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WO1996035662A1 - Procede de production d'acide alkylenediaminediorganique et de ses sels - Google Patents

Procede de production d'acide alkylenediaminediorganique et de ses sels Download PDF

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Publication number
WO1996035662A1
WO1996035662A1 PCT/JP1996/001223 JP9601223W WO9635662A1 WO 1996035662 A1 WO1996035662 A1 WO 1996035662A1 JP 9601223 W JP9601223 W JP 9601223W WO 9635662 A1 WO9635662 A1 WO 9635662A1
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Prior art keywords
acid
cooh
hooc
amino
comparative example
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PCT/JP1996/001223
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English (en)
Japanese (ja)
Inventor
Hiroshi Yamamoto
Satoru Koide
Yasuyuki Takayanagi
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Nitto Chemical Industry Co., Ltd.
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Publication date
Priority claimed from JP7134690A external-priority patent/JPH08301824A/ja
Priority claimed from JP7186599A external-priority patent/JPH0920737A/ja
Priority claimed from JP7186598A external-priority patent/JPH0920736A/ja
Priority claimed from JP2300096A external-priority patent/JPH09194448A/ja
Priority claimed from JP3121696A external-priority patent/JPH09183759A/ja
Application filed by Nitto Chemical Industry Co., Ltd. filed Critical Nitto Chemical Industry Co., Ltd.
Publication of WO1996035662A1 publication Critical patent/WO1996035662A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
    • 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
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters

Definitions

  • the present invention relates to a method for producing an alkylenediamine diorganic acid and a salt thereof using an amino acid as a raw material.
  • the alkylenediamine diorganic acids and salts thereof are widely used for applications such as detergent compositions, detergent builders, heavy metal sequestering agents, and peroxide stabilizers.
  • sodium tripolyphosphate has an excellent chelating ability and has been used in detergent builders, but because it contains phosphorus, its release into the environment is a contributing factor in the eutrophication of rivers and lakes. And is not currently used.
  • Zeolite is used as one of the currently used detergent builders. The chelating power is weak.In addition, since it is an inorganic substance, it does not have biodegradability.Because zeolite after use is insoluble in water, drain pipes etc. There is a problem such as sticking to.
  • chelating compounds having sufficient chelating ability include amine polycarboxylic acids, and representative examples thereof include ethylenediaminetetraacetic acid (EDTA) and nitrile triacetic acid (NTA).
  • EDTA has an extremely stable chelating power and is widely used at present.However, when released into the environment due to poor biodegradability, EDTA solubilizes heavy metals harmful to living organisms. It is feared that it will accumulate inside.
  • NTA has biodegradability, it is suspected to be teratogenic, and it has been reported that its iron complex has carcinogenic properties.
  • Ethylenediaminedisuccinic acid (EDDS) and propanediaminedisuccinic acid (PDDS) are known as amine polycarboxylic acids having both practical chelating power and biodegradability. These disuccinic compounds have two asymmetric carbon atoms and have three types of optical isomers.
  • Several methods for producing these disuccinic acid compounds have been conventionally known. For example, as a method for producing racemic ethylenediaminedisuccinic acid, a method comprising adding two molecules of maleic acid to one molecule of ethylenediamine (Zhurnal Obshchei Khini, Vol. 49, p. 659, 1978) ) It has been known.
  • One method for producing S, S-ethylenediaminedisuccinic acid which is one of the optically active substances, is a method comprising adding two molecules of S-aspartic acid to one molecule of dibromoethane ( Inorganic Chemistry, Vol. 7, pp. 2405, 1968), or a method comprising adding two molecules of S-aspartic acid to one molecule of dichloroethane (Chm. Zvest i, Vol. 20, p. 414). , 1966).
  • Racemic ethylenediaminedisuccinic acid obtained by a conventional method comprising reacting maleic acid with ethylenediamine has three types of isomers as described above.
  • the S and S isomers have excellent biodegradability, but the S and S isomers account for only 25% of the total racemate, and the R and S They are present in larger amounts than S, S-forms. If R and R are poorly biodegradable and are released in large quantities into the environment, there is a concern that heavy metals may accumulate in the environment, similar to ethylenediaminetetraacetic acid.
  • the biodegradation rate of the R and S forms is slower than that of the S and S forms, and it is difficult to say that biodegradation is easy.
  • the conventional method of adding S-aspartic acid to dibromoethane is strongly reported that the yield of S, S-ethylenediaminedisuccinic acid obtained is as low as 25%. It is hardly practical for a manufacturing method.
  • the conventional method consisting of adding S-aspartic acid to dichloroethane is less reactive than the above-mentioned method using dibromoethane, and only traces of the desired S, S-ethylenediaminedisuccinic acid can be obtained.
  • the present invention provides an industrially advantageous method for producing an optically active substance, for example, an alkylenediamine diorganic acid such as S, S-ethylenediaminedisuccinic acid and S, S-propanediaminedisuccinic acid. More specifically, an object is to produce an alkylenediamine diorganic acid with high yield and high purity using an amino acid or the like as a raw material.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems.
  • the present invention relates to a method for producing an S, S-form alkylenediamine diorganic acid and a salt thereof in high yield and high purity by using an S-form amino acid as a raw material.
  • the present invention relates to a method for producing a Schiff base by condensing a compound having an aldehyde group on two amino acids or an acetal derivative thereof under an alkaline condition in the presence of a specific organic solvent, and then forming a metal hydride or a catalyst.
  • the present invention relates to a method for producing an S, S-form alkylenediamine diorganic acid and a salt thereof by catalytic hydrogenation in the presence of a compound (hereinafter referred to as a first method)
  • the present invention relates to an S, S-alkylenediamine diorganic acid, which is obtained by reacting two molecules of an amino acid with a dihaloalkane derivative or epichlorohydrin in the presence of an organic solvent under alkaline conditions in the presence of a metal ion.
