Siloxane derivatives of amino acids with surface active properties.

Abstract

The present disclosure provides siloxane derivatives of amino acids with surface active properties. The amino acids may be natural or synthetic amino acids, or may be obtained via ring-opening reactions of lactams such as caprolactam. The amino acids may be functionalized with siloxane groups to form compounds that are surface active and have surfactant properties. The compounds have low critical micelle concentration (CMC) and also the ability to reduce the surface tension of liquids.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 313,115, filed February 23, 2022, the entire contents of which are incorporated herein by reference.

[0002] The present disclosure relates to siloxane derivatives of amino acids and methods for their synthesis, which siloxane derivatives have surface active properties. [Background technology]

[0003] Surfactants (molecules with surface active properties) are an important class of molecules with highly sought-after characteristics. Surfactants can be nonionic, zwitterionic, cationic, or anionic. Often, these compounds are amphiphilic molecules with a water-insoluble hydrophobic "tail" group and a water-soluble hydrophilic "head" group. These compounds can adsorb at interfaces, such as interfaces between two liquids, between gas and liquid, or between solid and liquid. In the case of an interface between water and oil, the hydrophilic head group extends into the water while the hydrophobic tail extends into the oil. When added to water, the hydrophilic head group extends into the water while the hydrophobic tail extends into the air. The presence of surfactants disrupts the intermolecular interactions between water molecules and replaces them with weaker interactions between the water molecules and the surfactant. This results in a lowering of the surface tension and can also act to stabilize the interface.

[0004] At high enough concentrations, surfactants may form aggregates that limit the exposure of the hydrophobic tails to the polar solvent. One such aggregate is a micelle, where the molecules are arranged in a spherical shape with the hydrophobic tails on the inside of the sphere and the hydrophilic heads on the outside to interact with the polar solvent. The effect that any compound has on surface tension and the concentration at which it forms micelles can be useful as a defining feature of a surfactant.

[0005] Surfactants are widely used in commercial applications in a variety of formulations, from detergents to hair care products and cosmetics. Compounds with surface active properties are used as soaps, detergents, lubricants, wetting agents, foaming agents, and spreading agents, among others. Thus, there is a continuing need to identify and synthesize such compounds.

[0006] However, it can be difficult to predict from its structure alone whether any compound will have surface active properties or the necessary surface active properties required for the end use, let alone other important features such as interfacial adsorption kinetics, minimum achievable surface tension, and / or ability to wet hydrophobic and / or oleophobic surfaces, which are also essential to whether the compound will be a useful surfactant. For example, certain amino acids and their derivatives are desirable as building blocks for surfactants, but the selection of which amino acids to use is far from straightforward. Similarly, some siloxanes are known to have surface active properties, but again, it is very difficult to predict which siloxanes will be effective. The synthesis of such compounds adds an additional layer of difficulty due to differences in solubility that can be attributed to different elements and moieties present in the same molecule. There remains a need for highly effective surfactants that can be easily synthesized on a commercial scale via a convenient route. Summary of the Invention

[0007] The present disclosure provides siloxane derivatives of amino acids with surface active properties. The amino acids may be natural or synthetic amino acids or may be obtained via ring-opening reactions of molecules such as lactams, e.g. caprolactam. The amino acids may be functionalized with different types of siloxane groups to form compounds with surface active properties. Characteristically, these compounds may have a low critical micelle concentration (CMC) and / or the ability to reduce the surface tension of liquids.

[0008] The present disclosure provides compounds of formula I:

[0009] [ka]

[0010] In the formula, R 1 and R 2 may be the same or different and comprise at least one group selected from the group consisting of C1-C6 alkyl, optionally C1-C6 alkyl may comprise one or more of oxygen, nitrogen, or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 are alkenyl, alkynyl, ester, alcohol, aryl alkyl, alkoxy alkyl ether, alkyl phosphate, C3-C8 carboxylic acid, C1-C 10 an alkyl benzoic acid, or a C1-C6 linker attached to a second molecule of formula I, the second molecule being the same or different; n may be an integer from 1 to 12; and X may be selected from the group consisting of chloride, bromide, and iodide.

[0011] Specifically, R 3 is C2~C 10 Alkenyl, C2-C 10 Alkynyl, C2-C 12 Esters, C1-C 10 Hydroxyl, benzyl, C2-C 12 may be selected from the group consisting of an alkoxyalkyl ether, an alkyl phosphate, a C3-C8 carboxylic acid, a C1-C5 alkyl benzoic acid, or a three carbon linker attached to a second molecule of formula I, wherein the second molecule is identical to the first molecule.

[0012] More specifically, R 3 may be selected from the group consisting of the following formulas:

[0013] [ka]

[0014] Further compounds provided by the present disclosure include R 1 and R 2 is a compound of formula I where Other compounds provided by the present disclosure are compounds of formula I where n is 5.

[0015] The present disclosure further provides compounds of formula II:

[0016] [ka]

[0017] In the formula, R 1 and R 2 may be the same or different and comprise at least one group selected from the group consisting of C1-C6 alkyl, optionally C1-C6 alkyl may comprise one or more of oxygen, nitrogen, or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n and z may be independently selected from any integer from 1 to 12; m may be any integer from 1 to 12; and X may be independently selected from the group consisting of chloride, bromide, and iodide.

