WO2000038616A2

WO2000038616A2 - Delivery systems for acidic actives

Info

Publication number: WO2000038616A2
Application number: PCT/GB1999/004349
Authority: WO
Inventors: Keith Douglas Perring; Alec Birkbeck; Kathleen Mary Tuck
Original assignee: Quest International BV
Current assignee: Givaudan Nederland Services BV
Priority date: 1998-12-23
Filing date: 1999-12-22
Publication date: 2000-07-06
Anticipated expiration: 2001-06-23
Also published as: GB2359088A; GB2359088A8; WO2000038616A3; AU1875800A; GB9828290D0; GB0113850D0

Abstract

A delivery system comprises a mixture of at least one compound having formula (I), wherein R<1> and R<2> are independently hydrogen or a hydrocarbyl moiety such that R<1>COR<2> is an aldehyde or ketone, and Q is a substituted or unsubstituted C1 to C12 alkyl, alkenyl, aryl or alkaryl moiety, providing that from 1 to 3 contiguous carbon atoms of Q are part of the ring structure of formula (I); and an acceptable vehicle. Where the delivery system is a perfume composition, the acceptable vehicle conveniently comprises at least one fragance material. Many other vehicles are also possible, depending principally on the nature of the delivery system. The invention also provides a method for delivery hydroxy acids and aldehydes or ketones to a substrate comprising applying to the substrate a compound of formula (I), and a perfume composition comprising at least one compound of formula (I).

Description

Title: Delivery Systems for Acidic Actives

Field of the nvention

This invention relates to compositions, hereinafter called "delivery systems", containing a compound with the potential to release hydroxy carboxylic acids on decomposition, together with an aldehyde or ketone, and a method for delivering carboxylic acids and aldehydes or ketones to substrates.

Background to the Invention

Carboxylic acids are incorporated into many products as an agent to control the free concentration of hydroxonium ions, or of metal ions, but may fulfil other functional roles such as the provision of antimicrobial effects or the provision of other skin benefits. In situations where it is required to provide these functionalities on a surface such as skin, hair, hard surface or fabric surface then the delivery of the active substance(s) to the substrate becomes important. Moreover, if longevity of action is needed then the active substance must clearly be available for some time following delivery to the surface. These requirements are a particular problem with acids when the use of the product inevitably involves exposure of the product to water, such as during the use of personal wash products such as soap, shower gels and shampoos, since acids tend to be relatively hydrophilic, and will tend to wash away. This is particularly the case when the pH is sufficiently high so as to ionise the acid to form salts that may be solubilised in aqueous systems. In addition, the more_uelatile the acid, the less likely it is to be retained for any appreciable time on a surface.

Perfumes are incorporated into many consumer compositions in order to provide a number of olfactory benefits, for example, to cover the odour of base components and/or to provide odour cues to render compositions more attractive or pleasing to consumers. It is well known that perfumes which contain aldehydes or ketones may perform poorly in compositions containing active compound(s) which are chemically reactive to compounds incorporating carbonyl groups, for example, product compositions incorporating bleaching agents and alkalis. Yet another problem arises from the volatility of lower molecular weight perfume aldehydes or ketones in applications where it is required that the perfume should be substantive, by which it is meant that the perfume should continue to be appreciated by consumers for some time following product application to a substrate. For example, it is desirable that a substantive soap perfume is perceivable on skin an hour or more after washing. In other situations, it may be desirable to retain a perceivable odour for several hours.

It is consequently desirable to improve the delivery and retention of hydroxy carboxylic acids and aldehydes or ketones to substrates such as skin, hair, fabrics and hard surfaces.

Methods are known in the art which address the concerns of stability in the product, delivery to a substrate and retention on the substrate. For example, carriers such as cyclodextrins have been reported to improve perfume compatibility with product matrices, and also have been claimed to delay perfume evaporation from a surface. With regard to delivery from aqueous systems, however, their hydrophilic nature tends to make this difficult, and there are many reports in the literature claiming their use as solubilisers for poorly soluble materials in water. Alternatively, the encapsulation of material within a matrix which may be incorporated into consumer products to thereby deposit the material on target substrates is known. For example, the use of matrices based on starches (e.g. US 5 425 887) or of polymers (e.g. GB 2 090 278, US 4 303 548) is well documented, as is the use of porous carriers such as silicas (e.g. EP 0 332 259). Such techniques as these invariably entail further processing steps and/or material costs.

Examples are known of improved delivery of perfume materials via the use of precursors which break down to release the perfume. Acetals and ketals, for example, are known to release aldehydes or ketones, respectively, in acidic environments or upon thermal breakdown. US Patent 5 147 463 describes low odour cyclic acetals that release aldehydes on heating. WO 94/06441 discloses acetals and ketals which are stable in alkaline environments but will release aldehydes or ketones when exposed to normal skin pH ranges. US 4 697 025 discloses a method for delivery based on carboxyl acetals which release aldehydes thermally. None of the above examples discloses the possibility of delivering to a substrate a single non-ionising compound capable of releasing simultaneously an aldehyde or ketone and a functional carboxylic acid.

