Polyether derivatives, uses thereof and methods for their preparation

Abstract

The present invention relates to polyether derivatives, uses and methods of making thereof, such as to certain polyethers, polyether derivatives, and methods of making and utilizing the same. For example, the starting material can be, for example, Citronellol, Prenol, Isocitronellol, and Isoprenol.

Description

[0001] The applicant filed PCT application PCT / US2018 / 044657 on July 31, 2018, entitled "Polyether Derivatives, Uses and Preparation Methods Thereof". This PCT application entered the Chinese national phase on March 30, 2020, with application number 201880063571.6. This application is a divisional application of that Chinese application.

[0002] Cross-references to related applications

[0003] This application claims priority and benefit to U.S. Provisional Patent Application Serial No. 62 / 539,319, filed July 31, 2017; 62 / 617,924, filed January 16, 2018; and 62 / 662,177, filed April 24, 2018, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0004] This invention relates to some polyethers, polyether derivatives, and methods for preparing and using them. For example, the raw materials may be such as citronellol, prenol, isocitronellol, and isoprenol. Background of the Invention

[0005] Liquid polymers have important applications in cosmetics and personal care, and play a significant role in visual displays, rheology, tribology, and drug delivery. For example, they can be used as lubricants, emollients, or as protective barriers for skin healing and UV protection. Ideally, these substances can be produced in a convenient manner, readily derivatized to modify their function, and even more preferably prepared from safe and sustainable raw materials.

[0006] Citronellol, Prenol, and Isoprenol are all naturally occurring molecules and are widely available commercially. However, these molecules possess a combination of functional groups with low utilization rates that enable their polymerization and functionalization: isobutylene groups and alcohols.

[0007] This type of chemistry has been largely neglected in polymer chemistry. One reason for this may be the fact that the polymerization is an equilibrium reaction, and that readily available, abundant isobutylene alcohol is not always available. However, in recent years, the production of citronellol has grown rapidly, and one of the largest production routes uses prenol and isoprenol as intermediates, thereby greatly increasing its availability.

[0008] However, as mentioned above, the equilibrium nature of the polymerization reaction potentially makes the large-scale production of the required ethers challenging. Production strategies and methods capable of efficiently preparing these compounds are needed. Summary of the Invention

[0009] Amidst the remarkable advances in polymer science, PCT / US2015 / 047397 (equivalent to USUS2017 / 0283553) and PCT / US2015 / 016371 (equivalent to USUS2017 / 0057940) have taught how to utilize the aforementioned functionalities to prepare novel polyether compositions, the contents of which are incorporated herein by reference. These polyethers represent advancements in liquid polymer technology and offer benefits in numerous desirable areas of commercial application.

[0010] This disclosure builds upon the applicant's own aforementioned patent application by applying novel derivatization strategies and production methods. Furthermore, this disclosure teaches methods for the controlled release of monomers contained in the said polyether polymers, for applications such as fragrances and pest control.

[0011] Generally speaking, this disclosure provides compounds of the following formula Y:

[0012]

[0013] In this context, the dashed keys (A, B, and C) represent optional keys, and R... 1 It is an optional substitution of C1–C 12 Alkyl; R 2 It is H, C 1-20 Alkyl, aryl, aryl-C 1-2 Alkyl, optionally unsaturated alkyl esters or aryl esters, or R 2 It is a functional group:

[0014]

[0015] Where X is the expression -C(O)-R 3 -C(O)- diacyl group, wherein R 3 C is an optional substitute 1-22 Alkyl, optionally substituted C 2-22 Alkenyl or optionally substituted aryl;

[0016] And where n is an integer between 0 and 20;

[0017] The premise is that if intramolecular bridging bond A exists, then dashed bonds B and C do not exist, and substituent R... 2 It does not exist. This should be understood. This indicates an optional double bond (i.e., a single or double bond), and from this terminal group... There may be any one of the three optional keys shown (i.e., a double key) or none of the optional keys may exist (i.e., all are single keys).

[0018] On the other hand, this disclosure provides methods for producing the compound and methods for using the compound. Brief description of the attached diagram

[0019] Figure 1 Provides general descriptions of citronellol monoethers, polyethers, and citronellol monomers.

[0020] Figure 2 Provides general descriptions of isomeric citronellol monoethers, polyethers, and isomeric citronellol monomers.

[0021] Figure 3 Provides general descriptions of Prenol monoethers, polyethers, and Prenol monomers.

[0022] Figure 4 Provides a general description of Isoprenol monoethers, polyethers, and Isoprenol monomers.

[0023] Figure 5 Provide descriptions of citronellol-type monomers, monoethers, and polyethers derived from functional groups at the hydroxyl position by adding or modifying them.

[0024] Figure 6 Provide descriptions of renol-type monomers, monoethers, and polyethers derived from functional groups at the hydroxyl position by adding or modifying them.

[0025] Detailed Explanation

[0026] Not wanting to be bound by theory, isobutylene groups can form ethers with alcohols via acid catalysis. This chemistry has been used in other cases to form ether bonds in organic synthesis.

[0027] The equilibrium nature of the reaction may potentially make large-scale production of these ethers challenging. However, the inventors have discovered that, with monomer cycling, appropriate catalyst selection, and high-concentration reaction conditions, these molecules can be polymerized to a sufficient degree for many different applications. Furthermore, these low-molecular-weight polymers can be further derivatized to achieve higher molecular weights and to obtain new functional groups.

[0028] Figure 4 The diagram shows some monomers, dimers, trimers, and higher oligomers of citronellol-type and Prenol-type polymers. For the purposes of this invention, the term "citronellol" refers to both isomers included at the olefin position. Similarly, when the term "Prenol" is used, it also refers to the Isoprenol isomer. In one aspect, the invention contemplates mixtures of Prenol and citronellol polyethers.

[0029] Although some methods for preparing these ethers are described in PCT / US2015 / 047397 (US2017 / 0283553), the applicant has now discovered that using resin-bonded acid catalysts, such as Under completely solvent-free conditions, the polyether can be prepared in a shorter time with a higher degree of polymerization. On one hand, the polymerization can be carried out at or below room temperature, preferably at a slightly elevated temperature of 30 to 110°C, or even more preferably at 40-90°C (e.g., about 50°C). Furthermore, on the other hand, the polymerization can be carried out in a batch reactor, a semi-batch reactor, or even more preferably a continuous packed bed reactor of the type described in U.S. Provisional Application 62 / 384,939 and PCT / US2017 / 50808, the contents of which are incorporated herein by reference.

[0030] The applicant has unexpectedly discovered unique advantages in utilizing continuous, neat polymerization instead of traditional batch processing. Besides significantly reduced reaction times (e.g., seconds for continuous flow vs. days for batch-like conversions), the application of continuous, neat polymerization yields highly efficient chemical realizations not observed under batch conditions in some cases. For example, for Isoprenol polymerization, batch conditions produce complex mixtures with almost no apparent polymer formation, while under continuous reactor conditions, the desired homo-Isoprenol polymer is obtained in good yields as the major product within a short reaction time.

[0031] Unbound by theory, polyether formation can occur in equilibrium under acidic conditions. Therefore, exposure to acidic conditions during subsequent derivatization is unfavorable, lest depolymerization occur.

[0032] However, the applicant has discovered that transesterification can be completed under alkaline conditions to produce a wide variety of new and useful material compositions. Furthermore, alkaline Williamson-type etherification can be accomplished using organohalides. The functional groups produced by these methods can alter the hydrophilicity, hydrophobicity, and / or viscosity of the polyether. In addition, new functions can be introduced, such as UV protection, antioxidant, anti-aging, skin whitening, antibacterial, and / or other bioactivities. Representative descriptions of these modifications are shown in [reference to a document / document / etc.]. Figure 5 and 6 middle.

[0033] Furthermore, the applicant has discovered that the esterification reaction of the polymer with anhydrides can be carried out continuously with simple heating, in the presence or absence of a catalyst. Traditionally, esterification reactions are typically carried out batchwise in a solvent in the presence of a catalyst such as DMAP or an acid. However, due to the liquid nature and low volatility of these polymers, the polymers can be continuously derivatized without the presence of any solvent or catalyst.

[0034] For example, acetic anhydride can be added directly to mixtures of these polymers, and the mixture can be continuously passed through heating tubes or pipes at elevated temperatures, easily achieving conversion to the desired product without the addition of any catalyst or solvent. Furthermore, complete and continuous removal of any residual acetic anhydride or acetic acid byproducts can be achieved under reduced pressure or elevated temperatures, and any trace amounts of acid or color can be continuously removed using anion exchange media or activated carbon, respectively.

[0035] The unique benefits of the compounds disclosed herein derive from one or more of the following characteristics: the compounds are short-chain polymers; the compounds are prepared using a reversible polymerization reaction; the polymers are biodegradable and biocompatible; and the polymers can be produced using all-natural ingredients. These are important benefits in several commercial applications where these compounds can be utilized. The compounds disclosed herein are suitable as substitutes or alternatives to surfactants, polymers, and silicones in a variety of commercial products, such as cosmetic and pharmaceutical compositions, as adjuvants in crop care formulations, and as lubricants or solvents in enhanced oil recovery, fracturing, and oilfield applications. The compounds disclosed herein provide improved physical properties, such as appearance, odor, viscosity, refractive index, and / or surface tension. These compounds are short polymers with medium molecular weights (e.g., 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).

[0036] In some embodiments of this disclosure, the compounds disclosed herein are useful for: retaining aroma, fixing aroma, or using as aroma carriers; as odor neutralizers; in paints and coatings; as adjuvants for crop control; as cosmetic ingredients (e.g., as silicone or white oil substitutes); in nail polish; in writing or printing inks; as resins or resin substitutes; as insect repellents (e.g., mosquito repellents); and in sunscreen formulations.

[0037] The reversibility of the polymerization of the claimed compounds stems from the properties of these polymers, which possess adjacent oxygen and tertiary carbon atoms. Therefore, under conditions that promote the cleavage of the OC bond, the resulting tertiary carbocations are exceptionally stable. This leads to a readily adsorbed adjacent hydrogen atoms to regenerate the alcohol and olefin functional groups of the starting materials. The depolymerization reaction can be promoted by weakly acidic conditions (e.g., with Lewis or Brønsted acids), by thermal conditions, or by enzymatic conditions (e.g., enzymes found in naturally occurring bacteria).

[0038] The depolymerization property leads to biodegradation. This property also allows for the formation of compositions containing compounds in which the depolymerization of the polymer can be controlled to allow the slow release of polymer monomer components (e.g., citronellol) or shortened polymer components (e.g., citronellol dimers released through larger polymer depolymerization). This disclosure covers solid and / or liquid compositions containing polymers according to Formula I (or any one of 1.1-1.43) or Formula II (or any one of 2.1-2.27), wherein the formulation provides slow, controlled depolymerization of the polymer, and diffusion of the resulting monomers and / or shortened oligomers so that they can be released from the composition (e.g., by evaporation at the surface of the composition). The formulation may consist of components that promote the depolymerization (e.g., Lewis acids or Brønsted acids or enzymes), or the composition may be combined with a device containing an electrically heating element to promote thermal depolymerization. Monomers and / or shortened oligomers (e.g., citronellol or citronellol dimers or trimers) produced in this manner are beneficial for a variety of reasons, such as as flavoring agents, insect repellents, antioxidants, antimicrobial agents, or as active pharmaceutical ingredients (e.g., where the composition is a pharmaceutical composition).

[0039] The compounds disclosed herein are particularly suitable as alternatives to silicones, mineral oils, and / or paraffins in cosmetic compositions such as concealers, primers, and / or moisturizers.

