Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/50—Perfumes
  • C11D3/502—Protected perfumes
  • C11D3/507—Compounds releasing perfumes by thermal or chemical activation
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/35—Ketones, e.g. benzophenone
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/0216—Solid or semisolid forms
  • A61K8/0229—Sticks
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q13/00—Formulations or additives for perfume preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q15/00—Anti-perspirants or body deodorants
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/10—Washing or bathing preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/02—Preparations for cleaning the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/12—Preparations containing hair conditioners
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
  • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
  • C07C235/34—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
  • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D207/36—Oxygen or sulfur atoms
  • C07D207/38—2-Pyrrolones
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
  • C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
  • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
  • C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/57—Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances

Definitions

• the present invention relates to photo-labile pro-fragrance conjugates, which are capable of releasing a fragrance raw material in a sequence of chemical reaction steps that include a photo-activated release of a nitrogen-containing pro-fragrance compound.
• the conjugates are useful in formulating fragrance delivery systems.
• the conjugates of the present invention are capable of delivering any type of fragrance raw material.
• Pro-fragrances and pro-accords have been used to enhance the delivery of fragrance raw materials and to sustain their duration.
• pro-fragrances and pro-accords deliver alcohol, ketone, aldehyde, and ester fragrance raw materials via substrates which are hydrolyzed by one or more mechanisms, inter alia, the acidic pH of skin, nascent moisture.
• Fragrances or odors not only provide a pleasant aesthetic benefit, but also serve as a signal.
• foods which have soured or are no longer edible, may develop smells, which are repulsive and send a signal that they are no longer palatable. Therefore, the delivery of an aroma sensory signal is also a benefit, which a pro-fragrance can provide.
• fragrance or odor releasing compounds which involve release of fragrances by way of a controlled chemical cascade initiated by exposure to electromagnetic radiation, inter alia, UV light.
• the present invention provides a means for delivering a fragrance or an accord wherein the delivery of said fragrance or said accord is instigated by exposure to light.
• the present invention meets the aforementioned need in that it has been surprisingly discovered that fragrance raw materials can be delivered by photo-labile pro-fragrance conjugates.
• the photo-labile pro-fragrance conjugates of the present invention are activated by the exposure of the conjugates to electromagnetic radiation, which is the initial step in a chemical cascade resulting in the ultimate release of a fragrance raw material.
• One of the steps in the cascade involves photochemically initiated fragmentation of a chemical bond between a photo-labile unit and a nitrogen atom contained within a pro-fragrance unit.
• conjugates of the present invention comprise:
• the present invention also relates to a photo-labile fragrance conjugate delivery system comprising:
• a photo-labile unit which upon exposure to electromagnetic radiation is capable of releasing a pro-fragrance unit
• the present invention relates to photo-labile pro-fragrance conjugates, which are stable until activated by exposure to electromagnetic radiation.
• the conjugates of the present invention are capable of releasing any type of perfume raw material, inter alia, alcohols, ketones, aldehydes, via a single- or multi-step process that is initiated by the photo-induced fragmentation of a chemical bond between the photo-labile unit and a nitrogen atom in the pro-fragrance unit.
• the conjugates of the present invention can be depicted as compounds having a photo-labile unit and a pro-fragrance unit which are connected to one another directly or optionally by way of a linking unit.
• the conjugates can be represented by the formula:
• linking unit, L is present when the index n is equal to 1 and absent when n is equal to 0.
• photo-labile unit is defined herein as “a unit which upon exposure to electromagnetic radiation becomes the photo-fragment compound by fragmenting from the parent photo-labile pro-fragrance conjugate.” In some embodiments of the present invention it may be advantageous that the photo-fragment compound does not interfere with the aesthetic quality or character of the released fragrance or pro-fragrance compound. In the presence of light, the photo-labile unit serves to trigger the chemical reaction or reaction cascade that ends with the ultimate release of one or more fragrance raw materials.
• pro-fragrance unit is defined herein as “that portion of the photo-labile pro-fragrance conjugate, which gives rise to the fragrance compound or pro-fragrance compound as a result of exposure of the photo-labile pro-fragrance conjugate to electromagnetic radiation or “light.”
• pro-fragrance compound is defined herein as “a chemical species, which by undergoing one or more chemical transformations results in the release of one or more fragrance compounds.”
• Fragrance compounds and fragrance raw materials are terms which refer to the final “perfume” ingredients which are delivered and are used interchangeably herein.
• chemical transformation includes conversion to a species of different molecular formula by any means, inter alia, hydrolysis, photolysis, thermolysis, autoxidation, addition, elimination and substitution reactions, as well as conversion to a species with the same molecular formula, but having an altered chemical orientation, i.e., isomerized.
• the chemical cascade which begins the release of a fragrance raw material, may be controlled by requiring a certain wavelength of electromagnetic radiation to be present to initiate the release sequence.