[0018] One specific compound provided by the present disclosure, and referred to herein as Surfactant 1, is N-benzyl-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0019] [ka]

[0020] A further specific compound provided by the present disclosure, and referred to herein as Surfactant 2, is N-(2-ethoxy-2-oxoethyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0021] [ka]

[0022] A further specific compound provided by the present disclosure, and referred to herein as Surfactant 3, is N-allyl-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium iodide, having the formula:

[0023] [ka]

[0024] A further specific compound provided by the present disclosure, and referred to herein as Surfactant 4, is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxo-N-(prop-2-yn-1-yl)hexan-1-aminium bromide, having the formula:

[0025] [ka]

[0026] A further specific compound provided by the present disclosure, and referred to herein as Surfactant 5, is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(2-(2-methoxyethoxy)ethyl)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0027] [ka]

[0028] A further specific compound provided by the present disclosure, and referred to herein as Surfactant 6, is N-(3-(diethoxyphosphoryl)propyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0029] [ka]

[0030] A further specific compound provided by the present disclosure, and referred to herein as Surfactant 7, is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(3-hydroxypropyl)-N,N-dimethyl-6-oxohexan-1-aminium iodide, having the formula:

[0031] [ka]

[0032] A further specific compound provided by the present disclosure, and referred to herein as Surfactant 8, is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(2-hydroxyethyl)-N,N-dimethyl-6-oxohexan-1-aminium iodide, having the formula:

[0033] [ka]

[0034] A further specific compound provided by the present disclosure, and referred to herein as surfactant 9a, is N-(5-carboxypentyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0035] [ka]

[0036] A further specific compound provided by the present disclosure, and referred to herein as surfactant 9b, is N-(carboxymethyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0037] [ka]

[0038] Further specific compounds provided by the present disclosure, and referred to herein as Surfactant 10, are 1 ,N 3 -Bis(6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-6-oxohexyl)-N 1 ,N 1 ,N 3 ,N 3 -tetramethylpropane-1,3-diaminium dibromide, which has the following formula:

[0039] [ka]

[0040] A further group of specific compounds provided by the present disclosure, referred to herein as Surfactant 11, has the general formula:

[0041] [ka]

[0042] In the formula, q may be an integer of 1 to 10. A further specific compound provided by the present disclosure, and referred to herein as surfactant 11a, is N-(4-(4-carboxyphenyl)butyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0043] [ka]

[0044] A further specific compound provided by the present disclosure, and referred to herein as surfactant 11b, is N-(4-(4-carboxyphenyl)butyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0045] [ka]

[0046] The above and other features of the present disclosure, as well as the methods of achieving the same, will become more apparent and better understood by referring to the following description of the embodiments taken in conjunction with the accompanying drawings. [Brief description of the drawings]

[0047] [Figure 1] FIG. 1 shows a plot of surface tension versus concentration for Surfactant 2 described in Example 2b. [Diagram 2] FIG. 2 shows a plot of surface tension versus concentration for Surfactant 2 described in Example 3b. [Diagram 3] FIG. 3 shows a plot of surface tension versus concentration for Surfactant 3 described in Example 4b. [Figure 4]FIG. 4 shows a plot of surface tension versus concentration for Surfactant 4, as described in Example 5b. [Diagram 5] FIG. 5 shows a plot of surface tension versus concentration for Surfactant 5 described in Example 6b. [Figure 6] FIG. 6 shows a plot of surface tension versus concentration for Surfactant 6 described in Example 7b. [Figure 7] FIG. 7 shows a plot of surface tension versus concentration for Surfactant 7 described in Example 8b. [Figure 8] FIG. 8 shows a plot of surface tension versus concentration for Surfactant 8 described in Example 9b. [Figure 9] Figure 9a shows a plot of surface tension vs. concentration for surfactant 9a described in Example 11b.Figure 9b shows a plot of surface tension vs. concentration for surfactant 9b described in Comparative Example A2. [Figure 10] FIG. 10 shows a plot of surface tension versus concentration for surfactant 10 described in Example 10b. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0048] As used herein, the phrase "within any range defined between any two of the above values" literally means that any range from any two of the values ​​listed before the phrase may be selected, regardless of whether the values ​​are toward the lower value of the list or toward the higher value of the list. For example, a pair of values ​​may be selected from the two lower values, the two higher values, or a lower value and an upper value.

[0049] As used herein, the term "alkyl" means any saturated carbon chain which may be straight or branched and which may be substituted anywhere along the carbon chain.

[0050] As used herein, the phrase "surface active" means that the associated compound is capable of lowering the surface tension of the medium in which it is dissolved and / or the interfacial tension with other phases and therefore may adsorb to air-liquid interfaces and / or other interfaces. The term "surfactant" may be applied to such compounds.

[0051] With respect to terms of imprecision, the terms "about" and "approximately" may be used interchangeably and may be used to mean a measurement that includes the stated measurement and includes any measurement that is reasonably close to the stated measurement. A measurement that is reasonably close to the stated measurement deviates from the stated measurement by a reasonably small amount that is understood and readily ascertained by one of ordinary skill in the art. Such deviations may be attributed, for example, to measurement error or small adjustments made to optimize performance. In cases where one of ordinary skill in the art would determine that values ​​for such reasonably small differences are not readily ascertainable, the terms "about" and "approximately" may be understood to mean plus or minus 10% of the stated value.

[0052] The present disclosure provides siloxane derivatives of amino acids. The amino acids may be natural or synthetic amino acids, or may be obtained from ring-opening reactions of lactams, such as caprolactam. The compounds of the present disclosure have been shown to have surface active properties, and may be used, for example, as surfactants and wetting agents. In particular, the present disclosure provides compounds of formula I, as shown below:

[0053] The present disclosure provides compounds of formula I:

[0054] [ka]

[0055] In the formula, R 1 and R 2may be the same or different and comprise at least one group selected from the group consisting of C1-C6 alkyl, optionally C1-C6 alkyl may comprise one or more of oxygen, nitrogen, or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 may be selected from the group consisting of alkenyl, alkynyl, ester, alcohol, aryl alkyl, alkoxy alkyl ether, C3-C8 carboxylic acid, alkyl phosphate, or a C1-C6 linker attached to a second molecule of formula I, the second molecule being the same or different; n may be an integer from 1 to 12; and X may be selected from the group consisting of chloride, bromide, and iodide.

[0056] Specifically, R 3 is C2~C 10 Alkenyl, C2-C 10 Alkynyl, C2-C 12 Esters, C1-C 10 Hydroxyl, benzyl, C2-C 12 Alkoxyalkyl ethers, alkyl phosphates, C3-C8 carboxylic acids, C1-C 10 It may be an alkyl benzoic acid or a three carbon linker attached to a second molecule of formula I, wherein the second molecules are identical.

