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US3531526A - Diamine dioxide detergent compounds - Google Patents

Diamine dioxide detergent compounds Download PDF

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US3531526A
US3531526A US603439A US3531526DA US3531526A US 3531526 A US3531526 A US 3531526A US 603439 A US603439 A US 603439A US 3531526D A US3531526D A US 3531526DA US 3531526 A US3531526 A US 3531526A
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sodium
dioxide
diamine
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tetramethyl
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Ted J Logan
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
    • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
    • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds

Definitions

  • Detergent compositions containing these diamine dioxides and builders and/or other compounds especially detergent alkylbenzene sulfonates.
  • This invention relates to novel diamine dioxide detergents and to detergent compositions containing these compounds.
  • a compound there are several properties that are regarded as being essential for a compound to be suitable for use as a detergent. Foremost is the cleaning ability of the compound, i.e., its ability to remove soil, .e.g., from soiled clothing. In addition, the detergent should remain in active form under conditions of consumer usage, e.g., at high temperatures such as 140 F. and in aqueous solutions.
  • Detergent trialkyl amine oxides e.g., those described in Drew and Voss US. Pat. 3,223,647, granted Dec. 14, 1965, meet these criteria in that they clean as well as tetrapropylene benzene sulfonate and are thermally stable and resistant to hydrolysis under conditions ordinarily encountered during washing.
  • the diamine dioxides of the present invention have these properties in common with the detergent trialkyl amine oxides but also have other desirable properties which the trialkyl amine oxides do not have. For example, particular diamine dioxides of the present invention are very mild with respect to skin compared to detergent trialkyl amine oxides.
  • R is an alkyl radical containing from about 8 to about 18 carbon atoms and each R is selected from the group consisting of methyl, ethyl, propyl, hydroxyethyl, and hydroxypropyl radicals.
  • the alkyl radical R can be branched or straight chain. Each R can be the same or different within the same molecule.
  • the arrows are the conventional representation for semi-polar bonds.
  • Preferred diamine dioxides of the present invention are those wherein R has a chain length ranging from about 8 to about 10 carbon atoms. These preferred diamine dioxides are substantially milder with respect to skin than those of the present invention wherein R contains more than about 10 carbon atoms. Moreover, these preferred diamine dioxides exhibit an unexpectedly high degree of mildness compared to detergent trialkyl amine oxides.
  • the diamine dioxides of this invention can be prepared by oxidizing the corresponding diamines.
  • Hydrogen peroxide is a suitable oxidizing agent and can be conveniently 3 used as an aqueous solution containing 30% hydrogen peroxide. Reaction temperatures ranging from C. to about 100 C. and reaction times ranging from about 1 hour to about 200 hours can be employed.
  • LLower alcohols, e.g., ethanol or isopropanol, are suitable reaction solvents.
  • the corresponding diamines can be prepared employing as a starting material either fatty olefin epoxides or fatty olefin dichlorides. These materials are commercially available or are respectively prepared by oxidizing alphaolefin with peracetic acid and by chlorinating alpha-olefin with chlorine.
  • the fatty olefin epoxide route is preferred since this route gives yields of almost 100% based on the epoxide while the dichloride route gives only 60% yields based on the dichloride.
  • the corresponding diamines can be prepared employing fatty olefin epoxides as starting materials according to the following reaction equations wherein R and R are defined as hereinbefore.
  • the hydrophobic chain is attached to a carbon atom while in the Drew and Zimmerer compounds, the hydrophobic chain is attached to a nitrogen atom. Moreover, in the present diamine dioxides one of the nitrogen atoms is pendant from the long chain while in the Drew and Zimmerer compounds the hydrophobic group and the nitrogen atoms are all part of a single long chain.
  • the Drew and Zimmerer diamine dioxides are prepared by a condensation reaction between a fatty acid chloride and an amine, for example, an ethylene diamine, followed by reduction, for example, with lithium aluminum hydride, methylation, and oxidation.
  • an amine for example, an ethylene diamine
  • reduction for example, with lithium aluminum hydride, methylation, and oxidation.
  • 3,234,139 lauroyl chloride is condensed with N,N-dimethylethylenediamine to provide N,N-dimethyl-N'-lauroyl-ethylene-diarnine; this reaction product is reduced with lithium aluminum hydride to provide N,N-dimethyl-N-dodecylethylenediamine which in turn is methylated with formic acid and formaldehyde to provide N,N',N'-trim,ethyl-N-dodecylethylenediamine; this product is oxidized with hydrogen peroxide to produce its corresponding diamine dioxide.
  • a comparison of this method to the methods previously described for preparing the compounds of the present invention demonstrates the economic advantage of the present compounds over the Drew and Zimmerer compounds.
  • the hydrophobic-group-supplying reactants in the preparation of the present compounds are olefin epoxides or olefin dichlorides which are derived from relatively inexpensive alpha-olefins while the hydrophobic-group-supplying reactants in the preparation of the Drew and Zimmer compounds are relatively expensive fatty acid chlorides.
  • the disubstituted amines used as reactants in the preparation of the present compounds are much less expensive than the .alkylene diamines employed in preparing the Drew and Zimmerer compounds. More- Solvent Temperature Time Reaction:
  • Reactions I and III are carried out at a pressure ranging from atmospheric to 2000 p.s.i.
  • the mole ratio of secondary amine reactant to olefin epoxide or Z-chloroalkyldi-(substituted)amine ranges from 1:1 to about 15:1 and preferably from 4:1 to 12:1.
  • Reaction I is also described in US. Pat. 3,202,714 and Canadian 'Pat. 720,430.
  • the corresponding diamines can be prepared employing fatty olefin dichlorides as starting materials according to the following reaction equation wherein R and R are defined as hereinbefore.
  • R is an alkyl group having from 10 to 18 carbon atoms, each R is a methyl, ethyl or propyl radical, and n is 2 or 3.
  • the compounds of the present invention differ from these prior art compounds in that in the diamine diover, the hydrogen producing reducing agent which is employed in producing the Drew and Zimmerer compounds and which is not used in the preparation of the present compounds is quite expensive, especially if lithium aluminum hydride is employed as a reducing agent. Thus, the present compounds offer a rather substantial economic advantage over the Drew and Zimmerer compounds.
  • the compound of this invention are useful per se as detergent and surface active agents. Desirably they are used with other materials to form detergent compositions, as for example, liquid, bar, tablet, granular or other compositions.
  • Such detergent compositions can contain the diamine dioxides of this invention, and water-soluble inorganic alkaline builder salts, water-soluble organic sequestrant builder salts or mixtures thereof in a ratio of diamine dioxide to builder salt of about 4:1 to about 1:20.
  • Such detergent compositions ordinarily contain from 5% to 50% of detergent active and from 5% to of builder salt.
  • Granular detergent compositions preferably contain from about 5% to about 50% of the diamine dioxides of this invention and liquid formulations preferably contain from about 2% to about 30% of such diamine dioxides.
  • Granular detergents preferably contain at least an equal amount of alkaline builder salt.
  • Liquid formulations preferably contain from about 5% to about 40% of a watersoluble alkaline builder salt, the balance of the composition being a solvent such as Water, and/or other liquid vehicles.
  • Liquid formulations can also contain a hydrotroping electrolyte, e.g., sodium toluene sulfonate. All percentages and parts herein are by weight unless otherwise specified.
