JPS5822462B2 - Yuukikagobutsunoseihou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel compounds useful as complex forming agents for various metal and/or alkaline earth metal ions, methods for their production, and containing such compounds as functional components. Concerning detergent formulation.

Compounds having the ability to complex metals and/or alkaline earth metal ions responsible for the "hardness" of water, such as magnesium and calcium, are useful in a variety of applications, such as water treatment (e.g. softening, anti-scaling). is recognized.

(It should be noted that some complexing agents also exhibit the ability to prevent precipitation of hard ions from water even when used in stoichiometric amounts insufficient to sequester hard ions. It is.

Such reagents are said to exhibit a threshold effect.

) Additionally, some such compounds exhibit the ability to enhance, enhance, or assist in the cleaning performance of detergent formulations.For convenience, such ingredients are referred to as porcine science builders (1°).
It is called detergent composition agent).

However, in some applications, such as in mechanical dishwashing formulations, the functionality of such compounds may be merely a "constituent" or different from the performance of other ingredients. It's like a thing.

It has been a constant objective of those skilled in the art to provide new complexing agents and methods of their synthesis in view of the various obvious utilities of such materials.

Novel compounds useful as complexing agents for various metals and/or alkaline earth metal ions, particularly ions such as magnesium and calcium, and as functional ingredients in detergent formulations, and/or exhibiting surface-active properties. It is an object of the present invention to provide.

Therefore, the present invention involves reacting the conjugate base of a hemiketal of a ketomalonic acid diester and an alcohol containing an active alcoholic hydroxyl group with a bromo or iodoacetate ester to obtain the organic group corresponding to the residue of the alcohol removed, M represents an ester constituent group, and a represents an integer equal to the number of hydroxyl groups removed from the alcohol) Accordingly, the present invention also relates to a process for converting the ester compound into the free acid, alkali metal salt or ammonium salt form.

These compounds, their preparation and use will be understood from the following description of preferred embodiments.

Here, the expression "active alcoholic hydroxyl group-1" refers to diethyl ketomalonate and WJi\, and the formula (in the formula -0-, of course, combines with the cation of the conjugate base to form, for example, -0''Na It is used to mean an alcoholic human group that can be converted into a conjugate base group (base group) to produce a substituent represented by

The conversion of alcohols to their conjugated base forms is well understood.

The conjugate base is obtained by reacting the alcohol with a base strong enough to cause deprotonation of the hydroxy groups.

In general, deprotonation of the reaction group is easily accomplished using sodium, potassium, sodium hydride, potassium hydride, sodium or potassium tertiary butyl oxide, sodium or potassium amide, etc. be done.

This reaction is conveniently carried out at a temperature of the order of o'c to 115°C.
It is carried out in any of the solvents for alcohols, which are not sensitizingly reactive with strong bases.

Examples of suitable solvents for use with various alcohols include tetrahydrofuran, dimethyl sulfoxide,
Examples include dimethylformamide, ethyl ether, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, and others.

When the reaction component alcohol is a liquid, an excess of such alcohol can be used as a solvent.

Mixed solvents can be used if desired.

A more detailed discussion of converting alcohols to conjugate bases can be found in references such as Morrison and Boyd,
Organic Chem 1stry l 3rd edition 5th
pp. 26-7 (published by Marin & Bacon, Inc., 1993), by Hoyer and Houts [
The Chemistry of the Et
her linkage l Chapter 10, page 447 (Published by Interscience Publications 1967)
, and by Schmidt and Beyer [Method
n der Oro ni sehen Chemie (
Houben-Weyl) Volume VI/2 Oxygen Compounds 1 Part 2
(published in 1963), 56L and are found in the citations given in these documents.

The conjugate base form of the alcohol is then reacted with anhydrous diethyl coute malone I., preferably at a temperature of -50 DEG to 60 DEG C. and preferably in the solvent used for the preparation of the conjugate base.

The production of the reaction is performed using conventional analytical techniques such as hydrogen or carbon-13
It can be easily detected by nuclear magnetic resonance spectral shifts or by observing the disappearance of the yellow to yellow-green color characteristic of anhydrous diethyl ketomalonate.

When a polyhydric alcohol is reacted as described above, the resulting substituent undergoes transesterification (1-lansnisdellization) with another sterically accessible hydroxy group of the alcohol and is represented by the formula cyclic lactones containing moieties can be formed.