[0057] More specifically, R 3 may be selected from the group consisting of the following formulas:

[0058] [ka]

[0059] Further compounds provided by the present disclosure include R 1 and R 2is a compound of formula I where Other compounds provided by the present disclosure are compounds of formula I where n is 5.

[0060] As used herein, the phrase "n can be an integer from 1 to 12" means that n can be equal to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and / or 12, or can be within any range including any two of the above as endpoints.

[0061] As used herein, the phrase "C1-C6 alkyl" refers to a straight or branched chain alkyl group containing 1, 2, 3, 4, 5, and / or 6 carbons, or any range including any two of the above as endpoints.

[0062] As used herein, the phrase "C1-C6 linker" refers to a straight or branched alkyl chain containing 1, 2, 3, 4, 5, and / or 6 carbons, or any range including any two of the above as endpoints.

[0063] As used herein, "C2-C 10 The phrase "alkenyl" refers to straight or branched chain alkenyl groups containing 2, 3, 4, 5, 6, 7, 8, 9, and / or 10 carbons, or any range including any two of the above endpoints.

[0064] As used herein, "C2-C 10 The phrase "alkynyl" refers to straight or branched chain alkynyl groups containing 2, 3, 4, 5, 6, 7, 8, 9, and / or 10 carbons, or any range including any two of the above endpoints.

[0065] As used herein, "C2-C 12 The phrase "ester" refers to linear or branched ester groups having a total of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and / or 12 carbons, or any range including any two of the above as endpoints.

[0066] As used herein, "C2-C 12 The phrase "alkoxyalkyl ether" refers to straight or branched chain alkoxyalkyl ether groups having a total of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and / or 12 carbons, or any range including any two of the above endpoints.

[0067] As used herein, "C1-C 10 The phrase "hydroxyl" refers to a hydroxyl attached to a straight or branched chain alkyl group containing 1, 2, 3, 4, 5, 6, 7, 8, 9, and / or 10 carbons, or any range including any two of the above as endpoints.

[0068] As used herein, the phrase "C3-C8 carboxylic acid" refers to a carboxylic acid group attached to a straight or branched alkyl group containing 3, 4, 5, 6, 7, and / or 8 carbons, or any range including any two of the above endpoints.

[0069] As used herein, "C1-C 10 The phrase "alkylbenzoic acid" refers to a benzoic acid group attached to a straight or branched chain alkyl group containing 1, 2, 3, 4, 5, 6, 7, 8, 9, and / or 10 carbons, or any range including any two of the above endpoints.

[0070] As used herein, the phrase "n and z may be independently selected from any integer from 1 to 12" means that n and z may be independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and / or 12, or any range including any two of the above as endpoints.

[0071] As used herein, the phrase "m can be any integer from 1 to 12" means that m can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and / or 12, or any range including any two of the above as endpoints.

[0072] As used herein, the phrase "q can be any integer from 1 to 10" means that q can be 1, 2, 3, 4, 5, 6, 7, 8, 9, and / or 10, or any range including any two of the above as endpoints.

[0073] One specific compound provided by the present disclosure, and referred to herein as Surfactant 1, is N-benzyl-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0074] [ka]

[0075] A second specific compound provided by the present disclosure, referred to herein as Surfactant 2, is N-(2-ethoxy-2-oxoethyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0076] [ka]

[0077] A third specific compound provided by the present disclosure, and referred to herein as Surfactant 3, is N-allyl-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium iodide, having the formula:

[0078] [ka]

[0079] A fourth specific compound provided by the present disclosure, and referred to herein as Surfactant 4, is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxo-N-(prop-2-yn-1-yl)hexan-1-aminium bromide, having the formula:

[0080] [ka]

[0081] A fifth specific compound provided by the present disclosure, and referred to herein as Surfactant 5, is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(2-(2-methoxyethoxy)ethyl)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0082] [ka]

[0083] A sixth specific compound provided by the present disclosure, and referred to herein as Surfactant 6, is N-(3-(diethoxyphosphoryl)propyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0084] [ka]

[0085] A seventh specific compound provided by the present disclosure, and referred to herein as Surfactant 7, is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(3-hydroxypropyl)-N,N-dimethyl-6-oxohexan-1-aminium iodide, having the formula:

[0086] [ka]

[0087] An eighth specific compound provided by the present disclosure, and referred to herein as Surfactant 8, is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(2-hydroxyethyl)-N,N-dimethyl-6-oxohexan-1-aminium iodide, having the formula:

[0088] [ka]

[0089] A ninth specific compound provided by the present disclosure, and referred to herein as surfactant 9a, is N-(5-carboxypentyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0090] [ka]

[0091] A tenth specific compound provided by the present disclosure, and referred to herein as surfactant 9b, is N-(carboxymethyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0092] [ka]

[0093] An eleventh specific compound provided by the present disclosure, referred to herein as Surfactant 10, is N 1 ,N 3 -Bis(6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-6-oxohexyl)-N 1 ,N 1 ,N 3 ,N 3 -tetramethylpropane-1,3-diaminium dibromide, which has the following formula:

[0094] [ka]

[0095] A further group of specific compounds provided by the present disclosure, referred to herein as Surfactant 11, has the general formula:

[0096] [ka]

[0097] In the formula, q may be an integer of 1 to 10. A twelfth specific compound provided by the present disclosure, and referred to herein as surfactant 11a, is N-(4-(4-carboxyphenyl)butyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0098] [ka]

[0099] A thirteenth specific compound provided by the present disclosure, and referred to herein as surfactant 11b, is N-(4-(4-carboxyphenyl)butyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0100] [ka]

[0101] These compounds can be synthesized by a variety of methods. One such method involves reacting an amino acid, such as an N-alkylated or N-acylated amino acid, with a siloxane to convert the C-terminus of the amino acid to the desired siloxane derivative. For example, the N-terminus of the amino acid can be further alkylated to give a quaternary amine.

[0102] The amino acids may be natural or synthetic amino acids or may be derived from the ring-opening reaction of a lactam such as caprolactam. The ring-opening reaction may be either acid or alkali catalyzed, an example of an acid catalyzed reaction is shown in Scheme 1 below.