  • Water-soluble inorganic al-kaline builder salts which can be used in this invention alone or in admixture are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Ammonium or substituted ammonium, e.g., triethanol ammonium, salts of these materials can also be used. Specific examples of suitable salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium and potassium pyrophosphate, sodium and ammonium bicarbonate, potassium tripolyphosphate, sodium hexaphosphate, sodium sesquicarbonate, sodium orthophosphate and potassium bicarbonate.
  • the preferred inorganic alkaline builders according to this invention are alkali metal tripolyphosphates for built granular and tablet compositions and alkali metal pyrophoshates for built liquid compositions. Potassium is the preferred alkali metal used in liquid compositions and sodium finds best application for granular or tablet compositions.
  • alkali metal, ammonium or substituted ammonium amioncarboxylates e.g., sodium, and potassium ethylenediaminetetraacetate, sodium and potassium N-(Z-hydroxyethyl) ethylenediaminetriacetates, sodium and potassium nitrilotriacetates and sodium and potassium and triethanolammonium N-(2-hydroxyethyl)nitrilodiacetates.
  • alkali metal salts of phytic acid e.g., sodium phytate are also suitable as organic alkaline sequestrant builder salts (see US.
  • organic alkaline sequestrant builder salts are also suitable as organic alkaline sequestrant builder salts as described in the copending application of Francis L. Diehl, Ser. No. 269,359, filed Apr. 1, 1936 and now U.S. Pat. No. 3,308,067 (e.g., polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid and copolymers with themselves and other comparable monomers such as ethylene).
  • polycarboxylate polymers and copolymers as described in the copending application of Francis L. Diehl, Ser. No. 269,359, filed Apr. 1, 1936 and now U.S. Pat. No. 3,308,067 (e.g., polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid and copolymers with themselves
  • Polyphosphonates are also valuable builders in terms of the present invention, including specifically sodium and potassium salts of ethane-l-hydroxy-l,l-diphosphonic acid, sodium and potassium salts of methylene diphosphonic acid, sodium and potassium salts of ethylene diphosphonic acid, and sodium and potassium salts of ethane-1,1,2-triphosphonic acid.
  • the diamine dioxide compounds of this invention in combination with other cleaning agents such as anionic, ampholytic, Zwitterionic, and other nonionic organic detergent surfactant compounds.
  • other cleaning agents such as anionic, ampholytic, Zwitterionic, and other nonionic organic detergent surfactant compounds.
  • anionic detergents because of the sudsing characteristics of the latter.
  • the ratio of the di amine dioxide to such other detergent compound is from about :1 to 1:5. If it is desired to use such a diamine dioxide in admixture with another detergent compound as the active portion of a cleaning composition, the ratio of such a mixture to the builder salt should be Within the previously prescribed range of 4:1 to 1:20.
  • a composition prepared along these lines can contain from 5% to 50% of such a mixture and 5% to 85% of a builder salt selected from water-soluble inorganic alkaline builder salts, watersoluble organic sequestrant builder salts, and mixtures thereof, within the prescribed ratio range.
  • a builder salt selected from water-soluble inorganic alkaline builder salts, watersoluble organic sequestrant builder salts, and mixtures thereof, within the prescribed ratio range.
  • anionic soap detergents which can be used in admixture with the diamine dioxide, if desired, are the sodium, potassium, ammonium and alkylolammonium salts of higher detergent range fatty acids (C -C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • Suitable anionic organic non-soap detergents in the form of their water-soluble salts are: Alkylglycerylethersulfonates; alkyl sulfates; alkyl monoglyceride sulfates or sulfonates; alkylpolyethyleneoxy ether sulfates; acylsarcosinates; acyl esters of isethionates; N-acyl-N- methyl taurides; alkylbenezenesulfonates wherein the alkyl substituent is straight chain or branched chain, sulfonated alpha-olefins, e.g., such as described in copending application of Kessler et al. Ser. No.
  • alkylphenol polyethylenoxy sulfonates contain 10 to 20 carbon atoms. They are used in the form of water-soluble salts, the sodium, potassium, ammonium, and alkylammonium salts, for example. Specific examples are: sodium lauryl sulfate, sodium tallow alkyl sulfate; sodium salt of sulfonated alpha-trideceneg potassium N- methyl-N-lauroyl tauride; triethanolammonium tetrapropylbenzene sulfonate; sodium (linear) dodecyl benzene sulfonate.
  • nonionic organic detergents which can be used in the compositions of this invention, if desired, are: polyethylene oxide condensates of alkylphenols wherein the alkyl group contains from 8 to 15 carbon atoms (e.g., t-octylphenol) and the ethylene oxide is present in a molar ratio of ethylene oxide to alkylphenol in the range of 3:1 to 20:1; condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine wherein the molecular weight of the condensation products ranges from 5000 to 11,000; the condensation products of from about 5 to 30 moles of ethylene oxide with one mole of a straight or branched chain aliphatic alcohol containing from 8 to 18 carbon atoms, e.g., condensation product of 6 moles of ethylene oxide with one mole of lauryl alcohol; higher alkyl di-lower alkyl amine or phosphine oxides, e.g., dodecyldimethyl
  • Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, phosphinate, or phosphonate.
  • an anionic water solubilizing group e.g., carboxy, sulfonate, sulfate, phosphate, phosphinate, or phosphonate.
  • Examples of compounds falling within this definition are sodium 3-dodecylaminopropionate, sodium 3-(N- methyl-N-hexadecylamino)-2-hydroxypropane 1 sulfonate and its dodecyl homolog, sodium 3-dodecylaminopropane-l-sulfonate, sodium dodecyl-beta-alanine, sodium N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of United States Letters Patent No. 2,658,072, N-higher alkyl aspartic acids such as those produced according to the teaching of United States Letters Patent No. 2,438,091, and the products sold under the tradename Miranol and described in United States Letters Patent No. 2,528,378.
  • Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaterna1y ammonium, phosphonium, and ternary sulfonium compounds, in which the aliphatic radical may be straight chain or branched, and wherein one of the aliphatic substituents contains from about 10 to about 18 carbon atoms and one contains an anionic water solubilization group, e.g., carboxy, sulfonate, sulfate, phosphate, phosphinate, or phosphonate.
  • an anionic water solubilization group e.g., carboxy, sulfonate, sulfate, phosphate, phosphinate, or phosphonate.
  • Examples of compounds falling within this definition are: 3 (N,N dimethyl N hexadecylammonio) Z-hydroxypropane-l-sulfonate and the corresponding dodecyl and tetradecyl homologs and 3 (N,N dimethyl-N-dodecylammonio)-propane-l-sulfonate and the corresponding hexadecyl and tetradecyl homologs.
  • the detergent compositions of this invention can also contain any of the usual adjuvants, diluents and additives, for example, perfumes, anti-tarnishing agents, anti-redeposition agents, bacteriostatic agents, dyes, fluorescers, suds builders, suds depressors and the like, without detracting from the advantageous properties of the compositions.
  • adjuvants for example, perfumes, anti-tarnishing agents, anti-redeposition agents, bacteriostatic agents, dyes, fluorescers, suds builders, suds depressors and the like, without detracting from the advantageous properties of the compositions.
  • the weight ratio of diamine dioxide to alkylbenzenesulfonate ranges from about :1 to about 1:5.
  • the diamine dioxides are effective mildness additives for the alkylbenezenesulfonates; while the mixture of these ingredients is not as mild as the diamine dioxides themselves, this mixture is substantially more mild than would be expected from a consideration of each ingredient alone.
  • the mixtures in aqueous solution are substantially milder to the skin than either ingredient alone. These mildness effects are very advantageous since combinations of the alkylbenzenesulfonates and diamine dioxides in compositions of the present invention are very efiicient detergents.
