DE2521915A1 - NEW COMPOUNDS, PROCEDURES FOR THEIR PRODUCTION AND THEIR USE IN DETERGENT FORMULATIONS - Google Patents

Description

DR. BERG DIPL.-ING. STAPF

8 MUNICH 86, POST BOX 860245

Dr. Berg Dipl.-Ing. Stapf, 8 Munich 86, P. O. Box 86 0245 Your reference Our reference 8 MÖNCHEN 80 4 C ΜΛΙ Your ref. Our ref. MauerklrcherstraBe 45 '** · HHI

Lawyer File 26 OQO
Be / Ho

Monsanto Company St. Louis / USA

"New compounds, processes for their preparation and their use in detergent formulations ¹¹

This invention relates to compounds useful as complexing agents for various metal and / or alkaline earth metal ions are suitable processes for their preparation and detergent formulations which these compounds as

43-21-4178A GW -2-

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β (0811) 988272 Telegrams: BERGSTAPFPATENT Munich Banks: Bayerische Vereinsbank Munich 453100

987043 _ΤΕίΕ χ. 0524560 BERG d Hypo-Bank Munich 3892623

983310 'Postscheck Munich 653

contain functional components.

It is well known that compounds with the ability to form complexes with metal and / or alkaline earth metal ions, that contribute to water hardness, e.g. magnesium and calcium, for many purposes, such as water treatment (e.g. for softening, scale inhibition) are suitable. (It should be noted that some complexing agents still have the ability to To avoid precipitation of hardness ions from the water even if they are in stoichiometrically insufficient Quantities are used to sequester the hardness ions. Such agents have a "threshold" effect). Farther some compounds have the ability to improve the cleaning effect of detergent formulations, to potentiate or supplement and are therefore useful as functional components of these formulations. Conventionally, such ingredients are referred to as detergent builders, although for some purposes, e.g. in formulations for dishwashers, the functionality of such compounds is stronger or different appears to be from a simple "building" of the behavior of the other constituent parts of the Formulation.

The formation of new complexing agents and methods of making them have long been recognized by those skilled in the art

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With regard to the various recognized uses aimed at such materials.

The invention relates to new methods and compounds as complexing agents for various Metal and / or alkaline earth metal ions - especially for magnesium and calcium ions - and as functional components are suitable in detergent formulations and / or have surface-active properties.

The compounds of the invention have at least one

COOM COOM

I I

0 C 0 CH ₀

COOM

Substituents on (where M is alkali metal or ammonium) and are prepared by the fact that ■ the corresponding base of a hemiketal with a bromine or iodine acetate ester implements. These compounds, their preparation and uses will be further preferred by the following description of them Embodiments explained.

The compounds of the present invention correspond to alcohols having an active alcoholic hydroxyl group, by a substituent of the formula

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COOM COOM

I I

COOK

is replaced, in which M is an alkali metal or ammonium, as well as their acids and esters, provided that the part with that of the ■ '

GOOM COOM

I I

- 0 C 0 CH "

I.

COOM substituent is linked, not the formula

COOM

A C

A ^!

where A and A ^{1 are} hydrogen or methyl.

The term "active alcoholic hydroxy group" is used used here as having an alcoholic hydroxyl group referred to, which is convertible into a corresponding base group, which is with Djähylketomalonat to form a Substituents of the general formula

COOC ₂ H ₅

- 0 C 0 "

COOC ₂ H _{5 can} convert, where - 0 "" of course

-5-509849 / 1039

- 5 is linked to the cation of the corresponding base,

e.g. 0 "Na ⁺ .

The conversion of alcohols into their corresponding base forms is well known. The corresponding base is elucidated by reacting the alcohol with a sufficiently strong base to protonate a hydroxyl group. In general, effects the deprotonation of the reactive hydroxyl groups easily with sodium, potassium, sodium hydride, potassium hydride, sodium or potassium t-butoxide, sodium amide or potassium amide, etc. The reaction is conveniently effected at temperatures from 0 to 115 ⁰ G in any solvent for the alcohol which does not adversely react with the strong base. Examples of the solvents suitable for this purpose with various alcohols include tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, ethyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether or the like. In cases where the alcohol reactant is a liquid, excess alcohol can be used as a solvent. Mixed solvents can also be used if desired. Further details on the conversion of alcohols to corresponding bases can be found in: Morrison and Boyd, Organic Chemistry, 3rd Edition, Allyn and Bacon, Inc., (1973) pages 526, 527, Feuer and Hooz, The Chemistry of the Ether Linkage, edited by Patai, Interscience Publishers (1967), chapter

-6-509849 / 1039

10, page 447, and Schmidt and Bayer, Methods of Organic Chemistry (Houben-Weyl) Volume VI / 2, Georg Theime Verlag (1963) Oxygen Compounds 1, Part 2 and in the reference points indicated there.

The corresponding base formed from the alcohol is then combined with anhydrous diethyl ketomalonate, preferably at temperatures from -50 to 60 ° C and preferably in the solvent used to prepare the corresponding base around. The occurrence of the reaction can easily be determined by means of conventional analytical methods, for example by hydrogen or carbon-13 nuclear magnetic Resonance spectral shifts or by observing the disappearance of the characteristic yellow to yellow-green color of anhydrous diethyl ketomalonate

When polyhydroacyl alcohols, as indicated above, reacted are, the substituents formed therefrom can formula

GOOO ₂ H ₅ - OCO "

COOC ₂ H ₅

Transesterification with other sterically accessible hydroxyl groups of the alcohol suffer with the formation of a cyclic lactone, the one

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V ⁰

O - C - O '

COOC

2 ^Η 5

Part contains. Therefore, if an alcohol is tested in reactions as described above to see if all or some of its hydroxyl groups are "active" confirms the formation of either one

COOC ₂ H ₅

COOC ₂ H ₅

Substituents or of a lactone that is a

- C - 0 "I.
COOC ₂ H ₅

Part contains the presence of an active hydroxy group

For further description, the compounds of this invention can be represented by the general formula

COOM COOM

ι ι

R - (- 0 C 0 CH ₉ ) _o ,

^{ά a}

COOM

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wherein R is an organic residue that removes the residue of an alcohol with at least one active therefrom alcoholic hydroxyl group and a is an integer representing the number of the corresponding alcohol corresponds to removed hydroxyl groups.

Although the compounds of this invention are described above with reference to analogous alcohols, and preferably, As explained below, derived from alcohols, the compounds of this invention are not intended to be based on such Compounds that are actually restricted by alcohols descend. Thus, the compounds of this invention can also be made by synthetic methods which do not require compounds containing active hydroxyl groups as precursors. This one The chosen form of description is therefore only intended to facilitate understanding of the scope of the invention.

Examples of compounds of this invention include

COOM
ι Γι COOM
I. I.
pt CH ₂ I.
COOM substituted with a) alkanes, how COOM
i I.
C.
I.
COOM CH, COOM
- CH ₂ - 0

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COOM COOM

! I.

