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Publication numberUS3646219 A
Publication typeGrant
Publication dateFeb 29, 1972
Filing dateJan 19, 1970
Priority dateMar 13, 1967
Also published asUS3502731
Publication numberUS 3646219 A, US 3646219A, US-A-3646219, US3646219 A, US3646219A
InventorsDonald J Peterson
Original AssigneeProcter & Gamble
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Alkylthiomethyl phosphonium derivatives
US 3646219 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,646,219 ALKYLTHIOMETHYL PHOSPHONIUM DERIVATIVES Donald J. Peterson, Cincinnati, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio No Drawing. Original application Mar. 13, 1967, Ser. No.

622,419, now Patent No. 3,502,731, dated Mar. 24, 1970. Divided and this application Jan. 19, 1970, Ser. No. 4,042

Int. Cl. C07f 9/54; D06m 13/28 US. Cl. 260-6065 F 6 Claims ABSTRACT OF THE DISCLOSURE This invention is directed to organothiomethyl phosphonium halides which compounds find utility as textile softeners.

CROSS-REFERENCES TO RELATED APPLICATIONS This application is a division of US. patent application Ser. No. 622,419, filed Mar. 13, 1967, entitled Alkylthio- Methylmetal Compounds, Preparation Thereof, and Reactions Thereof, in the name of Donald 1. Peterson now US. Pat. 3,502,731.

BACKGROUND OF THE INVENTION This invention relates in part to alkyl methyl sulfide derivatives. Specifically this invention relates to alkylthiomethylphosphonium compounds.

The sulfide group, or thioether linkage, is a very useful group to have in a compound. For example, the sulfide group can be readily oxidized to form the more hydrophilic sulfoxide group and/or a sulfone group and can be reacted with e.g., an alkyl halide or pseudo halide to form the corresponding Sulfonium salts.

In US. Pat. 3,228,860, it was disclosed that a sulfoxide group would activate a hydrogen atom attached to an adjacent carbon atom sufficiently to permit the metalation of said carbon atom. Also, Corey and Seebach, J. Org. Chem., 31 4097 (1966) and Gilman and Webb J. Am. Chem. Soc., 62, 987 (1940) have reported the preparation of phenylthiomethyllithium. However, until the present invention, it had not been shown that one could metalate a carbon atom when the only activating group present in the compound to be metalated was an alkylthio group.

SUMMARY This invention relates primarily to the discovery that it possible to prepare alkylthiomethyl phosphonium compounds by reacting organic halides or pseudo halides with alkylthiomethylphosphines depictable by the formula RSCH phosphine.

Wherein R is a saturated alkyl group containing from 1 to 30 carbon atoms, from 0 to substituent oxygen atoms replacing methylene groups in alkyl and alkylene groups, and from 0 to 2 substituents selected from the group consisting of aryl groups, alkaryl groups, and tertiary amino groups, said substituents being placed so that no aryl moiety, oxygen atom, or nitrogen atom is attached to any carbon atom which is less than three atoms removed from the sulfur atom.

CONVENTIONAL ORGANIC HALIDES AND PSEUDO HALIDES R is preferably an alkyl group, either saturated or unsaturated, containing from one to carbon atoms. Examples of these groups are: methyl, ethyl, propyl, 2,4- hexadienyl, 2,4-dodecadienyl, 2,7-tetradecadienyl, 2,4,6-

dodecatrienyl, allyl, 3-dodecenyl, 8-tetradecenyl, 2-dodecynyl, 2,4-hexadiynyl, 2,4-dodecadiynyl, isopropyl, butyl, Z-butenyl, hexyl, octyl, decyl, tetrapropylene, dodecyl, tri decyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, eicosyl, and 2-octadecenyl groups.

R can also be an aralkyl group (benzyl, 12-phenyldodecyl, l-naphthylmethyl, 2-biphenyl-2-ethyl, etc.). Suitable substituted R groups include 4-methoxybenzy1, 3,6,9,12 tetraoxaoctadecyl, and 3 diethylaminopropyl groups.

