Fabric softener

Abstract

A fabric softener composition comprising: a. 1 to 20 wt.% of an ionic compound of general formula I; b. 0.1 to 20 wt.% of a fat-assisted softener; and c. water. #imgabs0#

Description

Technical Field

[0001] The present invention relates to fabric softeners comprising novel softening compounds and fat-assisted softeners. Background Art

[0002] Fabric softeners, also known as fabric conditioners, have been on the market for many years. Softeners have been developed over the years. Common softeners are quaternary ammonium cationic surfactants, especially ester-linked quaternary ammonium compounds.

[0003] However, there is a need for improved softening ingredients. More efficient softening allows for lower dosage or more concentrated products, which in turn leads to a number of environmental benefits. Summary of the invention

[0004] In a first aspect of the present invention, there is provided a fabric softener composition comprising:

[0005] a. 1 to 20 wt.% of an ionic compound of formula I:

[0006]

[0007] in

[0008] A is a tetravalent linker selected from A-1 to A-6

[0009]

[0010] Q1 to Q4, which may be identical or different from each other, are selected from hydrogen, R and X, and 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,

[0011] where R, which may be the same or different at each occurrence, is C5-C 27 aliphatic groups,

[0012] m, m', m" and m'" which may be the same or different at each occurrence are 0, 1, 2 or 3,

[0013] k, k', k", and k'" which may be the same or different are 0, 1, 2 or 3, and

[0014] X, which may be the same or different at each occurrence, is represented by Formula II

[0015]

[0016] wherein Z1, Z2 and Z3, which may be the same or different, are O, S or NH,

[0017] Y is a divalent C1-C6 aliphatic group,

[0018] R', R" and R'" which may be the same or different are hydrogen or C1 to C4 alkyl,

[0019] n and n' are 0 or 1, where the sum of n+n' is 1 or 2,

[0020] 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 group R may be the same or different at each occurrence, and

[0021] 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 substituents R, the difference in the number of carbon atoms of the two substituents R is 0, 1, 3 or greater than 3.

[0022] b. 0.1 to 20 wt.% of a fat softener; and

[0023] c. Water.

[0024] In a second aspect of the present invention there is provided the use of a fabric softener formulation as described herein for softening fabric. DETAILED DESCRIPTION

[0025] By reading the following detailed description, these and other aspects, features and advantages will become apparent to those of ordinary skill in the art. For the avoidance of doubt, any feature of one aspect of the present invention may be used in any other aspect of the present invention. The word "comprising" is intended to mean "including", but not necessarily "consisting of" or "composed of". In other words, the steps or options listed do not need to be exhaustive. It should be noted that the examples given in the following description are intended to illustrate the present invention and are not intended to limit the present invention to those examples themselves. Similarly, unless otherwise indicated, all percentages are weight / weight percentages. Except in the operating examples and comparative examples, or in the case of otherwise clearly indicated, all numbers representing the amount or reaction conditions of the material, the physical properties of the material and / or the use in this specification should be understood to be modified by the word "about". The numerical range represented in the format of "x to y" should be understood to include x and y. When multiple preferred ranges are described in the form of "x to y" for a particular feature, it will be understood that all ranges combining different endpoints are also considered.

[0026] Softening Compound:

[0027] The fabric softener composition of the present invention comprises a softening compound which is a novel ionic compound. The novel ionic compound has the general formula (I):

[0028]

[0029] in

[0030] A is a tetravalent linker selected from A-1 to A-6,

[0031]

[0032] Q1 to Q4, which may be identical to or different from each other, are selected from hydrogen, R and X, and 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,

[0033] where R, which may be the same or different at each occurrence, is C5-C 27 Aliphatic group, preferably C6-C 24 aliphatic groups,

[0034] m, m', m", and m'", which may be the same or different at each occurrence, are 0, 1, 2 or 3,

[0035] k, k', k", and k'", which may be the same or different, are 0, 1, 2 or 3, and

[0036] X, which may be the same or different at each occurrence, is represented by Formula II

[0037]

[0038] wherein Z1, Z2 and Z3, which may be the same or different, are O, S or NH,

[0039] Y is a divalent C1-C6 aliphatic group,

[0040] R', R" and R'", which may be the same or different, are hydrogen or C1 to C4 alkyl,

[0041] n and n' are 0 or 1, where the sum of n+n' is 1 or 2,

[0042] 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 group R may be the same or different at each occurrence, and

[0043] 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 substituents R, the difference in the number of carbon atoms of the two substituents R is 0, 1, 3 or greater than 3.

[0044] Suitable anions or anionic groups W are, for example, halides (such as chloride, fluoride, bromide or iodide), methylsulfate or the methylsulfate anion (CH3-OSO3 - ), sulfate anion, hydrogen sulfate anion (HSO4 - ) or an organic carboxylate anion such as acetate, propionate, benzoate, tartrate, citrate, lactate, maleate or succinate.

[0045] 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.

[0046] k, k', k'" and k"', which may be the same or different, are preferably 0, 1 or 2, and even more preferably 0 or 1.

[0047] The novel compounds of the present invention are quaternary ammonium derivatives and contain a tetravalent linker A and four substituents Q1 to Q4, which may be identical or different from each other at each occurrence. At least two of Q1 to Q4 are groups R, i.e. aliphatic groups containing 5 to 27, preferably 6 to 24 carbon atoms.

[0048] 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.

[0049] The aliphatic group R is advantageously selected from alkyl, alkenyl, alkadienyl, alktrienyl and alkynyl. The aliphatic group R may be linear or branched. Preferably, the aliphatic group R is independently selected from alkyl and alkenyl.

[0050] 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 C 6- C 21 Alkyl and C6-C 21 The alkenyl group is often selected from (i) C6-C 19 Alkyl and C6-C 19 an alkenyl group or selected from (ii) C6-C 17 Alkyl and C6-C 17 More preferably, R represents an alkyl group, typically C6-C 24 Alkyl, very often C6-C 21 Alkyl, often C6-C 19 Alkyl or C6-C 17Alkyl. Aliphatic groups, in particular alkyl groups, having 10 to 20, preferably 11 to 18, carbon atoms have been found to be advantageous in certain cases.

[0051] As preferred examples of the substituent R, there may be mentioned an acyclic aliphatic group, more preferably a straight-chain aliphatic group, still more preferably a straight-chain alkyl group.

[0052] 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.

[0053] 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, the difference in the number of carbon atoms of the two substituents R is 0, 1, 3 or greater than 3.

[0054] 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).

[0055] In the 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. n and n' can be 0 or 1, and the sum of n and n' is at least 1, preferably 1 or 2.

[0056] R', R" and R'" may be the same or different, and are preferably hydrogen or C1 to C4 alkyl, preferably methyl or ethyl, more preferably methyl. Preferably, at least one, more preferably at least two, more preferably all three of R', R" and R'" are C1 to C4 alkyl, preferably methyl or ethyl, most preferably methyl.

[0057] Y is preferably an acyclic divalent aliphatic group, more preferably a straight-chain divalent aliphatic group, still more preferably a straight-chain 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.

[0058] According to another preferred embodiment, the compounds according to the invention contain one or two radicals X and two and only two radicals R.

[0059] 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.

[0060] In the 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 connected to the same carbon atom of the linker A, and the two groups R are connected to the same or different carbon atoms of the linker A.

[0061] In the 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 two substituents Q1 to Q4 are represented by groups X, wherein the two groups X are directly connected to the nitrogen atom of the linker A. m - and -(CH2) m '-group connection.

[0062] In the 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 a group X, which is connected to two adjacent carbon atoms of the linker group A.

[0063] 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 a group X and a 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 and Z3 are O, and Y is CH2.

[0064] The compounds of the following formulae (IV) to (IX) represent a particularly preferred group of compounds according to the invention:

[0065]

[0066] Where s and s' can be the same or different and are 0, 1, 2 or 3,

[0067]

[0068] R, R', R", R'" and Y in formulae (IV) to (IX) have the meanings as defined above.

[0069] The ionic compounds used in the fabric softener of the present invention can be obtained by various different methods. The preferred method for making the compounds of the present invention comprises the reaction of a ketone having 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 making ketones along this route is disclosed in US2018 / 0093936, which is referenced for further details.

[0070] The synthesis of various compounds of the present invention using the lactones obtainable as described above as starting materials is now described. The process variants described below illustrate the synthesis of specific compounds, and those skilled in the art will vary the reactants and reaction conditions based on their expertise and taking into account the specific target product of the corresponding synthesis to prepare other compounds according to the present invention.

[0071] The fabric softening composition used in the present invention can be a diluted or concentrated fabric softener. Diluted products generally contain up to about 6%, typically about 1 to 5% by weight of the softening compounds described herein, while concentrated products can contain up to about 50% by weight, preferably about 5 to about 50%, more preferably 6 to 25% by weight of active substances. In general, the products of the present invention can contain 1 to 50% by weight, preferably 2 to 25% by weight of softening compounds, more preferably 2 to 20% by weight of softening compounds described herein.

[0072] The synthesis of compounds wherein A is A-6, illustrates an example of a compound of formula (IV) wherein J is J1.

[0073] In a first exemplary method, the ketone RC(=O)-R is first reacted with hydrogen (hydrogenation) to provide a secondary alcohol. The alcohol is then reacted with carbon monoxide by carbonylation. The carbonylation product (which is a carboxylic acid) is then esterified with a quaternary ammonium salt (e.g., choline chloride), thereby splitting the water and obtaining the desired compound of formula (IV). Alternatively, the carboxylic acid can first be condensed with an amino alcohol (e.g., dimethylaminoethanol) by esterification (releasing water), and the resulting amino ester can be quaternized with an alkylating agent.

[0074] The reaction scheme of the aforementioned sequence of steps is as follows:

[0075]

[0076] wherein L' is a monovalent leaving group such as, for example, a halide anion (particularly a chloride anion) or a methylsulfate group.

[0077] The first step in the above reaction scheme comprises reducing the lactone to a secondary alcohol. This step is followed by a second conversion consisting of inserting a carbonyl group to produce a carboxylic acid. Hydrogenation and carbonylation reactions of this general reaction sequence with active hydrogen and carbon monoxide, respectively, in the presence of a suitable catalyst are known to those skilled in the art and have been described in the literature. Those skilled in the art will consider the desired target compound and select a suitable catalyst and reaction conditions based on their expertise, so that no further details need to be given here.

[0078] 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 obtain a nitrile intermediate. The nitrile is then hydrated to obtain a carboxylic acid intermediate. The carboxylic acid can be converted to the desired quaternary ammonium compound in the same manner as described above. The reaction scheme for the aforementioned sequence of steps is as follows:

[0079]

[0080] wherein L' is as defined above.

[0081] For the aforementioned reaction sequence, the individual reaction steps of the sequence have been described in the literature and are known to the skilled person. The skilled person will consider the desired target compound, select suitable catalysts and reaction conditions based on his professional knowledge, so that no further details need to be given here.

[0082] Synthesis of compounds wherein A is A-6 and J is J3

[0083] Compounds of this type can be obtained by a sequence of steps comprising hydrogenation of the lactone to a secondary alcohol followed by a carbonate transmutation reaction involving dimethyl carbonate and the secondary alcohol thus obtained. A second carbonate transmutation reaction with dimethylaminoethanol followed by quaternization affords the desired product.

