Novel ammonium compounds useful as surfactants

Abstract

The present invention provides a compound of formula (I) having surfactant properties and improved biodegradability. [Formula 1] The present invention relates to novel monoammonium compounds of TIFF2023529969000046.tif72170. The present invention also relates to novel mixtures comprising such monoammonium and diammonium compounds.

Description

[Technical Field] 【0001】 The present invention relates to the use of novel ammonium compounds, particularly novel quaternary ammonium compounds and novel ammonium compounds, which can be derived from internal ketones obtained from fatty acids or their derivatives, as surfactants, either alone or in combination with other surfactants. 【0002】 This application claims priority to International Patent Application PCT / European Patent Application Publication No. 2020 / 066649, filed as an International Patent Application on 16 June 2020, and to U.S. Patent Application No. 63 / 128985, filed in the United States on 22 December 2020, the entire contents of each of these applications being incorporated herein by reference for any purpose. 【0003】 Ammonium compounds, which possess surfactant properties and can be used for various applications, are described in the literature and are commercially available in various types from various suppliers. 【0004】 International publication no. 97 / 08284 is a brochure that is [ka] (In the formula, R 1 ~R 3 R4 and R5 are independently selected from C1-C4 alkyl groups or C2-C4 alkenyl groups, a is 1-4, and R4 and R5 are independently C 12 ~C 22 (Selected from alkyl or alkenyl groups, the sum of the chain lengths of R4 and R5 is preferably at least 30.) The present invention discloses a composition comprising a Guerbet alcohol betaine ester represented by [formula]. Since the compound is derived from a Guerbet alcohol, the number of carbon atoms in the R4 and R5 groups always differs by 2. 【0005】 European Patent No. 721936 specifies the formula [ka] (In the formula, R 1~2 C is a linear or branched C 36 ~C 44 (It is an alkyl group or alkenyl group, where R2-R4 are C1-C5 alkyl groups or hydroxyalkyl groups, Y is a linear or branched C2-C4 alkylene group, m is a number from 0 to 20, and n is an integer from 1 to 6.) This relates to liquid quaternary ammonium compounds. The preferred compound of European Patent No. 721936 is derived from Guerbet alcohols, as in International Publication No. 97 / 08284, and is of the formula [ka] It is represented by [this]. 【0006】 German Patent Application Publication No. 3402146 relates to a quaternary ammonium compound. Similar to International Publication No. 97 / 08284 and European Patent No. 721936, this compound comprises two long-chain substituents that are esters of guerbeic acid. 【0007】 Aliphatic quaternary ammonium compounds are widely used as surfactants, but there is still a need for these compounds to possess a good combination of surfactant properties and biodegradability. Biodegradability has become increasingly important in recent years due to customer demand for more environmentally friendly products. It is crucial that improving biodegradability does not negatively affect the properties of the surfactant. 【0008】 Therefore, the object of the present invention was to provide a novel ammonium compound having good surfactant properties and good biodegradability. 【0009】 This objective is achieved by the compound of formula (I). Preferred embodiments of the present invention are also described in detail below. 【0010】 The novel ionic monoammonium compound according to the present invention is of formula (I) [Chemical formula] (wherein, R may be the same or different in each occurrence, and is a C5-C 27 aliphatic group, preferably a C6-C 24 aliphatic group, and Y is a divalent C1-C6 aliphatic group, and R’, R’’, and R’’’ may be the same or different and are hydrogen or a C1-C4 alkyl group) has. 【0011】 The aliphatic group R may not have a double bond and a triple bond. Instead, the aliphatic group R may contain at least one -C=C- double bond and / or at least one -C≡C- triple bond. 【0012】 The aliphatic group R is preferably selected from an alkyl group, an alkenyl group, an alkadienyl group, an alkatrienyl group, and an alkynyl group. 【0013】 <​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​Alkyl alkyl groups or C6-C 17 This represents an alkyl group. It has been found that alkyl groups having aliphatic groups, particularly 10 to 20 carbon atoms, preferably 10 to 17 carbon atoms, are very advantageous. 【0016】 Preferred examples of substituent R include an acyclic aliphatic group, more preferably a linear aliphatic group, and even more preferably a linear alkyl group. Excellent results were obtained when R was a linear alkyl group having 14 to 17 carbon atoms. 【0017】 The number of carbon atoms in R can be even or odd, and each R group may have the same number of carbon atoms, or the number of carbon atoms in each R group may be different. 【0018】 In some embodiments, either both R atoms have an even number of carbon atoms, or both R atoms have an odd number of carbon atoms. 【0019】 In some other embodiments, which are generally preferred for economic reasons, only one R has an odd number of carbon atoms, and only one R has an even number of carbon atoms. In certain embodiments that are advantageous from an economic standpoint, only one R has an odd number of carbon atoms n O It has a carbon atom n, where the other R is an even number E It has, where n E is, n O It is equal to -1. 【0020】 The number of carbon atoms in the two R groups is the number of pairs (n 1 ,n 2 Let it be represented as ), where n 1 n is the number of carbon atoms in the first R group, and 2 is the number of carbon atoms in the other R group. Exemplary and preferred pair (n 1 ,n 2 ) is selected from the following pairs: (10,11), (12,13), (14,15), (16,17), (10,13), (10,15), (10,17), (11,12), (11,14), (11,16), (12,15), (12,17), (13,14), (13,16), (14,17), and (15,16). Particularly preferred pairs are (n1 ,n 2 ) is selected from the following pairs: (14,15), (16,17), (14,17), and (15,16). 【0021】 R' is preferably a C1-C4 alkyl group, preferably methyl or ethyl, more preferably methyl. Similarly, R'' is preferably a C1-C4 alkyl group, preferably methyl or ethyl, more preferably methyl. Furthermore, R''' is preferably a C1-C4 alkyl group, preferably methyl or ethyl, more preferably methyl. Preferably, at least one, more preferably at least two, and more preferably all three of R', R'', and R''' are C1-C4 alkyl groups, preferably methyl or ethyl, most preferably methyl. 【0022】 Y is preferably an acyclic divalent C1-C6 aliphatic group, more preferably a linear divalent C1-C6 aliphatic group, and even more preferably a linear alkanediyl (commonly known as "alkylene") C1-C6 group. Furthermore, Y preferably has 1 to 4 carbon atoms. Exemplary Y are ethanediyl and methanediyl (commonly called "methylene"). Excellent results were obtained when Y was a methylene group. 【0023】 In some embodiments, the ionic compound of formula (I) is ionic compound C I * is selected from, where Y is methylene, R', R'' and R''' are methyl, and the two R groups are as follows: - Either one R is n-tetradecyl and the other R is n-pentadecyl, or - Either one R is n-hexadecyl and the other R is n-heptadecyl, or - One R is n-pentadecyl and the other R is n-hexadecyl, - One R is n-tetradecyl, and the other R is n-heptadecyl. 【0024】 In some other embodiments, the ionic compound of formula (I) is ionic compound C I Selected from compounds other than those marked with an asterisk (*). 【0025】 The present invention relates to formula (II) [ka] (In the formula, R, R', R'', R''', and Y are as defined and described above, and W is an anion or anionic group having w negative charges.) It is also directed toward electrically neutral compounds. Suitable anions or anionic groups W include, for example, halides such as chlorides, fluorides, bromides or iodides, methyl sulfate or methosulfate anions (CH3-OSO3 - ), methanesulfonate anion (CH3-SO3 - ), sulfate anion, hydrogen sulfate anion (HSO4 - ) or organic carboxylic acid anions such as acetic acid, propionic acid, benzoic acid, tartaric acid, citric acid, lactic acid, maleic acid, or succinic acid. 【0026】 In some embodiments, the electrically neutral compound of formula (II) is the electrically neutral compound C II * Selected from, here, [W] 1 / w is a chloride anion (Cl - w is equal to 1, Y is methylene, R', R'' and R''' are methyl, and the two R groups are as follows: - Either one R is n-tetradecyl and the other R is n-pentadecyl, or - Either one R is n-hexadecyl and the other R is n-heptadecyl, or - One R is n-pentadecyl and the other R is n-hexadecyl, - One R is n-tetradecyl, and the other R is n-heptadecyl. 【0027】 In some other embodiments, the electrically neutral compound of formula (II) is compound C IISelected from electrically neutral compounds other than those marked with *. 【0028】 The compounds according to the present invention can be obtained by various processes. A preferred process for producing the compounds of the present invention involves the reaction of an internal ketone of the formula RC(=O)-R, which can preferably be obtained by the decarboxylase ketonization of a fatty acid, a fatty acid derivative, or a mixture thereof. A preferred process for producing an internal ketone following this route is disclosed in U.S. Patent Application Publication No. 2018 / 0093936, which is referenced for further details. Next, two processes for synthesizing the compounds of the present invention using the internal ketone obtained as described above as a starting material will be described. 【0029】 The initial process begins with pyriketonization, followed by hydrogenation, dehydration, epoxidation (to obtain an epoxide), and epoxide ring-opening (to obtain a monohydroxyl monoester). After the epoxide ring-opening step, the monoester is converted to a compound according to formula (I) via an amine condensation step (as the final step). This is a multi-step process that applies Piria's technique. This process has the advantage of not using salts and relying on readily available chemical transformations. 【0030】 First process for the synthesis of the compound of formula (I) Pyriaketonization The basic reaction of the first step is, [ka] That is the case. 【0031】 This response is described in detail in U.S. Patent No. 10035746, International Publication No. 2018 / 087179, and International Publication No. 2018 / 033607. For further details, please refer to these publications. 【0032】 Hydrogenation This internal ketone is then subjected to hydrogenation, which can be carried out under standard conditions known to those skilled in the art for the hydrogenation reaction. [ka] 【0033】 The hydrogenation reaction is carried out in an autoclave reactor by contacting the internal ketone with hydrogen at a temperature in the range of 15°C to 300°C and a hydrogen pressure in the range of 1 bar to 100 bar. The reaction can be carried out in the presence of an optional solvent, but the use of such a solvent is not essential, and the reaction can also be carried out without the addition of a solvent. Examples of suitable solvents include methanol, ethanol, isopropanol, butanol, THF, methyl-THF, hydrocarbons, water, or mixtures thereof. A suitable transition metal-based catalyst should be used for this reaction. Examples of suitable catalysts include heterogeneous transition metal catalysts such as supported-dispersed transition metal catalysts or homogeneous organometallic complexes of transition metals. Examples of suitable transition metals are Ni, Cu, Co, Fe, Pd, Rh, Ru, Pt, and Ir. Examples of suitable catalysts include Pd / C, Ru / C, Pd / Al2O3, Pt / C, Pt / Al2O3, Raney nickel, Raney cobalt, etc. After the reaction is complete, the desired alcohol can be recovered after appropriate work-up. Those skilled in the art will know the typical technique, so further details are not necessary here. Details of this step are described, for example, in U.S. Patent No. 10035746, which is referenced herein. 