US00757617OB2

(12) United States Patent (10) Patent No.: US 7,576,170 B2 Perry et al. (45) Date of Patent: Aug. 18, 2009

(54) CYCLIC SILOXANE COMPOSITIONS FOR 6,046,156 A 4/2000 Perry THE RELEASE OF ACTIVE INGREDIENTS 6,054,547 A 4/2000 Perry et al. 6,063,365 A 5, 2000 Schefer et al. (75) Inventors: Robert J. Perry, Niskayuna, NY (US); 6,075,111 A 6/2000 Perry et al. Mark D. Leatherman, Elmsford, NY 6,077.923 A 6/2000 Perry et al. (US); Shahid Murtuza, Albany, NY 6,083,901 A 7/2000 Perry et al. (US) 6,121,343 A 9/2000 Hongo et al. 6,143,309 A 11/2000 Legrow et al. (73) Assignee: Momentive Performance Materials, 6,153,578 A 11/2000 Perry Albany, NY (US) 6,200,949 B1 3/2001 Reijmer et al. 6,228,380 B1 5, 2001 LeGrow et al. (*) Notice: Subject to any disclaimer, the term of this 6,262,287 B1 7/2001 Anderson et al. patent is extended or adjusted under 35 6,267,977 B1 7/2001 LeGrow et al. U.S.C. 154(b) by 993 days. 6,309,715 B1 10/2001 Lindauer et al. 6,322,777 B1 1 1/2001 Perry et al. (21) Appl. No.: 10/742,415 6,325,274 B2 12/2001 Esumi et al. 6,325,859 B1 12/2001 De Roos et al. (22) Filed: Dec. 19, 2003 6,435,423 B2 8/2002 Hurry et al. (65) Prior Publication Data 6,624,136 B2 9, 2003 Guerinet al. 2002/0156223 A1 10/2002 Boudjouket al. US 2005/O136O22 A1 Jun. 23, 2005 (51) Int. Cl. FOREIGN PATENT DOCUMENTS COSL 83/06 (2006.01) COSL 83/05 (2006.01) EP 106.124 A2 9, 1983 C08G 77/12 (2006.01) EP 106.124 B1 9, 1983 C08G 77/14 (2006.01) EP 273266 A2 12/1987 C08G 77/16 (2006.01) EP 273266 A3 12/1987 EP O334490 A2 2, 1989 (52) U.S. Cl...... 528/37; 528/25; 528/29: EP O334490 A3 2, 1989 528/31:528/33 EP O334490 B1 2, 1989 (58) Field of Classification Search ...... None EP 878497 A2 5, 1998 See application file for complete search history. EP 878497 A3 5, 1998 (56) References Cited EP O 878 497 A 11, 1998 EP O982 022 A 3, 2000 U.S. PATENT DOCUMENTS EP O982 O23 A 3, 2000 3,215,719 A 11, 1965 Allen et al. EP O998 911 A 5, 2000 3,271,305 A 9, 1966 Allen et al. 4,445,641 A 5, 1984 Baker et al. 4,500,725 A 2f1985 Yemoto et al. (Continued) 4,524,018 A 6, 1985 Yemoto et al. 4,908,208 A 3, 1990 Lee OTHER PUBLICATIONS 5,008, 115 A 4, 1991 Lee et al. 5,049,182 A 9, 1991 Scher et al. Daum, Jeremy et al: “Synthesis and characterization of novel 5,071,704 A 12/1991 Fischel-Ghodsian cyclosiloxanes and their self- and co-condensation with silanol-ter 5,130,171 A 7, 1992 Prud’Homme et al. minated polydimethylsiloxane' Polymer Reprints, vol. 45, No. 2, 5,139,864 A 8, 1992 Lindauer 2004, pp. 539-540, XP009048491.ISSN: 0032-3934, table 1. 5,160.494. A 1 1/1992 Krzysik et al. 5,176,903. A 1/1993 Goldberg et al. (Continued) 5,185,155 A 2f1993 Behan et al. Primary Examiner Michael J Feely 5,213,409 A 5, 1993 Fisher (74) Attorney, Agent, or Firm Kenneth S. Wheelock 5,234,689 A 8, 1993 Lindauer et al. 5,324.444 A 6/1994 Berry et al. (57) ABSTRACT 5,372,806 A 12/1994 Holloway 5,378.468 A 1/1995 Sufis et al. 5,387,411 A 2/1995 Abrutyn et al. Cyclic siloxanes that contain releasable active ingredients are 5,387,622 A 2f1995 Yamamoto described. The active ingredient can be an or enoliz 5.449,512 A 9, 1995 Simmons able carbonyl-containing compound Such as a ketone, alde 5.490,982 A 2f1996 Sicilliano hyde, or ester. The product siloxanes are useful in a variety of 5,500,223. A 3, 1996 Behan et al. personal and household care products where slow or con 5,525,555 A 6, 1996 Zank trolled release of active ingredient is desired. A preferred 5,525,588 A 6, 1996 Michetti embodiment utilizes substituents that when released as active 5,587,151 A 12/1996 Richard et al. 5,847,179 A 12/1998 LeGrow et al. ingredients are fragrant. 5,867,755 A 2, 1999 Sato 6,042,792 A 3, 2000 Shefer et al. 21 Claims, No Drawings US 7,576,170 B2 Page 2

FOREIGN PATENT DOCUMENTS trichlorophenylsilane and propyl and butyl alcohols'. EP 1178.107 A2 T 2000 XP00233 18909, Database accession No. 1988:75470, compounds EP 1178.107 A3 T 2000 under the registry Nos. 112671-14-4. 112671-15-5, 112671-21-3, EP 1116515 A2 12/2000 11261-22-4, 11267-28-0 & 112671-34-8 abstract—& Voprosky EP 1116515 A3 12/2000 Khimii I Khimicheskoi Tekhnologii, vol. 81, 1986, pp. 79-90, EP 1133929 A1 3, 2001 XPOO9048490 ISSN: 0321-4059. GB 971 309 A 9, 1964 Sprung M M et al: “The partial hydrolysis of GB 2041964. A 1, 1980 methyltrimethoxysilane” Journal of the American Chemical Society, GB 2042890 A 1, 1980 vol. 77, Aug. 5, 1955, pp. 4173-4 175, XP001206395, ISSN: 0002 JP 11047581 A 2, 1999 7863, Compounds II. JP 2002O2O783. A 1, 2002 WO WO9628497 A1 9, 1996 Okawara.

III US 7,576,170 B2 5 6

-continued -continued IV

10 where R' and R are each independently selected from the group consisting of hydrogen or C-C monovalent hydro carbon radicals. The quantity V is greater than or equal to 3. and the quantities w and u are each independently at least 1, 15 with the proviso that w--u must be equal to or greater than 3. R and R are each independently selected from the group consisting of H or C-C monovalent hydrocarbon radicals. The cyclic hydride employed may be a mixture of cyclics of -- --catalyst various sizes and concentrations. The following synthetic examples are intended to illustrate the general synthetic reactions schemes that a person having ordinary skill in the art of siloxane chemistry would typically employ in order to prepare the active-containing cyclic silox 25 anes used by the present invention. These reaction schemes are thus illustrative only and do not represent the only Syn thetic pathways that may be utilized. 30

Reaction scheme I:

The reaction of a carbonyl-containing active, as depicted in reaction schemes II and III, requires the establishment a car bonyl-enol tautomeric equilibrium, which is assisted by a base Such as triethylamine or a silanolate salt. Tautomerism is the chemical phenomenon of the establish ment of an equilibrium between two or more structurally distinct compounds. In nearly all cases, the difference between one tautomeric form of the equilibrium compounds and the other is the isomeric placement of a hydrogenatom. A prevalent form of tautomerism is the tautomeric equilibrium established between a carbonyl compound (i.e. one contain ing a carbonyl group) and having a hydrogen atom alpha to the carbonyl group, i.e. an a hydrogen:

When the starting active ingredient is an alcohol, as depicted in reaction scheme I, the corresponding alkoxysi loxane is produced, preferably in the presence of a suitable 55 catalyst. H. O f H

