New quaternary ammonium compounds

Abstract

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

Description

[0001] Citation of related applications: This application claims priority from European application No. 19305787.4 filed on June 19, 2019, the entire contents of which are incorporated herein by reference for all purposes.

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

[0003] Fatty quaternary ammonium compounds which have surfactant properties and can be used for corresponding applications have already 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 R4 and R5 are independently selected from C 12 to C 22 The sum of the chain lengths of the alkyl or alkenyl radicals, R4 and R5 is preferably at least 30. Since the compounds are derived from Guerbet alcohols, the number of carbon atoms in the radicals R4 and R5 always differs by 2.

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

[0008]

[0009] where R 1-2 Is a straight chain or branched chain C 36 -C 44 alkyl or alkenyl group, R2 to R4 are C1-C5 alkyl or hydroxyalkyl groups, Y is a linear or branched C2-C4 alkylene group, m is a number from 0 to 20 and n is an integer from 1 to 6. 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] Although fatty quaternary ammonium compounds are widely used as surfactants, there is still a need for compounds of this type which 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. An improvement in biodegradability should not negatively impact surfactant properties.

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

[0014] This object is achieved with the compounds of formula (I). Preferred embodiments of the present invention are also described in detail below.

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

[0016]

[0017] wherein A is a tetravalent linking group selected from the group consisting of A-1 to A-6,

[0018]

[0019] Q1 to Q4 may be the same as or different from each other and are selected from the group consisting of hydrogen, R and X,

[0020] where R, which may be the same or different at each occurrence, is C5-C 27 Aliphatic groups, preferably C6 to C 24 aliphatic groups,

[0021] m, m', m", and m'" may be the same or different at each occurrence and are 0, 1, 2, or 3,

[0022] k, k', k", k'' and k"', which may be the same or different, are 0, 1, 2 or 3, and

[0023] X, which may be the same or different at each occurrence, is represented by Formula II

[0024]

[0025] in

[0026] Z1, Z2 and Z3, which may be the same or different, are O, S or NH,

[0027] Y is a divalent C1-C6 aliphatic group,

[0028] R', R" and R'", which may be the same or different, are hydrogen or a C1 to C4 alkyl group,

[0029] n and n' are 0 or 1, where the sum of n + n' is 1 or 2,

[0030] wherein at least one of the groups Q1 to Q4 is represented by X, and at least two of the groups Q1 to Q4 are represented by R, which may be the same or different at each occurrence, and

[0031] Wherein, if the ionic compound is such that: (i) A is represented by A-6, wherein m, m', m", and m'" are equal to 0, (ii) one and only one of Q1 to Q4 is represented by a substituent X and n in the substituent X is equal to 0, and (iii) two and only two of Q1 to Q4 are represented by a substituent R, then the difference in the number of carbon atoms of the two substituents R is 0, 1, 3, or greater than 3.

[0032] m, m', m", m'" may be the same or different at each occurrence, and are preferably 0, 1, or 2, and even more preferably 0 or 1.

[0033] k, k', k'" and k"', may be the same or different, and are preferably 0, 1 or 2, and even more preferably 0 or 1.

[0034] The novel compounds according to the invention are quaternary ammonium derivatives and comprise a tetravalent linker A and four substituents Q1 to Q4 which may be identical or different from one another on each occurrence. At least two of Q1 to Q4 are radicals R, i.e. aliphatic radicals containing from 5 to 27, preferably from 6 to 24, carbon atoms.

[0035] The aliphatic group R may be free of any double bonds and any triple bonds. Alternatively, the aliphatic group R may contain at least one —C═C— double bond and / or at least one —C≡C— triple bond.

[0036] The aliphatic radical R is advantageously chosen from alkyl radicals, alkenyl radicals, alkadienyl radicals, alktrienyl radicals and alkynyl radicals.

[0037] The aliphatic group R may be straight-chain or branched.

[0038] Preferably, the aliphatic groups R are independently selected from alkyl and alkenyl groups.

[0039] More preferably, the aliphatic groups R are independently selected from alkyl and alkenyl groups, typically selected from C6-C 24 Alkyl and C6-C 24 Alkenyl groups, very often selected from C6-C 21 Alkyl and C6-C 21 Alkenyl groups, and are often selected from (i) C6-C 19 Alkyl and C6-C 19 Alkenyl group or selected from (ii) C6-C 17Alkyl and C6-C 17 More preferably, R represents an alkyl group, typically a C6-C 24 Alkyl groups, very often representing C6-C 21 Alkyl groups, often representing C6-C 19 Alkyl group or C6-C 17 Alkyl groups. Aliphatic groups, in particular alkyl groups, having 10 to 20, preferably 11 to 17 or 10 to 17, carbon atoms have been found to be advantageous in certain cases.

[0040] As preferred examples of the substituent R, a non-cyclic aliphatic group, more preferably a straight-chain aliphatic group, still more preferably a straight-chain alkyl group can be mentioned.

[0041] The number of carbon atoms of R may be an even number or an odd number, and each group R may have the same number of carbon atoms, or the number of carbon atoms of different groups R may be different.

[0042] If A is represented by A-6, wherein m, m', m", and m'" are equal to 0, (ii) one and only one of Q1 to Q4 is represented by a substituent X and n in the substituent X is equal to 0, and (iii) two and only two of Q1 to Q4 are represented by a substituent R, then the difference in the number of carbon atoms of the two substituents R is 0, 1, 3 or greater.

[0043] In the ionic compound of the present invention, at least one of the substituents Q1 to Q4 is represented by a group X represented by the above formula (II).

[0044] In group X, preferably at least one, more preferably at least two and most preferably all three of the substituents Z1, Z2 and Z3 are oxygen. Compounds in which all three substituents Z1, Z2 and Z3 are oxygen are ester (n+n' is 1) or carbonate (n+n' is 2) derivatives.

[0045] n and n′ may be 0 or 1 and the sum of n and n′ is at least 1, preferably 1 or 2.

[0046] R', R" and R'" may be the same or different, and are preferably hydrogen or a C1 to C4 alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group. Preferably at least one, more preferably at least two, more preferably all three of R', R" and R'" are C1 to C4 alkyl groups, preferably a methyl group or an ethyl group, most preferably a methyl group.

[0047] Y is preferably an acyclic divalent aliphatic group, more preferably a linear divalent aliphatic group, still more preferably a linear alkanediyl (alkylene) group and preferably has 1 to 6, even more preferably 1 to 4 carbon atoms. In compounds where n' is 1, the aliphatic group Y preferably has at least two carbon atoms, in particular 2 to 6 carbon atoms.

[0048] According to another preferred embodiment, the compounds of the invention contain one or two radicals X and two and only two radicals R.

[0049] In a first group of preferred compounds of the present invention, A is represented by A-6, m, m', m" and m'" are 0, Z1 to Z3 are O, and the compound contains two groups R and one group X. In a preferred subgroup of this embodiment, n is 0 and n' is 1 or n is 1.

[0050] In a second group of preferred compounds, A is represented by A-3 or A-4, m, m', m", m'" and k'" are 0 and two of the substituents Q1 to Q4 are represented by a group X, wherein the two Xs are attached to the same carbon atom of the linker A and the two groups R are attached to the same or different carbon atoms of the linker A.

[0051] In a third group of preferred compounds, A is represented by A-1, m and m' are 1, m" and m'" are 0, k is 0 and the two substituents Q1 to Q4 are represented by groups X, wherein the two groups X are attached to -(CH2) which is directly attached to the nitrogen atom of the linker A. m - and -(CH2) m '-group.

[0052] In a fourth group of preferred compounds, A is represented by A-2, k' is 0, k" is 1, m is 1, m', m" and m"' are 0, and two of the substituents Q1 to Q4 are represented by groups X attached to two adjacent carbon atoms of the linker A; in other words, one first group X is attached to a first carbon atom of the linker A and the other group X is attached to the other carbon of the linker A, and the first carbon atom of the linker A and the other carbon atom of the linker A are adjacent to each other.

[0053] In a fifth group of preferred compounds, A is represented by A-5, m, m', m", m'" and k"" are 0, two of the substituents Q1 to Q4 are X, wherein each methine group of the linker A carries one group X and one group R, wherein X and R may be the same or different at each occurrence. In a preferred subgroup of this embodiment, n is 1, n' is 0, Z2 is O and Y is CH2. In a very preferred subgroup of this embodiment, n is 1, n' is 0, Z1 and Z2 are O and Y is CH2.

[0054] The compounds of the following formulae (IV) to (IX) represent a group of particularly preferred compounds according to the present invention.

[0055]

[0056]

[0057] Where s and s', which may be the same or different, are 0, 1, 2 or 3,

[0058]

[0059] R, R', R", R'" and Y in formulae (IV) to (IX) have the same meanings as defined above for formula (I).

[0060] Compounds of formula (X) and (XI), of which compounds of formula (VIII) and (IX), respectively, represent subsets, are also very preferred:

[0061]

[0062] R, R', R", R'" and Y in formulae (X) and (XI) have the same meanings as defined above for formula (I).

[0063] Another embodiment of the present invention relates to an electrically neutral compound of formula (III)

[0064]

[0065] wherein A, Q1 to Q4 are as defined and described above, W is an anion or anionic group having w negative charges, and r is the number of substituents Q1 to Q4 represented by the group X. 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 - ) or an organic carboxylate anion such as acetate, propionate, benzoate, tartrate, citrate, lactate, maleate or succinate.

[0066] The compounds according to the present invention can be obtained by a variety of different methods. A preferred method for producing the compounds of the present invention comprises the reaction of a lactone of the formula RC(=O)-R, which can preferably be obtained by decarboxylation of a fatty acid, a fatty acid derivative, or a mixture thereof. A suitable method for producing lactones according to this route is disclosed in US 2018 / 0093936, and further details are provided in that patent.

[0067] The synthesis of various compounds of the present invention using the obtainable lactones as indicated above as starting materials will now be described. The process variants described hereinafter illustrate the synthesis of specific compounds, and the skilled person will modify the reactants and reaction conditions to produce other compounds according to the present invention based on their expertise and taking into account the specific target product of the respective synthesis.

[0068] The synthesis of compounds wherein A is A-6 is exemplified by compounds of formula (IV) wherein J is J1.

[0069] In a first exemplary method, the ketone RC(=O)-R is first reacted with hydrogen (hydrogenation) to provide a secondary alcohol. This alcohol is then reacted with carbon monoxide via a carbonylation reaction. The carbonylation product, a carboxylic acid, is then subjected to an esterification reaction with a quaternary ammonium salt (e.g., choline chloride), thereby separating water and obtaining the desired compound of formula (IV). Alternatively, the carboxylic acid can first be condensed with an amino alcohol (e.g., dimethylaminoethanol) via an esterification reaction (with the release of water), and the resulting amino ester can be quaternized with an alkylating agent.

[0070] The reaction scheme of the aforementioned steps is as follows:

[0071]

[0072] wherein L' is a monovalent leaving group such as, for example, a halide anion (particularly a chloride anion) or a methylsulfate group.

[0073] The first step in the above reaction scheme comprises that the lactone is reduced to a secondary alcohol. This step is followed by a second conversion consisting of the insertion of carbon monoxide (carbonyl group) to produce carboxylic acid. Hydrogenation and the carbonylation reaction of this general reaction sequence carried out with active hydrogen and carbon monoxide respectively in the presence of a suitable catalyst are known to the technician and have been described in the literature. The technician will consider the desired target compound based on its professional knowledge and select suitable catalyst and reaction conditions, so there is no need to provide further details at this point.

[0074] An alternative route to compounds of formula (IV) includes a hydrocyanation step and consists of the following sequence: HCN is added to a ketone to provide a hydroxynitrile intermediate. The hydroxynitrile is then dehydrated and hydrogenated in one step to provide a nitrile intermediate. The nitrile is then hydrated to provide a carboxylic acid intermediate. The carboxylic acid can be converted to the desired quaternary compound in the same manner as described above. The reaction scheme for the aforementioned sequence of steps is as follows:

[0075]

[0076] wherein L' is as defined above.

[0077] As for the aforementioned reaction sequence, the individual reaction steps of this sequence have been described in the literature and are known to the skilled person. The skilled person will select suitable catalysts and reaction conditions based on his or her professional knowledge taking into account the desired target compound, so that no further details need to be given here.

[0078] Synthesis of compounds wherein A is A-6 and J is J3

[0079] Compounds of this type can be obtained by a sequence of steps comprising hydrogenation of a lactone to a secondary alcohol, followed by a transcarbonate reaction involving dimethyl carbonate and the secondary alcohol thus obtained. A second transcarbonate reaction with dimethylaminoethanol followed by quaternization gives the desired product.

[0080] In the first step, the hydrogenation of the lactone to the secondary alcohol can be carried out in an autoclave preferably equipped with a stirring device (such as, for example, a Rushton turbine) without the addition of any solvent. The lactone and a suitable catalyst (such as palladium or ruthenium metal / carbon) are introduced into a reactor, which is then sealed. The reactor is then preferably purged with hydrogen. The temperature is then raised to a temperature higher than the melting point of the ketone (the temperature is generally in the range of 80°C to 120°C) and the mixture is stirred. The temperature is then raised to approximately 120°C to 180°C (preferably approximately 150°C) and the mixture is stirred at this elevated temperature while maintaining a superatmospheric hydrogen pressure (10 to 80 bar) until the reaction is complete.

[0081] At the end of the reaction, the mixture is allowed to cool to a temperature slightly above the melting point of the alcohol, the pressure is released and the catalyst can be filtered to obtain the secondary alcohol:

[0082]

[0083] In a subsequent step, the secondary alcohol is carbonated to obtain a carbonate derivative. This step can be carried out, for example, in the presence of an excess of dialkyl carbonate Alk 1 -OC(=O)-O-Alk 2 In which Alk 1 and Alk 2 The dialkyl carbonates are preferably dimethyl carbonate (DMC), wherein Alk 1 and Alk 2 Instead of the dialkyl carbonates described above, carbonation can be achieved using carbonates with one or more aromatic groups (hereinafter, "aromatic carbonates"); such carbonates generally conform to the formula Hyd 1-OC(=O)-O-Hyd 2 , where Hyd 1 and Hyd 2 Represent C1-C independently of each other 18 Hydrocarbon, the premise is Hyd 1 and Hyd 2 At least one (possibly both) of the two is an aromatic group; Hyd 1 and Hyd 2 can be notably selected from alkyl groups having 1 to 8 carbon atoms, phenyl groups and phenyl groups substituted by at least one alkyl group having 1 to 4 carbon atoms, with the proviso that Hyd 1 and Hyd 2 At least one of the phenyl groups is optionally substituted. Of particular interest are compounds of the formula Hyd 1 -OC(=O)-O-Hyd 2 The carbonate is diphenyl carbonate.

[0084] The reaction can be carried out by heating a mixture of secondary alcohol in dialkyl carbonate or aromatic hydrocarbon group in the presence of a catalyst at a temperature preferably between 50° C. and 250° C. Aliphatic or aromatic alcohol produced as a by-product during the reaction can be distilled off during the reaction.

[0085] At the end of the reaction, the dialkyl carbonate or aromatic dihydrocarbyl carbonate can be evaporated and the residue can be used as such in a second trans-carbonation reaction with a dialkylaminoethanol.

[0086] The reaction steps are shown in the following reaction scheme:

[0087]

[0088] In the next step of the exemplary method, the secondary alcohol-derived carbonate obtained as described above is reacted with a dialkylaminoethanol of the formula HO-CH2-CH2-NR'R" (e.g., preferably dimethylaminoethanol, DMAE) according to the following reaction:

[0089]

[0090] This second trans-carbonation can use for example NaOMe as catalyst (for example from previous step) in suitable solvent (for example toluene) to carry out.Usually the mixture of initial asymmetric carbonate alkyl ester or carbonate aromatic hydrocarbon secondary alkyl ester, dialkylaminoethanol and catalyst in toluene is heated to about 120 ℃.During the reaction, the aliphatic or aromatic alcohol (for example by distillation) that forms should be removed.When the reaction finishes, usually wash organic phase with water to remove catalyst and unreacted dialkylaminoethanol and by solvent evaporation.Resistates is redissolved in suitable solvent (for example ethanol) to precipitate out the fatty carbonate dialkyl ester that may form.After filtration, product is obtained after solvent evaporation.

[0091] In a final step, the product obtained in the above described step is subjected to an alkylation with an alkylating agent of the general formula R"'-L", wherein L" is a monovalent anion or anionic group such as, for example, methylsulfate, preferably a dialkylsulfate, even more preferably dimethylsulfate (DMS), to obtain the desired quaternary ammonium derivative according to the invention:

[0092]

[0093] To one equivalent of a dialkyl sulfate (e.g., DMS) in a suitable solvent (e.g., methanol) is gradually added a concentrated solution of a carbonate-amine in the same solvent under stirring at room temperature at a rate that avoids a significant temperature increase due to the reaction exotherm. After the addition is complete, the mixture is allowed to stir at room temperature (e.g., one hour) and the volatiles (solvent) are removed under vacuum to provide the final product, which is typically a white wax.

[0094] The skilled person will select appropriate reaction conditions and reactants for the process steps described above based on his expert knowledge and taking into account the desired end product, so that no details need to be given here.

[0095] The synthesis of compounds wherein A is A-3 or A-4, which exemplarily shows compounds of formula (V) or (VI):

[0096] In the first step, the lactone is subjected to a condensation reaction with a dialkyl malonate (e.g. dimethyl malonate) in the presence of a catalyst in an organic solvent at a temperature ranging from 110° C. to 250° C., preferably from 125° C. to 175° C., even more preferably about 140° C. A suitable and preferred solvent for this reaction is xylene, and a preferred catalyst is potassium tert-butoxide, the amount of which is generally in the range of from 2 to 10 mol %, preferably from 3 to 8 mol %, based on the molar amount of the lactone.

[0097] A lactone (e.g., as described in US 2018 / 093936), a dialkyl malonate (e.g., dimethyl malonate), and a catalyst are dissolved in a solvent (e.g., xylene) and reacted at an elevated temperature (e.g., about 140° C.) for a period of typically 1 to 72 hours. The water produced as a by-product can be removed by azeotropic distillation. At the end of the reaction, the reaction medium is then typically cooled to room temperature and the organic phase is washed with water to remove the catalyst.

[0098] The volatiles are then distilled off and the crude product is purified by redissolving the resulting oil in a suitable solvent (e.g., ethanol), allowing precipitation of heavier by-products such as ketalization / crotonylation adducts and remaining starting ketone. After filtration, the filtrate can be evaporated (to remove the solvent) to provide the desired adduct.

[0099] The reaction scheme for this first step is given below:

[0100]

[0101] Among them Alk 3 and Alk 4 and R and R may be the same or different and represent an alkyl group having 1 to 6 carbon atoms.

[0102] The product obtained in the first step can then be subjected to transesterification with a dialkylaminoethanol (e.g. dimethylaminoethanol). A suitable catalyst for this reaction step is dibutyltin oxide (generally in an amount of 2 to 10, preferably 3 to 8 mol % relative to the malonate adduct obtained in the first step), and a suitable solvent for the first step is xylene. The reaction temperature is again preferably in the range of from 110° C. to 170° C. and even more preferably around 140° C.

[0103] The malonate adduct obtained in the first step is dissolved in a solvent (e.g., xylene), an excess of dialkylethanolamine (from 100% to 500% excess based on stoichiometry) is added to the solution, followed by the addition of the catalyst. The mixture is then stirred at a temperature preferably in the range of 110° C. to 170° C., preferably approximately 140° C., and the alcohol formed is distilled from the reaction medium. After the reaction is complete, the organic phase is washed with water to remove excess dialkylaminoethanol, and the xylene is distilled off to provide the crude esteramine.

[0104] This second step can be represented by the following reaction scheme:

[0105]

[0106] In the third step, the esteramine obtained in the second step can be alkylated with an alkylating agent of the general formula R"'-L", wherein L" is a monovalent anion or anionic group (such as, for example, methyl sulfate), preferably a dialkyl sulfate, even more preferably dimethyl sulfate (DMS), to obtain the target quaternary ammonium compound of the present invention.

[0107] To an appropriate amount of alkylating agent in a suitable solvent, a concentrated solution of the esteramine 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.

[0108] After the addition is complete, the mixture is allowed to stir at room temperature (typically 15-30°C) and the volatiles (mainly solvent and traces of alkylating agent such as DMS) are removed under vacuum to afford the final product as a white wax.

[0109] The reaction scheme of step 3 can be depicted as follows (using methanol as solvent):

[0110]

[0111] The wedge-shaped bond shown on the right is a manifestation of the fact that the reaction product is a mixture of three isomers derived from the structure in the reaction scheme of the first step.

[0112] The skilled person will modify the aforementioned exemplary methods appropriately based on their expertise to obtain other compounds of formula (V) and (VI). They will select suitable reactants for reaction with the lactone and change the reaction conditions as needed for other reactant / lactone combinations.

[0113] The skilled person will adopt the reaction conditions based on his expert knowledge and taking into account the desired target compound.Such reaction steps have been described in the literature, so that no further details need to be given here.

[0114] Synthesis of compounds wherein A is A-1 as represented by formula (VII)

[0115] In the first step of this exemplary method, the lactone is subjected to reductive amination, for example, with hydrogen and ammonia according to the following reaction scheme:

[0116]

[0117] Reductive amination can be carried out in an autoclave using excess ammonia. The reactor is loaded with the ketone, ethanol (or another suitable solvent) as a solvent, and a suitable catalyst (e.g., Pt / C at a concentration of, for example, about 2 wt% relative to the ketone substrate). The reactor atmosphere is purged several times with high-pressure nitrogen. Ammonia is then added to the reactor and then hydrogen is added, and the temperature is raised to, for example, 120° C., while maintaining high pressure (e.g., 4 MPa) in the reactor. The reaction medium is stirred under these conditions until the reaction is complete.

[0118] The reaction product thus obtained is subsequently subjected to alkylation according to the following general scheme, as shown below for an alkyl chloroacetate as alkylating agent:

[0119]

[0120] Among them Alk 5 is an alkyl group having 1 to 6 carbon atoms.

[0121] The reaction can be preferably carried out using an alkyl chloroacetate (particularly preferably methyl chloroacetate) as the alkylating agent in a suitable solvent, or directly using the alkyl chloroacetate as the solvent (meaning an excess of reactant compared to the secondary alkylamine). A suitable base (e.g., sodium carbonate) should be used during the reaction to neutralize the HCl formed, and a catalyst (e.g., potassium iodide, KI) can optionally be used to accelerate the reaction. The mixture is then allowed to stir at a temperature ranging from 50°C to 250°C until the reaction is complete. At the end of the reaction, the salts are filtered out and the organic phase can be washed with water. The volatiles can then be removed under vacuum, and the crude product can then be used in the next step.

[0122] The crude product thus obtained can then be subjected to a transesterification reaction with a dialkylaminoethanol, for example dimethylaminoethanol (DMAE), optionally in the presence of a suitable catalyst as described above, according to the following reaction scheme:

[0123]

[0124] Reaction conditions can be selected as described above in the exemplary methods for synthesizing compounds wherein A is A-3 or A-4.

[0125] In the final step, the amine compound thus obtained is alkylated to obtain the desired compound according to the invention, as shown in the following reaction scheme for the alkylating agent R"'-L":

[0126]

[0127] The same conditions as described above for the methylation stage of compounds of formula (V) and (VI) may be employed.