[0040] In the first aspect, this disclosure provides ether compounds according to formula I (compound 1), such as citronellol and prenol ethers and polyethers:

[0041]

[0042] or its salt, wherein,

[0043] R 1 It is an optional substitution of C1–C 12 Alkyl groups (e.g., optionally further C1–C) 12 alkyl or aryl substituted C 1- C 12 alkyl);

[0044] R 2 It is H, C 1-20 Alkyl (e.g., lower alkyl (e.g., C10)) 1-6 alkyl) or C 1-12 alkyl), aryl (e.g., phenyl), aryl C 1-2 Alkyl (e.g., benzyl), optionally unsaturated alkyl esters (e.g., C(O)-C) 1-20 Alkyl esters or optionally substituted aryl esters (e.g., C(O)-aryl);

[0045] n is an integer between 0 and 20. It should be understood that... This indicates an optional double bond (i.e., a single or double bond), and from this terminal group... There may be any one of the three optional keys shown (i.e., a double key) or none of the optional keys may exist (i.e., all are single keys).

[0046] In other embodiments of the first aspect, this disclosure provides any one of the following:

[0047] 1.1 Compound 1, wherein R 1 It is an optional substitution of linear C 1- C 12 Alkyl or optionally substituted branched C 1- C 12 alkyl.

[0048] 1.2 Compound 1, where R 1 It is an unsubstituted linear C 1- C 12 Alkyl or unsubstituted branched C3-C 12 alkyl.

[0049] 1.3 Compound 1, wherein R 1 It is an unsubstituted linear C 1- C 12 alkyl.

[0050] 1.4 Compound 1, where R 1 It is an unsubstituted branch C3-C 12 alkyl.

[0051] 1.5 Compound 1, wherein R 1 It is CH2.

[0052] 1.6 Compound 1, where R 1 It is an unsubstituted branched or straight-chain C6 alkyl group.

[0053] 1.7 Compound 1, wherein R 1 It is CH2CH2CH(CH3)CH2CH2.

[0054] 1.8 Compound 1 or any one of 1.1-1.7, wherein R 2 It is H.

[0055] 1.9 Compound 1 or any one of 1.1-1.7, wherein R 2 It is an alkyl group (e.g., a lower alkyl group, e.g., C10) 1-6 Or C 1-12 )).

[0056] 1.10 Compound 1 or any one of 1.1-1.7, wherein R 2It is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, or n-decyl.

[0057] 1.11 Compound 1 or any one of 1.1-1.7, wherein R 2 It is aryl C 1-2 Alkyl groups (e.g., benzyl or phenylethyl).

[0058] 1.12 Compound 1 or any one of 1.1-1.7, wherein R 2 It is an aryl group (e.g., phenyl).

[0059] 1.13 Compound 1 or any one of 1.1-1.7, wherein R 2 It is an optional unsaturated alkyl ester (e.g., C(O)-C). 1-20 Alkyl or C(O)-C 1-6 alkyl).

[0060] 1.14 Compound 1 or any one of 1.1-1.7, wherein R 2 It is C(O)-C 1-6 Alkyl, optionally wherein R 2 It 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 alkyl.

[0061] 1.15 Compound 1 or any one of 1.1-1.7, wherein R 2 It is C(O)-C 1-6 Alkyl, and the C 1-6 The alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, or n-hexyl.

[0062] 1.16 Compound 1 or any one of 1.1-1.7, wherein R 2 It is an optional unsaturated C(O)-C 7-20 Alkyl, optionally wherein R 2 It is an optional 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 alkyl.

[0063] 1.17 Compound 1 or any one of 1.1-1.7, wherein R 2 It is a monounsaturated C(O)-C7-20 Alkyl, optionally wherein R 2 It is a 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 Alkyl (e.g., oleoyl).

[0064] 1.18 Compound 1 or any one of 1.1-1.7, wherein R 2 It is saturated C(O)-C 7-20 Alkyl, optionally wherein R 2 It is saturated 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 alkyl.

[0065] 1.19 Compound 1 or any one of 1.1-1.18, wherein R 2 The substituents are fatty acyl chains.

[0066] 1.20 Compound 1 or any one of 1.1-1.7, wherein R 2 It is an aryl ester (e.g., C(O)-aryl), such as benzoyl.

[0067] 1.21 Compound 1 or any one of 1.1-1.18, wherein R 2 The substituents also include cationic or anionic groups (e.g., R). 2 It is an alkyl, aryl, alkyl ester or aryl ester, wherein the alkyl or aryl group is substituted with a cationic (e.g., quaternary ammonium) or anionic (e.g., carboxylic acid or sulfonic acid) group.

[0068] 1.22 Compound 1 or any one of 1.1-1.18, wherein R 2 It is a polyether group, for example, where R 2 The substituents include polyethylene glycol chains.

[0069] 1.23 Compound 1 or 1.1 and any of the following, where n is 1.

[0070] 1.24 Compound 1 or 1.1 and any of the following, where n is greater than 1 (e.g., 2-20).

[0071] 1.25 Compound 1 or 1.1 and any of the following, where n is 2.

[0072] 1.26 Compound 1 or 1.1 and any of the following, wherein n is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0073] 1.27 Compound 1 or 1.1 and any of the following, where n is 2 or 3.

[0074] 1.28 Compound 1 or 1.1 and any of the following, wherein R 1 It is CH2CH2CH(CH3)CH2CH2, n is 1-3 (e.g., 1-2), and R 2 It is an optional unsaturated alkyl ester (e.g., C(O)-C). 1-20 Alkyl, or C(O)-C 1-6 alkyl).

[0075] Compound 1.29, 1.28, where R 2 It is C(O)-C 1-6 Alkyl, and the C 1-6 The alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, or n-hexyl.

[0076] Compound 1.30, 1.28, wherein R 2 It is a monounsaturated C(O)-C 7-20 Alkyl, optionally wherein R 2 It is a 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 Alkyl (e.g., oleoyl).

[0077] 1.31 Compound 1 or 1.1 and any of the following, wherein R 2 It refers to the anti-aging component, UV-absorbing component, antioxidant component, hydrophobic (lipophilic) component, or hydrophilic component mentioned in the text.

[0078] 1.32 Compound 1 or 1.1 and any of the following, wherein R 2 Not H, for example R 2 It is an alkyl group (e.g., a lower alkyl group, e.g., C10) 1-6 alkyl) or C 1-12 alkyl), aryl (e.g., phenyl), C 1- C2 alkyl aryl (e.g., benzyl), optionally unsaturated alkyl esters (e.g., C(O)-C) 1-20 Alkyl esters or aryl esters (e.g., C(O)-aryl), and the R mentioned above. 2Other implementation schemes.

[0079] 1.33 Compound 1 or 1.1 and any of the following, wherein the terminal group yes

[0080] 1.34 Compound 1 or 1.1 and any of the following, wherein the terminal group yes

[0081] 1.35 Compound 1 or 1.1 and any of the following, wherein the terminal group yes

[0082] 1.36 Compound 1 or 1.1 and any of the following, wherein the compound of formula I is:

[0083]

[0084] Where n: 0-20 (e.g., 1-3).

[0085] 1.37 Compound 1 or 1.1 and any of the following, wherein the compound of formula I is:

[0086] Where n: 0-20 (e.g., 1-3).

[0087] 1.38 Compound 1 or 1.1 and any of the following, wherein the compound of formula I is:

[0088]

[0089] Where n: 0-20 (e.g., 1-3).

[0090] 1.39 Compound 1 or 1.1 and any of the following, wherein the compound of formula I is

[0091]

[0092] Where n: 0-20 (e.g., 1-3).

[0093] 1.40 Compound 1 or 1.1 and any of the following, wherein the compound of formula I is:

[0094] Where n: 0-20 (e.g., 1-3), and R 2 It is defined in any of the above implementation schemes.

[0095] 1.41 Compound 1 or 1.1 and any of the following, wherein the compound of formula I is:

[0096]

[0097] Where n: 0-20 (e.g., 1-3).

[0098] 1.42 Compound 1 or 1.1 and any of the following, wherein the compound of formula I is:

[0099] Where n: 0-20 (e.g., 1-3), and R 2 It is defined in any of the above implementation schemes.

[0100] 1.43 Compound 1 or 1.1 and any of the following, wherein the compound of formula I is:

[0101]

[0102] Where n: 0-20 (e.g., 1-3).

[0103] As described in the preceding paragraphs, the terminal groups of compounds Y and I are optionally unsaturated alkyl groups having the following structures: Therefore, the group can be an isobutyl group, a 1-isobutylenyl group, or a 2-isobutylenyl group. In some embodiments, the group is a fully saturated isobutyl group. In these embodiments, the saturation property of the group is particularly advantageous because it provides increased chemical stability, inertness, and biocompatibility, since olefins, especially terminal olefins, are readily oxidized by air and / or bioconjugated.

[0104] In a second aspect, this disclosure provides a composition (composition 1) comprising compound 1 or 1.1 and any of the following, or compound 2 or 2.1 and any of the following, or compound 3 or 3.1 and any of the following, or a salt thereof, or any mixture thereof, in combination with at least one suitable solvent, carrier, or excipient. In other embodiments of the second aspect, this disclosure provides the following compositions:

[0105] 1.1 A fragrance composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0106] 1.2 A perfume composition containing compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0107] 1.3 A soap composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0108] 1.4 An insect repellent composition containing compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof, such as a mosquito repellent composition.

[0109] 1.5 An insecticidal composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0110] 1.6 A detergent composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0111] 1.7 A household cleaning composition containing compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0112] 1.8 An air freshener composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0113] 1.9 An indoor spray composition containing compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0114] 1.10 Incense box composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0115] 1.11 A candle composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0116] 1.12 Composition 1.11, wherein the composition further comprises a paraffin and / or beeswax matrix.

[0117] 1.13 Composition 1.12, wherein the composition comprises compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof, dispersed in a paraffin and / or beeswax matrix having a suitable candle wick embedded therein.

[0118] 1.14 A cosmetic composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0119] 1.15 A floral water composition containing compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0120] 1.16 A pre- and post-shaving wash composition containing compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0121] 1.17 A talc composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0122] 1.18 A hair care product composition containing compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0123] 1.19 A body deodorant composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0124] 1.20 An antiperspirant composition containing compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0125] 1.21 A shampoo composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0126] 1.22 A pet litter composition containing compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0127] 1.23 A topical skin care composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, 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 smoothers; skin healing agents; ultraviolet absorbers or scattering agents; chelating agents; anti-acne agents; anti-androgen agents; depilatory agents; keratolytic agents / peeling agents / exfoliants, 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.

[0128] 1.24 Composition 1.23, wherein the skin care application is a skin protectant.

[0129] 1.25 Composition 1.23, wherein the skin care application is a skin smoothing agent.

[0130] 1.26 Composition 1.23, wherein the skin care application is a sunscreen.

[0131] 1.27 A paint or coating composition containing compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0132] 1.28 A lubricant composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0133] 1.29 A plastic composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0134] 1.30 An antifoaming composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0135] 1.31 A hydraulic fluid composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0136] 1.32 An antimicrobial composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0137] 1.33 A crop care formulation containing compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, for example, said compound being an adjuvant in the crop care formulation.

[0138] 1.34 Formulations for enhanced oil recovery, fracturing and / or other oilfield applications, comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, wherein said compound is a lubricant or solvent in the formulation.

[0139] 1.35 Products comprising any of the foregoing compositions, wherein the composition is stored or contained in a container comprising an electrically heating element, wherein the actuation of the heating element results in heating of the composition, thermal decomposition of the compound, and release of volatile substances.

[0140] 1.36 A fragrance agent in a perfume composition, comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof, wherein said compound is used as a fragrance retainer, fragrance fixative, or fragrance carrier.

[0141] 1.37 A cosmetic composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof, wherein said compound is used as a substitute for silicone and / or a substitute for white oil.