Keto Form Enol Form Reaction scheme II: 60 Generally the equilibrium constant favors the keto form and the equilibrium lies well to the left. The extent of eno -- Hercatalyst lization is greatly affected by Solvent, concentration and tem 65 perature. When a strong base is present, both the enol and the keto form can lose a hydrogen ion (a proton), forming an enolate anion: US 7,576,170 B2 8 The syntheses described above are preferably performed in the presence of a catalyst. For active-containing siloxanes derived from alcohols, several families of catalysts can be used. These include but are not limited to transition metal catalysts, bases, and Lewis acids. Representative transition metal catalysts that may be used in forming the active-containing cyclic siloxanes of the present invention are illustrated by, but not limited to those that are suitable for hydrosilylation reactions. Many types of Since both of these structures differ only in the placement of 10 platinum catalysts for this reaction (hydrosilation or hydrosi electrons, these are canonical forms of the same ion rather lylation) are known, and Such platinum catalysts may be used than tautomeric isomers. Because oxygen is more electrone gative than carbon, the predominate canonical form is the one for the reaction in the present instance. The following where the ionic charge is more localized on the oxygenatom. examples are illustrative and are not intended to limit the While the tautomeric equilibrium between enols and ketones 15 Scope of catalysts that can be used. The platinum compound or aldehydes is not normally a preparative reaction, the equi can be selected from those having the formula (PtClOlefin) and H(PtClOlefin), as described in U.S. Pat. No. 3,159,601, librium must occur since ketones and aldehydes often react hereby incorporated by reference. A further platinum-con through their enol forms as they do instantly in the prepara taining material usable in the compositions of the present tion of the compounds of the present invention. This keto invention is the cyclopropane complex of platinum chloride enol tautomeric equilibrium is also established for esters or described in U.S. Pat. No. 3,159,662, hereby incorporated by organic acids, i.e. in the structures above when Rincludes an reference. Further, the platinum-containing material can be a oxygen bound to an appropriate R group, e.g. OR', the com complex formed from chloroplatinic acid with up to 2 moles pound is an organic ester. For a more detailed explanation of per gram of platinum of a member selected from the class this chemistry see J. March “Advanced Organic Chemistry.” 25 consisting of alcohols, ethers, aldehydes and mixtures of the John Wiley & Sons, New York (1985), pp. 66-68 and 527-529 above as described in U.S. Pat. No. 3,220,972, hereby incor and references therein. porated by reference. The catalysts preferred for use are Fragrant molecules, alcohols, ketones and aldehydes, may described in U.S. Pat. Nos. 3,715,334: 3,775,452; and 3,814, be reacted as the alcohol or enol tautomer to produce silicone 730 to Karstedt. Other platinum examples include dipotas or siloxanes bearing fragrant moieties. The reaction involves 30 sium tetrachloroplatinate, platinum metal and platinum reaction of the alcoholic or enolic form of the molecule with halides. Possible rhodium catalysts include but are not limited hydrogen, hydroxyl or halogen directly bonded to a silicon to tris(dibutylsulfide)rhodium(III)trichloride, chlorotris atom to form the fragrant derivative. The reaction involves (triphenylphosphine)rhodium(I), Rh(O), rhodium halides, formation of the conjugate base related to the alcohol or enol and complexes of the type (diolefin) RhCl where “diole 35 fin” refers to a diene or two monoalkenes,. Catalysts based on tautomeric form of the molecule: palladium, nickel, rhenium, ruthenium, osmium, copper, FragOH dissociates to H' and FragOT (conjugate base); cobalt, and iron may also be used. Furthermore, heteroge where FragOH is a fragrant alcohol or the enol form of a neous catalysts can be used, whereby catalytic metals or fragrant ketone or aldehyde. Aldehydes and ketones react metal complexes such as those mentioned above have been with alcohol(s) R'OH to form hemiacetals (derived from alde 40 Supported on a solid organic or inorganic Substance Such as hydes) or hemiketals (derived from ketones): RCH(O)+ silica, alumina, carbon, titania, Zirconia, diatomaceous earth, ROH->RCH(OH)(OR") hemiacetal, which has a conjugate clay, Zeolite, or a polymeric Substrate. Additional background base obtained by removing the hydroxyl hydrogen: RCH(O) concerning the art may be found in J. L. Spier, "Homogeneous (OR) and RC(O)R"+R'OH->RC(OH)(R'O)R" which has a Catalysis of Hydrosilation by Transition Metals, in Advances conjugate base likewise obtained by removing the hydroxyl 45 in Organometallic Chemistry, volume 17, pages 407 through hydrogen: RC(O)(R'O)R". As used herein the various Frag 447, F. G. A. Stone and R. West editors, published by the are fragrant moieties, i.e. monovalent radicals, either as a Academic Press (New York, 1979). neutrally charged monovalent radical (Frag or FragO) or as a Representative base catalysts that may be used in forming charged monovalent radical, derived from the conjugate the active-containing cyclic siloxanes of the present invention bases of fragrant molecules, e.g. Frag"+O’->FragO, where 50 are illustrated by but not limited to ionic compounds Such as the monovalent radicals are monovalent hydrocarbon radicals hydroxides, siloxane or polysiloxanes containing one or more having from one to one hundred carbon atoms, preferably silanolate groups, amides, alkoxides that possess a lithium, four to one hundred carbonatoms, more preferably five to one Sodium, potassium, rubidium, cesium, magnesium, calcium, hundred carbonatoms and most preferably six to one hundred strontium, or barium countercation. Nonionic bases Such as carbonatoms where the radical may also contain heteroatoms 55 Such as oxygen, Sulfur, nitrogen, phosphorus and the halo ammonia and amines can also be used as catalysts. gens fluorine, chlorine, bromine and iodine. Representative Lewis acid catalysts that may be used in While the tautomeric equilibrium between enols and their forming the active-containing cyclic siloxanes of the present corresponding carbonyl-containing compounds is not nor invention are illustrated by but not limited to BF. FeCls, mally a preparative reaction, the equilibrium must occur since 60 AlCls, ZnCl2, ZnBr, or Lewis acid catalysts of formula (V) carbonyl-containing compounds often react through their MRX, (V) enol forms, as they do instantly in the preparation of the compounds of the present invention. As the enol form reacts wherein M is B, Al, Ga. In or Tl; R are independently the to give the desired product, more of the carbonyl form tau same (identical) or different and represent a monovalent aro tomerizes to the enol form to maintain equilibrium until the 65 matic hydrocarbon radical having from 6 to 14 carbon atoms entirety of the carbonyl-containing compound has reacted to with at least one electron-withdrawing element or group Such give the enol-functionalized siloxane. as —CF —NO or —CN, or with at least two halogen US 7,576,170 B2 9 10 atoms; X is a halogenatom; S is 1, 2, or 3; and tis 0, 1 or 2; with neohesperidin dihydrochalcone, neomenthol, nerol, neroli the proviso that s+t=3, and more preferably a Lewis acid of dol, trans-2-cis-6-nonadienol, 1.3-nonanediol acetate, non formula (VI) adyl, 2-nonanol, cis-6-nonen-1-ol, trans-2-nonen-1-ol, nonyl alcohol, 1-octanol, 2-octanol, 3-octanol, cis-3-octen-1-ol. BRX, (VI) 5 cis-2-octen-1-ol, trans-2-octen-1-ol, cis-6-octen-1-ol, cis octen-1-ol. 1-octen-3-ol, , patchouli alcohol, wherein R'' are independently the same (identical) or differ 3-pentanol, n-pentanol. 2-pentanol, 1-penten-1-ol, cis-2- ent and represent a monovalent aromatic hydrocarbon radical penten-1-ol, perillyl alcohol. 2-phenoxyethanol arabinoga having from 6 to 14 carbon atoms with at least one electron lactan, B-, phenethyl salicylate, phenol, withdrawing element or group such as —CF, —NO or 10 phenylacetaldehyde glyceryl acetal, 3-phenyl-1-pentanol, —CN, or with at least two halogen atoms: X is a halogen 5-phenyl-1-pentanol, 1-phenyl-1-pentanol. 1-phenyl-2-pen atom; s is 1, 2, or 3; and t is 0, 1 or 2; with the proviso that tanol. 1-phenyl-3-methyl-1-pentanol, phytol, pinacol, poly s+t=3, most preferably B(CFs). alkylene glycols, polysorbate 20, polysorbate 60, polysorbate It should be noted that while the starting cyclic silicone 80, prenol, n-propanol, propenyl guaethol, propylene glycol, hydrides are generally unbranched molecules, hydrolysis 15 2-propylphenol, 4-propylphenol, resorcinol, retinol, salicyla before reaction of the active ingredient or after formation of ldehyde, Sorbitan monostearate, , , the active-containing siloxane can lead to branched struc Syringealdehyde, C-terpineol, tetrahydrogeraniol, tetrahy tures, as delineated by Subscripts q and t in formulas I and II, drolinalool, tetrahydromyrcenol, thymol, triethylcitrate, 1.2, respectively. 6-trihydroxyhexane, p-O.C.-trimethylbenzyl alcohol, 2-(5.5, Representative alcohols that may be used in forming the 6-trimethylbicyclo[2.2.1]hept-2-ylcyclohexanol, 5-(2,2,3- active-containing cyclic siloxanes of the present invention are trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol. 3.7-11 illustrated by, but not limited to acetovanillone, allyl amylg trimethyl-2,6,10-dodecatrien-1-ol. 3,7,11-trimethyl-1,6,10 lycolate, allyl isoamylglycolate, C.-amylcinammyl alcohol, dodecatrien-3-ol, 3.5.5-trimethyl-1-hexanol, 10-undecen-1- anisyl alcohol, benzoin, benzyl alcohol, benzyl salicylate, ol, undecyl alcohol, Vanillin, o-vanillin, vanillyl butyl ether, 1-butanol, butylated hydroxytoluene, butyl lactate, 2-t-butyl 25 4-vinylphenol, 2.5-Xylenol. 2,6-Xylenol. 3.5-Xylenol. 2,4-Xy 5-methylphenol, 2-t-butyl-6-methylphenol, carvacrol, car lenol, and Xylose. Veol, 4-carvomenthenol, cedrol, , cinnamic alco Representative carbonyl-containing actives or carbonyl hol, citronellol, o-cresol, m-cresol, p-cresol, crotyl alcohol, decahydro-2-naphthol. 1-decanol. 1-decen-3-ol, 9-decen-1- active ingredients that may be used in forming the fragrant ol, diethyl malate, diethyl tartrate, dihydrocarveol, dihy 30 cyclic siloxanes of the present invention are illustrated by, but dromyrcenol. 2,6-diisopropylphenol, dimethicone copolyol. not limited to 4-acetoxy-3-pentyl-tetrahydropyran, allyl cin 2,6-dimethoxyphenol, 1,1-dimethoxy-3,7-dimethyloctan-7- namate, allyl 2-ethylbutyrate, allyl cyclohexanepropionate, ol. 2,6-dimethyl-4-heptanol. 2,6-dimethylheptan-2-ol. 6,8- allyl heptanoate, allyl hexanoate, allyl isovalerate, allyl dimethyl-2-nonanol. 3,7-dimethyl-2,6-octadien-1-ol. 3,7- nonanoate, allyl octanoate, allyl phenoxyacetate, allyl phe dimethyl-1,6-octadien-3-ol, 3,7-dimethyl-1-octanol, 3.7- 35 nylacetate, allyl propionate, C.-amylcinnamyl acetate, amyl dimethyl-3-octanol, 3,7-dimethyl-6-octen-1-ol. 3,7- octanoate, anisyl acetate, anisylphenyl acetate, benzyl dimethyl-7-octen-1-ol. dimetol, 2-ethylfenchol, acetate, benzyl acetoacetate, benzyl butyrate, benzyl cin 4-ethylguaiacol, 2-ethyl-1-hexanol, ethyl 2-hydroxyben namate, benzyl isobutyrate, benzyl isovalerate, benzyl phe Zoate, ethyl 3-hydroxybutyrate, 3-ethyl-2-hydroxy-2-cyclo nylacetate, benzyl propionate, bornyl acetate, bornyl isoval penten-1-one, ethyl 2-hydroxycaproate, ethyl 3-hydroxyhex 40 anoate, ethyl lactate, ethyl maltol, p-ethylphenol, ethyl erate, bornyl valerate, butyl acetate, butyl butyrate, butyl salicylate, eugenol, farnesol, fenchyl alcohol, geraniol, glu butyryllactate, 4-t-butylcyclohexyl acetate, butylheptanoate, cose petaacetate, , glyceryl monostearate, guaiacol, butyl hexanoate, butyl isobutyrate, butyl isovalerate, butyl 1-heptanol, 2-heptanol, 3-heptanol, cis-4-heptenol, cis-3- laurate, butyl propionate, butyl stearate, 3-butylidenephtha heptenol, n-hexanol, 2-hexanol, 3-hexanol, cis-2-hexenol, 45 lide, butyl 2-methylbutyrate, butyl 10-undeceneoate, Y-buty cis-3-hexenol, trans-3-hexenol, 4-hexenol, cis-3-hexenyl rolactone, carvyl acetate, carvyl propionate, caryophyllene hydrocinnamyl alcohol, 2-hydroxybenzoate, 2-hydroxyac acetate, cedryl acetate, trans-cinnamyl acetate, trans-cin etophenone, 4-hydroxybenzyl alcohol, 3-hydroxy-2-bu namylbutyrate, cinnamyl cinnamate, cinnamyl isobutyrate, tanone, hydroxycitronellal, 4-(4-hydroxy-3-methoxyphe citronellyl acetate, citronellyl butyrate, citronellyl isobu nyl)-2-butanone, 2-hydroxy-3-methyl-2-cyclopenten-1-one, 50 4-(p-hydroxyphenyl)-2-butanone, 2-hydroxy-3.5.5-trim tyrate, citronellyl propionate, citronellyl Valerate, cyclohex ethyl-2-cyclohexenone, 6-isoascorbic acid, isoborneol. aneethyl acetate, cyclohexyl acetate, cyclohexyl butyrate, isoeugenol, isophytol, , p-isopropylbenzyl cyclohexyl isovalerate, cyclohexyl propionate, 6-decallac alcohol, 4-isopropylcylcohexanol, 3-isopropylphenol, 4-iso tone, e-decalactone, y-decalactone, 4-decanolide, decyl propylphenol, 2-isopropylphenol, isopulegol, lauryl alcohol, 55 acetate, decyl butyrate, decyl propionate, diethyl malonate, linalool, maltol, menthol, 4-methoxybenzyl alcohol, 2-meth diethyl sebacate, diethyl Succinate, dihydrocarvyl acetate, oxy-4-methylphenol, 2-methoxy-4-propylphenol, 2-meth dihydrocoumarin, dihydromyrcenyl acetate, dihydro-nor-di oxy-4-vinylphenol, C.-methylbenzyl alcohol, 2-methylbu cyclopentadienyl acetate, dihydroterpinyl acetate, 3.7-dim tanol, 3-methyl-2-butanol, 3-methyl-2-buten-1-ol, 2-methyl ethyl-1,6-octadien-3-yl acetate, 3,7-dimethyl-1,6-octadien 3-buten-2-ol, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 60 4-methyl-2,6-dimethoxyphenol, methyl N-3,7-dimethyl-7- 3-yl propionate, 3.7-dimethyloctan-3-yl acetate, C.C.- hydroxyoctylideneanthranilate, methyl 3-hydroxyhexanoate, dimethylphenethyl acetate, C.C.-dimethylphenethylbutyrate, 6-methyl-5-hepten-2-ol, 2-methylpentanol, 3-methyl-3-pen 6,10-dimethyl-5.9-undecadien-2-yl acetate, 6-dodecallac tanol, 2-methyl-4-phenylbutan-2-ol, 2-methyl-3-phenylpro tone, e-dodecalactone, Y-dodecalactone, ethyl acetate, ethyl pan-2-ol, methyl salicylate, 3-methyl-5-(2.2.3,-trimethyl-3- 65 acetoacetate, ethyl 6-acetoxyhexanoate, ethyl 2-acetyl-3- cyclopenten-1-yl)-4-penten-2-ol, 2-methyl-2-vinyl-5-(1- phenylpropionate, ethylbenzoylacetate, 2-ethylbutyl acetate, hydroxy-1-methyl ethyl)-3,4-dihydrofuran, myrtenol, ethyl butyrate, ethyl cinnamate, ethyl cyclohexanepropi US 7,576,170 B2 11 12 onate, ethyl decanoate, ethylene brassylate, ethyl 2-ethyl-6, isobutyrate, octyl isovalerate, octyl octanoate, octyl propi 6-dimethyl-2-cyclohexenecarboxylate, ethyl 2,3-epoxybu onate, oxacycloheptadec-10-en-2-one, ()-pentadecalactone, tyrate, ethyl 2-methyl-4-penteneoate, ethylheptanoate, ethyl pentyl acetate, penty1 butyrate, pentyl hexanoate, pentyl hexanoate, ethyl trans-3-hexenoate, 2-ethylhexyl acetate, octanoate, phenethyl acetate, phenethylbutyrate, phenethyl ethyl isobutyrate, ethyl isovalerate, ethyl laurate, ethyl 2-mer cinnamate, phenethyl hexanoate, phenethyl isobutyrate, captopropionate, ethyl 3-mercaptopropionate, ethyl 2-meth phenethyl isovalerate, phenethyl 2-methylbutyrate, phen ylbutyrate, ethyl 2-methylpentanoate, ethyl (methylthio)ac ethyl 2-methylbutyrate, phenethyl 2-methylpropionate, etate, ethyl myristate, ethylnonanoate, ethyl octanoate, ethyl phenethyl octanoate, phenethyl phenylacetate, phenethyl palmitate, ethyl phenylacetate, ethyl 3-phenylpropionate, 10 propionate, phenoxyethyl propionate, 2-phenoxyethyl 2-me ethyl 3-phenyl-2,3-epoxybutyrate, ethyl 3-phenylpropionate, thylpropionate, 3-phenyl-2-propenyl propionate, 3-phenyl ethyl propionate, ethyl stearate, ethyl 2.3.6.6-tetramethyl-2- propyl acetate, 2-phenylpropyl butyrate, 2-phenylpropyl cyclohexencarboxylate, ethyl (p-tolyloxy)acetate, ethyl isobutyrate, 2-phenylpropyl isovalerate, piperonyl acetate, undecanoate, ethyl Valerate, eugenyl acetate, fenchyl acetate, piperonyl isobutyrate, prenyl acetate, propyl acetate, propyl geranyl acetate, geranyl butyrate, geranyl phenylacetate, 15 butyrate, propylheptanoate, propylhexanoate, 3-propylide geranyl propionate, guaiacyl phenylacetate, guaicwood nephthalide, propyl isobutyrate, propyl propionate, propyl acetate, Y-heptalactone, heptyl acetate, heptylbutyrate, heptyl phenylacetate. Sucrose octaacetate, terpinyl acetate, terpinyl isobutyrate, ()-6-hexadecenlactone, 6-hexalactone, Y-hexa butyrate, terpinyl isobutyrate, terpinyl propionate, Ö-nonalac lactone, 3-hexenyl acetate, cis-3-hexenyl 2-methylbutanoate, tone, tetrahydrofurfuryl acetate, tetrahydrofurfuryl butyrate, cis-3-hexenyl cis-3-hexenoate, cis-3-hexenyl phenylacetate, tetrahydrofurfuryl propionate, tetrahydrolinallyl acetate, 2.6. trans-2-hexenyl acetate, hexyl acetate, hexylbutyrate, hexyl 6,8-tetramethyl-tricyclo5.3.1.0(1.5)udecan-8-yl acetate, hexanoate, hexyl isobutyrate, hexyl propionate, hexyl 2-me p-tolyl acetate, p-tolyl isobutyrate, p-tolyl phenylacetate, tri thylbutanoate, hexyl 3-methylbutanoate, hexyl phenylacetate, acetin, tributyl acetylcitrate, tributyrin, tripropionin, 3.5.5- isoamyl acetate, isoamyl acetoacetate, isoamyl butyrate, 25 trimethylhexyl acetate, 6-undecalactone, Y-undecalactone, isoamyl cinnamate, isoamylhexanoate, isoamyl isobutyrate, Y-Valerolactone, Vanillin acetate, Vanillyl isobutyrate, 1-vi isoamyl isovalerate, isoamyl laurate, isoamyl nonanoate, nyl-2-(1-methylpropyl)cyclohexyl acetate, and whiskey lac isoamyl octanoate, isoamyl phenylacetate, isoamyl propi tOne. onate, isobornyl acetate, isobomyl propionate, isobutyl 30 Representative carbonyl-containing actives that may also acetate, isobutylbutyrate, isobutyl cinnamate, isobutyl hex be used informing the fragrant cyclic siloxanes of the present anoate, isobutyl isobutyrate, isobutyl 2-methylbutyrate, invention are illustrated by but not limited to butyraldehyde, isobutyl propionate, isoeugenylacetate, isopropyl cinnamate, citronellal, decanal, cis-4-decenal, trans-4-decenal, 2,4-dim isobutyl phenylacetate, isopropyl acetate, isopropylbutyrate, ethyl-3-cyclohexen-1-carbaldehyde, 2,6-dimethyl-5-hepte isopropyl isobutyrate, isopropyl myristate, isopropyl palmi 35 nal,3,7-dimethyloctanal, 2-ethylbutyraldehyde, glutaric dial tate, isopropyl phenylacetate, lauryl acetate, linallyl acetate, dehyde, heptanal, cis-4-heptenal, hexanal, linallyl butyrate, linallyl isovalerate, menthalactone, menthyl hydrocinnamaldehyde, isobutyraldehyde, 3-(p-isopropy acetate, menthyl cyclohexanecarboxylate, menthyl isovaler lphenyl)propionaldehyde, isovaleraldehyde, lauric aldehyde, ate, 4-methoxybenzyl acetate, 4-methoxybenzyl propionate, 2-methylbutyraldehyde, 2-methyl-3-(p-isopropylphenyl) 2-methoxyphenyl acetate, 2-methoxy-4-(1-propenyl)phenyl 40 propionaldehyde, 2-methylpentanal, 4-(4-methyl-3-pente acetate, methyl acetate, C.-methylbenzyl acetate, C.-methyl nyl)-3-cyclohexen-1-carbaldehyde, 4-methylphenylacetal benzyl butyrate, C.-methylbenzyl propionate, 2-methylbutyl dehyde, 3-(methylthio)butanal, 2-methyl-4-(2,6,6-trimethyl acetate, 2-methylbutylbutyrate, 2-methylbutyl isovalerate, 2-cyclohexen-1-yl)butanal, 2-methylundecanal, nonanal, 3-methylbutyl 2-methylbutanoate, 2-methylbutyl 2-meth 45 cis-6-nonenal, octanal, phenylacetaldehyde, 2-phenylpropi ylbutanoate, methyl p-t-butylphenylacetate, methylbutyrate, onaldehyde, 3-phenylpropionaldehyde, propionaldehyde, methyl cinnamate, methyl decanoate, methyl heptanoate, p-tolylacetaldehyde, tridecanal. 2,4,6-trimethyl-3-cyclo methyl hexanoate, methyl isobutyrate, methyl isovalerate, hexen-1-carbaldehyde, 2,6,10-trimethyl-9-undecanal, 7-un methyl laurate, methyl N-2-methyl-3-(4-t-butylphenylpropy decenal, 8-undecenal, 9-undecenal, 10-undecenal, and Valer lidene) anthranilate, methyl (methylthio)acetate, methyl 50 aldehyde. 2-(methylthio) propionate, methyl myristate, methyl Representative carbonyl-containing actives that may also nonanoate, methyl octanoate, methyl palmitate, 4-(4-methyl be used informing the fragrant cyclic siloxanes of the present 3-pentenyl)-3-cyclohexenylmethylacetate, methyl 2-methyl invention are illustrated by but not limited to acetanisole, butyrate, 2-methyl-6-methylen-7-octen-2-yl acetate, methyl 55 1'-acetonaphthone, 2-acetonaphthone, acetone, acetophe 4-methylvalerate, methyl 2-methylpentanoate, methyl phe none, 2-acetoxy-2,5-dimethyl-3(2H)furanone, 2-acetylcy noxyacetate, 4-methylphenyl phenylacetate, 2-methyl-3- clopentanone, 4-acetyl-1,1-dimethyl-6-t-butylindan, phenylpropan-2-yl acetate, methyl 3-phenylpropionate, 7-acetyl-1.1.3.4.4.6-hexamethylindan, 2-acetyl-2-thiazoline, methyl propionate, 2-methylpropyl phenylacetate, methyl 6-acetyl-1,1,2,4,4,7-hexamethyltetralin, allyl C-ionone, ben phenylacetate, 2-methyl-3-phenylpropan-2-yl acetate, 60 Zylideneacetone, 2,3-butanedione, 2-sec-butylcyclohex methyl Stearate, methyl (p-tolyloxy)acetate, methyl 9-unde anone, 5-t-butyl-3,5-dinitro-2,6-dimethylacetophenone, cenoate, methyl Valerate, myrtenyl acetate, neryl acetate, butyrophenone, camphor, 2-decanone, 3-decanone, 3-decen neryl butyrate, neryl isobutyrate, Ö-nonalactone, Y-nomalac 2-one, dihydrocarvone, dihydro-p-ionone, dihydrojasmone, tone, 1.3-nonanediol diacetate, nonyl acetate, nopyl acetate, 65 4,5-dihydro-3(2H)-thiophenone, 2',4'-dimethylacetophe octahydrocoumarin, Y-octalactone, 1-octen-3-yl acetate, none, 3,4-dimethyl-1,2-cyclopentadione, 3.5-dimethyl-1,2- 1-octen-3-yl butyrate, octyl acetate, octyl butyrate, octyl cyclopentadione, 2,6-dimethyl-4-heptanone, 1,3-diphenyl-2- US 7,576,170 B2 13 14 propanone, 4-(1-ethoxyvinyl)-3,3,5,5-