[0103] [ka]

[0104] The amino acid may have as few as one or as many as 12 carbons between the N-terminus and the C-terminus, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbons. The alkyl chain may be branched or straight. The alkyl chain may be interrupted by nitrogen, oxygen, or sulfur. The alkyl chain may be further substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carboxyl, and carboxylate. The N-terminal nitrogen may be acylated or alkylated with one or more alkyl groups. For example, the amino acid may be 6-(dimethylamino)hexanoic acid.

[0105] The siloxane may be substituted with one or more alkoxy groups, such as methoxy, ethoxy, isopropoxy, tertiary butoxy, etc. The siloxane may be further substituted with one or more alkyl groups, such as propyl, in which case the alkyl groups may be further substituted with a suitable functional group, such as nitrogen, that allows the siloxane to be coupled to an amino acid. For example, the siloxane may be 3-aminopropyltris(trimethylsiloxy)silane.

[0106] Siloxane derivatives of amino acids can be synthesized as shown in Scheme 2 below. As shown, 6-aminohexanoic acid can be alkylated at the N-terminus by treatment with formaldehyde in formic acid under reflux to give 6-(dimethylamino)hexanoic acid. This free carboxylic acid is then coupled with 3-aminopropyl(trismethylsiloxy)silane in refluxing toluene to give the desired siloxane derivative.

[0107] [ka]

[0108] The N-terminal nitrogen can be further derivatized to modify or improve water solubility and surface active properties. A sample synthetic scheme is shown below in Scheme 3, where the N-terminal nitrogen is alkylated to give a quaternary amine.

[0109] [ka]

[0110] Suitable alkylating agents may include, for example, benzyl bromide, ethyl bromoacetate, allyl iodide, propargyl bromide, 1-bromo-2-(2-methoxyethoxy)ethane, bromophosphonate, 3-iodopropanol, 3-bromopropanol, 2-iodoethanol, 2-bromoethanol, 6-bromohexanoic acid, 4-(4-bromobutyl)benzoic acid, and 4-(bromomethyl)benzoic acid. Two molecules of formula I may be linked by treating the N-terminal nitrogen with a bifunctional alkylating agent, such as, for example, 1,3-dibromopropane.

[0111] The compounds of the present disclosure exhibit surface active properties. These properties can be measured and expressed by various methods. One way that surfactants can be expressed is by the critical micelle concentration (CMC) of the molecule. CMC can be defined as the concentration of surfactant that forms micelles, and at a higher concentration, any additional surfactant is incorporated into the micelle.

[0112] For example, a compound of formula (I) may have a critical micelle concentration (CMC) of about 0.0010 mmol to about 10.0000 mmol, or 0.0500 mmol to about 5.0000 mmol, or about 0.0500 mmol to about 2.0000 mmol, or about 0.0600 mmol, or about 1.3600 mmol, or within any range defined between any two of the above values ​​as endpoints.

[0113] As the surfactant concentration increases, the surface tension decreases. When the surface is completely covered with surfactant molecules, micelles start to form. This point represents the CMC, or minimum surface tension. Adding more surfactant does not further affect the surface tension. The CMC can therefore be measured by observing the change in surface tension as a function of surfactant concentration. One such method for measuring this value is the Wilhelmy plate method. A Wilhelmy plate is usually a thin iridium-platinum plate attached to a balance by wires and positioned perpendicular to the air-liquid interface. The balance is used to measure the force exerted on the plate by wetting. This value is then used to calculate the surface tension (γ) according to equation 1: Equation 1: γ = F / l cosθ where l is equal to the wetted perimeter (2w+2d, where w and d are the thickness and width of the plate, respectively), and for cosθ, the contact angle between the liquid and the plate is assumed to be 0 in the absence of existing literature values.

[0114] Another parameter used to evaluate the performance of surfactants is the dynamic surface tension. Dynamic surface tension is the value of the surface tension over time for a particular surface or interface. For liquids to which surfactants have been added, this may differ from the equilibrium value. Immediately after the surface is created, the surface tension is equal to that of the pure liquid. As mentioned above, surfactants are surface tension reducers, so the surface tension decreases until it reaches an equilibrium value. The time required to reach equilibrium depends on the diffusion and adsorption rates of the surfactant.

[0115] The minimum surface tension plateau value achievable with the compounds of formula (I) may be from about 10.00 mN / m to about 28.00 mN / m, or from about 20.00 mN / m to about 25 mN / m, or from about 20.00 mN / m to about 23.00 mN / mm, or any range defined between any two of the above values ​​as endpoints.

[0116] One way to measure dynamic surface tension is with a maximum bubble pressure tensiometer. This device measures the maximum internal pressure of a bubble formed in a liquid by a capillary. The measured value corresponds to the surface tension at a given surface time, which is the time from the start of bubble formation to the maximum pressure. The dependence of surface tension on surface time can be measured by varying the rate at which the bubbles are generated.

[0117] Surface active compounds may also be evaluated by their wetting ability on solid substrates, measured by contact angle. When a liquid drop contacts a solid surface in a third medium, such as air, a three-phase line is formed between the liquid, the gas, and the solid. The angle between the surface and the unit vector of surface tension, which plays a role in the three-phase line and is tangent to the drop, is expressed as the contact angle. The contact angle (also known as the wetting angle) is a measure of the wettability of a solid by a liquid. In the case of complete wetting, the liquid spreads completely on the solid and the contact angle is 0°. Wetting properties are typically measured at concentrations between 1 and 10 x CMC for any compound, but are not concentration-dependent properties. Thus, measurements of wetting properties may be measured at concentrations higher or lower than this.

[0118] In one method, an optical contact angle goniometer can be used to measure contact angles. This instrument uses a digital camera and software to determine the contact angle by analyzing the contour shape of a stationary drop of liquid on a surface.

[0119] Potential applications for the surface active compounds of the present disclosure include formulations for use as shampoos, hair conditioners, detergents, spot free rinse solutions, floor and carpet cleaners, cleaners for graffiti removal, wetting agents for crop protection, adjuvants for crop protection, and wetting agents for aerosol spray coatings.