  • the present invention relates to a method for producing a salt. (Hereinafter, this method is called the second method.)
  • the organic acid is selected from the group consisting of amino acids and derivatives thereof, and taurine and derivatives thereof.
  • the amino acid that can be used in the present invention may be in any form, such as solid amino acid or its metal salt or an aqueous solution of metal salt, as long as it can be used industrially.
  • a solid amino acid or an alkali metal salt thereof When a solid amino acid or an alkali metal salt thereof is used, its purity is 70% or more, preferably 95%.
  • an aqueous solution When an aqueous solution is used, an aqueous solution of an alkali metal S-aspartate is preferably used in order to more efficiently perform a force reaction operation.
  • the concentration of the aqueous solution of the alkali metal S-aspartate that can be used in the reaction step is 50 to 300 g ZL, preferably 100 to 260 g ZL in terms of acid.
  • the alkali metal salt may be any of a lithium salt, a sodium salt, a potassium salt, and a rubidium salt. Industrially, sodium salts or potassium salts are used. Preferably, a sodium salt is used.
  • Organic acids are glycine, N-methyldaricin, taurine, N-methyltaurine, taurine-N-acetic acid, S-aspartic acid, N-methyl-S-aspartic acid, N-methyl-S-glutamic acid, S-aspartic acid 1-N-acetic acid, S-glutamic acid 1-N-acetic acid, 1-amino-1,2,3-propanetricarboxylic acid, 2-amino-1,2,3-propanetricarboxylic acid, N-methyl_1 —Amino-1,2,3-propanetricarboxylic acid and N-methyl-1-amino-1,2,3-propanetricarboxylic acid.
  • Amino acids and their derivatives include glycine, N-methylglycine, S-aspartic acid, N-methyl-S-aspartic acid, N-methyl-S-glutamic acid, S-aspartic acid-N-acetic acid, and S-glutamic acid-N- —Acetic acid, 1-amino-1,2,3-propanetricarboxylic acid, 2-amino-1,2,3-prono. Carboxylic acid, N-methyl-1-amino-1,2,3-propanetricarboxylic acid and N-methyl-1-amino-1,2,3-propanetricarboxylic acid.
  • Examples of the compound having an aldehyde group used in the first method of the present invention include glioxal, chloroacetaldehyde, acrolein, methacrolein and the like. Further, acetal derivatives of the above compounds having an aldehyde group can also be used. As the compound having an aldehyde group, any of industrially available forms can be used. From the viewpoint of handling, the above compound or an aqueous solution thereof having a purity of 20 to 100% by weight is used.
  • an aqueous solution of glyoxal When an aqueous solution of glyoxal is used as the compound having an aldehyde group, its concentration is from 20 to 50% by weight, preferably from 35 to 40% by weight. H is adjusted to 1-4, preferably 2-3. When an aqueous solution of acrolein or methacrolein is used, its concentration is 20 to 100% by weight, preferably 80 to 90% by weight. In the case of an aqueous solution of gloroacetaldehyde, the concentration is 20 to 100% by weight, preferably 40 to 60% by weight. When an aqueous solution of an acetal derivative of chloroacetaldehyde is used, the concentration is 8%. It is at least 0% by weight, preferably at least 95% by weight. As the type of acetal, dimethyl acetal, dimethyl acetal, and ethylene acetal, which can be easily adjusted and have a certain level of water solubility, are preferable.
  • a Schiff base for condensing two molecules of an amino acid or the like with one molecule of the compound having an aldehyde group under neutral to alkaline conditions is used.
  • a production step a Schiff base reduction step in which the reaction product, a Schiff base, is reduced by catalytic hydrogenation in the presence of a metal hydride or a catalyst, and an S, S form obtained through the reduction step. It comprises a purification step of separating and purifying alkylenediamine dicarboxylic acid and its salt.
  • one molecule of chloroacetaldehyde is subjected to nucleophilic addition to the amino group of one molecule of amino acid (such as S-aspartic acid) under alkaline conditions to give 2-oxoethylamino acid.
  • the Schiff base which is the reaction product, is reduced to form an alkali metal salt of ethylenediamine diorganic acid (S, S-ethylenediamindisuccinic acid). It comprises a purification step of separating and purifying the S-form diamine-type biodegradable chelating agent and its salt.
  • the nucleophilic addition step and the Schiff base group generation step may be performed continuously or stepwise.
  • the amount of the amino acid used in the nucleophilic addition step is in the range of 1.8 to 2.6 times, preferably 1.9 to 2.2 times, the mole of chloroacetoaldehyde or its acetal derivative. This amount is used in order to carry out the subsequent step of generating a Schiff base continuously, so that about twice the molar amount of the amino acid with respect to chloroacetaldehyde or its acetal derivative is previously present.
  • 0.8 to 6 times, preferably 0.9 to 1 mol, of chloroacetaldehyde or an acetal derivative thereof is used. It is desirable to use twice the molar amount of the amino acid.
  • the compound having an aldehyde group is acrolein or methacrolein
  • one molecule of acrolein or methacrolein is converted to one molecule of amino acid (S-aspartic acid).
  • Conjugate addition to the amino group of the above) under the conditions of the ionic force to produce 3-oxopropylamino acid, and the aldehyde group of the reaction product, 2-oxopropylamino acid Furthermore, a Schiff base generation step of dehydrating and condensing the amino group of one molecule of amino acid (such as S-aspartic acid), and a Schiff base reduction in which the reaction product is reduced by catalytic hydrogenation in the presence of a metal hydride or a catalyst And a purification step of separating and purifying the diamine-type biodegradable chelating agent and its salt obtained through the reduction step.
  • the conjugate addition step and the Schiff base generation step may be performed continuously or stepwise.
