Keto-ammonium compounds

Abstract

The present invention relates to novel keto-ammonium compounds having surfactant properties and improved biodegradability.

Description

[0001] This application claims priority from European application No. 19306538.0 filed on November 29, 2019, the entire contents of which are incorporated by reference into the present application for all purposes.

[0002] The present invention relates to novel keto-ammonium compounds, in particular novel keto-ammonium compounds derived from lactones obtained from fatty acids or derivatives thereof, and the use of these novel compounds as surfactants.

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

[0004] WO 97 / 08284 discloses a composition comprising a Guerbet alcohol betaine ester represented by the following general formula

[0005]

[0006] Where R 1 To R 3 independently selected from C1 to C4 alkyl groups or C2-C4 alkenyl groups, a is from 1 to 4, and R 4 and R 5 Independently selected from C 12 To C 22 An alkyl or alkenyl group, R 4 and R 5 The sum of the chain lengths of is preferably at least 30. Since the compounds are derived from Guerbet alcohols, the radical R 4 and R 5 The number of carbon atoms always differs by 2.

[0007] EP 721 936 relates to liquid quaternary ammonium compounds having the general formula

[0008]

[0009] Where R 1-2 Is a straight or branched chain C 36 -C 44 An alkyl or alkenyl group, R 2 To R 4 is a C1-C5 alkyl or hydroxyalkyl group, Y is a linear or branched C2-C4 alkylene group, m is a number from 0 to 20 and n is an integer from 1 to 6. As in WO 97 / 08284, the preferred compound of EP 721 936 is derived from Guerbet alcohols and is represented by the formula

[0010]

[0011] DE 3402146 relates to quaternary ammonium compounds. As in WO 97 / 08284 and EP 721 936, the compounds contain two long-chain substituents which are esters of Guerbet acids.

[0012] WO 2018 / 087181 describes in its paragraphs

[00161] to

[00199] an amine compound having the formula

[0013]

[0014] wherein R1 and R2 independently represent hydrogen, a straight or branched hydrocarbon group having 1 to 24 carbon atoms (which may be optionally substituted and / or interrupted by one or more heteroatoms or groups containing heteroatoms), ethylamine or [poly(ethyleneimine)]ethylamine, hydroxyethyl, [poly(ethyleneimine)]ethanol or N,N-dialkylaminoalkyl, and wherein R1 and R2 may also form an alkanediyl group; R3 represents hydrogen, a straight or branched hydrocarbon group having 1 to 24 carbon atoms (which may be optionally substituted and / or interrupted by one or more heteroatoms or groups containing heteroatoms), or an aromatic or heterocyclic group (which may be optionally substituted by one or more branched or straight hydrocarbon groups which may optionally contain one or more heteroatoms); and R' n and R' m WO'181 further describes in paragraphs

[00193] to

[00200] the quaternization reaction of the above amine compounds to provide quaternary ammonium salts having the formula

[0015]

[0016] An alkylating agent of formula R4X is used, wherein R4 represents a straight or branched hydrocarbon radical having 1 to 10 carbon atoms, which may optionally be substituted and / or interrupted by substituted or unsubstituted aromatic groups and / or heteroatoms or heteroatom-containing groups (such as -CH3, -CH-CH2CH3, benzyl or furfuryl), and wherein X is a leaving group (such as chlorine). Although WO'181 may at most generally indicate by its paragraphs

[00440] or

[00480] that the above quaternary ammonium salts may perhaps have some surfactant properties, WO'181 is completely silent about the ability of such fatty quaternary ammonium compounds to or not exhibit biodegradability. In addition, the applicant synthesized these fatty quaternary ammonium compounds and observed that they were unstable, which made them unsuitable for use as surfactants from a practical point of view: they undergo decomposition at room temperature, releasing ammonium compounds of formula R1R2R4NHX, such as malodorous trimethylammonium chloride.

[0017] Although fatty quaternary ammonium compounds are widely used as surfactants, there is still a need for compounds of this type that have a good combination of surfactant properties on the one hand and biodegradability on the other hand. Biodegradability has become increasingly important in recent times due to consumer desires to have more environmentally friendly products. However, improvements in biodegradability should not negatively affect surfactant properties.

[0018] It was therefore an object of the present invention to provide novel ammonium compounds having good surfactant properties and good biodegradability.

[0019] This object is achieved by compounds of the formula (I).

[0020] Preferred embodiments of the invention are set forth in the dependent claims and in the following detailed description.

[0021] The novel ionic compounds according to the present invention have the general formula (I)

[0022]

[0023] Where R and R', which may be the same or different at each occurrence, are C4-C 27 Aliphatic groups,

[0024] X is a monovalent group represented by formula (II)

[0025]

[0026] Where R 1 and R 2 , which may be the same or different, are hydrogen or a C1 to C4 alkyl group,

[0027] R 3 It is hydrogen,

[0028] R x is hydrogen or an aliphatic group having 1 to 6 carbon atoms, and

[0029] where * indicates the position where the monovalent group is attached to the rest of the ionic compound,

[0030] X' is hydrogen or a monovalent group represented by formula (II) or

[0031] wherein X and X' together form a divalent radical having formula (III)

[0032]

[0033] Where R x , which may be the same or different, are hydrogen or an aliphatic group having 1 to 6 carbon atoms, and

[0034] R4 and R 5 , which may be the same or different, are hydrogen or a C1 to C4 alkyl group, and

[0035] where * indicates the position at which the divalent group is bonded to the rest of the ionic compound.

