Citronellol Alkoxylate Surfactant

Abstract

The present invention relates to novel derivatives of citronellol and polycitronellol, in particular alkoxylated derivatives of citronellol and polycitronellol, as well as methods for their preparation, compositions containing them and methods for their use, in particular as surfactants.

Description

[Technical field]

[0001] Cross-references to related applications This application is an international patent application claiming priority to and the benefit of U.S. Provisional Application No. 63 / 222,170, filed June 15, 2021, the contents of which are incorporated herein by reference in their entirety.

[0002] The present invention relates to novel derivatives of citronellol and polycitronellol, in particular propoxylated and ethoxylated derivatives of citronellol and polycitronellol, as well as methods for their preparation, compositions containing them, and methods for their use, in particular as surfactants. [Background technology]

[0003] Surfactants are a multi-million dollar annual industry. Surfactants are generally molecules with at least one strong polar or ionic functional group and at least one strong non-polar or hydrophobic functional group, generally located at opposite ends of a mostly linear molecule. Thus, one end of the surfactant molecule is usually hydrophilic and the other end is hydrophobic. The unique chemical property of surfactants is their ability to dissolve in both aqueous and non-polar (hydrophobic) media due to this amphiphilic split structure. Surfactants are used in a variety of products and are often used in conjunction with aqueous and hydrophobic environments, especially when used in soaps and cleaning products. Functionally, surfactants are often used as wetting agents, detergents, soaps, emulsifiers, foaming agents and dispersants. They are commonly used in a variety of multi-component compositions to stabilize interactions between hydrophobic and hydrophilic components.

[0004] There are a variety of different classes of commercially available surfactants, many of which are derived from petrochemical feedstocks. These include anionic surfactants, such as sulfates, sulfonates, phosphates and carboxylates; cationic surfactants, such as quaternary amines; zwitterionic surfactants, such as betaines, sultaines and amine oxides; and nonionic surfactants, such as alkoxylates and polyhydroxy fatty acid esters.

[0005] The use of alkoxylates, i.e., poly(ethylene glycol) or poly(propylene glycol) moieties, is common to several classes of surfactants. These include alkylphenol ethoxylates and propoxylates, such as nonylphenol ethoxylate, fatty alcohol ethoxylates and propoxylates, e.g., cetyl propoxylate, fatty acid ethoxylates and propoxylates, fatty amine ethoxylates and propoxylates, monoalkanolamide ethoxylates, sorbitan ester ethoxylates, ethoxylated glycosides and glycerol esters (e.g., glycerol propoxylate), and polyether polymers, such as poly(ethylene oxide), poly(propylene oxide), and ethylene oxide / propylene oxide copolymers.

[0006] Many alkoxylated surfactants are increasingly coming under strict scrutiny due to their toxicity or lack of biodegradability leading to environmental persistence. For example, nonylphenol ethoxylates, once very common in detergents, textile manufacturing and land drilling, have been banned in Europe since 2005 due to their environmental toxicity and persistence. However, in 2013, nonylphenol ethoxylates still account for almost half of the world's nonionic surfactant products, despite increasing calls for a ban at the international level.

[0007] There is therefore an urgent need for alkoxylated surfactants, in particular new surfactants with improved stability, improved biodegradability and / or improved environmental impact. It is particularly important that new surfactants be available that are sourced from renewable resources.

[0008] Terpene alcohols such as citronellol are renewable resources. Citronellol can be naturally sourced from plant species such as citronella grass, or produced semi-synthetically by hydrogenation of geraniol or nerol, which are derived from geranium grass and lemongrass, respectively. Geraniol and nerol, as well as other related terpenes, can also be derived from the pyrolysis products of β-pinene and are widely available from many plants, such as cumin, hemp, hops, cannabis, pineapple fruit, and Clausena anisata.

[0009] Terpene alcohol derivatives include polymers and oligomers of terpene alcohols. For example, citronellol has the following structure: [ka] [In the formula, n is an integer of 0 to 20 (e.g., 0 to 3)] The polyether polymers are formed into useful oligomeric and polymeric products having the following properties: Citronellol dimers, trimers and other oligomers have been published, for example in US Patent Application No. 2017 / 0283553, US Patent Application No. 2020 / 0165383 and US Patent Application No. 2020 / 0392287, the contents of which are incorporated herein by reference in their entirety. One of the benefits of this class of polymers is the reversibility of the polymerization chemistry that produces the polymer from citronellol. As a result, these polyether polymers are biodegradable and spontaneously revert back to citronellol. Thus, polycitronellol-based alkoxylated polymers are also believed to be biodegradable, which provides a more environmentally friendly and renewable resource. Summary of the Invention

[0010] In a first aspect, the present invention provides citronellol and polycitronellol alkoxylate surfactants derived from citronellol monomers or polycitronellol oligomers and their derivatives. These compounds are useful in a wide variety of compositions and applications. For example, these compounds can be used as wetting agents, detergents, soaps, emulsifiers, foaming agents, dispersants, buffers, preservatives, and are particularly useful as ingredients in personal care compositions, cosmetic compositions, food compositions, and crop care compositions.

[0011] In a second aspect, the present invention provides methods for preparing such compounds.

[0012] In a third aspect, the present invention provides compositions and products comprising such compounds. In some embodiments, the compounds are useful in a variety of applications, such as, or as ingredients in, cosmetics, soaps, hair care products, fragrances, sunscreens, household cleaning products (e.g., laundry detergents), plasticizers, paints, coatings, lubricants, surfactants, pesticides, and herbicides.

[0013] Detailed Description of the Invention As used herein, the term "polycitronellol" refers to a compound having the following structure: [ka] [In the formula, n is an integer of 0 to 20 (e.g., 0 to 3)] Polycitronellol refers to a saturated or unsaturated polymer having the formula: ##STR00001## Other polymeric derivatives of citronellol (i.e., having different structures or bond properties) are possible, but are not encompassed by the term "polycitronellol" as used herein. The polycitronellol polymers described herein are derived from the polymerization of alcohol and alkene groups of citronellol via an alkene addition reaction. These polymers may undergo depolymerization based on an elimination mechanism to give alcohol and alkene products.

[0014] In a first embodiment of the first aspect, the present invention provides a compound of general formula (IA) (Compound 1A) or a compound of general formula (IB) (Compound 1B), each in free or salt form: : [ka] [ka] [During the ceremony, n is an integer from 0 to 20 (e.g., 0 to 10); m is an integer from 1 to 100 (e.g., 25 to 75); X is selected from a bond, CH2, CH2CH2, CH2C(O)-, -CH2CH2C(O)-, CH2C(O)O-, -CH2CH2C(O)O-, -C(O)-, -C(O)-O-, -C(O)-N(R)-, -S(O)-, -S(O2)-, -S(O2)-O-, and -S(O2)-N(R)-; Y is selected from CH2, CH2CH2, -C(O)-, -C(O)-O-, -C(O)-N(R)-, -S(O)-, -S(O2)-, -S(O2)-O-, and -S(O2)-N(R)-; R is selected from H and C1-C6 alkyl (e.g., methyl) optionally substituted with one or more OH; R 1 is a bond, C1-C 20 Alkyl, C2-C 20 Alkenyl and C6-C 20 aryl; R 2 are H, OH, NH2, NH(C1-C 12 Alkyl), N(C1-C 12 Alkyl)(C1-C 12 alkyl), -COOH, C1-C6 alkyl, -O-C1-C 12 Alkyl, -O-C6-C 20 Aryl, -C(O)-C1-C 12 Alkyl, -C(O)-C6-C 20 Aryl, -OC(O)-C1-C 12 Alkyl, -OC(O)-C6-C20 Aryl, -C(O)-O-C1-C 12 Alkyl, -C(O)-O-C6-C 20 Aryl, -OC(O)-O-C1-C 12 Alkyl, -OC(O)-O-C6-C 20 Aryl, -C(O)-NH2, -C(O)-NH(C1-C 12 alkyl), -C(O)-N(C1-C 12 Alkyl)2, -C(O)-NH-aryl, -OC(O)-NH(C1-C 12 alkyl), -OC(O)-N(C1-C 12 Alkyl)2, -OC(O)-NH-Aryl, -SO3H, -SO2NH2, -S(O)-C1-C 12 Alkyl, -S(O)-C6-C 20 Aryl, -S(O)2-C1-C 12 Alkyl, -S(O)2-C6-C 20 Aryl, -OS(O)2-C1-C 12 Alkyl, -OS(O)2-C6-C 20 Aryl, -S(O)2-O-C1-C 12 Alkyl, -S(O)2-O-C6-C 20 Aryl, -S(O)2-NH(C1-C 12 alkyl), -S(O)2-N(C1-C 12 alkyl), -OS(O)-OH, -OP(O)(OH) and -P(O)(OH); Here, C1-C 12 Alkyl and C6-C 20 The aryl moieties are independently halo (-F, -Cl, -Br or -I), -CN, OH, NH, NH(C1-C 12 Alkyl), N(C1-C 12 Alkyl)(C1-C 12 alkyl), -COOH, -O-C1-C 12 Alkyl, -C(O)-C1-C 12 Alkyl, -OC(O)-C1-C 12 Alkyl, -C(O)-O-C1-C 12and optionally further substituted with one or more groups selected from alkyl, SO3H, -SO2NH2, -OS(O)2-OH, -OP(O)2(OH) and -P(O)(OH).

