CA1088096A - Carboxymethoxymalonic acid derivatives as detergent builders - Google Patents

Abstract

ABSTRACT
Organic compounds having a substituent represented by the formula

Description

09~

This invention relates to novel compounds useful as complexing agents for various metal and/or alkaline earth metal ions, to processes for their preparation and to detergent formu-lations containing such compounds as functional ingredients.
It is well recognized that compounds having the ability to complex metal and/or alkaline earth metal ions which contri-bute to water "hardness", e.g. magnesium and calcium are useful in a variety of applications such as water treatment (e.g., softening, scale inhibition). (It is noted that some complex-ing agents also exhibit the ability of preventing precipitationof hardness ions from water even when used in quantities stoi-chiometrically insufficient to sequester the hardness ions.
Such agents are said to exhibit "threshold" effect.) Addition-ally, some such compounds exhibit the ability to enhance, potentiate or supplement the cleaning ability of detergent formulations and are useful as functional ingredients thereof.
Conventionally, such ingredients are referred to as detergency "builders" although in some applications, e.g., machine dish-washing formulations, the functionality of such compounds appear to be more than or different from a mere "building" of the performance of other ingredients of the formulation.
The provision of novel complexing agents and methods for their synthesis has long been a continuing objective of those skilled in the art in view of the varied, recognized utilities of such materials.
It is an object of this invention to provide novel pro-~ cesses and compounds useful as complexing agents for various metal and/or alkaline earth metal ions - particularly ions such as magnesium and calcium - and which are useful as functional ingredients in detergent formulations and/or exhibit surface active properties.

~o~

The compounds of the invention are characterized by the presence of at least one f OOM COOM

COOM
substituent (M being alkali metal or ammonium) and are prepared by reacting the conjugate base of a hemiketal with a bromo or iodo acetate ester. These compounds, their preparation and use will be understood from the following description of the pre-ferred embodiments.
The compounds of the present invention correspond to alcohols having an active alcoholic hydroxy group replaced with a substituent represented by the formula f OOM COOM
_o f o CH2 COOM
wherein M is alkali metal or ammonium and acids and esters thereof, provided, that the moiety to which the COOM COOM
- o f o CH2 COOM
substituent is attached is other than COOM
A C
. A' wherein A and A' are hydrogen or methyl.
The term "active alcoholic hydroxy group" is used to denote an alcoholic hydroxy group convertible to a con-jugate base group reactive with diethyl ketomalonate to form a substituent represented by the formula . -- 2 --10~809~

Cl OOC2H5 o--Cl--o~

(The - O will, of course be associated with the cation of the conjugate base, e.g. - O Na+) The conversion of alcohols to their conjugate base forms is well understood. The conjugate base is obtained by reacting the alcohol with a base sufficiently strong to deprotonate a hydroxy group. Generally, deprotonization of reactive hydroxy groups is readily accomplished with sodium, potassium, sodium hydride, potassium hydride, sodium or potassium t-butoxide, sodium or potassium amide, etc. The reaction is conveniently conducted at temperatures of the order of 0C to 115C in any solvent for the alcohol which is not adversely reactive with the strong base. Examples of solvents suitable for use with various alcohols include, tetrahydrofuran, dimethylsulfoxide, dimethylformamide, ethyl-ether, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, or the like. In those instances where the reactant alcohol is a liquid, an excess of such alcohol may be employed as the sol-vent. Mixed solvents can be used, if desired. More detailed discussion of the conversion of alcohols to conjugate bases is found in such references as Morrison and Boyd, Organic Chemistry, 3rd edition, Allyn and Bacon, Inc. (1973) pp.
526,527; Feuer and Hooz, The Chemistry of the Ether Linkage, edited by Patai, Interscience Publishers (1967)~ Chapter 10, p. 447; and Schmidt and Bayer, Methoden Der Organischen Chemie (Houben-Weyl) Band VI/2, Georg Theime Verlag, (1963) Saurstoff Vergindunger 1, Teil 2 and bibliographies provided in the foregoing references.

