Terpenol Ether

Abstract

This application relates to novel ether derivatives of terpenes, particularly derivatives of terpene alcohols, and methods for their preparation, compositions containing same and methods of their use.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This international application claims priority to and the benefit of U.S. Provisional Application No. 63 / 189,545, filed May 17, 2021, the contents of which are incorporated herein by reference in their entirety.

[0002] FIELD OF THEINVENTION This application relates to novel derivatives of terpenes, in particular ether derivatives of terpene alcohols, and methods for their preparation, compositions containing same and methods of their use. [Background technology]

[0003] background Terpenes and terpene derivatives constitute one of the most versatile, commercially popular and industrially important classes of natural products. Terpenes occur in all living organisms, and are particularly abundant in plants, from which they are industrially isolated. The commercial availability and low cost of terpenes continues to drive innovation in chemical derivatives that are utilized in polymer science, the flavor and fragrance industry, the cosmetics industry, the pharmaceutical industry, and as surfactants, plastic additives and other industrial applications.

[0004] Basic terpenes (C 5n H 8n Although some terpenes (derivatives, n=1, 2, 3, etc.) are inexpensive and widely available, chemically functionalized terpenes (terpenoids), especially terpene alcohols, are more useful. Common monoterpene alcohols include: [ka]

[0005] In addition to the monoterpene alcohols, there are also the following sesquiterpene alcohols which are inexpensive and widely available: [ka]

[0006] Terpene alcohol derivatives also include polymers and oligomers of terpene alcohols. For example, citronellol forms useful oligomeric and polymeric products having the following structures: [ka] [Wherein, n is 0-20 (e.g., 0-3).] Dimers, trimers and other oligomers of citronellol have been described. See, for example, US2017 / 0283553, US2020 / 0165383 and US2020 / 0392287, the contents of each of which are incorporated herein by reference in their entirety.

[0007] Fatty acid esters and ethers are a multi-million dollar per year industry. While natural lipids and oils are esters of fatty acids and glycerol, the most commercially useful fatty acid esters are esters of fatty acids and monohydroxy alcohols, especially hydrophobic monohydroxy alcohols such as fatty alcohols. Similarly, fatty acid ethers - derived from alcohol analogs of fatty acids, etherified to secondary alcohols - are also extremely useful. These compounds have a variety of uses, for example, as emollients, lubricants, antifoaming agents, adjuvants, and more. These compounds are commonly found in personal care and cosmetic compositions. Summary of the Invention [Problem to be solved by the invention]

[0008] There remains a need in the art for new compounds with new or different properties, such as improved stability, improved biodegradability, improved environmental impact, etc. It would be particularly advantageous to obtain new fatty acid ethers from renewable resources. [Means for solving the problem]

[0009] Summary of the Invention The present invention provides terpene alcohols and oligomers and their derivatives, and terpene alcohol ethers and bis(terpene alcohol) ethers derived from fatty alcohols such as lauryl alcohol, palmityl alcohol, myristyl alcohol and its derivatives.These compounds are useful in many types of compositions and in many roles.For example, these compounds can be used as emollients, lubricants, defoamers, adjuvants and other applications, and are particularly useful as ingredients in personal care compositions and cosmetic compositions.

[0010] In a second aspect, the present invention provides methods for preparing such compounds.

[0011] In a third aspect, the invention provides compositions and products comprising such compounds, which in certain embodiments are useful in a variety of applications, including as or in cosmetics, soaps, hair care products, fragrances, sunscreens, plastic additives, paints, coatings, lubricants and surfactants. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Detailed Description of the Invention The term "terpene alcohol" as used herein refers to a natural terpene or terpenoid that has or has been modified to have at least one alcohol functional group. The term includes both naturally occurring terpene alcohols and alcohols derived from naturally occurring terpenes by double bond oxidation, ketone reduction, and the like. The term "terpene derivatives" or "terpene alcohol derivatives" as used herein includes saturated and partially saturated derivatives of terpenes and terpene alcohols. Terpenes, terpene alcohols and other terpenoids generally have one, two, three or more double bonds. In saturated derivatives, all double bonds are hydrogenated, while in partially saturated derivatives, at least one double bond is hydrogenated but at least one double bond is not. In this specification, double bonds of aromatic rings are included; thus, benzene rings may be considered to be partially saturated to form cyclohexadiene or cyclohexene rings or fully saturated to form cyclohexane rings.

[0013] In a first aspect, the present invention provides a compound of general formula (I) in free or salt form: [ka] [wherein A is a terpene alcohol or derivative thereof core, and B is (i) a saturated or unsaturated hydrocarbon chain of a natural or unnatural fatty alcohol or a derivative thereof; or (ii) a core of a terpene alcohol or a derivative thereof, which may be the same or different as the substituent A It is. The present invention provides a terpene alcohol ether compound (Compound 1) of the formula: It is further understood that "derivatives thereof" includes, but is not limited to, hydrogenated derivatives thereof, including partially hydrogenated and fully hydrogenated derivatives of unsaturated fatty acids. In a preferred embodiment, the product compound of formula I is an isodecyl ether (i.e., either or both of group A or group B are isodecyl groups).

[0014] In the term "A is a terpene alcohol or derivative thereof core", it is understood that the terpene alcohol or derivative thereof from which the compound of formula I is derived has the formula A-OH. Thus, the ether functionality of the compound of formula I is formed or can be formed by the following condensation reaction: [ka] Similarly, "B is a saturated or unsaturated hydrocarbon chain of a natural or unnatural fatty alcohol or derivative thereof" is understood to mean that the group B is derived from a fatty alcohol having the formula B-OH. It is further understood that, as a convention, the term fatty alcohol refers to an alcohol analog of a fatty acid with the same number of carbon atoms and with any double bonds in the same positions. Thus, for purposes of terminology equivalence, a fatty acid of the formula R-COOH corresponds to a fatty alcohol of the formula R-CH2OH.

[0015] In a further embodiment of the first aspect, the present invention provides: 1.1 Compound 1, wherein A is a terpene alcohol or derivative thereof core, wherein the terpene is a monoterpene, sesquiterpene, diterpene, sesterterpene or triterpene.

[0016] 1.2 Compound 1, wherein A is a terpene alcohol or derivative core, wherein the terpene is a monoterpene or a sesquiterpene.

[0017] 1.3 Compound 1, where A is a terpene alcohol or derivative core, where the terpene is a monoterpene (e.g., A is an isodecyl moiety).

[0018] 1.4 Compound 1, wherein A is a terpene alcohol or derivative thereof core, wherein the terpene alcohol is selected from citronellol, isocitronellol, geraniol, nerol, menthol, myrcenol, linalool, thymol, α-terpineol, β-terpineol, γ-terpineol, borneol, farnesol, nerolidol and carotol.

[0019] 1.5 Compound 1.4, wherein the terpene alcohol is selected from citronellol, geraniol, nerol, myrcenol, linalool and farnesol.

[0020] 1.6 Compound 1.5, wherein the terpene alcohol is selected from citronellol, myrcenol, linalool and farnesol.

[0021] 1.7 Compound 1, wherein A is a terpene alcohol or derivative core, wherein the terpene alcohol or derivative is an oligomer of citronellol.

[0022] 1.8 Any of compounds 1 or 1.1-1.7, wherein the terpene alcohol or derivative thereof has its natural unsaturation.

[0023] 1.9 Any of compounds 1 or 1.1-1.7, wherein the terpene alcohol or derivative thereof is partially unsaturated (e.g., monounsaturated or diunsaturated).