[0015] In a further embodiment of the first aspect, the present invention provides: 1.1 Compounds of formula IA. 1.2 Compound of formula IB. 1.3 Compound 1.2, wherein n is an integer from 0 to 10, for example, from 0 to 8, or from 0 to 6 or from 0 to 5, or is any of 0, 1, 2, 3 or 4. 1.4 Compound 1.2, wherein n is 0, 1, 2 or 3. 1.5 Compound 1.2, where n is 0. 1.6 Compound 1.2, where n is 1. 1.7 Any of compounds 1.1 to 1.6, wherein m is an integer from 1 to 75, for example, 1 to 25, 25 to 50, 50 to 75, 25 to 75, 1 to 10, 11 to 20, 21 to 30, 31 to 40, 41 to 50, 51 to 60, 61 to 75, or any combination thereof. 1.8 Any of compounds 1.1 to 1.7, wherein X is selected from a bond, CH2, -C(O)-, -C(O)-O-, and -C(O)-N(R)-. 1.9 Any of compounds 1.1 to 1.7, wherein X is selected from -S(O)-, -S(O2)-, -S(O2)-O-, and -S(O2)-N(R)-. 1.10 Any of compounds 1.1 to 1.7, wherein X is selected from a bond, CH2, -C(O)-, and -C(O)-O-. 1.11 Any of compounds 1.1 to 1.7, wherein X is a bond. 1.12 Any of compounds 1.1 to 1.11, wherein Y is selected from CH2, CH2CH2, -C(O)-, -C(O)-O-, and -C(O)-N(R)-. 1.13 Any of compounds 1.1 to 1.11, wherein Y is selected from -S(O)-, -S(O2)-, -S(O2)-O-, and -S(O2)-N(R)-. 1.14 Any of compounds 1.1 to 1.11, wherein Y is selected from CH2, CH2CH2, and -C(O)-. 1.15 Any of compounds 1.1 to 1.11, wherein Y is selected from CH2 and CH2CH2. 1.16 Any of compounds 1.1 to 1.13, wherein R is H. 1.17 Any of compounds 1.1 to 1.13, wherein R is C1-C6 alkyl (e.g., methyl, ethyl, propyl). 1.18 Any of compounds 1.1-1.13, wherein R is C1-C6 alkyl substituted with one or more OH, e.g., R is selected from hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl. 1.19 Compound 1.18, wherein R is selected from -CH2CH2OH, -CH(OH)CH3, -CH(OH)CH2(OH), -CH2CH2CH2OH, -CH2CH(OH)CH3, -CH(OH)CH2CH3, -CH2CH(OH)CH2OH, -CH(OH)CH2CH2OH, -CH(OH)CH(OH)CH3 and -CH(OH)CH(OH)CH2OH. 1.20 R 1 is bonded, C1-C 20 Alkyl and C2-C 20 Any of compounds 1.1 to 1.19, wherein the compound is selected from alkenyl. 1.21 R 1 C 6-18 Alkyl, e.g., C 6-12 Alkyl, C 12-18 Alkyl, C 6-10 Alkyl, C 10-14 Alkyl or C 14-18 Compound 1.20, which is an alkyl. 1.22 R 1 C 6-18 Alkenyl, e.g., C 6-12 Alkenyl, C 12-18 Alkenyl, C 6-10 Alkenyl, C 10-14 Alkenyl or C 14-18alkenyl, each of which may optionally be mono- or di-unsaturated. 1.23 R 1 C 1-3 Compound 1.20, which is alkyl, for example, CH2 or CH2CH2. 1.24 R 2 H, OH, NH2, NH(C1-C 12 Alkyl), N(C1-C 12 Alkyl)(C1-C 12 Any of compounds 1.1 to 1.23, wherein the compound is selected from -COOH. 1.25 R 2 is C1-C6 alkyl, -O-C1-C 12 Alkyl, -O-C6-C 20 Aryl, -C(O)-C1-C 12 Alkyl, -C(O)-C6-C 20 Aryl, -OC(O)-C1-C 12 Alkyl, -OC(O)-C6-C 20 Aryl, -C(O)-O-C1-C 12 Alkyl, -C(O)-O-C6-C 20 Aryl, -OC(O)-O-C1-C 12 Alkyl, -OC(O)-O-C6-C 20 Aryl, -C(O)-NH2, -C(O)-NH(C1-C 12 alkyl), -C(O)-N(C1-C 12 Alkyl)2, -C(O)-NH-aryl, -OC(O)-NH(C1-C 12 alkyl), -OC(O)-N(C1-C 12 Any of compounds 1.1 to 1.23, wherein the compound is selected from -OC(O)-NH-aryl and -OC(O)-alkyl). 1.26 R 2 -SO3H, -SO2NH2, -S(O)-C1-C 12 Alkyl, -S(O)-C6-C 20 Aryl, -S(O)2-C1-C 12 Alkyl, -S(O)2-C6-C 20 Aryl, -OS(O)2-C1-C12 Alkyl, -OS(O)2-C6-C 20 Aryl, -S(O)2-O-C1-C 12 Alkyl, -S(O)2-O-C6-C 20 Aryl, -S(O)2, NH(C1-C 12 alkyl), -S(O)2-N(C1-C 12 Any of compounds 1.1 to 1.23, wherein the compound is selected from -OS(O)2-OH, -OP(O)2(OH) and -P(O)(OH). 1.27 R 2 is C1-C6 alkyl, -O-C1-C 12 Alkyl, -C(O)-C1-C 12 Alkyl, -OC(O)-C1-C 12 Alkyl, -C(O)-O-C1-C 12 Alkyl, -OC(O)-O-C1-C 12 Alkyl, -C(O)-NH2, -C(O)-NH(C1-C 12 alkyl), -C(O)-N(C1-C 12 alkyl)2, -OC(O)-NH(C1-C 12 alkyl), -OC(O)-N(C1-C 12 Alkyl)2), -SO3H, -SO2NH2, -S(O)-C1-C 12 Alkyl, -S(O)2-C1-C 12 Alkyl, -OS(O)2-C1-C 12 Alkyl, -S(O)2-O-C1-C 12 Alkyl, -S(O)2, NH(C1-C 12 alkyl), -S(O)2-N(C1-C 12 Any of compounds 1.1 to 1.23, wherein the compound is selected from -OS(O)2-OH, -OP(O)2(OH) and -P(O)(OH). 1.28 R 2 Any of compounds 1.1 to 1.23, wherein is selected from H, OH, NH2, NHCH3, NH(CH3)2, OCH3, -C(O)CH3, -OC(O)-CH3, -COOH, -SO3H, -OS(O)2-OH, -OP(O)2(OH) and -P(O)(OH)2. 1.29 R 2 Any of compounds 1.1-1.28, wherein the alkyl and / or aryl portions of are each unsubstituted. 1.30 R 2 each of the alkyl and / or aryl portions independently represents halo (-F, -Cl, -Br or -I), -CN, OH, NH, NH(C1-C 12 Alkyl), N(C1-C 12 Alkyl)(C1-C 12 alkyl), -COOH, -O-C1-C 12 Alkyl, -C(O)-C1-C 12 Alkyl, -OC(O)-C1-C 12 Alkyl, -C(O)-O-C1-C 12 Any of compounds 1.1 to 1.28, further substituted with one or more groups selected from alkyl, -SO3H, -SO2NH2, -OS(O)2-OH, -OP(O)2(OH) and -P(O)(OH)2. 1.31 R 2 each of the alkyl and / or aryl portions independently represents halo (-F, -Cl, -Br or -I), -CN, OH, NH, NH(C1-C 12 Alkyl), N(C1-C 12 Alkyl)(C1-C 12 Any of Compounds 1.1 to 1.28, which is further substituted with one or more groups selected from: -alkyl), -COOH, -SO3H, -SO2NH2, -OS(O)2-OH, -OP(O)2(OH) and -P(O)(OH). 1.32 R 2 Any of Compounds 1.1-1.28, wherein the alkyl and / or aryl portions are each independently further substituted with one or more groups selected from halo (-F, -Cl, -Br or -I), -OH, NH2, -COOH, -SOH, -SO2NH2, -OS(O)2-OH, -OP(O)2(OH) and -P(O)(OH). 1.33 R 2Any of Compounds 1.1-1.28, wherein the alkyl and / or aryl portions are each independently further substituted with one or more groups selected from halo (-F, -Cl, -Br or -I), -OH, NH2, -COOH and -SO3H. 1.34 R 2 Any of compounds 1.1-1.28, wherein the alkyl and / or aryl moieties are each independently further substituted with one or more OH. 1.35 R 2 Any of Compounds 1.1-1.23, wherein is selected from C1-C6 alkyl, -O-C1-C6 alkyl, -C(O)-C1-C6 alkyl, -OC(O)-C1-C6 alkyl, -C(O)-O-C1-C6 alkyl, -OC(O)-O-C1-C6 alkyl, each of said alkyls is optionally substituted with one or more OH. 1.36 R 2 Any of Compounds 1.1-1.23, wherein is selected from -O-C1-C3 alkyl, -C(O)-C1-C3 alkyl, -OC(O)-C1-C3 alkyl, -C(O)-O-C1-C3 alkyl, -OC(O)-O-C1-C3 alkyl, each of said alkyls optionally substituted with one or more OH. 1.37 Compound 1.36, wherein each of said C1-C3 alkyls is selected from -CH2CH2OH, -CH(OH)CH3, -CH(OH)CH2(OH), -CH2CH2CH2OH, -CH2CH(OH)CH3, -CH(OH)CH2CH3, -CH2CH(OH)CH2OH, -CH(OH)CH2CH2OH, -CH(OH)CH(OH)CH3 and -CH(OH)CH(OH)CH2OH. 1.38 Compound 1.37, wherein each of said C1-C3 alkyls is selected from -CH2CH2OH, -CH(OH)CH2(OH), -CH2CH(OH)CH3, -CH2CH(OH)CH2OH, and -CH(OH)CH(OH)CH2OH. 1.39 R 2is selected from -OCH2CH2OH, -OCH2CH(OH)CH3, -OCH2CH(OH)CH2OH, -(CO)-CH2CH2OH, -(CO)-CH2CH(OH)CH3, -C(O)-CH2CH(OH)CH2OH, -O(CO)-CH2CH2OH, -O(CO)-CH2CH(OH)CH3, -OC(O)-CH2CH(OH)CH2OH, -(CO)-O-CH2CH2OH, -(CO)-O-CH2CH(OH)CH3 and -C(O)-O-CH2CH(OH)CH2OH. 1.40 X is a bond and Y is H; or X is a bond, Y is -C(O)-, and R 1 is CH2 or CH2CH2, and R 2 is -COOH; or X is a bond, Y is -C(O)-, and R 1 is CH2 or CH2CH2, and R 2 is -SO3H or -OS(O)2OH; or X is a bond and Y is -S(O)2-, R 1 is a bond and R 2 is OH; or X is a bond, Y is -C(O)-, and R 1 is a bond and R 2 is CH2CH2OH; or X is a bond, Y is -C(O)-, and R 1 is a bond and R 2 is CHCH(OH)CHOH; or X is a bond, Y is -C(O)-, and R 1 is a bond and R 2 is CH3, Any of the compounds 1.1 to 1.39 above. 1.41 Any of the compounds according to 1.1 to 1.40 above, containing a -COOH, -SO3H, -OS(O)2-OH, -OP(O)2(OH) or -P(O)(OH)2 group, said group being in the form of a salt, for example an alkali metal salt (for example a lithium, sodium or potassium salt) or an alkaline earth metal salt (for example a magnesium or calcium salt). 1.42 Any of the compounds according to 1.1 to 1.41 above, containing a basic amine group (e.g., -NH2), said group being in the form of an acid addition salt, e.g., a salt with a strong Bronsted acid (e.g., hydrochloride, sulfate, phosphate). 1.43 End groups of compounds of formula IA or IB [ka] Each of them, [ka] Any of the compounds according to 1.1 to 1.42 above, 1.44 End groups of compounds of formula IA or IB [ka] Each of them, [ka] Any of the compounds according to 1.1 to 1.43 above,