The invention provides a means of improving the delivery and/or retention of aldehydes, ketones, and functional hydroxy carboxylic acids. In view of this ability to deliver certain compounds to a desired substrate, the composition of the invention has been termed, hereinafter, a "delivery system".

Summary of the Invention

According to the invention a delivery system comprises a mixture of at least one cyclic compound having the formula (I), below,

(I)

1 2 1 2 wherein R and R are, independently, hydrogen or a hydrocarbyl moiety such that R COR is an aldehyde or ketone, and Q is a substituted or unsubstituted C. to C₁₂ alkyl, alkenyl, aryl or alkaryl moiety, providing that from 1 to 3 contiguous carbon atoms of Q are part of the ring structure of the compound of formula (I); and an acceptable vehicle.

The compound of formula (I) breaks down or decomposes on hydrolysis to give an aldehyde or ketone and a hydroxy acid, and can thus release and deliver to a desired substrate in use the two products resulting from decomposition.

A preferred embodiment of the invention comprises delivery systems incorporating

1 2 compounds of formula (I) wherein R COR is an aldehyde or ketone which possesses an odour which may be employed by itself or within a perfume composition to enhance the odour performance of delivery systems of the invention. The phrase 'odour performance' refers to consumer acceptability associated with the use of the composition. This may be the acceptability associated with the composition itself in its packaging, or, for example, for a hair product, it may be the olfactory characteristics of dry hair after shampooing or conditioning the hair.

1 2

In one embodiment, R and R are, independently, hydrogen or hydrocarbyl groups containing from 1 to 16 carbon atoms, preferably from 1 to 10 carbon atoms and more preferably 1 to 8 carbon atoms. For applications in which the compound of formula (I) is

1 2 selected so that R COR is an aldehyde or ketone having the ability to enhance the odour performance of delivery systems, it is preferable that the number of carbon atoms in R and

2

R combined is from 1 to 14, and particularly preferred forms of this embodiment are

1 2 characterised by compounds of formula (I) in which R COR is an aldehyde or ketone with a molecular mass of 220 atomic mass units (amu) or less, preferably of 185 amu or less and, more preferably, of atomic mass 170 amu or less.

Other preferred embodiments of the invention comprise delivery systems containing compounds of formula (I) which have a low solubility in water, and, therefore, tend to have relatively greater deposition onto substrates. Where the compound of formula (I) has a lower solubility in water than that of the hydroxy acid released on breakdown, so delivery can be improved. Solubility can be measured directly, but, conveniently, it is possible to estimate solubilities using the partition coefficient of the compound between octanol and water. The octanol-water partition coefficient (or its common logarithm Jog P') is known in the literature as an indicator of hydrophobicity and water solubility (see, for example, Hansch and Leo, Chemical Reviews, 526 to 616, (1971), 71; Hansch, Quinlan and Lawrence, J. Organic Chemistry, 347 to 350 (1968), 33). Where values of log P are not available in the literature they may be measured directly, or approximately estimated using mathematical algorithms. Software providing such estimations is available commercially, for example 'LogP' from Advanced Chemistry Design Inc. A material with a low log P is difficult to deliver to substrates from aqueous systems since such materials tend to be solubilised and be rinsed away. Such materials may also be similarly removed from a surface by the exposure of the surface to water after application of the substance to the surface, e.g., from perspiration, rain or the use of other aqueous products. This is particularly so for acidic compounds exposed to a pH which is sufficiently high to allow the generation of salts. In such cases log P must be quite high for satisfactory delivery and retention. The present invention can overcome or reduce difficulties in delivery of hydroxy acids with low log P by delivering the material in the form of a compound of formula (I) having a higher log P than that of the hydroxy acid released on decomposition. The present invention is therefore particularly useful for the delivery of a hydroxy acid with a low log P, eg a log P of less than 6, and especially for an acid with a log P less than 4 or less than 3. For example, salicylic acid, a known antimicrobial acid, has a log P in the region of 2.2, and salicylic acid will have a significant solubility in water even when not ionised, so that salicylic acid is normally difficult to deliver to substrates from aqueous systems. By delivering salicylic acid from a compound of formula (I) having a higher log P, so delivery is improved. Preferred forms of compound of formula (I) for use in the invention therefore comprise those having a log P which is at least 3.0, preferably at least 4.0 or, more preferably, at least 5.0

Particularly preferred compounds of formula (I) useful in the invention are compounds which are degraded in use to produce an α-hydroxy alkanoic acid or a ring-substituted hydroxy benzoic acid such as salicylic acid.

