Bio-based surfactants

Abstract

Compounds of general formula (Ia), (Ib) and (Ic), R 50 and R 60 are different from each other, and -R 70 , -ZR 70 , -Z-OH, -Z-NH2, -Z-SH, -Z-OC(O)R 70 , -OC(O)R 70 , -COOH and its corresponding salts, -C(O)NH2, -C(O)NH-R 70 , -C(O)N-(R 70 )2, -COOR 70 , -Z-COOH and its corresponding salts, -ZC(O)NH-R 70 , -ZC(O)NH2, -ZC(O)N-(R 70 )2, -Z-COOR 70 , -CH(COOH)2 and its corresponding salts, -CH(COOR 70 )2, and -Z-SO3 - wherein R 70 is a straight or branched chain C1-C 20 Alkyl, (C1-C 10 )-Alkyloxy-(C1-C 10 )-Alkyl, C2-C 10 Alkenyl, C6-C 12 Aryl, C3-C 10 cycloalkyl, cycloalkylalkyl, and cycloalkylalkenyl, wherein Z is a straight or branched C1-C 10 Alkyl, straight or branched chain C3-C 10 Cycloalkyl, linear or branched C6-C 10 Aryl or (C1-C 10 )-Alkyloxy-(C1-C 10 )-alkyl, cycloalkylalkyl and cycloalkylalkenyl. JPEG2025511992000055.jpg101128

Description

[Technical field]

[0001] The present invention relates to novel compounds and their use as biosurfactants. [Background technology]

[0002] Surfactants are a type of chemical product used in a wide range of applications and fields, including detergent, medical, pharmaceutical, food and paint industries. With the advent of the COVID-19 pandemic, the demand for surfactants has increased due to the ability of these compounds in soap and sanitizing compositions to disrupt the lipid membrane of the SARS-CoV-2 virus, neutralizing the virus.

[0003] Given the huge market and great demand for surfactants, it is important that their production does not rely exclusively on fossil-based sources, but it is increasingly essential that they are synthesised and sourced from renewable raw materials that have a lesser impact on the second current global challenge: climate change.

[0004] Furthermore, given that surfactants have a short life span and generally tend to wash off and end up outdoors, their structure must have degradable products and be compatible with the environment they end up in, so that they do not accumulate and cause harm to various species and ecosystems.

[0005] Biosurfactants (sophorolipids, rhamnolipids) are commercially available. Sophorolipids are commercialized by Ecover™, Saraya™, Intobio™, Evonik™ and Allied Carbon Solutions™. They all have a critical micelle concentration (CMC) 7-10 times lower than that of SDS, but they need to be produced using yeast (average fermentation period: 7 days) and fatty acids from tropical plants, which is still an environmental pressure due to the problem of deforestation.

[0006] U.S. Patent Application Publication No. 2021 / 353517(A1) discloses a method for producing a bio-based surfactant including an alkyl disulfate salt, the method comprising the steps of methanolyzing a medium-chain-length polyhydroxyalkanoic acid (mcl-PHA) to obtain a hydroxy fatty acid methyl ester monomer (HFAME), reducing the HFAME to obtain a 1,3 alkyl diol, sulfate- ing the 1,3 alkyl diol to obtain a 1,3 alkyl disulfate, and neutralizing the alkyl disulfate to obtain a bio-based surfactant including a 1,3 alkyl disulfate salt.

[0007] In particular, sugar (or its derivatives) based surfactants have attracted much attention and development due to the variety of chemical reactions possible on the hydroxyl groups of their core structure. Typical sugar-based molecules or derivatives that can be chemically reacted to form surfactants are xylose, glucose, sorbitol, sorbitan, arabinose, isosorbide, and uronic acids. Among the possible reactions that have been investigated in the production of sugar-based surfactants, the most common is the esterification of the hydroxyl groups of the sugar with long-chain acids, as is the case for the commercial Span and Tween® derived from sorbitol. Other important reactions of sugars to produce surfactants are etherification to form simple ethers, or reaction with long-chain aldehydes to form stable acetals. Finally, in the case of uronic acids, amide-based surfactants can be synthesized. Some of these reactions, although successful (such as the case for the commercial sorbitan-based esters), are based on sugars or derivatives that undergo several synthetic steps of reduction, isomerization or dehydration of more abundant sugars before becoming surfactants, which increases the environmental and energy impacts of each synthetic step. Summary of the Invention

[0008] It is therefore an object of the present invention to provide bio-based surfactants which can be synthesised in a few steps directly from renewable sources.

[0009] This problem is solved by the compounds according to claim 1. Further preferred embodiments are the subject matter of the dependent claims. [Brief description of the drawings]

[0010] [Figure 1a] Emulsion formation of the extract of a mixture of compounds 2' and 3' in a system containing ethyl acetate and water (vial 1) compared with pure 1-octanol in the same system (vial 2) and the system itself (vial 3). [Figure 1b] Optical microscope images of water / oil emulsions (1 mL water + 2 mL cyclohexane containing 0.1% 3,5-O-dodecylidene-xylose emulsifier) ​​at days 0, 7, 14, and 30. [Figure 1c] Optical microscope images of water / oil emulsion (1 mL water + 2 mL cyclohexane containing 0.1% 2-((dodecyloxy)methyl)tetrahydrofuran-3,4-diol) at days 0, 7, 14, and 30. [Diagram 2] Long-term stability study at room temperature of w / o emulsion (67% water and 33% cyclohexane) containing 1% 3,5-O-dodecylidene-xylose. [Figure 3A] Gas chromatography-mass spectrometry spectra of 3,5-O-octylidene-xylose (MAX8), 3,5-O-decylidene-xylose (MAX10), and 3,5-O-dodecylidene-xylose (MAX12). [Figure 3B] Gas chromatography-mass spectrometry spectra of 3,5-O-octylidene-xylose (MAX8), 3,5-O-decylidene-xylose (MAX10), and 3,5-O-dodecylidene-xylose (MAX12). [Figure 4A] Gas chromatography-mass spectrometry spectra of dioctylidene-xylose (DAX8), didecylidene-xylose (DAX10), and didodecylidene-xylose (DAX12). [Figure 4B]Gas chromatography-mass spectrometry spectra of dioctylidene-xylose (DAX8), didecylidene-xylose (DAX10), and didodecylidene-xylose (DAX12). [Diagram 5] Gas chromatography-mass spectrometry spectrum of 3,5-O-(E)-dodec-2-en-1-ylidene-xylose (MAX12:1(2)). [Figure 6] Gas chromatography-mass spectrometry spectrum of 3,5-O-octadecylidene-xylose (MAX18). [Figure 7] Interfacial tension of the cyclohexane-water interface at different concentrations of MAXn. [Figure 8] Amphiphilic molecules obtained from hydrogenolysis of didodecylidene-xylose and interfacial tension measurements of the obtained amphiphilic molecules at different concentrations between cyclohexane and water. [Figure 9] (A) Interfacial tension measurements of hydrocracking mixtures of DAX12, DAX10 and DAX8, and (B) performance of the hydrocracking mixture of DAX12 under different reaction conditions. [Figure 10] Interfacial tension at the cyclohexane-water (50.2 Mn / M) interface for 1,2-o-dodecylidene α-d-xylofuranose and several of the most common commercial surfactants at different concentrations. [Figure 11] Interfacial tension at the cyclohexane-water (50.2 Mn / M) interface for different concentrations of 2-((dodecyloxy)methyl)tetrahydrofuran-3,4-diol and some of the most common commercial surfactants. [Figure 12] Interfacial tension at the cyclohexane-water (50.2 mN / m) interface for different concentrations of 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (GMAX) and some of the most common commercial surfactants. [Figure 13] Interfacial tension at the cyclohexane-water (50.2 mN / m) interface for different concentrations of 3,5-O-(E)-dodec-2-en-1-ylidene-xylose (MAX12:1(2)) and some of the most common commercial surfactants. [Figure 14]Interfacial tension at the cyclohexane-water (50.2 mN / m) interface for different concentrations of 3,5-O-octadecylidene-xylose (MAX18) and some of the most common commercial surfactants. [Figure 15] Interfacial tension versus concentration for 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (GMAX), the sodium salt of 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (SGMAX), and some of the most common commercially available anionic surfactants. [Figure 16] Accelerated aqueous decomposition of MAX12 in boiling water. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] As described in detail below, the compounds of formula Ia, Ib, Ic, II and III can be obtained based on aldehyde-assisted biomass fractionation and acetal functionalization from sugar-based molecules.The compounds of the present invention are biodegradable and do not have adverse effects on human and animal health.In addition, the compounds of the present invention are derived from renewable resources, so they have no or very limited adverse effects on fauna, flora and ecosystems.Furthermore, the synthesis of the compounds according to the present invention is simple, allowing large-scale production of bio-based surfactants.

[0012] The present invention relates to compounds of formula (Ia), (Ib) or (Ic) [ka] (In the formula, R 50 and R 60 are different from each other, -R 70 , -ZR 70 , -Z-OH, -Z-NH2, -Z-SH, -Z-OC(O)R 70 , -OC(O)R 70 , -COOH and its corresponding salts, -C(O)NH2, -C(O)NH-R 70 , -C(O)N-(R 70 )2, -COOR 70, -Z-COOH and its corresponding salts, -ZC(O)NH-R 70 , -ZC(O)NH2, -ZC(O)N-(R 70 )2, -Z-COOR 70 , -CH(COOH)2 and its corresponding salts, -CH(COOR 70 )2, and -Z-SO3 - is selected from the group consisting of In the formula, R 70 is a straight or branched chain C1-C 20 Alkyl, (C1-C 10 )-Alkyloxy-(C1-C 10 )-Alkyl, C2-C 15 Alkenyl, C6-C 12 Aryl, C3-C 10 selected from the group consisting of cycloalkyl, cycloalkylalkyl, and cycloalkylalkenyl; In the formula, Z is a linear or branched C1-C 10 Alkyl, straight or branched C3-C 10 Cycloalkyl, linear or branched C6-C 10 Aryl or (C1-C 10 )-Alkyloxy-(C1-C 10 )-alkyl, cycloalkylalkyl and cycloalkylalkenyl.