  • the amount of the amino acid used in the conjugate addition step is in the range of 1.8 to 2.6 moles, preferably 1.9 to 2.2 moles, relative to acrolein or methacrolein. This amount is used in order to carry out the subsequent step of generating a Schiff base continuously, so that about twice the amount of amino acid relative to acrolein or methacrolein is previously present.
  • the subsequent step of generating a Schiff base is carried out stepwise, 0.8 to 1.6 times the amount of acrolein or methacrolein, preferably 0.9 to 1.2 times the molar amount of acrolein or methacrolein. It is desirable to use amino acids.
  • the pH in the Schiff base generation step is set to be neutral to weakly alkaline by adding an alkali metal hydroxide or an aqueous solution thereof.
  • an alkali metal hydroxide or an aqueous solution thereof Lithium, sodium and potassium are used as the alkali metal, and potassium and sodium are preferably used.
  • an amino acid alkali metal salt or an aqueous solution thereof may be used.
  • the setting pH in the Schiff base generation step is appropriately selected in the range of 5 to 13, preferably 9 to 12. If the pH is more than 13, coloring due to decomposition of the compound having an aldehyde group is remarkable, while if the pH is less than 5, amino acid solubility is reduced, so that generation of Schiff bases does not proceed smoothly. .
  • the advantage of this method is that the amino acid present in the reaction solution at a high concentration has a strong buffering action, so that it is kept almost constant during the pH step once set.
  • the initial pH in the nucleophilic addition step is set to neutral to weak alkaline by adding an alkali metal hydroxide or an aqueous solution thereof.
  • an alkali metal hydroxide or an aqueous solution thereof Lithium, sodium and potassium are used as alkali metals. Preferably, potassium and sodium are used.
  • an amino acid alkali metal salt or an aqueous solution thereof may be used.
  • a method of dropping chloroacetaldehyde or an acetal derivative thereof into an aqueous solution of an amino acid at a rate that does not accumulate in the reaction solution is most commonly employed. You. A method is also possible in which an alkaline aqueous solution of an amino acid is added dropwise to an aqueous solution of chloroacetoaldehyde or an aqueous suspension of chloroacetaldehyde acetal. The temperature of the reaction solution at the time of dropping is 0 to
  • the temperature is 60 ° C, preferably 0 to 50 ° C. A sharp rise in temperature during the dropping causes a significant coloration of the reaction solution, which greatly reduces the reaction yield of the desired 2-oxoethylamino acid.
  • the pH in the nucleophilic addition step ranges from 7 to 13, preferably from 8 to 12. If 11 exceeds 13, chloroacetaldehyde or its acetal derivative will be significantly decomposed, and if pH is less than 7, reactivity will be significantly reduced.
  • the pH is usually set at the same time as the dropwise addition of chloroacetaldehyde or an acetal derivative thereof, and simultaneously with the addition of an equimolar 20 to 50% by weight aqueous solution of an alkali metal hydroxide. At this time, the same alkali metal hydroxide used for setting the initial pH in the nucleophilic addition step is selected.
  • the dropping and aging temperature in the nucleophilic addition step is 10 to 100 ° C, preferably 40 to 100 ° C.
  • the dropping time is in the range of 1 to 24 hours, preferably 1 to 4 hours, and the aging time is in the range of 1 to 5 hours, preferably 1 to 3 hours.
  • chloroacetaldehyde is used in the nucleophilic addition step
  • 2-oxoethyl amino acid is directly produced.
  • 2-oxoethyl amino acid is first produced by deacetalizing the addition product.
  • the deacetalization step required when using an acetal of chloroacetaldehyde can usually be carried out continuously only by changing the reaction solution PH after the nucleophilic addition step.
  • the pH in the deacetalization step is in the range of 2 to 6, preferably 2.5 to 5.5.
  • an aqueous solution of 10 to 100% by weight, preferably 20 to 60% by weight of sulfuric acid is used.
  • the forming temperature is in the range of 10 to 100 ° C, preferably 40 to 70 ° C.
  • the aging time is in the range of 1 to 5 hours, preferably 1 to 3 hours.
  • the deacetalization step if the pH value of the reaction solution after aging is readjusted to the pH value immediately after the nucleophilic addition step, it is possible to shift to the next step, the Schiff base generation step. At this time, the same 20 to 50% by weight aqueous solution of an alkali metal hydroxide used for setting the initial pH in the nucleophilic addition step is used for readjustment of pH.
  • the Schiff base generation step in the present invention is advantageously carried out continuously from the nucleophilic addition step or the deacetalization step which is the preceding step.
  • nucleophilic addition step and the deacetalization step when chloroacetaldehyde or an acetal derivative thereof is reacted in the presence of about twice the molar amount of an amino acid, one more amino acid is produced after the formation of 2-year-old oxoethylamino acid. Dehydration condensation produces a Schiff base.
  • nucleophilic addition proceeds irreversibly while the Schiff base formation is reversible, so even if the Schiff base generation might precede the nucleophilic addition, The ability of oxoethyl amino acid to generate Schiff bases.
  • the pH is in the range of 7 to 13, preferably 8 to 12.
  • the ripening temperature ranges from 0 to 60 ° C, preferably from 0 to 50 ° C.
  • the aging time ranges from 0 to 24 hours, preferably from 0 to 4 hours.
  • the amount of the amino acid added stepwise is 0.8 to 1.6 times mol, preferably 0.9 to 1.2 times mol based on chloroacetaldehyde or its acetal used in the nucleophilic addition step. It is. In this case, it is preferable to use an alkali metal salt of an amino acid in the range of pH 7 to 13 and preferably pH 8 to 12 in order to suppress a rapid change in pH of the reaction solution.
  • the aging time is in the range of 2 to 24 hours, preferably 1 to 4 hours.