Delivery systems according to the invention may consist of or comprise a wide variety of products including personal care products, particularly those used during personal washing, and other product formats where it is desired to have longevity of effect and/or resistance to loss of active compounds from skin or hair following application. Personal care products utilising the delivery systems of the present invention may be, for example: shampoos, hair conditioning formulations, soap bars, liquid soaps, shower gels, bath products, talcum powders, antiperspirants, deodorants, skin creams, skin lotions or personal perfumes. Compounds of formula (I), perfume compositions containing them or other delivery systems of the invention, may also be incorporated into or comprise fabric treatment products for use in washing, rinsing or other treatment of fabrics. Such products may be, for example: detergent compositions for fabric washing, rinse conditioner compositions for softening washed fabrics during a rinsing step, additive compositions for use jointly with either of the above or fabric treatment compositions designed to be applied to dry fabrics, for example in the form of a spray.

Other delivery systems of the invention may consist of or comprise household products such as hard surface cleaners, toilet blocks, and disinfectants.

Any of the above-mentioned personal care products, fabric treatment products or household products can take a variety of forms including powders, bars, sticks, tablets, mousses, gels, liquids, and sprays.

A particularly useful delivery system according to the invention comprises a composition containing at least one compound of formula (I) and at least one compound which is known to be useful for its olfactory properties (hereinafter called a fragrance material). Such a composition is herein described as a perfume composition and this perfume composition can be a delivery system on its own or can be incorporated into delivery systems such as those disclosed above. When the delivery system of the current invention is a perfume composition, then the acceptable vehicle of the delivery system is at least one fragrance material.

A perfume composition comprises at least one compound of formula (I) and at least one fragrance material, and, optionally, a solvent, formulated to have certain useful fragrance characteristics. In most cases perfume compositions are formulated to have a fragrance generally considered at least inoffensive and, preferably, pleasing to intended users of the composition. Perfume compositions are used for imparting a desired odour to the skin and/or any product for which an agreeable odour is indispensable or desirable. Fragrance materials which can be advantageously combined with compounds of formula (I) in perfume compositions are, for example, natural products such as extracts, essential oils, absolutes, resinoids, resins, concretes etc. and synthetic materials such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, ketals, nitriles, etc., including saturated and unsaturated compounds, aliphatic, carbocyclic and heterocyclic compounds.

Such fragrance materials are mentioned, for example, in S. Arctander, "Perfume and Flavor Chemicals" (Montclair, N.J., 1969), in S. Arctander "Perfume and Flavor Materials of Natural Origin" (Elizabeth, N.J., 1960) and in "Flavor and Fragrance materials - 1991", Allured Publishing Co. Wheaton, 111. USA.

Examples of fragrance materials which can be used in perfume compositions of the current invention include: geraniol, geranyl acetate, linalol, linalyl acetate, tetrahydrolinalol, citronellol, citronellyl acetate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcenol, terpineol, terpinyl acetate, nopol, nopyl acetate, 2-phenylethanol, 2- phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, styrallyl acetate, benzyl benzoate, amyl salicylate, dimethylbenzylcarbinol, trichloromethylphenylcarbinyl acetate, p-tert-butylcyclohexyl acetate, isononyl acetate, vetiveryl acetate, vetiverol, hexylcinnamaldehyde, 2-methyl-3-(p-tert-butylphenyl)propanal, 2-methyl-3-(p-isopropyl- phenyl)propanal, 3-(p-tert-butylphenyl)propanal, 2,4-dimethylcyclohex-3-enyl carboxaldehyde, tricyclodecenyl acetate, tricyclodecenyl propionate, 4-(4-hydroxy-4-methyl- pentyl)-3-cyclohexenecarboxaldehyde, 4-(4-methyl-3-pentenyl)-3-cyclohexene carboxaldehyde, 4-acetoxy-3-pentyltetrahydropyran, 3-carboxymethyl-2- pentylc^clopentane, 2-n-heptylcyclopentanone, 3-methyl-2-pentyl-2-cyclopentenone, n- decanal, n-dodecanal, 9-decenol-l, phenoxyethyl isobutyrate, phenylacetaldehyde dimethylacetal, phenylacetaldehyde diethylacetal, geranyl nitrile, citronellyl nitrile, cedryl acetate, 3-isocamphylcyclohexanol, cedryl methyl ether, isolongifolanone, aubepine nitrile, aubepine, heliotropin, coumarin, eugenol, vanillin, diphenyl oxide, hydroxycitronellal, ionones, methylionones, isomethylionones, irones, cis-3-hexenol and esters thereof, indan musks, tetralin musks, isochroman musks, macrocyclic ketones, macrolactone musks, ethylene brassylate. Solvents which can be used for perfume compositions according to the invention are, for example, ethanol, isopropanol, diethyleneglycol monoethyl ether, dipropyleneglycol, diethyl phthalate, tri ethyl citrate, isopropyl myristate etc.