【0034】 Those skilled in the art will select appropriate reaction conditions based on their professional experience, taking into account the specific target compound to be synthesized. Therefore, further details are unnecessary here. 【0035】 dehydration In the next step, the alcohol thus obtained is subjected to a dehydration reaction to obtain an internal olefin. This reaction can also be carried out under standard conditions known to those skilled in the art for each dehydration reaction (e.g., U.S. Patent No. 1,0035746, Example 4), so no further details are needed here. [ka] 【0036】 The dehydration reaction is carried out by heating a secondary alcohol in a reaction zone in the presence of a suitable catalyst at a temperature in the range of 100°C to 400°C. The reaction can be carried out in the presence of an optional solvent, but the use of such a solvent is not essential, and the reaction can also be carried out without the addition of a solvent. Examples of solvents include hydrocarbons, toluene, xylene, or mixtures thereof. The use of a catalyst is essential in this reaction. A suitable catalyst is an acidic (Lewis or Brønsted) catalyst, which can be either a heterogeneous solid acid catalyst or a homogeneous catalyst. Examples of heterogeneous catalysts include alumina (Al2O3), silica (SiO2), aluminosilicates such as zeolites (Al2O3-SiO2), phosphoric acid supported on silica or alumina, and acidic resins such as Amberlite®. Homogeneous catalysts can also be used, and suitable acids include: H2SO4, HCl, trifluoromethanesulfonic acid, p-toluenesulfonic acid, AlCl3, FeCl3, etc. The water generated during the reaction can be removed from the reaction medium during the reaction. After the reaction is complete, the desired olefin can be recovered after appropriate work-up. Those skilled in the art will know typical techniques, which are described, for example, in U.S. Patent No. 1,0035746, so no further details are needed here. 【0037】 As shown above, in the ionic monoammonium compound of formula (I), embodiments in which only one R has an odd number of carbon atoms and only one R has an even number of carbon atoms are generally preferred for economic reasons. As is now evident, this can occur when both Rs are derived from carboxylic acids having an even number of carbon atoms, and this is generally advantageous from an economic standpoint since naturally occurring fatty carboxylic acids (typically having an even number of carbon atoms) are widely available. This can also occur when both Rs are derived from carboxylic acids having an odd number of carbon atoms. In particular, when only one R has an odd number of carbon atoms n O It has other R atoms with an even number of carbon atoms n E It has, where n E ga n O Embodiments equal to -1 may occur when the internal olefin is obtained from a single carboxylic acid having an even number of carbon atoms. For illustrative purposes, pairs (n) represent the number of carbon atoms of the two R groups. 1 ,n 2 The internal olefins selected from (14,15), (16,17), (14,17) and (15,16) can be obtained starting from the following carboxylic acids or mixtures of carboxylic acids: palmitic acid alone, stearic acid alone, oleic acid alone, a mixture of palmitic acid and stearic acid or oleic acid, or a mixture of palmitic acid and stearic acid and oleic acid, and a mixture of stearic acid and oleic acid. 【0038】 On the other hand, if only one R is derived from a carboxylic acid having an even number of carbon atoms and only one R is derived from a carboxylic acid having an odd number of carbon atoms, then an internal olefin and an ionic monoammonium compound of formula (I) are obtained in which both R ultimately have an even number of carbon atoms, or both R ultimately have an odd number of carbon atoms. 【0039】 Epoxy This internal olefin can then be oxidized to the respective epoxides in which the double bond is replaced by an epoxide group, according to the following scheme (where the reactants are merely examples of the group of compounds that perform their respective functions). [ka] Here, R** is a hydrocarbon group that can be substituted and / or interrupted by hydrogen, a heteroatom, or a heteroatom-containing group, or R** may be an acyl group of the formula R***-C(=O)-, where R*** may be synonymous with R**. 【0040】 Epoxidation reactions are advantageously carried out by contacting the internal olefin with a suitable oxidizing agent in a reaction zone typically ranging from 15°C to 250°C. 【0041】 Suitable oxidizing agents include peroxide compounds such as hydrogen peroxide (H2O2) that can be used in aqueous solution form, peracids of formula R****-CO3H (e.g., metachloroperoxybenzoic acid, peracetic acid, etc.), and organic peroxides such as hydrocarbyl (e.g., alkyl) hydroperoxides of formula R****'-O2H (e.g., cyclohexyl hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide), where R**** in peracids or R****' in hydrocarbyl (e.g., alkyl) hydroperoxides are hydrocarbon groups (e.g., alkyl groups) that can be substituted and / or interrupted by heteroatoms or heteroatom-containing groups. 【0042】 The reaction can be carried out in the presence of an optional solvent, but the use of such a solvent is not essential, and the reaction can also be carried out without the addition of a solvent. Examples of suitable solvents include: CHCl3, CH2Cl2, tert-butanol, or mixtures thereof. 【0043】 When H2O2 is used as an oxidizing agent, the presence of an organic carboxylic acid during the reaction can be beneficial because it reacts with H2O2 to produce a more reactive peracid compound in situ. Examples of suitable carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, and benzoic acid. 【0044】 A catalyst can also be used to accelerate the reaction. Suitable catalysts include Lewis acids or Brønsted acids, such as perchloric acid (HClO4), trifluoromethanesulfonic acid, heterogeneous titanium silicalite (TiO2-SiO2), heterogeneous acidic resins such as Amberlite® resin, homogeneous organometallic complexes of manganese, titanium, vanadium, rhenium, and tungsten, and polyoxymethylates. 【0045】 After performing appropriate work-up at the end of the reaction, the desired epoxide can be recovered, and those skilled in the art will know the typical techniques, so there is no need to elaborate further here. 【0046】 This epoxide can be used directly in the next step without further purification. 【0047】 Epoxide ring-opening reaction Subsequently, the epoxide ring-opening reaction can be achieved by reacting the epoxide with a carboxylic acid reagent to obtain the monohydroxyl monoester compound of formula (III). [ka] The above compounds can be synthesized according to the following scheme. [ka] Here, regardless of where it is located in the above compound, L is a leaving group, t is an integer equal to 1 or greater than or equal to 2. U u+ It is a cation, u is an integer that fixes the positive charge of the cation, and R and Y are as described above. 【0048】 The ring-opening reaction of epoxides is performed by epoxide and formula (IV): [LY-CO2H] (t-1)- [Uu+ ] (t-1) / u (IV) (In the formula, L, Y, t, U u+ (and u are as described above.) This is done by contacting the reagent with a carboxylic acid reagent. 【0049】 Surprisingly, the applicant has found that using such carboxylic acid reagents, epoxides can be directly converted to monohydroxyl monoesters. 【0050】 If t is equal to 1, no cation is present. Otherwise, the epoxide ring-opening reaction occurs by contacting the epoxide with the carboxylic acid of the following formula. LY-CO2H 【0051】 In carboxylic acid reagents, if the leaving group L already carries a negative charge (i.e., if (t-1) is 1 or greater, i.e., if t is 2 or greater), U is added to the reactant to ensure electrical neutrality. u+ There must be a cation represented as (where u is preferably 1, 2, or 3, more preferably 1). Some examples of this cation include H + , alkali metal cations (e.g., Na + or K + ), alkaline earth metal cations (e.g., Ca 2+ ), Al 3+ And ammonium may be selected. 【0052】 The properties of the detaching group L are not particularly limited, as long as the following reaction step (i.e., amine condensation, as will be detailed later) can occur. The detaching group L is advantageously a nuclear release group. A nuclear release group is particularly, - Halogen, - Formula R a -O-SO2-O-(wherein, R a C1-C can be optionally halogenated. 20 (representing a hydrocarbyl group) (hydrocarbyloxysulfonyl) oxy group, - Formula R a-SO2-O-(wherein, R a C1-C can be optionally halogenated. 20 (Hydrocarbyl sulfonyl)oxy group of a hydrocarbyl group (showing CF3-SO2-O- etc.), and - expression - The oxysulfonyl oxy group of O-SO2-O- (this is a detaching group L that already has one negative charge on the terminal oxygen atom) You can choose from these options. 【0053】 Hydrocarbyl group R a When present in the above formula, R can always be an aliphatic group or an aromatic group such as phenyl or p-tolyl. a These are typically linear or branched C1-C6 alkyl groups, which are often linear C1-C4 alkyl groups such as methyl, ethyl, or n-propyl. 【0054】 The withdrawing group L is preferably selected from the following: - Halogens such as fluorine, chlorine, bromine, or iodine - Formula R a -O-SO2-O-(wherein, R a C1~C 20 (Hydrocarbyloxysulfonyl)oxy group of a hydrocarbyl group (e.g., CH3-O-SO2-O-), and - expression - O-SO2-O- oxysulfonyl oxy group. 【0055】 An example of a compound where t is equal to 1 is CH3-O-SO3-CH2-COOH, which can be represented as 2-((methoxysulfonyl)oxy)acetic acid. Yet another example of a compound where t is equal to 1 and therefore no cation exists is chloroacetic acid, bromoacetic acid, and 2-chloropropionic acid. 【0056】 An example where t is equal to 2 is [LY-COOH] (t-1)- [U u+ ] (t-1) / u[O-SO2-O-CH2-COOH] - [Na + One example is sodium carboxymethyl sulfate. 【0057】 This reaction can be carried out in the presence of a solvent. However, the presence of such a solvent is not essential, and the reaction can also be carried out without adding a solvent. Examples of suitable solvents include: toluene, xylene, hydrocarbons, DMSO, Me-THF, THF, or mixtures thereof. 【0058】 The reaction is advantageously carried out under an inert atmosphere, such as a nitrogen or noble gas atmosphere. An argon atmosphere is one example of a suitable inert atmosphere. 【0059】 The reaction can be carried out in the absence of a catalyst. A catalyst may also be used during the reaction; preferred catalysts are Brønsted acid catalysts or Lewis acid catalysts. Preferred examples of catalysts include: H2SO4, p-toluenesulfonic acid, trifluoromethanesulfonic acid, HCl, or heterogeneous acidic resins such as Amberlite® resin, AlCl 3、 FeCl3, SnCl4 etc. 【0060】 The total number of moles of the carboxylic acid reagent of formula (IV) that come into contact with the epoxide throughout the entire reaction is, advantageously, more than half the total number of moles of the epoxide, preferably at least the same as the total number of moles of the epoxide, and more preferably at least twice the total number of moles of the epoxide. Furthermore, the total number of moles of the carboxylic acid reagent that come into contact with the epoxide throughout the entire reaction is, advantageously, up to 10 times the total number of moles of the epoxide. 