US3637496A

US3637496A - Phosphiniminosulfoxonium compounds and process for preparing the same

Info

Publication number: US3637496A
Application number: US852873A
Authority: US
Inventors: Ted J Logan; Terence W Rave
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1966-10-25
Filing date: 1969-08-25
Publication date: 1972-01-25
Anticipated expiration: 1989-01-25

Abstract

The phosphiniminosulfoxonium salts and a process for preparing these salts are disclosed. The phosphiniminosulfoxonium salts are useful as emulsifying fabric softening and antibacterial agents.

Description

K nited States Patent Logan et a1.

[is] 3,637,496 1 Jan. 25, 1972 PHOSPHINIMINOSULFOXONIUM COMPOUNDS AND PROCESS FOR I PREPARING THE SAME Inventors: Ted J. Logan, Colerain Township, Hamilton County, Ohio; Terence W. Rave, Wilmington, Del.

Assignee: The Procter & Gamble Company, Cincinnati, Ohio 1 Filed: Aug. 25, 1969 Appl. No.: 852,873

Related U.S. Application Data Division of Ser. No. 589,208, Oct. 25, 1966, Pat. No. 3,524,881.

U.S. C1 ..252/8.75, 117/139.5, 252/152, 252/355, 424/215, 260/551 Int. Cl ..C07c 145/00, D06m 9/00, C1 1d 1/00 Field ofSearch ..252/8.75, 152; 117/1395 Primary ExaminerHerbert B. Guynn Assistant Examiner-Harris A. Pitlick Attorney-Robert B. Aylor [57] ABSTRACT The phosphiniminosulfoxonium salts and a process for preparing these salts are disclosed. The phosphiniminosulfoxonium salts are useful as emulsifying fabric softening and antibacterial agents.

4 Claims, No Drawings PHOSPHlNlMINOSULFOXONlUM COMPOUNDS AND PROCESS FOR PREPARING THE SAME CROSS REFERENCE linkage, which linkage is explained hereinafter. Compounds containing this linkage are not known to have been described in the prior art.

There are several fabric softening agents which are commercially available and which are of much different chemical structure from the compounds of the present invention. Some of these commercially available softening agents, while effectively softening fabric thereby reducing or eliminating harsh feel, resist removal when the softened fabric is washed and upon continued reapplication can waterproof the fabric or garment to which they are applied. This waterproofing effect is undesirable especially in the case of, for example, towels, diapers, underwear, etc. Removable softening agents, such as certain of the compounds of the present invention, which after two washings of the fabric or garment to which they have been applied are more than 70 percent removed, are advantageous in that'the tendency of the garments to which the agents are applied to become waterproofed is lessened, especially when compared to the softening agents which are commercially available.

it is, therefore, an object of this invention to provide novel phosphiniminosulfoxonium salts which are effective as removable softening agents, that is, which after two washings of the fabric or garment to which they have been applied are more than about 70 percent removed.

lt is a further object of this invention to provide novel phosphiniminosulfoxonium salts which are effective as emulsifying agents and antibacterial agents.

It is another object of this invention to prepare phosphiniminosulfoxonium salts by reacting N-alkali-metal sulfoximines with trisubstituted phosphine dihalides or dipseudohalides.

According to this invention, it has been found that phosphiniminosulfoxonium salts having the following structural formula are effective as emulsifying agents, removable softening agents, and antibacterial agents:

wherein R and R are each radicals selected from the group consisting of aliphatic radicals containing from one to about 20 carbon atoms, phenyl, and substituted phenyl; R, R and R are each radicals selected from the group consisting of aliphatic radicals containing from one to about four carbon which permits adequate solubility and hydrolytic stability of the salt. For an emulsifying agent, either R or R or both of these radicals is an aliphatic radical containing from about 12 to about 20 carbon atoms. For a removable fabric softening agent R and R are each aliphatic radicals'containing from about l2 to about 20 carbon atoms and R, R and R are each aliphatic radicals containing from one to about four carbon atoms. All of the above compounds are antibacterial agents.

jl eabove structural formula and more particularly the linkage in this structural formula is a resonance structure. Thus, this structural formula represents the following structural formulas which are in resonance and in which R, R, R, R, R, and X are defined as above:

In these structural formulas R,R, R, R, and R can each be of different chain lengths within the same compounds. The aliphatic radicals in this structural formula can be saturated or unsaturated and branched or'straight chain. For example, these aliphatic radicals can be alkyl, substituted alkyl, alkenyl, and substituted alkenyl radicals. The term alkyl" is used herein to include only saturated carb'on chains. The term "alkenyl" is used herein to include carbon chains containing one or more'double bonds.