ν / Xl «2 —--- · olio W —————— ^ VJ ——— · ———- oHrt

JC- C.

COOM

(Both of the above compounds are particularly preferred embodiments of the invention with regard to it excellent detergency builder behavior. It should also be noted that these connections are easy are biodegradable, which is quite unexpected in view of the resistance of a carboxylated analog against biodegradation,

COOM COOM COOM

I I

(TfJ _____ (\ ___ ΓΙ _______ A Λ1ΤΤ

OJIp ——— U —— L »——— υ Oün

COOM

this is described analogously in US Pat. No. 3,742,045).

COOM COOM

I I

ΓΉ ( ρTT ^ π ___— ρ _______ ο ______ pw

¹¹ ι ²

COOM

(Substituted long-chain alkanes, e.g. C ₁₀ to C ₂₀ , of this type have properties both as surface-active agents and as complexing agents and are therefore also used as emulsifiers, foam-forming agents, etc.

useful).

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CH ₂ CH ₂ CH ₂ -

CH COOM COOM
C.

C.
0 -C

0OM
CHo-

H ₂ C

COOM COOM - 0 - C - 0 - CH;

CH ₅ CH _9-0

COOM COOM CCOM

I I

- CO-CH ₀

COOM

COOM

Γ °

COOM

COOM CH ₂

CH-

CH9

OOM COOM
C-0-

00M

, CH -CHo-CH ₉ CH.

ETC.

b) Cycloalkanes, such as

.CH:

CH

CH

COOM
• CH — 0 C 0-

CH;

■ CH2 '

0OM

: 00Μ ^{: Η} 2

COOM COOM

H ₂ CO CO HC

COOM

"CH O

-CH-COOM I.

• c -

I COOM

COOM

- CH-

c) alkanoia, such as COOM COOM

HO - ^ - CH ₇ CH ₇ - 0 - C - O - CH-

COOM

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d) ether, like

COOM COOM

^^ ch h (ch. ch ₂ -o) ₉ -ch ₉

C 0 CH.

I.
COOM

CH,

I ³

H (CH CH ₂ -O) ₅ CH ₂ CH ₂ -

COOM II - C - 0 - CH I
COOM

COOM 2

COOM COOM

₂ ο - C - 0 CH ₂ -CH ₂ -

COOM

-0 - CH ₂ CH ₂ - 0 - C - 0 - CH

COOM C -

COOM

COOM

etc.

e) aromatics, such as

COOM I

C ΟΙ COOM

COOM \

H (CH ₂ CH ₂ O) ₄ CH ₂ -

COOM

C-0-

COOM

COOM CH-,

CH ₃ -CH- CH _f

COOM C - COOM COOM CH ₀

-12-

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COOM COOM

I I

-C-0 -CH ₂ ·

COOM

COOM COOM

COOM

The parts with which the

COOM COOM
'I.

- 0 C - 0 CH ₂

COOM

Substituents connected may have further substituents that are not chemically incompatible with the

- COOM COOM

I I

I ²

COOM

Share.

For convenience, the compounds of this invention are illustrated above in the salt forms. It however, it should be pointed out that they can also exist in the sster and acid forms. It has already been

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leads that in some cases, for example in the case of a connection such as

COOM COOM

I I

HG — CHq ——CH / p ~~ - 0 —— C —— ~ 0 ——— CHp

COOM

the corresponding ester and the acid forms can have a lactone structure, such as

CHp C

I I OCHpCOO Ethyl or Hydrogen CH ₂ ./C^ *

^^ COO Ethyl or Hydrogen

According to the process of this invention, such compounds are prepared by reacting a corresponding base of a hemicetal or ketomalonic acid diester and an alcohol having an active alcoholic hydroxyl group with a bromine or iodine acetate ester. Such a reaction gives the ester forms of the compounds described above. By reacting these ester forms with an alkali metal hydroxide, the corresponding alkali metal salt forms are obtained, which can be converted to the corresponding acid forms by conventional acidification processes. The ammonium salt forms are obtained in a suitable manner by neutralizing these acid forms with ammonia or ammonium hydroxide »

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According to one embodiment of the invention, an alcohol which contains an active alcoholic hydroxyl group is reacted with a strong base to form the corresponding base form of the alcohol. Such reactions have already been described in the explanation of the term "active alcoholic hydroxyl groups". In general, it is preferred to use sodium or potassium metals or hydrides to convert the - OH groups into --O ^- Na ⁺ or --O "- K ⁺ groups, provided the alcohols are sufficiently acidic to react with these bases .

The corresponding base form of the alcohol is then set with a ketomalonic acid diester

COOX

C-O

I.
COOX

to form a corresponding base of a hemiketal of the ester and alcohol by converting the -O "" - substituents the base corresponding to the alcohol to one

COOX - OCO "*
COOX

Substituent is and if, for example, the -O ~ substituent is connected to an Kohlenetoffatom, located in the vicinity of a hydroxy-substituted carbon

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- 15 atom is located, a lactone is formed, which is the part

O GOOX

contains. In the foregoing formulas, X can be any organic part because of its chemical reactivity or steric hindrance does not participate in the reaction. The reaction takes place in all cases where X is a lower alkyl group such as methyl or ethyl is. However, it is generally desirable that as far as it is from the viewpoint of chemical reactivity and steric hindrance appears to be possible, X corresponds to the organic part to which the Corresponding base form of the alcoholic hydroxy group is linked to the formation of a mixture of products to avoid transesterification reactions and the difficulties encountered in the separation of such mixtures.

The reaction with the Ketomalonsäurediester is preferably carried out in the same solvent system that was used to convert the alcohol into its corresponding base at temperatures from -50 to 60 ^0C, preferably -20 to $ ü ° C. According to a further embodiment of the invention, the alcohol can first be converted into a hemi

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be converted into ketal by reaction with the ketomalonic acid diester and then reacted with a strong base to form the product that forms the part

COOX I

- 0 C

COOX or 0

O COOX

contains. In general, however, the conversion of the alcohol to its corresponding base form is described below Reaction with the ester preferred.

When the starting alcohol has more than one active hydroxyl group contains, the amount of reactants and the severity of the reaction conditions in the above-described Reaction determines whether only one or more such groups should be displaced in the reactions.

- 0 C 0 or

I ν C-O

COOX N. • ^

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containing product is then reacted with a bromine or iodine acetate ester ZCELCOOX (where Z is Br or I) for conversion of the -O ~ substituent into a -OCHpCOOX substituent um, whereby the ester form of the compounds described is obtained as the product.

The bromoacetate or iodoacetate can be added as such or formed in situ, including, for example, a Mixture of sodium iodide and chloroacetate used. the Reaction temperatures are not critical, with a temperature range from -20 to 100 ° C. usually being satisfactory is.