That is, all or some of the hydroxy groups are [
- The formation of any of the lactones containing a substituent or moiety is not active when the alcohol is tested in a reaction to determine whether it is active or not.
- Confirms the existence of the human r7 group.

Incidentally, the compounds of the present invention have the formula (wherein R is an organic group corresponding to the residue of an alcohol from which at least one active alcohol hydroxy group has been removed, and a is C. is an integer equal to the number of hydroxy groups removed from the corresponding alcohol.

Although the compounds of the present invention are described above with reference to analog alcohols and are preferably derived from alcohols as explained hereinafter, the compounds of the present invention may actually be derived from alcohols. It should be understood that there is no intention to limit it to what is guided.

In fact, the compounds of the invention can be prepared by synthetic techniques that do not require active hydroxy-containing compounds as precursors.

Therefore, the foregoing description is only intended to facilitate understanding of the present invention.

Examples of the compounds of the present invention include the following θ) substituted with: This is a particularly preferred embodiment of the present invention.

Furthermore, these compounds are found to be easily biodegradable.

This is completely unexpected given that the carboxylated analogues shown in US Pat. No. 3,742,045 are resistant to biodegradation.

[Substituted long-chain (eg Cl0=C20) alkanes of this type exhibit surface activity as well as complex-forming properties and are therefore further useful as emulsifiers, defoamers, etc.

](b) Cycloalkane e.g. can be given.

The moiety to which the substituent is attached may have other substituents that are not chemically incompatible with the moiety.

For convenience, the compounds of the invention are exemplified above in the form of salts.

However, the corresponding ester and acid forms will be apparent to those skilled in the art.

It is pointed out that in some cases, in the case of compounds such as eg, the corresponding ester and acid forms of the compounds will exhibit lactone structures such as eg.

According to the process of the invention, such compounds are prepared by reacting the conjugate base of a hemiketal of a ketomalonic acid diester and an alcohol having an active alcoholic hydroxy group with a bromo or iodoacetate ester.

Such reactions produce ester forms of the compounds.

Reaction of such ester forms with alkali metal hydroxides produces the corresponding alkali metal salt forms.

This can be converted into the corresponding acid form by conventional acidification operations.

Ammonium salt forms are most conveniently obtained by neutralizing such acid forms with ammonia or ammonium hydroxide.

In one aspect of the invention, an alcohol containing an active alcoholic hydroxy group is reacted with a strong base to form the conjugate base form for the alcohol.

Such a reaction is called "active alcoholic hydroxyl group"
Previously stated in the discussion of the definition of

Generally, for alcohols that are acidic enough to react with these bases, thorium or potassium metal or hydrides can be used to convert the OH groups to -ONa+ or 10- to 10- groups. preferable.

This conjugated base form of the alcohol is then reacted with a ketomalonic acid diester to convert the 10-substituent group of the alcohol conjugate base into a substituent, thereby producing the conjugate base of the hemiketal of the ester and the alcohol.

And, for example, if this -0 monosubstituent is bonded to a carbon atom adjacent to a hydroxy-substituted carbon atom, a lactone containing moiety is formed.

In the above formula, X can be any organic moiety that does not interfere with the reaction due to chemical reactivity or steric hindrance.

This reaction proceeds in all cases where X is lower alkyl, such as methyl or ethyl.

However, if it is permissible from the viewpoint of chemical reactivity and steric hindrance, transesterification
In order to avoid the formation of mixtures of products by reaction and the difficulties associated with the separation of such mixtures, X corresponds to the organic moiety to which the conjugated base form of the alcoholic hydroxyl group is attached. It is generally desirable to have

The reaction with the ketomalonic acid diester is preferably carried out in the same solvent system used to convert the alcohol to its conjugate base, preferably from -50° to 60°C, preferably from -20° to
It is carried out at a temperature of 30°C.

In another embodiment of the invention, the alcohol can be first converted to a hemiketal by reaction with a ketomalonic acid diester and then a product containing or can be produced by reaction with a strong base.

However, it is generally preferred to convert the alcohol to its conjugated base form and then carry out the reaction with the ester.

If the starting alcohol contains more than one active hydroxy group, the amounts of reactants used in the reaction and the severity of the reaction conditions are such that only one such group is reacted. Determine whether some or only a few are replaced.

