JPH05331099A - Glyceric acid derivative and its production - Google Patents

Abstract

PURPOSE:To enable industrially advantageous production of a new glyceric acid derivative which is useful as a water-soluble metal dispersant or a chelating agent by reaction of glyceric acid with a specific halogen-substituted aliphatic carboxylic acid chloride in the presence of an alkaline substance followed by salt interchange. CONSTITUTION:The reaction of glyceric acid of formula I (R<3> is H, cationic group, 1 to 5C alkyl) such as DL-glyceric acid) with a compound of formula II [A is halogen; R<1> is H, formula: COOM (M is alkali, alkaline earth metal or ammonium or 1 to 36C alkylammonium), formula: CH2COOM; is 1-20C alkylene; n is 1, 0] such as sodium monochloracetate is effected in the presence of an alkaline substance such as tetrabutylammonium bromide to give the objective glyceric acid derivative of formula III [X, Y is H, group of formula IV and group of formula V (R<2> is 2 to 3C alkylene; p is 0 to 10)].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel glyceric acid derivative and a method for producing the same, and more particularly to a glyceric acid derivative useful as a water-soluble metal dispersant and a method for producing the same. This substance is used as a chelating agent for household and industrial use.

[0002]

BACKGROUND OF THE INVENTION Chelating agents are used in various fields for the purpose of sequestering metal ions mainly by removing calcium and magnesium ions in hard water and removing their harmful poisons. ing. In the textile and dyeing industry, natural fibers are mixed with metals derived from insecticide / sterilization, and synthetic fibers are mixed with metals from equipment. Therefore, in the washing step, these metals combine with the soap and deposit in the fiber, but a chelating agent is used to prevent this. Also, in the bleaching step, bleaching is performed using hydrogen peroxide or the like, but a trace amount of metal ions (especially iron,
Copper and manganese) cause decomposition of the bleaching agent, so a chelating agent is added here as well to prevent this. Furthermore,
In the dyeing process, a trace metal that causes color change and color unevenness is trapped by a chelating agent.

In the metal / plating industry, in order to clean the metal surface, alkali cleaning is performed using a chelating agent. Also,
When dipping plating is called copper plating, the Cu (I
The use of (I) -chelating agent has the effect of binding the iron (II) ions generated by the reaction, keeping the dissolved state, and enabling fine and uniform plating. In household use, various detergents are used to remove dirt from textiles, tableware, and the body, and the surfactant acting as this reacts with calcium or magnesium in tap water to interfere with washing. So usually,
The detergent contains a builder as a chelating agent,
It effectively disperses calcium and magnesium to bring out the performance of surfactants. Further, the builder has the effect of removing calcium ions existing as a binder for fibers and stains by chelating them and improving the removal of stains.

Conventionally, sodium tripolyphosphate (STPP) and ethylenediaminetetraacetate (EDTA) have been used as these chelating agents, but STPP is in the direction of eutrophication of lake water, and EDTA is in the direction of restricted use from virulent bacteria. .. Therefore, as an alternative, organic nitrogen-containing compounds, carbonates,
There are zeolites and acrylic acid oligomers. However, each of these substances has the following problems. It is feared that nitrogen-containing compounds have poor biodegradability. Carbonates also form an insoluble precipitate of insoluble calcium carbonate. Zeolites are widely used,
It is a water-insoluble substance, and has the drawback of clogging sewers and the like if used in excess. Further, the acrylic acid oligomer has a problem of low biodegradability. Therefore, it is required to develop a chelating agent which is water-soluble, has excellent biodegradability and safety, and has high metal complex forming ability and metal dispersing ability.

[0005]

As a result of intensive studies to solve the above problems, the present inventors have found that a specific novel glyceric acid derivative can achieve the above object, and completed the present invention. .. That is, the present invention provides a glyceric acid derivative represented by the general formula (I) and a method for producing the same.