In general, the reactions described can be carried out at atmospheric pressure, although in some cases it may be desirable to use reflux or pressure conditions to avoid excessive loss of reactants or solvents , or to enable higher temperatures to be used.

The reaction of the esters with alkali metal hydroxide leads to the formation of the alkali metal salt forms of the desired product compounds, which can be converted into the acid form by acidification (for example by means of a strongly acidic ion exchange resin such as sulfonated polystyrene or by a strong mineral acid).

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Obtained by reacting the acid form with ammonium hydroxide the ammonium salt forms of the compounds.

As previously discussed, the acid and ester forms of the compounds are used as intermediates in the manufacture of the Salt forms valuable.

COOM 0 - COOM I. I. Λ
I. - CH ₂ COOM

Substituents on these compounds exhibit sequestering and detergent builder functionality. More useful Functionalities can be provided by the part where the

COOM 0 - COOM I. I. C.
I. - CH ₂ COOM

Substituents are linked, are formed.

As already mentioned in the description, the parts can be attached to the

COOM COOM

t I

_____ yj -_-_—. ^ _ — ___ y —__ — _ Vyü

COOM

Substituents connected aind, aliphatic, alicyclic, aromatic, alkylarooatieche, alcohol and ether parts

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Contents derived from aliphatic alcohols or alicyclic Alcohols, aromatic alcohols, alkylaromatisehen Alcohols, polyhydric alcohols and hydroxy ethers can be derived.

Preferred classes of compounds according to the invention are those where the part with which the

COOM COOM

I I

Pi _____ π r \ nu

- (j ———- \ j —— yj _— V _- , ji

COOM
Substituents are connected, is formed from:

1) An alkane with 1 to 20 carbon atoms. The substituted ones C ^ to C alkanes form one particularly effective builder functionality while the higher alkanes provide additional surfactant functionality.

2) Polyalkylene oxides ^ in particular with polyethylene oxides

2 to 20 molecular parts of ethylene oxide, which is used as a solubilizing agent Agents with sequestering properties are effective.

3) alkylbenzenes (preferably with alkyl chains from 5 to 20, especially 8 to 15 carbon atoms), which are surfactants with sequestering properties. Links, where the

COOM COOM

ι ι

- 0 C 0 CH ₀

I ²

COOM -20-

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Substitutes associated with the benzene ring will be special preferred.

In general, compounds wherein the

COOM COOM I I

—— O ——— 0 ———— 0 —— CH I ²

COOM

Substituents make up at least 50 %, preferably at least 85% by weight of the compound, preferred for purposes where sequestering or builder functionality is of primary importance. It is also generally preferred that such substituents be attached to the non-carboxylated carbon atoms. In general, compounds having one or two such substituents are preferred in view of their ease of preparation.

For detergency builder purposes, the use of the alkali metal salts, in particular the sodium salts are preferred. However, it can be used in some formulations (such as liquid formulations where greater builder solubility is desired) the use of ammonium or Alkanolammonium salts may be desirable.

The detergent formulations can contain at least 1 wt and preferably at least 5 wt. # of the salt forms of the invention Connections included. To maximize

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In order to achieve parts for the builder formulations of this invention, the use of 5 "to 75 7 ° of these salts is particularly preferred. Such salt compounds can be the sole detergent builder or the compounds can be used in conjunction with other detergent builders which are present in the formulation from 0 to 95% by weight. Builders that can be used with the salt compounds prepared by the process of the invention include water-soluble inorganic builder salts such as alkali metal polyphosphates, i.e. the tripolyphosphates and pyrophosphates, alkali metal carbonates, borates, bicarbonates and silicates and water-soluble organic builders, the aminopolycarboxylic acids and salts, such as alkali metal nitrilotriacetates, cycloalkanepolycarboxylic acids and their salts, ether polycarboxylates, alkyl polycarboxylates, epoxypolycarboxylates, tetrahydrofuran polycarboxylates, such as 1,2,3,4- or 2,2,5,5-benzo-tetrahydrofarboxylates, oxo-tetra-carboxylates dated starches, amino (trimethylene phosphonic acid) and their salts, diphosphonic acids and their salts (for example methylenediphosphonic acid, 1-hydroxyethylidenediphosphonic acid) and the like.

The detergent formulations will generally contain 5 to 95% by weight of total builder (although if desired, larger or smaller amounts can be used), which as already mentioned, exclusively by the.after this Invention prepared builder salt compounds or by

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Mixtures of such compounds with other builders can be formed. The total amount of builder used will depend on the intended use of the detergent formulation, the other ingredients of the formulation, the Ρττ conditions, and the like. For example, heavy duty detergent powders will usually contain 20 to 60 percent builders, liquid dishwashing detergents 11 to 12 percent builder, and dishwasher formulations will usually contain 60 to 90 percent builders. The optimal builder level, as well as the optimal mixtures of builders of this invention with other builders, can be determined for the various purposes by routine testing according to conventional detergent formulation rules.

The detergent formulations will generally contain a water soluble detergent surfactant, although the surfactant component can be omitted from formulations for dishwashers. It can be all water-soluble anionic, nonionic, zwitterionic and amphoteric surfactants can be used.

Examples of suitable anionic surfactants include soaps such as the salts of fatty acids with about 9-20 Carbon atoms, e.g. salts of fatty acids derived from coconut oil and tallow, alkylbenzenesulfonates, im particular linear alkylbenzenesulfonates in which the alkyl group Has 10 to 16 carbon atoms, alcohol- -25-

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sulfates, ethoxylated alcohol sulfates, hydroxyalkyl sulfonates, Alkenyl and alkyl sulfates and sulfonates, monoglyceride sulfates, acid condensates of fatty acid chlorides with hydroxyalkyl sulfonates and the like.

Examples of suitable nonionic surfactants include alkylene oxide (e.g. ethylene oxide) condensates of mono- and polyhydroxy alcohols, alkyl phenols, fatty acid amides and fatty amines, amine oxides, sugar derivatives such as sucrose monopalmitate, long-chain tertiary phosphine oxides, dialkyl sulfoxides, fatty acid amides (e.g. mono- or diethanolamides of fatty acids having 10 to 18 carbon atoms) and the like.

Examples of suitable zwitterionic surfactants include derivatives of aliphatic quaternary ammonium compounds indications, such as 3 ~ (N, N-dimethyl-N-hexadecylammonium) propane-1-sulfonate and 3- (N, M-dimethyl-N-hexadecylammonium) -2-hydroxypropane-1-sulfonate.

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

It should be noted that the above examples of surfactants are not exhaustive, and so are numerous others Surfactants are known to the person skilled in the art. It is on-

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indicate that the selection and use the surfactants should be made according to the well-known teachings of detergent formulation. For example anionic surfactants, especially linear alkyl benzene sulfonate preferred for heavy-duty detergents, while non-ionic surfactants with low foaming Use in formulations for dishwashers are preferred.