10~809~;

The conjugate base form of the alcohol is then reacted with anhydrous diethylketomalonate, preferably at temperatures of from -50 to 60C and preferably in the solvent used for preparation of th~ conjugate base. The occurrence of the reaction is readily detected by conventional analytical techniques e.g. hydrogen or carbon 13 nuclear mag-netic resonance spectral shifts or by observance of the dis-appearance of the characteristic yellow to yellow-green color of anhydrous diethylketomalonate.
When polyhydroxy alcohols are reacted as above resulting O--lC--O~

substituents may undergo transesterification with other sterically accessible hydroxy groups of the alcohol to form a cyclic lactone containing a /\C~O
O lC O

moiety. Thus, when an alcohol is tested in reactions as des-cribed above to determine if all or some of its hyroxy groups are "active" the formation of either a - --T -substituent or a lactone containing a \C~O
~0- 1 0~

2 5 o9f~

moiety sonfirms the presence of an active hydroxy group.
By way of further description, the compounds of this invention can be represented by the formula COOM COOM
R ( O - f CH2 )a COOM
in which R is an organic radical corresponding to the residue of an alcohol having at least one active alcoholic hydroxy group removed therefrom and a is an integer equal to the number of hydroxy groups removed from the corresponding alcohol.
Although the compounds of this invention are des-cribed above by reference to analogous alcohols and are, as hereinafter explained, preferably derived from alcohols, no intention to limit the compounds of this invention to those actually derived from alcohols should be implied. In fact, the compounds of this invention can be prepared by synthetic techniques not requiring active hydroxy containing compounds as precursors. Therefore, this mode of description is merely intended to facilitate an understanding of the scope of the invention.
Examples of the compounds of this invention include COOM f OOM

COOM

substituted:
a) alkanes such as f OOM ~OOM
CH3 O f -- H2 COOM
COOM COOM

COOM

10880~6 (The above two compounds are particularly preferred embodiments of the invention in view of excellent performance as detergency builders. It is further noted that these compounds are readily biodegradable which is quite unexpected in view of the resis-tance to biodegradability of a carboxylated analog, fOOM fOOM fOOM

C~I2 --C CH2 COOM
which analog is disclosed in U.S. patent 3,742,045.) fOOM fOOM
CH (CH ) O f - O - CH
COOM
(Substituted long chain alkanes, e.g. Cl0 to C20, of this type l0 exhibit surface active properties as well as complexing proper-ties and are, therefore, additionally useful as emulsifiers, foaming agents, etc.);

ICOOM ICOOM

OOM
CH - CH - CH CH 'H CH CH3 COOM COOM COOM COOM
H21 - - f CH2 CH2 CH2 CH2 ~ _ O- CH2 COOM OOM
ICOOM ~OOM ICOOM fOOM

¦ 1OOM ¦ COOM

etc.
b) cycloalkanes such as .

10~0~

~ 2 CH2 fOOM fOOM
C ~ CH- O - f o CH2 fOOM ,COOM COOM OOM
~CH2 CH2 I f H C- O - ~CH - CH CH IC CH2 OOM COOM
c) alkanols such as COOM COOM
HO--CH~------CH2 0 1--O--CH2 OOM
d) ethers such as COOM COOM
H(CH2 CH2 O)g --CH ~ 2 O

f H3 COOM fOOM
H (CH- CH2 - )5 CH~CH2 1 - CH2 OOM
COOM f ooM T T

~OOM COOM
etc.
e) aromatics such as COOM COOM

COOM

COOM COOM
H~CH2 CH2 o~ 4 CH2- CH2- ~ - O- C 1H2 COOM
TOOM ICOOM

COOM

, .~ .~ .

10~096 fOOM ~OOM
.: H3C- ~ -O - C o CH
OOM
- ,COOM ,COOM

~ ~ O CH2 OOM
etc.
The moieties to which the fOOM fOOM
O - C- O CH
COOM
substituents are attached may bear other substituents which are not chemically incompatible with the COOM fOOM

O--~ O CH2 COOM
moiety.
For convenience, the compounds of this invention have been exemplified above in the salt forms; however, the corresponding ester and acid forms will be apparent to those skilled in the art. It is pointed out that in some instances, for example in the case of a compound such as fOOM fOOM
HO CH CH - O- C - O - CH
OOM
the corresponding ester and acid forms may exhibit a lactone structure such as / ~
CH2 /OCH2COO ethyl or hydrogen \ O/ \COO ethyl or hydrogen 10~09~

