JPS6354390A - Novel methyl alpha-d-glucopyranoside compound, production thereof and sequestering agent containing said compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula [R1-R4 are H, -CH2 COOM (M is cation residue of alkali metal, amine or ammonia), -CH(COOM)2 or -(C2H4O)mCOOM (m is 1-10), provided that at least one of R1-R4 is -CH2 COOM, -CH(COOM)2- or -(C2H4O)mCH2COOM]. USE:A sequestering agent. PREPARATION:Methyl alpha-D-glucopyranoside is reacted with ethyl diazoacetate or diazomalonate and the resultant product is hydrolyzed.

Description

Detailed Description of the Invention 1-1 The present invention relates to a novel methyl α-D-glucopyranoside compound and a method for producing the same, and the novel methyl α-D-glucopyranoside compound of the present invention is used as a sequestering agent It is useful as such.

Sequestering agents are widely used to remove harmful heavy metals from industrial wastewater or soil, and as detergent builders.

Known examples of such metal ion sequestering agents include polyamine condensates of acrylic acid esters, condensed phosphates, carbonates, bicarbonates, zeolites, nitrilo I-triacetates, citrates, and the like.

Currently, condensed phosphates are the most comprehensive and most widely used, but since condensed phosphates contaminate environmental water quality such as lake water due to phosphorus, they are not used as builders. is in the direction of being regulated or prohibited.

Although various types of compound 1 are known as metal ion sequestering agents that do not contain phosphorus, a satisfactory one has not been obtained.

For example, polyamine condensates of acrylic acid esters and citrates have a high chelating effect, but are expensive and impractical. Zeola and Ito have insufficient builder performance,
Although nitrilotriacetate has excellent chelating power, it is undesirable because it contains a nitrogen source and causes eutrophication of lake water. Carbonates and bicarbonates are too alkaline and have poor cleaning power enhancement effects.

In recent years, organic builders such as ether polycarboxylic acids have been studied as phosphorus-free sequestering agents, but no satisfactory product has yet been found.

An object of the present invention is to provide a novel sequestering agent that is safe, does not contain phosphorus, and has excellent builder ability.

口II卆・7t・目の- The above objects of the present invention are solved by using a specific novel methyl α-D-glucopyranoside compound.

That is, the present invention relates to general formula (I) [wherein R1,
R2, R and R4 each represent a hydrogen atom, -CH2CO○M, -CH(COOM)2 or (C2H40)111082000M, and at least one of R1, R2, R3 and R4 is -CH2COOM, -CH(C00M) 2 or -
(C2H4O)mCH2COOM, where M represents a cationic residue of an alkali metal, amine or ammonia,
m represents the average number of added moles of 1 to 109] A novel methyl α-D-glucopyranoside compound and its production method, and at least one methyl α-D-glucopyranoside represented by the general formula (I>) The present invention relates to a metal ion sequestering agent characterized by consisting of a compound.

The methyl α-D-glucopyranoside f-sound product of the present invention is:
As is clear from the structural formula shown in general formula (1), these are 0-carboxymethylated products of methyl α-D-glucopyranoside, and both are novel f-hybrid compounds.

Typical examples of the methyl α-D-glucopyranoside (hyperoxygenate) of the present invention are shown below.

(1) R 1 , R2 , R3 and R of general formula (I)
Those in which all 4 are -CH2COOM are hereinafter abbreviated as tetrabasic acid salts).

(2) In general formula (I), R4 is a hydrogen atom and R1, R2 and R3 are -CH2C○○M (hereinafter abbreviated as tribasic acid salt) 9 (3) In general formula (I) R3 and R4 are hydrogen atoms, R
Those in which I and R2 are -CI-12COOM are hereinafter abbreviated as dibasic acid salts).

141 - Rr -R2, f''23 and R4 of general formula (I) are ゛PbeteCH(COOM)2 (hereinafter abbreviated as hebasic acid salt).

(5) Those in which R3, R2, R3 and R4 of general formula (I) are all (CzHtO) or CH2C00M; hereinafter referred to as E O (1' addition acid).

In the methyl α-D-glucopyranoside compound represented by the general formula (I), M is an alkali metal, and amine is an ammonia cation/residue, with sodium being most preferred.