  • the alkylbenzenesulfonates in compositions of this invention are the water-soluble salts, such as the alkali metal (e.g., sodium and potassium) ammonium and substituted ammonium (e.g., triethanolamine) salts, of sulfonated alkylbenzene in which the alkyl radicals contain from about 9 to about carbon atoms.
  • the linear alkylbenzenesulfonates for example, linear dodecylbenezenesulfonate.
  • grade 10 represents ideal or perfect skin (soft, smooth and flexible) and the efiect of a theoretically perfectly mild detergent; grade 1 represents severely irritated skin. Other values represent gradations of severity between these extremes.
  • Grade 1 in a guinea pig immersion test indicates severely thickened, dry, cracked and bleeding skin, i.e., extreme irritation.
  • Grade 1 in exaggerated tests on human subjects indicates severe redness and dryness of the skin. Thus, the exaggerated tests on animals are much more extreme than those conducted on human subjects.
  • the graded guinea pig immersion tests at 37 C. for a 4 /2-hour period per day for 3 consecutive days.
  • the animals are graded 3 days after the last immersion.
  • the grades given in the examples are the average of the results on not less than three animals. It will be understood by those with experience in biological experiments that there is variation in the reactions of individuals, within a group, to exposure to chemical solutions; this is true whether the individuals are guinea pigs or humans.
  • reaction mixture was then removed from the autoclave liner by washing with 2000 ml. diethyl ether and 2000 ml. water. The washed reaction mixture was then held under a vacuum of 20 mm. Hg for 45 minutes to remove excess dimethylamine. 2000 ml. of diethyl ether was then added to the residue and this mixture was washed with 2000 ml. of 10% hydrochloric acid. The ether layer contained vinyl chlorides and was discarded. The acid layer was basified with 10% NaOH to liberate the diamine, which was extracted with petroleum ether, dried, and the ether evaporated to give 42 grams of the diamine.
  • the solution was then heated on a steam bath under a nitrogen stream to strip off remaining ethanol.
  • the resutling aqueou solution amounted to 128.4 grams and contained 25% by weight N,N,N',N'-tetramethyl 1,2 diaminododecane- N,N'-dioxide.
  • the lower (aqueous) layer was drawn off and was extracted 2 times, each time with 50 ml. of petroleum ether. These petroleum ether extracts were combined with the previously separated upper (organic) layer, and this combination was washed with 50 ml. of 40% aqueous dimethylamine followed by 50 ml. of water. The organic layer was then dried over sodium and mag nesium sulfate and filtered. Solvent was then stripped off from the filtrate in vacuo to provide 189 grams to crude l-epoxydecane which was about 60-65% pure. This material was used hereinafter without further purification.
  • the solution was filtered through glass fiber filter paper.
  • the resulting aqueous solution amounted to about 65 grams and contained 25% by weight of N,N,N,N- tetramethyl-1,2-diaminodecane-N,N'-dioxide.
  • N,N,N,N' tetramethyl 1,2 diaminododecane-N,N- dioxide, N,N,N', 'N' tetramethyl-1,2-diaminotetradecane- N,N'-dioxide, and N,N,N,N-tetramethyl-1,2-diaminohexadecane-N,N-dioxide were prepared following the above procedure except respectively employing l-dodecene, 1- tetradecene and l-hexadecene instead of l-decene in forming the olefin epoxide reactant and thereafter reacting the corresponding l-epoxyalkanes, 2-hydroxyalkyldimethylamines, 2-chloroalkyldimethylarnine hydrochlorides, and N,N,N',N'-tetramethyl-1,2-diaminoalkanes.
  • N,N,N',N'-tetrapropyl-1,2-diaminodecane-N,N'-dioxide can be prepared following the procedure employed in Example II except for substituting dipropylamine for the dimethylamine employed in that example.
  • N,N,N-tri methyl-N'-hydroxyethyl-1,Z-diaminodecane-N,N'-dioxide can be prepared following the procedure in Example II except for substituting methyl(hydroxyethyl) amine for the dimethylamine in the reaction with 2-chlorodecyldimethylamine hydrochloride and oxidizing the formed N,N,N'- trimethyl-N'-hydroxyethyl-1,2-diaminodecane to its corresponding dioxide.
  • the above-synthesized diamine dioxides were effective cleaners, espectially for washing dishes.
  • a one to one weight mixture of either N,N,N',N'- tetramethyl 1,2 diaminotetradecane N,N' dioxide or N,N,N,N' tetramethyl 1,2 diamniohexadecane N,N'- dioxide with sodium dodecyl-benzenesulfonate is substantially milder in the above test than the same concentrations of either ingredient alone.
  • Tetrapotassium propane-1,1,3,3-tetraphosphonate 20.0 Sodium silicate (Na O:SiO 1:1.6) 3.8 Potassium toluene sulfonate 8.5
  • diamine dioxide compounds of the present invention can be incorporated into many other liquid or granular detergent compositions with suitable adjustments being made in the other components.
  • the present diamine dioxides can also be employed as detergent actives in other compositions, e.g., in shampoos.
  • a detergent diamine dioxide which has the structural formula
  • R is an alkyl radical containing from 8 to 10 carbon atoms.
  • N,N'di(hydroxyethyl-N,N' -dimethyll,2diaminooctadecane-N,N'dioxide should read N,N'- di(hydroxyethyl)-N,N' -dimethyl-l,2diaminooctadecaneN,N' dioxide--.

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Description

United States Patent 3,531,526 DIAMINE DIOXIDE DETERGENT COMPOUNDS Ted J. Logan, Colerain Township, Hamilton County, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Dec. 21, 1966, Ser. No. 603,439 Int. Cl. C07c 87/14 US. Cl. 260-583 3 Claims ABSTRACT on THE DISCLOSURE A detergent diamine dioxide having the structural formula wherein R is an alkyl radical containing from about 8 to about 18 carbon atoms and each R is selected from the group consisting of methyl, ethyl, propyl, hydroxyethyl, and hydroxypropyl radicals. Preferred members of the class which are especially mild are those wherein R contains from about 8 to about carbon atoms, for example, N,N,N',N-tetramethyl-1,2-diaminodecane N, N-dioxide and N,=N,N,N'-tetramethyl 1,2-diaminododecane-N,N-dioxide. Detergent compositions containing these diamine dioxides and builders and/or other compounds especially detergent alkylbenzene sulfonates.
This invention relates to novel diamine dioxide detergents and to detergent compositions containing these compounds.
There are several properties that are regarded as being essential for a compound to be suitable for use as a detergent. Foremost is the cleaning ability of the compound, i.e., its ability to remove soil, .e.g., from soiled clothing. In addition, the detergent should remain in active form under conditions of consumer usage, e.g., at high temperatures such as 140 F. and in aqueous solutions.
Detergent trialkyl amine oxides, e.g., those described in Drew and Voss US. Pat. 3,223,647, granted Dec. 14, 1965, meet these criteria in that they clean as well as tetrapropylene benzene sulfonate and are thermally stable and resistant to hydrolysis under conditions ordinarily encountered during washing. The diamine dioxides of the present invention have these properties in common with the detergent trialkyl amine oxides but also have other desirable properties which the trialkyl amine oxides do not have. For example, particular diamine dioxides of the present invention are very mild with respect to skin compared to detergent trialkyl amine oxides.