[0016] In a second embodiment of the first aspect, the present invention provides a compound of general formula (II-A) (compound 2A) or a compound of general formula (II-B) (compound 2B), each in free or salt form: [ka] [ka] [During the ceremony, n is an integer from 0 to 20 (e.g., 0 to 10); m is an integer from 1 to 100 (e.g., 25 to 75); X is selected from a bond, CH2, CH2CH2, CH2C(O)-, -CH2CH2C(O)-, CH2C(O)O-, -CH2CH2C(O)O-, -C(O)-, -C(O)-O-, -C(O)-N(R)-, -S(O)-, -S(O2)-, -S(O2)-O-, and -S(O2)-N(R)-; Y is selected from CH2CH2, -C(O)-, -CH2CH2-C(O)-, -CH2CH2-C(O)-O-, -S(O)-, or -S(O2)-; R is selected from H and C1-C6 alkyl (e.g., methyl) optionally substituted with one or more OH; Each R 3 are independently H, C1-C 20 Alkyl, C2-C 20 Alkenyl, -C(O)-C1-C 20 Alkyl, -C(O)-C2-C 20 Alkenyl, -(CH2CH2O) m -CH2CH2OH, -(CH2CH2O) m -CH2CH2O-C1-C 20 Alkyl, -(CH2CH2O) m -CH2CH2O-C2-C 20 Alkenyl, -(CH2CH2O) m -CH2CH2O-C(O)-C1-C 20 Alkyl, -(CH2CH2O) m -CH2CH2O-C(O)-C2-C 20 Alkenyl, -(CH2CH(CH3)O) m -CH2CH(CH3)OH, -(CH2CH(CH3)O) m -CH2CH(CH3)O-C1-C 20 Alkyl, -(CH2CH(CH3)O) m -CH2CH(CH3)O-C2-C 20 Alkenyl, -(CH2CH(CH3)O) m -CH2CH(CH3)OC(O)-C1-C 20 Alkyl and -(CH2CH(CH3)O) m -CH2CH(CH3)OC(O)-C2-C20 alkenyl, -CH2CH2OH, -CH2CH(CH3)OH, -CH2COOH, -CH2CH2COOH, -S(O)2-OH and -P(O)2(OH); R 3 One or both of the formula: [ka] (wherein X, Y, n, and m are each independently as defined above). have

[0017] In a further embodiment of the first aspect, the present invention provides: 2.1 Compound of formula II-A. 2.2 Compound of formula II-B. 2.3 Compound 2.2, wherein n is an integer from 0 to 10, for example, from 0 to 8, or from 0 to 6, or from 0 to 5, or any of 0, 1, 2, 3 or 4. 2.4 Compound 2.2, wherein n is 0, 1, 2 or 3. 2.5 Compound 2.2, where n is 0. 2.6 Compound 2.2, where n is 1. 2.7 Any of compounds 2.1 to 2.6, wherein m is an integer from 1 to 75, e.g., 1 to 25, 25 to 50, 50 to 75, 25 to 75, 1 to 10, 11 to 20, 21 to 30, 31 to 40, 41 to 50, 51 to 60, 61 to 75, or any combination thereof. 2.8 Any of compounds 2.1 to 2.7 selected from CH2, -C(O)-, -C(O)-O- and -C(O)-N(R)-. 2.9 Any of compounds 2.1 to 2.7, wherein X is selected from -S(O)-, -S(O2)-, -S(O2)-O-, and -S(O2)-N(R)-. 2.10 Any of compounds 2.1 to 2.7, wherein X is selected from a bond, CH2, -C(O)-, and -C(O)-O-. 2.11 Any one of compounds 2.1 to 2.7, wherein X is a bond. 2.12 Any one of compounds 2.1 to 2.11, wherein Y is selected from CH2CH2, -C(O)-, -CH2CH2-C(O)-, and -CH2CH2-C(O)-O-. 2.13 Any of compounds 2.1 to 2.11, wherein Y is selected from -S(O)- and -S(O2)-. 2.14 Any of compounds 2.1 to 2.11, wherein Y is CH2CH2. 2.15 Any of compounds 2.1 to 2.11, wherein Y is -C(O)-. 2.16 Any of compounds 2.1 to 2.15, wherein R is H. 2.17 Any of compounds 2.1-2.15, wherein R is C1-C6 alkyl (e.g., methyl, ethyl, propyl). 2.18 Any one of compounds 2.1-2.15, wherein R is C1-C6 alkyl substituted with one or more OH, e.g., R is selected from hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl. 2.19 Compound 2.18, where R is selected from -CH2CH2OH, -CH(OH)CH3, -CH(OH)CH2(OH), -CH2CH2CH2OH, -CH2CH(OH)CH3, -CH(OH)CH2CH3, -CH2CH(OH)CH2OH, -CH(OH)CH2CH2OH, -CH(OH)CH(OH)CH3, and -CH(OH)CH(OH)CH2OH. 2.20 R 3 H, C1-C 20 Alkyl and C2-C 20 Any of compounds 2.1 to 2.19, wherein the compound is selected from alkenyl. 2.21 R 3 C 6-18 Alkyl, e.g., C 6-12 Alkyl, C 12-18 Alkyl, C 6-10 Alkyl, C 10-14 Alkyl or C 14-18 Compound 2.20, which is an alkyl. 2.22 R 3 C 6-18Alkenyl, e.g., C 6-12 Alkenyl, C 12-18 Alkenyl, C 6-10 Alkenyl, C 10-14 Alkenyl or C 14-18 alkenyl, each of which may optionally be mono- or di-unsaturated. 2.23 R 3 C 1-3 Compound 2.20, which is alkyl, for example, CH2 or CH2CH2. 2.24 R 3 -C(O)-C1-C 20 Alkyl or -C(O)-C2-C 20 Any of compounds 2.1 to 2.19, which is alkenyl. 2.25 R 3 -C(O)-C 6-18 Alkyl, e.g., -C(O)-C 6-12 Alkyl, -C(O)-C 12-18 Alkyl, -C(O)-C 6-10 Alkyl, -C(O)-C 10-14 Alkyl or -C(O)-C 14-18 The compound 2.24 is an alkyl group. 2.26 R 3 -C(O)-C 6-18 Alkenyl, for example, -C(O)-C 6-12 Alkenyl, -C(O)-C 12-18 Alkenyl, -C(O)-C 6-10 Alkenyl, -C(O)-C 10-14 Alkenyl or -C(O)-C 14-18 alkenyl, each of which may optionally be mono- or di-unsaturated. Compound 2.24. 2.27 R 3 -(CH2CH2O) m Any of compounds 2.1 to 2.19, wherein m is -CH2CH2OH and m is an integer from 1 to 75, for example, 1 to 25, 25 to 50, 50 to 75, 25 to 75, 1 to 10, 11 to 20, 21 to 30, 31 to 40, 41 to 50, 51 to 60, 61 to 75, or any combination thereof. 2.28 R 3 -(CH2CH2O) m -CH2CH2O-C1-C 20 Alkyl, -(CH2CH2O) m -CH2CH2O-C2-C 20 Alkenyl, -(CH2CH2O) m -CH2CH2O-C(O)-C1-C 20 Alkyl and -(CH2CH2O) m -CH2CH2O-C(O)-C2-C 20 Any of compounds 2.1 to 2.19, wherein the compound is selected from alkenyl. 2.29 Compound 2.28, wherein m is an integer from 1 to 75, e.g., 1 to 25, 25 to 50, 50 to 75, 25 to 75, 1 to 10, 11 to 20, 21 to 30, 31 to 40, 41 to 50, 51 to 60, 61 to 75, or any combination thereof. 2.30 Said C1-C 20 Alkyl is C 6-18 Alkyl, e.g., C 6-12 Alkyl, C 12-18 Alkyl, C 6-10 Alkyl, C 10-14 Alkyl or C 14-18 Compound 2.28 or 2.29, which is alkyl. 2.31 C2-C 20 Alkenyl is C 6-18 Alkenyl, e.g., C 6-12 Alkenyl, C 12-18 Alkenyl, C 6-10 Alkenyl, C 10-14 Alkenyl or C 14-18 Compound 2.28 or 2.29, which is alkenyl. 2.32 R 3 but: [ka] (In the formula, X, Y and m are as defined in any one of 2.1 to 2.19). Any of compounds 2.1 to 2.19, wherein 2.33 R 3 but: [ka] (In the formula, X, Y and m are as defined in any one of 2.1 to 2.19). Any one of compounds 2.1 to 2.19, wherein: Any one of compounds 2.1 to 2.19, wherein: 2.34 R 3 Any of compounds 2.1 to 2.19, wherein is -CH2CH2OH, -CH2CH(CH3)OH, -CH2COOH, -CH2CH2COOH, -S(O)2-OH or -P(O)2(OH). 2.35 X is a bond and Y is CH2CH2; or X is a bond and Y is -C(O)-; or X is a bond and Y is -CH2CH2-C(O)-; or X is a bond and Y is -S(O)2-; Any of the compounds described above in 2.1 to 2.34. 2.36 R 3 is H, compound 2.35. 2.37 R 3 is -CH2CH2OH, -CH2CH(CH3)OH, -CH2COOH, -CH2CH2COOH, -S(O)2-OH or -P(O)2(OH). 2.38 The compound is of formula II-A, where R 3 but: [ka] where X, Y, and m are as defined for the compound of formula II-A (i.e., all values ​​of X, Y, and m are the same throughout the compound). Compound 2.35. 2.39 The compound is of formula II-B, where R 3 but: [ka] where X, Y, and m are as defined for the compound of formula II-A (i.e., all values ​​of X, Y, and m are the same throughout the compound). , compound 2.34. 2.40 Any of the compounds according to 2.1 to 2.39 above, containing a -COOH, -S(O)2-OH or -P(O)2(OH) group, said group being in the form of a salt, for example an alkali metal salt (e.g. a lithium, sodium or potassium salt) or an alkaline earth metal salt (e.g. a magnesium or calcium salt). 2.41 Any of the compounds according to 2.1 to 2.40 above, containing a basic amine group (e.g., -NH2), said group being in the form of an acid addition salt, for example a salt with a strong Bronsted acid (e.g., hydrochloride, sulfate, phosphate). 2.42 End groups of compounds of formula II-A or II-B: [ka] Each of them, [ka] Any of the compounds 2.1 to 2.41 above, 2.43 End groups of compounds of formula II-A or II-B: [ka] Each of them, [ka] Any of the compounds according to 2.1 to 2.42 above,

