Polyether derivatives, their use and process for preparation

Abstract

The present invention relates to certain polyethers, polyether derivatives and methods of making and using these polymers. For example, the starting materials can be, for example, citronellol, prenol, isocitronellol and isoprenol.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Provisional Patent Application No. 62 / 539,319, filed July 31, 2017, U.S. Provisional Patent Application No. 62 / 617,924, filed January 16, 2018, and U.S. Provisional Patent Application No. 62 / 662,177, filed April 24, 2018, the contents of each of which are incorporated herein by reference in their entireties.

[0002] Field The present invention relates to certain polyethers, polyether derivatives and methods of making and using same. For example, the starting materials can be, for example, citronellol, prenol, isocitronellol and isoprenol. [Background technology]

[0003] background Liquid polymers have important utility in cosmetic and personal care applications, with important roles in display devices, rheology, tribology and drug delivery. For example, they can be used as lubricants, emollients or as protective barriers for skin treatment and UV protection. Ideally, these materials can be produced in a facile manner, easily derivatized to modify functionality, and even more preferably produced from safe and sustainable raw materials.

[0004] Citronellol, prenol and isoprenol are all naturally occurring molecules that are also commercially available on a large scale, however these molecules have a combination of functional groups that are underutilized for polymerizing and functionalizing them, an isobutylene group and an alcohol.

[0005] This type of chemistry has been largely ignored in polymer chemistry, in part because polymerization is an equilibrium reaction and isobutylene alcohol is not always readily available in abundance. However, in recent years, citronellol production has increased rapidly, and the largest production routes also use prenol and isoprenol as intermediates, greatly increasing availability. Summary of the Invention [Problem to be solved by the invention]

[0006] However, as noted above, the equilibrium nature of the polymerization reaction can make the production of the desired ethers challenging on a large scale. There is a need for preparative strategies and methods that allow for the efficient production of these compounds. [Means for solving the problem]

[0007] overview In a surprising advance in polymer science, PCT / US2015 / 047397 (US counterpart US2017 / 0283553) and PCT / US2015 / 016371 (US counterpart US2017 / 0057940), the contents of each of which are incorporated herein by reference, teach how to utilize these functionalities in the preparation of novel polyether compositions. These polyethers represent an advancement in liquid polymer technology and offer many desirable advantages for commercial applications.

[0008] The present invention contemplates building upon Applicant's own aforementioned patent applications by utilizing novel derivatization strategies and manufacturing methods. In still further aspects, the present invention teaches methods for the controlled release of monomers contained within these polyether polymers, for use in, for example, fragrances and pest control.

[0009] In general, the present invention provides compounds of formula Y: [ka] [wherein the dotted bonds (A, B, and C) represent optional bonds, and R 1 is optionally substituted C1-C 12 R is alkyl; 2 is H, C 1-20 Alkyl, aryl, aryl-C 1-2 alkyl, optionally unsaturated alkyl ester or aryl ester, or R 2 The part: [ka] where X is of the formula -C(O)-R 3 -C(O)- diacyl moiety, where R 3 is optionally substituted C 1-22 Alkyl, optionally substituted C 2-22 alkenyl or optionally substituted aryl; and n is an integer from 0 to 20; However, if the intramolecular cross-link A exists, the dotted bonds B and C do not exist, and the substituent R 2 does not exist.] [ka] represents any double bond (i.e., single or double bond), and therefore the end group [ka] It is understood that the may have one of the three shown optional bonds present (i.e., double bonds) or all optional bonds absent (i.e., all single bonds).

[0010] In further aspects, the invention provides methods of making the compounds and methods of using the compounds. [Brief description of the drawings]

[0011] [Figure 1]1 provides general structural formulas for citronellol monoethers, polyethers and citronellol monomers.

[0012] [Diagram 2] 1 provides general structural formulas for the isomeric citronellol monoethers, polyethers and isomeric citronellol monomers.

[0013] [Diagram 3] Provides general structural formulas for prenol monoethers, polyethers and prenol monomers.

[0014] [Figure 4] 1 provides general structural formulas for isoprenol monoethers, polyethers and isoprenol monomers.

[0015] [Diagram 5] Provided are structural formulas for citronellol-type monomers, monoethers and polyethers in which the hydroxyl positions have been derivatized for the addition or modification of functionality.

[0016] [Figure 6] Structural formulas are provided for lenol-type monomers, mono- and polyethers in which the hydroxyl positions have been derivatized for the addition or modification of functionality. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] Without wishing to be bound by theory, isobutylene groups can react with alcohols under an acid catalyzed mechanism to form ethers, a chemistry that has been used in other instances to create ether bonds in organic synthesis.

[0018] The equilibrium nature of this reaction can make the production of these ethers on a large scale potentially challenging. However, the inventors have discovered that with monomer recycling, proper catalyst selection, and concentrated reaction conditions, these molecules can reach a sufficient degree of polymerization to be used in a wide variety of applications. Furthermore, these low molecular weight polymers can be further derivatized to reach much higher molecular weights and achieve new functionality.

[0019] Monomers, dimers, trimers and higher oligomers of citronellol-type and prenol-type polymers are shown in Figures 1-4. For purposes of the present invention, the term "citronellol" is intended to include both isomers at the olefin position. Similarly, when the term "prenol" is used, it is intended to include the isoprenol isomer as well. In certain embodiments, the present invention contemplates mixtures of prenol and citronellol polyethers.

[0020] While certain methods for producing these ethers are described in PCT / US2015 / 047397 (US2017 / 0283553), Applicants have now discovered that these polyethers can be produced at much higher degrees of polymerization and in shorter times under neat, solvent-free conditions using a resin-bound acid catalyst such as Amberlyst®. In certain embodiments, these polymerizations can be carried out at room temperature or below, preferably at slightly elevated temperatures, such as 30-110° C. or even more preferably 40-90° C. (e.g., about 50° C.). Additionally, in still other embodiments, these polymerizations can be carried out in batch reactors, semi-batch reactors or even more preferably continuous packed bed reactors of the type described in U.S. Provisional Application Nos. 62 / 384,939 and PCT / US2017 / 50808, the contents of each of which are incorporated herein by reference.

[0021] Applicants have unexpectedly discovered that there are unique advantages to using continuous neat polymerization instead of traditional batch processing. In addition to significant reductions in reaction time (e.g., seconds for continuous reactions versus days for similar batch conversion methods), in some cases, the use of continuous neat polymerization methods has provided efficient enablement of chemistry that could not be observed under batch conditions. For example, in the case of isoprenol polymerization, batch conditions provided a complex mixture with little apparent polymer formation, whereas continuous reactor conditions provided the desired homo-isoprenol polymer as the major product in good yield in short reaction times.

[0022] Without being bound by theory, polyether formation may occur at equilibrium under acidic conditions, and therefore it would be disadvantageous for these materials to be exposed to acidic conditions during subsequent derivatization to prevent depolymerization.

[0023] However, applicants have now discovered that transesterification under basic conditions can be used to produce a wide range of novel and useful compositions. Additionally, alkaline Williamson-type etherification can also be achieved with organic halides. The functionalities that can be produced from these approaches can modify the hydrophilicity, hydrophobicity and / or viscosity of these polyethers. Additionally, novel functionalities such as UV protection, antioxidant, anti-aging, skin whitening, antibacterial and / or other bioactivities can be introduced as well. Representative chemical structures of these modifications are shown in Figures 5 and 6.

[0024] Furthermore, applicants have discovered that esterification of these polymers can be carried out with anhydrides, continuously, with or without a catalyst, simply by the application of heat. Traditionally, esterification has been carried out in a solvent, often batchwise, in the presence of a catalyst such as DMAP or an acid. However, due to the liquid nature of these polymers and their low volatility, these polymers can be derivatized continuously without the need for the presence of any solvent or catalyst.

[0025] For example, acetic anhydride can be added directly to a mixture of these polymers, the mixture can be passed continuously through tubes or pipes heated to high temperatures, and conversion to the desired products can be easily carried out without the addition of any catalyst or solvent. Furthermore, complete and continuous removal of any remaining acetic anhydride or acetic acid by-product can be carried out under reduced pressure or at elevated temperatures, and removal of any traces of acid or color can also be carried out continuously with anion exchange media or activated carbon, respectively.

[0026] The specific advantages of the compounds disclosed herein stem from one or more of the following features: they are short chain polymers; they are produced using reversible polymerization reactions; they are biodegradable and biocompatible; and they are produced using all-natural ingredients. These are important advantages in many of the commercial applications in which these compounds may be used. The compounds disclosed herein are suitable as replacements or substitutes for surfactants, polymers and silicones in a variety of commercial products, such as cosmetic and pharmaceutical compositions, as adjuvants in crop protection products, and as lubricants or solvents in enhanced oil recovery, hydraulic fracturing and oil field applications. The compounds disclosed herein provide improved physical properties, such as appearance, odor, viscosity, refractive index and / or surface tension. The molecular weight of these compounds as short polymers of medium molecular weight is, for example, less than 20,000 daltons, or less than 15,000 daltons, or less than 10,000 daltons, or 100-10,000 daltons, or 100-5,000 daltons, or 100-3,000 daltons, or 100-1,500 daltons.

[0027] In certain embodiments of the invention, the compounds disclosed herein are useful as fragrance retainers, fragrance fixers or fragrance carriers; as malodor counteractants; in paints and coatings; as adjuvants for crop management; as cosmetic ingredients (e.g., as silicone replacements or white oil replacements); in nail polish; in writing or printing inks; as resins or resin replacements; as insect repellents (e.g., mosquito repellents); and in sunscreens.

[0028] The reversibility of the polymerization of the compounds of the present invention stems from the nature of these polymers with adjacent oxygen atoms and tertiary carbon atoms. That is, under conditions that promote the cleavage of the O-C bond, the resulting tertiary carbocation is unusually stable. This induces the easy abstraction of adjacent hydrogen atoms, leading to the regeneration of the alcohol and alkene functional groups of the starting material. Such depolymerization can be promoted by slightly acidic conditions (e.g., by Lewis or Bronsted acids), heating conditions, or enzyme conditions (by enzymes possessed by naturally occurring bacteria).

[0029] This depolymerization property leads to biodegradation. This property also allows the production of compositions containing compounds in which the depolymerization of the polymer can be controlled to allow for delayed release of monomeric polymeric components (e.g., citronellol) or shortened polymeric components (e.g., release of citronellol dimers by depolymerization from larger polymers). The present invention includes solid and / or liquid compositions containing polymers of formula I (or any of 1.1-1.43) or formula II (or any of 2.1-2.27), in which the composition is controlled for slow, controlled depolymerization of the polymer and the resulting monomers and / or shortened oligomers by diffusion (e.g., evaporation at the composition surface) so that they can be released from the composition. Such compositions may include components that accelerate such depolymerization (e.g., Lewis or Bronsted acids or enzymes) or such compositions may be accompanied by a device containing a heating element to accelerate thermal depolymerization. The monomers and / or shortened oligomers (e.g., citronellol or citronellol dimers or trimers) produced in this manner may themselves be useful for a number of reasons, for example, as fragrances, insect repellents, antioxidants, antibacterial agents or active pharmaceutical ingredients (e.g., when the composition is a pharmaceutical composition).

[0030] The compounds disclosed herein are particularly suitable as replacements for silicones, mineral oils and / or paraffins in cosmetic compositions, such as concealers, primers and / or moisturizers.