[0084] In the first step, the hydrogenation of the lactone to the secondary alcohol can be carried out in an autoclave, which is preferably equipped with a stirring device (e.g., a Rushton turbine) without any added solvent. The lactone and a suitable catalyst (e.g., palladium metal on carbon) are introduced into a reactor, which is then sealed. The temperature is then raised to above the melting point of the ketone (the temperature is generally in the range of 80-120° C.), and the mixture is stirred. The reactor atmosphere is purged with nitrogen several times, and then the reactor is purged with hydrogen. The temperature is then raised to about 120 to 180° C. (preferably about 150° C.), and the mixture is stirred at such a high temperature, maintaining a hydrogen pressure (10 to 80 bar) above atmospheric pressure until the reaction is complete.

[0085] At the end of the reaction, the mixture is cooled to a temperature slightly above the melting point of the alcohol, the pressure is released and the catalyst can be filtered off to obtain the secondary alcohol.

[0086]

[0087] 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 dimethyl carbonate (DMC), wherein Alk 1 and Alk 2 All are methyl.

[0088] The reaction can be carried out by heating the secondary alcohol mixture in the dialkyl carbonate in the presence of a catalyst at a temperature preferably from 50° C. to 250° C. The alcohol produced as a by-product during the reaction can be distilled off during the reaction.

[0089] At the end of the reaction, the dialkyl carbonate can be evaporated and the residue can be involved as such in a second trans-carbonation reaction with a dialkylaminoethanol.

[0090] This reaction step is shown in the following reaction scheme:

[0091]

[0092] 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:

[0093]

[0094] This second trans-carbonation can be carried out using, for example, NaOMe as a catalyst (e.g., from the previous step) in a suitable solvent (e.g., toluene). A mixture of the starting asymmetric alkyl secondary alkyl carbonate, dialkylaminoethanol, and catalyst in toluene is usually heated to about 120°C. During the reaction, the alcohol formed should be removed (e.g., by distillation). At the end of the reaction, the organic phase is usually washed with water to remove the catalyst and unreacted dialkylaminoethanol, and the solvent is evaporated. The residue is redissolved in a suitable solvent (e.g., ethanol) to precipitate the fatty dialkyl carbonate that may be formed. After filtration, the product is obtained after the solvent is evaporated.

[0095] In the final step, the product obtained in the above step is 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 dialkyl sulfate, even more preferably dimethyl sulfate (DMS), to obtain the desired quaternary ammonium derivative according to the present invention:

[0096]

[0097] To one equivalent of a dialkyl sulfate (eg DMS) in a suitable solvent (eg methanol) is gradually added a concentrated solution of the carbonate-amine in the same solvent with stirring at room temperature at a rate that avoids a significant temperature increase due to the reaction exotherm.

[0098] After the addition is complete, the mixture is stirred at room temperature (eg, 1 hour) and the volatiles (solvent) are removed under vacuum to give the final product, typically as a white wax.

[0099] A person skilled in the art 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.

[0100] The synthesis of compounds wherein A is A-3 or A-4, shows examples of compounds of formula (V) or (VI):

[0101] In the first step, a condensation reaction is carried out between a lactone and a dialkyl malonate (e.g. dimethyl malonate) in the presence of a catalyst in an organic solvent at a temperature in the range of 110 to 250° C., preferably in the range of 125 to 175° C., even more preferably about 140° C. A suitable and preferred solvent for the reaction is xylene, and a preferred catalyst is potassium tert-butoxide, the amount of which is generally in the range of 2 to 10 mol %, preferably 3 to 8 mol %, based on the molar amount of the lactone.

[0102] The lactone (e.g., as described in US2018 / 093936), dialkyl malonate (e.g., dimethyl malonate) and 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 typically subsequently cooled to room temperature, and the organic phase is washed with water to remove the catalyst.

[0103] The volatiles are then distilled off and the crude product is purified by redissolving the resulting oil in a suitable solvent (e.g., ethanol) to precipitate heavier byproducts such as ketal / crotonyl adducts as well as remaining starting ketone. After filtration, the filtrate can be evaporated (removing the solvent) to give the desired adduct.

[0104] The reaction scheme for this first step is as follows:

[0105]

[0106] Among them, Alk 3 and Alk 4 The may be the same or different and represent an alkyl group having 1 to 6 carbon atoms.

[0107] The product obtained in the first step can then be transesterified with a dialkylaminoethanol, such as dimethylaminoethanol. A suitable catalyst for this reaction step is dibutyltin oxide (usually 2 to 10, preferably 3 to 8 mol % relative to the amount of malonate adduct obtained in the first step), and as for the first step, a suitable solvent is xylene. The reaction temperature is again preferably in the range of 110 to 170° C., even more preferably about 140° C.

[0108] The malonate adduct obtained in the first step is dissolved in a solvent (e.g. xylene), an excess of dialkylethanolamine (100% to 500% excess based on stoichiometry) is added to the solution, followed by a catalyst. The mixture is then stirred at a temperature preferably in the range of 110° C. to 170° C., preferably about 140° C., and the alcohol formed is distilled off from the reaction medium. After the reaction is complete, the organic phase is washed with water to remove excess dialkylaminoethanol, and xylene is distilled off to obtain crude esteramine.

[0109] This second step can be represented by the following reaction scheme

[0110]

[0111] 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 dialkyl sulfate, even more preferably dimethyl sulfate (DMS), to obtain the target quaternary ammonium compound of the present invention.

[0112] A concentrated solution of the esteramine in a suitable solvent is gradually added to an appropriate amount of the alkylating agent in the same solvent with stirring (usually at room temperature) at a rate that avoids a significant temperature increase due to the reaction exotherm.

[0113] After the addition is complete, the mixture is stirred 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 give the final product as a white wax.

[0114] The reaction scheme of step 3 can be described as follows (using methanol as solvent):

[0115]

[0116] The wedged bond shown on the right represents the fact that the reaction product is a mixture of three isomers of the structure derived from the reaction scheme of the first step.

[0117] Those skilled in the art will appropriately modify the aforementioned exemplary methods based on their expertise to obtain other compounds of formula (V) and (VI). They will select suitable reactants for reacting with the lactone, and will change the reaction conditions for other reactant / lactone combinations as needed.

[0118] The person skilled in the art will adapt the reaction conditions based on his expert knowledge and taking into account the desired target compound.The reaction steps themselves have been described in the literature, so that no further details need to be given here.

[0119] Synthesis of compounds represented by formula (VII) wherein A is A-1.

[0120] 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:

[0121]

[0122] Reductive amination can be carried out in an autoclave using excess ammonia. The reactor is loaded with the ketone, ethanol as a solvent (or another suitable solvent) and a suitable catalyst (e.g., Pt / C at, for example, about 2 wt % relative to the ketone substrate concentration). The reactor atmosphere is purged several times with high pressure nitrogen. Ammonia is then added to the reactor, followed by hydrogen, 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 those conditions until the reaction is complete.

[0123] The reaction product thus obtained is subsequently alkylated according to the following general scheme, which is shown for an alkyl chloroacetate as alkylating agent:

[0124]

[0125] Among them, Alk 5 is an alkyl group having 1 to 6 carbon atoms.

[0126] The reaction can be preferably carried out using an alkyl chloroacetate (particularly preferably methyl chloroacetate) as an alkylating agent in a suitable solvent or directly using an alkyl chloroacetate as a solvent (meaning that the reactant is in excess compared to the secondary alkylamine). During the reaction, a suitable base (e.g. sodium carbonate) should be used to neutralize the HCl formed, and a catalyst (e.g. potassium iodide, KI) can be optionally used to accelerate the reaction. The mixture is then stirred at a temperature ranging from 50° C. to 250° C. until the reaction is complete. At the end of the reaction, the salt is filtered off and the organic phase can be washed with water. The volatiles can then be removed under vacuum, and the crude product is then taken into the subsequent steps.

[0127] The crude product thus obtained can then be subjected to a transesterification reaction with a dialkylaminoethanol, such as dimethylaminoethanol (DMAE), optionally in the presence of a suitable catalyst as described above, according to the following reaction scheme:

[0128]

[0129] The reaction conditions can be selected as described above in the exemplary methods for synthesizing compounds wherein A is A-3 or A-4.

[0130] In the last step, the amine compound thus obtained is alkylated to obtain the desired compound according to the present invention, as shown in the following reaction scheme for the alkylating agent R"'-L":

[0131]

[0132] The same conditions as described above for the methylation stage of compounds of formula (V) and (VI) may be used.

[0133] Synthesis of compounds as exemplified by formula (IX) wherein A is represented by A-5

[0134] The corresponding compounds can preferably be obtained by two methods. The first method starts with Piria ketonization, followed by hydrogenation, dehydration, epoxidation + hydration and esterification. This is a multi-step method plugged into the Piria technology, but has the advantages of being salt-free and relying on chemical transformations that can be easily performed.

[0135] Ketosis

[0136] The basic reaction of the first step is:

[0137]

[0138] This reaction has been fully described in U.S. Pat. No. 10,035,746, WO 2018 / 087179 and WO 2018 / 033607, to which reference is made for further details.

[0139] hydrogenation

[0140] The lactone is then subjected to hydrogenation, which can be carried out under standard conditions known to those skilled in the art for hydrogenation reactions:

[0141]

[0142] The hydrogenation reaction is carried out by contacting the ketone with hydrogen in an autoclave reactor at a temperature ranging from 15°C to 300°C and 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. As examples of suitable solvents, mention can be made of: methanol, ethanol, isopropanol, butanol, THF, methyl-THF, hydrocarbons, water or mixtures thereof. The reaction should use a suitable catalyst based on a transition metal. As examples of suitable catalysts, mention can be made of heterogeneous transition metal-based catalysts, such as, for example, supported dispersed transition metal-based catalysts or homogeneous organic metal complexes of transition metals. Examples of suitable transition metals are: Ni, Cu, Co, Fe, Pd, Rh, Ru, Pt, Ir. As examples of suitable catalysts, mention can be made of 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 inspection. Representative techniques are known to those skilled in the art, so no further details need to be given here. The details of this process step can be found, for example, in U.S. Patent No. 10,035,746, which is referenced herein.

[0143] The skilled person will select appropriate reaction conditions based on his professional experience and taking into account the specific target compound to be synthesized.

[0144] Therefore, no further details need to be given here.

[0145] Dehydration

[0146] In the next step, the alcohol thus obtained is dehydrated to obtain the internal olefin. This reaction can also be carried out under standard conditions known to those skilled in the art for corresponding dehydration reactions (e.g. U.S. Pat. No. 10,035,746, Example 4), so no further details need to be given here:

[0147]

[0148] The dehydration reaction is carried out by heating the secondary alcohol at a temperature ranging from 100° C. to 400° C. in the presence of a suitable catalyst 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 without any added solvent. As examples of solvents, mention may be made of: hydrocarbons, toluene, xylene or mixtures thereof. A catalyst must be used for this reaction. Suitable examples of catalysts are acidic (Lewis or Brosted) catalysts, which are heterogeneous solid acid catalysts or homogeneous catalysts. As examples of heterogeneous catalysts, mention may be made of alumina (Al2O3), silica (SiO2), aluminosilicates (Al2O3-SiO2) such as zeolites, phosphoric acid supported on silica or alumina, acidic resins such as etc. Homogeneous catalysts may also be used, and the following suitable acids may be mentioned: H2SO4, HCl, trifluoromethanesulfonic acid, p-toluenesulfonic acid, AlCl3, FeCl3, etc. The water generated during the reaction may be distilled off from the reaction medium during the reaction. At the end of the reaction, the desired olefin may be recovered after appropriate inspections. Representative techniques are known to those skilled in the art and are described, for example, in U.S. Patent No. 10035746, so no further details need be given here.