Diamine dioxides are described in Drew and Zimmerer U.S. Pat. 3,234,139, granted Feb. 8, 1966, having similar detergency and mildness properties to the diamine dioxides of the present invention. Despite this similarity in properties, the present compounds distinguish over the Drew and Zimmerer compounds because of substantial differences in chemical structure between these two classes of compounds which are described hereinafter. Furthermore, the present compounds and the Drew and Zimmerer compounds are prepared by entirely different synthetic routes, and there is no way of interconverting the two types of compounds. As is demonstrated hereinafter, the routes to the present compounds offer a substantial eco- 3,531,526 Patented Sept. 29, 1970 nomic advantage over the routes to the Drew and Zi-mmerer compounds.
The detergent diamine dioxides of the present invention which provide the above-noted advantages have the following structural formula:
wherein R is an alkyl radical containing from about 8 to about 18 carbon atoms and each R is selected from the group consisting of methyl, ethyl, propyl, hydroxyethyl, and hydroxypropyl radicals. The alkyl radical R can be branched or straight chain. Each R can be the same or different within the same molecule. The arrows are the conventional representation for semi-polar bonds.
Examples of the compounds of this invention are:
N,N,N',N-tetramethyll ,2-diaminodecane-N,N'-dioxide N,N,N,N'-tetramethyl-1,2-diaminoundecane-N,N'-
dioxide N,N,N',N'-tetramethyl-1,2-diaminododecane-*N,N'-
dioxide N,N,N,N-tetramethyl-1,2-diaminotridecane-N,N'-
dioxide N,N,N,N-tetramethyl-1,Z-diaminotetradecane-N,N'-
dioxide N,N,N,N-tetramethyl-1,2-diaminopentadecane-N,N'-
dioxide N,N,N,N'-tetramethyl-1,2-diaminohexadecane-N,N'-
dioxide N,N,N',N'-tetramethyl-1,2-diaminoheptadecane-N,N'-
dioxide N,N,N,N'-tetramethy1-l,Z-diaminooctadecane-N,N'-
dioxide N,N-diethyl-N',N'-dimethyll,2-diaminodecane-N,N-
dioxide N,N,N'-trimethyl-N'-propyl-1,2-diaminododecane-N,N-
dioxide N,N,N-trimethyl-N'-hydroxyethyl-1,2-diaminooctadecane-N,N'-dioxide N,N'-dimethyl-N,N'-di (hydroxyethyl) -1,2-dia-minotetradecane-N,N-dioxide It appears that only certain of the diamine dioxides with the above structural formula have the aforementioned desired characteristics; in these diamine dioxides, R and R must be as described above. If R is longer in chain length than 18 carbon atoms or shorter in chain length than 8 carbon atoms, desired detergency characteristics are not obtained. Likewise, if any R contains more than 3 carbon atoms, desired detergency characteristics are not obtained. Moreover, if R contains more than about 18 carbon atoms or if any R contains more than three carbon atoms, the solubility of the compounds is decreased.
Preferred diamine dioxides of the present invention are those wherein R has a chain length ranging from about 8 to about 10 carbon atoms. These preferred diamine dioxides are substantially milder with respect to skin than those of the present invention wherein R contains more than about 10 carbon atoms. Moreover, these preferred diamine dioxides exhibit an unexpectedly high degree of mildness compared to detergent trialkyl amine oxides.
The diamine dioxides of this invention can be prepared by oxidizing the corresponding diamines. Hydrogen peroxide is a suitable oxidizing agent and can be conveniently 3 used as an aqueous solution containing 30% hydrogen peroxide. Reaction temperatures ranging from C. to about 100 C. and reaction times ranging from about 1 hour to about 200 hours can be employed. LLower alcohols, e.g., ethanol or isopropanol, are suitable reaction solvents.
The corresponding diamines can be prepared employing as a starting material either fatty olefin epoxides or fatty olefin dichlorides. These materials are commercially available or are respectively prepared by oxidizing alphaolefin with peracetic acid and by chlorinating alpha-olefin with chlorine. The fatty olefin epoxide route is preferred since this route gives yields of almost 100% based on the epoxide while the dichloride route gives only 60% yields based on the dichloride.
The corresponding diamines can be prepared employing fatty olefin epoxides as starting materials according to the following reaction equations wherein R and R are defined as hereinbefore.
These reactions can be carried out under the following conditions:
oxides of the present invention the hydrophobic chain is attached to a carbon atom while in the Drew and Zimmerer compounds, the hydrophobic chain is attached to a nitrogen atom. Moreover, in the present diamine dioxides one of the nitrogen atoms is pendant from the long chain while in the Drew and Zimmerer compounds the hydrophobic group and the nitrogen atoms are all part of a single long chain.
The Drew and Zimmerer diamine dioxides are prepared by a condensation reaction between a fatty acid chloride and an amine, for example, an ethylene diamine, followed by reduction, for example, with lithium aluminum hydride, methylation, and oxidation. For example, in Example I of US. Pat. 3,234,139 lauroyl chloride is condensed with N,N-dimethylethylenediamine to provide N,N-dimethyl-N'-lauroyl-ethylene-diarnine; this reaction product is reduced with lithium aluminum hydride to provide N,N-dimethyl-N-dodecylethylenediamine which in turn is methylated with formic acid and formaldehyde to provide N,N',N'-trim,ethyl-N-dodecylethylenediamine; this product is oxidized with hydrogen peroxide to produce its corresponding diamine dioxide. A comparison of this method to the methods previously described for preparing the compounds of the present invention demonstrates the economic advantage of the present compounds over the Drew and Zimmerer compounds. More particularly, the hydrophobic-group-supplying reactants in the preparation of the present compounds are olefin epoxides or olefin dichlorides which are derived from relatively inexpensive alpha-olefins while the hydrophobic-group-supplying reactants in the preparation of the Drew and Zimmer compounds are relatively expensive fatty acid chlorides. Furthermore, the disubstituted amines used as reactants in the preparation of the present compounds are much less expensive than the .alkylene diamines employed in preparing the Drew and Zimmerer compounds. More- Solvent Temperature Time Reaction:
I None, water, or lower alcohol O.300 C 1-10 hrs. II Chloroform or carbon tetrachloride-.. 0 O.solvent boiling point. 30 min-24 hrs III 025% water 50 C 300 C hrs.
Reactions I and III are carried out at a pressure ranging from atmospheric to 2000 p.s.i. In Reactions I and III the mole ratio of secondary amine reactant to olefin epoxide or Z-chloroalkyldi-(substituted)amine ranges from 1:1 to about 15:1 and preferably from 4:1 to 12:1. Reaction I is also described in US. Pat. 3,202,714 and Canadian 'Pat. 720,430.
The corresponding diamines can be prepared employing fatty olefin dichlorides as starting materials according to the following reaction equation wherein R and R are defined as hereinbefore.
wherein R is an alkyl group having from 10 to 18 carbon atoms, each R is a methyl, ethyl or propyl radical, and n is 2 or 3. The compounds of the present invention differ from these prior art compounds in that in the diamine diover, the hydrogen producing reducing agent which is employed in producing the Drew and Zimmerer compounds and which is not used in the preparation of the present compounds is quite expensive, especially if lithium aluminum hydride is employed as a reducing agent. Thus, the present compounds offer a rather substantial economic advantage over the Drew and Zimmerer compounds.
Turning now to detergent utility, the compound of this invention are useful per se as detergent and surface active agents. Desirably they are used with other materials to form detergent compositions, as for example, liquid, bar, tablet, granular or other compositions. Such detergent compositions can contain the diamine dioxides of this invention, and water-soluble inorganic alkaline builder salts, water-soluble organic sequestrant builder salts or mixtures thereof in a ratio of diamine dioxide to builder salt of about 4:1 to about 1:20. Such detergent compositions ordinarily contain from 5% to 50% of detergent active and from 5% to of builder salt.
