators, corrosion inhibitors, optical brighteners, fragrances, dyes, or Formulation aids, such as Sodium sulfate.
  • the compounds mentioned can also be used in their properties as complexing agents, builders and bleach stabilizers in washing and cleaning formulations together with other agents of the prior art, the general properties with regard to sequestration, incrustation inhibition, primary washing action and bleaching action can possibly be significantly improved .
  • aqueous formaldehyde solution 100 g (1 mol) of 30% strength by weight aqueous formaldehyde solution are initially introduced, and a solution of 52 g (0.5 mol) of serine in 250 g of water, in which: a pH of 8.5 was previously set with 37 g of 40% NaOH.
  • aqueous solution of serine-N, N-diacetonitrile prepared under 1 is added dropwise to 102 g (1.02 mol) of 40% strength by weight aqueous sodium hydroxide solution at 95 to 110 ° C. in the course of 1 hour. After stirring for a further 3 hours at 100 ° C., no more ammonia development is found (total 0.94 mol).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (2)

  1. Procédé de préparation de composés de la formule I
    Figure imgb0004
     dans laquelle Y représente le reste -COOH, qui se présente éventuellement sous forme d'un sel de métal alcalin, d'ammonium ou d'ammonium substitué,
    ou bien Y représente le reste -CN et
    X représente un radical hydroxyle où le radical acide carboxylique de ce fait présent peut éventuellement se trouver sous la forme d'un sel de métal alcalin, d'ammonium ou d'ammonium substitué, ou bien X représente un reste -NR³R⁴ où R³ et R⁴ peuvent être identiques ou différents et représentent chacun un atome d'hydrogène ou un radical alkyle qui comporte de 1 à 4 atomes de carbone,

    caractérisé en ce que l'on fait réagir une mole de sérine, éventuellement sous forme d'un sel de métal alcalin ou de l'amide d'acide, éventuellement substitué par un ou deux radicaux alkyle comportant de 1 à 4 atomes de carbone sur l'atome d'azote amidique, dans de l'eau, un solvant organique ou leurs mélanges, avec 2 à 2,6 moles de formaldéhyde et 2 à 2,3 moles d'acide cyanhydrique liquide, à des températures de 0 à 45°C, ou avec 2 à 2,3 moles de cyanure de métal alcalin, à des températures de 40 à 100°C et on hydrolyse éventuellement les radicaux amide et les radicaux nitrile présents en présence d'un acide ou d'une base et on isole éventuellement l'acide libre ou un sel de celui-ci répondant à la formule I.
  2. Sérine-N,N-diacétonitrile servant de produit intermédiaire pour la préparation d'acide sérine-N,N-diacétique ou ses sels.
EP88105376A 1987-04-11 1988-04-02 Procédé de préparation de la N,N-dicarboxyméthyl-sérine et de ses dérivés Expired - Lifetime EP0287885B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88105376T ATE72229T1 (de) 1987-04-11 1988-04-02 Verfahren zur herstellung von serin-n,ndiessigs|ure und derivaten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873712329 DE3712329A1 (de) 1987-04-11 1987-04-11 Verfahren zur herstellung von serin-n,n-diessigsaeure und derivaten, ihre verwendung insbesondere als komplexbildner und diese enthaltende wasch- und reinigungsmittel
DE3712329 1987-04-11

Publications (2)

Publication Number Publication Date
EP0287885A1 EP0287885A1 (fr) 1988-10-26
EP0287885B1 true EP0287885B1 (fr) 1992-01-29

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Country Status (8)

Country Link
US (2) US4973730A (fr)
EP (1) EP0287885B1 (fr)
JP (1) JPS63267751A (fr)
AT (1) ATE72229T1 (fr)
AU (1) AU608592B2 (fr)
CA (1) CA1313673C (fr)
DE (2) DE3712329A1 (fr)
ES (1) ES2028924T3 (fr)

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JPH10168485A (ja) * 1996-12-13 1998-06-23 Kao Corp 高密度洗剤組成物
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JP3290382B2 (ja) 1997-07-18 2002-06-10 花王株式会社 粉末洗剤組成物
JPH11217590A (ja) * 1998-02-04 1999-08-10 Kao Corp 漂白洗浄剤組成物
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Also Published As

Publication number Publication date
US5019296A (en) 1991-05-28
AU1446388A (en) 1988-10-13
ES2028924T3 (es) 1992-07-16
ATE72229T1 (de) 1992-02-15
JPS63267751A (ja) 1988-11-04
US4973730A (en) 1990-11-27
DE3868118D1 (de) 1992-03-12
DE3712329A1 (de) 1988-10-20
EP0287885A1 (fr) 1988-10-26
AU608592B2 (en) 1991-04-11
CA1313673C (fr) 1993-02-16

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