[0006]

[Chemical 8]

[Wherein M: the same or different, alkali metal, alkaline earth metal, ammonium, total carbon number 1 to 36
Shows an alkylammonium, an alkanolammonium having a total carbon number of 2 to 9, or a basic amino acid group. X, Y: Hydrogen atom, or

[0008]

[Chemical 9]

A group represented by Here, R ¹ represents a hydrogen atom or a group represented by —COOM, —CH ₂ COOM or —CH (OH) COOM, M represents the above meaning, n represents 1 or 0, and Z represents the number of carbon atoms. 1-20 linear or branched alkylene groups, or

[0010]

[Chemical 10]

A group represented by the formula (wherein R ² represents an alkylene group having 2 to 3 carbon atoms and p represents a number of 0 to 10).
However, the case where both X and Y are hydrogen atoms is excluded. The glyceric acid derivative represented by the general formula (I) provided by the present invention has the general formula (II)

[0012]

[Chemical 11]

(In the formula, R ³ represents a hydrogen atom, a cation group or an alkyl group having 1 to 5 carbon atoms.) Or its salt or its ester (hereinafter referred to as glyceric acid (II)). Is manufactured by performing any of the steps (a) to (f) below. Step (a) A step of reacting the glyceric acid (II) with the compound represented by the general formula (III) in the presence of an alkaline substance, and if necessary, salt exchange.

[0014]

[Chemical formula 12]

(In the formula, A represents a halogen atom, and R ¹ , Z
, N, M have the above-mentioned meanings. ) Step (b ) A step of reacting glyceric acid (II) with a compound represented by the general formula (IV) in the presence of a copper catalyst, then hydrolyzing the obtained product, and further performing salt exchange if necessary. ..

[0016]

[Chemical 13]

(Wherein R ¹ , Z and n have the above-mentioned meanings,
R ⁴ represents an alkyl group having 1 to 5 carbon atoms. ) Step (c) The glyceric acid (II) is reacted with the compound represented by the general formula (V) in the presence of an alkaline substance, and then the obtained product is hydrolyzed, and if necessary, salt exchange is carried out. Process. CH ₂ ═CH—Q (V) (wherein Q represents a group represented by —CN or —COOR ⁴ and R ⁴ has the above-described meaning.) Step (d) Glyceric acid (II) A step of reacting with an acid or maleic anhydride in the presence of Ca (OH) ₂ and then performing salt exchange.

Step (e) Glyceric acid (II) is reacted with a compound represented by the general formula (VI) in the presence of an acid or base catalyst, followed by hydrolysis if necessary, and salt exchange if necessary. Process.

[0019]

[Chemical 14]

(In the formula, R ³ has the above-mentioned meaning.) Step (f) An alkylene oxide having 2 to 3 carbon atoms is added to glyceric acid (II), and then the resulting product is added to the molecule. The existing hydroxymethyl group is oxidized to carboxylic acid,
If necessary, salt exchange.

The above steps (a) to (f) will be described in more detail. Step (a) a glyceric acid (II) and a compound represented by the general formula (III), an alkali metal or alkaline earth metal hydroxide,
Alkaline substances such as oxides or carbonates (NaOH, KOH,
The glyceric acid derivative represented by the general formula (I) can be obtained by reacting in the presence of (Na ₂ CO ₃ , K ₂ CO _3, etc.) and optionally salt-exchange.

Examples of the compound represented by the general formula (III) include ω-monochlorofatty acid sodium and ω-monobromofatty acid potassium. The reaction is carried out by adding an alkaline substance as an aqueous solution and dropping it into a mixture of glyceric acid (II) and a compound represented by the general formula (III) (which may contain a solvent) or by adding an alkaline substance. It can be carried out by a method of dropping an aqueous solution of a compound represented by the general formula (III) into a mixture with glyceric acid (II). If too much water stays during the dropping, the decomposition of the carboxyalkylating agent (compound represented by general formula (III)) will be promoted. Therefore, use benzene, dioxane, ethylene glycol dimethyl ether, etc. as the solvent, and mix with this. It is effective to carry out the reaction while azeotropically distilling off the existing water. In order to carry out the reaction smoothly, the reaction rate is further increased by using a phase transfer catalyst such as tetrabutylammonium salt as the catalyst. In addition, a part of the compound represented by the general formula (III) in this reaction is