The product containing or is then reacted with a bromo or iodoacetate ester zCH2C00X (Z is Br or Generate it as a thing.

, bromoacetate or iodoacetate can be added neat or generated in situ by using a mixture of thorium iodide and chloroacetate.

The reaction temperature is not critical; a temperature range of -20 DEG to 100 DEG C. is usually satisfactory.

Generally, the reactions described above can be carried out under atmospheric pressure, but in some cases reflux means or pressure controls may be used to prevent excessive loss of reaction components or solvent or to allow the use of higher temperatures. It is desirable to give

Reaction of the ester with an alkali metal hydroxide produces the alkali metal salt form of the product compound, which can be made into an acid by acidification (e.g. with a strongly acidic ion exchange resin such as sulfonated polystyrene or with a strong mineral acid). It can be converted into a shape.

The reaction of the acid form of the compound with ammonium hydroxide produces the ammonium salt form of the compound as a product.

As discussed above, the resulting acid and ester forms of the compounds are useful as intermediates in the preparation of salt forms.

Substituents on such compounds provide capping agent and butadiency builder functions.

Other useful functions may be provided by the moiety to which the substituent is attached.

As can be seen from the above discussion, the moieties to which substituents can be attached can be derived from aliphatic alcohols, alicyclic alcohols, aromatic alcohols, alkyl aromatic alcohols, polyhydric alcohols, and hydroxy ethers, respectively. aliphatic, alicyclic, aromatic,
Mention may be made of alkyl aromatic, alcohol and ether moieties.

A preferred class of product compounds has substituents is a compound in which the moiety to which is bonded is as follows.

) Alkanes containing 1 to 20 carbon atoms.

Substituted C1-C4 alkanes provide particularly effective builder functionality, while higher alkanes also provide surface-active functionality.

(2) Polyalgylene oxide, especially polyethylene oxide containing 2 to 20 molecular proportions of ethylene oxide, is an effective solubilizer with sequestrant properties.

(3) Alkylbenzenes (preferably those with alkyl chains containing 5 to 20, most preferably 8 to 15 carbon atoms) are surface active with sequestrant properties.

Particularly preferred are compounds in which the substituent is bonded to the benzene ring.

Generally, the substituents will be present in a small amount (at least 50% by weight, preferably at least 8% by weight of the compound).
Compounds making up 5% by weight are preferred for applications where capping agent or builder functionality is of primary importance.

Additionally, it is generally preferred that such substituents are attached to a non-carboxylated carbon atom.

Generally, compounds having one or two such substituents are preferred from the standpoint of ease of synthesis.

In butadiene sea builder applications, it is preferred to use alkali metal salts, especially thorium salts.

However, in some formulations (eg liquid formulations where greater builder solubility is desired) it may be desirable to use ammonium or alkanol ammonium salts.

The detergent formulation contains at least 1% by weight and preferably at least 5% by weight of the product compound in salt form.

In order to obtain the maximum advantage of the builder composition of the present invention,
Particular preference is given to using 5% to 75% of these salts.

Such salt compounds may be single butadiency builders, or they may be used in combination with other builders which may constitute from 0 to 95% by weight of the total builders in the formulation.

By way of example, builders that can be used in combination with the salt compounds produced by the process of the invention include water-soluble inorganic builder salts such as alkali metal polyphosphates, tripolyphosphates and pyrophosphates, alkali metal carbonates, borates, Water-soluble organic builders including bicarbonates and silicates and aminopolycarboxylic acids and salts such as alkali metal dil-IJ lotriacetates, citaloalkane polycarboxylic acids and salts, ether polycarboxylates, alkyl polycarboxylates, epoxies Polycarboxylate, tetrahydrofucine polycarboxylate such as 1, 2, 3, 4 or 2, 2, 5, 5
-Tetrahydrofuran tetracarboxylate, benzene polycarboxylate, oxidized starch, amine (trimethylenephosphonic acid) and its salts, diphosphonic acid and its salts (e.g. methylene diphosphonic acid, -hydroxyethylidene diphosphonic acid), and others. .

Detergent formulations generally contain 5-95% by weight total builder.

However, larger or smaller amounts may be used if desired.

This may be the bilgoux salt compound prepared according to the invention alone or a mixture of such a compound with other builders, as described above.

The total amount of builder used depends on the intended use of the detergent formulation, other formulation ingredients, pH conditions, etc.

