Siloxane derivatives of amino acids having surface-active properties

Abstract

To provide siloxane derivatives of amino acids that may have low critical micelle concentrations (CMC) and / or the ability to lower the surface tension of a liquid.SOLUTION: The amino acid can be naturally-occurring or synthetic, or they may be obtained via a ring-opening reaction of a lactam, such as caprolactam. The amino acid may be functionalized with a siloxane group to form a compound that is surface-active and has surfactant characteristics.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 62 / 890,341, entitled "SILOXANE DERIVATIVES OF AMINO ACIDS HAVING SURFACE-ACTIVE PROPERTIES," filed August 22, 2019, the entire disclosure of which is 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 those between two liquids, between gas and liquid, or between solid and liquid. In the case of the water-oil interface, the hydrophilic head group extends into the water, while the hydrophobic tail group extends into the oil. When added to water, the hydrophilic head group extends into the water, while the hydrophobic tail group extends into the air. The presence of surfactants disrupts the intermolecular interactions between water molecules, replacing them with weaker interactions between the water molecules and the surfactant. This results in a reduction of surface tension and can also act to stabilize the interface.

[0004] At sufficiently high concentrations, surfactants can form aggregates, limiting the exposure of their hydrophobic tails to polar solvents. 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, which interact with polar solvents. The effect that any compound has on surface tension and the concentration at which it forms micelles can be useful as a typical characteristic for surfactants.

[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. Therefore, there is a continuing need to identify and synthesize such compounds.

[0006] However, it can be difficult to predict whether any compound will have surface-active properties from its structure alone, let alone other important features that are also essential for whether the compound will be a useful surfactant, such as interfacial adsorption kinetics, achievable minimum surface tension, and / or wetting ability of hydrophobic and / or oleophobic surfaces. 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 intuitive. Similarly, some siloxanes have been found to have surface-active properties, but it is still very difficult to predict which siloxanes will be effective. The synthesis of such compounds is made even more difficult by differences in solubility, which may be due 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 simple route. Summary of the Invention

[0007] The present disclosure provides siloxane derivatives of amino acids that have 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. 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, where optionally the C1-C6 alkyl may comprise one or more 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 is an integer from 1 to 12; The terminal nitrogen can optionally be R 3 In this case, R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl; and An optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride, bromide, and iodide.

[0011] Further compounds provided by the present disclosure are compounds of formula Ia:

[0012] [ka]

[0013] 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, where optionally the C1-C6 alkyl may comprise one or more 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; m is an integer from 1 to 6; the terminal nitrogen is optionally R 3 is further substituted with, in this case, R 3 is selected from the group consisting of hydrogen, oxygen, and C1-C6 alkyl, the alkyl chain optionally being substituted with one or more substituents selected from the group consisting of carboxyl, carboxylate, and sulfonate; and An optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride, bromide, and iodide.

[0014] Further compounds provided by the present disclosure are compounds of formula Ib:

[0015] [ka]

[0016] 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, where optionally the C1-C6 alkyl may comprise one or more 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; p is 5; The terminal nitrogen can optionally be R 3is further substituted with, in this case, R 3 is selected from the group consisting of hydrogen, oxygen, and C1-C6 alkyl, the alkyl chain optionally being substituted with one or more substituents selected from the group consisting of carboxyl, carboxylate, and sulfonate; and An optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride, bromide, and iodide.

[0017] Still other compounds provided by the present disclosure include compounds having R 1 and R 2 is methyl. Other compounds provided by the present disclosure are compounds of formula I, where n is 5.

[0018] Still other compounds provided by the present disclosure include compounds having R 1 and R 2 is methyl. Still other compounds provided by the present disclosure include compounds in which R 3 is hydrogen.

[0019] Other compounds provided by the present disclosure are compounds of Formula Ib, wherein the counterion is selected from the group consisting of chloride, bromide, and iodide. Further compounds provided by the present disclosure are compounds of formula Ib, where the counterion is chloride.

[0020] Other compounds provided by the present disclosure include compounds having R 3 is methyl. Other compounds provided by the present disclosure are compounds of formula Ib, where the counterion is iodide.

[0021] Still other compounds provided by the present disclosure include compounds having R 3 is oxygen. Further compounds provided by the present disclosure include compounds having R 3is a C1-C6 alkyl substituted with a sulfonate.