In accordance with the process of this invention, such compounds are prepared by reacting a conjugate base of a hemiketal of a ketomalonic acid diester and an alcohol having an active alcoholic hydroxy group with a bromo or iodo acetate ester. Such reaction yields the ester forms of the above de-scribed compounds. Reaction of such ester forms with an alkali metal hydroxide yields the corresponding alkali metal salt forms which can be converted to the corresponding acid forms by conventional acidulation procedures. The ammonium salt forms are most conveniently obtained by neutralization of such acid forms with ammonia or ammonium hydroxide.
In one embodiment of the invention an alcohol con-taining an active alcoholic hydroxy group is reacted with a strong base to form the conjugate base form for the alcohol.
Such reactions have previously been described in the discussion of the definition of "active alcoholic hydroxy groups". In general, the use of sodium or potassium metals or hydrides to convert - OH groups to -O Na+ or -O g groups is preferred in the case of alcohols sufficiently acidic to react with these bases.
The conjugate base form of the alcohol is then reacted with a ketomalonic acid diester COOX
C=O
COOX
to form a conjugate base of a hemiketal of the ester and alcohol by converting the -O substituent of the alcohol con-jugate base to a COOX
O I O~
COOX

- ~ _ g 10~809~;

substituent, if for example the-O substituent is attached to a carbon atom adjacent to an hydroxy substituted carbon atom forming a lactone containing the moiety.

C/

\0/ \COOX
In the above formulae,X may be any organic moiety which will not, by virtue of chemical reactivity or stearic hindrance, interfere with the reaction. The reaction will proceed in all cases wherein X is a lower alkyl such as methyl or ethyl.
However, it is generally desirable, where permissible from the standpoint of chemi~al reactivity and stearic hindrance, that X correspond to the organic moiety to which the conjugate base form of the alcoholic hydroxy group is attached in order to prevent formation of a mixture of products via transesterifica-tion reactions and the difficulties attendant to separation of such mixtures.
The reaction with the ketomalonic acid diester is preferably conducted in the same solvent system used in con-verting the alcohol to its conjugate base at temperatures from -50 to 60C, preferably from -20to 30C. In another embodi-ment of the invention the alcohol can first be converted to ahemiketal by reaction with the ketomalonic acid diester followed by reaction with strong base to form the COOX
O ~ O~
COOX

' -- 10 --10~809~

or /\C~
~/
\o/\coox containing product. Generally, however, conversion of the alcohol to its conjugate base form followed by reaction with the ester is preferred.
When the starting alcohol contains more than one active hydroxy group, the quantities of reactants and severity of reaction conditions employed in the foregoing reaction will determine whether only one or more of such groups are replaced in the reactions.
The fOOX / ~ ~ o o f O or Cl~
COOX ~_ o~
\o/ ~COOX
containing product is then reacted with a bromo or iodo acetate ester ZCH2COOX ~Z is Br or I) to convert the-O substituent to a -OCH2COOZ substituent thereby yielding the ester form of the product compounds described.
The bromoacetate or iodoacetate may be added as such or produced in situ, e.g., by using a mixture of sodium iodide and chloroacetate. Reaction temperatures are not criti-cal, a temperature range of -20to 100C usually being satis-factory.
In general, the reactions described can be con-ducted at atmospheric pressure, although, in some instances, it may be desirable to provide reflux means or pressure to prevent excessive loss of reactants or solvents, or to permit use of higher temperatures.

,~J - 1 1 -1(W~09t;

Reaction of the esters with alkali metal hydroxide yields the alkali metal salt forms of the product compounds which can be converted to the acid form by acidulation (for example, by means of a strong acid ion exchange resin such as sulfonated polystyrene or by a strong mineral acid).
Reaction of the acid form with ammonium hydroxide will yield the ammonium salt forms of the product compounds.
As discussed above, the acid and ester forms of the product compounds are useful as intermediates for prepara-10 tion of the salt forms.
The ~OOM f OOM

--O I ~H2 COOM
substituents of such compounds provide sequestrant and deter-gency builder functionality. Other useful functionality may be provided by the moiety to which the fOOM fOOM
O f - O CH
COOM
substituents are attached.
As seen from the foregoing discussion, the moieties to which fOOM ICOOM
- O - f - O CH
COOM
substituents may be attached include aliphatic, alicyclic, aromatic, alkyl aromatic, alcohol, and ether moieties which are, respectively, derivable from aliphatic alcohols, alicyclic alcohols, aromatic alcohols, alkyl aromatic alcohols, poly-hydroxy alcohols, and hydroxy ethers.