For example, common laundry powder formulations typically contain 20% to 60%
Contains a builder.

Liquid dishwashing formulations contain 11% to 12% builder, and mechanical dishwashing formulations contain 60% to 90% builder.

The optimum level of builder content for various applications, as well as the optimum mixture of the builders of the present invention with other builders, can be determined by basic testing in accordance with normal detergent formulation practices.3 Detergent formulations are generally water-soluble detergents. Although a surfactant is included, the surfactant component may be omitted from the mechanical dishwashing formulation.

Any water-soluble anionic, nonionic, zwitterionic or zwitterionic surfactant can be used.

Examples of suitable anionic surfactants include soaps, such as salts of fatty acids containing about 9 to 20 carbon atoms, such as salts of fatty acids derived from coconut oil and tallow, alkylbenzene sulfonates, especially those whose alkyl group has 10 ~
Linear alkylbenzene sulfonates containing 16 carbon atoms, alcohol sulfates, ethoxylated alcohol sulfates, hydroxyalkyl sulfonates, alkenyl and alkyl sulfates and sulfonates, monoglyceride sulfates, acid condensates of fatty acid chlorides and hydroxyalkyl sulfonates, etc. can give.

Examples of suitable nonionic surfactants include monohydric and polyhydric alcohols, alkyl phenols, fatty acid amides and condensates of alkylene oxides (e.g. ethylene oxide) of aliphatic amines, amine oxides, sugar derivatives e.g. monopalmide of sucrose. tates, long-chain tertiary phosphine oxides, dialkyl sulfoxides, fatty acid amides (eg, mono- or ditanolamides of fatty acids containing 10 to 18 carbon atoms), and others.

Examples of suitable zwitterionic surfactants include derivatives of aliphatic quaternary ammonium compounds such as 3-(N-N-dimethyl-N-hexatecylammonio)propane-1= Sulfonate and 3-(N
-N-dimethyl-N-hexatecylammonio)-2-
Hydroxypropane-1-sulfonate is mentioned.

Examples of suitable zwitterionic surfactants include betaines, sulfobetaines and fatty acid imidazole carboxylates and sulfonates.

The above examples of surfactants are by no means exhaustive (
Many other surfactants are known to those skilled in the art.

Additionally, the selection and use of surfactants is in accordance with well-understood detergent formulation practices.

For example, anionic surfactants, particularly linear alkylbenzene sulfonates, are preferred for use in general laundry formulations, while low-foaming nonionic surfactants are preferred for use in mechanical dishwashing formulations. .

The amount of surfactant used in a detergent formulation depends on the surfactant selected and the intended use of the formulation.

Generally, the formulation contains 5 to 50% by weight surfactant.

However, larger amounts of surfactant, up to 95% or more, can be used if desired.

For example, common laundry powder formulations usually contain 5% to 50% surfactant, preferably 15% to 25%, machine dishwashing formulations 0.5% to 5%, and liquid dishwashing formulations 20% to 5%.
Contains 45% surfactant.

The weight ratio of surfactant to builder is generally 1:1.
It is within the range of 2 to 2:1.

In addition to the builder and surfactant components, detergent formulations may contain fillers such as sodium sulfate and small amounts of bleaches, dyes, optical brighteners, soil redeposition inhibitors, fragrances, and the like.

In mechanical dishwashing compositions, the surfactant is a low-foaming anionic or preferably nonionic surfactant, which constitutes 0-5% of the formulation.

The expression "low sudsing" surfactant means that during the washing and rinsing cycles, in the sudsing test described below,
By this we mean a surfactant which reduces the rotation of the jet spray arm of a cleaning machine by 15% or less, preferably by 10% or less.

In the foaming test, 1.5'? of surfactant in a 1969 KitchenAid Home Detachment Washer Model 15 manufactured by Hobart Manufacturing Company. Add to KO3-16.

The machine is equipped with means for calculating the rotation of the washer jet spray arm during wash and rinse cycles.

The machine is operated using a distilled water supply at a machine entry temperature of 40°C.

Calculate the number of rotations of the jet spray arm during wash and rinse cycles.

The results are compared to those obtained by operating the machine without the surfactant charge and the % reduction in rotational speed is determined.

Of course, the surfactant should be compatible with the chlorine-containing components discussed hereinafter.