[0022] One specific compound provided by the present disclosure is 6-(dimethylamino)-N-( 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexanamide, having the formula:

[0023] [ka]

[0024] A second specific compound provided by the present disclosure is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexaminium chloride, having the formula:

[0025] [ka]

[0026] A third specific compound provided by the present disclosure is 36-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide, having the following formula:

[0027] [ka]

[0028] A fourth specific compound provided by the present disclosure is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-amine oxide, having the following formula:

[0029] [ka]

[0030] A fifth specific compound provided by the present disclosure is 4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane- 3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate and has the following formula:

[0031] [ka]

[0032] A sixth specific compound provided by the present disclosure is 5-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)pentane-1-sulfonate, having the following formula:

[0033] [ka]

[0034] The above and other features of the present disclosure, as well as the manner in which they are achieved, will become more apparent and will be better understood by referring to the following description of the embodiments taken in conjunction with the accompanying drawings. [Brief explanation of the drawings]

[0035] [Figure 1] FIG. 1 shows a plot of surface tension versus concentration measured at pH=7 for Surfactant 2 with chloride as the counterion, as described in Example 1b. [Figure 2] FIG. 2 shows a plot of surface tension versus concentration for surfactant 3, as described in Example 2b. [Figure 3] FIG. 3 shows a plot of dynamic surface tension as a function of time for surfactant 3, as described in Example 2b. [Figure 4] FIG. 4 shows a plot of surface tension versus concentration for surfactant 4, as described in Example 3b. [Figure 5] FIG. 5 shows a plot of dynamic surface tension as a function of time for surfactant 4, as described in Example 3b. [Figure 6] FIG. 6 shows a plot of surface tension versus concentration for surfactant 5, as described in Example 4b. [Figure 7] FIG. 7 shows a plot of dynamic surface tension as a function of time for surfactant 5, as described in Example 4b. DETAILED DESCRIPTION OF THE INVENTION

[0036] 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 end of the list or toward the upper end of the list. For example, a pair of values ​​may be selected from the two lower values, the two upper values, or a lower value and an upper value.

[0037] As used herein, the term "alkyl" means any saturated carbon chain, which may be straight or branched. 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.

[0038] With respect to imprecision terms, the terms "about" and "approximately" may be used interchangeably and refer to a measurement that includes the stated measurement and 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. If one of ordinary skill in the art determines that a value for such a reasonably small difference is not readily ascertainable, then the terms "about" and "approximately" may be understood to mean plus or minus 10% of the stated value.

[0039] The present disclosure provides siloxane derivatives of amino acids. The amino acids may be natural or synthetic, or may be obtained from the ring-opening reaction of lactams such as caprolactam. The compounds of the present disclosure have been shown to have surface-active properties and can be used, for example, as surfactants and wetting agents. In particular, the present disclosure provides compounds of Formula I shown below:

[0040] [ka]

[0041] In the formula, R 1 and R 2 may be the same or different and are at least one group selected from the group consisting of C1-C6 alkyl, where optionally the C1-C6 alkyl may include one or more oxygen, nitrogen, or sulfur atoms or substituents containing one or more 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 is an integer from 1 to 12; The terminal nitrogen can optionally be R 3 is further substituted with, in this case, R 3is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl; and An optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride, bromide, and iodide.

[0042] The present disclosure further provides compounds of formula Ia:

[0043] [ka]

[0044] 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, where optionally the C1-C6 alkyl may comprise one or more 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; m is an integer from 1 to 6; The terminal nitrogen can optionally be R 3 is further substituted with, in this case, R 3 is selected from the group consisting of hydrogen, oxygen, and C1-C6 alkyl, the alkyl chain optionally being substituted with one or more substituents selected from the group consisting of carboxyl, carboxylate, and sulfonate; and An optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride, bromide, and iodide.

[0045] The present disclosure further provides compounds of formula Ib:

[0046] [ka]

[0047] 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, where optionally the C1-C6 alkyl may comprise one or more 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; p is 5; The terminal nitrogen can optionally be R 3 is further substituted with, in this case, R 3 is selected from the group consisting of hydrogen, oxygen, and C1-C6 alkyl, the alkyl chain optionally being substituted with one or more substituents selected from the group consisting of carboxyl, carboxylate, and sulfonate; and An optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride, bromide, and iodide.