[0024] 1.10 Any of compounds 1 or 1.1-1.7, wherein the terpene alcohol or derivative thereof is fully saturated (eg, the terpene alcohol is a fully saturated monoterpene derivative, such as an isodecyl moiety).

[0025] 1.11 A [ka] Compound 1 is selected from the group consisting of:

[0026] 1.12 A [ka] Compound 1 is selected from the group consisting of:

[0027] 1.13 A [ka] Compound 1 is selected from the group consisting of:

[0028] 1.14 A [ka] Compound 1 is selected from the group consisting of:

[0029] 1.15 A [ka] Compound 1.

[0030] 1.16 A [ka] Compound 1 is selected from the group consisting of:

[0031] 1.17 A [ka] Compound 1 is selected from the group consisting of:

[0032] 1.18 A [ka] Compound 1.

[0033] 1.19 A [ka] [In the formula, n is an integer of 0 to 20 (e.g., 0 to 3, 0, 1, or 2).] Compound 1.

[0034] 1.20 A [ka] [In the formula, n is an integer of 0 to 20 (e.g., 0 to 3, 0, 1, or 2).] Compound 1.

[0035] 1.21 Compound 1 or any of 1.1-1.20, wherein B is a saturated or unsaturated hydrocarbon chain of a C4-C28 fatty alcohol or a derivative thereof (i.e., group B has a C4-C28 hydrocarbon chain).

[0036] 1.22 Compound 1 or any of 1.1-1.20, wherein B is a saturated or unsaturated hydrocarbon chain of a C6-C12 fatty alcohol or a derivative thereof (i.e., group B has a C6-C12 hydrocarbon chain).

[0037] 1.23 Any of compounds 1 or 1.1-1.20, wherein B is a saturated or unsaturated hydrocarbon chain of a C13-C21 fatty alcohol or a derivative thereof (i.e., group B has a C13-C210 hydrocarbon chain).

[0038] 1.24 Any of compounds 1 or 1.1-1.20, wherein B is a saturated or unsaturated hydrocarbon chain of a C22-C28 fatty alcohol or a derivative thereof (i.e., group B has a C22-C28 hydrocarbon chain).

[0039] 1.25 Compound 1 or any of 1.1-1.20, wherein B is a saturated or unsaturated hydrocarbon chain of a C8, C9, C10, C12, C14, C16 or C18 fatty alcohol or a derivative thereof (i.e., group B has a C87, C9, C10, C12, C14, C16 or C18 hydrocarbon chain).

[0040] 1.26 Any of compounds 1, 1.1-1.25, wherein B is an unsaturated, e.g., mono-, di- or tri-unsaturated hydrocarbon chain.

[0041] 1.27 B is -(CH2) x CH=CH(CH2) yCompound 1.26 is CH3, where x is an integer from 4 to 19 (e.g., 3, 4, 5, 8, or 12) and y is an integer from 1 to 8 (e.g., 1, 2, 3, 4, 5, 7, or 8).

[0042] 1.28 B is -(CH2) x CH=CH(CH2) a CH=CH(CH2) y Compound 1.26: CH3, where x is an integer from 4 to 19 (e.g., 3, 4, 5, 8, or 12), a is an integer from 1 to 5 (e.g., 1 or 3), and y is an integer from 1 to 8 (e.g., 1, 2, 3, 4, 5, 7, or 8).

[0043] 1.29 B is -(CH2) x CH=CH(CH2) a CH=CH(CH2) a CH=CH(CH2) y Compound 1.26: CH3, where x is an integer from 4 to 19 (e.g., 3, 4, 5, 8, or 12), a and b are each independently an integer from 1 to 5 (e.g., 1, 3, or 5), and y is an integer from 1 to 8 (e.g., 1, 2, 3, 4, 5, 7, or 8).

[0044] 1.30 Any of compounds 1.1 to 1.29 in which each double bond (-CH=CH-) has a cis orientation.

[0045] 1.31 Any of compounds 1.1-1.29 in which each double bond (-CH=CH-) has a trans orientation.

[0046] 1.32 Any of compounds 1.1 to 1.29, in which at least one double bond (-CH=CH-) has a cis orientation and one double bond has a trans orientation.

[0047] 1.33 B is a saturated hydrocarbon chain, e.g., B is -(CH2) xAny of compounds 1, 1.1 to 1.25, wherein x is an integer from 4 to 27 (e.g., 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, or 27).

[0048] 1.34 Compound [ka] wherein x is an integer selected from 4, 5, 6, 7, 8, 9, 11, 13, 15, and 17. Compound 1 or any of 1.1 to 1.33 selected from the group consisting of:

[0049] 1.35 Compound 1.34, wherein x is an integer selected from 8, 9 and 11.

[0050] 1.36 Compound 1.34, where x is 8.

[0051] 1.37 Compound 1.34, where x is 9.

[0052] 1.38 Compound 1.34, where x is 11.

[0053] 1.39 Compound 1.34, where x is 17.

[0054] 1.40 Compound 1 or any of 1.1-1.39, wherein the group A is an isodecyl group selected from, for example, 2,4-dimethyloctan-2-yl, 2,6-dimethyl-octan-1-yl, 2,6-dimethyloctan-2-yl, 3,7-dimethyloctan-1-yl and 3,7-dimethyloctan-3-yl.

[0055] 1.41 Group B is CH3(CH2) 15 -, CH3(CH2) 11 - or cis-CH3(CH2)7CH=CH(CH2)8-, any of compounds 1 or 1.1 to 1.40.

[0056] 1.42 Compound [ka] Compound 1 or any of 1.1 to 1.41 selected from the group consisting of:

[0057] 1.43 Compound [ka] Compound 1 or any of 1.1 to 1.41 selected from the group consisting of:

[0058] 1.44 Compound [ka] Compound 1 or any of 1.1 to 1.41 selected from the group consisting of:

[0059] 1.45 Compound [ka] Compound 1 or any of 1.1 to 1.41 selected from the group consisting of:

[0060] 1.46 Any of compounds 1.1-1.45, wherein the compound has a single asymmetric center in substituent A, which center has the R configuration.

[0061] 1.47 Any of compounds 1.1-1.45, wherein the compound has a single asymmetric center in substituent A and said center has the S configuration.

[0062] 1.48 Any of compounds 1.1-1.45, wherein the compound has two or three asymmetric centers in substituent A, each of which has the R configuration.

[0063] 1.49 Any of compounds 1.1-1.45, wherein the compound has two or three asymmetric centers in substituent A, each of which has the S configuration.

[0064] 1.50 Any of compounds 1 or 1.1-1.20, wherein B is a terpene alcohol or derivative core, wherein the terpene is a monoterpene, sesquiterpene, diterpene, sesterterpene or triterpene.

[0065] 1.51 Compound 1.50, wherein B is a terpene alcohol or derivative core, wherein the terpene is a monoterpene or a sesquiterpene.

[0066] 1.52 Compound 1.50, where B is a terpene alcohol or derivative core, where the terpene is a monoterpene (eg, B is an isodecyl moiety).

[0067] 1.53 B is a terpene alcohol or derivative core, wherein the terpene alcohol is selected from citronellol, isocitronellol, geraniol, nerol, menthol, myrcenol, linalool, thymol, α-terpineol, β-terpineol, γ-terpineol, borneol, farnesol, nerolidol and carotol, compound 1.50.

[0068] 1.54 Compound 1.53, wherein the terpene alcohol is selected from citronellol, geraniol, nerol, myrcenol, linalool, and farnesol.

[0069] 1.55 Compound 1.55, wherein the terpene alcohol is selected from citronellol, myrcenol, linalool, and farnesol.