[0036] Aliphatic groups R and R ’ It may be free of any double bonds and any triple bonds. Alternatively, the aliphatic groups R and / or R' may contain at least one -C=C- double bond and / or at least one -C≡C- triple bond.

[0037] The aliphatic groups R and R′ are advantageously chosen from alkyl groups, alkenyl groups, alkadienyl groups, alktrienyl groups and alkynyl groups.

[0038] The aliphatic groups R, R' can each be straight-chain or branched.

[0039] Preferably, the aliphatic groups R and R' are independently selected from alkyl and alkenyl groups.

[0040] More preferably, the aliphatic groups R and R' are both independently selected from alkyl and alkenyl groups, typically selected from C4-C 24 Alkyl and C4-C 24 Alkenyl groups, very often selected from C4-C 20 Alkyl and C4-C 20 The alkenyl group is often selected from (i) C4-C 18 Alkyl and C4-C 18 an alkenyl group or selected from (ii) C4-C 16 Alkyl and C4-C 16 More preferably, R and R' represent an alkyl group, typically a C4-C 24 Alkyl groups, very often representing C4-C 20 Alkyl groups, often representing C4-C 18 Alkyl group or C4-C 16 Alkyl group.

[0041] Aliphatic groups R and R' having 6 to 24, preferably 8 to 24, more preferably 8 to 20, still more preferably 10 to 20 and most preferably 10 to 16 carbon atoms have been found to be advantageous in certain circumstances. In particular, alkyl and alkenyl groups having 6 to 24, preferably 8 to 24, more preferably 8 to 20, still more preferably 10 to 20 and most preferably 10 to 16 carbon atoms have been found to be advantageous as R and R' groups. More particularly, alkyl groups having 6 to 24, preferably 8 to 24, more preferably 8 to 20, still more preferably 10 to 20 and most preferably 10 to 16 carbon atoms have been found to be advantageous as R and R' groups.

[0042] An acyclic aliphatic group, more preferably a straight-chain aliphatic group, still more preferably a straight-chain alkyl group can be mentioned as preferred examples of the substituents R and R'.

[0043] The number of carbon atoms of R or R' may be an even number or an odd number, and each group R and R' may have the same number of carbon atoms, or the number of carbon atoms of the groups R and R' may be different.

[0044] If R x is an aliphatic group, it may not contain any double bonds and any triple bonds. x It may contain at least one -C=C-double bond and / or at least one -C≡C-triple bond.

[0045] According to a preferred embodiment, R x It's hydrogen.

[0046] The ionic compound in one embodiment of the present invention contains one substituent X represented by the above formula (II) and hydrogen as a substituent X'.

[0047] In this embodiment, R 1 and R 2 , which may be the same or different, are hydrogen or a C1 to C4 alkyl group, preferably methyl or ethyl, more preferably methyl. Preferably R 1 and R 2 At least one of is, more preferably R 1 and R 2 Both are C1 to C4 alkyl groups, preferably methyl or ethyl, most preferably methyl. 3 It's hydrogen.

[0048] According to another preferred embodiment of the present invention, both X and X' are represented by formula (II).

[0049] In this other embodiment, R 1 and R 2, which may be the same or different, are hydrogen or a C1 to C4 alkyl group, preferably methyl or ethyl, more preferably methyl. Preferably R 1 and R 2 At least one of is, more preferably R 1 and R 2 Both are C1 to C4 alkyl groups, preferably methyl or ethyl, most preferably methyl. 3 It's hydrogen.

[0050] According to a third preferred embodiment of the present invention, X and X' together form a divalent radical having formula (III)

[0051]

[0052] Where R x , which may be the same or different at each occurrence, is hydrogen or an aliphatic radical having 1 to 6 carbon atoms, R 4 and R 5 , which may be the same or different, are hydrogen or a C1 to C4 alkyl group, and wherein * indicates the position at which the divalent radical is bonded to the rest of the ionic compound.

[0053] R 4 and R 5 , which may be the same or different, are hydrogen or a C1 to C4 alkyl group; preferably, R 4 and R 5 At least one of is an alkyl group (most preferably a methyl group) and more preferably R 4 and R 5 Both are alkyl groups (most preferably methyl groups).

[0054] Preferred compounds of the present invention are represented by the following formulas I' to I'":

[0055]

[0056] Among them, R, R', R 1 , R 2 , R 4 and R 5 has the meaning as defined in claim 1 and described above. Preferably, R 1 , R 2 , R 4 and R 5 It's methyl.

[0057] Another embodiment of the present invention relates to an electrically neutral compound having formula (IV)

[0058]

[0059] wherein R, R', X and X' are as defined and described above, W is an anion or anionic group having w negative charges, and r is the number of charges carried by the substituents X and X' represented by the group having formula (II) or (III).