[0048] One specific compound provided by the present disclosure is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexanamide (Surfactant 1), which has the formula:

[0049] [ka]

[0050] A second specific compound provided by the present disclosure is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexaminium chloride (Surfactant 2), having the formula:

[0051] [ka]

[0052] A third specific compound provided by the present disclosure is 3 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide (Surfactant 3), having the formula:

[0053] [ka]

[0054] A fourth specific compound provided by the present disclosure is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-amine oxide (Surfactant 4), having the following formula:

[0055] [ka]

[0056] In the above structures, the "N→O" notation is intended to mean a non-ionic bonding interaction between the nitrogen and oxygen. A fifth specific compound provided by the present disclosure is 4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate (Surfactant 5), having the following formula:

[0057] [ka]

[0058] A sixth specific compound provided by the present disclosure is 5-((6-((3-(1,1, 1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)pentane-1-sulfonate, having the formula:

[0059] [ka]

[0060] 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 amino acid C-terminus to the desired siloxane derivative. The amino acid N-terminus may be further protonated, alkylated, or oxidized to, for example, obtain a quaternary amine or N-oxide.

[0061] The amino acids may be natural or synthetic, or may be derived from the ring-opening reaction of a lactam such as caprolactam. The ring-opening reaction may be acid or alkali catalyzed, an example of an acid catalyzed reaction is shown in Scheme 1 below.

[0062] [ka]

[0063] The amino acid may have as few as one carbon or as many as 12 carbons between the N-terminus and C-terminus. 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.

[0064] The siloxane may be substituted with one or more alkoxy groups, such as methoxy, ethoxy, isopropoxy, tert-butoxy, etc. The siloxane may be further substituted with one or more alkyl groups, such as propyl, in which case the alkyl group may be further substituted with a suitable functional group to enable coupling of the siloxane to an amino acid, such as nitrogen. For example, the siloxane may be 3-aminopropyltris(trimethylsiloxy)silane.

[0065] Siloxane derivatives of amino acids may be synthesized as shown in Scheme 2 below. As shown, 6-aminohexanoic acid is treated with formaldehyde in formic acid at reflux to give 6-(dimethylamino)hexanoic acid. This free carboxylic acid is then coupled to 3-aminopropyl(trismethylsiloxy)silane in refluxing toluene to give the desired siloxane derivative.

[0066] [ka]

[0067] The N-terminal nitrogen may be further derivatized to modify or improve water solubility and surface active properties. A sample synthesis scheme is shown below in Scheme 3, where the N-terminal nitrogen is treated with hydrochloric acid to give the corresponding hydrochloride salt.

[0068] [ka]

[0069] The N-terminal nitrogen may be alkylated. A sample synthetic scheme is shown below, where the N-terminal nitrogen is treated with methyl iodide to give the corresponding quaternary amine salt.

[0070] [ka]

[0071] The N-terminal nitrogen may be treated with hydrogen peroxide in refluxing water to give the corresponding N-oxide, as shown in Scheme 5 of the sample synthesis scheme below.

[0072] [ka]

[0073] The compounds of the present disclosure exhibit surface-active properties. These properties can be measured and expressed by a variety of methods. One way surfactants can be expressed is by the molecule's critical micelle concentration (CMC). The CMC can be defined as the concentration of surfactant that forms micelles, above which any additional surfactant is incorporated into the micelles.

[0074] As surfactant concentration increases, surface tension decreases. When the surface is completely covered with surfactant molecules, micelles begin 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 typically 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 an existing literature value.

[0075] Another parameter used to evaluate the performance of surfactants is dynamic surface tension. Dynamic surface tension is the value of the surface tension of a particular surface or interface over time. 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 reduce the surface tension, 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.

[0076] One method for measuring dynamic surface tension is with a maximum bubble pressure tensiometer. This device measures the maximum internal pressure of a bubble formed in a liquid using 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.

[0077] Surface-active compounds can also be evaluated by their ability to wet on solid substrates, as measured by contact angle. When a liquid droplet 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 is tangent to the droplet and plays a role in the three-phase line, 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 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 a given compound, but since it is not a concentration-dependent property, measurements of wetting properties may be measured at higher or lower concentrations.

[0078] 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 sedentary drop of liquid on a surface.

[0079] 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.

[0080] Those skilled in the art will appreciate that small differences between compounds can lead to significantly different surfactant properties, and therefore different compounds may be used for different substrates and in different applications. will be done.

[0081] The following non-limiting examples are provided to illustrate the different properties of different surfactants. Table 1 below associates surfactant abbreviations with their corresponding chemical structures.