[0013] Residues: Straight or branched C1-C 20 The term "alkyl" refers to a straight or branched hydrocarbon chain containing 1 to 20 carbon atoms. Examples of said term as used herein include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 3-methylbutyl, sec-pentyl, and 2-methylbutan-2-yl.

[0014] Residues: (C1-C 10 )-Alkyloxy-(C1-C 10 The term "alkyl" refers to the residue -(C-C 10 )-O-(C1-C 10)-, i.e., a straight or branched hydrocarbon chain preferably containing 1 to 20 carbon atoms, at least two of which are single-bonded to oxygen. Examples of said terms as used herein include 2-ethylethoxy, 2-ethylpropoxy, 2-ethylpropoxy, 1-ethylbutoxy, 3-ethylbutoxy, and 2-ethylpropoxy.

[0015] Residues: Straight or branched C2-C 20 The term "alkenyl" refers to a straight or branched hydrocarbon chain containing 2 to 20 carbon atoms, including at least one double bond. The double bond may be at any position in the straight or branched hydrocarbon chain. In a branched hydrocarbon chain, the double bond is typically located between two adjacent carbon atoms in the longest continuous carbon chain, which may include one or more branches. Preferably, the position of the double bond is directly adjacent to the ring system, i.e., the alpha position of the ring system. One possible example is -CH=CH-(CH2)8-CH3.

[0016] "C6~C 12 The term "aryl" refers to an aromatic carbocyclic ring system having any suitable number of ring atoms and any suitable number of rings. Aryl groups can contain any suitable number of carbon ring atoms, for example, 6, 7, 8, 9, 10, 11, or 12 ring atoms, and 6 to 10 or 6 to 12 ring members. Aryl groups can be monocyclic or fused to form bicyclic or tricyclic groups, or joined by bonds to form biaryl groups. Representative aryl groups include phenyl, naphthyl, and biphenyl. Some aryl groups have 6 to 12 ring members (e.g., phenyl, naphthyl, or biphenyl). Other aryl groups have 6 to 10 ring members (e.g., phenyl or naphthyl). Some other aryl groups have 6 ring members (e.g., phenyl).

[0017] The term "cycloalkyl" means a non-aromatic monocyclic ring system containing 3 to 10 carbon atoms, preferably 5 to 10 carbon atoms. Preferred cycloalkyl rings contain about 5 to about 7 ring atoms. Non-limiting examples of suitable monocyclic cycloalkyls include cyclopentyl, cyclohexyl, cycloheptyl, and the like.

[0018] The term "cycloalkylalkyl" refers to the residue -R a R b where R a is an alkylene group having 1 to 8 carbon atoms, R b is a cycloalkyl group as defined above.

[0019] The term "cycloalkylalkenyl" refers to the residue -R a 'R b where R a R ' is an alkenylene group having 2 to 8 carbon atoms; b is a cycloalkyl group as defined above.

[0020] The term "or its corresponding salt" refers to a carboxylate formed by reaction of a carboxylic acid with a base, i.e., sodium carboxylate.

[0021] The compounds of the present invention are preferably used as non-ionic surfactants, which generally comprise an acetal-stabilized sugar core and a residue R (e.g., R 11 or R 31 ) and have the same properties as polyoxyethylene surfactants and sugar-derived polyols.

[0022] Polyoxyethylene surfactants exhibit inverse solubility properties and can precipitate with increasing temperature. At low temperatures, the chains of polyoxyethylene surfactants can interact with water molecules, keeping the surfactant molecules soluble in aqueous solutions. However, as the temperature increases, the thermal motion of water molecules becomes more active, which reduces the strength of the hydrogen bond interactions between the POE chains and the water molecules.

[0023] Sugar-derived polyols, such as compounds with a sugar core functionalized with pH-responsive functional groups, e.g., carboxylic acid (-COOH) or amine (-NH2), are highly pH-responsive. Their solubility is strongly pH-dependent, and some bonds are not very stable under very acidic or very basic conditions. Thus, they can be easily degraded after use without putting a burden on the environment. On the other hand, by exchanging functional groups, sugar-derived polyols can be adapted from working in a lower pH range to working in a form adapted to a higher pH range.

[0024] These combined properties allow the compounds according to the present invention to exhibit complex and multi-responsive behavior when the temperature and pH of the solution are changed. The resulting potential applications include use as thermoresponsive and chelating amino acid modified surfactants, thermoresponsive functional surfactants, tethered lipid membranes with variable hydrophilic cushions, or hydrophilic and thermoresponsive drug carriers. Furthermore, these compounds can be used as surfactants in household and industrial cleaning agents.

[0025] Due to the diversity of residues in the claimed compounds, different types of effects can be expected.

[0026] Compounds containing ester groups are more susceptible to hydrolysis, especially in alkaline conditions, which means that esters are preferably used as emulsifiers and stabilizers under neutral conditions in personal care, food, and pharmaceutical applications.

[0027] Compounds containing amide groups are relatively more stable than those containing ester groups and tend to be hydrolyzed only under harsh conditions, such as strong acid (e.g., H2SO4) in combination with heat or strong base (e.g., NaOH) in combination with heat.

[0028] Compounds containing alkyl ether groups are relatively stable in alkaline environments, but can be transformed under acid catalysis into furans and then into humins (sugar degradation products). They can be used for cleaning under mild conditions, such as in personal care, dishwashing liquids, but also in applications where alkaline conditions are required. Compounds with alkyl ether groups are expected to be resistant to hard water conditions (between 120 and 180 mg CaCO3 / L).

[0029] Compounds containing carboxylic acid groups open up many application possibilities due to their pH-responsiveness. The degree of ionization of the carboxylic acid residue depends on the pH of the solution. Furthermore, the high reactivity of the carboxylic acid residue allows the preparation of surfactants tailored to specific purposes. The simultaneous presence of ether units and carboxylic acid residues allows the preparation of surfactants with long alkyl chains (C 12 ~C 18 Clear solutions of surfactants having the formula (I) can be obtained in alkaline and acidic solutions, which are extremely stable in hard water and high salinity conditions. Combined with low toxicity, stability against hydrolysis, oxidizing agents and high temperatures, the surfactants will find application in a variety of fields, most notably as detergents, and in home and body care products, for oil recovery enhancement, and as additives in the textile and metal processing industries.

[0030] A preferred embodiment of the present invention is a compound (Ib) or (Ic) in which R 50 or R 60 -R 70 where -R 70 Straight chain C7~C 19 Alkyl, preferably straight chain C9-C 17 Alkyl, more preferably linear C 11 The compound (Ib) or (Ic) is

[0031] Linear alkyl chains, especially dodecanal (C 12The linear alkyl chains (Ib) or (Ic) can be used as starting materials for the production of compounds (Ib) or (Ic) with linear alkyl chains. These linear alkyl chains can be synthesized sustainably in industry using vegetable oils such as coconut oil, palm oil, or castor oil through a process involving hydrolysis, reduction, and selective oxidation. Compared to alkenyl, alkoxy, and aryl, linear alkyl chains, especially dodecanal, are relatively low-cost raw materials. In the acetalization reaction, the strong electrophilicity of the carbonyl group in the alkyl aldehyde allows the production of highly stable products in high yields. C 11 Compounds (Ib) and (Ic) having alkyl chains are 11 Due to the alkyl chain, they have a desirable balance of hydrophilic and hydrophobic properties, a unique property that is valued in a variety of applications where a balance between water and oil solubility is required.

[0032] A preferred embodiment of the present invention is compound (Ib), wherein R 50 -R 70 where -R 70 Straight chain C7~C 19 Alkyl, preferably straight chain C9-C 17 Alkyl, more preferably linear C 11 The compound (Ib) is alkyl.

[0033] A preferred embodiment of the present invention is compound (Ic), wherein R 60 -R 70 where -R 70 Straight chain C7~C 19 Alkyl, preferably straight chain C9-C 17 Alkyl, more preferably linear C 11 The compound (Ic) is an alkyl group.

[0034] A preferred embodiment of the present invention is compound (Ib), wherein R 50 -R 70 where -R 70 is linear C2~C 15 Alkenyl, preferably straight chain C9-C13 Alkenyl, more preferably linear C 11 The compound (Ib) is alkenyl.

[0035] A preferred embodiment of the present invention is compound (Ib), wherein R 50 -R 70 where -R 70 is linear C2~C 15 Alkenyl, preferably straight chain C9-C 13 Alkenyl, more preferably linear C 11 alkenyl, the double bond being preferably in the alpha position.

[0036] The present invention further relates to a compound of general formula (V) [ka] (In the formula, R 90 is a straight or branched chain C1-C 20 Alkyl, (C1-C 10 )-Alkyloxy-(C1-C 10 )-Alkyl, C2-C 10 Alkenyl, C6-C 12 Aryl, C3-C 10 cycloalkyl, cycloalkylalkyl, and cycloalkylalkenyl.

[0037] One embodiment of the present invention relates to compound (V), wherein R 90 are -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11 CH3, -(CH2) 12 CH3, -(CH2) 13 CH3 and -(CH2) 14 CH3, preferably -(CH2) 11 CH3.

[0038] One embodiment of the present invention is the compound (Va) [ka] Regarding.

[0039] Compound (V) can be synthesized by palladium-catalyzed hydrogenolysis of starting material compound (Ia) having a symmetric chain group. This synthesis is easy to carry out and reduces costs. As described above, 11 The compound (Ia) having an alkyl chain has a desirable balance of hydrophilicity and hydrophobicity. 11 The compound (Ia) having an alkyl chain is the preferred starting material, which is 12 This results in a compound (Va) having an alkyl residue.