Examples of suitable non-ionic surface-active materials include ethoxylated alkylphenols, ethoxylated alcohols (both mono- and dihydroxyalcohols), polyoxyalkylene glycols, aliphatic polyethers, and the like.

Approximately 1,400 to 22,000 are widely used on the market.
Condensates of molecular weight polyoxypropylene glycol with ethylene oxide (ethylene oxide constitutes 5 to 35% by weight of the condensate) are advantageously used, for example, in the mechanical dishwashing formulations of the invention.

Suitable low-foaming anionic surfactants include alkyldiphenyl ether sulfonates, such as alkyldiphenyl ether sulfonates. ,l
Mention may be made of umdodecyl diphenyl ether disulfonate and alkylnaphthalene sulfonate.

Mixtures of suitable low foaming surfactants can be used if desired.

Additionally, the mechanical dishwashing formulation contains sufficient chlorine-producing compounds to provide 0.5% to 2% available chlorine.

For example, this formulation may contain 0.5% to 5%, preferably 1% to 3%
% chlorocyanurate or 10% to 30% chlorinated trisodium phosphate.

Suitable rosocyanurates include sodium and potassium dichlorocyanurate, [(monotrichloro)tetra(monopotassium dichloro)]pentaisocyanurate,
(Monotrichloro)(monopotassium dichloro)diisocyanurate.

The mechanical dishwashing formulation further comprises SiO of 1:1 to 3.2:1 preferably about 2.4:1 to prevent corrosion of metal parts of the dishwasher and to provide glaze protection for china.
Soluble sodium silicate with a molar ratio of 2 to Na2O
It should contain ~30%.

Mechanical dishwashing compositions generally contain low amounts of builders (at least 10%, preferably at least 20%, and up to about 90%).
Contains up to builder.

The novel salt compounds of this invention should constitute at least 5% by weight of the mechanical dishwashing formulation.

The invention is further illustrated by the following examples.

All parts and percentages herein are by weight unless otherwise specified.

Example ■ A slurry of 701 sodium hydride in 150 ml of tetrahydrofuran is prepared and 125 ml of methanol is added.

Maintain temperature below 35°C.

The mixture is stirred at 25°-30°C for about 1 hour and cooled to about 0°C.

Add about 4097 dimethyl ketomalonate, then 4
Add 44 grams of methyl bromoacetate.

This mixture is stirred for about 1 hour.

The temperature is kept below 10°C.

The temperature is then gradually increased and the reaction mixture is refluxed for 18 hours.

Tetrahydrofuran is evaporated and the residue is dissolved in a mixture of water and ethyl ether.

The mixture is decomposed and the ether layer containing the product is removed and washed with water.

The ether was dried over CaSO4, evaporated, and the residue was distilled in vacuo to give trimethyl 2-(
Carboxymethoxy)-2-methoxymalonate is collected at 110°-113°C/0.05 mmHg.

A solution of 466 grams of the above ester product in 466 grams of methanol is added to 100 grams of 25% aqueous sodium hydroxide solution.

(After adding about % of the ester solution, its temperature is about 60℃
and 200 ml of water is added.

Complete the ester addition and add 300 ml water and 500 ml methanol.

) Cool the slurry to about 25°C with stirring and filter.

This solid product is trisodium 2-(carboxymethoxy)-2-methoxymalonate.

Example ■ A slurry of 41.62 ml of sodium hydride in 1200 ml of tetrahydrofuran is prepared and 13
Add 07711 ethanol.

Keep the temperature below 30°C.

The mixture is cooled to about 5°C and held at that temperature for about 2 hours, after which the temperature of the 4001 diethyl ketomalonate is maintained below 10°C.

Then ethylbromoacetate-1-(384?
) and keep the temperature below 5°C for 2 hours.

The mixture is then warmed to 25°C and kept at about that temperature for 12 hours with stirring.

The temperature is then raised to 40° C. and kept at that temperature for 1 hour. 6 Tetrahydrofuran is evaporated and the residue is dissolved in ether and washed with water.

The ether fraction is separated and dried over calcium sulfate.

The ether is evaporated and the product triethyl 2-
(Carboxymethoxy)-2-ethoxymalonate is separated from the residue by distillation.

Said ester product 547? in 200 ml of ethanol.
of the solution is added to 1020 grams of 25% aqueous sodium hydroxide solution.

Keep the temperature below 45°C.