[0070] 1.56 B is a terpene alcohol or derivative core, where the terpene alcohol or derivative is an oligomer of citronellol, compound 1.50.

[0071] 1.57 Any of compounds 1 or 1.50-1.56, wherein the terpene alcohol or derivative thereof has its natural unsaturation.

[0072] 1.58 Any of compound 1 or 1.50-1.56, wherein the terpene alcohol or derivative thereof is partially unsaturated (e.g., monounsaturated or diunsaturated).

[0073] 1.59 Any of compounds 1 or 150-1.56, wherein the terpene alcohol or derivative thereof is fully saturated (eg, the terpene alcohol is a fully saturated monoterpene derivative, such as an isodecyl moiety).

[0074] 1.60 B [ka] Compound 1.50 is selected from the group consisting of:

[0075] 1.61 B [ka] Compound 1.50 is selected from the group consisting of:

[0076] 1.62 B [ka] Compound 1.50 is selected from the group consisting of:

[0077] 1.63 B [ka] Compound 1.50 is selected from the group consisting of:

[0078] 1.64 B [ka] , Compound 1.50.

[0079] 1.65 B [ka] Compound 1.50 is selected from the group consisting of:

[0080] 1.66 B [ka] Compound 1.50 is selected from the group consisting of:

[0081] 1.67 Compound 1.50, in which the group B is an isodecyl group selected from, for example, 2,4-dimethyloctan-2-yl, 2,6-dimethyl-octan-1-yl, 2,6-dimethyloctan-2-yl, 3,7-dimethyloctan-1-yl and 3,7-dimethyloctan-3-yl.

[0082] 1.68 Compound 1.50, wherein the groups A and B are each independently an isodecyl group, e.g., A and B are each independently selected from 2,4-dimethyloctan-2-yl, 2,6-dimethyl-octan-1-yl, 2,6-dimethyloctan-2-yl, 3,7-dimethyloctan-1-yl, and 3,7-dimethyloctan-3-yl.

[0083] 1.69 Compound [ka] Compound 1.50 is selected from the group consisting of:

[0084] 1.70 Any compound 1.50 to 1.70, wherein the compound has a single asymmetric center in substituent B, which center has the R configuration.

[0085] 1.71 Any compound 1.50-1.70, wherein the compound has a single asymmetric center in substituent B, which center has the S configuration.

[0086] 1.72 Any of compounds 1.50-1.70, wherein the compound has two or three asymmetric centers in substituent B, each of which has the R configuration.

[0087] 1.73 Any of compounds 1.50-1.70, wherein the compound has two or three asymmetric centers in substituent B, each of which has the S configuration.

[0088] 1.74 Any of compounds 1 or 1.1 to 1.73, wherein the compound has a refractive index of 1.35 to 1.55, for example, 1.40 to 1.50 or 1.42 to 1.48 or 1.43 to 1.46 or 1.44 to 1.45.

[0089] 1.75 Any of compounds 1 or 1.1-1.74, wherein the compound has a surface tension of 15-35 mN / m, for example, 20-30 mN / m or 22-28 mN / m or 23-27 mN / m or 24-26 mN / m or about 25 mN / m.

[0090] As used herein, the term "isodecyl" refers to any 10 carbon saturated alkyl chain that is not linear (i.e., not n-decyl).

[0091] The compounds provided by the present invention provide a number of improved benefits over existing compounds used for the same purposes. For example, compounds 1 and onward provide one or more of: (a) low melting point, (b) good lubricity, (c) good spreading (e.g., good spontaneous spreading on skin), (d) high refractive index, (e) good hydrolytic stability, and (f) good enzymatic stability. Without being bound by theory, it is believed that the compounds having isodecyl groups disclosed herein provide particularly beneficial improvements over prior literature compounds, for example, due to the increased degree of branching of the alkyl chains. Surface tension is one of the physical factors that aid in providing compounds with improved emollience, lubricity, spreadability, and "sparkle" (i.e., appearance on skin and hair) compared to known compounds used for similar purposes. Preferably, the compounds of the present invention have a surface tension of 15 to 35 millinewtons per meter (mN / m). The refractive index is important from an appearance standpoint, as a higher refractive index provides a more shining or glossy product. Preferably, the compounds of the present invention have a refractive index of 1.35 to 1.55.

[0092] The term "alkyl" as used herein refers to a monovalent or divalent, branched or unbranched saturated hydrocarbon group having 1 to 20 carbon atoms, typically, but not necessarily, 1 to about 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, and the like. The term alkyl can also include cycloalkyl groups. Thus, for example, the term C6 alkyl includes cyclohexyl groups, the term C5 includes cyclopentyl groups, the term C4 includes cyclobutyl groups, and the term C3 includes cyclopropyl groups. Furthermore, since an alkyl group can be branched or unbranched, any alkyl group of n carbon atoms includes cycloalkyl groups of less than n carbons substituted by further alkyl substituents. Thus, for example, the term C6 alkyl also includes methylcyclopentyl groups or dimethylcyclobutyl groups or ethylcyclobutyl groups or trimethylcyclopropyl, ethylmethylcyclopropyl, or propylcyclopropyl groups.

[0093] The term "alkenyl" as used herein refers to a mono- or divalent, branched or unbranched unsaturated hydrocarbon group typically, but not necessarily, containing from 2 to about 12 carbon atoms and from 1 to 10 carbon-carbon double bonds, such as ethylene, n-propylene, isopropylene, n-butylene, isobutylene, t-butylene, octylene, etc. As with the term "alkyl," the term "alkenyl" also encompasses both branched and unbranched cycloalkenyl groups with double bonds that are optionally endocyclic or exocyclic.

[0094] The term "alkynyl" as used herein refers to a mono- or divalent, branched or unbranched unsaturated hydrocarbon group typically, but not necessarily, containing from 2 to about 12 carbon atoms and from 1 to 8 carbon-carbon triple bonds, such as ethyne, propyne, butyne, pentyne, hexyne, heptyne, octyne, etc. As with the term "alkyl," the term "alkynyl" also encompasses both branched and unbranched cycloalkynyl groups with triple bonds that are optionally endocyclic or exocyclic.

[0095] As used herein, the term "aryl" refers to an aromatic hydrocarbon moiety containing at least one aromatic ring of 5 to 6 carbon atoms, including, for example, aromatic hydrocarbons having two fused rings and 10 carbon atoms (i.e., naphthalene).

[0096] By "substituted" as in "substituted alkyl," "substituted alkenyl," "substituted alkynyl," etc., it is meant that at least one hydrogen atom bonded to a carbon atom in an alkyl, alkenyl, alkynyl, or other moiety is replaced with one or more non-hydrogen substituents, e.g., functional groups.

[0097] The terms "branched" and "straight-chain" (or "unbranched") refer to, for example, a ~C b When used in reference to an alkyl moiety of a carbon atom, it applies to the carbon atom that defines the alkyl moiety. For example, for a C4 alkyl moiety, its branched embodiment includes isobutyl, and its unbranched embodiment is n-butyl. However, isobutyl is also considered to be itself a linear C3 alkyl moiety (propyl) substituted with a C1 alkyl (methyl).