tetramethylcyclohexanone, p-ethylacetophenone, ethyl vinyl ketone, geranylacetone, 2.3-heptanedione, 2-heptanone, 3-heptanone, 4-heptanone, 3,4-hexanedione, 3-hexanone, 4-hexen-3-one, 2-hexylidene cyclopentanone, C.-ionone, B-ionone, 4-isobutyl-2,6-dimethyl-3,5-dinitroacetophenone, isophorone, 6-isopropyldecahydro-2-naphthone, cis-as mone, livescone, 4-methoxyacetophenone, 4-(p-methox yphenyl)-2-butanone, 4'-methylacetophenone, 3-methyl-1,2- 10 cyclohexanedione, 3-methyl-2-cyclohexen-1-one, 2-(2-(4- methyl-3-cylcohexen-1-yl)propyl)cyclopentanone, 3-methyl-2-cyclopenten-1-one, methyl dihydrojasmonate, methyl ethylketone, 2-methyl-3-heptanone, 5-methyl-2-hep 15 ten-4-one, 6-methyl-5-hepten-2-one, 5-methyl-cC.-ionone, 1-(2-methyl-5-isopropyl-2-cyclohexenyl)-1-propanone, 4-methyl-2-pentanone, 3-methyl-2-(2-pentenyl)-2-cyclo penten-1-one, 4-methyl-1-phenyl-2-pentanone, 2-methyltet rahydrofuran-3-one, 2-methyltetrahydrothiophen-3-one, 2-nonanone, 3-nonanone, 2-octanone, 3-octanone, 1-octen 3-one, 3-octen-2-one, 4-oxoisophorone, 2-pentadecanone, 2,3-pentanedione, 2-pentanone, 3-pentanone, 3-penten-2- 25 one, 1-phenyl-1,2-propandione, propiophenone, pulegone, 2-tridecanone, 2.2,6-trimethylcyclohexanone, 4-(2,6,6-trim ethyl-2-cylcohexen-1-yl)-3-methyl-3-buten-2-one, 2-unde canone, and 6-undecanone. 30 The active-releasing siloxanes of the present invention are prepared via displacement of a hydride from a cyclic silyl hydride. Thus an organohydrogen siloxane having formula III or IV: 35 where the components and Subscripts satisfy the previous definitions and requirements. This siloxane undergoes a slow III hydrolysis under most conditions of use whereby the siloxane releases an active ingredient upon hydrolysis. This imparts a 40 desirable effect to many different useful compositions such as cosmetics and household products. The active-releasing compounds of the present invention are particularly Suited to incorporation into personal care IV 45 products to impart a long-lasting, desirable effect to the prod ucts. Suitable uses include but are not limited to deodorants; antiperspirants; skin creams; facial creams; hair care products Such as shampoos, mousses, and styling gels; insect repel lants; protective creams; shaving creams; after shave: cologne; perfume; color cosmetics such as lipsticks, founda 50 tions, blushes, makeup, and mascara; and other cosmetic formulations where other silicon containing components may have been added and where a certain effect is desired. where R' and R are each independently selected from the Incorporation of small amounts of the compositions of the group consisting of hydrogen or C-C monovalent hydro 55 present invention into fragrance products such as shaving carbon radicals. The quantity V is greater than or equal to 3. lotions, colognes, toilet water, and perfumes can impart a desirable long lasting fragrance to these products. Further, the and the quantities w and u are each independently at least 1, fragrant cyclic siloxanes of the present invention may be with the proviso that w--u must be equal to or greater than 3. incorporated into other products where it is desirable to mask R and R are each independently selected from the group 60 unpleasant odors with a pleasant fragrance, for example consisting of H or C-C monovalent hydrocarbon radicals. household cleaning products such as waxes and polishes, The cyclic hydride employed may be a mixture of cyclics of automobile cleaning products such as waxes and polishes, various sizes and concentrations. detergents, textile coatings, paints, and varnishes. In addition, the active-containing cyclic siloxanes of the The cyclic silicone hydride is reacted under conditions as 65 present invention may be used in laundry applications such as outlined above to produce an active-releasing siloxane having rinse additives, softeners and the like, subject to the limitation formula I or II: that the active-containing cyclic siloxanes of the present US 7,576,170 B2 15 16 invention be compatible or capable of being rendered com (42 mg of solution, 100 ppm Rh) were stirred together at patible with the product in which it is incorporated. ambient temperature. A mixture of cyclic silicone hydrides Experimental (3.37 g., 0.055 molhydride) was added dropwise over 75 min and stirred for an additional 75 min. The solution was heated EXAMPLE1 5 to 70° C., at which gas evolution was observed. After stirring at 70° C. for 18.5 h, the solution was dark gray-green. The Citronellol (5.89 g, 0.038 mol) and a mixture of cyclic flask was cooled to ambient temperature, and the volatiles silicone hydrides (2.0 g, 0.033 mol) were added together, were removed under vacuum at 70° C./1.2 mm Hg for 1.5 h. mixed and treated with potassium silanolate-functionalized The product was filtered to give 7.65 g product (76.5%). silicone (0.02 g, 0.015 mmol). After stirring for 15 min, the 10 solution was heated to 60°C. for 18h. Volatiles were removed EXAMPLE 7 by vacuum stripping at 80°C./6 mm Hg for 1 h to give product (6.5g, 91%). In a roundbottom flask, citronellol (7.26g, 0.046 mol) and a 1.36% Rh solution of ("BuS)RhCls in (35 mg of EXAMPLE 2 15 solution, 100 ppm Rh) were stirred together at ambient tem perature. A mixture of cyclic silicone hydrides (2.83 g, 0.046 A mixture of cyclic silicone hydrides (6.50 g., 0.108 mol mol hydride) was added dropwise over 55 min. The solution hydride) was charged to a roundbottom flask. Citronellol was heated to 70° C.; gas evolution was observed within (18.58 g., 0.119 mol) and a 10.9% solution of Pt(0) in divi minutes. After stirring at 70° C. for 40h, the flask was cooled nyltetramethylsiloxane (28.9 mg of solution, 126 ppm Pt) 20 to ambient temperature, and the volatiles were removed under were miscibilized and added dropwise to the hydride over 45 vacuum at 70°C/1-2 mm Hg for 1 h. The product was filtered min. Gas evolution was observed. The flask was then heated to give 7.85g of dark gray fluid (78.5%). to 70° C. for 68 h, after which volatiles were removed from the pale brown solution by vacuum stripping at 70° C./2 mm Hg for 3 h to give 22.77 g product (98%). 25 EXAMPLE 8 EXAMPLE 3 In a roundbottom flask, acetophenone (6.74g, 0.056 mol) and 4.3% KOH-equivalent potassium silanolate-functional A mixture of cyclic silicone hydrides (7.75 g, 0.129 mol silicone (0.073 g, 56 umol) were dissolved in 15 mL toluene hydride) was charged to a roundbottom flask, which was at ambient temperature. The pure cyclic silicone hydride 1.3, heated to 70° C. Phenethyl alcohol (17.32g, 0.142 mol) and 5,7-tetramethycyclotetrasiloxane (3.37 g., 0.056 molhydride) a 10.9% solution of Pt(O) in divinyltetramethylsiloxane (6.7 was added dropwise over 30 min. Gas evolution was mg of solution, 29 ppm Pt) were miscibilized and added observed. Following the addition, the solution stirred at ambi dropwise to the hydride over 2 h. Gas evolution was observed. ent temperature for 2 h. The solution was then heated to 70° C. The paleyellow solution stirred at 70° C. for 5.5 d, after which and stirred for 2 h. Volatiles were removed at 70° C./5 mm Hg volatiles were removed from the solution by vacuum strip 35 for 1.5 h. The product was filtered to give 8.30 g of pale ping at 80° C.71 mm Hg for 4 h to give 23.14 g product orange fluid (83%). (99.5%). EXAMPLE 4 EXAMPLE 9 40 In a roundbottom flask, tris(pentafluorophenyl)borane In a roundbottom flask, hexanal (6.33 g, 0.063 mol), tolu (42.7 mg, 83.4 umol) was dissolved in eugenol (15.04 g. ene (15g), triethylamine (0.012 g, 0.126 mmol), and a 10.9% 0.092 mol) to give a bright yellow solution. A mixture of solution of Pt(O) in divinyltetramethylsiloxane (17 mg of cyclic silicone hydrides (5 g, 0.083 mol hydride) was added solution, 150 ppm Pt) were stirred for 10 min at ambient dropwise, clouding the solution. The addition was complete 45 temperature. The pure cyclic silicone hydride 1,3,5,7-tetram in 7 min, giving a milky mixture. After 30 min of stirring, gas ethylcyclotetrasiloxane was added dropwise over 15 min. evolution was observed, and the mixture cleared to give a pale Gas evolution was observed, and the mixture was heated to yellow solution which stirred at ambient temperature for a and held at 70° C. for 24 h. after which an another charge of total of 14.5 h. Volatiles were removed under vacuum at 70° the 10.9% solution of Pt(O) in divinyltetramethylsiloxane (17 C./0.1 mm Hg for 5 h. The mixture was filtered, yielding 50 mg of solution added, 300 ppm Pt total) was added. The 17.89 pale yellow liquid (97%). mixture was stirred another 12 hat 70° C. then stripped at 70° C./3 mm Hg for 1.5 h to give a maroon fluid 8.3 g of maroon EXAMPLE 5 fluid (83%). In a roundbottom flask, 2-isopropylphenol (13.94g, 0.102 EXAMPLES 10-14 mol) and tris(pentafluorophenylborane) (0.052 g, 101 umol) 55 were stirred for 15 min, giving a pale green-yellow solution. Hydrolysis of Products From Examples 2,4,5,6, and A mixture of cyclic silicone hydrides (6.23 g, 0.102 mol 8, Respectively hydride) was added dropwise over 1 h. Hydrogen gas evolu tion was observed during the addition. The solution was 60 The general procedure for hydrolysis is as follows: stirred for 40 min at ambient temperature, then at 50° C. for A solution of the active ingredient-functional silicone (1.0 2.5 h. Volatiles were removed under vacuum at 70° C. (3 mm g), tetrahydrofuran (10g), and bibenzyl internal standard (0.4 Hg) for 1.5h, yielding 16.5 g (82.5%). g) was prepared. The Solution was analyzed by gas chroma EXAMPLE 6 tography, then 0.50 mL of 1% (wt.) aqueous sodium hydrox 65 ide solution was added (except for example 9, in which 0.125 In a roundbottom flask, phenethyl alcohol (6.74 g., 0.055 mL of 1% aqueous Sodium hydroxide Solution was used). The mol) and a 1.36% Rh solution of ("BuS)RhCls in ethanol mixture was stirred and periodically sampled for gas chroma US 7,576,170 B2 17 18 tography analysis. Tables 1-5 demonstrate the release profiles determined in examples 10-14, respectively. TABLE 5-continued