[0040] The compounds of the general formula (Ia), (Ib), (Ic) and (V) of the present invention can be used as surfactants, preferably as emulsifiers, foam stabilizers, wetting agents, emollients in cosmetics, surfactants in food, anti-splash agents for fried foods, or surfactants in pharmaceuticals. In particular, they can maintain emulsion stability over time, even under different conditions such as temperature changes or exposure to air. Moreover, they show high compatibility with other ingredients and produce stable and consistent emulsions.

[0041] The present invention also relates to compounds of the general formula (I), (II) and (III) [ka] (In the formula, R 11 and R 12 Or R 21 and R 22 Or R 31 and R 32 are both hydrogen or CHR 50 together with R to form a cyclic moiety, or 11 and R 12 Or R 21 and R 22 Or R 31 and R32 One of them is hydrogen and the other is -CHR 70 and In the formula, R 13 and R 14 or R 23 and R 24 or R 33 and R 34 are both hydrogen or CHR 60 together to form a cyclic moiety, R 50 and R 60 are different from each other, -R 70 , -ZR 70 , -Z-OH, -Z-NH2, -Z-SH, -Z-OC(O)R 70 , -OC(O)R 70 , -COOH, -C(O)NH2, -C(O)NH-R 70 , -C(O)N-(R 70 )2, -COOR 70 , -Z-COOH, -ZC(O)NH-R 70 , -ZC(O)NH2, -ZC(O)N-(R 70 )2, -Z-COOR 70 , -CH(COOH)2, -CH(COOR 70 )2, and -Z-SO3 - is selected from the group consisting of In the formula, R 70 is a straight or branched chain C1-C 20 Alkyl, (C1-C 10 )-Alkyloxy-(C1-C 10 )-Alkyl, C2-C 10 Alkenyl, C6-C 12 Aryl, C3-C 10 selected from the group consisting of cycloalkyl, cycloalkylalkyl, and cycloalkylalkenyl; In the formula, Z is a linear or branched C1-C 10 Alkyl, straight or branched C3-C 10 Cycloalkyl, straight or branched C6-C 10 Aryl, (C1-C 10 )-Alkyloxy-(C1-C 10cycloalkylalkyl, and cycloalkylalkenyl; however, R 11 , R 12 , R 13 and R 14 or R 21 , R 22 , R 23 and R 24 or R 31 , R 32 , R 33 and R 34 Not all of it is hydrogen, R 11 and R 12 or R 21 and R 22 or R 31 and R 32 One of them is hydrogen and the other is -CHR 70 If so, then R 13 and R 14 or R 23 and R 24 or R 33 and R 34 -CHR 60 (In the formula, R 60 is R 70 which together with the group (a) form a cyclic moiety.

[0042] One embodiment of the present invention relates to compound Ia. [ka] (In the formula, R 50 and R 60 is defined as follows: [Table 1]

[0043] One embodiment of the present invention relates to compound Ia. [ka] (In the formula, R 50 and R 60is defined as follows: [Table 2]

[0044] One embodiment of the present invention is compound Ib [ka] (In the formula, R 50 -R 70 , -Z-OC(O)-R 70 , -C(O)-OR 70 , -ZC(O)OR 70 , -C(O)NH-R 70 , -ZC(O)NH-R 70 , -CH(COOR 70 )2, preferably -ZC(O)-OR 70 , -C(O)-OR 70 and -R 70 and most preferably selected from the group consisting of -C(O)-O(CH2)4CH3, -C(O)-O(CH2)5CH3, -C(O)-O(CH2)6CH3, -C(O)-O(CH2)7CH3, -C(O)-O(CH2)8CH3, -C(O)-O(CH2)9CH3, -C(O)-O(CH2) 10 CH3, -C(O)-O(CH2) 11 CH3, -C(O)-O(CH2) 12 CH3, -C(O)-O(CH2) 13 CH3, -C(O)-O(CH2) 14 CH3, -CH2-C(O)-O(CH2)4CH3, -CH2-C(O)-O(CH2)5CH3, -CH2-C(O)-O(CH2)6CH3, -CH2-C (O)-O(CH2)7CH3, -CH2-C(O)-O(CH2)8CH3, -CH2-C(O)-O(CH2)9CH3, -CH2-C(O)-O(CH2) 10 CH3, -CH2-C(O)-O(CH2) 11 CH3, -CH2-C(O)-O(CH2) 12 CH3, -CH2-C(O)-O(CH2) 13CH3, -CH2-C(O)-O(CH2) 14 CH3, -(CH2)2-C(O)-O(CH2)4CH3, -(CH2)2-C(O)-O(CH2)5CH3, -(CH2)2-C(O)-O(CH2)6CH3, -(CH2)2-C(O)-O(CH2)7CH3, -(CH2)2-C(O)-O(CH2)8CH3, -(CH2)2-C(O)-O(CH2)9CH3, -(CH2)2-C(O)-O(CH2) 10 CH3, -(CH2)2-C(O)-O(CH2) 11 CH3, -(CH2)2-C(O)-O(CH2) 12 CH3, -(CH2)2-C(O)-O(CH2) 13 CH3, -(CH2)2-C(O)-O(CH2) 14 CH3, -(CH2)3-C(O)-O(CH2)4CH3, -(CH2)3-C(O)-O(CH2)5CH3, -(CH2)3-C(O)-O(CH2)6CH3, -(CH2)3-C(O)-O(CH2)7CH3, -(CH2)3-C(O)-O(CH2)8CH3, -(CH2)3-C(O)-O(CH2)9CH3, -(CH2)3-C(O)-O(CH2) 10 CH3, -(CH2)3-C(O)-O(CH2) 11 CH3, -(CH2)3-C(O)-O(CH2) 12 CH3, -(CH2)3-C(O)-O(CH2) 13 CH3, -(CH2)3-C(O)-O(CH2) 14 CH3, -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11 CH3, -(CH2) 12 CH3, -(CH2) 13 CH3, and -(CH2) 14 relates to those selected from the group consisting of).

[0045] One embodiment of the present invention is compound Ic

Chemical formula

[0046] One embodiment of the present invention is compound Ic [ka] (In the formula, R 60 -R 70 and -R 70 are -CH3, -(CH2)CH3, -(CH2)2CH3, -(CH2)3CH3, -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11CH3, -(CH2) 12 CH3, -(CH2) 13 CH3, -(CH2) 14 CH3, -(CH2) 15 CH3, -(CH2) 16 CH3, -(CH2) 17 CH3, -(CH2) 18 CH3 and -(CH2) 19 CH3; Preferably, -R 70 are -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3 and -(CH2) 10 CH3; More preferably, -R 70 is -(CH2) 10 (CH3).

[0047] Another aspect of the invention relates to a compound of formula (I), (II) or (III): [ka] [ka] [ka] (In the formula, R 50 , R 60 and R 70 has the same definition as above.

[0048] In the compounds of formula (I), (II) or (III), preferably R 50 and R 60 At least one of the groups is -Z-OC(O)R 70 , -COOR 70 and -Z-COOR 70 and the other is selected from the group consisting of -Z-OH, -COOH and -Z-COOH.

[0049] One embodiment of the present invention relates to compound Id [ka] (In the formula, R 70 are -CH3, -(CH2)CH3, -(CH2)2CH3, -(CH2)3CH3, -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11 CH3, -(CH2) 12 CH3, -(CH2) 13 CH3, -(CH2) 14 CH3, -(CH2) 15 CH3, -(CH2) 16 CH3, -(CH2) 17 CH3, -(CH2) 18 CH3 and -(CH2) 19 CH3; Preferably, R 70 are -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11 CH3, -(CH2) 12 CH3, -(CH2) 13 CH3, -(CH2) 14 CH3; More preferably, R 70 are -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3 and -(CH2) 10 CH3; Most preferably, R 70 is -(CH2) 10 (CH3).

[0050] One embodiment of the present invention is the compound Ie [ka] (In the formula, R 70are -CH3, -(CH2)CH3, -(CH2)2CH3, -(CH2)3CH3, -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11 CH3, -(CH2) 12 CH3, -(CH2) 13 CH3, -(CH2) 14 CH3, -(CH2) 15 CH3, -(CH2) 16 CH3, -(CH2) 17 CH3, -(CH2) 18 CH3 and -(CH2) 19 CH3; Preferably, R 70 are -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11 CH3, -(CH2) 12 CH3, -(CH2) 13 CH3 and -(CH2) 14 CH3; More preferably, R 70 are -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3 and -(CH2) 10 CH3; Most preferably, R 70 is -(CH2) 10 (CH3).