【0061】 This reaction is advantageously carried out in a reactor where the epoxide is in a molten state. It has also been found that the reaction is advantageously carried out in a reactor where the carboxylic acid reagent of formula (IV) is in a molten state. Preferably, the reaction is carried out in a reactor where both the epoxide and the carboxylic acid reagent are in a molten state. 【0062】 Advantageously, the epoxide is gradually added to a reactor containing the entire amount of the carboxylic acid reagent of formula (IV). Preferably, the epoxide is continuously added to a reactor containing the entire amount of the carboxylic acid reagent, for example, under a feed batch process. The applicant has observed that it is possible to limit the self-condensation of the epoxide by gradually, preferably continuously, contacting the epoxide with the entire amount of carboxylic acid. 【0063】 Epoxide ring-opening reactions can generally be carried out at temperatures ranging from about 20°C to about 200°C in the presence of an optional solvent. To enable a sufficient reaction rate, the reaction is preferably carried out at a temperature of at least 25°C, more preferably at least 45°C, and even more preferably at least 55°C. On the other hand, the applicant has surprisingly found that carrying out the reaction at high temperatures generates large amounts of ketones, diesters, and dehydration byproducts. Therefore, the reaction is preferably carried out at a temperature of less than 120°C, more preferably less than 100°C, and even more preferably at a maximum of 85°C. 【0064】 The temperature can be kept constant throughout the reaction. However, to achieve the best compromise between reaction rate (conversion rate) and selectivity in monohydroxy monoesters, it is preferable that the reaction temperature rises slightly during the reaction, while always remaining within the range defined by the specified lower and upper limits above, for example, [45°C, 120°C], preferably [55°C, 85°C]. 【0065】 Therefore, the reaction related to opening the epoxide ring of an epoxide to obtain a monohydroxyl monoester is preferably carried out according to a process that includes the following steps: - In the first step S1, the epoxide is reacted with the carboxylic acid reagent of formula (IV) for a time t1 sufficient to convert more than 50 mol% of the epoxide f1 to a monohydroxyl monoester at a temperature T1 of 20°C to 70°C. - A second step S2 involves reacting the unconverted epoxide and unconverted carboxylic acid reagent from step S1 at a temperature T2 above 70°C but below 120°C for a time t2 sufficient to convert more than 80 mol% of the epoxide f2 to a monohydroxyl monoester. 【0066】 Preferably, in a reactor containing the entire amount of the carboxylic acid reagent of formula (IV), the entire amount of the epoxide is added gradually or more preferably continuously during part or all of step S1 over a time t'1 representing at least 25%, preferably at least 40%, of the total time t1 of step S1. 【0067】 T1 is preferably at least 35°C, more preferably at least 45°C, and even more preferably at least 55°C. Good results were obtained when T1 was about 65°C. 【0068】 f1 is preferably 70 mol%. 【0069】 t1 is generally in the range of 10 minutes to 10 hours. Preferably, t1 is at least 30 minutes, more preferably at least 1 hour. Furthermore, preferably, t1 is at most 4 hours, more preferably at most 2 hours. 【0070】 T2 is preferably at least 75°C. Furthermore, T2 is preferably at most 95°C, and more preferably at most 85°C. Good results were obtained when T2 was about 80°C. 【0071】 f2 is preferably 90 mol%, more preferably 95 mol%, and even more preferably 98 mol%. 【0072】 t2 is generally in the range of 10 minutes to 10 hours. t2 is preferably at least 30 minutes, more preferably at least 1 hour. t2 is preferably up to 4 hours, more preferably up to 2 hours. 【0073】 The entire reaction can be carried out at or below atmospheric pressure. Preferably, it is carried out at atmospheric pressure or under light vacuum, i.e., at a pressure of 90 kPa to atmospheric pressure (approximately 1 atm = 101.325 kPa). More preferably, it is carried out at atmospheric pressure. 【0074】 The above operating conditions maximize the amount of monohydroxy monoester, and formula (V) [ka] The primary objective is to minimize the amount of diester co-products; however, a certain amount of such diesters is generally co-produced. The molar ratio of diester to (monohydroxyl-monoester + diester) is generally less than 50%, often up to 30%, and sometimes up to 15%, 5%, or even 2%. 【0075】 Other operating conditions can be applied to further suppress the production of diester compounds and enable higher selectivity in monohydroxyl-monoester compounds. For example, the following can be mentioned: (c1) The total number of moles of the carboxylic acid reagent of formula (IV) that come into contact with the epoxide throughout the entire reaction is equal to a maximum of 1.10 times the total number of moles of the epoxide, and in some cases to 0.10 to 1.00 times the total number of moles of the epoxide or 0.50 to 0.90 times the total number of moles of the epoxide. • (c2) The total epoxide ring-opening reaction between the epoxide and the carboxylic acid reagent of formula (IV) shall be carried out at a temperature T of up to 20°C to 70°C, preferably up to 65°C, and possibly up to 60°C or up to 50°C. (c3) Since a diester of formula (V) is formed by a successive esterification reaction between the monohydroxy monoester compound of formula (III) and the carboxylic acid reagent, the reaction can be interrupted, for example, by cooling the reaction medium to a temperature at which the esterification reaction converting (III) to (V) no longer proceeds (e.g., at a temperature below 30°C), or by removing the carboxylic acid reagent of formula (IV) (e.g., by distillation under vacuum), or by neutralizing the carboxylic acid reagent by adding at least an equivalent amount of base (e.g., aqueous NaOH solution), and Apply (c4)(c1) and (c2), or (c1) and (c3), or (c2) and (c3), or (c1), (c2) and (c3). 【0076】 However, applying at least one of (c1), (c2), and (c3) generally has adverse effects on productivity, reaction rate, and / or yield in monohydroxy monoesters. 【0077】 Furthermore, as will be seen later, co-produced diesters can lead to the acquisition of diammonium compounds exhibiting excellent biodegradability and surfactant properties, such as the monoammonium compound of formula (I). Therefore, according to some embodiments of the present invention, it has been found advantageous to enable the production of a certain amount of diester together with a monohydroxyl monoester. 【0078】 To facilitate the removal of water and the acquisition of the diester, step S2 of the detailed process described above can be partially or completely carried out under vacuum, usually at a pressure P2 of less than 50 kPa, preferably up to 30 kPa, more preferably up to 10 kPa, and even more preferably up to 3 kPa, for example, about 1 kPa. For example, step S2 can be carried out in two stages: first, maintaining a temperature T2 at a pressure P21 of 90 kPa to atmospheric pressure (about 1 atm = 101.325 kPa), preferably atmospheric pressure; and then reducing and maintaining a pressure P22 of less than 50 kPa, preferably up to 30 kPa, more preferably up to 10 kPa, and even more preferably up to 3 kPa. The reduction in pressure P2 can be advantageously carried out in conjunction with an increase in temperature T2 during step S2. The second step S2 can be partially or completely carried out at a temperature T2 of at least 85°C but less than 120°C. For example, step S2 can be carried out in two parts: first, maintaining the temperature T2 at a temperature T21 that is 70°C or higher but less than 85°C; and then raising the temperature T2 to a temperature T22 that is at least 85°C but less than 120°C, and maintaining it at that temperature. The first and second parts of step S2 related to the rise in temperature T2 preferably coincide with the first and second parts of step S2 defined for the decrease in pressure P2, i.e., preferably carried out within the same period of time. 【0079】 At the end of the reaction, the desired monohydroxyl-monoester compound of formula (III) can be optionally combined with the diester compound of formula (V) and recovered after appropriate work-up. Those skilled in the art are familiar with typical techniques, so no further details are needed here. 【0080】 Amine condensation The monohydroxyl-monoester compound of formula (III) can be converted to the ionic monoammonium compound of formula (I) [or its electrically neutral homologue of formula (II)] by the following reaction scheme. [ka] Here, R, R', R'', R''', Y, L, U, t, and u are as described above in this specification. 【0081】 Optionally, the monohydroxy monoester compound of formula (III) is converted to the ionic monoammonium compound of formula (I) (or its electrically neutral homologue), and the diester compound of formula (V) is converted to formula (VI). [ka] The diammonium compound (or its electrically neutral homologue) can be converted by the following reaction scheme. [ka] 【0082】 The amine condensation reaction is carried out by optionally contacting the intermediate monohydroxy monoester compound of formula (III) with the diester of formula (V) and ammonia or an amine of formula NR'R''R''' (wherein R', R'' and R''' may be the same or different, hydrogen or a C1-C4 alkyl group, and preferred R', R'' and R'''' are exactly the same as defined above in relation to the ionic monoammonium compound of formula (I)). 【0083】 The reaction can be carried out at a temperature in the range of 15°C to 250°C in the presence of a suitable solvent. Examples of suitable solvents include THF, Me-THF, methanol, ethanol, isopropanol, DMSO, toluene, xylene, or mixtures thereof. Alternatively, the reaction can be carried out without the addition of a solvent. 【0084】 In this reaction, L in monohydroxy monoester or diester (t-1)- There is a nucleophilic attack of ammonia or amine that substitutes L (t-1)- It acts as a leaving group. t-This becomes the counter anion of the final ammonium compound. In monohydroxyl-monoester or diester reagents, if the leaving group is already negatively charged (this is when (t-1) is 1 or greater or t is 2 or greater), the general chemical formula [U u+ ] t / u [L t- The salt of ] is also formed. 【0085】 Other synthesis processes of the compound of formula (I) Acyloin condensation An alternative process for the synthesis of the compound of formula (I) proceeds via acyloin condensation according to the following scheme. [ka] Here, R****** is an alkyl group having 1 to 6 carbon atoms. 【0086】 Acyloin condensation is generally carried out by reacting an ester (typically a fatty acid methyl ester) with metallic sodium as a reducing agent. The reaction is carried out in a high-boiling point aromatic solvent such as toluene or xylene, in which the metal can be dispersed at a temperature above its melting point (around 98°C in the case of sodium). The reaction can be carried out at a temperature in the range of 100°C to 200°C. At the end of the reduction, the reaction medium can be carefully quenched with water, and the organic phase containing the desired acyloin product can be separated. The final product can be obtained after appropriate work-up, and those skilled in the art will know the typical techniques, so no further details are needed here. 【0087】 This type of reaction is described in the literature, for example, Hansley, J.Am.Chem.Soc 1935, 57, 2303-2305 or van Heyningen, J.Am.Chem.Soc. 1952, 74, 4861-4864 or Rongacli et al., Eur.J.Lipd Sci.Technol. 2008, 110, 846-852, which are referenced herein for further details. 【0088】 Hydrogenation of keto alcohols [ka] This reaction can be carried out using the conditions described above for a variation of the first process for the production of the compound of formula (I). 【0089】 The resulting diol can then be directly esterified with a carboxylic acid reagent of formula (IV) according to the classical Fischer esterification reaction. The standard conditions for carrying out the esterification reaction are well known to those skilled in the art and therefore do not need to be described in further detail here. During the reaction, there are two alcohol functional groups that can be esterified, so first there is the formation of a hydroxy monoester (III), which can then be converted to a bisester (V) in a subsequent reaction. The ratio between monoester (III) and diester (IV) can be controlled in this step by limiting the conversion from (III) to (V) according to methods (c1) and / or (c3) shown in paragraph

