US3736339A - Sodium exo-cis-1,4-endoxo-1-substituted cyclohex-5-ene-2,3-dicarboxylate compounds - Google Patents

Abstract

THE USE OF EXO-CIS-1,4-ENDOXO-ALICYCLIC-2,3-DICARBOXYLATES SUCH AS SODIUM EXO-CIS-1,4-ENDOXOCYCLOHEXENE-2,3DICARBOXYLATE AND DERIVATIVES THEREOF AS BUILDERS IN DETERGENT COMPOSITIONS.

Description

United States Patent Office Patented May 29, 1973 3,736,339 SODIUM EXO-CIS 1,4-ENDOXO-1-SUBSTITUTED CYCLOHEX 5-ENE-2,3-DICARBOXYLATE COM- ABSTRACT OF THE DISCLOSURE The use of exo-cis-1,4-endoxo-alicyclic-2,3-dicarboxylates such as sodium exo-cis-1,4-endoXocyclohexene-2,3- dicarboxylate and derivatives thereof as builders in detergent compositions.

BACKGROUND OF THE INVENTION Field of the invention Detergent compositions containing detergent builders.

Background In recent years, studies have been conducted concerning the problems of eutrophication. Eutrophication can be defined as a natural process of enrichment of waters with nutrients, such as phosphorus and nitrogen, at a slow rate. Eutrophication can be detrimental, since it may cause increased algal growth and algal scums which are unaesthetic, odorous, distasteful and often clog filters of water treatment plants.

It has been postulated that various human activities have accelerated the process. Contributing factors in the eutrophication of lakes, streams and estuaries are natural runotf, agricultural drainage, ground water, precipitation, sewage and Waste efiluents. Although there is no present adequate proof, it has been postulated that the phosphorus-containing builders present in detergent compositions can be a factor in eutrophication, and therefore any substitutes which do not contain phosphorus may decrease to some extent the eutrophication problem. Thus, those skilled in the art have expended a great deal of time and money to find suitable materials to reduce or replace the existing phosphate builders in detergent compositions. However, most builders which have been discovered to date have been unsatisfactory for one or many possible reasons and are normally less eflicient than the existing phosphorus builder materials.

The exo-cis-1,4-endoxo-alicyclic (or cycloaliphatic)- 2,3-dicarboxy1ates and derivatives thereof used as builders in accordance with the present invention not only permit the reduction or replacement of existing phosphate and nitrogen-containing builders in detergent compositions, but in addition, aiford a detergent composition containing a builder which is biodegradable.

SUMMARY OF THE INVENTION It is an object of the present invention to provide detergent compositions containing builder compounds which are free of phosphorus and are efficient detergent builders.

It is another object of the invention to provide compositions containing builder compounds which can be synthesized from low most raw materials at reasonable prices.

Still another object of the present invention is to provide new organic compounds which may be utilized as builders in detergent compositions.

DESCRIPTION OF THE INVENTION It has now been discovered that certain oxygen-bridged bicyclic or tricyclic diand polycarboxylates can serve as effective detergent builders in detergent compositions.

The builders employed in accordance with the present invention can be generally described as exo-cis-1,4-endoxo-alicyclic-2,3-dicarboxylate water-soluble salts having the general formula:

Formula I o o OM Z Y COOM wherein Z is a bivalent radical consisting of 1-4 carbon atoms wherein said radical may contain additional substituents selected from the group consisting of halogen, hydroxyl, phenylene, carboxyalkyl, arylalkyl, alkoxyalkyl, oxoalkyl or hydroxyalkyl containing 1-3 carbon atoms in the alkyl chain; at least one of Y is hydrogen and the other is selected from the group consisting of hydrogen, chloro or lower alkyl containing 1-3 carbon atoms; and X and X are independently selected from the group consisting of hydrogen, hydroxymethyl, fi-cyanoethyl, ,B-cyanoethoxymethyl, carboxyethoxymethyl, dimethoxymethyl, diethoxymethyl, dioxolanyl and carboxyloweralkyl containing 1-3 carbon atoms; and M is hydrogen or a cation selected from the group consisting of alkali metals, ammonium and substituted ammonium radicals.