[0142] 1.38 Nail polish composition containing compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0143] 1.39 A writing or printing ink composition containing compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof.

[0144] 1.40 An adhesive composition comprising compound 1 or any one of 1.1 and below, or compound 2 or any one of 2.1 and below, or compound 3 or any one of 3.1 and below, or a salt thereof, or any mixture thereof, mixed with one or more natural or synthetic resins.

[0145] In another embodiment, this disclosure provides compound 1 or any one of 1.1-1.43, or compound 2 or any one of 2.1-2.27, or compound 3 or any one of 3.1-3.15, for use in composition 1 or any one of 1.1-1.40.

[0146] Thirdly, this disclosure provides methods for preparing compound 1 or 1.1 and any of the following or salts thereof (wherein R...). 2 The preparation method of (method 1) of H) wherein the method comprises the following steps: (1) introducing compound A into a reactor:

[0147]

[0148] Among them, R 1 It is an optional substitution of C1–C 12 Alkyl groups (e.g., optionally C1–C) 12 alkyl or aryl substituted C 1- C 12 alkyl);

[0149] (2) The compound is exposed to a solid ion exchange resin, thereby polymerizing compound A to obtain compound 1 according to formula I:

[0150]

[0151] Among them, R 1 It is an optional substitution of C1–C 12 Alkyl groups (e.g., optionally further C1–C) 12 alkyl or aryl substituted C 1- C 12 Alkyl); and R therein 2It is H, and n is an integer between 0 and 20;

[0152] (3) Separate and / or purify (e.g., by distillation) compound 1, such as a group of related compounds 1, where n varies in a range, for example where n is 0-5 or 5-10 or 10-15 or 15-20, or where n has any specific value in the integer range of 0-20.

[0153] In other embodiments of the third aspect, this disclosure provides the following:

[0154] 1.1 Method 1, wherein polymerization is carried out on an ion exchange resin at elevated temperatures (e.g., 30 to 120°C).

[0155] 1.2 Method 1.1, wherein polymerization is carried out at 40-90°C on an ion exchange resin.

[0156] 1.3 Method 1.2, wherein polymerization is carried out at about 50°C on an ion exchange resin.

[0157] 1.4 Method 1 or any of 1.1-1.4, wherein the solid exchange resin is an acid catalyst bonded to the resin, such as a resin functionalized with carboxylic acid or sulfonic acid groups.

[0158] 1.5 The method of any of the foregoing methods, wherein polymerization is carried out in a batch reactor.

[0159] 1.6 The method of any of the foregoing methods, wherein polymerization is carried out in a continuous packed bed reactor.

[0160] 1.7 The method of any of the foregoing methods, wherein the monomer of formula A is polymerized by acid catalysis, followed by distillation and recycling of any unpolymerized monomer.

[0161] 1.8 The method of any of the foregoing methods, wherein the resin-bonded acid catalyst is selected from Silicycle propane sulfonic acid, montmorillonite, or... (For example, macroporous or cellular resins or silica covalently bonded to sulfonic or carboxylic acid groups).

[0162] The method in 1.9 and 1.7, wherein the catalyst is

[0163] 1.10 The method of any of the foregoing methods, wherein compound 1 is purified by fractional distillation.

[0164] 1.11 The method of any of the foregoing methods, wherein compound 1 is compound 1.8 or any embodiment thereof.

[0165] 1.12 The method of any one of the foregoing methods further comprises the following steps: optionally in the absence of a base or catalyst, and optionally under continuous conditions, compound 1 of formula I (wherein R...) 2 It is H) that reacts with a suitable reagent to make R 2 Converted to alkyl ester or aryl ester groups (e.g., to produce compounds 1.13-1.20 or any of the embodiments thereof), such as the R group of said alkyl ester. 2 It is methyl, and the reaction utilizes an enone as a suitable reagent, or the R of said alkyl ester. 2 It is a methyl group, and the reaction utilizes acetic anhydride as a suitable reagent.

[0166] Method 1.13 of 1.12, wherein the esterification reaction is a basic transesterification reaction of functionalized esters.

[0167] 1.14 Method 1 or any one of 1.1-1.11, further comprising compound 1 of formula I (wherein R 2 The step is to react H with a suitable reagent to form compound 2 of formula II.

[0168] Method 1.15 of 1.14, wherein the esterification reaction is a basic transesterification reaction of a functionalized diester.

[0169] 1.16 Method 1 or any one of 1.1-1.11, further comprising compound 1 of formula I (where R 2 It is H) that reacts with a suitable reagent to convert R 2 The step of converting to an alkyl ether or aryl ether group (e.g., to produce compounds 1.9-1.12 or any of the embodiments thereof).

[0170] Method 1.17 of 1.16, wherein etherification is a Williamson-type etherification reaction using a suitable alkyl halide and a base.

[0171] 1.18 Any of the foregoing methods, where R 1 It is an optional substitution of linear C 1- C 12 Alkyl or optionally substituted branched C 1- C 12 alkyl.

[0172] 1.19 Method 1 or any of 1.1-1.17, where R 1 It is an unsubstituted linear C 1- C 12 Alkyl or branched C3-C 12 alkyl.

[0173] 1.20 Method 1 or any of 1.1-1.17, where R 1It is an unsubstituted linear C 1- C 12 alkyl.

[0174] 1.21 Method 1 or any of 1.1-1.17, where R 1 It is an unsubstituted branch C3-C 12 alkyl.

[0175] 1.22 Method 1 or any of 1.1-1.17, where R 1 It is CH2.

[0176] 1.23 Method 1 or any of 1.1-1.17, where R 1 It is an unsubstituted branched or straight-chain C6 alkyl group.

[0177] 1.24 Method 1 or any one of 1.1-1.17, where R 1 It is CH2CH2CH(CH3)CH2CH2.

[0178] 1.25 Method 1 or 1.1 and any of the following, wherein said method also produces compound 3 or 3.1 and any of the following, or a salt thereof.

[0179] 1.26 Method 1 or 1.1 and any of the following, wherein the method further comprises the step of reducing the terminal 1-isobutylyl or 2-isobutylyl group of the compound of formula I to form a compound of formula I containing a terminal isobutylyl group.

[0180] Method 1.27 of 1.26, wherein the reduction comprises hydrogenation on a transition metal catalyst (e.g., platinum, palladium, rhodium, ruthenium, or nickel) at a 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).

[0181] Method 1.28 of 1.27, wherein the reduction comprises an alcohol solvent (e.g., methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, or mixtures thereof).

[0182] In any specific aspect of method 1 or 1.1-1.28, this disclosure also provides, as needed, a method (method 3) for preparing ester compound 1A according to formula I:

[0183]

[0184] Among them, R 1 It is an optional substitution of C1–C 12Alkyl groups (e.g., optionally further C1–C) 12 alkyl or aryl substituted C 1- C 12 Alkyl); and wherein R 2 It is (C=O)C 1-4 Alkyl groups (e.g., methyl groups), and n is an integer from 0 to 20;

[0185] The method includes an alcohol compound 1 of formula I (wherein R) 2 (is H) and R in it 2 It is (C=O)C 1-4 The reaction of alkyl anhydrides of the formula R2O(C=O)OR2 with alkyl (e.g., methyl) groups, wherein the reaction is carried out under continuous flow conditions (e.g., in a continuous flow reactor) without a base or catalyst.

[0186] In other embodiments of this aspect of method 3, this disclosure also provides:

[0187] 3.1 Method 3, where R 2 It is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl.

[0188] 3.2 Method 3 or 3.1, where R 2 It is methyl or ethyl, for example, methyl.

[0189] 3.3 Method 3 or any of 3.1-3.2, where n is 0-15, for example n is 0-10 or 1-4 or 3-6 or approximately 2.

[0190] 3.4 Method 3 or any of 3.1-3.3, wherein the reaction temperature is 50℃-200℃, for example 75℃-150℃ or 100℃-120℃.

[0191] 3.5 Method 3 or any of 3.1-3.4, wherein the reaction product from the flow reactor is recycled through the reactor at least once to increase the yield, for example 1-5 times, such as about 5 times.

[0192] In another aspect, compound 1, for example, produced according to method 1 and the following, can be further modified by the following modifications, which have the benefit of more than doubling the molecular weight of the mono- and polyether. In this aspect, the ether produced according to method 1 and the following is treated with a diacid, or even more preferably by a diester transesterification reaction. As shown in Table 1, the ether can be esterified on each side of the diacid to produce extended and modified polymers.

[0193] Therefore, in a fourth aspect, this disclosure provides ethers and polyether diester compounds according to formula II (compound 2) or salts thereof, said compounds being derivatives of the polymer of compound 1:

[0194]

[0195] in,

[0196] R 1 It is an optional substitution of C1–C 12 Alkyl groups (e.g., optionally further C1–C) 12 alkyl or aryl substituted C 1- C 12 alkyl);

[0197] n 1 and n 2 Each is an integer between 0 and 20; and

[0198] X is the formula -C(O)-R 3 -C(O)- diacyl group, wherein R 3 C is an optional substitute 1-22 Alkyl, optionally substituted C 2-22 Alkenyl or optionally substituted aryl. It should be understood that... This indicates an optional double bond (i.e., a single or double bond), and thus a terminal group. It is possible to have any one of the three optional keys shown (i.e., a double key) or none of the optional keys exist (i.e., all are single keys).

[0199] In other embodiments of the fourth aspect, this disclosure provides any of the following:

[0200] 2.1 Compound 2, where R 1 It is an optional substitution of linear C 1- C 12 Alkyl or optionally substituted branched C 1- C 12 alkyl.

[0201] 2.2 Compound 2, where R 1 It is an unsubstituted linear C 1- C 12 Alkyl or branched C3-C 12 alkyl.

[0202] 2.3 Compound 2, where R 1 It is an unsubstituted linear C 1- C 12 alkyl.

[0203] 2.4 Compound 2, where R 1 It is an unsubstituted branch C3-C12 alkyl.

[0204] 2.5 Compound 2, where R 1 It is CH2.

[0205] 2.6 Compound 2, where R 1 It is an unsubstituted branched or straight-chain C6 alkyl group.

[0206] 2.7 Compound 2, where R 1 It is CH2CH2CH(CH3)CH2CH2.

[0207] 2.8 Compound 2 or any one of 2.1-2.7, where R 3 It is unreplaced C 1-22 Alkyl groups, such as straight-chain unsubstituted C4 groups 1-22 Alkyl or branched unsubstituted C 1-22 alkyl.

[0208] 2.9 Compound 2 or any one of 2.1-2.7, where R 3 It is unreplaced C 1-16 Alkyl groups, such as straight-chain unsubstituted C4 groups 1-16 Alkyl or branched unsubstituted C 1-16 alkyl.

[0209] 2.10 Compound 2 or any one of 2.1-2.7, wherein R 3 It is unreplaced C 1-10 Alkyl groups, such as straight-chain unsubstituted C4 groups 1-10 Alkyl or branched unsubstituted C 1-10 alkyl.

[0210] 2.11 Compound 2 or any one of 2.1-2.7, wherein R 3 It is unreplaced C 1-6 Alkyl groups, such as straight-chain unsubstituted C4 groups 1-6 Alkyl or branched unsubstituted C 1-6 alkyl.

[0211] 2.12 Compound 2 or any one of 2.1-2.7, wherein R 3 Selected from methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2- or -CH2CH(CH3)-), and butylene (e.g., -CH2CH2CH2CH2- or -CH2CH(CH3)CH2- or -CH(CH3)CH2CH2-).

[0212] 2.13 Compound 2 or any one of 2.1-2.7, wherein R 3 It is unreplaced C2-22 Alkenyl groups, such as straight-chain unsubstituted C4 groups 2-22 Unsubstituted alkenyl or branched C 2-22 Alkenyl groups, wherein optionally any of the alkenyl groups is monounsaturated.