• a certain wavelength of electromagnetic radiation For example, “outside light”, which typically comprises the full range of UV light, may be required to initiate the release of the fragrance precursor.
• high temperatures may also initiate the chemical cascade.
• the present invention relates to conjugates, which upon exposure to visible light or other forms of electromagnetic radiation, inter alia, UV light, releases a fragrance raw material after a series of chemical transformations, wherein said series involves at least two discrete steps.
• the photo-labile pro-fragrance conjugates of the present invention comprise:
• the conjugates of the present invention comprise a chemical species having a photo-activated unit which is bonded to the nitrogen atom of a pro-fragrance compound, a fragrance raw material, or a linking unit which is subsequently bonded to the nitrogen atom of a pro-fragrance compound, or a fragrance raw material, wherein said chemical bond is capable of being broken when said conjugate is exposed to electromagnetic radiation.
• hydrocarbyl is defined herein as “any unit which comprises carbon and hydrogen atoms, whether linear, branched, cyclic, and regardless of how many of the hydrogen atoms are substituted for with a suitable “substituted” unit as defined herein below.”
• suitable “substituted” unit as defined herein below.
• Non-limiting examples of “hydrocarbyl” units include methyl, benzyl, 6-hydroxyoctanyl, m-chlorophenyl, 2-(N-methylamino)propyl, and the like.
• unit which can substitute for hydrogen and “substituted” are used throughout the specification and for the purposes of the present invention these terms are defined as “chemical moieties which can replace a hydrogen atom on a hydrocarbon chain, an aryl ring, and the like, or replacement of a hydrogen atom, two hydrogen atoms, or three hydrogen atoms from a carbon atom to form a moiety, or the replacement of hydrogen atoms from adjacent carbon atoms to form a moiety.”
• a substituted unit that requires a single hydrogen atom replacement includes halogen, hydroxyl, and the like.
• a two-hydrogen atom replacement includes carbonyl, oximino, and the like.
• Three hydrogen replacement includes cyano, and the like.
• substituted is used throughout the present specification to indicate that a moiety, inter alia, aromatic ring, alkyl chain, can have one or more of the hydrogen atoms replaced by a substituent.
• 4-hydroxyphenyl is a “substituted aromatic carbocyclic ring”
• 3-guanidinopropyl is a “substituted C 3 alkyl unit.”
• R 30 is hydrogen, C 1 -C 20 linear or branched alkyl, C 6 -C 20 aryl, C 7 -C 20 alkylenearyl, and mixtures thereof; M is hydrogen, or a salt forming cation.
• Suitable salt forming cations include, sodium, lithium, potassium, calcium, magnesium, ammonium, and the like.
• Non-limiting examples of an alkylenearyl unit include benzyl, 2-phenylethyl, 3-phenylpropyl, 2-phenylpropyl.
• the photo-labile units of the present invention may be any moiety, which is capable of instigating the release of a fragrance raw material by breaking the chemical bond between the photo-labile unit and one of three components:
• a first aspect of photo-labile units according to the present invention relate to units which are aryl acrylic acid units having the formula:
• R is a fragrance raw material or a unit capable of releasing a fragrance raw material; each R 1 is independently hydrogen, a unit which can substitute for hydrogen, C 1 -C 12 substituted or unsubstituted hydrocarbyl unit, each R 2 is independently hydrogen, C 1 -C 12 substituted or unsubstituted hydrocarbyl unit, and mixtures thereof; X is selected from the group consisting of —OH, —OC(O)R 12 , —OC(O)OR 12 , —NHR 12 , and mixtures thereof; R 12 is H, C 1 -C 12 substituted or unsubstituted alkyl, and mixtures thereof.
• These units are capable of releasing a fragrance raw material unit, a pro-fragrance unit, or a linking group bonded fragrance raw material unit or pro-fragrance unit; the photo-fragment compound having the formula:
• Non-limiting examples of photo-labile units included in this first aspect include a pro-fragrance wherein X is —NH 2 , the R 1 unit is hydroxy, and both R 2 units are hydrogen which relates to 3-(2-amino-4-hydroxyphenyl)-acrylamide fragrance raw materials having the formula:
• a second aspect of the present invention relates to a photo-labile pro-fragrance conjugates having the formula:
• R 1 is one or more electron donating groups; non-limiting examples of which include hydroxy, C 1 -C 12 linear or branched alkoxy, —N(R 12 ) 2 , and mixtures thereof; R 12 is H, C 1 -C 12 alkyl, and mixtures thereof, and the like.
• a third aspect of the photo-labile units relates to aryl units having the formula:
• a fourth aspect of the photo-labile units relates to aryl units having the formula:
• B is a photo-labile unit which reactivity is enhanced or modulated by the aryl unit which comprises the balance of the photo-labile component.
• One embodiment of this aspect relates to silicon atom comprising units having the formula:
• an optional linking unit, L may be desired or necessary.