The hydroxy sulfides can be oxidized to the corresponding sulfoxides and/or sulfones or they can be reacted with an excess of the conventional organic halides and pseudo halides to give the corresponding sulfonium salts. Many of these compounds are known. As with the corresponding dialkyl sulfoxides, the hydroxyalkyl and alkoxyalkyl sulfoxides are detergents when they contain one long alkyl chain of from 8 to 20 carbon atoms and the sulfoxides and sulfones are fabric softeners for cotton when they contain two long alkyl chains. Hydroxy and alkoxy sulfoxides containing less than about 8 carbon atoms are excellent solvents for, e.g., glycerides. Sulfonium salts containing two long alkyl chains are substantive fabric softeners for cotton when applied from dilute solutions.

REACTION WITH ALKYL OR ARYL, HALO AND PSEUDO HALO PHOSPHINES Alkylthiomethylmetal compounds react readily with trihalophosphines, haloalkylphosphines, and haloarylphosphines according to the following equation:

wherein each R in the above equation is an alkyl, aryl, aralkyl, or alkaryl group containing 1 to 30 carbon atoms, 1 to 10 oxygen atoms as substituents replacing methylene groups in alkyl and alkylene groups, and 0 to 5 substituent tertiary amino groups wherein X is either a halogen atom, either chlorine, bromine, or iodine or a pseudo halogen group such as R"O, -NR and -SO R", wherein R" is selected from the group consisting of alkyl, aryl, alkaryl and aralkyl groups containing from 1 to 30 carbon atoms, from 0 to 10 substituent oxygen atoms replacing methylene groups in alkyl and alkylene groups and from 0 to 5 substituent tertiary amino groups, M is an alkali metal, eg sodium, potassium or lithium and wherein n is either 0, 1 or 2. These compounds will undergo several reactions. For example, the compounds can be oxidized step-wise as described hereinbefore to the following compounds.

R in the above formulas and equations is preferably either a phenyl group or an alkyl chain containing from 1 to 20 carbon atoms. Examples of these groups are: methyl, ethyl, propyl, 2,4-hexadienyl, 2,4-dodecadienyl, 2,7-tetradecandienyl, 2,4,6-dodecatrienyl, allyl, 3-d0decenyl, 8-tetradecenyl, 2-dodecynyl, 2,4-hexadiynyl, 2,4- dodecadiynyl, isopropyl, butyl, 2-butenyl, hexyl, octyl, decyl, tetrapropylene, dodecyl, tridecyl, tetnadecyl, hexadecyl, octadecyl, eicosyl, and 2-octadecenyl groups.

R can be an aryl group (e.g., phenyl, biphenyl, or naphthyl groups); an alkaryl group (4-decylphenyl, 4- methyl-l-naphthyl, ethyldiphenyl, Z-methylphenyl, etc.)

or an aralkyl group [benzyl, 12-phenyldodecyl, l-naphthylmethyl, 2-(4-biphenyl)-ethyl, etc.) These groups are also preferred. Suitable substituted R groups include 4- anet-hoxyphenyl, 3,6,9,l2 tetraoxaoctadecyl, 3,6 di(di methylamino)hexyl, and 3-diethylaminopropyl groups.

The preferred X is chlorine.

The products of the reactions of alkylthiomethylmetal compounds with the phosphites and halophosphines and the oxidized and/or sulfurized analogs of said products have the generic formula:

wherein y is or 1, Q is O) or S), each 2 is 0, l or 2, when Q is O), 0 or 1 when Q is S) and 0 when y is 0, L is an integer from one to three, and R and R have the definitions given hereinbefore.

The compounds which contain phosphine oxide moieties are surface active agents useful for forming oil in water emulsions when one of the R groups contains about 8 to about 24 carbon atoms and the other R groups are short alkyl groups. All of these compounds have herbicidal characteristics and are lubricant additives as discussed hereinbefore. When there are two long alkyl groups of from 12 to 24 carbon atoms in these compounds they are textile softeners for cotton when used at a level of about 1% by weight of the cloth and applied in a padding bath.

All of the above compounds which contain sulfide groups and phosphine groups can be converted to phosphonium compounds with a conventional organic halide or pseudo halide R X as hereinbefore described according to the following equation:

When the phosphonium compounds contain one long alkyl chain of from about 8 to about 14 carbon atoms they are effective surface active agents. When the compounds contain two long alkyl chains of from 16 to about 24 carbon atoms these compounds are substantive textile softeners.

The phosphoniu-m compounds can be reacted with, e.g., sodium hydroxide according to the disclosure in the copending application of Hays, Ser. No. 329,281, filed Dec. 9, 1963, to form the phosphine oxide compounds described hereinbefore which contain sulfide groups.

