Novel ammonium compounds for use as surfactants

Abstract

The present invention relates to novel monoammonium compounds of formula (I) having surfactant properties and improved biodegradability. The present invention also relates to novel mixtures comprising such monoammonium compounds and diammonium compounds.

Description

[0001] The present invention relates to novel ammonium compounds, in particular novel quaternary ammonium compounds derived from internal ketones, which themselves can be obtained from fatty acids or derivatives thereof, and the use of these novel ammonium compounds as surfactants, alone or in mixture with other surfactants.

[0002] This application claims priority to PCT Patent Application Nr PCT / EP 2020 / 066649 filed on June 16, 2020 and to US Application Nr 63 / 128985 filed on December 22, 2020, the entire contents of each of these applications are incorporated herein by reference for all purposes.

[0003] Ammonium compounds having surfactant properties and which can be used in corresponding applications have been described in the literature and are commercially available in a plurality of different types from various suppliers.

[0004] WO 97 / 08284 discloses compositions comprising Guerbet alcohol betaine esters represented by the following formula

[0005]

[0006] wherein R 1 to R 3 are independently selected from C1to C4alkyl groups or C2-C4alkenyl groups, a is from 1 to 4, and R4and R5are independently selected from C 12 to C 22 alkyl or alkenyl groups, the sum of the chain lengths of R4and R5is preferably at least 30. Since the compounds are derived from Guerbet alcohols, the number of carbon atoms in the groups R 4 and R 5 always differs by 2.

[0007] EP 721 936 relates to liquid quaternary ammonium compounds of the following formula

[0008]

[0009] wherein R 1-2 is a linear or branched C 36 -C 44 alkyl or alkenyl group, R2to R4are C1-C5alkyl or hydroxyalkyl groups, Y is a linear or branched C2-C4alkylene group, m is a number from 0 to 20 and n is an integer from 1 to 6. As in WO 97 / 08284, the preferred compounds of EP 721 936 are derived from Guerbet alcohols and are represented by the following formula

[0010]

[0011] DE 3402146 relates to quaternary ammonium compounds. As in WO 97 / 08284 and EP 721 936, the compounds comprise two long chain substituents which are esters of a gellert acid.

[0012] While fatty quaternary ammonium compounds are widely used as surfactants, there is still a need for this type of compounds having a good combination of surfactant properties on the one hand and biodegradability on the other hand. Biodegradability has become increasingly important in recent years as consumers desire products which are more environmentally friendly. The improvement of biodegradability should not negatively affect the surfactant properties.

[0013] It is therefore an object of the present invention to provide new ammonium compounds having good surfactant properties and good biodegradability.

[0014] This object is achieved by the compounds of formula (I). Preferred embodiments of the present invention are also detailed hereinafter.

[0015] The novel ionic monoammonium compounds according to the present invention have the formula (I)

[0016]

[0017] wherein R, which can be the same or different at each occurrence, is a C5-C 27 aliphatic group, preferably a C6to C 24 aliphatic group,

[0018] Y is a divalent C1-C6aliphatic group, and

[0019] R', R" and R'" which can be the same or different, are hydrogen or a C1to C4alkyl group.

[0020] The aliphatic group R can be free of any double bond and any triple bond. Alternatively, the aliphatic group R can comprise at least one -C=C- double bond and / or at least one -C≡C- triple bond.

[0021] The aliphatic group R is advantageously selected from the group consisting of alkyl groups, alkenyl groups, alkdienyl groups, alkatrienyl groups and alkynyl groups.

[0022] The aliphatic group R can be linear or branched.

[0023] Preferably, the aliphatic group R is independently selected from the group consisting of alkyl and alkenyl groups.

[0024] More preferably, the aliphatic group R is independently selected from the group consisting of alkyl and alkenyl groups, typically from the group consisting of C6-C 24 alkyl and C6-C 24 alkenyl groups, very often from the group consisting of C6-C 21 alkyl and C6-C21 alkyl and C6-C 19 alkyl and C6-C 19 alkyl and C6-C 17 alkyl and C6-C 17 alkyl and C6-C 24 alkyl and C6-C 21 alkyl and C6-C 19 alkyl and C6-C 17 alkyl and C6-C O It has been found that aliphatic groups, in particular alkyl groups, having 10 to 20, preferably 10 to 17 carbon atoms are more advantageous.

[0025] As preferred examples of substituents R, one can mention non-cyclic aliphatic groups, more preferably straight-chain aliphatic groups, still more preferably straight-chain alkyl groups. Excellent results are obtained when R is a straight-chain alkyl group having from 14 to 17 carbon atoms.

[0026] The number of carbon atoms of R can be even or odd, and each group R can have the same number of carbon atoms, or the number of carbon atoms of different groups R can be different.

[0027] In some embodiments, both R have an even number of carbon atoms, or both R have an odd number of carbon atoms.

[0028] In some other embodiments, it is generally preferred for economic reasons that one and only one R has an odd number of carbon atoms and one and only one R has an even number of carbon atoms. In particular embodiments that are advantageous from an economic point of view, one and only one R has an odd number of carbon atoms n O and the other R has an even number of carbon atoms n E where n E is equal to n O - 1.

[0029] Let us denote the number of carbon atoms of the two R groups by the pair (n 1 , n 2 ), where n 1 is the number of carbon atoms of the first R group and n 2 is the number of carbon atoms of the other R group. Exemplary and preferred pairs (n 1 , n 2 ) are (14, 14), (15, 15), (16, 16), (17, 17), (14, 15), (14, 16), (14, 17), (15, 16), (15, 17), (16, 17), (14, 14, 14, 14), (14, 14, 14, 15), (14, 14, 14, 16), (14, 14, 14, 17), (14, 14, 15, 15), (14, 14, 15, 16), (14, 14, 15, 17), (14, 14, 16, 16), (14, 14, 16, 17), (14, 14, 17, 17), (14, 15, 15, 15), (14, 15, 15, 16), (14, 15, 15, 17), (14, 15, 16, 16), (14, 15, 16, 17), (14, 15, 17, 17), (14, 16, 16, 16), (14, 16, 16, 17), (14, 16, 17, 17), (14, 17, 17, 17), (15, 15, 15, 15), (15, 15, 15, 16), (15, 15, 15, 17), (15, 15, 16, 16), (15, 15, 16, 17), (15, 15, 17, 17), (15, 16, 16, 16), (15, 16, 16, 17), (15, 16, 17, 17), (15, 17, 17, 17), (16, 16, 16, 16), (16, 16, 16, 17), (16, 16, 17, 17), (16, 17, 17, 17), (17, 17, 17, 17).) 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 (n 1 ,n 2 ) are selected from the following pairs: (14, 15), (16, 17), (14, 17), and (15, 16).

[0030] R’ is preferably a Ci to C4 alkyl group, preferably methyl or ethyl, more preferably methyl. Likewise, R” is preferably a Ci to C4 alkyl group, preferably methyl or ethyl, more preferably methyl. Also likewise, R”’ is preferably a Ci to C4 alkyl group, preferably methyl or ethyl, more preferably methyl. Preferably at least one, more preferably at least two, more preferably all three of R’, R”, and R”’ are Ci to C4 alkyl groups, preferably methyl or ethyl, most preferably methyl.

[0031] Y is preferably an acyclic divalent Ci-C6 aliphatic group, more preferably a straight chain divalent Ci-C6 aliphatic group, still more preferably a straight chain alkanediyl (often referred to as “alkylene”) Ci-C6 group. Further, Y preferably has from 1 to 4 carbon atoms. Exemplary Y’s are ethanediyl and methanediyl (often referred to as “methylene”). Excellent results are obtained when Y is a methylene group.

[0032] In some embodiments, the ionic compound of formula (I) is selected from the ionic compounds C I * wherein Y is methylene, R’, R”, and R”’ are methyl, and the two R groups are such that:

[0033] - one R is n-tetradecyl and the other R is n-pentadecyl, or

[0034] - one R is n-hexadecyl and the other R is n-heptadecyl, or

[0035] - one R is n-pentadecyl and the other R is n-hexadecyl,

[0036] - one R is n-tetradecyl and the other R is n-heptadecyl.

[0037] In some other embodiments, the ionic compound of formula (I) is selected from the compounds other than ionic compound C I *.

[0038] The present invention also relates to electrically neutral compounds of formula (II)

[0039]

[0040] wherein R, R', R", R'" and Y are as defined and described above, and W is an anion or an anionic group with w negative charges. Suitable anions or anionic groups W are, for example, halide ions such as chloride, fluoride, bromide or iodide, methylsulfate or methylsulfate anion (CH3-OSO3 - ), methanesulfonate anion (CH3-SO3 - ), sulfate anion, hydrogen sulfate anion (HSO4 - ) or organic carboxylate anions such as acetate, propionate, benzoate, tartrate, citrate, lactate, maleate or succinate.

[0041] In some embodiments, the electrically neutral compound of formula (II) is selected from the electrically neutral compounds C II * wherein [W] 1 / w is a chloride anion (CI - , w equals 1), Y is a methylene group, R', R" and R'" are methyl groups, and the two R groups are either:

[0042] - one R is n-tetradecyl and the other R is n-pentadecyl, or

[0043] - one R is n-hexadecyl and the other R is n-heptadecyl, or

[0044] - one R is n-pentadecyl and the other R is n-hexadecyl,

[0045] - one R is n-tetradecyl and the other R is n-heptadecyl.

[0046] In some other embodiments, the electrically neutral compound of formula (II) is selected from the electrically neutral compounds other than compound C II *.

[0047] The compounds according to the present application can be obtained by a variety of methods. Preferred methods for manufacturing the compounds of the present application include the reaction of a lactone of formula R-C(=0)-R, which can preferably be obtained by decarboxylative ketonization of a fatty acid, a fatty acid derivative or a mixture thereof. Suitable methods for manufacturing the lactones following this route are disclosed in US 2018 / 0093936, further details are found in this patent. Two methods for synthesizing the compounds of the present application using the lactones obtainable as indicated above as starting materials are now described.

[0048] The first method starts from the Piria ketonization followed by hydrogenation, dehydration, epoxidation (to obtain the epoxide) and epoxide ring opening reaction (to obtain the mono-hydroxy-mono-ester). The epoxide ring opening reaction step is followed by an amine condensation step (as final step) to convert the mono-ester into a compound according to formula (I). This is a multi-step method according to Piria technology. It has the advantage of being salt-free and relies on chemical transformations that can be easily performed.

[0049] First method for the synthesis of compounds of formula (I)

[0050] Piria ketonization

[0051] The basic reactions in the first step are:

[0052]

[0053] This reaction has been fully described in US patent 10035746, WO 2018 / 087179 and WO 2018 / 033607, further details are referred to this patent.