[0128] Synthesis of compounds wherein A is represented by A-5 as exemplified by formulae (IX) and (XI)

[0129] The corresponding compounds can preferably be obtained by two methods. The first method starts with Piria ketonization, followed by hydrogenation, dehydration, epoxidation (to obtain epoxides), hydration (to obtain diols) and esterification (to obtain certain diesters). This is a multi-step process based on Piria technology. It has the advantages of being salt-free and relying on readily available chemical transformations.

[0130] As an alternative to the above sequence of reactions, it is possible to bypass the hydration step (ie diol formation) by converting the epoxide directly to the diester, provided that a suitable esterifying agent is used, as will be described in detail later.

[0131] The esterification step may be followed by an amine condensation step (as a final step) to convert the diester into a compound conforming to formula (IX) or (XI).

[0132] Finally, starting from the diols, it is also possible to obtain compounds according to formula (IX) or (XI) in one reaction step, ie to carry out the esterification and amine condensation in one step, provided that another suitable esterification is used, as will be described in detail later.

[0133] A first method for synthesizing a compound wherein A is represented by A-5 as exemplified by formulae (IX) and (XI)

[0134] Pyriadonization

[0135] The basic reaction in the first step is:

[0136]

[0137] This reaction has been fully described in U.S. Pat. No. 10,035,746, WO 2018 / 087179, and WO 2018 / 033607, and further details are found in these patents.

[0138] hydrogenation

[0139] The lactone is then subjected to hydrogenation, which can be carried out under standard conditions known to the skilled person for hydrogenation reactions:

[0140]

[0141] The hydrogenation reaction is carried out by contacting the acetone with hydrogen 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 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. Examples of suitable solvents include methanol, ethanol, isopropanol, butanol, THF, methyl-THF, hydrocarbons, water, or mixtures thereof. A suitable catalyst based on a transition metal should be used for the reaction. Examples of suitable catalysts include 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. Examples of suitable catalysts include Pd / C, Ru / C, Pd / Al2O3, Pt / C, Pt / Al2O3, Raney nickel, Raney cobalt, etc. At the end of the reaction, the desired alcohol can be recovered after appropriate post-treatment. The skilled person is aware of representative techniques and therefore does not need to provide further details here. The details of this method step can be found, for example, in U.S. Patent No. 10,035,746, referenced herein.

[0142] The skilled person will select suitable reaction conditions based on his professional experience and taking into account the specific target compound to be synthesized. Therefore, no further details need to be given here.

[0143] dehydration

[0144] In the next step, the alcohol thus obtained is subjected to a dehydration to obtain an internal olefin. This reaction can also be carried out under standard conditions known to the skilled person for corresponding dehydration reactions (e.g., U.S. Pat. No. 10,035,746, Example 4), so that no further details need to be given here:

[0145]

[0146] The dehydration reaction is carried out by heating the secondary alcohol in the presence of a suitable catalyst at a temperature ranging between 100° C. and 400° C. in a reaction zone. 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 in the absence of any added solvent. As examples of solvents, hydrocarbons, toluene, xylene or mixtures thereof can be mentioned. A catalyst must be used for the reaction. Suitable examples of catalysts are acidic (Lewis or Bronsted) catalysts, heterogeneous solid acid catalysts or homogeneous catalysts. As examples of heterogeneous catalysts, aluminum oxide (Al O), silicon dioxide (SiO), aluminosilicates (Al O -SiO) such as zeolites, phosphoric acid supported on silicon dioxide or aluminum oxide, acidic resins such as etc. Homogeneous catalysts may also be employed, and suitable acids include H2SO4, HCl, trifluoromethanesulfonic acid, p-toluenesulfonic acid, AlCl3, FeCl3, etc. The water produced during the reaction can be distilled from the reaction medium during the reaction. At the end of the reaction, the desired olefin can be recovered after appropriate post-treatment. Representative techniques are known to those skilled in the art and are described, for example, in U.S. Patent No. 10,035,746, so further details are not required here.

[0147] Epoxidation

[0148] The internal olefin can thereafter be oxidized to the corresponding epoxide, wherein the double bond is replaced by an epoxy group, according to the following scheme (wherein the reactants are merely examples of corresponding groups of compounds for the corresponding functional groups):

[0149]

[0150] wherein R** may be hydrogen or a hydrocarbon group which may be substituted and / or interrupted by heteroatoms or groups containing heteroatoms, or R** may be an acyl group of the general formula R***-C(=O)-, wherein R*** may have the same meaning as R**.

[0151] The epoxidation reaction is advantageously carried out by contacting the internal olefin with a suitable oxidizing agent in a reaction zone at a temperature generally ranging from 15°C to 250°C.

[0152] As suitable oxidizing agents, mention may be made of peroxide compounds such as hydrogen peroxide (H2O2) in the form of an aqueous solution, organic peroxides such as peracids of the general formula R****-CO3H (e.g., m-chloroperbenzoic acid, peracetic acid, etc.), hydrocarbon (e.g., alkyl) hydroperoxides of the general formula R****'-O2H (e.g., cyclohexyl hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide), wherein R**** in the peracid or R****' in the hydrocarbon (e.g., alkyl) hydroperoxide is a hydrocarbon group (e.g., an alkyl group) which may be substituted and / or interrupted by heteroatoms or groups containing heteroatoms.

[0153] 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 in the absence of any added solvent. As examples of suitable solvents, mention can be made of: CHCl , CH 2 Cl 2 , tert-butyl alcohol or a mixture thereof.

[0154] When H O is used as the oxidizing agent, the presence of an organic carboxylic acid during the reaction may be beneficial since it will generate a peracid compound in situ by reacting with H O. As examples of suitable carboxylic acids, there may be mentioned: formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, etc.

[0155] Catalysts may also be used to promote the reaction. Suitable catalysts are Lewis acids or Bronsted acids, and mention may be made of, for example: perchloric acid (HClO4), trifluoromethanesulfonic acid, heterogeneous titanium silicalite (TiO2-SiO2), heterogeneous acidic resins such as Resins, homogeneous organic metal complexes of manganese, titanium, vanadium, rhenium, tungsten, polyoxometalates, etc.

[0156] 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 be given here.

[0157] In style Among the epoxides, it has been found that R, which may be the same or different at each occurrence, generally represents C5-C 27 Aliphatic groups, those wherein R has at least 10 carbon atoms, and especially those wherein R has from 10 to 20 carbon atoms, are particularly advantageous for preparing compounds of formula (IX) and (XI) useful as surfactants, exhibiting an excellent balance of properties. However, such epoxides, which may be represented by formula (XII)

[0158]

[0159] where R f , can be the same or different each time it appears, indicating C 10 -C 27 Aliphatic groups are rarely disclosed in the literature and, to the best of the applicant's knowledge, these two rare disclosures are completely irrelevant to the technical field of the present invention, namely the synthesis of surfactants.

[0160] In US 3,974,224 (BAYER), it is taught that oxirane is prepared by reacting an oxirane compound of the general formula

[0161]

[0162] The reaction with hydrogen peroxide in the presence of a boron compound can be used to prepare an aldehyde compound. 1 and R 2Independently of one another (emphasis added), select from a wide list of chemical moieties as described in column 1, 1.52-61; some of the possible moieties are alkyl moieties, but in this case, C2-C6 alkyl groups are preferred over other higher alkyl groups. In the extensive list of specifically proposed oxirane compounds, only three oxiranes, namely 2,3-diondecyloxirane, 2,3-didodecanyloxirane and 2-hexadecyl-3-octadecyloxirane, conform to formula (XII). US '224 makes no mention of how to synthesize any of the listed oxiranes, including the three oxiranes conforming to formula (XII). Besides the fact that the disclosure of the above three oxiranes in US '224 is irrelevant to the present invention and appears to be incidental, it is precisely impossible to implement because US '223 does not provide any instructions on how to make these oxiranes.

[0163] Mori and Argade described in European Journal of Organic Chemistry, 1994, Vol. 7, pp. 695-700 the synthesis of (9Z,25S,26R,43Z)-25,26-epoxy-9,43-pentadecyldiene and its enantiomers, components of the nymph recognition pheromone produced by the nymphs of the gray cockroach (Nauphoeta cinerea), by carbon chain extension of (2S,3R)-4-acetoxy-2,3-epoxy-1-butanol. In this paper, four C 51 epoxides; all of which qualify as 2-tetracosenyl-3-pentacosenyloxirane or 25,26-epoxy-pentacosyldiene. This further disclosure of oxiranes conforming to formula (XII) is likewise unrelated to the present invention and appears to be incidental.

[0164] It was therefore a further object of the present invention to provide novel epoxy compounds which can be used to prepare quaternary ammonium compounds having good surfactant properties and good biodegradability.

[0165] This further object is achieved with the epoxy compounds described hereinafter under item A.1 ("invention A"):

[0166] - Item A.1: An epoxy compound of formula (XII)

[0167]

[0168] where R f , can be the same or different each time it appears, indicating C 10 -C 27 aliphatic groups,

[0169] The exception is 2-tetracosenyl-3-pentacosenyl oxirane.

[0170] Preferred and / or specific embodiments of the present invention A are set out below:

[0171] - Item A.2: Epoxides as described in Item A.1, except for 2,3-diondecyloxirane, 2,3-didodecanyloxirane and 2-hexadecyl-3-octadecyloxirane;

[0172] - Item A.3: An epoxy compound as described in Item A.1 or A.2, wherein each R f Contains at least 12 carbon atoms and at least one R f Contains at least 13 carbon atoms;

[0173] - Item A.4: An epoxy compound as described in Item A.3, wherein R f (i.e. each R f ) contains at least 14 carbon atoms;

[0174] - Item A.5: An epoxy compound as described in Item A.1, A.2, A.3 or A.4, wherein R f (i.e. each R f ) contains up to 24 carbon atoms;

[0175] - Item A.6: An epoxy compound as described in Item A.5, wherein R f Contains up to 20 carbon atoms;

[0176] - Item A.7: An epoxy compound as described in Item A.6, wherein R f Contains up to 17 carbon atoms;

[0177] - Item A.8: An epoxy compound as described in Item A.1 or A.2, wherein R f Containing from 10 to 20 carbon atoms;

[0178] - Item A.9: An epoxy compound as described in Item A.1 or A.2, wherein R f Containing from 11 to 17 carbon atoms;

[0179] - Item A.10: An epoxy compound as described in any one of Items A.1 to A.9, wherein both R f The total number of carbon atoms in the group is at least 30;

[0180] - Item A.11: An epoxy compound as described in any one of Items A.1 to A.10, wherein R f (i.e. each R f) does not contain any double bond and any triple bond;

[0181] - Item A.12: An epoxy compound as described in any one of Items A.1 to A.10, wherein R f selected from alkyl and alkenyl groups;

[0182] - Item A.13: An epoxy compound as described in Item A.12, wherein R f is an alkyl group;

[0183] - Item A.14: An epoxy compound as described in any one of Items A.1 to A.13, wherein R f It is a straight chain;

[0184] - Item A.15: An epoxy compound as described in Item A.1 or A.2, wherein R f is a straight-chain alkyl group having from 14 to 17 carbon atoms;

[0185] - Item A.16: An epoxy compound as described in any of Items A.1 to A.15, wherein one and only one R f has an odd number of carbon atoms and one and only one R f Have an even number of carbon atoms;

[0186] When two R f This can occur when both are derived from carboxylic acids with an even number of carbon atoms, and this can be advantageous from an economic point of view, since fatty carboxylic acids of natural origin

[0187] - which typically have this even number of carbon atoms - are widely available;

[0188] When two R f This can also occur when both are derived from carboxylic acids with an odd number of carbon atoms;

[0189] On the other hand, when one and only one R f Derived from a carboxylic acid having an even number of carbon atoms and one and only one R f When derived from a carboxylic acid having an odd number of carbon atoms, an epoxide compound as described in any one of items A.1 to A.15 is obtained, wherein either two R f All have an even number of carbon atoms or two R f have an odd number of carbon atoms; in practice, although carboxylic acids of different chain lengths generally have similar reactivities, two of the R f The first epoxide having an even number of carbon atoms and two of R f a mixture of second epoxides each having an odd number of carbon atoms;

[0190] - Item A.17: An epoxy compound as described in any of Items A.1 to A.15, wherein one and only one R f With an odd number of carbon atoms n O At the same time, another R f Has an even number of carbon atoms n E , where n E Equal to n O -1; this may occur when the epoxide is obtained from one and only one carboxylic acid having an even number of carbon atoms, and for the same reasons as above, this may also be advantageous from an economic point of view;

[0191] - Item A.18: An epoxy compound as described in any one of Items A.1 to A.15, wherein both R f The number of carbon atoms in a group is represented by the pair (n1, n2), where n1 is the first R f The number of carbon atoms in the group and n2 is the second R f The number of carbon atoms of the group, the pair (n1, n2) 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).

[0192] - Item A.19: An epoxy compound as described in Item A.18, wherein two R f The pair (n1, n2) of the number of carbon atoms of the group is selected from the following pairs: (14, 15), (16, 17), (14, 17) and (15, 16);

[0193] To obtain the epoxide according to item A.19, it is possible to start notably from the following carboxylic acids or mixtures of carboxylic acids: palmitic acid alone, stearic acid alone, oleic acid alone, palmitic acid in a blend with stearic acid or with oleic acid or with stearic acid and oleic acid, and stearic acid in a blend with oleic acid;

[0194] - Item A.20: An epoxide as described in any one of Items A.1 to A.19, which is a cis-epoxide of formula (XIIa)

[0195]

[0196] A mixture of a trans-epoxide of formula (XIIb)

[0197]

[0198] Such mixtures may notably result from the epoxidation of a mixture of cis-olefins and trans-olefins;

[0199] - Item A.21: An epoxide as described in any one of Items A.1 to A.19, which is a cis-epoxide of formula (XIIa)

[0200]

[0201] - Item A.22: An epoxide as described in any one of Items A.1 to A.19, which is a trans-epoxide of formula (XIIb)

[0202]

[0203] The cis-epoxides of item A.21 and the trans-epoxides of item A.22 can notably be obtained by separating them from a mixture of the cis-epoxides and trans-epoxides of item A.20 by any conventional separation means;

[0204] - Item A.23: A method for obtaining an epoxide as described in any one of Items A.1 to A.22, comprising reacting an olefin of the formula

[0205]

[0206] where R f , which may be the same or different at each occurrence, as previously described herein,

[0207] reaction with an oxidizing agent of the formula R**OOH, wherein R** is hydrogen or a hydrocarbon group which may be substituted and / or interrupted by heteroatoms or groups containing heteroatoms, or R** is an acyl group of the general formula R***-C(═O)-, wherein R*** has the same meaning as R**, to form an epoxide and a compound of the formula R**OH;

[0208] - Item A.24: A method as described in Item A.23, wherein the oxidizing agent is a peracid of the general formula R****-CO3H, wherein R**** is a hydrocarbon group which may be substituted and / or interrupted by heteroatoms or groups containing heteroatoms, such as peracetic acid;

[0209] - Item A.25: A method as described in item A.23, wherein the oxidizing agent is hydrogen peroxide;

[0210] - Item A.26: A process as described in Item A.25, wherein the olefin is reacted with hydrogen peroxide in the presence of an organic carboxylic acid such as acetic acid;

[0211] - Item A.27: A method as described in any one of items A.23 to A.26, comprising:

[0212] - Make the first carboxylic acid of the following formula

[0213]

[0214] undergoing a pyriacontination reaction with another carboxylic acid of the formula

[0215]

[0216] where R f , which may be the same or different in each carboxylic acid, as previously described herein,

[0217] The first carboxylic acid and the further carboxylic acid may thus be identical to or different from each other (when R f With another carboxylic acid in the formula R f -CH2- are the same, they are the same as each other),

[0218] In order to obtain the following formula of ketone

[0219]

[0220] where R f , which may be the same or different at each occurrence, as previously described herein;

[0221] - hydrogenation of the acetone with hydrogen to obtain methanol of the formula

[0222]

[0223] and

[0224] - dehydrating the methanol to obtain an olefin of the formula

[0225]

[0226] - Item A.28: Use of an epoxide as described in any one of items A.1 to A.22 for the manufacture of a surfactant;

[0227] - Item A.29: Use of an epoxide as described in any one of Items A.1 to A.22 or the use as described in Item A.28 for the manufacture of a compound of formula (XI)

[0228]

[0229] Wherein, in formula (XI), R, which may be the same or different at each occurrence, is equal to R f , R fhave the meanings as described above, and R', R", R'" and Y have the meanings as described above for formula (I);

[0230] - Item A.30: Use of an epoxide as described in any one of items A.1 to A.22 for the manufacture of a compound other than the compound of formula (XI) described above, for example for the manufacture of a polymer (possibly an oligomer) such as a polyether, or for the manufacture of a cyclic carbonate.

[0231] The epoxide can be used directly in the next step without further purification. This next step can be a hydration step (to form the diol followed by an esterification step) or a direct esterification step.

[0232] Epoxide hydration (diol formation)

[0233] The epoxide can then be hydrated to the corresponding diol according to the following scheme:

[0234]

[0235] The ring-opening reaction can be carried out by contacting the epoxide with water, usually in the presence of a suitable catalyst and usually at a temperature ranging from 15° C. to 150° C. As examples of catalysts, there may be mentioned Bronsted or Lewis acid catalysts such as: H 2 SO 4 , HCl, perchloric acid (HClO 4 ), trifluoromethanesulfonic acid, p-toluenesulfonic acid, heterogeneous acidic resins such as Resin, etc.

[0236] The reaction can be carried out in the presence of an optional solvent to facilitate the contact of the reagents, and mention can be made of: Me-THF, THF, DMSO, tert-butanol, methanol, ethanol, isopropanol, acetonitrile, or a mixture thereof. The reaction can also be carried out without any added solvent.

[0237] At the end of the reaction, the desired diol can be recovered after appropriate work-up, and the skilled person is aware of representative techniques, so that no further details need be given here.

[0238] In style Among the diols, it has likewise been found that R, which may be the same or different at each occurrence, generally represents C5-C 27 Aliphatic groups, those wherein R has at least 10 carbon atoms, and especially those wherein R has from 10 to 20 carbon atoms, are particularly advantageous for preparing compounds of formula (IX) and (XI) useful as surfactants, exhibiting an excellent balance of properties. However, such diols, which may be represented by formula (XIII)

[0239]

[0240] where R f , can be the same or different each time it appears, indicating C 10 -C 27 Aliphatic groups are rarely disclosed in the literature, and this little disclosure is completely irrelevant to the technical field of the present invention, namely the synthesis of surfactants.

[0241] The website of PubChem discloses several alkanediols that conform to formula (XIII). Except for some alkanediols that will be cited and reviewed later, the alkanediols of PubChem appear to be purely theoretical structures, and their properties are estimated by predictive models. As such alkanediols, the following alkanediols can be cited: docosane-11,12-diol, tricosane-11,12-diol, tetracosane-12,13-diol, pentacosane-12,13-diol, hexacosane-12,13-diol, heptacosane-11,12-diol, octacosane-12,13-diol, octacosane-14,15-diol, nonacosane-14,15-diol, triacontan-15,16-diol, undecane-15,16-diol, dotriacontan-14,15-diol, dotriacontan-15,16-diol. The invention relates to the invention of the present invention, which is characterized in that the diols are 1,2-diol, 1,4-diol, 1,6-diol, 1,8-diol, 2,1-diol, 2,2-diol, 3,-diol, 4,-diol, 5,-diol, 6,-diol, 7,-diol, 8,-diol, 9,-diol, 10,-diol, 11,-diol, 12,-diol, 13,-diol, 14,-diol, 15,-diol, 16,-diol, 17,-diol, 18,-diol, 20,-diol, 21,-diol, 22,-diol, 23, ...24,-diol, 25,-diol, 26,-diol, 27,-diol, 28,-diol, 29,-diol, 30,-diol, 31,-diol, 32,-diol, 33,-diol, 34,-diol, 35,-diol, 36,-diol, 37,-diol, 38,-diol, 39,-diol, 40,-diol,

[0242] Tornabene et al., Lipids, Vol. 6, No. 3, pp. 190-195 (1971), characterized the branched monounsaturated hydrocarbons of Sarcina lutea and Sarcina flava. Within the framework of this characterization, olefins were converted into trimethylsilyl ether (TMSE) derivatives; such TMSE derivatives were obtained by oxidation of the olefins with osmium tetroxide to form diol intermediates. These characterization efforts led to the identification of some C 23 -C 30Identification of branched olefins: branched 11-tricosene, branched 11-tetracosene, branched 12-tetracosene, branched 12-pentacosene, branched 12-hexacosene, branched 13-hexacosene, branched 12-heptacosene, branched 13-heptacosene, branched 13-octacosene, branched 14-octacosene, branched 14-nonacosene, and branched 15-triacontene. While this should not be construed as an admission by the applicant, it is possible to speculate that upon forming the TMSE derivatives useful for characterization, diol intermediates corresponding to the previously cited olefins were obtained. Furthermore, two GC peaks (designated peaks "a" and "b" in Table 1) are tentatively (with emphasis) attributed to linear 13-heptacosene and linear 14-nonacosene. The disclosure of Tornabene is not relevant to the present invention and would be incidental if considered relevant to the assessment of the novelty of the present invention.

[0243] Subramanian et al., Tetrahedron, Vol. 42, No. 14, pp. 3967-3972 (1986), describe a multistep process for the synthesis of 13-heptacosene. Heptacosane-13,14-diol, used as an intermediate in this synthesis, is obtained by first reducing the isopropylidene derivative of dimethyl-13,14-dihydroxyheptacosane-1,27-dioate with lithium aluminum hydride to give 1,13,14,27-tetrahydroxyheptacosane, followed by tosylation of the acetonide of the tetraol, reduction with Zn-NaI, and acid hydrolysis. This disclosure of a diol conforming to formula (XIII) is not relevant to the present invention and appears to be incidental.

[0244] KR20060060776 (Eung Ju Oh) describes the synthesis of poly[3,4-alkoxythiophene] and poly[3,4-ethylenedioxythiophene] useful in organic electronics applications. Docosane-11,12-diol is used in the synthesis of these polymers. This additional disclosure of a diol conforming to formula (XIII) is clearly unrelated to the present invention and appears to be incidental.

[0245] It was therefore a further object of the present invention to provide novel diols which can be used to prepare quaternary ammonium compounds having good surfactant properties and good biodegradability.

[0246] This further object is achieved with the diols described hereinafter under item B.1 ("invention B"):

[0247] - Item B.1: Diol of formula (XIII)

[0248]

[0249] where Rf , can be the same or different each time it appears, indicating C 10 -C 27 aliphatic groups,

[0250] Exceptions include docosane-11,12-diol and heptacosane-13,14-diol.

[0251] Preferred and / or specific embodiments of the present invention B are set out below:

[0252] - Item B.2: Diols as described in Item B.1, with the exception of branched tricosane-11,12-diol, branched tetracosane-11,12-diol, branched tetracosane-12,13-diol, branched pentacosane-12,13-diol, branched hexacosane-12,13-diol, branched hexacosane-13,14-diol, branched heptacosane-12,13-diol, branched heptacosane-13,14-diol, branched octacosane-13,14-diol, branched octacosane-14,15-diol, branched nonacosane-14,15-diol and branched triacontan-15,16-diol.