[0083] . 【0090】 Finally, the mixture of esters (III) and (IV) is converted to the corresponding ammonium compounds (I) and (VI), respectively, according to the conditions previously described for the quaternization reaction. 【0091】 The exemplary process described above is an example of a preferred process, and other preferred processes for synthesizing compounds according to the present invention may exist. Therefore, the process described above is not limited to the methods for producing compounds according to the present invention. 【0092】 Compounds of formula (I) (and their electroneutral homologs) can be used as surfactants. Surfactants are compounds that reduce the surface tension (or interfacial tension) between two liquids, between a liquid and a gas, or between a liquid and a solid. Surfactants can act as detergents, wetting agents, emulsifiers, foaming agents, and dispersants. 【0093】 Surfactants are typically amphiphilic organic compounds, meaning they possess both a hydrophobic group (tail) and a hydrophilic group (head). Therefore, surfactants contain both water-insoluble (or oil-soluble) and water-soluble components. Surfactants diffuse in water and adsorb to the interface between air and water, and to the interface between oil and water when water is mixed with oil. The water-insoluble hydrophobic groups extend from the bulk aqueous phase into the air or oil phase, while the water-soluble head groups remain in the aqueous phase. 【0094】 The adsorption of cationic surfactants to negatively charged surfaces is a crucial property for surfactants. This property is typically related to the minimum concentration of surfactant required to aggregate a suspension of negatively charged cellulose nanocrystals (CNCs, commonly used as reference materials) in an aqueous medium. Continuous changes in size can be monitored and tracked by dynamic light scattering (DLS). 【0095】 According to the protocol described in EKOikonomou et al., J.Phys.Chem.B, 2017, 121(10), 2299-307, the adsorption properties of ammonium compounds can be investigated by monitoring the ratio X = [surfactant] / [CNC] or mass fraction M = [surfactant] / ([surfactant]+[CNC]) at a fixed [surfactant]+[CNC]=0.01 wt% in aqueous solution, which is necessary to induce aggregation of cellulose nanocrystals. 【0096】 The biodegradability of the compounds of the present invention can be determined by procedures described in the prior art and known to those skilled in the art. Details regarding one such method, OECD Standard 301, are described in the Experimental Section below. 【0097】 Compounds of formula (I) (or their electrically neutral homologs) exhibit excellent surfactant properties and biodegradability. 【0098】 The above compounds can be used in various aqueous or hydroalcoholic formulations, in which case they can be used in the above formulations as a single ammonium compound exhibiting surfactant properties, that is, in the absence of other monoammonium compounds exhibiting surfactant properties and di- or greater ammonium compounds exhibiting surfactant properties in these formulations. 【0099】 The applicant has observed compounds of formula (I) structured in a lamellar form, generally such as multilayer vesicles, in aqueous or hydroalcoholic formulations. This lamellar structure is generally based on ammonium surfactants structured in a micelle form, but resulted in aqueous or hydroalcoholic formulations exhibiting substantially higher viscosity than the same formulations. This high viscosity is well-suited for some applications, while somewhat lower viscosity is desirable for other applications. 【0100】 On the other hand, many diammonium compounds are structured in the form of micelles, and as a result, aqueous or hydroalcoholic formulations exhibit low viscosity. While this low viscosity is well-suited to certain applications, for other applications, a higher viscosity is desired, which may be equivalent to the viscosity achieved with the compound of formula (I), or intermediate between the viscosity achieved with the compound of formula (I) and the viscosity achieved with the diammonium compound. 【0101】 In addition to exhibiting excellent surfactant properties and fairly good to excellent biodegradability, there is a need for materials that can form aqueous or hydro-alcoholic formulations with a wide range of viscosities to meet the diverse viscosity requirements of various end applications. 【0102】 This need is for mixture M Q And, - At least one ionic monoammonium compound of formula (I) as described above, and - Formula (VII) [ka] (In the formula, A is A-1 to A-6 [ka] A tetravalent linker selected from the group consisting of, m, m', m'', m''' may be the same or different in each occurrence, and are 0, 1, 2, or 3. k, k', k'', k'''', and k'''' may be the same or different, and are 0, 1, 2, or 3. Q1 to Q4 may be the same or different from each other, and are selected from the group consisting of R and X. R may be the same or different in each occurrence, as previously defined for compound (I), X may be the same or different in each occurrence, as in equation (VIII) [ka] Represented by, Two and only two of Q1-Q4 are represented by X, and two and only two of the base Q1-Q4 are represented by R. Y may be the same or different in each occurrence, as previously defined for compound (I), R', R'', and R'''' may be the same or different in each occurrence, as previously defined for compound (I), and n and n' may be the same or different in each occurrence, and are 0 or 1, where the sum of n + n' is 1 or 2. at least one ionic diammonium compound Mixture M containing Q It is satisfied by. 【0103】 This necessity is for mixture M' Q And, - At least one electroneutral compound of formula (II) as described above (i.e., an electroneutral homolog of the compound of formula (I) as described above), and - Formula (IX) [ka] (i.e., the electrically neutral homologs of the compounds of formula (VII) as described above) (wherein A and Q1 - Q4 may be the same as or different from each other and are as described above for the compounds of formula (VII), and W is an anion or an anionic group having w negative charges) at least one electrically neutral compound of mixture M' containing Q is also satisfied by 【0104】 Examples of suitable anions or anionic groups W are as defined above for the electrically neutral compounds of formula (II). 【0105】 The applicant has found that the diammonium compounds of formula (VII) exhibit excellent surfactant properties, similar to the monoammonium compounds of formula (I). 【0106】 The applicant has also found that the diammonium compounds of formula (VII) exhibit fairly good to excellent biodegradability, while emphasizing compounds of formula (VI) which exhibit excellent biodegradability similar to the compounds of formula (I). <ocks: 【0107】 <ocks: Finally, the applicant has found that the diammonium compounds of formula (VII), especially compounds of formula (VI), can be structured in the form of micelles to form aqueous or hydroalcoholic formulations having a lower viscosity than the compounds of formula (I). 【0108】 Mixture M Q By adjusting the respective amounts of the compounds of formula (I) and the compounds of formula (VII) (or their electrically neutral homologs in mixture M’ Q ), aqueous or hydroalcoholic formulations with a wide range of viscosities can be prepared to meet the various viscosity requirements demanded by different end - use applications. 【0109】 s Preferably, the compounds of formula (VII) are selected from the group consisting of compounds of formula (VI), (X), (XI), (XII) and (XIII) as represented below. [ka] [ka] Here, R, R', R'', R''', and Y may be the same or different in each occurrence, as described above for compound (I), and s and s' may be the same or different, and are 0, 1, 2, or 3. 【0110】 Preferably, the compound of formula (VII) is the compound of formula (VI). 【0111】 mixture M Q The ratio of the weight of compound (I) to the combined weight of compound (VII) in the compound (I) w I,VII M Q The ratio can vary greatly depending on the intended use. I,VII The percentage is generally in the range of 1% to 99%, and very often 10% to 90%. The above percentages may be at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, or at least 80%. Furthermore, the above percentages may be up to 80%, up to 70%, up to 60%, up to 50%, up to 40%, up to 30%, or up to 20%. Examples of preferred ranges are [20%,90%], [30%,90%], [40%,90%], [50%,90%], [60%,90%], [20%,80%], [30%,80%], [40%,80%], [50%,80%], [60%,80%], [20%,70%], [30%,70%], [40%,70%], [50%,70%], and [60%,70%]. These exemplified ranges are mixtures M in which the compound of formula (VII) is the compound of formula (VI). Q It can be particularly well suited to a variety of applications using it. 【0112】 Similarly, mixture M' QThe ratio w of the weight of compound (II) to the combined weight of compound (II) and compound (IX) in [compound (II) and compound (IX)] II,IX is M ’Q which can vary greatly depending on the intended use for which M is to be used. The ratio w II,IX is generally in the range of 1% to 99%, and very often in the range of 10% to 90%. The above ratio can be at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70% or at least 80%. Further, the above ratio can be at most 80%, at most 70%, at most 60%, at most 50%, at most 40%, at most 30% or at most 20%. Examples of suitable ranges are [20%, 90%], [30%, 90%], [40%, 90%], [50%, 90%], [60%, 90%], [20%, 80%], [30%, 80%], [40%, 80%], [50%, 80%], [60%, 80%], [20%, 70%], [30%, 70%], [40%, 70%], [50%, 70%] and [60%, 70%]. These exemplified ranges are particularly well-suited to various uses using mixture M ’Q in which the compound of formula (IX) is an electrically neutral equivalent of the compound of formula (VI). 【0113】 Some non-optimized mixtures M’ Q are described in Examples 11 and 12 of International Patent Application PCT / European Patent Application Publication No. 2020 / 066649. The mixture of Example 11 contains a quaternary monoammonium compound and a diquaternary ammonium compound in a weight ratio w II / IX of about 2 / 97 and the mixture of Example 12 contains the same compounds in a weight ratio w II / IX of about 5 / 92 . In both examples, the combined weight of the quaternary monoammonium compound and the diquaternary ammonium compound constitutes about 97% of the total weight of the mixture. The quaternary monoammonium compounds of Examples 11 and 12 are, as described above, the electrically neutral compound C II *. Generally, the mixture M’ Q is different from the mixtures of Examples 11 and 12, i.e., generally, M’Q is, equation C II Unlike a mixture comprising at least one electroneutral compound of formula (II) selected from * and at least one electroneutral compound of formula (IX), where the electroneutral compound of formula (II) and the electroneutral compound of formula (IX) are in weight ratio w II / IX Approximately 2 / 97 (typically) 2 / 96 ~ 2 / 98 (meaning) or about 5 / 92 (typically) 5 / 91 ~ 5 / 93 In the above, the combined weight of the electroneutral compound of formula (II) and the electroneutral compound of formula (IX) is given by mixture M' Q It accounts for approximately 97% (typically meaning 96% to 98%) of the total weight. 