Novel ester compounds

Abstract

The present disclosure is directed to certain polyether esters of di- and tri-carboxylic acid, and methods of making and using the same, such as maleate, fumarate, itaconate, citraconate, mesaconate, citrate, and tartrate, esters of polycitronellol and other polyterpenols. Such products can be prepared from renewable resources and the functional groups can include a wide variety of unsubstituted, substituted, saturated, unsaturated, cyclic, and acyclic molecular structures.

Description

NOVEL ESTER COMPOUNDSCROSS-REFERENCE TO RELATED APPLICATIONSThis application is an international application which claims priority to, and the benefit of, U.S. Provisional Application Ser. No. 63 / 655,873, filed on June 4, 2024, the contents of which are hereby incorporated by reference in its entirety.FIELD

[0001] The present disclosure is directed to certain polyether esters of di- and tri-carboxylic acid, and methods of making and using the same, such as maleate, fumarate, itaconate, citraconate, mesaconate, citrate, and tartrate, esters of polycitronellol and other polyterpenols. Such products can be prepared from renewable resources and the functional groups can include a wide variety of unsubstituted, substituted, saturated, unsaturated, cyclic, and acyclic molecular structures.BACKGROUND

[0002] Liquid polymers have important utility in cosmetic and personal care applications and play critical roles in visual displays, rheology, tribology, and drug delivery. For example, they can be used as lubricants, emollients, or as protective barriers for skin healing and UV protection. Ideally, these materials can be produced in a facile manner, be easily derivatized to modify function, and even more preferably be made from safe and sustainable raw materials.

[0003] These liquid polymers are endowed with active chemical functionality, such as primary alcohol, which can be reacted with di- and tri-carboxylic acid esters to form a new type of polymer with promising properties and sustainability. Furthermore, this invention discloses new sustainable polymer for cosmetic formulations (skincare, color cosmetic and hair care) and material science applications with enhanced performance, owing to their biocompatibility and high surface area. In addition, the surface chemistry of these polymers can be easily modified for tuning properties for specific applications.

[0004] US2017 / 0283553, the contents of which are incorporated herein by reference, discloses how to make and use polyether polymers derived by the homopolymerization of alkenyl alcohols, such as prenol, citronellol, and the like. The resulting polyether polymers represent an advance in liquid polymer technology and carry with them many desirable benefits forcommercial fields of application. In addition, US 2020 / 0165383, US2023 / 0295374, US2023 / 0063141, US2023 / 0057412, the contents of each of which are incorporated herein by reference, have taught how to further derivatize such polyether polymers to increase their functionality and usefulness, such as by forming monoester and monoether derivatives thereof. In particular, these disclosures provided polycitronellol polymers, and simple monoester and monoether derivatives of polycitronellol (such as polycitronellol acetate). The aforementioned patent applications did not, however, disclose esters of dicarboxylic or tricarboxylic acids.

[0005] The present disclosure builds on these prior art teachings by providing novel derivatization strategies and methods of production to produce new polymers and polymer derivatives with novel and useful properties.BRIEF SUMMARY

[0006] The present disclosure provides novel compounds according to Formula I below: O OR-OX O,RFormula I wherein X is selected from Ci-2oalkylene, C2-2oalkenylene, Cs-ncycloalkylene, C4- i2cycloalkenylene, aryl, heteroaryl, biaryl, and 5-6-membered heterocycloalkyl, each optionally substituted by one or more of =0, OH, ORa, SH, SRa, NH2, NHRa, NRaRb, and -C(O)OR, and wherein R is a terpene alcohol or poly(monoterpenyl)oxy moiety and Raand Rbare each independently selected from optionally substituted -C(0)-Ci-2oalkyl (e.g., C1-6 alkyl), optionally substituted -C(0)-C2-2oalkenylene, and optionally substituted -C(O)-aryl.

[0007] The compound of Formula I may be a diester of a dicarboxylic acid, formed or formable by reacting a dicarboxylic acid of formula HOC(O)-X-C(O)OH with an alcohol of the formula R-OH. The compound of Formula I may also be a triester of a tricarboxylic acid, formed or formable by reacting a tricarboxylic acid of formula HOC(O)-X-C(O)OH with an alcohol of the formula R-OH, when the group X in the acid HOC(O)-X-C(O)OH the group X includes an additional -C(O)OH group. Likewise, the compound of Formula I may be a poly carboxylic ester, in the case where the group X of Formula I includes more than one -C(O)OR group. Preferably the compound of Formula I is an ester of an acid selected from malic, itaconic, fumaric, citraconic, mesaconic, or citric acid.

[0008] It some embodiments, the compound of Formula I may also embrace polycarboxylic esters wherein one or more of the ester groups are “reversed,” that is, wherein the ester is derived from a hydroxy moiety in the group X of Formula I acylated with a carboxylic acyl moiety to form the ester group (i.e., an -OC(O)Ra) group.

[0009] The Compounds of Formula I are biorenewable, biodegradable, and biocompatible. When used alone, or with other cosmetically acceptable ingredients, they can impart excellent compatibility, feel, and softness to the specific product and application, esters can be used in personal care, especially in hair care and skin care applications. These compounds also have the benefit of being low e-factor, low carbon-footprint, long lasting, highly miscible, easy to formulate, super sensory, non-greasy, slippery and odorless. These new compounds will also be useful in a variety of material science applications including, but not limited to, lubrication and friction modifier compositions.

[0010] Preferably, the compounds disclosed herein are liquids at room temperature, and / or at temperatures above or below room temperature (e.g.., 10 to 30 °C).

[0011] By careful selection of the acid and alcohol components of the esters of Formula I, the properties of the resulting compound may be optimized for performance, such as by controlling functional group density, distances between esters groups, and properties such as reactivity, deposition, heat protection, frizz, shine, feel, and volume.

[0012] For example, in some embodiments the moiety -C(O)-X-C(O)- in the compound of Formula I includes a double bond such as to form an alpha, beta-unsaturated carbonyl function, which can act as a Michael acceptor in a 1,4-addition reaction (Michael addition reaction). In such a reaction, this Michael acceptor group can react with a natural Michael donor group, such as the carboxy group, hydroxy group, amino group, or sulfhydryl group, of an alcohol, carbohydrate, fatty acid, fatty alcohol, amino acid, polypeptide, protein, or other biological compound. This can enable the compound of Formula I to not only deposit onto the hair or skin surface, but also to stick to the said surface for an extended period of time. Because the Michael reaction is reversible, the compounds of Formula I can catalyze the formation of disulfide linkages and hence can reestablish cross-linking between protein chains in damaged hair and skin, providing a favorable effect in hair and skin repair of, for example, damage associated with heat styling, chemical treatment, color treatment, and cold and hot weather. The compounds can thus improve the structure, strength, stability, and elasticity of the hair and skin.

[0013] The compound of Formula I are also capable of penetrating on a molecular level in all hair and skin types, which aids their ability to effectively restore healthy hair and skin. They can help to maintain a natural hair shaft as well as skin to provide resistance to various environmental constraints and attacks such as friction, tension, flexion, UV radiation and chemical insults.

[0014] In another aspect, the present disclosure provides a method of making a compound of Formula I by reacting an alcohol of the formula R-OH (e.g., a poly(monoterpenyl) alcohol, such as polycitronellol), with a dicarboxylic, tricarboxylic, or polycarboxylic acid, or with esters, acyl halides, or anhydrides thereof, e.g., compounds of the formulas A-C(O)-X(-C(O)-A)-C(O)-A, wherein each A is independently OH, ORX, or halogen, wherein Rxis a Ci-6 alkyl (e.g., methyl or ethyl). Preferably, the alcohol R-OH is a poly(monoterpenyl) alcohol, such as a poly citronellol. Preferably, the acid is selected from malic, itaconic, fumaric, citraconic, mesaconic, or citric acid, or an ester thereof (e.g., dimethyl maleate, dimethyl itaconate, dimethyl fumarate, dimethyl citraconate, dimethyl mesaconate, tri ethyl citrate).

[0015] In some embodiments, the compounds of Formula I may be made by reacting 1 equivalent of an ester compound of the formula A-C(O)-X(-C(O)-A)-C(O)-A, wherein each A is independently ORX, and Rxis a Ci-6 alkyl (e.g., methyl or ethyl), with 2 to 3 equivalents of an alcohol, such as poly citronellol. Optionally, the reaction further comprises a base.