• An example of a compound having an L unit present has the formula:
• One aspect of the present invention relates to L units which are —OC(O)—, —NR 3 C(O)—, —OC(R 3 R 4 )—, and —C(O)— carbonyl units.
• any suitable unit which facilitates the breakdown of the released pro-fragrance can serve as a linking unit in the photo-activated pro-fragrance conjugates of the present invention.
• the pro-fragrance unit is released from the photo-labile unit when a linker unit is present, the release of the photo-fragment compound and pro-fragrance or fragrance compound is accompanied by the release of a linker compound.
• the linker compound is CO2.
• the linker compound released can be an aldehyde or a ketone.
• the aldehyde or ketone released is a perfume raw material.
• Non-limiting examples of photo-activated compounds comprising an L unit include:
• Pro-fragrance units are released from the parent conjugate molecules when the conjugate is fragmented by a photochemical reaction.
• the pro-fragrance units of the present invention are attached to the photo-labile units either directly or by way of an optional linking unit, L.
• fragrance raw materials can be released from the same form of pro-fragrance.
• the two primary aspects of the present invention as it relates to release of a pro-fragrance unit are determined by the type of reaction which ultimately releases the final fragrance raw material.
• the first aspect relates to type A release which involves a retro-Michael reaction
• the second aspect relates to type B release which involves a hydrolysis reaction.
• the first aspect of the pro-fragrance unit component of the present invention relates to the release of fragrance raw material precursors which undergo a retro-Michael reaction.
• reaction cascade which releases the fragrance raw material via retro-Michael reaction is believed to proceed according to the general scheme as depicted below for the release of a ⁇ , ⁇ -unsaturated ketone, inter alia, damascone.
• pro-fragrances which comprise this aspect of the present invention have the formula:
• each R 3 is independently hydrogen, substituted or unsubstituted C 1 -C 30 hydrocarbyl, and mixtures thereof.
• each R 4 is independently selected from the group consisting of:
• two R 4 units can be taken together to form one or more aromatic or non-aromatic, heterocyclic or non-heterocyclic, single rings, fused rings, bicyclo rings, spiroannulated rings, or mixtures thereof, said rings comprising from 3 to 20 carbon atoms and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and mixtures thereof;
• G 1 and G 2 are each independently hydrogen, C 1 -C 20 linear or branched hydrocarbyl, —Y, —C(O)Y, and mixtures thereof;
• Y is C 6 -C 10 substituted or unsubstituted cyclic alkyl.
• Non-limiting examples of embodiments of Y include 2,6,6-trimethylcyclohex-2-enyl, 2,6,6-trimethylcyclohex-1-enyl, 2,6,6-trimethylcyclohex-1-enyl, 2,6,6-trimethylcyclohex-3-enyl, and the like.
• Another embodiment of this aspect of the present invention relates to pro-fragrances having the formula:
• G 1 and G 2 are each independently —CH 3 , —C(O)CH 3 , —Y, —C(O)Y, and mixtures thereof;
• Y is selected from the group consisting of:
• photo-labile pro-fragrance which comprises a linking unit and which releases a fragrance raw material ( ⁇ -damascone) via retro-Michael reaction.
• R 3 units in another aspect of the present invention can be taken together with an R 1 or R 2 unit of the photo-labile unit or with an L unit to form a C 2 -C 6 heterocyclic ring for example, the conjugate having the formula:
• the second aspect of the pro-fragrance unit component of the present invention relates to the release of fragrance raw material precursors which undergo a hydrolysis step in the cascade releasing the fragrance raw material.
• reaction cascade which releases the fragrance raw material via hydrolysis reaction is believed to proceed according to the general scheme as depicted below for the release of an aldehyde, inter alia, citral.
• a first photo-isomerization step :
• each of which is capable of releasing an aldehyde having the formula R 5 CHO.
• heterocyclic ring embodiment which comprises the pro-fragrance units of the present invention which have the general formula:
• Z is oxygen or sulfur; in one embodiment comprising oxazolidines, Y is oxygen and the index m is 1.
• R 5 and R 6 units are selected such that upon hydrolysis of the pro-fragrance compound, aldehyde or ketone fragrance raw materials are released.
• R 6 is hydrogen.
• R 5 units can be any substituted or unsubstituted hydrocarbyl unit, non-limiting examples of which include R 5 units which comprise:
• R 6 units comprise:
• R 5 and R 6 units can be taken together to form a substituted or unsubstituted ring having in the ring from 3 to 10 carbon atoms; for example, R5 and R 6 taken together can be fused ring comprising ketones, inter alia, nootkatone; or mono-cyclic ketones, inter alia, menthone, isomenthone, carvone, and fenchone.