[0031] In a first aspect, the present invention provides a compound of formula I [ka] [In the formula, R 1 is optionally substituted C1-C 12 Alkyl (e.g., optionally further C1-C 12 C1-C substituted with alkyl or aryl 12 alkyl); R 2 is H, C 1-20 Alkyl (e.g., lower alkyl (e.g., C 1-6 Alkyl) or C 1-12 alkyl), aryl (e.g., phenyl), aryl C1-2 alkyl (e.g., benzyl), optionally unsaturated alkyl esters (e.g., C(O)-C 1-20 alkyl) or an optionally substituted aryl ester (e.g., C(O)-aryl); n is an integer from 0 to 20. The present invention provides ether compounds (compound 1), such as citronellol and prenol ethers and polyethers or salts thereof. [ka] represents any double bond (i.e., single or double bond), and therefore the end group [ka] It is understood that the may have one of the three shown optional bonds present (i.e., double bonds) or all optional bonds absent (i.e., all single bonds).

[0032] In a further embodiment of the first aspect, the present invention provides any of the following: 1.1 R 1 Optionally substituted linear C1-C 12 Alkyl or optionally substituted branched C-C 12Compound 1 is an alkyl group. 1.2 R 1 Unsubstituted linear C1-C 12 Alkyl or unsubstituted branched C3-C 12 Compound 1, which is an alkyl group. 1.3 R 1 Unsubstituted linear C1-C 12 Compound 1, which is an alkyl group. 1.4 R 1 Unsubstituted branched C3-C 12 Compound 1, which is an alkyl group. 1.5 R 1 Compound 1, in which is CH2. 1.6 R 1 is an unsubstituted branched or straight chain C6 alkyl. 1.7 R 1 Compound 1, wherein is CH2CH2CH(CH3)CH2CH2. 1.8 R 2 is H. 1.9 R 2 is alkyl (e.g., lower alkyl (e.g., C 1-6 ) or C 1-12 ) Compound 1 or any of 1.1 to 1.7. 1.10 R 2 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, or n-decyl. 1.11 R 2 Aryl C 1-2 Any of compounds 1 or 1.1-1.7, which is alkyl (eg, benzyl or phenethyl). 1.12 R 2 is aryl (eg, phenyl). 1.13 R 2 is an optionally unsaturated alkyl ester (e.g., C(O)-C 1-20 Alkyl or C(O)-C 1-6 any of compounds 1 or 1.1 to 1.7, wherein 1.14 R 2 is C(O)-C 1-6 alkyl, optionally where R 2 is C(O)-C 1-5 Alkyl, C(O)-C 1-4 Alkyl, C(O)-C 1-3 Alkyl or C(O)-C 1-2 Any of compounds 1 or 1.1-1.7, wherein 1.15 R 2 is C(O)-C 1-6 is an alkyl group, 1-6 Any of compounds 1 or 1.1-1.7, wherein alkyl is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, or n-hexyl. 1.16 R 2 is optionally unsaturated C(O)-C 7-20 alkyl, optionally where R 2 is optionally unsaturated C(O)-C 10-20 Alkyl, C(O)-C 12-20 Alkyl, C(O)-C 14-20 Alkyl or C(O)-C 16-18 Alkyl or C(O)-C 17 Any of compounds 1 or 1.1-1.7, wherein 1.17 R 2 Monounsaturated C(O)-C 7-20 alkyl, optionally where R 2 Monounsaturated C(O)-C 10-20 Alkyl, C(O)-C 12-20 Alkyl, C(O)-C 14-20 Alkyl or C(O)-C 16-18 Alkyl or C(O)-C 17 Any of compounds 1 or 1.1-1.7, which is alkyl (eg, oleoyl). 1.18 R 2 is saturated C(O)-C 7-20 alkyl, optionally where R 2 is saturated C(O)-C 10-20 Alkyl, C(O)-C12-20 Alkyl, C(O)-C 14-20 Alkyl or C(O)-C 16-18 Alkyl or C(O)-C 17 Any of compounds 1 or 1.1-1.7, wherein 1.19 R 2 Any of compounds 1 or 1.1-1.18, wherein the substituent is a fatty acyl chain. 1.20 R 2 is an aryl ester (eg, C(O)-aryl), such as benzoyl. 1.21 R 2 The substituent may further comprise a cationic or anionic moiety (e.g., where R 2 is an alkyl, aryl, alkyl ester, or aryl ester, wherein the alkyl or aryl is substituted with a cationic (e.g., quaternary ammonium) or anionic (e.g., carboxylic acid or sulfonic acid) moiety. 1.22 R 2 is a polyether moiety, e.g., where R 2 Any of compounds 1 or 1.1 to 1.18, in which the substituent comprises a polyethylene glycol chain. 1.23 Compound 1 or any of 1.1 onwards, where n is 1. 1.24 Compound 1 or any of 1.1 onwards, where n is greater than 1 (e.g., 2 to 20). 1.25 Any of compounds 1 or 1.1 and subsequent thereto, where n is 2. 1.26 Compound 1 or any of 1.1 et seq., wherein n is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. 1.27 Compound 1 or any of 1.1 et seq., where n is 2 or 3. 1.28 R 1 is CH2CH2CH(CH3)CH2CH2, n is 1-3 (e.g., 1-2) and R 2 is an optionally unsaturated alkyl ester (e.g., C(O)-C 1-20 Alkyl or C(O)-C 1-6Any of compounds 1 or 1.1 et seq., wherein R is an alkyl group. 1.29 R 2 is C(O)-C 1-6 is an alkyl group, 1-6 Compound 1.28, where alkyl is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, or n-hexyl. 1.30 R 2 Monounsaturated C(O)-C 7-20 alkyl, optionally where R 2 Monounsaturated C(O)-C 10-20 Alkyl, C(O)-C 12-20 Alkyl, C(O)-C 14-20 Alkyl or C(O)-C 16-18 Alkyl or C(O)-C 17 Compound 1.28, which is an alkyl (e.g., oleoyl). 1.31 R 2 Any of compounds 1 or 1.1 et seq., wherein is an anti-aging moiety, a UV absorbing moiety, an antioxidant moiety, a hydrophobic (lipophilic) moiety, or a hydrophilic moiety as described herein. 1.32 R 2 There is no H, for example, R 2 is alkyl (e.g., lower alkyl (e.g., C 1-6 Alkyl) or C 1-12 alkyl), aryl (e.g., phenyl), C1-C2 alkylaryl (e.g., benzyl), optionally unsaturated alkyl esters (e.g., C(O)-C 1-20 alkyl) or aryl ester (e.g., C(O)-aryl) and the above R 2 A further embodiment of any of compounds 1 or 1.1 et seq. 1.33 Terminal groups [ka] but [ka] Either compound 1 or 1.1 or later. 1.34 Terminal groups [ka] but [ka] Either compound 1 or 1.1 or later. 1.35 Terminal group [ka] but [ka] Either compound 1 or 1.1 or later. 1.36 Compounds of formula I [ka] (In the formula, n is 0 to 20 (e.g., 1 to 3).) Either compound 1 or 1.1 or later. 1.37 A compound of formula I [ka] (In the formula, n is 0 to 20 (e.g., 1 to 3).) Either compound 1 or 1.1 or later. 1.38 Compounds of formula I [ka] (In the formula, n is 0 to 20 (e.g., 1 to 3).) Either compound 1 or 1.1 or later. 1.39 Compounds of formula I [ka] (In the formula, n is 0 to 20 (e.g., 1 to 3).) Either compound 1 or 1.1 or later. 1.40 Compounds of formula I [ka] [In the formula, n is 0 to 20 (e.g., 1 to 3), and R 2 is as defined in any of the previous embodiments. Either compound 1 or 1.1 or later. 1.41 Compounds of formula I [ka] (In the formula, n is 0 to 20 (e.g., 1 to 3).) Either compound 1 or 1.1 or later. 1.42 Compounds of formula I [ka] [In the formula, n is 0 to 20 (e.g., 1 to 3), and R 2 is as defined in any of the previous embodiments. Either compound 1 or 1.1 or later. 1.43 Compounds of formula I [ka] (In the formula, n is 0 to 20 (e.g., 1 to 3).) Either compound 1 or 1.1 or later.

[0033] As described in the paragraph above, the terminal group of the compound of formula Y and the compound of formula I is represented by the structure [ka] The alkyl group is an optionally unsaturated alkyl group having the formula: ##STR00001## This group may therefore be an isobutyl group, a 1-isobutenyl group or a 2-isobutenyl group. In some embodiments, this group is a fully saturated isobutyl group. In such embodiments, the saturation of this group is particularly advantageous since it increases chemical stability, inertness and biocompatibility since alkenes, especially terminal alkenes, may be susceptible to air oxidation and / or bioconjugation.