【0114】 mixture M Q and M' Q This mixture M' may contain, respectively, an ionic compound of formula (I) and an ionic compound of formula (VII) or an electroneutral compound of formula (II) and an electroneutral compound of formula (IX) in combined weights of at least 0.1%, at least 0.2%, at least 0.5%, at least 1%, at least 2%, at least 5%, at least 10%, at least 20%, at least 50%, or at least 90%. Q It can essentially consist of the electroneutral compound of formula (II) and the electroneutral compound of formula (IX). In addition to the ionic compound of formula (I) and the ionic compound of formula (VII), mixture M Q This may contain water or water and an alcohol such as ethanol, propanol, or butanol. Mixture M Q These can essentially consist of (i) an ionic compound of formula (I), (ii) an ionic compound of formula (VII), and (iii) water or a combination of water and an alcohol such as ethanol, propanol, or butanol. 【0115】 As with the following examples, throughout this description, the expanded formulas should be understood to include all potential enantiomers and diastereoisomers, where appropriate. Unless otherwise specified and without regard to a particular stereochemistry, each chiral molecule presented is in the form of its racemic mixture. 【0116】 If any disclosure of a patent, patent application, or publication incorporated herein by reference contradicts the description in this specification to such an extent that it could obscure the terminology, the description in this specification shall prevail. [Examples] 【0117】 Example 1 - C 16 ~C 18 (30:70) Synthesis of Quaternary Monoammonium Compounds of Formula (I) Starting from Fatty Acid Cutting Part 1.A - Internal C 31 ~C 35 Pyriaketonization as a countermeasure against ketone cuts The reaction was carried out under an inert argon atmosphere using a 200 mL quartz reactor equipped with a mechanical stirrer (A320 type stirrer made by 3D printing Inox SS316L), an insulated addition funnel, a distillation apparatus, a heating mat, and a temperature probe. 【0118】 The following were introduced into the reactor: - 12.5 g of MASCID® Acid 1865 (obtained from Musim Mas Group), which consists of 33.7 wt% palmitic acid and 65.3 wt% stearic acid (0.045 moles of fatty acid), and - 0.935g of MgO (0.023 moles). 【0119】 37.5 g (0.135 mol) of the same molten fatty acid mixture was added to an insulated funnel. 【0120】 Subsequently, the temperature of the reaction medium was raised to 250°C. When the temperature reached 150°C, stirring was started (1200 rpm). After reacting at 250°C for 2 hours, FTIR analysis showed that the starting fatty acid was completely converted to the intermediate magnesium carboxylate complex. 【0121】 Subsequently, the reaction temperature was further increased to 330°C, and the mixture was stirred at this temperature for 1 hour and 30 minutes to decompose the intermediate magnesium carboxylate complex into the target ketone. 【0122】 Next, 12.5 g of the molten fatty acid mixture was gradually added to the reactor using an addition funnel over 30 minutes, and the mixture was stirred for a further 1 hour at 330°C. FTIR analysis showed that the fatty acid and magnesium complex had been completely converted to the desired ketone. 【0123】 Subsequently, 12.5g of fatty acid was added over 30 minutes, followed by two additional cycles of stirring at 330°C for 1 hour. 【0124】 After the final cycle, the mixture was stirred for a further 1 hour and 00 minutes at 330°C to confirm that the intermediate magnesium complex had been completely converted to the desired ketone (confirmed by FTIR analysis). 【0125】 The reaction mixture was then cooled to room temperature, and the crude product was dissolved in hot CHCl3. This suspension was filtered over a silica plug (70 g), and the product was further eluted with an additional amount of CHCl3. 【0126】 After solvent evaporation, 41.83 g (0.086 mol) of the product was obtained as a white wax. This corresponds to a 96% isolation yield. 1 H NMR(CDCl3,400MHz)δ(ppm):2.45-2.25(t,J=7.6Hz,4H),1.62-1.46(m,4H),1.45-1.05(m,54H),0.86(t,J=6.8Hz,6H). 13C NMR(CDCl3,101MHz)δ(ppm):212.00,43.05,32.16,29.93,29.91,29.88,29.84,29.72,29.65,29.59,29.51,24.13,22.92,14.34 (terminal CH3). 【0127】 Part 1.B - Internal C 31 ~C 35 Hydrogenation reaction of ketone mixtures to fatty alcohol mixtures The following was added to a 100 mL autoclave equipped with a mechanical agitator (Rushton turbine): - 4.36 g of Ru / C (4.87% Ru) catalyst (5 wt% dry catalyst relative to the ketone; the catalyst contains 54.9% H2O), - 39.3g (87.2 mmol) of molten internal carbon 31 ~C 35 Ketone cut. 【0128】 The reaction was carried out under a hydrogen pressure of 20 bar. Following four nitrogen purges, three hydrogen purges at 20 bar were performed. The temperature of the reaction mixture was then set to 100°C to melt the ketone substrate. The mixture was left at 100°C for 10 minutes, after which stirring was slowly started at 200 rpm. Once adequate stirring was confirmed, the stirring speed was increased to 1200 rpm and the temperature was set to 150°C. 【0129】 After reacting at 150°C for 6 hours, heating was stopped and the mixture was cooled to 90°C while stirring. Then, stirring was stopped. After the mixture cooled to room temperature, the autoclave was carefully reduced in pressure. 【0130】 NMR analysis of the crude CDCl3 showed a ketone conversion rate of >99% and a molar purity of 99% for the fatty alcohol. The densely packed solid containing the product and catalyst was pulverized into a powder and introduced into a 1 L flask. 500 mL of chloroform was added, and the flask was heated to 60°C to completely dissolve the alcohol. This suspension was filtered over Celite at 60°C. The solid cake was washed several times with hot chloroform at 60°C. The filtrate was evaporated to obtain the desired internal C, corresponding to an isolation yield of approximately 90%. 31 ~C 35 A white powder with a weight purity of approximately 99% was obtained from the fatty alcohol mixture. 【0131】 Part 1.C - C 31 ~C 35 Dehydrogenation reaction of fatty alcohols to internal olefins All reactions were carried out under an inert argon atmosphere. 【0132】 The following was added to a 200 mL quartz reactor equipped with a heating mattress, a mechanical stirrer (A320 type stirring device manufactured by 3D printing with Inox SS316L), a condenser connected to a 50 mL two-necked distillate sampling flask, and a temperature probe: - C 31 ~C 35 41.3g of fatty alcohol (85 mmol, 1 equivalent), and - Al2O3-η4.13g (40mmol, 10wt%). 【0133】 The temperature of the reaction medium was raised to 150°C to dissolve the alcohol, and stirring was started (approximately 500 rpm). Next, the temperature was set to 300°C, and the mixture was stirred at 1000 rpm under argon. The progress of the reaction was monitored by NMR analysis using a borosilicate glass tube. 【0134】 After reacting at 300°C for 2 hours, NMR analysis using CDCl3 confirmed that the fatty alcohol was completely converted, and that 1.5 mol% of the ketone produced as a byproduct was present. 【0135】 Subsequently, stirring and heating were stopped, and the temperature was lowered to 80°C. The molten crude was transferred to a beaker. The reaction vessel and stirring device were washed with chloroform (Al2O3 is insoluble). 【0136】 The mixture was filtered, and the solvent was evaporated under vacuum to obtain 39 g of a clear yellow oily liquid. This oily liquid was solidified at room temperature to obtain a waxy white solid (purity 98 wt%) corresponding to a yield of 97% (NMR). 1 H NMR(CDCl3,400MHz)δ(ppm):5.38-5.29(m,2H),2.03-1.93(m,4H),1.35-1.19(m,55H(average number of H)),0.86(t,J=6.8Hz,6H). 13 C NMR(CDCl3,101MHz)δ(ppm):130.6,130.13,32.84,32.16,30.01,29.93,29.8,29.6,29.55,29.4,22.93,14.35 (terminal CH3). 【0137】 Part 1.D - Epoxylation of internal olefins 31~35 Oxirane is produced The reaction was carried out under an inert argon atmosphere. 【0138】 The following was added to a 300 mL double-jacketed reactor equipped with a mechanical agitator (propeller with four inclined plows) and baffles, a condenser and a temperature probe: - C 31~35 Internal olefin (purity 98 wt%, 80 mmol) 38.2 g, - 6.9 mL of acetic acid (7.2 g, 120 mmol), and - Amberlite (registered trademark) IR 120H resin 11.3g (30wt%). 【0139】 The mixture was heated to 75°C to melt the aliphatic alkene. Next, stirring was started, and while monitoring the temperature of the reaction medium to prevent a rise in the reactant temperature (exothermic reaction), 12.3 mL (13.7 g, 120 mmol) of 30% H2O2 was slowly added to the mixture using an addition funnel. This took approximately 20 minutes. During the addition, stirring was increased to improve phase transition due to the non-uniformity of the reaction medium. 【0140】 After the addition was complete, the temperature of the reaction medium was raised to 85°C and stirred at this temperature for 6 hours and 10 minutes. NMR analysis confirmed that the conversion rate was approximately 99% and the selectivity was 98%. 【0141】 Subsequently, heating was stopped, and when the reaction mixture temperature reached approximately 50°C, 150 mL of chloroform was added. The mixture was transferred to a separatory funnel, and the organic phase was washed three times with 150 mL of water. Residual resin catalyst in the aqueous phase was removed during phase separation. The aqueous phase was extracted twice with 50 mL of chloroform. The organic phase was dried over MgSO4, filtered, and evaporated to obtain 39.2 g of a white solid with a purity of 98 wt% (epoxide + by-product dialcohol). The yield, considering purity, was 99%. 1 H NMR(CDCl3,400MHz)δ(ppm):2.91-2.85(m,1.5H),2.65-2.6(m,0.5H),1.53-1.36(m,4H),1.35-1.19(m,55H(average number of H)),0.86(t,J=6.8Hz,6H). 13 C NMR(CDCl3,101MHz)δ(ppm):58.97,57.28,32.18,31.96,29.72,29.6,29.4,27.86,26.95,26.63,26.09,22.72,14.15 (terminal CH3). 【0142】 Part 1. E-chloroacetic acid monoester C is formed by epoxide ring-opening using chloroacetic acid. 31~35 generate [ka] The reaction was carried out under an inert argon atmosphere. 44.2 g (463 mmol, 5 equivalents) of chloroacetic acid was added to a 500 mL three-necked round-bottom flask equipped with a magnetic stirrer, heater, condenser, temperature probe, and insulated addition funnel. 【0143】 In an insulated additive funnel maintained at 80°C, molten C 31~35 45 g of aliphatic epoxide (purity: 99.97 wt%, 92.6 mmol, 1 equivalent) was added. 【0144】 The first step of hydroxyester formation by oxirane ring-opening was carried out at 65°C to suppress the formation of ketones and dehydration byproducts. The molten aliphatic epoxide was gradually added dropwise over 1 hour and 20 minutes while stirring at 65°C to a reaction medium containing molten chloroacetic acid. The gradual addition of the epoxide was done to limit the byproducts formed by condensation between the two epoxide molecules. At the end of the epoxide addition, the mixture was stirred at 65°C for 1 hour and 30 minutes. 【0145】 The second step of hydroxyester formation by oxirane ring opening was carried out by additional stirring at 80°C for 1 hour. 【0146】 Crude NMR analysis (CDCl3) confirmed the complete conversion of the starting epoxide and the composition of an 88:12 mol% monoester:bisester mixture. 