[0023]

[Chemical 15]

(In the formula, R ¹ , Z and n have the above-mentioned meanings), and sodium chloride is also produced as a by-product, so it is necessary to remove them after the reaction is completed. As means for this, electrodialysis or recrystallization in a water-alcohol system can be used.

Step (b) The glyceric acid (II) and the compound represented by the general formula (IV) are reacted at 60 to 120 ° C. in the presence of copper powder to give the glyceric acid (II) and the general formula (IV). A glyceric acid derivative represented by the general formula (I) can be obtained by obtaining an adduct with the compound represented by, hydrolyzing the ester group in the adduct, and performing salt exchange if necessary. Here, as the compound represented by the general formula (IV), methyl diazoacetate, ethyl diazoacetate, methyl diazosuccinate, ethyl diazosuccinate,
Examples thereof include methyl diazomalonate and ethyl diazomalonate. In this reaction, a part of the compound represented by the general formula (IV) is

[0026]

[Chemical 16]

(Wherein R ¹ , Z and n have the above-mentioned meanings), which are esters in the adduct of the glyceric acid (II) and the compound represented by the general formula (IV). The groups can be easily removed by distillation before hydrolysis or by purification on a silica gel column.

Step (c) Glyceric acids (II) and general formula (V) are reacted by reacting glyceric acids (II) with a compound represented by general formula (V) in the presence of an alkaline substance. A glyceric acid derivative represented by the general formula (I) can be obtained by obtaining an adduct with a compound, hydrolyzing a nitrile group or an ester group in the adduct, and salt exchange if necessary.

Step (d) The glycerin represented by the general formula (I) is prepared by adding glyceric acid (II) and maleic acid or maleic anhydride under alkaline conditions with calcium hydroxide as a catalyst and salt exchange. An acid derivative is obtained. Examples of the alkaline substance that makes the reaction system alkaline include hydroxides of alkali metals or alkaline earth metals.

Step (e) Glyceric acids (II) and the compound represented by the general formula (VI) are mixed with BF ₃ .O (C ₂ H ₅ ) ₂ , p-toluenesulfonic acid (PTS) and H ₂ SO _{2. 4} , in the presence of an acidic substance such as a cation exchange resin or a basic substance such as NaOC ₂ H ₅ , NaOCH ₃ , t-C ₄ H ₉ OK, Ca (OH) ₂ or the like, and the ester group is hydrolyzed if necessary. The glyceric acid derivative represented by the general formula (I) can be obtained by decomposing and further salt exchange if necessary.

Step (f) Glyceric acids (II) are reacted with an alkylene oxide having 2 to 3 carbon atoms in the presence of an acid or a basic substance, and the hydroxymethyl group present in the molecule of the obtained product is converted into P
If O ₂ or air is blown in the presence of a noble metal catalyst such as d or Pt to oxidize at room temperature to 100 ° C. to form a —OCH ₂ COOM group (M has the above-mentioned meaning), if necessary, salt exchange may be performed to obtain the compound of the general formula ) The glyceric acid derivative represented by this is obtained.

The glyceric acid (II) used as the raw material of the present invention is produced by a conventionally known method. That is, glyceric acid can be obtained by oxidizing glycerin with nitric acid.