The term cis as used herein refers to the fact that both carboxylate groups are on the same side of the ring.

The term exo as used herein refers to the fact that the carboxylate groups are on the same side of the alicyclic ring as the oxygen bridge.

Thus the compounds of the present invention may be bior tricyclic compounds embracing in their basic structure a hydroaromatic or aliphatic ring wherein (in reference to Formula I), the 1-4 position ring carbon atoms are bridged with an oxygen atom and carboxylate salt functions are attached to the 2 and 3 position carbon atoms. In the case of tricarboxylate salts, the third carboxylate group is attached as part of substituent in the 1 position.

The compounds employed in the present invention are for the most part known or can be prepared in accordance with procedures well known in the art. For example, Diels-Alder reactions, which yield some of the types of compounds of interest, may be conducted in accordance with the teaching of Kloetzel on pages 1-60 of Organic Reactions, volume 4, John Wiley and Son, Inc. (1948), or the teachings of Holmes on pp. 60-174 of the same volume or according to the method of Woodward and Baer (I. Am. Chem. Soc., 70, 1161 (1948), or the teachings of US. Pat. No. 3,047,433. The preparation of other compounds described in the present invention will be apparent from the discussion hereinafter.

As may be appreciated, the aforementioned compounds may exist in several isomeric forms. As may be further appreciated, compounds of the present invention may be employed as builders in detergent compositions in the form of the anhydride, the free acid or a water-soluble salt thereof. Of course, when the anhydride or free acid form is employed, there must be present in the detergent composition sufficient alkali or neutralizing agents such as sodium hydroxide or carbonate to form the corresponding salt in situ. Accordingly in the preferred embodiment of the invention, it is most desirable to use the exo-cis-l,4-endoxo-alicylic-2,3-dicarboxylates in the form of their Water soluble salts and preferably the alkali metal ('K, Na), ammonium and substituted ammonium salts such as the mono-di and triethanolammonium, tetramethylammonium, methylammonium and morpholinium salts.

Laboratory studies have indicated that in regard to detergency building characteristics, best results are obtained by utilization of the more stable exo-cis isomer, although mixtures containing both endo and exo-cis isomers are useful, since a substantial proportion of the endo-cis isomer contained in the mixture is capable of isomerizing to the exo isomer.

Laboratory evidence further indicates that the unique building activity of the compound of Formula I appears to be related to the particular spatial relationship of the oxygen to the dicarboxylate functions, i.e., that the 2,3- carboxylate groups are cis to one another and that they also are on the same side of the alicyclic ring as the oxygen bridge, i.e., in the exo position.

Notwithstanding the activity exhibited by the compounds of the present invention broadly, certain of the compounds of Formula I exhibit outstanding superior properties as detergent builders. These include compounds of the type wherein Z is a bivalent radical of 2 carbon atoms and thus embrace compounds including in their structures a basic six-membered ring which is hydroaliphatic or hydroaromatic but also contains an oxygen bridge. Within this class, of particular note are:

(1) disodium exo-cis-1,4-endoxo-cyclohexene-2,3-dicarboxylate;

(2) disodium exo-cis-l,4-endoxo-cyclohexane-2,3-dicarboxylate;

(3) disodium exo-cis-l,4-endoxo-l-diethoxymethyl-A cyclohexene-2,3-dicarboxylate;

(4) disodium exo-cis-1,4-endoxo-1-(2-rn-dioxanyl)-A cyclohexene-2,3-dicarboxylate;

(5) disodium exo-cis-l,4-endoxo-1-hydroxymethyl-A cyclohexene-2,B-dicarboxylate;

(6) disodium exo-cis-l,4 endoxo-1-[(fi-cyanoethoxy) methyl]-A -cyclohexene-2,3-dicarboxylate;

(7) trisodium exo-cis-1,4-endoxo-l-(B-carboxyethoxymethyl)-A -cyclohexene-2,3-dicarboxylate.