[0016] In another aspect, the present disclosure provides methods of using, and uses of, the compound of Formula I, such as use in personal care products, especially in hair care and skin care products. These structurally unique liquid polymers have many useful and beneficial properties, such as, one or more of, being: bio-renewable, biocompatible, biodegradable, low e- factor, low carb on -footprint, long-lasting, highly miscible, easy to formulate, super-sensory, non- greasy, slippery, and odorless.

[0017] In a further aspect, the present disclosure provides cosmetic and personal care compositions comprising the Compounds of Formula I. The compounds disclosed herein can be formulated without water, so they can be used in waterless, water-free, and anhydrous cosmetics. Therefore, this will reduce their water footprint, and will decrease the carbon footprint of the supply chain.DETAILED DESCRIPTION

[0018] The term terpene alcohol refers to natural or semisynthetic terpene derivatives having a hydroxyl group, including but not limited to, citronellol, prenol, geraniol, nerol, farnesol, linalool, perillyl alcohol, menthol, borneol, carveol, and cinnamyl alcohol.

[0019] For the purposes of this invention, the term ‘citronellol’ is meant to include both isomers at the olefinic position. Similarly, when the term ‘prenol’ is used, it is meant to include isoprenol isomers as well.

[0020] The term poly(monoterpenyl) alcohol means an alcohol-terminated homopolymer of a monoterpene, such as citronellol, and this includes dimers, trimers, oligomers, and short polymers of any length within the ranges disclosed herein. In a preferably embodiment, the short polymers range from 2 to 200 monomers in length, e.g., 2 to 100, or 2 to 80, or 2 to 60, or 2 to 50, or 2 to 40, or 2 to 30, or 2 to 25, or 2 to 20, or 2 to 15, or 2 to 12, or 2 to 10, monomers in length.

[0021] The unique benefits of the compounds disclosed herein derive from one or more of the following features: the compounds are derived from short-chain polymers and natural carboxylic acids or ester; the compounds are made using a reversible polymerization reaction; the compounds are biodegradable and biocompatible; and the compounds may be manufactured using all-natural ingredients. These are important benefits in many of the commercial applications in which these compounds may be used. The compounds disclosed herein are suitable as replacement or substitutes for emollients or surfactants (e.g., octyldodecanol), polymers, and silicones in a variety of commercial products, such as in cosmetics and pharmaceutical compositions, and as adjuvants in crop care formulations, and as lubricants or solvents in enhanced oil recovery, fracking and oil field applications. The compounds disclosed herein offer improved physical characteristics, such as appearance, odor, viscosity, refractive index and / or surface tension. The nature of these compounds as derivatives of short polymers of moderate molecular weight (e.g., less than 20,000 Daltons, or less than 15,000 Daltons, or less than 10,000 Daltons, or less than 5,000 Daltons, or less than 3,000 Daltons, or 100-10,000 Daltons, or 100-5,000 Daltons, or 100-3,000 Daltons, or 100-1,500 Daltons, or 100-1000 Daltons) makes them desirable for numerous uses.

[0022] In a first aspect, the present disclosure provides Compounds (Compound 1) according to Formula I below:Formula I wherein X is selected from Ci-2oalkylene, C2-2oalkenylene, Ca-ncycloalkylene, C4- ncycloalkenylene, aryl, heteroaryl, biaryl, and 5-6-membered heterocycloalkyl, each optionally substituted by one or more of =0, OH, 0Ra, SH, SRa, NH2, NHRa, NRaRb, and -C(O)OR, and wherein R is a terpene alcohol or poly(monoterpenyl)oxy moiety and Raand Rbare each independently selected from optionally substituted -C(0)-Ci-2oalkyl (e.g., C1-6 alkyl), optionally substituted -C(0)-C2-2oalkenylene, optionally substituted -C(0)- aryl.