[0018] In a third embodiment of the first aspect, the present invention provides a compound of general formula (III-A) (compound 3A) or a compound of general formula (III-B) (compound 3B), in free or salt form: [ka] [ka] [During the ceremony, n is an integer from 0 to 20 (e.g., 0 to 10); m is an integer from 1 to 100 (e.g., 25 to 75); X is selected from a bond, CH2, CH2CH2, CH2C(O)-, -CH2CH2C(O)-, CH2C(O)O-, -CH2CH2C(O)O-, -C(O)-, -C(O)-O-, -C(O)-N(R)-, -S(O)-, -S(O2)-, -S(O2)-O-, and -S(O2)-N(R)-; Y is selected from CH2, CH2CH2, -C(O)-, -C(O)-O-, -C(O)-N(R)-, -S(O)-, -S(O2)-, -S(O2)-O-, and -S(O2)-N(R)-; R is selected from H and C1-C6 alkyl (e.g., methyl) optionally substituted with one or more OH; R 1 is a bond, C1-C 20 Alkyl, C2-C 20 Alkenyl and C6-C 20 aryl; R 2 are H, OH, NH2, NH(C1-C 12 Alkyl), N(C1-C 12 Alkyl)(C1-C 12 alkyl), -COOH, C1-C6 alkyl, -O-C1-C 12 Alkyl, -O-C6-C 20 Aryl, -C(O)-C1-C 12 Alkyl, -C(O)-C6-C 20 Aryl, -OC(O)-C1-C 12 Alkyl, -OC(O)-C6-C 20 Aryl, -C(O)-O-C1-C 12 Alkyl, -C(O)-O-C6-C 20 Aryl, -OC(O)-O-C1-C 12 Alkyl, -OC(O)-O-C6-C 20 Aryl, -C(O)-NH2, -C(O)-NH(C1-C 12 alkyl), -C(O)-N(C1-C 12Alkyl)2, -C(O)-NH-aryl, -OC(O)-NH(C1-C 12 alkyl), -OC(O)-N(C1-C 12 Alkyl)2, -OC(O)-NH-Aryl, -SO3H, -SO2NH2, -S(O)-C1-C 12 Alkyl, -S(O)-C6-C 20 Aryl, -S(O)2-C1-C 12 Alkyl, -S(O)2-C6-C 20 Aryl, -OS(O)2-C1-C 12 Alkyl, -OS(O)2-C6-C 20 Aryl, -S(O)2-O-C1-C 12 Alkyl, -S(O)2-O-C6-C 20 Aryl, -S(O)2-NH(C1-C 12 alkyl), -S(O)2-N(C1-C 12 alkyl), -OS(O)-OH, -OP(O)(OH) and -P(O)(OH); C1-C 12 Alkyl and C6-C 20 Each aryl moiety is selected from the group consisting of halo (-F, -Cl, -Br or -I), -CN, OH, NH, NH(C1-C 12 Alkyl), N(C1-C 12 Alkyl)(C1-C 12 alkyl), -COOH, -O-C1-C 12 Alkyl, -C(O)-C1-C 12 Alkyl, -OC(O)-C1-C 12 Alkyl, -C(O)-O-C1-C 12 and optionally further substituted with one or more groups selected from alkyl, SO3H, -SO2NH2, -OS(O)2-OH, -OP(O)2(OH) and -P(O)(OH).

[0019] In a further embodiment of the first aspect, the present invention provides: 3.1 Compound of formula III-A. 3.2 Compound of formula III-B. 3.3 Compound 3.2, wherein n is an integer from 0 to 10, for example, 0 to 8 or 0 to 6, or 0 to 5, or 0, 1, 2, 3 or 4. 3.4 Compound 3.2, wherein n is 0, 1, 2 or 3. 3.5 Compound 3.2, where n is 0. 3.6 Compound 3.2, where n is 1. 3.7 Any of compounds 3.1 to 3.6, wherein m is an integer from 1 to 75, e.g., 1 to 25, 25 to 50, 50 to 75, 25 to 75, 1 to 10, 11 to 20, 21 to 30, 31 to 40, 41 to 50, 51 to 60, 61 to 75, or any combination thereof. 3.8 Any of compounds 3.1 to 3.7, wherein X is selected from a bond, CH2, -C(O)-, -C(O)-O-, and -C(O)-N(R)-. 3.9 Any of compounds 3.1 to 3.7, wherein X is selected from -S(O)-, -S(O2)-, -S(O2)-O-, and -S(O2)-N(R)-. 3.10 Any of compounds 3.1-3.7, wherein X is selected from a bond, CH2, -C(O)-, and -C(O)-O-. 3.11 Any of compounds 3.1 to 3.7, wherein X is a bond. 3.12 Any of compounds 3.1 to 3.11, wherein Y is selected from CH2, CH2CH2, -C(O)-, -C(O)-O-, and -C(O)-N(R)-. 3.13 Any of compounds 3.1 to 3.11, wherein Y is selected from -S(O)-, -S(O2)-, -S(O2)-O-, and -S(O2)-N(R)-. 3.14 Any of compounds 3.1 to 3.11, wherein Y is selected from CH2, CH2CH2, and -C(O)-. 3.15 Any of compounds 3.1-3.11, wherein Y is selected from CH2 and CH2CH2. 3.16 Any of compounds 3.1 to 3.13, wherein R is H. 3.17 Any of compounds 3.1-3.13, wherein R is C1-C6 alkyl (e.g., methyl, ethyl, propyl). 3.18 Any of compounds 3.1-3.13, wherein R is C1-C6 alkyl substituted with one or more OH, e.g., R is selected from hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl. 3.19 Compound 3.18, where R is selected from -CH2CH2OH, -CH(OH)CH3, -CH(OH)CH2(OH), -CH2CH2CH2OH, -CH2CH(OH)CH3, -CH(OH)CH2CH3, -CH2CH(OH)CH2OH, -CH(OH)CH2CH2OH, -CH(OH)CH(OH)CH3, and -CH(OH)CH(OH)CH2OH. 3.20 R 1 is bonded, C1-C 20 Alkyl and C2-C 20 Any of compounds 3.1 to 3.19, wherein the compound is selected from alkenyl. 3.21 R 1 C 6-18 Alkyl, e.g., C 6-12 Alkyl, C 12-18 Alkyl, C 6-10 Alkyl, C 10-14 Alkyl or C 14-18 The compound 3.20 is an alkyl group. 3.22 R 1 C 6-18 Alkenyl, e.g., C 6-12 Alkenyl, C 12-18 Alkenyl, C 6-10 Alkenyl, C 10-14 Alkenyl or C 14-18 alkenyl, each of which may optionally be mono- or di-unsaturated. 3.23 R 1 C 1-3 Compound 3.20, which is alkyl, for example, CH2 or CH2CH2. 3.24 R 2 H, OH, NH2, NH(C1-C 12Alkyl), N(C1-C 12 Alkyl)(C1-C 12 Any of compounds 3.1 to 3.23, wherein the compound is selected from -alkyl) and -COOH. 3.25 R 2 is C1-C6 alkyl, -O-C1-C 12 Alkyl, -O-C6-C 20 Aryl, -C(O)-C1-C 12 Alkyl, -C(O)-C6-C 20 Aryl, -OC(O)-C1-C 12 Alkyl, -OC(O)-C6-C 20 Aryl, -C(O)-O-C1-C 12 Alkyl, -C(O)-O-C6-C 20 Aryl, -OC(O)-O-C1-C 12 Alkyl, -OC(O)-O-C6-C 20 Aryl, -C(O)-NH2, -C(O)-NH(C1-C 12 alkyl), -C(O)-N(C1-C 12 Alkyl)2, -C(O)-NH-aryl, -OC(O)-NH(C1-C 12 alkyl), -OC(O)-N(C1-C 12 Any of compounds 3.1 to 3.23, wherein the compound is selected from -OC(O)-NH-aryl, -OC(O)-alkyl, and -OC(O)-NH-aryl. 3.26 R 2 -SO3H, -SO2NH2, -S(O)-C1-C 12 Alkyl, -S(O)-C6-C 20 Aryl, -S(O)2-C1-C 12 Alkyl, -S(O)2-C6-C 20 Aryl, -OS(O)2-C1-C 12 Alkyl, -OS(O)2-C6-C 20 Aryl, -S(O)2-O-C1-C 12 Alkyl, -S(O)2-O-C6-C 20 Aryl, -S(O)2, NH(C1-C 12 alkyl), -S(O)2-N(C1-C 12Any of compounds 3.1 to 3.23, wherein the compound is selected from -OS(O)2-OH, -OP(O)2(OH) and -P(O)(OH)2. 3.27 R 2 is C1-C6 alkyl, -O-C1-C 12 Alkyl, -C(O)-C1-C 12 Alkyl, -OC(O)-C1-C 12 Alkyl, -C(O)-O-C1-C 12 Alkyl, -OC(O)-O-C1-C 12 Alkyl, -C(O)-NH2, -C(O)-NH(C1-C 12 alkyl), -C(O)-N(C1-C 12 alkyl)2, -OC(O)-NH(C1-C 12 alkyl), -OC(O)-N(C1-C 12 Alkyl)2), -SO3H, -SO2NH2, -S(O)-C1-C 12 Alkyl, -S(O)2-C1-C 12 Alkyl, -OS(O)2-C1-C 12 Alkyl, -S(O)2-O-C1-C 12 Alkyl, -S(O)2, NH(C1-C 12 alkyl), -S(O)2-N(C1-C 12 Any of compounds 3.1 to 3.23, wherein the compound is selected from -OS(O)2-OH, -OP(O)2(OH) and -P(O)(OH)2. 3.28 R 2 Any of compounds 3.1 to 3.23, wherein is selected from H, OH, NH2, NHCH3, NH(CH3)2, OCH3, -C(O)CH3, -OC(O)-CH3, -COOH, -SO3H, -OS(O)2-OH, -OP(O)2(OH) and -P(O)(OH)2. 3.29 R 2 Any of compounds 3.1-3.28, wherein the alkyl and / or aryl portions of are each unsubstituted. 3.30 R 2each of the alkyl and / or aryl portions independently represents halo (-F, -Cl, -Br or -I), -CN, OH, NH, NH(C1-C 12 Alkyl), N(C1-C 12 Alkyl)(C1-C 12 alkyl), -COOH, -O-C1-C 12 Alkyl, -C(O)-C1-C 12 Alkyl, -OC(O)-C1-C 12 Alkyl, -C(O)-O-C1-C 12 Any of compounds 3.1 to 3.28, further substituted with one or more groups selected from alkyl, -SO3H, -SO2NH2, -OS(O)2-OH, -OP(O)2(OH) and -P(O)(OH)2. 3.31 R 2 each of the alkyl and / or aryl portions independently represents halo (-F, -Cl, -Br or -I), -CN, OH, NH, NH(C1-C 12 Alkyl), N(C1-C 12 Alkyl)(C1-C 12 Any of compounds 3.1 to 3.28, which is further substituted with one or more groups selected from: -alkyl), -COOH, -SO3H, -SO2NH2, -OS(O)2-OH, -OP(O)2(OH) and -P(O)(OH). 3.32 R 2 Any of Compounds 3.1-3.28, wherein the alkyl and / or aryl portions are each independently further substituted with one or more groups selected from halo (-F, -Cl, -Br or -I), -OH, NH2, -COOH, -SO3H, -SO2NH2, -OS(O)2-OH, -OP(O)2(OH) and -P(O)(OH). 3.33 R 2 Any of compounds 3.1 to 3.28, wherein the alkyl and / or aryl portions are each independently further substituted with one or more groups selected from halo (-F, -Cl, -Br or -I), -OH, NH2, -COOH and SO3H. 3.34 R 2Any of compounds 3.1-3.28, wherein the alkyl and / or aryl moieties are each independently further substituted with one or more OH. 3.35 R 2 Any of compounds 3.1-3.23, wherein is selected from C1-C6 alkyl, -O-C1-C6 alkyl, -C(O)-C1-C6 alkyl, -OC(O)-C1-C6 alkyl, -C(O)-O-C1-C6 alkyl, -OC(O)-O-C1-C6 alkyl, each of the alkyls is optionally substituted with one or more OH. 3.36 R 2 Any of compounds 3.1 to 3.23, wherein each of the alkyl groups is optionally substituted with one or more OH. 3.37 Compound 3.36, wherein each of said C1-C3 alkyls is selected from -CH2CH2OH, -CH(OH)CH3, -CH(OH)CH2(OH), -CH2CH2CH2OH, -CH2CH(OH)CH3, -CH(OH)CH2CH3, -CH2CH(OH)CH2OH, -CH(OH)CH2CH2OH, -CH(OH)CH(OH)CH3 and -CH(OH)CH(OH)CH2OH. 3.38 Compound 3.37, wherein each of the C1-C3 alkyls is selected from CH2CH2OH, CH(OH)CH2(OH), CH2CH(OH)CH3, CH2CH(OH)CH2OH, and CH(OH)CH(OH)CH2OH. 3.39 Compound 3.37, wherein each of said C1-C3 alkyls is selected from: -OCH2CH2OH, -OCH2CH(OH)CH3, -OCH2CH(OH)CH2OH, -(CO)-CH2CH2OH, -(CO)-CH2CH(OH)CH3, -C(O)-CH2CH(OH)CH2OH, -O(CO)-CH2CH2OH, -O(CO)-CH2CH(OH)CH3, -OC(O)-CH2CH(OH)CH2OH, -(CO)-O-CH2CH2OH, -(CO)-O-CH2CH(OH)CH3 and -C(O)-O-CH2CH(OH)CH2OH. 3.40 X is a bond and Y is H; or X is a bond, Y is -C(O)-, and R 1 is CH2 or CH2CH2 and R 2 is -COOH; or X is a bond, Y is -C(O)-, and R 1 is CH2 or CH2CH2 and R 2 is -SO3H or -OS(O)2OH; or X is a bond, Y is -S(O)2-, and R 1 is a bond and R 2 is OH; or X is a bond, Y is -C(O)-, and R 1 is a bond and R 2 is CH2CH2OH; or X is a bond, Y is -C(O)-, and R 1 is a bond and R 2 is CHCH(OH)CHOH; or X is a bond, Y is -C(O)-, and R 1 is a bond and R 2 is CH3, Any compound between 3.1 and 3.39. 3.41 Any of compounds 3.1 to 3.40 containing the group -COOH, -SO3H, -OS(O)2-OH, -OP(O)2(OH) or -P(O)(OH)2, which is in the form of a salt, for example an alkali metal salt (e.g. lithium, sodium or potassium salt) or an alkaline earth metal salt (e.g. magnesium or calcium salt). 3.42 Any of the compounds 3.1 to 3.41 above, which contain a basic amine group (e.g., -NH2) in the form of an acid addition salt, for example a salt with a strong Bronsted acid (e.g., hydrochloride, sulfate, phosphate). 3.43 End groups of compounds of formula III-A or III-B [ka] Each of them, [ka] That is, Any of the compounds 3.1 to 3.42 above. 3.44 End groups of compounds of formula III-A or III-B [ka] Each of them, [ka] Any of the compounds according to 3.1 to 3.43 above,