The manufacturing method of the methyl α-1)-glufviranoside r-hyde compound of the present invention differs slightly depending on its structural formula, and an example thereof is shown below.

Methyl α-D-glucopyranoside 1Hnia 1 in (1) to (3) above is obtained by reacting ethyl diazoacetate using methyl α-D-glucopyranoside as a raw material and then hydrolyzing it to form methyl α-1] -Glucopyranoside〇-
A carboxymethylated product is obtained. Note that (2) or (
3) To produce the methyl α-D-glucopyranoside compound, follow steps 1. Did you replace the hydroxyl group of methyl α-D-glucobylanoside with 1-rich chlorite or benzaldehyde? After reacting with ethyl cyazoacetate, substituent 3 may be hydrolyzed by 14°.

To produce the basic acid salt of (4) above, methyl α-D
- Obtained by using glucopyranoside as a raw material, reacting it with diethyl diazomalonate, and then hydrolyzing it for 14".

In order to produce the EO acid monomer of (5) above, methyl α-
After ethylene oxide is added to D-glucopyranoside, it may be heated with a contact acid using a platinum catalyst or the like.
The methyl α-D-glucopyranoside compound of the present invention is exemplified below with a reaction formula showing a typical method for producing it.The methyl α-D-glucopyranoside compound of the present invention is a novel carbon compound. However, the manufacturing method thereof is not limited to the following examples.

Below are blank spaces (1) Example of manufacturing 41g base salt (2) Example of manufacturing tribasic acid salt t31 Example of manufacturing dibasic acid salt i41 Example of manufacturing basic acid salt The detergency of the methyl α-D-glucopyranoside compound of the present invention as a detergent builder is equivalent to or more effective than that of organic building blocks such as sodium oxadiacetate and citric acid. Therefore, it can not only be used in Germany, but also
It becomes possible to use it in combination with other builders or to further reduce the amount of active agent blended.

The sequestering agent of the present invention is also effective in preventing the formation of sgale in boilers and the like and in removing the formed scale.

The reason why the metal ion sequestering agent of the present invention has excellent Ki-1 ability is thought to be due to the action of the ether group and carboxyl group in the molecule, but the detailed mechanism of action is unknown.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

1. In a three-loaf flask with a diazoacetic acid inlet fitted with a soil stirrer, a reflux condenser, and a syringe cap, add methyl α-D.
- Weigh out 15 g (0.0257 mol) of glucopyranoside and 1 g of copper powder, heat them to 90°C in an oil bath, stir vigorously, and then add 14 g (0.128 mol) of ethyl diazoacetate to the syringe using a syringe. It dripped slowly through the carb. A rubber tube was connected to a gas meter from the tip of the reflux condenser, and the amount of nitrogen gas generated by the reaction was measured, and the result matched the calculated value. After the dropping, the copper powder was filtered out by suction, and the resulting light brown wrinkles were scraped off using silica gel (Wakogel C200, manufactured by Wako Junwara) using loform-ethyl acetate (10:1 v/v) as a developing solvent. According to the column chromatography used, the purity is TL
It was confirmed by C and HPLC that it was a single component. Its structure was confirmed by IR and NMR.

・Elemental analysis experimental value: C, 51.84$; H, 6
,718% Calculated value (C23H38014): C, 51,
30%; H, 7,06%・Refractive index: nF = 1.
467 Then, the obtained 2 was dissolved in water-ethanol (1:4v/v) in which 1.1 times equivalent of sodium hydroxide was dissolved,
Reflux was performed for 4 hours. This was then poured into a large amount of ethanol, and the precipitated sodium salt was filtered off and dried to obtain a nearly theoretical amount of tetrabasic acid sodium salt 3.

When we measured the IR of this thing, it was 1600 cm-1 (
-COO-), a characteristic absorption band was observed.

Example 2 Weighed 2 g of methyl α-D-glucopyranoside, 3.1 g of trityl chloride and 10 ml of pyridine, and mixed them at room temperature.
The reaction was stirred for hours, and hexane:chloroform (95:
5v/v) purification by repeating recrystallization from the solution, 4
was obtained in a yield of 45.1% (melting point 145.5-150.0).
℃). Then, the mixture was stirred with 10 ml of 75% acetic acid at room temperature for 2 hours to obtain the detritylated product 5 with a yield of 72.1%.