• each R 7 is independently selected from any substituted or unsubstituted hydrocarbyl unit, non-limiting embodiments are selected from the group consisting of:
• R 8 is:
• R 9 is hydrogen, C 1 -C 15 substituted linear alkyl, C 11 -C 15 unsubstituted linear alkyl, C 1 -C 15 substituted branched alkyl, C 11 -C 15 unsubstituted branched alkyl, C 2 -C 22 substituted or unsubstituted linear alkenyl, C 3 -C 22 substituted or unsubstituted branched alkenyl, or mixtures thereof, wherein said substitution is not halogen or thioalkyl; R 9 is methyl, R 9 is hydrogen and Z is oxygen or sulfur when an oxazolidine is formed from the methyl esters of serine, threonine, cysteine, and the like;
• R 10 is hydrogen, C 1 -C 6 substituted or unsubstituted linear alkyl, C 3 -C 6 substituted or unsubstituted branched alkyl, or mixtures thereof;
• each R 11 is independently;
• each of the ring carbon atoms may have one or both of the hydrogen atoms substituted as defined herein above or taken together to form an aromatic or non-aromatic, carbocyclic or heterocyclic ring, for example:
• R 6 is selected from the group consisting of hydrogen and methyl; each R 7 is independently hydrogen, methyl, —C(O)OR 9 and mixtures thereof; R 9 is hydrogen, C 1 -C 12 alkyl, and mixtures thereof.
• Hydrolysis based release of the fragrance raw material can proceed by way of any hydrolyzable pro-fragrance compound which is initiated by the release of the pro-fragrance unit from a photo-labile pro-fragrance conjugate.
• the ionone series of ketone fragrance raw materials unlike the damascone series delivered by Type A Release, are formed into photo-labile pro-fragrance conjugates in which the photo-labile unit is connected to a pro-fragrance unit consisting of a pro-fragrance compound that is an imine or an enamine that are themselves formed from the reaction of an aldehyde or ketone fragrance raw material with an amine compound.
• the imine- or iminium-based pro-fragrance compounds are released upon activation of the conjugate.
• the following is an example of a photo-labile pro-fragrance conjugate that is capable of releasing an enamine-based pro-fragrance compound of the present invention.
• Type B Release photo-activated pro-fragrances can also comprise a suitable linking group for example a compound having the formula:
• Type B Release relates to aminals or ketals having, for example, the formula:
• R′OH can be a fragrance raw material or not a fragrance raw material depending on the needs of the formulator.
• a non-limiting example of an aminal according to the present invention has the formula:
• the formulator when using aminals to deliver two fragrance raw materials can make use of the R 3 nitrogen unit to control the release rate of the fragrance raw materials once the photo-labile unit has released the pro-fragrance component.
• the formulator can make use of the R 3 nitrogen unit to control the physical properties of the photo-labile pro-fragrance conjugate. Such properties include, but are not limited to, the ability of the conjugate to deposit on a desired surface in an aqueous wash environment.
• a further example of Type B Release relates to conjugates which are activated by the breaking of the bond between the photo-labile unit and the pro-fragrance unit, wherein an intramolecular reaction ensues which displaces a pro-fragrance compound which then hydrolyzes to release the fragrance raw material.
• a non-limiting general example is the amino-amide photo-labile pro-fragrance conjugate depicted in the scheme below:
• fragrance raw materials are herein defined as compounds having a molecular weight of at least 100 g/mol and which are useful in imparting an odor, fragrance, essence, or scent either alone or in combination with other “fragrance raw materials”.
• fragrance raw materials which comprise an amino unit can be directly attached to the photo-labile unit and, therefore, released directly without further reaction.
• fragment raw materials comprise inter alia alcohols, ketones, aldehydes, esters, ethers, nitriles, and alkenes such as terpenes.
• a listing of common “fragrance raw materials” can be found in various reference sources, for example, “Perfume and Flavor Chemicals”, Vols. I and II; Steffen Arctander Allured Pub. Co. (1994) and “Perfumes: Art, Science and Technology”; Müller, P. M. and Lamparsky, D., Blackie Academic and Professional (1994) both incorporated herein by reference.
• fragrance raw material ketones which are capable of being released by the compounds of the present invention include 1-(2,6,6-trimethylcyclohex-2-enyl)-2-butene-1-one ( ⁇ -damascone), 1-(2,6,6-trimethyl-cyclohex-1-enyl)-2-butene-1-one ( ⁇ -damascone), 1-(2-methylene-6,6-dimethyl-cyclohexanyl)-2-butene-1-one ( ⁇ -damascone), 1-(2,6,6-trimethylcyclohex-3-enyl)-2-butene-1-one ( ⁇ -damascone), 4-(2,6,6-trimethylcyclohex-2-enyl)-3-butene-2-one ( ⁇ -ionone), 4-(2,6,6-trimethylcyclohex-1-enyl)-3-butene-2-one ( ⁇ -ionone), 4-(2,6,6-trimethylcyclohex-1-enyl)-3-butene-2-one
• Aldehydes which are releasable from the photo-activated conjugates of the present invention include but are not limited to phenylacetaldehyde, p-methyl phenylacetaldehyde, p-isopropyl phenylacetaldehyde, methyinonyl acetaldehyde, phenylpropanal, 3-(4-t-butylphenyl)-2-methyl propanal, 3-(4-t-butylphenyl)-propanal, 3-(4-methoxyphenyl)-2-methylpropanal, 3-(4-isopropylphenyl)-2-methylpropanal, 3-(3,4-methylenedioxyphenyl)-2-methylpropanal, 3-(4-ethylpheny)-2,2-dimethylpropanal, phenylbutanal, 3-methyl-5-phenylpentanal, hexanal, trans-2-hexenal, cis-
• odor detection threshold is defined as the level at which a fragrance raw material is perceptible to the average human.