[0120] Those skilled in the art will appreciate that slight differences between compounds can lead to significantly different surfactant properties, and therefore different compounds may be used with different substrates in different applications. Those skilled in the art will further appreciate that, as further shown below, surfactant properties may not be predictable based on chemical structure. For example, R 3 Surfactants 9a and 9b, which differ only in the number of methylene groups, exhibit different surfactant properties. Surprisingly, surfactant 9b exhibits very good activity, as further described below, while surfactant 9a exhibits poorer surfactant properties.

[0121] The following non-limiting embodiments are provided to illustrate the different properties of different surfactants. Table 1 below provides the association between surfactant abbreviations and their corresponding chemical structures.

[0122] [Table 1-1]

[0123] [Table 1-2]

[0124] [Table 1-3]

[0125] These compounds can be effective as wetting or foaming agents, dispersing agents, emulsifying agents, and surfactants that are useful as detergents, among other uses. The amount of a compound disclosed herein used in the formulation can be as low as about 0.001%, about 0.05%, about 0.1%, about 0.5%, about 1%, about 2%, or about 5% by weight, or as high as about 8%, about 10%, about 15%, about 20%, or about 25% by weight, or within any range defined between any two of the above values. EXAMPLES

[0126] Nuclear magnetic resonance (NMR) spectroscopy was performed on a Bruker 500 MHz spectrometer. The critical micelle concentration (CMC) was determined by the Wilhelmy plate method using a tensiometer (DCAT 11, DataPhysics Instruments GmbH) equipped with a Pt-Ir plate at 23 °C. The dynamic surface tension was determined using a maximum bubble pressure tensiometer (Kruss BP100, Kruss GmbH) at 23 °C. The contact angle was determined using an optical contact angle goniometer (OCA 15 Pro, DataPhysics GmbH) equipped with a digital camera.

[0127] Example 1: Synthesis of 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexanamide 6-(Dimethylamino)hexanoic acid (2.00 g, 12.56 mmol, 1 equiv.) was dissolved in toluene (50 mL) in a 100 mL round bottom boiling flask equipped with a Dean Stark trap, followed by the addition of 3-aminopropyltris(trimethylsiloxy)silane (5.48 mL, 13.81 mmol, 1.1 equiv.). The reaction vessel was heated and the reaction was refluxed for 24 hours until no water was separated in the Dean Stark tube. The solvent was removed in vacuo to give the desired siloxane derivative as a yellow oil in 94% yield. 1 H NMR(500MHz,DMSO)δ:0.09(s,27H),0.28-0.31(m,2H),1.12-1.26(m,2H),1.27-1.30(m,4H),1.38 -1.41(m,2H),1.94(t,J=7.3Hz,2H),2.00(s,6H),2.06-2.03(m,2H),2.89(dd,J=12.9,6.8Hz,2H).

[0128] Example 2a: Synthesis of N-benzyl-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide (Surfactant 1)

[0129] [ka]

[0130] The siloxane derivative described in Example 1 (1 g, 2.02 mmol) was dissolved in dimethylformamide (DMF) (15 mL). Benzyl bromide (518 mg, 3.03 mmol) was added and the mixture was heated to 70° C. for 12 h. The solvent was removed in vacuo and the crude product was washed twice with acetone to remove excess benzyl bromide, yielding surfactant 1 as a yellow solid (1.1 g).

[0131] Example 2b: Characterization of the physical properties of surfactant 1 The critical micelle concentration (CMC) of surfactant 1 was measured. From the surface tension versus concentration in water, the CMC was determined to be approximately 9.883 mmol at pH 8. The plateau value of the minimum surface tension achievable with this surfactant was approximately 20.67 mN / m, indicating that this surfactant has significant interfacial activity. These results are plotted as surface tension versus concentration in Figure 1.

[0132] Example 3a: Synthesis of N-(2-ethoxy-2-oxoethyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide (Surfactant 2)

[0133] [ka]

[0134] The siloxane derivative described in Example 1 (1 g, 2.02 mmol) was dissolved in DMF (15 mL) and ethyl bromoacetate (0.25 mL, 2.4 mmol) was added. The mixture was stirred at 70° C. for 12 h. The solvent was removed in vacuo and the crude product was washed twice with hexane to give surfactant 2 as a brown liquid (900 mg).

[0135] Example 3b: Characterization of the physical properties of surfactant 2 The critical micelle concentration (CMC) of surfactant 2 was measured. From the change in surface tension with concentration in water, the CMC was determined to be approximately 0.2171 mmol. The plateau value of the minimum surface tension achievable with this surfactant was approximately 20.36 mN / m, indicating that this surfactant has significant interfacial activity. These results are plotted as surface tension versus concentration in Figure 2.

[0136] Example 4a: Synthesis of N-allyl-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium iodide (Surfactant 3)

[0137] [ka]

[0138] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was added to acetonitrile (10 mL), followed by sodium carbonate (0.26 g) and then allyl iodide (674 mg). The reaction was refluxed at 40° C. for 14 h. Residual sodium carbonate was removed by filtration and the filtrate was concentrated. The crude product was washed twice with hexane to remove excess allyl iodide, yielding surfactant 3 as a brown liquid (850 mg).

[0139] Example 4b: Characterization of the physical properties of surfactant 3 The critical micelle concentration (CMC) of surfactant 3 was measured. From the surface tension versus concentration in water, the CMC was determined to be approximately 1.3599 mmol. The plateau value of the minimum surface tension achievable with this surfactant was approximately 20.67 mN / m, indicating that this surfactant has significant interfacial activity. These results are plotted as surface tension versus concentration in Figure 3.

[0140] Example 5a: Synthesis of 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxo-N-(prop-2-yn-1-yl)hexan-1-aminium bromide (Surfactant 4)

[0141] [ka]

[0142] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was dissolved in dimethylformamide (DMF) (15 mL). Propargyl bromide (674 mg, 2.4 mmol) was added and the mixture was stirred at 70° C. for 12 h. The solvent was removed in vacuo and the crude product was washed twice with hexane to give surfactant 4 as a brown liquid (850 mg).

