Sulfonated and sulfated aryl-alkyl compounds useful as surfactants

Abstract

The present invention relates to sulfonated and sulfated compounds obtainable from aryl aliphatic ketones, to a process for producing such compounds and to the use of these compounds as surfactants alone or in combination with other surfactants.

Description

[0001] This application claims priority from European application No. 22182457.6 filed on July 1, 2022, the entire contents of which are incorporated by reference into this application for all purposes.

[0002] Technical Field and Background Art

[0003] The present invention relates to sulfonated and sulfated compounds obtainable from arylaliphatic ketones, to processes for producing such compounds and to the use of such compounds as surfactants, either alone or in admixture with other surfactants.

[0004] WO 2018 / 229285 A1 discloses a method for cross-ketonization between aryl carboxylic acids and aliphatic carboxylic acids using metal-based compounds. The resulting aryl aliphatic ketones can be used to prepare surfactants.

[0005] It is generally desirable to provide new families of surfactants having a good toxicity and environmental profile, which new families further exhibit a good biodegradability profile. Summary of the invention

[0006] It was therefore an object of the present invention to provide compounds which are useful as surfactants and which have a good toxicity and environmental profile and a good, preferably improved, biodegradability profile.

[0007] This object is solved by compounds of formula I as defined in claims 1 to 8 and by compositions comprising a mixture of two or more compounds of formula I as defined in claims 9 and 10 and by compositions comprising at least one compound of formula I and at least one further surfactant as defined in claim 11, wherein the at least one further surfactant is not a compound of formula I.

[0008] Another object of the present invention is to provide a process for preparing a compound of formula I as defined in any one of claims 1 to 8.

[0009] This object is solved by a method as defined in any one of claims 12 to 16 of the present application.

[0010] Finally, the object of the present invention is to provide specific uses of the compound of formula I according to any one of claims 1 to 8 or the composition according to any one of claims 9 to 11.

[0011] This object is solved by the subject matter claimed in claim 17 of the present application. DETAILED DESCRIPTION

[0012] Compounds of the present invention

[0013] The present invention provides a compound having formula I

[0014]

[0015] wherein Ar represents an aryl group;

[0016] R1 is H or a group of formula OR, wherein R is H or SO3X, wherein X is an alkali metal, an alkaline earth metal or ammonium of the general formula R'R"R"'R""N, wherein R', R", R"' and R"" are independently selected from hydrogen or a hydrocarbon group, which hydrocarbon group may be optionally substituted and / or interrupted by one or more heteroatom-containing groups;

[0017] R2 is H or SO3X, wherein X is an alkali metal, alkaline earth metal or ammonium having the general formula R'R"R"'R""N, wherein R', R", R"' and R"" are independently selected from hydrogen or a hydrocarbyl group which may be optionally substituted and / or interrupted by one or more heteroatom-containing groups;

[0018] The premise is

[0019] R1 and R2 are different groups

[0020] When R2 is SO3X, R1 is H or OR, where R is H

[0021] When R2 is H, R1 is OR, where R is SO3X

[0022] R3 is C2-C 26 Aliphatic group.

[0023] It has been found that the compounds of the present invention provide a good toxicity and environmental profile. In addition, the compounds of the present invention show a good biodegradability profile, which has been found to be improved compared to the corresponding aryl-alkyl ketone sulfonates Ar-C(=O)-CH(SO3X)-R3 of the general formula VI. Aryl-alkyl ketone sulfonates are known, for example, from WO2018 / 229285A1.

[0024] In the context of the present invention, "aryl" (Ar) means an aromatic group, i.e., a cyclic conjugated unsaturated hydrocarbon ring having multiple delocalized π electrons following Huckel's rule; it also encompasses polycyclic aromatic groups, wherein the cyclic aromatic rings may be fused or connected by C-C bonding; it also encompasses heteroaromatic groups, i.e., cyclic or polycyclic conjugated unsaturated rings containing one or more heteroatoms, having multiple delocalized π electrons following Huckel's rule (e.g., furan, pyridine, pyrrole, as will be described in further detail below). The aryl group may optionally be further substituted by one or more functional groups.

[0025] An example of an aromatic ring as an aryl group Ar is a phenyl group which may optionally be further substituted by one or more functional groups. Ar may represent a substituted phenyl group having the formula

[0026]

[0027] Where X1, X2, X3, X4 and X5 can be the same or different, indicating

[0028] -hydrogen or a C1-C2- 24 a straight-chain or branched hydrocarbon group, which may optionally be substituted and / or interrupted by one or more heteroatoms or heteroatom-containing groups,

[0029] -halogen,

[0030] -hydroxy (-OH) or alkoxy (-OR), wherein R is a straight-chain or branched hydrocarbon radical having 1 to 24 carbon atoms, which may be optionally substituted and / or interrupted by one or more heteroatoms or heteroatom-containing groups,

[0031] -amino (-NRR'), wherein R and R' independently represent hydrogen or a straight-chain or branched hydrocarbon radical having 1 to 24 carbon atoms, which may optionally be substituted and / or interrupted by one or more heteroatoms or heteroatom-containing groups,

[0032] -acyl (-(C=O)-R), wherein R represents hydrogen or a C1-C2-6-yl radical having 1 to 24 carbon atoms 24 a straight-chain or branched hydrocarbon group, which may optionally be substituted and / or interrupted by one or more heteroatoms or heteroatom-containing groups,

[0033] -carboxyl (-COOH) or alkoxycarbonyl (-(C=O)-OR), wherein R represents a C1-C1-C2- 24 a straight-chain or branched hydrocarbon group, which may optionally be substituted and / or interrupted by one or more heteroatoms or heteroatom-containing groups,

[0034] -carbamoyl (-(C=O)-NRR'), in which R and R' independently represent hydrogen or a straight-chain or branched hydrocarbon radical having 1 to 24 carbon atoms, which may optionally be substituted and / or interrupted by one or more heteroatoms or heteroatom-containing groups,

[0035] -alkylsulfonyl (-SO2-R) or alkylsulfinyl (-SO-R) or alkylthio (-SR), wherein R represents a C1-C1-C2- 24 A straight or branched hydrocarbon group which may be optionally substituted and / or interrupted by one or more heteroatoms or heteroatom-containing groups.

[0036] Examples of heteroaromatic rings as the aromatic group Ar include pyridyl, furyl, pyrrolyl, thiophenyl, pyrazolyl, imidazolyl, benzimidazolyl, indolyl, quinolyl, isoquinolyl, purinyl, pyrimidinyl, thiazolyl, pyrazinyl, pyridazinyl, oxazolyl and triazolyl, which may be further substituted by one or more functional groups.

[0037] For example, Ar may represent an optionally substituted 2-pyridyl, 3-pyridyl or 4-pyridyl group having the formula

[0038]

[0039] Wherein X1, X2, X3 and X4 may be the same or different and have the same meanings as above.

[0040] Ar may also represent an optionally substituted furan-2-yl or furan-3-yl radical having the formula

[0041]

[0042] Wherein X1, X2 and X3 may be the same or different and have the same meanings as above.