[0082] [Table 1]

[0083] Each of the five compounds is effective as a surfactant and is useful as a wetting or foaming agent, dispersing agent, emulsifier, and detergent, among other uses. Surfactants 1 and 2 are candidates for use as foaming or wetting agents in a variety of surface cleaning and personal care product formulations.

[0084] Surfactant 3 is cationic. These surfactants are suitable for the applications mentioned above, and It is useful both in some further special applications, such as in personal hair care products, as a surface treatment, and can also be used to create water repellent surfaces.

[0085] Surfactant 4 is non-ionic and can be used in shampoos, detergents, hard surface cleaners, and a variety of other surface cleaning formulations. Surfactant 5 is zwitterionic. These surfactants are useful as co-surfactants in all of the applications mentioned above.

[0086] The amount of a compound disclosed herein used in the formulation may 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 any range defined between any two of the above values.

[0087] Example Nuclear magnetic resonance (NMR) spectroscopy was performed on a Bruker 500 MHz spectrometer. The critical micelle concentration (CMC) was determined at 23 °C using a tensiometer (DCAT 11, DataPhysics Instruments GmbH) equipped with a Pt-Ir plate by the Wilhelmy plate method. The dynamic surface tension was determined at 23 °C using a maximum bubble pressure tensiometer (Kruss BP100, Kruss GmbH). The contact angle was determined using an optical contact angle goniometer (OCA 15 Pro, DataPhysics GmbH) equipped with a digital camera.

[0088] Example 1a: Synthesis of 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexanamide (Surfactant 1) and 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium salt (Surfactant 2)

[0089] [ka]

[0090] 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 refluxed for 24 h until no more water separated in the Dean-Stark tube. The solvent was removed in vacuo to afford surfactant 1 as a yellow oil in 94% yield. 1H 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=12.9,6.8 Hz, 2H) In its neutral form, surfactant 1 is slightly soluble in pure water without the addition of a hydrotrope or other surfactant, but becomes surface active when protonated under slightly acidic conditions (surfactant 2). Acidic conditions may be created by the addition of any acid or acidic buffer in the pH range of 4 to 7. Surfactant 2 may also be prepared in non-aqueous solution, for example, by injecting gaseous HCl into toluene in the presence of surfactant 1.

[0091] Example 1b: Identification of the critical micelle concentration (CMC) of surfactant 2 The critical micelle concentration (CMC) of surfactant 2 was tested with chloride counterions and determined to be approximately 2 mmol. The minimum surfactant plateau value achievable with this surfactant is approximately 23 mN / m. Figure 1 is a plot of these results, showing surface tension versus concentration.

[0092] Example 2a: Synthesis of 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide (Surfactant 3)

[0093] [ka]

[0094] Surfactant 1 (1.00 g, 2.02 mmol, 1 equiv.) was dissolved in acetonitrile (10 mL) in a 100 mL round-bottom flask. Na2CO3 (0.26 g, 2.42 mmol, 1.2 equiv.) was then added, and the mixture was stirred for 10 min. Methyl iodide (0.377 mL, 6.06 mmol, 3 equiv.) was added, and the reaction was heated at 40 °C for 24 h. The cooled reaction mixture was filtered, and the solvent was removed in vacuo to give surfactant 3 as a slightly yellow solid in quantitative yield. 1 H NMR(500 MHz,DMSO)δ0.09(s,27H),0.38-0.42(m,2H),1.23-1.26(m,2H),1.37-1.40(m,2H),1.52-1.55(m,2H), 1.65-1.69(m,2H),2.08(t,J=7.4Hz,2H),2.99(dd,J=13,6.9Hz,2H),3.04(s,9H),),3.24-3.33(m,2H) The pure product is soluble in water and has surfactant properties. The halogen anion can be obtained directly from the N-alkylation reaction, and other desired counter anions can be obtained by anion exchange.

[0095] Example 2b: Identification of the physical properties of surfactant 3 The critical micelle concentration (CMC) for surfactant 3 was measured. From the change in surface tension with concentration in water, the CMC was determined to be approximately 1.6 mmol. The plateau value of the minimum surface tension that can be reached with this surfactant is approximately 20 mN / m, indicating that this surfactant has significant interfacial activity. These results are plotted as surface tension versus concentration and are shown in Figure 2.