TABLE 1. Hydrolysis of product from Example 8. Relative acetophenone Hydrolysis of product from Example 2. Time (h) concentration Relative citronellol 27.17 O921 Time (h) concentration 49.75 1.121 71.66 1.156 O.OS O.303 10 140.92 12O2 5.25 O.432 21.00 O.S83 29.58 O621 37.76 O.662 EXAMPLES 15 and 16 45.66 O663 54.11 O.696 15 78.05 0.723 Hydrolysis of Products From Examples 3 and 8, 144.77 O.757 Respectively 219.8O O.749 The general procedure for hydrolysis is as follows: A 3.3 cm by 3.3 cm swatch of untreated cotton cloth was soaked with each material Such that the molar equivalents of TABLE 2 active ingredient were equal between all of the samples. Each Hydrolysis of product from Example 4. Swatch was kept in a small aluminum pan, and all of the pans were kept in an open-top box in the same room at ambient Relative eugenol temperature and humidity. The samples were Smelled at Time (h) concentration 25 timed intervals and rated for strength of scent (Ono scent, O.OO O.238 5=same strength as pure active ingredient from the bottle). 1.58 1.154 6.17 1.169 Data are presented in Tables 6 and 7. In both examples 15 22.50 1.163 (Table 6) and 16 (Table 7), it can be seen that the cloth treated 47.OO 1.189 with the siloxane derivative of the present invention release a 30 stronger odor for a longer period of time.