[0020] In a fourth embodiment of the first aspect, the present invention provides a compound of general formula (IV-A) (compound 4A), or a compound of general formula (IV-B) (compound 4B), in free or salt form: [ka] [ka] [During the ceremony, n is an integer from 0 to 20 (e.g., 0 to 10); m is an integer from 1 to 100 (e.g., 25 to 75); X is selected from a bond, CH2, CH2CH2, CH2C(O)-, -CH2CH2C(O)-, CH2C(O)O-, -CH2CH2C(O)O-, -C(O)-, -C(O)-O-, -C(O)-N(R)-, -S(O)-, -S(O2)-, -S(O2)-O-, and -S(O2)-N(R)-; Y is selected from CH2CH2, -C(O)-, -CH2CH2-C(O)-, -CH2CH2-C(O)-O-, -S(O)-, or -S(O2)-; R is selected from H and C1-C6 alkyl (e.g., methyl) optionally substituted with one or more OH; Each R 3 are independently H, C1-C 20 Alkyl, C2-C 20 Alkenyl, -C(O)-C1-C 20 Alkyl, -C(O)-C2-C 20 Alkenyl, -(CH2CH2O) m -CH2CH2OH, -(CH2CH2O) m -CH2CH2O-C1-C 20 Alkyl, -(CH2CH2O) m -CH2CH2O-C2-C 20 Alkenyl, -(CH2CH2O) m -CH2CH2O-C(O)-C1-C 20 Alkyl, -(CH2CH2O) m -CH2CH2O-C(O)-C2-C 20 Alkenyl, -(CH2CH(CH3)O) m -CH2CH(CH3)OH, -(CH2CH(CH3)O) m -CH2CH(CH3)O-C1-C 20 Alkyl, -(CH2CH(CH3)O) m -CH2CH(CH3)O-C2-C 20 Alkenyl, -(CH2CH(CH3)O) m -CH2CH(CH3)OC(O)-C1-C 20 Alkyl and -(CH2CH(CH3)O) m-CH2CH(CH3)OC(O)-C2-C 20 alkenyl, -CH2CH2OH, -CH2CH(CH3)OH, -CH2COOH, -CH2CH2COOH, -S(O)2-OH and -P(O)2(OH); R 3 may be one or both of the formula: [ka] (wherein X, Y, n, and m are each independently as defined above). has the following characteristics.