Granular detergent compositions preferably contain from about 5% to about 50% of the diamine dioxides of this invention and liquid formulations preferably contain from about 2% to about 30% of such diamine dioxides. Granular detergents preferably contain at least an equal amount of alkaline builder salt. Liquid formulations preferably contain from about 5% to about 40% of a watersoluble alkaline builder salt, the balance of the composition being a solvent such as Water, and/or other liquid vehicles. Liquid formulations can also contain a hydrotroping electrolyte, e.g., sodium toluene sulfonate. All percentages and parts herein are by weight unless otherwise specified.
Water-soluble inorganic al-kaline builder salts which can be used in this invention alone or in admixture are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Ammonium or substituted ammonium, e.g., triethanol ammonium, salts of these materials can also be used. Specific examples of suitable salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium and potassium pyrophosphate, sodium and ammonium bicarbonate, potassium tripolyphosphate, sodium hexaphosphate, sodium sesquicarbonate, sodium orthophosphate and potassium bicarbonate. The preferred inorganic alkaline builders according to this invention are alkali metal tripolyphosphates for built granular and tablet compositions and alkali metal pyrophoshates for built liquid compositions. Potassium is the preferred alkali metal used in liquid compositions and sodium finds best application for granular or tablet compositions.
Examples of suitable organic alkaline sequestrant builder salts used in this invention alone or in admixture are alkali metal, ammonium or substituted ammonium amioncarboxylates, e.g., sodium, and potassium ethylenediaminetetraacetate, sodium and potassium N-(Z-hydroxyethyl) ethylenediaminetriacetates, sodium and potassium nitrilotriacetates and sodium and potassium and triethanolammonium N-(2-hydroxyethyl)nitrilodiacetates. Mixed salts of these polycarboxylates are also suitable. The alkali metal salts of phytic acid, e.g., sodium phytate are also suitable as organic alkaline sequestrant builder salts (see US. Pat. 2,739,942). Also suitable as organic alkaline sequestrant builder salts are the water-soluble salts of polycarboxylate polymers and copolymers as described in the copending application of Francis L. Diehl, Ser. No. 269,359, filed Apr. 1, 1936 and now U.S. Pat. No. 3,308,067 (e.g., polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid and copolymers with themselves and other comparable monomers such as ethylene).
Polyphosphonates are also valuable builders in terms of the present invention, including specifically sodium and potassium salts of ethane-l-hydroxy-l,l-diphosphonic acid, sodium and potassium salts of methylene diphosphonic acid, sodium and potassium salts of ethylene diphosphonic acid, and sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Other examples include the alkali metal salts of ethane2carboxy-1,1-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy-l,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,1- 3 ,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and propane-1,2,2,3-tetraphosphonic acid.
Besides the builders being used together with the present diamine dioxides, it is also possible according to the present invention to use the diamine dioxide compounds of this invention in combination with other cleaning agents such as anionic, ampholytic, Zwitterionic, and other nonionic organic detergent surfactant compounds. When it is desired to use such diamine dioxide compounds in combination with other detergent compounds, they are preferably utilized with anionic detergents because of the sudsing characteristics of the latter. The ratio of the di amine dioxide to such other detergent compound is from about :1 to 1:5. If it is desired to use such a diamine dioxide in admixture with another detergent compound as the active portion of a cleaning composition, the ratio of such a mixture to the builder salt should be Within the previously prescribed range of 4:1 to 1:20. A composition prepared along these lines can contain from 5% to 50% of such a mixture and 5% to 85% of a builder salt selected from water-soluble inorganic alkaline builder salts, watersoluble organic sequestrant builder salts, and mixtures thereof, within the prescribed ratio range.
Examples of anionic soap detergents which can be used in admixture with the diamine dioxide, if desired, are the sodium, potassium, ammonium and alkylolammonium salts of higher detergent range fatty acids (C -C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. Examples of suitable anionic organic non-soap detergents in the form of their water-soluble salts are: Alkylglycerylethersulfonates; alkyl sulfates; alkyl monoglyceride sulfates or sulfonates; alkylpolyethyleneoxy ether sulfates; acylsarcosinates; acyl esters of isethionates; N-acyl-N- methyl taurides; alkylbenezenesulfonates wherein the alkyl substituent is straight chain or branched chain, sulfonated alpha-olefins, e.g., such as described in copending application of Kessler et al. Ser. No. 561,397, filed June 29, 1966; alkylphenol polyethylenoxy sulfonates. In these compounds the alkyl and acyl groups, respectively, contain 10 to 20 carbon atoms. They are used in the form of water-soluble salts, the sodium, potassium, ammonium, and alkylammonium salts, for example. Specific examples are: sodium lauryl sulfate, sodium tallow alkyl sulfate; sodium salt of sulfonated alpha-trideceneg potassium N- methyl-N-lauroyl tauride; triethanolammonium tetrapropylbenzene sulfonate; sodium (linear) dodecyl benzene sulfonate.
Examples of other nonionic organic detergents which can be used in the compositions of this invention, if desired, are: polyethylene oxide condensates of alkylphenols wherein the alkyl group contains from 8 to 15 carbon atoms (e.g., t-octylphenol) and the ethylene oxide is present in a molar ratio of ethylene oxide to alkylphenol in the range of 3:1 to 20:1; condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine wherein the molecular weight of the condensation products ranges from 5000 to 11,000; the condensation products of from about 5 to 30 moles of ethylene oxide with one mole of a straight or branched chain aliphatic alcohol containing from 8 to 18 carbon atoms, e.g., condensation product of 6 moles of ethylene oxide with one mole of lauryl alcohol; higher alkyl di-lower alkyl amine or phosphine oxides, e.g., dodecyldimethylamine oxide or dodecyldimethyl phosphine oxide; alkyl methyl sulfoxides such as dodecyl methyl sulfoxide.
Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, phosphinate, or phosphonate. Examples of compounds falling within this definition are sodium 3-dodecylaminopropionate, sodium 3-(N- methyl-N-hexadecylamino)-2-hydroxypropane 1 sulfonate and its dodecyl homolog, sodium 3-dodecylaminopropane-l-sulfonate, sodium dodecyl-beta-alanine, sodium N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of United States Letters Patent No. 2,658,072, N-higher alkyl aspartic acids such as those produced according to the teaching of United States Letters Patent No. 2,438,091, and the products sold under the tradename Miranol and described in United States Letters Patent No. 2,528,378.
Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaterna1y ammonium, phosphonium, and ternary sulfonium compounds, in which the aliphatic radical may be straight chain or branched, and wherein one of the aliphatic substituents contains from about 10 to about 18 carbon atoms and one contains an anionic water solubilization group, e.g., carboxy, sulfonate, sulfate, phosphate, phosphinate, or phosphonate. Examples of compounds falling within this definition are: 3 (N,N dimethyl N hexadecylammonio) Z-hydroxypropane-l-sulfonate and the corresponding dodecyl and tetradecyl homologs and 3 (N,N dimethyl-N-dodecylammonio)-propane-l-sulfonate and the corresponding hexadecyl and tetradecyl homologs.
The detergent compositions of this invention can also contain any of the usual adjuvants, diluents and additives, for example, perfumes, anti-tarnishing agents, anti-redeposition agents, bacteriostatic agents, dyes, fluorescers, suds builders, suds depressors and the like, without detracting from the advantageous properties of the compositions.