The substituents in the substituted alkyl and substituted alkenyl radicals include, for example, chloro, hydroxy, and phenyl radicals. The substituents in 'the substituted phenyl radicals include, .for example, methyl, ethyl propyl, chloro, and hydroxy radicals.

The exactnature of the anionic portion of the above phosphiniminosulfoxonium salts is thought to be immaterial so far as the utility of these new compounds is concerned. Accordingly, virtually any organic or inorganic cation which permits adequate solubility of the phosphiniminosulfoxonium salts, Le, a solubility of at least about 10 ppm. in water, and which permits hydrolytic stability of the salts, i.e., which provides stable anionic and cationic moieties upon solution in .water, is suitable depending upon availability and cost factors. Thus, X in the above structural formula can suitably be, e.g., a halide anion such as chloride, bromide, iodide, or fluoride anion; a sulfonate anion, such. as methane sulfonate or ptoluene sulfonate anion; sulfate, nitrate, chlorate, and other anions, for example, fluoroborate and hexachloroantimonate anions.

Preferably, the aliphatic radicals in the present phosphiniminosulfoxonium salts are alltyl radicals, and the anion, X is a halide, most preferably, chloride, bromide or iodide anion.

Useful phosphiniminosulfoxonium compounds, none of ,which are known to be described in the prior art, and, which .are exemplary of those within the present invention, are set forth in table l below wherein R, R, R, R, R, and X are apatoms, phenyl and substituted phenyl; and X is an anion plied in the TABLE I R R R R R X Utility (1) Meth l Methyl Methyl Methyl Antibacterial.

Ethyl-.. Ethyl do Do. MethyL. 3-iodopropenyL. Butyl. Do. .do.. Methyl tbyl D0. Chloromethy d Chlorornethy D0. Decyl Butyl ButyL Methyl D0. Dogeiblyg (straight Methyl MethyL. do Methyl Emulslfier c a dscyl 0:-. g-s-flf-a ty Hexyl 94 0 6 1 2 TABLE I R R R R R X Utility (9) Tetradecyl Butyl Butyl Hydroxymethyl Methyl Br- Do. (10) Hexadecyl Methyl Methyl Methyl Elcosyl I- Softener,

emulsifier. (11) Octadocyl ..do ...do Hexadecyl. 01- Do. (12) Oleyl .do do Oleyl Br- D0. (13) Eicosyl 3-hydroxyd Dodecyl NO Do propenyl. (14).. Methyl Methyl do "do"-.. Oetadecyl Cl- Emulsifier. (15) Phenyl- MethyL. Antibacterial.

6) 3-phenylpr d Do. Methyl] PhenyL. Do. p-Met ylpheny Butyl C D0. (19) Dodecyl do Methyl HexadecyL. Softener,

(tetrapropylene). emulsifier.

' Where the valence of the anion is greater than 1, a number of cations equal tpthis valence are present in each saltmolecule.

structural formula set forth above. The utilities indicated for each particular compound in table I are not necessarily exclusive.

The emulsifying phosphiniminosulfoxonium salts of the present invention ordinarily can be used to produce oil-inwater emulsions that are stable for more than 1 hour, the weight ratio of emulsifier to oil phase generally ranging from about 121,000 to about 3: l.

The antibacterial phosphiniminosulfoxonium salts of the present invention can be dissolved in water or other inert carrier in the range of about 10 ppm. to about l,000 ppm. and the solution used for antibacterial, e.g., disinfecting, purposes.

The softener phosphiniminosulfoxonium salts of the present invention effectively soften fabric, for example, towels, thereby reducing or eliminating harsh feel. Moreover, they are removable softening agents, and after two washings of the fabric or garment to which they have been applied are more than 70 percent removed from the fabric or garment. This reduces the tendency of such fabric or garment to become waterproofed after multiple applications of softening agent and preserves the ability of towels, undenvear, etc., to absorb moisture. Thus these salts are suitably used as active ingredien ts in fabric softener compositions.

A The fabric softener compositions referred to above can be in the form of liquids, granular products, tablets, and in other forms.