The amount of surfactant used in the detergent formulations will depend on the surfactant selected and the end use of the formulation. In general, the formulations should contain from 5 to 50 percent by weight of surfactant, although amounts of 95 percent or more of surfactant can be used if desired. In general laundry powder usually contain 5 to $ 50, preferably 15 to 25 ° i surfactant formulations for dishwashing 0.5 to 5 io, liquid rinse 20 to 45 fo. The surfactant to builder weight ratio will generally be in the range from 1:12 to 2½.

In addition to the builder and surfactant components, the Detergent formulations fillers such as sodium sulfate and small amounts of bleaches, dyes, optical brighteners, agents that redeposition dirt prevent containing fragrances and the like.

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- 2.0 -

In the case of dishwasher preparations, the surfactant be an anionic, or preferably nonionic, low foaming surfactant that is 0 to 5 $ the formulation can form »

The term "surfactant with low foaming" denotes a surfactant which, in the foaming test described below, reduces the revolutions of the wash spray arm during the washing and rinsing sequences by less than 15 % , preferably less than 10%.

In the foaming test, 1.5 g of surfactant are placed in a 1969 Kitchen-Aid Home Dishwasher, Model No. "KOS-16, manufactured by Hobart Manufacturing Company which includes means to rotate the wash spray arm during counting the wash and rinse cycles. The machine is running using distilled water with an initial machine temperature operated by 40 0. The number of rotations of the spray arm during the washing and rinsing processes is counted. The results are compared with the conditions obtained when using the machine works without surfactant loading and the decrease of the The number of revolutions is determined in percent.

The surfactant should of course be compatible with the chlorine-containing component described below be. Examples of suitable nonionic surfactants

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include ethoxylated alkylphenols, ethoxylated alcohols, both mono- and dihydroxy alcohols, polyoxyalkylene glycols, aliphatic polyethers and the like. The condensates of polyoxypropylene glycols used on an industrial scale with molecular weights of about HOO Ms 2200 with ethylene oxide (the ethylene oxide being 5 to 35 Weight $ of the condensate forms) can, for example, advantageously used in the dishwashing machine formulations of this invention »

Suitable low sudsing anionic surfactants include alkyl diphenyl ether sulfonates such as sodium dodecyl diphenyl ether sulfonates and alkyl naphthalene sulfonates.

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

In addition, dishwashing machine formulations will contain sufficient chlorine-providing compounds to produce 0.5-2 $ available chlorine. For example, the formulation may contain 0.5 to 5, preferably 1 $, i to 3 or 10 to 30 ° chlorocyanurate fo chlorinated trisodium phosphate. Suitable chlorocyanurates include sodium and potassium dichlorocyanurate, / TMonotrichlor) tetra (monopotassium dichlor) _J7-penta isocyanurate, (monotrichlor) - (monopotassium dichlor) diisocyanurate.

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Preparations for dishwashers should furthermore contain 5 to 30 io soluble sodium silicate with a Na ₂ O molar ratio of 1 * 1 to 3.2: 1, preferably about 2.4: 1, in order to inhibit the corrosion of the metal parts of the dishwashers and to form an overglaze protection for fine porcelain.

Dishwasher preparations will generally be at least $ 10, preferably at least $ 20 Builders included up to a maximum of approximately $ 90 Builders. The new salt compounds of this invention should at least 5 percent by weight of the dishwasher formulation form.

The invention is further illustrated by the following examples in which all parts and percentages apply relate to weight unless otherwise stated.

example 1

A suspension of 70 g of sodium hydride in 1500 ml of tetrahydrofuran is produced and 125 ml of methanol are added, the temperature being kept below 35 ^° C. The mixture is stirred for about 1 hour at 25 to 3O ⁰ C and cooled to about 0 C. then 444 g of methyl bromoacetate Add approximately 409 g dimethyl ketomalonate to. The mixture is stirred for about 1 hour, the temperature being kept below 10 ^° C. The temperature

509849/1 039

is then slowly increased and the reaction mixture 18 hours held at reflux.

The tetrahydrofuran is evaporated and the residue is dissolved in a mixture of water and ethyl ether. You leave that The mixture separates and removes the product contained in the ether layer and washes with water. The ether dries one over CaSO., evaporated and the residue distilled under vacuum, whereby one trimethyl-2- (carboxymethoxy) -2-methoxymalonate

COOCH, COOCH,

OH - 0 - I - - 0 - CH

COOCH ₃

at 110 to 113 C / 0.05 torr. A solution of 466 g of the ester product given above in 466 g of methanol is added to 1000 g of 25% aqueous sodium hydroxide solution. (After about half of the Esterlösung was added are added at a temperature of about 60 ⁰ C, 200 ml of water. After completion Esterzugabe are one 300 ml of water and 500 ml of methanol).

Cool the slurry to about 25 ° C with stirring and filter. The solid product is trisodium 2- (carboxymethoxy) -2-methoxymalonate "

COONa COONa CH ₃ C 0 CH ₂ -29-

COONa 509849/1 039

Example 2

Prepare a slurry of 41.6 g of sodium hydride in 1200 ml tetrahydrofuran and starts passing to 130 ml of ethanol, keeping the temperature below 3O ⁰ C. The mixture is cooled to about 5 ° C, this temperature for about 2 hours at reserves, after which 400 g Diäthylketomalonat added, keeping the temperature below 1O ⁰ C. Ethyl bromoacetate (384 g) is then added and the temperature is kept below 5 ° C. for 2 hours. The mixture is then heated to 25 ° C. and this temperature is maintained for about 12 hours with stirring. The temperature is then increased and kept at 40 ^° C. for 1 hour.

The tetrahydrofuran is evaporated and the residue is dissolved with ether and washed with water. The ether fraction separates one off and dried over calcium sulfate. Then you evaporate

the ether and receives triethyl-2- (oarboxymethoxy) -2-ethoxymalonate as product ,

COOCH ₂ CH ₅ COOCH ₂ CH ₅

CH ₅ - CH ₂ - 0 C 0 CH ₂

COOGH ₂ CH ₅

which is separated from the residue by distillation.

A solution of 547 g of the above ester in 200 ml of ethanol are added to 1,020 g of 25 $ aqueous sodium hydroxide solution, keeping the temperature below 45 ⁰ C. The GE-

-30-

5098 49/103 9

50 -

mixing thick and 300 ml of ethanol to form a stirrable slurry to which is heated to 45 ° C, after 2 hours at 25 ⁰ C.kühlt and left to stand for 12 hours. Additional ethanol (100 ml) is added and the slurry is filtered to separate the solid trisodium 2- (carboxymethoxy) -2-ethoxymalonate.