[0023] In further embodiments of the first aspect, the disclosure provides any of the following:1.1 Compound 1, wherein X is selected from Ci-2oalkylene, C2-2oalkenylene, C3- ncycloalkylene, and C4-i2cycloalkenylene, each optionally substituted;1.2 Compound 1, wherein X is selected from Ci-2oalkylene, and Cs-ncycloalkylene, each optionally substituted;1.3 Compound 1, wherein X is Ci-2oalkylene (e.g., Ci-iealkylene, or Ci-ioalkylene, or Ci- ealkylene), each optionally substituted;1.4 Compound 1, wherein X is selected from C2-2oalkenylene, and C4-i2cycloalkenylene, each optionally substituted;1.5 Compound 1, wherein X is C2-2oalkenylene (e.g., C2-iealkenylene, or C2-ioalkenylene, or C2-ealkenylene), each optionally substituted;1.6 Compound 1, or any of 1.1-1.5, wherein said Ci-2oalkylene is a linear Ci-2oalkylene (e.g., -CH2-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)8-,-(CH2)io-,-(CH2)i2-,-(CH2)i6-, or -(CH2)20-), optionally substituted;1.7 Compound 1, or any of 1.1 -1.5, wherein said Ci-2oalkylene is a branched Ci-2oalkylene (e g., -CH2CH(CH3)-, -CH(CH3)CH2-, or -CH(CH3)CH(CH3)-), optionally substituted;1.8 Compound 1, or any of 1.1-1.5, wherein said C2-2oalkenylene is a linear C2-2oalkenylene (e.g., -CH=CH-, -CH2-CH=CH-, -CH=CH-CH2-, -CH2CH=CHCH2-, -CH=CH-(CH2)8-, -(CH2)6- -CH=CH-)), optionally substituted;1 .9 Compound 1 , or any of 1 .1 -1 .5, wherein said C2-2oalkenylene is a branched C2- 2oalkenylene (e.g., -(C=CH2)-, -C(CH3)=CH, -CH=C(CH3)-, -CH2(C=CH2)-, -(C=CH2)CH2-), optionally substituted;1.10 Compound 1.8 or 1.9, wherein said C2-2oalkenylene its double bond in (E)- stereochemistry;1.11 Compound 1.8 or 1.9, wherein said C2-2oalkenylene its double bond in (Z)- stereochemistry;1.12 Compound 1, or any of 1.1-1.5, wherein said C3-i2cycloalkylene is cyclopropylene (e.g.,1,1- or 1,2-cyclopropylene), cyclobutylene (e.g., 1,1- or 1,2- or 1,3 -cyclobutylene), cyclopentylene (e.g., 1,1- or 1,2- or 1,3-cyclopentylene), or cyclohexylene (e.g., 1,1- or 1,2- or 1,3- or 1,4-cyclohexylene), each optionally substituted;1.13 Compound 1, or any of 1.1-1.5, wherein said C4-i2cycloalkenylene is cyclobutenylene (e.g., 1,2-cyclobut-l-enylene), cyclopentenylene (e.g., 1,2-cyclopent-enylene), or cyclohexenylene (e.g., 1,2-cyclohex-l-enylene), each optionally substituted;1.14 Compound 1, or any of 1.1-1.5, wherein said C4-i2cycloalkylene or C4-i2cycloalkenylene is bicyclic, e.g., a bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, bicyclo[3.2.2]nonane, bicyclo[2.2.1]heptene, bicyclo[2.2.2]octene, or bicyclo[3.2.2]nonene, each optionally substituted;1.15 Any of Compounds 1.1-1.14, wherein said Ci-2oalkylene, C2-2oalkenylene, C3. ncycloalkylene, or C4-i2cycloalkenylene is unsubstituted (i.e., not further substituted);1.16 Any of Compounds 1.1-1.14, wherein said Ci-2oalkylene, C2-2oalkenylene, C3. i2cycloalkylene, or C4-i2cycloalkenylene is further substituted by one or more =0, OH, ORa, SH, SRa, NH2, NHRa, NRaRb, and -C(O)OR;1.17 Compound 1.16, wherein said Ci-2oalkylene, C2-2oalkenylene, C3-i2cycloalkylene, or C4- i2cycloalkenylene is further substituted by one or more =0;1.18 Compound 1.16 or 1.17, wherein said Ci-2oalkylene, C 2-20 alkenyl ene, C3-i2cycloalkylene, or C4-i2cycloalkenylene is further substituted by one or more OH, SH, or NH2;1.19 Compound 1.16 or 1.17, wherein said Ci-2oalkylene, C2-2oalkenylene, C3-i2cycloalkylene, or C4-i2cycloalkenylene is further substituted by one or more 0Ra, SRa, NHRa, or NRaRb;1.20 Compound 1.16 or 1.19, wherein Raand Rbare each independently optionally substituted -C(0)-Ci-2oalkyl (e.g., C1-6 alkyl);1 .21 Compound 1 .16 or 1 .19, wherein Raand Rbare each independently optionally substituted -C(0)-C2-2oalkenylene;1.22 Compound 1.16 or 1.19, wherein Raand Rbare each independently optionally substituted -C(O)-aryl;1.23 Any one of Compounds 1.16-1.22, wherein said Ci-galkylene, C2-salkenylene, C3- i2cycloalkylene, or C4-i2cycloalkenylene is further substituted by one or more -C(O)OR;1.24 Compound 1.23, wherein said Ci-2oalkylene, C2-2oalkenylene, Ca-ncycloalkylene, or C4- ncycloalkenylene is further substituted by one -C(O)OR;1.25 Any one of Compounds 1.16-1.22, wherein said Ci-2oalkylene, C2-2oalkenylene, C3- i2cycloalkylene, or C4-i2cycloalkenylene is further substituted only by one or more -C(O)OR, e.g., only one -C(O)OR;1.26 Compound 1, wherein X is selected from aryl, heteroaryl, and biaryl, each optionally substituted;1.27 Compound 1, wherein X is aryl, e.g., phenyl or naphthyl, optionally substituted by one or more of OH, ORa, SH, SRa, NH2, NHRa, NRaRb, and -C(O)OR;1.28 Compound 1, wherein said aryl is phenyl;1.29 Compound 1.28, wherein the acyl substituents of the compound of Formula I on the phenyl ring are positioned in a 1,4-substitution pattern, or a 1,3-substituted pattern, or a 1,2- substitution pattern;1.30 Any of Compounds 1.27-1.29, wherein said aryl (e.g., phenyl) is not further substituted;1.31 Any of Compounds 1.27-1.29, wherein said aryl (e.g., phenyl) is substituted by one or more OH, SH, or NH2;1.32 Any of Compounds 1.27-1.29, wherein said aryl (e.g., phenyl) is substituted by one or more ORa, SRa, NHRa, orNRaRb;1.33 Compound 1.27 or 1.32, wherein Raand Rbare each independently optionally substituted -C(0)-Ci-2oalkyl (e.g., C1-6 alkyl);1.34 Compound 1.27 or 1.32, wherein Raand Rbare each independently optionally substituted -C(0)-C2-2oalkenylene;1 .35 Compound 1 .27 or 1 .32, wherein Raand Rbare each independently optionally substituted -C(O)-aryl;1.36 Any of Compounds 1.27-1.35, wherein said aryl (e.g., phenyl) is substituted by one or more -C(O)OR;1.37 Compound 1.36, wherein said aryl (e.g., phenyl) is substituted by one -C(O)OR;1.38 Any one of Compounds 1.31-1.37, wherein said aryl (e.g., phenyl) is further substituted only by one or more -C(O)OR, e g., only one -C(O)OR;1.39 Compound 1, wherein X is heteroaryl, optionally substituted by one or more of OH, ORa, SH, SRa, NH2, NHRa, NRaRb, and -C(O)OR;1.40 Compound 1.39, wherein said heteroaryl is selected from pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, thiophenyl, furanyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, isoxazolyl, isothiazolyl, pyrazolyl, quinolinyl, isoquinolinyl, quinazolinyl, and indolyl;1.41 Compound 1.40, wherein said heteroaryl is furanyl, e.g., 2, 3 -di substituted furanyl or 2,5- di substituted furanyl;1.42 Any of Compounds 1.39-1.41, wherein said heteroaryl (e.g., furanyl) is not further substituted;1.43 Any of Compounds 1.39-1.41, wherein said heteroaryl (e.g., furanyl) is substituted by one or more OH, SH, or NH2;1.44 Any of Compounds 1.39-1.41, wherein said heteroaryl (e.g., furanyl) is substituted by one or more ORa, SRa, NHRa, or NRaRb;1.45 Compound 1.39 or 1.44, wherein Raand Rbare each independently optionally substituted -C(0)-Ci-2oalkyl (e.g., Ci-6alkyl);1.46 Compound 1.39 or 1.44, wherein Raand Rbare each independently optionally substituted -C(0)-C2-2oalkenylene;1 .47 Compound 1 .39 or 1 .44, wherein Raand Rbare each independently optionally substituted -C(O)-aryl;1.48 Any of Compounds 1.39-1.47, wherein said heteroaryl (e.g., furanyl) is substituted by one or more -C(O)OR;1.49 Compound 1.48, wherein said heteroaryl (e.g., furanyl) is substituted by one -C(O)OR;1.50 Any of Compounds 1.39-1.48, wherein said heteroaryl (e.g., furanyl) is further substituted only by one or more -C(O)OR, e.g., only one -C(O)OR;1.51 Compound 1, wherein X is biaryl (e.g., 1,1’ -biphenyl), optionally substituted by one or more of OH, ORa, SH, SRa, NH2, NHRa, NRaRb, and -C(O)OR;1.52 Compound 1.51, wherein said biaryl (e.g., 1,1 ’-biphenyl) is not further substituted;1.53 Compound 1.51, wherein said biaryl (e.g., 1,1 ’-biphenyl) is substituted by one or more OH, SH, orNH2;1.54 Compound 1.51, wherein said biaryl (e.g., 1,1 ’-biphenyl) is substituted by one or more ORa, SRa, NHRa, or NRaRb;1.55 Compound 1.54, wherein Raand Rbare each independently optionally substituted -C(O)- Ci-2oalkyl (e.g., Ci-6 alkyl);1.56 Compound 1.54, wherein Raand Rbare each independently optionally substituted -C(O)- C2.2oalkenylene;1.57 Compound 1.54, wherein Raand Rbare each independently optionally substituted -C(O)- aryl;1.58 Any of Compounds 1.51-1.57, wherein said biaryl (e.g., l,l’-biphenyl) is substituted by one or more -C(O)OR;1.59 Compound 1.58, wherein said biaryl (e.g., l,l’-biphenyl) is substituted by one -C(O)OR;1.60 Compound 1.59, wherein said biaryl (e.g., 1,1 ’-biphenyl) is further substituted only by one or more -C(O)OR, e.g., only one -C(O)OR;1.61 Compound 1, wherein X is 5-6 membered heterocycloalkyl, optionally substituted by one or more of OH, ORa, SH, SRa, NH2, NHRa, NRaRb, and -C(O)OR;1.62 Compound 1.61, wherein said heterocycloalkyl is selected from aziridinyl, azetidinyl, oxetanyl, tetrahydrofuranyl, pyrrolidinyl, piperidinyl, piperazinyl, and morpholinyl;1.63 Compound 1.62, wherein said heterocycloalkyl is tetrahydrofuranyl or pyrrolidinyl, e.g., 2, 3 -di substituted or 2, 5 -di substituted tetrahydrofuranyl or pyrrolidinyl;1 .64 Any of Compounds 1 .61-1 .63, wherein said heterocycloalkyl (e.g., tetrahydrofuranyl or pyrrolidinyl) is not further substituted;1.65 Any of Compounds 1.61-1.63, wherein said heterocycloalkyl (e.g., tetrahydrofuranyl or pyrrolidinyl) is substituted by one or more OH, SH, or NH2;1.66 Any of Compounds 1.61-1.63, wherein said heterocycloalkyl (e.g., tetrahydrofuranyl or pyrrolidinyl) is substituted by one or more ORa, SRa, NHRa, or NRaRb;1.67 Compound 1.61 or 1.66, wherein Raand Rbare each independently optionally substituted -C(0)-Ci-2oalkyl (e.g., C1-6 alkyl);1.68 Compound 1.61 or 1.66, wherein Raand Rbare each independently optionally substituted -C(0)-C2-2oalkenylene;1.69 Compound 1.61 or 1.66, wherein Raand Rbare each independently optionally substituted -C(O)-aryl;1.70 Any of Compounds 1.61-1.69, wherein said heterocycloalkyl (e.g., tetrahydrofuranyl or pyrrolidinyl) is substituted by one or more -C(O)OR;1.71 Compound 1.70, wherein said heterocycloalkyl (e.g., tetrahydrofuranyl or pyrrolidinyl) is substituted by one -C(O)OR;1.72 Any of Compounds 1.61-1.71, wherein said heterocycloalkyl (e.g., tetrahydrofuranyl or pyrrolidinyl) is further substituted only by one or more -C(O)OR, e.g., only one -C(O)OR;1.73 Compound 1, or any of 1.1-1.72, wherein the compound of Formula I is selected from the group consisting of1.74 Compound 1, or any of 1.1-1.73, wherein R is a terpene alcohol moiety;1.75 Compound 1.74, wherein the terpene alcohol moiety is selected from the group consistingMenthol Carveol , Perillyl alcohol, , and1.76 Compound 1, or any of 1.1-1.75, wherein R is poly(monoterpenyl)oxy moiety;1.77 Compound 1.76, wherein R has the structure:, wherein n is an integer from 0-10(e.g., 1-10, or 2-10, or 0-8, or 1-8, or 2-8, or 0-6, or 1-6, or 2-6);1.78 Compound 1, wherein the compound is a compound of the structure:Compound 55 wherein R has the structure:, wherein n is an integer from 0- 10 (e.g., 1-10, or 2-10, or 0-8, or 1-8, or 2-8, or 0-6, or 1-6, or 2-6);1.79 Compound 1, or any of 1.1-1.78, wherein the Compound is a liquid at room temperature (e.g., 10 to 30 °C, or 15 to 30 °C, or 20 to 30 °C);1.80 Compound 1, or any of 1.1-1.79, wherein the Compound has a molecular weight of less than 20,000 Daltons, or less than 15,000 Daltons, or less than 10,000 Daltons, or less than 5,000 Daltons, or less than 3,000 Daltons, or 100-20,000 Daltons, or 100-15,000 Daltons, or 100-10,000 Daltons, or 100-5,000 Daltons, or 100-3,000 Daltons, or 100-1,500 Daltons, or 100-1000 Daltons).