The mixture thickens. Add 300 ml of ethanol to form a stirrable slurry that is warmed to 45°C, cooled to 25°C after 2 hours and left for 12 hours.

Additional ethanol (100 ml) is added and the slurry is filtered to separate solid trisodium 2-(carboxymethoxy)-2-ethoxymalonate as the product.

Example IIJ 7 in 50nl dimethylformamide at 25°C.
A solution of 582 dodecyl alcohol in 50 ml of dimethylformamide is added to the slurry of 2 thorium hydroxide.

The mixture was heated at 25°C for 1 hour and then at 40°C for an additional 1 hour.
Stir for an hour.

This mixture was cooled to about -20°C and 50°C. Add noethyl ketomalonate.

After stirring for several minutes, add 48 grams of ethyl bromoacetate.

The temperature is maintained between -7° and -30°C.

The reaction mixture is allowed to warm to 25°C and stirred for 12 hours.

The product ester, l.ethyl 2-(carboxymethoxy)-2-dodecoxymalonate, is isolated by extraction with ethyl ether and purified by distillation.

25% aqueous sodium hydroxide solution cooled in a water bath 125
Add 50 ml of the above ester product to the methanol solution.

Another 100 rnl of methanol is added and the resulting slurry is stirred for 1 hour at 25°C.

The slurry is then filtered to separate solid trisodium 2-(carboxymethoxy)-2-dodecoxymalonate as a product.

Example 1 ■ 300 ml! Diethylene glycol (14P) is added to a slurry of thorium hydride in about 6.42 mm dimethylformamide.

The mixture is cooled to 0°C and stirred until the reaction is apparently complete and cooled to -50°C.

Add about 51' of diethylketomalone, then 4.
Add 8 grams of ethyl bromoacetate.

The temperature is gradually increased to about -20°C.

Foaming is observed at this point.

After foaming has ceased, the temperature is increased to 25°C and the mixture is stirred for 12 hours.

Dimethylformamide was evaporated and the product residue, hexaethyl 4,4,12,12-tetoxycarboxy-3,5,8,11,13-pentaoxapentadecanedioether-1, was washed with water and molecularly distilled. refine.

Reaction of the ester with aqueous sodium hydroxide produces hexasodium 4,4,12,12-tetracarboxy-3,5,8,11,13-pentaoxapentadecanedioe-1.

Example■ A solution of 101 phenols in dimethylformamide is
Upon completion of the reaction, the mixture is cooled to -20'C and 1742 g of diethyl ketomalonate and then 167 g of ethyl bromoacetate are added.

The mixture is warmed to room temperature and stirred for 2 hours.

This ester product, triethyl 2-(carboxymethoxy)-2-phenoxymalonate, is prepared by reaction with aqueous sodium hydroxide to form its salt, trisodium 2-(carboxymethoxy)-2-phenoxymalonate.
- Conversion to phenoxymalonate.

Example VI-XLIX One mole of the active hydroxy-containing compound shown in the following table
Add slowly to a slurry of 241 sodium salt in dimethylformamide or tetrahydrofuran solvent.

The amount of solvent is sufficient to allow the reaction mixture to be stirred, and additional solvent is added during the reaction if necessary.

In order to minimize the formation of by-products due to transesterification, 1 mole of diethyl ketomalonate is added, keeping the temperature as low as possible consistent with a reasonable reaction rate.

Add 1 mole of ethyl bromoacetate and raise the temperature to about 70°C.

Upon completion of the reaction, the solvent is removed under reduced pressure and the product ester residue shown in Table I below is purified by conventional extraction and/or distillation techniques.

Dissolve the ester in ethanol and add aqueous hydroxide
, IJum to produce the salt products shown in Table I.

For example, the product salts prepared according to Examples ■ to XLIX are described in the paper by Matzner et al.
ltsas Replacements for So
diumTripolyphosphate l (T
It was found to be an effective sealant when its sealant function was tested using the method described in En5ide Detergents Vol. 10, No. 3, pp. 119-125 (1973).

Example LI 50% of the builders shown in Table 2 below, average molecular weight approximately 230
17% of a linear alkylbenzene sulfonate having
A detergent formulation containing 6% sodium silicate and the balance being thorium sulfate is prepared.

This formulation is tested in 200 ppm hardness water at 49° C. containing 0.15% detergent formulation by washing identically soiled cloth pieces (as listed in the table) using the same washing technique.