[0034] In a second aspect, the present invention provides a composition (Composition 1) comprising Compound 1 or any of 1.1 onwards or Compound 2 or any of 2.1 onwards or Compound 3 or any of 3.1 onwards or any salt thereof or any mixture thereof in combination with at least one suitable solvent, carrier or excipient. In a further embodiment of this second aspect, the present invention provides the following composition: 1.1 A fragrance composition comprising any one of compound 1 or 1.1 or later, compound 2 or 2.1 or later, compound 3 or 3.1 or later, or a salt thereof, or any mixture thereof. 1.2 A perfume composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.3 A soap composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.4 An insect repellent composition, such as a mosquito repellent composition, comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.5 An insecticidal composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.6 A cleaning composition comprising compound 1 or any of 1.1 et seq. or compound 2 or any of 2.1 et seq. or compound 3 or any of 3.1 et seq. or a salt thereof or any mixture thereof. 1.7 A household cleaning composition comprising compound 1 or any of 1.1 et seq. or compound 2 or any of 2.1 et seq. or compound 3 or any of 3.1 et seq. or a salt thereof or any mixture thereof. 1.8 A deodorant composition comprising any one of compound 1 or 1.1 or later, any one of compound 2 or 2.1 or later, any one of compound 3 or 3.1 or later, a salt thereof, or any mixture thereof. 1.9 A room spray composition comprising compound 1 or any of 1.1 et seq. or compound 2 or any of 2.1 et seq. or compound 3 or any of 3.1 et seq. or a salt thereof or any mixture thereof. 1.10 A pomander composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.11 A candle composition comprising compound 1 or any of 1.1 et seq. or compound 2 or any of 2.1 et seq. or compound 3 or any of 3.1 et seq. or a salt thereof or any mixture thereof. 1.12. Composition 1.11, wherein the composition further comprises a paraffin wax and / or beeswax base. 1.13 Composition 1.12, wherein the composition consists of compound 1 or any of 1.1 et seq. or compound 2 or any of 2.1 et seq. or compound 3 or any of 3.1 et seq. or a salt thereof or any mixture thereof dispersed in a paraffin wax and / or beeswax base with a suitable core embedded therein. 1.14 A cosmetic composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.15 A lotion composition comprising any one of compound 1 or 1.1 or later, compound 2 or 2.1 or later, compound 3 or 3.1 or later, or a salt thereof, or any mixture thereof. 1.16 A pre- and after-shave composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.17 A talcum powder composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.18 A hair care product composition comprising compound 1 or any of 1.1 or greater, or compound 2 or any of 2.1 or greater, or compound 3 or any of 3.1 or greater, or a salt thereof, or any mixture thereof. 1.19 A body deodorant composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.20 An antiperspirant composition comprising compound 1 or any of 1.1 or later, compound 2 or any of 2.1 or later, compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.21 A shampoo composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.22 A pet litter composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.23 A topical skin care composition comprising Compound 1 or any of 1.1 or later, or Compound 2 or any of 2.1 or later, or Compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof, optionally wherein the skin care application may be selected from skin conditioning agents; skin penetration enhancers; skin protectants; skin soothing agents; skin therapeutic agents; UV absorbers or scattering agents; scavenging agents; anti-acne agents; anti-androgens; depilatories; keratolytic / scaling / scrubbing agents such as salicylic acid; panthenol moisturizers, such as D-panthenol; soluble or colloidally soluble moisturizers, such as hyaluronic acid and starch grafted sodium polyacrylate; and sunscreens. 1.24 Composition 1.23, wherein the skin care application is a skin protectant. 1.25 Composition 1.23, wherein the skin care application is a skin soothing agent. 1.26 Composition 1.23, wherein the skin care application is a sunscreen. 1.27 A paint or coating composition comprising compound 1 or any of 1.1 et seq. or compound 2 or any of 2.1 et seq. or compound 3 or any of 3.1 et seq. or a salt thereof or any mixture thereof. 1.28 A lubricating composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.29 A plastic composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.30 An antifoam composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.31 A hydraulic fluid composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.32 An antibacterial composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.33 A crop protection formulation comprising compound 1 or any of 1.1 et seq. or compound 2 or any of 2.1 et seq. or compound 3 or any of 3.1 et seq., for example, said compound is an adjuvant in the crop protection formulation. 1.34 A formulation for enhanced oil recovery, hydraulic fracturing, and / or other oil field applications comprising Compound 1 or any of 1.1 et seq. or Compound 2 or any of 2.1 et seq. or Compound 3 or any of 3.1 et seq., e.g., the compound is a lubricant or solvent in the formulation. 1.35 An article of manufacture comprising any of the above compositions, said composition being stored or contained in a receptacle containing a heating element, where activation of the heating element results in heating of the composition, thermal decomposition of the compounds and release of volatile substances. 1.36 A fragrance or perfume composition comprising compound 1 or any of 1.1 et seq. or compound 2 or any of 2.1 et seq. or compound 3 or any of 3.1 et seq. or a salt thereof or any mixture thereof, wherein said compound is used as an odor retainer, odor fixer or odor carrier. 1.37 A cosmetic composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof, wherein said compound is used as a silicone replacement and / or a white oil replacement. 1.38 A nail polish composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.39 A writing ink or printing ink composition comprising compound 1 or any of 1.1 or later, or compound 2 or any of 2.1 or later, or compound 3 or any of 3.1 or later, or a salt thereof, or any mixture thereof. 1.40 Adhesive compositions comprising compound 1 or any of 1.1 et seq. or compound 2 or any of 2.1 et seq. or compound 3 or any of 3.1 et seq. or salts thereof or any mixtures thereof in admixture with one or more natural or synthetic resins.

[0035] In other embodiments, the invention provides Compound 1 or any of 1.1-1.43, or Compound 2 or any of 2.1-2.27, or Compound 3 or any of 3.1-3.15, for use in Composition 1 or any of 1.1-1.40.

[0036] In a third aspect, the present invention provides compounds 1 or any of 1.1 et seq., 2is H), or a salt thereof (Method 1), the method comprising: (1) providing in a reactor a compound of formula A: [ka] [In the formula, R 1 is optionally substituted C1-C 12 Alkyl (e.g., optionally further C1-C 12 C1-C substituted with alkyl or aryl 12 alkyl). introducing a compound of (2) exposing the compound to a solid ion exchange resin, thereby inducing polymerization of the compound of formula A to form a compound of formula I: [ka] [In the formula, R 1 is optionally substituted C1-C 12 Alkyl (e.g., optionally further C1-C 12 C1-C substituted with alkyl or aryl 12 alkyl); and 2 H and n is an integer of 0 to 20. preparing a compound 1 represented by the formula: (3) isolating and / or purifying (e.g., by distillation) compound 1, e.g., a group of related compounds 1 where n varies within a range, e.g., n is 0-5 or 5-10 or 10-15 or 15-20, or n has any particular integer value in the range of 0-20. The process includes:

[0037] In a further embodiment of the third aspect, the present invention provides: 1.1 Method 1, where polymerization takes place on an ion exchange resin at high temperatures (e.g., 30-120°C). 1.2 Method 1.1, where polymerization takes place on an ion exchange resin at 40-90°C. 1.3 Method 1.2, where the polymerization takes place on an ion exchange resin at about 50°C. 1.4 Any of methods 1 or 1.1-1.4, wherein the solid exchange resin is a resin functionalized with a resin-bound acid catalyst, such as a carboxylic acid or sulfonic acid moiety. 1.5 Any of the preceding processes, wherein the polymerization occurs in a batch reactor. 1.6 Any of the preceding processes, wherein the polymerization occurs in a continuous packed bed reactor. 1.7 Any of the preceding processes wherein monomers of formula A are polymerized by acid catalysis, followed by distillation and recycling of any unpolymerized monomer. 1.8 Any of the preceding processes, wherein the resin-bound acid catalyst is selected from Silicycle propane sulfonic acid, Montmorillonite, or Amberlyst® (e.g., macroreticular or porous resins or silica covalently bonded to sulfonic or carboxylic acid groups). 1.9 The method of 1.7, wherein the catalyst is Amberlyst®. 1.10 Any of the preceding methods, wherein compound 1 is purified by fractional distillation. 1.11 Any of the preceding methods, wherein compound 1 is compound 1.8 or any embodiment thereof. 1.12 Compound 1 of formula I, where R 2 is H) and R 2 with suitable reactants to convert R of the alkyl ester to an alkyl ester or aryl ester moiety (e.g., to produce compounds 1.13-1.20 or any of its embodiments), optionally in the absence of a base or catalyst and optionally under continuous conditions. 2 is methyl, and the reaction uses ketene as a suitable reactant, or R 2 Any of the preceding processes, wherein is methyl and the reaction further comprises the step of using acetic anhydride as a suitable reactant. 1.13 Method 1.12, wherein the esterification is an alkaline transesterification reaction using a functionalized ester. 1.14 Compound 1 of formula I, where R 2Any of Methods 1 or 1.1-1.11, further comprising reacting (wherein R is H) with suitable reactants to form compound 2 of Formula II. 1.15 Method 1.14, wherein the esterification is an alkaline transesterification reaction using a functionalized diester. 1.16 Compound 1 of formula I, where R 2 is H) and R 2 Any of Methods 1 or 1.1-1.11, further comprising reacting with a suitable reactant to convert to an alkyl ether or aryl ether moiety (e.g., to prepare compounds 1.9-1.12, or any of its embodiments). 1.17 Method 1.16, where the etherification is a Williamson type etherification reaction using an appropriate alkyl halide and base. 1.18 R 1 Optionally substituted linear C1-C 12 Alkyl or optionally substituted branched C-C 12 Any of the preceding methods wherein the alkyl group is alkyl. 1.19 R 1 Unsubstituted linear C1-C 12 Alkyl or branched C3-C 12 any of methods 1 or 1.1 to 1.17, wherein the alkyl is alkyl. 1.20 R 1 Unsubstituted linear C1-C 12 any of methods 1 or 1.1 to 1.17, wherein the alkyl is alkyl. 1.21 R 1 Unsubstituted branched C3-C 12 any of methods 1 or 1.1 to 1.17, wherein the alkyl is alkyl. 1.22 R 1 is CH2, any of methods 1 or 1.1 to 1.17. 1.23 R 1 Any of methods 1 or 1.1 to 1.17, wherein is an unsubstituted branched or straight chain C6 alkyl. 1.24 R 1 is CH2CH2CH(CH3)CH2CH2, 1.25 Any of Methods 1 or 1.1 et seq., wherein the method also produces Compound 3 or any of 3.1 et seq. or a salt thereof. 1.26 Any of methods 1 or 1.1 et seq., wherein the method further comprises reducing the terminal 1-isobutenyl or 2-isobutenyl group of the compound of formula I to produce a compound of formula I having a terminal isobutyl group. 1.27 Process 1.26, wherein the reduction comprises hydrogenation over a transition metal catalyst (e.g., platinum, palladium, rhodium, ruthenium or nickel), optionally under pressure (e.g., 15-1000 psi or 30-500 psi, 50-500 psi, 100-500 psi, 200-500 psi, 250-500 psi, 300-500 psi, 350-450 psi or about 400 psi). 1.28 Method 1.27, wherein the reduction involves an alcohol solvent (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol or mixtures thereof).

[0038] In certain embodiments of Methods 1 or any of 1.1-1.28, optionally the present invention further comprises a compound of formula I [ka] [In the formula, R 1 is optionally substituted C1-C 12 Alkyl (e.g., optionally further C1-C 12 C1-C substituted with alkyl or aryl 12 alkyl); and R 2 is (C=O)C 1-4 alkyl (e.g., methyl), and n is an integer from 0 to 20. The present invention provides a method for producing an ester compound 1A (Method 3) of the formula: The method comprises reacting an alcohol compound 1 of formula I, where R is H, with an alkyl anhydride of formula R0(C=O)OR, where R 2 is (C=O)C 1-4The method includes reacting a cycloalkyl group (eg, alkyl (eg, methyl)) with a cycloalkyl group (eg, alkyl (eg, methyl)), which reaction is carried out under continuous flow conditions (eg, in a continuous flow reactor) in the absence of a base or a catalyst.

[0039] In further embodiments of this aspect of Method 3, the present invention also provides: 3.1 R 2 is selected from methyl ethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl or t-butyl. 3.2 R 2 is methyl or ethyl, for example methyl. 3.3 Any of methods 3 or 3.1 to 3.2, wherein n is 0 to 15, for example, n is 0 to 10 or 1 to 4 or 3 to 6 or about 2. 3.4 Any of Methods 3 or 3.1 to 3.3, wherein the reaction temperature is 50°C to 200°C, for example, 75°C to 150°C or 100°C to 120°C. 3.5 Any of Methods 3 or 3.1-3.4, wherein the reaction product from the flow reactor is recycled through the reactor at least once, e.g., 1-5 times, e.g., about 5 times, to improve yield.

[0040] In yet other embodiments, for example, compounds 1 et seq. produced by method 1 et seq. may be subjected to further modification with the advantage of more than doubling the molecular weight of the mono- and polyethers. In this embodiment, the ethers produced by method 1 et seq. are subjected to processing via transesterification of diacids or, even more preferably, diesters. As shown in Table 1, the ethers can be esterified on each side of a diacid to produce extended and modified polymers.

[0041] Therefore, in a fourth aspect, the present invention provides a polymeric derivative of Compound 1, represented by Formula II. [ka] [In the formula, R 1 is optionally substituted C1-C 12Alkyl (e.g., optionally further C1-C 12 C1-C substituted with alkyl or aryl 12 alkyl); n 1 and n 2 are each independently an integer from 0 to 20; and X is of the formula -C(O)-R 3 -C(O)- diacyl moiety, where R 3 is optionally substituted C 1-22 Alkyl, optionally substituted C 2-22 alkenyl or optionally substituted aryl. The present invention provides an ether and polyether diester compound (Compound 2) represented by the following formula: or a salt thereof. [ka] represents any double bond (i.e., single or double bond), and therefore the end group [ka] It is understood that the may have one of the three shown optional bonds present (i.e., double bonds) or all optional bonds absent (i.e., all single bonds).