[0253] - Item B.3: The diols as described in Item B.2, wherein linear heptacosane-13,14-diol and linear nonacosane-14,15-diol are further excluded.

[0254] - Item B.4: diols as described in item B.1 or B.2 or B.3, with the further exception of the alkanediols listed in "Pubchem" as detailed above;

[0255] - Item B.5: A diol as described in any one of Items B.1 to B.4, wherein R f (i.e. each R f ) does not contain any double bond and any triple bond;

[0256] - Item B.6: A diol as described in any one of Items B.1 to B.4, wherein R f is an alkyl group;

[0257] - Item B.7: A diol as described in any one of Items B.1 to B.6, wherein R f It is a straight chain;

[0258] - Item B.8: A diol as described in any one of Items B.1 to B.7, wherein each R f Contains at least 12 carbon atoms and at least one R f Contains at least 13 carbon atoms;

[0259] - Item B.9: A diol as described in Item B.8, wherein R f (i.e. each R f ) contains at least 14 carbon atoms;

[0260] - Item B.10: A diol as described in any one of Items B.1 to B.9, wherein R f Contains up to 24 carbon atoms;

[0261] - Item B.11: A diol as described in Item B.10, wherein R f Contains up to 20 carbon atoms;

[0262] - Item B.12: A diol as described in Item B.11, wherein R f Contains up to 17 carbon atoms;

[0263] - Item B.13: A diol as described in any one of Items B.1 to B.7, wherein R f Containing from 10 to 20 carbon atoms;

[0264] - Item B.14: A diol as described in Item B.13, wherein R f Containing from 11 to 17 carbon atoms;

[0265] - Item B.15: A diol as described in any one of Items B.1 to B.14, wherein both R f The total number of carbon atoms in the group is at least 30;

[0266] - Item B.16: A diol as described in any one of Items B.1 to B.7, wherein R f is a straight-chain alkyl group having from 14 to 17 carbon atoms;

[0267] - Item B.17: A diol as described in any of Items B.1 to B.16, wherein one and only one R f has an odd number of carbon atoms and one and only one R f Has an even number of carbon atoms, probably C 33 Diol, C 41 Diol, C 45 Diol, C 47 Diol, C 49 Diol, C 51 Diol, C 53 diol or C 55 diols;

[0268] - Item B.18: A diol as described in any one of items B.1 to B.16, two R f All have an odd number of carbon atoms or two Rf All have an even number of carbon atoms, possibly C 44 Diol, C 46 Diol, C 48 Diol, C 50 Diol, C 52 Diol, C 54 diol or C 56 diols;

[0269] - Item B.19: A diol as described in any of items B.1 to B.16, wherein one and only one R f With an odd number of carbon atoms n O At the same time, another R f Has an even number of carbon atoms n E , where n E Equal to n O -1;

[0270] - Item B.20: A diol as described in any one of items B.1 to B.19 except B.18, wherein the two groups R f The number of carbon atoms is represented by the pair (n1,n2), where n1 is the first R f The number of carbon atoms in the group and n2 is the second R f The number of carbon atoms of the group, the pair (n1, n2) 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).

[0271] - Item B.21: A diol as described in Item B.20, wherein two groups R f The pair (n1, n2) of the number of carbon atoms is selected from the following pairs: (14, 15), (16, 17), (14, 17) and (15, 16);

[0272] - Item B.22: at least one kilogram of a package containing a diol as described in any one of items B.1 to B.21;

[0273] - Item B.23: A diol mixture comprising R having n3 and (n3-1) carbon atoms, respectively f The first diol is characterized by a group, and R has n4 and (n4-1) carbon atoms respectively. f The second diol is characterized by a group, and R has n3 and (n4-1) carbon atoms respectively. fThe third diol is characterized by a group and R having n4 and (n3-1) carbon atoms respectively. f a fourth diol characterized by a group wherein n3≤n4+2, and wherein the first diol, the second diol, the third diol, and the fourth diol are as described in any one of items B.1 to B.17 or item B.21;

[0274] - Item B.24: A method for obtaining a diol as described in any one of Items B.1 to B.21, comprising reacting an epoxide compound of the formula

[0275]

[0276] where R f , which may be identical or different at each occurrence, as described herein before within the framework of invention B,

[0277] reacts with water;

[0278] - Item B.25: A process as described in Item B.24, wherein the reaction is carried out in the presence of a Bronsted or Lewis catalyst;

[0279] - Item B.26: The method described in item B.24 or B.25, which comprises making an olefin of the formula

[0280]

[0281] where R f , which may be identical or different at each occurrence, as described herein before within the framework of invention B;

[0282] reaction with an oxidizing agent of the formula R**OOH, wherein R** is hydrogen or a hydrocarbon radical which may be substituted and / or interrupted by heteroatoms or groups containing heteroatoms, or R** is an acyl radical of the general formula R***-C(═O)-, wherein R*** has the same meaning as R**, to form a compound of the formula R**OH and an epoxide of the formula (XII) to be reacted with water;

[0283] - Item B.27: A process as described in Item B.26, wherein the oxidizing agent is a peracid of the general formula R****-CO3H, wherein R**** is a hydrocarbon group which may be substituted and / or interrupted by heteroatoms or groups containing heteroatoms, such as peracetic acid;

[0284] - Item B.28: A method as described in item B.26, wherein the oxidizing agent is hydrogen peroxide;

[0285] - Item B.29: A process as described in Item B.28, wherein the olefin is reacted with hydrogen peroxide in the presence of an organic carboxylic acid such as acetic acid

[0286] - Item B.30: A method as described in any of items B.26 to B.29, comprising:

[0287] - Make the first carboxylic acid of the following formula

[0288]

[0289] undergoing a pyriacontination reaction with another carboxylic acid of the formula

[0290]

[0291] where R f , which may be the same or different in each carboxylic acid, as previously described herein,

[0292] The first carboxylic acid and the further carboxylic acid may thus be identical to or different from each other (when R f With another carboxylic acid in the formula R f -CH2- are the same, they are the same as each other),

[0293] In order to obtain the following formula of ketone

[0294]

[0295] where R f , which may be the same or different at each occurrence, as previously described herein;

[0296] - hydrogenation of the acetone with hydrogen to obtain methanol of the formula

[0297]

[0298] and

[0299] - dehydrating the methanol to obtain an olefin of the formula

[0300]

[0301] - Item B.31: Use of a diol as described in any of items B.1 to B.21 or a diol mixture as described in item B.23 for the manufacture of a surfactant;

[0302] - Item B.32: Use of a diol as described in any one of Items B.1 to B.21 for the manufacture of a compound of formula (XI)

[0303]

[0304] Wherein, in formula (XI), R, which may be the same or different at each occurrence, is equal to R f , R fhave the meanings as described above, and R', R", R'" and Y have the meanings as described above for formula (I);

[0305] - Item B.33: Use of a diol as described in any one of items B.1 to B.21 for the manufacture of a compound other than the compound of formula (XI) described above, for example for the manufacture of a polymer (possibly an oligomer) such as a polyether or polyester.

[0306] Esterification (starting from diol)

[0307] Diols can be esterified according to the following reaction scheme:

[0308]

[0309] in

[0310] where R, which may be the same or different at each occurrence, is C5-C 27 Aliphatic groups, preferably C6 to C 24 aliphatic groups,

[0311] L is a leaving group,

[0312] Y is a divalent C1-C6 aliphatic group,

[0313] R***** is hydrogen or a C1-C6 alkyl group,

[0314] t is an integer equal to 1 or equal to or greater than 2,

[0315] U u+ is a cation, and

[0316] u is an integer that determines the positive charge of the cation.

[0317] The diol is first esterified by contacting it with an esterifying agent, which is a carboxylic acid or an ester of a carboxylic acid of the general formula:

[0318] [LY-CO2R*****] (t-1)- [U u+ ] (t-1) / u

[0319] wherein Y is a divalent hydrocarbon radical containing between 1 and 6 carbon atoms, more precisely a divalent C1-C6 aliphatic radical, and wherein L is a leaving group.

[0320] Y is preferably a non-cyclic divalent aliphatic group, more preferably a straight-chain divalent aliphatic group, still more preferably a straight-chain alkanediyl (alkylene) group. Y preferably has from 1 to 6, more preferably from 1 to 4 carbon atoms, still more preferably 1 or 2 carbon atoms. The most preferred Y is -CH2-.

[0321] When t is equal to 1, there is no cation. In other words, the esterification is carried out by contacting the diol with a carboxylic acid or an ester of a carboxylic acid of the formula:

[0322] LY-CO2R*****.

[0323] In the case where the leaving group L already carries a negative charge in the carboxylic acid or ester reactant (which is the case when (t-1) is equal to or greater than 1 or when t is equal to or greater than 2), it is marked as U u+ (where u is preferably 1, 2 or 3, even more preferably 1) must be present in the reactants to ensure electroneutrality (in this case, the cation has u + The cation may be selected, for example, from H + , alkali metal cations, alkaline earth metal cations (such as Na + , K + , Ca 2+ ), Al 3+ and ammonium, to mention just a few examples.

[0324] The nature of the leaving group L is not particularly limited, provided that the next reaction step (i.e. amine condensation, as will be described in detail later) can take place. The leaving group L is advantageously a nucleophilic group. It can notably be selected from

[0325] -halogen,

[0326] -Formula R a -O-SO2-O-(alkyloxysulfonyl)oxy group, wherein R a represents a C1-C 20 Hydrocarbyl groups,

[0327] -Formula R a -SO2-O-(alkylsulfonyl)oxy group, wherein R a represents a C1-C 20 a hydrocarbyl group (such as in CF3-SO2-O-), and

[0328] -Mode - The oxysulfonyloxy group of O-SO2-O- (which is the leaving group L already carrying a negative charge on the terminal oxygen atom) is selected from the group consisting of:

[0329] Hydrocarbyl group R a , wherever present in the formulae hereinbefore, may notably be an aliphatic group or an aromatic group such as phenyl or p-tolyl. The aliphatic group R a Typically it is a C1-C6 alkyl group, which may be straight-chain or branched; typically it is a straight-chain C1-C4 alkyl group, such as methyl, ethyl or n-propyl.

[0330] The leaving group L is preferably selected from:

[0331] - halogen, such as fluorine, chlorine, bromine or iodine,

[0332] -Formula R a -O-SO2-O-(alkyloxysulfonyl)oxy group, wherein R a Indicates C1-C 20 Hydrocarbyl groups, such as CH3-O-SO2-O-, and

[0333] -Mode - O-SO2-O-oxysulfonyloxy group.

[0334] An example of a compound where t is equal to 1 is the compound CH3-O-SO3-CH2-COOR*****, where R***** is H, resulting in the compound CH3-O-SO3-CH2-COOH, which can be designated as 2-((methoxysulfonyl)oxy)acetic acid.

[0335] As further examples of compounds in which t is equal to 1 and therefore no cation is present, mention may be made of: chloroacetic acid, bromoacetic acid and 2-chloropropionic acid.

[0336] An example where t is equal to 2 is sodium carboxymethyl sulfate, where [LY-COOR*****] (t-1)- [U u+ ] (t-1) / u is [Na + ][O-SO2-O-CH2-COOR*****] -

[0337] Where R***** is H, U is Na, and therefore [U u+ ] t / u [L t- ] is Na2SO4.

[0338] The esterification can be preferably carried out at a temperature ranging from 50° C. to 250° C. in the presence of an optional 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, there can be mentioned: toluene, xylene, hydrocarbons, DMSO, Me-THF, THF or mixtures thereof.

[0339] Water formed as a by-product during the reaction can be removed from the reaction medium by distillation during the course of the reaction.

[0340] A catalyst may also be employed during the reaction, and suitable catalysts are Bronsted or Lewis acid catalysts. As preferred examples of catalysts, there may be mentioned: H2SO4, p-toluenesulfonic acid, trifluoromethanesulfonic acid, HCl, or heterogeneous acidic resins such as Resin, AlCl3, etc. At the end of the reaction, the desired diester can be recovered after appropriate work-up, and the skilled person is aware of representative techniques, so that no further details need be given here.

[0341] As will be seen later, the diester of formula (XIV)

[0342]

[0343] It can be easily converted into compounds of formula (XI) as previously represented, which exhibit excellent surfactant properties.

[0344] To the best of the applicant's knowledge, the diester of formula (XIV) is new. A web publication on Mol-instincts (https: / / www.molinstincts.com / structure / Coixenolide-cstr-CT1013031379.html) proposes the structural formula of coixenolide, an alkaloid drug component that can be extracted from Job's tears, which is notably able to inhibit cancer cell growth. From a purely structural point of view, the proposed formula of coixenolide may be the closest technology to the diester of formula (XIV). However, coixenolide does not contain any leaving groups, making it quite difficult or even impossible to convert it into a compound that will exhibit excellent surfactant properties, similar to those of the compound of formula (XI). In addition, coixenolide is difficult to obtain and costly, which would make it meaningless from an industrial and economic point of view to modify it or even attempt to modify it to obtain surfactant properties that may be similar to those of the compound of formula (XI).

[0345] Therefore, another object of the present invention is to provide novel diester compounds which can be used to prepare quaternary ammonium compounds having good surfactant properties and good biodegradability.

[0346] This further object is achieved with the diester compounds described hereinafter under item C.1 ("invention C"):

[0347] - Item C.1: A diester compound of formula (XIV)

[0348]

[0349] in

[0350] -R, which can be the same or different in each occurrence, means C5-C 27 aliphatic groups;

[0351] -Y is a divalent C1-C6 aliphatic group;

[0352] -L is a leaving group; and

[0353] -t is an integer equal to 1 or equal to or greater than 2.

[0354] It should be understood that in formula (XIV), Y and L (t-1)- It may be the same or different at each occurrence, as in the case of R.

[0355] Preferred and / or specific embodiments of the present invention C are set out below:

[0356] - Item C.2: A diester compound as described in Item C.1, wherein Y (i.e., each Y) is a non-cyclic divalent aliphatic group;

[0357] - Item C.3: A diester compound as described in Item C.2, wherein Y is a linear divalent aliphatic group;

[0358] - Item C.4: A diester compound as described in Item C.3, wherein Y is a linear alkanediyl group;

[0359] - Item C.5: A diester compound as described in any one of Items C.1 to C.4, wherein Y has from 1 to 6 carbon atoms;

[0360] - Item C.6: A diester compound as described in Item C.5, wherein Y has from 1 to 4 carbon atoms;

[0361] - Item C.7: A diester compound as described in Item C.6, wherein Y has 1 or 2 carbon atoms;

[0362] - Item C.8: A diester compound as described in Item C.7, wherein Y is CH2;

[0363] - Item C.9: A diester compound as described in any one of Items C.1 to C.8, wherein the leaving group L is a nucleophilic group;

[0364] - Item C.10: A diester compound as described in any one of Items C.1 to C.9, wherein the leaving group L is selected from halogen, a -O-SO2-O-(alkyloxysulfonyl)oxy group, formula R a -SO2-O- (alkylsulfonyl) oxygen group and formula - O-SO2-O-oxysulfonyloxy group, where Ra , wherever present in the foregoing formula herein, represents a C1-C 20 Hydrocarbyl groups;

[0365] - Item C.11: A diester compound as described in Item C.10, wherein the leaving group L is selected from halogen and a group of formula R a -O-SO2-O-(alkyloxysulfonyl)oxy group, wherein R a Indicates C1-C 20 Hydrocarbyl groups;

[0366] - Item C.12: A diester compound as described in Item C.11, wherein the leaving group L is a halogen selected from fluorine, chlorine, bromine and iodine;

[0367] - Item C.13: A diester compound as described in Item C.12, wherein the leaving group L is chlorine;

[0368] - Item C.14: A diester compound as described in Item C.10 or C.11, wherein the hydrocarbon group R a It is an aliphatic group;

[0369] - Item C.15: A diester compound as described in Item C.14, wherein the hydrocarbon group R a is a C1-C6 alkyl group, which may be linear or branched;

[0370] - Item C.16: A diester compound as described in Item C.15, wherein the hydrocarbon group R a is a straight chain C1-C4 alkyl group, preferably a methyl group;

[0371] - Item C.17: A diester compound as described in any one of Items C.1 to C.16, wherein R (i.e., each R) is C6 to C 24 aliphatic groups;

[0372] - Item C.18: A diester compound as described in Item C.17, wherein R contains from 10 to 20 carbon atoms;

[0373] - Item C.19: A diester compound as described in Item C.18, wherein R contains from 11 to 17 carbon atoms;

[0374] - Item C.20: A diester compound as described in any one of Items C.1 to C.19, wherein the total number of carbon atoms of the two R groups is at least 30;

[0375] - Item C.21: A diester compound as described in any one of items C.1 to C.20, wherein R does not contain any double bond and any triple bond;

[0376] - Item C.22: A diester compound as described in Item C.21, wherein R is an alkyl group;

[0377] - Item C.23: A diester compound as described in any one of Items C.1 to C.22, wherein R is a linear chain;

[0378] - Item C.24: A diester compound as described in any one of Items C.1 to C.16, wherein R is a linear alkyl group having from 14 to 17 carbon atoms;

[0379] - Item C.25: A diester compound as described in any one of items C.1 to C.24, 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;

[0380] - Item C.26: A diester compound as described in any one of items C.1 to C.24, wherein both R have an even number of carbon atoms or both R have an odd number of carbon atoms;

[0381] - Item C.27: A diester compound as described in any one of Items C.1 to C.24, wherein one and only one R has an odd number of carbon atoms n O At the same time, the other R has an even number of carbon atoms n E , where n E Equal to n O -1;

[0382] - Item C.28: A diester compound as described in any one of items C.1 to C.27, wherein the number of carbon atoms of the two R groups is represented by a pair (n1, n2), n1 is the number of carbon atoms of the first R group and n2 is the number of carbon atoms of the second R group, and the pair (n1, n2) 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).

[0383] - Item C.29: A method for obtaining a diester compound as described in any one of Items C.1 to C.28, comprising: reacting a diol of the following formula

[0384]

[0385] Contacting with a carboxylic acid or an ester of a carboxylic acid of the following general formula:

[0386] [LY-CO2R*****] (t-1)- [U u+ ] (t-1) / u

[0387] in

[0388] - R, Y, L and t are as described herein before within the framework of invention C;

[0389] -R***** is hydrogen or a C1-C6 alkyl group,

[0390] -U u+ is a cation, and

[0391] -u is an integer that determines the positive charge of the cation (e.g. for H + NH4 + or 1 for an alkali metal cation or 2 for an alkaline earth metal cation);

[0392] - Item C.30: A method for synthesizing a diester as described in Item C.29, comprising:

[0393]

[0394] wherein R is as described herein before, reacted with water to obtain a diol of the formula

[0395]

[0396] - Item C.31: The method described in Item C.30, which comprises making an olefin of the formula

[0397]

[0398] wherein R is as described herein before, reacted with an oxidizing agent of the formula R**OOH, wherein R** is hydrogen or a hydrocarbon group which may be substituted and / or interrupted by heteroatoms or groups containing heteroatoms, or R** is an acyl group of the general formula R***-C(=O)-, wherein R*** has the same meaning as R**, to form a compound of the formula R**OH and a compound of the formula to be reacted with water. Epoxy compounds;

[0399] - Item C.32: The method as described in item C.31, comprising:

[0400] - Make the first carboxylic acid of the following formula

[0401]

[0402] undergoing a pyriacontination reaction with another carboxylic acid of the formula

[0403]

[0404] wherein R, which may be the same or different in each carboxylic acid, is as previously described herein,

[0405] wherein the first carboxylic acid and the further carboxylic acid may thus be identical to or different from one another,

[0406] In order to obtain the following formula of ketone

[0407]

[0408] wherein R, at each occurrence, may be the same or different, as previously described herein;

[0409] - hydrogenation of the acetone with hydrogen to obtain methanol of the formula

[0410]

[0411] and

[0412] - dehydrating the methanol in order to obtain an olefin of the formula to be reacted with an oxidizing agent

[0413]

[0414] - Item C.33: Use of a diester compound as described in any one of items C.1 to C.28 for the manufacture of a surfactant;

[0415] - Item C.34: Use of a diester compound as described in any one of Items C.1 to C.28 or as described in Item C.33 for the manufacture of a compound of formula (XI)

[0416]

[0417] wherein R and Y are as described above within the framework of the present invention C, and R', R" and R'" have the meanings as described above for formula (I);

[0418] - Item C.35: Use of a diester compound as described in any one of Items C.1 to C.28 for the manufacture of a compound other than the compound of formula (XI) as described above, for example, for the manufacture of a compound other than the compound of formula (XI) as described in Item C.34 (wherein two -N + R'R"R"' are all -SO3 - This can be achieved by reacting the diester with a sulfite or bisulfite such as sodium sulfite or sodium bisulfite.

[0419] Direct esterification (starting from epoxides, including epoxide ring opening)

[0420] Applicants have surprisingly discovered that when and only when a carboxylic acid is used as the esterifying agent [LY-CO2R*****] (t-1)- [U u + ] (t-1) / u In other words, when the esterification agent [LY-CO2R*****] (t-1)- [U u+ ] (t-1) / u With the formula [LY-CO2H] (t-1)- [U u + ] (t-1) / u When L, Y, t, U u+ Epoxides can be directly esterified to diesters as described previously herein in conjunction with the esterification of diols.

[0421] Epoxide ring opening and esterification then proceed according to the following reaction scheme:

[0422]

[0423] in

[0424] R, which may be the same or different at each occurrence, is C5-C 27 Aliphatic groups, preferably C6 to C 24 aliphatic groups,

[0425] L is a leaving group,

[0426] Y is a divalent C1-C6 aliphatic group,

[0427] t is an integer equal to 1 or equal to or greater than 2,

[0428] U u+ is a cation, and

[0429] u is an integer that determines the positive charge of the cation.

[0430] Epoxide ring opening and esterification are carried out by reacting the epoxide with a carboxylic acid of the following general formula:

[0431] [LY-CO2H] (t-1)- [U u+ ] (t-1) / u

[0432] wherein L is a leaving group, Y is a divalent C1-C6 aliphatic group, t is an integer equal to 1 or equal to or greater than 2, U u+ is a cation, and u is an integer determining the positive charge of the cation.

[0433] The information about L, Y, t, and U provided before this article u+All details relating to the esterification of U with diols are also valid and applicable herein in relation to the direct esterification of epoxides, so that such details need not be repeated.

[0434] In particular, when t is equal to 1, no cation is present. In other words, the esterification is carried out by contacting the epoxide with a carboxylic acid of the formula:

[0435] LY-CO2H.

[0436] To the best of the applicant's knowledge, epoxides with two long aliphatic chains such as The direct esterification of epoxides is novel wherein each R, which may be the same or different at each occurrence, is C5-C 27 Aliphatic group.

[0437] A thermodynamic study of the reaction of bromomethyloxirane with dichloroacetic acid can be found in Ber. Bunsenges. Phys. Chem., 100, 1335-1340 (1996), No. 8. The moieties of bromomethyloxirane "corresponding to" R in the above formula are H and CHBr, respectively, and the moiety of dichloroacetic acid "corresponding to" Y in the esterifying agent formula is -CHCl-. Neither these "R-equivalent" nor "Y-equivalent" moieties are aliphatic groups.