[0213] 2.14 Compound 2 or any one of 2.1-2.7, where R 3 It is unreplaced C 2-16 Alkenyl groups, such as straight-chain unsubstituted C4 groups 2-16 Unsubstituted alkenyl or branched C 2-16 Alkenyl groups, wherein optionally any of the alkenyl groups is monounsaturated.

[0214] 2.15 Compound 2 or any one of 2.1-2.7, wherein R 3 It is unreplaced C 2-10 Alkenyl groups, such as straight-chain unsubstituted C4 groups 2-10 Unsubstituted alkenyl or branched C 2-10 Alkenyl groups, wherein optionally any of the alkenyl groups is monounsaturated.

[0215] 2.16 Compound 2 or any one of 2.1-2.7, where R 3 It is unreplaced C 2-6 Alkenyl groups, such as straight-chain unsubstituted C4 groups 2-6 Unsubstituted alkenyl or branched C 2-6 Alkenyl groups, wherein optionally any of the alkenyl groups is monounsaturated.

[0216] 2.17 Compound 2 or any one of 2.1-2.7, wherein R 3 Selected from vinylidene (-CH=CH-), propenyne (-CH=CHCH2- or -CH2C(=CH2)-), and butenyl (e.g., -CH=CHCH2CH2- or -CH2CH=CHCH2- or -CH2CH(=CH2)CH2-).

[0217] 2.18 Compound 2 or any one of 2.1-2.7, where R 3 It is an aryl group, such as a substituted or unsubstituted phenyl group.

[0218] 2.19 Compound 2 or 2.1 and any of the following, where n 1 and / or n 2 It is 1.

[0219] 2.20 Compound 2 or 2.1 and any of the following, where n 1 and / or n 2 Greater than 1 (e.g., 2-20).

[0220] 2.21 Compound 2 or 2.1 and any of the following, where n 1 and / or n 2 It is 2.

[0221] 2.22 Compound 2 or 2.1 and any of the following, where n 1 and / or n 2 It is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0222] 2.23 Compound 2 or 2.1 and any of the following, where n 1 and / or n 2 It's either 2 or 3.

[0223] 2.24 Compound 2 or 2.1 and any of the following, where n 1 and n 2 They are the same integer.

[0224] 2.25 Compound 2 or 2.1 and any of the following, wherein the terminal group yes

[0225]

[0226] 2.26 Compound 2 or 2.1 and any of the following, wherein the terminal group yes

[0227]

[0228] 2.27 Compound 2 or 2.1 and any of the following, wherein the terminal group yes

[0229]

[0230] In some embodiments, compound 2 may be described as shown in Table 1.

[0231]

[0232] Table 1. Examples of diesters formed from citronellol and prenol-derived oligomers.

[0233] Fifthly, compounds 1 and 1 produced according to method 1 and the following can form cyclic molecules during their respective polymerization reactions, wherein the formed cyclic molecules may possess useful chelating, smoothing, and softening properties. In some embodiments, the compounds can be separated by distillation or used directly. Examples of the molecules are shown in Table 2 below.

[0234] Table 2

[0235]

[0236] Therefore, in a fifth aspect, this disclosure provides a cyclic compound (compound 3) according to formula III or a salt thereof:

[0237]

[0238] in,

[0239] R 1 It is an optional substitution of C1–C 12 Alkyl groups (e.g., optionally further C1–C) 12 alkyl or aryl substituted C 1- C 12 Alkyl); and

[0240] n is an integer between 0 and 20.

[0241] In other embodiments of the fifth aspect, the present invention provides any one of the following:

[0242] 3.1 Compound 3, where R 1 It is an optional substitution of linear C 1- C 12 Alkyl or optionally substituted branched C 1- C 12 alkyl.

[0243] 3.2 Compound 3, where R 1 It is an unsubstituted linear C 1- C 12 Alkyl or branched C3-C 12 alkyl.

[0244] 3.3 Compound 3, where R 1 It is an unsubstituted linear C 1- C 12 alkyl.

[0245] 3.4 Compound 3, where R 1 It is an unsubstituted branch C3-C 12 alkyl.

[0246] 3.5 Compound 3, where R 1 It is CH2.

[0247] 3.6 Compound 3, where R 1 It is an unsubstituted branched or straight-chain C6 alkyl group.

[0248] 3.7 Compound 3, where R 1 It is CH2CH2CH(CH3)CH2CH2.

[0249] 3.8 Compound 3 or 3.1 and any of the following, where n is 0-10.

[0250] 3.9 Compound 3 or 3.1 and any of the following, where n is 0-5.

[0251] 3.10 Compound 3 or 3.1 and any of the following, where n is 0.

[0252] 3.11 Compound 3 or 3.1 and any of the following, where n is 1.

[0253] 3.12 Compound 3 or 3.1 and any of the following, where n is 2.

[0254] 3.13 Compound 3 or 3.1 and any of the following, wherein n is 0, 1, 2, 3 or 4.

[0255] 3.14 Compound 3 or 3.1 and any of the following, where n is 0, 1, 2 or 3.

[0256] 3.15 Compound 3 or 3.1 and any of the following, wherein n is 0, 1 or 2.

[0257] In some embodiments, the UV-absorbing portion 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, p-aminobenzoic acid, benzoic acid, 3,3-diphenylcyanoacrylate, diethylaminohydroxybenzoylbenzoate, and methoxycinnamic acid.

[0258] In some implementations, the anti-aging and / or antioxidant components include, but are not limited to, hyaluronic acid, ascorbic acid, azelaic acid, carnosine, glycolic acid, nicotinic acid, phenolic acid, phenolic ethers, benzophenone, sulfites, sulfonates, sulfonates, and phosphates.

[0259] In some embodiments, the hydrophobic portion includes acetates, propionates, straight-chain or branched fatty acids, straight-chain or branched alkyl chains, organosilicones, fluoroalkanes, and graphene derivatives. The hydrophilic portion includes sulfonates, ethoxylates, polyglycerols, polypropylene glycols, carbohydrates, and carboxylic acids, as well as other polyols.

[0260] For example, compounds 1 and any of the following produced according to method 1, such as citronellol and Prenol polyether, may also be linked (e.g., esterified or etherified) to other bioactive molecules such as antimicrobial compounds, pharmaceutical compounds, skin repair compounds, and sensient molecules such as coolants, anti-inflammatory agents, and / or warming agents.

[0261] Compounds 1 and 2, 3 and 4, produced according to method 1 and any of the following methods, can be used in a variety of applications. They can be used in cosmetic formulations, paints or coatings, personal care products, household products such as cleaning products, electronics, lubricants, plastics, defoamers, improved oil and gas recovery (including fracturing and other oilfield applications), pharmaceutical applications, crop care formulations, and hydraulic fluids. The compounds disclosed herein are suitable as substitutes or alternatives to surfactants, polymers, silicones, and solvents in the various applications described herein. These materials, particularly those with lower molecular weights, can also be advantageously used as insect repellents. Compounds 1 and 2, 3 and 4, produced according to method 1 and any of the following methods, can be used, for example, with or blended with insecticides, repellents, and bioactive ingredients. In some embodiments, compounds 1 and 2, 3 and 4 produced according to method 1 and any of the following methods may be used specifically for retaining fragrance, fixing fragrance, or as a fragrance carrier; as an odor counteractor; in paints and coatings; as an adjuvant for crop control; as a cosmetic ingredient (e.g., as a substitute for silicone or white oil); in nail polish; in writing or printing inks; as a resin or resin substitute; as an insect repellent (e.g., a mosquito repellent); and in sunscreen formulations.

[0262] Sixthly, this disclosure provides a method for using compounds 1 and any of the following produced by method 1, compounds 2 and any of the following and compounds 3, such as compounds of formula I, in a composition (e.g., composition 1 and any of the following, such as fragrance compositions, perfumes, soaps, insect repellents and pesticides, detergents, household cleaners, air fresheners, room sprays, incense boxes, candles, cosmetics, colognes, pre- and post-shave shampoos, talcum powder, hair care products, body deodorants, antiperspirants, shampoos, skin care applications, pharmaceuticals, antimicrobial agents, pet bedding, crop care preparations, or oilfield, fracturing, or enhanced oil recovery preparations).

[0263] Therefore, this disclosure provides a method (method 2) for producing composition 1 or any of compositions 1.1-1.40 by using compound 1 or any of compounds 1.1-1.43, or compound 2 or any of compounds 2.1-2.27, or compound 3 or any of compounds 3.1-3.15, or any combination thereof.

[0264] In other embodiments of the sixth aspect, method 2 may provide any of the following:

[0265] 2.1 The method of method 2, wherein any one of compounds 1-1.43 (e.g., citronellol and / or Prenol polymer of formula I) or compounds 2-2.27 or compounds 3-3.15 is used in the fragrance composition.

[0266] 2.2 The method of method 2, wherein any one 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 the perfume.

[0267] 2.3 The method of method 2, wherein any one 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 soap.

[0268] 2.4 The method of method 2, wherein any one 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 the insect repellent.

[0269] 2.5 The method of method 2, wherein any one 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 the insecticide.

[0270] 2.6 The method of method 2, wherein any one 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 the detergent.

[0271] 2.7 The method of method 2, wherein any one 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 household cleaner.

[0272] 2.8 The method of method 2, wherein any one 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 the air freshener.

[0273] 2.9 The method of method 2, wherein any one 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 indoor spray.

[0274] 2.10 The method of method 2, wherein any one 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 the incense box.

[0275] 2.11 The method of method 2, wherein any one 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 the candle.

[0276] 2.12 The method of method 2, wherein any one 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 cosmetic product.

[0277] 2.13 The method of method 2, wherein any one 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 the toilet water.

[0278] 2.14 The method of method 2, wherein any one 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 pre- and post-shaving shampoos.

[0279] 2.15 The method of method 2, wherein any one of compounds 1-1.43 (e.g., citronellol and / or Prenol polymer of formula I) or compounds 2-2.27 or compounds 3-3.15 is used in talc.

[0280] 2.16 The method of method 2, wherein any one 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 hair care product.

[0281] 2.17 The method of method 2, wherein any one 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 body deodorant.

[0282] 2.18 The method of method 2, wherein any one 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 the antiperspirant.

[0283] 2.19 The method of method 2, wherein any one 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 the shampoo.

[0284] 2.20 Method 2, wherein any one 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 pet bedding.

[0285] 2.21 The method of Method 2, wherein compounds 1-1.43 (e.g., citronellol and / or prenol polymers of Formula I produced by Method 1 and any of the following) or compounds 2-2.27 or compounds 3-3.15 are applied topically to a skin care application, wherein the skin care application may be selected from skin conditioning agents; skin penetration enhancers; skin protectants; skin smoothers; skin healing agents; ultraviolet absorbers or scatterers; chelating agents; anti-acne agents; anti-androgen agents; depilatory agents; keratolytic agents / peeling agents / exfoliants, 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.

[0286] Method 2.22 is the same as method 2.21, in which the skin care application is a skin protectant.

[0287] Method 2.23 is the same as method 2.21, in which the skin care application is a skin smoothing agent.

[0288] Method 2.24 is the same as method 2.21, in which the skin care application is sunscreen.

[0289] 2.25 The method of method 2, wherein any one 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 paints or coatings.

[0290] 2.26 The method of method 2, wherein any one 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 the lubricant.

[0291] 2.27 The method of method 2, wherein any one 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 the plastic.

[0292] 2.28 The method of method 2, wherein any one 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 the medicament.

[0293] 2.29 The method of method 2, wherein any one of compounds 1-1.43 (e.g., citronellol and / or Prenol polymer of formula I) or compounds 2-2.27 or compounds 3-3.15 is used in a crop care formulation, for example, wherein the compounds are adjuvants to the crop care formulation.