[0042] In a further embodiment of the fourth aspect, the present invention provides any of the following: 2.1 R 1 Optionally substituted linear C1-C 12 Alkyl or optionally substituted branched C-C 12 Compound 2, which is an alkyl group. 2.2 R 1 Unsubstituted linear C1-C 12 Alkyl or branched C3-C 12 Compound 2, which is an alkyl group. 2.3 R 1 Unsubstituted linear C1-C 12 Compound 2, which is an alkyl group. 2.4 R 1 Unsubstituted branched C3-C12 Compound 2, which is an alkyl group. 2.5 R 1 Compound 2, wherein is CH2. 2.6 R 1 is an unsubstituted branched or straight chain C6 alkyl. 2.7 R 1 Compound 2, wherein is CH2CH2CH(CH3)CH2CH2. 2.8 R 3 is unsubstituted C 1-22 Alkyl, e.g., linear unsubstituted C 1-22 Alkyl or branched unsubstituted C 1-22 Any of compounds 2 or 2.1-2.7, wherein: 2.9 R 3 is unsubstituted C 1-16 Alkyl, e.g., linear unsubstituted C 1-16 Alkyl or branched unsubstituted C 1-16 Any of compounds 2 or 2.1-2.7, wherein: 2.10 R 3 is unsubstituted C 1-10 Alkyl, e.g., linear unsubstituted C 1-10 Alkyl or branched unsubstituted C 1-10 Any of compounds 2 or 2.1-2.7, wherein: 2.11 R 3 is unsubstituted C 1-6 Alkyl, e.g., linear unsubstituted C 1-6 Alkyl or branched unsubstituted C 1-6 Any of compounds 2 or 2.1-2.7, wherein: 2.12 R 3 is selected from methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2- or -CH2CH(CH3)-), butylene (e.g., -CH2CH2CH2CH2- or -CH2CH(CH3)CH2- or -CH(CH3)CH2CH2-). 2.13 R 3 is unsubstituted C 2-22 Alkenyl, e.g., straight-chain unsubstituted C 2-22 Alkenyl or branched unsubstituted C 2-22alkenyl, optionally wherein any of said alkenyls are monounsaturated. 2.14 R 3 is unsubstituted C 2-16 Alkenyl, e.g., straight-chain unsubstituted C 2-16 Alkenyl or branched unsubstituted C 2-16 alkenyl, optionally wherein any of said alkenyls are monounsaturated. 2.15 R 3 is unsubstituted C 2-10 Alkenyl, e.g., straight-chain unsubstituted C 2-10 Alkenyl or branched unsubstituted C 2-10 alkenyl, optionally wherein any of said alkenyls are monounsaturated. 2.16 R 3 is unsubstituted C 2-6 Alkenyl, e.g., straight-chain unsubstituted C 2-6 Alkenyl or branched unsubstituted C 2-6 alkenyl, optionally wherein any of said alkenyls are monounsaturated. 2.17 R 3 is selected from ethylene (-CH=CH-), propylene (-CH=CHCH2- or -CH2C(=CH2)-), butylene (e.g., -CH=CHCH2CH2- or -CH2CH=CHCH2- or -CH2CH(=CH2)CH2-). 2.18 R 3 is aryl, eg, substituted or unsubstituted phenyl. 2.19 n 1 and / or n 2 Either compound 2 or 2.1 or later, where is 1. 2.20 n 1 and / or n 2 is greater than 1 (e.g., 2 to 20), either compound 2 or 2.1 or later. 2.21 n 1 and / or n 2Either compound 2 or 2.1 or later, where is 2. 2.22 n 1 and / or n 2 is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, either compound 2 or 2.1 or later. 2.23 n 1 and / or n 2 Either compound 2 or 2.1 or later, where is 2 or 3. 2.24 n 1 and n 2 Either compound 2 or 2.1 or later, where 2.25 Terminal groups [ka] but [ka] Either compound 2 or 2.1 onwards. 2.26 Terminal groups [ka] but [ka] Either compound 2 or 2.1 onwards. 2.27 Terminal groups [ka] but [ka] Either compound 2 or 2.1 onwards.

[0043] In certain embodiments, compound 2 can be described as shown in Table 1. [Table 1]

[0044] In the fifth embodiment, for example, compound 1 or later produced by method 1 or later can form cyclic molecules during their respective polymerization reactions, where the cyclic molecules formed can have useful chelating, lubricating and softening properties.In some embodiments, these compounds can be isolated by distillation or can be used as is.Examples of these molecules are shown in Table 2 below. [Table 2]

[0045] Therefore, in a fifth aspect, the present invention provides a compound of formula III TIFF0007665178000037.tif5379 [In the formula, R 1 is optionally substituted C1-C 12 Alkyl (e.g., optionally further C1-C 12 C1-C substituted with alkyl or aryl 12 alkyl); and n is an integer from 0 to 20. or a salt thereof (Compound 3).

[0046] In a further embodiment of the fifth aspect, the present invention provides any of the following: 3.1 R 1 Optionally substituted linear C1-C 12 Alkyl or optionally substituted branched C-C 12 Compound 3, which is an alkyl group. 3.2 R 1 Unsubstituted linear C1-C 12 Alkyl or branched C3-C 12 Compound 3, which is an alkyl group. 3.3 R 1 Unsubstituted linear C1-C 12 Compound 3, which is an alkyl group. 3.4 R 1 Unsubstituted branched C3-C 12 Compound 3, which is an alkyl group. 3.5 R 1 is CH2, compound 3. 3.6 R 1 is an unsubstituted branched or straight chain C6 alkyl. 3.7 R 1 Compound 3, wherein is CH2CH2CH(CH3)CH2CH2. 3.8 Compound 3 or any of 3.1 and subsequent thereto, wherein n is 0 to 10. 3.9 Compound 3 or any of 3.1 and subsequent thereto, wherein n is 0 to 5. 3.10 Compound 3 or any of 3.1 through 3.1, where n is 0. 3.11 Compound 3 or any of 3.1 et seq., where n is 1. 3.12 Compound 3 or any of 3.1 through 3.1, where n is 2. 3.13 Compound 3 or any of 3.1 et seq., where n is 0, 1, 2, 3 or 4. 3.14 Compound 3 or any of 3.1 et seq., where n is 0, 1, 2 or 3. 3.15 Compound 3 or any of 3.1 et seq., where n is 0, 1 or 2.

[0047] In some embodiments, the UV absorbing moiety includes, but is not limited to, conjugated aromatic esters, conjugated aromatic ethers, and conjugated olefins. Specific examples include, but are not limited to, cinnamic acid, cinnamic acid derivatives, salicylic acid, salicylic acid derivatives, dimethylaminobenzoic acid, para-aminobenzoic acid, benzoic acid, 3,3-diphenylcyanoacrylate, diethylaminohydroxybenzoylbenzoate, and methoxycinnamic acid.

[0048] In certain embodiments, the anti-aging and / or antioxidant moieties include, but are not limited to, hyaluronic acid, ascorbic acid, azelaic acid, carnosine, glycolic acid, nicotinic acid, phenolic acids, phenolic ethers, benzophenones, sulfites, sulfones, sulfonates, and phosphates.

[0049] In some embodiments, the hydrophobic moieties include acetates, propionates, linear or branched fatty acids, linear or branched alkyl chains, organosilicones, fluoroalkanes, and graphene derivatives.The hydrophilic moieties include sulfonates, ethoxylates, polyglycerols, polypropylene glycols, carbohydrates, and carboxylic acids, as well as other polyols.

[0050] For example, compounds 1 et seq., e.g., citronellol and prenol polyethers, produced by method 1 et seq., can also be conjugated (e.g., esterified or etherified) with other biologically active molecules, e.g., antibacterial compounds, pharmaceutical compounds, skin treatment compounds, and sensitive molecules, e.g., cooling agents, anti-inflammatory agents, and / or warming agents.

[0051] For example, compounds 1 and onwards, compounds 2 and onwards and compounds 3 and onwards produced by method 1 and onwards can be used for many applications. They can be used in cosmetic formulations, paints or coatings, personal care products, household products, such as cleaning products, electronics, lubricants, plastics, defoamers, enhanced oil and gas recovery (including hydraulic fracturing and other oil field applications), pharmaceutical applications, crop protection formulations and hydraulic fluids. The compounds disclosed herein are suitable as replacements or substitutes for surfactants, polymers, silicones and solvents in these various applications. These materials, especially low molecular weight molecules, can also be advantageously used as insect repellents. For example, compounds 1 and onwards, compounds 2 and onwards and compounds 3 and onwards produced by method 1 and onwards can be used or incorporated as insecticides, insect repellents and bioactive ingredients. In certain embodiments, for example, Compound 1 or later, Compound 2 or later, and Compound 3 or later, produced by methods such as Method 1 or later, may be particularly useful as fragrance retainers, fragrance fixers, or fragrance carriers; as malodor counteractants; in paints and coatings; as adjuvants for crop management; as cosmetic ingredients (e.g., as silicone or white oil replacements); in nail polish; in writing or printing inks; as resins or resin replacements; as insect repellents (e.g., mosquito repellents); and in sunscreen formulations.

[0052] In a sixth aspect, the present invention provides a method of using Compound 1 onwards, Compound 2 onwards and / or Compound 3 onwards, e.g. a compound of Formula I, produced by Method 1 onwards, in a composition (e.g. Composition 1 onwards, e.g. fragrance compositions, perfumes, soaps, insect repellents and insecticides, cleaning agents, household cleaners, deodorants, room sprays, pomanders, candles, cosmetics, toners, pre- and aftershave lotions, talcum powders, hair care products, body deodorants, antiperspirants, shampoos, skin care applications, pharmaceuticals, antibacterial, pet litter, crop protection agents or oil field, hydraulic fracturing or enhanced oil recovery formulations).

[0053] Thus, the present invention provides a method (Method 2) of using compound 1 or any of 1.1 to 1.43, or compound 2 or any of 2.1 to 2.27, or compound 3 or any of 3.1 to 3.15, or any combination thereof, in the preparation of composition 1 or any of compositions 1.1 to 1.40.