[0051] One embodiment of the present invention relates to compound IIa. [ka] (In the formula, R 50 and R 60 is defined as follows: [Table 3]

[0052] One embodiment of the present invention is compound IIb [ka] (In the formula, R 50 is -Z-OC(O)R 70 , -COOR 70 and -Z-COOR 70 and most preferably selected from the group consisting of -CH2-OC(O)(CH2)4CH3, -CH2-OC(O)(CH2)5CH3, -CH2-OC(O)(CH2)6CH3, -CH2-OC(O)(CH2)7CH3, -CH2-OC(O)(CH2)8CH3, -CH2-OC(O)(CH2)9CH3, -CH2-OC(O)(CH2) 10 CH3, -CH2-OC(O)(CH2) 11 CH3, -CH2-OC(O)(CH2) 12 CH3, -CH2-OC(O)(CH2) 13 CH3, -CH2-OC(O)(CH2) 14 CH3, -(CH2)2-OC(O)(CH2)4CH3, -(CH2)2-OC(O)(CH2)5CH3, -(CH2)2-OC(O)(CH2)6CH3, -(CH2)2-OC(O)(CH2) 7CH3, -(CH2)2-OC(O)(CH2)8CH3, -(CH2)2-OC(O)(CH2)8CH3, -(CH2)2-OC(O)(CH2)9CH3, -(CH2)2-OC(O)(CH2) 10 CH3, -(CH2)2-OC(O)(CH2) 11 CH3, -(CH2)2-OC(O)(CH2) 12 CH3, -(CH2)2-OC(O)(CH2) 13 CH3, -(CH2)2-OC(O)(CH2) 12CH3、-(CH2)3-OC(O)(CH2)4CH3、-(CH2)3-OC(O)(CH2)5CH3、-(CH2)3-OC(O)(CH2)6CH3、-(CH2)3-OC(O)(CH2) 7CH3、-(CH2)3-OC(O)(CH2)8CH3、-(CH2)3-OC(O)(CH2)8CH3、-(CH2)3-OC(O)(CH2)9CH3、-(CH2)3-OC(O)(CH2) 10 CH3、-(CH2)3-OC(O)(CH2) 11 CH3、-(CH2)3-OC(O)(CH2) 12 CH3、-(CH2)3-OC(O)(CH2) 13 CH3、-(CH2)3-OC(O)(CH2) 12 CH3、-(CH2)4-OC(O)(CH2)4CH3、-(CH2)4-OC(O)(CH2)5CH3、-(CH2)4-OC(O)(CH2)6CH3、-(CH2)4-OC(O)(CH2) 7CH3、-(CH2)4-OC(O)(CH2)8CH3、-(CH2)4-OC(O)(CH2)8CH3、-(CH2)4-OC(O)(CH2)9CH3、-(CH2)4-OC(O)(CH2) 10 CH3、-(CH2)4-OC(O)(CH2) 11 CH3、-(CH2)4-OC(O)(CH2) 12 CH3、-(CH2)4-OC(O)(CH2) 13 CH3、-(CH2)4-OC(O)(CH2) 12 CH3、-(CH2)5-OC(O)(CH2)4CH3、-(CH2)5-OC(O)(CH2)5CH3、-(CH2)5-OC(O)(CH2)6CH3、-(CH2)5-OC(O)(CH2) 7CH3、-(CH2)5-OC(O)(CH2)8CH3、-(CH2)5-OC(O)(CH2)8CH3、-(CH2)5-OC(O)(CH2)9CH3、-(CH2)5-OC(O)(CH2) 10 CH3、-(CH2)5-OC(O)(CH2) 11 CH3、-(CH2)2-OC(O)(CH2) 12 CH3、-(CH2)5-OC(O)(CH2) 13 CH3、-(CH2)5-OC(O)(CH2)12 CH3、-COO(CH2)5CH3、-COO(CH2)6CH3、-COO(CH2)7CH3、-COO(CH2)8CH3、-COO(CH2)9CH3、-COO(CH2) 10 CH3、-COO(CH2) 11 CH3、-COO(CH2) 12 CH3、-COO(CH2) 13 CH3、-COO(CH2) 14 CH3、-CH2-C(O)O(CH2)4CH3、-CH2-C(O)O(CH2)5CH3、-CH2-C(O)O(CH2)6CH3、-CH2-C(O)O(CH2)7CH3、-CH2-C(O)O(CH2)8CH3、-CH2-C(O)O(CH2)9CH3、-CH2-C(O)O(CH2) 10 CH3、-CH2-C(O)O(CH2) 11 CH3、-CH2-C(O)O(CH2) 12 CH3、-CH2-C(O)O(CH2) 13 CH3、-CH2-C(O)O(CH2) 14 CH3、-(CH2)2-C(O)O(CH2)4CH3、-(CH2)2-C(O)OCH2)5CH3、-(CH2)2-C(O)OCH2)6CH3、-(CH2)2-C(O)OCH2)7CH3、-(CH2)2-C(O)O(CH2)8CH3、-(CH2)2-C(O)O(CH2)8CH3、-(CH2)2-C(O)O(CH2)9CH3、-(CH2)2-C(O)OCH2) 10 CH3、-(CH2)2-C(O)O(CH2) 11 CH3、-(CH2)2-C(O)OCH2) 12 CH3、-(CH2)2-C(O)O(CH2) 13 CH3、-(CH2)2-C(O)O(CH2) 12CH3、-(CH2)3-C(O)O(CH2)4CH3、-(CH2)3-C(O)O(CH2)5CH3、-(CH2)3-C(O)O(CH2)6CH3、-(CH2)3-C(O)O(CH2)7CH3、-(CH2)3-C(O)O(CH2)8CH3、-(CH2)3-C(O)O(CH2)8CH3、-(CH2)3-C(O)O(CH2)9CH3、-(CH2)3-C(O)O(CH2) 10 CH3、-(CH2)3-C(O)O(CH2) 11 CH3、-(CH2)3-C(O)O(CH2) 12 CH3、-(CH2)3-C(O)OCH2) 13 CH3、-(CH2)3-C(O)O(CH2) 12 CH3、-(CH2)4-C(O)O(CH2)4CH3、-(CH2)4-C(O)O(CH2)5CH3、-(CH2)4-C(O)O(CH2 )6CH3、-(CH2)4-C(O)O(CH2)7CH3、-(CH2)4-C(O)O(CH2)8CH3、-(CH2)4-C(O)O(CH2)8CH3、-(CH2)4-C(O)O(CH2)9CH3、-(CH2)4-C(O)O(CH2) 10 CH3、-(CH2)4-C(O)O(CH2) 11 CH3、-(CH2)4-C(O)O(CH2) 12 CH3、-(CH2)4-C(O)O(CH2) 13 CH3、-(CH2)4-C(O)O(CH2) 12 CH3、-(CH2)5-C(O)O(CH2)4CH3、-(CH2)5-C(O)O(CH2)5CH3、-(CH2)5-C(O)O(CH2)6CH3、-(CH2)5-C(O)O(CH2) 7CH3、-(CH2)5-C(O)O(CH2)8CH3、-(CH2)5-C(O)OCH2)8CH3、-(CH2)5-C(O)O(CH2)9CH3、-(CH2)5-C(O)O(CH2) 10 CH3、-(CH2)5-C(O)O(CH2) 11 CH3、-(CH2)2-C(O)O(CH2) 12 CH3、-(CH2)5-C(O)O(CH2) 13CH3, and -(CH2)5-C(O)O(CH2) 12 CH3).

[0053] One embodiment of the present invention is compound IIc [ka] (In the formula, R 60 -R 70 , -Z-OC(O)-R 70 , -C(O)-OR 70 , -ZC(O)OR 70 , -C(O)NH-R 70 , -ZC(O)NH-R 70 and -CH(COOR 70 )2, preferably -ZC(O)-OR 70 , -C(O)-OR 70 and -R 70 and most preferably selected from the group consisting of -C(O)-O(CH2)4CH3, -C(O)-O(CH2)5CH3, -C(O)-O(CH2)6CH3, -C(O)-O(CH2)7CH3, -C(O)-O(CH2)8CH3, -C(O)-O(CH2)9CH3, -C(O)-O(CH2) 10 CH3, -C(O)-O(CH2) 11 CH3, -C(O)-O(CH2) 12 CH3, -C(O)-O(CH2) 13 CH3, -C(O)-O(CH2) 14 CH3, -CH2-C(O)-O(CH2)4CH3, -CH2-C(O)-O(CH2)5CH3, -CH2-C(O)-O(CH2)6CH3, -CH2-C (O)-O(CH2)7CH3, -CH2-C(O)-O(CH2)8CH3, -CH2-C(O)-O(CH2)9CH3, -CH2-C(O)-O(CH2) 10 CH3, -CH2-C(O)-O(CH2) 11 CH3, -CH2-C(O)-O(CH2) 12 CH3, -CH2-C(O)-O(CH2) 13 CH3, -CH2-C(O)-O(CH2) 14CH3, -(CH2)2-C(O)-O(CH2)4CH3, -(CH2)2-C(O)-O(CH2)5CH3, -(CH2)2-C(O)-O(CH2)6CH3, -(CH2)2-C(O)-O(CH2)7CH3, -(CH2)2-C(O)-O(CH2)8CH3, -(CH2)2-C(O)-O(CH2)9CH3, -(CH2)2-C(O)-O(CH2) 10 CH3, -(CH2)2-C(O)-O(CH2) 11 CH3, -(CH2)2-C(O)-O(CH2) 12 CH3, -(CH2)2-C(O)-O(CH2) 13 CH3, -(CH2)2-C(O)-O(CH2) 14 CH3, -(CH2)3-C(O)-O(CH2)4CH3, -(CH2)3-C(O)-O(CH2)5CH3, -(CH2)3-C(O)-O(CH2)6CH3, -(CH2)3-C(O)-O(CH2)7CH3, -(CH2)3-C(O)-O(CH2)8CH3, -(CH2)3-C(O)-O(CH2)9CH3, -(CH2)3-C(O)-O(CH2) 10 CH3, -(CH2)3-C(O)-O(CH2) 11 CH3, -(CH2)3-C(O)-O(CH2) 12 CH3, -(CH2)3-C(O)-O(CH2) 13 CH3, -(CH2)3-C(O)-O(CH2) 14 CH3, -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11 CH3, -(CH2) 12 CH3, -(CH2) 13 CH3, and -(CH2) 14 selected from the group consisting of).

[0054] One embodiment of the present invention is compound IId

Chemical formula

[0055] One embodiment of the present invention is compound IIe [ka] (In the formula, R 70 are -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11 CH3, -(CH2) 12 CH3, -(CH2) 13 CH3 and -(CH2) 14 CH3).