[0033]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 DL-glyceric acid dicarbox
Synthesis of sodium salt of cimethylated compound

[0035]

[Chemical 17]

15.6 g (0.1 m of 68% DL-glyceric acid aqueous solution)
ol), sodium monochloroacetate 209.7 g (1.8 mol),
Tetrabutylammonium bromide (TBAB) 1.6g (0.0
(05 mol), 150 g of water, and 350 g of dioxane were charged into a 2-liter four-necked flask, and the temperature was raised to 96 ° C. 150 g (1.8 mol) of 48% aqueous sodium hydroxide solution was added dropwise over 60 minutes. The temperature was maintained at the same temperature for 60 minutes, and then water and dioxane were completely distilled off. Dissolve the solid after the reaction in 300 g of water,
Add 16.7 g (0.2 mol) of 48% sodium hydroxide aqueous solution to add 2
Reflux for hours. After cooling the reaction solution to room temperature, insoluble matter was removed by filtration. Next, the pH was adjusted to 8.4 and desalting was performed by electrodialysis. Water is distilled off from the desalted solution
27.8 g was obtained. From the NMR, the OH group of the raw material was completely OCH ₂ COONa
It was confirmed that it was replaced with. Also in IR, absorption by OH stretching was not observed, and absorption by COONa was observed at 1588 cm ^-1 and absorption by -COC- (ether) at 1140 cm ^-1 . From the above, it was confirmed that the target compound was produced.

Example 2 Dicarboxyl DL-glycerate
Synthesis of sodium salt of cimethylated compound

[0038]

[Chemical 18]

68% DL-glyceric acid aqueous solution 31.2 g (0.2 mo
l), sodium hydroxide 5.0g (1.25mol), tetrabutylammonium bromide 3.2g (0.01mol), dioxane
200 g was placed in a 2-liter four-necked flask and dehydrated at 96 ° C for 2 hours. After adding 300 g of dioxane, 4
720.5 g (1.0 mol) of 0% sodium monochloroacetate aqueous solution was added dropwise over 3 hours, followed by aging for 2 hours. Dioxane and water were distilled off from the reaction solution, and water was added to the obtained white solid while stirring until the inside of the system became almost transparent. The insoluble matter was removed by filtration, the pH was adjusted to 8.5, and desalting was performed by electrodialysis. Water was distilled off from the desalted solution to obtain the target compound 46.1.
g was obtained. From NMR, it was confirmed that the OH group of the raw material was completely replaced with OCH ₂ COONa. Also in IR, absorption by OH stretching was not observed, and absorption by COONa was observed at 1589 cm ^-1 and absorption by -COC- (ether) at 1142 cm ^-1 . From the above, it was confirmed that the target compound was produced.

Example 3 Dicarboxylic acid of DL-glyceric acid
Synthesis of sodium salt of cimethylated compound

[0041]

[Chemical 19]

68% DL-glyceric acid aqueous solution 15.6 g (0.1 m
ol) was added with 100 g of ethanol and dehydrated under reduced pressure at 80 ° C. After depressurizing at 60 ° C. for 1 hour to completely remove ethanol and water, 3 g of copper powder was added and the temperature was raised to 93 ° C. Then ethyl diazoacetate was added dropwise with vigorous stirring. Ethyl diazoacetate was added dropwise while tracking the reaction by IR and GC, and it was confirmed by GC that the peak of the raw material had disappeared and absorption of OH had disappeared by IR, and the addition was completed. The amount of ethyl diazoacetate dropped is
41.2 g (0.36 mol), the dropping time was 3 hours. The reaction was cooled to 60 ° C and 200 g of ethyl acetate and 10 g of activated carbon were added
After stirring for 30 minutes, copper powder and activated carbon were removed by filtration.
After distilling off ethyl acetate with a rotary evaporator, a low boiling by-product was removed by distillation, and the product was purified by a silica gel column (eluent: chloroform to ethyl acetate) to obtain 9.7 g of a light brown oily substance. The compound obtained by IR or NMR has the formula (VII)

[0043]

[Chemical 20]

It was confirmed that・ IR analysis; C-H stretching: 2986 cm ^-1 , C = O stretching (ester): 1755 cm ^-1 , -C-O-C-stretching (ether): 1143 cm ^-1・ NMR analysis; 4.7 ppm -COOCH ₂ COO ,