[0294] 2.30 Method 2, wherein any one of compounds 1-1.43 (e.g., citronellol and / or Prenol polymer of formula I) or compounds 2-2.27 or compounds 3-3.15 is used in a formulation for enhanced oil recovery, fracturing and / or other oilfield applications, for example, wherein said compounds are lubricants or solvents of said formulations.

[0295] 2.31 The method of method 2, wherein any one 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 fragrance retainer, fragrance fixative or as a fragrance carrier (e.g. in a fragrance composition or perfume composition).

[0296] 2.32 The method of method 2, wherein any one of compounds 1-1.43 (e.g., citronellol and / or Prenol polymer of formula I) or compounds 2-2.27 or compounds 3-3.15 is used as a silicone substitute and / or white oil substitute (e.g. in cosmetic compositions).

[0297] 2.33 Method 2, wherein any one 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 the nail polish composition.

[0298] 2.34 The method of method 2, wherein any one 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 writing ink or printing ink composition.

[0299] 2.35 The method of method 2, wherein any one 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 the adhesive composition (e.g., mixed with one or more natural or synthetic resins).

[0300] 2.36 The method of method 2, wherein any one 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 an odor counteractor (e.g., in fragrances, perfumes, antiperspirants, deodorants or other personal care compositions).

[0301] On the other hand, any of compounds 1–1.43 (e.g., citronellol and / or Prenol polymers of formula I) can be used in methods to enhance oil and gas recovery.

[0302] Another advantage of the materials described in this article is that they are expected to be fully biodegradable and biocompatible.

[0303] During the evaluation of the polyethers, it was surprisingly observed that for citronellol-type polymers, depolymerization into monomers spontaneously occurred at -180°C. This thermal depolymerization property, or similar enzymatic and / or acid-catalyzed depolymerization property, could be advantageously used for the controlled delivery of citronellol monomers over time.

[0304] On the one hand, thermal depolymerization can be used to deliver monomers in a controlled release into the air. On the other hand, the present invention contemplates the use of compounds such as Compound 1 and any of the following and / or Compound 2 and any of the following, produced according to method 1 and any of the following, for example in candles or heat dispensers (for odor control and / or insect control), in low-pH industrial cleaners (where the depolymerized monomer components are released over time to promote a beneficial odor), and in laundry detergents (which utilize enzymes to digest polymers over time to produce a fresh odor over a longer period).

[0305] On the other hand, the fragrance composition of this application comprises, for example, compounds 1 and 2 produced according to method 1 and any of the following and / or compounds 2 or 3 and any of the following, and the fragrance composition is selected from perfumes, soaps, insect repellents and pesticides, detergents, household cleaners, air fresheners, room sprays, fragrance boxes, candles, cosmetics, colognes, pre- and post-shave lotions, talcum powder, hair care products, body deodorants, antiperspirants, shampoos, colognes, shower gels, hair gels, and pet bedding.

[0306] On the other hand, compounds such as compound 1 and any of the following and / or compound 2 or 3, produced according to method 1 or any of the following, can be used in the antifungal composition. In this respect, the antifungal composition comprises, for example, a polyether of compound 1 and any of the following and / or compound 2 or 3, produced according to method 1 or any of the following, and at least one type of compound selected from aliphatic or aromatic aldehydes, aliphatic or aromatic alcohols, acetals, and esters that exhibit synergistic effects in the presence of the aforementioned fragrance component, thereby potentially reducing the content of the active ingredient to a lower level than when each is used alone.

[0307] On the other hand, compounds such as compound 1 and any of the following, produced according to method 1 and / or compound 2 or 3 and any of the following, can be applied topically to skin care applications. For example, skin care applications may be selected from skin conditioning agents; skin penetration enhancers; skin protectants; skin smoothers; skin healing agents; UV absorbers or scatterers; chelating agents; anti-acne agents; anti-androgen agents; depilatory agents; keratolytic agents / peeling agents / exfoliants, 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.

[0308] On the other hand, mono- and / or polyethers of compound 1 and any of the following and / or compound 2 or 3, produced according to method 1 or any of the following, can be used in delivery systems, such as any fragrance delivery system that requires a prolonged, defined release of the aforementioned fragrance compounds. For example, the fragrance delivery system described herein can be used, for example, in functional perfumes, in articles exposed to sunlight during use, or in articles applied to other articles subsequently exposed to sunlight.

[0309] In another embodiment, this disclosure provides a delivery system 4.0, which includes, for example, air fresheners in liquid and solid forms, as well as the delivery system of the present invention. Further examples include delivery systems that deliver window and household cleaners, cleaners for all purposes, and furniture polishes. The surfaces have been cleaned with the cleaners. In another example, the delivery system includes detergents and fabric softeners, and may also include the delivery system of the present invention, as well as clothing washed or treated with the detergents or softeners.

[0310] On the other hand, mono- and / or polyethers of, for example, compounds 1 and any of the following and / or compounds 2 or 3 produced according to method 1 can be used in the drug delivery system. In some embodiments, delivery system 4.0 may comprise any of the following delivery systems:

[0311] 4.1 A drug delivery system comprising any one of compounds 1-36 of formula I (e.g., citronellol and / or Prenol polymers of formula I), compounds 2-2.27 or compounds 3-3.15, or any salt thereof or mixture thereof.

[0312] 4.2 A fragrance delivery system comprising any one of compounds 1-36 of formula I (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.

[0313] 4.3 A detergent delivery system comprising any one of compounds 1-36 of formula I (e.g., citronellol and / or Prenol polymers of formula I), compounds 2-2.27 or compounds 3-3.15 or any salt thereof or mixture thereof.

[0314] 4.4 A household cleaning agent delivery system comprising any one of the compounds of formula I (e.g., citronellol and / or Prenol polymers of formula I), compounds 2-2.27 or compounds 3-3.15, or any salt thereof or mixture thereof.

[0315] On the other hand, the present invention also provides a method for oxidizing the double bonds of any compound according to formula Y, such as compounds 1–1.43 (e.g., polymers of formula I citronellol and / or prenol) or any of compounds 2–2.27, to form an epoxide. The epoxide derivative can be used for any use disclosed herein with respect to compounds 1 or 1.1–1.43 or compounds 2 or 2.1–2.27, and can be used in any method described in method 2 or any of 2.1–2.36. The epoxide derivative can also be used as an intermediate to produce other compounds, which themselves can be used for any use disclosed herein with respect to compounds 1 or 1.1–1.43 or compounds 2 or 2.1–2.27, and can be used in any method described in method 2 or any of 2.1–2.36.

[0316] For example, in one embodiment of this aspect, the present invention provides a method for epoxidizing compound 1, as described above, to produce epoxide compound 1E:

[0317]

[0318] The epoxide can be used as an intermediate, for example, in an epoxide ring-opening reaction to produce polymer derivatives such as ethers, amines, and esters, which can be used for any of the uses disclosed herein with respect to compound 1 or 1.1-1.43 or compound 2 or 2.1-2.27, and can be used in any of the methods described in method 2 or 2.1-2.36. The ring-opening reaction includes, but is not limited to, hydrolysis, alcoholysis, ammonolysis, and carboxylate ring-opening. Thus, for example, the ring-opening reaction can produce the following products (or any regioisomers of which double bond addition):

[0319]

[0320] Where R 1 and R 2 As defined in compound 1, where X is O, NH or NR. 3 And R 3 It is an optional substitution of C1–C 12 alkyl.

[0321] Details of one or more embodiments of the invention are set forth in the description which follows. Unless otherwise defined, 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 pertains. In case of conflict, this specification shall prevail.

[0322] Unless otherwise stated, it should be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be restrictive. Many terms will be used in this specification and the following claims, and these terms should be defined as having the definitions set forth below.

[0323] As used in this text, the singular forms “a / an” and “the” include plural indicators unless the context clearly indicates otherwise. Thus, for example, reference to “a (a) reactant” includes not only a single reactant but also a composition or mixture of two or more different reactants; reference to “a (a) substituent” includes a single substituent as well as two or more substituents, etc.

[0324] As used herein, the phrases “for example,” “such as,” or “including” are intended to introduce examples that further clarify more general topics. These examples are provided only to aid understanding of this disclosure and are not intended to be limiting in any way. Furthermore, as used herein, the terms “may,” “optional,” “optionally,” or “maybe” mean that the situation subsequently described may or may not occur, thus the description includes both the case where the event occurs and the case where the event does not occur. For example, the phrase “optionally exist” means that an object may or may not exist; therefore, the description includes both the case where said object exists and the case where said object does not exist.

[0325] As used in the text, the phrase “having a form” or “having a structure” is not intended to be restrictive and is used in the same way as the commonly used term “containing”.

[0326] 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, the chiral center is not identified, but these formulas still include chiral isomers.

[0327] Some of the compounds of this invention may exist in tautomeric form, which are also intended to be included within the scope of this invention.

[0328] "Tautomer" refers to a compound whose structure differs significantly in atomic arrangement but exists in an easy and rapid equilibrium. It should be understood that the compounds of this invention can be described as different tautomers. It should also be understood that when a compound has tautomer forms, all tautomer forms are contemplated within the scope of this invention, and the naming of the compound does not exclude any tautomer form. Furthermore, even if a tautomer may be described, this invention includes all tautomers of that compound.

[0329] As used herein, the term "salt" may include acid addition salts, including hydrochlorides, hydrobromates, phosphates, sulfates, hydrogen sulfates, alkyl sulfonates, aryl sulfonates, acetates, benzoates, citrates, maleates, fumarates, succinates, lactates, and tartrates; alkali metal cations such as Na + K + Li + Alkaline earth metal salts such as Mg 2+ or Ca 2+ Or organic amine salts, or organic phosphonium salts.

[0330] As used herein, the term "alkyl" refers to a monovalent or divalent, branched or straight-chain saturated hydrocarbon group having 1 to 22 carbon atoms, typically (but not necessarily) containing 1 to about 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, octyl, etc.

[0331] As used in this article, the term "alkenyl" refers to a monovalent or divalent, branched or straight-chain unsaturated hydrocarbon group that typically (but not necessarily) contains 2 to about 12 carbon atoms and 1-10 carbon-carbon double bonds, such as ethylene, n-propylene, isopropylene, n-butene, isobutene, tert-butene, octene, etc.

[0332] As used in this article, the term "alkynyl" refers to a monovalent or divalent, branched or straight-chain unsaturated hydrocarbon group that typically (but not necessarily) contains 2 to about 12 carbon atoms and 1-8 carbon-carbon triple bonds, such as acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne, etc.

[0333] As used herein, the term "aryl" refers to an aromatic hydrocarbon group comprising at least one aromatic ring with 5-6 carbon atoms, including, for example, aromatic hydrocarbons having two fused rings and 10 carbon atoms (i.e., naphthalene).

[0334] The word "substituted" in "substituted alkyl", "substituted alkenyl", "substituted alkynyl", etc., means that in an alkyl, alkenyl, alkynyl or other group, at least one hydrogen atom bonded to a carbon atom is substituted by one or more non-hydrogen substituents, such as by a functional group.

[0335] When used to refer to, for example, C a -C b When referring to an alkyl group with one carbon atom, the terms "branched" and "straight-chain" (or "unbranched") apply to those carbon atoms that define the alkyl group. For example, for a C4 alkyl moiety, its branched embodiment should include isobutyl, while its unbranched embodiment should be n-butyl. However, isobutyl can also be considered a straight-chain C3 alkyl group (propyl) substituted with a C1 alkyl (methyl).