[0438] Garcia et al., Journal of Industrial Microbiology, 28, 173-179 (2002), 173-179, achieved enzymatic esterification of 1,2-epoxy-5-hexene with 2-chlorobutyric acid in the presence of immobilized lipase from Mucor miehei to obtain the 2-chloroester. The moieties of 1,2-epoxy-5-hexene "corresponding to" R in the above formula are H and -(CH2)2-CH=CH2. Garcia did not consider enzymatic esterification of epoxides, whose "R-equivalent" moieties would all be aliphatic. Needless to say, Garcia did not consider direct epoxidation of epoxides, whose "R-equivalent" moieties would all be aliphatic in the absence of an enzyme as a catalyst.

[0439] More generally, none of these background art citations dealing with the esterification of epoxides having one and only one aliphatic or haloaliphatic group describe or suggest the epoxides (where each R g , which may be the same or different at each occurrence, will be an aliphatic or halogenated aliphatic radical) and the general formula [LY-CO2H] (t-1)- [U u+ ] (t-1) / u Carboxylic acid (where L, Y, t, Uu+ and esterification as previously described herein).

[0440] Therefore, another object of the present invention is to provide a method for esterifying such optionally halogenated In particular, another object of the present invention is a novel, efficient and cost-effective process for the preparation of dialiphatic epoxides of formula A novel, efficient and cost-effective process for obtaining diesters from long-chain dialiphatic epoxides which can be used to make quaternary ammonium compounds having good surfactant properties and good biodegradability.

[0441] This further object is achieved with the method described below under item D.1 ("invention D"):

[0442] - Item D.1: A method for obtaining a diester having the general formula (XV)

[0443]

[0444] The method comprises treating an epoxide of formula (XVI)

[0445]

[0446] Reaction with carboxylic acid of formula (XVII)

[0447] [LY-CO2H] (t-1)- [U u+ ] (t-1) / u (XVII)

[0448] Wherein, wherever used in the above formula:

[0449] -R g , which may be the same or different at each occurrence, is an aliphatic group or a halogenated aliphatic group;

[0450] -Y is a divalent C1-C6 aliphatic group;

[0451] -L is a leaving group;

[0452] -t is an integer equal to 1 or equal to or greater than 2;

[0453] -U u+ is a cation, and

[0454] -u is an integer that determines the positive charge of the cation (e.g. for H + NH4 + or 1 for an alkali metal cation or 2 for an alkaline earth metal cation).

[0455] It should be understood that similarly R g, Y and L (t-1)- Can be the same or different on each occurrence.

[0456] Preferred and / or specific embodiments of the present invention D are set out below:

[0457] - Item D.2: A process as described in item D.1, wherein the reaction is carried out by eliminating one mole of water from one mole of epoxide, as can be represented by the following:

[0458]

[0459] - Item D.3: A process as described in item D.1 or D.2, wherein the reaction is carried out in a reaction medium and water is removed from the reaction medium by distillation during the reaction;

[0460] - Item D.4: A method as described in item D.1, D.2 or D.3, wherein the reaction is carried out in the absence of an enzyme;

[0461] - Item D.5: A method as described in any one of items D.1 to D.4, wherein the reaction is carried out under an inert atmosphere such as nitrogen or a noble gas atmosphere;

[0462] - Item D.6: A method as described in item D.5, wherein the inert atmosphere is an argon atmosphere;

[0463] - Item D.7: A process as described in any one of Items D.1 to D.6, wherein the total number of moles of the carboxylic acid of formula (XVII) contacted with the epoxide during the entire reaction exceeds the number of moles of the epoxide;

[0464] - Item D.8: A process as described in item D.7, wherein the total number of moles of the carboxylic acid of formula (XVII) contacted with the epoxide during the entire reaction is at least two times higher than the number of moles of the epoxide;

[0465] - Item D.9: A process as described in item D.8, wherein the total number of moles of the carboxylic acid of formula (XVII) contacted with the epoxide during the entire reaction is at least four times higher than the number of moles of the epoxide;

[0466] - Item D.10: A process as described in any one of Items D.1 to D.9, wherein the total number of moles of the carboxylic acid of formula (XVII) contacted with the epoxide during the entire reaction is at most ten times higher than the number of moles of the epoxide;

[0467] - Item D.11: A process as described in item D.10, wherein the total number of moles of the carboxylic acid of formula (XVII) contacted with the epoxide during the entire reaction is at most eight times higher than the number of moles of the epoxide;

[0468] - Item D.12: A process as described in any one of items D.1 to D.11, wherein the reaction is carried out in a reactor in which the epoxide is in a molten state;

[0469] - Item D.13: A process as described in any one of items D.1 to D.12, wherein the reaction is carried out in a reactor in which the carboxylic acid of formula (XVII) is in a molten state;

[0470] - Item D.14: A process as described in any one of Items D.1 to D.13, wherein the epoxide is added gradually to a reactor containing the entire amount of the carboxylic acid of formula (XVII);

[0471] - Item D.15: A process as described in item D.14, wherein the epoxide is added continuously to the reactor containing the total amount of the carboxylic acid of formula (XVII);

[0472] The Applicant has observed that bringing the epoxide into contact stepwise, preferably continuously, with the entire amount of carboxylic acid makes it possible to limit the self-condensation of the epoxide;

[0473] - Item D.16: A method as described in any of items D.1 to D.15, comprising:

[0474] - a first step S1 in which the epoxide is reacted with a carboxylic acid of formula (XVII) at a temperature T1 below 100° C. for a time t1 sufficient to convert more than f1=80 mol.% of the epoxide into a monohydroxy-monoester of formula (XVIII):

[0475]

[0476] - a second step S2, in which the monohydroxy-monoester and the epoxide not converted into the monohydroxy-monoester in step S1 are reacted with the carboxylic acid of formula (XVII) at a temperature T2 of at least 100° C. for a time t2 sufficient to form the diester of formula (XV) in a molar amount greater than f2=50 mol.% of the total amount of epoxide reacted with the carboxylic acid;

[0477] The Applicant has surprisingly found that firstly reacting an epoxide with a carboxylic acid at a temperature T1 below 100° C. for a time t1 sufficient to convert more than f1=80 mol.% of the epoxide into a monohydroxy-monoester (step S1), and then increasing the temperature to convert the monohydroxy-monoester into a diester (step S2) makes it possible to limit the formation of ketones and dehydration by-products;

[0478] - Item D.17: A process as described in item D.16, wherein during step S1, the entire amount of the epoxide is gradually added to the reactor containing the entire amount of the carboxylic acid of formula (XVII);

[0479] - Item D.18: A process as described in item D.17, wherein during step S1, the entire amount of the epoxide is continuously added to the reactor containing the entire amount of the carboxylic acid of formula (XVII);

[0480] - Item D.19: A method as described in any of items D.16 to D.18, wherein T1 is at most 80°C;

[0481] - Item D.20: A method as described in item D.19, wherein T1 is at most 70° C.;

[0482] - Item D.21: A method as described in any of items D.16 to D.20, wherein T1 is at least 25°C;

[0483] - Item D.22: A method as described in item D.21, wherein T1 is at least 40°C, preferably at least 55°C, more preferably at least 60°C;

[0484] - Item D.23: A process as described in any one of items D.16 to D.22, wherein f1 = 90 mol.%;

[0485] - Item D.24: A process as described in item D.23, wherein f1 = 95 mol.%;

[0486] - Item D.25: A process as described in item D.24, wherein f1 = 98 mol.%;

[0487] - Item D.26: A method as described in any of items D.16 to D.25, wherein t1 ranges from 10 min to 10 h;

[0488] - Item D.27: A method as described in item D.26, wherein t1 is at least 30 min, possibly at least 45 min;

[0489] - Item D.28: A method as described in item D.26 or D.27, wherein t1 is at most 4 h, preferably from 30 min to 3 h;

[0490] - Item D.29: A method as described in any of items D.16 to D.28, wherein T2 is at least 120°C;

[0491] - Item D.30: A method as described in item D.29, wherein T2 is at least 130° C.;

[0492] - Item D.31: A method as described in any of items D.16 to D.30, wherein T2 is at most 250° C.,

[0493] - Item D.32: A process as described in item D.31, wherein T2 is at most 200°C, preferably at most 170°C, more preferably at most 150°C;

[0494] - Item D.33: A process as described in any one of Items D.16 to D.32, wherein the diester of formula (XV) is formed in a molar amount greater than f2 = 65 mol.%;

[0495] - Item D.34: A process as described in item D.33, wherein f2 = 70 mol.%;

[0496] - Item D.35: A process as described in item D.34, wherein f2=75 mol.%; preferably, the diester of formula (XV) is formed with a molar f2 of at least 80 mol.%;

[0497] - Item D.36: A method as described in any of items D.16 to D.35, wherein t2 ranges from 1 h to 30 h;

[0498] - D.37: A method as described in D.36, wherein t2 ≥ 3 h;

[0499] - D.38: A method as described in D.37, wherein t2 ≥ 4 h;

[0500] - Item D.39: A method as described in item D.36, D.37 or D.38, wherein t2 is at most 10 h;

[0501] - Item D.40: A method as described in item D.39, wherein t2 ≤ 7 h;

[0502] - Item D.41: A method as described in any of items D.16 to D40, wherein step S2 is carried out at a pressure P2 of at most 90 kPa, preferably from 50 kPa to 90 kPa, more preferably from 70 kPa to 90 kPa, for example about 80 kPa;

[0503] - Item D.42: A method as described in any of items D.16 to D40, wherein step S2 is carried out at a pressure P2 of from 95 kPa to 99 kPa, preferably from 96 kPa to 98 kPa, for example about 97.5 kPa;

[0504] The Applicant has observed that carrying out step S2 under low vacuum makes it easier to remove the water formed as a by-product of the esterification;

[0505] Item D.43: A method as described in item D.41 or D.42, comprising, after step S2 is completed, gradually reducing the pressure P2 to a pressure P3 below 100 kPa, preferably at most 50 kPa, more preferably at most 20 kPa, for example about 10 kPa;

[0506] The Applicant has observed that this enables the distillation of excess carboxylic acid and increases the conversion of the monohydroxy-monoester to the diester;

[0507] - Item D.44:: A process as described in any one of items D.1 to D.43, wherein the reaction is carried out in the presence of a Bronsted acid or Lewis acid catalyst;

[0508] - Item D.45: A method as described in any one of items D.1 to D.43, wherein the reaction is carried out in an atmosphere selected from H2SO4, p-toluenesulfonic acid, trifluoromethanesulfonic acid, HCl, AlCl3 and a heterogeneous acidic catalyst such as in the presence of a resin catalyst;

[0509] - Item D.46: A process as described in any one of items D.1 to D.43, wherein the reaction is carried out in the absence of any catalyst;

[0510] - Item D.47: A method as described in any one of items D.1 to D.46, wherein the reaction is carried out in the absence of a solvent;

[0511] - Item D.48: A process as described in any one of items D.1 to D.46, wherein the reaction is carried out in the presence of a solvent such as toluene, xylene, a hydrocarbon, DMSO, Me-THF or THF;

[0512] - Item D.49: A method as described in any of items D.1 to D.48, wherein R g (i.e. each R g ) is an aliphatic group;

[0513] - Item D.50: A method as described in any one of items D.1 to D.49, wherein R g Contains at least 2, possibly at least 3 or at least 4 carbon atoms;

[0514] - Item D.51: A method as described in any of items D.1 to D.50, wherein R g Contains up to 4 carbon atoms;

[0515] - Item D.52: A method as described in any of items D.1 to D.50, wherein R g Contains at least 5 carbon atoms;

[0516] - Item D.53: A method as described in any of items D.1 to D.48, wherein R g (i.e. each R g ), which can be the same or different each time it appears, represents C5-C 27 Aliphatic group, i.e. R g has the same definition as R as previously described, and the diester obtained by the present process is the diester as previously described in item C.1 in connection with present invention C;

[0517] - Item D.54: A process as described in item D.53, wherein the diester obtained is a diester as described in any one of items C.2 to C.28;

[0518] - Item D.55: A method as described in item D.53 or D.54, comprising making reacting an olefin with an oxidizing agent of the formula R**OOH, wherein R** is as described in item C.31;

[0519] - Item D.56: A method as described in item D.55, comprising obtaining a compound of formula by applying the reaction scheme as described in item C.32. of olefins;

[0520] - Item D.57: A method as described in any one of items D.1 to D.56, wherein U u+ Selected from H + NH4 + , alkali metal cations, alkaline earth metal cations and Al +3 ;

[0521] - Item D.58: Monohydroxy-monoester compound of formula (XVIII):

[0522]

[0523] in

[0524] -R g , which may be the same or different at each occurrence, is an aliphatic group or a halogenated aliphatic group,

[0525] -Y is a divalent C1-C6 aliphatic group,

[0526] -L is a leaving group, and

[0527] -t is an integer equal to 1 or equal to or greater than 2;

[0528] - Item D.59: A monohydroxy-monoester compound as described in item D.58, wherein R g (i.e. each Rg ), which can be the same or different each time it appears, represents C5-C 27 Aliphatic group, i.e. R g has the same definition as R as previously described;

[0529] - Item D.60: A monohydroxy-monoester compound as described in item D.59, wherein R, Y, L, and t meet one or more of the characteristics as described in any one of items C.2 to C.28 in relation to the diester of invention C;

[0530] - Item D.61: Use of a monohydroxy-monoester compound as described in item D.58, D.59 or D.60 for the production of a diester compound;

[0531] - Item D.62: The use as described in item D.61, wherein the monohydroxy-monoester compound is as described in item D.59 or D.60, and the diester compound is as described in any one of items C.1 to C.28.

[0532] Amine condensation starting from diester

[0533] The diester compound of formula (XIV) can be converted into the ionic compound of formula (XI) (or its neutral homologue) by the following reaction scheme:

[0534]

[0535] in

[0536] -R, Y, L, t, U u+ and U are as described previously herein, and

[0537] - R', R" and R'" are C1 to C4 alkyl groups, preferably methyl or ethyl, most preferably methyl.

[0538] The amine condensation reaction is carried out by contacting the intermediate diester obtained as described above with an amine of the general formula NR'R"R"', wherein R', R" and R'" are C1 to C4 alkyl groups, preferably methyl or ethyl, most preferably methyl.

[0539] The reaction can be carried out at a temperature ranging from 15° C. to 250° C. in the presence of a suitable solvent. Examples of suitable solvents include THF, Me-THF, methanol, ethanol, isopropanol, DMSO, toluene, xylene, or mixtures thereof. Alternatively, the reaction can also be carried out in the absence of any added solvent.

[0540] During this reaction, the presence of L in the substituted diester (t-1)- Nucleophilic attack of amine, L (t-1)-Plays the role of leaving group. Then L t- becomes the counter anion of the final quaternary ammonium compound. In the case where the leaving group already carries a negative charge in the diester reactant (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 (having the general chemical formula [U] as shown in the above equation scheme). u+ ] t / u [L t- ]).

[0541] Esterification and amine condensation / direct quaternization starting with diols

[0542] By Starting from a diol wherein R is as described herein before, the applicant has found that compounds according to formula (IX) or (XI) can be obtained in one reaction step, i.e. the esterification and amine condensation are achieved in one step, provided that another suitable esterification agent is used.

[0543] The suitable esterifying agent can generally be defined as an activated form of an amino acid of formula (XIXa) or an ester thereof

[0544] R'R"R"' + NYC(=O)-O - (XIXa)

[0545] or activated forms of their hydrohalide adducts of formula (XIXb)

[0546] R'R"R"' + NYC(=O)-OH X - (XIXb)

[0547] in

[0548] - R', R" and R'", which may be the same or different, are hydrogen or a C1 to C4 alkyl group,

[0549] -Y is a divalent C1-C6 aliphatic group, and

[0550] -X represents a halogen atom such as chlorine or bromine.

[0551] The activated forms of the amino acids of formula (XIXa) or their esters or their hydrohalide adducts of formula (XIXb) are advantageously selected from:

[0552] -acyl halide of formula (XX)

[0553] R'R"R"' + NYC(=O)-XX - (XX)

[0554] wherein R', R", R'", Y and X are as previously described for formulae (XIXa) and (XIXb); in particular, it may be of the formula R'R"R"' + NYC(=O)-Cl Cl - of acyl chloride.

[0555] Other suitable activated forms of amino acids or esters thereof of formula (XIXa) or their hydrohalide adducts of formula (XIXb) include acyl azides of formula (XXI)

[0556] R'R"R"' + NYC(=O)-N=N + =N - (XXI)

[0557] and acyl imidazole or acyl imidazolium.

[0558] Several publications describe the direct esterification of polyols, in which the hydroxyl groups are primary (emphasis added), with amino acids or their esters.

[0559] For example, Stakleff in Acta Biomaterialia, 9, 5132-5142 (2013) teaches the reaction of hexanediol with phenylalanine or leucine in the presence of p-toluenesulfonic acid.

[0560] Lele et al., Synthetic Communications, 29:10, 1727-1739 (1999), achieved the coupling of poly(ethylene glycol) and amino acid hydrochlorides mediated by dicyclohexylcarbodiimide.

[0561] et al. in Carbohydrate Polymers, 41, 277-283 (2000), prepare betaine starch esters from starch and betaine acid chloride in the presence of dioxane as solvent and pyridine as nucleophile and catalyst:

[0562]

[0563] Betaine acid chloride has long been prepared by reacting glycine betaine with thionyl chloride in dichloromethane.

[0564] On the other hand, none of these prior art addresses the possibility of directly quaternizing polyols carrying two or more secondary hydroxyl groups, whose reactivity differs significantly from that of polyols carrying primary hydroxyl groups, as can now be achieved within the framework of the present invention.

[0565] Therefore, another object of the present invention is to provide a method for directly quaternizing a A new, efficient and simple method for the preparation of diols wherein R h , which may be the same or different at each occurrence, represents an aliphatic group. In particular, another object of the present invention is to provide a method for directly quaternizing A novel, efficient and simple process for the preparation of diols (having R as described herein before) thereby obtaining quaternary ammonium compounds having good surfactant properties and good biodegradability.

[0566] This further object is achieved with the method described below under item E.1 (“invention E”):

[0567] - Item E.1: A method for obtaining a quaternary ammonium compound having the following general formula

[0568]

[0569]

[0570] The method comprises making a diol of the formula

[0571]

[0572] reacting with an amino acid or a derivative thereof or an activated form of a hydrohalide adduct thereof,

[0573] in

[0574] - an amino acid or a derivative thereof having the formula (XIXa)

[0575] R'R"R"' + NYC(=O)-O - (XIXa),

[0576] and their hydrohalide adducts have the formula (XIXb)

[0577] R'R"R"' + NYC(=O)-OH X - (XIXb),

[0578] -R h , which may be the same or different at each occurrence, is an aliphatic radical

[0579] - R', R" and R'" are hydrogen or a C1 to C4 alkyl group,

[0580] -Y is a divalent C1-C6 aliphatic group, and

[0581] -X represents a halogen atom such as chlorine or bromine.

[0582] It will be understood that in formula (XXII), as R h , Y, R', R" and R'" may be the same or different at each occurrence.

[0583] Preferred and / or specific embodiments of the present invention E are set out below:

[0584] - Item E.2: A method as described in Item E.1, wherein the activated form of the amino acid or its derivative or its hydrohalide adduct is an acyl halide of formula (XX)

[0585] R'R"R"' + NYC(=O)-XX - (XX)

[0586] wherein R', R", R'", Y and X are as previously described for formula (XXII);

[0587] - Item E.3: A method as described in Item E.2, which comprises reacting an amino acid of formula (XIXa) or a derivative thereof and / or a hydrohalide adduct thereof of formula (XIXb) with a reagent selected from a sulfinyl halide, an oxalyl halide, a phosphorus trihalide, a phosphorus pentahalide or a phosphorus oxyhalide, preferably reacting an amino acid of formula (XIXa) or a derivative thereof and / or a hydrohalide adduct thereof of formula (XIXb) with a reagent selected from thionyl chloride (SOCl2), oxalyl chloride [(COCl)2], phosphorus trichloride (PCl3), phosphorus pentachloride (PCl5) and phosphorus oxychloride (POCl3), more preferably reacting an amino acid of formula (XIXa) or a derivative thereof and / or a hydrohalide adduct thereof of formula (XIXb) with thionyl chloride to obtain an acyl halide of formula (XX);

[0588] - Item E.4: A method as described in Item E.1, wherein the activated form of the amino acid or its derivative or its hydrohalide adduct is an acyl azide of formula (XXI)

[0589] R'R"R"' + NYC(=O)-N=N + =N - (XXI)

[0590] wherein R', R", R'", Y and X are as previously described for formula (XXII);

[0591] - Item E.5: A method as described in any one of items E.1 to E.4, wherein X is chloride;

[0592] - Item E.6: A method as described in any of items E.1 to E.5, wherein Rg Contains at least 2, possibly at least 3 or at least 4 carbon atoms;

[0593] - Item E.7: A method as described in any one of items E.1 to E.6, wherein R g Contains up to 4 carbon atoms;

[0594] - Item E.8: A method as described in any of items E.1 to E.6, wherein R g Contains at least 5 carbon atoms;

[0595] - Item E.9: A method as described in Item E.8, wherein R g (i.e. each R g ), which can be the same or different each time it appears, represents C5-C 27 Aliphatic group, i.e. R g has the same definition as R as previously described, for example, with respect to present invention C, and the quaternary ammonium compound obtained by the present process has the formula (XI);

[0596] - Item E.10: A method as described in item E.9, wherein R is as described in any one of items C.2 to C.28;

[0597] - Item E.11: A method as described in any one of Items E.1 to E.10, wherein Y is selected from -CH2-, -CH(CH3)-, -CH[CH(CH3)2]-, -CH[CH2-CH(CH3)2]- and -CH[CH(CH3)-CH2-CH3]-;

[0598] - Item E.12: A method as described in Item E.11, wherein Y is -CH2-;

[0599] - Item E.13: A method as described in any one of items E.1 to E.12, wherein at least one of R', R", and R'" is a C1 to C4 alkyl group;

[0600] - Item E.14: A method as described in item E.13, wherein R′ is a C1 to C4 alkyl group, R″ is a C1 to C4 alkyl group and R′″ is a C1 to C4 alkyl group;

[0601] - Item E.15: A method as described in Item E.14, wherein R', R" and R'" are methyl;

[0602] - Item E.16: A method as described in any one of items E.1 to E.15, wherein the amino acid of formula (XIXa) or a derivative thereof is trimethylglycine and the hydrohalide adduct of formula (XIXb) is betaine hydrochloride.

[0603] Second method for synthesizing a compound wherein A is represented by A-5 as exemplified by formulae (IX) and (XI)

[0604] Occasional marriage condensation

[0605] An alternative method for the synthesis of compounds according to the invention, wherein A is represented by A-5 and is shown in the following schemes for compounds of formula (IX) and (XI), proceeds via acyloin condensation according to the following scheme:

[0606]

[0607] wherein R****** is an alkyl group having from 1 to 6 carbon atoms.