The nature of the acceptable vehicle which is a component of the delivery system of the invention will vary widely, depending principally upon the nature of the delivery system. As mentioned hereinbefore, the acceptable vehicle may be a fragrance material. When the delivery system is a product designed for washing, such as a shampoo, a personal or domestic soap or a laundry composition, the acceptable vehicle may be any surfactant which is generally incorporated into such a product or other component of such products, as, for example, emollients or whitening agents. When the delivery system is a rinse or softener composition, typical acceptable vehicles will include surfactants, fatty alcohols, colours and preservatives. When the delivery system is a composition of domestic use, the acceptable vehicle may be, for example, a suitable surfactant, a bleach, a disinfectant or a solvent. The physical nature of the acceptable vehicle may also vary with the form of the delivery system. For example, when the composition is a powder, stick, or other solid product, the acceptable vehicle may be, for example, a filler or similar material, when the delivery system is a spray the acceptable vehicle may be, for example, a propellant and when the consumer product is a gel or mousse, the acceptable vehicle may be, for example, a thickening agent or other material which produces an appropriate structure. In other applications acceptable vehicles of the delivery systems will consist of materials normally used in compositions of use in the application and appropriate acceptable vehicles will be apparent to a person skilled in the art.

In the-p-reparation of products which consist of or comprise delivery systems of the invention which contain perfume compositions it is possible to incorporate the perfume composition directly into a product, but it is also possible to absorb the perfume composition onto a carrier material and then mix the perfume-plus-carrier mixture with the compound of formula (I). This approach may notably be used when the final product is a solid. The carrier will usually be an inert particulate carrier and could be organic or inorganic. Especially useful carriers are particulate silicas. Other techniques providing enhanced delivery and/or compatibility benefits which may be used in connection with the present invention include, for example, encapsulation. Compounds of formula (I) are, in general, compatible with the great majority of fragrance materials, and may be conveniently dosed into products via perfume compositions, as hereinbefore described although it may be desirable in certain cases not to include any fragrance materials.

1 2 .

For the compounds of formula (I), in which either R or R is hydrogen, aldehydes will be released on breakdown. In products where the breakdown occurs not only on a substrate but also in the product (e.g. in laundry powders) it may be necessary to use fragrance materials which blend well with aldehydes. Preferred fragrance materials for use in such cases comprise fragrances materials of a floral or floral-citrus nature.

Particularly useful delivery systems of the invention comprise at least 0.01% by weight of at least one compound of formula (I). Generally at least 0.05% by weight of at least one compound of formula (I) will be present and sometimes 1% or more by weight of at least one compound of formula (I) is present. Normally, the delivery system of the invention will contain up to about 20% and, typically, up to about 5% by weight of at least one compound of formula (I).

When the delivery system of the invention consists of or comprises a perfume composition, the amount of fragrance material(s) in such compositions will frequently be in the range from 0.01% to 20% by weight with respect to total composition, more usually 0.1% to 10% by weight. The incorporation of fragrance materials into similar compositions is known, and existiτrg*techniques may be used for incorporating fragrance materials in accordance with any embodiments of this invention.

According to a further aspect of the invention, a method of delivering simultaneously a hydroxy acid and an aldehyde or a ketone to a substrate comprises applying to said substrate a compound having the formula (I), below

1 2 1 2 wherein R and R are, independently, hydrogen or a hydrocarbyl moiety such that R COR is an aldehyde or ketone, and Q is a substituted or unsubstituted C, to C-₂ alkyl, alkenyl, aryl or alkaryl moiety, providing that from 1 to 3 contiguous carbon atoms of Q are part of the ring structure of the compound of formula (I).

In preferred embodiments of the method of the invention the compound of formula (I) has the preferred structure described hereinbefore in respect of the compound of formula (I) useful in the delivery systems of the invention.

The method of the invention is suitable for the treatment of a wide variety of substrates including human skin, hair, fabrics and hard surfaces.

The invention also includes within its scope a perfume composition comprising at least one compound of formula (I).

The compounds of formula (I) may be prepared by any technique which is suitable for their preparation. Typically, they are prepared by dehydration of a mixture of an appropriate aldehyde or ketone and a hydroxy acid in the presence of a dehydrating catalyst, such as an acid. Conveniently, such a mixture is heated as a suspension or solution in an inert diluent at reflux, while water is removed azeotropically.

The invention is illustrated by the following, non-limiting Examples. In the Examples all % are % by weight unless otherwise specified. EXAMPLE 1 Synthesis of 5-Methyl-2-Nonyl-l,3-Dioxolan-4-one (A)

A suspension of decanal (20 g, 128 mmol), D/L lactic acid (15 g) and camphor sulphonic acid (lg) in toluene (250 ml) was heated under reflux with the azeotropic removal of water for 2 hours. The suspension was cooled, solid sodium bicarbonate (5 g) was added, the suspension filtered and the solvents removed in vacuo to yield the crude acetal. Further purification by distillation at 90 to 95° C and 1.3 Pa gave the acetal (A) (24 g) as a mixture of diastereoisomers, in the form of a colourless oil.