[0054] In further embodiments of the sixth aspect, method 2 may provide any of the following: 2.1 The method of Method 2, wherein any of compounds 1-1.43 (e.g., citronellol and / or prenol polymers of formula I) or compounds 2-2.27 or compounds 3-3.15 are used in the fragrance composition. 2.2 The method of method 2, wherein any of compounds 1-1.43 (e.g., citronellol and / or prenol polymers of formula I) or compounds 2-2.27 or compounds 3-3.15 are used in a perfume. 2.3 The method of Method 2, wherein any of compounds 1-1.43 (e.g., citronellol and / or prenol polymers of formula I) or compounds 2-2.27 or compounds 3-3.15 are used in a soap. 2.4 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 is used in an insect repellent. 2.5 The method of Method 2, wherein any of compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or compounds 2-2.27 or compounds 3-3.15 are used in an insecticide. 2.6 The method of Method 2, wherein any of compounds 1-1.43 (e.g., citronellol and / or prenol polymers of formula I) or compounds 2-2.27 or compounds 3-3.15 are used in a cleaning agent. 2.7 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 are used in a household cleaning product. 2.8 The method of Method 2, wherein any of compounds 1-1.43 (e.g., citronellol and / or prenol polymers of formula I) or compounds 2-2.27 or compounds 3-3.15 are used in a deodorant. 2.9 The method of Method 2, wherein any of compounds 1-1.43 (e.g., citronellol and / or prenol polymers of formula I) or compounds 2-2.27 or compounds 3-3.15 are used in a room spray. 2.10 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 are used in a pomander. 2.11 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 is used in a candle. 2.12 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 are used in a cosmetic product. 2.13 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 are used in a lotion. 2.14 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 are used in a pre- and aftershave lotion. 2.15 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 is used in a talcum powder. 2.16 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 are used in a hair care product. 2.17 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 are used in a body deodorant. 2.18 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 are used in an antiperspirant. 2.19 The method of Method 2, wherein any of compounds 1-1.43 (e.g., citronellol and / or prenol polymers of formula I) or compounds 2-2.27 or compounds 3-3.15 are used in a shampoo. 2.20 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 are used in the pet litter. 2.21 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I prepared by Method 1 or later) or Compounds 2-2.27 or Compounds 3-3.15 are topically provided and used in a skin care application, wherein the skin care application may be selected from skin conditioning agents; skin penetration enhancers; skin protectants; skin soothing agents; skin therapeutic agents; UV absorbers or scatterers; scavengers; anti-acne agents; anti-androgens; depilatories; keratolytic / desquamating / scrubbing agents such as salicylic acid; panthenol moisturizers such as D-panthenol; soluble or colloidal soluble moisturizers such as hyaluronic acid and starch grafted sodium polyacrylate; and sunscreens. 2.22 The method of method 2.21, wherein the skin care application is a skin protectant. 2.23 The method of Method 2.21, wherein the skin care application is a skin soothing agent. 2.24 The method of method 2.21, wherein the skin care application is a sunscreen. 2.25 The method of Method 2, wherein any of compounds 1-1.43 (e.g., citronellol and / or prenol polymers of formula I) or compounds 2-2.27 or compounds 3-3.15 are used in a paint or coating. 2.26 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 are used in the lubricant. 2.27 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 are used in a plastic. 2.28 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 are used in medicine. 2.29 The method of method 2, wherein any of compounds 1-1.43 (e.g., citronellol and / or prenol polymers of formula I) or compounds 2-2.27 or compounds 3-3.15 are used as a crop protection formulation, e.g., wherein the compound is an adjuvant in a crop protection agent. 2.30 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 are used in a formulation for enhanced oil recovery, hydraulic fracturing and / or other oil field applications, e.g., wherein the compound is a lubricant or solvent in the formulation. 2.31 The method of Method 2, wherein any of compounds 1-1.43 (e.g., citronellol and / or prenol polymers of formula I) or compounds 2-2.27 or compounds 3-3.15 are used as a fragrance retainer, fragrance fixative or fragrance carrier (e.g., in a fragrance or perfume composition). 2.32 The method of Method 2, wherein any of compounds 1-1.43 (e.g., citronellol and / or prenol polymers of formula I) or compounds 2-2.27 or compounds 3-3.15 are used as a silicone substitute and / or white oil substitute (e.g., in a cosmetic composition). 2.33 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 are used in a nail polish composition. 2.34 The method of Method 2, wherein any of compounds 1-1.43 (e.g., citronellol and / or prenol polymers of formula I) or compounds 2-2.27 or compounds 3-3.15 are used in a writing ink or printing ink composition. 2.35 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 is used in an adhesive composition (e.g., in admixture with one or more natural or synthetic resins). 2.36 The method of Method 2, wherein any of Compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I) or Compounds 2-2.27 or Compounds 3-3.15 is used as a malodor counteractant (e.g., in a fragrance, perfume, antiperspirant, deodorant or other personal care composition).

[0055] In a further embodiment, any of compounds 1-1.43 (eg, the citronellol and / or prenol polymers of formula I) may be used in enhanced oil and gas recovery methods.

[0056] An added advantage of these materials described herein is that they are predicted to be fully biodegradable and biocompatible.

[0057] During a series of evaluations of these polyethers, it was surprisingly observed that depolymerization of citronellol-type polymers back to monomers occurred spontaneously at about 180° C. This thermal depolymerization, or similar enzyme- and / or acid-catalyzed depolymerizations, could be advantageously used to provide citronellol monomer in a controlled manner over time.

[0058] In some embodiments, thermal depolymerization can be used to deliver monomer into the air in a controlled release. In some embodiments, the present invention contemplates the use of compounds 1 et seq. and / or 2 et seq., produced by method 1 et seq., in, for example, candles or heat dispensers used for odor control and / or mosquito control, low pH industrial cleaners in which the depolymerized monomer components can be released over time to promote beneficial odors, and laundry detergents that use enzymes to digest the polymer over time to provide a long-lasting fresh scent.

[0059] In other embodiments, the fragrance composition comprises a compound 1 or later and / or a compound 2 or 3 or later, e.g., produced by method 1 or later, and the fragrance composition is selected from perfumes, soaps, insect repellents and insecticides, cleaning products, household cleaners, deodorants, room sprays, pomanders, candles, cosmetics, toners, pre- and aftershave lotions, talcum powders, hair care products, body deodorants, antiperspirants, shampoos, colognes, shower gels, hairsprays, and pet litter.

[0060] In another embodiment, the compounds 1 or later and / or compounds 2 or 3 or later, for example, produced by method 1 or later, may be used in an antifungal composition. In this embodiment, the antifungal composition comprises at least one type of compound selected from the group consisting of aliphatic or aromatic aldehydes, aliphatic or aromatic alcohols, acetals and esters, which exhibit a synergistic effect in the presence of polyethers 1 or later and compounds 2 or 3 or later, produced by method 1 or later, and the fragrance ingredients described above, thereby allowing the amount of active ingredient to be reduced and each to be contained in a lower dose than when used alone.

[0061] In other embodiments, for example, compound 1 or later and / or compound 2 or 3 or later, prepared by method 1 or later, can be used for topical application in skin care application.For example, skin care application can be selected from skin conditioning agent;skin penetration enhancer;skin protectant;skin soothing agent;skin treatment agent;ultraviolet ray absorber or scattering agent;scavenger;anti-acne agent;anti-androgenic agent;hair remover;keratolytic / scaling / scrubbing agent, such as salicylic acid agent;panthenol moisturizer, such as D-panthenol;soluble or colloidal soluble moisturizer, such as hyaluronic acid and starch graft sodium polyacrylate;and sunscreen.

[0062] In other embodiments, the mono- and / or polyethers of compounds 1 and / or 2 or 3 and / or 3, for example, prepared by method 1 and / or 3, can be used in a delivery system, for example, any perfume delivery system in which a long-term constant release of the above-mentioned fragrance compounds is desired. For example, the perfume delivery system described herein can be applied to, for example, functional perfumes, articles that are exposed to sunlight during use, or other articles that are subsequently exposed to sunlight.

[0063] In further embodiments, the present invention provides a delivery system 4.0, for example, comprising a liquid or solid deodorant with the delivery system of the present invention. Still further examples include delivery systems that deliver window and household cleaners, all-purpose cleaners, and furniture polishes. Surfaces that are cleaned with such cleaners. In further examples, the delivery system includes a cleaner, and a fabric softener may also be included in the delivery system of the present invention, and the clothes are washed or treated with such cleaner or fabric softener.

[0064] In yet other embodiments, the mono- and / or polyethers of Compound 1 et seq. and / or Compound 2 or 3 et seq., prepared by, for example, Method 1 et seq., may be used in a drug delivery system. In some embodiments, Delivery System 4.0 may include any of the following delivery systems: 4.1 A drug delivery system comprising a compound of formula I, any of Compounds 1-36 (e.g., citronellol and / or prenol polymers of formula I), Compounds 2-2.27, or Compounds 3-3.15, or any salt thereof, or mixtures thereof. 4.2 A perfume delivery system comprising a compound of formula I, any of Compounds 1-36 (e.g., citronellol and / or prenol polymers of formula I), Compounds 2-2.27 or Compounds 3-3.15, or any salt thereof, or mixtures thereof. 4.3 A detergent delivery system comprising a compound of any of the formulas Compounds 1-36 (e.g., citronellol and / or prenol polymers of Formula I), Compounds 2-2.27, or Compounds 3-3.15, or any salt thereof, or mixtures thereof. 4.4 A household cleaning delivery system comprising a compound of formula I, any of Compounds 1-36 (e.g., citronellol and / or prenol polymers of formula I), Compounds 2-2.27, or Compounds 3-3.15, or any salt thereof, or mixtures thereof.

[0065] In another aspect, the present invention provides a method of epoxidizing the double bond of any compound of formula Y, such as any of compounds 1-1.43 (e.g., citronellol and / or prenol polymers of formula I) or compounds 2-2.27, to form further epoxides. Such epoxide derivatives may be useful in any of the uses disclosed herein for any of compounds 1 or 1.1-1.43 or compounds 2 or 2.1-2.27, and may be used in any of the methods described by method 2 or any of 2.1-2.36. Such epoxide derivatives may also be useful as intermediates for the preparation of further compounds that may themselves be useful in any of the uses disclosed herein for any of compounds 1 or 1.1-1.43 or compounds 2 or 2.1-2.27, and may be used in any of the methods described by method 2 or any of 2.1-2.36.

[0066] For example, in an embodiment of this aspect, the present invention provides a method for epoxidizing compound 1, described herein above, to provide epoxide compound 1E. [ka]

[0067] Such epoxides may be useful, for example, as intermediates in epoxide ring-opening reactions to obtain polymer derivatives such as ethers, amines, and esters, which may be useful for any of the uses disclosed herein for any of compounds 1 or 1.1-1.43 or compounds 2 or 2.1-2.27, and may be used in any of the methods described by method 2 or any of 2.1-2.36. Such ring-opening reactions include, but are not limited to, hydrolysis, alcoholysis, aminolysis, and carboxylate ring-opening. Thus, for example, such ring-opening reactions may produce the following products (or any double bond addition regioisomers thereof): [ka] [In the formula, R 1 and R 2 is as defined for compound 1, and X is O, NH, or NR 3 and R 3 is optionally substituted C1-C 12 It is alkyl.

[0068] The details of one or more embodiments of the present invention are set forth below. Unless otherwise specified, 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 case of conflict, the present specification controls.

[0069] It is to be understood that, unless otherwise specified, the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. In this specification and the claims that follow, reference will be made to a number of terms that shall be defined below.

[0070] As used herein, the singular includes the plural unless the context clearly dictates otherwise. Thus, for example, reference to a "reactant" includes not only one reactant but also a combination or mixture of two or more different reactants, reference to a "substituent" includes two or more substituents as well as a single substituent, etc.

[0071] The terms "for example," "such as," or "including" as used herein introduce examples that further clarify a more general subject matter. These examples are provided only to aid in the understanding of the present disclosure and are not intended to be limiting in any manner. Furthermore, the terms "may," "optionally," "optionally," or "may optionally" as used herein mean that the subsequently described circumstance may or may not occur, such that the description includes cases where the circumstance occurs and cases where it does not occur. For example, the term "optionally present" means that the item may or may not be present, and thus the description includes cases where the item is present and cases where the item is not present.