[0043] Ar may also represent an optionally substituted 1H-pyrrol-2-yl or 1H-pyrrol-3-yl group having the formula:

[0044]

[0045] wherein X1, X2, X3 and X4 may be the same or different and have the same meanings as above. Ar may also represent an optionally substituted thiophene-2-yl or thiophene-3-yl having the following formula:

[0046]

[0047] In some embodiments, the substituent X is carried by two adjacent carbon atoms in phenyl, pyridyl, furanyl, pyrrolyl or thienyl. i and X i+1 Together they form an optionally substituted cyclic moiety which is an aromatic, heteroaromatic or non-aromatic group.

[0048] In a preferred embodiment of the present invention, the aryl group Ar is a phenyl group.

[0049] In the context of the present invention, "R3" generally represents C2-C 26 Aliphatic group, preferably C2-C 18 Aliphatic groups, more preferably C6-C 16 An aliphatic group, even more preferably C 10 -C 16 Aliphatic group.

[0050] The aliphatic group R3 may not contain any double bonds and any triple bonds. Alternatively, the aliphatic group R3 may also contain at least one CC double bond and / or at least one CC triple bond.

[0051] The aliphatic group R3 may be linear or branched, and is preferably a linear alkyl group.

[0052] The aliphatic group R3 is advantageously selected from alkyl, alkenyl, alkadienyl, alktrienyl. Preferably, it is selected from alkyl, alkenyl and alktrienyl.

[0053] More preferably, the aliphatic group R3 is selected from alkyl and alkenyl groups, typically selected from C2-C 26 Alkyl and C2-C 26 Alkenyl, preferably selected from C2-C 18 Alkyl and C2-C 18 Alkenyl, more preferably selected from C6-C 16 Alkyl and C6-C 16 Alkenyl, more preferably selected from C 10 -C 16 Alkyl and C 10 -C 16 Alkenyl.

[0054] Even more preferably, R3 represents an alkyl group, typically a C2-C 26 Alkyl, preferably C2-C 18 Alkyl, more preferably C6-C 16 The alkyl group may be a branched or linear alkyl group, and is preferably a linear alkyl group.

[0055] The cation X in the SO3X group of the compounds of the present invention is selected from alkali metals, alkaline earth metals and ammonium.

[0056] Suitable alkali metals for use as group X in the present invention include lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), with lithium, sodium and potassium being preferred alkali metals and sodium being a particularly preferred alkali metal.

[0057] Alkaline earth metals suitable for use as group X in the present invention include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba), with magnesium and calcium being preferred alkaline earth metals.

[0058] Ammoniums suitable for use as group X in the present invention have the general formula R'R"R"'R""N, wherein R', R", R"' and R"" are independently selected from hydrogen or a hydrocarbon group, which hydrocarbon group may be optionally substituted and / or interrupted by one or more heteroatom-containing groups. As used herein, the term "hydrocarbon group" includes aromatic and aliphatic groups, which may be optionally substituted and / or interrupted by one or more heteroatom-containing groups. Such heteroatom-containing groups include nitrogen-containing groups, such as primary, secondary and tertiary amines; and oxygen-containing groups, such as hydroxyl and ether groups. Preferred ammoniums suitable for use as group X in the present invention include, for example, NH4, N(CH3)4, triethanolammonium.

[0059] Preferred compounds of formula I are defined as follows:

[0060] R1 is OSO3X - wherein X is as defined above and in the claims, R2 is H, R3 is a linear alkyl C6-C 16 ;and

[0061] R1 is OH, R2 is SO3X - wherein X is as defined above and in the claims, and R3 is a linear alkyl C6-C 16 ;and

[0062] R1 is H, R2 is SO3X - wherein X is as defined above and in the claims, and R3 is a linear alkyl C6-C 16 .

[0063] More preferred compounds of formula I are defined as follows:

[0064] Ar is phenyl, R1 is OSO3X - where X is sodium, R2 is H, and R3 is a straight chain alkyl C6-C 16 ;and

[0065] Ar is phenyl, R1 is OH, R2 is SO3X - where X is sodium, and R3 is a straight chain alkyl C6-C 16 ;and

[0066] Ar is phenyl, R1 is H; R2 is SO3X - where X is sodium, and R3 is a straight chain alkyl C6-C 16 .

[0067] The biodegradability of the compounds of the invention can be determined following well-known standard protocols according to OECD guidelines, such as, for example, the OECD 301F protocol. An alternative protocol developed by the inventors for determining the biodegradability of the compounds of the invention disclosed herein is described in the Examples section.

[0068] Compositions of the present invention

[0069] The invention also relates to compositions comprising a mixture of two or more compounds as defined herein having formula I. Such compositions can be prepared, for example, by mixing the corresponding compounds together or they are obtainable by the process of the invention described below.

[0070] In one embodiment, the composition of the present invention, for example, comprises a first compound having Formula I, wherein R1 is OH, R2 is SO3X—wherein X is as defined above and in the claims, and R3 is a linear alkyl C6-C 16 and a second compound of formula I, wherein R1 is H, R2 is SO3X - wherein X is as defined above and in the claims, R3 is a linear alkyl C6-C 16 Preferably, the first compound is defined as follows: Ar is phenyl, R1 is OH, R2 is SO3X, wherein X is sodium, and R3 is a linear alkyl C6-C 16 ; and the second compound is defined as follows: Ar is phenyl, R1 is H, R2 is SO3X-wherein X is sodium, R3 is a linear alkyl C6-C 16 Such a composition is obtainable from alternative b. of the process of the invention as described hereinafter.

[0071] Furthermore, the invention relates to compositions comprising at least one compound of formula I and a further surfactant, wherein the surfactant is not a surfactant according to the compound of formula I. Such compositions can be prepared by mixing the components of the composition together.

[0072] Method of the present invention

[0073] Furthermore, the present invention provides a process for the preparation of a compound of formula I as described herein.

[0074] Overview

[0075] The process of the present invention starts from a mixture of Ar-COOH (II) and R3-CH2-COOH (III) to produce an aromatic aliphatic ketone having the formula IV: Ar-C(=O)-CH2-R3 (IV), wherein Ar and R3 are as defined above and in the claims. The process of the present invention further comprises derivatizing the aromatic aliphatic ketone having the formula IV: Ar-C(=O)-CH2-R3 (IV) by a hydrogenation-sulfation sequence (alternative a.) or a sulfonation-hydrogenation sequence (alternative b.) to produce a compound having the formula I.

[0076] To prepare a compound of formula I wherein R1 is OSO3X wherein X is as defined above and in the claims, R2 is H, R3 is C2-C 26aliphatic groups), the process according to the invention is carried out according to alternative a., which comprises the following steps:

[0077] a. a decarboxylative cross-ketonization between Ar-COOH (II) and R3-CH2-COOH (III) in the presence of a metal-based catalyst, wherein Ar and R3 are as defined in any one of the preceding claims, thereby obtaining an arylaliphatic ketone having the formula IV: Ar-C(=O)-CH2-R3 (IV), wherein Ar and R3 are as defined above,

[0078] b. hydrogenating the aromatic aliphatic ketone of formula IV obtained in step a. in the presence of H2 and a catalyst to obtain a secondary alcohol of formula V: Ar-CH(OH)-CH2-R3(V), wherein Ar and R3 are as defined above,

[0079] c. The secondary alcohol having formula V obtained in step b. is sulfated with a sulfating agent and then neutralized with XOH or X(OH)2.