[0098] Unless otherwise specified, any carbon atom with an open valence may be substituted with further functional groups. Exemplary functional groups are halo, hydroxyl, sulfhydryl, C1-C 20 Alkoxy, C2-C 20 Alkenyloxy, C2-C 20 Alkynyloxy, C5-C 20 Aryloxy, acyl (C2-C 20 Alkylcarbonyl (-CO-alkyl) and C6-C 20 Arylcarbonyl (-CO-aryl), acyloxy (-O-acyl), C2-C 20 Alkoxycarbonyl (-(CO)-O-alkyl), C6-C 20 Aryloxycarbonyl (-(CO)-O-aryl), halocarbonyl (-CO)-X, where X is halo), C2-C 20 Alkylcarbonate (-O-(CO)-O-alkyl), C6-C 20Arylcarbonato (-O-(CO)-O-aryl), carboxy (-COOH), carboxylato (-COO - ), carbamoyl (-(CO)-NH2), mono-substituted C1-C 20 Alkylcarbamoyl(-(CO)-NH(C1-C 20 alkyl)), di-substituted alkylcarbamoyl (-(CO)-N(C1-C 20 alkyl)2), mono-substituted arylcarbamoyl (-(CO)-NH-aryl), thiocarbamoyl (-(CS)-NH2), carbamido (-NH-(CO)-NH2), cyano (-C≡N), isocyano (-N + ≡C - ), cyanate (-OC≡N), isocyanate (-ON + ≡C - ), isothiocyanato (-SC≡N), azido (-N=N + =N - ), formyl (-(CO)-H), thioformyl (-(CS)-H), amino (-NH2), mono- and di-(C1-C 20 Alkyl)-substituted amino, mono- and di-(C5-C 20 Aryl)-substituted amino, C2-C 20 Alkylamide (-NH-(CO)-alkyl), C5-C 20 Arylamide (-NH-(CO)-aryl), imino (-CR=NH, where R=hydrogen, C1-C 20 Alkyl, C5-C 20 Aryl, C6-C 20 Alkaryl, C6-C 20 aralkyl, etc.), alkylimino (-CR=N(alkyl), where R=hydrogen, alkyl, aryl, alkaryl, etc.), arylimino (-CR=N(aryl), where R=hydrogen, alkyl, aryl, alkaryl, etc.), nitro (-NO2), nitroso (-NO), sulfo (-SO2-OH), sulfonato (-SO2-O - ), C1-C 20 Alkylsulfanyl (-S-alkyl; also known as "alkylthio"), arylsulfanyl (-S-aryl; also known as "arylthio"), C1-C 20Alkylsulfinyl (-(SO)-alkyl), C5-C 20 Arylsulfinyl (-(SO)-aryl), C1-C 20 Alkylsulfonyl (-SO2-alkyl), C5-C 20 Arylsulfonyl (-SO2-aryl), phosphono (-P(O)(OH)2), phosphonato (-P(O)(O - )2), phosphinato (-P(O)(O - )), phospho (-PO2), phosphino (-PH2), mono- and di-(C1-C 20 Alkyl)-substituted phosphino, mono- and di-(C5-C 20 aryl)-substituted phosphino; and hydrocarbyl moieties, such as C-C 20 Alkyl (C1-C 18 Contains alkyl, and also C1-C 12 alkyl and further including C1-C6 alkyl), C2-C 20 Alkenyl (C2-C 18 Alkenyl, including C2-C 12 alkenyl and further including C2-C6 alkenyl), C2-C 20 Alkynyl(C2-C 18 Alkynyl, including C2-C 12 alkynyl and further including C2-C6 alkynyl), C5-C 30 Aryl (C5-C 20 Aryl and further C5-C 12 (including aryl) and C6-C 20 Aralkyl(C6-C 20 Aralkyl and C6-C 12 Examples of "substituents" include, but are not limited to, alkyl, aryl, arylalkyl ...

[0099] In a second aspect, the present invention provides a method for preparing compounds 1 onwards, comprising reacting a compound of formula A with a compound of formula B or an activated halide or sulfonate thereof in a condensation reaction to form a compound of formula I. [ka] wherein the substituents A and B are as defined above. In an embodiment, the reaction is carried out by reacting a compound of formula A with a compound of formula B, optionally under dehydrating conditions, in the presence of an acid catalyst. Preferably, the acid catalyst is selected from sulfuric acid, hydrochloric acid, phosphoric acid, toluenesulfonic acid, methanesulfonic acid, or an acidic ion exchange resin, such as Amberlyst-type resin. In an embodiment, the reaction further comprises a dehydrating agent, such as sodium sulfate, magnesium sulfate, phosphorus pentoxide, or the like. In a preferred embodiment, the reaction optionally comprises a mixture of sulfuric acid and magnesium sulfate in a hydrocarbon solvent, such as heptane. In an embodiment, magnesium sulfate is first suspended in a hydrocarbon solvent, such as heptane, and concentrated sulfuric acid is added to form a solid MgSO4 / H2SO4 adduct that can be used directly as an acid catalyst for the condensation reaction after solvent removal. Preferably, this solid adduct is added directly to the solvent-free reaction components (e.g., when the terpene alcohol of formula A and / or the acid of formula B are liquids). In some embodiments, the reaction is carried out by reacting the compound of formula A with the activated derivative of the compound of formula B, such as the halide or sulfonate of the compound of formula B. In some embodiments, the reaction is carried out by reacting the compound of formula B with the activated derivative of the compound of formula A, such as the halide or sulfonate of the compound of formula A. In some embodiments, the reaction is carried out under basic conditions, for example, in the presence of a base (e.g., hydroxide base, alkoxide base, carbonate base, bicarbonate base, hydride base, organometallic base or amide base), by reacting the compound of formula A with the compound of formula B, or its ester, activated ester or acyl halide. In some embodiments, the reaction is carried out by reacting the compound of formula A in a salt, such as lithium salt, sodium salt or potassium salt, with the compound of formula B, or its ester, activated ester or acyl halide. In some embodiments, the salt is formed in situ.Suitable bases include sodium hydroxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium isopropoxide, sodium butoxide, sodium tert-butoxide, sodium carbonate, sodium bicarbonate, sodium hydride, sodium amide, potassium hydroxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium isopropoxide, potassium tert-butoxide, potassium carbonate, potassium bicarbonate, potassium hydride, potassium amide, lithium hydroxide, lithium methoxide, lithium tert-butoxide, lithium carbonate, lithium amide, lithium diisopropylamide, lithium hexamethyldisilazide, lithium tetramethylpiperidide, n-butyllithium, s-butyllithium and t-butyllithium.

[0100] In another embodiment of the second aspect, the present invention provides a method for preparing compounds 1 onwards, comprising reacting a compound of formula E with a compound of formula B in an electrophilic alkene addition reaction to form a compound of formula I, wherein a compound of formula E can be formed by dehydration of a compound of formula A: [ka] where the substituents A and B are as defined above, and the structure of formula E is attached to the structure of formula A such that removal of the H atom from the OH group and the adjacent carbon atom results in a compound of formula E. Such addition reactions can proceed under acidic conditions, e.g., by combining a compound of formula E and a compound of formula B in the presence of an acid catalyst, using the conditions described in the previous paragraph. Dehydration reactions can also proceed under productive conditions, if desired, by combining a compound of formula A with an acid catalyst under dehydrating conditions, e.g., using the conditions described in the previous paragraph.

[0101] For example, compounds of formula A having each of the following substructures can be provided, upon removal of water, to the corresponding compounds of formula E: [ka]

[0102] Suitable solvents and reaction conditions (concentrations, times, temperatures) for carrying out the reaction are generally known to those skilled in the art and are in no way limited to the present disclosure. Depending on the choice of reagents, suitable solvents may include one or more of non-polar, polar protic and / or polar aprotic solvents, such as hydrocarbons, ethers and esters.

[0103] In an embodiment, the reaction is carried out at a temperature of -25°C to 200°C. In a preferred embodiment, the reaction is carried out at 25 to 150°C or 50 to 100°C. In an embodiment, the reaction is carried out for 0.1 to 100 hours. In a preferred embodiment, the reaction is carried out for 0.5 to 12 hours, or 0.5 to 6 hours, or 1 to 3 hours.