Certain mixtures of the diamine dioxides of this invention and alkylbenzenesulfonates exhibit unexpectedly high degrees of mildness with respect to skin. In these mixtures, the weight ratio of diamine dioxide to alkylbenzenesulfonate ranges from about :1 to about 1:5. When the preferred diamine dioxides herein, i.e., those wherein R is an alkyl radical containing from about 8 to about 10 carbon atoms, are employed in these mixtures, the diamine dioxides are effective mildness additives for the alkylbenezenesulfonates; while the mixture of these ingredients is not as mild as the diamine dioxides themselves, this mixture is substantially more mild than would be expected from a consideration of each ingredient alone. When the diamine dioxides of the present invention wherein R is an alkyl radical containing more than about 10 carbon atoms are employed in these mixtures, the mixtures in aqueous solution are substantially milder to the skin than either ingredient alone. These mildness effects are very advantageous since combinations of the alkylbenzenesulfonates and diamine dioxides in compositions of the present invention are very efiicient detergents. The alkylbenzenesulfonates in compositions of this invention are the water-soluble salts, such as the alkali metal (e.g., sodium and potassium) ammonium and substituted ammonium (e.g., triethanolamine) salts, of sulfonated alkylbenzene in which the alkyl radicals contain from about 9 to about carbon atoms. Especially preferred for use herein are the linear alkylbenzenesulfonates, for example, linear dodecylbenezenesulfonate. Also useful herein are alkylbenzenesulfonates having their alkyl chain derived from propylene, for example, tetrapropylene benzene sulfonate. These alkylbenzenesulfonates are commonly used as a sodium salt.
In the testing of detergent compounds and compositions for mildness and for the unexpected mildness efliect, skin is contacted by immersion or other means with a solution of the detergent under standardized conditions as more fully described below. A 1 to 10 scale is used to rate the effects of prolonged exposure on the skin. Grade 10 represents ideal or perfect skin (soft, smooth and flexible) and the efiect of a theoretically perfectly mild detergent; grade 1 represents severely irritated skin. Other values represent gradations of severity between these extremes. Grade 1 in a guinea pig immersion test indicates severely thickened, dry, cracked and bleeding skin, i.e., extreme irritation. Grade 1 in exaggerated tests on human subjects indicates severe redness and dryness of the skin. Thus, the exaggerated tests on animals are much more extreme than those conducted on human subjects.
There is a good correlation between the results of exaggerated exposure tests on animals and the results of normal use tests on humans; the former can be relied on to grade the relative mildness of detergents toward the human skin.
As used in examples, the graded guinea pig immersion tests at 37 C. for a 4 /2-hour period per day for 3 consecutive days. The animals are graded 3 days after the last immersion. The grades given in the examples are the average of the results on not less than three animals. It will be understood by those with experience in biological experiments that there is variation in the reactions of individuals, within a group, to exposure to chemical solutions; this is true whether the individuals are guinea pigs or humans.
The following examples are illustrative of the present invention and are not to be construed in any way as limiting its scope.
8 EXAMPLE I Preparation of N,N,N,N'-tetramethyl-1,2- diaminododecane-N,N-dioxide 1,2-dichlorododecane was prepared by adding chlorine to a solution of l-dodecene in chloroform at 50 C. as described by W. I. Lyness and F. W. Quackenbush, J. Am. Chem. Soc. 32, 520 (1955). Distillation of the reaction product through a 2-foot spinning band column gave a 63% yield of substantially pure 1,2-dichlorododecane having a boiling point of C. at 0.8 mm. Hg.
In a glass autoclave liner at 25 C. was placed 240 grams (1 mole) of the above-prepared 1,2-dichlorododecane and 500 grams (11 moles) dimethylamine and 156 grams water. The mole ratio of dimethylamine to 1,2- dichlorododecane was 11:1 and water amounted to 21 percent by weight of the reactants. The glass liner was placed in an autoclave. Nitrogen was then admitted into the autoclave to provide an inert atmosphere over the reactants. The reactants were rocked in the autoclave for 1 hour at 200 C. at 1000 p.s.i.g. After this reaction period, the reactants were allowed to cool in the autoclave to room temperature, that is, 25 C. the reaction mixture was then removed from the autoclave liner by washing with 2000 ml. diethyl ether and 2000 ml. water. The washed reaction mixture was then held under a vacuum of 20 mm. Hg for 45 minutes to remove excess dimethylamine. 2000 ml. of diethyl ether was then added to the residue and this mixture was washed with 2000 ml. of 10% hydrochloric acid. The ether layer contained vinyl chlorides and was discarded. The acid layer was basified with 10% NaOH to liberate the diamine, which was extracted with petroleum ether, dried, and the ether evaporated to give 42 grams of the diamine.
37.4 grams (0.146 mole) of this diamine was dissolved in 100 ml. of ethanol. This solution was then cooled to 5 C. To this cooled solution was added over a minute period 91 ml. of an aqueous solution containing 30% by weight hydrogen peroxide. This mixture was stirred at a temperature ranging from 25 C. to 70 C. without the application of external heat for 92 hours. At this point platinum black was added to the reaction mixture to decompose excess peroxide, and then stirring was continued for an additional 24 hours. The platinum black was then filtered off and the ethyl alcohol partially stripped off on a steam bath. The resulting solution was extracted 2 times, each time with 50 ml. of petroleum ether, to remove unoxidized starting materials. The solution was then heated on a steam bath under a nitrogen stream to strip off remaining ethanol. The resutling aqueou solution amounted to 128.4 grams and contained 25% by weight N,N,N',N'-tetramethyl 1,2 diaminododecane- N,N'-dioxide.
EXAMPLE II Preparation of N,N,N',N-tetramethyl-1,2- diaminodecane-N,N-dioxide 156 grams (1.1 moles) of l-decene was placed in a roundbottomed flask together with 18.7 grams (0.23 mole) of sodium acetate. This mixture was heated to 40 C. To this mixture was added dropwise 88.7 grams of an aqueous solution containing 40% by weight peracetic acid (1.15 moles peracetic acid). During this addition, the temperature of the mixture was maintained at 40 C. After the addition was completed the mixture was stirred at room temperature for 16 hours. The mixture was then poured into a separatory funnel and allowed to separate into two layers. The lower (aqueous) layer was drawn off and was extracted 2 times, each time with 50 ml. of petroleum ether. These petroleum ether extracts were combined with the previously separated upper (organic) layer, and this combination was washed with 50 ml. of 40% aqueous dimethylamine followed by 50 ml. of water. The organic layer was then dried over sodium and mag nesium sulfate and filtered. Solvent was then stripped off from the filtrate in vacuo to provide 189 grams to crude l-epoxydecane which was about 60-65% pure. This material was used hereinafter without further purification.
189 grams of the above crude l-epoxydecane and 157 grams (3.5 moles) of dimethylamine were then placed in a glass autoclave liner. The glass liner was placed in an autoclave. Nitrogen was then admitted into the autoclave to provide an inert atmosphere over the reactants. The reactants were rocked in the autoclave for 4 hours at 200 C. at 1000 p.s.i.g. After this reaction period, the reactants were allowed to cool in the autoclave to room temperature, i.e., 25 C. The reaction mixture was then removed from the autoclave liner and dissolved in 500 ml. of dilute HCl. This solution was extracted 4 times, each time with 100 ml. of diethyl ether and the extracts discarded. The acid solution was then made basic with 10% NaOH. Two layers then formed. The organic layer was separated and extracted 2 times, each time with 100 ml. of diethyl ether. The extracts were combined, dried over sodium sulfate and magnesium sulfate, and filtered. The solvent was stripped off in vacuo to provide 143.4 grams of substantially pure 2-hydroxydecyldimethylamine.