[0060] Suitable anions or anionic groups W are, for example, halides such as chloride, fluoride, bromide or iodide, methyl sulfate or methosulfate anions (CH3-OSO3 - ), sulfate anion, hydrogen sulfate anion (HSO4 - ), carbonate anion (CO3 2- ), bicarbonate anion (HCO3-) or an organic carboxylate anion such as acetate, propionate, benzoate, tartrate, citrate, lactate, glyoxylate, glycolate, gluconate, maleate, fumarate or succinate.

[0061] The compounds according to the present invention can be obtained by a variety of different methods. A preferred method for making the compounds of the present invention comprises the reaction of a ketone having the formula R-CH2-C(=O)-CH2-R', which can preferably be obtained by decarboxylation of a fatty acid, a fatty acid derivative or a mixture thereof. A suitable method for making ketones according to this route is disclosed in US2018 / 0093936, and further details are found in the patent.

[0062] If the lactone used as reactant in the exemplary method described above is obtained from a natural fatty acid having an even number of carbon atoms, the number of carbon atoms of the groups R and R' in the compound having formula (I) is preferably any one of the following pairs:

[0063] (4,4), (6,6), (8,8), (10,10), (12,12), (14,14), (16,16)

[0064] (6,8), (6,10), (6,12), (6,14), (6,16)

[0065] (8,10), (8,12), (8,14), (8,16)

[0066] (10,12), (10,14), (10,16)

[0067] (12,14), (12,16)

[0068] (14,16)

[0069] Other pairs are possible and will be obtained if the lactone is derived from a fatty acid containing an odd number of carbon atoms.

[0070] The synthesis of the compounds of the invention using the lactones obtainable as indicated above as starting materials can preferably be carried out using the so-called Mannich reaction or Mannich condensation as first step.

[0071] The Mannich reaction is an organic reaction consisting of an aminoalkylation occurring on a carbon attached to at least one hydrogen atom and immediately adjacent to the carbonyl functionality by condensation between a substrate containing an enolizable carbonyl group (e.g., a ketone or aldehyde) and an aldehyde and a primary or secondary amine or ammonia. The final product is a β-amino-carbonyl compound, also known as a Mannich base. In the Mannich reaction, primary or secondary amines or ammonia are used for the activation of the aldehyde. Tertiary amines do not form the NH bond of the intermediate electrophilic iminium and are therefore generally not used.

[0072] The mechanism of the Mannich reaction starts with a free amine and an aldehyde (for formaldehyde as the active aldehyde, R x will be hydrogen) to form an electrophilic iminium ion:

[0073]

[0074] Where R x , R 1 and R 2 As defined in claim 1.

[0075] In the second step, the compound with a carbonyl functional group (in this case, a lactone) attacks the iminium ion after tautomerization to form the nucleophilic enol form to form the final product of the Mannich condensation reaction:

[0076]

[0077] Among them, R, R', R 1 and R 2 Has the meaning as defined in claim 1.

[0078] Although formaldehyde (methylene oxide, where R x is hydrogen), but other aldehydes may be used, in which case the reaction should be more generally defined as an aminoalkylation rather than an aminomethylation.

[0079] Commercially available formaldehyde sources exist in different forms, all of which can be used for the purpose of carrying out the Mannich reaction. Formaldehyde can be used directly as a gas or in the form of an aqueous formaldehyde solution (often called "formalin"). In this aqueous solution, formaldehyde molecules in the monomeric state coexist with oligomers, which generally have a degree of polymerization of 10 or less. Other sources of formaldehyde are: 1,3,5-trioxane, which is a solid cyclic trimer of formaldehyde, which is easily decomposed into formaldehyde by acid or by heating in an organic solvent, or paraformaldehyde, which is a crystalline polymer with a degree of polymerization generally less than 50, which becomes water-soluble after depolymerization, which is generally achieved by heating.

[0080] In some cases, aqueous formaldehyde (35-40% w / w) solutions have proven to be advantageous in the Mannich reaction and are also preferred for the preparation of the compounds according to the invention.

[0081] Alternatively, reactants that can be easily decomposed into formaldehyde in situ can be used. In this case, preferred reactants are 1,3-dioxolane (which decomposes into formaldehyde and diols by reaction with water), dimethoxymethane (which decomposes into formaldehyde and methanol by reaction with water), diethoxyethane (which decomposes into formaldehyde and ethanol by reaction with water).

[0082] If aldehyde R is used x -CHO instead of formaldehyde, the nitrogen atom of the amine used is attached to the carbon atom of the carbonyl group of the substrate next to a hydrogen atom and a radical R derived from the aldehyde reactant. x .

[0083] The presence of an aldehyde in the Mannich reaction enables the reaction to proceed either via a methylene group (if formaldehyde is used as the reactive aldehyde) or via an alkylene group -CHR x - Attachment of a substrate containing a carbonyl group to an amine moiety.

[0084] When aldehydes other than formaldehyde are used as the reactive aldehyde, a decrease in reactivity is generally observed due to the increased steric requirements and the lower electrophilicity of the aminoalkylating agent. In addition, the stereochemistry of the resulting product is affected by the formation of chiral centers in the molecule. If other chiral centers are present in the carbonyl-containing substrates or amines used, or if the reactive center of the acetone substrate is prochiral, the formation of several diastereomers occurs.