[0096] The dynamic surface tension of surfactant 3 was determined using a maximum bubble pressure tensiometer, which measures the change in surface tension of a newly created air-water interface over time. Figure 3 shows the results as surface tension versus time. A plot is shown showing that surfactant 3 completely saturated the interface in less than 500 ms, making it extremely fast in terms of interfacial adsorption.

[0097] In addition to Surfactant 3's ability to lower both interfacial and surface tension, formulations containing only the surfactant also possess exceptional wetting properties. For example, hydrophobic substrates such as polyethylene and polypropylene exhibit complete surface wetting with a contact angle of 0°. On oleophobic and hydrophobic substrates such as Teflon, the measured contact angle was extremely small, at 10.5° (Table 2).

[0098] [Table 2]

[0099] Example 3a: Synthesis of 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-amine oxide (surfactant 4)

[0100] [ka]

[0101] Surfactant 1 (1.00 g, 2.02 mmol, 1 equiv.) was added to distilled water (80 mL) in a 100 mL round-bottom flask, followed by 50% hydrogen peroxide (1.15 mL, 20.2 mmol, 10 equiv.). The reaction was refluxed for 12 h and then concentrated in vacuo. The residue was washed three times with acetone to give surfactant 4 in 99% yield. 1 H NMR(500MHz,DMSO)δ0.09(s,27H),0.38-0.44(m,2H),1.21-1.25(m,2H),1.35-1.42(m,2H),1.50-1 .55(m,2H),1.71-1.75(m,2H),2.05-2.08(m,2H),2.97-3.00(m,2H),3.01(s,9H),3.11-3.14(m,2H) Example 3b: Identification of the physical properties of surfactant 4 The critical micelle concentration (CMC) for surfactant 4 was measured. From the change in surface tension with concentration in water, the CMC was determined to be approximately 0.49 mmol. The plateau value of the minimum surface tension that can be reached with this surfactant is approximately 20 mN / m, indicating that this surfactant has significant interfacial activity. These results are plotted as surface tension versus concentration and are shown in Figure 4.

[0102] The dynamic surface tension of surfactant 4 was determined using a maximum bubble pressure tensiometer. Figure 5 shows a plot of the results as surface tension versus time, demonstrating that surfactant 4 penetrates the newly created air-water interface. It was completely saturated within 1 second, indicating high speed in terms of interfacial adsorption.

[0103] In addition to Surfactant 4's ability to lower both interfacial and surface tension, formulations containing only Surfactant 4 at concentrations between 1 and 100x CMC also possess exceptional wetting properties. For example, an aqueous solution of Surfactant 4 at a concentration of 10x CMC exhibits a contact angle of 0° on hydrophobic substrates such as polyethylene and polypropylene, and a contact angle of 10.6° on oleophobic and hydrophobic substrates such as Teflon. These contact angles are significantly smaller than the contact angle of water on the same substrates (Table 3).

[0104] [Table 3]

[0105] Example 4a: Synthesis of 4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate (surfactant 5)

[0106] [ka]

[0107] Surfactant 1 (1.00 g, 2.02 mmol, 1 equiv.) was added to ethyl acetate (EtOAc) (30 mL) in a 100 mL round-bottom flask, followed by 1,2-butanesultone (0.27 mL, 2.2 mmol, 1.1 equiv.). The reaction was refluxed for 12 h, after which the solvent was removed and the resulting white waxy solid was washed with acetone to give surfactant 5 in 50% yield. 1 H NMR(500MHz,DMSO)δ0.10(s,27H),0.38-0.46(m,2H),1.23-1.27(m,2H),1.37-1.68(m,10H), 1.73-1.78(m,2H),2.45-2.48(m,2H),2.97-3.01(m,8H),3.18-3.21(m,2H),3.23-3.27(m,2H) Example 4b: Identification of the physical properties of surfactant 5 The critical micelle concentration (CMC) for surfactant 5 was measured. From the change in surface tension with concentration in water, the CMC was determined to be approximately 0.39 mmol. The plateau value of the minimum surface tension that can be reached with this surfactant is approximately 21 mN / m, indicating that this surfactant has significant interfacial activity. These results are plotted as surface tension versus concentration and are shown in Figure 6.

[0108] The dynamic surface tension of surfactant 5 was determined using a maximum bubble pressure tensiometer. Figure 7 shows a plot of the results as surface tension versus time, demonstrating that surfactant 5 completely saturated the newly created air-water interface within 1 second, making it fast in terms of interfacial adsorption.