【0147】 Part 1. Selective additional reactions of F-chloroacetic acid result in chloroacetic acid monoester C 31~35 Perform a partial conversion to the corresponding diester. [ka] The condenser was replaced with a curved distillation column, and the previously obtained crude mixture, having the reaction medium, i.e., an 88:12 mol% monoester:bisester mixed composition, was heated to 90°C, and then the excess chloroacetic acid was distilled, and the pressure was gradually reduced to 10 mbar to remove the water formed as a byproduct. 【0148】 After distillation at 90°C (10 mbar) for 1 hour and 30 minutes, 1H NMR analysis confirmed that the monoester:bisester ratio was 74:26 mol%, indicating the presence of residual chloroacetic acid. 【0149】 At this stage, distillation was stopped and the mixture was allowed to cool to room temperature. Next, the crude was solubilized in 150 ml of toluene and transferred to a separatory funnel. The organic phase was washed three times with 150 ml of 0.1 M NaOH aqueous solution, followed by washing with 150 ml of brine. The organic phase was separated, dried over MgSO4, filtered, and evaporated to obtain 53 g of residual beige oily liquid. 【0150】 After solvent evaporation 1 From 1H NMR (CDCl3), the approximate composition of the beige oily liquid was found to be 66 wt% (70 mol%) of hydroxy chloroacetate, 26 wt% (25 mol%) of bis-chloroacetate, 5 wt% (3 mol%) of monoester dimer, 2 wt% (1 mol%) of bis-ester dimer, 0.2 wt% (0.3 mol%) of ketone, and 0.2 wt% (1 mol%) of chloroacetate. 【0151】 The final yield of mono-chloroacetic acid + bis-ester, taking into account the purity of the mixture, was approximately 88%. 1 ¹H NMR (CDCl3, 400MHz) δ(ppm): 5.11-5.02 (m, 2H, diester), 4.96-4.83 (m, 1H, monoester), 4.07 (s, 1H, monoester), 4.06 (s, 1H, monoester), 4.04 (s, 2H, diester), 4.03 (s, 2H, diester), 3.74-3.67 (m, 1H, isomer 1, monoester), 3.64-3.54 (m, 1H, isomer 2, monoester), 1.73-1.61 (m, 2H, monoester), 1.61-1.48 (m, 4H, diester), 1.48-1.36 (m, 2H, monoester), 1.36-1.12 (m, 55H (average number)), 0.86 (t, J=6.8Hz, 6H). 13C NMR(CDCl3,101MHz)δ(ppm):167.39,167.27,167.15,167,79.84,78.97,76.21,75.83,72.95,72.41,41.06,4 1.01,40.90,40.80,33.63,32.18,31.98,30.57,29.75,29.72,29.65,29.59,29.5,29.42,28.85,28.61,25.9 25.6,24.48 25.33,24.97,22.74,14.15 (terminal CH3). 【0152】 Part 1.G - Classification to quaternary status using NMe3 [ka] The reaction was carried out under an inert argon atmosphere. The following was added to a 1 L double-jacketed reactor equipped with a mechanical stirrer, condenser, temperature probe, a trap containing 0.1 N HCl solution, followed by a second trap containing activated carbon pellets: - A mixture of approximately 72 wt% (74 mol%) of hydroxy chloroacetate and approximately 28 wt% (26 mol%) of bis-chloroacetate in 52 g (92.4 wt% purity, 80 mmol, 1 equivalent), obtained at the completion of Part 1-F, and - Trimethylamine / THF solution (13 wt%) 171 ml (320 mmol, 4 equivalents). 【0153】 The reaction mixture was heated to 40°C and stirred at 1000 rpm. 1 The reaction was tracked by 1H NMR analysis. After stirring at 40°C for 6 hours, NMR analysis (CD3OD) showed that the chloroacetic acid ester was completely converted and the corresponding glycine betaine ester was selectively formed, with an approximate composition of: 70 mol% glycine betaine hydroxy ester and 25 mol% glycine betaine bis ester. 【0154】 The contents of the reactor were removed, washed with THF, and the solvent was evaporated under vacuum to obtain 58.8 g of beige wax with the following weight composition: glycine betaine monohydroxyester 65.2 wt%, glycine betaine bisester 27.6 wt%, dimer monoester 4.7 wt%, dimer bisester 2.2 wt%, and ketone 0.18 wt%. 【0155】 The comprehensive yield of glycine betaine monohydroxyester + glycine betaine bisester, considering product purity, was 98%. The weight ratio of glycine betaine monohydroxyester to (glycine betaine monohydroxyester + glycine betaine bisester) was 70%. 1 1H NMR (MeOD-d4) , 400MHz)δ(ppm): 5.17-5.06(m,2H, dicoat), 5.02-4.87(m,1H, monocoat), 5.26-4.17 / 4.84-4.76 / 4.6-4.51 / 4.47-3.32(m,2H: monocoat, 4H: dicoat), 3.41(s,18H, isomer 1, dicoat), 3.38(s,18H, isomer 2, dicoat), 3.36(s,9 H, monocoat), 3.72-3.64 (m, 1H, isomer 1, monocoat), 3.56-3.47 (m, 1H, isomer 2, monocoat), 1.75-1.53 ​​(m, 2H, monocoat), 1.53-1.44 (m, 4H, dicoat), 1.44-1.35 (m, 2H, monocoat), 1.35-1.12 (m, 55H (average number)), 0.86 (t, J=6.8Hz, 6H). 13 C NMR(MeOD-d4,101MHz)δ(ppm):165.46,165.17,81.33,80.77,77.17,76.46,72.35,72.18,63.89,63.81,63.54,63.08,54.46,54. 37,54.22,33.70,32.51,32.06,31.18,30.27,30.03,29.94,29.8,29.04,28.8,26.6,26.3,26.1,26,25.8,23.24,14.45 (terminal CH3). 【0156】 Part 1. H-chloroacetic acid monoester C 31~35 Refinement of crude material rich in The crude mixture with an 88:12 mol% monoester:biester composition obtained at the end of Part 1-E is cooled to room temperature. Next, this crude mixture is solubilized in toluene and transferred to a separatory funnel. The organic phase is washed three times with aqueous NaOH solution (0.1 M), then washed with brine. The organic phase is separated, filtered and evaporated, and chloroacetic acid monoester C is obtained. 31~35 A purified product rich in [the substance] is obtained. The monoester:bisester mixture composition of this purified product is approximately 88:12 mol%, and the total content of monoester + bisester is approximately 95 wt.%. 【0157】 Part 1. I-chloroacetic acid monoester C 31~35 Quaternary densification using NMe3, a coarse material rich in [unclear] The quaternization reaction of the purified product obtained at the end of Part 1.H is achieved using the same quaternization reaction and purification protocol described in Part 1.G. 【0158】 Finally, we obtain a purified surfactant material QA2 having a mixed composition of approximately 90:10 wt% glycine betaine monohydroxyester:glycine betaine bisester, with a total content of glycine betaine bisester + glycine betaine monoester of approximately 95 wt%. 【0159】 Example 2 - Measurement of biodegradability The biodegradability of the test material is measured according to the 301 F OECD protocol. 【0160】 A measured amount of an inoculated mineral medium containing a test substance at a known concentration is stirred in a flask (Oxitop (trademark) respirometric flask) sealed for up to 28 days at a constant temperature (20 ± 2 °C) so as to be about 50 to 100 mg ThOD / l (theoretical oxygen demand) as the nominal sole source of organic carbon. In this test, an Oxitop (trademark) respirometric bottle is used to access the biodegradability of the test sample. A closed culture BOD flask at a temperature of 20 ± 2 °C is used for 28 days. 【0161】 The carbon dioxide released is absorbed by pellets of sodium hydroxide or potassium hydroxide present in the headspace of the bottle. The amount of oxygen taken up by the microbial population during the biodegradation process (biological oxidation of the test substance) (= oxygen consumption, expressed in mg / l) decreases the pressure in the headspace (ΔP measured by a pressure switch) and is mathematically converted to mg O2 consumption / liter. The inoculum corresponds to municipal activated sludge washed with a mineral medium (ZW medium) to reduce the amount of DOC (dissolved oxygen carbon). Control solutions containing sodium acetate as a reference substance and toxicity control solutions (test substance + reference substance) are used for verification purposes. The reference substance, sodium acetate, is tested in one bottle (corresponding to a nominal concentration of 129 mg / l, 100 mg ThOD / l) to confirm the viability of the inoculum. The toxicity control corresponds to a mixture of the reference substance and the test substance. It is confirmed whether the test substance is toxic to the inoculum (if toxic, the test may need to be repeated at a lower test substance concentration if possible, in light of the sensitivity of the test method). 【0162】 The compounds and mixtures of compounds of the present invention are usually poorly soluble in water (also, for those soluble in water, the metabolites after hydrolysis containing an alkyl chain often have very low solubility in water), so a specific protocol named "emulsion protocol" is used. This protocol can improve the bioavailability of substances with low water solubility in the inoculated aqueous phase. 【0163】 The emulsion protocol involves adding the test substance in the bottle through an emulsion-like stock solution. 【0164】 The emulsion is a 50 / 50 v / v mixture of the stock solution of the test substance dissolved in a non-biodegradable surfactant (Synperonic® PE 105 at 1 g / l) and mineral silicone oil AR20 (Sigma). 【0165】 The initial dissolution of the test substance in the non-biodegradable surfactant solution often requires stirring with a magnetic stirrer followed by ultrasonic treatment. 【0166】 After dissolution is complete, the aqueous solution and the mineral silicone oil are mixed in a 50 / 50 volume / volume ratio. This emulsion is maintained by stirring with a magnetic stirrer and sampled for addition to the corresponding bottles to achieve the required test substance concentration. 【0167】 During the test, two emulsion controls are run in parallel to remove the values from the emulsion bottles containing the test substance added through the emulsion stock solution. 【0168】 The biodegradability test is achieved with the glycine betaine monohydroxy ester / glycine betaine bisester mixtures QA1 and QA2 of 70 / 30 w / w and 90 / 10 w / w in Example 1. The biodegradability after 28 days is at least about 60% (OECD 301F). As reported later in Table 4 herein, compounds QA1 and QA2, like glycine betaine bisester ingested alone, show a final biodegradability of over 60% after 28 days. 【0169】 Therefore, the glycine betaine monohydroxy - ester and glycine betaine bisester contained in the mixture of Example 1 show excellent biodegradability. This beneficial effect is achieved without adversely affecting the surfactant properties of the compounds. 【0170】 Example 3 - Evaluation of adsorption properties to nanocellulose crystals The adsorption of cationic surfactants to negatively charged surfaces is an important property in various applications. This property relates to the minimum concentration of cationic surfactant required to generate aggregates of negatively charged cellulose nanocrystals (CNCs) in a suspension in an aqueous medium. The size of the aggregates can be monitored by dynamic light scattering (DLS). 【0171】 Following the protocol described in the literature (Reference: EKOikonomou, et al., J.Phys.Chem.B, 2017, 121(10), pp2299-2307), the adsorption properties of ammonium compounds can be investigated by monitoring the ratio X = [surfactant] / [CNC] or mass fraction M = [surfactant] / ([surfactant]+[CNC]) at a fixed [surfactant]+[CNC]=0.01 wt% in aqueous solution, which is necessary to induce aggregation of cellulose nanocrystals. 【0172】 The aggregation range of CNC corresponds to the range of ratio X (or M) that induces aggregation of CNC, i.e., the range in which the aggregation size measured by DLS is higher than that of a pure aqueous solution of CNC or an aqueous solution of 0.01 wt% surfactant. 【0173】 Table 1 summarizes the X and M ranges of CNC aggregation for the 70 / 30 w / w and 90 / 10 w / w glycine betaine monohydroxyester / glycine betaine bisester mixtures QA1 and QA2 of Example 1. Fentacare® TEP is used for comparison. Fentacare® TEP is a commercially available surfactant that represents the benchmark. 【0174】 The smaller the range of cohesion degree X or M, the better the adsorption to negatively charged surfaces. 【0175】 [Table 1] 【0176】 This data shows that the surfactant properties of the mixtures of the compounds of formulas (I) and (VI) according to the invention are superior compared to the commercial surfactant Fentacare® TEP. 