• ODT odor detection threshold
• GC gas chromatograph
• Determination of Odor Detection Thresholds is as follows.
• a gas chromatograph is characterized to determine the exact volume of material injected by a syringe, the precise split ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chain-length distribution.
• the airflow rate in accurately measured and, assuming the duration of a human inhalation to last 0.02 minutes, the sampled volume is calculated. Since the precise concentration at the detector at any point in time is known, the mass per volume inhaled is known and hence the concentration of material.
• solutions are delivered to the sniff port at the back-calculated concentration.
• GC 5890 Series II with FID detector 7673 Auto sampler Column: J&W Scientific DB-1, length 30 m, i.d. 0.25 mm, film thickness 1 m.
• Split Injection 17/1 split ratio
• Detector temperature 285° C.
• Temperature Information
• a general first procedure relates to the conversion of a starting material having formula 1 to the aryl acrylamide photo-labile pro-fragrance 3 by way of the intermediate aryl acrylic acid 2 as depicted in the following scheme:
• Step (2) preparation of 1-[2-(2,4-Dimethyl-cyclohex-3-enyl)-oxazolidin-3-yl]-3-(2-hydroxy-phenyl)-propenone (7):
• Step (2) preparation of 3-(2,4-Dihydroxy-phenyl)-1- ⁇ 2-methyl-2-[2-(2,6,6-trimethyl-cyclohex-1 -enyl)-ethyl]-[1,3]oxazinan-3-yl ⁇ -but-2-en-1-one (9):
• Step (2) Preparation of 3-(2,4-Dihydroxy-phenyl)-N-[1 -methyl-3-oxo-3-(2,6,6-trimethyl-cyclohex-3-enyl)-propyl]-acrylamide (11):
• reaction mixture is partitioned between ether (200 mL) and water (400 mL); the organic layer is removed and washed with ether (200 mL). The combined organic layers are washed sequentially with saturated sodium bicarbonate solution (200 mL) and brine (200 mL). The organic layer is dried over anhydrous magnesium sulfate, vacuum filtered and concentrated to give 3-(2,4-dihydroxy-phenyl)-acrylic acid 1,5-dimethyl-1-vinyl-hex-4-enyl ester as an oil that is purified by flash chromatography to give 11 as a colorless solid.
• Step (1) To a 0° C. stirred solution of 96 g (0.50 mol) of 1-(2,6,6-trimethyl-cyclohex-3-enyl)-but-2-en-1-one ( ⁇ -damascone) in 250 mL of ethanol is added 47 g (0.25 mol) of N 1 -[3-(3-Amino-propylamino)-propyl]-propane-1,3-diamine. The reaction is allowed to warm to room temperature.
• Step (2) which is conversion of starting material 12 to intermediate 13 can be a accomplished by the method described in Synthetic Comm. 1991, 21, 351 included herein by reference.
• the present invention relates to a photo-labile fragrance delivery system which delivers a photo-labile pro-fragrance conjugate.
• the pro-fragrance relies upon the photo-initiated cascade to deliver the fragrance raw material. Because it is not necessary that the pro-fragrance compound immediately begins releasing an aldehyde or ketone once the photo-labile unit has released said pro-fragrance compound, the formulator may form a wide array of delivery systems.
• the systems of the present invention comprise several embodiments having various ranges of pro-fragrance conjugate, for example:
• a photo-labile unit which upon exposure to electromagnetic radiation is capable of releasing a pro-fragrance unit as a pro-fragrance compound
• Another aspect of the present invention relates to conjugates of the present invention that comprise a photo-labile pro-fragrance conjugate comprising a photo-labile unit which upon exposure to electromagnetic radiation is capable of releasing a pro-fragrance unit as a fragrance compound.
• the photo-labile pro-fragrances of the present invention have wide utility in perfumes and fine fragrances.
• This embodiment of the present invention comprises:
• the carrier for fine fragrances and perfumes is ethanol or ethanol/water.
• other pro-fragrances, pro-accords, and the like can be included, especially species which take advantage of the differential pH of skin.