According to the present invention, excellent cleaning results can be obtained by using the builders described above with a wide range of detergent surface active materials and mixtures thereof in solid or liquid form. The builders can be used singularly, in combination with each other as the sole builder in the detergent composition or in combination with other well-known detergent builders such as sodium nitrilotriacetate, sodium ethylenedia-minetetraacetate, sodium tripolyphosphate, sodium and potassium pyrophosphate, and sodium polyacrylate, sodium carbonate, sodium silicate and the like.

In the detergent compositions of the present invention, the only essential ingredients are the detergent surface active material and the builder. The weight percent of the builder present in the detergent composition will range from about 5 to about 90% and preferably from about 210 to about 60% and more preferably 35-50% by weight of the total weight of the composition. When expressed as a weight ratio of builder to surfactant, the builders used in the instant invention will generally be present in a ratio of about 1:10 to about 10:1, and preferably 2:1-5 :1 depending on the end use or whether a heavy-duty or light-duty detergent is desired.

Similarly, in detergent compositions suitable for Washing dishes in mechanical dishwashers, the ratio of builder to detergent may be as high as 50:1.

The detergent surface "active compounds which can be used in the compositions of this invention include anionic, nonionic, zwitterionic, ampholytic detergent compounds and mixtures thereof. These suitable substances are outlined at length below.

(a) Anionic detergent compositions which can be used in the compositions of this invention include both soap and non-soap detergent compounds. Examples of suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C -C Particularly useful are the sodium or potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap and tall oil. Examples of anionic organic non-soap detergent compounds are the water soluble salts, alkali metal salts of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting. of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of the synthetic detergents which form a part of the compositions of the present invention are the sodium or potassium alkyl sulfates especially those obtained by sulfating the higher alcohols (C -C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene-sulfonates in which the alkyl group contains from about 9 to about 20 carbon atoms and in which the benzene ring is attached to the alkyl chain at either the one position or at the secondary positions such as in sodium linear alkyl (C C secondary benzene sulfonate, sodium p-(Z-dodecyl) benzene sulfonate, sodium p-(2-octadccyl)benzene sulfonate, sodium p- (3-dodecyl)benzene sulfonate and 3-phenyldodecanesulfonate; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide per molecule and in which the alkyl radicals contain about 9 to about 18 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl taurine in which the fatty acids, for example, are derived from coconut; alkane sulfonates such as those derived by reacting alpha-olefins containing 8 to 20 carbon atoms with sodium bisulfite and those derived by reacting parafiins with S0 and C1 and then hydrolyzing with a base to produce a random sulfonate; alpha-olefin sulfonates such as those derived by reacting alpha-olefins with $0 and then neutralizing the reaction product; and others known in the art.

(b) Nonionic synthetic detergents may be broadly de fined as compounds which do not ionize in water solution. For example, a well-known class of nonionic synthetic detergents is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide with an hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 1,500 to 1,800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include:

(1) The polyethylene oxide condensates of alkylphenols, e.g., the condensation products of alkylphenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkylphenols. The alkyl substituent in such compounds may be derived from polymerized propylene, disobutylene, octene, dodecene, or nonene, for example.

(2) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said hydrophobic base having a molecular weight of the order of 2,500 to 3,000 are satisfactory.

(3) The condensation product of aliphatic alcohols (primary or secondary) having from 8 to 18 carbon atoms, in either straight chain or branched cham configuration, with ethylene oxide, e.g., a coconut alcoholethylene oxide condensate having from 6 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms or a random secondary C C alcohol-ethylene oxide condensate having 6 to 15 moles of ethylene oxide per mole of alcohol.

(4) Long chain tertiary amine oxides corresponding to the following general formula, R R R N O, wherem R is an alkyl radical of from about 8 to 18 carbon atoms and R and R are each methyl, ethyl or hydroxy ethyl radicals. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of amme oxides suitable for use in this invention include dimethyldodecylamine oxide, dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyltetradecylamine oxide and d1- methylhexadecylam ine oxide, N-bis(hydroxyethyl) dodecylamine oxide.