[0054] Hydrogenation

[0055] The lactone is then subjected to hydrogenation, which can be performed under standard conditions known to the skilled person for hydrogenation reactions:

[0056]

[0057] The hydrogenation reaction is performed by contacting the lactone with hydrogen gas in an autoclave reactor at a temperature ranging from 15°C to 300°C and at a hydrogen pressure ranging from 1 bar to 100 bar. The reaction can be performed in the presence of an optional solvent, but the use of such a solvent is not mandatory and the reaction can also be performed without any added solvent. As examples of suitable solvents, one can mention: methanol, ethanol, isopropanol, butanol, THF, methyl-THF, hydrocarbons, water or mixtures thereof. A suitable catalyst based on a transition metal should be employed for this reaction. As examples of suitable catalysts, one can mention heterogeneous transition metal-based catalysts such as for example supported dispersed transition metal-based catalysts or homogeneous organometallic complexes of transition metals. Examples of suitable transition metals are: Ni, Cu, Co, Fe, Pd, Rh, Ru, Pt, Ir. As examples of suitable catalysts, one can mention Pd / C, Ru / C, Pd / AI2O3, Pt / C, Pt / AI2O3, Raney nickel, Raney cobalt, etc. At the end of the reaction, the desired alcohol can be recovered after appropriate work-up. The skilled person is aware of the representative techniques, so further details are not required here. Details of this method step can be found for example in US patent 10035746, referred to herein.

[0058] The skilled person will select the appropriate reaction conditions based on his expertise and taking into account the specific target compound to be synthesized. Therefore, no further details are required here.

[0059] Dehydration

[0060] In a next step, the alcohol thus obtained is subjected to dehydration to obtain the internal olefin. This reaction can also be performed under standard conditions known to the skilled person for the corresponding dehydration reaction (e.g. US patent 10035746, example 4), so that no further details are required here:

[0061]

[0062] The dehydration reaction is performed by heating the secondary alcohol in the presence of a suitable catalyst in the reaction zone at a temperature ranging between 100°C and 400°C. The reaction can be performed in the presence of an optional solvent, but the use of such a solvent is not mandatory and the reaction can also be performed without any added solvent. As examples of solvents, one can mention: hydrocarbons, toluene, xylene or mixtures thereof. The reaction must employ a catalyst. Suitable examples of catalysts are acidic (Lewis or Bronsted) catalysts, heterogeneous solid acid catalysts or homogeneous catalysts. As examples of heterogeneous catalysts, one can mention aluminium oxide (AI2O3), silicon dioxide (SiO2), aluminosilicates (AI2O3-SiO2) such as zeolites, phosphoric acid supported on silica or alumina, acidic resins such as Amberlyst® Homogeneous catalysts can also be employed and one can mention the following suitable acids: H2SO4, HC1, triflic acid, p-toluene sulfonic acid, AICI3, FeCI3, etc. The water produced during the reaction can be distilled from the reaction medium during the course of the reaction. At the end of the reaction, the desired olefin can be recovered after appropriate work-up. The skilled person is aware of the representative techniques and they are described for example in US patent 10035746 so that no further details are required here.

[0063] As shown above, in the ionic monoammonium compound of formula (I), it is generally preferred for economic reasons, the embodiment wherein one and only one R has an odd number of carbon atoms and one and only one R has an even number of carbon atoms. It is now apparent that this is possible when both R originate from carboxylic acids having an even number of carbon atoms, and is generally advantageous from an economic point of view, since naturally sourced fatty carboxylic acids - which typically have such even number of carbon atoms - are widely available; this is also possible when both R originate from carboxylic acids having an odd number of carbon atoms. In particular, when the internal olefin is obtained from one and only one carboxylic acid having an even number of carbon atoms, it can occur that one and only one R has an odd number of carbon atoms n Owhile the other R has an even number of carbon atoms n E of the embodiments, wherein n E equals n O - 1. For illustrative purposes, the internal olefins with (n 1 , n 2 ) representing the number of carbon atoms of the two R groups are selected from (14, 15), (16, 17), (14, 17) and (15, 16) can be obtained starting from the following carboxylic acids or carboxylic acid mixtures: palmitic acid alone, stearic acid alone, oleic acid alone, palmitic acid in admixture with stearic acid or with oleic acid or with stearic acid and oleic acid, and stearic acid in admixture with oleic acid.

[0064] On the other hand, when one and only one R originates from a carboxylic acid having an even number of carbon atoms and one and only one R originates from a carboxylic acid having an odd number of carbon atoms, internal olefins and finally ionic monoammonium compounds of formula (I) are obtained, wherein both R have an even number of carbon atoms or both R have an odd number of carbon atoms.

[0065] epoxidation

[0066] The internal olefins can thereafter be oxidized to the corresponding epoxides, wherein the double bond is replaced by an epoxy group, according to the following scheme, wherein the reactants are only examples of the corresponding groups of the compounds for the corresponding functional groups:

[0067]

[0068] wherein R** can be a hydrogen or a hydrocarbon group which can be substituted and / or interrupted by a heteroatom or a heteroatom-containing group, or R** can be an acyl group of formula R***-C(=0)-, wherein R*** can have the same meaning as R**.

[0069] The epoxidation reaction is advantageously carried out by contacting the internal olefin with a suitable oxidizing agent in the reaction zone at a temperature typically ranging from 15 °C to 250 °C.

[0070] As suitable oxidizing agents, peroxide compounds can be mentioned, such as hydrogen peroxide (H2O2) which can be employed in the form of an aqueous solution, organic peroxides such as peracids of formula R****-CO3H (for example meta-chloroperoxybenzoic acid, peracetic acid, etc.), hydrocarbyl (e.g. alkyl) hydroperoxides of formula R****'-O2H (for example cyclohexyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide), wherein R**** in the peracids or R****' in the hydrocarbyl (e.g. alkyl) hydroperoxides is a hydrocarbon group (e.g. alkyl group) which can be substituted and / or interrupted by a heteroatom or a heteroatom-containing group.

[0071] The reaction can be carried out in the presence of an optional solvent, but the use of such a solvent is not mandatory, and the reaction can also be carried out without any added solvent. As examples of suitable solvents, mention can be made of: CHCI3, CH2CI2, t-butanol or mixtures thereof.

[0072] When H2O2 is used as oxidizing agent, the presence of an organic carboxylic acid during the reaction can be beneficial, as it will generate in situ, by reaction with H2O2, a more reactive peracid compound. As examples of suitable carboxylic acids, mention can be made of: formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, etc.

[0073] A catalyst can also be used to promote the reaction. Suitable catalysts are Lewis or Bronsted acids, and mention can be made for example of: perchloric acid (HCIO4), triflic acid, heterogeneous titanium silicalite (TiO2-SiO2), heterogeneous acidic resins such as Amberlyst® resins, homogeneous organometallic complexes of manganese, titanium, vanadium, rhenium, tungsten, polyoxometalates, etc. Suitable catalysts are Lewis or Bronsted acids, and mention can be made for example of: perchloric acid (HCIO4), triflic acid, heterogeneous titanium silicalite (TiO2-SiO2), heterogeneous acidic resins such as Amberlyst® resins, homogeneous organometallic complexes of manganese, titanium, vanadium, rhenium, tungsten, polyoxometalates, etc.

[0074] At the end of the reaction, the desired epoxide can be recovered after appropriate work-up, and the skilled person is aware of representative techniques, so that no further details need to be given here.

[0075] The epoxide can be used directly in the next step without further purification.

[0076] Epoxide ring opening reaction

[0077] The epoxide ring opening reaction can then be achieved by reacting the epoxide with a carboxylic acid reagent to obtain a mono-hydroxy-mono-ester compound of formula (III)

[0078]

[0079] According to the following scheme:

[0080]

[0081] wherein, anywhere in the above compounds,

[0082] L is a leaving group,

[0083] t is an integer equal to 1 or equal to or greater than 2,

[0084] U u+ is a cation,

[0085] u is an integer determining the positive charge of the cation, and

[0086] R and Y are as described previously.

[0087] The epoxide ring opening reaction is carried out by contacting the epoxide with a carboxylic acid reagent of formula (IV):

[0088] [L-Y-CO2H] (t-1)- [U u+ ] (t-1) / u (IV)

[0089] wherein L, Y, t, U u+ and u are as described previously.

[0090] The present applicant has surprisingly found that, when using such a carboxylic acid reagent, the epoxide can be directly converted into a mono-hydroxy-mono-ester.

[0091] When t is equal to 1, there is no cation. In other words, the epoxide ring opening reaction is carried out by contacting the epoxide with a carboxylic acid having the following formula:

[0092] L-Y-CO2H.

[0093] In case the leaving group L already carries a negative charge in the carboxylic acid reagent (which is the case when (t-1) is equal to or larger than 1, i.e. when t is equal to or larger than 2), a cation, marked U u+ (wherein u is preferably 1, 2 or 3, more preferably 1) must be present in the reactant to ensure electrical neutrality. This cation can for example be selected from H + , an alkali metal cation (e.g. Na + or K + ), an alkaline earth metal cation (e.g. Ca 2+ ), Al 3+ and ammonium, to mention just a few examples.

[0094] The nature of the leaving group L is not particularly limited, provided that the next reaction step (i.e. the amine condensation, as will be detailed later) can take place. The leaving group L is advantageously a nucleofugal group. It can notably be selected from

[0095] - halogen,

[0096] - a (hydroxyalkyl)sulfonyl)oxy group of formula R a -O-SO2-O- wherein R a represents a C1-C 20 hydrocarbyl group which can optionally be halogenated,

[0097] - a (hydroxyalkyl)sulfonyl)oxy group of formula R a -SO2-O- wherein R a represents a C1-C 20 hydrocarbyl group which can optionally be halogenated (as in CF3-SO2-O-), and

[0098] - oxyalkylsulfonyloxy groups of formula -O-SO2-O- (which are leaving groups L already carrying one negative charge on the terminal oxygen atom).

[0099] hydrocarbyl group R a , wherever present in the formulae herein before, can be notably an aliphatic group or an aromatic group such as phenyl or p-tolyl. The aliphatic group R a is typically a C1-C6 alkyl group, which can be linear or branched; it is typically a linear C1-C4 alkyl group such as methyl, ethyl or n-propyl.

[0100] The leaving group L is preferably selected from:

[0101] - halogen such as fluorine, chlorine, bromine or iodine,

[0102] - (hydrocarbyloxy)sulfonyl)oxy groups of formula R a -O-SO2-O- wherein R a represents a C1-C 20 hydrocarbyl group such as CH3-O-SO2-O-, and

[0103] - oxyalkylsulfonyloxy groups of formula - O-SO2-O-.

[0104] An example of a compound wherein t is equal to 1 is CH3-O-SO3-CH2-COOH, which can be named 2-((methoxysulfonyl)oxy)acetic acid. As further examples of compounds wherein t is equal to 1 and thus wherein no cation is present, one can mention: chloroacetic acid, bromoacetic acid and 2-chloropropionic acid.

[0105] An example of t equal to 2 is carboxymethylsodium sulfate, wherein [L-Y-COOH] (t-1)- [O u+ ] (t-1) / u is [O-SO2-O-CH2-COOH] - [Na + ].

[0106] The reaction can be carried out in the presence of a solvent. However, the presence of such a solvent is not mandatory and the reaction can also be carried out without any added solvent. As examples of suitable solvents, one can mention: toluene, xylene, hydrocarbons, DMSO, Me-THF, THF or mixtures thereof.

[0107] The reaction is advantageously carried out under an inert atmosphere such as a nitrogen or noble gas atmosphere. An argon atmosphere is an example of a suitable inert atmosphere.