For example, a liquid fabric softener composition can comprises from about I to about 15 percent by weight of softening phosphiniminosulfoxonium salt and from about 85 to about 99 percent water. Such compositions also contain preferably from about I to about 50 percent, and more preferably from about I to about 10 percent, by weight of an alcohol containing from one to about four carbon atoms, such as, for example, ethanol or isopropanol, in place of an equal weight of water. This alcoholic component reduces the viscosity of the softener composition thereby causing it to be more readily pourable and also reduces the tendency of the composition to become a gel. This alcoholic ingredient also desirably acts as a freeze point depressant thereby reducing the possibility of the composition freezing during shipping whereby the compositions container is possibly ruptured. Thus, a preferred liquid fabric softener composition herein consists essentially by weight of from about 1 to about 15 percent phosphiniminosulfoxonium salt, from about 1 to about 50 percent alcohol, and from about 35 to about 98 percent water while an especially preferred liquid fabric softener composition herein consists essentially by weight of from about I to about 15 percent phosphiniminosulfoxonium salt, from about I to about 10 percent alcohol, and from about 75 to about 98 percent water. Optional ingredients for the present liquid fabric softener compositions include, for example, perfume, coloring agent, and up to about l percent or more of a nonionic detergent such as, for example, nonyl phenoxy polyoxyethylene ethanol, containing 5 to 25 moles of ethylene oxide per mole of phenol, to help stabilize the composition These softener compositions are applied, for example, by the housewife to fabric during laundering. The housewife can cause the application of such a softener composition simply by adding it, for example, by pouring, into the rinse water which is present during the rinse cycle of washing machine operation. For effective softening, the fabric softener composition is added to the rinse water in amount sufficient to provide a concentration of phosphiniminosulfoxonium salt in the rinse water ranging from about 10 to about 500 ppm. and preferably from about 25 to about 100 ppm.

Turning now to further uses of the present phosphiniminosulfoxonium salts, these compounds can be added as emulsifiers, removable softening agents, or antibacterial additives to various detergent compositions, and ordinarily comprise from about l to about l5 percent by weight of such detergent compositions. The detergent active in these detergent compositions is any detergent which is compatible with the phosphiniminosulfoxonium salt additive. Ordinarily, this detergent active is a nonionic, zwitterionic, or ampholytic synthetic detergent. The detergent active ordinarily comprises from about 5 to about 95 percent by weight of these detergent compositions.

The above-mentioned nonionic synthetic detergents can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which can be aliphatic or alkylaromatic in nature. The number of the hydrophilic or polyoxyalkylene radicals which are condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

For example, a well-known class of nonionic synthetic detergents is made available on the market under the trade name Pluronic." These compounds are formed by condensing ethylene oxide with a hydrophobic base fonned 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 about 1,500 to l,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 products is retained up to the point where polyoxyethylene content is about 50 percent of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include:

1. The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl radical containing from about six to l2 carbon atoms in either 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 alkyl phenol. The alkyl substituent in such compounds can be derived from diisobutylene, octane, nonane, or polymerized propylene, for example.

2. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamineproducts which may be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. For example, compounds containing from about 40 to about percent polyoxyethylene by weight and having a molecular structure of about 5,000 to about I 1,000, 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 base having a molecular weight of the order of 2,500 to 3,000, are satisfactory.

3. The condensation product of aliphatic alcohols having from eight to 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol/ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction of the condensate having from 10 to 14 carbon atoms.

4. Trialkyl amine oxides and trialkyl phosphine oxides wherein one alkyl radical contains from about 10 to about 18 carbon atoms, from zero to about five ether linkages, and from zero to about two hydroxy groups and wherein the other two alkyl radicals each contain from one to about three carbon atoms, from zero to about two ether linkages, and from zero to about two hydroxy groups. Specific examples are dodecyl diethanol amine oxide and tetradecyl dimethyl phosphine oxide.

5. Dialkyl sulfoxide detergents having the formula T BE: :39..

wherein R is a hydrocarbon group containing from about to about 20 carbon atoms, from zero to about five ether linkages, and from zero to about three hydroxyl groups, there being at least one moiety of R which constitutes a carbon chain containing no ether linkages and containing about 10 to 18 carbon atoms, and wherein R is a short alkyl chain con taining from about one to about three carbon atoms having zero to two hydroxyl groups attached to said short alkyl chain. Specific examples of such sulfoxides are octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradecyl methyl sulfoxide,

wherein R" contains from about 10 to about 18 carbon atoms and from about zero to about five ether linkages, wherein R and R are each selected from the group consisting of alkyl groups containing from one to about three carbon atoms, wherein R" is selected from the group consisting of alkylene and hydroxy substituted alkylene groups containing from one to about four carbon atoms, and wherein Z is selected from the group consisting of groups. Specific examples of such compounds are l-(hexadecyladimethylammonio)propane-3-sulfonate, l-(dodecyldimethylammonio)-butane-3-sulfonate, and l-(dodecyldimethylammonio) acetate. Some other common examples of these detergents are described in US. Pat. Nos. 2,082,275; 2,129,264; 2,217,846; 2,255,082; and 2,702,279.