[0045]

[Chemical 21]

1.3 ppm-CH ₃ 6.3 g of the obtained compound was dissolved in 50 g of ethanol, 3.3 g of sodium hydroxide and 100 g of water were added, and the ester group was hydrolyzed under reflux for 3 hours. After cooling, the reaction solution was adjusted to pH 7 and water and ethanol were distilled off. The obtained solid is
Water-methanol reprecipitation purification was repeated 3 times to obtain a light brown powder.
7.1 g was obtained. In IR, C = O Stretching disappeared and changed 15
Since absorption by -COONa was observed at 90 cm ^-1 , it was confirmed that the target compound was formed.

Example 4 DL-glyceric acid disuccinic acid
Synthesis of sodium salt of ether

[0048]

[Chemical formula 22]

68% DL-glyceric acid aqueous solution 156 g (1.0 mo
l), 132 g (3.3 mol) of sodium hydroxide, 111 g (1.5 mol) of calcium hydroxide and 600 g of water were charged in a 3 liter four-necked flask and stirred at 90 ° C. for 30 minutes. The reaction solution
Cool to 60 ° C and add 294.3 g (3.0 mol) of maleic anhydride.
It was added over 2 hours so that the temperature did not exceed 70 ° C. After the addition, the temperature was raised to 75 ° C. and aging was performed for 18 hours. After allowing the reaction solution to cool, a solution of 159 g (1.5 mol) of sodium carbonate / 300 g of water was added. After stirring at 50 ° C for 1 hour, the mixture was left to stand and precipitated Ca
CO ₃ was filtered off. After adjusting the pH to 8.6, the white solid obtained by distilling off water was dissolved in 600 g of water, and 3600 g of methanol was added to this solution for decantation. This operation was repeated twice, and the obtained white viscous material was washed with acetone and then dried to obtain 351.1 g of a white solid. Since the hydroxyl value (OHV) is 20.8, the average degree of etherification of the obtained target product is 1.9 / 2 (that is, 1.9 out of 2 hydroxyl groups).
Were etherified). 15 by IR analysis
Absorption of -COONa to 90cm ^-1 is absorption was observed by -C-O-C- (ether) to 1139cm ^-1, the resulting compound was confirmed to be the desired product.

Example 5 DL-glyceric acid diepoxy
Synthesis of sodium salt of succinic acid adduct

[0051]

[Chemical formula 23]

25.3 g of trans-epoxysuccinic acid (0.19 mo
l), ethanol 523g (11.4mol), cation exchange resin N
13 g of AFION (NR-50) was charged and esterification was carried out at 80 ° C. for 16 hours. The cation exchange resin was filtered off and ethanol was distilled off to give trans-epoxysuccinic acid ethyl ester in a yield of 9
Obtained at 2.5%. 68% glyceric acid in water in another reactor 7.
Azeotropic dehydration was performed by adding 8 g (0.05 mol) and 100 g of toluene. Make sure that the distillation of water has run out, BF ₃ · O (C
₂ H ₅ ) ₂ 0.35 g (0.0025 mol) was added, and the temperature was raised to 50 ° C. Next, 28.4 g (0.15 mol) of trans-epoxysuccinic acid ethyl ester synthesized above was added dropwise little by little. After aging at 50 ° C. for 2 hours, the solution was neutralized with a 10% Na ₂ CO ₃ aqueous solution and the solvent was distilled off. 50 g of water was added to the residue and it was added with 80 ml of diethyl ether to 2
Extract twice, wash with 5% NaCl aqueous solution 3 times, and wash the ether layer with Na.
After drying over ₂ SO ₄ , the ether was distilled off to obtain 7.2 g of a transparent oily substance. 7.2 g of the obtained compound was dissolved in 20 g of ethanol,
To this, 15 g of 48% NaOH aqueous solution was added, and hydrolysis was carried out at 82 ° C. for 5 hours. After cooling, the pH was adjusted to 9.1 and ethanol and water were distilled off. The obtained white solid was decanted three times with water-methanol, and the precipitate was washed with acetone,
After drying, 6.8 g of the desired product was obtained. COON at 1590 cm ^-1 from IR analysis
The absorption of -a-C-O-C- (ether) was observed at 1134 cm ^-1 , and it was confirmed that the obtained compound was the target compound.