[0080] To prepare a first compound of formula I wherein R1 is OH, R2 is SO3X wherein X is as defined above and in the claims, and R3 is C2-C 26 aliphatic groups),

[0081] or a second compound of Formula I (wherein R1 is H, R2 is SO3X--wherein X is as defined above and in the claims, and R3 is an aliphatic C2-C 26 Group),

[0082] or a mixture of a first compound and a second compound having formula I, the process of the present invention is carried out according to alternative b., which alternative comprises the following steps:

[0083] a. a decarboxylative cross-ketonization between Ar-COOH (II) and R3-CH2-COOH (III) in the presence of a metal-based catalyst, wherein Ar and R3 are as defined in any one of the preceding claims, thereby obtaining an arylaliphatic ketone having the formula IV: Ar-C(=O)-CH2-R3 (IV), wherein Ar and R3 are as defined above,

[0084] b. Sulfonating the aromatic aliphatic ketone of formula IV obtained in step a. with a sulfonating agent, followed by neutralization with XOH or X(OH)2, thereby obtaining an aromatic aliphatic ketone sulfonate of formula VI: Ar-C(=O)-CH(SO3X)-R3(VI), wherein Ar, X and R3 are as defined above,

[0085] c. hydrogenating the arylaliphatic ketone sulfonate of formula VI obtained in step b. in the presence of H2 and a catalyst.

[0086] Step a. – Decarboxylation cross-ketolysis

[0087] Step a. of the process according to the invention is a decarboxylative cross-ketonization reaction between an aromatic carboxylic acid Ar-COOH (II) and an aliphatic carboxylic acid R3-CH2-COOH (III) acid to provide an aromatic aliphatic ketone having the formula IV: Ar-C(=O)-CH2-R3 (IV) - wherein Ar and R3 are as defined above and in the claims, constituting part of both alternatives a. and b. of the process according to the invention.

[0088] The starting materials Ar-COOH (II) and R3-CH2-COOH (III) used in the process of the present invention are commercially available or can be synthesized by a skilled person according to his common knowledge.

[0089] Decarboxylation cross ketone is preferably carried out as catalytic decarboxylation cross ketone. Such a procedure is known from WO 2018 / 229285A1 (see, for example, WO 2018 / 229285A1, page 4, lines 9-34). The catalytic decarboxylation cross ketone of aryl carboxylic acids and aliphatic carboxylic acids as described in detail in WO 2018 / 229285 A1 can be similarly applied in the context of the present invention to provide an aryl aliphatic ketone having formula IV: Ar-C(=O)-CH2-R3(IV).

[0090] If necessary, the skilled person according to his common general knowledge can also modify the decarboxylative cross-ketolation procedures applied in the art for the purposes of the present invention.

[0091] Alternative a.: Steps b. and c. – Hydrogenation-Sulfation-Neutralization

[0092] In the following, the hydrogenation-sulfation sequence of steps b. and c. according to alternative a. of the process according to the invention will be described further.

[0093] Step b. of alternative a.: In the process of the present invention according to alternative a., an aromatic aliphatic ketone having formula IV: Ar-C(=O)-CH2-R3 (IV) is hydrogenated in the presence of H2 and a catalyst to obtain a secondary alcohol having formula V: Ar-CH(OH)-CH2-R3 (V), wherein Ar and R3 are as defined above and in the claims.

[0094] The catalytic hydrogenation of arylaliphatic ketones to obtain the corresponding arylaliphatic alcohols is a standard reaction generally known to the skilled worker.

[0095] In the process of the present invention, the hydrogenation step is carried out in the presence of a metal-based catalyst, preferably a transition metal-based catalyst, which is typically palladium on carbon (Pd / C).

[0096] In the present invention, the hydrogenation step can be carried out in a reactor / autoclave at a hydrogen (H2) pressure of up to 100 bar (such as, for example, 80 bar, 60 bar, 40 bar or 20 bar), at a temperature of up to 150°C, preferably up to 100°C (such as, for example, 90°C).

[0097] The catalytic hydrogenation can be carried out in a solution using an additional solvent. In that case, the skilled person can select a suitable solvent from a range of standard solvents widely used in organic synthesis according to his common knowledge. As examples of typical solvents used in the catalytic hydrogenation reaction, mention may be made of, for example, methanol, ethanol, isopropanol, tert-butyl alcohol, THF, Me-THF, saturated hydrocarbons or mixtures thereof.

[0098] The reaction can also be carried out without using a solvent. In that case, the catalytic hydrogenation is typically carried out at a temperature at which the substrate is present in molten form.

[0099] The skilled person is able to control the progress of the reaction using standard techniques such as NMR according to his common general knowledge.

[0100] The skilled person, according to his common general knowledge, is able to purify the product mixture resulting from the hydrogenation step using common purification and separation techniques such as distillation methods, precipitation / crystallization methods (if applicable) and chromatography methods (including, for example, flash chromatography and HPLC).

[0101] The procedure for catalytic hydrogenation of aromatic aliphatic ketones is described, for example, in US2020 / 0339748A1 (see paragraphs

[0265] -

[0270] of US2020 / 0339748 A1), which can be similarly applied to the method of the present invention. In this preferred embodiment, the reaction is carried out without any solvent, and a substoichiometric amount of a base (e.g., NaOH) is used as an additive to enhance the hydrogenation selectivity of the desired benzyl alcohol derivative.

[0102] If necessary, the skilled person, based on his common general knowledge, is also able to modify the arylaliphatic ketone hydrogenation procedures applied in the art for the purposes of the present invention.

[0103] Step c. of alternative a.: The secondary alcohol of formula V obtained from step b.: Ar-CH(OH)-CH2-R3(V) wherein Ar and R3 are as defined above and in the claims is then subjected to a sulfation step with a sulfating agent, said sulfation being followed by neutralization with a base XOH or X(OH2) to obtain a compound of formula I wherein R1 is OSO3X wherein X is as defined above and in the claims, R2 is H, and R3 is C2-C 26 Aliphatic group.

[0104] The sulfation of secondary alcohols is a standard reaction which forms part of the common general knowledge of the skilled worker.

[0105] In the context of the present invention, the sulfation of the secondary alcohol of formula V: Ar-CH(OH)-CH2-R3(V) can be carried out using known sulfating agents. The sulfating agents that can be used in the present invention are, for example, selected from the group consisting of SO3, chlorosulfonic acid (ClSO3H), oleum and aminosulfonic acid (H3NSO3). Preferably, SO3 or chlorosulfonic acid (ClSO3H) is used as the sulfating agent in the method of the present invention.

[0106] Sulfation can be carried out in solution. The technician can select a suitable solvent from the standard range of solvents widely used in organic synthesis according to his common knowledge, and these standard ranges of solvents include but are not limited to for example CH2Cl2, CHCl3, CCl4, pyridine, ethyl acetate, dioxane, diglyme, THF, 2-methyl-THF, hydrocarbons or their mixtures.

[0107] Alternatively, the sulfation can be carried out without any solvent when the alcohol is in its molten state.