• acid labile pro-fragrances include orthoesters, acetals, ketals, and the like. Therefore, the combination of a photo-labile pro-fragrance and an acid labile pro-fragrance which releases the same fragrance raw material, inter alia, damascone, citronellal, is one aspect encompassed by the present invention.
• fragrance and “fine fragrance” are essentially synonymous and are used collectively or interchangeably throughout the present specification and are taken to mean the more concentrated forms of fragrance-containing compositions. Aspects of the present invention which apply to “perfumes” will therefore apply equally to “fine fragrances” and vice versa.
• colognes, eau de toilettes, after shaves, and other fragrance-containing embodiments are perfumes or fine fragrances which have a greater degree of dilution, usually by a volatile carrier such as ethanol.
• An example of a skin care composition of the present invention comprises an ester having a total number of carbon atoms in excess of about 28, for example lauryl laurate, lauryl myristate, myristyl myristate, behenyl caprate, cetearyl palmitate, behenyl stearate, more preferably cetearyl palmitate and cetyl stearate.
• the present compositions in addition to the esters described herein above, contain an emollient material in an amount such that the amount of ester plus emollient is from about 0.2%, preferably from about 4% to about 25%, preferably to about 18% of the total composition.
• One function of the emollient is to ensure that the ester is plasticized sufficiently to allow it to be in a film-like state on the skin.
• the emollient in the present compositions is selected from the group consisting of fatty alcohols, esters having fewer than about 24 total carbon atoms (e.g. isopropyl palmitate), branched chain esters having greater than about 24 total carbon atoms (e.g.
• esters those having fewer than 24 carbon atoms or branched and having more than 24 carbon atoms, if used as an emollient should preferably be used in an mount equal to about a third of the long chain ester.
• the particular emollient selected depends in part on the particular ester selected since proper plasticization, as indicated above, is desired.
• the emollient for the esters having more than 28 carbon atoms is preferably selected from the group consisting of squalane, liquid or solid paraffins and mixtures of fatty alcohols with squalane or paraffins.
• Typical fatty alcohols and fatty acids useful in the present compositions include those having from 12-22 carbon atoms such as cetyl alcohol, myristyl alcohol, stearyl alcohol, stearic acid and palmitic acid.
• Paraffins include, for example, mineral oil, petrolatum and paraffin wax. It is preferred that distilled water be used in the present compositions.
• the oil phase of the present compositions may contain a variety of materials including:
• Oils such as castor oil, jojoba oil, cottonseed oil, peanut oil and sesame
• Waxes such as ceresin wax, carnuba wax, beeswax and castor wax
• Lanolin its derivatives and components such as acetylated lanolin, lanolin alcohols and lanolin fatty acids.
• Lanolin fatty acids are described in U.S. Pat. No. Re. 29,814, Oct. 24, 1978 to W. E. Snyder incorporated herein by reference.
• Sterols such as cholesterol and phytosterol.
• These optional oil phase materials may comprise up to about 80% of the oil phase, preferably up to about 35%. When used at these levels, the optional components do not impair the occlusive nature of the compositions and add to the composition's total cosmetic performance.
• the water phase of the compositions may contain many different materials including:
• Humectants such as sorbitol, glycerine, propylene glycol, alkoxylated glucose and hexanetriol at a level of from about 1% to about 20%.
• Thickening agents such as carboxyvinyl polymers, ethyl cellulose, polyvinyl alcohol, carboxymethyl cellulose, vegetable gums and clays such as Veegum.RTM. (magnesium aluminum silicate, R. T. Vanderbilt, Inc.) at a level of from about 0.01% to about 6%;
• Preservatives such as the methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid (Parabens-Mallinckrodt Chemical Corporation) EDTA and imidazolidinyl urea (Germall 115-Sutton Laboratories) at a level of from about 0.2% to about 2.5%; and
• An alkaline agent such as sodium hydroxide to neutralize, if desired, part of the fatty acids or thickener which may be present. All of the percentages of these additional water phase components are of the total composition.
• the present compositions may also contain agents suitable for aesthetic purposes such as dyes.
• the compositions of the present invention are preferably substantially free of materials that adversely affect their performance. Therefore, such things as polyethylene glycols are preferably present only at levels below about 1% of the total composition.
• the pH of the present compositions is preferably in the range of about 7.5-10.
• compositions which comprise the skin lotion embodiments of the present invention generally have a lotion consistency and may be in the form of oil-in-water or water-in-oil emulsions with the former being preferred because of their more pleasing cosmetic properties.
• the compositions of the present invention are preferably made by the method comprising the steps of;
• Step (a) is carried out by heating the oil phase materials to a temperature of about 75° C. to about 100° C.
• Step (b) is carried out by heating the water phase materials to a temperature about the same as that of the oil phase.
• the emulsion is formed by slowly adding the oil phase prepared in step (a) to the water phase prepared in step (b) with stirring.