COOUa COONa ι I

₇ ; ■ "" ■ "" CHq Ό ————— C ———— 0 ■ -—— ~ CH _n 3 I , 2

COONa

Example 3

A solution of 58 g of dodecyl alcohol in 50 ml is added Dimethylformamide at 25 C to a slurry of 7 g of sodium hydride in 500 ml of dimethylformamide. One stirs the mixture for 1 hour at 25 C and then another hour

de at 40

The mixture is cooled to about -2O ⁰ C and 50 g of Diäthylketomalonat to. After several minutes of stirring, 48 g of ethyl bromoacetate are added, the temperature being kept between -7 ° and -30 ° C. The reaction mixture is then allowed to warm to 25 ° C. and stirred for a further 12 hours.

The ester product triethyl 2- (carboxymethoxy) -2-dodecoxymalonate is separated

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COOCH ₀ CH ,, COOCH ₀ CH, 2 3 j ^

0 - 0 0 CH ₂

COOCH ₂ CH ₃

by extraction with ethyl ether and purified by distillation.

About 75 g of the ester obtained above in 50 ml of methanol are added to 125 g of a 25 ^ - igen aqueous sodium hydroxide solution. A further 100 ml of methanol are then added and the resulting slurry is stirred 1 hour at 25 ° C. The slurry is then filtered for the separation of the solid trisodium 2- (carboxymethoxy) -2-dodecoxymalonate.

COONa COONa

I I

COONa

Example 4

Diethylene glycol (14 g) is added to a slurry of about 6.4 g of sodium hydride in 300 ml of dimethylformamide. The mixture is cooled to 0 ° C. and stirred until the reaction appears to have ended and then cooled to -50 ° C. 50 g of diethyl ketomalonate and then 48 g of ethyl bromoacetate are then added. The temperature is raised langsam.auf about -20 ⁰ C to obtain at this temperature foaming

509849/1039

observed. After foaming has ended, increase the Temperature to 25 ° C and the mixture is stirred for a further 12 hours.

The dimethylformamide is evaporated and the residue is purified as a result of hexaethyl-4,4,12,12-tetracarboxy-3,5,8,11,13-pentaoxapentadecanedioate
COOCH ₂ CH ₃ COOCH ₂ CH ₃ COOCH ₂ CH ₃ COOCII ₂ CH ₃

CII ₂ 0 - C 0 - CII ₂ CII ₂ - 0 - CH ₂ CH ₂ - 0 - C 0 -

COOCH ₂ CH ₃ COOCH ₂ CH ₃

by washing with water and molecular distillation.

By reacting the above ester with aqueous sodium hydroxide, hexasodium 4,4,12,12-tetracarboxy-3,5,8,11,13-pentaoxapentadecanedioate is obtained

COONa COONa COONa COONa

CH ₂ --- 0- C 0 CH ₂ CH ₂ 0 -CH ₂ CH ₂ 0-C-O CH ₂

COONa " COONa

Example 5

A solution of 10 g of phenol in dimethylformamide is added to a slurry of 24 g of sodium hydride in 500 ml of dimethylformamide. After completion of the reaction the mixture is cooled to -20 ⁰ C and 174 g Diäthylketomalonat, then 167 g of ethyl bromoacetate to.

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

509849/1039

The ester product, triethyl-2- (carboxymethoxy) -2-phenoxy malonat

COOCH CH, COOCHpCH

I I

0 C 0 CH ₀

I ²

C00CH ₂ CH,

is converted into the salt trisodium 2- (carboxymethoxy) -2-phenoxymalonate

COONa COONa II

- 0 C 0 - CH ₂

COONa

by reaction with aqueous sodium hydroxide.

Examples 6-49

One mole of the compounds containing active hydroxyl groups indicated in Table I below are added slowly to a slurry of 24 g sodium hydride in dimethylformamide or tetrahydrofuran solvent. The amount of solvent is sufficient to make the reaction mixture stirrable and to add more solvent one during the reaction as needed. One mole of diethyl ketomalonate is added while maintaining the temperature holds down as this allows a reasonable reaction rate to prevent the formation of by-products to reduce transesterification.

-34- 509849/1039

Adding 1 mol of ethyl bromoacetate to and raised the temperature to about 70 ⁰ C ₀

After the reaction has ended, the solvent is removed under reduced pressure and purifies the ester residue product given in Table I by means of conventional Extraction and / or distillation processes.

The ester is dissolved in ethanol and reacted with aqueous sodium hydroxide to give that shown in Table I. Salt product received.

Table Is

09843 / 103S

Table I.

cn o co

Example hydroxyl group-containing compound

Ester product (5) Salt product (5)

C ₂₀ H ₄ IOH - t ^C 20 ^H 4th COOCH- COOCH ₀ CH- Γ COOCHoCH- ^C 20 ^H 41 COONa
i COONa
I. * I. 6th , CH ₃ COOCH ₂ CH ₃ -CH ₂ - (Ih ₂ 0 -C 0
I. -CH ₂ I. OH ^C "3 _χ ρ C "0 2 CH ₃
I. CQONa COONa OH CH ₃ (CH ₂ ) ₉ CHCH ₃ I.
j 0 COOCH ₂ CH ₃ • * HC -
ι · COONa
j COONa " ^CH 2 7th I.
CH ₃ -CH-CH ₃ cih ' COOCiI ₇ CII, COOCH ₉ CH,
j £ · ό I.
~ o ~~ "c ~ u" -CH ₂ CH,
I. —-C 0 - -CH ₂ I ³ COONa Oh * CH ₇
I. COOCfI ₂ CH ₃ ; CH ₇
·, I 2 8th CH ₃ CH ₂ CHCH ₂ CH ₃ HC-T 0 HP—— ·
(JlI ₂ COONa COONa
Ii CH ₂ COOC-I ₇ CH ₇
I I 3 CU ₃ 0 -C 0 -CH ₀
I 2 ^CH 3. CH ₇ -
I. COONa CH ₇
I. COOCH ₂ CH ₃ HC - HC - • CCH ₂ ) COONa 9 (CH ₂ ) 9 COOCH ₉ CH ₇
I. CH ₃ I.
- 0 · —C * —- ~ 0 "-
j I. 0 - C 0 ₉ COONa ι
VU
CTi
I. coo: h ₂ ch ₃