[0149] Epoxidation and epoxide hydration

[0150] The internal olefin can then be oxidized to the corresponding diol, where the double bond is replaced by two hydroxyl groups, according to the following scheme (where the reactants are merely examples of corresponding groups of compounds for performing the corresponding functions):

[0151]

[0152] Wherein R** may be hydrogen or a hydrocarbon group which may be substituted and / or interrupted by a heteroatom or a group containing a heteroatom, or R** may be an acyl group of the general formula R***-C(=O)-, wherein R*** may have the same meaning as R**.

[0153] The epoxidation reaction is carried out by contacting the internal olefin with a suitable oxidant at a temperature of 15° C. to 250° C. in a reaction zone. As suitable oxidants, there may be mentioned peroxide compounds such as hydrogen peroxide (H2O2), which may be used in the form of aqueous solutions, organic peroxides such as peracids of the general formula R****-CO3H (e.g., meta-chloroperbenzoic acid, peracetic acid, etc.) or alkyl hydroperoxides of the general formula R*****-O2H (e.g., cyclohexyl hydroperoxide, isopropylbenzene hydroperoxide, tert-butyl hydroperoxide), wherein R**** in the peracid or alkyl hydroperoxide is a hydrocarbon group which may be substituted and / or interrupted by heteroatoms or heteroatom-containing groups. The reaction may be carried out in the presence of an optional solvent, but the use of such a solvent is not mandatory, and the reaction may also be carried out without any added solvent. As examples of suitable solvents, there may be mentioned: CHCl3, CH2Cl2, tert-butyl alcohol or mixtures thereof. In the case of using H2O2 as the oxidant, the presence of an organic carboxylic acid during the reaction may be beneficial, since it will generate the peracid compound in situ by reacting with H2O2. As examples of suitable carboxylic acids, there may be mentioned: formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, etc. A catalyst may also be used to promote the reaction. Suitable catalysts are Lewis or Bronsted acids, and there may be mentioned, for example: perchloric acid (HClO4), trifluoromethanesulfonic acid, heterogeneous titanium silicalite (TiO2-SiO2), heterogeneous acidic resins such as Homogeneous organometallic complexes of manganese, titanium, vanadium, rhenium, tungsten, polyoxometellates, etc. At the end of the reaction, the desired epoxide can be recovered after appropriate workup, and those skilled in the art know representative techniques, so no further details need to be given here. The epoxide can be directly involved in the hydration step without further purification.

[0154] The ring-opening reaction can be carried out by contacting the epoxide with water in the presence of a suitable catalyst at a temperature of 15° C. to 150° C. As examples of catalysts, there can be mentioned Bronsted acid or Lewis acid catalysts such as: H2SO4, HCl, perchloric acid (HClO4), trifluoromethanesulfonic acid, p-toluenesulfonic acid, heterogeneous acidic resins such as Etc. The reaction can be carried out in the presence of an optional solvent to facilitate reagent contact, and the solvent can be mentioned: Me-THF, THF, DMSO, tert-butyl alcohol, methanol, ethanol, isopropanol, acetonitrile or a mixture thereof. The reaction can also be carried out without adding any solvent. At the end of the reaction, the desired diol can be recovered after appropriate inspections, and those skilled in the art know representative techniques, so no further details need to be given here.

[0155] Esterification and amine condensation

[0156]

[0157] wherein R***** is hydrogen or C1-C6 alkyl.

[0158] The esterification is first carried out by contacting the diol with a carboxylic acid or carboxylic acid ester of the general formula:

[0159] [LY-CO2R*****] (t-1)- [U u+ ] (t-1) / u

[0160] wherein Y is a divalent hydrocarbon group containing 1 to 6 carbon atoms, and L is a leaving group.

[0161] In the case where the leaving group L in the carboxylic acid or ester reactant is already negatively charged (this 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+ A cation having 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 + Such cations may be selected, for example, from H + , alkali metal or alkaline earth metal cations (such as Na + , K + , Ca 2+ )、Al 3+ or ammonium, to name a few.

[0162] An example of a compound where t is equal to 1 is the compound CH3-O-SO3-CH2-COOR*****, where for R***** is H, resulting in the compound CH3-O-SO3-CH2-COOH, which may be referred to as 2-((methoxysulfonyl)oxy)acetic acid.

[0163] 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*****]– , where R***** is H, U is Na, and therefore [U u+ ] t / u [L t- ] is Na2SO4.

[0164] As other 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.

[0165] The esterification can preferably be carried out in the presence of an optional solvent at a temperature in the range of 50° C. to 250° C. 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, mention may be made of: toluene, xylene, hydrocarbons, DMSO, Me-THF, THF or mixtures thereof. The water formed as a by-product during the reaction can be removed from the reaction medium by distillation during the reaction. A catalyst can also be used during the reaction, suitable catalysts being Bronsted or Lewis acid catalysts. As preferred examples of catalysts, mention may be made of: H2SO4, p-toluenesulfonic acid, trifluoromethanesulfonic acid, HCl or heterogeneous acidic resins, such as AlCl3 etc. At the end of the reaction, the desired diester can be recovered after appropriate work-up, and the skilled person knows the representative techniques, so no further details need be given here.

[0166] 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, preferably methyl or ethyl, most preferably methyl. The reaction can be carried out at a temperature ranging from 15°C to 250°C in the presence of a suitable solvent. As examples of suitable solvents, there can be mentioned: 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. During this reaction, the presence of L in the substituted diester (t-1)- Nucleophilic attack of amine, L (t-1)- Acts as a leaving group. t- It then becomes the counter anion of the final quaternary ammonium compound. In the case where the leaving group in the diester reactant is already negatively charged (this is the case when (t-1) is equal to or greater than 1 or when t is equal to or greater than 2), a salt is also formed as a byproduct of the reaction (having the general chemical formula [U u+ ] t / u [L t- ], as shown in the above reaction scheme).

[0167] Odd marriage condensation

[0168] An alternative process for the synthesis of compounds according to the invention, wherein A is represented by A-5 and is carried out by acyloin condensation according to the following scheme as shown in the scheme below for compounds of formula (IX):

[0169]

[0170] wherein R****** is an alkyl group having 1 to 6 carbon atoms.

[0171] Acyloin condensation is usually carried out by reacting an ester (usually a fatty acid methyl ester) with sodium metal as a reducing agent. The reaction can be 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 of 100° C. to 200° C. At the end of the reduction, the reaction medium can be carefully quenched with water, and the organic phase containing the desired acyloin product can be separated. The final product can be obtained after appropriate inspection, and the skilled person knows the representative techniques, so no further details need be given here.

[0172] 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 Rongacli et al., Eur. J. Lipd Sci. Technol. 2008, 110, 846-852, to which reference is hereby made for more details.

[0173] Ketoalcohol hydrogenation

[0174]

[0175] This reaction can be carried out using the conditions described above for the first process variant for making compounds of formula (IX) (respectively, compounds wherein A is represented by A-5).

[0176] The subsequent reaction steps are also as described above for the first process variant for preparing the compound of formula (IX) (respectively, the compound wherein A is represented by A-5).

[0177] Suitable methods for preparing compounds wherein A is represented by A-2, more particularly for preparing compounds of formula (VIII), are described in the experimental section below.

[0178] The exemplary methods described above are examples of suitable methods, that is, there may be other suitable methods for synthesizing the compounds according to the present invention. Therefore, in terms of the preparation methods of the compounds according to the present invention, the methods described above are not limiting.

[0179] 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 and VIII is preferably any one of the following pairs.

[0180] (5, 5), (7, 7), (9, 9), (11, 11), (13, 13), (15, 15), (17, 17)

[0181] (7, 9), (7, 11), (7, 13), (7, 15), (7, 17)

[0182] (9, 11), (9, 13), (9, 15), (9, 17)

[0183] (11, 13), (11, 15), (11, 17)

[0184] (13, 15), (13, 17)

[0185] (15, 17)

[0186] If the lactone is derived from a fatty acid containing an odd number of carbon atoms, other pairs are possible and will be obtained.

[0187] For compounds of formula VI and IX, if the lactone used as a reactant in the exemplary method described above is derived from a natural fatty acid having an even number of carbon atoms, the number of carbon atoms of the two groups R is preferably any one of the following pairs:

[0188] (4, 5), (6, 7), (8, 9), (10, 11), (12, 13), (14, 15), (16, 17)

[0189] (7, 8), (7, 10), (7, 12), (7, 14), (7, 16)

[0190] (9, 10), (9, 12), (9, 14), (9, 16)

[0191] (11, 12), (11, 14), (11, 16)

[0192] (13, 14), (13, 16)

[0193] (15, 16)

[0194] If the lactone is obtained from a fatty acid containing an odd number of carbon atoms, other pairs are possible and will be obtained.

[0195] Compounds wherein A is represented by A-5, in particular compounds of formula (IX), have a particularly interesting and advantageous spectrum of surfactant properties on the one hand, and biodegradability properties on the other hand. As biodegradability becomes an increasingly important aspect of surfactant products, compounds wherein A is represented by A-5, in particular compounds of formula (IX) in this group, constitute preferred embodiments of the present invention.

[0196] 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, between a liquid and a gas, or between a liquid and a solid. Surfactants can be used as detergents, wetting agents, emulsifiers, foaming agents, and dispersants.

[0197] Surfactants are generally organic compounds that are amphiphilic, meaning that they contain a hydrophobic group (their tail) and a hydrophilic group (their head). Therefore, surfactants contain a water-insoluble (or oil-soluble) component and a water-soluble component. In the case of a mixture of water and oil, the surfactant will diffuse in the water and adsorb at the interface between air and water or at the interface between oil and water. The water-insoluble hydrophobic group can extend out of the bulk water phase into the air or into the oil phase, while the water-soluble head group remains in the water phase.

[0198] The adsorption of cationic surfactants on negatively charged surfaces is an important property of such surfactants. This property is usually associated with the minimum concentration of surfactant required to produce aggregation of negatively charged cellulose nanocrystals (CNCs, which are usually used as reference material) suspensions in aqueous media. The continuous change in size can be monitored and tracked by dynamic light scattering (DLS).

[0199] According to the protocol described in EKOikonomou et al., "Fabric softener-cellulose nanocrystal interaction: a model for assessing surface deposition on cotton", J. Phys. Chem. B, 2017, 121(10), 2299-307, the adsorption characteristics of quaternary ammonium compounds can be studied by monitoring the ratio X = [surfactant] / [CNC] or the mass fraction M = [surfactant] / ([surfactant + [CNC]) required to induce the agglomeration of cellulose nanocrystals at [surfactant] + [CNC] = 0.01 wt% fixed in aqueous solution.

[0200] The biodegradability of the compounds of the invention can be determined according to procedures described in the prior art and known to the skilled person. Details on one such method OECD Standard 301 are given in the experimental part below.