[0024] The compounds of Formula I (Compound 1, or any of 1.1 et seq., or any mixtures thereof) may be formulated into various specialty chemical compositions or products, including personal care, hair care and skin care composition and products, in order to alter, modify and improve the function of such compositions or products. The functionality of the compound depends on its size and composition, and new and renewable compositions are highly desired as they have the potential to improve application performance. Depending on the functional group density, these compounds may provide long lasting moisturized feel, smooth feel, and / or manageability and control to the hair after it is dried.

[0025] The Compounds disclosed herein can be used for hair formulations and treatments that repair and strengthen damaged hair. They can also add strength to hair fibers while also improving its health and sensorial feel.

[0026] In second aspect, the present disclosure provides a composition (Composition 1), which composition comprises Compound 1 or any of 1.1 et seq., or any mixtures thereof, in combination with at least one suitable solvent, carrier, or excipient. In further embodiments of the second aspect, the present disclosure provides Compositions as follows:1.1 A fragrance composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof.1.2 A perfume composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof.1.3 A soap composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof.1.4 A pomander composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof.1.5 A cosmetic composition comprising Compound 1 or any of 1.1 et seq, or any mixture thereof, such as, for example, a lipstick, lip balm, lip gloss, eye shadow, liquid highlighter (e.g., for the cheeks), a skin ointment, skin lotion, or a skin balm.1.6 A toilet water composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof.A pre- and / or aftershave lotion composition comprising Compound 1 or any of 1 .1 et seq., or any mixture thereof. A talcum powder composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof. A hair-care product composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof, for example, a hair styling product (e.g., hair spray, hair gel, or hair drying cream, mousse) or hair cleaning product (e.g., shampoo or conditioner). A body deodorant composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof. An anti -perspirant composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof. A shampoo composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof. A topically applied skin care composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof, optionally wherein the skin care application may be selected from skin-conditioning agents; skin penetration enhancing agents; skin protectants; skin soothing agents; skin healing agents; ultraviolet light absorbers or scattering agents; sequestrants; antiacne agents; anti -androgens; depilation agents; keratolytic agents / desquamation agents / exfoliants such as salicylic acid; panthenol moisturizer such as D-panthenol; soluble or colloi daily-soluble moisturizing agents such as hyaluronic acid and starch-grafted sodium polyacrylates; and sunscreens. Composition 1.13, wherein the skin care application is a skin protectant. Composition 1.13, wherein the skin care application is a skin soothing agent or skin moisturizing agent (e.g., in a moisturizing lotion). Composition 1.13, wherein the skin care application is a sunscreen. An antimicrobial composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof. A mesogen comprising Compound 1 or any of 1.1 et seq., or any mixture thereof. A writing and / or printing ink composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof.A dye composition or pigment composition comprising Compound 1 or any of 1 .1 et seq., or any mixture thereof, e.g., further comprising a dye and / or pigment. A paint or coating composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof, e.g., further comprising a dye and / or pigment. A skin-tone evening composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof. An anti -hyperpigmentation composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof. An anti -hypopigmentation composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof. A cross-linking, temporary stiffening, or permanent stiffening, composition comprising Compound 1 or any of 1.1 et seq., or any mixture thereof, e g., in combination with a crosslinking agent, or a temporary or permanent stiffening agent. Composition 1, or any of 1.1-1.25, wherein the composition comprises, or consists of, Compound 1 or any of 1.1 et seq., dissolved or suspended in a solvent or mixture of solvents, e.g., ester, alkane, aromatic, alcohol, or ether solvents. Composition 1, or any of 1.1-1.25, wherein the composition is a solution or suspension of Compound 1 or any of 1.1 et seq., in a solvent or mixture of solvents, e.g., ester, alkane, aromatic, alcohol, or ether solvents. Composition 1.26 or 1.27, wherein the solvents are selected from Cl-4 esters (e.g., methyl acetate, ethyl acetate, isopropyl acetate), C4-18 esters, C3-10 alkanes (e.g., hexane, heptane, octane), C10-18 alkanes (linear or branched), C2-10 alcohols (e.g., ethanol, propanol, isopropanol), C2-10 ethers (e.g., diethyl ether, diisopropyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane), and C6-12 aromatics (e.g., toluene, xylenes). Composition 1, or any of 1.1-1.28, wherein the composition further comprises one or more natural oils. Composition 1, or any of 1.1-1.29, wherein the composition further comprises one or more alpha-hydroxy acids, beta-hydroxy acids, or salicylic acid. Composition 1, or any of 1.1-1.30, wherein the composition further comprises one or more synthetic layers double hydroxide clays.1 .32 Composition 1 , or any of 1 .1 -131 , wherein the composition further comprises a mesoporous magnesium carbonate, e.g., Upsalite®.1.33 Composition 1, or any of 1.1-1.32, wherein the composition further comprises a keratolytic agent, e.g., salicylic acid, lactic acid, or urea.1.34 Composition 1, or any of 1.1-1.33, wherein the composition further comprises cannabidiol (CBD), tetrahydrocannabinol (THC), or hemp seed oil.1.35 Composition 1, or any of 1.1-1.34, wherein the composition further comprises one or more snow fungus extracts.1.36 Composition 1, or any of 1.1-1.35, wherein the composition further comprises Rosa canina fruit oil.1.37 Composition 1, or any of 1.1-1.36, wherein the composition is acid free, quat free, cruelty free, phosphate free, gluten free, paraben free, phthalate free, preservative free, nut free, peg free, formaldehyde free, sulfate free, and / or thiol free.

[0027] In another embodiment, the present disclosure provides Compound 1, or any of 1.1-1.80, for use in Composition 1, or any of 1.1-1.37.

[0028] The Compounds disclosed herein, when infused with natural oil and other nourishing ingredients, can help to repair damaged or weakened hair. These restorative formulas can deeply hydrate normal to dry hair, for a healthier look and feel.

[0029] The Compositions disclosed herein, when added to a natural formulation, can provide fullness, control, volume, heat protection, and more.

[0030] The Compositions disclosed herein are designed to deliver customizable, lasting hold without sacrificing a soft, touchable feel.

[0031] The Compositions disclosed herein can be specially formulated to soothe the scalp and maintain a healthy balance so that the hair can flourish.

[0032] The Compositions disclosed herein can be used to repair and strengthen damaged hair, and to add strength to hair fibers while also improve hair health and sensorial feel.

[0033] The Compositions disclosed herein can be formulated to deliver the Compounds alone or with a natural oil to stop irritation in the scalp which stems from using hair dye or even a dry shampoo or over-washing hair with sulfate-base products.

[0034] In terms of maintaining a healthy scalp, the Compounds disclosed herein can be used with moisturizing scalp oils or hair masks to soothe scalp on the regular basis.

[0035] The Compositions disclosed herein can be designed to protect hair from sunlight and thus can keep natural hair color and prevent progressive damage to lipids within the hair. Thus, they can prevent hair from becoming frizzy and more susceptible to fractures (split ends) with combing friction.

[0036] The Compounds disclosed herein can be used alone or with antioxidants to prevent progressive hair damage caused by free radicals and reactive oxygen species (ROS).