[0108] The reaction can be carried out without any catalyst. A catalyst can also be employed during the reaction, and suitable catalysts are Bronsted or Lewis acid catalysts. As preferred examples of catalysts, mention can be made of: H2SO4, p-toluenesulfonic acid, triflic acid, HC1 or a heterogeneous acidic resin such as Amberlyst®. resins, A1C13, FeC13, SnC14, etc.

[0109] The total number of moles of carboxylic acid reagent of formula (IV) which is in contact with the epoxide throughout the course of the reaction is advantageously not less than half the total number of moles of epoxide; preferably at least as high as the total number of moles of epoxide, and more preferably at least twice as high as the total number of moles of epoxide. Furthermore, the total number of moles of carboxylic acid reagent which is in contact with the epoxide throughout the course of the reaction is advantageously at most ten times as high as the total number of moles of epoxide.

[0110] The reaction is advantageously carried out in a reactor in which the epoxide is in a molten state. It has also been found advantageous that the reaction is carried out in a reactor in which the carboxylic acid reagent of formula (IV) is in a molten state. Preferably, the reaction is carried out in a reactor in which both the epoxide and the carboxylic acid reagent are in a molten state.

[0111] Advantageously, the epoxide is added stepwise to the reactor containing the total amount of carboxylic acid reagent of formula (IV); preferably, it is added continuously to the reactor containing the total amount of carboxylic acid reagent, for example in a fed-batch process. The Applicant has observed that bringing the epoxide into contact with the total amount of carboxylic acid stepwise, preferably continuously, makes it possible to limit the self-condensation of the epoxide.

[0112] The epoxide ring-opening reaction can be carried out at a temperature generally ranging from about 20°C to about 200°C, in the presence of an optional solvent. In order to allow a sufficient reaction rate, the reaction is preferably carried out at a temperature of at least 25°C, more preferably at least 45°C, still more preferably at least 55°C. On the other hand, the Applicant has surprisingly found that carrying out the reaction at high temperature leads to the formation of significant amounts of ketone, diester and dehydration by-products. The reaction is therefore carried out at a temperature of preferably less than 120°C, more preferably less than 100°C, and still more preferably at most 85°C.

[0113] The temperature can remain constant throughout the reaction. However, in order to achieve the best compromise between the reaction rate (conversion) and the selectivity towards mono-hydroxy-mono-ester, the reaction temperature is preferably slightly increased over the course of the reaction, while always remaining within the range defined by the lower and upper limits specified above, for example [45°C, 120°C], preferably [55°C, 85°C].

[0114] The reaction of interest according to the present application, i.e. the opening of the epoxide ring of an epoxide to obtain a monohydroxy-monoester, is desirably carried out according to a process comprising:

[0115] - a first step S1 in which the epoxide is reacted with the carboxylic acid reagent of formula (IV) at a temperature T1 ranging from 20°C to 70°C for a time t1 sufficient to convert more than fi = 50 mol.% of the epoxide into monohydroxy-monoester;

[0116] - a second step S2 in which the epoxide not converted in step S1 and the carboxylic acid reagent not converted are reacted at a temperature T2 higher than 70°C but lower than 120°C for a time t2 sufficient to convert more than f2 = 80 mol.% of the epoxide into monohydroxy-monoester.

[0117] Preferably, during part or all of step S1, during a period of time t'1 representing at least 25%, preferably at least 40%, of the total time t1 of step S1, the entire amount of epoxide is added stepwise, or even better continuously, in the reactor containing the entire amount of carboxylic acid reagent of formula (IV).

[0118] T1 is preferably at least 35°C, more preferably at least 45°C, still more preferably at least 55°C. Good results are obtained when T1 is about 65°C.

[0119] fi is preferably 70 mol.%.

[0120] The range of t1 is generally from 10 min to 10 h. t1 is preferably at least 30 min, more preferably at least 1 h. Furthermore, t1 is preferably at most 4 h, more preferably at most 2 h.

[0121] T2 is preferably at least 75°C. Furthermore, T2 is preferably at most 95°C, more preferably at most 85°C. Good results are obtained when T2 is about 80°C.

[0122] f2 is preferably 90 mol.%, more preferably 95 mol.%, still more preferably 98 mol.%.

[0123] The range of t2 is generally from 10 min to 10 h. t2 is preferably at least 30 min, more preferably at least 1 h. t2 is preferably at most 4 h, more preferably at most 2 h.

[0124] The overall reaction can be carried out at atmospheric pressure or under lower than atmospheric pressure. It is preferably carried out at atmospheric pressure or under light vacuum, that is to say at a pressure ranging from 90 kPa to atmospheric pressure (about 1 atm = 101.325 kPa). More preferably, it is carried out at atmospheric pressure.

[0125] Although the above operating conditions are largely aimed at maximizing the amount of mono-hydroxy-mono-ester and minimizing the amount of di-ester by-product of formula (V)

[0126]

[0127] However, an amount of such di-ester is generally co-produced. The molar ratio of di-ester to (mono-hydroxy-mono-ester + di-ester) is generally lower than 50%, often at most 30%, possibly at most 15% or even at most 5% or 2%.

[0128] Further operating conditions can be applied which further limit the production of di-ester compounds and allow a higher selectivity of mono-hydroxy-mono-ester compounds. For example, one can mention:

[0129] • (cl) the total number of moles of carboxylic acid reagent of formula (IV) in contact with the epoxide throughout the course of the reaction is equal to at most 1.10 times the total number of moles of epoxide, possibly from 0.10 to 1.00 times the total number of moles of epoxide, or from 0.50 to 0.90 times the total number of moles of epoxide,

[0130] • (c2) the entire epoxide ring-opening reaction of the epoxide with the carboxylic acid reagent of formula (IV) is carried out at a temperature T of at most 20°C to 70°C, preferably at most 65°C, possibly at most 60°C or at most 50°C,

[0131] • (c3) since the di-ester of formula (V) is formed by successive esterification reactions of the mono-hydroxy-mono-ester compound of formula (III) with the carboxylic acid reagent, it is possible to interrupt the progress of the reaction, for example by cooling the reaction medium at a temperature at which the esterification reaction of (III) into (V) no longer proceeds, for example at a temperature lower than 30°C, or by removing the carboxylic acid reagent of formula (IV) (for example by distillation under vacuum) or by adding at least an equivalent amount of base (for example NaOH aqueous solution) to neutralize the carboxylic acid reagent, and

[0132] • (c4) application of (cl) and (c2), or (cl) and (c3), or (c2) and (c3), or (cl), (c2) and (c3).

[0133] However, the application of at least one of (cl), (c2) and (c3) generally has a detrimental effect on the productivity of mono-hydroxy-mono-ester, the reaction rate and / or the yield.

[0134] In addition, as will be seen later, as for the mono-ammonium compounds of formula (I), the co-produced di-ester can lead to the obtaining of di-ammonium compounds which exhibit outstanding biodegradability and surfactant properties, and therefore, according to some embodiments of the application, it has been found advantageous to allow the co-production of an amount of di-ester with mono-hydroxy-mono-ester.

[0135] To facilitate the removal of water and to obtain diesters (but in an amount lower than the amount of mono-hydroxy-mono-esters), step S2 of the above detailed process can be performed partly or completely under vacuum, typically at a pressure P2 lower than 50 kPa, preferably at most 30 kPa, more preferably at most 10 kPa, still more preferably at most 3 kPa, for example about 1 kPa. For example, step S2 can be performed in two parts, wherein the temperature T2 is first maintained at a pressure P21 from 90 kPa to atmospheric pressure (1 atm ~ = 101.325 kPa), preferably at atmospheric pressure, and then the pressure P2 is lowered and maintained at a pressure P22 lower than 50 kPa, preferably at most 30 kPa, more preferably at most 10 kPa, still more preferably at most 3 kPa. The lowering of the pressure P2 can advantageously be performed with an increase of the temperature T2 during step S2: the second step S2 can be performed partly or completely at a temperature T2 of at least 85°C but lower than 120°C; for example, step S2 can be performed in two parts, wherein the temperature T2 is first maintained at a temperature T21 from 70°C but lower than 85°C, and then the temperature T2 can be increased and maintained at a temperature T22 of at least 85°C but lower than 120°C. With respect to the increase of the temperature T2, the first and second parts of step S2 are preferably respectively matched with the first and second parts of step S2 as defined for the lowering of the pressure P2, i.e. preferably occur over the same time period.

[0136] At the end of the reaction, the desired mono-hydroxy-mono-ester compound of formula (III), optionally in combination with a di-ester compound of formula (V), can be recovered after appropriate work-up and the skilled person is aware of representative techniques, so that no further details need to be given here.

[0137] Amine condensation

[0138] The mono-hydroxy-mono-ester compound of formula (III) can be converted into the ionic mono-ammonium compound of formula (I) [or its electrically neutral homologue of formula (II)] by the following reaction scheme:

[0139]

[0140] wherein R, R’, R”, R”’, Y, L, U, t and u are as described previously herein.

[0141] Optionally, together with the conversion of the mono-hydroxy-mono-ester compound of formula (III) into the ionic mono-ammonium compound of formula (I) (or its electrically neutral homologue), the di-ester compound of formula (V) can be converted into the di-ammonium compound of formula (VI)

[0142]

[0143] (or its electrically neutral homologue) by the following reaction scheme:

[0144]

[0145] The amine condensation reaction is carried out by contacting the intermediate mono-hydroxy-mono-ester compound of formula (III), optionally together with the di-ester of formula (V), with ammonia or an amine of formula NR’R”R’”, wherein R’, R” and R’”, which can be identical or different, are hydrogen or Ci to C4alkyl, and preferably R’, R” and R’” are all as defined above for the ionic mono-ammonium compound of formula (I).

[0146] The reaction can be carried out at a temperature ranging from 15°C to 250°C in the presence of a suitable solvent. As examples of suitable solvents, mention can be made of THF, Me-THF, methanol, ethanol, isopropanol, DMSO, toluene, xylene or mixtures thereof. Alternatively, the reaction can also be carried out in the absence of any added solvent.

[0147] During this reaction, there is a nucleophilic attack by ammonia or the amine on L (t-1)- of the substituted mono-hydroxy-mono-ester or di-ester; L (t -1)- plays the role of leaving group. L t- then becomes the counter anion of the final ammonium compound. In the case where the leaving group already carries a negative charge in the mono-hydroxy-mono-ester or di-ester reagent (which is the case when (t-1) is equal to or greater than 1 or when t is equal to or greater than 2), there is also the formation of a salt as a by-product of the reaction (with the general chemical formula [U u+ ] t / u [L t- ]).

[0148] Other methods for the synthesis of compounds of formula (I)

[0149] Pinacol condensation

[0150] An alternative method for the synthesis of compounds of formula (I) is carried out by pinacol condensation according to the following scheme:

[0151]

[0152] wherein R**** is an alkyl group having from 1 to 6 carbon atoms.

[0153] The pinacol condensation is generally carried out by reacting an ester, typically a fatty acid methyl ester, with sodium metal as reducing agent. The reaction is carried out in a high boiling aromatic solvent such as toluene or xylene, where the metal can be dispersed at a temperature above its melting point, in the case of sodium about 98°C. The reaction can be carried out at a temperature ranging from 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 pinacol product can be isolated. The final product can be obtained after appropriate work-up and the skilled person is aware of representative techniques, so that no further details need to be given here.