The ampholytic detergents mentioned above are represented by detergents such as dodecyl-beta-alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the f teaching of US. Pat. No. 2,658,072, N-higher alkylaspartic acids such as those produced according to the teaching of US. Pat. No. 2,438,091, and the products sold under the trade name Miranol and described in US. Pat. No. 2,528,378.

The detergent compositions herein must not contain water soluble alkaline detergency builder salts, either of the organic or inorganic types. This is because the phosphiniminosulfoxonium salts of the present invention are stable only in the pH range of 6 to 8 and are preferably maintained and employed at a pH of 7; the use of builder salts in the detergent composition ordinarily would provide a washing solution pH of from about 9 to about 12 under which conditions the present phosphin iminosulfoxonium salts tend to hydrolyze and lose their effectiveness. Thus, the detergent compositions herein must have a pH ranging from about 6 to about 8, preferably 7.

The present detergent compositions, when they are in the form of liquids, can optionally contain from about 1 percent to about 50 percent preferably from about 1 percent to about 10 percent, by weight of an alcohol containing one to about four carbon atoms such as, for example, isopropanol or ethanol, to reduce the viscosity of the composition thereby causing it to be more readily pourable and also to reduce the tendency of the composition to become a gel.

Theses detergent compositions can also contain many of the usual adjuvants, diluents, and additives, for example, an-

titarnishing agents (e.g., benzotrianole), antiredeposition agents (e.g., alkali metal and ammonium salts of carboxymethyl cellulose), bacteriostatic agents, dyes or pigments, gsuds builders, suds depressors, and the like, without detracting from the advantageous properties of the composition.

Normally the organic detergent components, the phosphiniminosulfoxonium salt component, and the minor ingredients are incorporated into the composition prior to the conversion of the composition into final product form, e.g., detergent granules, flakes, etc., but they also can be added individually in the form of particles or as liquids.

Turning now to the process for preparing the abovedescribed phosphiniminosulfoxonium salts, these salts can be prepared by a process comprising reacting an N-alkali-metal sulfoximine with a trisubstituted phosphine dihalide or dispseudohalide.

The N-alkali-metal sulfoximine for use herein has the structural formula 0 RsRtSr N M wherein R and R are defined as previously and M is an alkali metal selected from the group consisting of sodium, potassium and lithium.

The trisubstituted phosphine dihalide or dipseudohalide for use herein has the structural formula RR'R PY wherein R, R, and R are defined as previously and Y is selected from the group consisting of l) halogens, for example, chlorine, bromine, and iodine atoms, and (2) pseudohalogens, for example, cyanide and azide moieties. Each Y can be the same or different in the same compound except that both Y's cannot be azide.

The above N-alkali-metal sulfoximines are reacted with the above trisubstituted phosphine dihalides or dipseudohalides in an inert atmosphere, for example, under argon, at a temperature ranging from about 0 to about 50 C. for a period of time ranging from about 0.5 to about 30 hours to provide essentially complete reaction. Room temperature is a preferred reaction temperature. Reaction times ranging from about 1 to about 20 hours are preferred. 5

A reaction solvent is employed in this process which is compatible with the above reactants and with the reaction product. This reaction solvent is preferably an aliphatic or aromatic hydrocarbon such as benzene, hexane, toluene, and the like.

The following equation represents a typical example of the was prepared as follows: 31.2 grams (0.4 mole) of dimethyl reaction of this process sulfoxide was dissolved in 500 ml. chloroform. To this solution was added 120 ml. concentrated sulfuric acid. To the resulting mixture, stirred rapidly and under argon, was added 52 grams Cum CH3) 1 NM CBH OHmP Ch 16 hours 5 (0.8 mole) sodium azide overa 2-hour period. After this addi- 20-30C. tion period, the mixture was stirred for 16 hours at 4045 C.