[0336] Examples of functional groups include, but are not limited to, halogenated, hydroxyl, thiol, and C. 1- C 24 Alkoxy, C2-C 24 alkenyloxy group, C2-C 24 Acryloxy group, C5-C 20 aryloxy groups, acyl groups (including C2-C) 24 Alkyl carbonyl (-CO-alkyl) and C6-C 20 aryl carbonyl (-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 halogenated), C2-C 24 Alkyl carbonates (-O-(CO)-O-alkyl), C6-C 20 Aryl carbonates (-O-(CO)-O-aryl), carboxyl groups (-COOH), and carboxylate groups (-COO)- ), carbamoyl (-(CO)-NH2), monosubstituted C 1- C 24 Alkyl carbamoyl (-(CO)-NH(C) 1- C 24 Alkyl), disubstituted alkylcarbamoyl (-(CO)-N(C) 1- C 24 Alkyl)2), monosubstituted aryl carbamoyl (-(CO)-NH-aryl), thiocarbamoyl (-(CS)-NH2), carbamoylamino (-NH-(CO)-NH2), cyano (-C≡N), isocyano (-N) + ≡C - ), cyanate group (-OC≡N), isocyanate group (-ON) + ≡C - ), isothiocyanate group (-SC≡N), azide group (-N=N) + =N - ), formyl (-(CO)-H), thioformyl (-(CS)-H), amino (-NH2), mono- and di-(C 1- C 24 Alkyl)-substituted amino, mono- and di-(C5-C) 20 aryl)-substituted amino groups, C2-C 24 Alkyl amide (-NH-(CO)-alkyl), C 5- C 20 Aryl amide (-NH-(CO)-aryl), imino (-CR=NH, where R=hydrogen, C=NH) 1- C 24 Alkyl, C5-C 20 Aryl, C6-C 20 Alkyl, C6-C 20 Aryl alkyl, etc.), alkylimino (-CR=N(alkyl), where R=hydrogen, alkyl, aryl, alkylaryl, etc.), arylimino (-CR=N(aryl), where R=hydrogen, alkyl, aryl, alkylaryl, etc.), nitro (-NO2), nitroso (-NO), sulfonyl (-SO2-OH), sulfonate (-SO2-O) - C 1- C 24 Alkylthioalkyl (-S-alkyl; also known as "alkylthio"), arylthioalkyl (-S-aryl; also known as "arylthio"), C 1- C 24 alkylsulfinyl (-(SO)-alkyl), C5-C 20 arylsulfinyl (-(SO)-aryl), C 1- C 24 alkylsulfonyl (-SO2-alkyl), C5-C20 arylsulfonyl (-SO2-aryl), phosphonate (-P(O)(OH)2), phosphonate radical (-P(O)(O)2) - )2) Phosphite group (-P(O)(O) - ), dioxinyl (-PO2), phosphinyl (-PH2), mono- and di-(C 1- C 24 Alkyl-substituted phosphinyl, mono- and di-(C5-C) 20 Aryl-substituted phosphine groups; and hydrocarbon groups such as C 1- C 24 Alkyl (including C) 1- C 18 Alkyl groups, further including C 1- C 12 alkyl groups, and further including C 1- C6 alkyl), C2-C 24 Alkenyl (including C2-C) 18 Alkenyl groups, further including C2-C 12 Alkenyl groups, and further including C2-C6 alkenyl groups), C2-C 24 Alkyne groups (including C2-C) 18 Alkyne groups, further including C2-C 12 Alkynyl groups, and further including C2-C6 alkynyl groups, C5-C 30 Aryl (including C5-C) 20 Aryl, and further including C5-C 12 aryl) and C6-C 30 Araneyl groups (including C6-C) 20 Aryl alkyl groups, and further including C6-C 12 (Aryl groups). Furthermore, if permitted by specific groups, the aforementioned functional groups may be further substituted by one or more other functional groups or by one or more hydrocarbon groups, such as those specifically listed above. For example, alkyl or alkenyl groups may be branched. For example, a "substituent" is an alkyl group such as a methyl group.

[0337] As used herein, the term "fragrance composition" refers to a mixture of fragrance components, such as polyether compounds comprising any of Method 1 and below and Method 2 and below, and, if desired, auxiliary substances dissolved in a suitable solvent or mixed with a powdered substrate, for providing the desired odor to the product.

[0338] The polyether compounds of Compound 1 and any of the following, Method 1 and any of the following, and Method 2 and any of the following can be used with, for example, perfumes, soaps, insect repellents and pesticides, detergents, household cleaners, air fresheners, room sprays, incense boxes, candles, cosmetics, toilet water, pre- and post-shave lotions, talcum powder, hair care products, body deodorants, antiperspirants, shampoos, colognes, shower gels, hair sprays, and pet bedding.

[0339] Mixtures of fragrances, ingredients, and flavor components that can be used in combination with disclosed compounds to produce fragrance compositions include, but are not limited to, natural products (including extracts, animal products, and essential oils, anhydrous, resinoids, resins, and gels) and synthetic fragrance materials and animal products. The synthetic fragrance materials include, but are not limited to, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, phenols, ethers, lactones, furansketals, nitriles, acids, and hydrocarbons, including saturated and unsaturated compounds, as well as aliphatic carbocyclic and heterocyclic compounds.

[0340] As used herein, “citronellol polymer” and “Prenol polymer” refer to all derivatives and cyclic forms of citronellol and Prenol polymers.

[0341] In this specification, for convenience, the structural formula of a compound may represent a certain isomer in some cases; however, this invention includes all isomers, such as geometric isomers, optical isomers based on asymmetric carbon, stereoisomers, tautomers, etc. Furthermore, compounds represented by the formulas may exist in polymorphs; it should be noted that any crystal form, mixture of crystal forms, or its anhydrides or hydrates are included within the scope of this invention.

[0342] Unless otherwise stated, all percentages used in this document are by volume.

[0343] Unless otherwise stated, all ratios used in this document are in moles. Detailed Implementation

[0344] Example

[0345] Example 1: Synthesis of Citronellol Polymer

[0346] Citronellol (250 g) was mixed with 5 g of Amberlyst cationic resin in a solvent-free environment and stirred at room temperature for 5 days. (The process was repeated in the original text.) 1¹H NMR revealed that >80% polymerization had occurred. (Note: The reaction time can be significantly shortened by increasing the catalyst concentration and temperature). The reaction mixture was then diluted with hexane and filtered to remove the catalyst. The organic phase was then washed with an aqueous sodium bicarbonate solution to remove any residual acid, followed by a single wash with DI water. Hexane was then removed under reduced pressure using a rotary evaporator. 269 g of the substance was obtained and further distilled.

[0347] Distillation at 0.5–1.5 mbar and a head temperature of 60–65 °C yielded a fraction containing fairly clean citronellol (37.5 g). Distillation at 0.2–0.45 mbar and a head temperature of 115–132 °C yielded a second fraction containing >95% pure citronellol dimer (46.9 g). The remainder was retained in the distillation vessel and appeared to be a higher MW polyether.

[0348] Example 2: Continuous citronellol polymerization on cation exchange resin

[0349] A 6-foot-long, 0.01-inch-wall-thick, 0.25-inch smooth-bore stainless steel tube was filled with Amberlyst resin and coiled, with PTFE tubing attached to one end for continuous flow. The coil was heated to 50°C in an oil bath, and 300g of citronellol was pumped into the filled coil at a rate of 2ml / min. The material exiting the coil had reached a high degree of polymerization, such as... 1 The results of H-NMR analysis show that the number of protons associated with methylene groups adjacent to ether oxygen atoms (-3.3 ppm) is significantly increased compared to the number of protons associated with methylene groups adjacent to alcohol oxygen atoms (-3.6 ppm). The integral ratio for these two different groups of protons was found to be approximately 1:1.

[0350] The tube was then rinsed with a minimal amount of hexane, and the separated material was washed with a 10% sodium carbonate aqueous solution. Hexane was then removed by vacuum distillation, yielding a residue weighing 315 g. This material was further distilled under vacuum (0.7 mbar) and elevated temperatures (up to 160 °C) to remove monomers and dimers, yielding a clear, odorless liquid as identified below, where n averages 1-4:

[0351]

[0352] The compound of Example 2 was 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.

[0353] In addition, other distillation fractions produce other citronellol oligomers, including citronellol dimers, and citronellol polymers in which n averages 3-6.

[0354] Example 3: Citronellol Polymer Acetate

[0355] To 702 g of the compound from Example 2 (citronellol polymer, n = 1-4), 1.0 L of tetrahydrofuran (THF) and 18.33 g of N,N-dimethylaminopyridine (DMAP) were added. The solution was stirred and cooled in an ice bath. Acetic anhydride (229 g) was added dropwise, and the solution was then warmed to room temperature and stirred overnight. The reaction was confirmed to be complete by thin-layer chromatography (TLC), and the reaction was quenched by the slow addition of 100 mL of water. After stirring for three hours, THF was removed under reduced pressure on a rotary evaporator, and the organic phase was diluted with MTBE and washed with 10% sodium carbonate until the pH was 8. Phase separation was performed, the organic phase was dried with sodium sulfate, and filtered. The substance was decolorized with activated carbon and then further distilled under reduced pressure to remove trace amounts of solvent to give 676 g of a clear, odorless liquid, wherein the average n is 1-4:

[0356]

[0357] The compound of Example 3 was 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.

[0358] Following a similar method, the compound of Example 2 (citronellol polymer, n = 3-6) was reacted with acetic anhydride and DMAP in a THF solvent and purified to obtain citronellol polymer acetate, wherein n averaged 3-6.

[0359] Example 4: Citronellol Polybutyrate

[0360] The corresponding butyrate ester was prepared by replacing acetic anhydride with butyric anhydride, as described in Example 3. A clear, odorless liquid was determined as follows, where n averaged 1-4:

[0361]

[0362] The compound of Example 4 was 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.

[0363] Example 5: Citronellol Dimer Oleate

[0364]

[0365] 10 g of citronellol dimer (prepared according to Example 1) and 9 g of methyl oleate were thoroughly mixed in a 250 mL flask with stirring. 0.1 g of sodium methoxide was slowly added to the reaction mixture. The reaction mixture was stirred at 80 °C for 5 hours, during which methanol was continuously distilled off the reaction mixture. The completion of the reaction was monitored by TLC, GC, and NMR. The reaction was quenched using a 50% acetic acid solution in dH₂O. The reaction mixture was extracted with hexane and concentrated under reduced pressure. 16 g of crude product was obtained and further purified by column chromatography. 3 g of the pure product was separated by chromatography and identified by NMR as the oleate ester of citronellol dimer.

[0366] Example 6: Adipate of citronellol dimer

[0367]

[0368] 10 g of citronellol dimer and 3 g of dimethyl adipate were thoroughly mixed in a 250 mL flask with stirring. 0.1 g of sodium methoxide was slowly added to the reaction mixture. The reaction was carried out at 80 °C for 4 hours. During the reaction, methanol was distilled off the reaction mixture. TLC, GC, and NMR were used to monitor the reaction. The reaction was quenched with a 50% acetic acid solution in dH₂O. The reaction mixture was extracted with hexane and concentrated.

[0369] Example 7: Cyclic Citronellol Dimer

[0370] The crude fraction of 8 g of citronellol polymer from Example 2 was used to purify the cyclic citronellol dimer by column chromatography. 0.2 g of pure solid cyclic dimer was isolated, and its structure was confirmed by NMR.