[0104] The compounds of formula A and compounds of formula B (if applicable) used in the preparation of compound 1 or later of the present invention are terpene alcohols or derivatives thereof (e.g., hydrogenated terpene alcohols).Preferably, the terpene alcohols are obtained or isolated from natural renewable resources.For example, each of the following terpene alcohols can be obtained by extraction from a number of plant species: citronellol, isocitronellol, geraniol, nerol, menthol, myrcenol, linalool, thymol, α-terpineol, β-terpineol, γ-terpineol, borneol, farnesol, nerolidol and carotol.Essential oils from many trees and plants, such as rose oil, palmarosa oil, citronella oil, lavender oil, coriander oil, thyme oil, peppermint oil and pint oil, have significant amounts of these terpene alcohols.

[0105] In a preferred embodiment, however, terpene alcohols can be derived from naturally occurring terpenes by semi-synthesis (e.g., double bond hydration). Terpenes are much more abundant in nature than their corresponding terpene alcohols. Common terpenes include alpha-pinene, beta-pinene, alpha-terpinene, beta-terpinene, gamma-terpinene, delta-terpinene (terpinolene), myrcene, limonene, camphene, carene, sabinene, alpha-ocimene, beta-ocimene, alpha-thujene and beta-thujene. Alpha-pinene is the most abundant naturally occurring terpene in nature, and is present in high concentrations in various tree resins and oils, such as pint oil and oleoresin (and its derivative turpentine). Many terpene oils can be derived from the terpenes present in turpentine, pint oil and similar substances. Turpentine is a major by-product in the paper and pulp industry, therefore the use of this material as a source of terpene alcohols is both economical and environmentally friendly.

[0106] Additionally, terpene alcohols can be produced semisynthetically from isobutylene, isoprenol or ethanol. Ethanol, as well as methanol and tert-butanol, can be produced in large quantities by fermentation of biorenewable sugars such as corn, cane sugar or sugar beet. Isobutylene can be produced by removal of tert-butanol or by mixed oxidation and aldol condensation to acetaldehyde and acetone from ethanol, and isoprenol can be produced by reaction of isobutylene with formaldehyde, which can be produced by methanol oxidation. Methanol and ethanol can also be derived from by-product fractions of commercial ethanol distillation (e.g., in the production of distilled spirits). In these routes, the compounds of the present invention can all be produced entirely from biorenewable resources such as trees and plants.

[0107] Thus, in certain embodiments of the present invention, the method of producing Compound 1 or later may further comprise one or more of the following steps: (1) harvesting one or more grains or cereals (e.g., corn, beets, sugarcane, barley, wheat, rye, or sorghum); (2) fermenting such harvested grains or cereals; and (3) producing one or more C.I. 1-4 obtaining an aliphatic alcohol (e.g., methanol, ethanol, isobutanol, tert-butanol, or any combination thereof); (4) converting the alcohol to isobutylene and / or isoprenol; (5) converting the isobutylene or isoprenol to one or more terpenes (e.g., alpha-pinene, beta-pinene, alpha-terpinene, beta-terpinene, gamma-terpinene, delta-terpinene (terpinolene), myrcene, limonene, camphene, carene, sabinene, alpha-ocimene, beta-ocimene, alpha-thujene, and beta-thujene); (6) producing essential oils and woody plant oils; Extracting or isolating one or more terpenes from naturally occurring plant and tree extracts, such as oils (e.g., rosin, damar, mastic, sandarac, frankincense, elemi, turpentine, copaiba, oleoresin, pint oil, cannabis oil, coriander oil), and (7) converting such terpenes to one or more terpene alcohols (e.g., citronellol, isocitronellol, geraniol, nerol, menthol, myrcenol, linalool, thymol, α-terpineol, β-terpineol, γ-terpineol, borneol, farnesol, nerolidol, and carotol).

[0108] In another aspect, the present invention provides a composition comprising Compound 1 or any of 1.1-1.75, optionally mixed with one or more pharma- ceutically acceptable, cosmetically acceptable, or industrially acceptable additives or carriers, such as solvents, oils, surfactants, emollients, diluents, glidants, abrasives, wetting agents, polymers, plasticizers, catalysts, antioxidants, colorants, flavors, fragrances, antiperspirants, antibacterial agents, antifungal agents, hydrocarbons, stabilizers, or viscosity control agents. In some embodiments, the composition is a pharmaceutical composition or a cosmetic composition or a sunscreen composition or a plasticizing composition or a lubricant composition or a personal care composition (e.g., a soap, a skin cream or lotion, a balm, a shampoo, a body wash, a moisturizing cream, a deodorant, an antiperspirant, an aftershave, a cologne, a perfume, or other hair care or skin care product) or a cleaning composition (e.g., a surface cleaner, a metal cleaner, a wood cleaner, a glass cleaner, a body cleaner such as a soap, a dishwashing surfactant, or a laundry surfactant) or a deodorant spray.

[0109] In a preferred embodiment, such compositions include a compound of the present invention having an isodecyl group. In a particularly preferred embodiment, such compositions also include other additives having a decyl or isodecyl group, such as decyl or isodecyl alcohol, decane or isodecanoic acid, decyl or isodecyl ether or decyl or isodecyl ester. For example, such compositions may include a combination of one or more of the isodecyl compounds of Examples 1-13.

[0110] The compounds of the present invention, e.g., Compound 1 et seq., may be used with, for example, perfumes, soaps, insect repellents and insecticides, surfactants, household cleaners, air fresheners, room sprays, pomanders, candles, cosmetics, lotions, pre- and after-shave lotions, talcum powders, hair care products, body deodorants, antiperspirants, shampoos, colognes, shower gels, hairsprays, and pet litters.

[0111] Perfume materials and ingredients and perfume ingredient mixtures which may be used in combination with the compounds of the present invention to prepare perfume compositions include, but are not limited to, extracts, animal products and natural products including essential oils, absolutes, resinoids, resins and concretes and synthetic perfume materials and animal products including, but not limited to, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, phenols, ethers, lactones, furan skeletons, nitriles, acids and hydrocarbons including both saturated and unsaturated compounds and aliphatic carbocyclic and heterocyclic compounds.

[0112] In certain embodiments, the present invention provides personal care compositions including, but not limited to, soaps (liquid or solid), body washes, skin and hair wipes, skin creams and lotions (e.g., facial creams and lotions, face oils, eye creams, other anti-wrinkle products), ointments, sunscreens, emulsions, hair shampoos and / or conditioners, deodorants, antiperspirants, other conditioning products for hair, skin and nails (e.g., shampoos, conditioners, hairsprays, hair styling gels, hair mousses), decorative cosmetics (e.g., nail polish, eyeliner, mascara, lipstick, foundation, concealer, blusher, bronzer, eye shadow, lip liner, lip balm), and skin cosmetics.

[0113] In certain embodiments, the personal care composition may include organically sourced ingredients, vegan ingredients, gluten-free ingredients, eco-friendly ingredients, natural ingredients (e.g., soybean oil, beeswax, rosemary oil, vitamin E, coconut oil, herbal oils, etc.), comedogenic ingredients, naturally occlusive plant-based ingredients (e.g., cocoa butter, shea butter, mango butter), non-comedogenic ingredients, bactiol (a plant-derived compound used as a hypoallergenic natural alternative to retinol), color actives (e.g., pigments and dyes); therapeutic actives (e.g., vitamins, alpha hydroxy acids, corticosteroids, amino acids, collagen, retinoids, antimicrobial compounds), sunscreen ingredients and / or UV absorbing compounds, reflective compounds, oils (e.g., castor oil and olive oil or high viscosity oils), film formers, high molecular weight esters, antiperspirant actives, glycol solutions, water, alcohols, emulsifiers, gelling agents, emollients, water, polymers, hydrocarbons, conditioning agents, and / or fatty esters.