・Elemental analysis value experimental value: C, 50.18%; H, 7
, 22' calculated value (C, gH320s□): C, 5+1.
43$: H, 7,13′￥.

Then, according to Example 1, the corresponding tribasic acid 1 Heliu J and salt 7 were obtained.

・TR(cm-') 1600 (-Coo-) Example 3 j-1 Shichikouhan-point) L~ 198.3g (1,13ff1 mole) of zinc chloride was mixed with 250g (1 mole of methyl α-D-glucopyranoside) of methyl α-D-glucopyranoside. , 29 moles)
The mixture was added to a solution of 750 ml of benzaldehyde (Bfa amount) and stirred at room temperature for 18 hours. The reaction solution was poured into cold water 4I2, hexane 3501 was added, and after stirring for 1 hour,
Suction filtration was performed. The filtrate was washed with cold water and hexane to obtain 8 in the form of white crystals. The melting point of this substance is 169.4~
It was 169.8'C (literature value 167.5-16a5'C).

Then, in the same manner as in [Example], 1.2 times the equivalent of 75°6
Debenzylidene was removed by stirring and reacting with an aqueous dichloroacetic acid solution for 1 hour at 0'C. Column chromatography using chloroform-ethyl acetate 1:1 (v/v) as a developing solvent and silica gel (Wakogel C-2oo, Wako Pure Chemical Industries, Ltd. (Nakasha)) Elemental analysis value Experimental value: C, 49,1) IIχ ;H
,7,01)% Calculated value (C15H260to):C,4
9.18%, H, 7.10%, and then the corresponding dibasic acid, IR (Cm") 1600.1320 <-COO'-) Example J A according to Example 1
F-W') 1.70 g (0,0084 mol) of JL Do-methyl α~D-glucopyranoside was treated in the same manner as in Example 1 to add 6.80 g (0,0084 mol) of cyasima\diethyl conate.
37 mol) at 90°C, the resulting light brown shiro・
・Clean the knob with chloroform-ethyl acetate <1:1v, /v
) as the developing solvent, silica gel (Wako gel (>20
The product was purified by column chromatography using Wako Pure Chemical Industries, Ltd. (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain 12 with a yield of 50.1%.

, elemental analysis value experimental value: C, 511,85%; H, 6,58% Calculation 1st shift (C35H54021): C, 50,85%:
H, 6,5B Then, according to Example 1, the corresponding base acid IR (cm ratio) 1600, 1350 (-COO-) Example 5
L month 1 ■ "l": thing "ke J Sho - In a stainless steel autoclave equipped with a stirrer, 10.0 g of methyl α-D-glucopyranoside, 0.1 g of powdered sulfur and lithium hydroxide, and 17.9 g of ethylene oxide. g (7.9 times mole)
was weighed out, and a stirring reaction was carried out at 80°C for 7 hours in an argon atmosphere. After the reaction was completed, the reaction mixture was neutralized with glacial acetic acid and dried under reduced pressure to obtain E() in the form of a light brown syrup.
The number of EOf01 moles was determined by R and GPC, and the number of H P
It was confirmed by LC that there was no unreacted raw material, and in a round bottom reaction vessel equipped with a stirrer, 1 g of EO (1 g of solids, 4 ml of water, and 0.5 g of 5゛16 platinum carbon catalyst) were poured and stirred. Oxygen '5 at 80°C: 120 ml/
After the reaction, the catalyst was filtered off and the water was distilled off to obtain EO in the form of a colorless syrup.
) (Gamic acid 1 arsenic was obtained. The neutralization value of this product was 290.
．． It was 3.

Example 6 The following cleaning test was conducted to see the effect of using the sequestering agent of the present invention as a cleaning agent Virgoo.

The cleaning test used artificially contaminated genuine cotton, and the judgment was made by measuring the reflectance of the uncontaminated original cloth and the cloth before and after washing, and the cleaning power was calculated using the following formula. For comparison, each time measurements were taken using commercially available sodium tripolyphosphate and sodium oxadiacetate.