[0371] Example 8: Evaluation of insecticidal efficacy

[0372] Citronellol dimer (sample A; produced according to Example 1), citronellol dimer acetate (sample B; produced according to Example 3), and citronellol polymer acetate (n = 3-6) (sample C; produced according to Example 3) were compared with the standard insect repellent DEET (di-ethyl-m-toluamide) using an in vitro method with female yellow fever mosquitoes (Aedes aegypti). Mosquitoes were exposed to treatments applied to 3 cm diameter collagen membranes placed in warm, blood-filled wells in a multi-well plate. The wells were preheated to 96-100°F, and then whole blood containing ATP and citrate was poured into each well to completely fill it. Vacuum grease was applied and the membranes were fixed in place. 25 μL of test solution was applied to each membrane and allowed to dry. The plate was then placed in a plastic box containing 250 adult female mosquitoes. The number of mosquito detection events was recorded over a 20-minute period. The entire process was repeated until five replicates were completed. The treatment position in the plate was rotated each time to eliminate any positional bias. Fresh blood and mosquitoes were used repeatedly. The percentage of rejection was calculated by comparing the membranes to a negative control membrane treated with water only. It was found that all three citronellol derivatives produced rejection levels substantially similar to those of a 20% DEET isopropanol solution compared to the water positive control (all four showed approximately 97-99% rejection).

[0373] Mosquito probe 39 0 0.4 0.6 0.6 Rejection % - 100％ 99.1％ 98.8％ 98.1％

[0374] Example 9: Reduction of unsaturated citronellol homopolymer

[0375]

[0376] As shown above, the citronellol homopolymer obtained essentially according to Example 2 (where n averages 1-4) was catalytically hydrogenated to produce the corresponding saturated compound. In a pressure reactor, 100 g of the citronellol homopolymer was combined with 5% palladium on carbon (250 mg) in ethanol (100 mL). The reaction mixture was shaken at 400 psi under a hydrogen atmosphere for 72 hours at room temperature. The reaction mixture was then filtered through diatomaceous earth, and the ethanol was removed by vacuum distillation to give a colorless liquid (quantitative yield). Proton NMR confirmed the complete absence of olefin protons in the product.

[0377] Example 10: Insecticidal activity of citronellol polymer solution

[0378] Citronellol polymeric acetate (n = 3-6) (sample C; fraction produced according to Example 2) was dissolved in isopropanol (IPA) solvent at concentrations of 1 wt%, 5 wt%, or 20 wt%. This was compared with a 20 wt% DEET IPA solution as a control. The method was as described in Example 8. The results are summarized in the table below.

[0379]

[0380] The results showed that there was a dose-response relationship between the concentration of citronellol polymer and its mosquito-repellent effect.

[0381] Example 11: Evaluation of paint and coating compositions

[0382] Citronellol polymeric acetate (n=3-6) (Sample C; produced according to Example 3) or citronellol polymeric alcohol (n=3-6) (Sample D; produced according to Example 2) were mixed with one of three commercially available base coating formulations (Base A, Base B, Base C) at a ratio of 1:1 or 3:1. The physical properties of the mixtures important for paint and coating applications were evaluated. The following table shows the compositions of Base A, Base B, and Base C:

[0383]

[0384] Apply three portions of the mixture side-by-side to a pine board and brush back and forth. Analyze the following criteria: gloss, color quality, oiliness, coating uniformity, smoothness, and water resistance (beading). The comparison results are shown in the table below:

[0385]

[0386] The results showed that the addition of the compounds according to this disclosure can enhance the coating uniformity and smoothness of both acrylic and shellac base formulations. Furthermore, it was found that both citronellol polymers tested were freely miscible with each of the three base formulations.

[0387] Example 12: Evaluation of Fragrance Fixation

[0388] A blotter study was conducted to evaluate the odor retention of two common fragrance components, linalool and 1-(3,3-dimethylcyclohexyl)ethyl formate. A 50% w / w ethanol solution of linalool or purified aphermate was mixed with citronellol polymer acetate (n=3-6) (sample C; produced according to Example 3) or citronellol polymer alcohol (n=3-6) (sample D; produced according to Example 2) at a ratio of approximately 3:1 (fragrance:polymer). Approximately 18-25 mg of each sample was applied to blotter paper. The study was conducted under ambient conditions (indoor, room temperature, and ambient humidity). The odor intensity was assessed periodically, and the results are listed in the table below.

[0389]

[0390] The results showed that the fragrance mixed with the citronellol polymer according to this disclosure retained a significant aromatic odor for 5-7 hours, which was not present when the pure composition was imprinted.

[0391] Example 13: Evaluation of hair removal performance

[0392] Pure citronellol polymer acetate (n=3-6) (sample C; produced according to Example 3) and pure citronellol polymer alcohol (n=3-6) (sample D; produced according to Example 2) were compared with commercially available anti-tangling hair care products. Commercially available 100% pure human hair extensions were washed with shampoo and towel-dried to remove excess water. The length, thickness, texture, and appearance of the extensions were substantially the same. A small amount of sample (approximately 150-200 mg) was then manually and evenly distributed onto the hair. The hair was observed immediately after the sample was distributed and after the hair sample had been air-dried for less than 30 minutes (under ambient conditions). According to the label, the commercially available product contained (in descending order of concentration) a mixture of cyclopentasiloxane, dimethiconal, dimethyl silicone crosspolymer, benzophenone-3, fragrance, benzyl butyrate, and benzylphenyl methylpropionaldehyde.

[0393] The following observations were made:

[0394]

[0395]

[0396] The results indicate that both tested polymers according to the invention reduce the curl of natural human hair to a better extent than comparable commercially available products, while polymer C provides the best texture and feel for the treated hair.

[0397] Example 14: Evaluation of Odor Reduction

[0398] A malodorous composition was prepared by mixing 60 μL of methyl sulfide and 60 μL of allyl sulfide in a 10 mL glass vial. Ethanol was added to the purified malodorous mixture to produce an odor compound solution at a concentration of 1 ppm or 100 ppm. A mixture was then prepared by mixing a commercially available scented oil, or citronellol polymer acetate (n=3-6) (sample C; produced according to Example 3), or citronellol polymer alcohol (n=3-6) (sample D; produced according to Example 2) with the malodorous ethanol solution at a ratio of 9:1 w / w. Commercially available scented oil samples, as well as samples of commercially available scented oil mixed with samples C and D at a ratio of 9:1 w / w, were also used for comparison. Blotting paper samples were immersed to the same depth in each test sample to absorb the same amount of liquid onto the paper. Each blotting paper was then placed in its own 400 g lidded container, sealed, and left for 1 hour. The container was then opened, and the odor emitted was evaluated immediately. The results are shown in the table below:

[0399]

[0400]

[0401] The results showed that the polymers according to the present invention can effectively mask or minimize the strong, unpleasant odor (i.e., rotten egg smell) caused by volatile organic sulfur compounds. It was also unexpectedly found that the polymer of sample D appeared to enhance the pleasant aroma of commercially available essential oils.

[0402] Example 15: Cosmetic Composition

[0403] According to the table below, moisturizing lotions, cosmetic primers, and cosmetic concealers were prepared using citronellol polymer acetate (n=3-6) (sample C; prepared according to Example 3): (percentages shown are w / w):

[0404]

[0405]

[0406] Each emulsion composition was prepared as follows: First, water and glycerol were mixed in a beaker and heated to approximately 70-75°C. In a second beaker, the oil phase (cetyl alcohol, stearic acid, isopropyl myristate, glyceryl stearate, a mixture of triglycerides, and sample C) was combined and also heated to approximately 70-75°C. Then, the hot oil phase and hot water phase were added sequentially to the plastic beaker, and the beaker was immediately immersed in a cold water bath. The mixture was then stirred at high speed using a hand-held electric stirrer. At approximately 30-40°C, preservatives and fragrances were added to the resulting homogeneous emulsion and gently mixed. Both compositions had a pH of 5-5.5.

[0407] The control lotion was found to be homogeneous with a slightly firm texture. It dried easily after being applied to the skin. In contrast, the lotion composition containing sample C felt softer and smoother on the skin and did not dry out.

[0408] The makeup primer composition was prepared as follows: Propylene glycol was heated to 70-75°C in a beaker, and then dimethylsilyl silica was slowly added under stirring to form a homogeneous gel. Then, sample C was slowly added under stirring, followed by cooling of the mixture. Finally, after the mixture cooled to below 40°C, a preservative was added. The resulting product was a homogeneous gel that, when applied to the skin, had a velvety feel. Compared to similar commercially available silicone-based makeup primers, the makeup primer of this invention provides a smoother and more radiant appearance on the skin.

[0409] The concealer composition was prepared as follows: First, water and glycerin were combined in a beaker and heated to approximately 70-75°C. In a second beaker, the oil phase (a mixture of cetyl alcohol, triglyceride, silica, and sample C) was combined and also heated to approximately 70-75°C. Then, titanium dioxide and iron oxide colorants were ground using a mortar and pestle and mixed with propylene glycol. Next, the propylene glycol / colorant mixture was added to the oil phase and mixed. Then, the hot oil phase and hot water phase were added sequentially to a plastic beaker, and the beaker was immediately immersed in a cold water bath, mixing with a spatula while cooling. This yielded a two-phase heterogeneous mixture containing the oil phase and an oil / water emulsion.

[0410] The oil phase was found to exhibit highly pigmenting properties, thus demonstrating excellent coverage. The entire formulation is a smooth, matte material, and once applied to the skin, it provides a soft, velvety feel. Compared to commercially available concealers, this concealer exhibits a more matte finish, except for its moisturizing properties.

[0411] Example 16: Double bond epoxidation

[0412]

[0413] In a 250 mL three-necked round-bottom flask, 25.5 g (108.5 mmol) of the polymer from Example 2 (n = 3-6) and 100 mL of toluene were placed. Solid 3-chloroperoxybenzoic acid (mCPBA, 10.5 g, 60.8 mmol) was slowly added. The reaction was stirred at room temperature for another 15 hours. A saturated sodium sulfite solution (50 mL) was added to the reaction mixture to quench the reaction, and the mixture was stirred for 2 hours. The organic phase was washed with a 10% sodium carbonate solution until pH 8. The organic phase was dried over sodium sulfate and concentrated to give the crude polymer epoxide product. To remove residual benzoic acid, the crude product was dissolved in 100 mL of MTBE and stirred with a 10% sodium carbonate solution (50 mL) for 15 hours. After phase separation, the solvent in the organic phase was evaporated to give the final crude product, yielding 23 g. Proton NMR showed a diagnostic peak for the epoxide at approximately 2.66 ppm (CDCl3 solvent). Differential scanning calorimetry (DSC) showed that the epoxide reacted at ~150-170℃. Further experiments confirmed that the crude epoxide product successfully reacted with an amine nucleophile in a ring-opening reaction.

[0414] Example 17: Continuous Acylation Improved by Citronellol Polymers

[0415] 200 g of citronellol polymer alcohol (n = 3-6) (sample D; produced according to Example 2) was mixed with 60.5 ml of acetic anhydride and pumped at 10 ml / min through a 6 ft long stainless steel tube (0.25 inch in diameter), which was coiled to be maintained in an oil bath at 100-105°C. The material was continuously circulated through the tube until the reaction was judged to be more than 97% complete (approximately 5 times through the coil). The product was separated by dissolving the crude product in hexane, washing the organic phase with water, then washing with a 10% sodium carbonate aqueous solution, followed by vacuum removal of the solvent. The product was analyzed and found to be consistent with the citronellol polymer acetate (n = 3-6) obtained according to Example 3.

[0416] Alternatively, in some experiments, acetic acid and residual acetic anhydride can be removed directly by distillation.

[0417] Example 18: Continuous polymerization of Isoprenol

[0418] Amberlyst cation exchange resin was packed into a 6-ft long stainless steel tube (0.25 inches in diameter) and coiled to fit into an oil bath maintained at approximately 50°C. 66 g of Isoprenol was then passed through the tube at a flow rate of 1.9 g / min. The product... 1 ¹H NMR (CDCl₃) analysis showed the main polymerization product, with no residual monomers and trace amounts of isoprene. Diagnostic peaks of the polymerization product were observed as follows: a geminimethyl peak at 1.0–1.25 ppm, an adjacent methylene peak at 1.5–1.75 ppm, and a methylene peak adjacent to the ether bond at 3.5–3.75 ppm. After distillation of the low-boiling oligomer at 120 °C and 1.2 mbar, the residue... 1 ¹H NMR showed only trace amounts of olefin protons, indicating a high degree of polymerization.