[0037] The Compounds disclosed herein can be used at a variety of pH levels (from highly acidic to highly basic), without compromising the stability of the respective compositions.

[0038] The Compounds disclosed herein are safe and sustainable and can be used with any “pharmaceutically acceptable” or “cosmetically acceptable” compositions to repair or improve hair and skin conditions.

[0039] In the Compositions disclosed herein, the Compounds can be used to replace silicones for equivalent or superior performances in skin moisturizing, hair build-up, hair antifrizz, hair heat protection, foam reductant and skin-feel.

[0040] The Compounds disclosed herein can be used alone or with beta hydroxy acid, salicylic acid, and any other alpha hydroxy acids (AHAS) for scalp exfoliation. These types of formulations can expedite scalp’s cell turnover and get rid of buildup to promote healthy hair. Gentle chemical exfoliation with these types of liquid polymers can help reduce flaking and makes sure hair follicles are not clogged with product buildup, oil, and keratin debris, which can prevent hair from growing and cause bumps on the scalp (like ingrown hairs) that create itching and discomfort.

[0041] The Compounds disclosed herein can be used as “bond builders” that work to build new bonds (e.g., disulfide bonds) that support the strand where bond breakage has happened. They can also work by strengthening bonds from being broken in the first place. They can help rebuild bonds usually broken due to heat damage, they hold the fiber together, keeping it compact, and return resilience to hair so it can bounce back after being stressed.

[0042] The Compounds disclosed herein can be used as or with an acid free, quat free, cruelty free, phosphate free, gluten free, paraben free, phthalate free, preservative free, nut free, peg free, formaldehyde free, sulfate free and thiol free formulations.

[0043] The Compounds disclosed herein can be used for “skinification” of hair care. This involves treating the scalp with the same care and attention as the face, using these polymersalone or with products like scalp peels and serums that are designed to improve scalp health and, by extension, hair health.

[0044] The Compounds disclosed herein can be used alone or with other sustainable cosmetic ingredients to hydrate the scalp and can enhance the elasticity in the strands, which helps promote healthy hair growth.

[0045] The Compounds disclosed herein will be highly sustainable and eco-friendly. They will require minimal or no preservatives in their compositions. They will have small and less sophisticated packaging, and hence, will have better shelflife and last longer due to less dilution, compared to competitor products.

[0046] The Compounds disclosed herein can be used with synthetic layered double hydroxide clays (LDHs) and can serve as rheology modifiers, mattifying agents, multifunctional excipients, absorbents and texturing agents in hair and skin care application. This combination can also be used in photoprotection and masking of bad odor and test and modified release.

[0047] The Compounds disclosed herein can be used with Upsalite® (a mesoporous magnesium carbonate) in a variety of color cosmetic applications including hair and skin care.

[0048] The Compounds disclosed herein can be used with keratolytic agents to dissolve skin flakes and scales. So, removing these scales and flakes not only will improve the appearance of the skin and minimize dandruff, but it will also help other topical medications to penetrate the skin better.

[0049] The Compounds disclosed herein can be used in combination with common keratolytic agents including salicylic acid, lactic acid, and urea to improve a multitude of skin conditions including calluses, acne, and psoriasis.

[0050] The Compounds disclosed herein can be used with CBD (cannabidiol), THC (tetrahydrocannabinol), and hemp seed oil to create formulated hair and skin-care products to calm post- workout redness, soothe irritation, and nourish dehydrated, stressed skin. In the above formulations, other natural ingredients can be present optionally, including red grape seed, pomegranate seed, broccoli, petitgrain, bergamot, cranberry, and lemon balm.

[0051] The Compounds disclosed herein can be used as a lubricant or friction modifier composition for lubricants.

[0052] The Compounds disclosed herein can be used as additives to provide antioxidants, antifatigue, anti-wear, and deposit control properties to lubricants.

[0053] The Compounds disclosed herein are nature derived and made from renewable resources, can be used with exosomes, neurocosmetics, and supercharged actives for personalized skincare.

[0054] The Compounds disclosed herein can support the activity of sirtuin network to directly impact in the skin and increasing skin cells area.

[0055] The Compounds disclosed herein can be used with the snow fungus extracts to reduce trans epidermal water loss (TEWL) and hence will be able to prevent excessive water evaporation from the skin, leading to improved hydration.

[0056] The Compounds disclosed herein can be used as an ingredient, with a composition containing biological molecules, to signal cells to communicate, regenerate, and repair.

[0057] The Compounds disclosed herein can be used with Rosa canina fruit oil to moisturize skin as well as providing beneficial fatty acids that soothe and strengthen skin’s barrier.

[0058] The Compositions disclosed herein can recover the lipid layer of the hair cuticle and improve its overall appearance.

[0059] In organic chemistry, transesterification reactions are extremely important synthetic manipulation where an alcohol reacts with an ester to form another new ester. If a small diester or tri-ester compound and a primary alcohol are subjected to transesterification, in presence of a base, it forms a new compound with an ester functionality at the end. Thus, for example, the Compounds of the present disclosure can be made according to the following exemplary scheme:Scheme 1

[0060] In some embodiments, the compounds of Formula I may be made by reacting 1 equivalent of a diester compound of the formula A-C(O)-X-C(O)-A, wherein each A is independently ORX, and Rxis a Ci-6 alkyl (e.g., methyl or ethyl), with 2 to 3 equivalents of an alcohol, such as poly citronellol. In some embodiments, the compounds of Formula I may be made by reacting 1 equivalent of a triester compound of the formula A-C(O)-X(-C(O)-A)-C(O)- A, wherein each A is independently ORX, and Rxis a Ci-6 alkyl (e.g., methyl or ethyl), with 2 to 3 equivalents of an alcohol, such as poly citronellol. Optionally, the reaction further comprises a base.

[0061] Suitable bases for the transesterification reaction include, but are not limited to, potassium methoxide, sodium methoxide, potassium ethoxide, sodium ethoxide, potassium tert- butoxide, sodium tert-butoxide, lithium isopropoxide, aluminum isopropoxide, lithium hydroxide, aluminum alkoxide, lithium methoxide, titanium isopropoxide, sodium hydride, and a combination thereof

[0062] In a third aspect, the disclosure provides a method of making Compound 1 or any of 1. 1 et seq. (Method 1), by reacting an alcohol of the formula R-OH (e.g., a poly(monoterpenyl) alcohol, such as polycitronellol), with a dicarboxylic, tricarboxylic, or polycarboxylic acid, or with esters, acyl halides, or anhydrides thereof, e.g., compounds of theformulas A-C(O)-X(-C(O)-A)-C(O)-A, wherein each A is independently OH, ORX, or halogen, wherein Rxis a Ci-6 alkyl (e.g., methyl or ethyl).

[0063] In a particular embodiment, the method comprises the steps of (1) introducing into a reactor an alcohol of the formula R-OH (such as a poly(monoterpenyl) alcohol, such as polycitronellol), and a dicarboxylic, tricarboxylic, or polycarboxylic acid, or an ester, acyl halide, or anhydride thereof, e.g., compounds of the formulas A-C(O)-X-C(O)-A or A-C(O)-X(-C(O)- A)-C(O)-A, wherein each A is independently OH, ORX, or halogen, and (2) exposing said mixture to a base for a sufficient amount of time to form the Compound of Formula I; and (3) isolating and / or purifying (e.g., by distillation) the Compound 1, e.g., a group of related Compounds 1 having different values of the integers n, wherein X and R, are as defined in any embodiment of Compound 1 et seq. Preferably, in step (1), the alcohol R-OH is combined with an ester of the formula A-C(O)-X-C(O)-A or A-C(O)-X(-C(O)-A)-C(O)-A, wherein each A is independently ORX, and Rxis a Ci-6 alkyl (e.g., methyl or ethyl).