[0201] Co-softener:

[0202] The fabric softener of the present invention preferably comprises a fatty auxiliary softener. These are usually present at 0.1% to 20%, especially 0.4% to 15%, preferably 1% to 15%, based on the total weight of the composition.

[0203] In the context of the present invention, a fat co-softener is considered to be a material comprising an aliphatic carbon chain. Preferably, the carbon chain comprises more than 6 carbons, more preferably more than 8 carbons, and preferably less than 30 carbons. The aliphatic chain may be saturated or unsaturated, and may be branched or unbranched.

[0204] Preferred fat softeners include fatty esters, fatty alcohols, fatty acids and combinations thereof. Useful fatty esters include fatty monoesters, such as glycerol monostearate, fatty sugar esters and fatty acid monoesters. Useful fatty acids include hardened tallow fatty acids or hardened vegetable fatty acids (available under the trade name Pristerene TM Available from Croda). Fatty alcohols that can be used include tallow alcohol or plant alcohol, particularly preferably hardened tallow alcohol or hardened plant alcohol (available under the trade name Stenol TM and Hydrenol TM Available from BASF and under the trade name Laurex TM CS was purchased from Huntsman).

[0205] Preferably, the fat co-softener has a fatty chain length of C12 to C22, preferably C14 to C20.

[0206] The weight ratio of softening active substance to fat co-softener is preferably from 10:1 to 1:2, more preferably from 5:1 to 1:2, most preferably from 3:1 to 1:2, for example from 2:1 to 1:1.

[0207] Fat co-softeners are known to reduce softening levels when used in combination with triethanolamine esterquats, however surprisingly demonstrate softening benefits when combined with the described softening actives.

[0208] spices:

[0209] The fabric softener of the present invention preferably comprises 0.1 to 30 wt.% of perfume material, i.e. free perfume and / or perfume microcapsules. As known in the art, free perfume and perfume microcapsules provide perfume access to consumers at different points in the laundry process. It is particularly preferred that the fabric softener of the present invention comprises a combination of both free perfume and perfume microcapsules.

[0210] Preferably, the fabric softener of the present invention comprises 0.1 to 20 w.t.% perfume material, more preferably 0.5 to 15 w.t.% perfume material, most preferably 1 to 10 w.t.% perfume material.

[0211] Useful flavor components may include materials of natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components can be found in the existing literature, for example, Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947, by MB Jacobs, Van Nostrand ed.; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, NJ (USA). These substances are well known to those skilled in the art of flavoring, seasoning and / or aromatic consumer products.

[0212] Free Fragrance:

[0213] The fabric softener of the present invention preferably comprises 0.1 to 15 wt.% of free perfume, more preferably 0.5 to 8 wt.% of free perfume.

[0214] Particularly preferred fragrance components are blooming fragrance components and substantive fragrance components. Blooming fragrance components are defined by a boiling point below 250°C and a LogP greater than 2.5. Substantive fragrance components are defined by a boiling point greater than 250°C and a LogP greater than 2.5. Boiling points are measured at standard pressure (760 mm Hg). Preferably, the fragrance composition will contain a mixture of blooming and substantive fragrance components. The fragrance composition may contain other fragrance components.

[0215] It is common for multiple flavor components to be present in free oil flavor compositions. In the compositions used in the present invention, it is envisioned that three or more, preferably four or more, more preferably five or more, most preferably six or more different flavor components will be present. An upper limit of 300 flavor components may be used.

[0216] Microcapsules of spices:

[0217] The fabric softener of the present invention preferably comprises 0.1 to 15 wt.% of perfume microcapsules, more preferably 0.5 to 8 wt.% of perfume microcapsules. The weight of the microcapsules is the weight of the as supplied material.

[0218] When the perfume component is encapsulated, suitable encapsulating materials may include, but are not limited to, amino plastics, proteins, polyurethanes, polyacrylates, polymethacrylates, polysaccharides, polyamides, polyolefins, gums, silicones, lipids, modified celluloses, polyphosphates, polystyrenes, polyesters or combinations thereof. Particularly preferred materials are amino plastic microcapsules, such as melamine formaldehyde or urea formaldehyde microcapsules.

[0219] The perfume microcapsules of the present invention may be breakable microcapsules and / or moisture-activated microcapsules. "Breakable" means that the perfume microcapsules will break when force is applied. Moisture-activated means that the perfume is released in the presence of water. The fabric softener of the present invention preferably comprises breakable microcapsules. Moisture-activated microcapsules may additionally be present. Examples of microcapsules that may be breakable include aminoplast microcapsules.

[0220] The perfume component contained in the microcapsules may comprise fragrance-emitting materials and / or pro-perfume materials.

[0221] Particularly preferred perfume components contained in the microcapsules are fragrance-releasing perfume components and direct perfume components. The fragrance-releasing perfume component is defined by a boiling point below 250°C and a LogP greater than 2.5. Preferably, the encapsulated perfume composition comprises at least 20 wt.% of fragrance-releasing perfume ingredients, more preferably at least 30 wt.%, and most preferably at least 40 wt.% of fragrance-releasing perfume ingredients. The direct perfume component is defined by a boiling point greater than 250°C and a LogP greater than 2.5. Preferably, the encapsulated perfume composition comprises at least 10 wt.% of direct perfume ingredients, more preferably at least 20 wt.%, and most preferably at least 30 wt.% of direct perfume ingredients. The boiling point is measured at standard pressure (760 mmHg). Preferably, the perfume composition will comprise a mixture of fragrance-releasing and direct perfume components. The perfume composition may comprise other perfume components.

[0222] It is common for a plurality of perfume components to be present in the microcapsules. In the compositions used in the present invention, it is envisaged that three or more, preferably four or more, more preferably five or more, and most preferably six or more different perfume components are present in the microcapsules. An upper limit of 300 perfume components may be used.

[0223] The microcapsules may contain perfume components and a carrier for the perfume ingredient, such as zeolite or cyclodextrin.

[0224] Nonionic surfactants:

[0225] The composition may also contain nonionic surfactants. Typically, these may be included for the purpose of stabilizing the composition. Suitable nonionic surfactants include addition products of ethylene oxide and / or propylene oxide with fatty alcohols, fatty acids and fatty amines. Any alkoxylated material of the specific type described below may be used as a nonionic surfactant.

[0226] Suitable surfactants are substantially water-soluble surfactants of the general formula (X):

[0227] RY-(C2H4O)z-CH2-CH2-OH(X)

[0228] wherein R is selected from primary, secondary and branched alkyl and / or acyl hydrocarbon groups; primary, secondary and branched alkenyl hydrocarbon groups; and primary, secondary and branched alkenyl substituted phenolic hydrocarbon groups; the hydrocarbon groups having a chain length of 8 to about 25, preferably 10 to 20, for example 14 to 18 carbon atoms.

[0229] In the general formula of ethoxylated nonionic surfactants, Y is generally:

[0230] -O-, -C(O)O-, -C(O)N(R)- or -C(O)N(R)R-,

[0231] wherein R has the meaning given above for formula (X) or may be hydrogen; and z is at least about 8, preferably at least about 10 or 11.

[0232] Preferably, the HLB of the nonionic surfactant is from about 7 to about 20, more preferably from 10 to 18, for example from 12 to 16. Genapol based on coconut oil chain and 20 EO groups TM C200 (Clariant) is an example of a suitable nonionic surfactant.

[0233] If present, the nonionic surfactant is present in an amount of 0.01 wt% to 10 wt%, more preferably 0.1 to 5 wt%, based on the total weight of the composition.

[0234] One class of preferred nonionic surfactants includes addition products of ethylene oxide and / or propylene oxide with fatty alcohols, fatty acids and fatty amines. These are preferably selected from addition products of (a) an alkoxide selected from ethylene oxide, propylene oxide and mixtures thereof and (b) a fatty material selected from fatty alcohols, fatty acids and fatty amines.

[0235] Suitable surfactants are substantially water-soluble surfactants of the general formula (XI):

[0236] RY-(C2H4O)z-CH2-CH2-OH(XI)

[0237] Wherein R is selected from primary, secondary and branched alkyl and / or acyl hydrocarbon groups (when Y=-C(O)O, R≠acyl hydrocarbon group); primary, secondary and branched alkenyl hydrocarbon groups; and primary, secondary and branched alkenyl substituted phenolic hydrocarbon groups; the hydrocarbon group has a chain length of 10 to 60, preferably 10 to 25, for example 14 to 20 carbon atoms.

[0238] In the general formula of ethoxylated nonionic surfactants, Y is generally:

[0239] -O-, -C(O)O-, -C(O)N(R)- or -C(O)N(R)R-,

[0240] wherein R has the meaning given above for formula (XI) or may be hydrogen; and z is at least about 6, preferably at least about 10 or 11.

[0241] Lutensol based on C16:18 chain and 25 EO groups TM AT25 (BASF) is an example of a suitable nonionic surfactant. Other suitable surfactants include Renex 36 (Trideceth-6) from Croda; Tergitol 15-S3 from Dow Chemical Co.; Dihydrol LT7 from Thai Ethoxylate Ltd; Cremophor CO40 from BASF, and Neodol 91-8 from Shell.

[0242] Cationic polymers:

[0243] The compositions of the present invention may comprise a cationic polymer. This refers to a polymer having an overall positive charge.

[0244] The cationic polymers may be naturally derived or synthetic. Examples of suitable cationic polymers include: acrylate polymers, cationic amino resins, cationic urea resins and cationic polysaccharides including: cationic cellulose, cationic guar gum and cationic starch.

[0245] The cationic polymers of the present invention can be categorized as polysaccharide-based cationic polymers or non-polysaccharide-based cationic polymers.

[0246] Cationic polymers based on polysaccharides include cationic cellulose, cationic guar gum and cationic starch. Polysaccharides are polymers composed of monosaccharide monomers linked together by glycosidic bonds.

[0247] The cationic polysaccharide based polymers present in the composition of the invention have a modified polysaccharide backbone in that additional chemical groups have reacted with some of the free hydroxyl groups of the polysaccharide backbone to provide an overall positive charge to the modified cellulose monomer units.

[0248] The preferred polysaccharide polymer is cationic cellulose. This refers to a polymer having a cellulose backbone and an overall positive charge.

[0249] Cellulose is a polysaccharide having glucose as its monomer, specifically, it is a linear polymer of D-pyranose glucose units linked via β-1,4 glycosidic bonds, and is a linear, unbranched polymer.

[0250] The cationic cellulose based polymers of the present invention have a modified cellulose backbone, the modification being that additional chemical groups have reacted with some of the free hydroxyl groups of the polysaccharide backbone to provide an overall positive charge to the modified cellulose monomer units.

[0251] A preferred class of cationic cellulose polymers suitable for use in the present invention are those having a cellulose backbone modified to introduce a quaternary ammonium salt. Preferably, the quaternary ammonium salt is attached to the cellulose backbone via a hydroxyethyl or hydroxypropyl group. Preferably, the charged nitrogen of the quaternary ammonium salt has one or more alkyl substituents.

[0252] An exemplary cationic cellulose polymer is a salt of hydroxyethyl cellulose reacted with a trimethyl ammonium substituted epoxide, known in the art as Polyquaternium 10 according to the International Nomenclature of Cosmetic Ingredients, and commercially available from Amerchol Corporation, a subsidiary of The Dow Chemical Company, sold as the Polymer LR, JR and KG series of polymers. Other suitable types of cationic cellulose include polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with a lauryl dimethyl ammonium substituted epoxide, known in the art as Polyquaternium 24 according to the International Nomenclature of Cosmetic Ingredients. These materials are available from Amerchol Corporation, sold as Polymer LM-200.