  • the two-stage stepwise implementation is disadvantageous from the viewpoint of the complexity of the process and the length of aging time, but it is not suitable for isolating 2-year-old oxoethylamino acid or its alkali metal salt. Adopted accordingly.
  • the pH in the conjugate addition step is set to be neutral to weakly alkaline by adding an alkali metal hydroxide or an aqueous solution thereof.
  • the alkali metal sodium Na and K are used, and preferably Na is used.
  • an alkali metal salt of an amino acid or an aqueous solution thereof may be used.
  • the set pH in the conjugate addition step is in the range of 7 to 13, preferably 8 to 12. If the pH exceeds 13, coloring due to polymerization degradation of acrolein is remarkable.On the other hand, if the pH is less than 7, the production of 3-oxopropylamino acid does not proceed smoothly due to a decrease in reactivity. As a result, the compound having an aldehyde group is decomposed by polymerization.
  • the setting pH in the conjugate addition step is a very important factor, but the advantage of this method is that it was set once because of the strong buffering action of amino acids present in high concentrations in the reaction solution. The pH value is kept almost constant during the process.
  • a method of dropping acrolein or methacrolein into an alkaline aqueous solution of amino acid at a rate that does not accumulate in the reaction solution is most commonly used Is done.
  • a method of dropping an alkaline aqueous solution of an amino acid into an aqueous solution of acrolein or methacrolein is also possible, but the polymerization decomposition of acrolein, which is present in a large excess in the reaction solution, may unnecessarily occur during the dropping. In the case of misalignment, heat is generated at the time of dropping.
  • the temperature of the reaction solution at the time of dropping 0 ⁇ 6 0 D C, preferably in the range of 0 ⁇ 5 0 ° C.
  • the rapid rise in temperature during the dropping causes a significant coloration of the reaction solution, and the reaction yield of the desired 3-oxopropylamino acid in the conjugate addition step is greatly reduced.
  • the ripening temperature in the conjugate addition step is in the range of 0 to 60 ° C, preferably 0 to 50 ° C.
  • the aging time is in the range of 1 to 24 hours, preferably 1 to 4 hours. Attaching a cooling pipe to the reactor through dripping and maturation in the conjugate addition step to prevent loss due to vaporization of acrolein or methacolein is necessary from the viewpoint of safety in order to make the reaction proceed efficiently. preferable.
  • the step of generating a Schiff base in the present invention is carried out continuously from the conjugate addition step which is the preceding step. That is, in the conjugate addition step, when acrolein or methacrolein is reacted in the presence of about twice the molar amount of amino acid, 3-oxo is obtained. Following the formation of the propyl amino acid, another molecule of the amino acid is dehydrated and condensed to form a Schiff base. In this continuous process, conjugate addition proceeds irreversibly, whereas Schiff base formation is reversible, so even if Schiff base formation might precede conjugate addition, 3- The ability of xopropylamino acid to generate Schiff bases.
  • the pH is in the range of 7 to 13, preferably 8 to 12.
  • the ripening temperature ranges from 0 to 60 ° C, preferably from 0 to 50 ° C.
  • the aging time is in the range of 0 to 24 hours, preferably 0 to 4 hours.
  • the amount of the amino acid added stepwise is 0.8 to 1.6 times, preferably 0.9 to 1.2 times, the mole of acrolein or methacrolein.
  • an amino acid alkali metal salt in the range of pH 7 to 13 and preferably pH 8 to 12 in order to suppress a rapid change in pH of the reaction solution.
  • the aging time is in the range of 2 to 24 hours, preferably 1 to 4 hours.
  • the two-stage stepwise operation is disadvantageous from the viewpoint of the complexity of the process and the length of the aging time, but it is desirable to isolate 3-oxopropylamino acid or its metal salt. Is adopted according to the purpose.
  • the above-described nucleophilic addition step is unnecessary, and the thick base generating step can be directly performed to synthesize an ethylenediamine-type chelating agent.
  • a method of dropping glyoxal into a neutral to alkaline aqueous solution of amino acid and a method of dropping a neutral to alkaline aqueous solution of amino acid into glyoxal
  • the method is adopted, but in each case, heat is generated at the time of dropping.
  • the temperature of the reaction solution at the time of dropping 0 ⁇ 5 0 ° C, preferably 0 to 3 0 D C, more preferably it is desirable that the control in the range of 0 to 1 0 ° C.
  • the rapid rise in temperature during dropping causes the reaction solution to be markedly colored, which may cause the This causes a serious decrease in yield.
  • the hydrogenation reaction carried out in the Schiff base reduction step in the present invention is carried out by a catalytic hydrogenation reaction using a catalyst or a reduction reaction with a metal hydride.
  • a heterogeneous catalyst of a heavy metal such as Nigel, palladium, rhodium, ruthenium, or platinum is used.
  • nickel is the best in terms of reactivity and availability of raw materials, and is used as Raney Ni.
  • P d- (:, R h- C, R h - A 1 2 0 3, as such P t 0 2, recovery and reuse It is desirable to do.
  • the amount of the catalyst used in the catalytic hydrogenation reaction in the Schiff base reduction step is 1 to 30 mol%, preferably 5 to 10 mol%, based on the compound having an aldehyde group used in the Schiff base generation step. is there.
  • the catalytic hydrogenation reaction in the Schiff base reduction step is started by adding a catalyst directly to the reaction product after the Schiff base generation step and stirring vigorously under a hydrogen atmosphere.
  • the hydrogen pressure ranges from 0 to 100 atm, preferably from 20 to 50 atm.
  • the reaction temperature in the catalytic hydrogenation reaction in the Schiff base reduction step is in the range of 20 to 100 ° C, preferably 40 to 70 ° C.
  • the aging time ranges from 1 to 24 hours, preferably from 2 to 5 hours.
  • the used catalyst is quickly filtered by gradient filtration after standing sedimentation or by filtration using a filtering agent such as celite. The separated catalyst is washed and activated. The power to be recycled ⁇ desirable.