[0109] Finally, an aqueous solution of surfactant 5 at a concentration of 10×CMC exhibits a contact angle of 0° on hydrophobic substrates such as polyethylene and polypropylene, and a contact angle of 10.2° on oleophobic and hydrophobic substrates such as Teflon. These contact angles are significantly smaller than the contact angle of water on the same substrates (Table 4).

[0110] [Table 4]

[0111] Example 5: Formulations for shampoos In this example, a formulation for use as a shampoo is provided. The formulation is useful for imparting a smooth, silky feel to hair. The ingredients of the formulation are shown in Table 4 below. In addition, the formulation may contain other natural oils and ingredients, as well as vitamins for consumer appeal, in amounts less than 1% by weight.

[0112] [Table 5]

[0113] Example 6: Formulations for hair conditioners In this example, a formulation for use as a hair conditioner is provided. This formulation can be used to replace or reduce polyquaternium-10, polyquaternium-7, and dimethicone oil while maintaining the easy combing and silky soft feel that hair conditioners provide. The formulation is shown in Table 5 below.

[0114] [Table 6]

[0115] Example 7: Formulations for car wash detergents to remove stubborn stains from surfaces In this example, a formulation for a car wash detergent to remove tough stains from surfaces is provided. The formulation is shown in Table 6 below.

[0116] [Table 7]

[0117] Example 8: Formulation for spot-free rinse or dry solution In this example, a formulation for a spot-free rinse or dry solution is provided. This solution can be applied to the windows or body of a vehicle after the main wash is complete. The formulation is shown in Table 7 below.

[0118] [Table 8]

[0119] Example 9: Formulations for heavy duty carpet cleaners In this example, a formulation for a heavy-duty carpet cleaner is provided. This cleaner is a high foaming deep cleaner. The formulation is shown in Table 8 below.

[0120] [Table 9]

[0121] Example 10: Formulations for heavy-duty surface cleaners In this example, a formulation for a heavy-duty surface cleaner is provided. This cleaner can be used for manual or automatic surface cleaning machines. The formulation is shown in Table 9 below.

[0122] [Table 10]

[0123] Example 11: Formulations for concentrated graffiti removal detergents In this example, a formulation for a concentrated graffiti removal cleaner is provided. This cleaner can be used with high-pressure hoses. The formulation is shown in Table 10 below.

[0124] [Table 11]

[0125] Example 12: Formulations for wetting agents in aerosol sprays In this example, a formulation for a wetting adjuvant for an aerosol spray is provided. The aerosol spray can be used to apply insecticides or other crop protection agents. The provided formulation provides superior wetting and better performance due to its low CMC, thereby reducing the risk of insecticides. The aim is to reduce the amount of surfactant chemicals in agricultural chemicals and other crop protection products (typically 2-5%), thus offering a more environmentally friendly option. The formulations are shown in Table 11 below.

[0126] [Table 12]

[0127] Example 13: Formulation of additives for aerosol spray paints In this example, a formulation for an additive for water-based aerosol spray paints or coatings is provided. The formulation is intended to provide good dynamic wetting on the surface of the aerosol droplets upon application, thus preventing paint craters and other such problems. The formulation is shown in Table 12 below.

[0128] [Table 13]

[0129] Aspects Aspect 1 is a compound of formula I:

[0130] [ka]

[0131] 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, where optionally the C1-C6 alkyl may comprise one or more 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 is an integer from 1 to 12; The terminal nitrogen can optionally be R 3 is further substituted with, in this case, R 3 is hydrogen, oxygen, selected from the group consisting of hydroxyl, and C1-C6 alkyl; and An optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride, bromide, and iodide.

[0132] Aspect 2 is a compound according to aspect 1 represented by formula Ia:

[0133] [ka]

[0134] 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, where optionally the C1-C6 alkyl may comprise one or more 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; m is an integer from 1 to 6; The terminal nitrogen can optionally be R 3 is further substituted with, in this case, R 3is selected from the group consisting of hydrogen, oxygen, and C1-C6 alkyl, the alkyl chain optionally being substituted with one or more substituents selected from the group consisting of carboxyl, carboxylate, and sulfonate; and An optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride, bromide, and iodide.

[0135] Aspect 3 is a compound according to either aspect 1 or 2 represented by formula Ib:

[0136] [ka]

[0137] 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, where optionally the C1-C6 alkyl may comprise one or more 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; p is 5; The terminal nitrogen can optionally be R 3 is further substituted with, in this case, R 3 is selected from the group consisting of hydrogen, oxygen, and C1-C6 alkyl, the alkyl chain optionally being substituted with one or more substituents selected from the group consisting of carboxyl, carboxylate, and sulfonate; and An optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride, bromide, and iodide.