TABLE 6 TABLE 3 Hydrolysis of product from Example 5. Relative odor of fabric Swatches (Example 15). 35 Siloxane Relative 2-isopropylphenol Hours Control from Ex. 3 Time (h) concentration O 5 4 O.OO O.163 5 4 4 O.92 1316 21.5 4 4 5.50 1.351 40 28.9 3 4 21.83 1.335 46.3 3 3 46.33 1.352 52.8 3 4 78.1 3 4 1643 3 2 215.3 2 3 TABLE 4 45 237.1 1 1 Hydrolysis of product from Example 6. Relative phenethyl alcohol TABLE 7 Time (h) concentration 50 O.OO O.230 Relative odor of fabric Swatches (Example 16). 2.25 O.958 6.83 1.205 Siloxane Hours Control from Ex. 8 23.17 1.300 27.33 1.226 O.O 49.66 1.3O2 55 4.7 21.1 28.6 46.0 TABLE 5 S2.6 77.8 Hydrolysis of product from Example 8. 60 1640 215.1 Relative acetophenone 236.8 Time (h) concentration O.OO O.311 What is claimed is: 2.25 O448 5.75 O.S32 65 1. An alcohol or carbonyl compound releasing siloxane 20.66 O.899 selected from the group of siloxanes consisting of siloxanes having the formulas US 7,576,170 B2 19 20 3. The alcohol or carbonyl compound releasing siloxane of claim 2 wherein said siloxane releases an alcohol.

4. The siloxane of claim 3 wherein the alcohol released is selected from the group of fragrant alcohols consisting of acetovanillone, allyl amylglycolate, allyl isoamylglycolate, C.-amylcinammyl alcohol, anisyl alcohol, benzoin, benzyl alcohol, benzyl salicylate, 1-butanol, butylated hydroxytolu ene, butyl lactate, 2-t-butyl-5 methylphenol, 2-t-butyl-6-me thylphenol, carvacrol, carveol, 4-carvomenthenol, cedrol, 10 cetyl alcohol, cinnamic alcohol, citronellol, o-cresol, m-cresol, p-cresol, crotyl alcohol, decahydro-2-naphthol, 1-decanol. 1-decen-3-ol, 9-decen-1-ol, diethyl malate, diethyl tartrate, dihydrocarveol, dihydromyrcenol. 2,6-diiso propylphenol, dimethicone copolyol. 2,6-dimethoxyphenol, 15 1,1-dimethoxy-3,7-dimethyloctan-7-ol. 2,6-dimethyl-4-hep tanol. 2,6-dimethylheptan-2-ol. 6,8-dimethyl-2-nonanol, 3,7-dimethyt-2,6-octadien-1-ol. 3,7-dimethyl-1,6-octadien 3-ol, 3,7-dimethyl-1-octanol. 3,7-dimethyl-3-octanol, 3.7- dimethyl-6-octen-1-ol. 3,7-dimethyl-7-octen-1-ol, dimetol, 2-ethylfenchol, 4-ethylguaiacol, 2-ethyl-1-hexanol, ethyl 2-hydroxybenzoate, ethyl 3-hydroxybutyrate, 3-ethyl-2-hy droxy-2-cyclopenten-1-one, ethyl 2-hydroxycaproate, ethyl 3-hydroxyhexanoate, ethyl lactate, ethyl maltol, p-ethylphe nol, ethyl salicylate, eugenol, fameSol, fenchyl alcohol, 25 geraniol, glycerol, glyceryl monostearate, guaiacol, 1-hep tanol, 2-heptanol, 3-heptanol, cis-4-heptenol, cis-3-heptenol, n-hexanol, 2-hexanol, 3-hexanol, cis-2-hexenol, cis-3-hex enol, trans-3-hexenol, 4-hexenol, cis-3-hexenyl hydrocin namyl alcohol, 2-hydroxybenzoate, 2-hydroxyacetophe 30 none, 4-hydroxybenzyl alcohol, 3-hydroxy-2-butanone, hydroxycitronellol, 4-(4-hydroxy-3-methoxyphenyl)-2-bu tanone, 2-hydroxy-3-methyl-2-cyclopenten-1-one, 4-(p-hy droxyphenyl)-2-butanone, 2-hydroxy-3.5.5-trimethyl-2-cy clohexenone, 6-isoascorbic acid, isobomeol, isoeugenol, 35 isophytol, isopropyl alcohol, p-isopropylbenzyl alcohol, where R' and Rare independently hydrogen or monovalent 4-isopropylcylcohexanol, 3-isopropylphenol, 4-isopropy C-C hydrocarbon radical, the Subscript n is at least 1 or lphenol, 2-isopropylphenol, isopulegol, lauryl alcohol, lina greater, while the Subscripts p and q are independently posi lool, maltol, menthol, 4-methoxybenzyl alcohol, 2-methoxy tive Subject to the limitation that n+p+q is greater than or 4-methylphenol, 2-methoxy-4-propylphenol, 2-methoxy-4- equal to 3: Rand Rare each independently hydrogen or a 40 vinylphenol, C.-methylbenzyl alcohol, 2-methylbutanol, monovalent C-C hydrocarbon radicals; the Subscripts rand 3-methyl-2-butanol, 3-methyl-2-buten-1-ol, 2-methyl u are each independently at least 1 or greater, while the 3-buten-2-ol, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, Subscripts S and t are each independently positive subject to 4-methyl-2,6-dimethoxyphenol, methyl N-3,7-dimethyl-7- the limitation that the Sum r-s+t+u is greater than or equal to hydroxyoctylideneanthranilate, methyl 3-hydroxyhexanoate, 4; and O-Frag is independently active alkoxide or enolate 45 6-methyl-5-hepten-2-ol, 2-methylpentanol, 3-methyl-3-pen moieties derived from corresponding active alcohols or car tanol, 2-methyl-4-phenylbutan-2-ol, 2-methyl-3-phenylpro bonyl-containing compounds. pan-2-ol, methyl salicylate, 3-methyl-5-(2.2.3,-trimethyl 2. The alcohol or carbonyl compound releasing siloxane of 3-cyclopenten-1-yl)-4-penten-2-ol. 2-methyl-2-vinyl-5- claim 1 having the formula: (1-hydroxy-1-methyt ethyl)-3,4-dihydrofuran, myrtenol, 50 neohesperidin dihydrochalcone, neomenthol, nerol, neroli