[0253] Typical examples of preferred cationic cellulose polymers include cocodimonium hydroxypropyloxyethylcellulose, lauryldimonium hydroxypropyloxyethylcellulose, stearyldimonium hydroxypropyloxyethylcellulose and stearyldimonium hydroxyethylcellulose; cellulose 2-hydroxyethyl 2-hydroxy 3-(trimethylammonium)propyl ether salt, polyquaternium-4, polyquaternium-10, polyquaternium-24 and polyquaternium-67, or mixtures thereof.

[0254] More preferably, the cationic cellulose polymer is a quaternized hydroxyether cellulose cationic polymer. These are commonly known as polyquaternium-10. Suitable commercially available cationic cellulose polymer products for use according to the present invention are sold by Amerchol Corporation under the trade name UCARE.

[0255] The counterions of the cationic polymer are freely selected from the group consisting of halides: chloride, bromide and iodide; or from the group consisting of hydroxide, phosphate, sulfate, hydrogen sulfate, ethyl sulfate, methyl sulfate, formate and acetate.

[0256] Non-polysaccharide based cationic polymers consist of structural units which may be nonionic, cationic, anionic or mixtures thereof. The polymer may contain non-cationic structural units, but the polymer must have a net cationic charge.

[0257] Cationic polymers can consist of only one type of structural unit, i.e., the polymer is a homopolymer. Cationic polymers can consist of two types of structural units, i.e., the polymer is a copolymer. Cationic polymers can consist of three types of structural units, i.e., the polymer is a terpolymer. Cationic polymers can contain two or more types of structural units. The structural units can be described as a first structural unit, a second structural unit, a third structural unit, etc. The structural units or monomers can be incorporated into the cationic polymer in a random form or in a block form.

[0258] The cationic polymer may comprise nonionic structural units derived from monomers selected from the group consisting of (meth)acrylamide, vinyl formamide, N,N-dialkyl acrylamide, N,N-dialkyl methacrylamide, C1-C12 alkyl acrylates, C1-C12 hydroxyalkyl acrylates, polyalkylene glycol acrylates, C1-C12 alkyl methacrylates, C1-C12 hydroxyalkyl methacrylates, polyalkylene glycol methacrylates, vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ethers, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, vinyl caprolactam, and mixtures thereof.

[0259] The cationic polymer may comprise cationic structural units derived from monomers selected from the group consisting of N,N-dialkylaminoalkyl methacrylates, N,N-dialkylaminoalkyl acrylates, N,N-dialkylaminoalkyl acrylamides, N,N-dialkylaminoalkyl methacrylamides, methylamidoalkyl trialkyl ammonium salts, acrylamidoalkyl trialkyl ammonium salts, vinylamines, vinylimines, vinylimidazoles, quaternized vinylimidazoles, diallyldialkylammonium salts, and mixtures thereof.

[0260] Preferably, the cationic monomer is selected from: diallyldimethylammonium salt (DADMAS), N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate (DMAM), [2-(methacrylamido)ethyl]trimethylammonium salt, N,N-dimethylaminopropylacrylamide (DMAPA), N,N-dimethylaminopropylmethacrylamide (DMAPMA), acrylamidopropyltrimethylammonium salt (APTAS), methacrylamidopropyltrimethylammonium salt (MAPTAS), quaternized vinylimidazole (QVi) and mixtures thereof.

[0261] The cationic polymer may comprise anionic structural units derived from monomers selected from acrylic acid (AA), methacrylic acid, maleic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropyl methanesulfonic acid (AMPS) and its salts, and mixtures thereof.

[0262] Some of the cationic polymers disclosed herein will require stabilizers, i.e., materials that exhibit yield stress in the auxiliary laundry compositions of the present invention. Such stabilizers may be selected from: linear structuring systems, such as hydrogenated castor oil or trihydroxystearin, such as Thixcin from Elementis Specialties, crosslinked polyacrylic acids, such as Carbopol from Lubrizol, and gums, such as carrageenan.

[0263] Preferably, the cationic polymer is selected from the group consisting of: cationic polysaccharides and acrylate polymers. More preferably, the cationic polymer is a cationic acrylate polymer.

[0264] The molecular weight of the cationic polymer is preferably greater than 20 000 g / mol, more preferably greater than 25 000 g / mol. The molecular weight is preferably less than 2 000 000 g / mol, more preferably less than 1 000 000 g / mol.

[0265] The fabric softener according to the present invention preferably comprises the cationic polymer in an amount of 0.1 to 10 wt.% of the formulation, preferably 0.25 to 7.5 wt.% of the formulation, more preferably 0.35 to 5 wt.% of the formulation.

[0266] The composition may contain other ingredients of fabric softener liquids known to those skilled in the art. Among these materials, mention may be made of: defoamers, insect repellents, coloring or tinting dyes, preservatives (e.g. bactericides), pH buffers, perfume carriers, hydrotropes, anti-redeposition agents, detergents, polyelectrolytes, shrinkage inhibitors, wrinkle inhibitors, antioxidants, dyes, colorants, sunscreens, corrosion inhibitors, drape-imparting agents, antistatic agents, chelating agents and ironing aids. The product of the invention may contain pearlescent agents and / or sunscreens. A preferred chelating agent is HEDP, which is an abbreviation for etidronic acid or 1-hydroxyethane 1,1-diphosphonic acid.

[0267] In one aspect of the invention, fabrics are washed with a fabric softener composition as described herein. The treatment is preferably carried out during a wash process. This can be hand washing or machine washing. Preferably, the fabric softener is used in the rinse stage of the wash process.

[0268] Preferably, for a 3 to 7 kg load of laundry, the fabric is treated with a dosage of 10 to 100 ml of fabric softener. More preferably, for a 3 to 7 kg load of laundry, 10 to 80 ml.

[0269] One aspect of the present invention is a method of softening fabrics wherein the fabrics are contacted with a fabric softener as described herein during the rinse stage of a laundering process.

[0270] One aspect of the present invention is the use of a fabric softener as described herein for softening fabrics.

[0271] Example :

[0272] Example 1 - Synthesis of a quaternary ammonium compound of formula IV starting from 12-tricosanol, wherein J is J3, i.e. wherein n and n' in the group X are each 1

[0273] According to US-A 2018 / 093936 (see Example 3 in this document), catalytic hydrogenation is carried out from C 23 12-Tricosanoic acid ketone to obtain C 23 12-Tricosanol.

[0274] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0275] 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.

[0276] 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 stirred at room temperature before the addition of 0.1 g of solid KOH (1.7 mmol, 1.6 mol%) followed by 18.26 g of carbonyldiimidazole (112.7 mmol, 1 eq.) and another 20 mL of toluene.

[0277] The mixture was then stirred at 70°C; at this temperature, the mixture became transparent. 1 The progress of the reaction was followed by H-NMR and after 3 h at 70 °C, 99% alcohol conversion was achieved.

[0278] All volatiles were then removed by distillation at 50° C., 9 mbar, yielding 59.4 g of a residue which was used in the next stage without purification.

[0279] The residue was then dissolved in a mixture of 40 mL CHCl3 and 40 mL acetonitrile, and 15.74 g choline chloride (112.7 mmol, 1 eq.) were added at room temperature. The mixture was then stirred at 50°C overnight.

[0280] During the reaction, the reaction medium turned homogeneous and green. 1 The progress of the reaction was followed by H-NMR and a conversion of 89% was obtained at this stage. The solvent was then removed under vacuum to give about 79.1 g of crude product.

[0281] The crude residue was purified by silica gel chromatography (330 g silica) to remove impurities and imidazole byproduct (specification <0.5 wt % imidazole) using ethyl acetate / methanol (AcOEt / MeOH) eluent (from 100% AcOEt to 50:50 AcOEt:MeOH).

[0282] 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 remaining three fractions were collected and purified again.

[0283] For the second silica gel chromatography, 200 g of silica and the same elution system were used. Two fractions were collected: the first was a mixture of product and imidazole, while the second was the pure product.

[0284] Finally, the first fraction was purified again using 30 g of silica gel and the same elution system to afford additional amounts of product.

[0285] All clean fractions were collected to give 39.8 g of product as a white wax, corresponding to 70% isolated yield.

[0286] 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).

[0287] 13 C 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).

[0288] Example 2 - Synthesis of a quaternary ammonium compound of formula IV starting from 16-triacontanol, wherein J is J3, i.e. wherein n and n' in the group X are each 1

[0289] According to US-A US2018 / 093936 (see Example 3 in this document), catalytic hydrogenation from C 31 16 Tri-undecanoic acid to obtain C 31 16 Heteronecontanol.

[0290] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0291] 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.

[0292] 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 stirred at room temperature before the addition of 0.1 g of solid KOH (1.7 mmol, 1.7 mol%) followed by 17.0 g of carbonyldiimidazole (105 mmol, 1.05 eq.) and another 50 mL of toluene.

[0293] The mixture was then stirred at 60°C; at this temperature, the mixture became transparent. 1 The progress of the reaction was followed by H-NMR and after 1 hour at 60 °C, 99% alcohol conversion was achieved.

[0294] All volatiles were then removed by vacuum to give a white residue which was used in the next stage without purification.

[0295] The residue was then dissolved in a mixture of 80 mL CHCl3 and 80 mL acetonitrile, and 13.95 g choline chloride (99.9 mmol, 1 eq.) was added at room temperature. The mixture was then stirred at 55°C overnight.

[0296] pass 1 The 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 CHCl3).

[0297] 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, a conversion level of 78% was reached.

[0298] 0.2 g of KOH was further added, followed by stirring under reflux for 12 hours.

[0299] At this stage, the conversion level was 83% and the color of the mixture was brown.

[0300] The solvent was then removed under vacuum to give about 84 g of crude product.

[0301] The crude residue was purified by silica gel chromatography (2 columns with 330 g silica) to remove impurities and imidazole byproduct (specification < 0.5 wt % imidazole) using AcOEt / MeOH eluent (from 100% AcOEt to 50:50 AcOEt:MeOH).

[0302] Four fractions were collected: the first fraction corresponded to the intermediate imidazole carbonate, while the second fraction corresponded to the imidazole. The third fraction contained a mixture of imidazole and the desired product, and the last fraction corresponded to the desired product.

[0303] The fourth fraction from each column was collected and subjected to a second silica gel chromatography. 330 g of silica was used with the same elution system to provide the desired product with good purity.

[0304] 36.6 g of product were obtained as a white wax, corresponding to an isolated yield of 60%.

[0305] 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).

[0306] 13 C 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).

[0307] Example 3 - From C 31 -16-triacontanone starting with the synthesis of a mixture of quaternary ammonium compounds, wherein A is represented by A-2 or A-3 (a mixture of compounds of formula (V) and (VI))

[0308] Knoevenagel condensation to give the diester intermediate:

[0309]

[0310] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0311] Fresh commercially available anhydrous CHCl3, anhydrous THF, and anhydrous pyridine were used as received.

[0312] 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 was charged with 36.5 mL of TiCl4 (63.00 g, 0.332 mol) followed by 146.3 mL of CHCl3.