Then, to this mixture was added 200 ml. water. The resulting mixture separated into two layers, an aqueous layer and a chloroform layer. Solid potassium hydroxide was added to the separated aqueous layer to adjust the pH to 8. The resulting mixture was filtered to remove potassium sulfate which had The reactants in this process are not readily available combeen f d as a result f h H adjusting Step Th filt t merciany but can be P p by a number of methods- For was then evaporated to dryness in vacuo. The resulting white p i N-alkali'meial sulfoximines can be Prepared by solid was extracted twice, each time with 100 ml. of methylene reacting a dialkyl sulfoximine with an aliphatic hydrocarbon chloride. The combined extracts were dried over magnesium alkali metal salt. This reaction is conveniently carried out in sulfate and the" evaporated to yield a whim SOHL This white benzene reaction solvent without external heating at a temsolid was distilled at approximately 1 mm Hg at a pot Perature ranging fmm perature of 125 c. The fraction distilling at 95-98 c. was

atmosphere Such as argon a reaction time fanging from 20 collected. This fraction crystallized to yield 22.0 grams of subabout 0.5 hour to about 20 hours or more. Dialkyl sulfoxstamiany pure dimethylsulfoximina imines are prepared by reacting dialkyl sulfoxides with hydrazoic acid in chloroform at 40-50 C. with stirring for 16 hours; this preparation is described by H. R. Bentley, E. E. McDermott, and J. K. Whiteside, Proc. Royal Society, 1388, 265 (1951).

The trisubstituted dihalide or dipseudohalide can be conveniently prepared, for example, by reacting trisubstituted phosphines with a halogen or pseudohalogen. This reaction is carried out with no external heating, for example, in a solvent such as benzene and in an inert atmosphere such as argon. Reaction is substantially complete within about 10 minutes. The preparation of trisubstituted phosphines is described in the copending application of Hays, Ser. No. 461,669, filed June 7, 1965 now US. Pat. No. 3,389,183.

It is noted that the reactants in the above process for the production of phosphiniminosulfoxonium salts contain as anion-producing constituents only halogens and the pseudohalogens, azide and cyanide. This limitation in the structure of the reactants is essential for the production of high yields of phosphiniminosulfoxonium salt since reactants containing, for example, oxygen-containing anion-producing constituents, produce high yields of byproducts. Thus, this process is advantageously used directly only to produce phosphiniminosulfoxonium halides, azides and cyanides. However, the anions in A portion of this dimethylsulfoximine was converted to N- lithiodimethylsulfoximine,

as follows: In a 100 ml. one-necked round-bottomed flask was placed 4.64 grams (50 moles) of the above-prepared 30 dimethylsulfoximine, and 50 ml. of benzene under an atmosphere of argon. A solution of dimethylsulfoximine in benzene was then formed by means of vigorous stirring with a magnetic stirrer. To this solution at room temperature was added 35.75 ml. of 1.40 normal solution of n-butyllithium- 5 hexane solution (50 mmoles of n-butyllithium) over a 10- minute period. The resulting milky white solution was stirred for 2 hours under argon without addition of external heat. The resulting solution containing N-lithiodimethylsulfoximine was used hereinafter without isolation or purification of the formed intermediate.

Dimethyldodecylphosphine dichloride was then prepared as follows: In a one-necked 1,000 ml. round-bottomed flask equipped with a rubber cap and filled with argon was placed 11.60 grams moles) of dimethyldodecylphosphine and the phosphiniminosulfoxonium salt products produced by this 9 of l'l benzene- The fomfed SOIUUOHI 1' Sill-fed process can be converted to other anions by conventional vigorously While 1,230 chlorine gas was mlected techniques, for example, by means of an ion exchang the capped flask. The reaction mixture was then stirred for 1 column. hour at room temperature. The resulting solution containing All percentages and parts herein are by weight unless other- 50 dimethyldodecylphosphine dichloride was used hereinafter wise specified. In all rea tions herein where u h rea tion i without isolation or purification of the formed intermediate. carried out under an inert atmosphere, any inert atmosphere The above dimethyldodecylphosphine was prepared by the can be employed; for example, these reactions can be carried method of Hays, previously referred to.

out in a vacuum or under inert gases such as argon, nitrogen, At this point the above-formed N-lithiodimethylsulfoximine or helium. solution was added to the above-formed dimethyl- The following examples are illustrative of the present invendodecylphosphine dichloride solution. This addition was cf? tion and are not to be construed in any way as limiting the fected over a IO-minute period with all compounds under arscope of the invention. gon. The resulting mixture was stirred for 16 hours with no external heating (the mixture was at 2530 C.) to provide an EXAMPLE I insoluble white solid and a clear supernatant. This mixture was PREPARATION OF filtered. The solid was extracted two times, each time with 50 ml. of methyl cyanide, and the extracts were centrifuged to DIMETHYLDODECYLPHOSPHINIMINO' deposit lithium chloride. The centrifugate was then added to DMETHYLSULFOXONIUM CHLORIDE the filtrate, and the combined liquids were evaporated to dryness in vacuo to give a gummy white solid. Recrystallization of this solid from benzene-hexane (1:1 volume mixture) yielded 01 O 8.83 grams of dimethyldodecylphosphiniminodimethylsulfox- G"H25(CH3)P=% (CH3)Z onium chloride. This compound is an effective emulsifier for oi1-inwater emulsions and an effective antibacterial agent.