dol, trans-2-cis-6-nonadienol, 1.3-nonanediol acetate, non adyl, 2-nonanol, cis-6-nonen-1-ol, trans-2-nonen-1-ol, nonyl alcohol, 1-octanol, 2-octanol, 3-octanol, cis-3-octen-1-ol. cis-2-octen-1-ol, trans-2-octen-1-ol, cis-6-octen-1-ol, cis 55 octen-1-ol. 1-octen-3-ol, oleyl alcohol, patchouli alcohol, 3-pentanol, n-pentanol. 2-pentanol, 1-penten-1-ol, cis-2- penten-1-ol, perillyl alcohol. 2-phenoxyethanol arabinoga lactan, B-phenethyl alcohol, phenethyl salicylate, phenol, phenylacetaldehyde glyceryl acetal, 3-phenyl-1-pentanol, 60 5-phenyl-1-pentanol, 1-phenyl-1-pentanol. 1-phenyl-2-pen tanol. 1-phenyl-3-methyl-1-pentanol, phytol, pinacol, poly alkylene glycols, polysorbate 20, polysorbate 60, polysorbate 80, prenol, n-propanol, propenylguaethol, propylene glycol, 2-propyiphenol, 4-propyiphenol, resorcinol, retinol, salicyla 65 ldehyde, Sorbitan monostearate, Sorbitol, Stearyl alcohol, Syringealdehyde, C-terpineol, tetrahydrogeraniol, tetrahy drolinalool, tetrahydromyrcenol, thymol, triethylcitrate, 1.2, US 7,576,170 B2 21 22 6-trihydroxyhexane, p-O.C.-trimethylbenzyl alcohol, 2-(5.5, lacetate, guaicwood acetate, y-heptalactone, heptyl acetate, 6-trimethylbicyclo 2.2.1]hept-2-ylcyclohexmlol, 5-(2,2,3- heptyl butyrate, heptyl isobutyrate, ()-6-hexadecenlactone, trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol. 3.7-11 6-hexalactone, Y-hexalactone, 3-hexenyl acetate, cis-3-hex trimethyl-2,6,10-dodecatrien-1-ol. 3.7.11-trimethyl-1,6,10 enyl 2-methylbutanoate, cis-3-hexenyl cis-3-hexenoate, cis dodecatrien-3-ol, 3.5.5-trimethyl-1-hexanol, 10-undecen-1- 3-hexenyl phenylacetate, trans-2-hexenyl acetate, hexyl ol, undecyl alcohol, Vanillin, o-vanillin, vanillyl butyl ether, 4-vinylphenol, 2.5-Xylenol. 2,6-Xylenol. 3.5-Xylenol. 2,4-Xy acetate, hexylbutyrate, hexyl hexanoate, hexyl isobutyrate, lenol, and Xylose. hexyl propionate, hexyl 2-methylbutanoate, hexyl 3-meth 5. A composition comprising the siloxane of claim 3. ylbutanoate, hexyl phenylacetate, isoamyl acetate, isoamyl 6. The alcohol or carbonyl compound releasing siloxane of 10 acetoacetate, isoamylbutyrate, isoamyl cinnamate, isoamyl claim 2 wherein said siloxane releases a carbonyl compound. hexanoate, isoamyl isobutyrate, isoamylisovalerate, isoamyl 7. The siloxane of claim 6 wherein the carbonyl compound laurate, isoamyl nonanoate, isoamyl octanoate, isoamyl phe released is selected from the group consisting of glucose nylacetate, isoamyl propionate, isobomyl acetate, isobornyl pentaacetate, 4-acetoxy-3-pentyl-tetrahydropyran, allyl cin propionate, isobutyl acetate, isobutylbutyrate, isobutyl cin namate, allyl 2-ethylbutyrate, allyl cyclohexanepropionate, 15 namate, isobutyl hexanoate, isobutyl isobutyrate, isobutyl allyl heptanoate, allyl hexanoate, allyl isovalerate, allyl 2-methylbutyrate, isobutyl propionate, isoeugenyl acetate, nonanoate, allyl octanoate, allyl phenoxyacetate, allyl phe isopropyl cinnamate, isobutyl phenylacetate, isopropyl nylacetate, allyl propionate, C.-amylcinnamyl acetate, amyl acetate, isopropylbutyrate, isopropyl isobutyrate, isopropyl octanoate, anisyl acetate, anisylphenyl acetate, benzyl myristate, isopropyl palmitate, isopropyl phenylacetate, lau acetate, benzyl acetoacetate, benzyl butyrate, benzyl cin ryl acetate, linallyl acetate, linallylbutyrate, linallylisovalerate, namate, benzyl isobutyrate, benzyl isovalerate, benzyl phe menthalactone, menthyl acetate, menthyl cyclohexanecar nylacetate, benzyl propionate, bomyl acetate, bomyl isoval boxylate, menthyl isovalerate, 4-methoxybenzyl acetate, erate, bomyl Valerate, butyl acetate, butyl butyrate, butyl 4-methoxybenzyl propionate, 2-methoxyphenyl acetate, butyryllactate, 4-t-butylcyclohexyl acetate, butylheptanoate, 25 2-methoxy-4-( 1 -propenyl)phenyl acetate, methyl acetate, butyl hexanoate, butyl isobutyrate, butyl isovalerate, butyl C.-methylbenzyl acetate, C.-methylbenzyl butyrate, C.-meth laurate, butyl propionate, butyl stearate, 3-butylideneph ylbenzyl propionate, 2-methylbutyl acetate, 2-methylbutyl thatide, butyl 2-methytbutyrate, butyl 10-undeceneoate, butyrate, 2-methylbutyti isovalerate, 3-methylbutyl 2-meth y-butyrolactone, carvyl acetate, carvyl propionate, caryo 30 ylbutanoate, 2-methylbutyl 2-methylbutanoate, methyl p-t- phyllene acetate, cedryl acetate, trans-cinnamyl acetate, butylphenylacetate, methyl butyrate, methyl cinnamate, trans-cinnamyl butyrate, cinnamyl cinnamate, cinnamyl methyl decanoate, methyl heptanoate, methyl hexanoate, isobutyrate, citronellyl acetate, citronellylbutyrate, citronel methyl isobutyrate, methyl isovalerate, methyl laurate, lyl isobutyrate, citronellyl propionate, citronellyl Valerate, methyl N-2-methyl-3-(4-t-butylphenylpropylidene) anthra cyclohexaneethyl acetate, cyclohexyl acetate, cyclohexyl 35 nilate, methyl (methylthio)acetate, methyl 2-(methylthio) butyrate, cyclohexyl isovalerate, cyclohexyl propionate, propionate, methyl myristate, methyl nonanoate, methyl Ö-decalactone, e-decalactone, y-decalactone, 4-decanolide, octanoate, methyl palmitate, 4-(4-methyl-3-pentenyl)-3-cy decyl acetate, decylbutyrate, decyl propionate, diethyl mal clohexenylmethyl acetate, methyl 2-methylbutyrate, 2-me onate, diethyl sebacate, diethyl Succinate, dihydrocarvyl thyl-6-methylen-7-octen-2-yl acetate, methyl 4-methylvaler acetate, dihydrocoumarin, dihydromyrcenyl acetate, dihy 40 ate, methyl 2-methylpentanoate, methyl phenoxyacetate, dro-nor-dicyclopentadienyl acetate, dihydroterpinyl acetate, 4-methylphenyl phenylacetate, 2-methyl-3-phenylpropan-2- 3,7-dimethyl-1,6-octadien-3-yl acetate, 3,7-dimethyl-1,6- y1 acetate, methyl 3-phenylpropionate, methyl propionate, octadien-3-yl propionate, 3.7-dimethyloctan-3-yl acetate, 2-methyipropyl phenylacetate, methyl phenylacetate, 2-me C.C.-dimethylphenethyl acetate, O.C.-dimethylphenethyl 45 thyl-3-phenylpropan-2-yl acetate, methyl Stearate, methyl butyrate, 6,10-dimethyl-5.9-undecadien-2-yl acetate, (p-tolyloxy)acetate, methyl 9-undecenoate, methyl Valerate, 6-dodecalactone, e-dodecalactone, Y-dodecalactone, ethyl myrtenyl acetate, neryl acetate, neryl butyrate, neryl isobu acetate, ethyl acetoacetate, ethyl 6-acetoxyhexanoate, ethyl tyrate.ö-nonalactone, Y-nomalactone, 1.3-nonanediol diac 2-acetyl-3-phenylpropionate, ethyl benzoylacetate, 2-ethyl etate, nonyl acetate, nopyl acetate, octahydrocoumarin, Y-oc butyl acetate, ethylbutyrate, ethyl cinnamate, ethylcyclohex 50 talactone, 1-octen-3-yl acetate, 1-octen-3-yl butyrate, octyl anepropionate, ethyl decanoate, ethylene brassylate, ethyl acetate, octyl butyrate, octyl isobutyrate, octyl isovalerate, 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate, ethyl 2.3- octyl octanoate, octyl propionate, oxacycloheptadec-10-en epoxybutyrate, ethyl 2-methyl-4-penteneoate, ethyl hep 2-one, () -pentadecalactone, pentyl acetate, pentylbutyrate, tanoate, ethylhexanoate, ethyl trans-3-hexenoate, 2-ethyl 55 pentylhexanoate, pentyl octanoate, phenethyl acetate, phen hexyl acetate, ethyl isobutyrate, ethyl isovalerate, ethyl ethylbutyrate, phenethyl cinnamate, phenethyl hexanoate, laurate, ethyl 2-mercaptopropionate, ethyl 3-mercaptopropi phenethyl isobutyrate, phenethyl isovalerate, phenethyl onate, ethyl 2-methylbutyrate, ethyl 2-methylpentanoate, 2-methylbutyrate, phenethyl 2-methylbutyrate, phenethyl ethyl (methylthio)acetate, ethyl myristate, ethyl nonanoate, 2-methylpropionate, phenethyl octanoate, phenethyl pheny ethyl octanoate, ethyl palmitate, ethyl phenylacetate, ethyl 60 lacetate, phenethyl propionate, phenoxyethyl propionate, 3-phenylpropionate, ethyl 3-phenyl-2,3-epoxybutyrate, ethyl 2-phenoxyethyl 2-methylpropionate, 3 -phenyl-2-propenyl 3-phenylpropionate, ethyl propionate, ethyl Stearate, ethyl propionate, 3-phenylpropyl acetate, 2-phenylpropylbutyrate, 2.3.6.6-tetramethyl-2-cyclohexencarboxylate, ethyl (p-toly 2-phenylpropyl isobutyrate, 2-phenylpropyl isovalerate, pip loxy)acetate, ethyl undecanoate, ethyl Valerate, eugenyl 65 eronyl acetate, piperonyl isobutyrate, prenyl acetate, propyl acetate, fenchyl acetate, geranyl acetate, geranyl butyrate, acetate, propyl butyrate, propyl heptanoate, propyl hex geranyl phenylacetate, geranyl propionate, guaiacyl pheny anoate, 3-propylidenephthalide, propyl isobutyrate, propyl US 7,576,170 B2 23 24 propionate, propyl phenylacetate. Sucrose octaacetate, terpi 3-penten-2-one, 1 -phenyl-1,2-propandione, propiophenone, nyl acetate, terpinyl butyrate, terpinyl isobutyrate, terpinyl pulegone, 2-tridecanone, 2.2,6-trimethylcyclohexanone, propionate, Ö-nonalactone, tetrahydrofurfuryl acetate, tet 4-(2,6,6-trimethyl-2-cyleohexen- 1 -yl)-3-methyl-3-buten rahydrofurfuryl butyrate, tetrahydrofurfuryl propionate, tet 2-one, 2-undecanorte, and 6-undecanone. rahydrolinallyl acetate, 2.6,6,8-tetramethyl-tricyclo (5.3.10 8. A composition comprising the siloxane of claim 6. (1.5)udecan-8-yl acetate, p-tolyl acetate, p-tolyl isobutyrate, 9. A composition comprising the siloxane of claim 2. p-tolyl phenylacetate, triacetin, tributyl acetylcitrate, tribu 10. The alcohol or carbonyl compound releasing siloxane tyrin, tripropionin, 3.5.5-trimethylhexyl acetate, Ö-undeca of claim 1 having the formula: lactone, Y-undecalactone, Y-Valerolactone, Vanillin acetate, 10 vanillyl isobutyrate, 1-vinyl-2-(1-methylpropyl)cyclohexyl acetate, whiskey lactone, butyraldehyde, citronellal, decanal, cis-4-decenal, trans-4-decenal, 2,4-dimethyl-3-cyclohexen 1-carbaldehyde, 2,6-dimethyl-5-heptenal, 3,7-dimethylocta nal, 2-ethylbutyraldehyde, glutaric dialdehyde, heptanal, cis 15 4-heptenal, hexanal, hydrocinnamaldehyde, isobutyraldehyde, 3 -(p-isopropylphenyl) propionaldehyde, isovaleraldehyde, laurie aldehyde, 2-methylbutyraldehyde, 2-methyl-3-(p-isopropylphenyl)propionaldehyde, 2-methyl pentanal, 4-(4-methyl-3-pentenyl)-3-cyclohexen-1-carbal dehyde, 4-methyiphenylacetaldehyde, 3 -(methylthio)buta nal, 2-methyl4-(2,6,6-trimethyl-2-cyclohexen-1-yl)butanal, 2-methylundecanal, nonanal, cis-6-nonenal, octanal, pheny lacetaldehyde, 2-phenyipropionaldehyde, 3 -phenyipropi 25 onaldehyde, propionaldehyde, p-tolylacetaldehyde, trideca nal, 2,4,6-trimethyl-3-cyclohexen-1-carbatdehyde, 2,6,10 trimethyl-9-undecanal, 7-undecenal, 8-undecenal, 11. The alcohol or carbonyl compound releasing siloxane 9-undecenal, 10-undecenal, Valeraldehyde, acetanisole, 30 of claim 10 wherein said siloxane releases an alcohol. 