  • the filtrate obtained is a colorless or slightly brownish, slightly viscous, transparent liquid that can be used directly in the subsequent evaporation to dryness or acid precipitation crystallization steps.
  • the catalytic hydrogenation reaction is carried out in the Schiff base reduction step, and when the reaction yield is high, the desired alkali metal salt of alkylenediamine diorganic acid can be directly obtained when the reaction yield is high.
  • the purpose is to obtain.
  • the evaporating and drying step of the present invention is obtained by subjecting a slurry obtained by heating and concentrating the reaction product after the Schiff base reduction step by catalytic hydrogenation reaction to powder crystallization by a spray drying method. At that time, prior to heat concentration, an aqueous solution of alkali metal hydroxide is added to the reaction product after the Schiff base reduction step, and the pH is adjusted appropriately. Thereby, 2 to 4 alkali metal salts of alkylenediamine diorganic acids can be produced.
  • Examples of the metal hydride used in the Schiff base reduction step include NaBH 3 CN, Na BH 4 , and NaH 2 PO 2 , and the set pH at the time of the reaction is different.
  • the set pH is 5 to 12, preferably 5 to 7.
  • the set pH is 9 to 13, preferably 10 to 12.
  • setting the pH 8 to 1 preferably 1 0 to 1 2.
  • the reaction temperature in the Schiff base reduction step using a metal hydride is in the range of 0 to 100 ° C, preferably 20 to 50 ° C.
  • the aging time ranges from 1 to 36 hours, preferably from 4 to 8 hours.
  • the resulting reaction solution is a yellow-brown or brown-colored liquid, and is used directly in the subsequent acid precipitation crystallization step.
  • the acid precipitation crystallization step in the present invention is achieved by adding a mineral acid to the reaction solution obtained after the Schiff base reduction step.
  • the mineral acid used include sulfuric acid, hydrochloric acid, and nitric acid.
  • sulfuric acid is preferably used.
  • the sulfuric acid is selected from industrially available ones having a purity of 60 to 98%, and the reaction solution obtained by the hydrolysis step is subjected to PH I. 0 to 3.0, preferably 1.5 to 2.5.
  • the required amount to adjust the volume is used.
  • the temperature at the time of dropping sulfuric acid is in the range of 10 to 100 ° C, preferably 40 to 80 ° C, and the dropping time is in the range of 0.5 to 3 hours, preferably 1 to 2 hours.
  • the alkylenediamine diorganic acid which is the target substance, is obtained by aging the reaction product after addition of sulfuric acid at 0 to 50 ° C, preferably 10 to 40 ° C, for 0 to 72 hours, preferably 1 to 5 hours.
  • the obtained crystals are obtained by suction filtration or centrifugal filtration.
  • the target crystals obtained are usually mother liquors containing a trace amount of sulfate attached to the crystal surface. If the catalytic hydrogenation reaction is used in the Schiff base reduction step, which is sufficiently pure without recrystallization except for washing with a small amount of water, it is particularly advantageous in the acid precipitation crystallization step. This means that by-products other than sodium sulfate generated by the neutralization reaction are not generated, which is a very advantageous process when considering waste liquid treatment in industrial production.
  • dihaloalkanes and derivatives thereof that can be used in the method of the present invention include dichloroethane, dichloropropane, 2,3-dichlorosuccinic acid, dimethyl 2,3-dichlorosuccinate, 2,3-dichloropropionic acid, Dimethyl 2,3-dichloropropionate, 2,3-Dichloropropionitrile, 2,4-Dichloroglutaric acid, 2,4-Methyl dichloroglutanolate, Dibromoethane, Dibromopropane, 2,3-Dibromosuccinic acid , 2,3-Dimethyl succinate, 2,3-Dibromopropionic acid, 2,3-Dimethyl dimethyl dibromopropionate, 2,3-Dibromopropionitrile, 2,4-Dibromoglutaric acid, 2,4 — And methyl dipromoglutarate.
  • Dihalothane and the like are used as raw materials having excellent availability, and 2,3-dihalosuccinic acid and the like are used as raw materials for imparting excellent chelating power to the intended alkylenediamine diorganic acid. Further, the diclo-mouth is preferred from the viewpoint of the ability to use both the dichloro-form and the dibromo-form, availability of raw materials, and wastewater treatment.
  • the dibromo compound has excellent reactivity, and it requires special care, such as strong toxicity, which has advantages such as not necessarily requiring the addition of an organic solvent in the reaction process.
  • epichlorohydrin can also be used to link two organic acids.
  • Epichlorohydrin is a raw material with excellent availability and reactivity.
  • the amount of the dihaloalkane, its derivative or epichlorohydrin used in the method of the present invention is preferably 0.5 to 10 times mol per mol of an organic acid such as an amino acid. Is 1 to 5 moles. In particular, it is excellent in reactivity, and it is desirable for the addition method to gradually add dropwise into the reaction system. When using dichloroethane, dichloropropane, etc., it is possible to use a large excess in order to improve the reaction rate. After the reaction is completed, unreacted dihaloalkane is recovered by distillation, two-phase separation, etc. It is possible to use.
  • the pH at the start of the reaction is adjusted by adding an alkali metal hydroxide or an aqueous solution thereof.
  • alkali metal hydroxide used include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and the like. Of these, sodium hydroxide or potassium hydroxide is used industrially, and preferably sodium hydroxide is used.
  • the alkali metal hydroxide of the alkali metal used for adjusting the pH and the alkali metal of the alkali metal salt of the organic acid should be the same. Is preferred.
  • organic solvent used in the method of the present invention examples include ethylene glycol, ethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, diethylene glycol monoalkyl ethers, and triethanolamine.
  • ethylene glycol, diethylene glycol, and triethylene glycol are used.