[0064] In further embodiments of the third aspect, the disclosure provides the following:1.1 Method 1, wherein the reactants are combined in a suitable solvent;1.2 Method 1 or 1.1, wherein a dicarboxylic, tricarboxylic, or polycarboxylic acid is used, optionally along with a coupling agent (e.g., a carbodiimide reagent);1.3 Method 1 or 1.1, wherein a dicarboxylic, tricarboxylic, or polycarboxylic acyl halide (e.g., acyl chloride) or acid anhydride is used;1.4 Method 1 or 1.1, wherein a dicarboxylic, tricarboxylic, or polycarboxylic ester is used (e.g., a methyl or ethyl ester);1.5 Method 1 or any of 1.1-1.4, wherein the reaction occurs at a temperature between 40 and 150°C, e.g., between 50 and 120°C, or at about 80 °C.1.6 Any of Methods 1 or 1.1-1.5, wherein the base is a Bronsted base;1.7 Method 1.6, wherein the Bronsted base is a hydroxide, alkoxide, carbonate, or bicarbonate base, e.g., a sodium, potassium, lithium, calcium, magnesium, or aluminum salt thereof;1.8 Method 1.7, wherein the Bronsted base is a hydroxide or alkoxide base, e.g., a sodium, potassium, lithium, calcium, magnesium, or aluminum salt thereof;1.9 Method 1.7, wherein the Bronsted base is an alkoxide base, e.g., a sodium, potassium, lithium, calcium, magnesium, or aluminum salt thereof;1.10 Method 1 .9, wherein the Bronsted base is a methoxide, ethoxide, propoxide, isopropoxide, n-butoxide, s-butoxide, or t-butoxide base, e.g., a sodium, potassium, lithium, calcium, magnesium, or aluminum salt thereof;1.11 Method 1.10, wherein the Bronsted base is potassium methoxide, sodium methoxide, potassium ethoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide, lithium isopropoxide, or aluminum isopropoxide, e.g., lithium methoxide, sodium methoxide or potassium methoxide;1.12 Method 1.11, wherein the Bronsted base is lithium methoxide;1.13 Method 1 or any of 1.1-1.12, wherein 0.5 to 3 equivalents of based is used, e.g., 1 to 3 equivalents, or 1.5-3 equivalents, or 2-3 equivalents (e.g., wherein the reactant is a carboxylic acid, acyl halide, or acid anhydride);1.14 Method 1 or any of 1.1-1.12, wherein 0.001 to 0.25 molar equivalents of base is used, e.g., 0.001 to 0.20 molar equivalents, or 0.001 to 0.10 molar equivalents, or 0.001 to 0.05 molar equivalents, or 0.01 to 0.05 molar equivalents, or about 0.025 molar equivalents, based on molar amount of the alcohol R-OH (i .e., the amount of alcohol R-OH is 1.0 equivalent) (e.g., wherein the reactant is an ester);1.15 Method 1 or any of 1.1-1.15, wherein the alcohol R-OH is reacted with a dicarboxylic, tricarboxylic, or polycarboxylic ester;1.16 Method 1.15, wherein the ester is of the formula A-C(O)-X-C(O)-A or A-C(O)-X(-C(O)- A)-C(O)-A, wherein each A is independently ORX, and Rxis a Ci-6 alkyl (e.g., methyl or ethyl1.17 Any of Methods 1.13-1.16, wherein 0.25 to 0.5 equivalents of the ester are reacted with 1.0 equivalent of the alcohol;1.18 Method 1 or any of 1.1-1.17, wherein the reaction occurs for 1 to 48 hours, e.g., 1 to 24 hours, or 1 to 18 hours, or 1 to 12 hours, or 6 to 18 hours, or about 12 hours or about 24 hours;1.19 Method 1 or any of 1.1-1.18, wherein the product of Formula I is purified by organic- aqueous extraction, optionally followed by distillation.

[0065] In another embodiment, the present disclosure provides a Compound made according to Method 1, or any of Methods 1.1-1.19.

[0066] In a fourth aspect, the present disclosure provides a method of using Compound 1 et seq., e.g., produced by Method 1, et seq., in a composition (e.g., Composition 1, et seq., for example, a fragrance, perfume, soap, pomander, cosmetic, toilet water, pre- and aftershavelotion, talcum powder, hair-care product, body deodorant, anti -perspi rant, shampoo, skin care product, pharmaceutical, or antimicrobial, as described in Composition 1, or any of Compositions 1.1-1.37).

[0067] Thus, the present disclosure provides a method (Method 2) of using Compound 1, or any of 1.1-1.80, in the manufacture of Composition 1, or any of Compositions 1.1-1.37.

[0068] In further embodiments of the fourth aspect, Method 2 may provide any of the following:2.1 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a fragrance composition.2.2 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a perfume.2.3 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a soap.2.4 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a pomander.2.5 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a cosmetic.2.6 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a toilet water.2.7 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a pre- and aftershave lotion.2.8 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a talcum powder.2.9 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a hair-care product.2.10 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a body deodorant.2.11 The method of Method 2, wherein Compound 1 or any of 1.1- 1.80, is used in an antiperspirant.2.12 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a shampoo.2.13 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a topically applied in a skin care application, wherein the skin care application may be selected from skinconditioning agents; skin penetration enhancing agents; skin protectants; skin soothing agents; skin healing agents; ultraviolet light absorbers or scattering agents; sequestrants; anti -acneagents; anti-androgens; depilation agents; keratolytic agents / desquamation agents / exfoliants such as salicylic acid; panthenol moisturizer such as D-panthenol; soluble or colloidally-soluble moisturizing agents such as hyaluronic acid and starch-grafted sodium polyacrylates; and sunscreens.2.14 The method of Method 2.13, wherein the skin care application is a skin protectant.2.15 The method of Method 2.13, wherein the skin care application is a skin soothing agent.2.16 The method of Method 2.13, wherein the skin care application is a sunscreen.2.17 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a pharmaceutical.2.18 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a mesogen.2.19 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a writing and / or printing ink composition.2.20 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a dye composition or pigment composition.2.21 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a paint or coating composition.2.22 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in a skin-tone evening composition.2.23 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in an antihyperpigmentation composition.2.24 The method of Method 2, wherein Compound 1 or any of 1.1-1.80, is used in an antihypopigmentation composition.

[0069] An added benefit of these materials described herein is that they are expected to be fully biodegradable and biocompatible.

[0070] In another aspect, the fragrance compositions of the present application, comprising the compounds of Compound 1, et seq., e.g., as produced by Method 1, et seq., and the fragrance composition is selected from: perfumes, soaps, pomanders, cosmetics, toilet waters, pre- and aftershave lotions, talcum powders, hair-care products, body deodorants, anti-perspirants, shampoo, cologne, shower gel, and hair spray.

[0071] In another aspect the compounds of Compound 1, et seq., e.g., as produced by Method 1, et seq., may be topically applied in a skin care application. For example, the skin careapplication may be selected from skin-conditioning agents; skin penetration enhancing agents; skin protectants; skin soothing agents; skin healing agents; ultraviolet light absorbers or scattering agents; sequestrants; anti-acne agents; anti -androgens; depilation agents; keratolytic agents / desquamation agents / exfoliants such as salicylic acid; panthenol moisturizer such as D- panthenol; soluble or colloidally-soluble moisturizing agents such as hyaluronic acid and starch- grafted sodium polyacrylates; and sunscreens.

[0072] In another aspect, the polyethers of Compound 1, et seq., as produced by Method 1 et seq., may be used in a delivery system, for example, in any fragrance delivery system in which a prolonged, defined release of the above-mentioned fragrant compounds is desired. For example, fragrance delivery systems as described herein may be used, e.g., in functional perfumery, in articles which are exposed to daylight when in use or which are applied to other articles which thereafter are exposed to daylight.

[0073] The details of one or more embodiments of the invention are set forth in the accompanying description below. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the case of conflict, the present specification will control.

[0074] Unless otherwise indicated, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the definitions set forth below.