[0056] One embodiment of the present invention relates to compound IIIa. [ka] (In the formula, R 50 and R 60 is defined as follows: [Table 4]

[0057] One embodiment of the present invention is compound IIIb [ka] (In the formula, R 50 -R 70 , -Z-OC(O)R 70 , -COOR 70and -Z-COOR 70 selected from the group consisting of, most preferably, -CH2-OC(O)(CH2)4CH3, -CH2-OC(O)(CH2)5CH3, -CH2-OC(O)(CH2)6CH3, -CH2-OC(O)(CH2)7CH3, -CH2-OC(O)(CH2)8CH3, -CH2-OC(O)(CH2)9CH3, -CH2-OC(O)(CH2) 10 CH3, -CH2-OC(O)(CH2) 11 CH3, -CH2-OC(O)(CH2) 12 CH3, -CH2-OC(O)(CH2) 13 CH3, -CH2-OC(O)(CH2) 14 CH3, -(CH2)2-OC(O)(CH2)4CH3, -(CH2)2-OC(O)(CH2)5CH3, -(CH2)2-OC(O)(CH2)6CH3, -(CH2)2-OC(O)(CH2)7CH3, -(CH2)2-OC(O)(CH2)8CH3, -(CH2)2-OC(O)(CH2)8CH3, -(CH2)2-OC(O)(CH2)9CH3, -(CH2)2-OC(O)(CH2) 10 CH3, -(CH2)2-OC(O)(CH2) 11 CH3, -(CH2)2-OC(O)(CH2) 12 CH3, -(CH2)2-OC(O)(CH2) 13 CH3, -(CH2)2-OC(O)(CH2) 12 CH3, -(CH2)3-OC(O)(CH2)4CH3, -(CH2)3-OC(O)(CH2)5CH3, -(CH2)3-OC(O)(CH2)6CH3, -(CH2)3-OC(O)(CH2)7CH3, -(CH2)3-OC(O)(CH2)8CH3, -(CH2)3-OC(O)(CH2)8CH3, -(CH2)3-OC(O)(CH2)9CH3, -(CH2)3-OC(O)(CH2) 10 CH3, -(CH2)3-OC(O)(CH2) 11 CH3, -(CH2)3-OC(O)(CH2) 12 CH3, -(CH2)3-OC(O)(CH2) 13 CH3, -(CH2)3-OC(O)(CH2) 12CH3、-(CH2)4-OC(O)(CH2)4CH3、-(CH2)4-OC(O)(CH2)5CH3、-(CH2)4-OC(O)(CH2)6CH3、-(CH2)4-OC(O)(CH2)7CH3、-(CH2)4-OC(O)(CH2)8CH3、-(CH2)4-OC(O)(CH2)8CH3、-(CH2)4-OC(O)(CH2)9CH3、-(CH2)4-OC(O)(CH2) 10 CH3、-(CH2)4-OC(O)(CH2) 11 CH3、-(CH2)4-OC(O)(CH2) 12 CH3、-(CH2)4-OC(O)(CH2) 13 CH3、-(CH2)4-OC(O)(CH2) 12 CH3、-(CH2)5-OC(O)(CH2)4CH3、-(CH2)5-OC(O)(CH2)5CH3、-(CH2)5-OC(O)(CH2)6CH3、-(CH2)5-OC(O)(CH2)7CH3、-(CH2)5-OC(O)(CH2)8CH3、-(CH2)5-OC(O)(CH2)8CH3、-(CH2)5-OC(O)(CH2)9CH3、-(CH2)5-OC(O)(CH2) 10 CH3、-(CH2)5-OC(O)(CH2) 11 CH3、-(CH2)2-OC(O)(CH2) 12 CH3、-(CH2)5-OC(O)(CH2) 13 CH3、-(CH2)5-OC(O)(CH2) 12 CH3、-COO(CH2)5CH3、-COO(CH2)6CH3、-COO(CH2)7CH3、-COO(CH2)8CH3、-COO(CH2)9CH3、-COO(CH2) 10 CH3、-COO(CH2) 11 CH3、-COO(CH2) 12 CH3、-COO(CH2) 13 CH3、-COO(CH2) 14CH3、-CH2-C(O)O(CH2)4CH3、-CH2-C(O)O(CH2)5CH3、-CH2-C(O)O(CH2)6CH3、-CH2-C(O)O(CH2)7CH3、-CH2-C(O)O(CH2)8CH3、-CH2-C(O)O(CH2)9CH3、-CH2-C(O)O(CH2) 10 CH3、-CH2-C(O)O(CH2) 11 CH3、-CH2-C(O)O(CH2) 12 CH3、-CH2-C(O)O(CH2) 13 CH3、-CH2-C(O)O(CH2) 14 CH3、-(CH2)2-C(O)O(CH2)4CH3、-(CH2)2-C(O)OCH2)5CH3、-(CH2)2-C(O)OCH2)6CH3、-(CH2)2-C(O)OCH2)7 CH3、-(CH2)2-C(O)O(CH2)8CH3、-(CH2)2-C(O)O(CH2)8CH3、-(CH2)2-C(O)O(CH2)9CH3、-(CH2)2-C(O)OCH2) 10 CH3、-(CH2)2-C(O)O(CH2) 11 CH3、-(CH2)2-C(O)OCH2) 12 CH3、-(CH2)2-C(O)O(CH2) 13 CH3、-(CH2)2-C(O)O(CH2) 12 CH3、-(CH2)3-C(O)O(CH2)4CH3、-(CH2)3-C(O)O(CH2)5CH3、-(CH2)3-C(O)O(CH2)6CH3、-(CH2)3-C(O)O(CH2)7CH3、-(CH2)3-C(O)O(CH2)8CH3、-(CH2)3-C(O)O(CH2)8CH3、-(CH2)3-C(O)O(CH2)9CH3、-(CH2)3-C(O)O(CH2) 10 CH3、-(CH2)3-C(O)O(CH2) 11 CH3、-(CH2)3-C(O)O(CH2) 12 CH3、-(CH2)3-C(O)OCH2) 13 CH3、-(CH2)3-C(O)O(CH2) 12CH3, -(CH2)4-C(O)O(CH2)4CH3, -(CH2)4-C(O)O(CH2)5CH3, -(CH2)4-C(O) O(CH2)6CH3, -(CH2)4-C(O)O(CH2)7CH3, -(CH2)4-C(O)O(CH2)8CH3, -(CH2)4-C(O)O(CH2)8CH3, -(CH2)4-C(O)O(CH2)9CH3, -(CH2)4-C(O)O(CH2) 10 CH3, -(CH2)4-C(O)O(CH2) 11 CH3, -(CH2)4-C(O)O(CH2) 12 CH3, -(CH2)4-C(O)O(CH2) 13 CH3, -(CH2)4-C(O)O(CH2) 12 CH3, -(CH2)5-C(O)O(CH2)4CH3, -(CH2)5-C(O)O(CH2)5CH3, -(CH2)5-C(O)O(CH2)6CH3, -(CH2)5-C(O)O(CH2) 7CH3, -(CH2)5-C(O)O(CH2)8CH3, -(CH2)5-C(O)OCH2)8CH3, -(CH2)5-C(O)O(CH2)9CH3, -(CH2)5-C(O)O(CH2) 10 CH3, -(CH2)5-C(O)O(CH2) 11 CH3, -(CH2)2-C(O)O(CH2) 12 CH3, -(CH2)5-C(O)O(CH2) 13 CH3 and -(CH2)5-C(O)O(CH2) 12 CH3).

[0058] One embodiment of the present invention is compound IIIc [ka] (In the formula, R 60 -R 70 , -Z-OC(O)-R 70 , -C(O)-OR 70 , -ZC(O)OR 70 , -C(O)NH-R 70 , -ZC(O)NH-R 70 , -CH(COOR70 ) selected from the group consisting of 2, preferably -Z-C(O)-OR 70 , -C(O)-OR 70 and -R 70 selected from the group consisting of, most preferably, -C(O)-O(CH2)4CH3, -C(O)-O(CH2)5CH3, -C(O)-O(CH2)6CH3, -C(O)-O(CH2)7CH3, -C(O)-O(CH2)8CH3, -C(O)-O(CH2)9CH3, -C(O)-O(CH2) 10 CH3, -C(O)-O(CH2) 11 CH3, -C(O)-O(CH2) 12 CH3, -C(O)-O(CH2) 13 CH3, -C(O)-O(CH2) 14 CH3, -CH2-C(O)-O(CH2)4CH3, -CH2-C(O)-O(CH2)5CH3, -CH2-C(O)-O(CH2)6CH3, -CH2-C(O)-O(CH2)7CH3, -CH2-C(O)-O(CH2)8CH3, -CH2-C(O)-O(CH2)9CH3, -CH2-C(O)-O(CH2) 10 CH3, -CH2-C(O)-O(CH2) 11 CH3, -CH2-C(O)-O(CH2) 12 CH3, -CH2-C(O)-O(CH2) 13 CH3, -CH2-C(O)-O(CH2) 14 CH3, -(CH2)2-C(O)-O(CH2)4CH3, -(CH2)2-C(O)-O(CH2)5CH3, -(CH2)2-C(O)-O(CH2)6CH3, -(CH2)2-C(O)-O(CH2)7CH3, -(CH2)2-C(O)-O(CH2)8CH3, -(CH2)2-C(O)-O(CH2)9CH3, -(CH2)2-C(O)-O(CH2) 10 CH3, -(CH2)2-C(O)-O(CH2) 11 CH3, -(CH2)2-C(O)-O(CH2) 12 CH3, -(CH2)2-C(O)-O(CH2) 13 CH3, -(CH2)2-C(O)-O(CH2) 14CH3, -(CH2)3-C(O)-O(CH2)4CH3, -(CH2)3-C(O)-O(CH2)5CH3, -(CH2)3-C(O)-O(CH2)6CH3, -(CH2)3 -C(O)-O(CH2)7CH3, -(CH2)3-C(O)-O(CH2)8CH3, -(CH2)3-C(O)-O(CH2)9CH3, -(CH2)3-C(O)-O(CH2) 10 CH3, -(CH2)3-C(O)-O(CH2) 11 CH3, -(CH2)3-C(O)-O(CH2) 12 CH3, -(CH2)3-C(O)-O(CH2) 13 CH3, -(CH2)3-C(O)-O(CH2) 14 CH3, -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11 CH3, -(CH2) 12 CH3, -(CH2) 13 CH3 and -(CH2) 14 CH3).