143.4 grams (0.7 mole) of this 2-hydroxydecyldimethylamine was dissolved in one liter of chloroform and this solution was cooled to 5 C. with an ice bath. Anhydrous HCl was then bubbled into the solution with the temperature maintained at 5-10 C. until the solution was saturated,, as evidenced by the evolution of HCl. A solution of 95 grams (0.8 mole) of thionyl chloride in chloroform was added dropwise while maintaining the temperature at 5-10 C. After this addition period the reaction mixture was allowed to warm to room temperature and to stand for 16 hours. The volatiles and solvent were then stripped off in vacuo, leaving a solid brown residue. This material was recrystallized from 1:1 ethyl acetatezethanol to provide 125.8 grams of 2-chlorodecyldimethylamine hydrochloride.
In a glass autoclave liner was placed 76.8 grams (0.3 mole) of the above-prepared 2-chlorodecyldimethylamine hydrochloride, 135 grams (3.0 moles) of dimethylamine and 8 ml. water. The glass liner was then placed in an autoclave. Nitrogen was admitted into the autoclave to provide an inert atmosphere over the reactants. The reactants were rocked in the autoclave for 6 hours at 100 C. at 800 p.s.i.g. The contents of the autoclave were then allowed to cool to room temperature over a 16-hour period. The contents of the liner were dissolved in 500 ml. of diethyl ether and the ether solution was washed with water. The ethereal solution was dried over sodium sulfate and magnesium sulfate and filtered. Solvent was stripped off from the filtrate in vacuo and the residue distilled through a Vigreux column. The fraction having a boiling point of 83 C. at 0.45 mm. Hg and amounting to 52.6 grams was substantially pure N,N,N,N'-tetramethyl-1,2-diaminodecane.
28.5 grams (0.125 mole) of the above prepared N,N,N',N-tetramethyl-1,2-diaminodecane and 43.8 ml. water were admixed. This mixture was then cooled to 20 C. To this cooled mixture was added dropwise over a 60-minute period 9.5 grams of 30% aqueous hydrogen peroxide solution (0.28 mole hydrogen peroxide). During this addition period the temperature of the reaction mixture was maintained in the range of 20 C. to 40 C. when the addition was completed, the reaction mixture was stirred for 24 hours without the addition of external heat at a temperature ranging from 20 C. to 30 C. At the end of this reaction period platinum black was added to the reaction mixture to decompose the excess hydrogen peroxide still present. When the decomposition was completed, as indicated by the cessation of gas evolution, the solution was filtered through glass fiber filter paper. The resulting aqueous solution amounted to about 65 grams and contained 25% by weight of N,N,N,N- tetramethyl-1,2-diaminodecane-N,N'-dioxide.
N,N,N,N' tetramethyl 1,2 diaminododecane-N,N- dioxide, N,N,N', 'N' tetramethyl-1,2-diaminotetradecane- N,N'-dioxide, and N,N,N,N-tetramethyl-1,2-diaminohexadecane-N,N-dioxide were prepared following the above procedure except respectively employing l-dodecene, 1- tetradecene and l-hexadecene instead of l-decene in forming the olefin epoxide reactant and thereafter reacting the corresponding l-epoxyalkanes, 2-hydroxyalkyldimethylamines, 2-chloroalkyldimethylarnine hydrochlorides, and N,N,N',N'-tetramethyl-1,2-diaminoalkanes.
N,N,N',N'-tetrapropyl-1,2-diaminodecane-N,N'-dioxide can be prepared following the procedure employed in Example II except for substituting dipropylamine for the dimethylamine employed in that example. N,N,N-tri methyl-N'-hydroxyethyl-1,Z-diaminodecane-N,N'-dioxide can be prepared following the procedure in Example II except for substituting methyl(hydroxyethyl) amine for the dimethylamine in the reaction with 2-chlorodecyldimethylamine hydrochloride and oxidizing the formed N,N,N'- trimethyl-N'-hydroxyethyl-1,2-diaminodecane to its corresponding dioxide.
The above-synthesized diamine dioxides were effective cleaners, espectially for washing dishes.
The following aqueous solution (distilled water) were compared in grade guinea pig immersion tests:
Test Solution:
0.2% N,N,N',N'-tetramethyl-1,2-diaminodecane- N,N-dioxide 9.3 0.2% -N,N,N',N-tetramethyl-1,2-diaminododecane- N,N'-dioxide 9.3 0.2% N,N,N',N'-tetramethyl-1,2-diaminotetradecane-N,N'-dioxide 3.3 0.2% N,N,N',N-tetramethyl-1,Z-diaminohexadecane- N,N'-dioxide 2.0 0.2% dodecyldimethylamine oxide 2.0 0.2% sodium dodecylbenzenesulfonate (tetrapropylene) 3.0
The above data demonstrates that N,N,N,N'-tetrarnethyl-l,2-diaminodecane-N,N-dioxide and N,N,N,N'- tetramethyl-1,2-diaminododecane-N,N-dioxide exhibit a substantially higher degree of mildness than dodecyldimethylamine oxide. Moreover, a one to one weight mixture of either of these two diamine dioxides with sodium dodecylbenzenesulfonate gives a very high degree of mildness in the above test which would not be expected from the individual results demonstrating the unexpected mildness additive effects of the diamine dioxides of the present invention wherein R in the structural formula has a chain length ranging from about 8 to about 10 carbon atoms. A one to one weight mixture of either N,N,N',N'- tetramethyl 1,2 diaminotetradecane N,N' dioxide or N,N,N,N' tetramethyl 1,2 diamniohexadecane N,N'- dioxide with sodium dodecyl-benzenesulfonate is substantially milder in the above test than the same concentrations of either ingredient alone.
The following examples illustrate detergent compositions containing the diamine dioxides of this invention which can be used under conditions of ordinary usage to clean, for example, soiled clothing or dishes.
1 1 EXAMPLE III Solidgranules Percent N,N,N',N'-tetramethyl-1,2diaminohexadecane- N,N'-dioxide 5.0 Sodium (linear) dodecylbenzenesulfonate 12.5 Sodium tripolyphosphate 50.0 Sodium silicate (N21 O:SiO =1:2.5) 10.0 Sodium sulfate 17.5
Moisture 5.0
EXAMPLE IV Compressed granulestablet Percent N,N,N',N'-tetramethyl-1,2-diaminotet1'adecane- -N,N'-di0xide 10.0 Sodium (linear) dodecylbenzenesulfonate 21.0 Tetrasodium pyrophosphate 52.0 Trisodium phosphate 10.0 Moisture 7.0
EXAMPLE V Solidgranules Percent N,N'-di(hydroxyethyl-N,N'-dimethyl-1,2-diaminooctadecane-N,N'-dioxide 12.0 Sodium (linear) dodecylbenzenesulfonate 20.0
Trisodium ethane-l-hydroxy-l,1,2-triphosphonate 64.0
Moisture 4.0
EXAMPLE VI Solidgranules Percent N,N,N',N-tetrapropyl-1,2-diaminododecane N,N-
dioxide 5.0 Sodium (linear) dodecylbenzenesulfonate 15.0 Sodium tripolyphosphate 50.0 Sodium sulfate 25.0
Moisture 5.0
EXAMPLE VII Solidgranules Percent N,N,N tri(hydroxyethyl)-N'-ethyl 1,2-diaminododecane-N,N'-di0xide 10.0 Sodium (tetrapropylene) dodecylbenzenesulfonate 10.0 Sodium tripolyphosphate 50.0 Sodium sulfate 25.0 Moisture 5.0
EXAMPLE VIII Solidgranules Percent 3-(N,N-dimethyl-N-hexadecylammonio) propanel-sulfonate 30.0 N,N,N,N-tetramethyl-1,Z-diaminodecane N,N'-
dioxide 15.0 Sodium tripolyphosphate 35.0 Sodium carbonate 10.0 Sodium silicate (Na O:SiO =1:2.5) 5.0 Moisture 5.0
EXAMPLE IX Solid-granules Percent N,N,N',N-tetramethy1 1,2 diaminododecane-N,
N'-dioxide 20.0 Sodium tallow alcohol sulfate 10.0 Trisodium ethane-l-hydroxyy-l,l-diphosphonate 20.0 Sodium tripolyphosphate 10.0 Sodium nitrilotriacetate 10.0 Sodium sulfate 8.0 Sodium silicate (Na O:SiO =1:2.5) 11.0 Moisture 11.0
1 2 EXAMPLE X Liquid Percent N,N,N,N'-tetramethyl 1,2 diaminodecane-N,N'-
dioxide 5 .0 Sodium salt of SO -sulfonated 1:1 weight mixture of alpha-dodecene and alpha-tetradecene 10.0 Tetrapotassium pyrophosphate 19.0 Sodium silicate (Na O:SiO :1:1.6) 3.8 Potassium toluene sulfonate 8.5
Carboxymethyl hydroxyethyl cellulose .3 Balance water.