CD CJl

Table I - continued

10 CH ₂ CH 3 ■ ₂ 0H CH ₂ CH ₃ COOCH ₂ CH ₇ "COOCH ₉ CH,
3 1 2 3 I. CH ₇ COOCILCH, COOCH ₉ CH- "CH CH ₇ CH ^ rnnwa
V _- I - X ^ W b * W » COONa COONa • if
2 25219 ' CH- CCHJ-CHCH ₇
■ j 2 j * · OH I i
Pll / T ¹ TT "^ ΓΜΤ Pll .. .... C \ P ... —... Π PX I """" II ^ ^J I
. HC 0 - C 0 CH,
ι ι 2 I.
/ ■ / - "Ti ^ ρττ ρττ
3 * ώ 'ο 2 Ch ₂ —-C cn UIl-T ^ LH-J 3 UlI- LlIo U--L 0 CH ₂ CH ₉ COOCH ₀ CH,
ι ² 2 3 '
ZH ₃ -CH-CH ₃ : h ₂ 11 (CH ₂ ) ₃ .CH ₃ CCOCH ₉ CH ₃ : h ₃ (CH ₂ ) ₂ CH ₃ COONa
1 CH ₃ (CH ₂ ) ₅ CH-CH _(CH2) 3CH3 CuOCH ₂ CH
CH ₃ (CH ₂ ) ₅ CHCH ₂ - 0 - C - 0 -
. '2 , COOCH ₇ CH,
I * 3
-CH ₂ I.
(CH ₉ ) -CHCH -, - O- COONa I.
CH ₇ ■ CH ₃ COOC-I ₂ CH ₃ 3 COGNa I. ΟΙ
O 12th CH
I ³ rn-r-πι η -r - ~ t COOCH ₉ CH-,
ι .2 3 ^{: H} 3 . i
_p η
Li U
j CH ₇ COONa COONa,
I! ' ) 849 CHw-C-CH ₇ OH Oil * f \ u LiIl ^ U "Vj J
I I CH ₂ COONa —C— CHo- 0— Ο
Ι I * -> CH ₃ I. CH ₃ COOCn ₂ CH ₃ ^{: H} 3 - O CH - » 13th CH ₇ -CH-CH,
ο j 3 CH ₃ -CI-H-CH-
I. CH ₃ • COONa 039 ■ CH
I ²
HC-OH
I. -CH-CH ₃ I.
~] .CH ₂
CH ₃ CH-CH ₃ : h ₃ - CH ₂ , COONa HC — bC Ο
ι \ I 1 · 1
CH. '' COONa
-CH-CH

Cj «Τ -Z 'CM O X O -CJ CJ-

O
O
CJ CJ

CM

cd -O *

O I O O 'O CJ CJ CJ

Φ rH ι-)

it

X CJ

CM

to

CM

-CJ

CJ-

CJ O O CJ-

CM J

-G — CJ-

to X CJ CM

X CJ O O CJ

CM

-υ-

IO

CJ

-CM

ιο

X CJ

tO CM I

χ χ I

CJ CJ Ci-

tO X CJ

ΓΜ

CM

• CJ - CJ ■

X -O

X CJ

CJ CM

X CJ O «Ν

O X O CJ

.J-. I.

CJ CM O

CJ O O CJ-

to

CJ

CM

CJ

-CJ

ITS

VD

CM

to

-38-

5D9849 / 1039

H H CD

φ m ■ ρ

Ci 1 . 00 U C *
-? ■ • f I. COONa U > c5 • JP \ - 38 - CM 1 O • CS a: • K) [T CM .CS
.0.- I. ■ IO rc
U CD <M I. COON I. • 0. CD' ■ · I. I. to O
O Is Λ, 0 I. Jl d U rc Ji rc *O As CM d 0 m
υ - u
t Q COON; ·% ■ '
O CV U u— I. U ONa C U -U 0 -u - U U I. Ö O ο a: O 0 O ONa u- I.
O
I. IJ O 1 to O O U- it 0 ONa I. O a • 5 'COONa
C - 0
COONa rc -u COONa U rc O
CVJ - υ 0 ? U CM CJ —Υ
O
I. u— rc • ι CM
rc 9 I J 1 CJ O CJ \ K)
U -U- K) JL CJ <> 4 C. ^ι -Π I. O ) 4th O O tol j o rc m /
CM
U O
I. I. j to Cj '/ CJ U Lr K) A. \ K)
U X 'S rc TC rc j KS
rc
U J . CJ rc
U U U CM to
rc
CJ rc
O
I. CM rc σ \
ι— CJ I. O CM • υ -C O rc C. CJ- -u - CM j— to CJ <
C. ■ 3:
U O to I. K) CM rc j U to U to CM O O rc CM rc O υ— u -
I. U D.
J- U U CM u O: I.
O CM O CM
"τ · O -U CJi rc
U O U -U O tO f ^^^ J O O U— O CJ- O K) O CJ ^ ^- "/ CJ . u - K) ^ K) O rc U to CJ CM U K) • to ■ ID CM rc
U - * ° f G O U CM [j J υ -7 CM O O rc
U O I. / G U - O O ■ f— \ /
rc 0 -U O CM CJ 0 u - rc υ - CJ gate' -C to rc 1 I. C. rc K) / 0 U -rc ' Ki > ; ho- < U O j? CM CM u 'Ά U M. CM
CM ►τ « U ■ O C. C. 3 - )

509849/1039

rf

d ο υ-

χ -cj

CJ CJ (J - CJ - U

CJ CTi -P

(D rH rH

CJ
IN THE approx < CJ
O -U IDOÜ CJ - ro D.
approx O -IDOO

CJ-U

CM

-40-

509849/1039

-P Φ CQ

■ Ρ

H H

α)

• N I. £ Π CM τ CM OJ O • d CJ CJ ^: 2: rf o4 • OJ to CJ • CM nc to • 2: " CD « to • I. ■ \ CJ te . rs ns O O TZ a: ■ ~ ™ · ~ Z -CJ COO ^: K • I. CJ "T CJ CJ -CJ O O O -CJ COO CJ O I. 0 Cl CM 1 1 O J ™
\O O -CJ U O T (N) O I. 0 tM ! O O CJ- CJ- CJ- CJ -CJ CJ I. ■ o I CJ c— r-l I
CJ .J CJ O CJ O . CJ. O
I. .1 O I '
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I. CJ COO O CJ ] O O O CtJ -C CJ- O O O - to • Ί CJ CJ- CJ— COO M. C. 1
cU I. O ? s «5 I.
-CJ CSI D. O 2: tO to J- to 0 O O as J ¹ ^^ ta U I.
O -0 O O U U O = CJ O to υ A. A. O K · - « -y CJ ^ O CJx- O U T «Μ CJ O O to O !
O -CJ O • u— -U I Ί CJ to CM CM ns to to T CJ ^ * - ^ »* 4 r-1 -CJ <M CJ U U O I · CM CM * O O ic. CJ- I. O CJ O r ι O Cs! —CJ— O O to Q -CJ K I. O J O -r T CJ I. -U / * CM CJ- CJ O O (Vi I. 1 ^: ■ - « i I. M. CJ -Ο U ^ l -U O ι CJ O I. • -CJ - eg CJ- O to CM O K ■ O G O CJ O V J CM O * · ac. . CJ- ns CJ 0 I. O O I.
^: CJ -CJ O to I. CJ - Λ O = CJ Ii Ί to ILA ►7- O -u- η J K a: ij O o4 O I. OK O Cl CJ to O co a:
CJ - I. O. I. J 0 O I. O I. JP CJ υ O I. S ^ iH CJ cn c \

