SULFONATE DERIVATIZED PERFUMES

Abstract: The present invention relates to novel sulfonates based upon alcohol perfumes. The sulfonates have general formulas of (I) and (II) where R and Z are independently selected from the group consisting of nonionic or anionic, substituted or unsubstituted C1-C30 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl or aryl group; Y is a radical that, upon hydrolysis of the sulfonate, forms an alcohol with a boiling point at 760 mm Hg of less than about 300 DEG C that is a perfume; and excluding geranyl and neryl methanesulfonates. Preferably these sulfonate compounds are incorporated into laundry and cleaning compositions.

Description: SU FONATE DERIVATIZED PERFUMES TECHNICAL FIELD The present invention relates to novel sulfonates based upon alcohol perfumes These sulfonate compounds are perfume alcohol deπvatives. compπsing a radical that upon hvdrolysis forms an alcohol with a boiling point at 760 mm Hg of less than about 300 °C that is a perfume Preferably these sulfonate compounds are incorporated into laundry and cleaning compositions BACKGROUND OF THE INVENTION Consumer acceptance of cleaning and laundry products is determined not only by the performance achieved with these products but the aesthetics associated therewith The perfume systems are therefore an important aspect of the successful formulation of such commercial products What perfume system to use for a given product is a matter of careful consideration by skilled perfumers While a wide array of chemicals and ingredients are available to perfumers, considerations such as availability, cost, and compatibility with other components in the compositions limit the practical options Thus, there continues to be a need for low-cost, compatible perfume mateπais useful for cleaning and laundry compositions It has been discovered that sulfonates of certain perfume alcohols are particularly well suited for laundry and cleaning compositions In particular, it has been discovered that sulfonates of perfume alcohols will hydrolvze to give an alcohol perfume and the corresponding salt In addition, hydrolyzable sulfonates of perfume alcohols provide release of the perfume over a longer peπod of time than by the use of the perfume itself in the laundry/cleaning compositions Such mateπais therefore provide perfumers with more options for perfume ingredients and more flexibility in formulation considerations These and other advantages of the present invention will be seen from the disclosures hereinafter BACKGROUND ART Sulfonate chemistry is descπbed more generally in March, ADVANCED ORGANIC CHEMISTRY 4th Ed , pp 352-353, 372, 404-405, 498-499 (John Wiley & Sons, N Y . 1992) Geranyl and neryl methanesulfonates are described as synthetic intermediates in Bunton, et al., Cyclization and Allylic Rearrangement m Solvolvses on Monoterpenoids, J Org Chem , Vol 44, No 18, pp 3239 ( 1979) SUMMARY OF THE INVENTION The present invention relates to novel sulfonate compounds used to provide alternative means of perfume delivery for a wide variety of consumer products The novel sulfonates have the general formulas of (I) and (II) (I) (ID wherein R and Z are independently selected from the group consisting of nonionic or anionic, substituted or unsubstituted C1-C 3 0 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryi or aryl group, Y is a radical that, upon hydrolysis of said sulfonate, forms an alcohol with a boiling point at 760 mm Hg of less than about 300 °C that is a perfume, and excluding geranyl and neryl methanesulfonates All percentages and ratios used herein are by weight of the total composition DETAILED DESCRIPTION OF THE INVENTION The sulfonates have the general formulas (I) and (II). (I) O II R— S— O— Y II O (II) wherein R and Z are independently selected from the group consisting of nonionic or anionic. substituted or unsubstituted C C 0 straight, branched or cvclic alkyl, alkenyl, alkynyl, alkylaryl or aryl group, Y is a radical that, upon hydrolysis of said sulfonate. forms an alcohol with a boiling point at 760 mm Hg of less than about 300 °C that is a perfume, and excluding geranyl and neryl methanesulfonates Preferably, R and Z are selected from the group consisting of substituted or unsubstituted Ci - C 2 o straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, aryl group or ring containing a herteroatom Y is preferably a radical that upon hydrolysis of said sulfonate forms perfume alcohol selected from the group consisting of phenoxanol floralol, β-citroneilol, nonadyi alcohol, cyclohexyl ethanol, phenyl ethanol, isoborneol, fenchol, 10 isocyclogeranol; (±)-linalool; 20 dihydromyrcenol, 25 2-phenyl-l -propanol. 