All parts, percentages and ratios herein are by weight unless otherwise specified. The following examples are illustrative of the invention and should not be taken as limiting the scope of the claims.

EXAMPLE I Preparation of methylthiomethyllithium 5.8 gm. (0.05 mole) of N,N,N,N'-tetramethylethylenediamine (TMEDA) was added to 36 ml. of 1.4 molar (0.05) n-butyllithium in hexane to form 0.05 mole of the n-butyllithium-TMEDA complex. (The temperature in these reactions was held below about C. by means of a water bath.) 3.1 g. (0.05 mole) of dimethyl sulfide was added to the complex and after about a quarter of an hour a white precipitate had formed. This precipitate was composed of lithium methyl mercaptide and methylthiomethyllithium. After about four hours, the resulting reaction mixture containing the methylthiomethyllithium (MTML) was used in the following reactions. All reactions herein (including Examples II-XVI) were carried out in an inert atmosphere of nitrogen.

When in the above example the following alkyl methyl sulfides are substituted on a molar basis for the dimethyl sulfide, substantially equivalent results are obtained in that the corresponding alkylthiomethyllithium compounds are prepared: methyl, ethyl, n-propyl, isopropyl, n-pentyl, isopentyl, n-hexyl, 2,2-dimethylpentyl, n-heptyl, n-octyl, 2,2-dimethy1hexyl, isooctyl, Z-ethylhexyl, n-nonyl, n-decyl,

tripropylene, undecyl, n-dodecyl, tetrapropylene, tridecyl, n-tetradecyl, pentadecyl, n-hexadecyl, n-octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexylrnethyl, methylcyclohexyl, 2-cyclohexyldodecyl, 12-cyclohexyldodecyl, 4- dodecylcyclohexyl, cyclooctyl, phenyl, biphenyl, naphthyl, 3-phenyldodecyl, 4-methyldecyl, 4-phenyloctyl, 4-decyl, 4-phenylbutyl, 3-methyldecyl, 3-(1-naphthyl)propyl, 4- (l-naphthyDbutyl, 3-ethyl-3-(4-biphenyl)propyl, and 3- ,(4-biphenyl)propyl methyl sulfides.

When in the above example the following metalating agents are substituted on a molar basis for n-butyllithium- TMEDA complex substantially equivalent results are obtained in that the alkylthiomethylrnetal compounds are prepared: phenylsodium; phenylpotassium; methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, tetrapropylene, hexadecyl, dodecyl, octadecyl, and eicosyl sodiums and potassiums; the complexes of methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, tetrapropylene, hexadecyl, dodecyl, octadecyl and eicosyl lithiurns with N-methyl, N-ethyl, N-propyl, N-butylpropylenediamine, N-dodecyl, N,N',N- trimethylmethylenediamine, N-octyl, N,N,N'-triethylbutylenediamine, N,N,N,N'-tetraethylpropylenediamine, or N-eicosyl, N,N,N'-trirnethylethylenediamine or tbutyllithium with diazabicyclo(2.2.2.)-octane.

When in the above example the following saturated hydrocarbons are substituted, either wholly or in part (e.g., 1:1 mixtures), for the hexane, substantially equivalent results are obtained in that the alkylthiomethylmetal compounds are prepared: pentane, octane, isooctane, nonane, decane, isododecane, and cyclohexane.

EXAMPLE II Reaction of chlorodiphenylphosphine with methylthiomethyllithium 0.2 mole of the filtrate of Example I Was added dropwise over a period of one hour to a solution of 44 g. (0.2 mole) of chlorodiphenyiphosphine in ml. of tetrahydrofuran. The mixture was stirred for an additional two hours and the reaction mixture was carefully hydrolyzed with 100 ml. of 2.5 molar ammonium chloride. The organic layer was dried, concentrated and distilled under reduced pressure to give 24.4 g. of (methylthiomethyl)diphenylphosphine, B.P. l65 C. (0.5 mm.). The product gave rise to a P NMR signal at +21 ppm. in CHCl and H NMR signals centered at 72.8 (aromatic), 7.08 (methylene, doublet, 1:3 cps), and 8.02

(methyl, singlet) in the correct area ratios.