Long chain tertiary phosphine oxldes corresponding to the following formula RRRP- O, wherein is an alkyl, alkenyl or monohydroxyalkyl radical ranging from to 18 carbon atoms in chain length and R and R" are each alkyl or monohydroxyalkyl groups contaming from 1 to 3 carbon atoms. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of suitable phosphine oxides are:

dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylstearylphosphinc oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, bis(hydroxymethyl)dodecylphosphine ox de, bis(2-hydroxyethyl)dodecylphosphine oxide, 2-hydroxypropylmethyltetradecylphosphine oxide, dimethyloleylphosphine oxide, and dimethyl-Z-hydroxydodecylphosphme oxide.

(6) Dialkyl sulfoxides corresponding to the following formula, RR'S O, wherein R is an alkyl, alkenyl, betaor gamma-monohydroxyalkyl radical or an all yl or betaor gamma-monohydroxyalkyl radical containlng one or two other oxygen atoms in the chain, the R groups ranging from 10 to 18 carbon atoms in chain length, and wherein R is methyl, ethyl or alltylol. Examples of suitable sulfoxide compounds are:

dodecyl methyl sulfoxide,

tetradecyl methyl sulfoxide,

3-hydroxytn'decyl methyl sulfoxide Z-hydroxydodecyl methyl sulfoxide 3-hydroxy-4-decyloxybutyl methyl sulfoxide, 3-hydroXy-4-dodecylcoxybutyl methyl sulfoxide, 2-hydroxy-3-decyloxypropyl methyl sulfoxide, Z-hydroxy-3-dodecyloxypropyl methyl sulfoxide, dodecyl ethyl sulfoxide,

Z-hydroxydodecyl ethyl sulfoxide, and dodecyl-Z-hydroxy ethyl sulfoxide.

(c) Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group. Examples of compounds falling within this definition are sodium-3-dodecylaminopropionate and sodium-3-dodecylaminopropanesulfonate and sodium N-Z-hydroxydodecyl- N-methyl-taurate.

(d) Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium compounds, sulfonium compounds and phosphoniurn compounds in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group. Examples of compounds falling within this definition are 3 (N,N-dimethyl-N-hexadecylamrnonio)propane-l-sulfonate, 3 (N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate, 3 (dodecylmethylsulfonium) propane sulfonate, and 3-(cetylmethylphosphonium) ethane sulfonate.

In addition to the essential ingredients in the detergent composition, other optional ingredients may also be added. Examples of the optional ingredients are perfumes, colorants, fabric softening agents, fungicides, germicides, enzymes, fluorescent dyes, antiredeposition agents, hydrotropes and in the case of liquid compositions, opacifiers and organic solvents. Other ingredients such as bleaches, i.e., sodium perborate with or without activators and inorganic salts such as sodium carbonate, sodium bicarbonate, sodium sulfate, sodium chloride and sodium silicate may also be present.

The detergent compositions of the present invention can be utilized in washing solutions over a pH range of from about 7-12 and more preferably 9-11 when used as laundry and dishwashing compositions.

In addition to the unique detergent building properties the compounds used in the present invention when employed in the free acid or as partly neutralized salts, are valuable in metal cleaning compositions under pH conditions of about 2 to about 5. Such compositions may therefore contain in addition to the surfactant all standard cleaning abrasives.

Still another embodiment of the present invention is the use of anhydrides of Formula I in conjunction with inorganic persalts such as sodium perborate and sodium percarbonate. It is believed that the hydrogen peroxide released when such persalts are dissolved in water reacts with the anhydrides to form peracids capable of bleaching. The peracids are ultimately converted to the dicarboxylate salts of Formula I and can then function as detergent builders. Thus,the anhydrides can be said to be dual-functioning, i.e., they are both bleach precursors in that they can form peracids and detergent builder precursors in that they can form dicarboxylate salts of Formula I.

It is intended to cover'all changes and modifications of the preferred embodiments of the invention, herein chosen for the purpose of illustration, which do not constitute departures from the spirit and scope of the invention.