【0177】 The surfactant properties of the compounds of formulas (I) and (VI) are also the same as those obtained individually. The surfactant properties of the compounds of formulas (I) and (VI) and their mixtures are even more similar to the properties of the mixtures of the compounds of formulas (X) and (XI) synthesized under Example 4 - Part B, where the values are reported in Table 5. 【0178】 Example 4 - Additional Mixtures of the Mono - Quaternary Ammonium Compound and Di - Quaternary Ammonium Compound of Formula (I) Part 4.A - C 31 Synthesis of the Di - Quaternary Ammonium Compound of Formula (VI) Starting from 16 - hentriacontanone a)C 31 Obtaining the internal olefin C 31 The internal olefin was obtained from palmitic acid according to the protocol described in Example 4 of U.S. Patent No. 10035746. 【0179】 b) Epoxidation of the internal olefin to an aliphatic epoxide 【Chemical formula】 The reaction was carried out under an inert argon atmosphere. 【0180】 C was placed in a 1L double - jacketed reactor equipped with a mechanical stirrer (a propeller with four pitched blades), a cooler, an addition funnel, and a temperature probe. 3161.9 g (0.142 mol) of alkene was added, followed by 16.3 mL (17.1 g, 0.285 mol) of acetic acid and 13.6 g (22 wt%) of Amberlite® IR 120H resin. This mixture was heated to 65°C to melt the fatty alkene. Stirring was started, and then 21.8 mL (24.2 g, 0.214 mol) of 30% aqueous H2O2 was slowly added to the mixture using an addition funnel at a rate that avoided a significant temperature increase. This took approximately 1 hour. After that, the temperature was raised to 75°C, and the reaction mixture was stirred overnight (after 15 minutes, NMR analysis showed that the conversion degree was already about 60%, indicating a selectivity of 99%). Next, 10.2 mL (11.3 g, 0.1 mol) of 30% H2O2 aqueous solution was slowly added. Four hours after the second addition of H2O2, NMR analysis confirmed that the conversion level was approximately 88% (selectivity 98%). Furthermore, 8.14 mL (8.55 g, 0.142 mol) of acetic acid and 11.6 mL of 30% H2O2 (12.91 g, 0.114 mol) were added to ultimately improve the conversion rate. 【0181】 This mixture was stirred at 75°C for two nights. 【0182】 Finally, NMR analysis confirmed a conversion level of 93% (95% selectivity). 【0183】 After the mixture was cooled to room temperature, 300 mL of chloroform was added. The mixture was transferred to a separatory funnel, the organic phase was washed three times with 300 mL of water, and then the aqueous phase was extracted twice with 100 mL of chloroform. The Amberlite® solid catalyst remained in the aqueous phase and was removed during the initial separation from the aqueous phase. The organic phase was collected, dried over MgSO4, filtered, and evaporated to obtain 65.3 g of a white solid with a purity of 91% w / w (epoxide + dialcohol). 【0184】 The yield, taking purity into consideration, was 92%. 1¹H NMR (CDCl3, 400MHz) δ(ppm): 2.91-2.85 (m, 2H, diastereomer 1), 2.65-2.6 (m, 2H, diastereomer 2), 1.53-1.00 (m, 54H), 0.86 (t, J=6.8Hz, 6H). 13 C NMR(CDCl3,101MHz)δ(ppm):58.97,57.28,32.18,31.96,29.72,29.6,29.4,27.86,26.95,26.63,26.09,22.72,14.15 (terminal CH3). 【0185】 c) Obtaining aliphatic diols by hydrolysis of fatty epoxides [ka] The reaction was carried out under an inert argon atmosphere. 【0186】 A 1L double-jacketed reactor equipped with a mechanical agitator (propeller with four inclined plows), a cooler, and a temperature probe was filled with C 31 82.9 g of epoxide (94.5 wt% purity, 0.174 mol) was added, followed by 480 mL of methyl-THF. 【0187】 The mixture was stirred at room temperature, and then 73 mL of a 3 M aqueous solution of H2SO4 was added. The mixture was then stirred at 80°C for 90 hours. NMR analysis indicated that the reaction was complete. The two-phase mixture was cooled to room temperature, and the organic phase was separated. Next, the solvent was removed under vacuum, and the residue was suspended in 200 mL of diethyl ether. This suspension was filtered, and the resulting solid was washed three times with 50 mL of diethyl ether. Finally, the white solid was washed twice with 50 mL of methanol and dried under vacuum to remove any trace of solvent. 【0188】 Ultimately, 75.53 g of the product was obtained as a white powder with a purity of 95.7% w / w, which corresponds to a yield of 89%. 1¹H NMR (CDCl3, 400MHz) δ(ppm): 3.61-3.55 (m, 2H, diastereomer 1), 3.43-3.25 (m, 2H, diastereomer 2), 1.88 (brd, J=2.4Hz, OH, diastereomer 2), 1.72 (brd, J=3.2Hz, OH, diastereomer 1), 1.53-1.10 (m, 54H), 0.86 (t, J=6.8Hz, 6H). 13 C NMR(CDCl3,101MHz)δ(ppm):74.71,74.57,33.66,31.96,31.23,29.71,29.39,26.04,25.68,22.72,14.15 (terminal CH3) 【0189】 d) Esterification of the fatty diol with trimethylglycine yields the compound of formula (VI). All reactions were carried out in carefully dried containers under an inert argon atmosphere. 【0190】 Commercially available fresh anhydrous CHCl3 (amylene-stabilized) and anhydrous toluene were used as is. 【0191】 Betaine hydrochloride (19.66 g, 128.4 mol) was washed 10 times with 20 mL of anhydrous THF, then dried under vacuum to remove any traces of solvent before use. 【0192】 The following was rapidly added to a 100 mL four-necked round-bottom flask equipped with a magnetic stirrer, heater, condenser, temperature probe, and curved distillation column, connected to two NaOH traps: 19.66 g (128.4 mmol) of dried betaine hydrochloride and SOCl2 (45.86g, 0.386mol) 28mL. 【0193】 The heterogeneous mixture was stirred, and then slowly heated to 70°C. When the temperature reached 68°C, gases (SO2 and HCl) were released, and it was confirmed that the mixture had turned a homogeneous yellow color. 【0194】 The mixture was then stirred at 70°C for 2 hours, and warm anhydrous toluene (25 mL, 80°C) was added to the container. After stirring the mixture, decantation was performed at 0°C (forming a yellowish-white precipitate), and the toluene in the upper phase was removed with a cannula. The toluene washing procedure was repeated 7 times to remove all excess SOCl2. NMR analysis showed that glycine betaine hydrochloride was completely converted, but NMe3 . The formation of HCl adducts was also confirmed (NMe3 in solid). . HCl content: 12.3mol%). 【0195】 Subsequently, 20 mL of dried CHCl3CH was added to solid betaine chloride. 【0196】 A solution of 26.19 g (56 mmol) of fatty diol in 390 mL of anhydrous CHCl was prepared at 55°C and added dropwise to a reaction vessel at room temperature with stirring (exothermic reaction and release of HCl were observed). The mixture was then stirred overnight at 55°C. Throughout the reaction, the mixture changed to a homogeneous orange color. NMR analysis showed a conversion degree of approximately 100%. 【0197】 The mixture was then cooled to room temperature, and the solvent was evaporated under vacuum. 【0198】 The residue was solubilized in methanol at 0°C, and the resulting precipitate was filtered. The filtrate was evaporated to obtain 39.7 g of crude material. 【0199】 The product was deposited on a sintered filter and washed with cyclohexane to remove any remaining organic impurities. The resulting washed solid was dried under vacuum to obtain 22 g of crude raw material. Final purification was performed with a mixed solvent of CH2Cl2 / cyclohexane 50:50. The solid was resolubilized in this solvent mixture at 50°C and cooled to room temperature. The formed precipitate was filtered, and the filtrate was evaporated to obtain 19 g of beige wax QA3 with the following composition: Glycine betaine diester 95 wt%, corresponding to the compound of formula (VI) Methyl betaine 1.5 wt%, Trimethylamine hydrochloride 2 wt%, Glycine betaine hydrochloride 1.5 wt%. 【0200】 The purification yield was 44%. The presence of the glycine betaine monoester compound of formula (I) was not confirmed in wax QA3. 1 H NMR(MeOD-d4,400MHz)δ(ppm):5.3-5.2(m,2H),4.68(d,J=16.8Hz,2H),4.50(d,J=16.8Hz,2H),4. 53(s,1H),4.48(s,1H),3.37(s,18H),1.75-1.55(m,4H),1.39-1.10(m,50H),0.9(t,J=6.8Hz,6H). 13 C NMR(MeOD-d4,101MHz)δ(ppm):164.58,75.76,62.43,53.10,31.68,30.05,29 .41,29.38,29.33,29.28,29.15,29.09,28.96,24.71,22.34,13.05 (terminal CH3). 【0201】 Part 4.B - C 31 Synthesis of a mixture of diquaternary ammonium compounds of formulas (X) and (XI) starting from -16-Hentriacontanone a) Obtain a diester intermediate by Kneefenagel condensation: [ka] All reactions were carried out in carefully dried containers under an inert argon atmosphere. 【0202】 Commercially available fresh anhydrous CHCl3, anhydrous THF, and anhydrous pyridine were used as is. 【0203】 36.5 mL of TiCl4 (63.00 g, 0.332 mol) was added to a 1 L double-jacket reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser, an addition funnel, and a temperature probe, followed by the addition of 6.3 mL of CHCl3 (145 ml). 【0204】 The mixture was stirred at -10°C, and anhydrous THF (358 mL) was slowly added through an addition funnel at a rate that did not cause the reaction medium temperature to exceed +5°C. A yellow precipitate appeared during the addition of THF. Next, 15.3 mL of dimethyl malonate (17.69 g, 0.134 mol) was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour to form a malonic acid complex. 【0205】 The mixture was then cooled to 0°C, and 71.80 mL of a solution of anhydrous pyridine (70.50 g, 0.891 mol) in 23 mL of THF was slowly added to the reactor. During the addition, the color of the mixture changed to red. The mixture was then stirred at room temperature for 20 minutes to induce deprotonation. 【0206】 Finally, 50.00g of C 31 0.111 moles of ketone were added to the reaction mixture and stirred overnight at room temperature, then for a day at 35°C. Next, 250 mL of water was carefully added to the reactor, followed by 250 mL of diethyl ether. The organic phase was separated and washed four times with 250 mL of water and once with 200 mL of saturated NaCl aqueous solution to remove the pyridinium salt. The aqueous phase was collected and re-extracted three times with 250 mL of diethyl ether. The final organic phase was dried over MgSO4, filtered, and evaporated under vacuum to obtain 70.08 g of crude orange oily liquid. At this stage, the crude product contained the starting ketone along with the main impurity corresponding to the condensation of two equivalents of ketone (aldolization + crotonization). 【0207】 (Since the by-products and starting ketones are insoluble in ethanol), the oily liquid was dissolved in ethanol, and then filtered through Celite, which allowed for easy purification of the product. 【0208】 The filtrate was evaporated, redissolved in CHCl3, filtered again, and evaporated to obtain 52.57 g of an oily liquid with a purity of 95% (RMN). 【0209】 The overall purification yield was 79%. 1H NMR(CDCl3,400MHz)δ(ppm):3.68(s,6H),2.32-2.19(m,4H),1.45-1.39(m,4H),1.30-1.10(m,48H),0.81(t,J=6.4Hz,6H). 13 C NMR(CDCl3,101MHz)δ(ppm):166.30,164.47,123.65,52.15,34.61,32.15,30.16,29.92,29.91,29.87,29.76,29.60,28.65,22.92,14.34 (terminal CH3). 【0210】 b) Transesterify with dimethylaminoethanol to obtain a diamine mixture intermediate: [ka] All reactions were carried out in carefully dried containers under an inert argon atmosphere. 【0211】 Commercially available fresh anhydrous toluene and dimethylaminoethanol were used as is. 【0212】 In a 2 L double-jacket reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser with a distillation apparatus, and a temperature probe, 42.7 g (75.6 mmol) of internal ketone / dimethyl malonate adduct was added, followed by 50 mL of toluene. This mixture was stirred at room temperature, and 30.4 mL of dimethylaminoethanol (26.9 g, 302.2 mmol, 4 equivalents) was added to the reaction system, followed by 50 mL of toluene. Next, 0.9 g (3.8 mmol, 5 mol%) of the catalyst, dibutyltin oxide, was added to the reaction system, followed by 200 mL of toluene. 