[0114] In some embodiments, the composition is gluten-free.

[0115] In some embodiments, the composition is formulated as oil-in-water emulsion or water-in-oil emulsion.In some embodiments, the composition can further comprise one or more hydrocarbons, such as heptane, octane, nonane, decane, undecane, dodecane, isododecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, henicosane, docosane and tricosane and any of its saturated linear or saturated branched isomers.

[0116] As used herein, the terms "for example," "for example," "such as," or "including" refer to the introduction of examples that further clarify a more general subject matter. These examples are provided only to aid in understanding the invention and are not intended to be limiting in any way. Furthermore, as used herein, the terms "may," "optionally," "optionally," or "may optionally" mean that the subsequently described circumstance may or may not occur, such that the description includes cases where the circumstance occurs and cases where the circumstance does not occur. For example, the term "optionally present" means that an item may or may not be present, and thus the description includes cases where the item is present and cases where the item is not present.

[0117] As used herein, the terms "having the formula" or "having the structure" are not intended to be limiting and are used in the same manner that the term "comprising" is generally used.

[0118] In the present specification, in some cases, the structural formula of a compound may conveniently represent a certain isomer, but the present invention includes all isomers, such as geometric isomers, optical isomers, etc., based on asymmetric carbons, stereoisomers, tautomers, etc. Furthermore, the compounds represented by the formulas described herein may have crystalline polymorphism. It is noted that any crystalline form, crystalline form mixture, or anhydride or hydrate thereof are included within the scope of the present invention.

[0119] "Tautomers" refer to compounds whose structures differ significantly in atomic arrangement, but which exist in easy and rapid equilibrium. It is understood that the compounds of the invention may be described as different tautomers. When a compound has tautomeric forms, it should also be understood that all tautomeric forms are intended to be within the scope of the invention, and the name of the compound does not exclude any tautomeric form. Additionally, although one tautomer may be described, the invention includes all tautomeric forms of the compound.

[0120] As used herein, the term "salt" includes hydrochloride, hydrobromide, phosphate, sulfate, hydrogen sulfate, alkylsulfonate, arylsulfonate, acetate, benzoate, citrate, maleate, fumarate, succinate, lactate and tartrate salts; Na + , K + , Li + Alkali metal cations such as Mg 2+ or Ca 2+ or organic amine salts or organic phosphonium salts.

[0121] All percentages used herein are by volume unless otherwise specified.

[0122] All percentages used herein are in molar terms unless otherwise specified.

[0123] While specific embodiments of the invention have been described with reference to preparations and schemes, it is to be understood that such embodiments are merely illustrative and set forth merely a few of the many possible specific embodiments which may represent applications of the principles of the invention. Various changes and modifications will be apparent to those skilled in the art upon consideration of the benefit of the invention and are deemed to be within the spirit and scope of the invention as further defined in the appended claims. EXAMPLES

[0124] Having now generally described, the following non-limiting examples are provided to further illustrate the invention.

[0125] The compounds disclosed herein can be prepared via several direct etherification or transetherification processes. One preferred method involves the use of a combination of MgSO4 and H2SO4 in a route similar to that used in the transesterification by Wright, et al. in Tetrahedron Letters, Vol. 38, No. 42, pp. 7345-7348, 1997. However, in an even more preferred method, the MgSO4 / H2SO4 catalyst is pre-prepared from a non-polar organic solvent such as heptane.

[0126] In this approach, MgSO4 is suspended in a solution with stirring under an inert atmosphere (e.g., 10 g MgSO4 in 40 g heptane) and concentrated H2SO4 is added dropwise to the solution. The mixture is stirred for a period of time, e.g., 15 minutes or 1 hour, and then the heptane phase is filtered to obtain a white solid powder that can be vacuum dried or blown dry with an inert atmosphere, e.g., nitrogen or argon. This white solid can then be used as a powerful esterification catalyst, particularly suitable for producing tertiary esters from tertiary alcohols and / or appropriately substituted olefins.

[0127] Example 1. Isodecyl palmitoyl ether (2,6-dimethyloctan-1-yl palmitoyl ether) In a 5 liter glass reaction vessel under inert atmosphere, 2,6-dimethyloctanol (1 equivalent) and palmitoyl alcohol (1 equivalent) are combined in hexane or heptane solvent and 50 grams of MgSO4 / H2SO4 solid catalyst is added per kilogram of 2,6-dimethyloctanal. The solution is then stirred at 80°C for 8 hours with nitrogen bubbling. The gas outlet of the glass reactor is connected to a condenser to condense and collect excess methanol. The reaction is then brought to room temperature and then 100 grams of potassium carbonate is slowly added to the solution. It is then stirred for 2 hours and filtered. The excess 2,6-dimethyloctanol and solvent are removed under reduced pressure and the desired product is further isolated by distillation.

[0128] Example 2. Isodecyl oleyl ether (2,4-dimethyloctan-2-yl oleyl ether) In a 5 liter glass reaction vessel, under inert atmosphere, 2,4-dimethyloctan-2-ol (1 equivalent) and oleyl alcohol (1 equivalent) are combined in hexane or heptane solvent and 50 grams of MgSO4 / H2SO4 solid catalyst is added per kilogram of 2,4-methyloctan-2-ol. The solution is then stirred at 100°C for 8 hours with nitrogen bubbling. The gas outlet of the glass reactor is connected to a condenser to condense and collect excess water. The reaction is then brought to room temperature and then 400 grams of potassium carbonate is slowly added to the solution. It is then stirred for 2 hours and filtered. The excess 2,4-methyloctan-2-ol and solvent are removed under reduced pressure and the desired product is further isolated by distillation.

[0129] Example 3. Isodecyl palmitoyl ether (3,7-dimethyloctan-1-yl palmitoyl ether) In a 5 liter glass reaction vessel under inert atmosphere, 3,7-dimethyl-1-octanol (also known as dihydrocitronellol or tetrahydrogeraniol) (1 equivalent) and palmitoyl alcohol (1 equivalent) are combined in hexane or heptane solvent and 50 grams of MgSO4 / H2SO4 solid catalyst is added per kilogram of 3,7-dimethyl-1-octanol. The solution is then stirred at 80°C for 8 hours with nitrogen bubbling. The gas outlet of the glass reactor is connected to a condenser to condense and collect excess methanol. The reaction is then brought to room temperature and then 100 grams of potassium carbonate is slowly added to the solution. It is then stirred for 2 hours and filtered. The excess 3,7-dimethyl-1-octanol and solvent are removed under reduced pressure and the desired product is further isolated by distillation.

[0130] Example 4. Isodecyl oleyl ether (3,7-dimethyloctan-1-yl oleyl ether) In a 5 liter glass reaction vessel, under inert atmosphere, 3,7-dimethyl-1-octanol (1 equivalent) and oleyl alcohol (1 equivalent) are combined in hexane or heptane solvent and 50 grams of MgSO4 / H2SO4 solid catalyst is added per kilogram of 3,7-dimethyl-1-octanol. The solution is then stirred at 100°C for 8 hours with nitrogen bubbling. The gas outlet of the glass reactor is connected to a condenser to condense and collect excess water. The reaction is then brought to room temperature and then 400 grams of potassium carbonate is slowly added to the solution. It is then stirred for 2 hours and filtered. The excess 3,7-dimethyl-1-octanol and solvent are removed under reduced pressure and the desired product is further isolated by distillation.