1'-acetonaphthone, 2'-acetonaphthone, acetone, acetophe 12. The siloxane of claim 11 wherein the alcohol released none, 2-acetoxy-2,5-dimethyl-3(2H)furanone, 2-acetylcy is selected from the group of fragrant alcohols consisting of clopentanone, 4-acetyl-1,1-dimethyl-6-t-butylindan, acetovanillone, allyl amylglycolate, allyl isoamylglycolate, 7-acetyl-1,1, 3.4.4.6-hexamethylindan, 2-acetyl-2-thiazo C.-amylcinammyl alcohol, anisyl alcohol, benzoin, benzyl line, 6-acetyl- 1.1.2.4.4.7-hexamethyl tetralin, allyl C-ion 35 alcohol, benzyl salicylate, 1-butanol, butylated hydroxytolu one, benzylideneacetone, 2.3 -butanedione, 2-sec-butylcy ene, butyl lactate, 2-t-butyl-5 methylphenol, 2-t-butyl-6-me clohexanone, 5 -t-butyl-3,5 -dinitro-2,6- thylphenol, carvacrol, carveol, 4-carvomenthenol, cedrol, dimethylacetophenone, butyrophenone, camphor, cetyl alcohol, cinnamic alcohol, citronellol, o-cresol, 2-decanone, 3 -decanone, 3 -decen-2-one, dihydrocarvone, m-cresol, p-cresol, crotyl alcohol, decahydro-2-naphthol, 40 1-decanol. 1-decen-3-ol, 9-decen-1-ol, diethyl malate, dihydro-p-ionone, dihydrojasmone, 4.5 -dihydro-3 (2H)- diethyl tartrate, dihydrocarveol, dihydromyrcenol. 2,6-diiso thiophenone, 2',4'-dimethytacetophenone, 3,4-dimethyl-1, propylphenol, dimethicone copolyol. 2,6-dimethoxyphenol, 2-cyclopentadione, 3.5 -dimethyl-1,2-cyclopentadione, 2.6- 1,1-dimethoxy-3,7-dimethyloctan-7-ol. 2,6-dimethyl-4-hep dimethyl-4-heptanone, 1.3 -diphenyl-2-propanone, 4 tanol. 2,6-dimethylheptan-2-ol. 6,8-dimethyl-2-nonanol, (1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone, p-ethy 45 3,7-dimethyt-2,6-octadien-1-ol. 3,7dimethyl-1, 6-octadein,- lacetophenone, ethyl vinyl ketone, geranylacetone, 2.3 -hep 3-ol, 3,7-dimethyl- 1 -octanol. 3,7-dimethyl-3-octanol, 3.7- tanedione, 2-heptanone, 3 -heptanone, 4-heptanone, 3,4-hex dimethyl-6-octen-1-ol. 3,7-dimethyl-7-octen-1-ol, dimetol, anedione, 3-hexanone, 4-hexen-3 -one, 2-hexylidene 2-ethylfenchol, 4-ethylguaiacol, 2-ethyl-1-hexanol, ethyl cyclopentanone, a-ionone, b-ionone, 4-isobutyt-2,6-dim 2-hydroxybenzoate, ethyl 3-hydroxybutyrate, 3 -ethyl-2-hy 50 droxy-2-cyclopenten-1-one, ethyl 2-hydroxycaproate, ethyl ethyl- 3.5-dinitroacetophenone, isophorone, 6-isopropyl 3-hydroxyhexanoate, ethyl lactate, ethyl maltol, p-ethylphe decahydro-2-naphthone, cis-asmone, livescone, 4-meth nol, ethyl salicylate, eugenol, fameSol, fenchyl alcohol, oxyacetophenone, 4-(p-methoxyphenyl)-2-butanone, geraniol, glycerol, glyceryl monostearate, guaiacol, 1-hep 4'-methylacetophenone, 3-methyl -1.2-cyclohexanedione, tanol, 2-heptanol, 3-heptanol, cis-4-heptenol, cis-3-heptenol, 3-methyl-2-cyclohexen-1-one, 2-(2-(4-methyl-3 -cylco 55 n-hexanol, 2-hexanol, 3-hexanol, cis-2-hexenol, cis-3-hex hexen- 1-yl) propyl)cyclopentanone, 3 -methyl-2-cyclo enol, trans-3-hexenol, 4-hexenol, cis-3-hexenyl hydrocin penten-1-one, methyl dihydroj asmonate, methyl ethyl namyl alcohol, 2- hydroxybenzoate, 2-hydroxyacetophe ketone, 2-methyl-3-heptanone, 5-methyl-2-hepten-4-one, none, 4-hydroxybenzyl alcohol, 3 hydroxy-2- butanone, 6-methyl-S -hepten-2-one, 5-methyl-O. -ionone, 1 -(2-me hydroxycitronellol, 4-(4-hydroxy-3-methoxyphenyl)-2-bu thyl-S -isopropyl-2-cyclohexenyl)-1-propanone, 4-methyl 60 tanone, 2-hydroxy-3-methyl-2-cyclopenten-1-one, 4-(p-hy 2-pentanone, 3-methyl -2-(2-pentenyl)-2-cyctopenten droxyphenyl)-2-butanone, 2-hydroxy-3.5.5-trimethyl-2-cy clohexenone, 6-isoascorbic acid, isobomeol, isoeugenol, 1-one, 4-methyl-1-phenyl-2-pentanone, 2-methyltetrahydro isophytol, isopropyl alcohol, p-isopropylbenzyl alcohol, furan -3-one, 2-methyltetrahydrothiophen-3 -one, 4-isopropylcylcohexanol, 3 -isopropylphenol, 4-isopropy 2-nonanone, 3 -nonanone, 2-octanone, 3 -octanone, 65 lphenol, 2-isopropylphenol, isopulegol, lauryl alcohol, lina 1-octen-3-one, 3 -octen-2-one, 4-oxoisophorone, 2-pentade lool, maltol, menthol, 4-methoxybenzyl alcohol, 2-methoxy canone, 2.3 -pentanedione, 2-pentanone, 3 -pentanone, 4-methylphenol, 2-methoxy-4-propylphenol, 2-methoxy-4- US 7,576,170 B2 25 26 vinylphenol, cc-methylbenzyl alcohol, 2-methylbutanol, dihydrocoumarin, dihydromyrcenyl acetate, dihydro -nor-di 3-methyl-2-butanol, 3 -methyl-2-buten- 1 -ol, 2-methyl cyclopentadienyl acetate, dihydroterpinyl acetate, 3.7-dim 3-buten-2-ol, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, ethyl-1,6-octadien-3-yl acetate, 3,7-dimethyl-1,6-octadien 4-methyl-2,6-dimethoxyphenol, methyl N-37 dimethyl-7- 3-yl propionate, 3.7-dimethyloctan-3-yl acetate, C.C.-dim hydroxyoctylideneanthranilate, methyl 3 -hydroxyhex ethyiphenethyl acetate, C.C.-dimethylphenethyl butyrate, anoate, 6-methyl-5 hepten-2-ol, 2-methylpentanol. 3 -me 6,10-dimethyl-5.9-undecadien-2-yl acetate, 6-dodecallac thyl-3 -pentanol, 2-methyl-4-phenylbutan-2-ol, 2-methyl tone, e-dodecalactone, Y-dodecalactone, ethyl acetate, ethyl 3-phenylpropan-2-ol, methyl salicylate, 3-methyl-5-(2.2.3,- acetoacetate, ethyl 6-acetoxyhexanoate, ethyl 2-acetyl trimethyl-3-cyclopenten- 1 -yl)-4-penten-2-ol, 2-methyl-2- 3 -phenylpropionate, ethyl benzoylacetate, 2-ethylbutyl vinyl-5 -(1 -hydroxy- 1 -methyt ethyl)-3,4 dihydrofuran, 10 acetate, ethyl butyrate, ethyl cinnamate, ethyl cyclohex myrtenol, neohesperidin dihydrochalcone, neomenthol, anepropionate, ethyl decanoate, ethylene brassylate, ethyl nerol, nerolidol, trans-2-cis-6-nonadienol, 1.3-nonanediol 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate, ethyl 2.3 - acetate, nonadyl, 2-nonanol, cis-6-nonen- 1 -ol, trans-2- epoxybutyrate, ethyl 2-methyl-4-penteneoate, ethyl hep nonen- 1 -ol, nonyl alcohol, 1-octanol, 2-octanol, 3-octanol, tanoate, ethylhexanoate, ethyl trans-3-hexenoate, 2-ethyl cis-3-octen-1-ol, cis-2-octen- 1 -ol, trans-2-octen- 1 -ol, cis 15 hexyl acetate, ethyl isobutyrate, ethyl isovalerate, ethyl lau 6-octen- 1 -ol, cis-octen- 1 -ol. 1-octen-3-ol, oleyl alcohol, rate, ethyl 2-mercaptopropionate, ethyl patchouli alcohol, 3 -pentanol, n-pentanol, 2-pentanol, 3-mercaptopropionate, ethyl 2-methylbutyrate, ethyl 2-meth 1-penten- 1 -ol, cis-2-penten-1-ol, perillyl alcohol. 2-phe ylpentanoate, ethyl (methylthio)acetate, ethyl myristate, noxyethanol arabinogalactan, B3-phenethyl alcohol, phen ethylnonanoate, ethyl octanoate, ethyl palmitate, ethyl phe ethyl salicylate, phenol, phenylacetaldehyde glyceryl acetal, nylacetate, ethyl 3 -phenylpropionate, ethyl 3 -phenyl 3-phenyl-1-pentanol, 5-phenyl -1 -pentanol, 1 -phenyl 2,3-epoxybutyrate, ethyl 3-phenylpropionate, ethyl propi 1-pentanol. 1 -phenyl-2-pentanol, 1 -phenyl-3 -methyl onate, ethyl stearate, ethyl 2.3.6.6-tetramethyl-2-cyclohexen i-pentanol, phytol, pinacol, polyalkylene glycols, polysor carboxylate, ethyl (p-tolyloxy)acetate, ethyl undecanoate, bate 20, polysorbate 60, polysorbate 80, prenol, n-propanol, ethyl Valerate, eugenyl acetate, fenchyl acetate, geranyl propenyl guaethol, propylene glycol, 2-propylphenol, 4-pro 25 acetate, geranylbutyrate, geranyl phenylacetate, geranyl pro pylphenol, resorcinol, retinol, Salicylaldehyde, Sorbitan pionate, guaiacyl phenylacetate, guaicwood acetate, Y-hepta monostearate, Sorbitol, Stearyl alcohol, Syringealdehyde, lactone, heptyl acetate, heptylbutyrate, heptyl isobutyrate, C-terpineol, tetrahydrogeraniol, tetrahydrolinalool, tetrahy ()-6-hexadecenlactone, 6-hexalactone, Y-hexalactone, 3-hex dromyrcenol, thymol, triethyl citrate, 1.2,6-trihydroxyhex enyl acetate, cis-3-hexenyl 2-methylbutanoate, cis-3-hexenyl ane, p-O.C.- trimethylbenzyl alcohol, 2-(5.5,6-trimethylbicy 30 cis-3-hexenoate, cis-3-hexenyl phenylacetate, trans-2-hex clo 2.2.1 hept-2-ylcyclohexmlol, 5 -(2.2.3 -trimethyl enyl acetate, hexyl acetate, hexylbutyrate, hexylhexanoate, 3-cyclopentenyl)-3-methylpentan-2-ol. 3.7-11-trimethyl - hexyl isobutyrate, hexyl propionate, hexyl 2-methylbu 2,6,10-dodecatrien- 1 -ol. 3.7.11 -trimethyl-1,6,10-dodec tanoate, hexyl 3-methylbutanoate, hexyl phenylacetate, atrien-3-ol, 3.5.5-trimethyl- 1 -hexanol, 10-undecen-1-ol. isoamyl acetate, isoamyl acetoacetate, isoamyl butyrate, undecyl alcohol, Vanillin, o-vanillin, vanillyl butyl ether, 35 isoamyl cinnamate, isoamylhexanoate, isoamyl isobutyrate, 4-vinylphenol, 2.5-xylenol. 