[0021] In a further embodiment of the first aspect, the present invention provides: 4.1 Compound of formula IV-A. 4.2 Compound of formula IV-B. 4.3 Compound 4.2, wherein n is an integer from 0 to 10, for example, 0 to 8, or 0 to 6, or 0 to 5, or 0, 1, 2, 3 or 4. 4.4 Compound 4.2, wherein n is 0, 1, 2 or 3. 4.5 Compound 4.2, where n is 0. 4.6 Compound 4.2, where n is 1. 4.7 Any of compounds 4.1 to 4.6, wherein m is an integer from 1 to 75, e.g., 1 to 25, 25 to 50, 50 to 75, 25 to 75, 1 to 10, 11 to 20, 21 to 30, 31 to 40, 41 to 50, 51 to 60, 61 to 75, or any combination thereof. 4.8 Any of compounds 4.1 to 4.7, wherein X is selected from CH2, -C(O)-, -C(O)-O-, and -C(O)-N(R)-. 4.9 Any of compounds 4.1 to 4.7, wherein X is selected from -S(O)-, -S(O2)-, -S(O2)-O-, and -S(O2)-N(R)-. 4.10 Any of compounds 4.1-4.7, wherein X is selected from a bond, CH2, -C(O)-, and -C(O)-O-. 4.11 Any of compounds 4.1 to 4.7, wherein X is a bond. 4.12 Any of compounds 4.1 to 4.11, wherein Y is selected from CH2CH2, -C(O)-, -CH2CH2-C(O)-, and -CH2CH2-C(O)-O-. 4.13 Any of compounds 4.1 to 4.11, wherein Y is selected from -S(O)- and -S(O2)-. 4.14 Any of compounds 4.1 to 4.11, wherein Y is CH2CH2. 4.15 Any of compounds 4.1 to 4.11, wherein Y is -C(O)-. 4.16 Any of compounds 4.1 to 4.15, wherein R is H. 4.17 Any of compounds 4.1-4.15, wherein R is C1-C6 alkyl (e.g., methyl, ethyl, propyl). 4.18 Any of compounds 4.1-4.15, wherein R is C1-C6 alkyl substituted with one or more OH, e.g., R is selected from hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl. 4.19 Compound 4.18, wherein R is selected from -CH2CH2OH, -CH(OH)CH3, -CH(OH)CH2(OH), -CH2CH2CH2OH, -CH2CH(OH)CH3, -CH(OH)CH2CH3, -CH2CH(OH)CH2OH, -CH(OH)CH2CH2OH, -CH(OH)CH(OH)CH3 and -CH(OH)CH(OH)CH2OH. 4.20 R 3 H, C1-C 20 Alkyl and C2-C 20 Any of compounds 4.1 to 4.19, which is alkenyl. 4.21 R 3 C 6-18 Alkyl, e.g., C 6-12 Alkyl, C 12-18 Alkyl, C 6-10 Alkyl, C 10-14 Alkyl or C 14-18 Compound 4.20, which is an alkyl. 4.22 R 3 C 6-18 Alkenyl, e.g., C 6-12 Alkenyl, C 12-18 Alkenyl, C 6-10 Alkenyl, C 10-14 Alkenyl or C 14-18 alkenyl, each of which may optionally be mono- or di-unsaturated. 4.23 R 3 C 1-3 Compound 4.20, which is alkyl, for example, CH2 or CH2CH2. 4.24 R 3 -C(O)-C1-C 20 Alkyl or -C(O)-C2-C 20 Any of compounds 4.1 to 4.19, which is alkenyl. 4.25 R 3 -C(O)-C 6-18 Alkyl, e.g., -C(O)-C 6-12 Alkyl, -C(O)-C 12-18 Alkyl, -C(O)-C 6-10 Alkyl, -C(O)-C 10-14 Alkyl or -C(O)-C 14-18 The compound 4.24 is an alkyl group. 4.26 R 3 -C(O)-C 6-18 Alkenyl, for example, -C(O)-C 6-12 Alkenyl, -C(O)-C 12-18 Alkenyl, -C(O)-C 6-10 Alkenyl, -C(O)-C 10-14 Alkenyl or -C(O)-C 14-18 alkenyl, each of which may optionally be mono- or di-unsaturated. Compound 4.24. 4.27 R 3 -(CH2CH2O) mAny of compounds 4.1 to 4.19, wherein m is -CH2CH2OH, and m is an integer of 1 to 75, for example, 1 to 25, 25 to 50, 50 to 75, 25 to 75, 1 to 10, 11 to 20, 21 to 30, 31 to 40, 41 to 50, 51 to 60, 61 to 75, or any combination thereof. 4.28 R 3 -(CH2CH2O) m -CH2CH2O-C1-C 20 Alkyl, -(CH2CH2O) m -CH2CH2O-C2-C 20 Alkenyl, -(CH2CH2O) m -CH2CH2O-C(O)-C1-C 20 Alkyl and -(CH2CH2O) m -CH2CH2O-C(O)-C2-C 20 Any of compounds 4.1 to 4.19, wherein the compound is selected from alkenyl. 4.29 Compound 4.28, wherein m is an integer from 1 to 75, e.g., 1 to 25, 25 to 50, 50 to 75, 25 to 75, 1 to 10, 11 to 20, 21 to 30, 31 to 40, 41 to 50, 51 to 60, 61 to 75, or any combination thereof. 4.30 Said C1-C 20 Alkyl is C 6-18 Alkyl, e.g., C 6-12 Alkyl, C 12-18 Alkyl, C 6-10 Alkyl, C 10-14 Alkyl or C 14-18 Compound 4.28 or 4.29, which is an alkyl group. 4.31 C2-C 20 Alkenyl is C 6-18 Alkenyl, e.g., C 6-12 Alkenyl, C 12-18 Alkenyl, C 6-10 Alkenyl, C 10-14 Alkenyl or C 14-18 Compound 4.28 or 4.29, which is alkenyl. 4.32 R 3 but: [ka] (wherein X, Y and m are as defined in 4.1 to 4.19). Any of compounds 4.1 to 4.19, wherein 4.33 R 3 but: [ka] (wherein X, Y, n and m are as defined in 4.1 to 4.19). Any of compounds 4.1 to 4.19, wherein 4.34 R 3 Any of compounds 4.1 to 4.19, wherein is -CH2CH2OH, -CH2CH(CH3)OH, -CH2COOH, -CH2CH2COOH, -S(O)2-OH or -P(O)2(OH). 4.35 X is a bond and Y is CH2CH2; or X is a bond and Y is -C(O)-; or X is a bond and Y is CH2CH2-C(O)-; or X is a bond and Y is -S(O)2-; Any of compounds 4.1 to 4.34. 4.36 R 3 is H, compound 4.35. 4.37 R 3 Compound 4.35, wherein is -CH2CH2OH, -CH2CH(CH3)OH, -CH2COOH, -CH2CH2COOH, -S(O)2-OH or -P(O)2(OH). 4.38 The compound is of formula II-A, where R 3 but: [ka] wherein X, Y, and m are as defined for the compound of formula II-A (i.e., all values ​​of X, Y, and m are the same in the compound). Compound 4.35. 4.39 The compound is of formula II-B, where R3 but: [ka] wherein X, Y, and m are as defined for the compound of formula II-A (i.e., all values ​​of X, Y, and m are the same in the compound). , compound 4.34. 4.40 Any of compounds 4.1 to 4.39 above containing a -COOH, -S(O)2-OH or -P(O)2(OH) group, wherein said group is in the form of a salt, for example an alkali metal salt (e.g. a lithium, sodium or potassium salt) or an alkaline earth metal salt (e.g. a magnesium or calcium salt). 4.41 Any of the compounds of 4.1 to 4.40 above containing a basic amine group (e.g., -NH2), which is in the form of an acid addition salt, for example a salt with a strong Bronsted acid (e.g., hydrochloride, sulfate, phosphate). 4.42 End groups of compounds of formula II-A or II-B [ka] Each of them, [ka] Any of the compounds according to 4.1 to 4.41 above, 4.43 End groups of compounds of formula II-A or II-B [ka] Each of them, [ka] Any of the compounds according to 4.1 to 4.42 above,

[0022] 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, etc. The term alkyl can also include cycloalkyl groups. Thus, for example, the term C6 alkyl encompasses cyclohexyl groups, the term C5 encompasses cyclopentyl groups, the term C4 encompasses cyclobutyl groups, and the term C3 encompasses cyclopropyl groups. Furthermore, since alkyl groups can be branched or unbranched, any alkyl group of n carbon atoms encompasses cycloalkyl groups of less than n carbons substituted by further alkyl substituents. Thus, for example, the term C6 alkyl also encompasses methylcyclopentyl groups, or dimethylcyclobutyl or ethylcyclobutyl groups, or trimethylcyclopropyl, ethylmethylcyclopropyl or propylcyclopropyl groups.

[0023] The term "alkenyl" as used herein typically, but not necessarily, refers to a monovalent or divalent branched or unbranched unsaturated hydrocarbon group 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, optionally with endocyclic or exocyclic double bonds.

[0024] 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 aromatic hydrocarbons having two fused rings and 10 carbon atoms (i.e., naphthalene).

[0025] 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.

[0026] The terms "branched" and "straight-chain" (or "unbranched") refer to, for example, a ~C b When used in reference to an alkyl moiety of carbon atoms, it applies to those carbon atoms that define the alkyl moiety. For example, for a C4 alkyl moiety, its branched embodiment includes isobutyl, while its unbranched embodiment includes n-butyl. However, isobutyl is also classified as a straight chain C3 alkyl moiety (propyl) itself substituted with a C1 alkyl (methyl).

[0027] Unless otherwise specified, any carbon atom having an open valence may be substituted with one or more additional functional groups. Examples of functional groups include, but are not limited to: 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 (wherein X is halo), C2-C 20 Alkylcarborato (-O-(CO)-O-alkyl), C6-C 20 Arylcarbonato (-O-(CO)-O-aryl), carboxy (-COOH), carboxylate (-COO - ), carbamoyl (-(CO)-NH2), monosubstituted C1-C 20Alkylcarbamoyl(-(CO)-NH(C1-C 20 alkyl)), disubstituted alkylcarbamoyl (-(CO)-N(C1-C 20 alkyl)2), monosubstituted arylcarbamoyl (-(CO)-NH-aryl), thiocarbamoyl (-(CS)-NH2), carbamide (-NH-(CO)-NH2), cyano (-C≡N), isocyano (-N + ≡C - ), cyanate (-OC≡N), isocyanate (-ON + ≡C - ), isothiocyanate (-SC≡N), azide (-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 (R=hydrogen, C1-C 20 Alkyl, C5-C 20 Aryl, C6-C 20 Alkaryl, C6-C 20 aralkyl, -CR=NH), alkylimino (R=hydrogen, alkyl, aryl, alkaryl, etc., -CR=N(alkyl)), arylimino (R=hydrogen, alkyl, aryl, alkaryl, etc., -CR=N(aryl)), nitro (-NO2), nitroso (-NO), sulfo (-SO2-OH), sulfonate (-SO2-O - ), C1-C 20 Alkylsulfanyl (-S-alkyl; also known as "alkylthio"), arylsulfanyl (-S-aryl; also known as "arylthiol"), C1-C 20 Alkylsulfinyl (-(SO)-alkyl), C5-C 20 Arylsulfinyl (-(SO)-aryl), C1-C 20 Alkylsulfonyl (-SO2-alkyl), C5-C20 Arylsulfonyl (-SO2-aryl), phosphono (-P(O)(OH)2), phosphonato (-P(O)(O - )2), phosphinate (-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 C1-C 20 Alkyl (C1-C 18 Contains alkyl, C1-C 12 alkyl, further including C1-C6 alkyl), C2-C 20 Alkenyl (C2-C 18 Contains alkenyl, C2-C 12 alkenyl, further including C2-C6 alkenyl), C2-C 20 Alkynyl(C2-C 18 Alkynyl, C2-C 12 alkynyl, further including C2-C6 alkynyl), C5-C 30 Aryl (C5-C 20 Contains aryl, C5-C 12 (further including aryl) and C6-C 20 Aralkyl(C6-C 20 C6-C, including aralkyl 12 In addition, the functional groups may be further substituted, if a particular group permits, with one or more additional functional groups or one or more hydrocarbyl moieties, such as those specifically listed above. For example, the alkyl or alkenyl group may be branched. For example, the "substituent" may be an alkyl group, such as a methyl group.

[0028] In a second aspect, the present invention provides a method for making any of the compounds described herein, e.g., Compound 1 or Compound 2 or subsequent compounds, comprising the steps of reacting citronellol or a polycitronellol polymer with an alkoxylating agent to obtain an alkoxylated derivative, and optionally subsequently reacting the alkoxylated derivative with one or more suitable reagents to obtain the final compound. For example, a compound of formula IA may be formed as follows: [ka] [In the formula, substituents X, Y, R 1 and R 2 and m is as defined above.

[0029] Suitable reactants, solvents and reaction conditions (concentration, time, temperature) for carrying out the reaction are generally known to those skilled in the art and are not limited in any way in the present invention. Depending on the choice of reactants, suitable solvents may include non-polar, polar protic and / or polar aprotic solvents, such as hydrocarbons, ethers and esters.