NMR ¹³C(100 MHz) 14.03, 15.84, 16.21, (CH₃), 22.61, 22.68, 22.88, 29.13, 29.16, 29.21, 29.36, 29.37, 31.80, 33.91, 34.47 (CH₂), 70.13, 71.37 (CH), 104.26, 104.77, (CH), 173.92 (q)ppm.

EXAMPLE 2 Synthesis of 2-[2'-(4"Jert.butylphenyl)-r-methylethyl]-5-Phenyl-l,3-

Dioxolan-4-one (B)

A suspension of lilial (50 g, 229 mmol), D/L mandelic acid (42 g, 276 mmol) and p-toluene sulphonic acid (2 g) in cyclohexane (200 ml) was heated under reflux with azeotropic removal of water for 12 hours. (Lilial is a Trade Mark of Givaudan, and comprises 2- methyl-3 (para-t-butylphenyl) propionaldehyde). The solution was cooled, solid sodium bicarbonate (15 g) was added, the suspension filtered and the solvents removed in vacuo to yield the crude acetal. Further purification by column chromatography on silica (300 mL) with cy lohexane then 1:99 diethyl ether: cyclohexane gave the acetal (B) (38.4 g) as a mixture of diastereoisomers, in the form of a pale yellow oil.

NMR ^I3C(100MHz)12.51, 12.54, 12.72, 12.80 (CH₃), 26.89 (q), 31.37 (CH₃), 34.38 (q), 36.12, 36. 23, 36.31, 36.41, 36.67 (CH₂), 38.62, 38.71, 39.41, 39.63 (CH), 76.76, 77.21 (CH), 106.04, 106.06, 107.38, 107.55 (CH), 125.33, 125.75, 125.81, 126.93, 126.97, 128.63, 128.75, 128.83, 128.85, 125.87, 128.92, 129.05, 129.19, 129.21 (CH), 133.49, 133.52, 133.70, 133.72, 135.77, 135.79 (q), 149.14, 149.16, 149.17 (q), 171.46, 171.48, 171.59, 171.63 (q)ρρm. EXAMPLE 3 Synthesis of 2,5-Dimethyl-2-[4-methylpent-3-enyl]-l,3-Dioxolan-4-one (C)

A suspension of 6-methylhept-5-ene-2-one (12.6 g, 100 mmol), D/L lactic acid (10 g, 1 lOmmol) and camphor sulphonic acid (200 mg) in toluene (80 ml) was heated under reflux with azeotropic removal of water for 7.5 hours. The solution was cooled, solid sodium bicarbonate (4 g) was added, the suspension filtered and the solvents removed in vacuo to yield the crude acetal. Further purification by distillation at 90° C and 1.3 Pa gave compound (C) as a mixture of diastereoisomers (13 g) in the form of an unstable pale yellow oil.

NMR ¹³C(100 MHz) 15.78, 16.96, 17.05, 17.68, 17.95 (CH₃), 21.52, 22.13, 22.26 (CH₂), 24.28, 25.58, 25.87 (CH₃), 39.16, 39.52 (CH₂), 70.28, 70.90, 72.53, 72.96 (CH), 110.49, 111.50, 112.00 (q), 122.58, 122.72 (CH), 132.52, 132.68 (q), 173.87, 173.92 (q) ppm

EXAMPLE 4 Synthesis of 2-Methyl-4H-l,3-Benzodioxin-4-one (D)

This was prepared following the literature procedure of D.T.Mowry, W.H. Yanko and E.L. Ringwald, described in J.Am. Chem. Soc, 1947, (59, 2358-2361.

Examples 5 to 8 describe the preparation of various benzodioxinones based on the procedure of P. Perlmutter and E. Puniani, Tetrahedron Letters , 1996, 37, 3755-3756.

EXAMPLE 5 Synthesis of 2-[2'-(4"Jert.butylphenyl)-l '-methylethyl]-4H-l,3- benzodioxin-4-one (F)

Phenyl 2-hydroxybenzoate (or phenyl salicylate) (E) was prepared according to the literature procedure described by A.R. Bader and A.D. Kontowicz in J. Am. Chem. Soc, 1953, 75, 5413-5417.

A mixture of phenyl salicylate (E, 15 g, 70 mmol), l,4-diazabicyclo(2.2.2)octane (8 g, 71 mmol), and lilial (14.3 g, 70 mmol) was warmed to 40°C for 5 minutes then allowed to stand at ambient temperature for a further 72 hours. The suspension was diluted with cyclohexane (50 ml). Further purification by column chromatography on silica (300 mL) using cyclohexane then 1 :99 diethyl ether: cyclohexane as eluent gave the benzodioxinone (F) as a colourless oil (15g, 66 %).