The reflectivity of the unwashed and washed ql-o contaminated cloth pieces was measured instrumentally and the difference is reported as ΔRd in Table 2.

A high ΔRd value indicates a correspondingly high detergent effectiveness.

The data presented in Table 2 demonstrate that the salt forms of the compounds of this invention are effective butadiene sea builders.

EXAMPLE LTI An aqueous solution of the salt product prepared according to Examples 1 to XLIX is reacted with hydrochloric acid to form the corresponding acid form of the product.

The reaction of the acid with ammonium hydroxide produces the corresponding ammonium salt, which was found to be an effective sequestering agent when tested according to the procedure referred to in Example 2.

The technical matters disclosed by the present invention will be summarized and listed below.

(i) reacting the conjugate base of the hemiketal of a ketomalonic acid diester and an active alcoholic hydroxy-containing alcohol with a bromo or iodoacetate ester to form the ester form of said organic compound, and the alkali metal salt form of said organic compound being desired; the ester form is reacted with an alkali metal hydroxide to form the alkali metal salt form, and the alkali metal hydroxide is reacted with the alkali metal hydroxide if the acid form of the organic compound is desired. acidifying the salt form to produce the acid form;
and if an ammonium salt form of said organic compound is desired, said acid form is reacted with ammonia or ammonium hydroxide to produce said ammonium salt form, characterized in that the formula (wherein M is an alkali metal or ammonium), and a method for producing an acid or ester thereof.

2. The conjugate base of a hemiketal of a ketomalonic diester and an alcohol containing an active alcoholic hydroxy group is produced by reacting a conjugate base of an alcohol having an active alcoholic hydroxy group with a ketomalonic diester. The method according to item 1 above.

3. Said conjugate base of a hemiketal of a ketomalonic diester and an activated alcoholic hydroxy group-containing alcohol is reacted with the active alcohol-4 hydroxy group-containing alcohol to form a hemiketal, which is then treated with a sufficiently strong base. 2. The method according to claim 1, characterized in that it is produced by converting the hemiketal into its conjugate base by reacting with.

4. (a) Compounds corresponding to alcohols containing at least one active alcoholic hydroxyl group substituted with a substituent of the formula (wherein M is an alkali metal or ammonium) (where A and A' are (other than formula A'-C-OH, each of which is hydrogen or methyl and where X is hydrogen, methyl, ethyl, alkali metal or ammonium)
, 1 to 95% by weight and (b) 0.5 to 95% by weight of a surfactant selected from the group consisting of water-soluble anionic, nonionic, zwitterionic and zwitterionic surfactants. A detergent formulation characterized by:

5, (a) 5 to 90% by weight of the nor compound of item 4 above, (b) 0 to 0 selected from the group consisting of low foaming anionic and nonionic surfactants and mixtures thereof. 5% by weight surfactant, (e) potassium dichlorocyanurate, sodium dichlorocyanurate, [(monotrichloro)tetra-(monopotassium dichloro)]penterisocyanurate (monotrichloro)(monopotassium dichloro)diyne cyanurate and chlorinated trisodium phosphate and 0.
(d) 5% soluble sodium silicate having a SiO2 to Na2O molar ratio of 1:1 to 3.2:1; A mechanical dishwashing composition containing ~30% by weight.

Claims (1)

[Scope of Claims] 1. A compound of the formula (wherein R is the alcohol) characterized in that the conjugate base of a hemikecool of a ketomalonic acid diester and an active alcoholic and doxy group-containing alcohol is reacted with a bromo or iodoacetate ester. an organic group corresponding to the residue of an alcohol from which active alcoholic hydroxy groups have been removed, M represents an ester constituent group, and a represents an integer equal to the number of hydroxy groups removed from said alcohol). Methods for making the represented compounds. 2. Reacting the conjugate base of the hemiketal of a ketomalonic acid diester and an activated alcoholic hydroxy group-containing alcohol with a bromo or iodoacetate ester to form the ester form of the organic compound, and then converting the ester form of the compound into a free acid or alkali. The formula (wherein R is an organic group corresponding to the residue of the alcohol from which the active alcoholic hydroxyl group has been removed, M is hydrogen, alkali metal or ammonium, and a represents an integer equal to the number of hydroxy groups removed from said alcohol.