[0131] Example 5. Isodecyl lauryl ether (3,7-dimethyloctane-1-yl lauryl ether) In a 5 liter glass reaction vessel, under inert atmosphere, 3,7-dimethyl-1-octanol (1 equivalent) and lauryl alcohol (1 equivalent) are combined in hexane or heptane solvent and 50 grams of MgSO4 / H2SO4 solid catalyst is added per kilogram of 3,7-dimethyl-1-octanol. The solution is then stirred at 100°C for 8 hours with nitrogen bubbling. The gas outlet of the glass reactor is connected to a condenser to condense and collect excess water. The reaction is then brought to room temperature and then 400 grams of potassium carbonate is slowly added to the solution. It is then stirred for 2 hours and filtered. The excess 3,7-dimethyl-1-octanol and solvent are removed under reduced pressure and the desired product is further isolated by distillation.

[0132] Example 6. Isodecyl palmitoyl ether (3,7-dimethyloctan-3-yl palmitoyl ether) In a 5-liter glass reaction vessel, under inert atmosphere, 3,7-dimethyl-3-octanol (also known as tetrahydrolinalool) (1 equivalent) and palmitoyl alcohol (1 equivalent) are combined in hexane or heptane solvent, and 50 grams of MgSO4 / H2SO4 solid catalyst is added per kilogram of 3,7-dimethyl-1-octanol. The solution is then stirred at 80°C for 8 hours with nitrogen bubbling. The gas outlet of the glass reactor is connected to a condenser to condense and collect excess methanol. The reaction is then brought to room temperature, and 100 grams of potassium carbonate are then slowly added to the solution. It is then stirred for 2 hours and filtered. The excess 3,7-dimethyl-3-octanol and solvent are removed under reduced pressure, and the desired product is further isolated by distillation.

[0133] Example 7. Isodecyl palmitoyl ether (2,6-dimethyloctan-2-yl palmitoyl ether) 2,6-Dimethyloctan-2-ol (tetrahydromyrcenol) (1 equivalent) is combined with palmitoyl alcohol (1 equivalent) in hexane or heptane solvent and 50 grams of MgSO4 / H2SO4 solid catalyst is added per kilogram of 2,6-dimethyloctanal in a 5 liter glass reaction vessel under inert atmosphere. The solution is then stirred at 80°C for 8 hours with nitrogen bubbling. The gas outlet of the glass reactor is connected to a condenser to condense and collect excess methanol. The reaction is then brought to room temperature and then 100 grams of potassium carbonate is slowly added to the solution. It is then stirred for 2 hours and filtered. The excess 2,6-dimethyloctan-2-ol and solvent are removed under reduced pressure and the desired product is further isolated by distillation.

[0134] Example 8. Tetrahydromyrcene from tetrahydromyrcenol (2,6-dimethyloct-2-ene as the major isomer) 300 g of tetrahydromyrcenol is combined with 20 g of Amberlyst H+ resin in a round bottom flask equipped with a stir bar and distillation accessories. The material is heated to 80° C. under reduced pressure with a light nitrogen bubbling rig. Over a period of approximately 6 hours, H2O is distilled off with traces of organics synchronous with the vapor phase. When H2O is no longer present in the distillate and GC FID indicates complete conversion, the reaction is stopped and allowed to come to room temperature. The reaction mixture is then filtered through a pad of celite and silica to remove any residual catalyst. 181 g (69% yield) of a clear, low viscosity liquid is obtained as a mixture of olefin isomers. The major isomers show: 1 H NMR (CDCl3) δ:0.87-0.93 (m, 6H); 1.11-1.24 (m, 2H); 1.31-1.43 (m, 3H); 1.63-1.65 (s, 3H); 1.71-1.73 (s, 3H); 1.91-2.10 (m, 2H); 5.11-5.18 (m, 1H)

[0135] Example 9. Tetrahydromyrcene from tetrahydrolinalool ((Z)-3,7-dimethyloct-3-ene as the major isomer) 400 g of tetrahydrolinalool is combined with 40 g of Amberlyst H+ resin in a round bottom flask equipped with a stir bar and distillation accessories. The material is heated to 80° C. under reduced pressure with a light nitrogen bubbling rig. Over a period of approximately 5 hours, H2O is distilled off with traces of organics synchronous with the vapor phase. When H2O is no longer present in the distillate and GC FID indicates complete conversion, the reaction is stopped and allowed to come to room temperature. The reaction mixture is then filtered through a pad of celite and silica to remove any residual catalyst. 234 g (66% yield) of a clear, low viscous liquid is obtained as a mixture of olefin isomers. 1 H NMR (CDCl3) δ:0.86-0.94 (m, 9H); 0.96-1.03 (m, 1H); 1.12-1.28 (m, 2H); 1.34-1.45 (m, 1H); 1.52-1.72 (m, 3H); 1.94-2.09 (m, 3H); 5.08-5.26 (m, 1H)

[0136] Example 10. Diisodecyl ether (2,6-dimethyloctan-2-yl 3,7-dimethyloctan-1-yl ether) 3,7-Dimethyl-1-octanol (also known as tetrahydrogeraniol) (20 g, 0.126 mol) is combined with tetrahydromyrcene (2,6-dimethyloct-2-ene, from Example 8) (40 g, 0.285 mol). 5.0 g of Amberlyst H+ resin is then added to the reaction and stirred in a round bottom flask equipped with a stir bar at room temperature for 2 days. The reaction mixture is then filtered through a pad of silica and celite. The clear liquid is placed under distillation to remove any residual 3,7-dimethyl-1-octanol and tetrahydromyrcene. 31.8 g (84.4% of theoretical) is obtained as a clear low-viscosity liquid. 1 H NMR (CDCl3), δ:0.83-0.87 (m, 15H); 1.05-1.17 (m, 8H); 1.20-1.38 (m, 12H); 1.39-1.45 (m, 2H); 1.47-1.57 (m, 3H); 3.25-3.36 (m, 2H)

[0137] Example 11. Diisodecyl ether (3,7-dimethyloctan-3-yl 3,7-dimethyloctan-1-yl ether) 3,7-Dimethyl-1-octanol (1.0 equivalent) is combined with tetrahydromyrcene (3,7-dimethyloct-3-ene, from Example 9) (approximately 2.2 equivalents). The reaction is then added with 1.0 g of Amberlyst H+ resin per 5 grams of alcohol and stirred for 3 days at room temperature in a round bottom flask equipped with a stir bar. The reaction mixture is then filtered through a pad of silica and celite. The clear liquid is placed under distillation to remove any remaining 3,7-dimethyl-1-octanol and tetrahydromyrcene.

[0138] Example 12: Isodecyl cetyl ether Tetrahydromyrcene (2,6-dimethyloct-2-ene, from Example 8) (50 g, 0.357 mol) is combined with cetyl alcohol (21.6 g, 0.089 mol) at room temperature, then the mixture is warmed to 40° C. to melt and dissolve the cetyl alcohol. 4 g of Amberlyst H+ resin is then added to the reaction and stirred overnight. NMR and TLC show that the reaction is nearly complete. The reaction is stirred for 1 day, then worked up by passing the warm mixture through a pad of Celite to remove the catalyst, then distilling off the excess tetrahydromyrcene. 31 g of a clear, free-flowing oil is obtained (91% of theory). 1 H NMR (CDCl3): δ 0.82-0.92 (m, 9H); 1.05-1.15 (m, 8H); 1.23-1.38 (m, 32H); 1.38-1.45 (m, 3H); 1.47-1.55 (m, 2H)

[0139] Example 13: Isodecyl behenyl ether Tetrahydromyrcene (3,7-dimethyloct-3-ene, from Example 9) (75 g, 0.53 mol) is combined with behenyl alcohol (43.6 g, 0.134 mol) at room temperature and the mixture is then warmed to 60° C. to melt and dissolve the behenyl alcohol. 10 g of Amberlyst H+ resin is then added to the reaction and stirred overnight. NMR and TLC indicate that the reaction is greater than 50% complete. The reaction is stirred for 1 day and then worked up by passing the warm mixture through a pad of Celite to remove the catalyst and then distilling off the excess tetrahydromyrcene to give a semi-soft white solid, 49 g (83% of theory).