NMR(lOOMHz) 12.99, 13.00 (CH₃), 26.84 (CH₂), 31.20 (CH₃), 34.30 (q) 36.35, 36.40 (CH₂), 38.58, 38.60 (CH), 102.95, 103.04 (CH), 114.46, 114.49 (q), 116.59, 123.14, 123.17, 125.30, 128.77, 128.79, 130.15, 135.91, 135.96, 136.04, 136.07 (CH), 149.03, 158.43, 148.48, 162.32, 162.33 (q) ppm.

EXAMPLE 6 Synthesis of 2-[2'-(4"-isopropylphenyl)-l'-methylethyl]-4H-l,3- benzodioxin-4-one (G)

A mixture of phenyl salicylate (15 g, 70 mmol), l,4-diazabicyclo(2.2.2)octane (8 g, 71 mmol), and cyclamen aldehyde (13.3 g, 70 mmol) was warmed to 40°C for 5 minutes then allowed to stand at ambient temperature for a further 72 hours. The suspension was diluted with cyclohexane (50 ml). Further purification by column chromatography on silica (300 mL) using cyclohexane then 1:99 diethyl ether: cyclohexane as eluent gave the benzodioxinone (G) as a mixture of diastereoisomers, in the form of a colourless oil (6.22g, 28 %).

NMR ^I3C(100 MHz) 13.13, 13.15 (CH/CH₃), 24.10, 24.12, 24.13 (CH CH₃), 27.5 (CH₂) 33. 78 (CH₃), 36.66 (CH₂), 38.78, 38.82 (CH), 103.12, 102.20 (CH), 114.61, 114.63 (q), 116.77, 123.33-_* 126.62, 129.19, 129.22, 130.34, 136.24 (CH), 136.28 (q), 146.94, 158.60, 158.65, 162.58 ppm(q).

EXAMPLE 7 Synthesis of 2-(l'-methyldecyl)-4H-l,3-benzodioxin-4-one (H)

A mixture of phenyl salicylate (21.5 g, 100 mmol), l,4-diazabicyclo(2.2.2)octane (11 g, 100 mmol), and 2-methylundecanal (17 g, 92 mmol) was warmed to 40°C for 5 minutes then allowed to stand at ambient temperature for a further 72 hours. The suspension was diluted with cyclohexane (50 ml). Further purification by column chromatography on silica (400 mL) using cyclohexane then 1 :99 diethyl etheπcyclohexane as eluent gave the benzodioxinone (H) as a mixture of diastereoisomers, in the form of a colourless oil (15g, 54 %).

NMR ¹³C(100 MHz) 13.15, 14.07 (CH₃), 22.63, 27.51, 29.27, 29.51, 29.53, 29.68, 31.84 (CH₂), 36.68 (CH)J 04.07, 104.09 (CH), 114.49 (q), 116.61, 116.63, 121.59, 123J3J29.58, 130.14, 136.04, 136.42 (CH), 158.55, 158.57, 162.55 ppm(q).

EXAMPLE 8 Synthesis of 2-[3'-(tricyclo[[5.2J.0²'Jdec-8-ylidenyl)propyl]-4H-l,3-

Benzodioxin-4-one (I)

A mixture of phenyl salicylate (15 g, 70 mmol), l,4-diazabicyclo(2.2.2)octane (5.8 g, 52 mmol), and 4-tricyclo[5.2J.02,6]dec-8-ylidenebutanal (10 g, mmol) was warmed to 40°C for 5 minutes then allowed to stand at ambient temperature for a further 72 hours. The suspension was diluted with cyclohexane (50 ml). Further purification by column chromatography on silica (400 mL) using cyclohexane then 1 :99 diethyl etheπcyclohexane as eluent gave the benzodioxinone (I) as a colourless oil (7g, 54 %).

NMR ¹³C(100 MHz) 22.53, 22.55, 23.13, 27.77, 32.58, 32.89, 37.95 (CH₂), 41.03, 44.46, 47.38, 47.75, 48.05, 49.60, (CH), 101.40, 101.50, (CH), 114.79, 114.89116.78, 116.79, 123.46, 130.41, 136.32, 136.35 (CH), 147.04, 147.08, 147.73, 158.64, 158.66, 162.53, 162.56 (q) ppm .

EXAMPLES 9 to 12

Personal cleansing compositions were prepared according to the following compositions, using established techniques well known to those in the art. Percentages refer to percentage by weight of the final composition. Example 9 Example 10

Component Shampoo Shower gel

Sodium laureth-2 sulphate 16.0% 7% Cocamidopropyl betaine 1.0% 3.0% Magnesium laureth sulphate - 3.5% DMDM Hydantoin¹ 0.2% 0.3% Coconut diethanolamide 2.0% _ PEG-7 Glyceryl cocoate² 3.0% Ethylene glycol distearate 1.5% Antil 141 Liquid³ 0.8% Compound of Example 1 0.1% Compound of Example 2 0.3% Perfume 0.6% 0.9% Water q.s. to 100%-

¹ DMOM Hydrantoin is a preservative ex Lon-za.