[0419] Under similar conditions, Isoprenol was observed to convert to polymers significantly better than Prenol.

[0420] In addition, this application also provides the following implementation schemes:

[0421] 1. Compounds according to formula Y:

[0422]

[0423] The dashed keys (A, B, and C) represent optional keys, and R... 1 It is an optional substitution of C1–C 12 Alkyl; R 2 It is H, C 1-20 Alkyl, aryl, aryl-C 1-2 Alkyl, optionally unsaturated alkyl esters or aryl esters, or R 2It is a functional group:

[0424]

[0425] Where X is the expression -C(O)-R 3 -C(O)- diacyl group, wherein R 3 C is an optional substitute 1-22 Alkyl, optionally substituted C 2-22 Alkenyl or optionally substituted aryl;

[0426] And where n is an integer between 0 and 20;

[0427] The premise is that if intramolecular bridging bond A exists, then dashed bonds B and C do not exist, and substituent R... 2 It does not exist.

[0428] 2. The compound according to embodiment 1, wherein the compound according to formula Y is an ether compound according to formula I or a salt thereof.

[0429]

[0430] in,

[0431] R 1 It is an optional substitution of C1–C 12 Alkyl groups (e.g., optionally further C1–C) 12 alkyl or aryl substituted C 1- C 12 alkyl);

[0432] R 2 It is H, C 1-20 Alkyl (e.g., lower alkyl (e.g., C10)) 1-6 alkyl) or C 1-12 alkyl), aryl (e.g., phenyl), aryl C 1-2 Alkyl (e.g., benzyl), optionally unsaturated alkyl esters (e.g., C(O)-C) 1-20 Alkyl esters or optionally substituted aryl esters (e.g., C(O)-aryl);

[0433] n is an integer between 0 and 20.

[0434] 3. The compound according to embodiment 2, wherein R 1 It is an unsubstituted linear C 1- C 12 Alkyl or unsubstituted branched C3-C 12 alkyl.

[0435] 4. The compound according to embodiment 2 or 3, wherein R 1 It is an unsubstituted branched or straight-chain C6 alkyl group.

[0436] 5. The compound according to embodiment 4, wherein R 1 It is CH2CH2CH(CH3)CH2CH2.

[0437] 6. The compound according to any one of embodiments 2-5, wherein R 2 It is an alkyl group (e.g., a lower alkyl group, e.g., C10) 1-6 ), or C 1-12 ).

[0438] 7. The compound according to any one of embodiments 2-5, wherein R 2 It is an optional unsaturated alkyl ester (e.g., C(O)-C). 1-20 Alkyl or C(O)-C 1-6 alkyl).

[0439] 8. The compound according to embodiment 7, wherein R 2 It is C(O)-C 1-6 Alkyl, optionally wherein R 2 It 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 alkyl.

[0440] 9. The compound according to any one of embodiments 2-8, wherein n is greater than 1 (e.g., 2-20).

[0441] 10. The compound according to any one of embodiments 2-9, wherein R 1 It is CH2CH2CH(CH3)CH2CH2, n is 1-3 (e.g., 1-2), and R 2 It is C(O)-C 1-6 Alkyl, and the C 1-6 The alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, or n-hexyl.

[0442] 11. The compound according to embodiment 2, wherein the compound is:

[0443]

[0444] Where R 2 n is the same as defined in implementation scheme 2.

[0445] 12. The compound according to embodiment 1, wherein the compound according to formula Y is an ether and polyether diester compound according to formula II or a salt thereof:

[0446]

[0447] in,

[0448] R 1 It is an optional substitution of C1–C 12 Alkyl groups (e.g., optionally further C1–C) 12 alkyl or aryl substituted C 1- C 12 alkyl);

[0449] n 1 and n 2 Each is an integer between 0 and 20; and

[0450] X is the formula -C(O)-R 3 -C(O)- diacyl group, wherein R 3 C is an optional substitute 1-22 Alkyl, optionally substituted C 2-22 Alkenyl or optionally substituted aryl.

[0451] 13. The compound according to embodiment 12, wherein R 1 It is an unsubstituted linear C 1- C 12 Alkyl or branched C3-C 12 alkyl.

[0452] 14. The compound according to embodiment 13, wherein R 1 It is CH2CH2CH(CH3)CH2CH2.

[0453] 15. The compound according to embodiment 13 or 14, wherein R 3 It is unreplaced C 1-10 Alkyl groups, such as straight-chain unsubstituted C4 groups 1-10 Alkyl or branched unsubstituted C 1-10 Alkyl, or R therein 3 It is unreplaced C 1-6 Alkyl groups, such as straight-chain unsubstituted C4 groups 1-6 Alkyl or branched unsubstituted C 1-6 alkyl.

[0454] 16. The compound according to embodiment 13, wherein R 3 It is unreplaced C 2-22 Alkenyl groups, such as straight-chain unsubstituted C4 groups 2-22 Unsubstituted alkenyl or branched C 2-2 Alkenyl groups, wherein optionally any of the alkenyl groups is monounsaturated.

[0455] 17. The compound according to embodiment 13, wherein R3 It is an aryl group, such as a substituted or unsubstituted phenyl group.

[0456] 18. The compound according to any one of embodiments 13-17, wherein n 1 and / or n 2 Greater than 1 (e.g., 2-20).

[0457] 19. The compound according to embodiment 1, wherein the compound according to formula Y is a compound according to formula III or a salt thereof:

[0458]

[0459] in,

[0460] R 1 It is an optional substitution of C1–C 12 Alkyl groups (e.g., optionally further C1–C) 12 alkyl or aryl substituted C 1- C 12 Alkyl); and

[0461] n is an integer between 0 and 20.

[0462] 20. The compound according to embodiment 19, wherein R 1 It is an unsubstituted linear C 1- C 12 Alkyl or branched C3-C 12 Alkyl groups, for example, where R 1 It is CH2CH2CH(CH3)CH2CH2.

[0463] 21. The compound according to embodiment 19 or 20, wherein n is 0-5, for example, n is 0, 1, 2 or 3.

[0464] 22. A composition comprising the compound according to any one of embodiments 1-21, any salt thereof, or any mixture thereof, and at least one suitable solvent, carrier, or excipient.

[0465] 23. The composition according to embodiment 22, which is a fragrance composition, or perfume composition, or soap composition, or insect repellent composition, or insecticide composition, or detergent composition, or household cleaner composition, or air freshener composition, or room spray composition, or sachet composition, or candle composition, or cosmetic composition, or cologne composition, or pre- and post-shave shampoo composition, or talcum powder composition, or hair care product composition, or body deodorant composition, or antiperspirant composition, or shampoo composition, or pet bedding composition, or topical skin care composition, or paint or coating composition, or lubricant composition, or plastic composition, or defoamer composition, or hydraulic fluid composition, or antimicrobial composition.

[0466] 24. The composition according to embodiment 22 is a fragrance composition, an insect repellent composition, a candle composition, or a cosmetic composition.

[0467] 25. Preparation of R 2 The method of H according to embodiment 2, comprising the steps of:

[0468] (1) Introduce compound A into the reactor:

[0469]

[0470] Among them, R 1 It is an optional substitution of C1–C 12 Alkyl groups (e.g., optionally further C1–C) 12 alkyl or aryl substituted C 1- C 12 Alkyl); and

[0471] (2) The compound is exposed to a solid ion exchange resin, thereby polymerizing compound A to obtain R according to embodiment 2. 2 It is a compound of H; and

[0472] (3) Separate and / or purify (e.g. by distillation) the compound, such as a group of related compounds 1, wherein n varies in a range, such as n being 0-5 or 5-10 or 10-15 or 15-20, or n having any specific value in the integer range of 0-20.

[0473] 26. The method according to embodiment 25, further comprising R 2 It is the reaction of a compound of formula I with H and a suitable reagent to react R 2 The step of converting to alkyl ester or aryl ester groups.

[0474] 27. The method according to embodiment 25, further comprising R 2 It is the reaction of a compound of formula I with H and a suitable reagent to react R 2 The step of converting to an alkyl ether or aryl ether group.

[0475] 28. A method for producing a composition according to any one of embodiments 20-24 using a compound according to any one of embodiments 2-20.

[0476] 29. A method for preparing ester compound 1A according to formula I:

[0477]

[0478] Where R 1 It is an optional substitution of C1–C 12 Alkyl groups (e.g., optionally further C1–C) 12 alkyl or aryl substituted C 1- C 12 Alkyl); and R 2 It is (C=O)C 1-4 Alkyl groups (e.g., methyl); and n is an integer from 0 to 20;

[0479] The method comprises an alcohol compound 1 of formula I wherein R2 is H and wherein R 2 It is (C=O)C 1-4 The reaction of alkyl (e.g., methyl) alkyl anhydrides of the formula R2O(C=O)OR2, wherein the reaction is carried out under continuous flow conditions (e.g., in a continuous flow reactor) in the absence of a base or catalyst.

Claims

1. Compounds according to Formula I: in, terminal groups yes ; R 1 It is CH2CH2CH(CH3)CH2CH2; R 2 It is H or an optional unsaturated C(O)-C 1-20 Alkyl; and n is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

2. The compound according to claim 1, wherein R 2 It is an unsaturated C(O)-C 1-6 alkyl.

3. The compound according to claim 1, wherein R 2 It is saturated C(O)-C 7-20 alkyl.

4. The compound according to claim 1, wherein R 2 It's H.

5. The compound according to claim 1, wherein R 2 It is an unsaturated C(O)-C 7-20 alkyl.

6. The compound according to claim 5, wherein R 2 It is C(O)-C 17 alkyl.

7. The compound according to claim 1, wherein R 2 It is C(O)-C 1-6 alkyl and the C 1-6 The alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, or n-hexyl.

8. The compound according to any one of claims 1-7, wherein n is 1, 2, 3, 4, 5, 6 or 7.

9. The compound according to any one of claims 1-7, wherein n is 1, 2 or 3.

10. The compound according to claim 1, wherein R 1 It is CH2CH2CH(CH3)CH2CH2, where n is 1, 2, 3, 4, 5, 6, or 7, and R 2 It is C(O)-C 1-6 Alkyl and the C 1-6 The alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, or n-hexyl.

11. The compound according to claim 1, wherein R 1 It is CH2CH2CH(CH3)CH2CH2, where n is 1, 2, 3, 4, 5, 6, or 7, and R 2 It's H.

12. The compound according to claim 1, wherein R 1 It is CH2CH2CH(CH3)CH2CH2, where n is 1, 2, 3, 4, 5, 6, or 7, and R 2 It is C(O)-C 1-6 alkyl and the C 1-6 The alkyl group is selected from methyl, ethyl, propyl and isopropyl.

13. A composition comprising the compound or any mixture thereof according to any one of claims 1-12, and at least one suitable solvent, carrier or excipient.

14. The composition of claim 13, wherein it is a fragrance composition, or a perfume composition, or a soap composition, or an insect repellent composition, or an insecticide composition, or a detergent composition, or a household cleaner composition, or an air freshener composition, or a room spray composition, or a scent box composition, or a candle composition, or a cosmetic composition, or a cologne composition, or a pre- and post-shave shampoo composition, or a talcum powder composition, or a hair care product composition, or a body deodorant composition, or an antiperspirant composition, or a shampoo composition, or a pet bedding composition, or a topical skin care composition, or a paint or coating composition, or a lubricant composition, or a plastic composition, or a defoamer composition, or a hydraulic fluid composition, or an antimicrobial composition.

15. The composition according to claim 14, wherein it is a fragrance composition, an insect repellent composition, a candle composition, or a cosmetic composition.

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