Dimethylsulfoximine, EXAMPLE 0 PREPARATION OF DIMETHYLOCTADECYLPHOSPHINIMINO- HEXADECYLMETHYLSULFOXONIUM CHLORIDE 01 e l ia a1( a)i H1) nH Hexadecylmethylsulfoximine,

was prepared as follows: 5.0 grams (17.35 mmoles) hexadecylmethylsulfoxide was dissolved in 50 ml. chloroform. To this solution was added 5.1 ml. concentrated sulfuric acid. To the resulting mixture, stirred rapidly and under argon, was added 2.21 grams (34 mmoles) sodium azide over a 2 hour period. After this addition period the mixture was refluxed (at about 6l C.) for l6 hours. The mixture was then cooled to room temperature. To this mixture was added 30 ml. of water. The resulting mixture separated into two layers, an aqueous layer and a chloroform layer. The pH of the aqueous layer was adjusted to about 7.5 by the addition of solid potassium hydroxide to the mixture comprising both the water and chloroform layers; the pH of the chloroform layer became about 5.5. The chloroform layer was decanted. The aqueous layer was extracted two times, each time with 100 ml. of methylene chloride. These extracts were combined with the chloroform layer and the combined liquids were dried over sodium sulfate and then evaporated to yield a white solid. The white solid was recrystallized once from l:l by volume benzene-hexane to give 3.45 grams of hexadecylmethylsulfoxmine.

This hexadecylmetliylsulfoximine was converted to N- lithi0hexadecylmethylsulfoximine,

as follows: in a 200 ml. one-necked round-bottomed flask was placed 3.43 grams (1 1.3 mmoles) of the above-prepared hexadecylmethylsulfoximine and W0 ml. benzene under an atmosphere of argon. A solution of hexadecylmethylsulfoximine in benzene was then formed by means of vigorous stirring with a magnetic stirrer. To this solution at room temperature was added 8.2 ml. of 1.36 normal solution of n-butyllithium-hexane solution (1 equivalent of n-butyllithium) over a giveminute period. The resulting solution was stirred under argon for 3 hours without addition of external heat. The resulting solution was stirred under argon for 3 hours without addition of external heat. The resulting solution containing N- lithiohexadecylmethylsulfoximine was used hereinafter WiIllQli isolation or purification of the formed intermediate.

Dimethyloctadecylphosphine dichloride was then prepared as follows: in a one-necked 500 ml. round-bottomed flask equipped with a rubber cap and filled with argon was placed 3.50 grams (11.2 mmoles) dimethyloctadecylphosphine and 150 ml. of dry benzene. The formed solution was stirred vigorously while 279 ml. (1 1.3 mmoles) chlorine gas was injected into the capped flask. The reaction mixture was then stirred for l hour at room temperature. The resulting solution containing dimethyloctadecylphosphine dichloride was used hereinafter without isolation or purification of the formed intermediate. The above dimethyloctadecylphosphine was prepared by the method of Hays, previously referred to.

At this point the above-formed N-lithiohexadecylmethylsulfoximine solution was added to the above-formed dimethyloctadecylphosphine dichloride solution. This addition was effected over a 5 minute period with all compounds under argon. The resulting mixture was stirred for 16 hours at a temperature ranging from 2530 C. (no external heating) to provide an insoluble white solid and a clear supernatant. The solid was recrystallized twice from a 1:1 by volume mixture of methyl alcohol and methyl cyanide to yield 1.79 grams of dimethyloctadecylphosphiniminohexadecylmethylsulfoxonium chloride. This compound is an effective and removable fabric softener.

Other phosphiniminosulfoxonium salts are prepared by the method of example ll if molar equivalents of other N-alkalimetal sulfoximines are substituted for the N-lithiohexadecylmethylsulfoximine in example ll and/or molar equivalents of other tn'substituted phosphine dihalides or dipseudohalides are substituted for the dimethyloctadecylphosphine dichloride in example I]. For example, N-sodiomethylpalmitoleylsulfoximine is reacted with dimethyltetrapropylenephosphinedibromide to produce the softener dimethyltetrapropylenephosphiniminomethylpalmitoleylsulfoxonium bromide; N-potassiodibutylsulfoximine is reacted with trimethylphosphine dicyanide to produce the antibacterial compound trimethylphosphiniminobutylsulfoxonium cyanide, and N-lithioethyl-p-ethylphenylsulfoximine is reacted with dibutylphenylphosphinemonoiodidemonoazide to form an antibacterial mixture of dibutylphenylphosphiniminoethyl-pethylphenylsulfoxonium iodide and azide.