[0608] Acyloin condensation is usually carried out by reacting an ester (typically a fatty acid methyl ester) with sodium metal as a reducing agent. The reaction is carried out in a high boiling point aromatic solvent such as toluene or xylene, wherein the metal can be dispersed at a temperature above its melting point (about 98° C. in the case of sodium). 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 acyloin product can be separated. The final product can be obtained after appropriate post-processing, and the skilled person is aware of representative techniques, so no further details need be given here.

[0609] Reactions of this type have 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 reference is therefore made for further details.

[0610] Ketone-alcohol hydrogenation

[0611]

[0612] The reaction can be performed using the conditions described above for the first process variant for the preparation of compounds of formula (IX) and (XI), respectively, wherein A is represented by A-5.

[0613] The subsequent reaction steps are also as described above for the first process variant for the preparation of compounds of the formula (IX) and (XI), respectively, wherein A is represented by A-5.

[0614] Suitable methods for making compounds wherein A is represented by A-2, more particularly for making compounds of formula (VIII), are described in the experimental section hereinafter.

[0615] The exemplary methods described above are examples of suitable methods, i.e., there may be other suitable methods for synthesizing the compounds according to the present invention. Therefore, with respect to the methods for making the compounds according to the present invention, the methods described above are not limited.

[0616] If the lactone used as reactant in the exemplary process described above is obtained from a natural fatty acid having an even number of carbon atoms, the number of carbon atoms of the two groups R in the compounds of the formulae IV, V, VII, VIII and X is preferably any one of the following pairs:

[0617] (5,5), (7,7), (9,9), (11,11), (13,13), (15,15), (17,17)

[0618] (7,9), (7,11), (7,13), (7,15), (7,17)

[0619] (9,11), (9,13), (9,15), (9,17)

[0620] (11,13), (11,15), (11,17)

[0621] (13,15), (13,17)

[0622] (15,17).

[0623] In particular, if the lactone used as reactant in the exemplary process described above is obtained from one or more carboxylic acids having an even number of carbon atoms ranging from 12 to 18, the number of carbon atoms of the two groups R in the compounds of formulae IV, V, VII, VIII and X is one or more of the following pairs:

[0624] (11,11), (13,13), (15,15), (17,17)

[0625] (11,13), (11,15), (11,17)

[0626] (13,15), (13,17)

[0627] (15,17).

[0628] Other pairs are possible and will be obtained if the lactone is derived from a fatty acid containing an odd number of carbon atoms.

[0629] If the lactone used as a reactant in the exemplary methods described above is derived from a natural fatty acid having an even number of carbon atoms, then for the compounds of formulae VI, IX and XI, the number of carbon atoms of the two groups R is preferably any one of the following pairs:

[0630] (4,5), (6,7), (8,9), (10,11), (12,13), (14,15), (16,17)

[0631] (4,7), (4,9), (4,11), (4,13), (4,15), (4,17)

[0632] (5,6), (5,8), (5,10), (5,12), (5,14), (5,16)

[0633] (6,9), (6,11), (6,13), (6,15), (6,17)

[0634] (7,8), (7,10), (7,12), (7,14), (7,16)

[0635] (8,11), (8,13), (8,15), (8,17)

[0636] (9,10), (9,12), (9,14), (9,16)

[0637] (10,13), (10,15), (10,17)

[0638] (11,12), (11,14), (11,16)

[0639] (12,15), (12,17)

[0640] (13,14), (13,16)

[0641] (14,17)

[0642] (15,16).

[0643] In particular, if the lactone used as reactant in the exemplary process described above is obtained from one or more carboxylic acids having an even number of carbon atoms ranging from 12 to 18, the number of carbon atoms of the two groups R in the compounds of formulae VI, IX and XI is one or more of the following pairs:

[0644] (10,11), (12,13), (14,15), (16,17)

[0645] (10,13), (10,15), (10,17)

[0646] (11,12), (11,14), (11,16)

[0647] (12,15), (12,17)

[0648] (13,14), (13,16)

[0649] (14,17)

[0650] (15,16)

[0651] Other pairs are possible and will be obtained if the lactone is obtained from a fatty acid containing an odd number of carbon atoms.

[0652] Compounds wherein A is represented by A-5 and in particular compounds of formula (XI), especially compounds of formula (IX), have particularly interesting and advantageous properties characteristic of surfactant properties on the one hand and biodegradability properties on the other hand. As biodegradability is becoming an increasingly important aspect of surfactant products, compounds wherein A is represented by A-5 and in particular compounds of formula (XI) in this group, especially compounds of formula (IX), constitute preferred embodiments of the present invention.

[0653] The compounds of the present invention can be used as surfactants. Surfactants are compounds that reduce the surface tension (or interfacial tension) between two liquids, a liquid and a gas, or a liquid and a solid. Surfactants can serve as detergents, wetting agents, emulsifiers, foaming agents, and dispersants.

[0654] 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. The surfactant 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 aqueous phase into the air or oil phase, while the water-soluble head group remains in the aqueous phase.

[0655] The adsorption of cationic surfactants on negatively charged surfaces is an important property for this type of surfactant. This property is generally 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) suspensions in aqueous media. The continuous change in size can be monitored and subsequently subjected to dynamic light scattering (DLS).

[0656] Following the protocol described in EKOikonomou et al., J. Phys. Chem. B, 2017, 121(10), 2299-307, the adsorption properties 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%.

[0657] 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 of one such method, OECD Standard 301, are given in the experimental part hereinafter.

[0658] Should the disclosure of any patents, patent applications, and publications incorporated herein by reference conflict with the description of the present application to the extent that a term is unclear, the present description shall take precedence.

[0659] Working Example

[0660] Example 1 - Synthesis of a quaternary ammonium compound of formula IV starting from 12-tricosanol wherein J is J3, ie wherein n and n' in the group X are each 1

[0661] According to US-A 2018 / 093936 (see Example 3 therein), the 23 12-Tricosanone to obtain C 23 12-Tricosanol.

[0662] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0663] Fresh commercially available anhydrous CHCl3 (pentene stabilized), anhydrous toluene, and anhydrous acetonitrile were used as received. Choline chloride (which is hygroscopic) was washed several times with anhydrous THF and dried under vacuum before use.

[0664] To a 500 mL round-bottom flask equipped with a condenser, temperature probe, heater, and magnetic stirrer was added 38.37 g of 12-tricosanol (112.7 mmol), followed by 150 mL of toluene. The mixture was then allowed to stir at room temperature, and then 0.1 g of solid KOH (1.7 mmol, 1.6 mol%) was added, followed by 18.26 g of carbonyldiimidazole (112.7 mmol, 1 eq) and an additional 20 mL of toluene.

[0665] The mixture was then allowed to stir at 70°C; at this temperature, the mixture became transparent. 1The progress of the reaction was followed by H-NMR, and after three hours at 70°C, 99% alcohol conversion was achieved.

[0666] All volatiles were then removed by distillation at 50° C., 9 mbar to afford 59.4 g of a residue which was used in the next stage without purification.

[0667] The residue was then dissolved in a mixture of 40 mL of CHCl 3 and 40 mL of acetonitrile, and 15.74 g of choline chloride (112.7 mmol, 1 equivalent) was added at room temperature. The mixture was then allowed to stir at 50° C. overnight.

[0668] During the reaction, the reaction medium becomes homogeneous and green. 1 The progress of the reaction was followed by H-NMR, and a conversion of 89% was achieved at this stage.

[0669] The solvent was then removed under vacuum to provide approximately 79.1 g of crude product.

[0670] The crude residue was purified by column chromatography on silica gel (330 g of silica) to remove impurities and imidazole byproduct (specification <0.5 wt% imidazole) using ethyl acetate / methanol (AcOEt / MeOH) eluent (proceeding from 100% AcOEt to 50:50 AcOEt:MeOH).

[0671] Five fractions were collected: the first fraction corresponding to the intermediate imidazole carbonate and the second fraction corresponding to the imidazole were discarded, and the three remaining fractions were collected and repurified.

[0672] For the second column chromatography on silica gel, 200 g of silica and the same eluent system were used. Two fractions were collected: the first was a mixture of product and imidazole, and the second was the pure product.

[0673] Finally, the first fraction was purified again using 30 g of silica gel and the same eluent system to provide additional amounts of product.

[0674] All clean fractions were collected to give 39.8 g of the product as a white wax, corresponding to 70% isolated yield.

[0675] 1 H NMR (CDCl3, 400 MHz) δ (ppm): 4.65 (quintet, 1H), 4.61-4.51 (m, 2H), 4.22-4.02 (m, 2H), 3.52 (s, 9H), 1.61-1.44 (m, 4H), 1.32-1.12 (m, 36H), 0.84 (t, J = 8.0 Hz, 6H).

[0676] 13C NMR (CDCl3, 101 MHz) δ (ppm): 154.21, 80.88, 64.92, 61.24, 54.59, 33.96, 32.10, 29.83, 29.82, 29.80, 29.70, 29.68, 29.54, 25.36, 22.88, 14.31 (terminal CH3).

[0677] Example 2 - Synthesis of quaternary ammonium compounds of formula IV starting from 16-triacontanol, wherein J is J3, ie wherein n and n' in the group X are each 1

[0678] According to US-A US2018 / 093936 (see Example 3 therein), the 31 16-Hexanedione to obtain C 31 16-triacontanol.

[0679] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0680] Fresh commercially available anhydrous CHCl3 (pentene stabilized), anhydrous toluene, and anhydrous acetonitrile were used as received. Choline chloride (which is hygroscopic) was washed several times with anhydrous THF and dried under vacuum before use.

[0681] To a 500 mL round-bottom flask equipped with a condenser, temperature probe, heater, and magnetic stirrer was added 45.2 g of 16-triacontanol (99.9 mmol), followed by 150 mL of toluene. The mixture was then allowed to stir at room temperature, and then 0.1 g of solid KOH (1.7 mmol, 1.7 mol%) was added, followed by 17.0 g of carbonyldiimidazole (105 mmol, 1.05 eq) and an additional 50 mL of toluene.

[0682] The mixture was then allowed to stir at 60°C; at this temperature, the mixture became transparent. 1 The progress of the reaction was followed by H-NMR, and after one hour at 60 °C, >99% alcohol conversion was achieved.

[0683] All volatiles were then removed by vacuum to afford a white residue which was used in the next stage without purification.

[0684] The residue was then dissolved in a mixture of 80 mL of CHCl 3 and 80 mL of acetonitrile, and 13.95 g of choline chloride (99.9 mmol, 1 eq.) was added at room temperature. The mixture was then allowed to stir at 55° C. overnight.

[0685] pass 1The progress of the reaction was followed by H-NMR, and only a weak conversion of 30% was obtained at this stage. This weak conversion can be explained by the decomposition of KOH (e.g. by reaction with CHCl 3 ).

[0686] 0.3 g of KOH (5.1 mmol) were then added and the mixture was stirred under reflux for a further 3 hours. According to NMR, the conversion level reached 78%.

[0687] Another 0.2 g of KOH was added again, followed by stirring under reflux for twelve hours.

[0688] At this stage, the conversion level was 83% and the color of the mixture was brown.

[0689] The solvent was then removed under vacuum to provide approximately 84 g of crude product.

[0690] The crude residue was purified by column chromatography on silica gel (2 columns of 330 g of silica) to remove impurities and imidazole byproduct (specification < 0.5 wt% imidazole) using AcOEt / MeOH eluent (proceeding from 100% AcOEt to 50:50 AcOEt:MeOH).

[0691] Four fractions were collected: the first fraction corresponded to the intermediate imidazole carbonate, the second fraction corresponded to imidazole, the third fraction contained a mixture of imidazole and the desired product, and the last fraction corresponded to the desired product.

[0692] The fourth fraction from each column was collected and subjected to a second column chromatography on silica gel. 330 g of silica was used with the same eluent system to provide the desired product with good purity.

[0693] 36.6 g of the product were obtained as a white wax, corresponding to a 60% isolated yield.

[0694] 1 H NMR (CDCl3, 400 MHz) δ (ppm): 4.66 (quintet, 1H), 4.62-4.52 (m, 2H), 4.24-4.04 (m, 2H), 3.53 (s, 9H), 1.62-1.46 (m, 4H), 1.34-1.14 (m, 52H), 0.85 (t, J = 6.8 Hz, 6H).

[0695] 13C NMR (CDCl3, 101 MHz) δ (ppm): 154.20, 80.87, 64.91, 61.23, 54.58, 33.96, 32.11, 29.90, 29.85, 29.82, 29.72, 29.69, 29.55, 25.36, 22.88, 14.31 (terminal CH3).

[0696] Example 3 - By C 31 A mixture of quaternary ammonium compounds (a mixture of compounds of formula (V) and (VI)) wherein A is represented by A-2 or A-3 is synthesized starting from 1,6-triacontanone

[0697] Knoevenagel condensation to provide the diester intermediate:

[0698]

[0699] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0700] Fresh commercially available anhydrous CHCl 3 , anhydrous THF and anhydrous pyridine were used as received.

[0701] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plow blades), a condenser, an addition funnel, and a temperature probe, 36.5 mL of TiCl 4 (63.00 g, 0.332 mol) was added, followed by 146.3 mL of CHCl 3 .

[0702] The mixture was stirred at -10°C and anhydrous THF (358 mL) was added slowly through an addition funnel at a rate to prevent the temperature of the reaction medium from rising above +5°C. During the THF addition, a yellow precipitate appeared. 15.3 mL of dimethyl malonate (17.69 g, 0.134 mole) was then added to the reaction mixture, which was then allowed to stir at room temperature for 1 hour to allow malonate complexation to occur.

[0703] The mixture was then allowed to cool to 0°C and 71.80 mL of anhydrous pyridine (70.50 g, 0.891 mole) dissolved 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.

[0704] Finally, 50.00 g of C 31At room temperature, ketone (0.111 mole) is added in the reaction mixture, allows it to stir overnight and at room temperature stir one day again at 35 ℃.Then the water of 250mL is carefully added in the reactor, the ether of adding 250mL is subsequently added.Separate organic phase and use the water washing of 250mL 4 times, and wash once so that remove pyridinium salt with the saturated NaCl aqueous solution of 200mL.Merge water and use the ether of 250mL to extract 3 times again.With final organic phase through MgSO Drying, filter and vaporising under vacuum to provide the thick orange oil of 70.08g.In this stage, crude product contains the starting ketone of residual quantity and the major impurity corresponding to the condensation (aldol condensation+crotonyl aldehyde) of the ketone of 2 equivalents.

[0705] The product can be easily purified by dissolving the oil in ethanol (the byproduct and starting ketone are insoluble in ethanol) followed by filtration through celite.

[0706] The filtrate was evaporated, redissolved in CHCl 3 , filtered again and evaporated to provide 52.57 g of an oil with 95% purity (RMN).

[0707] The overall purification yield was 79%.

[0708] 1 H NMR (CDCl3, 400MHz) δ (ppm): 3.68 (s, 6H), 2.32-2.19 (m, 4H), 1.45-1.39 (m, 4H), 1.30-1.10 (m, 48H), 0.81 (t, J = 6.4Hz, 6H).

[0709] 13 C NMR (CDCl3, 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).

[0710] Transesterification with dimethylaminoethanol provides a diamine mixture intermediate:

[0711]

[0712] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0713] Fresh commercially available anhydrous toluene and dimethylaminoethanol were used as received.

[0714] In a 2 L double jacketed reactor equipped with a mechanical stirrer (propeller with four tilted plow blades), a condenser with a distillation unit, and a temperature probe, 42.7 g of acetone / dimethyl malonate 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 equivalents) was added to the reaction system, followed by 50 mL of toluene. 0.9 g of the catalyst dibutyltin oxide (3.8 mmol, 5 mol%) was then added to the reaction mixture, followed by 200 mL of toluene.

[0715] The mixture was then allowed to stir at 120°C and the reaction progress was tracked by NMR analysis. In order to perform appropriate analysis, aliquots of the reaction medium were sampled and diluted in ether, quenched with water, decanted, and the organic phase was evaporated under vacuum to analyze in CDCl3 NMR solvent. After stirring at 120°C for 4 days, NMR analysis showed that the conversion level was approximately 83%, with 91% selectivity. In addition, by-product methanol was also present in the distillation flask. The reaction mixture was then allowed to cool at room temperature and quenched with 500mL of water. The medium was decanted, and the aqueous phase was extracted three times with 500mL of ether. The organic phase was collected and washed three times with 500mL of water and once with 500mL of a saturated NaCl aqueous solution to remove excess dimethylaminoethanol. The organic phase was then dried, filtered, and evaporated to give 47.9g of a thick dark oil. At this stage, the crude product contained a residual amount of the starting malonate.

[0716] The product was then purified by flash column chromatography on silica gel with a first eluent consisting of a CHCl 3 / AcOEt mixture by means of a gradient from 100% CHCl 3 to 100% AcOEt.

[0717] In order to remove all product from the column, the column was also flushed with an isopropanol + NEt3 mixture (10% NEt3 by volume), allowing additional pure product to be obtained.

[0718] Clean fractions were collected to give 27.8 g of pure product after evaporation of the solvent, corresponding to 54% isolated yield.

[0719] NMR analysis showed that the product was in the form of a mixture of two positional isomers with the following ratios: 54 mol% of the isomerized product (cis and trans diastereomers) and 46 mol% of the methylenated product.

[0720] 1H NMR (CDCl3, 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, Isomer 1+2), 3.99 (s, 1H, Isomer 2 cis or trans), 2.58-2.40 (m, 4H, Isomer 1+2), 2.32-2.24 (m, 4H, Isomer 1), 2.20 (s, 12H, Isomer 1), 2.19 (s, 12H, Isomer 2), 2.09-1.89 (m, 4H, Isomer 2 cis + trans), 1.45-0.99 (m, 51H, Isomer 1+2), 0.81 (t, J = 6.8 Hz, 6H).

[0721] 13 C NMR (CDCl3, 101 MHz) δ (ppm): 168.60, 168.41, 165.49, 164.05, 132.07, 131.57, 131.12, 130.77, 123.73, 63.35, 62.76, 58.08, 57.49, 57.45, 53.45, 45.73, 34.45, 30.07, 30.03, 29.72, 29.68, 29.58, 29.53, 29.45, 29.38, 28.46, 28.43, 28.27, 28.09, 22.70, 14.13 (terminal CH3).

[0722] Methylation to provide a mixture of compounds (V) and (VI):

[0723] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0724] Fresh commercially available anhydrous THF and dimethyl sulfate were used as received.

[0725] In the 1L double-jacketed reactor equipped with mechanical stirrer, condenser, addition funnel and temperature probe, add the dry THF of 100mL and the methyl sulfate of 6.9mL (9.14g, 72mmol, 2 equivalents).In addition funnel, prepare in advance the solution of esteramine (36mmol, 1 equivalent) in the THF of 154mL of 24.6g and at room temperature under agitation it is progressively added in the reactor so that the limit temperature raises.Then at room temperature mixture is stirred under argon, and the monitoring reaction process is analyzed by NMR. After 2 hours, make mixture reach 40 ℃ and add the methyl sulfate (2mmol, 0.06 equivalent) of 0.2mL to allow stirring and realize complete conversion.

[0726] The reaction was complete after stirring at 40°C for one hour, and all volatiles (THF and remaining DMS) were removed under vacuum to provide 33.15 g of 95 mol% pure product as a beige wax with 94% yield.

[0727] NMR analysis showed the presence of two positional isomers with a 55:45 ratio between the isomerized derivative (cis and trans diastereomers) and the conjugated non-isomerized methylenated derivative.

[0728] 1 H 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, isomer 1+2), 4.38 (s, 1H, isomer 2 cis or trans), 3.84-3.72 (m, 4H, isomer 1+2), 3. 69 (s, 6H, isomer 1+2), 3.22 (s, 18H, isomer 2), 3.21 (s, 18H, isomer 1), 2.50-2.35 (m, 4H, isomer 1), 2.22-2.02 (m, 4H, isomer 2 cis+trans), 1.60-1.09 (m, 35H, isomer 1+2), 0.90 (t, J=6.8 Hz, 6H).

[0729] 13 C NMR (MeOD, 101MHz) δ (ppm): 169.22, 169.01, 168.96, 165.52, 134.16, 133.22, 132 .94,131.74,65.90,65.81,60.23,60.18,59.73,55.27,54.66,54.62,35.66,35. 54,33.24,33.23,31.76,31.01,30.94,30.91,30.87,30.85,30.77,30.74,30.71,30.66,30.65,30.63,30.60,29.73,29.62,29.45,29.27,23.89,14.61 (terminal CH3).

[0730] Example 4 - by C 23 A mixture of quaternary ammonium compounds (a mixture of compounds of formula (V) and (VI)) wherein A is represented by A-2 or A-3 is synthesized starting from 1,2-tricosanone

[0731] Knoevenagel condensation to provide the diester intermediate:

[0732] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0733] Fresh commercially available anhydrous CHCl 3 , anhydrous THF and anhydrous pyridine were used as received.

[0734] In the 1L double-jacketed reactor that is equipped with mechanical stirrer (propeller with four tilted plow blades), condenser, addition funnel and temperature probe, add the TiCl of 48.6mL (84.02g, 0.443 mole), add the CHCl of 146mL subsequently.Mixture is stirred at-10 ℃ and slowly adds anhydrous THF (358mL) by addition funnel to avoid the temperature rise of reaction medium to exceed+5 ℃ speed.During THF intercalation, yellow precipitate occurs.Then 20.4mL dimethyl malonate (23.41g, 0.177 mole) is added in the reaction mixture, then allowed it to be at room temperature stirred 1 hour so that malonate complexing occurs.

[0735] The mixture was then allowed to cool to 0°C and 95.5 mL of anhydrous pyridine (93.44 g, 1.181 moles) 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.

[0736] Finally, 50.00 g of C 23 Ketone (0.148 mole) is added in the reaction mixture, allows it to stir overnight and under 35 ℃, stir one day again.Then the water of 250mL is carefully added in the reactor, adds the ether of 250mL subsequently.Separate organic phase and use the water washing of 250mL four times, and wash once so that remove pyridinium salt with the saturated NaCl aqueous solution of 200mL.Collect water and use the ether of 250mL to extract three times again.With final organic phase through MgSO Drying, filter and vaporising under vacuum to provide the thick orange oil of 69.5g.In this stage, crude product contains the starting ketone of residual quantity and the major impurity corresponding to the condensation (aldol condensation+crotonyl aldehyde) of the ketone of 2 equivalents.

[0737] The product can be easily purified by dissolving the oil in methanol (byproduct and starting ketone are insoluble in methanol) followed by filtration through celite.

[0738] The filtrate was evaporated to afford 54 g of an oil with 95% purity (RMN).

[0739] The overall purification yield was 77%.

[0740] 1H NMR (CDCl3, 400MHz) δ (ppm): 3.72 (s, 6H), 2.33-2.29 (m, 4H), 1.48-1.40 (m, 4H), 1.34-1.17 (m, 32H), 0.85 (t, J = 6.4Hz, 6H).

[0741] 13 C NMR (CDCl3, 101 MHz) δ (ppm): 166.28, 164.44, 123.63, 52.14, 34.6, 32.12, 30.13, 29.84, 29.73, 29.58, 29.55, 28.64, 22.90, 14.32 (terminal CH3).

[0742] Transesterification with dimethylaminoethanol provides a diamine mixture intermediate:

[0743] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0744] Fresh commercially available anhydrous toluene and dimethylaminoethanol were used as received.