[0108] The sulfation step may be carried out at a temperature ranging from -20°C to 120°C, preferably from 0°C to 80°C. Due to the exothermic nature of the reaction, the sulfation agent is typically added to the substrate at a relatively low temperature (e.g. in the range of -20°C to 10°C). The temperature is then typically increased in order to accelerate the reaction and increase the conversion rate. In case SO3 is used as the sulfation agent, the sulfation may be carried out using, for example, a so-called falling film reactor with gaseous SO3 diluted in dry air or dry nitrogen (e.g. 1 to 5% v / v).

[0109] The skilled person is able to monitor the progress of the sulfation reaction using standard techniques (such as NMR) according to his common general knowledge.

[0110] An aging step may optionally be included after the sulfation step in order to achieve complete conversion to sulfonic acid. Such an aging step may be carried out, for example, at a temperature between 15°C and 200°C.

[0111] The sulfation step is followed by a neutralization step in order to complete the formation of the desired product, ie the salt of the compound having formula (I).

[0112] Neutralization is carried out using a base compound having the general formula XOH or X(OH)2, wherein X is an alkali metal, alkaline earth metal or ammonium group as defined above. X may be, for example, Li, Na, K, Cs, NH4, triethanolammonium, Mg or Ca.

[0113] Neutralization using a base compound having the general formula XOH or X(OH)2 is typically carried out in an aqueous solution (or in a solvent mixture to which an aqueous solution of a base compound having the general formula XOH or X(OH)2 is added). Neutralization is typically carried out at a temperature in the range of 0°C to 100°C, preferably at a temperature in the range of 0°C to room temperature. For the purposes of the present invention, "room temperature" is defined herein as a range of 20°C to 30°C.

[0114] The skilled person, according to his common general knowledge, is able to purify the product mixture resulting from the sulfation and subsequent neutralization steps using common purification and separation techniques such as distillation methods, precipitation / crystallization methods (if applicable) and chromatography methods (including, for example, flash chromatography and HPLC).

[0115] If necessary, the skilled person, based on his common general knowledge, is also able to modify the sulfation procedures applied in the art for the purposes of the present invention.

[0116] An exemplary sulfation procedure with subsequent neutralization according to step c. of alternative a. of the process of the present invention is illustrated in the Examples section disclosed herein (see Example 3.2).

[0117] Alternative b.: Steps b. and c. - Sulfonation-Hydrogenation-Neutralization

[0118] In the following, the sulfonation-hydrogenation sequence of steps b. and c. according to alternative b. of the process according to the invention will be described further.

[0119] Step b. of alternative b.: In the process of the present invention according to alternative b., the aromatic aliphatic ketone having formula IV: Ar-C(=O)-CH2-R3(IV) obtained from the decarboxylation cross-ketonization step is sulfonated with a sulfonating agent and then neutralized with a base XOH or X(OH)2 to obtain an aromatic aliphatic ketone sulfonate having formula VI: Ar-C(=O)-CH(SO3X)-R3(VI), wherein Ar, X and R3 are as defined above and in the claims.

[0120] The sulfonation of arylaliphatic ketones using sulfonating agents is known to the skilled person and is described, for example, in WO 2018 / 229285A1 (see page 43, lines 5-22). Step b. of alternative b. in the process of the invention can be carried out according to the known procedure as described in WO 2018 / 229285 A1.

[0121] According to known procedures from WO 2018 / 229285 A1, the sulfonation step in the method of the present invention can be carried out using, for example, gaseous SO3 as a sulfonating agent, which is preferably diluted in dry air or dry nitrogen (e.g. 1 to 5% v / v). In this case, the sulfonation using diluted SO3 can be carried out using a so-called falling film reactor. Other sulfonating agents that can be used in the present invention include chlorosulfonic acid (ClSO3H), oleum and aminosulfonic acid (H3NSO3). Preferably, SO3 or chlorosulfonic acid (ClSO3H) is used as a sulfonating agent.

[0122] The reaction is typically carried out at a temperature in the range of -20°C to 200°C, preferably in the range of 0°C to 120°C. Due to the exothermic nature of the reaction, the sulfonating agent is typically added to the substrate at a relatively low temperature, for example in the range of -20°C to 10°C. After the addition is complete, the temperature is typically increased in order to accelerate the reaction and increase the conversion rate.

[0123] Sulfonation can be carried out in solution or in pure form. The technician can select a suitable solvent from the standard range of solvents widely used in organic synthesis according to his common knowledge, and these standard solvent ranges include but are not limited to for example CH2Cl2, CHCl3, CCl4, pyridine, ethyl acetate, dioxane, diglyme, THF, 2-methyl-THF, hydrocarbons or mixtures thereof.

[0124] The skilled person is able to monitor the progress of the sulfonation reaction using standard techniques (such as NMR) according to his common general knowledge.

[0125] An aging step may optionally be included after the sulfonation step in order to achieve complete conversion to the sulfonic acid. Such an aging step may be carried out, for example, at a temperature between 15°C and 200°C.

[0126] The sulfonation step is followed by a neutralization step to complete the salt formation of the desired product, ie, an arylaliphatic ketone sulfonate having the formula VI: Ar-C(=O)-CH(SO3X)-R3(VI).

[0127] Neutralization can be carried out as already described above in connection with step c. of alternative a. of the process according to the invention.

[0128] The skilled person, according to his common general knowledge, is able to purify the product mixture resulting from the sulfonation and subsequent neutralization steps using common purification and separation techniques such as distillation methods, precipitation / crystallization methods (if applicable) and chromatography methods (including, for example, flash chromatography and HPLC).

[0129] If necessary, the skilled person, based on his common general knowledge, is also able to modify the sulfonation procedures applied in the art for the purposes of the present invention.

[0130] An exemplary sulfonation procedure with subsequent neutralization according to step b. of alternative b. of the process of the invention is illustrated in the Examples section disclosed herein (see Examples 1.1, 2.1).

[0131] Step c. of alternative b.: The arylaliphatic ketone sulfonate of formula VI: Ar-C(=O)-CH(SO3X)-R3(VI) wherein Ar, X and R3 are as defined above and in the claims is subsequently subjected to a hydrogenation step in the presence of H2 and a catalyst to obtain a first compound of formula I (wherein R1 is OH, R2 is SO3X wherein X is as defined above, R3 is C2-C 26 aliphatic group), or a second compound of Formula I (wherein R1 is H, R2 is SO3X—wherein X is as defined above and in the claims, and R3 is C2-C 26 aliphatic group), or a mixture of the first compound and the second compound having formula I.

[0132] The catalytic hydrogenation of arylaliphatic ketones to obtain the corresponding arylaliphatic alcohols is a standard reaction generally known to the skilled worker.

[0133] In the context of step c. of alternative b., the catalytic hydrogenation can be carried out analogously as described above in conjunction with step b. of alternative a. of the process according to the invention.

[0134] The skilled person according to his common general knowledge is also able to adjust the hydrogenation conditions to favour the first compound of formula I and reduce the amount of the second compound of formula I formed or alternatively to favour the second compound of formula I and reduce the amount of the first compound of formula I. The skilled person according to his common general knowledge is able to control the progress of the reaction using standard techniques such as NMR.