[0138] Aspect 4 is a compound according to any one of aspects 1-3, wherein R 1and R 2 is methyl. Aspect 5 is the compound of aspect 1, wherein n is 5.

[0139] Aspect 6 is a compound according to any one of aspects 1 to 5, wherein R 3 is hydrogen. Aspect 7 is a compound according to any one of aspects 1-6, wherein the counterion is selected from the group consisting of chloride, bromide, and iodide.

[0140] Example 8 is the compound of example 7, wherein the counterion is chloride. Aspect 9 is a compound according to any one of aspects 1 to 5, wherein R 3 is methyl. Aspect 10 is the compound of aspect 9, wherein the counterion is selected from the group consisting of chloride, bromide, and iodide.

[0141] Example 11 is the compound of example 10, wherein the counterion is iodide. Aspect 12 is a compound according to any one of aspects 1-5, wherein R 3 is an oxygen atom.

[0142] Aspect 13 is a compound according to any one of aspects 1-5, wherein R 3 is a C1-C6 alkyl substituted with a terminal sulfonate. Example 14 is the compound of any one of Examples 1-3, wherein the compound is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexanamide and has the formula:

[0143] [ka]

[0144] Aspect 15 is the compound of any one of Aspects 6-8, wherein the compound is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexaminium chloride, having the formula:

[0145] [ka]

[0146] Aspect 15 is the compound of any one of Aspects 9-11, wherein the compound is 36-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide, having the formula:

[0147] [ka]

[0148] Example 17 is the compound of example 12, 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-oxohexane-1-amine oxide and has the formula:

[0149] [ka]

[0150] Example 18 is the compound of example 13, wherein the compound is 4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate and has the formula:

[0151] [ka]

[0152] Example 19 is the compound of example 13, wherein the compound is 5-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)pentane-1-sulfonate and has the formula:

[0153] [ka]

Claims

1. Water, and A compound of formula I, 【Chemistry 1】 In the formula, R １ and R ２ may be the same or different, C １ ~C ６ alkyl, and optionally, １ ~C ６ Alkyl may include one or more of oxygen, nitrogen, or sulfur atoms, or groups containing at least one of these atoms, and the C １ ~C ６ the alkyl chain of the alkyl 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 is an integer from 3 to 12, The terminal nitrogen can optionally be R ３ wherein R ３ is hydrogen, oxygen, hydroxyl, and C １ ~C ６ is selected from the group consisting of alkyl, and The optional counterion associated with said compound, when present, is selected from the group consisting of chloride, bromide, and iodide; compound, A liquid medium comprising:

2. R １ and R ２ 2. The liquid medium of claim 1, wherein is methyl.

3. 2. The liquid medium of claim 1, wherein n is 5.

4. R ３ 4. The liquid medium of claim 3, wherein is hydrogen.

5. 5. The liquid medium of claim 4, wherein the counterion is selected from the group consisting of chloride, bromide, and iodide.

6. 6. The liquid medium of claim 5, wherein the counterion is chloride.

7. R ３ 4. The liquid medium of claim 3, wherein is methyl.

8. 8. The liquid medium of claim 7, wherein the counterion is selected from the group consisting of chloride, bromide, and iodide.

9. 9. The liquid medium of claim 8, wherein the counterion is iodide.

10. R ３ The liquid medium according to claim 3 , wherein is an oxygen atom.

11. R ３ is a sulfonate-substituted C １ ~C ６ 4. The liquid medium of claim 3, wherein the alkyl group is alkyl.

12. 4. The liquid medium of claim 3, wherein the compound is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexanamide and has the formula: 【Chemistry 2】

13. 4. The liquid medium of claim 3, wherein the compound is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexaminium chloride, having the formula: 【Transformation 3】

14. 4. The liquid medium of claim 3, wherein the compound is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide, having the formula: 【Chemistry 4】

15. 4. The liquid medium of claim 3, 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-oxohexane-1-amine oxide and has the formula: 【Transformation 5】

16. 4. The liquid medium of claim 3, wherein the compound is 4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate and has the formula: 【Transformation 6】

17. 4. The liquid medium of claim 3, wherein the compound is 5-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)pentane-1-sulfonate and has the formula: 【Transformation 7】

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