2-ethylhexanol, OH cis-3-hexenol and/or 3,7-dimethyl-l-octanol The more preferred sulfonates are the p-toluenesulfonates (tosylates), 4- bromobenzenesulfonates (brosylates), and methanesulfonates (mesylates) of these alcohols The most preferred sulfonates are the tosylates, brosylates, and mesylates of β-citronellol, phenoxanol, cis-3-hexenol, and phenyl ethanol Of course, one of ordinary skill in the art will recognize that other sulfonates satisfying the general formula (I) or (II) can also be employed in the present invention Methods of Manufacture The following examples further describe and demonstrate embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention. It is recognized that the materials used to prepare the sulfonates herein preferably should not have other materials present that would change the essential perfume character of the perfume alcohol EXAMPLE 1 Phenoxanyl p-toluenesulfonate Phenoxanol (30 00 g, 0 168 mol) and pyridine (130 mL) are combined in a flask fitted with a condenser, internal thermometer, mechanical stirrer and argon inlet The solution is cooled to - 10 °C and to it is added p-toluenesulfonyl chloπde (39 28 g, 0 202 mol) in portions via Gooch tubing so as to maintain the reaction temperature between - 10-0 °C After 3 h water (20 mL) is added in portions so as to keep the temperature of the reaction below 5 °C The reaction mixture is warmed to room temperature and then poured into a separatory funnel containing 275 mL of ether The layers are separated and the organic layer is washed with 5 M H 2 S0 (75 mL), saturated CuSO 4 solution (75 mL), water (2 x 75 mL) and saturated NaHCO 3 solution (75 mL) After drying over MgSO 4) the organic layer is filtered and concentrated to leave a light yellow liquid as phenoxanyl p-toluenesulfonate Puπty of the product is determined by thin layer chromatography and the structure confirmed bv H and C NMR EXAMPLE 2 The procedure of Example 1 is repeated with the substitution of floraiol, β- citronellol, nonadyl alcohol, cyclohexyl ethanol, phenyl ethanol, isoborneol, fenchol, isocyclogeranol, (±)-lιnalool, dihydromyrcenol, 2-phenyl-l -propanol, 2-ethylheχanol, cιs-3-hexenol and/or 3,7-dιmethyl-l-octanoi for the phenoxanol EXAMPLE 3 b-Citronellyi p-toluenesulfonate b-Citronellol (21 05 g, 0 128 mol) and tetrahydrofuran (140 mL) are combined in a flask fitted with a condenser, internal thermometer, mechanical stirrer and argon inlet The solution is cooled to -78 °C and to it is added n-butylithium (56 3 mL, 0 141 mol, 2 5 M in hexanes) via syπnge The mixture is stirred for 60 min before a solution of p-toluenesulfonyl chloπde (39 28 g, 0 2019 mol) dissolved in 50 mL of tetrahydrofuran is added After addition is complete, the mixture is stirred for 30 min at -78 °C and then at room temperature overnight Ether (100 mL) is added and the mixture is quenched with water (100 mL) The organic layer is dned over MgSO4, filtered and concentrated to leave a yellow-orange liquid The oil is puπfied on silica gel eluting with 20% ethyl acetate in petroleum ether to give a light yellow liquid as b-citronellyl p-toluenesulfonate Puπty of the product is determined by thin layer chromatography and the structure confirmed by H and C NMR - 1 - EXAMPLE 4 2-Ethylhexanyl p-toluenesulfonate 2-Ethy!hexanol (50 51 g, 0 384 mol) and pyridine (260 mL) are combined in a flask fitted with a condenser, internal thermometer, mechanical stirrer and argon inlet The solution is cooled to -5 °C and to it is added p-toluenesulfonyl chloride (89 63 g, 0 416 mol) in portions via Gooch tubing so as to maintain the reaction temperature - 5-5 °C After 3 h, water (40 mL) is added in portions so as to keep the temperature of the reaction below 5 °C The reaction mixture is warmed to room temperature and then poured into a separatory funnel containing 540 L of ether The layers are separated and the organic layer is washed with 5 M H 2 SO (2 x 140 mL), saturated CuS04 solution (140 mL), water (2 x 140 mL) and saturated NaHCO3 solution (140 mL) After drying over MgSO4, the organic layer is filtered, and concentrated to leave a light yellow liquid as 2-ethyhexanyl p-toluenesulfonate Purity of the product is determined by thin layer chromatography and the structure confirmed by IH and 13C NMR. EXAMPLE 5 2-Ethylhexanyl 4-bromobenzenesulfonate The procedure for Example 3 is repeated with the substitution of 4 bromobenzenesulfonyl chloride for p-toluenesulfonyl chloride. EXAMPLE 6 Phenoxanyl methanesuifonate The procedure for Example 1 is repeated with the substitution of methanesulfonyl chloride for p-toluenesulfonyl chloride. EXAMPLE 7 Phenoxanyl (phenoxylacetyl) sulfonate The procedure for Example 1 is repeated with the