[0085] When an endotoxin of the formula R—CH2-C(═O)—CH2-R′ is used as a starting material for the Mannich reaction, there are two methylene groups available for reaction and therefore a mixture of keto-monoamine compounds (such as, for example, compounds of the formula (I′)) and keto-diamine compounds (such as, for example, compounds of the formula (I″)) is generally obtained. The ratio of keto-monoamine compounds to keto-diamine compounds can vary within a wide range and can be controlled by the molar ratio of the reactants and the reaction conditions, especially the reaction time. When higher molar amounts of amines and aldehydes are used in the Mannich reaction together with longer reaction times, a mixture enriched in keto-diamine compounds is obtained. The molar ratio of keto-monoamine to keto-diamine compounds can extend from 95:5 to 5:95, preferably from 90:10 to 10:90, and the skilled person will select the amounts of reactants and the reaction conditions in a suitable manner depending on whether a mixture enriched in keto-monoamine compounds is desired or whether an excess of keto-diamine compounds is desired. Working Examples 1 and 2 provide detailed information on how the ratio of the two possible products can be controlled and adjusted.

[0086] According to a preferred embodiment, the present invention relates to a mixture comprising a compound of formula (I) as defined above, wherein X is represented by formula (II) and X' is hydrogen, and a compound of formula (I) as defined above, wherein both X and X' are represented by formula (II), more specifically a mixture of a compound of formula (I') and a compound of formula (I")

[0087] The molar ratio of the two compounds in the mixture can be in the range from 95:5 to 5:95, preferably in the range from 90:10 to 10:90, particularly preferably in the range from 20:80 to 80:20.

[0088] The Mannich reaction is well known to those skilled in the art, who will select appropriate reaction conditions based on their expertise and the specific application and substrates used.

[0089] Generally speaking, the reaction can be carried out in an autoclave. The acetone and optionally a suitable solvent (e.g., methanol, ethanol, isopropanol, THF, methyl-THF, DMSO) are charged into a reactor, followed by a suitable amount of formaldehyde or other reactive aldehyde (preferably formaldehyde is used in the form of a 37% w / w aqueous solution) and a suitable amount of ammonia or a solvent having the formula NHR 1 R 2 Amine (R 1 and R 2 has the meaning as defined in claim 1) (preferably in its ammonium (NH4 + ) or protonated amine (H2NR 1 R 2+) in the form of a salt, typically a hydrochloride or a hydrogen sulfate: H2NR 1 R 2 .Cl or H2NR 1 R 2 .HSO4). An aqueous acid solution is also added as a catalyst (according to a preferred embodiment, a concentrated aqueous hydrochloric acid solution can be used), and the resulting mixture is then heated to a temperature in the range of from 50°C to 250°C, preferably from 80°C to 120°C, and the mixture is allowed to stir until complete conversion of the ketone is achieved. At the end of the reaction, the solvent is typically removed by distillation.

[0090] At the end of the Mannich reaction, especially in the case of the amine reactant NHR 1 R 2 In the case of using it in the form of a protonated amine salt, a product in the form of a protonated keto-amine salt can be obtained. The product can be used as is, or the free keto-amine Mannich base can be recovered by deprotonation using a suitable base. As examples of suitable bases, mention can be made of: NaOH, LiOH, KOH, Na2CO3, NaOCH3, NaOCH2CH3, etc. ... The deprotonation can be carried out in a suitable solvent, such as, for example: water, methanol, ethanol, isopropanol, DMSO, acetonitrile, THF, methyl-THF, diethyl ether, methyl tert-butyl ether, ethyl acetate, dioxane, toluene, xylene, CH2Cl2, CHCl3 or a mixture thereof. The deprotonation reaction can be carried out in a temperature range from 0°C to 100°C. The base can be used in a stoichiometric or excess amount, and the amount of the base can be adjusted to achieve a pH greater than 10.

[0091] Alternatively, instead of using formaldehyde, a reactant can be used in the process of the invention which decomposes into formaldehyde in situ under the reaction conditions. In this case, the reactant can also serve as a solvent and can be used in excess relative to the ketone. No additional solvent is therefore required. As examples of such formaldehyde-generating reactants, mention may be made of: 1,3-dioxolane or dimethoxymethane.

[0092] To obtain the ionic compounds according to the invention, the product obtained after the Mannich reaction should be alkylated or protonated.

[0093] Suitable reactions and their conditions are described in the literature and are known to the skilled person, so that no details need to be given here. The skilled person will select suitable reactants and reaction conditions based on his or her expert knowledge.

[0094] In the second step, the amine obtained as a result of the Mannich reaction can be alkylated with an alkylating agent having the general formula R"-L to obtain the target keto-ammonium compound of the present invention, wherein L is an anion or a leaving group resulting from the alkylation of an anionic group (such as, for example, methyl sulfate), preferably a dialkyl sulfate, even more preferably dimethyl sulfate (DMS).

[0095] To a suitable amount of the alkylating agent in a suitable solvent, a concentrated solution of the keto-amine in the same solvent is gradually added with stirring (usually at room temperature) at a rate that avoids a significant temperature increase due to the reaction exotherm.