When in the above example the following halo, halo alkyl or aryl phosphines are substituted on a molar basis for the chlorodiphenylphosphine, substantially equivalent results are obtained in that the corresponding (methylthiomethyl)alkyl or aryl phosphines are prepared:

phosphorus trichloride, phenylmethylchlorophosphine, diallylbromophosphine, dimethylchlorophosphine,

do decylmethylchlorophosphine, dimethyliodophosphine, dodecyldichlorophosphine, hexadecyldibromophosphine, (Z-OctadecynyD-1-naphthylchlorophosphine, 4-biphenylisopropylchlorophosphine, 3,6,9,12-tetraoxaoctadecylmethylbromophosphine, 4-methoxyphenyldichlorophosphine, and (3-diethylaminopropyl)phenylchlorophosphine.

When in the above example any of the alkylthiomethyl alkali metals of Example I are substituted for the methylthiomethyllithiurn a molar basis, substantially equivalent results are obtained in that the corresponding (alkylthiomethyl)alkyl or aryl phosphines are prepared.

These products are all useful as lubricant additives, herbicides, and intermediates in the preparation of other compounds as described in detail both hereinbefore and hereinafter.

EXAMPLE III Quaternization of (methylthiomethyl)diphenylphosphine Treatment of 1.5 ml. of the (methylthiomethyl)diphenylphosphine with an excess of methyl iodide in 20 ml. of acetone gave 2.45 g. of diphenylmethyl(methylthiomethyl)phosphonium iodide, M.P. 161.5-163.5 C. The NMR analysis in CDCl was: H signals centered at 72.18 (aromatic), 5.27 (methylene, doublet, 1:8 cps), 7.07 (EPCH3, doublet, J=13 cps.), and 7.71 (SCH singlet).

When in the above reaction any of the other phosphine reaction products of Example II are substituted on a molar basis for the (methylthiomethyl) diphenylphosphine, substantially equivalent results are obtained in that the corresponding phosphonium iodides are prepared.

When in the above reaction the following halides and pseudo halides are substituted on a molar basis for the methyl iodide, substantially equivalent results are obtained in that the corresponding phosphonium salts are prepared: ethyl; allyl; isopropyl; tetrapropylene; dodecyl; 2-do decynyl; 2,4-dodecadiynyl; 2,4-dodecadienyl; benzyl; 1- naphthylmethyl; (2-biphenyl)-2-ethyl; 4-methoxybenzyl; 3,6,9,12-tetraoxaoctyl; and 3-diethylaminopropyl chlorides, bromides, iodides and methyl sulfates.

EXAMPLE IV When in the previous Example II, the following solvents are substituted, either wholly or in part (e.g., 1:1 mixture), for the tetrahydrofuran, substantially equivalent results are obtained in that the reaction proceeds without interference: pentane; hexane; octane; icooctane; nonane; decane; isododecane; cyclohexane; diethyl ether; dibutyl ether; diphenyl ether; 1,2-dimethoxyethane; and diethylene glycol dimethyl ether.

EXAMPLE V When in the previous Example II, any of the alkylthiomethylmetal compounds of Example I are substituted for the methylthiomethyllithium or n-decylthiomethyl lithium compounds, substantially equivalent results are obtained in that analogous compounds are prepared.

EXAMPLE VI The detergent compounds of this invention can be used to formulate detergent compositions having the following formulas:

Spray-dried granular detergent Percent Detergent compounds of this application 17.5 Sodium sulfate 23 Sodium tripolyphosphate 50 Sodium silicate 6 Water 3.5