Test Example The Ca ion scavenging ability of the compounds obtained in Examples 1 and 3 and
The Ca ion stability constant pKCa ²⁺ was investigated by the method shown below. For comparison, Ca ion trapping ability and Ca ion stability constant pK Ca ²⁺ were similarly investigated for citric acid and zeolite which have been conventionally used as chelating agents. The results are shown in Table 2.

Method for measuring the ability to capture calcium ions
And chelate stability constant measurement methods All solutions were prepared using the following buffer solutions. _{Buffer; 0.1M NH 4 Cl-NH 4} OH buffer (pH 10) (1) Creating a calibration curve standard calcium ion solution to create a calibration curve showing the relationship between the logarithm and the potential of the calcium ion concentration such shown in FIG. 1 To create.

(2) Measurement of calcium ion-capturing ability A sample of 0.1 g is weighed in a 100 ml volumetric flask, and the volume is adjusted with the above buffer solution. To this, a CaCl ₂ solution (pH 10) equivalent to 20,000 ppm (calculated as CaCO ₃ ) is dropped from a buret (a blank is also measured). CaCl ₂ solution is added dropwise.
Add 0.1 to 0.2 ml each, read the potential at that time, and find the calcium ion concentration from the calibration curve in FIG.
The calcium ion concentration at the dropping amount A of the CaCl ₂ solution in FIG. 2 is the calcium ion trapping ability of the sample.

(3) Calculation of stability constant of calcium ion chelate Stability constant of calcium ion chelate (pK Ca ²⁺ ) is Ca
^Use the result of ²⁺ capture ability measurement. It is calculated as forming a 1: 1 complex when equimolar calcium is added to the sample. The stability constant of the complex can be calculated according to the following formula.

[0057]

[Equation 1]

[0058]

[Table 2]

[0059]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel glyceric acid derivative which is excellent in water solubility, biodegradability and dispersibility and which is useful as an unprecedented epoch-making chelating agent.

[Brief description of drawings]

FIG. 1 is a calibration curve showing the relationship between the logarithm of calcium ion concentration and the potential.

[Fig. 2] CaCl when measuring calcium ion-capturing ability
₂ is a graph showing the relationship between the dropping amount of _two solutions and the calcium ion concentration.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 12, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction content]

(In the formula, R ¹ , Z and n have the above-mentioned meanings), and sodium chloride is also produced as a by-product . these
If necessary to remove , electrodialysis or recrystallization in a water-alcohol system can be used as a means for removal .

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

(In the formula, R ¹ , Z and n have the above-mentioned meanings), but if these need to be removed,
Before hydrolysis of the ester group in the adduct of the glyceric acid (II) and the compound represented by the general formula (IV), it can be easily removed by distillation or by purification with a silica gel column.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