[0135] Furthermore, the skilled person, according to his common general knowledge, is able to purify the product mixture resulting from the hydrogenation step using common purification and separation techniques such as distillation methods, precipitation / crystallization methods (if applicable) and chromatography methods (including, for example, flash chromatography and HPLC).

[0136] The Examples section disclosed herein illustrates an exemplary hydrogenation procedure according to step c. of alternative b. of the process of the present invention (see Examples 1.2, 2.2).

[0137] Use of compounds of formula I

[0138] According to their advantageous properties in terms of their biodegradability profile as well as their toxicity and environmental profile, the compounds of the invention can be used as surfactants. As used herein, the term "surfactant" should be understood according to the common general knowledge of the skilled person.

[0139] The present invention shall be illustrated on the basis of the following examples.

[0140] Should the disclosure of any patents, patent applications, and publications incorporated herein by reference conflict with the description of the present application to the extent that a term may be unclear, the present description shall take precedence.

[0141] Examples

[0142] General Description

[0143] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0144] Fresh commercially available anhydrous CHCl3 (pentene-stabilized) and anhydrous dioxane were used as received.

[0145] The phenyl alkyl ketone precursors used in the following examples can be produced from benzoic acid and the corresponding fatty acid following the cross-ketonization procedure described in WO 2018 / 229285A1.

[0146] The abbreviation "PAK" refers to phenyl-alkyl ketone precursors obtained from cross-ketonization.

[0147] The abbreviation "PAKS" refers to phenyl-alkyl ketone sulfonates obtained from phenyl alkyl ketone ("PAK") precursors by sulfonation. The abbreviation "PAS" refers to phenyl-alcohol sulfonates obtained from phenyl-alkyl ketone sulfonates ("PAKS") by hydrogenation. PAS is typically obtained as a product mixture with the corresponding deoxygenated product.

[0148] The abbreviation "PAAS" refers to phenyl-alkyl carbinol sulfates obtained from phenyl-alkyl ketone ("PAK") precursors via a hydrogenation-sulfation sequence of phenyl-alkyl secondary alcohols ("PAAs").

[0149] Example 1

[0150] 1.1 Synthesis of PAKS-C from hexadecyl phenone 16 :

[0151]

[0152] In a 1 L double jacket reactor equipped with a mechanical stirrer (propeller with four inclined plows) and baffles, a condenser and a temperature probe, 38.6 g of 1-phenylhexadecane-1-one (hexadecylphenyl ketone) (weight purity>95%, 0.362 mol, 1 equivalent) and 257 mL (382 g) of anhydrous CHCl were added. The resulting solution was then heated to 45° C. and stirred at 750 rpm.

[0153] 186mL anhydrous CHCl3 (277g) was added to a 500mL three-necked round-bottom flask equipped with a magnetic stirrer, a condenser and a temperature probe. The solution was cooled to 0°C and 93mL (96g, 1.09mol, 3 equivalents) of 1,4-dioxane was slowly introduced under stirring. Then, 28mL (49g, 0.381mol, 1.05 equivalents) of chlorosulfonic acid were slowly introduced into the reaction vessel while monitoring the reaction medium temperature (exothermic). The mixture was then stirred at room temperature during 15 minutes.

[0154] A solution of ClSO3H:dioxane prepared in CHCl3 contained in a 500 mL flask was slowly added over 15 minutes with stirring to the 1 L reactor maintained at 45° C. The reaction mixture turned yellow upon addition.

[0155] After the addition, the temperature of the reaction mixture was then increased to 60°C and the progress of the reaction was followed by NMR analysis. After stirring at 60°C for 1 hour and 30 minutes, NMR analysis indicated a ketone conversion of about 99 mol%, with a crude molar composition of 90 mol% of the desired PAKS-C. 16 , 9 mol% O-sulfated by-products and 1 mol% starting phenyl alkyl ketone. An additional 2.4 ml of chlorosulfonic acid (4.3 g, 0.036 mol, 0.1 eq.) were added to achieve complete conversion.

[0156] At the end of the reaction (2h 45min under stirring at 60°C), volatiles were distilled off.After distillation, the temperature of the reaction mass was lowered to 10°C and 187mL of water was slowly added to the dark brown residue (exothermic) followed by 200mL of 10% NaOH aqueous solution (to reach pH=7).

[0157] The solution was then transferred to a 2L flask and 741 mL of n-butanol was introduced. The biphasic mixture was first decanted and the organic orange phase was evaporated (azeotropic distillation using n-BuOH helped remove water). 1 H NMR analysis showed the presence of 3.4 mol % sodium 2-ethoxyethyl sulfate and 11.3 mol % sodium ethyl sulfate.

[0158] The product was purified by washing the solid several times with CH3CN (the desired PAKS product is insoluble in CH3CN). The resulting product was then dried in vacuo to give 140 g of a white solid with a weight composition of 99% PAKS-C 16 , 0.5% O-sulfated byproducts (enol sulfate esters), 0.3% sodium ethyl sulfate, and 0.16% sodium 2-ethoxyethyl sulfate.

[0159] PAKS-C 16 The purified yield was 92%.

[0160] 1 H NMR (MeOD-d4, 400MHz) δ (ppm): 8.09 (d, J = 7.6Hz, 2H), 7.65-7.56 (m, 1H), 7.54-7.43 (m, 2H), 4. 94(dd,J=10.6Hz,J=3.8Hz,1H),2.42-2.03(m,2H),1.49-1.01(m,24H),0.89(t,J=6.8Hz,3H).

[0161] 13 C NMR (MeOD-d4, 101 MHz) δ (ppm): 198.38, 139.6, 134.52, 130.25, 129.74, 66.91, 33.2, 30.9, 30.88, 30.85, 30.79, 30.76, 30.69, 30.68, 30.59, 30.47, 28.57, 23.86, 14.58 (terminal CH3).

[0162] 1.2 By PAKS-C 16 Synthesis of PAS-C 16

[0163]

[0164] The reaction was carried out in an autoclave under a hydrogen pressure of 20 bar.

[0165] In a 750 ml autoclave reactor equipped with a mechanical stirrer (Rushton turbine) was added 70 g (99 wt%, 0.166 mol, 1 eq.) of PAKS-C 16 The obtained preformed solution was dissolved in 240 ml (189 g, 36 wt%) of ethanol.

[0166] 4.24 g Pd / C 3% (51 wt% water content, 3 wt% relative to ketone) were then added. The reactor was sealed and subjected to three nitrogen purges, followed by three hydrogen purges. The reaction mixture was then pressurized under 20 bar H2, stirred at 1000 rpm and heated at 90°C. After 4 hours and 00 minutes reaction time, the reaction mixture was cooled to room temperature and the reactor was finally depressurized.

[0167] NMR analysis in MeOD-d4 indicated the starting product PAKS-C 16 The total conversion of 1% and the following molar composition of the crude material: 89 mol% phenyl alcohol sulfonate, 9 mol% phenyl alkyl sulfonate (PAKS-C 16 -HDO) and 2 mol% sodium ethyl sulfate.

[0168] The reactor was drained and rinsed several times with ethanol.

[0169] The mixture was filtered through celite to separate the Pd / C catalyst, and the filter was rinsed with ethanol and methanol.