The measured results are shown in Table 1. The cleaning evaluation points in the table are 10 for sodium tripolyphosphate and 1 for oxadiacetic acid.
It is shown as a relative value of cleaning power when helium is O.

Table 1 [Washing conditions] Washing bag W: Terg-0-Tometer washing concentration: 0.12% Washing temperature: 25°C Washing time = 10 minutes bath Ratio: 301 sound Water used: 3° DH Tap water rinsing temperature: 25 ℃ Rinse time = 5 minutes [Detergent composition] 9δ Sodium dodecylbenzenesulfonate 2゜Sample Bilgu No. 252 Sodium silicate 5 Anhydrous sodium carbonate
3 carboxymethyl cellulose
0.5 anhydrous sodium sulfate 4
6.5 [Formula KoRf, : Reflectance of original fabric [1: Reflectance of fabric before washing FeF2: Reflectance of fabric after washing Example 7 Zeolite widely used in commercially available phosphorus-free detergents The results of the cleaning power test of the two-component Bilgoo with
The detergent composition shown in the table was the same as in Example 5, and the test was conducted with the total amount of water-soluble, luda, and □ synthetic zeolite being 25%.

The following is a blank space in Table 2. Example S The 71 ion sequestering agent of the present invention was evaluated by the method shown below.

Sample builder 1 in a 50m1 beaker with a rotor of 1.
Weigh out 0mg and add 50ml of 1.0\10-3M Calcium Chloride Kashisoru iR! :Added and dissolved. In addition, as an ionic strength adjuster - 1, 1 OM salt, 1 hicpotium water! 1. mlwokaZ 'y'Jt degree 11 =
0.081: Stir in a constant temperature bath at 30'C, and measure the calcium ion concentration after 10 minutes using a calcium ion electrode (MODEL 93 manufactured by Orion Co., Ltd.).
-20 > using an ion meter (Toa Denpa Kogyo KK
It was measured using a commercially available IIVI-20E (manufactured by IIVI-20E). The concentration of calcium ions sequestered by 1 g of sample builder is expressed as calculated value (mg>) of calcium ion sequestering agent of the present invention.The results are shown in Table 3. Table 3 Example 9 Metal ion sequestering agent of the present invention The dispersion power of manganese dioxide was evaluated by the method shown below.

Into a stoppered sample tube with 501 scale, add 1 to 1 Himangan 1.
A sample of Og and 0.05 hiro sample builder (aqueous solution) was taken and shaken 100 times. Then, 15 ml of the suspension was taken without disturbing the contents as much as possible. The amount of himanganese monoacid in the collected suspension was measured by the potassium permanganate method. The dispersing power was expressed by the number of mg of manganese dioxide suspended in 100 ml of suspension. 4th result
Shown in the table.

Below is a blank space in Table 4. Example 10 The biodegradability of the sequestering agent of the present invention was evaluated by the method shown below.

In other words, the biochemical oxygen consumption (BOD5) is
Sample solution 10100 according to S K 0102
It was determined from the amount of dissolved oxygen consumed when 0 pp was diluted with dilution water and allowed to stand at 20°C for 5 days, and expressed as the number of mg of oxygen consumed per 1 g of sample (mg O,/g).

Theoretical oxygen consumption (ThOD>) is the number of mg of oxygen consumed when the sample is completely immersed in acid (mgO/g)
was determined by calculation. Biodegradation rate (2) is BOD s
/ T h OD X 100.

The results obtained are shown in Table 5.

Table 5 below is a blank space Example 11 In order to examine the effect of the metal ion sequestering agent of the present invention on preventing scale generation, the metal ion sequestering agent (Synthesis Example 2) was dissolved in boiler water to a concentration of 10 ppm, and the mixture was operated for one year. did. As a result, no scale formation was observed.9 11 The effects of the novel methyl α-D-glucopyranoside compound of the present invention as a sequestering agent are listed below.

(1) Has excellent metal ion sequestration ability.

(2) Excellent biodegradability and high safety.

(3) It does not contain phosphorus or nitrogen sources that cause eutrophication, and is suitable as a detergent builder.