substitution chlorosuifonylacetyl chloride for p-toluenesulfonyl chloride. COMPOSITIONS The present invention also relates to a composition for providing a prolonged scent signal to surfaces, comprising (A) an amount, effective to provide prolonged scent signal, of sulfonate derivatized perfume compound, and (B) an effective amount of a earner material to deliver said compound to surfaces, wherein the sulfonate deπvatized perfume compound is selected from the group consisting of (I) O II R— S— O— Y II and (II) wherein R and Z are independently selected from the group consisting of nonionic or anionic, substituted or unsubstituted C 1 -C 30 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl or aryl group, Y is a radical that, upon hydrolysis of said sulfonate, forms an alcohol with a boiling point at 760 mm Hg of less than about 300 °C that is a perfume, and excluding geranyl and neryl methanesulfonate Preferably, R and Z are selected from the group consisting of substituted or unsubstituted C ; - C 2 o straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, aryl group or ring containing a herteroatom Y is preferably a radical that upon hydrolysis of said sulfonate forms perfume alcohol selected from the group consisting of phenoxanol, floraiol, β-citronellol, nonadyl alcohoi, cyclohexyl ethanol, phenyl ethanol, isoborneol, fenchol, isocyclogeranol; (±)-Iinalool, dihydromyrcenol, 2- phenyl-1 -propanol, 2-ethylhexanol, cis-3-hexenol and/or 3, 7-dimethyl-l-octanol The most preferred sulfonates are the p-toluenesulfonates (tosylates), 4- bromobenzenesulfonates (brosylates), and methanesulfonates (mesylates) of β- citronellol, phenoxanol, cιs-3-hexenol, and phenyl ethanol The earner and/or diluent employed in the instant compositions is a non-toxic, non-irritating substance which when mixed with the sulfonate denvatized perfume compound, promotes the deposition of said sulfonate derivatized perfume compound onto surfaces The compositions of the present invention preferably comprise from about 25% to about 95%, preferably from about 50% to about 90% of a liquid earner Preferably the carrier and/or diluent is pπmaπly water due to its low cost relative availability, safety, and environmental compatibility The level of water in the liquid earner is at least about 50%, preferably at least about 60%, by weight of the carrier Mixtures of water and low molecular weight, e g , <100 g/mol, organic solvent, e g , lower alcohol such as ethanol, propanol, isopropanol or butanol are useful as the carrier liquid Low molecular weight alcohols include monohydric, dihydπc (glycol, etc ) trihydric (glycerol, etc ), and higher polyhydric (polyols) alcohols

Claims: What Is Claimed Is 1 A sulfonate deπvatized perfume compound, selected from the group consisting of sulfonates having the formula (I), and (II) (I) (II) wherein R and Z are independently selected from the group consisting of nonionic or anionic, substituted or unsubstituted C 1 -C 30 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryi or aryl group, Y is a radical that, upon hydrolysis of said sulfonate, forms an alcohol with a boiling point at 760 mm Hg of less than 300 °C which are perfumes, and excluding geranyl and neryl methanesulfonate 2 The sulfonate deπvatized perfume compound of Claim 1 wherein Y is a radical that upon hydrolysis of said sulfonate forms perfume aicohol selected from the group consisting of phenoxanol, floraiol, β-citronellol, nonadol, cyclohexyl ethanol phenyl ethanoi, lsoborneol, fenchol, isocyclogeraniol, (±)-lιnalool dihydromyrcenol, 2-phenyl-l -propanol, 2-ethylhexanol, cιs-3-hexenol, 3,7-dιmethyi-l-octanol, and combinations thereof 3 The sulfonate denvatized perfume compound as claimed in any of the preceding Claims, wherein said sulfonate is selected from the tosylates, brosylates, and mesylates of said alcohol perfumes, and mixtures thereof 4 The sulfonate deπvatized perfume compound as claimed in any of the preceding Claims wherein said sulfonate is selected from the group of sulfonates denved from alcohoi perfumes consisting of β-citroneilol, phenoxanol cιs-3-hexenol, phenyl ethanol, and mixtures thereof A composition for providing a prolonged scent signal to surfaces, compπsing (A) an amount, effective to provide prolonged scent signal, of sulfonate derivatized perfume compound as claimed in any of the preceding Claims, and (B) an effective amount of a earner material to deliver said compound to surfaces

Inventors: HARTMAN FREDERICK ANTHONY, SIVIK MARK ROBERT, HARTMAN, FREDERICK, ANTHONY, SIVIK, MARK, ROBERT
Applicants: PROCTER & GAMBLE, THE PROCTER & GAMBLE COMPANY
Application year: 1996
Main classification: C07C309
IPC codes: C07C309, C11B9