[0154] This type of reaction has been described in the literature, for example in Hansley, J. Am. Chem. Soc 1935, 57, 2303-2305 or van Heyningen, J. Am. Chem. Soc. 1952, 74, 4861-4864 or in Rongacli et al., Eur. J. Lipd Sci. Technol. 2008, 110, 846-852, to which further details are therefore made reference.

[0155] Keto-alcohol hydrogenation

[0156]

[0157] The reaction can be carried out using the conditions described previously for the first process variant for the manufacture of compounds of formula (I).

[0158] The obtained diol can then be directly esterified with a carboxylic acid reagent of formula (IV) according to the classical Fischer esterification reaction. Standard conditions for carrying out the esterification reaction are well known in the art, so that no further details need to be given here. During the course of the reaction, due to the presence of two alcohol functions that can be esterified, a hydroxyl-monoester (III) is first formed, which can then be converted into a diester (V) in a consecutive reaction. The ratio between monoester (III) and diester (IV) can be controlled during this step by limiting the conversion of (III) into (V) according to the methods (cl) and / or (c3) given in paragraph

[0083] .

[0159] Finally, the mixture of esters (III) and (IV) is converted into the corresponding ammonium compounds (I) and (VI), respectively, according to the conditions of the quaternization reaction previously described.

[0160] The exemplary processes described before are examples of suitable processes, i.e. other suitable processes for the synthesis of compounds according to the present application can exist. Therefore, the processes described previously are not limiting in terms of processes for the manufacture of compounds according to the present application.

[0161] The compounds of formula (I) (and their electroneutral homologues) can be used as surfactants. Surfactants are compounds that lower 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.

[0162] Surfactants are typically organic compounds that are amphiphilic, meaning they contain both hydrophobic groups ("their tails") and hydrophilic groups ("their heads"). Thus, surfactants contain both water-insoluble (or oil-soluble) components and water-soluble components. Surfactants will spread in water and adsorb at the interface between air and water or at the interface between oil and water (in cases where water and oil are mixed). The water-insoluble hydrophobic groups can extend out of the bulk aqueous phase into the air or oil phase, while the water-soluble head groups remain in the aqueous phase.

[0163] The adsorption of cationic surfactants on negatively charged surfaces is an important property for such surfactants. This property is typically related to the minimum concentration of surfactant required to produce aggregation of a suspension of negatively charged cellulose nanocrystals (CNC, which are often used as a reference material) in an aqueous medium. The continuous change in size can be monitored and subsequently dynamic light scattering (DLS) is performed.

[0164] The adsorption properties of ammonium compounds can be investigated by monitoring the ratio X = [surfactant] / [CNC] or the mass fraction M = [surfactant] / ([surfactant + [CNC]) required to induce cellulose nanocrystal aggregation in aqueous solution at a fixed [surfactant] + [CNC] = 0.01 wt% following the protocol described in E. K. Oikonomou et al., J. Phys. Chem. B, 2017, 121 (10), 2299-307.

[0165] The biodegradability of the compounds of the present invention can be determined according to procedures described in the prior art and known to the skilled person. Details on one such method, OECD Guideline 301, are given in the experimental section below.

[0166] The compounds of formula (I) (or their electroneutral homologues) show outstanding surfactant properties and biodegradability.

[0167] It can be used as the only ammonium compound showing surfactant properties in various aqueous or water-alcohol formulations, i.e. in the absence of other monoammonium compounds showing surfactant properties and di- or higher ammonium compounds showing surfactant properties in these formulations.

[0168] The Applicant has observed that, in aqueous or water-alcoholic formulations, the compounds of formula (I) are generally structured in lamellar, such as multilamellar, vesicles. This lamellar structure generally causes the aqueous or water-alcoholic formulations to exhibit a viscosity significantly higher than the same formulations based on ammonium surfactants structured in micelles. This higher viscosity is very suitable for some applications, while for some other applications a slightly lower viscosity is required.

[0169] On the other hand, many diammonium compounds are structured in micelles, causing the aqueous or water-alcoholic formulations to exhibit a lower viscosity. This lower viscosity is very suitable for certain applications, while for other applications a higher viscosity is required, which can be similar to that obtained with the compounds of formula (I), or intermediate between that obtained with the compounds of formula (I) on the one hand and that obtained with the diammonium compounds on the other hand.

[0170] There is a need for materials further exhibiting outstanding surfactant properties and quite good to excellent biodegradability, able to form aqueous or water-alcoholic formulations within a wide range of viscosities, in order to meet the various viscosity requirements required by various end-use applications.

[0171] This is met with a mixture M Q comprising:

[0172] at least one ionic monoammonium compound of formula (I) as described above, and

[0173] at least one ionic diammonium compound of formula (VII)

[0174]

[0175] wherein

[0176] A is a tetravalent linking group selected from the group consisting of A-1 to A-6

[0177]

[0178] m, m', m" and m'" which can be the same or different at each occurrence, are 0, 1, 2 or 3,

[0179] k, k', k", k'" and k"", which can be the same or different, are 0, 1, 2 or 3, Q1to Q4, which can be the same as or different from each other, are selected from the group consisting of R and X,

[0180] R, which can be the same or different at each occurrence, is as previously defined for compound (I),

[0181] X, which can be the same or different at each occurrence, is represented by formula (VIII)

[0182]

[0183] wherein

[0184] two and only two of Q1to Q4are represented by X and two and only two of the groups Q1to Q4are represented by R,

[0185] Y, which can be the same or different at each occurrence, is as defined previously for compound (I),

[0186] R', R" and R' ', which can be the same or different at each occurrence, are as defined previously for compound (I), and

[0187] n and n', which can be the same or different at each occurrence, are 0 or 1, wherein the sum of n+n' is 1 or 2.

[0188] This need can also be met with a mixture M' Q comprising:

[0189] at least one electrically neutral compound of formula (II) as described above (i.e. an electrically neutral homologue of a compound of formula (I) as described above), and

[0190] at least one electrically neutral compound of formula (IX)

[0191]

[0192] (i.e. an electrically neutral homologue of a compound of formula (VII) as described above),

[0193] wherein A and Q1to Q4, which can be the same or different from each other, are as described above for the compound of formula (VII), and

[0194] W is an anion or an anionic group carrying w negative charges.

[0195] Examples of suitable anions or anionic groups W are as specified above for the electrically neutral compound of formula (II).

[0196] The present applicant has found that, as for the mono-ammonium compounds of formula (I), the di-ammonium compounds of formula (VII) show outstanding surfactant properties.

[0197] The present applicant has also found that the di-ammonium compounds of formula (VII) show quite good to excellent biodegradability, with emphasis on the compounds of formula (VI) which, as for the compounds of formula (I), show excellent biodegradability.

[0198] The Applicant has finally discovered that the diammonium compounds of formula (VII), notably the compounds of formula (VI), are constituted in the form of micelles and can form aqueous or water-alcohol formulations showing lower viscosity than the compounds of formula (I).

[0199] By adjusting the respective amounts of the compound of formula (I) and the compound of formula (VII) (or of the mixture M Q Q of their electrically neutral homologues) in the mixture Mit is possible to prepare aqueous or water-alcohol formulations in a wide range of viscosities, which comply with the various viscosity requirements required by various end-use applications.

[0200] Preferably, the compound of formula (VII) is selected from the group consisting of the compounds of formulae (VI), (X), (XI), (XII) and (XIII), represented hereinafter as follows:

[0201]

[0202]

[0203]

[0204]

[0205] wherein

[0206] R, R', R", R'" and Y, on each occurrence, can be the same or different, are as described above for compound (I), and

[0207] s and s', can be the same or different, are 0, 1, 2 or 3.

[0208] Preferably, the compound of formula (VII) is the compound of formula (VI).

[0209] The mixture M Q The ratio w I,VII of the weight of the compound (I) to the combined weight of the compound (I) and the compound (VII) in the mixture M Q can vary to a great extent, depending on the application in which M I,VIIThe range is typically from 1% to 99%, and very often from 10% to 90%. It can be at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, or at least 80%. Furthermore, it 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 exemplary ranges are notably well-suited for use with mixture M. Q Various applications, in which the compound of formula (VII) is the compound of formula (VI).

[0210] Similarly, mixture M' Q The ratio w of the weight of compound (II) to the combined weight of compound (II) and compound (IX) II,IX It can vary considerably, depending on where M' is intended to be used. Q Applications. Ratio w II,IX The range is typically from 1% to 99%, and very often from 10% to 90%. It can be at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, or at least 80%. Furthermore, it 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 exemplary ranges are notably well-suited for use with mixture M'. Q Various applications, in which the compound of formula (IX) is an electrically neutral homologue of the compound of formula (VI).

[0211] Some non-optimized mixtures M' have been described in Examples 11 and 12 of PCT / EP 2020 / 066649. Q The mixture in Example 11 contains a weight ratio w II / IX For the agreement 2 / 97Examples 11 and 12 are mixtures comprising a combination of a monoquaternary ammonium compound and a diquaternary ammonium compound, while the mixture of Example 12 comprises a monoquaternary ammonium compound and a diquaternary ammonium compound in a weight ratio w II / IX of about 1.0 to about 1.5. 5 / 92 of the same compound; in both examples, the combined weight of the monoquaternary ammonium compound and the diquaternary ammonium compound comprises about 97% of the total weight of the mixture. The monoquaternary ammonium compound of Examples 11 and 12 is the electrically neutral compound C II * as described above. Generally, the mixture M Q is different from a mixture similar to the mixtures of Examples 11 and 12, that is, generally, M Q is different from a mixture comprising at least one electrically neutral compound of formula (II) selected from the group consisting of compounds C II * and at least one electrically neutral compound of formula (IX), wherein the weight ratio w II / IX of the electrically neutral compound of formula (II) to the electrically neutral compound of formula (IX) is about 1.0 to about 1.5. 2 / 97 (typically meaning from 2 / 96 to 2 / 98 or about 5 / 92 (typically meaning from 5 / 91 to 5 / 93 ), and the combined weight of the electrically neutral compound of formula (II) and the electrically neutral compound of formula (IX) comprises about 97% (typically meaning from 96% to 98%) of the total weight of the mixture M Q .

[0212] The mixtures M Q and M Q may respectively comprise the ionic compound of formula (I) and the ionic compound of formula (VII), or the electrically neutral compound of formula (II) and the electrically neutral compound of formula (IX), in an amount 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% of the combined weight. The mixture M Q may consist essentially of the electrically neutral compound of formula (II) and the electrically neutral compound of formula (IX). In addition to the ionic compound of formula (I) and the ionic compound of formula (VII), the mixture M Q may comprise water or water plus an alcohol, such as ethanol, propanol, or butanol. The mixture M Q may consist essentially of (i) the ionic compound of formula (I), (ii) the ionic compound of formula (VII), and (iii) a combination of water and an alcohol, such as ethanol, propanol, or butanol.

[0213] Throughout the specification and the working examples below, any developed formulation should be understood as including, if appropriate, all potential enantiomers and diastereomers. Without specific stereochemistry, each chiral molecule presented is in the form of a racemic mixture, in the absence of a specific mention.