68% DL-glyceric acid aqueous solution 156 g (1.0 mo
l), 172 g ( 4.3 mol) of sodium hydroxide, 111 g (1.5 mol) of calcium hydroxide and 600 g of water were charged into a 3 liter four-necked flask and stirred at 90 ° C. for 30 minutes. The reaction solution
Cool to 60 ° C and add 294.3 g (3.0 mol) of maleic anhydride.
It was added over 2 hours so that the temperature did not exceed 70 ° C. After the addition, the temperature was raised to 75 ° C. and aging was performed for 18 hours. After allowing the reaction solution to cool, a solution of 159 g (1.5 mol) of sodium carbonate / 300 g of water was added. After stirring at 50 ° C for 1 hour, the mixture was left to stand and precipitated Ca
CO ₃ was filtered off. After adjusting the pH to 8.6, the white solid obtained by distilling off water was dissolved in 600 g of water, and 3600 g of methanol was added to this solution for decantation. This operation was repeated twice, and the obtained white viscous material was washed with acetone and then dried to obtain 351.1 g of a white solid. Since the hydroxyl value (OHV) is 20.8, the average degree of etherification of the obtained target product is 1.9 / 2 (that is, 1.9 out of 2 hydroxyl groups).
Were etherified). 15 by IR analysis
Absorption of -COONa to 90cm ^-1 is absorption was observed by -C-O-C- (ether) to 1139cm ^-1, the resulting compound was confirmed to be the desired product.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location B01J 31/12 C07C 51/41 59/10 8827-4H 59/125 Z 8827-4H 59/235 8827 -4H C09K 3/00 108 8517-4H C11D 3/20 // C02F 1/62 Z C07B 61/00 300

Claims (2)

[Claims] 1. A glyceric acid derivative represented by the general formula (I). [Chemical 1] [Wherein, M: the same or different, represents an alkali metal, an alkaline earth metal, ammonium, an alkylammonium having a total carbon number of 1 to 36, an alkanolammonium having a total carbon number of 2 to 9 or a basic amino acid group. X, Y: Hydrogen atom, or Represents a group represented by. Here, R ¹ is a hydrogen atom or --COOM,
Represents a group represented by --CH ₂ COOM or --CH (OH) COOM, M
Represents the above meaning, n represents 1 or 0, Z represents a linear or branched alkylene group having 1 to 20 carbon atoms, or (Provided that R ² represents an alkylene group having 2 to 3 carbon atoms, and p represents a number of 0 to 10). However, X, Y
Except when both are hydrogen atoms. ] 2. A compound represented by the general formula (II): (In the formula, R ³ represents a hydrogen atom, a cation group or an alkyl group having 1 to 5 carbon atoms.) A glyceric acid or a salt thereof or an ester thereof (hereinafter referred to as glyceric acid (II)) is described below. 2. The method for producing a glyceric acid derivative represented by the general formula (I) according to claim 1, wherein any of the steps (a) to (f) is performed. Step (a) A step of reacting the glyceric acid (II) with the compound represented by the general formula (III) in the presence of an alkaline substance, and if necessary, salt exchange. [Chemical 5] (In the formula, A represents a halogen atom and R ¹ , Z, n and M have the above-mentioned meanings.) Step (b) The glyceric acid (II) is treated with the compound represented by the general formula (IV) and copper. A step of reacting in the presence of a catalyst, then hydrolyzing the obtained product, and if necessary, salt exchange. [Chemical 6] (In the formula, R ¹ , Z and n have the above-mentioned meanings, and R ⁴ has 1 carbon atom.
The alkyl groups of 5 are shown. ) Step (c) The glyceric acid (II) is reacted with the compound represented by the general formula (V) in the presence of an alkaline substance, and then the obtained product is hydrolyzed, and if necessary, salt exchange is carried out. Process. CH ₂ ═CH—Q (V) (wherein Q represents a group represented by —CN or —COOR ⁴ and R ⁴ has the above-described meaning.) Step (d) Glyceric acid (II) A step of reacting with an acid or maleic anhydride in the presence of Ca (OH) ₂ and then performing salt exchange. Step (e) A step of reacting the glyceric acid (II) with the compound represented by the general formula (VI) in the presence of an acid or base catalyst, followed by hydrolysis if necessary, and salt exchange if necessary. [Chemical 7] (In the formula, R ³ has the above-mentioned meaning.) Step (f) A alkylene oxide having 2 to 3 carbon atoms is added to glyceric acid (II), and then the hydroxy existing in the molecule of the obtained product is added. Oxidize the methyl group to carboxylic acid,
If necessary, salt exchange.