It is effective in preventing the generation of 141 scale and removing the generated scale.

[Brief explanation of the drawing]

The drawings are IR spectra (KBr method) of the novel methyl α-D-glucopyranoside compound of the present invention, and each figure shows the IR spectra of the following compounds. Figure 1; Sodium salt of tetrabasic acid (Example 1) Figure 2; Sodium salt of tribasic acid (Example 2) Figure 3; Thorium salt of dibasic acid (Example 3) Figure 4; Sodium salt of tetrabasic acid (Example 3) Sodium salt (
Example 4) Figure 5, EO oil body oxide, I, lithium salt (
Example 5) Patent applicant: Kawaken Fine Chemical Co., Ltd. Procedural amendment written form) February 2, 1988

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R_1, R_2, R_3 and R_4 are hydrogen atoms, -CH_2COOM, -CH( COOM)_2 or -(C_2H_4O)_mCH_2COOM, R
At least one of _1, R_2, R_3 and R_4 is -CH_2COOM, -CH(COOM)_2 or -
(C_2H_4O)_mCH_2COOM, M represents a cationic residue of an alkali metal, amine or ammonia, and m represents an average number of added moles of 1 to 10. ] A novel methyl α-D-glucopyranoside compound represented by: 2. In the general formula (I), R_4 is a hydrogen atom, and R_1, R_2 and R_3 are each -CH_2C
Methyl α-D according to claim 1 which is OOM
- Glucopyranoside compounds. 3. In general formula (I), R_1, R_2, R_3
and R_4 are each -CH(COOM)_2, the methyl α-D-glucopyranoside compound according to claim 1. 4. In general formula (I), R_1, R_2, R_3
The methyl α-D-glucopyranoside compound according to claim 1, wherein and R_4 are each -(C_2H_4O)_mCH_2COOM. 5. Methyl α-D- according to claims 1 to 4, wherein in general formula (I), M is sodium.
Glucopyranoside compounds. 6. General formula (I)' characterized by reacting methyl α-D-glucopyranoside with ethyl diazoacetate or ethyl diazomalonate and then hydrolyzing it ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [However In the formula, R_1, R_2, R_3 and R_4 are each a hydrogen atom, -CH_2COOM or -CH
(COOM)_2, at least one of R_1, R_2, R_3 and R_4 is -CH_2COOM or -CH(COOM)_2, and M represents a cationic residue of an alkali metal, amine or ammonia. ] A method for producing a methyl α-D-glucopyranoside compound. 7. General formula (I)'' characterized by adding ethylene oxide to methyl α-D-glucopyranoside and then catalytically oxidizing it ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)'' [However, in the formula, R_1, R_2, R_3 and R_4 each represent a hydrogen atom or -(C_2H_4O)_mCH_2COOM, and R
At least one of _1, R_2, R_3 and R_4 is -(C_2H_4O)_mCH_2COOM, and M
represents a cationic residue of an alkali metal, amine or ammonia, and m represents an average number of added moles of 1 to 10. ] A method for producing a methyl α-D-glucopyranoside compound. 8. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R_1, R_2, R_3 and R_4 are hydrogen atoms, -CH_2COOM, -CH(COOM)_2 or -( C_2H_4O)_mCH_2COOM, R
At least one of _1, R_2, R_3 and R_4 is -CH_2COOM, -CH(COOM)_2 or -
(C_2H_4O)_mCH_2COOM, M represents a cationic residue of an alkali metal, amine or ammonia, and m represents an average number of added moles of 1 to 10. ] A sequestering agent characterized by comprising at least one methyl α-D-glucopyranoside compound represented by the following. 9. In general formula (I), R_4 is a hydrogen atom, and R_1, R_2 and R_3 are each -CH_2C
The sequestering agent according to claim 8, which is OOM. 10. In general formula (I), R_1, R_2, R_
9. The sequestering agent according to claim 8, wherein 3 and R_4 are each -CH(COOM)_2. 11. In general formula (I), R_1, R_2, R_
9. The sequestering agent according to claim 8, wherein 3 and R_4 are each -(C_2H_4O)_mCH_2COOM. 12. The sequestering agent according to claim 8, wherein in general formula (I), M is sodium.