[0745] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plow blades), a condenser with a distillation device and a temperature probe, 51.1 g of a solution of acetone / dimethyl malonate adduct (110 mmol, 1 equivalent) in 300 mL of toluene were added. The mixture was stirred at room temperature and 45.5 mL of dimethylaminoethanol (40.5 g, 450 mmol, 4 equivalents) was added to the reaction medium, followed by 1.37 g of the catalyst dibutyltin oxide (5.5 mmol, 5 mol%).

[0746] Then allow the mixture to stir at 120 ℃ and follow the reaction process by NMR analysis. In order to carry out appropriate analysis, the aliquots of the reaction medium are sampled and diluted in ether, quenched with water, decanted, and the organic phase is evaporated under vacuum to analyze in CDCl3 NMR solvent. After stirring at 120 ℃ for 2 days, allow the mixture to cool at room temperature and concentrate under vacuum. Then 200mL of water is added to the residue, and 200mL of ether is added subsequently. The organic phase is decanted and washed three times with 300mL of water and once with a saturated aqueous solution of 300mL of NaCl to remove excessive dimethylaminoethanol. Collect the aqueous phase and re-extract with 700mL of ether. Collect the organic phase, and then through MgSO4 drying, filter and evaporate. The obtained residue is redissolved in methanol and the solid of the precipitate is filtered. The filtrate is evaporated to provide a thick yellow oil of 59.04g. At this stage, the crude product contains the starting malonate and some by-products of the residual amount.

[0747] The product was then purified by flash column chromatography on silica gel using an eluent consisting of a CHCl 3 / isopropanol mixture by means of a gradient from 100% CHCl 3 to 100% isopropanol.

[0748] Clean fractions were collected to give 22.9 g of pure product after evaporation of the solvent, corresponding to 35% isolated yield.

[0749] NMR analysis showed that the product was in the form of a mixture of 2 positional isomers with the following ratios: 60 mol% of the isomerized product (cis and trans diastereomers) and 40 mol% of the methylenated product.

[0750] 1 H NMR (CDCl3, 400 MHz) δ (ppm): 5.45-5.15 (m, 1H: Isomer 2 cis + trans), 4.42 (s, 1H, Isomer 2 cis or trans), 4.24-4.08 (m, 4H, Isomer 1+2), 3.99 (s, 1H, Isomer 2 cis or trans), 2.65-2.40 (m, 4H, Isomer 1+2), 2.32-2.24 (m, 4H, Isomer 1), 2.20 (s, 12H, Isomer 1), 2.19 (s, 12H, Isomer 2), 2.10-1.90 (m, 4H, Isomer 2 cis + trans), 1.50-0.95 (m, 35H, Isomer 1+2), 0.81 (t, J = 6.4 Hz, 6H).

[0751] 13 C NMR (CDCl3, 101 MHz) δ (ppm): 168.81, 168.62, 165.71, 164.24, 132.27, 131.78, 131.33, 130.97, 123.95, 63.57, 62.98, 58.29, 57.69, 57.65, 53.71, 45.94, 34.66, 34.28, 32.13, 31.02, 30.23, 29.90, 29.87, 29.78, 29.65, 29.57, 29.55, 28.67, 28.64, 28.47, 28.29, 22.90, 14.33 (terminal CH3).

[0752] Methylation provides a mixture of compounds V and VI:

[0753] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0754] Fresh commercially available anhydrous THF and dimethyl sulfate were used as received.

[0755] In the 200mL double-jacketed reactor equipped with a mechanical stirrer (propeller with four tilted plow blades), a condenser, a feeding funnel and a temperature probe, 100mL of dry THF and 7.59mL of dimethyl sulfate (10.1g, 80mmol, 2 equivalents) were added. A solution of 22.94g of esteramine (40mmol, 1 equivalent) in 154mL of THF was prepared in advance in the feeding funnel and was progressively added to the reactor under stirring at room temperature to limit temperature increases. The mixture was then stirred at room temperature under argon, and the reaction process was monitored by NMR analysis. After stirring at room temperature for one hour, the reaction was completed, and all volatiles (THF and remaining DMS) were removed under vacuum to provide 32.6g of the product as a beige wax, with a 99% yield.

[0756] NMR analysis showed the presence of two positional isomers with a 60:40 ratio between the isomerized derivative (cis and trans diastereomers) and the conjugated non-isomerized methylenated derivative.

[0757] 1 H 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, isomer 1+2), 4.38 (s, 1H, isomer 2 cis or trans), 3.84-3.72 (m, 4H, isomer 1+2), 3. 69 (s, 6H, isomer 1+2), 3.22 (s, 18H, isomer 2), 3.21 (s, 18H, isomer 1), 2.50-2.35 (m, 4H, isomer 1), 2.22-2.02 (m, 4H, isomer 2 cis+trans), 1.60-1.09 (m, 35H, isomer 1+2), 0.90 (t, J=6.8 Hz, 6H).

[0758] 13 C NMR (MeOD, 101MHz) δ (ppm): 169.22, 169.01, 168.96, 165.52, 134.16, 133.22, 132 .94,131.74,65.90,65.81,60.23,60.18,59.73,55.27,54.66,54.62,35.66,35. 54,33.24,33.23,31.76,31.01,30.94,30.91,30.87,30.85,30.77,30.74,30.71,30.66,30.65,30.63,30.60,29.73,29.62,29.45,29.27,23.89,14.61 (terminal CH3).

[0759] Example 5 - by C 23 The synthesis of a compound wherein A is represented by A-1, specifically a compound of formula VII, is started by 1,2-tricosanone

[0760] Reductive amination to provide primary amines

[0761]

[0762] All reactions were carried out under an inert argon atmosphere.

[0763] In a 5 L three-necked round-bottom flask equipped with a magnetic stirrer, condenser, temperature probe and heater, a solution of tricosan-12-one (100 g, 0.295 mol, 1 eq) in 700 mL of methanol was prepared.

[0764] Then NH4OAc (227.386g, 2.95mol, 10 equivalents), followed by NaCNBH3 (74.15g, 1.18mol, 4 equivalents) were added to the mixture in small portions. The reaction medium was stirred at room temperature for 1 hour. Finally, the mixture was heated under reflux for 16 hours. The reaction medium was then cooled to room temperature and concentrated under vacuum.

[0765] Finally, 500mL of saturated NaHCO aqueous solution and 500mL of methyl tert-butyl ether (MTBE) are added to the residue and the mixture is stirred at room temperature for one hour. Concentrated NaOH aqueous solution is added to adjust the pH to about 9. The product is extracted with MTBE and the organic phase is washed with water and salt water several times. The organic phase is dried, filtered and concentrated under vacuum to provide a thick yellow oil of 100.4g.

[0766] The crude product was then purified by flash column chromatography over silica gel using a dichloromethane (DCM): methanol mixture as eluent with a gradient from DCM: MeOH = 100: 1 to DCM: MeOH = 10: 1 + 1% Et3N. After evaporation of the solvent, 93.5 g (0.275 mol) of pure light yellow oil were obtained.

[0767] Yield: 93%

[0768] Alkylation of primary amines to provide amino-diester intermediates

[0769]

[0770] The reaction was carried out under an inert argon atmosphere.

[0771] In a 1 L round bottom flask equipped with a condenser, temperature probe, magnetic stirrer and heater, add:

[0772] 62.0 g (0.18 mol, 1 equivalent) of C 23 Fatty primary amine.

[0773] 700 mL of methyl-THF.

[0774] 63.7 g of methyl 2-chloroacetate (0.59 mol, 3.3 eq.).

[0775] 81.5 g of K2CO3 (0.59 mol, 3.3 eq).

[0776] 97.94 g of KI (0.59 mol, 3.3 eq).

[0777] The mixture was then allowed to stir at reflux (78-80°C) overnight.

[0778] At the end of the reaction, the mixture was filtered and concentrated under vacuum to give 98.0 g of crude material which still contained methyl 2-chloroacetate.

[0779] The product was then purified by flash column chromatography over silica gel using petroleum ether:ethyl acetate mixture (50:1) as eluent to provide 52 g of pure material (0.108 mol) after evaporation of the solvent.

[0780] Yield: 60%

[0781] The ester is hydrolyzed to provide the iminodiacetic acid intermediate.

[0782]

[0783] In a 2 L round bottom flask equipped with a magnetic stirrer, add:

[0784] 27.3 g of NaOH (0.683 mol, 6.0 equivalents)

[0785] 300mL of water

[0786] 300 mL of methanol

[0787] 300 mL of THF

[0788] The obtained solution was then allowed to stir at 0°C and 55 g of amino-diester (0.113 mol, 1 eq.) was slowly added.

[0789] The reaction medium is then stirred at room temperature overnight.

[0790] At the end of the reaction, the pH was adjusted from 11 to 1 by adding concentrated HCl solution, and the product was extracted twice with 3 L of dichloromethane.

[0791] The organic phase was collected and washed several times with brine, dried over MgSO4, filtered and the solvent evaporated under vacuum to afford 55 g of the product which was used as such in the next step.

[0792] Quantitative yield

[0793] Esterification with dimethylaminoethanol to provide the diester intermediate

[0794]

[0795] The reaction was carried out under an inert argon atmosphere.

[0796] In a 2 L round bottom flask equipped with a magnetic stirrer, add:

[0797] 53.3 g (0.117 mol, 1 equivalent) of iminodiacetic acid intermediate

[0798] 2L of dichloromethane

[0799] 104.2 g of dimethylaminoethanol (1.17 mol, 10 equivalents)

[0800] 142 g of trimethylamine (1.40 mol, 12 equivalents)

[0801] 189.7 g of HOBt (1.40 mol, 12 equivalents)

[0802] The mixture was allowed to cool to 0°C and 220 g of EDCI (1.15 moles, 10 equivalents) was added to the reaction vessel.

[0803] The mixture was allowed to stir at room temperature for twenty hours to allow the reaction to complete.

[0804] The reaction mixture was then washed with water and the organic phase was dried over MgSO 4 , filtered and evaporated under vacuum to provide 118 g of crude product as a dark yellow oil.

[0805] The crude material was then purified by flash column chromatography over silica gel, using first a petroleum ether:CH2Cl2 mixture (9:1) as eluent and then a CH2Cl2:isopropanol (50:1)+1.5% NEt3 mixture.

[0806] Two fractions were obtained: the first fraction contained 31.0 g of product and the second fraction contained 35 g of material.

[0807] The second fraction was then purified a second time to provide 29.2 g of a dark yellow oil.

[0808] A total of 60.2 g (101 mol) of pure product were obtained as a yellow oil.

[0809] Yield: 86%

[0810] Quaternization to obtain a compound of formula (VII)

[0811] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0812] Fresh commercially available anhydrous THF and dimethyl sulfate were used as received.

[0813] In the 200mL double-jacketed reactor equipped with a mechanical stirrer (propeller with four tilted plow blades), a condenser, a charging funnel and a temperature probe, 100mL of dry THF and 8.0mL of dimethyl sulfate (10.6g, 84mmol, 2 equivalents) are added. In the charging funnel, a solution of esteramine (42mmol, 1 equivalent) of 25.2g in the THF of 154mL is prepared and at room temperature, under agitation, it is progressively added into the reactor to limit the temperature and raises. The mixture is then stirred at room temperature under argon, and the reaction process is monitored by NMR analysis. After stirring at room temperature for one hour, the reaction is completed, and all volatiles (THF and remaining DMS) are removed under vacuum to provide the product of 35.7g of beige wax with a quantitative yield.

[0814] 1 H NMR (MeOD, 400MHz) δ (ppm): 4.59-4.50 (m, 4H), 3.78-3.71 (m, 4H), 3.68 (s, 6H), 3.59-3.5 1(brs,4H),3.25(s,18H),2.68-2.54(m,1H),1.60-1.00(m,40H),0.90(t,J=6.4Hz,6H).

[0815] 13 C NMR (MeOD, 101MHz) δ (ppm): 173.02, 66.13, 65.49, 59.35, 55.26, 54.69, 54.34, 33.23, 32.82, 31.04, 30.95, 30.93, 30.91, 30.63, 28.27, 23.89, 14.61 (terminal CH3).

[0816] Example 6 - by C 31 The synthesis of a compound wherein A is represented by A-1, specifically a compound of formula VII, is started by 1,6-triacontanone

[0817] Reductive amination provides the primary amine.

[0818] According to the above example 5 for C 23 The same protocol as described for the derivatives.

[0819] Alkylation of the primary amine provides the amino-diester intermediate.

[0820] The reaction was carried out under an inert argon atmosphere.

[0821] In a 500 mL round bottom flask equipped with a condenser, temperature probe, magnetic stirrer and heater, add:

[0822] 18.0 g (40 mmol, 1 eq) of C 31 Fatty primary amine.

[0823] 500 mL of methyl-THF.

[0824] 12.48 g of methyl 2-chloroacetate (132 mmol, 3.3 eq).

[0825] 18.24 g of K2CO3 (132 mmol, 3.3 eq).

[0826] 21.92 g of KI (132 mol, 3.3 eq).

[0827] The mixture was then allowed to stir at reflux (78-80°C) overnight.

[0828] At the end of the reaction, the mixture was filtered through a plug of celite. The solid was washed with THF and the filtrate was concentrated under vacuum to provide a crude material still containing methyl 2-chloroacetate.

[0829] The product was then purified by flash column chromatography over silica gel using a petroleum ether:ethyl acetate mixture (100:1) as eluent to provide 22.4 g of pure material (37.6 moles) after evaporation of the solvent.

[0830] Yield: 94%

[0831] The ester is hydrolyzed to provide the imino-diacetic acid intermediate.

[0832] In a 1 L round bottom flask equipped with a magnetic stirrer, add:

[0833] 11.3 g of NaOH (0.282 mol, 6.0 equivalents)

[0834] 100mL of water

[0835] 100 mL of methanol

[0836] 100 mL of THF

[0837] The obtained solution was then allowed to stir at 0°C and 28 g of amino-diester (0.047 mol, 1 eq.) were slowly added.

[0838] The reaction medium is then stirred at room temperature overnight.

[0839] At the end of the reaction, the pH was adjusted from 11 to 2 by adding 1 M aqueous HCl solution, and the product was extracted with dichloromethane.

[0840] The organic phase was collected and washed several times with brine and finally concentrated. The residue was redissolved in THF and the organic solution was dried over MgSO4, filtered, and the solvent evaporated under vacuum to provide 26 g of the product (45.8 mmol), which was used as such in the next step.

[0841] Yield: 97%.

[0842] Esterification with dimethylaminoethanol provides the diester intermediate.

[0843] According to the same method as in Example 5, 23 The same protocol as described for the derivatives.

[0844] Quaternization to obtain the compound of formula VII

[0845] According to the same method as in Example 5, 23 The same protocol as described for the derivatives.

[0846] 1 H NMR (MeOD, 400MHz) δ (ppm): 4.52-4.36 (m, 4H), 3.71-3.61 (m, 4H), 3.58 (s, 6H), 3.46-3.3 9(brs,4H),3.15(s,18H),2.58-2.39(m,1H),1.60-1.00(m,56H),0.80(t,J=6.8Hz,6H).

[0847] 13 C NMR (MeOD, 101MHz) δ (ppm): 173.09, 66.09, 65.23, 59.31, 55.25, 54.69, 54.29, 33.25, 32.82, 31.03, 30.99, 30.96, 30.91, 30.87, 30.66, 28.24, 28.13, 23.91, 14.68 (terminal CH3).

[0848] Example 7 - Synthesis of Compounds of Formula (VIII) Starting from 16-heteronadecanone

[0849] Reductive amination to provide the aminodiol intermediate

[0850]

[0851] The reaction was carried out under an inert argon atmosphere.

[0852] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser and a temperature probe were added:

[0853] 50 g of 16-triacontanone (111 mmol, 1 equivalent)

[0854] 281 mL of CHCl3

[0855] 17.73 mL of 3-amino-1,2-propanediol (20.8 g, 222 mmol, 2 equivalents)

[0856] The mixture was then stirred at room temperature and 54.71 mL of Ti(OEt) 4 (59.52 g, 222 mmol, 2 eq) was added to the reactor. The mixture was then stirred at 65° C. overnight and it was observed that the mixture became homogeneous during the course of the reaction.

[0857] At the end of the reaction, the temperature was cooled to 40° C. and 56 mL of anhydrous methanol was added to the reactor, followed by careful and slow addition of 8.74 g of NaBH 4 (222 mmol, 2 eq.). Care was taken to avoid foaming during the addition of NaBH 4 .

[0858] The reaction medium is then stirred at 40° C. for three hours.

[0859] The mixture was then cooled to room temperature and 100 mL of water was added, followed by 100 mL of diethyl ether. During the addition of water, precipitation of TiO2 occurred.

[0860] The suspension was filtered, the solid was washed several times with ether and the two phases of the filtrate were separated. The organic phase was filtered again through celite and washed with water and brine. The organic phase was then dried over MgSO4, filtered and evaporated to provide the crude material (48.9 g) as a yellow paste.

[0861] The crude product was then purified by flash column chromatography over silica gel using a CHCl 3 :isopropanol mixture as eluent in a gradient from 100:0 to 50:50.

[0862] After evaporation of the solvent, 28.75 g of pure product were obtained (54.70 mmol).

[0863] Yield: 49%

[0864] 1H NMR (MeOD, 400MHz) δ (ppm): 3.78-3.64 (m, 1H), 3.62-3.42 (m, 2H), 2.78 (dd, J = 11. 6Hz, J=3.6Hz, 1H), 2.62-2.40 (m, 2H), 1.70-1.11 (m, 56H), 0.90 (t, J=6.4Hz, 6H).

[0865] 13 C NMR (MeOD, 101MHz) δ (ppm): 71.78, 66.46, 59.03, 51.08, 34.67, 33.26, 31.08, 31.0 4,30.97,30.95,30.92,30.83,30.80,30.66,26.87,26.85,23.91,14.62(terminal CH3).

[0866] Esterification with glycine betaine to provide the quaternary ammonium compound of formula VIII

[0867] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0868] Commercially available anhydrous THF, anhydrous toluene, and anhydrous CHCl3 stabilized with pentene were used as received.

[0869] Before use, glycine betaine hydrochloride was dried by washing with anhydrous THF several times followed by drying under vacuum.

[0870] In a 250 mL four-necked round bottom flask equipped with a condenser, a distillation apparatus connected to a NaOH trap, a temperature probe, a magnetic stirrer, and a heater, add:

[0871] 7.13 g of betaine hydrochloride (46.4 mmol)

[0872] Then 10 mL of SOCl2 (16.38 g, 136.9 mmol) was carefully introduced into the reactor vessel and the resulting suspension was gradually heated to 70° C. with stirring. It was observed that when the temperature reached 68° C., gas (SO2 and HCl) was released and the mixture turned homogeneously yellow.

[0873] The mixture was then allowed to stir at 70°C for two hours, and hot anhydrous toluene (25 mL, 80°C) was added to the vessel. The mixture was stirred and decanted at 0°C to precipitate the betaine acid chloride. The upper toluene phase was then removed by cannula, and the toluene washing operation was repeated four times to remove all excess SOCl2.

[0874] NMR analysis showed complete conversion of glycine betaine hydrochloride, but NMe 3 ·HCl adduct was also formed (NMe 3 ·HCl content in the solid: 19.3 mol %).

[0875] Then 20 mL of CHCl 3 was added to the solid betaine acid chloride.

[0876] A solution of the fatty diol (9.85 g, 18.7 mmol) in 30 mL of CHCl was then prepared and added dropwise to the betaine acid chloride / CHCl suspension at −3° C. at such a rate as to prevent the temperature of the reaction medium from exceeding 5° C. At the end of the addition, the mixture was allowed to warm to room temperature and then stirred at 50° C. overnight.

[0877] All volatiles were then removed under vacuum at 30°C to provide 16 g of a beige wax.

[0878] NMR analysis showed that the purity of the obtained product was about 73 wt % (the remaining by-products were: protonated starting alcohol, NMe 3 ·HCl, betaine hydrochloride and monoester).

[0879] Yield: 75% (14 mmol)

[0880] 1 H NMR (CDCl3-MeOD, 400MHz) δ (ppm): 5.55-5.63 (m, 1H), 4.93 (d, J = 16.8Hz, 1H), 4. 92(d,J=16.8Hz,1H),4.81(d,J=16.8Hz,1H),4.70(d,J=16.8Hz,1H),4.49(dd,J =12Hz,J=3.6Hz,1H),4.39(dd,J=12Hz,J=6.4Hz,1H),3.36(s,9H),3.33(s,9H), 3.32-3.28(m,2H),1.80-1.45(m,4H),1.45-1.10(m,52H),0.84(t,J=6.8Hz,6H).

[0881] 13 C NMR (MeOD, 101MHz) δ (ppm): 166.06, 71.18, 65.29, 64.59, 64.28, 61.35, 54.99, 54.87, 45.99, 45. 55,33.24,30.96,30.93,30.91,30.80,30.64,30.61,30.60,26.34,26.21,23.89,14.61(terminal CH3).

[0882] Example 8 - By C 31The synthesis of the quaternary ammonium compound wherein A is represented by A-5 and corresponds to formula (IX) is started by 1,6-heterononane

[0883] C was obtained from palmitic acid according to the protocol described in U.S. Pat. No. 10,035,746, Example 4. 31 Internal olefins.

[0884] Epoxidation of internal olefins to fatty epoxides

[0885]

[0886] The reaction was carried out under an inert argon atmosphere.

[0887] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plow 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 HO (30% concentration) was slowly added to the mixture using an addition funnel at a rate that avoided a significant temperature increase. This took about an hour. The temperature was then raised to 75°C and the reaction mixture was allowed to stir overnight (after 15 minutes, NMR analysis showed that the conversion level was already about 60% with 99% selectivity). Another 10.2 mL (11.3 g, 0.1 mol) of an aqueous solution of HO (30%) was then slowly added, and 4 hours after the second addition of HO, NMR analysis showed that the conversion level was about 88% (98% selectivity). Finally, an additional 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 performed in order to increase the conversion level.

[0888] The mixture was allowed to stir at 75°C for a second night.

[0889] Finally, NMR analysis showed a conversion level of 93% (95% selectivity).

[0890] 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 remains in the aqueous phase and is removed during the first separation from the aqueous phase.The organic phases are 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).

[0891] Taking the purity into account, the yield was 92%.

[0892] 1 H NMR (CDCl 3 , 400 MHz) δ (ppm): 2.91-2.85 (m, 2H, diastereomer 1), 2.65-2.6 (m, 2H, diastereomer 2), 1.53-1.00 (m, 54H), 0.86 (t, J=6.8 Hz, 6H).

[0893] 13 C NMR (CDCl3, 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).

[0894] Hydrolysis of fatty epoxides to provide fatty diols

[0895]

[0896] The reaction was carried out under an inert argon atmosphere.

[0897] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plow blades), a condenser and a temperature probe, 82.9 g of C 31 Epoxide (purity: 94.5 wt%, 0.174 mol) was added, followed by the addition of 480 mL of methyl-THF.

[0898] The mixture was allowed to stir at room temperature and then 73 mL of a 3M aqueous solution of H2SO4 was 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 three times with 50 mL of diethyl ether. Finally, the white solid was washed twice with 50 mL of methanol and dried under vacuum to remove traces of solvent.