[0096] After the addition is complete, the mixture is allowed to stir at room temperature (typically 15°C-30°C) and the volatiles (mainly solvent and trace amounts of alkylating agent (eg DMS)) are removed under vacuum to provide a alkylating agent with a substituent R 1 To R 3 The final keto-ammonium compound.

[0097] According to a preferred embodiment, the protonation or alkylation is carried out under an inert atmosphere.

[0098] In a preferred protonation procedure, water and an appropriate amount of an aqueous acid (e.g., hydrochloric acid) solution are added to a flask equipped with a stirring device and a condenser. The solution thus obtained is stirred at a temperature preferably in the range of from 0° C. to 10° C., and then the product obtained from the Mannich reaction is slowly added. If the viscosity of the system is too high, water can be added to reduce it.

[0099] The reaction mixture is stirred at a temperature preferably in the range of from 5 to 100° C., more preferably in the range of from 10 to 50° C. until the reaction is complete. Water may optionally be removed, for example by lyophilization, to obtain the desired keto-ammonium compound according to the invention.

[0100] By changing the conditions of the alkylation or protonation reaction, the keto-diamine compound obtained after the Mannich reaction (such as a non-alkylated or non-protonated precursor of compound I") can be converted into a compound having formula I, wherein the substituents X and X' together form a group having formula (III). Working Example 3 provides detailed information in this regard. The skilled person will adjust the reaction conditions in a suitable manner to guide the reaction towards the desired final compound.

[0101] During the cyclization reaction, a substituent X or X' having the formula -NR 1 R 2 R 3 An ammonium group (where R 1 To R 3 The definition of is provided above) acts as a leaving group. On the other hand, a substituent X or X' having the formula -NR 1R 2 An amino group of X acts as a nucleophile and in the group CHR belonging to another substituent X or X' x The cyclization reaction is thus favorable when the alkylating agent or acid used to alkylate or protonate the keto-diamine substrate is used in an equimolar amount relative to the keto-diamine substrate (meaning half of the equivalent relative to the amino group of the keto-diamine substrate). In addition, the use of a weaker acid (with pKa>1) such as a carboxylic acid can be favorable for the formation of the cyclized product upon heating in aqueous solution.

[0102] Other methods than the combination of the Mannich reaction followed by alkylation or protonation may be suitable for the synthesis of the compounds according to the invention and the skilled person is aware of such methods so that no further details need to be given here.

[0103] The compounds of the present invention can be used as surfactants. Surfactants are compounds that reduce the surface tension (or interfacial tension) between two immiscible liquids, liquid and gas or liquid and solid. Surfactants can serve as detergents, wetting agents, emulsifiers, foaming agents, and dispersants.

[0104] Surfactants are generally amphipathic organic compounds, meaning that they contain both a hydrophobic group (their tail) and a hydrophilic group (their head). Thus, surfactants contain both a water-insoluble (or oil-soluble) component and a water-soluble component. Surfactants will diffuse in water and adsorb at the interface between air and water or at the interface between oil and water (in the case where water and oil are mixed). The water-insoluble hydrophobic group can extend out of the bulk water phase into the air or oil phase, while the water-soluble head group remains in the water phase.

[0105] The adsorption of cationic surfactants on negatively charged surfaces is an important property for such surfactants. This property is usually related to the minimum concentration of surfactant required to produce aggregation of negatively charged cellulose nanocrystals (CNC, which is often used as a reference material) suspension in aqueous media. The continuous change of aggregate size can be monitored and subsequently subjected to dynamic light scattering (DLS).

[0106] According to the protocol described in EKOikonomou et al., J. Phys. Chem. B, 2017, 121(10), 2299-307, the adsorption characteristics of quaternary ammonium compounds can be studied by monitoring the ratio X = [surfactant] / [CNC] or the mass fraction M = [surfactant] / ([surfactant + [CNC]) required to induce aggregation of cellulose nanocrystals in aqueous solution at a fixed [surfactant] + [CNC] = 0.01 wt%.

[0107] The biodegradability of the compounds of the invention can be determined according to procedures described in the prior art and known to the skilled person. Details on one such method OECD Standard 301 are given in the experimental part below.

[0108] Should the disclosure of any patents, patent applications, and publications incorporated by reference into this application conflict with the description of the present application to the extent that it renders a term unclear, the present description shall take precedence.

[0109] Working Example

[0110] Example 1 - From C 31 16-Triuncontanone Synthesis of a mixture of compounds having formula I' and I" - a mixture enriched in a compound having formula I'

[0111] Synthesis of a mixture of ketoamine compounds

[0112]

[0113] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0114] In a 1 L round bottom flask equipped with a condenser, magnetic stirrer, heater and temperature probe add:

[0115] -70 g of 16-triacontanone (0.155 mol, 1 equivalent)

[0116] -45.22 g of dimethylamine hydrochloride (0.555 mol, 3.6 equivalents)

[0117] -330 mL of 1,3-dioxolane.

[0118] The mixture was allowed to stir at room temperature and 1.29 mL of aqueous HCl (37 wt%) (0.57 g HCl, 15.7 mmol, 10 mol%) was carefully added to the reaction vessel. The mixture was then allowed to stir at 90°C and the progress of the reaction was followed by NMR analysis.