[0075] As used herein, the following terms have the following meanings:(a) “Mesogen” means any polymeric compound or composition which displays liquid crystal properties (such as LCDs in consumer electronics);(b) “Cross-linking agent” means any polymeric compound or composition which enhances cotton’s dimensional stability, wrinkle resistance, and / or crease retention;(c) “Temporary or permanent stiffening agent” means any polymeric compound or composition which can be used in the process of cross-linking with fabric, such as, to play a crucial role in enhancing fabric properties, including making fabric more resilient and suitable for various end uses, particularly for cotton or linen;(d) “Skin-tone evening composition” means a composition which is applied to the skin to achieve a more uniform and balanced complexion, for example, any polymericcompound or composition which can be used for the purpose of “skin tone evening,” including to address irregularities such as hyperpigmentation, acne, scars, and redness;(e) “Super sensory” refers to the heightened sensory experience that a cosmetic product provides to the user including, but not limited to, feel, smell, and appearance;(f) “Exosomes” are microscopic extracellular vesicles produced within the body and secreted by skin cells, which can be used with any polymeric compound or composition in conjunction with in-office skin treatments or as part of a topical skincare regimen; exosomes have gained attention in the skincare industry due to their potential benefits including, but not limited to, anti-inflammatory properties, collagen boost, healing and rejuvenation, and environmental protection;(g) “Neurocosmetic” refers to certain beauty products designed, not only to protect and care for the skin, but also to enhance the user’s sense of well-being through the connection between the skin and the brain; neurocosmetic formulations incorporate specific compounds that create a multi-dimensional approach to skincare;(h) “Supercharged actives” refers to actives in a skin care composition enriched with the most potent ingredients to address or target the most universal skin concerns and / or deliver clinically tested visible results;(i) “Natural oils” generally refers to oils derived from plants, which can provide various benefits for the skin, and which are commonly used in cosmetic and skincare products due to their beneficial properties;(j) “Acid free” means free of, or low in (e.g., < 1 wt.%), alpha-hydroxy acids and / or beta-hydroxy acids;(k) “Quat free” means free of, or low in (e.g., < 1 wt.%), quaternary ammonium compounds, such as some cationic surfactants (e.g., benzalkonium);(l) “Cruelty free” means products or compositions that are not tested on animals, indicating avoidance of animal suffering and testing during product development;(m) “Phosphate free” means free of, or low in (e.g., < 1 wt.%), any phosphorus- containing compounds, including, but not limited to, inorganic orthophosphates, diphosphates (pyrophosphates), triphosphates, polyphosphates, phosphoric acid, andorganic phosphates, phosphonates, phosphites, phosphines, phosphides, and other organophosphates;(n) “peg free” means free of, or low in (e.g., < 1 wt.%), poly(ethylene glycol) polymers;(o) “Sulfate free” means free of, or low in (e.g., < 1 wt.%), any oxo-sulfur-containing compounds including, but not limited to, inorganic sulfates, sulfites, and bisulfites, sulfuric acid, sulfurous acid, and organic sulfates, sulfonates, sulfites, and sulfmites, including, for example, sulfate or sulfonate surfactants (e.g., sodium lauryl sulfate, sodium laureth sulfate);(p) “Thiol free” means free of, or low in (e.g., < 1 wt.%), any thiol-containing compounds, other than amino acids, polypeptides, and proteins, including, but not limited to, inorganic thiols or thiolates, and organic thiols and thiolates, as well as sulfide derivatives (dimers) thereof;(q) As used herein above, “free of, or low in” is intended to refer to added ingredients in compositions according to the present disclosure, as opposed to trace components which are the result of natural or artificial contamination, impurities, or natural products.

[0076] As used herein, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a reactant” includes not only a single reactant but also a combination or mixture of two or more different reactant, reference to “a substituent” includes a single substituent as well as two or more substituents, and the like.

[0077] As used herein, the phrases “for example,” “for instance,” “such as,” or “including” are meant to introduce examples that further clarify more general subject matter. These examples are provided only as an aid for understanding the disclosure, and are not meant to be limiting in any fashion. Furthermore, as used herein, the terms “may,” “optional,” “optionally,” or “may optionally” mean that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase “optionally present” means that an object may or may not be present, and, thus, the description includes instances wherein the object is present and instances wherein the object is not present.

[0078] As used herein, the phrase “having the formula” or “having the structure” is not intended to be limiting and is used in the same way that the term “comprising” is commonly used.

[0079] In some formulae of the present application, one or more chiral centers are identified by an asterisk placed next to the chiral carbon. In other formulae, no chiral center is identified, but the chiral isomers are nonetheless covered by these formulae.

[0080] Some compounds of the present invention can exist in a tautomeric form which is also intended to be encompassed within the scope of the present invention.

[0081] “Tautomers” refers to compounds whose structures differ markedly in arrangement of atoms, but which exist in easy and rapid equilibrium. It is to be understood that the compounds of the invention may be depicted as different tautomers, it should also be understood that when compounds have tautomeric forms, ail tautomeric forms are intended to be within the scope of the invention, and the naming of the compounds does not exclude any tautomeric form. Further, even though one tautomer may be described, the present invention includes all tautomers of the present compounds.

[0082] As used herein, the term “salt” can include acid addition salts including hydrochlorides, hydrobromides, phosphates, sulfates, hydrogen sulfates, alkyl sulfonates, aryl sulfonates, acetates, benzoates, citrates, maleates, fumarates, succinates, lactates, and tartrates; alkali metal cations such as Na+, K+, Li+, alkali earth metal salts such as Mg2+or Ca2+, or organic amine salts, or organic phosphonium salts.

[0083] The term “alkyl” and “alkylene” as used herein refers to a monovalent or bivalent, respectively, branched or unbranched saturated hydrocarbon group having from 1 to 22 carbon atoms, typically although, not necessarily, containing 1 to about 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, and the like.

[0084] Likewise, the term “cycloalkyl” and “cycloalkylene” as used herein refers to a monovalent or bivalent, respectively, branched or unbranched saturated cyclic hydrocarbon groups having from 3 to 22 ring carbon atoms, typically although, not necessarily, containing 3 to about 12 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. The term also embraces bicyclic fused and bicyclic bridged cyclohydrocarbons, including but not limited to, bicyclo[2.2.1]heptanes, bicyclo[2.2.2]octanes, and bicyclo[3.2.2]nonanes.

[0085] The term “alkenyl” and “alkenylene” as used herein refers to a monovalent or bivalent, respectively, branched or unbranched, unsaturated hydrocarbon group typically although not necessarily containing 2 to about 12 carbon atoms and 1-10 carbon-carbon double bonds, such as ethylene, n-propylene, isopropylene, n-butylene, isobutylene, t-butylene, octylene, and the like.

[0086] Thus, the term “alkenyl” and “alkenylene” embraces dienes, trienes, and polyenes, including 1,2-dienes (“-CH=C=CH-”), and substituted variations thereof. Thus, for example, “alkenyl” and “alkylene” embrace 1,2-propadiene, 1,2-butadiene, 1,2-pentadiene, 1,2-hexadiene,2.3-butadiene, 2,3 -pentadiene, 3,4-pentadiene, 2,3-hexadiene, 3,4-hexadiene, 1,3 -butadiene, 1,3- pentadiene, 2,4-pentadiene, 1,3 -hexadiene, 3,4-hexadiene, and 1,3, 5 -hexatri ene.

[0087] Likewise, the term “cycloalkenyl” and “cycloalkenylene” as used herein refers to a monovalent or bivalent, respectively, branched or unbranched unsaturated cyclic hydrocarbon groups having from 4 to 22 ring carbon atoms, typically although, not necessarily, containing 4 to about 12 carbon atoms, and at least one double bond, such as cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like. The term also embraces bicyclic fused and bicyclic bridged unsaturated cyclohydrocarbons, including but not limited to, bicyclo[2.2.1]heptenes, bicyclo[2.2.2]octenes, and bicyclo[3.2.2]nonenes.

[0088] As used herein, the term “cycloalkenyl” and “cycloalkenylene” also embraces cyclodienes, cyclotrienes, and cyclopolyenes, and substituted variations thereof. Thus, for example, “cycloalkenyl” and “cycloalkylene” embrace 1,3 -cyclobutadiene, 1,3-cyclopentadiene,1.3-cyclohexadiene, and 1,4-cyclohexadiene.

[0089] The terms “branched” and “linear” (or “unbranched”) when used in reference to, for example, an alkyl moiety of Cato Cb carbon atoms, applies to those carbon atoms defining the alkyl moiety. For example, for a C4 alkyl moiety, a branched embodiment thereof would include an isobutyl, whereas an unbranched embodiment thereof would be an n-butyl. However, an isobutyl would also qualify as a linear C3 alkyl moiety (a propyl) itself substituted by a Ci alkyl (a methyl).

[0090] As used herein, the term “=O” as a substituent of an otherwise defined group refers to a group wherein a methylene moiety (-CH2-) of the underlying group is replaced by a ketone (C=O). Thus, for example, a Ci-3alkyl moiety X, substituted at the center carbon by a “=O” group, would be an X moiety of the formula -CH2-C(O)-CH2-.

[0091] As used herein, the term “fragrance composition” means a mixture of fragrance ingredients, e.g., including the polyether compounds of Method 1, et seq., and Method 2, et seq., including auxiliary substances if desired, dissolved in a suitable solvent or mixed with a powdery substrate used to provide a desired odor to a product.

[0092] The polyether compounds of Compound 1, et seq., Method 1, et seq., and Method 2, et seq. may be used with e.g., with: perfumes, soaps, pomanders, cosmetics, toilet waters, pre- and aftershave lotions, talcum powders, hair-care products, body deodorants, anti-perspirants, shampoo, cologne, shower gel, and hair spray.