[0313] The mixture was stirred at -10°C and anhydrous THF (358 mL) was added slowly through the addition funnel at a rate to avoid the temperature of the reaction medium to rise 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 stirred at room temperature for 1 hour to allow malonate complexation to occur.

[0314] The mixture was then cooled to 0°C and 71.80 mL of anhydrous pyridine (70.50 g, 0.891 mole) solution 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 stirred at room temperature for 20 minutes to allow deprotonation to occur.

[0315] Finally, 50.00 g of C 31 Ketone (0.111 mole) is added in the reaction mixture, and it is stirred at room temperature overnight and stirred for another day at 35 ℃.Then 250mL water is carefully added in the reactor, and then 250mL diethyl ether is added.The organic phase is separated, washed 4 times with 250mL water, washed once with 200mL saturated NaCl aqueous solution, to remove pyridinium salt.Merge aqueous phase and extract 3 times again with 250mL diethyl ether.With final organic phase through MgSO4 drying, filter and evaporate under vacuum, obtain 70.08g crude orange oil.At this stage, crude product contains the starting ketone of residual amount and the main impurity corresponding to the condensation (aldol condensation reaction+crotonaldehyde reaction) of 2 equivalents of ketone.

[0316] The product can be easily purified by dissolving the oil in ethanol (the byproduct and starting ketone are insoluble in ethanol) and then filtering through celite.

[0317] The filtrate was evaporated, redissolved in CHCl3, filtered again and evaporated to give 52.57 g of an oil with a purity of 95% (RMN).

[0318] The overall purified yield was 79%.

[0319] 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).

[0320] 13C 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).

[0321] Transesterification with dimethylaminoethanol to obtain a diamine mixture intermediate:

[0322]

[0323] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0324] Fresh commercially available anhydrous toluene and dimethylaminoethanol were used as received.

[0325] In a 2L double jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plow blades), a condenser with a distillation device 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 eq.) was added to the reaction system, followed by 50 mL of toluene. Then 0.9 g of catalyst dibutyltin oxide (3.8 mmol, 5 mol%) was added to the reaction mixture, followed by 200 mL of toluene.

[0326] The mixture was then stirred at 120°C and the progress of the reaction was followed by NMR analysis. For proper analysis, an aliquot of the reaction medium was sampled and diluted in diethyl ether, quenched with water, decanted and the organic phase evaporated under vacuum for analysis in CDCl3 NMR solvent. After stirring at 120°C for 4 days, NMR analysis showed a conversion level of about 83% with a selectivity of 91%. 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 500 mL of water. The medium was decanted and the aqueous phase was extracted three times with 500 mL of diethyl ether. The organic phase was collected, washed three times with 500 mL of water and once with 500 mL of saturated NaCl aqueous solution to remove excess dimethylaminoethanol. The organic phase was then dried over MgSO4, filtered and evaporated to give 47.9 g of a crude dark oil. At this stage, the crude product contained a residual amount of the starting malonate.

[0327] The product was then purified by flash chromatography on silica gel, the first eluent consisting of a CHCl3 / AcOEt mixture with a gradient from 100% CHCl3 to 100% AcOEt.

[0328] In order to remove all the product from the column, isopropanol + NEt 3 The mixture (10% vol NEt3) was flushed through the column, allowing additional pure product to be obtained.

[0329] Clean fractions were collected to give 27.8 g of pure product after evaporation of the solvent, corresponding to an isolated yield of 54%.

[0330] 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.

[0331] 1 H 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 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).

[0332] 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).

[0333] Methylation to provide a mixture of compounds (V) and (VI):

[0334] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0335] Fresh commercially available anhydrous THF and dimethyl sulfate were used as received.

[0336] In the 1L double jacket reactor equipped with mechanical stirrer, condenser, feed funnel and temperature probe, add 100mL dry THF and 6.9mL dimethyl sulfate (9.14g, 72mmol, 2eq.).In the feed funnel, a solution of 24.6g esteramine (36mmol, 1eq.) in 154mL THF is initially prepared, and at room temperature, it is gradually added to the reactor with stirring to limit the temperature rise.Then the mixture is stirred at room temperature under argon, and the reaction process is monitored by NMR analysis.After 2 hours, the mixture is brought to 40 ℃ and 0.2ml dimethyl sulfate (2mmol, 0.06eq.) is added to allow stirring and to achieve complete conversion.

[0337] The reaction was complete after stirring at 40 °C for 1 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 in 94% yield.

[0338] NMR analysis showed the presence of 2 positional isomers with a ratio of 55:45 between the isomerized derivatives (cis and trans diastereomers) and the conjugated non-isomerized methylenated derivative.

[0339] 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).

[0340] 13C NMR (MeOD, 101MHz) δ (ppm): 169.22, 169.01, 168.96, 165.52, 134.16, 133.22, 132 .94, 131.74, 65.90, 65.81, 60.23, 60.18, 59.73, 55.27, 54.66, 54.62, 35.66, 35. 54, 33.24, 33.23, 31.76, 31.01, 30.94, 30.91, 30.87, 30.85, 30.77, 30.74, 30.71, 30.66, 30.65, 30.63, 30.60, 29.73, 29.62, 29.45, 29.27, 23.89, 14.61 (terminal CH3).

[0341] Example 4 - From C 23 -12-tricosanone starting with the synthesis of a mixture of quaternary ammonium compounds, wherein A is represented by A-2 or A-3 (a mixture of compounds of formula (V) and (VI))

[0342] Knoevenagel condensation to give the diester intermediate:

[0343] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0344] Fresh commercially available anhydrous CHCl3, anhydrous THF, and anhydrous pyridine were used as received.

[0345] 48.6 mL of TiCl4 (84.02 g, 0.443 mole) was added to 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, followed by 146 mL of CHCl3. The mixture was stirred at -10 °C and anhydrous THF (358 mL) was added slowly through an addition funnel at a rate to avoid a temperature increase of the reaction medium exceeding +5 °C. During the THF addition, a yellow precipitate appeared. Then 20.4 mL of dimethyl malonate (23.41 g, 0.177 mole) was added to the reaction mixture, which was then stirred at room temperature for 1 hour to allow malonate complexation to occur.

[0346] The mixture was then cooled to 0°C and a solution of 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 stirred at room temperature for 20 minutes to allow deprotonation to occur.

[0347] Finally, 50.00 g of C 23Ketone (0.148 mole) adds in the reaction mixture, makes it stir overnight at room temperature and stir one day again at 35 ℃.Then 250mL water is carefully added in the reactor, then adds 250mL diethyl ether.Separate organic phase, and wash four times with 250mL water, and wash once with 200mL saturated NaCl aqueous solution, to remove pyridinium salt.Collect water and extract three times again with 250mL diethyl ether.With final organic phase through MgSO4 drying, filter and evaporate under vacuum, obtain 69.5g rough orange oil.At this stage, crude product contains the starting ketone of residual quantity and the major impurity corresponding to the condensation (aldol condensation, butene aldehyde) of 2 equivalent ketones.

[0348] The product can be easily purified by dissolving the oil in methanol (the byproduct and starting ketone are insoluble in methanol) and then filtering through celite.

[0349] The filtrate was evaporated to give 54 g of an oil with a purity of 95% (RMN).

[0350] The overall purified yield was 77%.

[0351] 1 H 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).

[0352] 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).

[0353] Transesterification with dimethylaminoethanol provides a diamine mixture intermediate:

[0354] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0355] Fresh commercially available anhydrous toluene and dimethylaminoethanol were used as received.

[0356] 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 was charged with a solution of 51.1 g of lactone / dimethyl malonate adduct (110 mmol, 1 eq.) in 300 mL of toluene. The mixture was stirred at room temperature, and 45.5 mL of dimethylaminoethanol (40.5 g, 450 mmol, 4 eq.) was added to the reaction medium, followed by 1.37 g of catalyst dibutyltin oxide (5.5 mmol, 5 mol%).

[0357] The mixture was then stirred at 120°C and the progress of the reaction was followed by NMR analysis. For proper analysis, an aliquot of the reaction medium was sampled and diluted in diethyl ether, quenched with water, decanted and the organic phase evaporated under vacuum for analysis in CDCl3 NMR solvent. After stirring at 120°C for 2 days, the mixture was cooled at room temperature and concentrated under vacuum. 200 mL of water was then added to the residue, followed by 200 mL of diethyl ether. The organic phase was decanted and washed three times with 300 mL of water and once with 300 mL of saturated NaCl aqueous solution to remove excess dimethylaminoethanol. The aqueous phase was collected and re-extracted with 700 mL of diethyl ether. The organic phase was collected, then dried over MgSO4, filtered and evaporated. The obtained residue was redissolved in methanol, and the precipitated solid was filtered. The filtrate was evaporated to obtain 59.04 g of a crude yellow oil. At this stage, the crude product contained a residual amount of the starting malonate and some by-products.

[0358] The product was then purified by flash chromatography on silica gel, the eluent consisting of CHCl3 / isopropanol mixtures with a gradient from 100% CHCl3 to 100% isopropanol.

[0359] Clean fractions were collected and after evaporation of the solvent 22.9 g of pure product were obtained, corresponding to an isolated yield of 35%.

[0360] NMR analysis showed that the product was in the form of a mixture of 2 positional isomers with the following ratios: 60 mol % of isomerized product (cis and trans diastereomers) and 40 mol % of methylenated product.

[0361] 1H 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 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).

[0362] 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, 14.3 (terminal CH3).

[0363] Methylation to give a mixture of compounds V and VI:

[0364] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0365] Fresh commercially available anhydrous THF and dimethyl sulfate were used as received.

[0366] 100mL dry THF and 7.59mL dimethyl sulfate (10.1g, 80mmol, 2eq.) are added to a 200mL double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plow blades), a condenser, a feed funnel and a temperature probe. A solution of 22.94g esteramine (40mmol, 1eq.) in 154mL THF is preliminarily prepared in the feed funnel, and is gradually added to the reactor at room temperature with stirring to limit temperature rise. The mixture is then stirred at room temperature under argon, and the reaction process is monitored by NMR analysis. The reaction is completed after stirring at room temperature for 1 hour, and all volatiles (THF and remaining DMS) are removed under vacuum to obtain 32.6g of product, which is a beige waxy substance with a productive rate of 99%.

[0367] NMR analysis showed the presence of two positional isomers with a 60:40 ratio between the isomerized derivatives (cis and trans diastereomers) and the conjugated non-isomerized methylenated derivative.

[0368] 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).

[0369] 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).

[0370] Example 5 - From C 23 12 tricosanone is used to synthesize a compound wherein A is represented by A-1, in particular a compound of formula VII

[0371] Reductive amination to give primary amines

[0372]

[0373] All reactions were carried out under an inert argon atmosphere.

[0374] 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.

[0375] Then NH4OAc (227.386g, 2.95mol, 10eq.), then NaCNBH3 (74.15g, 1.18mol, 4eq.) are added in small portions to the mixture. The reaction medium is stirred at room temperature for 1 hour. Finally, the mixture is heated at reflux for 16 hours. The reaction medium is then cooled to room temperature and concentrated under vacuum.