[0030] In another aspect, the present invention provides a composition comprising compound 1A or 1B or any of 1.1-1.42, or compound 2A or 2B or any of 2.1-2.43, or compound 3A or 3B or any of 3.1-3.42, or compound 4A or 4B or any of 4.1-4.43, 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, antifungals, hydrocarbons, stabilizers, or viscosity modifiers. In some embodiments, the composition is a pharmaceutical composition, or a cosmetic composition, or a sunscreen composition, or a plasticizing composition, or a lubricating composition, or a personal care composition (e.g., a soap, a skin cream or lotion, a balm, a shampoo, a body wash, a hydrating cream, a deodorant, an antiperspirant, an aftershave lotion, 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 detergent or a laundry detergent), or an air freshener, or a crop care formulation (e.g., a herbicide, an insecticide).

[0031] The compounds of the invention, e.g., Compounds 1A, 1B, 2A, 2B, 3A, 3B, 4A, 4B and beyond, may be used with, for example: perfumes, soaps, insect repellents and insecticides, herbicides, detergents, household cleaners, air fresheners, room sprays, scented pellets, candles, cosmetics, lotions, pre- and aftershave lotions, talcum powders, hair care products, body deodorants, antiperspirants, shampoos, colognes, shower gels, hairsprays and pet toilets.

[0032] Perfumes and ingredients and mixtures of perfume ingredients that may be used in combination with the compounds described herein to prepare perfume compositions include, but are not limited to, natural products including extracts, animal products and essential oils, anhydrides, resinoids, resins and concretes, and synthetic perfume materials including, but not limited to, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, phenols, ethers, lactones, furans, ketals, nitriles, acids, and both saturated and unsaturated compounds and aliphatic carbocyclic and heterocyclic compounds and animal products.

[0033] In some embodiments, the present invention provides personal care compositions including, but not limited to, soaps (liquid or solid), body washes, skin and hair cleansers, skin creams and lotions (e.g., facial creams and lotions, facial oils, eye creams, other anti-wrinkle products), ointments, sunscreens, moisturizers, 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, blush, bronzer, eye shadow, lip liner, lip balm), and derma cosmetics.

[0034] In some embodiments, the personal care composition may include organically derived ingredients, vegan ingredients, gluten-free ingredients, environmentally 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 less irritating and natural alternative to retinol), coloring ingredients (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.

[0035] In some embodiments, the compositions of the present invention are gluten-free.

[0036] In some embodiments, the composition of the present invention can be 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 straight chain or saturated branched chain isomers.

[0037] As used herein, the phrases "for example," "for instance," "such as," or "including" are meant to introduce examples that further clarify a more general subject matter. These examples are provided solely for the purpose of understanding the invention and are not meant to be limiting in any manner. Furthermore, as used herein, the terms "may," "optional," "optionally," or "may optionally" mean that the subsequently described circumstance may or may not occur, such that the description includes instances when said circumstance occurs and instances when it does not. For example, the phrase "optionally present" means that the object may or may not be present, and as such, the description includes instances when the object is present and absent.

[0038] As used herein, the phrase "having the formula" or "having the structure" is not intended to be limiting and is used in the same manner that the term "comprising" is generally used.

[0039] In this specification, the structural formula of a compound may conveniently represent a specific isomer in some cases, but the present invention includes all isomers, such as geometric isomers, optical isomers based on asymmetric carbon, stereoisomers, tautomers, etc. Furthermore, for the compound represented by the formula described herein, crystal polymorphism may exist. It is noted that any crystal form, crystal form mixture, or anhydride or hydrate thereof are included within the scope of the present invention.

[0040] "Tautomer" refers to a compound that differs significantly in structure in the arrangement of atoms, but exists in easy and rapid equilibrium. It should be understood that the compounds of the present invention can be shown as different tautomers. It should also be understood that when a compound has tautomeric forms, all tautomeric forms are within the scope of the present invention, and the naming of the compound does not exclude any tautomeric form. Furthermore, even if one tautomer is described, the present invention includes all tautomers of the compound that exist.

[0041] As used herein, the term "salt" refers to acid addition salts, including hydrochloride, hydrobromide, phosphate, sulfate, hydrogen sulfate, alkylsulfonate, arylsulfonate, acetate, benzoate, citrate, maleate, fumarate, succinate, lactate, and tartrate; + , K + , Li + Alkali metal cations such as Mg 2+ or Ca 2+ or an organic amine salt or an organic phosphonium salt.

[0042] All percentages used herein are by volume unless otherwise specified.

[0043] All ratios used herein are molar ratios unless otherwise specified. EXAMPLES

[0044] The preparation of polycitronellol polymers and some of their derivatives is described, for example, in US 2017 / 0283553, U.S. Patent Application No. 2020 / 0165383, U.S. Patent Application No. 2021 / 0230364, WO 2021 / 133994, WO 2021 / 146461, WO 2021 / 146448 and WO 2021 / 178217, the contents of each of which are incorporated herein by reference in their entirety.

[0045] The compounds described herein can be prepared by a number of straightforward chemical reactions. In the following exemplary scheme, the moiety "A" represents citronellol or polycitronellol in saturated or unsaturated form: [ka]

[0046] Other compounds within the scope of the invention may be prepared by similar methods.

Claims

1. A compound of general formula (I-B) in free or salt form: 【Chemical 1】 or a compound of general formula (II-A) or a compound of general formula (II-B): [Chemical 2] or a compound of general formula (III-B): [Chemical Formula 3] or a compound of general formula (IV-A) or a compound of general formula (IV-B): 【Chemical Formula 4】 〔wherein, n is an integer from 0 to 20 (e.g., 0 to 10); m is an integer from 1 to 100 (e.g., 25 to 75); X is a bond, CH ２ , CH ２ CH ２ , CH ２ C(O)-, -CH ２ CH ２ C(O)-, CH ２ C(O)O-, -CH ２ CH ２ C(O)O-, -C(O)-, -C(O)-O-, -C(O)-N(R)-, -S(O)-, -S(O ２ ), -S(O ２ ), -O- and -S(O ２ ), -N(R)- and is selected from; For Formulas I-B and III-B, Y is CH ２ , CH ２ CH ２ , -C(O)-, -C(O)-O-, -C(O)-N(R)-, -S(O)-, -S(O ２ ), -S(O ２ )-O- and -S(O ２ )-N(R)-; and is selected from For Formulas II-A, II-B, IV-A and IV-B, Y is CH ２ CH ２ , -C(O)-, -CH ２ CH ２ -C(O)-, -CH ２ CH ２ -C(O)-O-, -S(O)- or -S(O ２ )- and is selected from; R is C which may be optionally substituted by H and one or more OH groups １ -C ６ selected from alkyl (e.g., methyl); R １ is a bond, C １ -C ２０ alkyl, C ２ -C ２０ alkenyl and C ６ -C ２０ is selected from aryl; R ２ is H, OH, NH ２ , NH(C １ -C １２ alkyl), N(C １ -C １２ alkyl)(C １ -C １２ alkyl), -COOH, C １ -C ６ alkyl, -O-C １ -C １２ alkyl, -O-C ６ -C ２０ aryl, -C(O)-C １ -C １２ alkyl, -C(O)-C ６ -C ２０ aryl, -O-C(O)-C １ -C １２ alkyl, -O-C(O)-C ６ -C ２０ aryl, -C(O)-O-C １ -C １２ alkyl, -C(O)-O-C ６ -C ２０ aryl, -O-C(O)-O-C １ -C １２ alkyl, -O-C(O)-O-C ６ -C ２０ aryl, -C(O)-NH ２ , -C(O)-NH(C １ -C １２ alkyl), -C(O)-N(C １ -C １２ alkyl) ２ , -C(O)-NH-aryl, -O-C(O)-NH(C １ -C １２ alkyl), -O-C(O)-N(C １ -C １２ alkyl) ２ , -O-C(O)-NH-aryl, -SO ３ H, -SO ２ NH ２ , -S(O)-C １ -C １２ alkyl, -S(O)-C ６ -C ２０ aryl, -S(O) ２ -C １ -C １２ alkyl, -S(O) ２ -C ６ -C ２０ aryl, -O-S(O) ２ -C １ -C １２ alkyl, -O-S(O) ２ -C ６ -C ２０ aryl, -S(O) ２ -O-C １ -C １２ alkyl, -S(O) ２ -O-C ６ -C ２０ aryl, -S(O) ２ -NH(C １ -C １２ alkyl), -S(O) ２ -N(C １ -C １２ alkyl) ２ , -O-S(O) ２ -OH, -O-P(O) ２ (OH) and -P(O)(OH) ２ selected from; Said C １ -C １２ alkyl and C ６ -C ２０ each of the aryl moieties is independently halo (-F, -Cl, -Br or -I), -CN, OH, NH ２ , NH(C １ -C １２ alkyl), N(C １ -C １２ alkyl)(C １ -C １２ alkyl), -COOH, -O-C １ -C １２ alkyl, -C(O)-C １ -C １２ alkyl, -O-C(O)-C １ -C １２ alkyl, -C(O)-O-C １ -C １２ alkyl, SO ３ H, -SO ２ NH ２ , -O-S(O) ２ -OH, -O-P(O) ２ (OH) and -P(O)(OH) ２ and may optionally be further substituted with one or more groups selected from; Each R ３ is independently H, C １ -C ２０ alkyl, C ２ -C ２０ alkenyl, -C(O)-C １ -C ２０ alkyl, -C(O)-C ２ -C ２０ alkenyl, -(CH ２ CH ２ O) ｍ -CH ２ CH ２ OH, -(CH ２ CH ２ O) ｍ -CH ２ CH ２ O-C １ -C ２０ alkyl, -(CH ２ CH ２ O) ｍ -CH ２ CH ２ O-C ２ -C ２０ alkenyl, -(CH ２ CH ２ O) ｍ -CH ２ CH ２ O-C(O)-C １ -C ２０ alkyl, -(CH ２ CH ２ O) ｍ -CH ２ CH ２ O-C(O)-C ２ -C ２０ alkenyl, -(CH ２ CH(CH ３ )O) ｍ -CH ２ CH(CH ３ )OH, -(CH ２ CH(CH ３ )O) ｍ -CH ２ CH(CH ３ )O-C １ -C ２０ alkyl, -(CH ２ CH(CH ３ )O) ｍ -CH ２ CH(CH ３ )O - C ２ - C ２０ alkenyl, -(CH ２ CH(CH ３ )O) ｍ - CH ２ CH(CH ３ )O - C(O) - C １ - C ２０ alkyl and -(CH ２ CH(CH ３ )O) ｍ - CH ２ CH(CH ３ )O - C(O) - C ２ - C ２０ alkenyl, - CH ２ CH ２ OH, - CH ２ CH(CH ３ )OH, - CH ２ COOH, - CH ２ CH ２ COOH, - S(O) ２ - OH and - P(O) ２ (OH) is selected from, or For a compound of formula II-A or II-B, one or both of the Rs ３ is of the formula: 【Chemical Formula 5】 has a structure of or For a compound of formula IV-A or IV-B, one or both of the Rs ３ is of the formula: 【Chemical Formula 6】 is a structure of〕