[0059] One embodiment of the present invention is compound IIId [ka] (In the formula, R 70 are -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11 CH3, -(CH2) 12 CH3, -(CH2) 13 CH3 and -(CH2) 14 CH3).

[0060] One embodiment of the present invention is compound IIIe [ka] (In the formula, R 70 are -(CH2)4CH3, -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11 CH3, -(CH2) 12 CH3, -(CH2) 13 CH3 and -(CH2) 14 CH3).

[0061] One embodiment of the present invention relates to compounds of general formula (I), (II) and (III), wherein R 11 and R 12 Or R 21 and R 22 Or R 31 and R 32 are both hydrogen or CHR 50 together with R to form a cyclic moiety, or 13 and R 14 Or R 23 and R 24 Or R 33 and R 34 are both hydrogen or CHR 60 together with R to form a cyclic moiety, 11 , R 12 , R 13 and R 14 or R 21 , R 22 , R 23 and R 24 or R 31 , R 32 , R 33 and R 34 Not all of the 50 or R 60 is a straight chain C1~C 10 Preferably, said compounds are selected from the group consisting of compounds Ia, Ib, Ic, IIa, IIb, IIc, IIIa, IIIb and IIIc, in which R 50 or R 60 is a straight chain C1~C 10Alkyl, most preferably C5-C 10 It is an alkyl.

[0062] One embodiment of the present invention relates to compounds of general formula (I), (II) and (III), wherein R 11 and R 12 or R 21 and R 22 or R 31 and R 32 is CHR 50 together with R to form a cyclic moiety, 13 and R 14 or R 23 and R 24 or R 33 and R 34 is CHR 60 Together with R to form a cyclic moiety, 50 and R 60 are different, -COOH and -C(O)NH-R 70 wherein R 70 is preferably a linear or branched C1-C 20 Alkyl, more preferably linear C5-C 15 Alkyl, most preferably linear C 10 ~C 15 Preferably, said compounds are selected from the group consisting of compounds Ia, IIa and IIIa, in which R 50 and R 60 is defined as follows: [Table 5]

[0063] One embodiment of the present invention relates to compounds of general formulae (I), (II) and (III), preferably compounds of formulae Ia, Ib, Ic, IIa, IIb, IIc, IIIa, IIIb and IIIc, in which R 50 and R 60 One of them is -Z-OC(O)R 70 , -COOR 70 , and -Z-COOR 70and the other, if present, is selected from the group consisting of -Z-OH, -COOH, and -Z-COOH, and Z is a straight or branched C1-C 10 alkyl, preferably a straight chain C1-C5 alkyl, most preferably a straight chain C1-C3 alkyl, where -R 70 is a straight or branched chain C1-C 20 Alkyl, preferably linear C5-C 15 Alkyl, most preferably linear C 10 ~C 15 It is an alkyl.

[0064] One embodiment of the present invention relates to compounds of general formulae (I), (II) and (III), preferably compounds of formulae Ia, Ib, Ic, IIa, IIb, IIc, IIIa, IIIb and IIIc, in which R 50 or R 60 is -C(O)NH-R 70 and ZC(O)NH-R 70 R 70 is a straight or branched chain C1-C 20 Alkyl, preferably linear C5-C 15 Alkyl, most preferably linear C 10 ~C 15 The surfactants are alkyl. The compounds are resistant to hydrolysis in alkaline media and provide antistatic properties. In addition, the compounds are generally less aggressive than compounds with sulfonic acid groups. Furthermore, the compounds do not over-strip, i.e., do not degrease and dry the skin or hair excessively or leave a "squeaky" feeling. Thus, the surfactants are particularly preferred for surfactant-assisted nanoparticle synthesis, oil recovery by surfactant flooding, foam boosters, and laundry applications. In addition, they are particularly useful as surfactants in oil recovery, as surfactants in nanoparticle-assisted synthesis, and as foam boosters and additives in cleaning formulations for laundry applications. In particular, the compounds have been found to provide low interfacial tension and low microemulsion viscosity.

[0065] One embodiment of the present invention relates to compounds of general formulae (I), (II) and (III), preferably compounds of formulae Ia, Ib, Ic, IIa, IIb, IIc, IIIa, IIIb and IIIc, in which R 50 or R 60 Z-SO3 - and Z-OH, preferably Z-SO3 - and -Z is preferably a linear or branched C1-C 10 alkyl, more preferably a straight chain C1-C5 alkyl, and most preferably a straight chain C1-C3 alkyl. Most preferably, the compound is selected from the group consisting of compounds Ia, IIa and IIIa, wherein R 50 is Z-OH, and R 60 Z-SO3 - and Z is preferably a linear or branched C1-C 10 The alkyl group is preferably a linear C1-C5 alkyl group, more preferably a linear C1-C3 alkyl group. The compounds are less stable than other surfactants, but provide excellent cleaning power and stable foaming. They are particularly preferred as foaming agents and detergents. Preferably, the compounds are used in shampoos as foaming agents or detergents. The shampoos preferably contain a significant proportion of the compounds in an aqueous medium having a pH of approximately neutral. The shampoos most preferably have a pH in the range of 6.5 to 7.5, more preferably 6.8 to 7.3. Such shampoos have excellent foaming properties and good rinsing properties. Furthermore, the foam stability is also good.

[0066] The compounds of the present invention, in particular the compounds according to the general formulae (Ia), (Ib), (Ic) and (V), can be used as surfactants, preferably as emulsifiers, foam stabilizers, wetting agents, emollients in cosmetics, surfactants in foods, anti-splash agents for fried foods, surfactants in pharmaceuticals, detergents or additives in cleaning products.

[0067] The present invention also includes compositions that contain a compound of the present invention and a significant amount of water. The inclusion of a higher amount of water is beneficial for incorporating more hydrophilic components into the composition.

[0068] In one embodiment of the invention, the compounds are used as emulsifiers, foam stabilizers, humectants, emollients in cosmetics, surfactants in food, anti-splash agents for fried foods, or surfactants in pharmaceuticals.

[0069] The compounds of the present invention can be easily obtained by the following reaction steps. [ka] [ka] [ka] DCC: dicyclohexylcarbodiimide EXAMPLES

[0070] Synthesis and characterization of docosanol-substituted xylose diglyoxylates (2, 3) [ka] The synthesis of diglyoxylated-xylose (1) from xylose and biomass is known to those skilled in the art. Docosanol (0.56 g, 1.7 mmol) dissolved in 25 mL of chloroform and diglyoxylated-xylose (1) (0.5 g, 1.9 mmol) dissolved in 15 mL of 1,4-dioxane were mixed in a 100 mL round-bottom flask. Sulfuric acid (98% purity, 200 mkl) was added to the reaction mixture and the reaction mixture was heated at 65° C. for 24 hours to obtain a slightly pink solution. The reaction mixture was analyzed by HPLC (C18 column, isopropanol / methanol 1:9 mobile phase) and TLC (hexane / ethyl acetate 1:8) to identify the hemiprotected products (2, 3 or their mixtures).

[0071] Synthesis and characterization of octanol-substituted xylose (2',3') diglyoxylates [ka] The synthesis of diglyoxylated-xylose (1) from xylose and biomass is known to those skilled in the art. 1-Octanol (0.2 g, 1.7 mmol) and diglyoxylated-xylose (1) (0.5 g, 1.9 mmol) were mixed in 30 mL of 1,4-dioxane in a 100 mL round-bottom flask. Sulfuric acid (98% purity, 200 mkl) was added to the reaction mixture, and the reaction mixture was heated at 85° C. for 5 h. The reaction mixture was analyzed by HPLC (C18 column, isopropanol / methanol 1:9 mobile phase) and TLC (hexane / ethyl acetate 1:8) to identify the monoprotected products (2', 3', or a mixture thereof).

[0072] The mixture was neutralized to pH 7 and dissolved in an immiscible system of ethyl acetate and water for rapid emulsification tests. Figure 1a shows the formation of an emulsion of the extract of a mixture of compounds 2' and 3' in a system containing ethyl acetate and water (vial 1) compared to pure 1-octanol (vial 2) and the system itself (vial 3) in the same system. It can be seen that phase separation occurs in vials 2 and 3, but not in vial 1.

[0073] Emulsion stability measurement Emulsions were prepared by mixing 1 mL of water (containing 1 mg / mL Acian Blue dye) with 2 mL of cyclohexane containing 3,5-O-dodecylidene-xylose or 2-((dodecyloxy)methyl)tetrahydrofuran-3,4-diol) at a concentration of 0.1%, then mixed by vortexing for 30 seconds.

[0074] During storage after preparation, the emulsions were characterized using a bright-field microscope (Leitz Ergolux). Figures 1b and 1c show that the aqueous bubbles in the oil phase can remain stable for at least 30 days without obvious coalescence. Furthermore, a water / oil emulsion (67% water and 33% cyclohexane) containing 1% 3,5-O-dodecylidene-xylose was stored for about one year to observe its possible destabilization. Figure 2 shows that after one year, a thin oil layer and a clear layer appeared, but most of the volume maintained the emulsion form.

[0075] Synthesis of 1,2-O-dodecylidene-xylose (6) and 3,5-O-dodecylidene-xylose (7) from xylose [ka] In a one-neck round-bottom flask, 1 molar equivalent of D-xylose was mixed with 0.9 molar equivalents of dodecanal and 0.1 molar equivalents of sulfuric acid catalyst in dioxane. The reaction was carried out at 65° C. for 24 hours. The solution was then neutralized with 1 M NaOH solution until the pH value was about 7. The solution was concentrated on a rotary evaporator under reduced pressure (80 mbar) with a bath temperature of 45° C. The residual viscous yellow oil was then washed with a brine solution and extracted with EtOAc. The organic phase was then evaporated on a rotary evaporator and purified using column chromatography to obtain a pale yellow solid and a yellowish oil. They were characterized by heteronuclear single quantum coherence spectroscopy (HSQC) NMR.