[0214] If the disclosure of any patents, patent applications, and publications that are incorporated herein by reference conflicts with the description of the present application to the extent that it can render ambiguous the terms used in the present application, the present description shall control.

[0215] Working Example

[0216] Example 1 - Synthesis of quaternary monoammonium compound of formula (I) from C 16 - C 18 (30:70) fatty acid fraction

[0217] Part 1. A - Peralidone to C 31 - C 35 Ketone fraction

[0218] The reaction was carried out under an inert argon atmosphere in a 200 mL quartz reactor equipped with a mechanical stirring (A320-type stirring mobile made with Inox SS316L 3D-printed), a thermally insulated addition funnel, a distillation setup, a heating pad and a temperature probe.

[0219] Into the reactor were introduced:

[0220] - 12.5 g of MASCID TM Acid 1865 (from Musim Mas Group) consisting of 33.7 wt% of palmitic acid and 65.3 wt% of stearic acid (0.045 mole of fatty acids), and

[0221] - 0.935 g of MgO (0.023 mole).

[0222] In the thermally insulated addition funnel was added 37.5 g of the same molten fatty acid mixture (0.135 mole).

[0223] The temperature of the reaction medium was then increased to 250°C. Once the temperature reached 150°C, stirring was initiated (1200 rpm). After a reaction time of 2h00 at 250°C, FTIR analysis showed complete conversion of the starting fatty acids into the intermediate magnesium carboxylate complex.

[0224] The temperature of the reaction medium was then increased to 250°C. Once the temperature reached 150°C, stirring was initiated (1200 rpm). After a reaction time of 2h00 at 250°C, FTIR analysis showed complete conversion of the starting fatty acids into the intermediate magnesium carboxylate complex.

[0225] Then, 12.5 g of the molten fatty acid mixture were added stepwise into the reactor through an addition funnel over 30 minutes and the mixture was stirred for another 1 h 00 at 330 °C. FTIR analysis showed complete conversion of the fatty acid and magnesium complex into the desired ketone.

[0226] Then two additional cycles were realized: addition of 12.5 g of fatty acid over 30 minutes, followed by stirring for another 1 h 00 at 330 °C.

[0227] After the last cycle, the mixture was allowed to stir for another 1 h 00 at 330 °C to ensure complete conversion of the intermediate magnesium complex into the desired ketone, which was confirmed by FTIR analysis.

[0228] The temperature of the reaction mixture was then allowed to cool at room temperature and the crude product was dissolved in hot CHCI3. The suspension was filtered over a plug of silica (70 g) and the product was further eluted with another amount of CHCI3.

[0229] After evaporation of the solvent, 41.83 g (0.086 mol) of product were obtained as a white wax, corresponding to a 96% isolated yield.

[0230] 1 H NMR (CDCI3, 400 MHz) δ (ppm): 2.45-2.25 (t, J = 7.6 Hz, 4H), 1.62-1.46 (m, 4H), 1.45-1.05 (m, 54H), 0.86 (t, J = 6.8 Hz, 6H).

[0231] 13 C NMR (CDCI3, 101 MHz) 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).

[0232] Part 1. Hydrogenation of the B-ketone mixture into C 31 -C 35 Internal fatty alcohol mixture

[0233] In a 100 mL autoclave equipped with a mechanical stirrer (Rushton turbine) were added:

[0234] - 4.36 g of Ru / C (4.87% Ru) catalyst (5% of dry catalyst with respect to ketone 5, catalyst containing 54.9% H2O)

[0235] - 39.3 g (87.2 mmol) of molten C 31 -C 35The ketone fraction.

[0236] The reaction was carried out under 20 bar of hydrogen pressure. Four nitrogen purges were performed followed by three purges of hydrogen at 20 bar. The temperature of the reaction mixture was then set at 100°C to melt the ketone substrate. The temperature was maintained at 100°C for 10 min and the stirring was started slowly at 200 rpm. When the proper stirring was confirmed, the stirring rate was increased to 1200 rpm and the temperature was set at 150°C.

[0237] After a reaction time of 6 h at 150°C, the heating was stopped and the mixture was allowed to cool at 90°C while stirring. The stirring was then stopped. The mixture was cooled to room temperature and the autoclave was carefully depressurized.

[0238] The NMR analysis of the crude in CDC13 showed a ketone conversion level > 99% and a molar purity of 99% for the fatty alcohol. The compact solid containing the product and the catalyst was ground into a powder and then introduced into a 1 L flask. 500 mL of chloroform were added and then the flask was heated at 60°C to completely dissolve the alcohol. The suspension was filtered over celite at 60°C. The solid filter cake was rinsed several times with hot chloroform at 60°C. The filtrate was evaporated to give the desired C 31 - C 35 White powder of the internal fatty alcohol mixture with a weight purity of about 99%, corresponding to an isolated yield of about 90%.

[0239] Part 1. C-C 31 - C 35 Dehydration of the fatty alcohol into an internal olefin

[0240] All the reactions were carried out under an inert argon atmosphere.

[0241] In a 200 mL quartz reactor equipped with a heating pad, a mechanical stirrer (A320-type stirring mobile made with Inox SS316L 3D-printing), a condenser wrapped and a temperature probe connected to a 50 mL two-neck distillate collection flask, were added:

[0242] - 41.3 g of C 31 - C 35 Fatty alcohol (85 mmol, 1 equivalent), and

[0243] - 4.13 g (40 mmol, 10 wt%) of AI2O3-η.

[0244] The temperature of the reaction medium was raised to 150°C to melt the alcohol and the stirring was started (about 500 rpm). Then, the temperature was set at 300°C and the mixture was allowed to stir at 1000 rpm under argon. The reaction progress was monitored thanks to NMR analysis using borosilicate glass tubes.

[0245] After 2 hours of reaction at 300°C, NMR analysis in CDC13showed complete conversion of the fatty alcohol and the presence of 1.5 mol% of ketone as by-product, which had been formed.

[0246] Stirring and heating were then stopped and the temperature was decreased to 80°C. The molten crude was transferred to a beaker. The reactor vessel and stirring moving device were rinsed with chloroform (AI2O3 is not soluble).

[0247] The mixture was filtered and the solvent was evaporated under vacuum to provide 39 g of a clear yellow oil, which solidified at room temperature to give a white solid in the form of a wax (98 wt% purity), corresponding to a 97% yield (NMR).

[0248] 1 H NMR (CDC13, 400 MHz) 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 = 6.8 Hz, 6H).

[0249] 13 C NMR (CDC13, 101 MHz) 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).

[0250] Part 1. D-epoxidation of internal olefins to provide C 31-35 oxirane

[0251] The reaction was carried out under an inert argon atmosphere.

[0252] In a 300 mL double-jacketed reactor, equipped with a mechanical stirrer (propeller with four inclined plows) and baffles, a condenser and a temperature probe, were added:

[0253] - 38.2 g of C 31-35 internal olefin (98 wt% purity, 80 mmol)

[0254] - 6.9 mL (7.2 g, 120 mmol) of acetic acid, and

[0255] - 11.3 g (30 wt%) of IR 120H resin.

[0256] The mixture was heated to 75°C to melt the fatty alkene. Stirring was then started and 12.3 mL (13.7 g, 120 mmol) of H2O2 30% was slowly added to the mixture using an addition funnel while monitoring the temperature of the reaction medium to prevent temperature increase of the reaction mass (exothermicity). This took about 20 min. During the addition, stirring was increased to improve mass transfer due to the heterogeneous nature of the reaction medium.

[0257] At the end of the addition, the temperature of the reaction medium was increased to 85°C and after 6 h10 at this temperature, NMR analysis showed a conversion level of about 99% with 98% selectivity.

[0258] Heating was then stopped and 150 mL of chloroform was added while the temperature of the reaction mass was about 50°C. The mixture was transferred to a separatory funnel and the organic phase was washed 3 times with 150 mL of water. The resin catalyst remained in the aqueous phase was removed during the phase separation. The aqueous phase was extracted twice with 50 mL of chloroform. The organic phase was dried over MgSO4, filtered and evaporated to provide 39.2 g of a white solid with 98 wt% purity (epoxide + diol by-products). The yield was 99% considering the purity.

[0259] 1 H NMR (CDCI3, 400 MHz) d (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 = 6.8 Hz, 6H).

[0260] 13 C NMR (CDCI3, 101 MHz) d (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).

[0261] Part 1. E-epoxide ring opening with chloroacetic acid to provide chloroacetic acid monoester C 31-35

[0262]

[0263] The reaction was carried out under an inert argon atmosphere. In a 500 mL three necked round bottom flask, equipped with a magnetic stirrer, a heater, a condenser, a temperature probe and a thermally isolated addition funnel, 44.2 g of chloroacetic acid (463 mmol, 5 eq) were added.

[0264] In a thermally isolated addition funnel maintained at 80°C, 45 g of molten C31-35 Fatty epoxide (purity: 99.97 wt%, 92.6 mmol, 1 eq).

[0265] The first step of formation of hydroxy-ester by oxirane ring opening is carried out at 65°C to limit the formation of ketone and dehydration by-products. The molten fatty epoxide is added gradually drop by drop to the reaction medium containing the molten chloroacetic acid under stirring at 65°C over 1 h20. The gradual addition of epoxide is carried out to limit the by-products formed by condensation between two epoxide molecules. At the end of the epoxide addition, the mixture is stirred at 65°C for 1 h30.

[0266] The second step of formation of hydroxy-ester by oxirane ring opening is carried out by additional stirring at 80°C for 1 h00.

[0267] NMR analysis of the crude (CDCI3) shows the complete conversion of the starting epoxide and of the 88:12 mol% monoester:diester mixture composition.

[0268] Part 1. F - Optional further reaction with chloroacetic acid to make chloroacetic acid monoester C 31-35 Part conversion into the corresponding diester

[0269]

[0270] The condenser is replaced by a curved distillation column and the temperature of the reaction medium, that is to say the crude previously obtained with a 88:12 mol% monoester:diester mixture composition, is raised to 90°C, followed by a gradual decrease of the pressure to 10 mbar in order to distil off the excess of chloroacetic acid and to remove the water formed as by-product.

[0271] After 1 h30 of distillation at 90°C (10 mbar), the 1H NMR analysis shows a ratio monoester:diester of 74:26 mol% with the remainder being chloroacetic acid.

[0272] At this stage, the distillation is stopped and the mixture is allowed to cool to room temperature. The crude is then dissolved in 150 ml of toluene and transferred into a separatory funnel. The organic phase is washed 3 times with 150 ml of aqueous NaOH solution (0.1 M) followed by 150 ml of brine. The organic phase is separated, dried over MgS04, filtered and evaporated to give 53 g of a residual beige oil.

[0273] After evaporation of the solvent 1H NMR (CDC13) showed the approximate composition of the beige oil to be: 66 wt% (70 mol%) of hydroxy-ester chloroacetic acid, 26 wt% (25 mol%) of di-ester chloroacetic acid, 5 wt% (3 mol%) of mono-ester dimer, 2 wt% (1 mol%) of di-ester dimer, 0.2 wt% (0.3 mol%) of ketone and 0.2 wt% (1 mol%) of chloroacetic acid.