EXAMPLE XI Liquid Percent N,N,N',N'-tetramethyl 1,2 .diaminododecane-N,
N-dioxide 12.0
Tetrapotassium propane-1,1,3,3-tetraphosphonate 20.0 Sodium silicate (Na O:SiO =1:1.6) 3.8 Potassium toluene sulfonate 8.5
Carboxymethyl hydroxymethyl cellulose .3 Balance water.
EXAMPLE X11 Solidgranules Percent N,N,N,N'-tetramethyl 1,2 diaminohexadeeane- N,N'-dioxide 5.0 Condensation product of 10 moles of ethylene oxide and one mole of tallow fatty alcohol 5 .0
Sodium (linear) tridecyl benzenesulfonate 10.0
Dodecyldimethyl phosphine oxide 5 .0 Coconut oil soap 5.0 Sodium tripolyphosphate 50.0 Tetrasodium ethylene diamine tetraacetate 20.0
Good detergency effects are also obtained when in the above examples the following builders, sodium or potassium salts, are substituted for all or part of those employed in such examples: tripolyphosphates; pyrophosphates; ethylene diaminetetraacetates; N-(Z-hydroxyethyl) ethylenediamine triacetates; nitrilo triacetates; N-(Z-hydroxyethyl)-nitril0 diacetates; phytates; polycarboxylate polymers; and polyphosphonates, e.g., ethane hydroxydiphosphonate.
It will be appreciated that the diamine dioxide compounds of the present invention can be incorporated into many other liquid or granular detergent compositions with suitable adjustments being made in the other components.
Materials which are considered normal and desirable additives in liquid or granular detergent compositions can be added to the compositions of this invention without adversely aifecting or modifying basic cleaning characteristics.
The present diamine dioxides can also be employed as detergent actives in other compositions, e.g., in shampoos.
What is claimed is:
1. A detergent diamine dioxide which has the structural formula;
wherein R is an alkyl radical containing from 8 to 10 carbon atoms.
2. A detergent diamine dioxide of claim 1, wherein R is an alkyl radical containing *8 carbon atoms.
3. A detergent diamine dioxide of claim 1, wherein R is an alkyl radical containing 10 carbon atoms.
(References on following page) 13 14 References Cited CHARLES B. PARKER, Primary Examiner UNITED STATES PATENTS R. L. RAYMOND, Assistant Examiner 3,098,794 7/1963 Dohr et a1. 3,373,107 3/1968 Rice et a1. 260-583 X 3,412,155 11/1968 Miller et al. 5 152 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,531,526 Dated September 29. 1970 Inventor(s) Ted J. Logan It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
I 1 Column 4, lines 31 and 32, "Zim-mer" should read -Zimmerer-. Column 4, line 50, "compound" should read -compounds-- Column 5, line 34, "Apr. 1, 1936" should read --Apr. 1, l963- Column 8, line 30, "the" should read --'I'he-- Column 9, line 15, the second "to" should read --of--.
Column 10, line 4, "when" should read --When--.
Column 10, line 37, "espectially" should read -especially--.
Column 10, line 38, "solution" should read -solutions-.
Column 10, line 41, after "Test Solution:" and before "0 .2%.
dioxide" should read Grade--.
Column 10, line 68, "N,N,N' ,N'tetramethyl-l,2-diamniohexa() decane-N,Ndiox-ide" should read --"N,N,N' ,N -tetramethyl l,2diaminohexadecane-N,N'dioxide-.
Column 11, lines 26 and 27, "N,N'di(hydroxyethyl-N,N' -dimethyll,2diaminooctadecane-N,N'dioxide" should read N,N'- di(hydroxyethyl)-N,N' -dimethyl-l,2diaminooctadecaneN,N' dioxide--.
01 12 l e C umn an 66, 0 N(CH 2 should read 0 -N(CH Signed and sealed this 22nd day of December 1970.
(S Afloat:
EdwardMFlemhenIr. WIHiIAM E. SGHUYIER, JR
Aflesting Officer Gomlssioner of Patents
US603439A 1966-12-21 1966-12-21 Diamine dioxide detergent compounds Expired - Lifetime US3531526A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4391726A (en) * 1980-11-28 1983-07-05 The Procter & Gamble Company Detergent composition containing low levels of amine oxides
US5560858A (en) * 1992-07-15 1996-10-01 The Procter & Gamble Company Dye transfer inhibiting compositions containing a metallocatalyst, a bleach and polyamine N-oxide polymer
US6417401B1 (en) * 1999-12-13 2002-07-09 Nova Molecular Technologies Inc Ether diamines amine oxides
US20070031370A1 (en) * 2005-08-04 2007-02-08 Carr Richard V Amine N-oxide based surfactants

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3098794A (en) * 1959-08-08 1963-07-23 Therachemie Chem Therapeut Process for treating human hair with amino oxide compositions
US3373107A (en) * 1964-07-16 1968-03-12 Milchem Inc Friction pressure reducing agents for liquids
US3412155A (en) * 1964-10-09 1968-11-19 Armour Ind Chem Co Fatty branched amine dioxides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3098794A (en) * 1959-08-08 1963-07-23 Therachemie Chem Therapeut Process for treating human hair with amino oxide compositions
US3373107A (en) * 1964-07-16 1968-03-12 Milchem Inc Friction pressure reducing agents for liquids
US3412155A (en) * 1964-10-09 1968-11-19 Armour Ind Chem Co Fatty branched amine dioxides

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4391726A (en) * 1980-11-28 1983-07-05 The Procter & Gamble Company Detergent composition containing low levels of amine oxides
US4470923A (en) * 1980-11-28 1984-09-11 The Procter & Gamble Company Detergent composition containing low levels of amine oxides
US5560858A (en) * 1992-07-15 1996-10-01 The Procter & Gamble Company Dye transfer inhibiting compositions containing a metallocatalyst, a bleach and polyamine N-oxide polymer
US6417401B1 (en) * 1999-12-13 2002-07-09 Nova Molecular Technologies Inc Ether diamines amine oxides
US20070031370A1 (en) * 2005-08-04 2007-02-08 Carr Richard V Amine N-oxide based surfactants

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