[0140] The compounds of the above examples are believed to provide a number of improved benefits over existing compounds used for the same purpose. For example, these compounds may provide one or more of: low melting point, (b) good lubricity, (c) good spreading (e.g., good spontaneous spreading on skin), (d) high refractive index, (e) good hydrolytic stability, and (f) good enzyme stability.

[0141] While the invention has been described in conjunction with the above embodiments, it should be understood that the above descriptions and examples are intended to be illustrative and not limiting of the scope of the invention. Other aspects, advantages and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains.

Claims

1. Compounds of general formula (I), in free or salt form: 【Chemistry 1】 [wherein A is a terpene alcohol or derivative thereof core, and B is (i) a saturated or unsaturated hydrocarbon chain of a natural or unnatural fatty alcohol or a derivative thereof; or (ii) a core of a terpene alcohol or a derivative thereof, which may be the same or different as the substituent A; It is. Terpene alcohol ether compound.

2. 2. The compound of claim 1, wherein A is a terpene alcohol or derivative thereof core, wherein the terpene is a monoterpene, sesquiterpene, diterpene, sesterterpene or triterpene.

3. 2. The compound of claim 1, wherein A is a core of a terpene alcohol or derivative thereof, wherein the terpene alcohol is selected from citronellol, isocitronellol, geraniol, nerol, menthol, myrcenol, linalool, thymol, a-terpineol, b-terpineol, g-terpineol, borneol, farnesol, nerolidol and carotol.

4. 4. The compound of claim 3, wherein the terpene alcohol is selected from citronellol, myrcenol, linalool and farnesol.

5. 2. The compound of claim 1, wherein the terpene alcohol or derivative thereof is fully saturated (e.g., the terpene alcohol is a fully saturated monoterpene derivative, e.g., an isodecyl moiety).

6. A 【Chemistry 2】 2. The compound of claim 1 selected from the group consisting of:

7. 2. The compound of claim 1, wherein B is a saturated or unsaturated hydrocarbon chain of a C4 to C28 fatty alcohol or a derivative thereof (ie, group B has a C4 to C28 hydrocarbon chain).

8. 2. The compound of claim 1, wherein B is an unsaturated, e.g., mono-, di- or tri-unsaturated hydrocarbon chain.

9. B is -(CH ２ ) ｘ CH=CH(CH ２ ) ｙ CH ３ 9. The compound of claim 8, wherein x is an integer from 4 to 19 (e.g., 3, 4, 5, 8, or 12) and y is an integer from 1 to 8 (e.g., 1, 2, 3, 4, 5, 7, or 8).

10. B is a saturated hydrocarbon chain, for example, B is -(CH ２ ) ｘ CH ３ 2. The compound of claim 1, wherein x is an integer from 4 to 27 (e.g., 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, or 27).

11. The compound 【Chemistry 3】 wherein x is an integer selected from 4, 5, 6, 7, 8, 9, 11, 13, 15 and 17.

2. The compound of claim 1 selected from the group consisting of:

12. The group A is, for example, an isodecyl group selected from 2,4-dimethyloctan-2-yl, 2,6-dimethyl-octan-1-yl, 2,6-dimethyloctan-2-yl, 3,7-dimethyloctan-1-yl and 3,7-dimethyloctan-3-yl, and optionally the group B is CH ３ (CH ２ ) １５ -, CH ３ (CH ２ ) １１ - or cis-CH ３ (CH ２ ) ７ CH=CH(CH ２ ) ８ -, a compound of claim 1.

13. The compound 【Chemistry 4】 【Chemistry 5】 2. The compound of claim 1 selected from the group consisting of:

14. 2. The compound of claim 1, wherein B is a terpene alcohol or derivative thereof core, wherein the terpene is a monoterpene, sesquiterpene, diterpene, sesterterpene or triterpene.

15. 2. The compound of claim 1, wherein B is a core of a terpene alcohol or derivative thereof, wherein the terpene alcohol is selected from citronellol, isocitronellol, geraniol, nerol, menthol, myrcenol, linalool, thymol, a-terpineol, b-terpineol, g-terpineol, borneol, farnesol, nerolidol and carotol.

16. 16. The compound of claim 15, wherein the terpene alcohol is selected from citronellol, myrcenol, linalool and farnesol.

17. 15. The compound of claim 14, wherein the terpene alcohol or derivative thereof is fully saturated (e.g., the terpene alcohol is a fully saturated monoterpene derivative, e.g., an isodecyl moiety).

18. B 【Chemistry 6】 2. The compound of claim 1 selected from the group consisting of:

19. 2. The compound of claim 1, wherein the group B is an isodecyl group, e.g. selected from 2,4-dimethyloctan-2-yl, 2,6-dimethyl-octan-1-yl, 2,6-dimethyloctan-2-yl, 3,7-dimethyloctan-1-yl and 3,7-dimethyloctan-3-yl, and optionally the groups A and B are each independently an isodecyl group, e.g. A and B are each independently selected from 2,4-dimethyloctan-2-yl, 2,6-dimethyl-octan-1-yl, 2,6-dimethyloctan-2-yl, 3,7-dimethyloctan-1-yl and 3,7-dimethyloctan-3-yl.

20. The compound 【Chemistry 7】 2. The compound of claim 1 selected from the group consisting of:

21. 21. A method for making a compound of any of claims 1 to 20, comprising reacting a compound of formula A with a compound of formula B or an activated halide or sulfonate thereof in a condensation reaction to form a compound of formula I. 【Chemistry 8】 [In the formula, the substituents A and B are as defined in any one of claims 1 to 20.]

22. 22. The process of claim 21, wherein the reaction comprises a mixture of sulfuric acid and magnesium sulfate, optionally in a hydrocarbon solvent such as heptane.

23. 22. The process of claim 21, wherein the reacting comprises adding solid magnesium sulfate / sulfuric acid adduct as a catalyst to a mixture of the compound of formula A and the compound of formula B, optionally without an additional solvent.

24. 21. A method for preparing a compound of any of claims 1-20, comprising reacting a compound of formula E with a compound of formula B in an electrophilic alkene addition reaction to form a compound of formula I, wherein the compound of formula E can be formed by dehydration of a compound of formula A. 【Chemistry 9】 wherein the substituents A and B are as defined in any one of claims 1 to 20, and the structure of formula E is attached to the structure of formula A such that removal of the OH group and the H atom from the adjacent carbon atom results in a compound of formula E.

25. A composition comprising a compound of any of claims 1 to 20, optionally in admixture with one or more pharma- ceutically acceptable, cosmetically acceptable or industrially acceptable excipients or carriers, such as solvents, oils, surfactants, emollients, diluents, glidants, abrasives, humectants, polymers, plasticizers, catalysts, antioxidants, colorants, flavors, fragrances, antiperspirants, antibacterial agents, antifungal agents, hydrocarbons, stabilizers or viscosity control agents.

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