[0093] Fragrance and ingredients and mixtures of fragrance ingredients that may be used in combination with the disclosed compound for the manufacture of fragrance compositions include, but are not limited to, natural products including extracts, animal products and essential oils, absolutes, resinoids, resins, and concretes, and synthetic fragrance materials which include, but are not limited to, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, phenols, ethers, lactones, furansketals, nitriles, acids, and hydrocarbons, including both saturated and unsaturated compounds and aliphatic carbocyclic and heterocyclic compounds, and animal products.

[0094] In the present specification, the structural formula of the compounds represents a certain isomer for convenience in some cases, but the present invention includes ail isomers, such as geometrical isomers, optical isomers based on an asymmetrical carbon, stereoisomers, tautomers, and the like. In addition, a crystal polymorphism may be present for the compounds represented by the formula, it is noted that any crystal form, crystal form mixture, or anhydride or hydrate thereof is included in the scope of the present invention.

[0095] All percentages used herein, unless otherwise indicated, are by volume.

[0096] All ratios used herein, unless otherwise indicated, are by molarity.EXAMPLESExample 1. Synthesis of Polycitronellol citrate triester

[0097] Polycitronellol (100.35 g) is degassed at 80 °C and 1-2 torr for 0.5 hours. The material is cooled and then lithium methoxide (0.19 g, 0.025 eq.) is added. The mixture is further degassed at 110-120 °C and 1-2 torr for 2 hours, then it is cooled to room temperature. Triethyl citrate (20.7g, 0.38 eq.) is added, and the mixture is stirred at 80 °C and 80 torr for 0.5 hours, then at 80 °C and 40 torr for 1 hour, then at 85 °C and 1-20 torr for 22 hours. The mixture is cooled down to room temperature, and sodium carbonate (10 g) is added, followed by phosphoric acid (85%, 1.1g) dropwise. The mixture is stirred at room temperature for 1 hour and then it is filtered through silica gel on a jacketed funnel (70 °C) to afford 85g of the product as a liquid (yield: 76%). Proton NMR conformed to the expected structure. 'H-NVIR (500 MHz, CDCh): 6 0.7-1.0 (m, 29H), 1.12 (s, 45H), 1.2-1.7 (82H), 1.9-2.1 (m, 6H), 2.7-2.9 (m, 6H), 3.2- 3.4 (m, 14H), 4.0-4.3 (m, 8H), 4.6-4.7 (m, 1H), 5.10 (t, 3H). Without being bound by theory, it is believed that selected peaks of the NMR spectrum may be assigned as follows to the structure of the compound:

[0098] The integrals of the NMR spectrum obtained are therefore believed to be consistent with a value of n of about 2.8, which is consistent with a predominant triester product containing small amounts of diester or monoester. Distillation, chromatography, or other methods may be used, if desired, to provide triester product in higher purity.

[0099] It is understood that the reaction conditions described above may be modified in order to isolate products with different values of n, such as, by altering the molar ratio between the reactants, altering the temperature or time of the reaction, or by employing standard techniques (such as distillation or chromatography) to separate fractions based on their molecular weight.

Claims

CLAIMSListing of Claims:

1. A compound according to Formula I below:Formula I wherein X is selected from Ci-2oalkylene, C2-2oalkenylene, Cs-ncycloalkylene, C4- i2cycloalkenylene, aryl, heteroaryl, biaryl, and 5-6-membered heterocycloalkyl, each optionally substituted by one or more of =0, OH, 0Ra, SH, SRa, NH2, NHRa, NRaRb, and - C(0)0R, and wherein R is a terpene alcohol or poly(monoterpenyl)oxy moiety and Raand Rbare each independently selected from optionally substituted -C(0)-Ci-2oalkyl (e.g., C1-6 alkyl), optionally substituted -C(0)-C2-2oalkenylene, optionally substituted -C(O)-aryl.

2. A compound according to claim 1, wherein X is selected from Ci-2oalkylene, C2- 2oalkenylene, Cs-ncycloalkylene, and C4-i2cycloalkenylene, each optionally substituted.

3. A compound according to claim 1, wherein X is Ci-2oalkylene (e.g., Ci-iealkylene, or Ci- loalkylene, or Ci-ealkylene), each optionally substituted.

4. A compound according to claim 1, wherein X is selected from C2-2oalkenylene, and C4- i2cycloalkenylene, each optionally substituted.

5. A compound according to claim 1, wherein X is C 2-20 alkenyl ene (e.g., C2-iealkenylene, or C2-ioalkenylene, or C2-ealkenylene), each optionally substituted.

6. A compound according to any one of claims 1-5, wherein said Ci-2oalkylene, C2- 2oalkenylene, Cs-ncycloalkylene, or C4-i2cycloalkenylene is further substituted by one or more =0.

7. A compound according to any one of claims 1-5, wherein said Ci-2oalkylene, C2- 2oalkenylene, Cs-ncycloalkylene, or C4-i2cycloalkenylene is further substituted by one or more OH, SH, or NH2.

8. A compound according to any one of claims 1-5, wherein said Ci-2oalkylene, C2- 2oalkenylene, Cs-ncycloalkylene, or C4-i2cycloalkenylene is further substituted by one or more 0Ra, SRa, NHRa, or NRaRb.

9. A compound according to any one of claims 1-5, wherein said Ci-2oalkylene, C2- salkenylene, C3-i2cycloalkylene, or C4-i2cycloalkenylene is further substituted by one or more -C(O)OR.

10. A compound according to any one of claims 1-5, wherein said Ci-2oalkylene, C2- salkenylene, C3-i2cycloalkylene, or C4-i2cycloalkenylene is further substituted by one - C(O)OR.

11. A compound according to claim 1, wherein X is aryl, e.g., phenyl or naphthyl, optionally substituted by one or more of OH, ORa, SH, SRa, NH2, NHRa, NRaRb, and -C(O)OR.

12. A compound according to claim 1, wherein X is heteroaryl, optionally substituted by one or more of OH, ORa, SH, SRa, NH2, NHRa, NRaRb, and -C(O)OR.

13. A compound according to claim 1, wherein X is biaryl (e.g., 1,1’ -biphenyl), optionally substituted by one or more of OH, ORa, SH, SRa, NH2, NHRa, NRaRb, and -C(O)OR.

14. A compound according to claim 1, wherein X is 5-6 membered heterocycloalkyl, optionally substituted by one or more of OH, ORa, SH, SRa, NH2, NHRa, NRaRb, and - C(O)OR.

15. A compound according to claim 1, wherein the compound of Formula I is selected from the group consisting of16. A compound according to any one of claims 1-15, wherein R is poly(monoterpenyl)oxy.

17. A compound according to claim 16, wherein R has the structure:, wherein n is an integer from 0-10 (e.g., 1-10, or 2-10, or 0-8, or 1-8, or 2-8, or 0-6, or 1-6, or 2-6).

18. A compound according to claim 1, wherein the compound of Formula I is a compound of the structure:wherein R has the structure:, wherein n is an integer from 0-10 (e.g., 1-10, or 2-10, or 0-8, or 1-8, or 2-8, or 0-6, or 1-6, or 2-6).

19. A fragrance, perfume, soap, pomander, cosmetic, toilet water, pre- and / or after-shave lotion, talcum powder, haircare product, body deodorant, anti-perspirant, shampoo, topical skin care, antimicrobial, mesogen, writing and / or printing ink, dye, pigment, paint or coating, skin-tone evening, anti-hyperpigmentation, anti-hypopigmentation, crosslinking, temporary stiffening, or permanent stiffening, composition comprising the Compound of any of claims 1-18, or a solution or suspension comprising the Compound of any of claims 1-18, dissolved or suspended in a solvent or mixture of solvents (e.g., ester, alkane, aromatic, alcohol, or ether solvents).

0. A method of making a compound according to any of claims 1-18, comprising the steps of (1) introducing into a reactor an alcohol of the formula R-OH (such as a poly(monoterpenyl) alcohol, such as polycitronellol), and a dicarboxylic, tricarboxylic, or polycarboxylic acid, or an ester, acyl halide, or anhydride thereof, e.g., compounds of the formulas A-C(O)-X-C(O)-A or A-C(O)-X(-C(O)-A)-C(O)-A, wherein each A is independently OH, ORX, or halogen, and (2) exposing said mixture to a base for a sufficient amount of time to form the Compound of Formula I; and (3) isolating and / or purifying (e.g., by distillation) the Compound 1, e.g., a group of related Compounds 1 having different values of the integers n, wherein X and R, are as defined in as defined in any of claims 1-18.

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