[0072] As used herein, the terms "having the formula" or "having the structure" are not intended to be limiting and are used in the same manner that the term "comprising" is commonly used.

[0073] In some formulas of this application, one or more chiral centers are identified by an asterisk placed next to the chiral carbon. In other formulas, no chiral centers are identified, but chiral isomers are nevertheless encompassed by these formulas.

[0074] Some compounds of the present invention can exist in tautomeric forms which are also intended to be included within the scope of the present invention.

[0075] "Tautomer" refers to a compound that differs significantly in structure due to the arrangement of atoms, but exists in easy and rapid equilibrium. It is understood that the compounds of the present invention may be depicted as different tautomers. When a compound has tautomeric forms, it is also to be understood that all tautomeric forms are intended to be within the scope of the present invention, and the name of the compound does not exclude any tautomeric form. Furthermore, even if one tautomer may be described, the present invention includes all tautomers of the compound.

[0076] As used herein, the term "salt" refers to acid addition salts, such as hydrochloride, hydrobromide, phosphate, sulfate, bisulfate, alkylsulfonate, arylsulfonate, acetate, benzoate, citrate, maleate, fumarate, succinate, lactate and tartrate salts; alkali metal cation salts, such as Na + , K + , Li + , alkaline earth metal salts, e.g. Mg 2+ or Ca 2+ Or it may comprise an organic amine salt or an organic phosphonium salt.

[0077] The term "alkyl" as used herein refers to a monovalent or divalent, branched or unbranched saturated hydrocarbon group containing from 1 to about 12 carbon atoms, typically, but not necessarily, having 1 to 22 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, and the like.

[0078] The term "alkenyl," as used herein, refers to a monovalent or divalent, branched or unbranched, unsaturated hydrocarbon group containing typically, but not necessarily, from 2 to about 12 carbon atoms and from 1 to 10 carbon-carbon double bonds, such as ethylene, n-propylene, isopropylene, n-butylene, isobutylene, t-butylene, octylene, and the like.

[0079] The term "alkynyl" as used herein refers to a monovalent or divalent, branched or unbranched, unsaturated hydrocarbon group containing typically, but not necessarily, 2 to about 12 carbon atoms and 1 to 8 carbon-carbon triple bonds, such as ethyne, propyne, butyne, pentyne, hexyne, heptyne, octyne, and the like.

[0080] As used herein, the term "aryl" refers to an aromatic hydrocarbon moiety containing at least one aromatic ring of 5 to 6 carbon atoms, including, for example, aromatic hydrocarbons having two fused rings and 10 carbon atoms (i.e., naphthalene).

[0081] "Substituted," as in "substituted alkyl," "substituted alkenyl," "substituted alkynyl," and the like, means that at least one hydrogen atom bonded to a carbon atom in the alkyl, alkenyl, alkynyl, or other moiety, is replaced with one or more non-hydrogen substituents, e.g., functional groups.

[0082] For example, C a ~C b The terms "branched" and "straight-chain" (or "unbranched") when used in reference to an alkyl moiety of a carbon atom, apply to the carbon atom that defines the alkyl moiety. For example, for a C4 alkyl moiety, a branched embodiment thereof includes isobutyl, while an unbranched embodiment thereof is n-butyl. However, isobutyl is also defined as a straight-chain C3 alkyl moiety (propyl) itself substituted with a C1 alkyl (methyl).

[0083] Examples of functional groups are halo, hydroxyl, sulfhydryl, C1-C 24 Alkoxy, C2-C 24 Alkenyloxy, C2-C 24 Alkynyloxy, C5-C 20 Aryloxy, acyl (C2-C 24 Alkylcarbonyl (-CO-alkyl) and C6-C 20 Arylcarbonyl (-CO-aryl), acyloxy (-O-acyl), C2-C 24 Alkoxycarbonyl (-(CO)-O-alkyl), C6-C 20 Aryloxycarbonyl (-(CO)-O-aryl), halocarbonyl (-CO)-X (where X is halo), C2-C 24 Alkylcarbonate (-O-(CO)-O-alkyl), C6-C 20 Arylcarbonato (-O-(CO)-O-aryl), carboxy (-COOH), carboxylate (-COO - ), carbamoyl (-(CO)-NH2), monosubstituted C1-C 24 Alkylcarbamoyl(-(CO)-NH(C1-C 24 alkyl)), disubstituted alkylcarbamoyl (-(CO)-N(C1-C24 alkyl)2), monosubstituted arylcarbamoyl (-(CO)-NH-aryl), thiocarbamoyl (-(CS)-NH2), carboxamido (-NH-(CO)-NH2), cyano (-C≡N), isocyano (-N + ≡C - ), cyanate (-OC≡N), isocyanate (-ON + ≡C - ), isothiocyanato (-SC≡N), azido (-N=N + =N - ), formyl (-(CO)-H), thioformyl (-(CS)-H), amino (-NH2), mono- and di-(C1-C 24 Alkyl) substituted amino, mono- and di-(C5-C 20 Aryl) substituted amino, C2-C 24 Alkylamide (-NH-(CO)-alkyl), C5-C 20 Arylamide (-NH-(CO)-aryl), imino (-CR=NH, where R=hydrogen, C1-C 24 Alkyl, C5-C 20 Aryl, C6-C 20 Alkaryl, C6-C 20 aralkyl, etc.), alkylimino (-CR=N(alkyl) (where R=hydrogen, alkyl, aryl, alkaryl, etc.), arylimino (-CR=N(aryl) (where R=hydrogen, alkyl, aryl, alkaryl, etc.), nitro (-NO2), nitroso (-NO), sulfo (-SO2-OH), sulfonato (-SO2-O - ), C1-C 24 Alkylsulfanyl (-S-alkyl; also known as "alkylthio"), arylsulfanyl (-S-aryl; also known as "arylthio"), C1-C 24 Alkylsulfinyl (-(SO)-alkyl), C5-C 20 Arylsulfinyl (-(SO)-aryl), C1-C 24 Alkylsulfonyl (-SO2-alkyl), C5-C 20 Arylsulfonyl (-SO2-aryl), phosphono (-P(O)(OH)2), phosphonato (-P(O)(O -)2), phosphinato (-P(O)(O - )), phospho (-PO2), phosphino (-PH2), mono- and di-(C1-C 24 Alkyl) substituted phosphino, mono- and di-(C5-C 20 aryl) substituted phosphino; and hydrocarbyl moieties, such as C1-C 24 Alkyl (C1-C 18 Contains alkyl, and also C1-C 12 alkyl and further including C1-C6 alkyl), C2-C 24 Alkenyl (C2-C 18 Alkenyl, including C2-C 12 alkenyl and further including C2-C6 alkenyl), C2-C 24 Alkynyl(C2-C 18 Alkynyl, including C2-C 12 alkynyl and further including C2-C6 alkynyl), C5-C 30 Aryl (C5-C 20 Aryl and further C5-C 12 (including aryl) and C6-C 30 Aralkyl(C6-C 20 Aralkyl and C6-C 12 Examples of functional groups include, but are not limited to, alkyl, aryl, arylalkyl ...

[0084] The term "perfume composition" as used herein means a mixture of perfume ingredients, including auxiliary substances, e.g., polyether compounds according to method 1 et seq. and method 2 et seq., optionally dissolved in a suitable solvent or mixed with a powdered substrate, used to provide a desired odor to a product.

[0085] The polyether compounds of Compound 1 et seq., Method 1 et seq. and Method 2 et seq. may be used with, for example, perfumes, soaps, insect repellents and insecticides, cleaning agents, household cleaners, deodorants, room sprays, pomanders, candles, cosmetics, lotions, pre- and after-shave lotions, talcum powders, hair care products, body deodorants, antiperspirants, shampoos, colognes, shower gels, hair sprays, and pet litters.

[0086] Perfumes and ingredients and mixtures of perfume ingredients that may be used in combination with the disclosed compounds to prepare perfume compositions include, but are not limited to, natural products including extracts, animal products and essential oils, absolutes, resinoids, resins and concretes, as well as compounds including alcohols, aldehydes, ketones, ethers, acids, esters, acetals, phenols, ethers, lactones, furans, ketals, nitriles, acids and hydrocarbons, both saturated and unsaturated, and synthetic perfume materials including aliphatic carbocyclic and heterocyclic compounds and animal products.

[0087] As used herein, "citronellol polymer" and "prenol polymer" are intended to include all derivatives and cyclic forms of citronellol and prenol and polymers.

[0088] In this specification, the structural formula of a compound may, for convenience, only describe a specific isomer, but the present invention includes all isomers, such as geometric isomers and optical isomers, based on asymmetric carbon, stereoisomers, tautomers, etc. Furthermore, crystal polymorphism may exist in the compound represented by the formula. It should be noted that any crystal form, mixture of crystal forms, or anhydrides or hydrates thereof are within the scope of the present invention.

[0089] All percentages used herein are by volume unless otherwise specified.

[0090] All ratios used herein are in molar terms unless otherwise specified. EXAMPLES

[0091] Example 1: Synthesis of citronellol polymer Citronellol (250 g) is combined with 5 g of Amberlyst cationic resin and stirred at room temperature for 5 days. 1 It is observed that >80% polymerization has occurred by H NMR (note, reaction times can be dramatically reduced by increasing catalyst concentration and temperature). The reaction mixture is then diluted with hexane and filtered to remove the catalyst. The organic phase is then washed once with aqueous sodium bicarbonate to remove residual acid, then with DI water. The hexane is then removed on a rotary evaporator under reduced pressure. 269 g of material is obtained, which is further distilled.

[0092] A nearly clear citronellol containing fraction (37.5 g) is obtained by distillation at 0.5-1.5 mbar and a head temperature of 60-65° C. A second fraction containing 46.9 g of citronellol dimer of >95% purity is obtained by distillation at 0.2-0.45 mbar and a head temperature of 115-132° C. The remainder of the material remains in the still pot and is believed to be a high MW polyether.

[0093] Example 2: Continuous citronellol polymerization on a cation exchange resin A 6 foot long, 0.25 inch smooth bore stainless steel pipe with 0.01 inch wall thickness is filled with Amberlyst resin, coiled, and PTFE tubing is attached to either end for continuous flow. The coil is heated to 50°C in an oil bath and 300 g of citronellol is pumped through the filled coil at a rate of 2 m / min. The material exiting the coil is 1 H-NMR analysis indicates that a high degree of polymerization has been reached. NMR shows a dramatic increase in the number of protons attached to the methylene groups adjacent to the ether oxygen atoms (approximately 3.3 ppm) compared to the protons attached to the methylene groups adjacent to the alcohol oxygen atoms (approximately 3.6 ppm). The integrated ratio reveals an approximately 1:1 ratio for these two different sets of protons.

[0094] The tube is then rinsed with a minimum of hexane and the isolated material is washed with 10% aqueous sodium carbonate. The hexane is then removed by vacuum distillation to give a residue weighing 315 g. This material is further distilled under reduced pressure (0.7 mbar) and at elevated temperatures (up to 160° C.) to remove monomer and dimer species to give a clear, odorless liquid identified as: [ka]

[0095] The compound of Example 2 is found to have a viscosity of 238.5 mPa at 25° C., a refractive index of 1.47 at 20° C. and a surface tension of 30.1 mN / m.