[0170] The filtrate was evaporated to give 70 g of a white product having the following weight composition: 91 wt % phenyl alcohol sulfonate, 8 wt % phenyl alkyl sulfonate and 0.7 wt % sodium ethyl sulfate, which corresponds to PAS-C 16 A yield of 88%.

[0171] 1 H NMR (MeOD-d4, 400 MHz) δ (ppm): 7.47-7.12 (m, 5H), 5.52 (s, alcohol sulfonate isomer 1, 1H), 4.79 (d, J = 9.5 Hz, alcohol sulfonate isomer 2, 1H), 3.45 (dd, J = 13.4 Hz, J = 3.0 Hz, alkyl sulfonate, 1H), 2.97-2.90 (m, alkyl sulfonate, 1H), 2.89-2.81 (m, alcohol sulfonate, 1H), 2.65 (dd, J = 13.7 Hz, J = 10.8 Hz, alkyl sulfonate, 1H), 1.95-1.59 (m, 2H), 1.4-0.94 (m, 24H), 0.90 (t, J = 6.8 Hz, 3H).

[0172] 13C NMR (MeOD-d4, 101 MHz) δ (ppm): 143.51, 142.66, 129.45, 129.26, 129.07, 128.13, 126.9, 76.73, 73.03, 67.32, 67.17, 33.21, 30.9, 30.85, 30.79, 30.67, 30.60, 30.36, 30.29, 30.25, 30.03, 29.06, 28.85, 24.24, 23.87, 14.58 (terminal CH3).

[0173] 1.3 By PAKS-C 16 Synthesis of PAS-C 16 and PAS-C 16 -HDO mixture

[0174]

[0175] The reaction was carried out in an autoclave under 2 bar hydrogen pressure.

[0176] In a 130 ml autoclave reactor equipped with a mechanical stirrer (Rushton turbine) was added 8.71 g (99 wt% purity, 0.021 mol) of PAKS-C 16 A prefabricated 18 wt % solution (from Example 1.1) was dissolved in 50 ml (39.58 g) of anhydrous ethanol (Sinopharm, H2O content ≤ 0.2%).

[0177] Then 1.61 g of Pd / C 5% (J&M, type 5R39, batch number C-8750, 45.9 wt% water content, 10 wt% dry catalyst relative to ketone) was added. The reactor was sealed and three nitrogen purges were performed, followed by three hydrogen purges. The reaction mixture was then pressurized under a constant 2 bar of H2, stirred at 1300 rpm and heated at 80°C. After 7.5 h reaction time, the reaction mixture was allowed to cool at room temperature and the reactor was finally depressurized.

[0178] in MeOD-d4 1 H NMR analysis indicated that the starting material was PAKS-C 16 The total conversion of 1% and the following molar composition of the crude solid: 22 mol% phenyl alcohol sulfonate (PAS-C 16 ), 69 mol% phenyl alkyl sulfonate (PAS-C 16- HDO) and 9 mol % of the by-product 1-cyclohexyl alkyl sulfonate was completely hydrogenated.

[0179] The reactor was drained and rinsed several times with absolute ethanol.

[0180] The mixture was passed through diatomaceous earth (Supelco, 545, particle size 0.02-0.1 mm, batch number K53174993120) was filtered to separate the Pd / C catalyst, and the filter was rinsed with anhydrous ethanol.

[0181] The filtrate was evaporated to give 8.47 g of a white product having the following weight composition: 22 wt% phenyl alcohol sulfonate (PAS-C 16 ), 68wt% phenyl alkyl sulfonate (PAS-C 16 -HDO) and 9 wt% of the fully hydrogenated by-product 1-cyclohexyl alkyl sulfonate.

[0182] 1 H NMR (300 MHz, MeOD-d4): δ (ppm) 7.42-7.15 (m, 5H), 5.52 (s, alcohol sulfonate isomer 1, 1H), 4.79 (d, J = 9.5 Hz, alcohol sulfonate isomer 2, 1H), 3.45 (dd, J = 13.6 Hz, J = 3.1 Hz, alkyl sulfonate, 1H), 2.96-2.82 (m, alkyl sulfonate and alcohol sulfonate, 2H), 2.64 (dd, J = 13.5 Hz, J = 10.8 Hz, alkyl sulfonate, 1H), 1.94-0.94 (m, 26H), 0.90 (t, J = 7.0 Hz, 3H).

[0183] 13 C{ 1 H} NMR (75 MHz, MeOD-d4): δ (ppm) 141.1, 130.2, 129.36, 129.28, 129.1, 128.9, 128.0, 127.2, 126.7, 76.5, 72.8, 67.0, 63.0, 38.1, 33.0, 30.8, 30.74, 30.72, 30.67, 30.63, 30.57, 30.52, 30.4, 30.3, 28.3, 24.0, 23.7, 14.5 (terminal CH3).

[0184] Example 2

[0185] 2.1 Synthesis of PAKS-C from octadecyl phenone 18

[0186]

[0187] In a 500 mL double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows) and baffles, a condenser and a temperature probe, 50 g of 1-phenyloctadecane-1-one (octadecylphenyl ketone) (0.145 mol, 1 eq.) and 168 mL (250 g) of anhydrous CHCl were added. The solution was then heated to 40° C. and stirred at 400 rpm.

[0188] 74.5mL anhydrous CHCl (111g) was added to a 500mL three-necked round-bottom flask equipped with a magnetic stirrer and a temperature probe. The solution was cooled to 0°C and 37.3mL (38.4g, 0.435mol, 3 equivalents) of 1,4-dioxane were slowly introduced under stirring (350rpm). Then, 10.1mL (17.75g, 0.152mol, 1.05 equivalents) of chlorosulfonic acid (ClSO3H) were slowly introduced into the reaction vessel over 10 minutes while monitoring the reaction medium temperature (exothermic). The mixture was then stirred at room temperature during 30 minutes.

[0189] Under stirring, the ClSO prepared in the CHCl in the 500mL flask H: dioxane solution was slowly added to the 500mL reactor maintained at 40°C in 35 minutes. The reaction mixture became yellow when added. After addition, the temperature of the reaction mixture was then increased to 60°C, and the reaction progress was tracked by NMR analysis. After stirring at 60°C for 1 hour and 30 minutes, NMR analysis indicated that the ketone was fully converted.

[0190] The volatiles were then removed by distillation (60° C., 20 mbar) and 60 mL of water were carefully added to the residue obtained at room temperature (exothermic).Finally, 64 mL of 10% aqueous NaOH solution were added to the mixture at room temperature with stirring in order to reach pH=7.

[0191] The resulting solution was then transferred to a 1 L flask and the water was removed under vacuum with the aid of azeotropic distillation using n-BuOH.

[0192] After evaporation, 66.5 g of a white solid was obtained, the weight composition of which was 93 wt% PAKS-C 18 , 6.2 wt% O-sulfated byproducts (enol sulfate esters) and 1.1 wt% residual starting ketone. PAKS-C 18 The yield was quantitative without considering the presence of salt.