【0213】 The mixture was then stirred at 120°C, and the progress of the reaction was tracked by NMR analysis. For proper analysis, aliquots of the reaction medium were sampled, diluted with diethyl ether, quenched with water, decanted, and the organic phase was evaporated under vacuum and analyzed with CDCl3 NMR solvent. After stirring at 120°C for 4 days, NMR analysis showed a conversion level of approximately 83% and a selectivity of 91%. In addition, by-product methanol was present in the distillation flask. The reaction mixture was then cooled to room temperature and quenched with 500 mL of water. The medium was decanted, and the aqueous phase was extracted three times with 500 mL of diethyl ether. The organic phase was collected and washed three times with 500 mL of water and once with 500 mL of saturated NaCl aqueous solution to remove excess dimethylaminoethanol. Next, the organic phase was dried over MgSO4, filtered, and evaporated to obtain 47.9 g of crude black oily liquid. At this stage, the crude oily liquid contained residual amounts of the starting material, malonic acid. 【0214】 Next, the product was purified by flash chromatography on silica gel. The initial eluent was a CHCl3 / AcOEt mixture, progressing through a gradient from 100% CHCl3 to 100% AcOEt. 【0215】 To remove all the product from the column, we washed it with an isopropanol + NEt3 mixture (10% vol NEt3), which allowed us to obtain an even purer product. 【0216】 After evaporating the solvent, the clarified fraction was collected to obtain 27.8 g of pure product (corresponding to a 54% isolation yield). 【0217】 NMR analysis revealed that the product was a mixture of diisomers in the following proportions: 54 mol% isomerized product (cis and trans diastereoisomers) and 46 mol% methylated product. 1¹H NMR (CDCl3, 400MHz) δ(ppm): 5.45-5.13 (m, 1H: 2 isomers cis + trans), 4.42 (s, 1H, 2 isomers cis or trans), 4.24-4.06 (m, 4H, isomer 1 + 2), 3.99 (s, 1H, 2 isomers cis or trans), 2.58-2.40 (m, 4H, isomer 1 + 2), 2.32-2.24 (m, 4H, isomer 1), 2.20 (s, 12H, isomer 1), 2.19 (s, 12H, isomer 2), 2.09-1.89 (m, 4H, 2 isomers cis + trans), 1.45-0.99 (m, 51H, isomer 1 + 2), 0.81 (t, J=6.8Hz, 6H). 13 C NMR(CDCl3,101MHz)δ(ppm):168.60,168.41,165.49,164.05,132.07,131.57,131.12,130.77,123.73,63.35,62.76,58.08,57.49,57 .45,53.45,45.73,34.45,30.07,30.03,29.72,29.68,29.58,29.53,29.45,29.38,28.46,28.43,28.27,28.09,22.70,14.13 (terminal CH3). 【0218】 c) Methylation yields a mixture of compounds (X) and (XI). All reactions were carried out in carefully dried containers under an inert argon atmosphere. 【0219】 Commercially available fresh anhydrous THF and dimethyl sulfate were used as is. 【0220】 100 mL of dry THF and 6.9 mL (9.14 g, 72 mmol, 2 equivalents) of dimethyl sulfate were added to a 1 L double-jacket reactor equipped with a mechanical stirrer, condenser, addition funnel, and temperature probe. A pre-preparation of a solution of 24.6 g (36 mmol, 1 equivalent) of esteramine in 154 mL of THF was made using the addition funnel and gradually added to the reactor while stirring at room temperature to suppress temperature rise. The mixture was then stirred at room temperature under an argon atmosphere, and the reaction progress was monitored by NMR analysis. After 2 hours, the mixture was heated to 40°C, and 0.2 mL of dimethyl sulfate (2 mmol, 0.06 equivalents) was added to enable stirring, achieving complete conversion. 【0221】 The reaction was completed after stirring at 40°C for 1 hour. All volatile substances (THF and the remaining DMS) were removed under vacuum, and 33.15 g of the product with a purity of 95 mol% was obtained as a beige wax QA4 in 94% yield. NMR analysis confirmed the presence of a 2-position isomer with a ratio of 55:45 between the isomerized derivative (cis and trans diastereoisomers) and the conjugated non-isomerized methylene derivative. 1 ¹H NMR (MeOD, 400MHz) δ (ppm): 5.60-5.25 (m, 1H: 2 isomers cis + trans), 4.80 (s, 1H, 2 isomers cis or trans), 4.75-4.50 (m, 4H, isomer 1 + 2), 4.38 (s, 1H, 2 isomers cis or trans), 3.84-3.72 (m, 4H, isomer 1 + 2) 3.69(s,6H,isomer 1+2),3.22(s,18H,isomer 2),3.21(s,18H,isomer 1),2.50-2.35(m,4H,isomer 1),2.22-2.02(m,4H,isomer 2 cis+trans),1.60-1.09(m,35H,isomer 1+2),0.90(t,J=6.8Hz,6H). 13C NMR(MeOD,101MHz)δ(ppm):169.22,169.01,168.96,165.52,134.16,133.22,132 .94,131.74,65.90,65.81,60.23,60.18,59.73,55.27,54.66,54.62,35.66,35. 54,33.24,33.23,31.76,31.01,30.94,30.91,30.87,30.85,30.77,30.74,30.71 ,30.66,30.65,30.63,30.60,29.73,29.62,29.45,29.27,23.89,14.61 (terminal CH3). 【0222】 Part 4.C - Additional mixtures of monoquaternary ammonium compounds and diquaternary ammonium compounds of formula (I) Eight additional surfactant materials are prepared by mixing surfactant materials QA1, QA2, QA3, and QA4 in various amounts. 【0223】 The wt% of monoquaternary ammonium compounds and diquaternary ammonium compounds of formula (I) contained in surfactant materials QA1, QA2, QA3, and QA4 are summarized below. The remaining wt% corresponds to impurities. 【0224】 [Table 2] 【0225】 The following mixtures QA5~QA 12 This is prepared by mixing QA1 to QA4 in appropriate proportions using conventional mixing techniques. 【0226】 [Table 3] 【0227】 Selectively, surfactant materials QA1~QA 12 It is made available in the form of an aqueous or hydroalcoholic solution. 【0228】 Example 5 - Additional Biodegradation Test The biodegradability of surfactant materials QA3 and QA4 was measured in accordance with OECD standard 301. 【0229】 The results of the biodegradability test are reported in Table 4. 【0230】 [Table 4] 【0231】 As a result, it was found that the glycine betaine bisester compound (surfactant material QA3) exhibited excellent biodegradability, and the mixture of quaternary ammonium compounds of surfactant material QA4 exhibited a degree of biodegradability. All of these were achieved without adversely affecting the surfactant properties of the compounds. 【0232】 Example 6 - Additional evaluation of adsorption properties to nanocellulose crystals The adsorption characteristics of surfactant materials QA3 and QA4 were measured according to the protocol described in Example 3. 【0233】 Table 5 summarizes the ranges of cohesion X and M for CNC. The smaller the range of cohesion X or M, the better the adsorption characteristics to negatively charged surfaces. 【0234】 [Table 5] 【0235】 For comparison, Fentacare® TEP was used. Fentacare® TEP is a representative commercially available surfactant for benchmarking. 【0236】 This data is from mixture QA5~QA 12This demonstrates that the surfactant properties of surfactant materials QA3 and QA4, which are useful for the preparation of (according to the present invention), are superior to those of the commercially available surfactant Fentacare (registered trademark) TEP. 【0237】 Overall, the compounds of formula (I) exhibit a good combination of good biodegradability and surfactant properties, a combination often not achieved with commercially available surfactants. Furthermore, since the compounds of formula (I) can be readily obtained starting from internal ketones readily available from fatty acids or fatty acid derivatives, they also offer economic advantages compared to prior art ammonium surfactants. 【0238】 The same attractive combination of surfactant and biodegradable properties can also be achieved by a mixture containing the compound of formula (I) and the compound of formula (VII). A further advantage of this mixture is that by varying the respective proportions of the compounds of formula (I) and (VII), the viscosity of aqueous or hydroalcoholic formulations prepared from this mixture can be adjusted over a wide range of values, making such mixtures usable in a wide range of applications requiring different levels of viscosity.

Claims

[Claim 1] Formula (II) (In the formula, R is C ６ ~C １７ Alkyl and C ６ ~C １７ Selected from alkenyl groups, Y is a methylene group, and R', R'' and R'''' are methyl, and W is an anion or anionic group having w negative charges, where w is 1 or 2. A compound of [unclear]. [Claim 2] R is C １０ ~C １７ Alkyl alkyl group or C １０ ~C １７ The compound according to claim 1, which is an alkenyl group. [Claim 3] The compound according to claim 1, wherein W is a halide anion and w is 1. [Claim 4] A monohydroxyl-monoester compound useful for preparing the compound of formula (II) described in claim 1, wherein formula (III) (In the formula, R may be the same or different in each occurrence, as defined in claim 1 or 2 for the compound of formula (II), Y may be the same or different in each occurrence, as defined in claim 1 for the compound of formula (II), L is - Halogen, - formula R ａ -O-SO ２ -O- (wherein R ａ represents an optionally halogenated C １ to C ２０ hydrocarbyl group) of (hydrocarbyloxysulfonyl) oxy group, - Formula R ａ -SO ２ -O- (wherein, R ａ C is optionally halogenated. １ ~C ２０ (Hydrocarbyl sulfonyl) oxy group (showing a hydrocarbyl group), and - expression － O-SO ２ -O- oxysulfonyloxy group (this is a leaving group L that already has one negative charge on the terminal oxygen atom) A leaving group selected from and t is an integer equal to 1 or greater than or equal to 2, U ｕ＋ It is a cation, (u is a positive integer that fixes the positive charge of the cation.) A monohydroxyl-monoester compound, which is a compound of [the specified compound]. [Claim 5] L is halogen, formula R ａ -O-SO ２ -O- (wherein, R ａ C １ ~C ２０ (Hydrocarbyloxysulfonyl) oxy group and formula － O-SO ２ The compound according to claim 4, wherein the nuclear release group is selected from the -O- oxysulfonyloxy group. [Claim 6] mixture M' Ｑ And, - At least one compound of formula (II) as described in any one of claims 1 to 3, and - Formula (IX) (In the formula, A is A-1 to A-6 A tetravalent linker selected from the group consisting of, m, m', m'', and m''' may be the same or different in each occurrence, and are 0, 1, 2, or 3. k, k', k'', k'''', and k'''' are the same or different, 0, 1, 2, or 3. Q １ ~Q ４ These may be identical or different from each other, and are selected from the group consisting of R and X. R may be the same or different in each occurrence, as defined in claim 1 or 2 for the compound of formula (II), X may be the same or different in each occurrence, as in equation (VIII) Represented by, Q １ ~Q ４ Two of these are represented by X, and the base Q. １ ~Q ４ The remaining two are represented by R, Y is as defined in claim 1 for the compound of formula (II), R', R'', and R''' may be the same or different in each occurrence, as defined in claim 1 for the compound of formula (II), W is an anion or anionic group having w negative charges, where w is 1 or 2, and n and n' may be the same or different in each occurrence, and are 0 or 1, where the sum of n + n' is 1 or 2. at least one electrically neutral compound Mixture M' containing Ｑ . [Claim 7] The aforementioned electroneutral compound is of formula (VI) (In the formula, R may be the same or different in each occurrence, as defined in claim 1 or 2 for the compound of formula (II), Y may be the same or different in each occurrence, as defined in claim 1 for the compound of formula (II), and R', R'', and R''' may be the same or different in each occurrence, as defined in claim 1 for the compound of formula (II), where W is a negatively charged anion or anionic group of w, and w is 1 or 2. The mixture according to claim 6, wherein the mixture is as described above. [Claim 8] The ratio of the weight of compound (II) to the combined weight of compound (IX) w ＩＩ，ＩＸ The mixture according to claim 6 or 7, wherein the amount is in the range of 10% to 90%. [Claim 9] A compound of formula (II) according to any one of claims 1 to 3, or a mixture M' according to any one of claims 6 to 8. Ｑ Its use as a surfactant.

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