• the pro-accords which comprise the fragrance delivery system or other ingredients may be added to the phase in which they are soluble prior to the mixing of the two phases or added directly to the mixed water and oil phases.
• the pro-accords of the present invention are also suitable for use in any odor controlling or fragrance mediating application.
• An example of this odor control capacity is animal litter and odor control articles useful in lining the cages, stalls, and other living areas of domesticated animals.
• U.S. Pat. No. 5,339,769 Toth et al., issued Aug. 23, 1994 describes a process for making an absorbent composition, which can well accommodate the pro-accord materials of the present invention.
• An example of a suitable litter material which comprises the photo-labile pro-fragrance conjugates of the present invention can be formed by the following process.
• a Glatt fluid bed granulator is charged with 1,0000 g of bentonite clay (90% of the particles being greater than 420 microns) and 10 g of a cellulose ether (MethocelTM K15M Premium, a cellulose ether having a viscosity of 15,000 centipoise (cps) as a 2% aqueous solution).
• the granulator is started and the product temperature is brought up to about 40° C.(outlet temperature).
• the outlet temperature reaches about 40° C.
• atomized water is sprayed onto the moving powders within the granulator.
• inlet air temperature is maintained at 70° C. to 80° C.; air atomization pressure is 28-35 psi; and the spraying cycle is for 45 seconds with a 15 second shaking time.
• the clay/cellulose ether agglomerates swell over time.
• the water hydrates the cellulose ether polymer, which produces adhesion to form the granule.
• the formation of the granule promotes aggregation of the small sized particles of the inert substrate, e.g. clay particles of about 50 to 600 microns.
• the formation of a granule significantly reduces the quality of dust in the final product while the litter forms an agglomerate when wetted.
• a concentrated solution, or a carrier alcohol-based admixture of the pro-accords may be delivered to the surface of the granule by a suitable means.
• a deodorant gel stick of the present invention having the composition given below, and being essentially free of water, is prepared as follows. TABLE I weight % Ingredients 5 6 7 8 Dipropylene glycol 39.85 51.95 75.10 71.15 Sodium Stearate 5.50 5.50 5.50 5.55 PPG-3 myristyl ether 29.40 25.33 15.00 19.30 Cyclomethicone-D5 21.00 13.33 — — Ethanol (absolute; 200 proof) 1.80 1.44 1.95 1.50 Zinc pyrithione 1 0.05 0.05 0.05 0.10 Conjugate 2 2.40 0.55 0.1 0.001
• a personnel cleanser composition is prepared by combining the following ingredients using conventional mixing techniques.
• TABLE II weight % Ingredients 9 10 11 12 Phase A Water QS 100 QS 100 QS 100 QS 100 Disodium EDTA 0.100 0.100 0.100 0.100 0.100 Glycerin 4.00 4.00 4.00 Methylparaben 0.200 0.200 0.200 0.200 C 10 -C 30 alkyl 0.150 0.150 0.150 acrylate crosspolymer 1 Carbomer 954 2 0.250 0.250 0.250 0.250 Water QS 100 QS 100 QS 100 QS 100 Phase B Stearic Acid 0.110 0.110 0.110 0.110 0.110 Stearyl alcohol 0.875 0.875 0.875 Cetyl alcohol 0.875 0.875 0.875 Propylparaben 0.150 0.150 0.150 Steareth-2 — 0.25 0.25 0.25 Steareth-21 — 0.50 0.50 0.50 Phase C Sodium hydroxide 3 0.130 0.130 0.130 0.130 Phase D Diisopropyl sebacate 1.
• the above Examples 8-11 can be suitably prepared as follows.
• the Phase A ingredients are mixed at room temperature to form a dispersion and heated with stirring to 70-80° C.
• Phase B is heated with stirring to 70-80° C.
• Phase B is then added to Phase A with mixing to form the emulsion.
• Phase C is added to neutralize the composition.
• the Phase D ingredients are added with mixing, followed by cooling to 45-50° C.
• the Phase E ingredients are then added with stirring, followed by cooling to 40° C.
• Phase F is heated with mixing to 40° C. and added to the emulsion, which is cooled to room temperature.
• the resulting cleansing composition is useful for cleansing the skin.
• the emulsion de-emulsifies upon contact with the skin.
• the present invention further relates to the use of photo-labile pro-fragrances in embodiments which do not contact human skin, inter alia, laundry detergent compositions, hard surface cleaning compositions, carpet cleaning compositions, and the like.
• the laundry detergent compositions of the present invention comprise a surfactant system.
• the surfactant systems of the present invention may comprise any type of detersive surfactant, non-limiting examples of which include one or more mid-chain branched alkyl sulfate surfactants, one or more mid-chain branched alkyl alkoxy sulfate surfactants, one or more mid-chain branched aryl sulfonate surfactants, one or more non mid-chain branched sulphonates, sulphates, cationic surfactants, zwitterionic surfactants, ampholytic surfactants, and mixtures thereof.