[0076] Synthesis of 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (9) from 3,5-O-dodecylidene-xylose (7) [ka] In a one-neck round-bottom flask, one molar equivalent of 3,5-O-dodecylidene-xylose (7) (MAX12) was mixed with two molar equivalents of glyoxylic acid monohydrate in dioxane. Amberlyst A15 was used as a catalyst, and molecular sieves were added to remove the water produced. The reaction was carried out at 80 °C for 4 h. The solution was then filtered and concentrated on a rotary evaporator under reduced pressure (80 mbar) with a bath temperature of 45 °C. The reaction mixture was then purified using column chromatography (hexane-ethyl acetate with 1% acetic acid) to give 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (9) (GMAX) as a pale yellow solid.

[0077] Synthesis of sodium 1,2-O-carboxylate-3,5-O-dodecylidene-xylose (10) from 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (9) [ka] One molar equivalent of 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (9) is reacted with one molar equivalent of sodium hydroxide solution to produce sodium 1,2-O-carboxylate-3,5-O-dodecylidene-xylose (10) at a pH of about 7.

[0078] Synthesis of didodecylidene-xylose (8) from xylose [ka] In a one-neck round-bottom flask, 1 molar equivalent of D-xylose was mixed with 2.05 molar equivalents of dodecanal and 0.2 molar equivalents of sulfuric acid catalyst in dioxane. The reaction was carried out at 65° C. for 24 hours. The solution was then neutralized with 1 M NaOH solution until the pH value was about 7. The solution was concentrated on a rotary evaporator under reduced pressure (80 mbar) with a bath temperature of 45° C. The resulting viscous pale yellow oil was then washed with a brine solution and extracted with EtOAc. The organic phase was then evaporated on a rotary evaporator and purified using flash chromatography. The product was collected and crystallized in hexane in a refrigerator to obtain white didodecylidene-xylose crystals (8).

[0079] Synthesis of 2-((dodecyloxy)methyl)tetrahydrofuran-3,4-diol [ka] Didodecylidene-xylose (8) was dissolved in cyclopentyl methyl ether (CPME) and transferred to a 50 mL Parr reactor with 10% Pd / C catalyst. The reactor was sealed, purged with hydrogen gas three times, hydrogen pressure was introduced (30 bar), and then heated to 135° C. with stirring for 15 h. After cooling to room temperature, the reactor was depressurized and the reaction mixture was filtered. The filtrate was rotary evaporated and the residue was purified by flash chromatography to give 2-((dodecyloxy)methyl)tetrahydrofuran-3,4-diol (11) and other dodecyl-xylose ethers and acetals.

[0080] 3,5-O-(E)-Dodec-2-en-1-ylidene-xylose (MAX12:1(2)) [ka] In a one-neck round-bottom flask, 1 molar equivalent of D-xylose (5) was mixed with 1.2 molar equivalents of (E)-2-dodecenal and 0.02 M sulfuric acid catalyst in dioxane. To shift the equilibrium towards the product, molecular sieves were added to remove the water produced. The reaction was carried out at 45° C. for 15 h. The solution was then neutralized with 1 M NaOH solution until the pH value was about 7. The solution was concentrated on a rotary evaporator under reduced pressure (80 mbar) with a bath temperature of 45° C. The residual viscous yellow oil was then washed with a brine solution and extracted with EtOAc. The organic phase was then evaporated on a rotary evaporator and purified using column chromatography to give two yellowish oils as products (12), which were characterized by NMR and GCMS.

[0081] Analysis method term In the context of the present invention, the terms MAXn and DAXn refer to xylose compounds, with the term "n" defining the length of the linear alkyl group that can vary. For example, the term MAX12 refers to 3,5-O-dodecylidene-xylose, the term MAX10 refers to 3,5-O-decylidene-xylose, and the term MAX8 refers to 3,5-O-octylidene-xylose. On the other hand, the term DAXn refers to the same xylose target, with the term "n" defining the length of both linear alkyl groups that can vary. For example, the term DAX12 refers to didodecylidene-xylose, the term DAX10 refers to didecylidene-xylose, and the term DAX8 refers to dioctylidene-xylose.

[0082] NMR All NMR spectra ( 1 H, 13 C, HSQC) were acquired using a Bruker Avance III 400 MHz spectrometer with standard Bruker pulse sequences.

[0083] GC-MS Gas chromatography-mass spectrometry spectra of 3,5-O-octylidene-xylose (MAX8), 3,5-O-decylidene-xylose (MAX10), 3,5-O-dodecylidene-xylose (MAX12) (all in Figure 3A), dioctylidene-xylose (DAX8), didecylidene-xylose (DAX10), didodecylidene-xylose (DAX12) (all in Figure 4A), 3,5-O-(E)-dodec-2-en-1-ylidene-xylose (MAX12:1(2)) (Figure 5), and 3,5-O-octadecylidene-xylose (MAX18) (Figure 6) were obtained using an Agilent 7890B Series GC equipped with an HP5-MS capillary column and an Agilent 5977A Series mass spectrometry detector (Figures 3B and 4B). For all the above compounds, silylation derivatization was applied by adding 100 μL of N-methyl-N-(trimethylsilyl)-trifluoroacetamide (MSTFA) and 100 μL of pyridine, and was detected after 30 min at room temperature. The GC-MS method was performed as follows: the injection temperature was 300°C. 1 μL of sample was injected in split mode (split ratio: 25:1) using an autosampler. The column was first held at 40°C for 3 min, then 30°C / min. -1 to 100°C at a rate of 40°C / min. -1 The mixture was heated to 300° C. at a heating rate of 0.1 to 100° C. and held for 5 minutes.

[0084] HPLC (pH 2 aqueous phase chromatography) HPLC analysis of the accelerated aqueous degradation of MAXn was performed using an HPX-87H column (300 mm × 7.8 mm; column temperature = 60 °C) with pH 2 water as the eluent (flow rate = 0.6 mL min -1 , V inj = 20 μL) on a 1260 Refractive Index Detector (RID) (G1362A).

[0085] Xylose acetal characterization data 1,2-O-dodecylidene-α-D-xylofuranose (Ic) [ka] 1 H NMR(400MHz, CDCl3)δ 5.96(d,J=3.7Hz,1H),5.17(t,J=4.7Hz,0.52H),4.92(t,J=4.8Hz,0.48H),4.49(d,J=3.6 Hz,1H),4.42-4.31(m,2H),4.16-3.93(m,4H),1.16-1.42(m,18H),0.86(t,J=6.7Hz,6H). 13 C NMR(101MHz,CDCl3)δ 106.91,105.62,104.65,104.55,86.43,86.22,81.47,78.79,77.09,76.96,61.33,61.20,34.72,34.09,32.0 3,29.80,29.76,29.75,29.73,29.71,29.63,29.62,29.56,29.54,29.48,29.46,23.85,23.65,22.80,14.24. HRMS(ナノチップ-ESI / LTQ-オービトラップ)m / z:[M+H] + C 17 H 33 O5 + The calculated value is 317.2323; the measured value is 317.2318.

[0086] 1,2-O-カルボキシリデン-3,5-O-ドデシリデン-キシロース(Ia)(GMAX)

change

[0087] 2-((dodecyloxy)methyl)tetrahydrofuran-3,4-diol (Va) [ka] 1 H NMR(400MHz,CDCl3)δ 4.27(dt,J=3.9,1.6Hz,1H),4.24-4.17(m,2H),4.16-4.09(m,1H),3.91-3.78(m,2H),3.74-3 .67(m,1H),3.58-3.42(m,2H),1.63-1.53(m,2H),1.34-1.22(m,18H),10.87(t,J=6.8Hz,3H). 13 C NMR(101MHz, CDCl3)δ 79.39,78.24,78.16,73.70,72.62,70.06,32.04,31.56,29.78,29.75,29.72,29.67,29.61,29.53,26.13,22.81,14.24. HRMS(ESI / QTOF)m / z:[M+Na] + C 17 H 34 NaO4 + Calculated value 325.23452; measured value 325.23455.

[0088] 3-O-Dodecyl-1,2-O-dodecylidene-xylose (Ie) [ka] 1H NMR (400MHz, CDCl3) δ 5.96 (d, J = 3.7 Hz, 1H), δ 5.17 (t, J = 4.7 Hz, 1H), δ 4.49 (dd, J = 3.7 Hz, 1H), δ 4.34-4.37(m,1H),4.09-4.14(m,1H),3.78-3.89(m,2H),3.40-3.56(m,2H),1.20-1.36(m,36H),0.87(t,J=7.08Hz,6H). 13 C NMR(101MHz,CDCl3)δ 106.79,104.68,86.28,80.59,76.99,72.72,69.45,34.77,32.94,32.05,29.83,29.80 ,29.78,29.76,29.73,29.67,29.65,29.58,29.56,29.53,26.25,23.70,22.83,14.25. HRMS (ESI / QTOF) m / z: [M+Na] + C 29 H 56 NaO5 + The calculated value is 507.4020; the measured value is 507.4026.

[0089] 5-O-ドデシル-1,2-O-ドデシリデン-キシロース(Id)

change

[0090] Didodecylidene-xylose (DAX12) (Ia) [ka] 1 H NMR(400MHz,CDCl3)δ 6.01(d,J=3.8Hz,1H),4.94(t,J=4.8Hz,1H),4.51-4.39(m,2H),4.32-4.22(m,1H),4.20(d,J=2.1Hz,1H ),4.02-3.98(m,1H),3.96-3.88(m,1H),1.72-1.55(m,4H),1.43-1.17(m,36H),0.87(t,J=6.98Hz,6H). 13 C NMR(101MHz,CDCl3)δ 105.48,105.34,100.57,84.42,78.48,72.55,66.22,34.81,34.77,32.06,32.05,29.76,29.68,2 9.64,29.62,29.58,29.51,29.48,29.39,29.32,29.21,24.85,23.97,23.92,23.80,22.83,14.26.