The halide and pseudohalide anions of the phosphiniminosulfoxonium salts formed in examples I and ll above can be converted to other anions by conventional ion exchange techniques. For example, the dimethyloctadecylphosphiniminohexadecylmethylsulfoxonium chloride formed in example ll can be converted to dimethyloctadecylphosphiniminohexadecylmethyl sulfoxonium nitrate or sulfate in this manner.

The following example illustrates a fabric softener composition containing the new phosphiniminosulfoxonium salts. This composition is applied to fabric as a water solution containing 50 p.p.m. phosphiniminosulfoxonium salt. When so applied these compositions provide effective softening and after two washings of the fabric or garment to which they have been ap plied, they are more than percent removed.

EXAMPLE lll A suitable liquid fabric softener composition contains:

Percent Dimethyloctadecylphosphinimino hexadecylmethylsulfoxonium chloride 5 lsopropanol 2 3,4,4"trichlorocarbanilide l The condensation product of 9 moles of ethylene oxide with l mole of nonyl phenol l Color 0003 Perfume 0.25 Water Balance Other new softening phosphiniminosulfoxonium salts, for example, any of the compounds listed in table I and classified as softeners, can be substituted for the dimethyloctadecylphosphiniminohexadecylmethylsulfoxonium chloride in the above example to provide compositions which provide the removable softening effect.

The following examples illustrate light-duty liquid detergent compositions containing as a softening agent the softening phosphiniminosulfoxonium salts of this invention. These detergent compositions are suitable for cleaning and softening delicate clothing such as sweaters or underwear. In these examples the compositions have a pH of about 7.

EXAMPLE lV Percent Dimethyloctadecylphosphiniminohexadeeylmethylsulfoxonium chloride Dimethyldodecylamine oxide Ethanol Water EXAMPLE v Percent Dicthyldodccylphosphiniminobutyldodccylsulfoxonium sulfate Dimethylhexadecylphosphine oxide Ethanol Water In the above examples IV and V, other new phosphiniminosulfoxonium salts, for example, any of the compounds listed in table I and classified as softeners, emulsifiers, or anitbacterial agents can be substituted for all or part of the phosphiniminosulfoxonium salts in the above examples IV and V to provide softening, emulsifying, or antibacterial effects, respectively. Moreover, various other detergent actives can be substituted for the detergent actives in examples IV and V, above. For example, betahydroxydodecylmethyl sulfoxide, lauryl alcohol condensed with moles of ethylene oxide, dodecylbeta-alanine, the sodium salt of N-dodecyl taurine, disodium N-dodecyl aspartate, and l-(hexadecyldimethylammonio)propane-J-sulfonate can replace the amine oxide and phosphine oxide detergent actives in examples IV and V. The compositions are light duty liquid detergents having removable softening properties. Moreover, these various detergent actives can replace the detergent actives in the compositions set forth in this paragraph wherein the phosphiniminosulfoxonium salts are added for emulsifying or antibacterial effect.

The previously described novel phosphiniminosulfoxonium salts also have utility as skin penetrating agents and as herbicides. Various of these salts are also wetting agents, detergents, solubilizing agents, gelling agents, and hydrotroping agents.

The foregoing description has been presented describing certain operable and preferred embodiments of this invention. Other variations will be apparent to those skilled in the art.

We claim:

1, A liquid fabric softener composition consisting essentially of by weight from about 1 percent to about percent of a phosphiniminosulfoxonium salt having the structural formula wherein R and R are each alkyl radicals containing from 12 to carbon atoms, wherein R, R and R are each alkyl radicals containing from one to four carbon atoms and wherein X is ,an anion selected from the group consisting of chloride, bromide, iodide, fluoride, sulfonate, sulfate, nitrate, chlorate, fluoroborate, and hexachloroantimonate, and from about percent to about percent water, said composition having a pH of from about 6 to about 8.

2. The liquid fabric softener composition of claim 1 containing from l percent to about 50 percent by weight of a monohydric alcohol containing 1 percent to about 50 percent atoms in place of an equal weight of water.

3. The method of softening fabric by the application of a water solution of a phosphiniminosulfoxonium salt having the structural formula wherein R and R are each alkyl radicals containing from 12 to 20 carbon atoms, wherein R, R and R are each alkyl radicals containing from one to four carbon atoms, and wherein X is an anion selected from the group consisting of chloride, bromide, iodide, fluoride, sulfonate, sulfate, nitrate, chlorate, fluoroborate, and hexachloroantimonate, said solution containing from about 10 to about 500 ppm. of said salt and solution having a pH of from about 6 to about 8.