  • the effect of the organic solvent used in the present invention is as follows: dihalothane, dichloropropane, dimethyl 2,3 dihalosuccinate, dimethyl 2,3-dihalopropionate, 2,3-dihalopropionitrile, 2,4-dihaloglutaric acid, 2,3 —
  • dihalothane dichloropropane
  • dimethyl 2,3 dihalosuccinate dimethyl 2,3-dihalopropionate
  • 2,3-dihalopropionitrile 2,4-dihaloglutaric acid
  • 2,3 This is particularly noticeable when a non-polar dihaloalkane derivative such as dimethyl dihaloglutarate is used, and the reaction rate is greatly improved.
  • the dihaloalkane derivative has an ester group or a nitrile group, these groups give a carboxyl group by being finally hydrolyzed in the reaction.
  • the amount of the organic solvent used is 5 to 40 volumes based on the aqueous solution of the alkali metal salt of the organic acid.
  • the pH of the reaction step in the method using a dihaloalkane, a derivative thereof or epichlorohydrin is in the range of 9 to 12, preferably in the range of 9.5 to 11.5. Tight control of the pH in the reaction process is crucial in terms of maintaining an adequate reaction rate and preventing unnecessary hydrolysis of dihaloalkane, its derivatives or epichlorohydrin.
  • Reaction temperatures range from 50 to 160 ° C. It is usually carried out at 110 ° C or less at normal pressure. Reaction times range from 2 to 40 hours, preferably from 4 to 16 hours.
  • As the reaction vessel an atmospheric pressure reaction vessel or a pressurized reaction vessel is selected according to the boiling point of the dihaloalkane derivative or the like to be used.
  • the amount of dihaloalkane or the like can be reduced.
  • 0.1 to 10% by volume and 0.5 to 5.0% by volume of an organic solvent are added to an aqueous alkali solution of L-aspartic acid to perform a pressurized reaction, thereby reducing the amount of dihalothane used. It can be reduced to 0.5 to 2.0 times mol, preferably 0.5 to 0.6 times mol, per 1 mol of L-aspartic acid.
  • the amount of residual dichloromethane at the end of the reaction is a trace amount, it can be completely removed by a simple drainage treatment such as degassing.
  • the metal ions used in the method of the present invention are Fe (II), Fe (III), Cu (II), Zn (II), Ni (II), Co (II), Mn (II), A 1 (III) ⁇ selected from heavy metals such as C d (II) and alkaline earth metals such as Mg (II), Ca (II) and Ba (II).
  • the chelate stability constant of the desired alkylenediamine diorganic acid varies depending on the compound, and generally tends to be larger for heavy metals and smaller for alkaline earth metals.
  • an alkylene diorganic acid crystal is obtained by acid precipitation crystallization after completion of the reaction, it is preferable to use an alkaline earth metal which is easy to decompose the complex.
  • the metal ion used in the method of the present invention has an important meaning that the target alkylenediamine diorganic acid, which accumulates in the system as the reaction proceeds, is protected as a stable metal complex from side reactions.
  • the target propanediamine-N, N-disuccinic acid reacts with another molecule of dichloropropane, and 3 -Hydroquinpropylpropanediamine-N, N-disuccinic acid It will be a by-product.
  • the effect of addition of the metal ion used in the method of the present invention is as follows: N-methylglycine, N-methyltaurine, N-methyl-S-aspartic acid, N-methyl-S-glutamic acid, S-aspartic acid-N-monoacetic acid Amino acids or organic acids having a monosubstituted amino group such as S-glutamic acid-N-monoacetic acid, aspartic acid-N-acetic acid, and organic acids; N-methyl-11-amino-1,2,3-propanetricarboxylic acid; Glycine, taurine, S-aspartic acid, S-glutamic acid, 1-amino-1,3-amino-1,2-amino-1,2-amino-1,2-amino-1,2,3-propanetricarboxylic acid, etc.
  • a raw material is an amino acid or organic acid having an unsubstituted amino group, such as 2,3-propanetricarboxylic acid or 2-amino-1,2,3-propanetricarboxylic acid
  • a raw material is an amino acid or organic acid having an unsubstituted amino group, such as 2,3-propanetricarboxylic acid or 2-amino-1,2,3-propanetricarboxylic acid
  • the reaction is carried out by the method of the present invention in the absence of metal ions, for example, when producing S, S-ethylenediaminedisuccinic acid, N-2-hydroxysethyl-1-S, S-ethylenediaminedisuccinic acid is produced as a by-product Is produced in large quantities, and the yield of the desired S, S-ethylenediaminedisuccinic acid is reduced.
  • N-2-hydroxyethyl mono-S, S-ethylenediaminedisuccinic acid can be obtained by adding dihaloethane to S, S-ethylenediaminedisuccinic acid once formed, or by dihaloethane to the raw material aspartic acid. It is by-produced through two reaction pathways, the pathway formed by the reaction of N-2-hydroxyethyl-1-s-aspartic acid and dihalothane, which are formed by addition.
  • N-2-hydroxyethyl monosulfonate is added to the main route of the reaction step of the present invention, i.e., the dihaloethane is added to S, S-ethylenediaminedisuccinic acid.
  • S-Ethylenediaminedisuccinic acid can be greatly reduced.
  • a method is used in which metal ions are added to the reaction solution as various metal salts.
  • the type of metal salt is selected from hydroxides, sulfates, hydrochlorides, nitrates, acetates, carbonates and the like, preferably hydroxides or sulfates, more preferably hydroxides. .
  • the metal ions may be added at the same time at the start of the reaction or may be added gradually as the reaction proceeds.
  • the reaction solution is treated with a mineral acid, Alkylenediamine diorganic acid can be obtained.
  • the metal ion used in the reaction must be removed after the reaction and prior to the acid precipitation step.