[0376] Finally, 500mL saturated NaHCO aqueous solution and 500mL methyl tert-butyl ether (MTBE) were added to the residue, and the mixture was stirred at room temperature for 1 hour. Concentrated NaOH aqueous solution was added to adjust the pH to about 9. The product was extracted with MTBE, and the organic phase was washed with water and brine several times. The organic phase was dried with KCO, filtered and concentrated in vacuo to obtain 100.4g of a crude yellow oil.

[0377] The crude product was then purified by flash chromatography on silica gel using dichloromethane (DCM):

[0378] Methanol mixture was used as eluent with a gradient of 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.

[0379] Yield: 93%

[0380] Alkylation of primary amines to provide amino-diester intermediates

[0381]

[0382] The reaction was carried out under an inert argon atmosphere.

[0383] In a 1 L round bottom flask equipped with a condenser, temperature probe, magnetic stirrer and heater, add:

[0384] 62.0 g (0.18 mol, 1 eq.) of C 23 Primary fatty amines.

[0385] 700 mL of methyl-THF.

[0386] 63.7 g methyl 2-chloroacetate (0.59 mol, 3.3 eq.).

[0387] 81.5g K2CO3 (0.59mol, 3.3eq.).

[0388] 97.94g KI (0.59mol, 3.3eq.).

[0389] The mixture was then stirred at reflux (78-80°C) overnight.

[0390] 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.

[0391] The product was then purified by flash chromatography on silica gel using a petroleum ether:ethyl acetate mixture (50:1) as eluent to afford 52 g of pure material (0.108 mol) after evaporation of the solvent.

[0392] Yield: 60%

[0393] The ester is hydrolyzed to give the iminodiacetic acid intermediate.

[0394]

[0395] In a 2 L round bottom flask equipped with a magnetic stirrer, add:

[0396] 27.3 g NaOH (0.683 mol, 6.0 eq.)

[0397] 300mL water

[0398] 300mL methanol

[0399] 300mL THF

[0400] The obtained solution was then stirred at 0° C., and 55 g of aminodiester (0.113 mol, 1 eq.) were slowly added.

[0401] The reaction medium is then stirred at room temperature overnight.

[0402] 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 using 3 L of dichloromethane.

[0403] The organic phases were collected and washed several times with brine, dried over MgSO4, filtered and the solvent evaporated under vacuum to give 55 g of product which was used as such in the next step.

[0404] Quantitative yield

[0405] Esterification with dimethylaminoethanol to obtain the diester intermediate

[0406]

[0407] The reaction was carried out under an inert argon atmosphere.

[0408] In a 2 L round bottom flask equipped with a magnetic stirrer, add:

[0409] 53.3 g (0.117 mol, 1 eq.) of iminodiacetic acid intermediate

[0410] 2L dichloromethane

[0411] 104.2 g dimethylaminoethanol (1.17 moles, 10 eq.)

[0412] 142 g trimethylamine (1.40 mol, 12 eq.)

[0413] 189.7 g HOBt (1.40 mol, 12 eq.)

[0414] The mixture was cooled to 0°C and 220 g EDCI (1.15 moles, 10 eq.) was added to the reaction vessel.

[0415] The mixture was stirred at room temperature for 20 hours, thereby allowing the reaction to reach completion.

[0416] The reaction mixture was then washed with water and the organic phase was dried over MgSO4, filtered and evaporated under vacuum to provide 118 g of the crude product as a dark yellow oil.

[0417] The crude material was then purified by flash chromatography on silica gel, using first a petroleum ether:CH2Cl2 mixture (9:1) as eluent and then a CH2Cl2:isopropanol (50:1)+1.5% NEt3 mixture.

[0418] Two fractions were obtained: a first fraction containing 31.0 g of product and a second fraction containing 35 g of material.

[0419] The second fraction was then purified a second time to give 29.2 g of a dark yellow oil. In total, 60.2 g (101 mmol) of pure product were obtained as a yellow oil.

[0420] Yield: 86%

[0421] Quaternization to obtain a compound of formula (VII)

[0422] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0423] Fresh commercially available anhydrous THF and dimethyl sulfate were used as received.

[0424] 100mL dry THF and 8.0mL dimethyl sulfate (10.6g, 84mmol, 2eq.) are added to a 200mL double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plow blades), a condenser, a feed funnel and a temperature probe. A solution of 25.2g esteramine (42mmol, 1eq.) in 154mL THF is prepared in a feed funnel, and is gradually added to the reactor at room temperature with stirring to limit temperature rise. The mixture is then stirred at room temperature under argon, and the reaction process is monitored by NMR analysis. The reaction is completed after stirring at room temperature for 1 hour, and all volatiles (THF and remaining DMS) are removed under vacuum to obtain 35.7g product in quantitative yield, which is a beige waxy substance.

[0425] 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).

[0426] 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).

[0427] Example 6 - From C 31 16-triacontanone is used to synthesize a compound wherein A is represented by A-1, in particular a compound of formula VII

[0428] Reductive amination affords the primary amine.

[0429] The same protocol was followed as described above in Example 5 for the C23 derivative.

[0430] Alkylation of the primary amine to give the amino-diester intermediate.

[0431] The reaction was carried out under an inert argon atmosphere.

[0432] In a 500 mL round bottom flask equipped with a condenser, temperature probe, magnetic stirrer and heater, add:

[0433] 18.0 g (40 mmol, 1 eq.) of C 31 Primary fatty amines.

[0434] 500 mL of methyl-THF.

[0435] 12.48 g of methyl 2-chloroacetate (132 mmol, 3.3 eq.).

[0436] 18.24g K2CO3 (132mmol, 3.3eq.).

[0437] 21.92 g KI (132 mol, 3.3 eq.).

[0438] The mixture was then stirred at reflux (78-80°C) overnight.

[0439] At the end of the reaction, the mixture was filtered through a plug of celite. The solids were washed with THF and the filtrate was concentrated in vacuo to give a crude material that still contained methyl 2-chloroacetate.

[0440] The product was then purified by flash chromatography on silica gel using a petroleum ether:ethyl acetate mixture (100:1) as eluent to give after evaporation of the solvent 22.4 g of pure material (37.6 mmol).

[0441] Yield: 94%

[0442] The ester is hydrolyzed to give the imino-diacetic acid intermediate.

[0443] In a 1 L round bottom flask equipped with a magnetic stirrer add:

[0444] 11.3 g NaOH (0.282 mol, 6.0 eq.)

[0445] 100ml water

[0446] 100ml methanol

[0447] 100ml THF

[0448] The obtained solution was then stirred at 0° C., and 28 g of the amino diester (0.047 mol, 1 eq.) were slowly added.

[0449] The reaction medium is then stirred at room temperature overnight.

[0450] 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.

[0451] 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 give 26 g of product (45.8 mmol) which was used as is in the next step.

[0452] Yield: 97%.

[0453] Esterification with dimethylaminoethanol affords the diester intermediate.

[0454] Follow the same procedure as in Example 5 for C 23 The same protocol as described for the derivatives.

[0455] Quaternization to obtain the compound of formula VII

[0456] Follow the same procedure as in Example 5 for C 23 The same protocol as described for the derivatives.

[0457] 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).

[0458] 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).

[0459] Example 7 - Synthesis of Compounds of Formula (VIII) Starting from 16-triacontanone

[0460] Reductive amination to give the aminodiol intermediate

[0461]

[0462] The reaction was carried out under an inert argon atmosphere.

[0463] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plow blades), a condenser and a temperature probe were added:

[0464] 50 g 16-triacontanone (111 mmol, 1 eq.)

[0465] 281mL CHCl3

[0466] 17.73 mL 3-amino-1,2-propanediol (20.8 g, 222 mmol, 2 eq.)

[0467] 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 reaction.

[0468] 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 NaBH4 (222 mmol, 2 eq.). Care was taken to avoid bubbling during the addition of NaBH4.

[0469] The reaction medium is then stirred at 40° C. for 3 hours.

[0470] The mixture was then cooled to room temperature and 100 mL of water was added followed by 100 mL of diethyl ether. TiO2 precipitation occurred during the water addition.

[0471] The suspension was filtered, the solid was washed several times with diethyl ether, and the two phase filtrate was separated. The organic phase was filtered through celite again and washed with water and brine. The organic phase was then dried over MgSO4, filtered and evaporated to give the crude material as a yellow paste (48.9 g).

[0472] The crude product was then purified by flash chromatography on silica gel using CHCl 3 :isopropanol mixture as eluent in a gradient from 100:0 to 50:50.

[0473] After evaporation of the solvent, 28.75 g of pure product (54.70 mmol) were obtained.

[0474] Yield: 49%

[0475] 1 H 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).

[0476] 13C 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).

[0477] Esterification with glycine betaine to obtain the quaternary ammonium compound of formula VIII

[0478] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0479] Commercially available anhydrous THF, anhydrous toluene, and anhydrous CHCl3 stabilized with pentene were used as received.

[0480] Glycine betaine hydrochloride was dried by washing several times with anhydrous THF and then dried under vacuum before use.

[0481] 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:

[0482] 7.13 g betaine hydrochloride (46.4 mmol)

[0483] Then 10 mL SOCl2 (16.38 g, 136.9 mmol) was carefully introduced into the reaction vessel, and the resulting suspension was gradually heated to 70° C. under stirring. When the temperature reached 68° C., release of gases (SO2 and HCl) was observed, and the mixture turned into a homogeneous yellow color.

[0484] The mixture was then stirred at 70°C for 2 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 phase of toluene was then removed by cannula, and the toluene washing operation was repeated four times to remove all excess SOCl2.

[0485] NMR analysis showed complete conversion of glycine betaine hydrochloride, but also formation of NMe3.HCl adduct (NMe3.HCl content in the solid: 19.3 mol %).

[0486] Then 20 mL of CHCl3 was added to the solid betaine acid chloride.

[0487] A solution of the fatty diol (9.85 g, 18.7 mmol) in 30 ml of CHCl3 was then prepared and added dropwise to the betaine acid chloride / CHCl3 suspension at -3°C at such a rate as to avoid a temperature of the reaction medium 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.

[0488] All volatiles were then removed in vacuo at 30°C to give 16 g of a beige wax.

[0489] NMR analysis showed that the purity of the obtained product was about 73 wt % (remaining by-products were: protonated starting alcohol, NMe3 HCl, betaine HCl and monoester).

[0490] Yield: 75% (14 mmol)

[0491] 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).

[0492] 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).

[0493] Example 8 - From C 31 The synthesis of the quaternary ammonium compound wherein A is represented by A-5 and corresponds to the formula (IX) is started by 1,6-triacontanone

[0494] According to the protocol described in Example 4 of U.S. Pat. No. 10,035,746, C was obtained from palmitic acid. 31 Internal olefins.

[0495] Epoxidation of internal olefins to fatty epoxides

[0496]

[0497] The reaction was carried out under an inert argon atmosphere.

[0498] 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 was charged with 61.9 g of C 31 Olefin (0.142 mol), then 16.3 ml (17.1 g, 0.285 mol) of acetic acid and 13.6 g (22 wt%) IR 120H. The mixture was heated to 65°C to melt the fatty olefins. Stirring was started and then 21.8 mL (24.2 g, 0.214 mol) of an aqueous solution of H2O2 (concentration 30%) was slowly added to the mixture using an addition funnel at a rate to avoid a significant increase in temperature. This took about an hour. The temperature was then raised to 75°C and the reaction mixture was stirred overnight (after 15 min, NMR analysis showed that the conversion level was already about 60% with a selectivity of 99%). Another 10.2 ml (11.3 g, 0.1 mol) of an aqueous solution of H2O2 (30%) was then slowly added and 4 hours after the second addition of H2O2, NMR analysis showed a conversion level of about 88% (98% selectivity). Finally, 8.14 ml of acetic acid (8.55 g, 0.142 mol) was added and then 11.6 ml of 30% H2O2 (12.91 g, 0.114 mol) was added to increase the conversion level.