[0119] After stirring at 90°C for 8 h, the mixture was allowed to cool to room temperature and an aqueous solution of NaOH (1 M) was carefully added to the reaction crude with stirring until the pH was greater than 11.

[0120] The product was then extracted three times with 350 mL of diethyl ether and the organic phase was washed five times with 350 mL of 0.5 M NaOH solution.

[0121] The organic phase was dried over MgSO4, filtered and the solvent removed under vacuum to provide 78 g of crude material. At this stage the product mixture contained approximately 5 mol% of methylened keto-amine byproducts, which could be converted to keto-diamines according to the procedure described below:

[0122] To the crude material in a 500 mL round bottom flask equipped with a mechanical stirrer, condenser, temperature probe and heater was added 150 mL of aqueous dimethylamine solution (40 wt %). The resulting mixture was stirred at 40°C overnight.

[0123] NMR analysis showed complete conversion of the methylened byproduct to the desired keto-diamine.

[0124] To the crude mixture was added 350 mL of diethyl ether followed by 100 mL of water, the organic phase was separated and the aqueous phase was extracted twice more with 350 mL of diethyl ether.

[0125] The organic phases were collected, washed several times with brine, dried over MgSO4 and filtered.After evaporation of the solvent, 64.85 g of crude material were recovered (yield: 86%).

[0126] NMR analysis showed that the mixture contained 72 mol % of keto-monoamine and 21 mol % of keto-diamine.

[0127] 1 H NMR (CDCl3, 400 MHz) δ (ppm): 2.82-2.70 (m, 2H, di-amine, two diastereomers), 2.69-2.58 (m, 1H, mono-amine), 2.54 (dd, J = 11.6 Hz, J = 9.2 Hz, 1H, mono-amine), 2.53-2.43 (m, 2H, di-amine, two diastereomers), 2.40 (dt, J = 7.2 Hz, J = 2.48 Hz, 2H, mono-amine), 2.1 7 (s, 12H, di-amine diastereomer 1), 2.16 (s, 12H, di-amine diastereomer 2), 2.15 (s, 6H, mono-amine), 2.13 (dd, J = 11.6 Hz, J = 5.2 Hz, 1H, mono-amine), 1.65-1.45 (m, 2H + 4H, mono-amine + diamine), 1.40-0.95 (m, 50H + 48H, mono-amine + di-amine), 0.86 (t, J = 6.4 Hz, 6H mono-amine + di-amine).

[0128] 13C NMR (CDCl3, 101 MHz) δ (ppm): 216.6 (di-amine, diastereomer 1), 216.2 (di-amine, diastereomer 2), 214.46 (mono-amine), 62.24 (mono-amine), 61.48 (di-amine, diastereomer 1), 61.26 (di-amine, diastereomer 2), 51.04 (mono-amine), 50.40 (di-amine, diastereomer 1), 50.32 (di-amine, Diastereomer 2), 46.12 (di-amine), 46.08 (mono-amine), 42.53 (mono-amine), 32.15, 30.75, 30.11, 29.98, 29.92, 29.89, 29.86, 29.80, 29.76, 29.71, 29.67, 29.59, 29.49, 27.77, 27.69, 27.63, 23.49, 22.92, 14.34 (terminal CH3).

[0129] Protonation of a mixture of ketoamine compounds

[0130] The reaction was carried out under an inert argon atmosphere.

[0131] In a 1 L round bottom flask equipped with a condenser, mechanical stirrer and temperature probe, add

[0132] -200mL of water

[0133] - 14.0 g of aqueous HCl (37 wt%) (0.142 mol).

[0134] The solution was allowed to stir at 0°C and the keto-amine mixture (64.85 g, 0.097 mol of mono-amine, 0.028 mol of di-amine, 1 eq) was gradually added to the reaction vessel. An additional 200 mL of water was added to reduce the solution viscosity.

[0135] The mixture was stirred at room temperature during 5 h, and after completion of the reaction the water was removed by lyophilization to afford a mixture of ammonium salts as a fine white powder (quantitative yield).

[0136] Example 2 - Synthesis of a mixture of compounds of formula I' and I" enriched in a compound of formula I"

[0137] Synthesis of a mixture of ketoamine compounds

[0138]

[0139] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0140] In a 1 L round bottom flask equipped with a condenser, magnetic stirrer, heater and temperature probe add:

[0141] -75 g of 16-triacontanone (0.166 mol, 1 equivalent)

[0142] - 27.61 g of dimethylamine hydrochloride (0.339 mol, 2.04 equivalents)

[0143] -380 mL of 1,3-dioxolane.

[0144] The mixture was allowed to stir at room temperature and 1.82 mL of aqueous HCl (37 wt%) (0.81 g HCl, 22 mmol, 13 mol%) was carefully added to the reaction vessel. The mixture was then allowed to stir at 90°C and the progress of the reaction was followed by NMR analysis.

[0145] After stirring at 90°C for two days, the mixture was allowed to cool to room temperature and an aqueous solution of NaOH (1 M) was carefully added to the reaction crude with stirring until the pH was greater than 11.

[0146] The product was then extracted with diethyl ether and the organic phase was washed several times with 0.5 M NaOH solution.