[0143] Example 5b: Characterization of the physical properties of surfactant 4 The critical micelle concentration (CMC) of surfactant 4 was measured. From the change in surface tension with concentration in water, the CMC was determined to be approximately 0.2419 mmol. The plateau value of the minimum surface tension achievable with this surfactant was approximately 20.54 mN / m, indicating that this surfactant has significant interfacial activity. These results are plotted as surface tension versus concentration in Figure 4.

[0144] Example 6a: Synthesis of 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(2-(2-methoxyethoxy)ethyl)-N,N-dimethyl-6-oxohexan-1-aminium bromide (Surfactant 5)

[0145] [ka]

[0146] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was dissolved in dimethylformamide (DMF) (15 mL). 1-Bromo-2-(2-methoxyethoxy)ethane (2.4 mmol) was added and the mixture was stirred at 70° C. for 12 h. The solvent was removed in vacuo and the crude product was washed twice with hexane to give surfactant 5 as a brown liquid (800 mg).

[0147] Example 6b: Characterization of the physical properties of surfactant 5 The critical micelle concentration (CMC) of surfactant 5 was measured. From the surface tension versus concentration in water, the CMC was determined to be approximately 0.4622 mmol. The plateau value of the minimum surface tension achievable with this surfactant was approximately 20.40 mN / m, indicating that this surfactant has significant interfacial activity. These results are plotted as surface tension versus concentration in Figure 5.

[0148] Example 7a: Synthesis of N-(3-(diethoxyphosphoryl)propyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide (Surfactant 6)

[0149] [ka]

[0150] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was dissolved in dimethylformamide (DMF) (20 mL). Bromophosphonate (4.04 mmol) was added and the mixture was stirred at 70° C. for 12 h. The solvent was removed in vacuo and the crude product was washed twice with hexane to give surfactant 6 as a brown liquid (900 mg).

[0151] Example 7b: Characterization of the physical properties of surfactant 6 The critical micelle concentration (CMC) of surfactant 6 was measured. From the surface tension versus concentration in water, the CMC was determined to be approximately 0.3989 mmol. The plateau value of the minimum surface tension achievable with this surfactant was approximately 20.48 mN / m, indicating that this surfactant has significant interfacial activity. These results are plotted as surface tension versus concentration in Figure 6.

[0152] Example 8a: Synthesis of 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(3-hydroxypropyl)-N,N-dimethyl-6-oxohexan-1-aminium iodide (Surfactant 7)

[0153] [ka]

[0154] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was dissolved in acetonitrile (10 mL). Sodium carbonate (0.26 g) was added, followed by 3-iodopropanol (674 mg). The mixture was stirred at 40° C. for 24 h. Residual base was removed by filtration and the filtrate was concentrated. The crude product was washed twice with hexane to remove excess iodopropanol, yielding surfactant 7 as a brown liquid (780 mg).

[0155] Example 8b: Characterization of the physical properties of surfactant 7 The critical micelle concentration (CMC) of surfactant 7 was measured. From the surface tension versus concentration in water, the CMC was determined to be approximately 0.4568 mmol. The plateau value of the minimum surface tension achievable with this surfactant was approximately 20.61 mN / m, indicating that this surfactant has significant interfacial activity. These results are plotted as surface tension versus concentration in Figure 7.

[0156] Example 9a: Synthesis of 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(2-hydroxyethyl)-N,N-dimethyl-6-oxohexan-1-aminium iodide (Surfactant 8)

[0157] [ka]

[0158] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was dissolved in acetonitrile (10 mL). 2-iodoethanol (4.04 mmol) was added and the mixture was stirred at 40° C. for 14 h. The solvent was removed and the crude product was washed twice with hexane to give surfactant 8 (910 mg).

[0159] Example 9b: Characterization of the physical properties of surfactant 8 The critical micelle concentration (CMC) of surfactant 8 was measured. From the surface tension versus concentration in water, the CMC was determined to be approximately 0.9986 mmol. The plateau value of the minimum surface tension achievable with this surfactant was approximately 20.41 mN / m, indicating that this surfactant has significant interfacial activity. These results are plotted as surface tension versus concentration in Figure 8.

[0160] Example 10a:N 1 ,N 3 -Bis(6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-6-oxohexyl)-N 1 ,N 1 ,N 3 ,N 3 Synthesis of -tetramethylpropane-1,3-diaminium dibromide (surfactant 10)

[0161] [ka]

[0162] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was dissolved in dimethylformamide (DMF) (20 mL). 1,2-dibromopropane (1 mmol) was added and the mixture was stirred at 70° C. for 12 h. The solvent was removed and the crude product was washed twice with hexane to give surfactant 10 as a brown liquid (900 mg).

[0163] Example 10b: Characterization of the physical properties of surfactant 10 The critical micelle concentration (CMC) of surfactant 10 was measured. From the change in surface tension with concentration in water, the CMC was determined to be about 0.0631 mmol. The plateau value of the minimum surface tension achievable with this surfactant was about 22.12 mN / m, indicating that this surfactant has surface activity. These results are plotted as surface tension versus concentration in Figure 10.

[0164] Example 11a: Synthesis of N-(5-carboxypentyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide (Surfactant 9a)

[0165] [ka]

[0166] The siloxane derivative described in Example 1 (1 g, 2.02 mmol) was dissolved in dimethylformamide (DMF) (15 mL) and 6-bromohexanoic acid (2.02 mmol) was added. The mixture was stirred at 70° C. for 12 hours, after which the solvent was removed in vacuo. The crude product was washed twice with hexane to give N-(5-carboxypentyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide as a viscous brown liquid (650 mg).

[0167] Example 11b: Characterization of the physical properties of surfactant 9a The critical micelle concentration (CMC) of surfactant 9a was measured. From the surface tension versus concentration in water, the CMC was determined to be approximately 0.2237 mmol. The plateau value of the minimum surface tension achievable with this surfactant was approximately 20.52 mN / m, indicating that this surfactant has excellent interfacial activity. These results are plotted as surface tension versus concentration in Figure 9a.