[0193] 1H NMR (MeOD-d4, 400 MHz) δ (ppm): 8.09 (d, J = 7.7 Hz, 2H), 7.64-7.56 (m, 1H), 7.54-7.46 (m, 2H), 7.42-7.26 (m, enol sulfate, 4H), 6.22 (t, J = 7.1 Hz, enol sulfate, 1H), 4.93 (dd, J = 10.7 Hz, J = 3.5 Hz, 1H), 2.43-2.36 (m, enol sulfate, 2H), 2.38-2.26 (m, 2H), 2.18-2.04 (m, 2H), 1.49-1.00 (m, 28H), 0.89 (t, J = 6.7 Hz, 3H).

[0194] 13 C NMR (MeOD-d4, 101 MHz) δ (ppm): 197.91, 139.73, 134.39, 130.25, 129.70, 67.04, 33.22, 30.9, 30.87, 30.77, 30.70, 30.67, 30.61, 30.49, 28.59, 23.88, 14.58 (terminal CH3).

[0195] 2.2 By PAKS-C 18 Synthesis of PAS-C 18

[0196]

[0197] The reaction was carried out in an autoclave under a hydrogen pressure of 20 bar.

[0198] In a 100 ml autoclave reactor equipped with a mechanical stirrer (Rushton turbine) was added 18 g (0.040 mol, 1 equivalent) of PAKS-C 18 and 1.1 g Pd / C 3% (51 wt% water content, 3 wt% relative to ketone). Then 70 mL (55.3 g, 33 wt%) ethanol was added to the solid.

[0199] The reactor was sealed and subjected to three nitrogen purges followed by three hydrogen purges. The reaction mixture was then pressurized at 20 bar H2, stirred at 1000 rpm and heated at 90°C. After 5 hours and 00 minutes reaction time, the reaction mixture was cooled to room temperature and the reactor was finally depressurized.

[0200] The reactor was drained and rinsed several times with ethanol and CHCl. ​​The mixture was filtered through a paper filter to separate the Pd / C catalyst, and the filter was rinsed with ethanol. The filtrate was evaporated to obtain 16.10 g of white product after complete drying.

[0201] The weight composition of the product is as follows: 83 wt% phenyl alcohol sulfonate, 10 wt% phenyl alkyl sulfonate, 7 wt% octadecylbenzene and 0.5 wt% sodium ethyl sulfate.

[0202] Taking purity into account, the yield was 83%.

[0203] 1 H NMR (MeOD-d4, 400 MHz) δ (ppm): 7.45-7.10 (m, 5H), 5.52 (s, alcohol sulfonate isomer 1, 1H), 4.79 (d, J = 9.5 Hz, alcohol sulfonate isomer 2, 1H), 3.45 (dd, J = 14.2 Hz, J = 3.1 Hz, alkyl sulfonate, 1H), 2.96-2.90 (m, alkyl sulfonate, 1H), 2.89-2.81 (m, alcohol sulfonate, 1H), 2.65 (dd, J = 13.5 Hz, J = 10.7 Hz, alkyl sulfonate, 1H), 1.85-1.50 (m, 2H), 1.4-0.8 (m, 28H), 0.90 (t, J = 6.8 Hz, 3H).

[0204] Example 3

[0205] 3.1 By PAK-C 16 Synthesis of PAA-C 16

[0206] Phenyl-alkyl alcohol compound PAA-C 16 The corresponding phenyl-alkyl ketone (PAK-C) can be prepared by catalytic hydrogenation according to the procedure described in US2020 / 0339748 A1 (see, for example, paragraphs

[0265] to

[0270] of US2020 / 0339748 A1). 16 ) precursors are obtained.

[0207] 3.2 By PAA-C 16 Synthesis of PAAS-C 16

[0208]

[0209] In a 100 mL three-necked round bottom flask equipped with a condenser, temperature probe, mechanical stirring device (propeller with 4 inclined plows), baffles and a hot plate was added 100 mL of pyridine (98 g, 1.24 moles, 8 equivalents).

[0210] The reaction mass was then cooled to 0°C and 11.6 mL of ClSO3H (20.33 g, 0.175 mol, 1.1 eq) was gradually added under stirring at 400 rpm (strong exotherm).

[0211] The mixture was then heated to 50°C, and 50 g of molten phenylhexadecane-1-ol (0.157 mol, 1 eq.) was gradually added to the reaction mixture over 20 minutes via an insulated dropping funnel maintained at 90°C with stirring at 500 rpm.

[0212] At the end of the addition, the reaction mixture was heated to 60°C and 1 H NMR analysis followed the progress of the reaction. After stirring at 60 °C for 2 hours and 00 minutes, 1 H NMR analysis showed complete and selective conversion of the starting alcohol to the desired sulfate ester.

[0213] The volatiles were then removed by distillation at 60° C. under vacuum (10 mbar), and 180 mL of water were added to the white residue. The obtained dispersion was then stirred at room temperature, and 2.2 equivalents (relative to HSO 3 Cl) of aqueous NaOH solution (5 M) were gradually added to the mixture for neutralization in order to reach pH=6.

[0214] 800 mL of CH3CN was then added to the aqueous mixture to precipitate the product. The white precipitate was filtered and washed several times with toluene followed by CHCl3 to remove the pyridinium salt to a level undetectable by NMR.

[0215] At this stage, product (62.3g) contains some residual inorganic salts.The white solid is dissolved among the 200mL EtOH so that precipitated inorganic salts, it is filtered out.Solid is washed several times with extracted product with 50mL EtOH.Evaporating solvent provides the first batch of product.The ethanol filtrate is concentrated, and in the concentrated solution, add CH3CN so that collect other product.With gained solid CH3CN and CHCl3 washing several times.

[0216] The two batches were then pooled and dried in vacuo to remove traces of solvent and to give 40.27 g of white product, which corresponds to 67% isolated yield.

[0217] 1 H NMR (MeOD-d4, 400MHz) δ (ppm): 7.45-7.15 (m, 5H), 5.26 (t, J = 6.7Hz, 1H), 2.0 4-1.88(m,1H),1.88-1.72(m,1H),1.55-1.05(m,26H),0.90(t,J=6.9Hz,3H).

[0218] 13C NMR (MeOD-d4, 101 MHz) δ (ppm): 143.23, 129.22, 128.53, 127.75, 82.13, 38.78, 33.23, 30.91, 30.88, 30.80, 30.76, 30.65, 30.63, 26.38, 23.89, 14.59 (terminal CH3).

[0219] Example 4

[0220] 4.1 By PAK-C 12-18 Synthesis of PAKS-C 12-18

[0221]

[0222] All reactions were performed in carefully dried vessels and under an inert argon atmosphere.

[0223] Fresh commercially available anhydrous CHCl 3 and 1,4-dioxane were used as received.

[0224] In a 1 L double jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows) and baffles, condenser and temperature probe were added:

[0225] -50g phenyl alkyl ketone C 12-18 The fraction (0.18 mol, 1 equivalent, has the following side alkyl chain length distribution: C 10 =0.8wt%, C 12 =57.3wt%, C 14 =21.1wt%, C 16 =9.8wt% and C 18 =10.9wt%)

[0226] -112 mL (167 g, 23 wt% concentration of reactants in solution) anhydrous CHCl3

[0227] The mixture was heated to 45°C and stirred at 600 rpm until the solids were completely dissolved at room temperature.