PEG-7 glyceryl cocoate is a solubiliser/emollient available from Croda. ³ Antil 141 is a thickener supplied by Th. Goldschmidt AG. Antil 141 is a Trade Mark. The properties of the above compositions such as colour, viscosity, pH etc. can optionally be modified with appropriate conventional agents.

Example 11 Example 12

Component Liquid Soap Liquid Soap (syndet type)

Sodium cocoyl isethionate 2.0% -

Prisavon 9270 ' - 20.0%

Lauryl diethanolamide - 4.0%

Glyceryl-3 oleate 1.0% -

Empicol ESB3² 30.0% -

Glycerine 4.0% 4.0%

Potassium chloride . 2.5%

Tegobetaine F50 10.0% EDTA, tetrasodium salt⁴ 0.5% Antil 141 Liquid 2.0% Compound of Example 1 0.2% Compound of Example 2 0.1% Perfume 0.75% 0.5 Water -to 100%-

Syndet type soap contains non-soap detergent active and is suitable for personal washing.

¹ Prisavon comprises potassium soaps of palm based acids, supplied by Unichema International. Prisavon 9270 is a Trade Mark.

Empicol ESB3 is a surfactant compπsing 27% aqueous sodium laureth sulphate, supplied by Albright & Wilson. Empicol ESB3 is a Trade Mark.

Tegobetaine F50 is a mild detergent, supplied by Th Goldschmidt AG. Tegobetaine F50 is a Trade Mark. ⁴ EDTA stands for ethylenediaminetetra-acetic acid.

Properties of the above formulations such as colour, viscosity, preservative content, pH etc. can be modified as desired by the addition of appropriate conventional agents.

EXAMPLES 13 and 14

Fabric treatment products were prepared in conventional manner, according to the following foimulations.

Example 13 Example 14 Cone. Laundry Cone. Fabric

Component Powder Softener

Cπ-Cι₄ alkyl benzene sulphonate 5.1% -

Dobanol 23-3^! 8.7% -

Dobanol 23-6.5² 7.3% -

Zeolite 4A³ 29.8% -

Sodium perborate⁴ 15.6% -

Sodium carbonate 9.7% _ Sodium silicate 1.5% -

TAED granules⁵ 8.2% -

Sodium sulphate 2.5% -

Sodium soap⁶ 1.5% -

Enzymes⁷ 0.8% -

Polyacrylate (MW 3000 to 4000)⁸ 3.1% -

Cationic active⁹ - 14.0%

Tallow alcohol 35EO¹⁰ - 1.2%

Calcium chloride - 0.10%

Perfume 0.75% 0.7%

Compound of Example 1 0.15% -

Compound of Example 2 - 0.15%

Water —to 100%

¹ Dobanol 23-3 is a detergent comprising a mixture of ethoxylated (3 mole average) C12 to C13 alcohols, ex Shell Chemical Co.. Dobanol 23-3 is a Trade Mark.

² Dobanol 23-6.5 is a detergent comprising a mixture of ethoxylated (6.5 mole average) C12 to C13 alcohols, ex Shell Chemical Co.. Dobanol 23-6.5 is a Trade Mark.

³ Zeolite 4A ex Grace and Co, which functions as an inorganic laundry builder.

⁴ Monohydrate.

⁵ TAED = tetraacetylethylenediamine sodium salt.

⁶ Sodium soap comprises technical grade sodium stearate, and is used as a processing aid. Enzymes comprise optional laundry lipases, proteases, amylases and cellulases.

Lύ Tnolecular weight polymer, used as an anti-redeposition agent.

⁹ Cationic active comprises di(hardened tallowyloxy trimethyl ammoniopropane chloride), ex Hoechst.

¹⁰ Tallow alcohol 35EO is a detergent comprising ethoxylated (35 mole average) stearyl alcohol).

Minor constituents such as dyes, foam-control agents, preservatives, etc. can be added to these compositions to modify the properties, if desired. EXAMPLES 15 and 16

Hard surface cleaners were prepared by conventional techniques, according to the following formulations.

Component Example 15 Example 16

Dobanol 91-6¹ 2.5% -

Imbentin 91-3.5² - 5.0%

Sodium dodecylbenzene sulphonate 4.5% -

Isopropyl alcohol 4.5% -

Butyl digol - 3.0%

Sodium cumene sulphonate - 1.0%

Fragrance 1.0% 1.0% pH control agents³ 0.75% 0.5%

Compound of Example 1 0.1 -

Compound of Example 2 - 0.25

Water -to 100%-

Dobanol 91-6 is a detergent comprising a mixture of ethoxylated (6 mole average) C9 to Cl l alcohols ex Shell Chemical Co.. Dobanol 91-6 is a Trade Mark.

Imbentin 91-3.5 is a detergent comprising a mixture of ethoxylated (3.5 mole average) C9 to Cl 1 alcohols, ex KolbAG. Imbentin 91-3.5 is a Trade Mark. ³ eg citric acid, triethanolamine etc, to regulate pH to 4 to 8.