[0096] Additionally, other distillation fractions produce other citronellol oligomers, including citronellol dimers and citronellol polymers, where n is an average of 3-6.

[0097] Example 3: Citronellol Polymer Acetate To 702 g of the compound of Example 2 (citronellol polymer, n=1-4) is added 1.0 L of tetrahydrofuran (THF) and 18.33 g of N,N-dimethylaminopyridine (DMAP). The solution is stirred and cooled in an ice bath. Acetic anhydride (229 g) is added dropwise, then the solution is allowed to warm to room temperature and stirred overnight. The reaction is confirmed to be complete by thin layer chromatography (TLC) and quenched by slow addition of 100 ml of water. After stirring for 3 hours, the THF is removed under reduced pressure on a rotary evaporator and the organic phase is diluted with MTBE and washed with 10% sodium carbonate until the pH is 8. The phases are separated and the organic phase is dried over sodium sulfate and filtered. The material is decolorized with activated charcoal and further distilled under reduced pressure to remove traces of solvent to give 676 g of a clear, odorless liquid, identified as follows (where n is on average 1-4): [ka]

[0098] The compound of Example 3 is found to have a viscosity of 39.3 mPa at 25° C., a refractive index of 1.4575 at 20° C. and a surface tension of 27.2 mN / m.

[0099] In a similar manner, the compound of Example 2 (citronellol polymer, n=3-6) is reacted with acetic anhydride and DMAP in THF solvent and purified to obtain citronellol polymer acetate (where n is 3-6 on average).

[0100] Example 4: Citronellol Polymer Butyrate By substituting butyric anhydride for acetic anhydride substantially as described in Example 3, the butanoate esters shown below (where n is 1-4 on average) are obtained as clear, odorless liquids. [ka]

[0101] The compound of Example 4 is found to have a viscosity of 55.7 mPa at 25° C., a refractive index of 1.4882 at 20° C. and a surface tension of 27.8 mN / m.

[0102] Example 5: Citronellol Dimer Oleate [ka] 10 g of citronellol dimer (prepared according to Example 1) and 9 g of methyl oleate are stirred in a 250 mL flask to mix thoroughly. 0.1 g of sodium methoxide is slowly added to the reaction mixture. The reaction is stirred at 80° C. for 5 hours while methanol is continuously distilled off from the reaction. The reaction is monitored for completion using TLC, GC and NMR. The reaction is quenched using 50% acetic acid in dH2O. The reaction mixture is extracted with hexane and concentrated under reduced pressure. 16 g of crude product is obtained and is further purified using column chromatography. After chromatography, 3 g of pure product is isolated and identified as oleate ester of citronellol dimer by NMR.

[0103] Example 6: Adipic acid diester of citronellol dimer [ka] 10g of citronellol dimer and 3g of dimethyl adipate were mixed thoroughly in a 250mL flask by stirring. 0.1g of sodium methoxide was slowly added to the reaction mixture. The reaction took 4 hours at 80°C. During the reaction, methanol was distilled off from the reaction mass. TLC, GC and NMR were used to follow the reaction. The reaction was quenched with 50% acetic acid in dH2O. The reaction mixture was extracted with hexane and concentrated to dryness.

[0104] Example 7: Cyclic Citronellol Dimer 8 g of the citronellol polymer crude distillation fraction from Example 2 is used to purify the cyclic citronellol dimer by column chromatography. 0.2 g of pure solid cyclic dimer was isolated and the structure was confirmed by NMR.

[0105] Example 8: Evaluation of insect repellency Citronellol dimer (Sample A; made according to Example 1), citronellol dimer acetate (Sample B; made according to Example 3) and citronellol polymer acetate (n=3-6) (Sample C; made according to Example 3) are compared to the standard insect repellent DEET (di-ethyl-meta-toluamide) in an in vitro method using female Aedes aegypti mosquitoes. Mosquitoes are exposed to the treatments applied to a 3 cm diameter collagen membrane placed over warm, blood-filled wells of a multi-well plate. The wells are pre-heated to 96-100°F and then citrated whole blood containing ATP is poured into each well to completely fill it. The membrane is applied and vacuum grease is used to ensure coverage. Twenty-five microliters of test solution is applied to each membrane and the solution is allowed to dry. The plate is then placed in a plastic box enclosure with 250 mature female mosquitoes. The number of events in which the mosquito probes the membrane is recorded for 20 minutes. The entire process is repeated until five replicates are completed. The treatment locations within the plate are rotated between each replicate to eliminate any positional bias. Fresh blood and mosquitoes are used during each replicate. Percent repellency is calculated by comparison to a negative control membrane treated with water only. All three citronellol derivatives are found to provide substantially similar repellency to a 20% DEET in isopropanol solution compared to the negative control (water) (all four approximately 97-99% repellency). [Table 3]

[0106] Example 9: Reduction of Unsaturated Citronellol Homopolymer [ka] Citronellol homopolymer obtained substantially according to Example 2, where n is an average of 1 to 4, is catalytically hydrogenated to give the corresponding saturated compound shown above. 100 g of citronellol homopolymer is combined with a solution of 5% palladium on carbon (250 mg) in ethanol (100 mL) in a pressure reactor. The reaction is carried out under 400 psi hydrogen atmosphere with shaking at room temperature for 72 hours. The reaction mixture is then filtered through Celite and the ethanol is removed by distillation under vacuum to give a colorless liquid (quantitative yield). Proton NMR confirms the complete disappearance of olefinic protons in the product.

[0107] Example 10: Insect repellency of citronellol polymer solutions Citronellol polymer acetate (n=3-6) (sample C; produced as a fraction in Example 2) is dissolved in isopropyl alcohol (IPA) solvent at 1 wt%, 5 wt% or 20 wt% concentration. This is compared with a 20 wt% DEET solution in IPA as a control. The procedure is as described in Example 8. The results are summarized in the table below. [Table 4]

[0108] The results show a dose-response relationship between citronellol polymer concentration and mosquito repellent efficacy.

[0109] Example 11: Evaluation of Paint and Coating Compositions Citronellol polymer acetate (n=3-6) (Sample C; made according to Example 3) or citronellol polymer alcohol (n=3-6) (Sample D; made according to Example 2) are mixed with one of three commercially available base coatings (Substrate A, Substrate B, Substrate C) in a 1:1 or 3:1 ratio. The mixtures are evaluated for physical properties important to paint and coating applications. The compositions of Substrate A, Substrate B, and Substrate C are shown in the table below. [Table 5]

[0110] The mixtures are applied in triplicate to pine boards with one back and forth brush stroke. They are analyzed for the following criteria: gloss, color, oiliness, evenness of application, smoothness and water repellency (beading). The comparative results are shown in the table below. [Table 6]

[0111] The results show that the addition of the compounds of the present invention can promote application uniformity and smoothness of both acrylic and shellac base formulations. Furthermore, both citronellol polymers tested are found to be freely miscible with each of the three base formulations.

[0112] Example 12: Evaluation of perfume fixative properties Blotting paper tests are performed to evaluate the odor retention of two common fragrance ingredients, linalool and 1-(3,3-dimethylcyclohexyl)ethyl formate (Aphermate). A 50% w / w solution of linalool in ethanol or Aphermate stock solution is mixed with citronellol polymer acetate (n=3-6) (sample C; made according to Example 3) or citronellol polymer alcohol (n=3-6) (sample D; made according to Example 2) in approximately a 3:1 ratio (fragrance:polymer). Approximately 18-25 mg of each sample is applied onto the blotter paper. The test is performed under ambient conditions (indoors, at room temperature and ambient humidity). The intensity of the fragrance odor is evaluated periodically and the results are shown in the table below. [Table 7]

[0113] The results show that the perfume mixed with the citronellol polymer of the present invention still retains a significant amount of fragrant odor even after 5-7 hours of storage, which is not present when the pure composition is blotted.

[0114] Example 13: Evaluation of anti-frizz properties Citronellol polymer acetate stock solution (n=3-6) (Sample C; made according to Example 3) and citronellol polymer alcohol stock solution (n=3-6) (Sample D; made according to Example 2) are compared to commercially available frizz-reducing hair care products. Commercially available 100% pure human hair hair extensions are washed, shampooed, and towel-dried to remove excess moisture. The hair extensions are all substantially the same in length, thickness, texture, and appearance. A small amount of sample (approximately 150-200 mg) is then spread evenly over the entire hair with both hands. Observe immediately after the sample has been spread over the entire hair and after the hair samples have been further air-dried (indoor ambient conditions) for less than 30 minutes. According to the label, the commercial products contain (in descending order of concentration): a mixture of cyclopentasiloxane, dimethiconal, dimethicone crosspolymer, benzophenone-3, fragrance, benzyl butanoate, and butylphenyl methylpropional.

[0115] The following observations were made: [Table 8]

[0116] These results show that both of the inventive polymers tested reduce frizz in natural human hair better than comparable commercial products, while the Sample C polymer provides the best texture and feel to the treated hair.

[0117] Example 14: Evaluation of malodor reduction Malodorous compositions are prepared by combining 60 microliters of methyl sulfide and 60 microliters of allyl sulfide in a 10 mL glass vial. Ethanol is added to this stock malodorous mixture to obtain a solution with a concentration of odorant compounds of 1 ppm or 100 ppm. Mixtures are then prepared by combining the malodorous ethanol solution with commercial perfume oil or citronellol polymer acetate (n=3-6) (sample C; made according to Example 3) or citronellol polymer alcohol (n=3-6) (sample D; made according to Example 2) in a 9:1 w / w ratio. Samples of commercial perfume oil and commercial perfume oil mixed with samples C and D in a 9:1 w / w ratio are also used for comparison. Blotting paper samples are dipped to the same depth into each test sample to allow the paper to absorb the same amount of liquid. Each blotter paper is then placed in its own 400 g lidded jar, the jars are sealed, and allowed to sit for 1 hour. The jars are then opened and the odor from the jars is immediately evaluated. The results are shown in the table below. [Table 9]

[0118] The results show that the polymers of the present invention can effectively mask or minimize the strong, noxious odors caused by volatile organic sulfides (i.e., rotten egg odor). It was also unexpectedly found that the polymer of Sample D appears to enhance the pleasant odor of a commercial perfume oil.

[0119] Example 15: Cosmetic Composition Moisturizing lotions, cosmetic primers and cosmetic sealers are prepared using citronellol polymer acetate (n=3-6) (Sample C; made according to Example 3) according to the tables below (percentages shown are w / w). [Table 10]

[0120] Each lotion composition was prepared by first combining the water and glycerol in one beaker and heating to approximately 70-75°C, and combining the oil phase (cetyl alcohol, stearic acid, isopropyl myristate, glyceryl stearate, triglyceride blend, and Sample C) in a second beaker and similarly heating to approximately 70-75°C. The hot oil phase is then sequentially placed in a plastic beaker, followed by the hot water phase, the beaker is immediately immersed in a cold water bath, and the mixture is mixed at high speed with a handheld electric mixer. To the resulting homogenous emulsion, at approximately 30-40°C, the preservatives, fragrance are added with gentle mixing. Both compositions have a pH of 5-5.5.

[0121] The control lotion is found to have a homogeneous and slightly hard texture. It dries quickly after application to the skin. In contrast, the lotion composition containing sample C is found to have a softer, smoother feel on the skin and does not dry out.