_,.;

108~096 Preferred classes of product compounds are those in which the moiety to which the fOOM fOOM

COOM
substituents are attached are:
1) an alkane containing 1 to 20 carbon atoms. Sub-stituted Cl to C4 alkanes provide particularly effective buil- -der functionality whereas the higher alkanes additionally pro-vide surfactant functionality.
2) polyalkylene oxides particularly polyethylene oxides containing 2 to 20 molecular proportions of ethylene oxide are effective solubilizing agents having sequestrant properties.

3) alkyl benzenes (preferably having alkyl chains containing 5 to 20, most preferably 8 to 15 carbon atoms) are surfactants having sequestering properties. Compounds wherein the ~OOM IOOM

COOM
substituent is attached to the benzene ring are particularly preferred.
In general, compounds in which the fOOM Cl OOM
--O--lC O CH2 COOM
substituents constitute at least 50%, preferably at least 85 of the weight of the compound are preferred for applications wherein sequestrant or builder functionality is of primary importance. It is further generally preferred that such sub-stituents be attached to uncarboxylated carbon atoms. Generally, lO~O9f~i compounds having one or two of such substituents are preferred from the standpoint of ease of synthesis.
In detergency builder applications,the use of the alkali metal salts, particularly the sodium salt is preferred.
However, in some formulations (such as liquid formulations where greater builder solubility is required) the use of ammon-ium or alkanol ammonium salts may be desirable.
The detergent formulations will contain at least 1% by weight and preferably at least 5% by weight of the salt forms of the product compounds. In order to obtain the maximum advantages of the builder compositions of this invention, the use of from 5~ to 75% of these salts is particularly preferred.
Such salt coumpounds can be the sole detergency builder or these compounds can be utilized in combination with other detergency builders which may constitute from 0 to 95~ by weight of the total builders in the formulation. By way of ex-ample, builders which can be employed in combination with such salt compounds produced by the process of this invention in-clude water soluble inorganic builder salts such as alkali metal polyphosphates, i.e., the tripolyphosphates and pyro-phosphates, alkali metal carbonates, borates, bicarbonates and silicates and water soluble organic builders including amino polycarboxylic acids and salts such as alkali metal nitrilotri-acetates, cycloalkane polycarboxylic acids and salts, ether polycarboxylates, alkyl polycarboxylates, epoxy polycarboxyl-ates, tetrahydrofuran polycarboxylates such as 1,2,3,4, or 2,2,5,5 tetrahydrofuran tetracarboxylates, benzene polycar-boxylates, oxidized starches, amino (trimethylene phosphonic acid) and its salts, diphosphonic acids and salts (e.g. methyl-ene diphosphonic acid; 1- hydroxy ethylidene diphosphonic acid) and the like.

~-lJ

108~096 The detergent formulations will generally contain from 5% to 95% by weight total builder (although greater or lesser quantities may be employed if desired) which, as in-dicated above, may be solely the builder salt compounds produced according to this invention or mixtures of such com-pounds with other builders. The total amount of builder em-ployed will be dependent on the intended use of the detergent formulation, other ingredients of the formulation, pH condi-tions and the like. For example, general laundry powder formula-tions will usually contain 20% to 60% builder; liquid dish-washing formulations 11% to 12% builder; machine dishwashing formulations 60% to 90% builder. Optimum levels of builder content as well as optimum mixtures of builders of this in-vention with other builders for various uses can be determined by routine tests in accordance with conventional detergent formulation practice.
The detergent formulations will generally contain a water soluble detergent surfactant although the surfactant ingredient may be omitted from machine dishwashing formula-tions. Any water soluble anionic, nonionic, zwitterionic oramphoteric surfactant can be employed.
Examples of suitable anionic surfactants include soaps such as the salts of fatty acids containing about 9 to 20 carbon atoms, e.g. salts of fatty acids derived from co-conut oil and tallow; alkyl benzene sulfonates - particularly linear alkyl benzene sulfonates in which the alkyl group con-tains from 10 to 16 carbon atoms; alcohol sulfates; ethoxyl~
ated alcohol sulfates; hydroxy alkyl sulfonates; alkenyl and alkyl sulfates and sulfonates; monoglyceride sulfates; acid condensates of fatty acid chlorides with hydroxy alkyl sul-fonates and the like.