[0091] Didecylidine-xylose (DAX10) (Ia) [ka] 1H NMR(400MHz, CDCl3)δ 5.99(d,J=4.0Hz,1H),4.94(t,J=4.8Hz,1H),4.50-4.39(m,1H),4.33-4.23(m,2H),4.20(d,J =2.2Hz,1H),3.96-3.82(m,2H),1.72-1.52(m,4H),1.44-1.22(m,28H),0.87(t,J=6.8Hz,6H). 13 C NMR(101MHz,CDCl3)δ 107.28,105.45,100.57,84.41,78.49,75.09,72.55,66.22,34.77,34.07,32.02,32.00,29.6 3,29.62,29.60,29.58,29.55,29.50,29.43,29.42,23.96,23.92,23.80,23.66,22.81,14.25.

[0092] ジオクチリデン-キシロース(DAX8)(Ia)

change

[0093] 3,5-O-(E)-ドデカ-2-エン-1-イリデン-キシロース(MAX12:1(2))(Ib)

change

[0094] 3,5-O-ドデシリデン-キシロース(MAX12)(Ib)

change

[0095] 3,5-O-オクタデシリデン-キシロース(MAX18)(Ib)

change

[0096] Interfacial tension measurement To test the amphiphilic properties of each molecule, we measured the water / oil interfacial tension using a pendant drop test. In a typical test, we slowly inject an organic solution containing the surfactant into the aqueous phase using a bent needle with a diameter of 1 mm. The interfacial tension is calculated by a force balance with the buoyancy force. The critical micelle concentration (CMC) can be determined by identifying the critical point of the interfacial tension-concentration graph. Figure 7 shows that among the tail lengths 8-12, MAX12 has the lowest CMC (0.35 mg / mL). The CMCs of MAX10 and MAX8 are approximately 2.5 mg / mL.

[0097] 8 shows that 2-((dodecyloxy)methyl)tetrahydrofuran-3,4-diol (e) has a CMC of about 0.5 g / L and can reduce the interfacial tension (cyclohexane / water) to a plateau value of about 1.0 mN / m. 1,2-O-dodecylidene-xylose (d) has a CMC of about 1 g / L and reduces the interfacial tension (cyclohexane / water) to a plateau value of about 2.7 mN / m.

[0098] The unpurified reaction mixture also has amphiphilic properties, which vary with alkyl chain length as shown in Figure 9a. 12 Among the various lengths, the DAXn reaction mixture shows the best ability to reduce the interfacial tension to a plateau value of about 3 mN / m (cyclohexane / water). The amphiphilic properties of this reaction mixture also show differences under different hydrogenolysis conditions. For example, as shown in Figure 9b, 15 hours at 135 °C reduced the interfacial tension (cyclohexane / water) to 6 mN / m at 0.5 g / L, while 3 hours at 200 °C reduced the interfacial tension (cyclohexane / water) to 11.5 mN / m at 0.5 g / L.

[0099] FIG. 10 shows the interfacial tension measurements at the cyclohexane-water (50.2 mN / m) interface of 1,2-O-dodecylidene α-D-xylofuranose (Ic) and some of the most popular commercial surfactants such as Span 20, Span 80 and ECOSURF SA-4 at different concentrations.

[0100] FIG. 11 shows the interfacial tension measurements for the cyclohexane-water (50.2 mN / m) interface of 2-((dodecyloxy)methyl)tetrahydrofuran-3,4-diol (Va) and some of the most common commercial surfactants such as Span 20, Span 80 and ECOSURF SA-4 at different concentrations.

[0101] FIG. 12 shows the interfacial tension measurements at the cyclohexane-water (50.2 mN / m) interface of 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (GMAX) (Ia) and some of the most popular commercial surfactants such as Span 20, Span 80 and ECOSURF SA-4 at different concentrations.

[0102] FIG. 13 shows the interfacial tension measurements at the cyclohexane-water (50.2 mN / m) interface of 3,5-O-(E)-dodec-2-en-1-ylidene-xylose (MAX12:1(2)) (Ib) and some of the most common commercial surfactants, such as Span 20, Span 80 and ECOSURF SA-4, at different concentrations.

[0103] FIG. 14 shows the interfacial tension measurements at the cyclohexane-water (50.2 mN / m) interface of 3,5-O-octadecylidene-xylose (MAX18) (Ib) and some of the most popular commercial surfactants such as Span 20, Span 80 and ECOSURF SA-4 at different concentrations.

[0104] surface tension measurement The amphiphilic properties of 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (GMAX) and sodium 1,2-O-carboxylate-3,5-O-dodecylidene-xylose (SGMAX), their ability to reduce the surface tension of water, were measured using a pendant drop test. A series of surfactant aqueous solutions of different concentrations are prepared, loaded into 1 mL syringes and attached to a Kruss SDA 30 drop shape analyzer. In a typical test, we slowly create a pendant drop of the surfactant aqueous solution and calculate the surface tension of water by analyzing the shape of the pendant drop (Young-Laplace equation) using Kruss Advance software (v.1.6.2.0). The critical micelle concentration (CMC) is determined by identifying the point at which a plateau begins to form in the surface tension-concentration graph (Figure 15).

[0105] Accelerated aqueous decomposition test To gain insight into the degradation products of 1,2-O-dodecylidene-xylose (MAX12) in water, an accelerated degradation study was performed by boiling it in water. Samples were taken at various time points and analyzed by HPLC (aqueous phase chromatography at pH 2, HPX-87H column (300 mm × 7.8 mm; 125-0140), 1260 refractive index detector (RID) (G1362A), flow rate = 0.6 mL min -1 , V inj = 20 μL, column temperature = 60°C). This shows that MAX12 can be cleaved into xylose and fatty aldehydes in boiling water in 2 days. To the best of our knowledge, fatty aldehydes can be oxidized to fatty acids catalyzed by aldehyde dehydrogenase enzymes. Xylose and fatty acids are easily biodegradable. This result indicates that MAX12 can be easily decomposed and degraded after use (Figure 16).

Claims

1. Compounds of general formula (Ia), (Ib) and (Ic): 【Chemistry 1】 (In the formula, R ５０ and R ６０ are different from each other, and -R ７０ , -ZR ７０ , -Z-OH, -Z-NH ２ , -Z-SH, -Z-OC(O)R ７０ , -OC(O)R ７０ , —COOH and its corresponding salts, —C(O)NH ２ , -C(O)NH-R ７０ , -C(O)N-(R ７０ ) ２ , -COOR ７０ , —Z—COOH and its corresponding salts, —Z—C(O)NH—R ７０ , -Z-C(O)NH ２ , -Z-C(O)N-(R ７０ ) ２ , -Z-COOR ７０ , -CH(COOH) ２ and its corresponding salts, -CH(COOR ７０ ) ２ , and -Z-SO ３ － is selected from the group consisting of In the formula, R ７０ is a straight or branched chain C １ ~C ２０ Alkyl, (C １ ~C １０ )-alkyloxy-(C １ ~C １０ )-alkyl, C ２ ~C １５ Alkenyl, C ６ ~C １２ Aryl, C ３ ~C １０ selected from the group consisting of cycloalkyl, cycloalkylalkyl, and cycloalkylalkenyl; In the formula, Z is a linear or branched C １ ~C １０ Alkyl, straight or branched chain C ３ ~C １０ Cycloalkyl, straight or branched chain C ６ ~C １０ Aryl or (C １ ~C １０ )-alkyloxy-(C １ ~C １０ )-alkyl, cycloalkylalkyl and cycloalkylalkenyl).

2. R ５０ or R ６０ Ga-R ７０ and In the formula, -R ７０ But linear C ７ ~C １９ Alkyl, preferably linear C ９ ~C １７ Alkyl, more preferably linear C １１ 2. A compound of general formula (Ib) or (Ic) according to claim 1, which is alkyl.

3. R ５０ Ga-R ７０ and In the formula, -R ７０ But linear C ７ ~C １９ Alkyl, preferably linear C ９ ~C １７ Alkyl, more preferably linear C １１ 3. The compound of general formula (Ib) according to claim 2, which is alkyl.

4. R ６０ Ga-R ７０ and In the formula, -R ７０ But linear C ７ ~C １９ Alkyl, preferably linear C ９ ~C １７ Alkyl, more preferably linear C １１ 3. The compound of general formula (Ic) according to claim 2, which is alkyl.

5. R ５０ or R ６０ One of them is -R ７０ and the other is —COOH or a corresponding salt thereof; In the formula, -R ７０ But linear C ７ ~C １９ Alkyl, preferably linear C １１ 2. The compound of general formula (Ia) according to claim 1, which is alkyl.

6. R ５０ Ga-R ７０ and In the formula, -R ７０ is a linear C ２ ~C １５ Alkenyl, preferably straight chain C ９ ~C １３ Alkenyl, more preferably linear C １１ 2. A compound of general formula (Ib) according to claim 1, which is alkenyl.

7. Compounds of general formula (V): 【Chemistry 2】 (In the formula, R ９０ is a straight or branched chain C １ ~C ２０ Alkyl, (C １ ~C １０ )-alkyloxy-(C １ ~C １０ )-alkyl, C ２ ~C １０ Alkenyl, C ６ ~C １２ Aryl, C ３ ~C １０ is selected from the group consisting of cycloalkyl, cycloalkylalkyl, and cycloalkylalkenyl.

8. R ９０ But linear C ７ ~C １９ Alkyl, more preferably linear C ９ ~C １７ Alkyl, most preferably linear C １１ ~C １５ 8. The compound of general formula (V) according to claim 7, which is alkyl.

9. 9. Use of a compound according to any one of claims 1 to 8 as a surfactant, preferably as an emulsifier, foam stabilizer, humectant, emollient in cosmetics, surfactant in food, anti-splash agent for fried foods, surfactant in pharmaceuticals, detergent or additive in cleaning products.

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