[0122] The primer composition is prepared by heating propylene glycol to 70-75°C in a beaker and then adding dimethylsilylated silica with stirring to form a homogeneous gel. Sample C is then slowly added with stirring, followed by cooling the mixture. The preservative is then added after the mixture has cooled to below 40°C. The resulting product is a homogeneous gel that has a velvety feel after application to the skin. Compared to similar commercially available silicone-based primers, the primer provides a smoother, more lustrous appearance to the skin.

[0123] The concealer composition is prepared by first mixing water and glycerol in one beaker, heating to about 70-75°C, and combining with the oil phase (cetyl alcohol, triglyceride mixture, silica, and Sample C) in a second beaker, also heating to about 70-75°C. The titanium dioxide and iron oxide colorants are then ground together in a mortar and pestle, and then combined with the propylene glycol. The propylene glycol / colorant mixture is then added to the oil phase and mixed. The hot oil phase is then placed in succession in a plastic beaker, followed by the hot water phase, and the beaker is immediately immersed in a cold water bath and mixed with a spatula while cooling. This results in a two-phase heterogeneous mixture that includes an oil phase and a mixed oil / water emulsion.

[0124] The oil phase is highly pigmented and therefore provides very good coverage. The entire formulation is soft matte, providing a soft, velvety feel after application to the skin. The concealer exhibits a more matte than wet nature compared to commercial concealers.

[0125] Example 16: Epoxidation of double bonds [ka] A 250 mL three-neck round bottom flask is charged with 25.5 g (108.5 mmol) of the polymer of Example 2 (n=3-6) and toluene (100 mL). 3-Chloroperbenzoic acid (mCPBA, 10.5 g, 60.8 mmol) is slowly added as a solid. The reaction is kept stirring for another 15 h at room temperature. Saturated sodium sulfite (50 mL) solution is added to the reaction mixture to quench and stir for 2 h. The organic phase is washed with sodium carbonate solution (10%) until pH 8. The organic phase is dried over sodium sulfate and concentrated to obtain the crude polymer epoxide product. To remove the residual benzoic acid, the crude product is dissolved in MTBE (100 mL) and stirred with sodium carbonate solution (10%) (50 ml) for 15 h. The solvent from the organic phase is evaporated after phase separation to obtain the final crude product in a yield of 23 g. Proton NMR shows the characteristic epoxide peak at approximately 2.66 ppm (CDCl3 solvent). Differential scanning calorimetry (DSC) shows that the epoxide reacts at approximately 150-170 °C. Further experiments confirm that the crude epoxide product reacts successfully with amine nucleophiles in a ring-opening reaction.

[0126] Example 17: Improvement of sequential acylation of citronellol polymers 200 g of citronellol polymer alcohol (n=3-6) (Sample D; prepared according to Example 2) is combined with 60.5 ml of acetic anhydride and pumped at 10 m / min through a 6 foot long stainless steel tube (0.25 inch diameter) coiled to fit into an oil bath maintained at 100-105° C. The reactants are continuously circulated through the tube (approximately 5 passes through the coil) until the reaction is judged to be greater than 97% complete. The product is obtained by dissolving the crude product in hexane and washing the organic phase with water, then 10% aqueous sodium carbonate, followed by solvent removal under reduced pressure. The product is analyzed and found to be identical to the citronellol polymer acetate (n=3-6) obtained according to Example 3.

[0127] In some other experiments, the acetic acid and residual acetic anhydride can be removed directly by distillation.

[0128] Example 18: Continuous polymerization of isoprenol A 6-foot long stainless steel tube (0.25 inch diameter) is packed with Amberlyst cation exchange resin and coiled to fit into an oil bath maintained at approximately 50° C. 66 g of isoprenol is fed into the tube at a flow rate of 1.9 g / min. 1 H NMR (CDCl3) analysis shows the formation of mainly polymerized products with no residual monomer and traces of isoprene. The characteristic peaks of the polymeric products are geminal dimethyl peaks at 1.0-1.25 ppm, vicinal methylene peaks at 1.5-1.75 ppm, and methylene adjacent to the ether linkage at 3.5-3.75 ppm. After distillation of the low boiling oligomers at 120 °C and 1.2 mbar, the residue 1 1 H NMR shows only traces of olefinic protons are present, indicating a high degree of polymerization.

[0129] Under similar conditions, isoprenol is observed to undergo much better conversion to polymer than prenol. Furthermore, the present invention includes the following aspects. 1. Formula Y: [ka] [wherein the dotted bonds (A, B, and C) represent optional bonds, and R 1 is optionally substituted C 1 -C 12 R is alkyl; 2 is H, C 1-20 Alkyl, aryl, aryl-C 1 - 2 alkyl, optionally unsaturated alkyl ester or aryl ester, or R 2 The part: [ka] where X is of the formula -C(O)-R 3 -C(O)- diacyl moiety, where R 3 is optionally substituted C 1-22 Alkyl, optionally substituted C 2-22 alkenyl or optionally substituted aryl; and n is an integer from 0 to 20; However, if the intramolecular bridge A exists, the dotted bonds B and C do not exist, and the substituent R 2 does not exist. A compound represented by the formula: 2. The compound of formula Y is a compound of formula I

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Claims

1. Formula I 【Chemistry 1】 [During the ceremony, R １ is optionally substituted C １－１２ Alkylene (e.g., optionally further １－１２ C substituted with alkyl or aryl １－１２ alkylene); and R ２ is C(O)-C １－２０ Alkyl, C １－２０ Alkyl (e.g., lower alkyl (e.g., C １－６ Alkyl) or C １－１２ alkyl), aryl (e.g., phenyl), aryl C １ - ２ alkyl (e.g., benzyl), or optionally substituted C(O)-aryl, and n is an integer from 1 to 20. A compound represented by the formula:

2. R １ CH ２ CH ２ CH(CH ３ )CH ２ CH ２ 2. The compound of claim 1,

3. R ２ C １－２０ 3. The compound of claim 1 or 2, which is alkyl.

4. R ２ C １－６ The compound of claim 3, wherein the aryl group is an alkyl group.

5. R ２ C １－１２ The compound of claim 3, wherein the aryl group is an alkyl group.

6. R ２ is C(O)-C １－２０ 3. The compound of claim 1 or 2, which is alkyl.

7. R ２ is C(O)-C １－６ The compound of claim 6, which is alkyl.

8. R ２ is C(O)-C １－３ The compound of claim 7, which is alkyl.

9. R ２ is C(O)-C １－２ The compound of claim 8 which is alkyl.

10. The compound according to any one of claims 1 to 9, wherein n is greater than 1.

11. The compound according to any one of claims 1 to 10, wherein n is 2 to 20.

12. R １ CH ２ CH ２ CH(CH ３ )CH ２ CH ２ n is 1, 2 or 3; R ２ is C(O)-C １－６ alkyl, １－６ 2. The compound of claim 1, wherein alkyl is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, or n-hexyl.

13. R １ CH ２ CH ２ CH(CH ３ )CH ２ CH ２ n is 1, 2 or 3; R ２ is C(O)-C １－６ alkyl, １－６ 2. The compound of claim 1, wherein alkyl is selected from methyl, ethyl, propyl, and isopropyl.

14. terminal group 【Chemistry 2】 but 【Chemistry 3】 The compound according to any one of claims 1 to 13,

15. terminal group 【Chemistry 4】 but 【Chemistry 5】 The compound according to any one of claims 1 to 13,

16. The formula: 【Chemistry 6】 [During the ceremony, n is an integer from 1 to 20; R ２ is H or C １－２０ Alkyl (e.g., lower alkyl (e.g., C １－６ Alkyl) or C １－１２ alkyl), aryl (e.g., phenyl), aryl C １ - ２ alkyl (e.g., benzyl), or optionally substituted C(O)-aryl; or n is an integer from 1 to 20, and R ２ is C(O)-C １－２０ It is alkyl. A compound represented by the formula:

17. R ２ C １－２０ 17. The compound of claim 16, which is alkyl.

18. R ２ is C(O)-C １－２０ 17. The compound of claim 16, which is alkyl.

19. R ２ is C(O)-C １－６ 20. The compound of claim 18, which is alkyl.

20. R ２ is C(O)-C １－６ alkyl, １－６ 17. The compound of claim 16, wherein alkyl is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, or n-hexyl.

21. R ２ is C(O)-C １－６ alkyl, １－６ 17. The compound of claim 16, wherein alkyl is selected from methyl, ethyl, propyl or isopropyl.

22. R ２ is C(O)-C １－６ alkyl, １－６ 17. The compound of claim 16, wherein the alkyl is methyl.

23. R ２ The compound of claim 16 , wherein

24. The compound according to any one of claims 16 to 23, wherein n is 2 to 20.

25. The compound according to any one of claims 16 to 23, wherein n is 1, 2 or 3.

26. Formula II 【Chemistry 7】 [During the ceremony, R １ is optionally substituted C １－１２ Alkylene (e.g., optionally further １－１２ C substituted with alkyl or aryl １－１２ alkylene); n1 and n2 are each independently an integer from 0 to 20; and X is a group of the formula -C(O)-R ３ -C(O)- diacyl moiety, where R ３ is optionally substituted C １－２２ Alkylene, optionally substituted C ２－２２ alkenylene or optionally substituted arylene. Compound.

27. R ３ 27. The compound of claim 26, wherein is arylene, e.g., substituted or unsubstituted phenylene.

28. Formula III 【Chemistry 8】 [During the ceremony, R １ is optionally substituted C １－１２ Alkylene (e.g., optionally further １ -C １２ C substituted with alkyl or aryl １－１２ alkylene); and and n is an integer from 1 to 20. Compound.

29. 29. A composition comprising a compound according to any of claims 1 to 28 or any mixture thereof in combination with at least one suitable solvent, carrier or additive, the composition being a fragrance composition or a perfume composition or a soap composition or an insect repellent composition or an insecticidal composition or a cleaning composition or a household cleaning composition or a deodorant composition or a room spray composition or a pomander composition or a candle composition or a cosmetic composition or a toner composition or a pre-shave or after-shave lotion composition or a talcum powder composition or a hair care composition or a body deodorant composition or an antiperspirant composition or a shampoo composition or a pet litter composition or a topical skin care composition or a paint or coating composition or a lubricating composition or a plastic composition or an antifoam composition or a hydraulic fluid composition or an antibacterial composition.

30. Claim 1 (wherein R ２ is H, (1) Add the following to the reactor: 【Chemistry 9】 [In the formula, R １ is optionally substituted C １－１２ Alkylene (e.g., optionally further １－１２ C substituted with alkyl or aryl １－１２ alkylene). introducing a compound of the formula: (2) exposing the compound of formula A to a solid ion exchange resin, thereby inducing polymerization of the compound of formula A to produce the compound of claim 1, ２ is H; and (3) isolating and / or purifying the compound (e.g., by distillation). A method comprising the steps of:

31. Formula I 【Chemistry 10】 [In the formula, R １ is optionally substituted C １－１２ Alkylene (e.g., optionally further １－１２ C substituted with alkyl or aryl １－１２ alkylene); and R ２ is (C=O)C １－４ alkyl (e.g., methyl), and n is an integer from 1 to 20. The method for preparing an ester compound 1A of formula I, comprising the steps of: ２ is H) and a carboxylic acid anhydride of formula ROR, where R is (C=O)C １－４ wherein the reaction is carried out in the absence of a base or a catalyst under continuous flow conditions (e.g., in a continuous flow reactor).

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