[0899] Finally, 75.53 g of the product were obtained as a white powder with a purity of 95.7% w / w, corresponding to a yield of 89%.

[0900] 1H NMR (CDCl3, 400 MHz) δ (ppm): 3.61-3.55 (m, 2H, diastereomer 1), 3.43-3.25 (m, 2H, diastereomer 2), 1.88 (brd, J = 2.4 Hz, OH, diastereomer 2), 1.72 (brd, J = 3.2 Hz, OH, diastereomer 1), 1.53-1.10 (m, 54H), 0.86 (t, J = 6.8 Hz, 6H).

[0901] 13 C NMR (CDCl3, 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)

[0902] Esterification of aliphatic diols with trimethylglycine provides compounds of formula IX

[0903] All reactions were carried out in carefully dried vessels and under an inert argon atmosphere.

[0904] Fresh commercially available anhydrous CHCl3 (pentene-stabilized) and anhydrous toluene were used as received.

[0905] Before use, betaine hydrochloride (19.66 g, 128.4 mmol) was washed ten times with 20 mL of anhydrous THF and then dried under vacuum to remove traces of solvent.

[0906] In a 100 mL four-necked round-bottom flask equipped with a magnetic stirrer, heater, condenser, temperature probe, and a curved distillation column connected to two traps of NaOH, quickly add:

[0907] 19.66 g of dry betaine hydrochloride (128.4 mmol) and

[0908] 28 mL of SOCl2 (45.86 g, 0.386 mol).

[0909] The heterogeneous mixture was stirred and the temperature was then slowly raised to 70° C. When the temperature reached 68° C., it was observed that gases (SO 2 and HCl) were released and the mixture turned into a homogeneous yellow color.

[0910] The mixture was then allowed to stir at 70°C for two hours, and hot anhydrous toluene (25 mL, 80°C) was added to the vessel. The mixture was stirred and then decanted at 0°C (a white-yellow precipitate formed), and the upper toluene phase was removed by cannula. The toluene washing operation was repeated seven times to remove all excess SOCl2. NMR analysis showed complete conversion of glycine betaine hydrochloride, but NMe3·HCl adduct was also formed (NMe3·HCl content in the solid: 12.3 mol%).

[0911] Then 20 mL of dry CHCl 3 was added to the solid betaine acid chloride.

[0912] A solution of 26.19 g (56 mmol) of aliphatic diol in 90 mL of anhydrous CHCl was prepared at 55° C. and added dropwise to the reaction vessel with stirring at room temperature (exothermicity and release of HCl were observed). The mixture was then allowed to stir at 55° C. overnight. During the reaction, the mixture uniformly turned orange. NMR analysis showed a conversion level of approximately 100%.

[0913] The mixture was then allowed to cool to room temperature and the solvent was evaporated under vacuum.

[0914] The residue was dissolved in methanol at 0° C. and the precipitate formed was filtered off. The filtrate obtained was then evaporated to give 39.7 g of crude product.

[0915] The product was then deposited on a sintered filter and washed with cyclohexane to remove any remaining organic impurities. The washed solid was dried under vacuum to provide 22 g of crude material. Final purification was performed with a 50:50 mixture of CHCl / cyclohexane; the solid was redissolved in this solvent mixture at 50°C and allowed to cool to room temperature. The resulting precipitate was filtered off, and after evaporation of the filtrate, 19 g of a beige wax having the following composition was obtained:

[0916] 95 wt% glycine betaine diester

[0917] 1.5 wt% betaine methyl ester

[0918] 2wt% trimethylamine hydrochloride

[0919] 1.5 wt% of glycine betaine hydrochloride.

[0920] The purification yield was 44%.

[0921] 1H NMR (MeOD-d4, 400MHz) δ (ppm): 5.3-5.2 (m, 2H), 4.68 (d, J = 16.8Hz, 2H), 4.50 (d, J = 16.8Hz, 2H), 4. 53(s,1H),4.48(s,1H),3.37(s,18H),1.75-1.55(m,4H),1.39-1.10(m,50H),0.9(t,J=6.8Hz,6H).

[0922] 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).

[0923] Example 9 - Evaluation of the adsorption properties of nanocellulose crystals

[0924] 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 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).

[0925] Following the protocol described in the literature (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%.

[0926] The range of CNC aggregation corresponds to the range of ratio X (or M) that triggers CNC aggregation, ie the range of aggregate size measured by DLS is higher than that of pure aqueous solution of CNC or aqueous solution of surfactant at 0.01 wt%.

[0927] The ranges of X and M for the aggregation of CNCs are summarized in Table 1. The lower the range of X or M, the better the adsorption characteristics on the negatively charged surface.

[0928] Table 1

[0929]

[0930] TEP was used as a comparison. TEP is a commercially available surfactant representing a benchmark.

[0931] The data show that compared with commercially available surfactants The surfactant properties of the compounds according to the invention are excellent compared to TEP.

[0932] The properties of the compounds of Examples 2 and 5 to 8 were similar to those of the compounds of Examples 1 , 3 and 4 in terms of adsorption to cellulose nanocrystals, the values of which are given in Table 1 .

[0933] Example 10 - Determination of Biodegradability

[0934] The biodegradability of the test substances has been measured according to the 301F OECD protocol.

[0935] In a closed flask (Oxitop TM A measured volume of inoculated mineral culture medium (containing a known concentration of the test substance so as to achieve approximately 50 to 100 mg ThOD / l (theoretical oxygen demand)) as the nominal sole source of organic carbon was stirred in a respirometry flask at a constant temperature (20 ± 2°C) for up to 28 days. TM Respirometry flasks To obtain biodegradability of test samples: Sealed incubation BOD flasks were used at a temperature of 20±2°C for 28 days.

[0936] 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 taken up by the microbial population during the biodegradation process (biooxidation of the test substance) (= oxygen consumption expressed in mg / l) reduces the pressure in the headspace (ΔP measured by a pressure switch) and is mathematically converted into mg of consumed O2 / liter. The inoculum corresponds to municipal activated sludge washed in a mineral culture medium (ZW culture medium) in order to reduce the DOC (dissolved oxygen carbon) content. A control solution containing the reference substance sodium acetate and a toxicity control (test substance + reference substance) are used for confirmation purposes. The reference substance sodium acetate has been tested in one bottle (at 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 the reference substance and the 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).

[0937] Since the substances of the invention are not very water-soluble 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.

[0938] The emulsion protocol involves adding the test substance to the bottle via a stock solution prepared in emulsion.

[0939] 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) was prepared and then mixed with mineral silicone oil AR 20 (Sigma).

[0940] The first dissolution of the test substance in the non-biodegradable surfactant solution usually requires stirring with a magnetic stirrer followed by sonication.

[0941] 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 to the corresponding bottles in order to achieve the desired test substance concentration.

[0942] 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 solutions.

[0943] The results of the biodegradability tests are summarized in Table 2

[0944] The following compounds Biodegradability after 28 days Example 2 0% (OECD 301F) Example 3 17% (OECD 301D) Example 7 15% (OECD 301F) Example 8 92% (OECD 301F)

[0945] The results show that the compound of Example 8 has the best biodegradability among the compounds used in the working examples, that is, the biodegradability of the compound according to the present invention (wherein A is represented by A-5 and specifically the compound of Formula IX) is higher than that of the other compounds. This beneficial effect is achieved without adversely affecting the surfactant properties of the compound.

[0946] Example 11 - Synthesis of Quaternary Diammonium Compounds Starting from 16-Hexadecanone

[0947] 16-Hentheconidine-one was purchased from TCI but can be obtained from palmitic acid following the pyriaconization protocol described in US 2018 / 0093936.

[0948] Hydrogenation of 16-triacontanone to 16-triacontanol

[0949] In a 100 mL autoclave equipped with a mechanical stirrer (Rushton turbine) were added:

[0950] - 4.36 g of Ru / C (4.87% Ru) catalyst (5 wt% dry catalyst relative to ketone, catalyst containing 54.9% H2O)

[0951] -39.3 g (87.2 mmol) of molten C 31 ketone.

[0952] The reaction was carried out under a hydrogen pressure of 20 bar. Four nitrogen purges were performed, followed by three hydrogen purges at 20 bar. The temperature of the reaction mixture was then set to 100°C to melt the ketone substrate. The temperature was maintained at 100°C for 10 minutes and stirring was slowly initiated at 200 rpm. Once adequate stirring was confirmed, the stirring rate was increased to 1200 rpm and the temperature was set to 150°C.

[0953] After 6 h of reaction time at 150° C., heating was stopped and the mixture was allowed to cool while stirring at 90° C. Stirring was then stopped. The mixture was cooled to room temperature and the autoclave was carefully depressurized.

[0954] The crude product was analyzed by NMR in CDCl3 and the ketone conversion level was >99% and the molar purity of the fatty alcohol was 99%. The dense solid containing the product and catalyst was ground into a powder and then introduced into a 1 L flask. 500 mL of chloroform was added and the flask was then heated at 60°C to completely dissolve the alcohol. The suspension was filtered through celite at 60°C. The solid filter cake was rinsed several times with hot chloroform at 60°C. The filtrate was evaporated to give 35.6 g (78.7 mmol) of the desired C 31 The fatty alcohol was obtained as a white powder with a purity of about 99% by weight, corresponding to an isolated yield of 90%.

[0955] Dehydration of 16-hexadecane to internal olefins

[0956] The reaction was carried out under an inert argon atmosphere. In a 200 mL quartz reactor equipped with a heating pad, a mechanical stirrer (by using an A320-type stirring mobile device made by 3D printing with Inox SS316L), a condenser connected to a 50 mL two-neck distillate collection flask and a temperature probe, the following were added:

[0957] -56.1g of C 31 Fatty alcohol (124 mmol, 1 equivalent)

[0958] -5.61 g (10 wt%) of Al2O3-η.

[0959] The temperature of the reaction medium was then raised to 150° C. to melt the alcohol and stirring was started (about 500 rpm). Finally, the temperature was set at 300° C. and the mixture was allowed to stir at 1000 rpm under argon. The progress of the reaction was monitored by NMR analysis using a borosilicate glass tube.

[0960] After 2 hours of reaction at 300° C., NMR analysis in CDCl 3 showed complete conversion of the fatty alcohol and the presence of 1.5 mol % of ketone which had been formed as a by-product.

[0961] Then stop stirring and heating. Reduce the temperature to 80 ℃ and transfer the molten crude product to a beaker. Rinse the reactor vessel and stirring mobile device with chloroform (Al2O3 is insoluble). The suspension is filtered and the solvent is evaporated under vacuum to provide 52.24 g (120.2 mmol) of a clear oil, which becomes a white solid (99 wt% purity) at room temperature, corresponding to a 97% isolated yield (NMR).

[0962] 1 H NMR (CDCl3, 400MHz) δ (ppm): 5.38-5.29 (m, 2H), 2.03-1.93 (m, 4H), 1.35-1.19 (m, 48H), 0.86 (t, J = 6.8Hz, 6H).

[0963] 13 C NMR (CDCl3, 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).

[0964] Epoxidation of internal olefins to ethylene oxide

[0965] The reaction was carried out under an inert argon atmosphere. In a double-jacketed 1 L reactor equipped with a mechanical stirrer (propeller with four inclined plow blades), a condenser and a temperature probe, 92.4 g of C 31 Olefin (0.212 mol), followed by 18.2 mL (19.1 g, 0.319 mol) of acetic acid and 27.7 g (30 wt%) of IR 120H resin.

[0966] The mixture was heated to 75°C to melt the fatty olefin. Stirring was then started and 32.6 mL (36.1 g, 0.319 mol) of a 30% aqueous H2O2 solution was slowly added to the mixture using an addition funnel while monitoring the temperature of the reaction mass to avoid a temperature increase. The addition took about one hour.

[0967] After the addition of H2O2 was complete, the temperature was raised to 85°C and the progress of the reaction was followed by NMR analysis. After a reaction time of 4 hours, the olefin conversion level was >99% with a selectivity to the desired epoxide of about 99% (traces of valuable diols were also formed during the reaction).

[0968] Then, the heating was stopped and 300 mL of chloroform was added to the reaction vessel at a temperature of about 50°C. The mixture was transferred to a separatory funnel. The organic phase was washed three times with 300 mL of water. The aqueous phase was then extracted twice with 100 mL of chloroform. During the phase separation from the aqueous phase, the The organic phase was dried over MgSO4, filtered and evaporated to give 95.3 g of a white solid with a purity of 98% w / w (epoxide + diol). Taking into account the purity, the yield was 97%.

[0969] 1 H NMR (CDCl3, 400MHz) δ (ppm): 2.91-2.85 (m, 1.5H), 2.65-2.6 (m, 0.5H), 1.53-1.36 (m, 4H), 1.35-1.19 (m, 48H), 0.86 (t, J = 6.8Hz, 6H).

[0970] 13 C NMR (CDCl3, 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).

[0971] Condensation with chloroacetic acid (with H2SO4 as optional catalyst)

[0972] The reaction was carried out in a 500 mL three-necked round-bottom flask equipped with a magnetic stirrer, heater, condenser, temperature probe, and an insulated addition funnel under an inert argon atmosphere. 128.7 g of chloroacetic acid (1.35 moles, 8 equivalents) was added to the round-bottom flask itself. 77.8 g of molten fatty epoxide (98 wt% purity, 0.169 moles, 1 equivalent) was added to the insulated addition funnel maintained at 65°C.

[0973] The first step of the intermediate hydroxy-ester formation is carried out by slowly adding the fatty epoxide to chloroacetic acid at 65° C. in order to limit the formation of ketone and epoxide self-condensation by-products. Therefore, the fatty epoxide is added dropwise to the reactor containing chloroacetic acid at 65° C. under stirring over 30 minutes.

[0974] At the end of the addition, the mixture was allowed to stir for another 20 min at 65° C. NMR analysis showed a conversion level of >99% of the starting epoxide.

[0975] Then, to form the final diester, 0.19 mL of 95% H2SO4 (3.37 mmol, 2 mol%) was added to the reactor and the condenser was replaced with a curved distillation column.

[0976] The mixture was allowed to stir at 140° C. for 3 h30 under a light vacuum (800 mbar) in order to remove the water formed as a by-product during the esterification reaction.

[0977] After 3 h30 at 140° C., NMR analysis showed a selectivity of 83 mol % (monoester+diester) and the following approximate crude mixture composition: 80 mol % diester, 3 mol % monoester, 2 mol % esterified dimer and 4 mol % ketone.

[0978] The mixture was then cooled at room temperature (about 23° C.) and 300 mL of toluene was added. The solution was transferred to a separatory funnel and the organic phase was washed three times with 500 mL of an aqueous NaOH solution (0.3 M) to remove excess chloroacetic acid. The organic phase was dried over MgSO , filtered and then evaporated to give 102.7 g of crude product.

[0979] The product can be easily purified by dissolving the oil in ethanol (the starting ketone is insoluble in ethanol) followed by filtration through celite. The filtrate was evaporated to provide 94 g of a black oil with 89 wt% diester purity, corresponding to an isolated yield (RMN) of 80%.

[0980] 1 H NMR (CDCl3, 400 MHz) δ (ppm): 5.11-5.02 (m, 2H), 4.04 (s, isomer 1, 2H), 4.03 (s, isomer 2, 2H), 1.66-1.49 (m, 4H), 1.43-1.19 (m, 50H), 0.86 (t, J = 6.8 Hz, 6H).

[0981] 13 C NMR (CDCl3, 101 MHz) δ (ppm): 167.14, 167, 76.22, 75.83, 40.92, 40.82, 31.96, 30.6, 29.72, 29.69, 29.63, 29.54, 29.39, 29.33, 29.28, 28.85, 25.47, 24.96, 22.72, 14.15 (terminal CH3).

[0982] Condensation with chloroacetic acid (with trifluoromethanesulfonic acid as an optional catalyst)

[0983] The reaction was carried out in a 500 mL three-necked round-bottom flask equipped with a magnetic stirrer, heater, condenser, temperature probe, and an insulated addition funnel under an inert argon atmosphere. 85.63 g of chloroacetic acid (0.897 mol, 5 equivalents) was added to the round-bottom flask itself. 83.3 g of molten fatty epoxide (97 wt% purity, 0.179 mol, 1 equivalent) was added to the insulated addition funnel.

[0984] The first step of monoester formation was carried out at 65°C in the absence of triflic acid to limit the formation of ketones and dehydration by-products. Therefore, the fatty epoxide was added dropwise to a reactor containing chloroacetic acid at 65°C with stirring over 2 hours to limit self-condensation of the fatty epoxide. At the end of the addition, the mixture was allowed to stand at 65°C with stirring for another hour. NMR analysis showed a conversion level of >99% of the starting epoxide.

[0985] To form the diester, 3.2 μL of 99% trifluoromethanesulfonic acid (0.036 mmol, 0.02 mol%) were then added to the reaction mixture. The condenser was replaced with a curved distillation column and the mixture was allowed to stir at 140° C. under a light vacuum (975 mbar) for 5 h 00 in order to remove the water formed as a by-product of the esterification reaction.

[0986] After 5 h00, NMR analysis showed a selectivity (monoester+diester) of 88 mol % and a composition of 82 mol % diester, 6 mol % monoester, 5 mol % esterified dimer and 3 mol % ketone.

[0987] The vacuum was then increased to 800 mbar and gradually increased to 10 mbar in order to distill off the chloroacetic acid, the triflic acid catalyst and to complete the conversion of the monoester to the diester.

[0988] In the flask, add 1% chloroacetic acid, 1% chloroacetic acid and 1% chloroacetic acid.In case all chloroacetic acid have been distilled out (by NMR analysis verification), allow the mixture to cool at room temperature and recover atmospheric pressure.Crude oil is transferred in the flask and is used for purification.By being dissolved in the ethanol (initial ketone is insoluble in ethanol), subsequently through diatomite filtration, can easily purified product.Filtrate is evaporated to provide the black oil of 107.3g, with the diester purity of 93wt%, corresponding to 89% separation yield.

[0989] 1 H NMR (CDCl3, 400 MHz) δ (ppm): 5.11-5.02 (m, 2H), 4.04 (s, isomer 1, 2H), 4.03 (s, isomer 2, 2H), 1.66-1.49 (m, 4H), 1.43-1.19 (m, 50H), 0.86 (t, J = 6.8 Hz, 6H).

[0990] 13 C NMR (CDCl3, 101 MHz) δ (ppm): 167.14, 167, 76.22, 75.83, 40.92, 40.82, 31.96, 30.6, 29.72, 29.69, 29.63, 29.54, 29.39, 29.33, 29.28, 28.85, 25.47, 24.96, 22.72, 14.15 (terminal CH3)

[0991] Quaternization reaction with NMe3

[0992] The reaction was carried out under an inert argon atmosphere. In a 1 L double-jacketed reactor equipped with a mechanical stirrer, a condenser and a temperature probe, the following were added:

[0993] - 107.3 g (93 wt% purity, 0.16 mol, 1 equivalent) of chloroacetic acid diester C 31

[0994] - 687 mL (1.28 mol, 8 equivalents) of a solution of trimethylamine (NMe3) in THF (about 2 mol / L), which had been previously dried over activated molecular sieves the day before.

[0995] The reaction mixture was heated at 40° C. and stirring was started at 1000 rpm. After 6 h, NMR analysis in d4-MeOH showed a conversion level of >99% of the starting diester, with a molar composition of glycine betaine diester of approximately 86 mol%. The reactor was drained, flushed with CH2Cl2, and the volatiles were evaporated under vacuum.

[0996] The brown solid was turned into powder, deposited on a sintered filter and washed five times with 200 mL of ethyl acetate. The solid was dried under vacuum.

[0997] The product was then transferred into a 1 L reactor equipped with a mechanical stirrer, condenser, heater, and temperature probe. The product was dissolved in 800 mL of chloroform and 150 g of activated carbon particles were added. The mixture was stirred at 40° C. for 2 hours to whiten the product.

[0998] After 2 h, the suspension was filtered through celite and the solvent was evaporated to provide 109 g of a brown wax having about 95 wt% of a quaternary diammonium compound of formula (IX), 2 wt% of a quaternary monoammonium, 0.1 wt% of C 31 The weight composition of the ketone and 4 wt% of the ether by-product. The purified yield of glycine betaine diester was about 87%.

[0999] Example 12 - By C 16 -C 18(30:70) Fatty acid fractions begin to synthesize quaternary diammonium compounds

[1000] Pyrialone to C 31 -C 35 Lactone fraction

[1001] The reaction was carried out under an inert argon atmosphere in a 200 mL quartz reactor equipped with mechanical stirring (A320-type stirring motion device manufactured by 3D-printing from Inox SS316L), an insulated addition funnel, a distillation apparatus, a heating pad, and a temperature probe.

[1002] Introduced into the reactor:

[1003] -12.5g of MASCID TM Acid 1865 (from Musim Mas Group), which consists of 33.7 wt% palmitic acid and 65.3 wt% stearic acid (0.045 moles of fatty acids), and

[1004] - 0.935 g of MgO (0.023 mole).

[1005] To the insulated addition funnel was added 37.5 g of the same molten fatty acid mixture (0.135 moles).

[1006] The temperature of the reaction medium was then raised to 250° C. Stirring was started (1200 rpm) once the temperature reached 150° C. After 2 h00 reaction time at 250° C., FTIR analysis showed complete conversion of the starting fatty acid into the intermediate magnesium carboxylate complex.

[1007] The temperature of the reaction mass was then further increased to 330°C, and the mixture was allowed to stir at this temperature for 1 h30 in order to allow the intermediate magnesium carboxylate complex to decompose into the desired ketone.

[1008] Then, 12.5 g of the molten fatty acid mixture were gradually added to the reactor via an addition funnel within 30 minutes, and the mixture was stirred for another 1 h00 at 330° C. FTIR analysis showed complete conversion of the fatty acid and magnesium complex to the desired ketone.

[1009] Two further cycles were then carried out: addition of 12.5 g of fatty acid within 30 minutes, followed by stirring at 330° C. for a further 1 h00.

[1010] After the final cycle, the mixture was allowed to stir at 330°C for an additional 1 h00 to ensure complete conversion of the intermediate magnesium complex to the desired ketone, which was confirmed by FTIR analysis.

[1011] The temperature of the reaction mixture was then allowed to cool at room temperature and the crude product was dissolved in hot CHCl 3. The suspension was filtered over a plug of silica (70 g) and the product was further eluted with additional amounts of CHCl 3.

[1012] After evaporation of the solvent, 41.83 g (0.086 mol) of the product were obtained as a white wax, corresponding to an isolated yield of 96%.

[1013] 1 H NMR (CDCl3, 400MHz) δ (ppm): 2.45-2.25 (t, J = 7.6Hz, 4H), 1.62-1.46 (m, 4H), 1.45-1.05 (m, 54H), 0.86 (t, J = 6.8Hz, 6H).

[1014] 13 C NMR (CDCl3, 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).

[1015] The ketone mixture is hydrogenated to C 31 -C 35 Fatty alcohol mixture

[1016] Following the same protocol as described in Example 11 under the section "Hydrogenation of 16-triacontanone to 16-triacontanol", the desired fatty alcohol mixture was obtained in excellent yields.

[1017] C 31 -C 35 Dehydration of fatty alcohols to internal olefins

[1018] All reactions were carried out under an inert argon atmosphere.