[0168] Comparative Example A1: Synthesis of N-(carboxymethyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide (surfactant 9b)

[0169] [ka]

[0170] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was dissolved in dimethylformamide (DMF) (15 mL). Bromoacetic acid (2.02 mmol) was added and the mixture was stirred at 70° C. for 12 h. The solvent was removed and the crude product was washed twice with hexane to give surfactant 9b as a brown liquid (700 mg).

[0171] Comparative Example A2: Characterization of the physical properties of surfactant 9b The critical micelle concentration (CMC) of surfactant 9b was measured. From the surface tension versus concentration in water, the CMC was determined to be approximately 17.28 mmol. The plateau value of the minimum surface tension achievable with this surfactant was approximately 29.16 mN / m. These results are plotted as surface tension versus concentration in Figure 9. The results illustrate the difficulty in predicting surfactant activity based on chemical structure, with surfactant 9a, which differs only in the number of methylene groups in the carboxylic acid, showing significantly better activity.

[0172] Example 12: Synthesis of N-(4-(4-carboxyphenyl)butyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide (surfactant 11a)

[0173] [ka]

[0174] To the siloxane derivative described in Example 1, 4-(4-bromobutyl)benzoic acid is added to obtain N-(4-(4-carboxyphenyl)butyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide.

[0175] Example 13: Synthesis of N-(4-carboxybenzyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide (surfactant 11b)

[0176] [ka]

[0177] To the siloxane derivative described in Example 1, 4-(bromomethyl)benzoic acid is added to obtain N-(4-carboxybenzyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide.

[0178] Aspects Aspect 1 is a compound of formula I,

[0179] [ka]

[0180] In the formula, R 1 and R 2are the same or different and comprise at least one group selected from the group consisting of C1-C6 alkyl, optionally C1-C6 alkyl may comprise one or more of oxygen, nitrogen, or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 are alkenyl, alkynyl, ester, alcohol, aryl alkyl, alkoxy alkyl ether, alkyl phosphate, C3-C8 carboxylic acid, C1-C 10 and a C1-C6 linker attached to a second molecule of formula I, the second molecule being the same or different; n is an integer from 1 to 12; and X is selected from the group consisting of chloride, bromide, and iodide.

[0181] Aspect 2 is the compound of aspect 1, wherein R 3 is C2~C 10 Alkenyl, C2-C 10 Alkynyl, C2-C 12 Esters, C1-C 10 Hydroxyl, benzyl, C2-C 12 Alkoxyalkyl ethers, alkyl phosphates, C3-C8 carboxylic acids, C1-C 10 and a three carbon linker attached to a second molecule of Formula I, the second molecule being identical to the first molecule.

[0182] Aspect 3 is a compound according to any of Aspects 1 or 2, wherein R 3 is selected from the formula consisting of:

[0183] [ka]

[0184] Aspect 4 is a compound according to any one of aspects 1 to 3, wherein R1 and R 2 is methyl. Aspect 5 is a compound according to any one of aspects 1 to 4, wherein n is 5.

[0185] Aspect 6 is a compound according to any one of Aspects 1-5, wherein the compound is N-benzyl-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide and has the formula:

[0186] [ka]

[0187] Aspect 7 is a compound according to any one of Aspects 1-5, wherein the compound is N-(2-ethoxy-2-oxoethyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide and has the formula:

[0188] [ka]

[0189] Example 8 is the compound of any one of Examples 1-5, wherein the compound is N-allyl-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium iodide, having the formula:

[0190] [ka]

[0191] Aspect 9 is the compound of any one of Aspects 1-5, wherein the compound is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxo-N-(prop-2-yn-1-yl)hexan-1-aminium bromide and has the formula:

[0192] [ka]

[0193] Aspect 10 is a compound according to any one of Aspects 1-5, wherein the compound is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(2-(2-methoxyethoxy)ethyl)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0194] [ka]

[0195] Example 11 is a compound according to any one of Examples 1-5, wherein the compound is N-(3-(diethoxyphosphoryl)propyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide, having the formula:

[0196] [ka]

[0197] Example 12 is a compound according to any one of Examples 1-5, wherein the compound is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(3-hydroxypropyl)-N,N-dimethyl-6-oxohexan-1-aminium iodide, having the formula:

[0198] [ka]

[0199] Example 13 is a compound according to any one of Examples 1-5, wherein the compound is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(2-hydroxyethyl)-N,N-dimethyl-6-oxohexan-1-aminium iodide, having the formula:

[0200] [ka]

[0201] Example 14 is a compound according to any one of Examples 1-5, wherein the compound is N-(5-carboxypentyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide and has the formula:

[0202] [ka]

[0203] Aspect 15 is a compound according to any one of aspects 1 to 5, wherein the compound is N 1 ,N 3-Bis(6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-6-oxohexyl)-N 1 ,N 1 ,N 3 ,N 3 -tetramethylpropane-1,3-diaminium dibromide, which has the following formula:

[0204] [ka]

[0205] Aspect 16 is a method for synthesizing a compound of formula I,

[0206] [ka]

[0207] In the formula, R 1 and R 2 are the same or different and comprise at least one group selected from the group consisting of C1-C6 alkyl, optionally C1-C6 alkyl may comprise one or more of oxygen, nitrogen, or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 are alkenyl, alkynyl, ester, alcohol, aryl alkyl, alkoxy alkyl ether, alkyl phosphate, C3-C8 carboxylic acid, C1-C 10and X is selected from the group consisting of an alkyl benzoic acid, an alkyl benzoate, and a C1-C6 linker attached to a second molecule of formula I, the second molecule being the same or different; n is an integer from 1 to 12; and X is selected from the group consisting of chloride, bromide, and iodide, and the method includes a ring-opening step of opening the lactam ring to obtain an amino acid having an N-terminus and a C-terminus, a first alkylation step of alkylating the N-terminus to obtain a tertiary amine, a coupling step of reacting the C-terminus with 3-aminopropyltris(trimethylsiloxy)silane to obtain a siloxane derivative, and a second alkylation step of alkylating the N-terminus to obtain a quaternary amine of formula I.