  • heavy metal ions are used as metal ions, it is necessary to remove and collect the metal ions from the viewpoint of preventing pollution.
  • a metal ion suitable for the target metal salt is selected, and after the reaction is completed, the reaction solution is concentrated to obtain the target metal salt.
  • the alkaline earth metal when used, the alkaline earth metal is easily desorbed from the alkylenediamine diorganic acid complex under acidic conditions, so that the alkaline earth metal is directly removed without previously removing the metal removal ion.
  • An acid precipitation step can be performed.
  • a mineral acid is used.
  • the mineral acids used include sulfuric acid, hydrochloric acid, nitric acid and the like.
  • sulfuric acid is used.
  • the concentration of sulfuric acid may be any commercially available concentration of 60 to 98%.
  • the pH of the solution is adjusted to a range of 1.0 to 3.0, preferably to a range of 1.5 to 2.5, and the temperature at the time of adding the mineral acid is 40 to 80 °. C range.
  • the addition time of the mineral acid is preferably 1-2 hours.
  • the acid precipitation step after addition of the mineral acid, after aging for 0 to 72 hours, preferably for 1 to 5 hours in the range of 0 to 50 ° C, preferably 10 to 40 ° C, It can be obtained by a crystal separation operation such as suction filtration or centrifugal separation.
  • the separated crystals are high-purity crystals that do not require any special treatment, so they are washed with a small amount of water, and then dried by warm air drying or the like to obtain high-purity alkylene diamine.
  • Organic acids can be obtained.
  • a metal ion suitable for the target metal salt is selected, and after the reaction is completed, the reaction solution is concentrated to obtain the target metal salt.
  • a 50% by weight aqueous suspension of Raney nickel (W6, 42.0 kg, 0.37 kmol) was added to the reaction solution, and the air in the reactor was sufficiently replaced with hydrogen gas.
  • the reactor was sealed and the hydrogen pressure was reduced to 50 atm.
  • the temperature of the reaction solution was gradually raised from 25 ° C to 50 ° C over 1 hour, and then increased to 50 ° C. Intense stirring was continued for 5.5 hours. During this time, each time the hydrogen pressure dropped to 35 atm, hydrogen was replenished to 50 atm. After allowing the reaction mixture to cool to room temperature, the supernatant was poured on a suction filtration device.
  • a hydrogenation reaction was performed using Raney nickel as a catalyst in the same manner as in Example 1 to obtain a pale brown filtrate (4,023 kg).
  • Raney nickel (W6, 50% by weight suspension, 42 kg, 0.37 kmol) was added to the reaction mixture, and the air in the reactor was sufficiently replaced with hydrogen gas. The reactor was sealed and the hydrogen pressure was reduced to 50 atm. Then, under vigorous stirring, gradually raise the temperature of the reaction solution from 25 ° C to 75 ° C over 1 hour, and then continue vigorous stirring for 50 hours at 5.5 ° C for 5.5 hours. Was. During this time, every time the hydrogen pressure dropped to 75 atm, hydrogen was replenished to 100 atm.
  • Example 5 As in Example 5, a nucleophilic addition reaction and a Schiff base generation reaction were continuously performed. A suspension prepared by previously dissolving NaBHh (43 kg, 1.13 kmol) in water (400 kg) was added to this reaction mixture at a reaction temperature of 10 ° C and stirring at 0.5 ° C. Added at time. Thereafter, the temperature of the reaction solution was raised to 45 ° C, and stirring was continued for another 5.5 hours.
  • Example 6 a nucleophilic addition reaction and a Schiff base generation reaction were continuously performed.
  • N a BH 4 43kg, 1. 13kmol
  • the suspension was allowed to create pre-dissolved in water (400 kg), the reaction temperature 10 ° C, under stirring, 0.5 Added at time. Thereafter, the temperature of the reaction solution was raised to 45 ° C, and stirring was continued for another 5.5 hours.
  • Raney nickel (W6, 50% by weight suspension, 42 kg, 0.37 kmol) was added to the reaction solution, and the air in the reactor was sufficiently replaced with hydrogen gas. The reactor was then sealed and the hydrogen pressure was increased to 50 atm. Then, under vigorous stirring, the temperature of the reaction solution was gradually increased from 25 ° C to 75 ° C over 1 hour, and then vigorous stirring was continued at 50 ° C for 5.5 hours. During this time, every time the hydrogen pressure dropped to 75 atm, hydrogen was collected to 100 atm. After allowing the reaction solution to cool to room temperature and standing, the supernatant was poured on a suction filtration device, and the residue was also placed on the suction filtration device and washed with water (150 kg) to obtain a filtrate (3,690 kg).
  • the filtrate (2,897 kg) obtained by heating and concentrating the filtrate was powder-dried at 120 ° C by a spray drying method, and the sodium salt of S, S-propanediaminedisuccinic acid (1,593 kg) was dried. , 3.85 kmol, crude yield 105%) as pale brown powder crystals (melting point 200 ° C).
  • the optical purity of the produced S, S-propanediaminedisuccinic acid was over 99%.
  • the components in the crude crystal were 98.3% by weight of S, S-propanediaminedisuccinic acid in terms of acid and 1.7% by weight of S-aspartic acid in terms of 1.7 acid.
  • Example 91 Compound of Comparative Example 74
  • Example 101 The same reaction as in Example 101 was carried out except that a 30% slurry of magnesium hydroxide (730 k) was used instead of ferrous sulfate heptahydrate.
  • a 30% slurry of magnesium hydroxide (730 k) was used instead of ferrous sulfate heptahydrate.
  • sulfuric acid was added to adjust the pH to 2
  • the precipitated S, S-ethylenediaminedisuccinic acid crystals were separated by filtration, washed with water, dried with hot air at 11 ° C, and dried with S, S-ethylenediamine.
  • Disuccinic acid (980 kg) was obtained as white crystals.