2 5 _X 21 91 5

-4 / 1-

S09849 / 1039

252191b

φ ■ ti

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LO

CM CM IO CJ te te O -u CM O I. CJ υ— ι O LO O O ££ ι -CJ CM U I. O -Ο
ι O I.
O CJ- CM te CJ CM CJ CM / "~ \
O CM

CM

LO

CM

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LO

CM O O O

CJ-

O * '■

CJ

CJ CM

VD

CM - LO CM - - - LO CM »—4
-U te te te te LO CM -CJ CJ U CJ ι · CM O • O O CJ O O l O CJ- CJ— -CJ - O
CJ- * LO I - O ~ CSJ O LO LO LO O U I. te ^ O "~ CM ""cm O ¹ CO CJ ö U -C CJ i— t COO CM, O O a: CJ- _ ^ j - -CJ J - CJ I. O te O CM CJ te Μ CJ Il CM · - " [i 1 CJ CJ 1! Λ CM to ^^^^ 32 te CJ CM CM > r CJ te CJ COO G- O CNJ CM te te CJ CJ O. to tr: tn CM υ O te CM CJ ^ r; D ^ CJ CJ I. O CJ CM r ^ » te CJ co CM to ³³ ί CM K) ' CJ ^ rc CJ-H CJ he «' <- » CM te U to CJ

-42 a-

5 0 9849/1039

-P • Η CD

• υ

ti

ο-

vi

O O

Ci

-P CD CQ

CJ-CJ-υ

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»Γ ¹

CJ

CJ O

CM

LT \

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CO CO

CJ

O O

CJ

CJ O

CC)

CD

ICM

(D • Η

• Η

φ m

8-i

O O

α-ο-ο

CJ

egg

O O

Γ-

CM

CJ

-43-

φ CD CM CM -P X CJ • Η -CJ
I. O Φ I.
O O CO -CJ φ LO I. φ • ' • Η CM -CJ- CQ CJ I. O O -P O οο CJ- * - * X
CM O U pi
N O O CO
τπ CJ-

LTv

U
Φ
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CO

φ
CJ

φ
-ρ

CD

-ρ C. φ

P.

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CJ

CJ II

CJ

CJ

t-r «

CJ H

CM

X CJ

X O co / - \

CM

X CJ

CJ

X CJ CM

CJ

X υ

CJ

to

/> - »CM

X CJ ν_ /

χ ■

CM

CJ

O (M

ο χ

CJ CJ

LO

CJ. O O

CJ

-CJ-

OO

r- \ CM

X CJ

CJ

III CJ

co

CM

CJ

^ I

UO

X ο

co * - \

CM

CJ

«Ι

CJ

OO CM

X CJ

LO

CM CJ

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CM

CJ

ro

X U

CM

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-43-

509849/1039

Table I - continued (belongs to page 43)

cn ο co OO ■ ΡΙΟ

Example salt product (5)

40

41

42

43

44

COONa COON

H (CH _{2) 5} CH-CHCH ₂ CHCH (CH _{2) s-O} u4 "CH ₂

COONa

H (CH ₂ )

COONa COONa -C - 0 - CH ₂

COONa

CO 2Na

CH ₃ (CH _{2) u} 0-CH ₂ -OCO-CH ₂ CO ₂ Na

CO ₂ Na

COONa COONa h-Q '~ C "' 0 '" CH ^
'COONa'

COONa

t) -C 0

COONa

COONa CH ₂

cn

cn ro

CD

cn

T afc hurry I - continued

O CO CO

HO (CH ₂ ) sO - COOC ₉ Mr. COOC ₉ H ₁ -
j 2 5 COOC ₂ H5 COOC ₉ H ₅ " ^% _;
■ I 0 CH ₂ C 0 CH ₂ HOCCH ₂ ) ₅ i
COONa COONa
ι ι COONa COONa COONa
j t KO (CH ₂ ) ₅ OH CH ₂ ^ O - C-OCCH ₂ 1-
COOC ^: 2 ^H S CCOC ₂ H ₅ . II
η /> η λττ
U Li ^^ U Un
j 2 L U -o-c - 0- ^CH 2. • COOC ₂ H • Hn d
COOC ₂ II ₅ COOC ₂ H ₅ ; COOC ₂ Hc COONa COONa COONa COONa . '45 COOC
-oi
O ^u V > 5 ° - 1
CH ₉ - CH ₂ -O- and
COONa: ■:
ι ·, COONa COONa HO (CH ₂ ) 2 COOC C-OCCH j) ₅ 0- -CH ₂ -CH ₂ • other 2 ^H 5 COONa COOC ₉ H ₁ .
I. ^b
P Λ fPTT 0 COOC ₉ H. ¹ COOC ₉ H ₁ -
J 2 _Ä . 2 5
Λ - Γ .- "..._. -— _ PTT . · HOCCH ₂ ) ₂ COONa
-r- ^ O — C 0 -
0 y • K0 (CH _{2) 20} OH COOC ₉ Mr.
ΓΗ ... n. Ly ^^ U I Uli
i · 2 ^H 5 U L LU-
I Δ COONa COOC ₂ H ₅ COOC ₂ H ₅ and . 46 COONa COON3 2'20 CII ₂ 0 C OCCH ₂ ) 2tf COONa

KTt I

-P
CU
CQ

CM

te

- (J

Z O O

CM

CD S2 O O CJ-

rt 'el

s: ο ϊ = 5 ο ι ο ο 'ο υ — υ— cj

• I ¹

2: ο

ο ι ο I

CJ CJ-

I. ο

CJ

CD ¹ XJ

O Ö

-CJ 3

to

CJ

O C

OK CJ CJ

LO

LO

CM O CNl

CJ ι CJ O O

ο ι ο

CJ O - CJ

approx ο

CJ-

CJ-

ο ο -α — cj

I. ο

CM

-υ

CJ U

-CJ

O CM

O 33 O CJ

LO

CM

CJ

CM

CJ

Ο .-- co

CM

to Ti

CJ O O

CJ-

CJ O O CJ

CM

irt

«Λ O

CM
CJ

f ■> ΐ

5098Α9 / 1039

521915

in

in

“J - X CM to to to CM O -O- • CM
X to CM CN »_ - - X O O
CM X X XX
CJ CN) CJ
fy-4 "-" t - ^ - l -O- CJ -CJ -O — CJ ~ U O X CM O CJ CJ CM -CJ— o — w— ο— O -CJ CJ CJ - O O 1 O O CJ- I. X
CN * O LO I. O • J— O O CJ X O CJ CJ r ι
σ i O CM I. O Ui O CJ I. O
CM
X CJ- X 1 -CJ CJ O I. CJ - ta CNl I. O X
CM O r O CJ CJ O -O O O to O CJ- Ö X
CM CJ
XX CJ— N
-P -CJ — υ - CL) to CQ £ CM O X I.
I. PH -CJ I.
M. to I. Λ X
CJ
· —-I ο CL CJ- r Γ ~ /1 ( CCi
EH

to

CJ

<M CJ

O— CJ CJ— O - CJ -

CTi

X
O

to

X CJ

cj-cj-o-

to fM to X X X X ~ o CM O ι — U— CJ X X CJ - -G-c -CJ-

-47-

509849/1039

Table I - continued (belongs to page 47)

Example 49

O CjO CO

CHoOH 1

CHCHr

I ³ O

CH ₉
I ²
CHCH,

CHCH.,

and

COONa COQNa

O-CV-O-CH

I.
COONa

COONa COOKa H-O-C-0 — CH "

CH ₂

CHCH ₃ COONa

CH.