[0147] The organic phase was dried over MgSO4, filtered and the solvent removed under vacuum to provide 87 g of crude material. The product mixture at this stage contained approximately 41 mol% of the methylened keto-amine byproduct, which was converted to the keto-diamine according to the procedure described below:

[0148] To the crude material in a 500 mL round bottom flask equipped with a mechanical stirrer, condenser, temperature probe and heater was added 150 mL of aqueous dimethylamine solution (40 wt %). The resulting mixture was stirred at 40°C overnight.

[0149] NMR analysis showed complete conversion of the methylened keto-amine byproduct to the desired keto-diamine.

[0150] The product was extracted using diethyl ether and the organic phase was washed several times with brine followed by aqueous NaOH (0.5 M) solution.

[0151] The organic phase was dried over MgSO4 and filtered.After evaporation of the solvent, 82.5 g of crude material were recovered.

[0152] NMR analysis showed that the mixture contained 71 mol % of keto-diamine and 14 mol % of keto-monoamine (6 mol % of methylened keto-diamine by-product was also present).

[0153] Protonation of a mixture of ketoamine compounds

[0154] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0155] In a 500 mL round bottom flask equipped with a condenser, mechanical stirrer and temperature probe, add

[0156] -65mL of water

[0157] - 4.9 g of aqueous HCl (37 wt%) (0.050 mol).

[0158] The solution was allowed to stir at 0°C and the keto-amine mixture (15.04 g, 4.4 mmol of mono-amine, 22.6 mmol of di-amine, 1.82 mmol of methylenediamine, 1 eq) was gradually added to the reaction vessel. An additional 100 mL of water was added to reduce the solution viscosity.

[0159] The mixture was stirred at room temperature during 18 h, and after completion of the reaction the water was removed by lyophilization to afford a mixture of ammonium salts as a fine white powder (quantitative yield).

[0160] Example 3 - Synthesis of compounds having formula I''

[0161] A keto-amine mixture enriched in compounds having formula I" was synthesized according to the protocol described in Example 2.

[0162] The mixture obtained had the following composition:

[0163] -71 mol% keto-diamine

[0164] -14 mol% keto-monoamine

[0165] - 6 mol % of methylened keto-diamine.

[0166] Under an inert argon atmosphere, add 2% NH4OH to a 500 mL round-bottom flask equipped with a magnetic stirrer, a heater and a temperature probe.

[0167] - 73.97 g of a keto-amine mixture having the above composition (111 mmol of diamine, 22 mmol of mono-amine, 9 mmol of methylenediamine), and

[0168] -125mL of isopropyl alcohol.

[0169] The mixture was allowed to cool to 10 °C and citric acid (23.46 g, 122 mmol) was gradually added to the reaction vessel.

[0170] At the end of the addition, the mixture was allowed to stir at room temperature overnight and the isopropanol was removed under vacuum to afford the crude material as an orange paste. The crude product at this stage contained some amount of dimethylammonium salts which were removed as described below.

[0171] The crude residue was redissolved in diethyl ether containing 3 vol% of isopropanol and the formed precipitate was removed by filtration.The filtrate was then washed twice with an aqueous solution of sodium citrate (0.5 M) (previously formed by neutralizing citric acid with one equivalent of NaOH).

[0172] The organic phase was then evaporated to provide 59.91 g of the quaternary ketone-ammonium compound as a beige powder. Yield: 66%

[0173] NMR data

[0174] 1 H NMR (CDCl3-MeOD , 400MHz) δ(ppm): 3.88-3.70(m,2H),3.55-3.40(m,2H),3.49(s,3H),3.26(s,3H),3.02-2.88(m,2H),2.81 (d,J=15.6Hz,2H),2.73(d,J=15.6Hz,2H),1.92-1.72(m,2H),1.45-1.00(m,50H),0.86(t,J=6.8Hz,6H).

[0175] 13 C NMR (CDCl3-MeOD, 101MHz) δ (ppm): 204.17,178.25,173.60,72.42,66.74,56.13,48.33,43.82,31 .79,29.60,29.52,29.50,29.43,29.26,29.21,26.65,26.62,25.70,25.59,22.50,13.59(terminal CH3).

[0176] Example 4 - Evaluation of the adsorption properties of nanocellulose crystals

[0177] 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 surfactants required to produce aggregation of negatively charged cellulose nanocrystals (CNCs) in suspension in aqueous media. Comparison of aggregate size can be monitored by dynamic light scattering (DLS).

[0178] According to the protocol described in the literature (reference: EKOikonomou et al., J. Phys. Chem. B, 2017, 121 (10), pp. 2299-2307), the adsorption characteristics of quaternary ammonium were studied by monitoring the ratio X = [surfactant] / [CNC] or the mass fraction M = [surfactant] / ([surfactant] + [CNC]) required to induce aggregation of cellulose nanocrystals in aqueous solution at a fixed [surfactant] + [CNC] = 0.01 wt%.

[0179] The range of CNC aggregation corresponds to the range of ratio X (or M) that triggers aggregation of CNCs, ie the range of aggregate size measured by DLS above that of pure aqueous solution of CNCs or aqueous solution of surfactant at 0.01 wt%.