EXAMPLE 1 Disodium exo-cis-1,4-endoxo-cyclohexane- 2,3-dicarboxylate To a Parr low pressure hydrogenator were added 50 gm. of exo-cis-1,4-endoxo-A -cyclohexene-2,3-dicarboxylic anhydride dissolved in ml. of anhydrous acetone and 0.6 gm. of 10% palladium on charcoal which was then pressurized to 40-50 p.s.i. with hydrogen. The apparatus was allowed to shake for a period of two hours whereupon hydrogenation was terminated and the contents of the bomb removed and filtered. Upon cooling the filtered solution to about 70 C., exo-cis-1,4-'endoxocyclohexane-2,3-dicarboxylic anhydride (25.7 gm.) in the form of a white crystalline precipitate was obtained and collected by suction filtration. The anhydride was then dissolved in 400 ml. of hot water to which 16 gm. (0.15 mole) of sodium carbonate were added and the resulting solution Was evaporated to dryness to yield disodium exocis-1,4-endxo-cyclohexane-2,3-dicarboxylate.

The corresponding ammonium and substituted ammonium salts are prepared by treating the anhydride with dilute ammonium hydroxide or an aqueous solution of the appropriately substituted amine. Corresponding mono-salts are prepared by employing half the stoichiometric quantities required for producing the disalt.

EXAMPLE 2 Exo-cis- 1,4-endox0- 1- B-cyanoethoxy methyl] -A cyclohexene-2,3-dicarboxylic anhydride A mixture of 15 gm. (0.1 mole) of fi-cyanoethylfurfuryl ether and 9.8 gm. (0.1 mole) of maleioanhydride in 100 ml. of ether were added to a 250 ml. onenecked, round bottomed flask fitted with a reflux con denser and drying tube. The mixture was then stirred for one day and allowed to stand for 2 /2 days, whereupon the ether layer from the resulting two-phase mixture was separated and evaporated without heat to yield a. viscous material, which upon extraction with ether to remove starting materials afforded 4.19 gm. of exo-cis-1,4-endoxo- 1-l({3-Cyanoethoxy)methyl] A cyclohexene-2,3-dicarboxylic anhydride.

EXAMPLE 3 Exo-cis-1,4-endoxo-1-(fi-carboxyethoxymethyl)-A -cyclohexene-Z,3dicarb0xylate, trisodium salt To a 250 ml. Erlenmeyer flask were added 9.8 gm. (0.1 mole) furfuryl alcohol and 0.1 gm. sodium. After stirring the mixture for three minutes, 9 gm. (0.105 mole) methyl acrylate were slowly added with stirring. After 5-10 min. the mixture was immersed in a water bath maintained at -70 C. The mixture was then fractionally distilled and methyl acrylate removed in the first fraction. The product, which distilled at 120130/23 mm. (16.5 gm.) was 2 [,8 (carboxylmethoxy)ethoxymethylJ-furan.

To a 250 ml. Erlenmeyer flask fitted with condenser and drying tube were added 6.9 g. (0.038 mole) of the substituted furan described above, ml. anhydrous ether and 3.8 g. (0.039 mole) maleic anhydride. The mixture was allowed to stand for three days and was then evaporated under vacuum without heat. The viscous liquid was shaken with an aqueous solution of sodium carbonate which was maintained at pH-6 by addition of small increments of sodium carbonate. The immiscible portion was extracted with ether, the ether fraction evaporated and the residue heated with an aqueous sodium carbonate solution maintained at pH-10 on a steam bath for 15 min. The solution Was evaporated under vacuum with heat to afiord the title compound.

What is claimed is:

1. Disodium exo cis 1,4-endoxo-1-[(fi'cyanoethoxy) methyl] -A -cyclohexene-2, 3 -dicarboxylate.

2. Trisodium exo-cis 1,4-endoxo-l-(fi-carboxyethoxymethyl) -A -cyclohexene-2,3-dicarboxylate.

References Cited Scarpa et al., C. A6, vol. 64 (1966), 17469e.

DONALD G. DAUS, Primary Examiner B. DENTZ, Assistant Examiner US. Cl. X.R. 25289