! hch,

.HCH ₃

COONa

i
0-c - O-

COONa

COONa

CH,

Example 50

To check their sequestering function, the salt products prepared according to Examples 1-49 were subjected to the methods described by Matzner and others in "Organic Builder Salts as Replacements for Sodium Tripolyphosphate", Tenside Detergents, 10, No. 3, pages 119-125 (1973) to determine effective sequestering agents are described.

Example 51

Were prepared detergent formulations containing 50 ^and / or the specified in Table II Builders, 17 ° / ° linear alkyl benzene sulfonate with an average molecular weight of about 230, 6 fO sodium silicate and containing the residual sodium sulfate. The formulations were tested by washing similar soiled fabric strips as indicated in the table in water of 200 ppm hardness at 49 ° C. using a 0.15% detergent formulation and similar washing procedures. The reflectivity of the soiled test strips before and after washing was measured with instruments and the difference reported in Table II as XX Pfl. High Z __ \ Rd values are indicative of a correspondingly high detergent effectiveness.

Table II: -48-

509849/1039

Si

Table II

Builder

Cotton fabric l

none (instead of the builder, sodium sulfate was used as filler)

COONa C 00Na

-O-C-O-CH

COONa

COONa

CH ₃ -OC - 0

COONa

COONa

16.9

14.6

Polyester / cotton fabric ^ rd

8.3

8.0

COONa

COONa

0 - C - 0 - CH COONa

14.4

6.4

COONa

COONa 0 - c - 0 - (CH ₀ )

COONa

8.9

The values reported in Table II indicate that the salt forms of the compounds of this invention are effective detergent builders are.

-49-

509849/1039

• SA

Example 52

Aqueous solutions of the salt products prepared according to Examples 1 to 49 were reacted with hydrochloric acid to to produce the corresponding acid forms. By reaction the acids with ammonium hydroxide give the corresponding ammonium salts, which are effective sequestering agents, when following the procedure described in Example 50 to be examined.

Claims : -50-

509849/1039

Claims (10)

Patent claims: 1. Alcohol derivatives, characterized in that at least one active alcoholic Hydroxy group through a substituent of the general formula COOM COOM ι \ _QE ioo: is replaced, in which M is alkali metal or ammonium, as well as their acids and esters, with the exception of the alcohol derivatives of connections of the i'ormel GOOX A ¹ - C OH, wherein each of the radicals A and A ^{1 is} hydrogen or methyl and X is hydrogen, methyl, ethyl, alkali metal or ammonium. 2. A compound according to claim 1, characterized in that the substituent with a non-carboxylated carbon atom is connected. 3. A compound according to claim 1, characterized in that the substituents constitute at least 50 % of the total weight of the compound. 509849/1039 4. A compound according to claim 1, characterized in that the substituents form at least 85 io of the total weight of the compound. 5. A compound according to claim 1, characterized that the part to which the substituent is attached is an aliphatic part, an alicyclic part Part or an aromatic part. 6. A compound according to claim 1, characterized in that the part with which the substituent is connected, an alkyl aromatic moiety Alcohol part, an ether part, a poly (alkylene oxide) part, part of the general formula ° n ^H 2n ₊ 1 where η is an integer from 1 to 20 or part of the formula is where m is an integer from 5 to 20. 7. Detergent formulation, characterized in that it contains: a) 1 to 95 wt. fo a compound corresponding to one Alcohol (any compound other than sol- COOX ehen the general i'orinel A ¹ -C - OH, wherein each 9/1039 the radicals A and A 'are hydrogen or methyl and X is hydrogen, methyl, ethyl, alkali metal or ammonium is), which has at least one active alcoholic hydroxyl group, which is represented by a substituent of the general formula COOM COOM - 0 C 0 CH ₂ COOM is replaced, wherein M is an alkali metal or ammonium, and b) 0.5 to 95% by weight of surfactant selected from water-soluble anionic, nonionic, amphoteric and / or zwitterionic surfactants. 8. Preparation for dishwashers, thereby marked that it contains " a) 5 to 90 wt. ^c / o of a compound according to claim 7 a) b) 0 to 5 o surfactant, namely anionic and / or non-ionic surfactant with low foaming wt. ^L? c) a chlorine-producing compound, namely potassium dichlorocyanurate, Sodium dichlorocyanurate, / TMonotrichlor) -tetra- (monopotassium dichloroJ7-penta-isocyanurate, (Monotrichlor) - (Monopotassium dichlor) diisocyanurate and / or chlorinated trisodium phosphate, wherein the chlorine donating compound is present in an amount sufficient that 0.5 to -53- 50S849 / 1 039 COOM.
ι 0 - COOM
ι I.
C ———
ι - CH ₂ COOM up to 2% by weight of chlorine is available, and d) 5 "to 30 wt. $ soluble sodium silicate with a SiOp to NapO molar ratio of 1: 1 Ms 3.2: 1. 9. Process for the preparation of organic compounds having a substituent of the general formula wherein M is an alkali metal or ammonium, as well as their Acids and esters, characterized that a corresponding base of a hemiketal of a ketomalonic acid diester and an alcohol with a active alcoholic hydroxyl group with a bromine or Iodoacetate ester reacts to form the ester form of the organic compounds, and that if the alkali metal salt form of the organic compounds is desired, the ester form reacts with an alkali metal hydroxide Formation of the alkali metal salt form, and that if the acid form of the organic compounds is desired, the alkali metal salt form acidifies to form the acid form, and that if the ammonium salt form of the organic Compounds desired, the acid form with ammonia or ammonium hydroxide to form the ammonium salt form implements. 10. The method according to claim 9, characterized in that - -54- 5098Λ9 / 1039 indicates that the corresponding base of a hemiketal of a ketomalonic acid diester and a Alcohol with an active alcoholic hydroxyl group is prepared by using a corresponding base of an alcohol with an active alcoholic hydroxyl group reacts with a ketomalonic acid diester. 1 1. The method according to claim 9 »characterized in that the corresponding base a hemiketal of a ketomalonic acid diester and an alcohol having an active alcoholic hydroxyl group by preparing an alcohol having an active alcoholic hydroxyl group with a ketomalonic acid diester reacts to form a hemiketal, and that the hemiketal is reacted with a base which is sufficient is strong to convert the hemiketal into its corresponding base. 509849/1039