[0208] Example 17 is the method of example 16, wherein the lactam is caprolactam. Example 18 is the method of any of Example 16 or Example 17, wherein in the first alkylation step, the tertiary amine is 6-(dimethylamino)hexanoic acid.

[0209] Example 19 is a method according to any one of Examples 16 to 18, wherein in the second alkylation step, the N-terminus is alkylated with an alkylating agent selected from the group consisting of benzyl bromide, ethyl bromoacetate, allyl iodide, propargyl bromide, 1-bromo-2-(2-methoxyethoxy)ethane, bromophosphonate, 3-iodopropanol, 3-bromopropanol, 2-iodoethanol, 2-bromoethanol, 6-bromohexanoic acid, and 1,3-dibromopropane.

Claims

1. A compound of formula I, 【Chemistry 1】 In the formula, R １ and R ２ are the same or different, and C １ ~C ６ alkyl, １ ~C ６ Alkyl may contain one or more of oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and said alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R ３ is an alkenyl, alkynyl, ester, alcohol, aryl alkyl, alkoxy alkyl ether, alkyl phosphate, C ３ ~C ８ Carboxylic acid, C １ ~C １０ an alkyl benzoic acid, and a C bonded to a second molecule of formula I １ ~C ６ linker, wherein the second molecule is the same or different; n is an integer from 1 to 12; and X is selected from the group consisting of chloride, bromide, and iodide; compound.

2. R ３ But, C ２ ~C １０ Alkenyl, C ２ ~C １０ Alkynyl, C ２ ~C １２ Estelle, C. １ ~C １０ Hydroxyl, benzyl, C ２ ~C １２ Alkoxyalkyl ether, alkyl phosphate, C ３ ~C ８ Carboxylic acid, C １ ~C １０ 2. The compound of claim 1, wherein said second molecule is selected from the group consisting of an alkyl benzoic acid and a three-carbon linker attached to a second molecule of formula I, said second molecule being identical to said first molecule.

3. R ３ is selected from the formula consisting of: 【Chemistry 2】 A compound according to claim 1 or claim 2.

4. R １ and R ２ The compound according to any one of claims 1 to 3, wherein is methyl.

5. The compound according to any one of claims 1 to 4, wherein n is 5.

6. The following formula: 【Chemistry 3】 The compound according to any one of claims 1 to 5, which is N-benzyl-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide having the formula:

7. The following formula: 【Chemistry 4】 The compound according to any one of claims 1 to 5, which is N-(2-ethoxy-2-oxoethyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide having the formula:

8. The following formula: 【Chemistry 5】 The compound according to any one of claims 1 to 5, which is N-allyl-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium iodide having the formula:

9. The following formula: 【Chemistry 6】 The compound according to any one of claims 1 to 5, which is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxo-N-(prop-2-yn-1-yl)hexan-1-aminium bromide having the formula:

10. The following formula: 【Chemistry 7】 The compound according to any one of claims 1 to 5, which is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(2-(2-methoxyethoxy)ethyl)-N,N-dimethyl-6-oxohexane-1-aminium bromide having the formula:

11. The following formula: 【Chemistry 8】 The compound according to any one of claims 1 to 5, which is N-(3-(diethoxyphosphoryl)propyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide having the formula:

12. The following formula: 【Chemistry 9】 The compound according to any one of claims 1 to 5, which is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(3-hydroxypropyl)-N,N-dimethyl-6-oxohexane-1-aminium iodide having the formula:

13. The following formula: 【Chemistry 10】 The compound according to any one of claims 1 to 5, which is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(2-hydroxyethyl)-N,N-dimethyl-6-oxohexane-1-aminium iodide having the formula:

14. The following formula: 【Chemistry 11】 The compound according to any one of claims 1 to 5, which is N-(5-carboxypentyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide having the formula:

15. The following formula: 【Chemistry 12】 N １ , N ３ -Bis(6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-6-oxohexyl)-N １ , N １ , N ３ , N ３ The compound according to any one of claims 1 to 5, which is tetramethylpropane-1,3-diaminium dibromide.

16. A method for the synthesis of a compound of formula I, comprising the steps of: 【Chemistry 13】 In the formula, R １ and R ２ are the same or different, and C １ ~C ６ alkyl, １ ~C ６ Alkyl may contain one or more of oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and said alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R ３ is an alkenyl, alkynyl, ester, alcohol, aryl alkyl, alkoxy alkyl ether, alkyl phosphate, C ３ ~C ８ Carboxylic acid, C １ ~C １０ an alkyl benzoic acid, and a C bonded to a second molecule of formula I １ ~C ６ linker, wherein the second molecule is the same or different; n is an integer from 1 to 12; and X is selected from the group consisting of chloride, bromide, and iodide; The method comprises: a ring-opening step of opening the lactam ring to obtain an amino acid having an N-terminus and a C-terminus; a first alkylation step of alkylating the N-terminus to obtain a tertiary amine; a coupling step of reacting the C-terminus with 3-aminopropyltris(trimethylsiloxy)silane to obtain a siloxane derivative; a second alkylation step to alkylate the N-terminus to give a quaternary amine of formula I; A method comprising:

17. 17. The method of claim 16, wherein the lactam is caprolactam.

18. 18. The method of claim 16 or 17, wherein in the first alkylation step, the tertiary amine is 6-(dimethylamino)hexanoic acid.

19. 19. The method of any one of claims 16 to 18, wherein in the second alkylation step, the N-terminus is alkylated with an alkylating agent selected from the group consisting of benzyl bromide, ethyl bromoacetate, allyl iodide, propargyl bromide, 1-bromo-2-(2-methoxyethoxy)ethane, bromophosphonates, 3-iodopropanol, 3-bromopropanol, 2-iodoethanol, 2-bromoethanol, 6-bromohexanoic acid, and 1,3-dibromopropane.

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