' 1 1()~809~

Examples of suitable nonionic surfactants include alkylene oxide (e.g., ethylene oxide) condensates of no and polyhydroxy alcohols, alkyl phenols, fatty acid amides,and fatty amines; amine oxides; sugar derivatives such as sucrose monopal-mitate; long chain tertiary phosphine oxides; dialkyl sulfoxides;fatty acid amides, (e.g., mono or diethanol amides of fatty acids containing 10 to 18 carbon atoms), and the like.
Examples of suitable zwitterionic surfactants in-clude derivatives of aliphatic quaternary ammonium compoundssuch as 3-(N,N-dimethyl-N-hexadecyl ammonio) propane-l-sulfon-ate and 3-(N,N-dimethyl-N-hexadecyl ammonio)-2-hydroxy propane-l-sulfonate.
Examples of suitable amphoteric surfactants include betains, sulfobetains and fatty acid imidazole carboxylates and sulfonates.
It will be understood that the above examples of suxfactants are by no means comprehensive and that numerous other surfactants are known to those skilled in the art. It will be further understood that the choiae and use of surfactants will be in accordance with well understood practices of detergent formulation. For example, anionic surfactants, particularly linear alkyl benzene sulfonate are preferred for use in general laundry formulations, whereas low foaming nonionic surfactants are preferred for use in machine dishwashing formulations.
The quantity of surfactant employed in the deter-gent formulations will depend on the surfactant chosen and the end u~e of the formulation. In general, the formulations will contain from 5% to 50% surfactant by weight, although as much as 95% or more surfactant may bg employed if desired. For example, general laundry powder formulations normally contain 30 5% to 50~, preferably 15% to 25% surfactant; machine dishwashing formulations .5% to 5%; liquid dishwashing formulations 20% to `
45%.The weight ratio of surfactant to builder will generally be in the range of from 1:12-to 2:1.
In addition to builder and surfactant components, detergent formulations may contain fillers such as sodium sulfate and minor amounts of bleaches, dyes, optical brighteners, soil anti-redeposition agents perfumes and the like.

1()~809~;

In machine dishwashing compositions the surfactant will be a low-foaming anionic or preferably, nonionic sur-factant which will constitute 0 to 5% of the formulation.
The term "low foaming" surfactant connotes a sur-factant whichj in the foaming test described below, reduces the revolutions of the washer jet-spray arm during the wash and rinse cycles less than 15%, preferably less than 10~.
In the foaming test, 1.5 grams of surfactant is added to a 1969 Kitchen-Aid Home Dishwasher, Model No. KOS-16, manufactured by Hobart Manufacturing Company which is provided with means for counting revolutions of the washer jet-spray arm during wash and rinse cycles. The machine is operated using distilled water feed at a machine entrance temperature of 40C.
The number of revolutions of the jet-spray arm during the wash and rinse cycles is counted. The results are compared with those obtained by operation of the machine using no sur-factant charge and the percentage decrease in the number of revolutions is determined.
The surfactant should, of course, be compatible with the chlorine containing component hereinafter discussed.
Examples of suitable nonionic surfactants include ethoxylated alkyl phenols, ethoxylated alcohols (both mono- and di-hydroxy alcohols), polyoxyalkylene glycols, aliphatic polyethers and the like. The widely commercially utilized condensates of polyoxypropylene glycols having molecular weights of from about 1400 to 2200 with ethylene oxide (the ethylene oxide consti-tuting 5 to 35 weight precent of the condensate) are, for example, advantageously used in the machine dishwashing for-mulations of this invention.
Suitable low foaming anionic surfactants include alkyl diphenyl ether sulfonates such as sodium dodecyl diphenyl ether disulfonates and alkyl naphthalene sulfonates.