[0274] The final yield of mono+di-ester chloroacetic acid was about 88% considering the purity of the mixture.

[0275] 1 H NMR (CDC13, 400 MHz) δ (ppm): 5.11-5.02 (m, 2H, di-ester), 4.96-4.83 (m, 1H, mono-ester), 4.07 (s, 1H, mono-ester), 4.06 (s, 1H, mono-ester), 4.04 (s, 2H, di-ester), 4.03 (s, 2H, di-ester), 3.74-3.67 (m, 1H, isomer 1, mono-ester), 3.64-3.54 (m, 1H, isomer 2, mono-ester), 1.73-1.61 (m, 2H, mono-ester), 1.61-1.48 (m, 4H, di-ester), 1.48-1.36 (m, 2H, mono-ester), 1.36-1.12 (m, 55H (average number)), 0.86 (t, J = 6.8 Hz, 6H).

[0276] 13 C NMR (CDC13, 101 MHz) δ (ppm): 167.39, 167.27, 167.15, 167, 79.84, 78.97, 76.21, 75.83, 72.95, 72.41, 41.06, 41.01, 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).

[0277] Part 1.G - Quaternization with NMe3

[0278]

[0279] The reaction was carried out under an inert argon atmosphere. In a double jacketed 1 L reactor, equipped with a mechanical stirrer, a condenser, a temperature probe, a collector containing a 0.1 N HCI solution, followed by a second collector containing activated carbon pellets, were added:

[0280] - 52 g (92.4 wt% purity, 80 mmol, 1 eq) of a mixture of about 72 wt.% (74 mol.%) of hydroxy-ester of chloroacetic acid and about 28 wt.% (26 mol.%) of bis-ester of chloroacetic acid, as obtained after completion of part 1-F,

[0281] and

[0282] - 171 ml (320 mmol, 4 eq) of trimethylamine / THF solution (13 wt% concentration).

[0283] The reaction mixture was then heated at 40°C and stirred at 1000 rpm. The progress of the reaction was followed by H NMR analysis. After 6h00 of stirring at 40°C, NMR analysis (CD3OD) showed the complete conversion of the chloroacetate and the selective formation of the corresponding glycine betaine esters, with an approximate composition as follows: 70 mol.% of glycine betaine hydroxy-ester and 25 mol.% of glycine betaine bis-ester. 1

[0284] The reactor was evacuated, rinsed with THF and the solvent evaporated under vacuum to provide 58.8 g of beige wax with the following weight composition: 65.2 wt.% of glycine betaine mono-hydroxy-ester, 27.6 wt.% of glycine betaine bis-ester, 4.7 wt.% of dimer mono-ester, 2.2 wt.% of dimer bis-ester and 0.18 wt.% of ketone.

[0285] The overall yield of glycine betaine mono-hydroxy-ester plus glycine betaine di-ester was 98% considering the product purity. The weight ratio of glycine betaine mono-hydroxy-ester to (glycine betaine mono-hydroxy-ester plus glycine betaine bis-ester) was 70%.

[0286] 1 H NMR (MeOD-d4, 400 MHz) δ (ppm): 5.17-5.06 (m, 2H, diquaternary salt), 5.02-4.87 (m, 1H, monoquaternary salt), 5.26-4.17 / 4.84-4.76 / 4.6-4.51 / 4.47-3.32 (m, 2H: monoquaternary salt, 4H: diquaternary salt), 3.41 (s, 18H, isomer 1, diquaternary salt), 3.38 (s, 18H, isomer 2, diquaternary salt), 3.36 (s, 9H, monoquaternary salt), 3.72-3.64 (m, 1H, isomer 1, monoquaternary salt), 3.56-3.47 (m, 1H, isomer 2, monoquaternary salt), 1.75-1.53 (m, 2H, monoquaternary salt), 1.53-1.44 (m, 4H, diquaternary salt), 1.44-1.35 (m, 2H, monoquaternary salt), 1.35-1.12 (m, 55H (average number)), 0.86 (t, J = 6.8 Hz, 6H).​

[0287] 13 C NMR (MeOD-d4, 101 MHz) 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).

[0288] Part 1.H - Purification of the crude glycine betaine mono-ester C 31-35 enriched chloroacetic acid mono-ester C

[0289] The crude material with 88:12 mol% mono-ester:di-ester mixture composition, obtainable after completion of Part 1-E, was cooled to room temperature. The crude material was then dissolved in toluene and transferred to a separatory funnel. The organic phase was washed with aqueous NaOH (0.1 M) 3 times, followed by brine. The organic phase was separated, dried over MgS04, filtered and evaporated to give purified material enriched in chloroacetic acid mono-ester C 31-35 enriched chloroacetic acid mono-ester C

[0290] Part 1.I - Quaternization of the crude glycine betaine mono-ester C 31-35 enriched chloroacetic acid mono-ester C

[0291] The quaternization reaction of the purified material obtained after completion of Part 1.H was achieved using the same quaternization reaction and purification protocol described in Part 1.G.

[0292] Finally, purified surfactant material QA2 with approximately 90:10 wt.% glycine betaine mono-hydroxy-ester:glycine betaine di-ester mixture composition was obtained, and the total content of glycine betaine di-ester plus glycine betaine mono-ester was about 95 wt.%.

[0293] Example 2 - Determination of biodegradability

[0294] The biodegradability of the test substance was measured according to the 301F OECD protocol.

[0295] The biodegradability of the test substance was measured according to the 301F OECD protocol.

[0295] TMRespirometric flasks) at constant temperature (20°C ± 2°C), a measured volume of inoculated mineral medium (containing a known concentration of test substance in order to reach about 50 to 100 mg ThOD / l (theoretical oxygen demand) as the sole source of organic carbon nominally) is stirred for up to 28 days. Oxitop TM Respirometric flasks in order to obtain the biodegradability of the test sample: the BOD flasks are sealed at a temperature of 20 ± 2°C using 28 days.

[0296] The released carbon dioxide is absorbed by the sodium or potassium hydroxide pellets present in the headspace of the bottle. The amount of oxygen absorbed by the microbial population during the biodegradation process (biological oxidation of the test substance) (= oxygen consumption expressed in mg / l) reduces the pressure of the headspace (ΔP measured by the pressure switch) and is mathematically converted in mg consumed O2 / litre. The inoculum corresponds to municipal activated sludge washed in mineral medium (ZW medium) in order to reduce the DOC (dissolved oxygen carbon) content. A control solution containing the reference substance sodium acetate as well as a toxicity control (test substance + reference substance) are used for validation purposes. The reference substance sodium acetate is tested in one flask (corresponding to a nominal concentration of 129 mg / l of 100 mg ThOD / l) in order to check the viability of the inoculum. The toxicity control corresponds to a mixture of the reference substance and the test substance; it will check if the test substance is toxic for the inoculum (if yes, the test has to be re-run with a lower concentration of test substance if it is feasible in terms of sensitivity of the method).

[0297] As the compounds and mixtures of compounds of the present invention are generally poorly soluble in water (and for those that are soluble in water, their metabolites containing alkyl chains after hydrolysis generally have very low solubility in water), we use a specific protocol called the "emulsion protocol". This protocol enables us to improve the bioavailability of poorly water-soluble substances in our aqueous phase with the inoculum.

[0298] The emulsion protocol consists in adding the test substance in the flasks through a stock solution prepared in an emulsion.

[0299] The emulsion is a 50 / 50 v / v mixture of a stock solution of the test substance dissolved in a non-biodegradable surfactant (1 g / l of PE105) and then mixed with mineral silicone oil AR 20 (Sigma).

[0300] The first dissolution of the test substance in the non-biodegradable surfactant solution generally requires a magnetic stirrer stirring followed by sonication.

[0301] Once the dissolution is complete, we mix the aqueous solution with the mineral silicone oil in a 50 / 50 volume / volume ratio. The emulsion is maintained by stirring with a magnetic stirrer and sampled for addition in the corresponding bottles in order to reach the required test substance concentration.

[0302] Two emulsion controls are run in parallel during the test in order to remove their values from the emulsion bottles containing the test substance added through the emulsion stock solution.

[0303] Biodegradability tests were performed on the 70 / 30 w / w and 90 / 10 w / w glycine betaine mono-hydroxy-ester / glycine betaine di-ester mixtures QA1 and QA2 of Example 1. The biodegradability was at least about 60% after 28 days (OECD 301F). Similar to glycine betaine di-ester used alone, as reported in Table 4 below, the compounds QA1 and QA2 showed a final biodegradation rate over 60% after 28 days.

[0304] Therefore, the glycine betaine mono-hydroxy-ester and glycine betaine di-ester contained in the mixtures of Example 1 show outstanding biodegradability. This beneficial effect is obtained without adversely affecting the surfactant properties of the compounds.

[0305] Example 3 - Evaluation of the adsorption properties on nanocellulose crystals

[0306] The adsorption of cationic surfactants on negatively charged surfaces is an important property for various applications. This property is related to the minimum concentration of cationic surfactant required to generate aggregation of negatively charged cellulose nanocrystals (CNC) in suspension in aqueous media. Comparison of the aggregate size can be monitored by dynamic light scattering (DLS).

[0307] The adsorption properties of ammonium compounds were investigated by monitoring the ratio X = [surfactant] / [CNC] or the mass fraction M = [surfactant] / ([surfactant]+[CNC]) required to induce cellulose nanocrystal aggregation at a fixed [surfactant]+[CNC] = 0.01 wt% in aqueous solution, following the protocol described in the literature (Ref: E.K. Oikonomou et al., J. Phys. Chem. B, 2017, 121(10), pp 2299-2307).

[0308] The range of CNC aggregation corresponds to the range of the ratio X (or M) that triggers the aggregation of CNCs, i.e. the range of aggregate size measured by DLS that is higher than that of a pure water solution of CNCs or of a water solution of surfactant at 0.01 wt%.

[0309] The ranges of aggregation X and M for the glycine betaine mono-hydroxy-ester / glycine betaine di-ester mixtures QA1 and QA2 of 70 / 30 w / w and 90 / 10 w / w of Example 1 are summarized in Table 1. TEP was used as a reference. TEP is a commercially available surfactant representing a benchmark.

[0310] The lower the range of aggregation X or M, the better the adsorption properties on negatively charged surfaces.

[0311] Table 1

[0312]

[0313] The data show that the mixtures of compounds of formula (I) and (VI) according to the present application have superior surfactant properties compared to the commercially available surfactant TEP. The surfactant properties of the mixtures of compounds of formula (I) and (VI) according to the present application are superior compared to TEP.

[0314] The surfactant properties of the compounds of formula (I) and (VI) are also considered individually. The surfactant properties of the compounds of formula (I) and (VI) and mixtures thereof are further similar to the properties of the mixtures of compounds of formula (X) and (XI) synthesized in Example 4 - Part B, the values of which are reported in Table 5.

[0315] Example 4 - Additional mixtures of mono- and di-quaternary ammonium compounds of formula (I)

[0316] Part 4. A - Synthesis of C 31 16-triacontanone to synthesize di-quaternary ammonium compounds of formula (VI)

[0317] a) Obtain C 31 Internal olefins

[0318] Obtain C from palmitic acid according to the protocol described in US patent 10035746, Example 4 31 Internal olefins.