2,6-Xylenol, 3.5-xylenol. 2,4- isoamyl isovalerate, isoamyl laurate, isoamyl nonanoate, Xylenol, and Xylose. isoamyl octanoate, isoamyl phenylacetate, isoamyl propi 13. A composition comprising the siloxane of claim 11. onate, isobomyl acetate, isobomyl propionate, isobutyl 14. The alcohol or carbonyl compound releasing siloxane acetate, isobutylbutyrate, isobutyl cinnamate, isobutyl hex of claim 10 wherein said siloxane releases a carbonyl com 40 anoate, isobutyl isobutyrate, isobutyl 2-methylbutyrate, pound. isobutyl propionate, isoeugenyl acetate, isopropyl cinnamate, 15. The siloxane of claim 14 wherein the carbonyl com isobutyl phenylacetate, isopropyl acetate, isopropylbutyrate, pound released is selected from the group consisting of glu isopropyl isobutyrate, isopropyl myristate, isopropyl palmi cose pentaacetate, 4-acetoxy-3-pentyl-tetrahydropyran, allyl tate, isopropyl phenylacetate, lauryl acetate, linallyl acetate, cinnamate, allyl 2-ethylbutyrate, allyl cyclohexanepropi 45 linallyl butyrate, linallyl isovalerate, menthalactone, menthyl onate, allylheptanoate, allylhexanoate, allylisovalerate, allyl acetate, menthyl cyclohexanecarboxylate, menthyl isovaler nonanoate, allyl octanoate, allyl phenoxyacetate, allyl phe ate, 4-methoxybenzyl acetate, 4-methoxybenzyl propionate, nylacetate, allyl propionate, C.-amylcinnamyl acetate, amyl 2-methoxyphenyl acetate, 2-methoxy-4-(1-propenyl)phenyl octanoate, anisyl acetate, anisylphenyl acetate, benzyl acetate, methyl acetate, C.-methylbenzyl acetate, C.-methyl acetate, benzyl acetoacetate, benzyl butyrate, benzyl cin 50 benzyl butyrate, C.-methylbenzyl propionate, 2-methylbutyl namate, benzyl isobutyrate, benzyl isovalerate, benzyl phe acetate, 2-methylbutylbutyrate, 2-methylbutytl isovalerate, nylacetate, benzyl propionate, bornyl acetate, bornyl isoval 3-methylbutyl 2-methylbutanoate, 2-methylbutyl 2-meth erate, bornyl valerate, butyl acetate, butyl butyrate, butyl ylbutanoate, methyl p-t-butylphenylacetate, methylbutyrate, butyryllactate, 4-t-butylcyclohexyl acetate, butylheptanoate, methyl cinnamate, methyl decanoate, methyl heptanoate, butyl hexanoate, butyl isobutyrate, butyl isovalerate, butyl 55 methyl hexanoate, methyl isobutyrate, methyl isovalerate, laurate, butyl propionate, butyl stearate, 3-butylideneph methyl laurate, methyl N-2-methyl-3-(4-t-butylphenylpro thatide, butyl 2-methytbutyrate, butyl 10-undeceneoate, Y-bu pylidene) anthranilate, methyl (methylthio)acetate, methyl tyrolactone, carvyl acetate, carvyl propionate, caryophyllene 2-(methylthio)propionate, methyl myristate, methyl acetate, cedryl acetate, trans-cinnamyl acetate, trans-cin nonanoate, methyl octanoate, methyl palmitate, 4-(4-me namylbutyrate, cinnamyl cinnamate, cinnamyl isobutyrate, 60 thyl-3-pentenyl)-3-cyclohexenylmethyl acetate, methyl 2 citronellyl acetate, citronellyl butyrate, citronellyl isobu methylbutyrate, 2-methyl-6-methylen-7-octen-2-yl acetate, tyrate, citronellyl propionate, citronellyl Valerate, cyclohex methyl 4-methylvalerate, methyl 2-methylpentanoate, aneethyl acetate, cyclohexyl acetate, cyclohexyl butyrate, methyl phenoxyacetate, 4-methylphenyl phenylacetate, cyclohexyl isovalerate, cyclohexyl propionate, 6-decallac 2-methyl-3-phenylpropan-2-yl acetate, methyl 3-phenylpro tone, e-decalactone, y-decalactone, 4-decanolide, decyl 65 pionate, methyl propionate, 2-methylpropyl phenylacetate, acetate, decyl butyrate, decyl propionate, diethyl malonate, methyl phenylacetate, 2-methyl-3 -phenylpropan-2-yl diethyl sebacate, diethyl Succinate, dihydrocarvyl acetate, acetate, methyl Stearate, methyl (p-tolyloxy)acetate, methyl US 7,576,170 B2 27 28 9-undecenoate, methyl Valerate, myrtenyl acetate, neryl none, 2-acetylcyclopentanone, 4-acetyl-1,1-dimethyl-6-t-bu acetate, neryl butyrate, neryl isobutyrate, Ö-nonalactone, tylindan, 7-acetyl-1, 1.3.4.4.6-hexamethylindan, 2-acetyl-2- Y-nomalactone, 1.3-nonanediol diacetate, nonyl acetate, nopyl thiazoline, 6-acetyl- 1,1,2,4,4,7-hexamethyl tetralin, allyl acetate, octahydrocoumarin, Y-octalactone, 1-octen-3-yl C-ionone, benzylideneacetone, 2.3 -butanedione, 2-sec-bu acetate, 1-octen-3-yl butyrate, octyl acetate, octyl butyrate, tylcyclohexanone, 5 -t-butyl-3,5-dinitro-2,6-dimethylac octyl isobutyrate, octyl isovalerate, octyl octanoate, octyl etophenone, butyrophenone, camphor, 2-decanone, 3 -de propionate, oxacycloheptadec-10-en-2-one, () -pentadeca canone, 3-decen-2-one, dihydrocarvone, dihydro-p-ionone, lactone, penty1 acetate, penty1 butyrate, pentyl hexanoate, dihydrojasmone, 4.5 -dihydro-3 (2H)-thiophenone, 2',4'- pentyl octanoate, phenethyl acetate, phenethyl butyrate, dimethytacetophenone, 3,4-dimethyl-1,2-cyclopentadione, phenethyl cinnamate, phenethylhexanoate, phenethyl isobu 10 3,5-dimethyl-1,2-cyclopentadione, 2,6-dimethyl-4-hep tyrate, phenethyl isovalerate, phenethyl 2-methylbutyrate, tanone, 1,3-diphenyl-2-propanone, 4-(1-ethoxyvinyl)-3,3,5, phenethyl 2-methylbutyrate, phenethyl 2-methylpropionate, 5-tetramethylcyclohexanone, p-ethylacetophenone, ethyl phenethyl octanoate, phenethyl phenylacetate, phenethyl vinyl ketone, geranylacetone, 2.3 -heptanedione, 2-hep propionate, phenoxyethyl propionate, 2-phenoxyethyl 2-me tanone, 3 -heptanone, 4-heptanone, 3,4-hexanedione, 3-hex thylpropionate, 3-phenyl-2-propenyl propionate, 3-phenyl 15 anone, 4-hexen-3-one, 2-hexylidene cyclopentanone, a-ion propyl acetate, 2-phenylpropyl butyrate, 2-phenylpropyl One, b-ionone, 4-isobutyt-2,6-dimethyl-3,5- isobutyrate, 2-phenylpropyl isovalerate, piperonyl acetate, dinitroacetophenone, isophorone, 6-isopropyldecahydro-2- piperonyl isobutyrate, prenyl acetate, propyl acetate, propyl naphthone, cis- aSmOne, livescone, butyrate, propylheptanoate, propylhexanoate, 3-propylide 4-methoxyacetophenone, 4-(p-methoxyphenyl)-2-butanone, nephthalide, propyl isobutyrate, propyl propionate, propyl 4'-methylacetophenone, 3-methyl -1.2-cyclohexanedione, phenylacetate. Sucrose octaacetate, terpinyl acetate, terpinyl 3-methyl-2-cyclohexen-1-one, 2-(2-(4-methyl-3 -cylco butyrate, terpinyl isobutyrate, terpinyl propionate, 6-nonalac hexen-1-yl) propyl)cyclopentanone, 3 -methyl-2-cyclo tone, tetrahydrofurfuryl acetate, tetrahydrofurfuryl butyrate, penten-1-one, methyl dihydro asmonate, methyl ethyl tetrahydrofurfuryl propionate, tetrahydrolinallyl acetate, 2.6. ketone, 2-methyl-3-heptanone, 5-methyl-2-hepten-4-one, 25 6-methyl-5-hepten-2-one, 5-methyl-O. -ionone, 1-(2-methyl 6,8-tetramethyl-tricyclo 5.3.1.0(1.5)udecan-8-yl acetate, 5-isopropyl-2-cyclohexenyl)-1-propanone, 4-methyl-2-pen p-tolyl acetate, p-tolyl isobutyrate, p-tolyl phenylacetate, tri tanone, 3-methyl -2-(2-pentenyl)-2-cyctopenten- 1-one, acetin, tributyl acetylcitrate, tributyrin, tripropionin, 3.5.5- 4-methyl-1-phenyl-2-pentanone, 2-methyltetrahydrofuran trimethylhexyl acetate, 6-undecalactone, Y-undecalactone, Y-Valerolactone, Vanillin acetate, Vanillyl isobutyrate, 1 -vi 3-one, 2-methyltetrahydrothiophen-3-one, 2-nonanone, 3 nyl-2-(1-methylpropyl)cyclohexyl acetate, whiskey lactone, 30 nonanone, 2-octanone, 3-octanone, 1-octen-3-one, 3-octen butyraldehyde, citronellal, decanal, cis-4-decenal, trans-4- 2-one, 4-oxoisophorone, 2-pentadecanone, 2.3 -pentanedi decenal, 2,4-dimethyl-3 -cyclohexen-1-carbaldehyde, 2.6- one, 2-pentanone, 3-pentanone, 3-penten-2-one, 1 -phenyl dimethyl-5-heptenal,3,7-dimethyloctanal, 2-ethylbutyralde 1.2-propandione, propiophenone, pulegone, 2-tridecanone, hyde, glutaric dialdehyde, heptanal, cis-4-heptenal, hexanal, 2.2,6-trimethylcyclohexanone, 4-(2,6,6-trimethyl-2-cyleo hydrocinnamaldehyde, isobutyraldehyde, 3 -(p-isopropy 35 hexen-1-yl)-3-methyl-3-buten-2-one, 2-undecanorte, and lphenyl)propionaldehyde, isovaleraldehyde, lauric aldehyde, 6-undecanone. 2-methylbutyraldehyde, 2-methyl-3-(p -isopropylphenyl) 16. A composition comprising the siloxane of claim 14. propionaldehyde, 2-methylpentanal, 4-(4-methyl-3-pente 17. A composition comprising the siloxane of claim 10. nyl)-3-cyclohexen- 1 -carbaldehyde, 4-methyiphenylacetal 18. A hydrolyzed product of the alcohol or carbonyl com dehyde, 3 -(methylthio)butanal, 2-methyl4-(2,6,6-trimethyl 40 pound releasing siloxane of claim 1, wherein the oxygen 2-cyclohexen- 1 -yl)butanal, 2-methylundecanal, nonanal, bound Frag radical is released from said siloxane and said cis-6-nonenal, octanal, phenylacetaldehyde, 2-phenyipropi oxygen is converted to an OH-moiety. onaldehyde, 3 -phenyipropionaldehyde, propionaldehyde, 19. A composition comprising the siloxane of claim 1. p-tolylacetaldehyde, tridecanal, 2,4,6-trimethyl-3 -cyclo 20. An article of manufacture comprising the siloxane of hexen-1-carbatdehyde, 2,6,10-trimethyl-9-undecanal, 7-un 45 claim 1. decenal, 8-undecenal, 9-undecenal, 10-undecenal, Valeralde 21. A composition consisting essentially of the siloxane of hyde, acetanisole, 1'-acetonaphthone, 2'-acetonaphthone, claim 1. acetone, acetophenone, 2-acetoxy-2,5-dimethyl-3(2H) fura