10~809~;

Mixtures of suitable low-foaming surfactants can be utilized if desired.
In addition, machine dishwashing formulations will contain sufficient chlorine providing compound to provide 0.5%
to 2% available chlorine. For example, the formulation may contain from 0.5% to 5%, preferably 1% to 3% of a chlorocyanu-rate or from 10% to 30% chlorinated trisodium phosphate. Suit-able chlorocyanurates are sodium and potassium dichlorecyanu-rate; [~monotrichloro) tetra-(monopotassium dichloro)] penta-isocyanurate; (monotrichloro) (monopotassium dichloro) diiso-cyanurate.
Machine dishwashing compositions should addition-ally contain from 5% to 30% soluble sodium silicate having an SiO2 to Na2O mole ratio of from 1:1 to 3.2:1 preferably about 2.4:1 to inhibit corrosion of metal parts of dishwashing machines and provide over-glaze protection to fine china.
Machine dishwashing compositions will generally contain at least 10%, preferably at least 20% builder, up to a maximum of about 90% builder. The new salt compounds of this invention should constitute at least 5% of the weight of the machine dishwashing formulation.
The invention is further illustrated by the following examples wherein all parts and percentages are by weight unless otherwise indicated.
EXAMPLE I
A slurry of 70 grams sodium hydride in 1500 ml.
tetrahydrofuran is prepared and 125 ml. methanol is added, the temperature being maintained below 35C. The mixture is stirred for about 1 hour at 25 to 30C and cooled to about 0C. About 409 grams dimethyl ketomalonate is added, following which 444 grams methyl bromoacetate is added. The mixture is stirred for about l hour, the temperature being maintained ..,,~ __ 1~)88096i below 10C. The temperature is then slowly raised and the reaction mixture refluxed for 18 hours.
The tetrahydrofuran is evaporated and the residue dissolved in a mixture of water and ethyl ether. The mixture is allowed to separate and the product containing ether layer is removed and washed with water. The ether is dried over CaSO4, evaporated and the residue vacuum distilled with tri-methyl 2-(carboxymethoxy)-2-methoxymalonate fOOCH3 fOOCH3 product being collected at 110 to 113C~0.05 mm Hg. A solu-tion of 466 grams of the above ester product in 466 grams methanol is added to 1000 grams of 25% sodium hydroxide a~ueous solution. (After about 1~2 of the ester solution has been added, the temperature is about 60C and 200 ml water is added;
ester addition is completed and 300 ml water and 500 ml meth-anol are added.) The slurry is cooled to about 25C, with stirring and filtered. The solid product is trisodium 2-(carboxymethoxy)-2-methoxymalonate.
~OONa fOONa COONa EXAMPLE II
A slurry of 41.6 grams sodium hydride in 1200 ml.
tetrahydrofuran is prepared and 130 ml. ethanol added, the temperature being maintained below 30C. The mixture is cooled to about 5C and maintained ato that temperature for about 2 hours after which 400 grams diethyl ketomalonate is added, the temperature being maintained below 10C. Ethyl bromoacetate (384 grams) is then added and the temperature maintained below .

09~

5C for 2 hours. The mixture is then warmed to 25C and maintained at about that temperature for 12 hours with stirring. The temperature is then raised to and maintained at 40C for 1 hour.
The tetrahydrofuran is evaporated and the residue 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-(carboxymethaxy)-2-ethoxymalonate Cl OOCH2CH3 fOOCH2CH3 (~OOCH2CH3 separated from the residue by distillation.
A solution of 547 grams of the above ester product in 200 ml. ethanol is added to 1020 grams 25% sodium hydroxide aqueous solution, the temperature being maintained below 45C.
The mixture becomes thick and 300 ml. ethanol is added to provide a stirrable slurry which is warmed to 45C, cooled to 25C after 2 hours, and allowed to stand for 12 hours. Addi-tional ethanol (lOOml.) is added and the slurry filtered to separate the solid trisodium 2-(carboxymethoxy)-2-ethoxy-malonate.
fOONa fOONa CH3 CH2 O f o_ CH2 COONa product.
EXAMPLE III
A solution of 58 grams dodecyl alcohol in 50 ml.
dimethyl formamide is added, at 25C, to a slurry of 7 grams sodium hydride in 500 ml. dimethyl formamide. The mixture is stirred at 25C for 1 hour and then at 40C for an additional hour.