[0499] The mixture was stirred at 75 °C for a second night.

[0500] Finally, NMR analysis showed a conversion level of 93% (95% selectivity).

[0501] The mixture was cooled to room temperature and then 300 ml of chloroform was added. The mixture was transferred to a separatory funnel, the organic phase was washed three times with 300 ml of water and then the aqueous phase was extracted twice with 100 ml of chloroform. The Amberlite solid catalyst remained in the aqueous phase and was removed with the aqueous phase during the first separation. The organic phase was collected, dried over MgSO4, filtered and evaporated to give 65.3 g of a white solid with a purity of 91% w / w (epoxide + diol).

[0502] Considering the purity, the yield was 92%.

[0503] 1H NMR (CDCl3, 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).

[0504] 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).

[0505] Hydrolysis of fatty epoxides to give fatty diols

[0506]

[0507] The reaction was carried out under an inert argon atmosphere.

[0508] 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.

[0509] The mixture is stirred at room temperature, and then 73mL 3M H2SO4 aqueous solution is added.Then the reaction medium is stirred at 80 ℃ for 90 minutes.NMR analysis shows that the reaction is complete.The two-phase mixture is cooled to room temperature and the organic phase is separated.Then the solvent is removed under vacuum, and the residue is suspended in 200ml diethyl ether.The suspension is filtered, and the resulting solid is washed 3 times with 50mL diethyl ether.Finally, the white solid is washed 2 times with 50mL methanol, and dried under vacuum to remove trace solvents.

[0510] Finally, 75.53 g of product were obtained as a white powder with a purity of 95.7% w / w, corresponding to a yield of 89%.

[0511] 1 H 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).

[0512] 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)

[0513] Esterification of aliphatic diols with trimethylglycine to give compounds of formula IX

[0514] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0515] Fresh commercially available anhydrous CHCl3 (pentene-stabilized) and anhydrous toluene were used as received.

[0516] 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 before use.

[0517] 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 NaOH traps, quickly add:

[0518] 19.66 g dry betaine hydrochloride (128.4 mmol) and

[0519] 28mL SOCl2 (45.86g, 0.386mol).

[0520] The heterogeneous mixture was stirred and the temperature was then slowly raised to 70° C. When the temperature reached 68° C., gas evolution (SO 2 and HCl) was observed and the mixture turned into a homogeneous yellow color.

[0521] The mixture was then stirred at 70°C for 2 hours, and hot anhydrous toluene (25 mL, 80°C) was added to the vessel. The mixture was stirred, then decanted at 0°C (a white-yellow precipitate was 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%).

[0522] Then 20 mL of anhydrous CHCl3 was added to the solid betaine acid chloride.

[0523] A solution of 26.19 g (56 mmol) of aliphatic diol in 90 ml of anhydrous CHCl3 was prepared at 55°C and added dropwise to the reaction vessel at room temperature with stirring (exothermic and HCl evolution was observed). The mixture was then stirred at 55°C overnight. During the reaction, the mixture turned a homogeneous orange color. NMR analysis showed a conversion level of about 100%.

[0524] The mixture was then cooled to room temperature and the solvent was evaporated under vacuum.

[0525] 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.

[0526] The product was then deposited on a sintered filter and washed with cyclohexane to remove some residual organic impurities. The resulting washed solid was dried under vacuum to give 22 g of crude material. Final purification was carried out with a mixture of CH2Cl2 / cyclohexane 50:50; the solid was redissolved in this solvent at 50°C and allowed to cool to room temperature. The precipitate formed was filtered off and, after evaporation of the filtrate, 19 g of a beige waxy substance were obtained, the composition of which was as follows:

[0527] 95wt% glycine betaine diester

[0528] 1.5wt% methyl betaine

[0529] 2wt% trimethylamine hydrochloride

[0530] 1.5 wt% of glycine betaine hydrochloride.

[0531] The purified yield was 44%.

[0532] 1 H NMR (MeOD-d4, 400MHz) δ (ppm): 5.3-5.2 (m, 2H), 4.68 (d, J = 16.8Hz, 2H), 4.50 (d, J = 16.8Hz, 2H), 4. 53 (s, 1H), 4.48 (s, 1H), 3.37 (s, 18H), 1.75-1.55 (m, 4H), 1.39-1.10 (m, 50H), 0.9 (t, J=6.8Hz, 6H).

[0533] 13C 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).

[0534] Example 9 - Fabric Softening Formulation

[0535] Table 1: Example fabric softening formulations

[0536]

[0537] Fabric softening actives 1 - a cationic polymer synthesized as in any one of Examples 1-8 2 -Flosoft270LS from SNF

[0538] The fabric softening composition can be prepared by the following method:

[0539] Heat the water in the container to ~50°C and add the cationic polymer under stirring, followed by the reflective agent and defoamer. Prepare the quaternary ammonium premix at ~65°C and add to the main mixing container under stirring. Add the fatty material and nonionic surfactant (if present). Cool the mixture to ~35°C and add the perfume ingredients.

[0540] Example 10 - Softening Comparison

[0541] The new ionic compound prepared according to Example 8 herein was compared with a typical quaternary ammonium compound having the general formula A:

[0542]

[0543] wherein each R is independently selected from a C12 to C20 alkyl or alkenyl group;

[0544] R1 represents CH3,

[0545] T represents O-CO,

[0546] n is a number selected from 1 to 4,

[0547] m is a number selected from 1, 2 or 3,

[0548] and X- is a chloride counter ion.

[0549] The softening compound is prepared with a fat softener in aqueous solution:

[0550]

[0551] The softening wash experiment was carried out using the Terg-O-Tometer v2 under the following conditions:

[0552] Fabric: 40g knitted cotton

[0553] Water volume: 1 liter

[0554] Water type: Demineralizing Rinse time: 10min

[0555] Spin: 30 seconds

[0556] Temperature: Ambient temperature (~20℃)

[0557] The fabric was pre-wetted in the Terg-O-Tometer, removed and gently squeezed to remove excess water. A softening compound solution was then pre-dispersed in the Terg-O-Tometer to provide 0.1% active (total softening active and fat co-softener). The pre-wetted fabric was added back to the Terg-O-Tometer.

[0558] After the rinse and spin cycle, the fabrics were dried at 20°C at 65% relative humidity.

[0559] Using Nu Cybertek Evaluate the relative hand value.

[0560] Table 2: Softening results

[0561] Relative feel value A 0.66 1 2.07 B 0.72 2 1.43

[0562] Higher numbers indicate softer fabrics. The ionic compound prepared according to Example 8 in combination with a fat co-softener exerts improved softening compared to quaternary ammonium compounds commonly used in fabric softener formulations.

Claims

1. A fabric softener composition comprising: a. 1 to 20 wt.% of an ionic compound of formula I: in A is a tetravalent linker selected from A-1 to A-6 Q1 to Q4 are selected from hydrogen, R and X; and wherein at least one of Q1 to Q4 is represented by X, and at least two of the groups Q1 to Q4 are represented by R, which group R may be the same or different at each occurrence; and W is an anion or anionic group with w negative charges, and r is the number of substituents Q1 to Q4 represented by the group X, where R, which may be the same or different at each occurrence, is C5-C 27 aliphatic groups, m, m', m" and m'" which may be the same or different at each occurrence are 0, 1, 2 or 3, k, k', k", k'" and k"" which may be the same or different are 0, 1, 2 or 3, and X which may be the same or different at each occurrence is represented by Formula II wherein Z1, Z2 and Z3, which may be the same or different, are O, S or NH, Y is a divalent C1-C6 aliphatic group, R', R" and R'" which may be the same or different are hydrogen or C1 to C4 alkyl, n and n' are 0 or 1, where the sum of n + n' is 1 or 2, and 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 substituents R, the difference in the number of carbon atoms of the two substituents R is 0, 1, 3 or greater than 3; b. 0.1 to 20 wt.% of a fat softener; and c. Water.

2. A fabric softener composition according to claim 1, wherein the ionic compound comprises one or two groups X and two and only two groups R.

3. The fabric softener composition according to claim 1 or 2, wherein n+n' of the ionic compound is 1.

4. The fabric softener composition according to claim 1 or 2, wherein n+n' of the ionic compound is 2.

5. The fabric softener composition according to claim 1 or 2, wherein n' of the ionic compound is 1 and Y of the ionic compound is a C2-C6 aliphatic group.

6. The fabric softener composition according to claim 1 or 2, wherein at least one of the substituents Z1, Z2 and Z3 is oxygen.

7. A fabric softener composition according to claim 1 or 2, wherein at least two of the substituents Z1, Z2 and Z3 are oxygen.

8. A fabric softener composition according to claim 1 or 2, wherein all three of the substituents Z1, Z2 and Z3 are oxygen.

9. The fabric softener composition according to claim 1 or 2, wherein A of the ionic compound is represented by A-6, m, m', m", and m'" are 0, Z1 to Z3 are O, and wherein the ionic compound comprises two groups R and one group X. 10 . The fabric softener composition according to claim 9 , wherein n of the ionic compound is 0 and n′ of the ionic compound is 1, or wherein n of the ionic compound is 1.

11. A fabric softener composition according to claim 1 or 2, wherein A of the ionic compound is represented by A-3, m, m', m", m'" and k'" are 0, and two of the substituents Q1 to Q4 are represented by a group X and two are represented by a group R, wherein both X are connected to the same carbon atom of the linker A, and the two groups R are connected to the same or different carbon atoms of the linker A.

12. A fabric softener composition according to claim 1 or 2, wherein A of the ionic compound is represented by A-4, m, m', m", and m'" are 0, and two of the substituents Q1 to Q4 are represented by a group X and two are represented by a group R, wherein both X's are attached to the same carbon atom of the linker A, and the two groups R's are attached to the same or different carbon atoms of the linker A.

13. The fabric softener composition according to claim 1 or 2, wherein A of the ionic compound is represented by A-1, m and m' are 1, m" and m'" are 0, k is 0, and two of the substituents Q1 to Q4 are represented by groups X, wherein both groups X are connected to the nitrogen atom of the linker A.

14. The fabric softener composition according to claim 1 or 2, wherein A of the ionic compound 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 a group X connected to the same carbon atom of the linker A.

15. A fabric softener composition according to claim 1 or 2, wherein A of the ionic compound is represented by A-5, m, m', m", m'" and k"" are 0, two of the substituents Q1 to Q4 are X, wherein each carbon atom 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.

16. The fabric softener composition according to claim 15, wherein in group X, n is 1, n' is 0, and Y of the ionic compound is CH2.

17. The fabric softener composition according to claim 1 or 2, wherein the fat co-softener is selected from the group consisting of fatty esters, fatty acids, fatty alcohols and combinations thereof.

18. Use of a fabric softener composition according to any one of claims 1 to 17 for softening fabrics.

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