EXAMPLE 17 Release of acidic active in a fabric conditioning treatment.

The deposition of aldehydes or ketones onto cloth from delivery systems in accordance with the invention may be used as an indicator of the in-use performance of these systems; it is anticipated that the gradual release of the carbonyl fragment is paralleled by release of the acidic active (provided the normal mode of hydro lytic decomposition is followed). 5-Methyl-2-Nonyl-l,3-Dioxolan-4-one (compound A from Example 1) was dosed into concentrated fabric conditioner (according to Example 14) at 0.36%. Terry Toweling cloth was rinsed in a solution of this conditioner (5g cloth, 0.5g fabric conditioner, 150 ml water) for 10 minutes using a Jencons flask shaker (Jencons is a Trade Mark). The cloth was then hand squeezed of excess rinse liquor (to 12g) and line-dried for 4 hours at room temperature. A sample (lg) of dry cloth was then analysed by automatic equilibrium headspace-gc. A large peak was observed in the headspace-gc trace which was identified as decanal by gc-ms. To check whether this amount of aldehyde could be present via the deposition of free decanal produced by partial degradation of compound A in the conditioner prior to fabric treatment, the experiment was repeated using free decanal in the conditioner, using an amount equivalent to total degradation of compound A. The amount of decanal in the headspace was found to be only about 15% of that produced when using compound A. It was therefore concluded that a delivery system including compound A had improved the delivery of aldehyde and acid to cloth.

Claims

1. A delivery system comprising a mixture of at least one compound having the formula

(I) below,

(I)

1 2 " 1 2 wherein R and R are independently hydrogen or a hydrocarbyl moiety such that R COR is an aldehyde or ketone, and Q is a substituted or unsubstituted C, to C-₂ alkyl, alkenyl, aryl or alkaryl moiety, providing that from 1 to 3 contiguous carbon atoms of Q are part of the ring structure of formula (I); and an acceptable vehicle.

1 2

2. A delivery system according to claim 1, wherein R and R are independently hydrogen or a hydrocarbyl moiety containing from 1 to 10 carbon atoms.

1 2

3. A delivery system according to claim 1 or 2, wherein R and R are hydrogen or

1 2 . hydrocarbyl moieties such that R COR is a ketone or aldehyde characterised by a molecular weight of less than 220 atomic mass units.

4. A dejivery system according to any one of the preceding claims, wherein the compound of formula (I) has a lower solubility in water than that of the hydroxy acid released on breakdown.

5. A delivery system according to any one of the preceding claims, wherein Q is a hydrocarbyl moiety such that the hydroxy acid released on breakdown of the compound of formula (I) is characterised by an octanol-water partition coefficient, expressed as a common logarithm, of less than 6 .

6. A delivery system according to any one of the preceding claims, wherein Q is a hydrocarbyl moiety such that the hydroxy acid released on breakdown of the compound of formula (I) is a ring substituted hydroxy benzoic acid.

7. A delivery system according to any of the preceding claims, wherein Q is a hydrocarbyl moiety such that the hydroxy acid released on breakdown of the compound of formula (I) is an α-hydroxy alkanoic acid.

8. A delivery system according to any one of the preceding claims, wherein Q is a hydrocarbyl moiety such that the hydroxy acid released on breakdown of the compound of formula (I) is salicylic acid.

9. A delivery system according to any one of the preceding claims, comprising a mixture of a compound of formula (I) and a fragrance material.

10. A delivery system according to any one of the preceding claims, comprising at least 0.01% by weight of at least one compound of formula (I).

11. A personal care product comprising a delivery system according to any one of the preceding claims.

12. A fabric treatment product comprising a delivery system according to any one of the preceding claims .

13. A hard surface cleaner, a toilet block or a disinfectant comprising a delivery system according to any one of the preceding claims.

14. A method for delivering hydroxy acids and aldehydes or ketones to a substrate comprising applying to said substrate a compound having the formula (I) below,

α)

1 2 1 2 wherein R and R are independently hydrogen or a hydrocarbyl moiety such that R COR is an aldehyde or ketone, and Q is a substituted or unsubstituted C. to C-₂ alkyl, alkenyl, aryl or alkaryl moiety, providing that from 1 to 3 contiguous carbon atoms of Q are part of the ring structure of the compound of formula-(I).

15. A method according to claim 14, wherein the substrate is human skin, hair, a fabric or a hard surface.

16. A perfume composition comprising at least one compound of formula (I) below

(I).

1 2 1 2 wherein R and R are independently hydrogen or a hydrocarbyl moiety such that R COR is an aldehyde or ketone, and Q is a substituted or unsubstituted C. to C_]2 alkyl, alkenyl, aryl or alkaryl moiety, providing that from 1 to 3 contiguous carbon atoms of Q are part of the ring structure of the compound of formula (I).