10~809~
The mixture is cooled to about -20C, and 50 grams of diethyl ketomalonate is added. After several minutes stirr-ing , 48 grams of ethyl bromoacetate is added, the temperature being maintained between -7 and -30C. The reaction mixture is allowed to warm to 25C and is stirred for 12 hours.
The product ester triethyl 2-(carboxymethoxy)-2-dodecoxymalonate ~CH2cH3 ~ 2 3 C12~2--5 (3 lC H2 is separated by extraction with ethyl ether and purified by distillation.
About 75 grams of the above ester product in 50 ml.
methanol is added to 125 grams of 25% sodium hydroxide aqueous solution cooled with an ice bath . An additional 100 ml.
methanol is added and the resultant slurry is stirred for 1 hour at 25C. The slurry is then filtered to separate solid trisodium 2-(carboxymethoxy)-2-dodecoxymalonate fOONa fOONa C H O Cl CH2 COONa product.
EXA~PLE IV
-Diethylené glycol (14 grams) is added to a slurry of about 6.4 grams sodium hydride in 300 ml. dimethyl forma-mide. The mixture is cooled to 0C and, stirred until reaction appears complete, and cooled to -50C. About 50 grams diethyl ketomalonate is added followed by addition of 48 grams ethyl bromoacetate.The temperature is raised slowly to about -20C
at which point foaming is observed. After foaming ceases, the temperature is raised to 25C the mixture is stirred for 12 hours.

108809~;

The dimethyl formamide is evaporated and the product residue hexaethyl 4,4,12,12-tetracarboxy-3,5,8,11,13-pentaoxa-pentadecandioate, 1 2 3 fOOCH2CH3 f~CH2CH3 1OOCH2CH3 H2---- lC --CH2CH2 0--CH2CH2 0--~ -- H2 purified by washing with water and molecular distillation.
Reaction of the above ester with aqueous sodium hydroxide yields hexasodium 4,4,12,12-tetracarboxy-3,5,8,11, 13-pentaoxapentadecandioate ~OONa ~OONa fOONa fOONa COONa COONa EXAMPLE V

A solution of 10 grams phenol in dimethyl forma-mide is added to a slurry of 24 grams sodium hydride in 500 ml.
dimethyl formamide. Upon completion of reaction, the mixture is cooled to -20C and 174 grams diethyl ketomalonate is added followed by 167 grams ethyl bromoacetate.
The mixture is warmed to room temperature and stirred for two hours.
The ester product triethyl 2-(carboxymethoxy)-2-phenoxymalonate fCH2CH3 fCH2CH3 ~)--O--lC CH2 is converted to the salt trisodium 2-(carboxymethoxy)-2-phen-oxymalonate COONa COONa - O C-----O CH

COONa by reaction with aqueous sodium hydroxide.

10~809~

EXAMPL~ YI - XLIX
.
One mole of the active hydroxy containing com-pounds shown in Table I, below is slowly added to a slurry of 24 grams sodium hydride in dimethyl formamide or tetrahydro-furan solvent. The quantity of solvent is sufficient to render the reaction mixture stirrable and additional solvent is added during the reaction as required. One mole of diethyl ketomalon-ate is added while maintaining the temperature as low as con-sistent with reasonable reaction rate in order to minimize formation of by-products via transesterification.
One mole of ethyl bromoacetate is added and the temperature increased to about 70C.
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 extrac-tion and/or distillation techniques.
The ester is dissolved in ethanol and reacted with aqueous sodium hydroxide to yield the salt product shown in Table I.

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EX~MPLE L
The product salts prepared according to Examples I
through XLIX when tested for sequestration function using the procedures described by Matzner et al, "Organic Builder Salts as Replacements for Sodium Tripolyphosphate", Tenside Detergents, 10, Heft 3, pages 119-125 (1973), are found to be effective sequestrants.

EXAMPLE LI
Detergent formulations containing 50% of the builder shown in Table 2 below; 17~ linear alkylbenzene sulfonate having an average molecular weight of about 230; 6% sodium silicate; remainder, sodium sulfate are prepared. The for-mulations are tested by washing identically soiled fabric swatches ~indicated in the Table) in water of 200 ppm hard-ness at 49C. containing 0.15% detergent formulation using identical washing techniques. The reflectivity of the soiled swatches before and after washing is measured instrumentally and the difference reported in Table 2 as ~ Rd. High ~ Rd values are indicative of correspondingly high detergency -;
effectiveness.