[1019] In a 200 mL quartz reactor equipped with a heating pad, a mechanical stirrer (by means of an A320-type stirring motion device manufactured by 3D printing in Inox SS316L), a condenser wrap connected to a 50 mL two-necked distillate collection flask, and a temperature probe were added:

[1020] -41.3g of C 31-35 Fatty alcohol (85 mmol, 1 eq), and

[1021] -4.13 g (40 mmol, 10 wt%) of Al2O3-η.

[1022] The temperature of the reaction medium was raised to 150° C. to melt the alcohol and stirring was started (about 500 rpm). The temperature was then set at 300° C. and the mixture was allowed to stir at 1000 rpm under argon. The progress of the reaction was monitored by NMR analysis using a borosilicate glass tube.

[1023] After 2 hours of reaction at 300° C., NMR analysis in CDCl 3 showed complete conversion of the fatty alcohol and the presence of 1.5 mol % of a ketone which had been formed as a by-product.

[1024] Then stop stirring and heating and reduce the temperature to 80° C. Transfer the molten crude product to a beaker. Rinse the reactor vessel and stirring motion device with chloroform (Al 2 O 3 is insoluble).

[1025] The mixture was filtered and the solvent was evaporated under vacuum to afford 39 g of a clear yellow oil which solidified at room temperature to give a white solid (98 wt% purity) in the form of a wax, corresponding to 97% yield (NMR).

[1026] 1 H NMR (CDCl 3 , 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).

[1027] 13 C NMR (CDCl3, 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).

[1028] Epoxidation of internal olefins to provide C 31-35 Ethylene oxide

[1029] The reaction was carried out under an inert argon atmosphere.

[1030] 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:

[1031] -38.2g of C 31-35 Olefin (98 wt% purity, 80 mmol)

[1032] - 6.9 mL (7.2 g, 120 mmol) of acetic acid, and

[1033] -11.3 g (30 wt%) IR 120H resin.

[1034] The mixture was heated to 75°C to melt the aliphatic olefin. Stirring was then started and 12.3 mL (13.7 g, 120 mmol) of HO 30% was slowly added to the mixture using an addition funnel while monitoring the temperature of the reaction medium to prevent the temperature of the reaction mass from increasing (exothermic). This took approximately 20 minutes. During this addition, stirring was increased to improve transfer due to the heterogeneous nature of the reaction medium.

[1035] At the end of the addition, the temperature of the reaction medium is raised to 85° C. and, after stirring at this temperature for 6 h 10, NMR analysis shows a conversion level of about 99%, with a selectivity of 98%.

[1036] The heating was then stopped and 150 mL of chloroform was added when the temperature of the reaction mass was approximately 50°C. The mixture was transferred to a separatory funnel and the organic phase was washed three times with 150 mL of water. The resin catalyst remaining in the aqueous phase was removed during phase separation. The aqueous phase was extracted twice with 50 mL of chloroform. The organic phase was dried over MgSO4, filtered, and evaporated to provide 39.2 g of a white solid with a purity of 98 wt% (epoxide + diol by-product). Considering the purity, the yield was 99%.

[1037] 1 H NMR (CDCl 3 , 400 MHz) δ (ppm): 2.91-2.85 (m, 1.5 H), 2.65-2.6 (m, 0.5 H), 1.53-1.36 (m, 4 H), 1.35-1.19 (m, 55 H (average number of H)), 0.86 (t, J=6.8 Hz, 6 H).

[1038] 13 C NMR (CDCl3, 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).

[1039] Condensation with chloroacetic acid to provide chloroacetic acid diester C 31-35 (with H2SO4 as optional solvent)

[1040] The reaction was carried out in a 250 mL three-necked round-bottom flask equipped with a magnetic stirrer, heater, condenser, temperature probe, and insulated addition funnel under an inert argon atmosphere. 59.2 g of chloroacetic acid (0.62 mol, 8 eq) was added to the round-bottom flask itself. 38.3 g of molten C was added to the insulated dropping funnel maintained at 60°C. 31-35Epoxide (purity: 98 wt%, 77.6 mmol, 1 eq).

[1041] The first step of hydroxy-ester formation is carried out at 70°C in the absence of sulfuric acid to limit the formation of ketone and dehydration by-products, and by gradual addition of the fatty epoxide to chloroacetic acid to limit epoxide self-condensation. The reaction mixture is allowed to stir at 70°C to melt the chloroacetic acid.

[1042] The molten epoxide was then added dropwise to the reaction mixture over 1 h00 with stirring in order to limit self-condensation of the epoxide.

[1043] At the end of the addition, the mixture was allowed to stir for a further 20 min at 70° C. At this stage, NMR analysis showed almost complete conversion of the epoxide to the intermediate monoester.

[1044] To convert the monoester into a diester, 87 μL of 95% H SO (1.6 mmol, 2 mol%) was added to the reaction mixture. The condenser was replaced by a curved distillation column and the mixture was allowed to stir at 140° C. for 6 h 30 while applying a vacuum of 800 mbar to facilitate water removal. After 6 h 30 reaction time, NMR analysis showed an estimated composition of the crude medium:

[1045] -79 mol% diester

[1046] -6 mol% monoester

[1047] -1 mol% of esterified dimer by-product, and

[1048] -5 mol% of ketone by-product.

[1049] The mixture was cooled at room temperature and 150 mL of toluene was added to the crude product. The organic solution was transferred into a separatory funnel and washed 7 times with 250 mL of a 0.15 M NaOH aqueous solution to remove excess chloroacetic acid. The aqueous phase was extracted 2 times with 100 mL of toluene.

[1050] The organic phase was collected and washed with 150 mL of aqueous HCl (0.1 N) and then with 150 mL of saturated NaCl solution. The organic phase was dried over MgSO 4 , filtered and then evaporated to give 48 g of crude product.

[1051] The product can be easily purified by dissolving the oil in isopropanol (the starting ketone is insoluble in isopropanol) followed by filtration through celite. The filtrate was evaporated to give 45.7 g of a black oil with an estimated purity of 91 wt% of the diester, corresponding to a yield (RMN) of 81%.

[1052] 1H NMR (CDCl3, 400 MHz) δ (ppm): 5.11-5.02 (m, 2H), 4.04 (s, isomer 1, 2H), 4.03 (s, isomer 2, 2H), 1.66-1.49 (m, 4H), 1.43-1.19 (m, 55H (average number of H)), 0.86 (t, J = 6.8 Hz, 6H).

[1053] 13 C NMR (CDCl3, 101 MHz) δ (ppm): 167.14, 167, 76.22, 75.83, 40.92, 40.82, 31.96, 30.6, 29.72, 29.69, 29.63, 29.54, 29.39, 29.33, 29.28, 28.85, 25.47, 24.96, 22.72, 14.15 (terminal CH3).

[1054] Quaternization with NMe3

[1055] The reaction was carried out under 5 bar nitrogen pressure. In a 750 mL autoclave equipped with a mechanical stirrer (Rushton turbine) were added:

[1056] - 45.7 g (91 wt% purity, 63 mmol, 1 equivalent) of chloroacetic acid diester C 31-35 ,and

[1057] 169 mL (316 mmol, 5 equivalents) of a solution of trimethylamine in THF (about 2 mol / L), which had been previously dried over molecular sieves activated the day before.

[1058] Three nitrogen purges were performed.The reaction mixture was heated at 40°C and stirring was started at 1000 rpm.

[1059] After a reaction time of 4 h 15 , NMR analysis in MeOD / CDCl 3 showed a conversion level of about 99% to the starting chloroacetic acid diester with about 81 mol % of the desired glycine betaine diester.

[1060] The mixture was allowed to cool at room temperature, the reactor was depressurized and the solution was then drained. The reactor was rinsed with CH2Cl2 and the solvent was evaporated to provide 43 g of crude product.

[1061] The solid was then deposited on a sintered filter and washed several times with ethyl acetate to remove some organic impurities. The solid was dried under vacuum and transferred into a 500 mL three-necked round bottom flask equipped with a magnetic stirrer, heater, condenser and temperature probe.

[1062] The product was dissolved in 250 mL of chloroform and 25 g of activated carbon were added. The reaction mixture was then heated under reflux for 2 hours to turn the product white.

[1063] After cooling at room temperature, the suspension was filtered through celite and then evaporated to give 33 g of a beige wax with the following approximate composition: 92 wt% quaternary diammonium compound of formula (IX), 5 wt% quaternary monoammonium compound and 3 wt% ether by-product.

[1064] 1 H NMR (MeOD-d4, 400 MHz) δ (ppm): 4.78 (s, 1H), 4.74 (s, 1H), 4.53 (s, 1H), 4.49 (s, 1H), 3.38 (s, 18H), 1.77-1.6 (m, 4H), 1.51-1.25 (m, 55H (average number of H)), 0.9 (t, J = 6.8 Hz, 6H).

[1065] 13 C NMR (MeOD-d4, 101 MHz) δ (ppm): 166.39, 166.12, 79.62, 78.17, 77.28, 64.25, 63.98, 54.8, 54.65, 33.21, 31.61, 30.95, 30.83, 30.69, 30.64, 30.5, 30.44, 29.81, 26.7, 26.21, 23.9, 14.58 (terminal CH3).

[1066] Example 13 - By C 16 -C 18 (60:40) Fatty acid fractions begin to synthesize quaternary diammonium compounds

[1067] Pyrialone to C 31 -C 35 Lactone fraction

[1068] The reaction was carried out under an inert argon atmosphere in a 200 mL quartz reactor equipped with a heating pad, mechanical stirring (A320-type stirring motion device manufactured by 3D-printing in Inox SS316L), an insulated addition funnel, a distillation apparatus and a temperature probe.

[1069] Introduced in the reactor itself:

[1070] - 15 g of MASCID with the following composition TM Acid 1801 (from Musim Mas Group): 60.9 wt% palmitic acid and 38.2 wt% stearic acid (0.056 moles of fatty acids), and

[1071] - 1.15 g of MgO (0.028 mol).

[1072] To the insulated addition funnel was added 45 g of the same molten fatty acid mixture (0.167 moles).

[1073] The temperature of the reaction mixture was then raised to 250° C. and stirring (1200 rpm) was started once the temperature had reached 150° C. After 1 h 15 reaction time at 250° C., FTIR analysis showed complete conversion of the starting fatty acid to the intermediate magnesium carboxylate complex.

[1074] The temperature of the reaction mass was then further increased to 330°C, and the mixture was allowed to stir at this temperature for 1 h30 in order to allow the magnesium complex to decompose into the desired ketone.

[1075] Then, 15 g of the molten fatty acid mixture was gradually added to the reactor via an addition funnel over 15 minutes, and the mixture was stirred for another hour at 330° C. FTIR analysis confirmed complete conversion of the fatty acid and magnesium complex to the desired ketone.

[1076] Two further cycles were then carried out: 15 g of fatty acid were added over 15 minutes, followed by stirring at 330° C. for one hour. After the final addition cycle, the mixture was allowed to stir at 330° C. for another hour to ensure complete conversion of the intermediate magnesium carboxylate complex to the desired ketone, as confirmed by FTIR and NMR analysis according to the following protocol: the sample was dissolved in chloroform and washed three times with 2N aqueous HCl, and the solvent was evaporated. NMR and IR analysis of the residue did not show the presence of any starting fatty acid that could have been formed by hydrolysis of the complex.

[1077] The temperature of the reaction mixture was allowed to cool at 60° C. and the crude product was dissolved in 350 mL of hot CHCl 3 (60° C.). The suspension was filtered on a plug of silica (100 g) and the product was further eluted with an additional amount of CHCl 3. After evaporation of the solvent, 50.5 g of crude product was obtained.

[1078] The product was washed three times with 200 mL of isopropanol on a sintered filter in order to remove traces of by-products. The solid was dried to afford the desired ketone as a white powder with a purity of 100 mol%, corresponding to a yield of 90%.

[1079] 1 H NMR (CDCl 3 , 400 MHz) δ (ppm): 2.35 (t, J=7.6 Hz, 4H), 1.62-1.46 (m, 4H), 1.34-1.16 (m, 54.8H (average number)), 0.86 (t, J=6.8 Hz, 6H).

[1080] 13 C NMR (CDCl3, 101 MHz) δ (ppm): 212.00, 43.06, 32.16, 29.92, 29.89, 29.85, 29.72, 29.66, 29.6, 29.52, 24.16, 22.93, 14.35 (terminal CH3).

[1081] The ketone mixture is hydrogenated to C 31 -C 35 Fatty alcohol mixture

[1082] Following the same protocol as described in Example 11 under the section "Hydrogenation of 16-triacontanone to 16-triacontanol", the desired fatty alcohol mixture was obtained in excellent yields.

[1083] C 31 -C 35 Dehydration of fatty alcohols to internal olefins

[1084] The reaction was carried out under an inert argon atmosphere. In a 200 mL quartz reactor equipped with a heating pad, a mechanical stirrer (by using an A320-type stirring motion device manufactured by 3D printing with Inox SS316L), a condenser wrap connected to a 50 mL two-neck distillate collection flask and a temperature probe, the following were added:

[1085] -43.6g of C 31-35 Fatty alcohol (92 mmol, 1 equivalent)

[1086] -4.4 g (43 mmol, 10 wt%) of Al2O3-η.

[1087] The reaction medium was first heated at 150° C. to melt the fatty alcohol mixture and stirring was started (about 500 rpm). The temperature was then raised to 300° C. and the mixture was allowed to stir at 1000 rpm under an argon atmosphere. The progress of the reaction was monitored by NMR analysis. After a reaction time of 2 hours at 300° C., NMR analysis in CDCl 3 showed complete conversion of the fatty alcohol and the presence of 0.3 mol % of ketone that had formed as a by-product.

[1088] Then stop stirring and heating to allow the crude medium to cool. Once the temperature has dropped to about 80°C, transfer the molten crude to a beaker. Rinse the reactor vessel and stirring motion device with chloroform (Al2O3 is insoluble).

[1089] The suspension was filtered to remove the catalyst and the solvent was evaporated under vacuum to afford 40.1 g of a clear yellow oil which solidified at room temperature to give a white dense solid (>99 wt% purity) in the form of a wax and 95% yield (NMR).

[1090] 1 H NMR (CDCl 3 , 400 MHz) δ (ppm): 5.42-5.29 (m, 2H), 2.04-1.9 (m, 4H), 1.35-1.19 (m, 52.8H (average number)), 0.86 (t, J=6.8 Hz, 6H).

[1091] 13 C NMR (CDCl3, 101 MHz) δ (ppm): 130.59, 130.13, 32.84, 32.16, 30.02, 29.93, 29.77, 29.6, 29.55, 29.4, 27.44, 22.93, 14.35 (terminal CH3).

[1092] Epoxidation of internal olefins to provide C 31-35 Ethylene oxide

[1093] The reaction was carried out under an inert argon atmosphere. In a 300 mL double-jacketed reactor equipped with a mechanical stirrer (propeller with four tilted plows) and baffles, a condenser, an addition funnel, and a temperature probe, the following were added:

[1094] -39g of C 31-35 Olefin (>99 wt% purity, 86 mmol)

[1095] - 7.3 mL (7.7 g, 128 mmol) of acetic acid, and

[1096] -11.7 g (30 wt%) IR 120H resin.

[1097] The mixture was heated to 75°C in order to melt the fatty olefins. The mixture was then stirred and 13.1mL (14.6g, 128 mmoles) of H2O2 30% was slowly added to the mixture using an addition funnel while monitoring the temperature of the reaction medium to prevent the temperature of the reaction mass from rising (slightly exothermic). This required approximately 20min. During the addition, due to the heterogeneous nature of the reaction medium, the stirring rate was increased to improve mass transfer. When the addition was completed, the temperature of the reaction medium was increased to 85°C. After stirring for 4h30, NMR analysis showed that the olefin conversion level was approximately 97%.

[1098] To complete the reaction, a further 4.4 mL (4.8 g, 43 mmol) of H2O2 30% were added to the reaction medium.After a total reaction time of 7 hours at 85°C, NMR analysis showed a complete conversion level of the olefin.

[1099] The stirring was then stopped to allow the liquid phase to separate in the reactor at 85°C. The resin had settled at the bottom of the reactor. The aqueous phase was removed by draining through the bottom valve. 100 mL of water was then added to the reactor and the mixture was allowed to stir for 15 minutes. The phases were separated again and the aqueous phase was removed.

[1100] Finally, the molten organic phase is discharged into The reaction mixture was stirred for 2 hours at 4 ℃ for 1 h. The reaction mixture was stirred for 2 hours at 4 ℃ for 3 hours. The ...

[1101] 1 H NMR (CDCl 3 , 400 MHz) δ (ppm): 2.91-2.85 (m, 1.5 H), 2.65-2.6 (m, 0.5 H), 1.53-1.36 (m, 4 H), 1.35-1.19 (m, 52.8 H (average number)), 0.86 (t, J=6.8 Hz, 6 H).

[1102] 13 C NMR (CDCl3, 101 MHz) δ (ppm): 58.97, 57.29, 32.18, 31.96, 29.73, 29.6, 29.49, 29.4, 27.86, 26.63, 26.09, 22.72, 14.15 (terminal CH3).

[1103] Catalyst-free condensation with chloroacetic acid provides chloroacetic acid diester C 31-35

[1104] The reaction was carried out under an inert argon atmosphere in a 500 mL three-necked round-bottom flask reactor equipped with a magnetic stirrer, heater, condenser, temperature probe, and an insulated addition funnel. 39.19 g of chloroacetic acid (410.5 mmol, 5 equivalents) was added to the bottom-bottom flask reactor itself. 38.6 g of molten fatty epoxide (purity: 99 wt%, 82.1 mmol, 1 equivalent) was added to the insulated addition funnel maintained at 65°C.

[1105] The first step of hydroxy-ester formation was performed at 65°C to limit the formation of ketone and dehydration byproducts. Therefore, the fatty epoxide was added dropwise to a reactor containing chloroacetic acid at 65°C with stirring over 1 h.30 to limit the self-condensation of two fatty epoxide molecules. Once the addition of the fatty epoxide was complete, the mixture was allowed to stir at 65°C for 30 min. NMR analysis showed a conversion level of >98% of the starting epoxide.

[1106] To form the final diester, the condenser was replaced with a curved distillation column and the mixture was allowed to stir for 5 h 30 at 140° C. under a light vacuum (975 mbar) to help remove the water formed as a by-product of the esterification reaction. After 5 h at 140° C., NMR analysis showed a selectivity of 92 mol% (monoester + diester) and the following approximate crude mixture composition: 90 mol% diester, 2 mol% monoester, 1 mol% esterified dimer, and 2 mol% ketone.

[1107] The chloroacetic acid of 1% chloroacetic acid and 1% chloroacetic acid are distilled out (by NMR analysis verification), and the mixture is allowed to cool to room temperature and recover atmospheric pressure.Then thick oil is transferred in the flask for purification.

[1108] The product can be easily purified by dissolving the oil in 300 mL of isopropanol (the starting ketone is insoluble in isopropanol) followed by filtration through celite. The filtrate is evaporated to provide 49.1 g of a black oil with a diester purity of 93 wt%, corresponding to an isolated yield (RMN) of 86%.

[1109] 1 H NMR (CDCl3, 400 MHz) δ (ppm): 5.11-5.02 (m, 2H), 4.04 (s, isomer 1, 2H), 4.03 (s, isomer 2, 2H), 1.66-1.49 (m, 4H), 1.43-1.19 (m, 52.8H (average number)), 0.86 (t, J = 6.8 Hz, 6H).

[1110] 13 C NMR (CDCl3, 101 MHz) δ (ppm): 167.14, 167, 76.22, 75.83, 40.92, 40.82, 31.96, 30.6, 29.73, 29.64, 29.54, 29.39, 29.28, 28.85, 25.47, 24.96, 22.72, 14.15 (terminal CH3).

[1111] Quaternization with NMe3

[1112] The reaction was carried out under an inert argon atmosphere. In a 1 L double-jacketed reactor equipped with a mechanical stirrer, a condenser and a temperature probe, the following were added:

[1113] -48.1 g (69 mmol, 1 equivalent) of chloroacetic acid diester C 31-35 (Purity: 93wt%)

[1114] - 334 mL (625 mmol, 9 equiv.) of a solution of trimethylamine in THF (about 2 mol / L).

[1115] The reaction mixture was then stirred (1000 rpm) at 40°C. After 3 h, the mixture was allowed to cool at room temperature and stirred overnight. The next day, NMR analysis (d4-MeOD) showed complete conversion of the starting diester to the desired product, glycine betaine diester, with a selectivity of approximately 92 mol% (NMR). The reactor was drained, rinsed with THF, and volatiles removed under vacuum.

[1116] The product was reduced to a powder, deposited on a sintered filter, and washed five times with 100 mL of ethyl acetate to remove organic impurities. The solid was dried under vacuum to provide 53 g of a brown wax with the following approximate weight composition: 94 wt% NQ19 quaternary diammonium, 2 wt% quaternary monoammonium, 0.1 wt% N(Me)3.HCl, and 3.5 wt% ether byproduct. The purified yield of the glycine betaine diester was 94%.

[1117] 1 H NMR (MeOD-d4, 400 MHz) δ (ppm): 5.3-5.13 (m, 2H), 4.79 (s, 1H), 4.75 (s, 1H), 4.53 (s, 1H), 4.49 (s, 1H), 3.38 (s, 18H), 1.78-1.63 (m, 4H), 1.49-1.2 (m, 52.8H (average number)), 0.9 (t, J = 6.8 Hz, 6H).

[1118] 13 C NMR (MeOD-d4, 101 MHz) δ (ppm): 166.39, 166.12, 79.62, 78.17, 77.28, 64.25, 63.98, 54.8, 54.65, 33.21, 31.61, 30.95, 30.83, 30.69, 30.64, 30.5, 30.44, 29.81, 26.7, 26.21, 23.9, 14.58 (terminal CH3).

[1119] In summary, the compounds of the present invention show a good combination of surfactant properties combined with reasonable to good biodegradability - a combination that in many cases cannot be achieved with commercial surfactants.

[1120] 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 prior art compounds.

Claims

1. An ionic compound having any of the following general formulas: as well as in R, which may be the same or different at each occurrence, is C5-C 27 aliphatic group, Y is a divalent C1-C6 aliphatic group, R', R" and R'" may be the same or different and are hydrogen or a C1 to C4 alkyl group, and s and s' may be the same or different and are 0, 1, 2 or 3.

2. The compound according to claim 1, wherein the compound has the following general formula:

3. The compound according to claim 1, wherein the compound has the following general formula: The compound according to claim 1 , wherein Y is a C 2 -C 6 aliphatic group.

5. An electrically neutral compound having any of the following general formulas: in R, which may be the same or different at each occurrence, is C5-C 27 aliphatic group, Y is a divalent C1-C6 aliphatic group, R', R" and R'", which may be the same or different, are hydrogen or a C1 to C4 alkyl group, s and s', which may be the same or different, are 0, 1, 2 or 3, W is an anion or anionic group having w negative charges, and r is 2.

6. The electrically neutral compound according to claim 5, wherein the electrically neutral compound has the following general formula:

7. The electrically neutral compound according to claim 5, wherein the electrically neutral compound has the following general formula:

8. Use of a compound according to any one of claims 1 to 4 as a surfactant.

9. Use of a compound according to any one of claims 5 to 7 as a surfactant.

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