[0180] The ranges of X and M for CNC aggregation are summarized in Table 1 (the CNCs used for these measurements had an average diameter of 104.6 + / - 4.8 nm and a polydispersity index of 0.20). The lower the range of aggregation X or M, the better the adsorption characteristics on negatively charged surfaces.

[0181] Table 1

[0182]

[0183]

[0184] TEP was used as a comparison. TEP is a benchmark commercially available surfactant.

[0185] The data show that compared with commercially available surfactants Compared with TEP, the compounds according to the present invention (Examples 1 to 3) have better surfactant properties and produce aggregation at lower surfactant concentrations.

[0186] Example 5 - Determination of Biodegradability

[0187] The biodegradability of the test substances has been measured according to the 301 F OECD protocol.

[0188] In a sealed flask (Oxitop TM A measured volume of inoculated mineral medium containing a known concentration of the test substance in order to reach about 50 to 100 mg ThOD / l (theoretical oxygen demand) as a nominal sole source of organic carbon was stirred in a respirometry flask at a constant temperature (20°C ± 2°C) for up to 28 days. TMRespirometry flasks To obtain the biodegradability of the test samples: Sealed culture BOD flasks were used at a temperature of 20 ± 2°C during 28 days.

[0189] The released carbon dioxide is absorbed by the sodium hydroxide or potassium hydroxide granules present in the headspace of the bottle. The amount of oxygen absorbed by the microbial population during the biodegradation process (biooxidation of the test substance) (= oxygen consumption expressed in mg / l) reduces the pressure of the headspace (ΔP measured by a pressure switch) and is mathematically converted in mg consumed O2 / liter. The inoculum corresponds to urban activated sludge washed in a 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 has been tested in one bottle (a nominal concentration of 129 mg / l corresponding to 100 mg ThOD / l) in order to check the viability of the inoculum. The toxicity control corresponds to a mixture of reference substance and test substance; it will check whether the test substance is toxic to the inoculum (if so, the test must be repeated with a lower test substance concentration, if feasible with regard to the sensitivity of the method).

[0190] Since the substances of the invention are not very soluble in water for most of them (if some are soluble in water, their metabolites containing alkyl chains after hydrolysis generally have very low solubility in water), we use a specific protocol called "emulsion protocol". This protocol allows us to increase the bioavailability of poorly water-soluble substances in the aqueous phase of our inoculum.

[0191] The emulsion protocol involved adding the test substances to the bottles via stock solutions prepared in emulsion.

[0192] The emulsion is dissolved in a non-biodegradable surfactant (1g / l A 50 / 50 v / v mixture of a stock solution of the test substance in ELISA PE 105) and then mixed with mineral silicone oil AR 20 (Sigma).

[0193] The first dissolution of the test substance in the non-biodegradable surfactant solution usually requires stirring with a magnetic stirrer followed by sonication.

[0194] Once dissolution is complete, we mix the aqueous solution with mineral silicone oil in a 50 / 50 v / v ratio. The emulsion is maintained by stirring with a magnetic stirrer and samples are taken for addition in the corresponding bottles in order to reach the desired test substance concentration.

[0195] Two emulsion controls were run in parallel during the test in order to remove their values ​​from the emulsion bottles containing the test substances added via the emulsion stock solution.

[0196] The results of the biodegradability tests are summarized in Table 2.

[0197] Compounds of Biodegradability after 28 days Example 1 51%(OECD 301F) Example 2 30% (OECD 301F)

[0198] The results showed that among the compounds used in the working examples, the compound of Example 1 had the best biodegradability.

[0199] Overall, the compounds according to the invention generally show a good combination of surfactant properties combined with fair to good biodegradability - a combination that in many cases cannot be achieved by commercially available cationic surfactants.

[0200] Since the compounds of the present invention are also easily obtainable starting from lactones which are readily obtainable from fatty acids or fatty acid derivatives, the compounds of the present invention also offer economic advantages over the prior art compounds.

Claims

1. An ionic compound selected from the group consisting of formula (I') and (I") Where R and R', which may be the same or different at each occurrence, are C8-C 20 Alkyl groups, R 1 and R 2 , which may be the same or different, are hydrogen or a C1 to C4 alkyl group.

2. The compound according to claim 1, wherein R 1 and R 2 is a C1 to C4 alkyl group.

3. The compound according to claim 2, wherein R 1 and R 2 It's methyl.

4. The compound according to claim 1, wherein R and R' have from 10 to 16 carbon atoms.

5. A mixture comprising a first ionic compound of the formula (I') according to claim 1, and a second ionic compound of the formula (I") according to claim 1.

6. The mixture according to claim 5, wherein The molar ratio of these two compounds is in the range from 90:10 to 10:

90.

7. An electrically neutral compound having the general formula (IV) in Selected from the general formula (I') and (I") Where R and R', which may be the same or different at each occurrence, are C8-C 20 Alkyl groups, Where R 1 and R 2 , which may be the same or different, are hydrogen or a C1 to C4 alkyl group, W is an anion or anionic group carrying w negative charges, and r is the number of charges carried by formula (I') or (I").

8. Use of the ionic compound according to any one of claims 1 to 4, or the mixture according to any one of claims 5 to 6, or the electrically neutral compound according to claim 7 as a surfactant.

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