Table 2 Co~ton Fabric Polyester/Cotton Builder ~Rd Fabric ~Rd none (a filler-sodium sulfate-is used in place of builder) C 13 <5 COONa COONa CH3CH2--C CH2 16.9 8.3 I

COONa fOONa fOONa CH3-O-C - O - CH2 14.6 8.0 COONa -F F
C12H25-O-lc- CH2 14.4 6.4 COONa ~COONa COONa ~CH2 - F - (~H2)2 J 15.2 8.9 COONa The data presented in Table 2 show the salt forms of the compounds of this invention to be effective detergency builders.

EXAMPLE LII
Aqueous solutions of the salt products prepared ac-cordirgto Examples I through XLIX are reacted with hydro-chloric acid to yield the corresponding acid forms. Reaction of the acids with ammonium hydroxide yields the correspond-ing ammonium salts which are found to be effective sequest-rants when tested according to the procedure referred in Example L.

Claims (8)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. A compound corresponding to an alcohol having an alcoholic moiety which is an alkanol or alkylene glycol of up to 20 carbon atoms characterized by having at least one active alcoholic hydroxy group replaced with a substituent represented By the formula wherein M is alkali metal or ammonium and acids and esters thereof.

2. A compound according to claim 1 characterized wherein said substituents constitute at least 50% of the total weight of the compound.

3. A compound according to claim 1 characterized wherein said substituents constitute at least 85% of the total weight of the compound.

4. A detergent formulation characterized by comprising (a) from 1% to 95% by weight of a compound corresponding to an alcohol having an alcoholic moiety which is an alkanol or alkylene glycol of up to 20 carbon atoms, having at least one active alcoholic hydroxy group replaced with a substituent represented by the formula wherein M is alkali metal or ammonium, and (b) from 0.5 to 95% by weight of a surfactant selected from the group consisting of water soluble anionic, nonionic, amphoteric and zwitterionic surfactants.

5. A machine dishwashing composition comprising (a) from 5 to 90% by weight of a compound corresponding to an alcohol having an alcoholic moiety which is an alkanol or alkylene glycol of up to 20 carbon atoms having at least one active alcoholic hydroxy group replaced with a substituent represented by the formula wherein M is alkali metal or ammonium, (b) from 0 to 5% by weight of a surfactant selected from the group consisting of low-foaming anionic and nonionic surfactants and mixtures thereof, (c) a chlorine providing material selected from the group consisting of potassium dichlorocyanurate; sodium dichlorocyanurate; [(monotrichloro) tetra-(monopotassium dichloro)] penta-isocyanurate; (monotrichloro) (monopotassium dichloro) diisocyanurate; chlorinated trisodium phosphate, said chlorine providing material being present in an amount sufficient to provide from 0.5% to 2% by weight available chlorine, and (d) from 5% to 30% by weight soluble sodium silicate having an SiO2 to Na2O mole ratio of from 1:1 to 3.2:1.

6. A process of making a compound corresponding to an alcohol having an alcoholic moiety which is an alkanol or alkylene glycol of up to 20 carbon atoms characterized by having at least one active alcoholic hydroxy group replaced with a substituent represented by the formula wherein M is alkali metal or ammonium and acids and esters thereof, said process comprising reacting a conjugate base of a hemiketal of a ketomalonic acid diester and an alcohol having an active alcoholic hydroxy group which is an alkanol or alkylene glycol of up to 20 carbon atoms, with a bromo or iodo acetate ester to yield the ester form of said organic compounds; and, when the alkali metal salt form of said organic compounds is desired, reacting said ester form with an alkali metal hydroxide to yield said alkali metal salt form; and, when the acid form of said organic compounds is desired, acidulating said alkali metal salt form to yield said acid form; and, when the ammonium salt form of said organic compounds is desired, reacting said acid form with ammonia or ammonium hydroxide to yield said ammonium salt form.

7. The process of claim 6 wherein said conjugate base of a hemiketal of a ketomalonic acid diester and said alcohol having an active alcoholic hydroxy group is prepared by reacting a conjugate base of an alcohol having an active alcoholic hydroxy group with a ketomalonic acid diester.

8. The process of claim 6 wherein said conjugate base of a hemiketal of a ketomalonic acid diester and said alcohol having an active alcoholic hydroxy group is prepared by reacting an alcohol having an active alcoholic hydroxy group with a ketomalonic acid diester to yield a hemiketal and reacting said hemiketal with a base sufficiently strong to convert said hemiketal to its conjugate base.