[0319] b) Internal olefin epoxidation to fatty epoxide

[0320]

[0321] The reaction was carried out under an inert argon atmosphere.

[0322] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plough blades), a condenser, an addition funnel and a temperature probe, 61.9 g of C 31 olefin (0.142 mol), followed by 16.3 mL (17.1 g, 0.285 mol) of acetic acid and 13.6 g (22 wt%) of IR 120H resin. The mixture was heated to 65 °C to melt the fatty olefin. Stirring was started and then 21.8 mL (24.2 g, 0.214 mol) of an aqueous solution of H2O2(concentration 30%) was slowly added to the mixture using an addition funnel at a rate to avoid significant temperature increase. This took about one hour. The temperature was then increased to 75 °C and the reaction mixture was allowed to stir overnight (NMR analysis after 15 min showed that the conversion level was already about 60% with 99% selectivity). Then another 10.2 mL (11.3 g, 0.1 mol) of an aqueous solution of H2O2(30%) was slowly added and after 4 hours after the second addition of H2O2, NMR analysis showed that the conversion level was about 88% (98% selectivity). A final addition of 8.14 mL of acetic acid (8.55 g, 0.142 mol) followed by 11.6 mL of 30% H2O2(12.91 g, 0.114 mol) was made in order to increase the conversion level.

[0323] The mixture was allowed to stir at 75 °C for a second night.

[0324] Finally, NMR analysis showed a conversion level of 93% (95% selectivity).

[0325] The mixture was allowed to cool to room temperature and then 300 mL of chloroform was added. The mixture was transferred to a separatory funnel and 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 solid catalyst remained in the aqueous phase and was removed during the first separation from the aqueous phase. The organic phase was collected, dried over MgSO4, filtered and evaporated to give 65.3 g of a white solid with a purity of 91% w / w (epoxide + diol).

[0326] The yield was 92% considering the purity.

[0327] 1 H NMR (CDC13, 400 MHz) δ (ppm): 2.91-2.85 (m, 2H, diastereoisomer 1), 2.65-2.6 (m, 2H, diastereoisomer 2), 1.53-1.00 (m, 54H), 0.86 (t, J = 6.8 Hz, 6H).

[0328] 13 C NMR (CDC13, 101 MHz) 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).

[0329] c) hydrolysis of the fatty epoxide to provide a fatty diol

[0330]

[0331] The reaction was carried out under an inert argon atmosphere.

[0332] In a 1 L double-jacketed reactor, equipped with a mechanical stirrer (propeller with four inclined plough blades), a condenser and a temperature probe, 82.9 g of C 31 Epoxide (purity: 94.5 wt%, 0.174 mol) followed by 480 mL of methyl-THF.

[0333] The mixture was allowed to stir at room temperature and then 73 mL of a 3M aqueous solution of H2SO4were added. The reaction medium was then stirred at 80°C for 90 minutes. NMR analysis showed that the reaction was complete. The two-phase mixture was allowed to cool to room temperature and the organic phase was separated. The solvent was then removed under vacuum and the residue was suspended in 200 mL of diethyl ether. The suspension was filtered and the resulting solid was washed 3 times with 50 mL of diethyl ether. Finally, the white solid was washed 2 times with 50 mL of methanol and dried under vacuum to remove traces of solvent.

[0334] Finally, 75.53 g of product were obtained as a white powder with a purity of 95.7% w / w, corresponding to a yield of 89%.

[0335] 1 H NMR (CDCI3, 400 MHz) δ (ppm): 3.61-3.55 (m, 2H, diastereoisomer 1), 3.43-3.25 (m, 2H, diastereoisomer 2), 1.88 (br d, J = 2.4 Hz, OH, diastereoisomer 2), 1.72 (br d, J = 3.2 Hz, OH, diastereoisomer 1), 1.53-1.10 (m, 54H), 0.86 (t, J = 6.8 Hz, 6H).

[0336] 13 C NMR (CDCI3, 101 MHz) 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)

[0337] d) esterification of the fatty diol with trimethylglycine to provide a compound of formula (VI)

[0338] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0339] Fresh commercial anhydrous CHCI3(pentene stabilized) and anhydrous toluene were used as received.

[0340] Betaine hydrochloride (19.66 g, 128.4 mmol) was washed ten times with 20 mL of dry THF prior to use and then dried under vacuum to remove traces of solvent.

[0341] In a 100 mL four-necked round bottom flask, equipped with a magnetic stirrer, a heater, a condenser, a temperature probe and a curved distillation column connected to two traps of NaOH, were rapidly added:

[0342] 19.66 g of dry betaine hydrochloride (128.4 mmol) and

[0343] 28 mL of SOCl2(45.86 g, 0.386 mol).

[0344] The heterogeneous mixture was stirred and then the temperature was slowly increased to 70°C. It was observed that when the temperature reached 68°C, gas (SO2 and HCI) was released and the mixture became homogeneous yellow.

[0345] The mixture was then allowed to stir at 70°C for two hours and hot dry toluene (25 mL, 80°C) was added to the vessel. The mixture was stirred and then decanted at 0°C (white-yellow precipitate formed) and the upper phase of toluene was removed by cannula. The operation of toluene washing was repeated seven times to remove all excess SOCl2. NMR analysis showed complete conversion of betaine glycine hydrochloride but also the formation of the NMe3-HCI adduct (NMe3-HCI content in the solid: 12.3 mol%).

[0346] Then 20 mL of dry CHCI3were added to the solid betaine chloroformate.

[0347] A solution of 26.19 g (56 mmol) of fatty diol in 90 mL of dry CHCI3was prepared at 55°C and added dropwise to the reaction vessel at room temperature under stirring (exothermicity and HCI emission were observed). The mixture was then allowed to stir at 55°C overnight. During the course of the reaction, the mixture homogeneously turned orange. NMR analysis showed a conversion level of about 100%.

[0348] The mixture was then allowed to cool to room temperature and the solvent was evaporated under vacuum.

[0349] The residue was dissolved in methanol at 0°C and the formed precipitate was filtered out. The obtained filtrate was then evaporated to give 39.7 g of crude product.

[0350] The product was then deposited on a sintered filter and washed with cyclohexane to remove some residual organic impurities. The resulting washed solid was dried under vacuum to provide 22 g of crude material. A final purification was performed with a CH2Cl2 / cyclohexane 50:50 mixture; the solid was again dissolved in this solvent mixture at 50°C and allowed to cool to room temperature. The formed precipitate was filtered off and 19 g of a beige wax QA3 with the following composition were obtained after evaporation of the filtrate:

[0351] 95 wt% of glycine betaine diester, corresponding to the compound of formula (VI)

[0352] 1.5 wt% of betaine methyl ester

[0353] 2 wt% of trimethylamine hydrochloride

[0354] 1.5 wt% of glycine betaine hydrochloride.

[0355] The purification yield was 44%. No presence of the glycine betaine monoester compound of formula (I) was identified in the wax QA3.

[0356] 1 H NMR (MeOD-d4, 400 MHz) δ (ppm): 5.3-5.2 (m, 2H), 4.68 (d, J = 16.8 Hz, 2H), 4.50 (d, J = 16.8 Hz, 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 = 6.8 Hz, 6H).

[0357] 13 C NMR (MeOD-d4, 101 MHz) 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).

[0358] Part 4. B - synthesis of a mixture of diquaternary ammonium compounds of formula (X) and (XI) starting from C 31 -16-hentriacontanone

[0359] a) Knoevenagel condensation to provide a diester intermediate:

[0360]

[0361] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0362] Fresh commercial anhydrous CHCI3, anhydrous THF and anhydrous pyridine were used as received.

[0363] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four tilted blades), a condenser, an addition funnel and a temperature probe, 36.5 mL of TiCI4(63.00 g, 0.332 mol) were added, followed by 146.3 mL of CHCI3.

[0364] The mixture was stirred at -10°C and anhydrous THF (358 mL) was slowly added through the addition funnel at a rate to avoid temperature increase of the reaction medium above +5°C. During THF addition, a yellow precipitate appeared. Then 15.3 mL of dimethyl malonate (17.69 g, 0.134 mol) were added to the reaction mixture which was then allowed to stir at room temperature for 1 hour to allow malonate complexation to occur.

[0365] The mixture was then allowed to cool to 0°C and a solution of 71.80 mL 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 turned red. The mixture was then allowed to stir at room temperature for 20 minutes to allow deprotonation to occur.

[0366] Finally, 50.00 g of C 31 Ketone (0.111 mol) was added to the reaction mixture, which was allowed to stir at room temperature overnight and for another day at 35°C. Then 250 mL of water were carefully added to the reactor, followed by 250 mL of diethyl ether. The organic phase was separated and washed 4 times with 250 mL of water and once with 200 mL of a saturated aqueous NaCI solution to remove the pyridinium salt. The aqueous phases were combined and re-extracted 3 times with 250 mL of diethyl ether. The final organic phase was dried over MgS04, filtered and evaporated under vacuum to provide 70.08 g of a crude orange oil. At this stage, the crude contained residual amounts of starting ketone and major impurities corresponding to condensation of 2 equivalents of ketone (aldol condensation + butenoylation).

[0367] The product can be easily purified by dissolving the oil in ethanol (byproducts and starting ketone are not soluble in ethanol), followed by filtration over celite.

[0368] The filtrate was evaporated, re-dissolved in CHCI3, filtered again and evaporated to provide 52.57 g of an oil with 95% purity (RMN).

[0369] The global purification yield was 79%.

[0370] 1H NMR (CDC13, 400 MHz) 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 = 6.4 Hz, 6H).

[0371] 13 C NMR (CDC13, 101 MHz) 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).

[0372] b) exchanged with dimethylaminoethanol ester to provide a diamine mixture intermediate:

[0373]

[0374] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0375] Freshly commercially available anhydrous toluene and dimethylaminoethanol were used as received.

[0376] In a 2L double jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plough blades), a condenser with distillation setup and a temperature probe, 42.7 g of the ketol / malonate dimethyl ester adduct (75.6 mmol) was added followed by 50 mL of toluene. The mixture was stirred at room temperature and 30.4 mL of dimethylaminoethanol (26.9 g, 302.2 mmol, 4 equiv.) was added to the reaction system followed by 50 mL of toluene. Then 0.9 g of the catalyst dibutyltin oxide (3.8 mmol, 5 mol%) was added to the reaction mixture followed by 200 mL of toluene.

[0377] The mixture was then allowed to stir at 120°C and the reaction progress was followed by NMR analysis. For proper analysis, an aliquot of the reaction medium was sampled and diluted in diethyl ether, quenched with water, decanted, and the organic phase evaporated under vacuum for analysis in CDC13NMR solvent. After 4 days of stirring at 120°C, NMR analysis showed a conversion level of about 83% with a 91% selectivity. In addition, the by-product methanol was also present in the distillation flask. The reaction mixture was then allowed to cool at room temperature and quenched with 500 mL of water. The medium was decanted and the aqueous phase extracted three times with 500 mL of diethyl ether. The organic phases were collected and washed three times with 500 mL of water and once with 500 mL of a saturated aqueous NaCI solution in order to remove the excess dimethylaminoethanol. The organic phase was then dried over MgS04, filtered and evaporated to give 47.9 g of a crude dark oil. At this stage, the crude contained residual amounts of the starting malonic ester.