  • the crystal was 100% in both chemical purity and optical purity. Table 4 shows the results.
  • Example 102 except that the addition of 30% slurry of magnesium hydroxide was omitted. The same reaction as described above was performed. Table 4 shows the results.
  • Example 101 The same reaction as in Example 101 was carried out using the equimolar metal salts shown in Table 4 in place of the magnesium hydroxide 30% slurry. Table 4 shows the results.
  • Metal ion used for the reaction
  • Reaction yield Yield of the target product, S, S-ethylenediaminedisuccinic acid
  • By-product formation rate Formation of the byproduct, N-2-hydroxyethyl-1-S, S-ethylenediaminedisuccinic acid rate
  • Example 102 The same reaction as in Example 102 was performed except that diethylene glycol was not added to the reaction solution and the temperature and pressure were changed in the pressurized reaction vessel. Table 5 shows the results. Table 5
  • Example 102 The same reaction as in Example 102 was performed except that the amounts of diethylene glycol and dichloroethane were changed as shown in Table 6. Table 6 shows the results.
  • an alkylene diamine diorganic acid having biodegradability and excellent chelating ability can be obtained in a high yield, and a detergent composition which does not adversely affect the environment. Applicable to detergent builder, heavy metal sequestrant, peroxide stabilizer, etc.

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Abstract

L'invention porte sur la production d'acide alkylènediaminédiorganique et de ses sels, consistant à faire réagir deux acides organiques choisis dans le groupe comprenant les acides aminés, leurs dérivés, la taurine et ses dérivés, ainsi qu'un composé bifonctionnel choisi dans le groupe constitué de composés d'aldéhyde, de leurs dérivés acétals, de dihaloalcanes et de leurs dérivés ainsi que d'épichlorohydrine dans des conditions alcalines.
PCT/JP1996/001223 1995-05-09 1996-05-09 Procede de production d'acide alkylenediaminediorganique et de ses sels WO1996035662A1 (fr)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
JP7/134690 1995-05-09
JP7134690A JPH08301824A (ja) 1995-05-09 1995-05-09 グリオキザールのシッフ塩基を経由した生分解性キレート剤、ｌ，ｌ−エチレンジアミンジコハク酸とそのアルカリ金属塩の製造方法
JP7186599A JPH0920737A (ja) 1995-06-30 1995-06-30 クロルアセトアルデヒドまたはそのアセタールを原料とする生分解性キレート剤、ｌ，ｌ−エチレンジアミンジコハク酸の製造方法
JP7186598A JPH0920736A (ja) 1995-06-30 1995-06-30 アクロレイン類を原料とする生分解性キレート剤、ｌ，ｌ−プロパンジアミンジコハク酸類とそのアルカリ金属塩の製造方法
JP7/186598 1995-06-30
JP7/186599 1995-06-30
JP30856295 1995-11-02
JP7/308562 1995-11-02
JP8/23000 1996-01-17
JP2300096A JPH09194448A (ja) 1996-01-17 1996-01-17 二分子のアミノ酸の連結によるジアミン型ポリアミノ酸の製造方法およびそれらを含む生分解性キレート剤
JP3121696A JPH09183759A (ja) 1995-11-02 1996-01-26 ジハロエタンを原料とするｌ，ｌ−エチレンジアミンジコハク酸の製造方法
JP8/31216 1996-01-26

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5885757A (en) * 1996-10-31 1999-03-23 Fuji Photo Film Co., Ltd. Aminopolycarboxylic acid chelating agent, heavy metal chelate compound thereof, photographic additive and processing method
CN114315621A (zh) * 2021-12-30 2022-04-12 深圳飞扬骏研新材料股份有限公司 一种脂肪族仲胺基酯树脂及其制备方法

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JPS54125621A (en) * 1978-03-20 1979-09-29 Kaken Pharmaceut Co Ltd Novel d-glutamic acid derivative, its preparation, and immunizator comprising it as active constituent
JPS6092250A (ja) * 1983-10-25 1985-05-23 Suntory Ltd Ν−置換グルタミン酸誘導体及びその製造方法
WO1995012570A2 (fr) * 1993-11-03 1995-05-11 The Associated Octel Company Limited Alkylation d'acides amines
JPH08165271A (ja) * 1994-12-12 1996-06-25 Nitto Chem Ind Co Ltd ２−ヒドロキシ−１，３−プロパンジアミンポリカルボン酸とそのアルカリ金属塩の製造法およびそれらを含む生分解性キレート剤

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JPS54125621A (en) * 1978-03-20 1979-09-29 Kaken Pharmaceut Co Ltd Novel d-glutamic acid derivative, its preparation, and immunizator comprising it as active constituent
JPS6092250A (ja) * 1983-10-25 1985-05-23 Suntory Ltd Ν−置換グルタミン酸誘導体及びその製造方法
WO1995012570A2 (fr) * 1993-11-03 1995-05-11 The Associated Octel Company Limited Alkylation d'acides amines
JPH08165271A (ja) * 1994-12-12 1996-06-25 Nitto Chem Ind Co Ltd ２−ヒドロキシ−１，３−プロパンジアミンポリカルボン酸とそのアルカリ金属塩の製造法およびそれらを含む生分解性キレート剤

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5885757A (en) * 1996-10-31 1999-03-23 Fuji Photo Film Co., Ltd. Aminopolycarboxylic acid chelating agent, heavy metal chelate compound thereof, photographic additive and processing method
US6340560B1 (en) 1996-10-31 2002-01-22 Fuji Photo Film Co., Ltd. Aminopolycarboxylic acid chelating agent, heavy metal chelate compound thereof, photographic additive and processing method
CN114315621A (zh) * 2021-12-30 2022-04-12 深圳飞扬骏研新材料股份有限公司 一种脂肪族仲胺基酯树脂及其制备方法

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