• the total amount of surfactant present in the compositions of the present invention is from about 10% by weight, in one embodiment of the present invention the range of surfactant is from about 10% to about 80% by weight, of said composition. Another embodiment the amount of surfactant is from about 10% to about 60%, wherein another embodiment comprises from about 15% to about 30% by weight, of said composition.
• Nonlimiting examples of surfactants useful herein include:
• R is C 4 -C 10 alkyl
• R 1 is selected from the group consisting of C 1 -C 4 alkyl, —(CH 2 CHR 2 O) y H, and mixtures thereof
• R 2 is hydrogen, ethyl, methyl, and mixtures thereof
• y is from 1 to 5
• x is from 2 to 4
• a particularly useful pseudoquat surfactant comprises R equal to an admixture of C 8 -C 10 alkyl, R 1 is equal to methyl; and x equal to 3; these surfactants are described in U.S. Pat. No. 5.916,862 Morelli et al., issued Jun. 29, 1999 included herein by reference;
• R 7 is C 5 -C 31 alkyl
• R 8 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl
• Q is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof; preferred alkoxy is ethoxy or propoxy, and mixtures thereof.
• the mid-chain branched alkyl sulfate surfactants of the present invention have the formula:
• alkyl alkoxy sulfates have the formula:
• alkyl alkoxylates have the formula:
• R, R 1 , and R 2 are each independently hydrogen, C 1 -C 3 alkyl, and mixtures thereof; provided at least one of R, R 1 , and R 2 is not hydrogen; preferably R, R 1 , and R 2 are methyl; preferably one of R, R 1 , and R 2 is methyl and the other units are hydrogen.
• the total number of carbon atoms in the mid-chain branched alkyl sulfate and alkyl alkoxy sulfate surfactants is from 14 to 20; the index w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1; provided w +x +y +z is from 8 to 14 and the total number of carbon atoms in a surfactant is from 14 to 20; R 3 is C 1 -C 4 linear or branched alkylene, preferably ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof.
• M denotes a cation, preferably hydrogen, a water soluble cation, and mixtures thereof.
• water soluble cations include sodium, potassium, lithium, ammonium, alkyl ammonium, and mixtures thereof.
• adjunct ingredients useful in the laundry compositions of the present invention
• said adjunct ingredients include builders, optical brighteners, soil release polymers, dye transfer agents, dispersents, enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anti corrosion agents, and mixtures thereof.
• granular compositions are generally made by combining base granule ingredients, e.g., surfactants, builders, water, etc., as a slurry, and spray drying the resulting slurry to a low level of residual moisture (5-12%).
• base granule ingredients e.g., surfactants, builders, water, etc.
• the remaining dry ingredients e.g., granules of the polyalkyleneimine dispersant
• the liquid ingredients e.g., solutions of the polyalkyleneimine dispersant, enzymes, binders and perfumes, can be sprayed onto the resulting granules to form the finished detergent composition.
• Granular compositions according to the present invention can also be in “compact form”, i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/l.
• the granular detergent compositions according to the present invention will contain a lower amount of “inorganic filler salt”, compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; “compact” detergents typically comprise not more than 10% filler salt.
• Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations.
• Liquid compositions according to the present invention can also be in “compact form”, in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents.
• Addition of the polyalkyleneimine dispersant to liquid detergent or other aqueous compositions of this invention may be accomplished by simply mixing into the liquid solutions the polyalkyleneimine dispersant.
• compositions of the present invention can be suitably prepared by any process chosen by the formulator, non-limiting examples of which are described in U.S. Pat. No. 5,691,297 Nassano et al., issued Nov. 11, 1997; U.S. Pat. No. 5,574,005 Welch et al., issued Nov. 12, 1996; U.S. Pat. No. 5,569,645 Dinniwell et al., issued Oct. 29, 1996; U.S. Pat. No. 5,565,422 Del Greco et al., issued Oct. 15, 1996; U.S. Pat. No. 5,516,448 Capeci et al., issued May 14, 1996; U.S. Pat. No. 5,489,392 Capeci et al., issued Feb. 6, 1996; U.S. Pat. No. 5,486,303 Capeci et al., issued Jan. 23, 1996 all of which are incorporated herein by reference.
• compositions 16-19 can be prepared or used according to any of U.S. Pat. No. 5,534,165 Pilosof et al., issued Jul. 9, 1996; U.S. Pat. No. 5,593,670 Trinh et al., issued Jan. 14, 1997; U.S. Pat. No. 5,686,097 Trinh et al., issued Sep. 16, 1997; U.S. Pat. No. 5,714,137 Trinh et al. issued Feb. 3, 1998; U.S. Pat. No. 5,939,060 Trinh et al., issued Aug. 17, 1999; U.S. Pat. No. 6,146,621 Trinh et al., issued Nov. 14, 2000; all of which are included herein by reference.

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