[0378] The product was then purified by flash column chromatography on silica gel with a first eluent consisting of a mixture of CHCI3 / AcOEt, with a gradient from 100% CHCI3to 100% AcOEt.

[0379] In order to remove all the product from the column, the column was also rinsed with an isopropanol + NEt3mixture (10% vol NEt3), allowing to obtain additional pure product.

[0380] The clean fractions were collected, giving after evaporation of the solvent 27.8 g of pure product, corresponding to a 54% isolated yield.

[0381] NMR analysis showed that the product was in the form of a mixture of two regioisomers in the following ratio: 54 mol% of isomerized product (cis and trans diastereoisomers) and 46 mol% of methyleneated product.

[0382] 1 H NMR (CDCI3, 400 MHz) δ (ppm): 5.45-5.13 (m, 1H: isomer 2 cis + trans), 4.42 (s, 1H, isomer 2 cis or trans), 4.24-4.06 (m, 4H, isomers 1 + 2), 3.99 (s, 1H, isomer 2 cis or trans), 2.58-2.40 (m, 4H, isomers 1 + 2), 2.32-2.24 (m, 4H, isomer 1), 2.20 (s, 12H, isomer 2), 2.09-1.89 (m, 4H, isomer 2 cis + trans), 1.45-0.99 (m, 51H, isomers 1 + 2), 0.81 (t, J = 6.8 Hz, 6H).

[0383] 13C NMR (CDCI3, 101 MHz) d (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).

[0384] c) methylation to provide a mixture of compounds (X) and (XI)

[0385] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0386] Fresh commercial anhydrous THF and dimethyl sulfate were used as received.

[0387] In a 1 L double-jacketed reactor equipped with a mechanical stirrer, a condenser, an addition funnel and a temperature probe, 100 mL of dry THF and 6.9 mL of dimethyl sulfate (9.14 g, 72 mmol, 2 equiv) were added. A solution of 24.6 g of the ester amine (36 mmol, 1 equiv) in 154 mL of THF was prepared beforehand in the addition funnel and added gradually into the reactor at room temperature under stirring in order to limit the temperature rise. The mixture was then stirred at room temperature under argon and the reaction progress was monitored by NMR analysis. After 2 hours, the mixture was brought to 40°C and 0.2 mL of dimethyl sulfate (2 mmol, 0.06 equiv) was added to allow stirring and achieve complete conversion.

[0388] The reaction was complete after one hour of stirring at 40°C and all volatiles (THF and remaining DMS) were removed under vacuum in order to provide 33.15 g of product in 95 mol% purity as beige wax QA4 with a 94% yield.

[0389] NMR analysis showed the presence of 2 regioisomers with a 55:45 ratio between the isomerized derivative (cis and trans diastereoisomers) and the conjugated non-isomerized methyleneated derivative.

[0390] 1H NMR (MeOD, 400 MHz) δ (ppm): 5.60-5.25 (m, 1H: isomer 2 cis + trans), 4.80 (s, 1H, isomer 2 cis or trans), 4.75-4.50 (m, 4H, isomers 1 + 2), 4.38 (s, 1H, isomer 2 cis or trans), 3.84-3.72 (m, 4H, isomers 1 + 2), 3.69 (s, 6H, isomers 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, isomers 1 + 2), 0.90 (t, J = 6.8 Hz, 6H).

[0391] 13 C NMR (MeOD, 101 MHz) 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).

[0392] Part 4. Additional mixtures of mono- and di-quaternary ammonium compounds of formula (I) C

[0393] Eight additional surfactant materials were prepared by mixing different amounts of the surfactant materials QA1, QA2, QA3 and QA4.

[0394] The weight percentages of mono- and di-quaternary ammonium compounds of formula (I) contained in the surfactant materials QA1, QA2, QA3 and QA4 are summarized here below, the remaining wt.% corresponding to impurities:

[0395] Table 2

[0396]

[0397] The following mixtures QA5 to QA 12 :

[0398] Table 3

[0399]

[0400]

[0401] Optionally, the surfactant materials QA1 to QA 12 are provided in the form of aqueous or water-alcoholic solutions.

[0402] Example 5 - Additional biodegradability tests

[0403] The biodegradability of the surfactant materials QA3 and QA4 was measured according to OECD standard 301.

[0404] The results of the biodegradability tests are reported in Table 4.

[0405] Table 4

[0406] Surfactant material Biodegradability after 28 days QA3 92% (OECD 301 F) ​ 17% (OECD 301 D)

[0407] The results show the outstanding biodegradability of the glycine betaine bis-ester compound (surfactant material QA3) and the general biodegradability of the mixture of di-quaternary ammonium compounds of surfactant materials QA4. All this is obtained without adversely affecting the surfactant properties of the compounds.

[0408] Example 6 - Additional evaluation of the adsorption properties on nanocellulose crystals

[0409] The adsorption properties of the surfactant materials QA3 and QA4 were measured according to the protocol described in Example 3.

[0410] The range of aggregation X and M of the CNCs is summarised in Table 5. The lower the range of aggregation X or M, the better the adsorption properties on negatively charged surfaces.

[0411] Table 5

[0412]

[0413]

[0414] TEP was used as a comparison. TEP is a commercial surfactant that represents a benchmark.

[0415] The data show that, in comparison with the commercial surfactant TEP, the surfactant materials QA3 and QA4 used to prepare the mixtures QA5 to QA 12 The surfactant properties of the surfactant materials QA3 and QA4 (according to the application) are excellent.

[0416] In summary, the compounds of formula (I) show a good combination of surfactant properties combined with good biodegradability - a combination that is not achieved in many cases by commercially available surfactants. Since the compounds of formula (I) are also easily accessible starting from lactones that are readily available from fatty acids or fatty acid derivatives, they also offer economic benefits over prior art ammonium surfactants.

[0417] An equally attractive combination of surfactant and biodegradability properties is achieved with mixtures comprising a compound of formula (I) and a compound of formula (VII). A further advantage of such mixtures is that by varying the respective ratios of the compounds of formula (I) and (VII) it is possible to adjust the viscosity of aqueous or water-alcohol formulations prepared from the mixtures within a wide range of values, thereby allowing the use of such mixtures in a wide range of applications where different levels of viscosity are required.

Claims

1. An ionic monoammonium compound of formula (I) (I) wherein R, which is the same or different at each occurrence, is C 10 -C 20 alkyl groups, Y is a linear divalent C1-C4 alkyl group, and R', R" and R'" are, on each occurrence, identical or different, a C1 to C4 alkyl group.

2. The compound of claim 1, wherein, R is C 10 -C 17 alkyl groups.

3. The compound according to any one of claims 1-2, wherein, Y is a methylene group.

4. The compound according to any one of claims 1-2, wherein, R', R" and R'" are methyl groups.

5. An electrically neutral compound of formula (II) (I) wherein R is as defined in any one of claims 1 to 2 for the compound of formula (I), Y is as defined in claim 1 or 3 for the compound of formula (I), R', R" and R'" are as defined in claim 1 or 4 for the compound of formula (I), and W is an anion or an anionic group bearing w negative charges.

6. The compound of claim 5, wherein, W is a halide anion and w is 1.

7. A mono-hydroxyl mono-ester compound for the preparation of the compound of formula (I) as claimed in claim 1 or of the compound of formula (II) as claimed in claim 5, said mono-hydroxyl mono-ester compound being a compound of formula (III) (III) wherein R, on each occurrence, is identical or different, is as defined in any one of claims 1 to 2 for the compound of formula (I), Y, on each occurrence, is identical or different, is as defined in claim 1 or 3 for the compound of formula (I), L is a leaving group, and t is an integer equal to 1 or equal to or greater than 2.

8. The compound of claim 7, wherein, L is a leaving group selected from the group consisting of halogen, a hydrocarbyl group of the formula R a a hydrocarbyloxy group of the formula -O-SO2-O-, wherein R a represents a C1-C 20 hydrocarbyl group, and an oxysulfonyloxy group of the formula - O-SO2-O-.

9. A mixture M Q comprising: - at least one ionic monoammonium compound of formula (I) as claimed in any one of claims 1 to 4, and - at least one ionic diammonium compound of formula (VII) (VII) wherein A is a tetravalent linker selected from the group consisting of A-1 to A-6 m, m', m" and m'", on each occurrence, are identical or different, 0, 1, 2 or 3, k, k', k", k'" and k"", identical or different, are 0, 1, 2 or 3, Qi to Q4, identical or different from each other, are selected from the group consisting of R and X, R, on each occurrence, is identical or different, is as defined in any one of claims 1 to 2 for the compound of formula (I), X, on each occurrence, is represented by formula (VIII) (VIII) wherein two and only two of Q1 to Q4 are represented by X, and two and only two of the groups Q1 to Q4 are represented by R, Y is as defined in claim 1 or 3 for the compound of formula (I), R', R" and R'", on each occurrence, are identical or different, are as defined in claim 1 or 4 for the compound of formula (I), and n and n', on each occurrence, are identical or different, are 0 or 1, with the sum of n + n' being 1 or 2.

10. The mixture of claim 9, wherein, the ionic diammonium compound is of formula (VI) (VI) wherein R, on each occurrence, is identical or different, is as defined in any one of claims 1 to 2 for the compound of formula (I), Y, on each occurrence, is identical or different, is as defined in claim 1 or 3 for the compound of formula (I), and R', R" and R'" are, on each occurrence, identical or different, defined as for the compounds of formula (I) in claim 1 or 4.

11. The mixture according to claim 9 or 10, wherein, the ratio w of the weight of the compound (I) to the combined weight of the compound (I) and the compound (VII) I,VII ranges from 10% to 90%.

12. The mixture of claim 11, wherein, the ratio w of the weight of the compound (I) to the combined weight of the compound (I) and the compound (VII) I,VII ranges from 50% to 90%.

13. A mixture M' Q It includes: - at least one electrically neutral compound of formula (II) according to claim 5 or 6, and - at least one electrically neutral compound of formula (IX) (IX) wherein A and Q1to Q4are as defined for the mixture M according to claim 9 Q (VII) as defined for the ionic diammonium compound of the formula (VII) comprised in the mixture M and W is an anion or an anionic group with w negative charges.

14. The mixture of claim 13, wherein, is a mixture M according to claim 10 Q comprising an ionic diammonium compound of formula (VI).

15. The mixture of claim 13, wherein, the ratio w of the weight of the compound (II) to the combined weight of the compound (II) and the compound (IX) II,IX is in the range from 10% to 90%.

16. The mixture of claim 15, wherein, the ratio w of the weight of the compound (II) to the combined weight of the compound (II) and the compound (IX) II,IX is in the range from 50% to 90%.

17. The ionic monoammonium compound of formula (I) according to any one of claims 1 to 4 or the electrically neutral compound of formula (II) according to claim 5 or 6 or the mixture M according to any one of claims 9 to 12 Q or the mixture M’ according to any one of claims 13 to 16 Q for use as a surfactant.

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