2. A compound of general formula (I-A) in free or salt form: 【Chemical Formula 7】 or a compound of general formula (III-A): 【Chemical 8】 〔wherein, m is an integer from 1 to 100 (e.g., 25 to 75); X is selected from a bond, CH₂, CH₂CH₂, CH₂C(O)-, -CH₂CH₂C(O)-, CH₂C(O)O-, -CH₂CH₂C(O)O-, -C(O)-, -C(O)-O-, -C(O)-N(R)-, -S(O)-, -S(O₂)-, -S(O₂)-O- and -S(O₂)-N(R)-; Y is selected from CH₂, CH₂CH₂, -C(O)-, -C(O)-O-, -C(O)-N(R)-, -S(O)-, -S(O₂)-, -S(O₂)-O- and -S(O₂)-N(R)-; R is selected from H and C₁-C₆ alkyl (e.g., methyl) optionally substituted with one or more OH; R₁ is selected from a bond, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl and C₆-C₂₀ aryl; R2 is selected from NH2, NH(C1-C12 alkyl), N(C1-C12 alkyl)(C1-C12 alkyl), -COOH, C1-C6 alkyl, -O-C1-C12 alkyl, -O-C6-C20 aryl, -C(O)-C1-C12 alkyl, -C(O)-C6-C20 aryl, -O-C(O)-C1-C12 alkyl, -O-C(O)-C6-C20 aryl, -C(O)-O-C1-C12 alkyl, -C(O)-O-C6-C20 aryl, -O-C(O)-O-C1-C12 alkyl, -O-C(O)-O-C6-C20 aryl, -C(O)-NH2, -C(O)-NH(C1-C12 alkyl), -C(O)-N(C1-C12 alkyl)2, -C(O)-NH-aryl, -O-C(O)-NH(C1-C12 alkyl), -O-C(O)-N(C1-C12 alkyl)2, -O-C(O)-NH-aryl, -SO3H, -SO2NH2, -S(O)-C1-C12 alkyl, -S(O)-C6-C20 aryl, -S(O)2-C1-C12 alkyl, -S(O)2-C6-C20 aryl, -O-S(O)2-C1-C12 alkyl, -O-S(O)2-C6-C20 aryl, -S(O)2-O-C1-C12 alkyl, -S(O)2-O-C6-C20 aryl, -S(O)2-NH(C1-C12 alkyl), -S(O)2-N(C1-C12 alkyl)2, -O-S(O)2-OH, -O-P(O)2(OH) and -P(O)(OH)2; Each of said C1-C12 alkyl and C6-C20 aryl moieties may be further optionally substituted with one or more groups selected from halo (-F, -Cl, -Br or -I), -CN, OH, NH2, NH(C1-C12 alkyl), N(C1-C12 alkyl)(C1-C12 alkyl), -COOH, -O-C1-C12 alkyl, -C(O)-C1-C12 alkyl, -O-C(O)-C1-C12 alkyl, -C(O)-O-C1-C12 alkyl, SO3H, -SO2NH2, -O-S(O)2-OH, -O-P(O)2(OH) and -P(O)(OH)2; Each R3 is independently H, C1-C20 alkyl, C2-C20 alkenyl, -C(O)-C1-C20 alkyl, -C(O)-C2-C20 alkenyl, -(CH2CH2O)m-CH2CH2OH, -(CH2CH2O)m-CH2CH2O-C1-C20 alkyl, -(CH2CH2O)m-CH2CH2O-C2-C20 alkenyl, -(CH2CH2O)m-CH2CH2O-C(O)-C1-C20 alkyl, -(CH2CH2O)m-CH2CH2O-C(O)-C2-C20 alkenyl, -(CH2CH(CH3)O)m-CH2CH(CH3)OH, -(CH2CH(CH3)O)m-CH2CH(CH3)O-C1-C20 alkyl, -(CH2CH(CH3)O)m-CH2CH(CH3)O-C2-C20 alkenyl, -(CH2CH(CH3)O)m-CH2CH(CH3)O-C(O)-C1-C20 alkyl and -(CH2CH(CH3)O)m-CH2CH(CH3)O-C(O)-C2-C20 alkenyl, -CH2CH2OH, -CH2CH(CH3)OH, -CH2COOH, -CH2CH2COOH, -S(O)2-OH and -P(O)2(OH); [

3. ] n is an integer from 0 to 10, for example, from 0 to 8, or from 0 to 6, or from 0 to 5, or any one of 0, 1, 2, 3 or 4, and m is an integer from 1 to 75, for example, from 1 to 25, from 25 to 50, from 50 to 75, from 25 to 75, from 1 to 10, from 11 to 20, from 21 to 30, from 31 to 40, from 41 to 50, from 51 to 60, from 61 to 75 or any combination thereof, the compound according to claim 1.

4. m is an integer from 1 to 75, for example, from 1 to 25, from 25 to 50, from 50 to 75, from 25 to 75, from 1 to 10, from 11 to 20, from 21 to 30, from 31 to 40, from 41 to 50, from 51 to 60, from 61 to 75 or any combination thereof, the compound according to claim 2.

5. X is a bond, CH ２ , -C(O)-, -C(O)-O- and -C(O)-N(R)-, where the compound is of formula I-A, I-B, III-A or III-B, Y is selected from CH₂, CH₂CH₂ and -C(O)-, and R₁ is selected from a bond, C₁-C₂₀ alkyl and C₂-C₂₀ alkenyl; or the compound is of formula II-A, II-B, IV-A or IV-B, Y is selected from CH₂CH₂, -C(O)-, -CH₂CH₂-C(O)- and -CH₂CH₂-C(O)-O-, and R₃ is selected from a bond, C₁-C₂₀ alkyl and C₂-C₂₀ alkenyl, the compound according to any one of claims 1 to 4.

6. R ２ is H, OH, NH ２ , NH(C １ -C １２ alkyl), N(C １ -C １２ alkyl)(C １ -C １２ alkyl), -COOH, C1-C6 alkyl, -O-C1-C12 alkyl, -O-C6-C20 aryl, -C(O)-C1-C12 alkyl, -C(O)-C6-C20 aryl, -O-C(O)-C1-C12 alkyl, -O-C(O)-C6-C20 aryl, -C(O)-O-C1-C12 alkyl, -C(O)-O-C6-C20 aryl, -O-C(O)-O-C1-C12 alkyl, -O-C(O)-O-C6-C20 aryl, -C(O)-NH2, -C(O)-NH(C1-C12 alkyl), -C(O)-N(C1-C12 alkyl)2, -C(O)-NH-aryl, -O-C(O)-NH(C1-C12 alkyl), -O-C(O)-N(C1-C12 alkyl)2) and -O-C(O)-NH-aryl;In some cases, R2 is selected from NH2, NHCH3, NH(CH3)2, OCH3, -C(O)CH3, -O-C(O)-CH3, -COOH, -SO3H, -O-S(O)2-OH, -O-P(O)2(OH), -P(O)(OH)2, -O-C1-C3 alkyl, -C(O)-C1-C3 alkyl, -O-C(O)-C1-C3 alkyl, -C(O)-O-C1-C3 alkyl, -O-C(O)-O-C1-C3 alkyl, where each of the C1-C3 alkyls is selected from CH2CH2OH, CH(OH)CH2(OH), CH2CH(OH)CH3, CH2CH(OH)CH2OH, CH(OH)CH(OH)CH2OH, -OCH2CH2OH, -OCH2CH(OH)CH3, -OCH2CH(OH)CH2OH, -(CO)-CH2CH2OH, -(CO)-CH2CH(OH)CH3, -C(O)-CH2CH(OH)CH2OH, -O(CO)-CH2CH2OH, -O(CO)-CH2CH(OH)CH3, -OC(CO)-CH2CH(OH)CH2OH, -(CO)-O-CH2CH2OH, -(CO)-O-CH2CH(OH)CH3, and -C(O)-O-CH2CH(OH)CH2OH, the compound according to claim 2 or 4.;

7. The compound according to claim 1, wherein the compound is a compound of formula II-A or II-B.

8. The compound according to claim 1, wherein the compound is a compound of formula IV-A or IV-B.

9. R ３ is H, C １ -C ２０ alkyl and C ２ -C ２０ The compound according to claim 7 or 8, selected from

10. R ３ is -C(O)-C １ -C ２０ alkyl or -C(O)-C ２ -C ２０ alkenyl, a compound according to claim 7 or 8.

11. R ３ is -CH ２ CH ２ OH, -CH ２ CH(CH ３ )OH, -CH ２ COOH, -CH ２ CH ２ COOH, -S(O) ２ -OH or -P(O) ２ (OH), a compound according to claim 7 or 8.

12. R ３ is: [Chemical Formula 7] The compound according to claim 7, which is

13. R ３ is: 【Chemical 8】 The compound according to claim 12, which is

14. R ３ is: 【Chemical Formula 9】 The compound according to claim 8, which is

15. R ３ is: 【Chemical Formula 10】 The compound according to claim 14, which is

16. The compound according to any one of claims 1 to 4, optionally in a mixture with one or more pharmaceutically acceptable, cosmetically acceptable or industrially acceptable excipients or carriers, such as solvents, oils, surfactants, skin softeners, diluents, flow promoters, abrasives, wetting agents, polymers, plasticizers, catalysts, antioxidants, colorants, flavoring agents, fragrances, antiperspirants, antibacterial agents, antifungal agents, hydrocarbons, stabilizers or viscosity regulators.

17. The composition according to claim 16, wherein the composition is a pharmaceutical composition, or a cosmetic composition, or a sunscreen composition, or a plasticizer composition, or a lubricant composition, or a personal care composition (for example, soap, skin cream or lotion, perfume oil, shampoo, body wash, moisturizing cream, deodorant, antiperspirant, aftershave lotion, cologne, perfume or other hair care or skin care products), or a cleaning composition (for example, surface cleaner, metal cleaner, wood cleaner, glass cleaner, body cleaner such as soap, dishwashing detergent or laundry detergent), or an air freshener, or a crop care formulation (for example, herbicide, insecticide).

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