Granular detergent Detergent compounds of this application 10 Sodium dodecylbenzenesulfonate (the dodecyl group being derived from tetrapropylene) 10 Sodium nitrilo triacetate 50 Sodium sulfate 3O Granular detergent Detergent compounds of this application 10 Condensation product of one mole of nonyl phenol and nine moles of ethylene oxide 10 Sodium pyrophosphate 50 Sodium carbonate 3 Trisodium phosphate 3 Sodium sulfate 24 Milled toilet bar Detergent compounds of this application m. 10 Sodium coconut oil soap Sodium tallow soap 65 Moisture 10 6 Milled toilet bar Detergent compounds of this application 50 Tallow fatty acid 25 Moisture 15 Constarch 5 Triethanolammonium ethylenediaminetetraacetate 5 Scouring cleanser Silica flour Detergent consisting of 85% trisodium phosphate and 15% of the detergent compounds of this application 15 Liquid detergent Sodium dodecyl benzene sulfonate 6 Detergent compounds of this application 6 Potassium pyrophosphate 20 Potassium toluene sulfonate 8 Sodium silicate 3.8 Carboxymethyl hydroxyethyl cellulose 0.3 Water Balance Liquid detergent Detergent compounds of this application 10 Tetrasodium ethylenediaminetetraacetate 25 Water 65 Examples of detergent compounds of this application include sodium, potassium, and ammonium decyl, dodecyl, and tetradecyl thioacetates; dodecylbis(methylthioethyl) phosphine oxide; octadecyl(ethylsulfinylmethyl)methylphosphine oxide; (tetradecylthiomethyl)dimethylphosphine oxide; and (octadecylsulfonylmethyl)diethylphosphine oxide. Other detergents disclosed herein and especially in Example III, can be substituted for the above examples to give substantially equivalent results in that the compositions have detergent properties. These detergent compositions are used according to the teachings of the prior art with respect to similar detergent compositions.

What is claimed is:

1. Compounds having the formula:

wherein R is a saturated alkyl grou containing from 1 to 30 carbon atoms, from 0 to 10 substituent oxygen atoms replacing methylene groups in alkyl and alkylene groups to form ether linkages, there being at least two carbon atoms separating each oxygen atom from any other oxygen atom, from O to 2 substituents selected from the group consisting of phenyl, naphthyl and biphenyl groups, said substituents being placed so that no aryl moiety or oxygen atom is attached to any carbon atom which is less than three atoms removed from the sulfur atom, wherein L is an integer from 1 to 3, wherein R is selected from the group consisting of alkyl and aralkyl groups containing from 1 to 30 carbon atoms and from 0 to 10 substituent oxygen atoms replacing methylene groups in alkyl and alkylene groups to form ether linkages, there being at least two carbon atoms separating each oxygen atom from any other oxygen atom, wherein X is selected from the group consisting of chlorine, bromine, and iodine atoms and wherein each R is selected from the group consisting of alkyl, aryl, aralkyl, and alkaryl groups containing from 1 to 30 carbon atoms, 1 to 10 oxygen atoms as substituents replacing methylene groups in alkyl and alkylene groups to form ether linkages, there being at least two carbon atoms separating each oxygen atom from any other oxygen atom.

2. The compounds of claim 1 wherein L is 2 or 3.

3. The compounds of Claim 1 wherein R contains from about 8 to about 14 carbon atoms.

7 8 4. The compounds of claim 1 wherein L is 1 and R OTHER REFERENCES contains from about 16 to about 24 carbon atoms.

5. The compounds of claim 1 wherein R is methyl, R fig jg fgix f b Abstracts VOL 9 is phenyl, R is methyl and L is I.

6. The compounds of claim 2 wherein R is methyl, R 5 TOBIAS LEVOW Primary Examiner is phenyl, and R is methyl.

W. F. W. BELLAMY, Assistant Examiner References Cited US Cl XR UNITED STATES PATENTS 252 86 3,299,143 1/ 1967 Grayson et a1 260-6065 In

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3958059 *Oct 1, 1973May 18, 1976The Procter & Gamble CompanyFabric treatment composition
US3959155 *Oct 1, 1973May 25, 1976The Procter & Gamble CompanyDetergent composition
Classifications
U.S. Classification568/11, 987/121, 510/150, 987/110, 987/125, 252/8.63, 987/134, 510/330, 510/395
International ClassificationC07F7/02, C07F1/02, C11D1/00, C07F9/53, D06M13/285, A01N57/18, C07F9/54, C07F9/50, C07F7/08, C07F1/00
Cooperative ClassificationC07F1/02, C07C323/00, C07F7/02, C07F1/005, Y10S516/02, C07F1/00, C07F9/5304, D06M13/285, C07F9/5407, A01N57/18, C07F9/5004, C07C321/00, C07F7/0818, C07F9/53
European ClassificationC07F9/53A1, C07F9/54A1, C07F9/50A1, C07C323/00, C07C321/00, C07F9/53, C07F7/02, D06M13/285, A01N57/18, C07F1/00B, C07F7/08C6D, C07F1/00, C07F1/02