4. A detergent composition consisting essentially of by weight (I) from about 1 to about 15 percent of a phosphiniminosulfoxonium salt having the structural formula wherein R and R are each radicals selected from the group consisting of alkyl radicals containing from one to 20 carbon atoms, and phenyl; R, R and R 'are each radicals selected from the group consisting of alkyl radicals containing from one to four carbon atoms, and phenyl; and X is an anion which permits solubility and hydrolytic stability of the salt; (ll) from about 5 to about percent of a compatible detergent selected from the group consisting of nonionic, zwitterionic, and ampholytic synthetic detergents; and (III) the balance, selected from the group consisting of water and a mixture of water and from about l to about 50 percent of a monohydric alcohol containing from one to about four carbon atoms, said composition having a pH of from about 6 to about 8.

Patent o, 3,637,496 Dated January 25, 1972 Inventor) Ted J. Logan and Terence W. Rave It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 41, after "ethyl" should read Column 2, Table I, under the heading X, "*SO4 should read Column 3, lines 43 and 44, "comprises" should read comprise.

Column 6, line 29, "benzotrianole" should read benzotriazole.

Column 6, lines 43 and 44, "'dispseudohalide" should read -dipseudohalide.

Column 8, line 44, "50 moles" should read --50.5 moles-.

Column 11, line 12, "anit" should read anti.

Column ll, line 20, after "oxide,", should read nonylphenol condensed with 9 moles of ethylene oxide,-

Column 12, line 4, "90 percent" should read 99 percent.

Column 12, line 8, delete "percent to about 50 percent" and insert therefor to about 4 carbon-.

Signed and sealed this 29th day of August 1972.

(SEAL) Attest:

EDvIARD M.FLETCHER,JR. ROBERT GOTTSGHALK Atte sting Officer Commissioner of Patent 5 ,2 3? UNITED STATES PATENT OFFICE 1 CERTIFICATE OF CORRECTION .Patent No. 6 I Dat d January 25, 1972 lnventofls) Ted J. Logan and Terence W. Rave It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 41, after "ethyl" should read Column 2, Table I, under the heading X, "*SO'4." should read Column 3, lines 43 and 44, "comprises" should read comprise.

Column 6, line 29, "benzotrianole" should read benzotriazole.

Column 6, lines 43 and 44, '"dispseudohalide" should read dipseudohalide--.

Column 8, line 44, "50 moles" should read- 50.5 moles.

Column 11, line 12, "anit" should read -anti-.

Column 11, line 20, after "ox ide,", should read nonylphenol condensed with 9 moles of ethylene oxide,-'

Column 12, line 4, "90 percent" should read 99 percent.

Column 12, line 8, delete "percent to about 50 percent" and insert therefor to about 4 carbon.

Signed and sealed this 29th day of August 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. I ROBERT GOTTSCHALK Atte sting Officer Commissioner of Patent-5|

Claims

2. The liquid fabric softener composition of claim 1 containing from 1 to about 50 percent by weight of a monohydric alcohol containing one to about four carbon atoms in place of an equal weight of water.
3. The method of softening fabric by the application of a water solution of a phosphiniminosulfoxonium salt having the structural formula wherein R and R4 are each alkyl radicals containing from 12 to 20 carbon atoms, wherein R1, R2 and R3 are each alkyl radicals containing from one to four carbon atoms, and wherein X is an anion selected from the group consisting of chloride, bromide, iodide, fluoride, sulfonate, sulfate, nitrate, chlorate, fluoroborate, and hexachloroantimonate, said solution containing from about 10 to about 500 p.p.m. of said salt and solution having a pH of from about 6 to about 8.
4. A detergent composition consisting essentially of by weight (I) from about 1 to about 15 percent of a phosphiniminosulfoxonium salt having the structural formula wherein R and R4 are each radicals selected from the group consisting of alkyl radicals containing from one to 20 carbon atoms, and phenyl; R1, R2 and R3 are each radicals selected from the group consisting of alkyl radicals containing from one to four carbon atoms, and phenyl; and X is an anion which permits solubility and hydrolytic stability of the salt; (II) from about 5 to about 95 percent Of a compatible detergent selected from the group consisting of nonionic, zwitterionic, and ampholytic synthetic detergents; and (III) the balance, selected from the group consisting of water and a mixture of water and from about 1 to about 50 percent of a monohydric alcohol containing from one to about four carbon atoms, said composition having a pH of from about 6 to about 8.