[0228] Into a 500 mL three-necked round-bottom flask equipped with a magnetic stirrer, a condenser and a temperature probe was introduced 92 mL of anhydrous CHCl 3 (137.5 g).

[0229] The solution was cooled at 0°C, stirred at 600 rpm, and 1,4-dioxane (46 mL, 47.5 g, 0.54 mole, 3 equivalents relative to the ketone) was introduced into the vessel (slightly exothermic).

[0230] Chlorosulfonic acid (15 mL, 26.5 g, 0.225 mole, 1.05 equivalents relative to ketone) was then gradually added to the solution via an insulated dropping funnel over a period of 10 minutes while controlling the rate of addition to prevent the temperature of the reaction mass from increasing by more than 10° C. (exothermic). At the end of the addition, the reaction mixture was stirred at 0° C. and allowed to warm at room temperature over a period of 15 minutes.

[0231] The obtained HSO 3 Cl:dioxane chloroform solution was slowly added via a Teflon cannula over 15 min to a 1 L reactor maintained at 45° C. Upon addition, the reaction mixture readily turned yellow.

[0232] At the end of the addition, the temperature of the reactor was increased to 60°C and after stirring at 600 rpm for 2 hours and 30 minutes, 1 H NMR analysis (based on MeOD) indicated a ketone conversion level of about 94%.

[0233] To achieve complete conversion, 2.4 mL of chlorosulfonic acid (4.23 g, 0.036 mol, 0.2 eq.) was finally added. The reaction was stirred at 60° C. until the conversion level exceeded 99%, which required another 3 hours of stirring. At this stage, the molar composition of the solid was 94 mol% ketosulfonic acid, 2.5 mol% enol sulfate ester and only 0.2 mol% starting phenyl alkyl ketone.

[0234] 1,4-dioxane and chloroform were then distilled off under vacuum using 3 traps (1 empty trap maintained at -78°C and 2 traps filled with 10 wt% NaOH solution) and wherein the collecting flask from the distillation apparatus was cooled at 0°C. The crude mixture was maintained at 60°C and the vacuum was gradually reduced by controlling the foam formation. During the distillation, the mixture became very viscous; therefore the stirring rate was reduced to 400 rpm.

[0235] At the end of the distillation, atmospheric pressure was reestablished and the temperature in the pot was lowered to 10° C. and 120 ml of water were carefully added to the dark brown residue (strong exotherm: internal temperature at the end of the addition=35° C.). The pH of the resulting orange solution was adjusted to about 7 by adding 90 ml of 10% NaOH.

[0236] The solution was then transferred to a 2 L flask and 366 mL of n-butanol were introduced. The phases were separated and the organic orange phase was evaporated with water via azeotropic distillation.

[0237] The final product was purified by dissolving the solid in 200 mL of ethanol (to precipitate the salt byproduct) followed by filtration and solvent evaporation.

[0238] During this phase, 1H NMR analysis showed that the product still contained 2.4 mol% 2-ethoxyethyl sodium sulfate and 10 mol% sodium ethyl sulfate, so the product was dissolved in 500 mL of diethyl ether and washed with 300 mL of saturated aqueous NaCl solution. The organic phase was separated and the aqueous phase was re-extracted with 500 mL of diethyl ether.

[0239] The two organic phases were combined, dried over Na2SO4, filtered and evaporated under vacuum (10 mbar) at 65° C. At this stage, the product still contained traces of NaCl, which were finally removed by precipitation using 300 mL of ethanol.

[0240] After filtration, the solvent was evaporated to give 61 g of a white solid having the following weight composition: 95.6% PAKS C 12-18 , 4% enol sulfate, 0.1% sodium ethyl sulfate and 0.3% sodium ethoxyethyl sulfate.

[0241] PAKS C 12-18 The purified yield was 89%.

[0242] 1 H NMR (CDCl3, 400MHz) δ (ppm): 8.11-8.08 (d, 2H), 7.63-7.58 (m, 1H), 7.53-7.48 (m, 2H) ), 4.96-4.2 (dd, 1H), 2.35-2.09 (m, 2H), 1.34-1.19 (m, 19H), 0.89 (t, J = 6.8Hz, 3H).

[0243] 13 C NMR (CDCl3, 101 MHz) δ (ppm): 198.27, 139.61, 134.51, 130.25, 129.73, 66.91, 33.2, 30.89, 30.86, 30.77, 30.73, 30.7, 30.54, 30.48, 28.57, 23.86, 14.58 (terminal CH3).

[0244] 4.2 By PAKS-C 12-18 Synthesis of PAS-C 12-18 and PAS-C 12-18 -HDO A mixture of

[0245]

[0246] The reaction was carried out in an autoclave under 2 bar hydrogen pressure.

[0247] In a 130 ml autoclave reactor equipped with a mechanical stirrer (Rushton turbine) was added 12.19 g (99 wt% purity) of PAKS-C 12-18The pre-made 18 wt% solution was dissolved in 70 ml (55.4 g) of anhydrous ethanol (Sinopharm Group, H2O content ≤ 0.2%).

[0248] Then 3.84 g of Pd / C 5% (J&M, model 5SA390000, batch number S321F02541, 52.4 wt% water content, 15 wt% dry catalyst relative to ketone) were added. The reactor was sealed and three nitrogen purges were performed, followed by three hydrogen purges. The reaction mixture was then pressurized under a constant 2 bar of H2, stirred at 1300 rpm and heated at 80°C. After 7.5 h reaction time, the reaction mixture was cooled to room temperature and the reactor was finally depressurized.

[0249] in MeOD-d4 1 H NMR analysis indicated the starting product PAKS-C 12-18 The total conversion of 1% and the following molar composition of the crude solid: 16 mol% phenyl alcohol sulfonate (PAS-C 12-18 ), 73 mol% phenyl alkyl sulfonate (PAS-C 12-18 -HDO) and 11 mol % fully hydrogenated 1-cyclohexyl alkyl sulfonate by-product.

[0250] The reactor was drained and rinsed several times with absolute ethanol.

[0251] The mixture was passed through diatomaceous earth (Supelco, 545, particle size 0.02-0.1 mm, batch number K53174993120) was filtered to separate the Pd / C catalyst, and the filter was rinsed with anhydrous ethanol.

[0252] The filtrate was evaporated to give 11.5 g of a white product having the following weight composition: 17 wt % phenyl alcohol sulfonate (PAS-C 12-18 ), 72wt% phenyl alkyl sulfonate (PAS-C 12-18 -HDO) and 11 wt% fully hydrogenated 1-cyclohexyl alkyl sulfonate by-product.

[0253] 1H NMR (300 MHz, MeOD-d4): δ (ppm) 7.43-7.12 (m, 5H), 5.52 (s, alcohol sulfonate isomer 1, 1H), 4.79 (d, J = 9.5 Hz, alcohol sulfonate isomer 2, 1H), 3.45 (dd, J = 13.7 Hz, J = 3.1 Hz, alkyl sulfonate, 1H), 2.97-2.83 (m, alkyl sulfonate and alcohol sulfonate, 2H), 2.65 (dd, J = 13.6 Hz, J = 10.7 Hz, alkyl sulfonate, 1H), 2.57 (t, J = 8.1 Hz, alkylbenzene, 1H), 1.89-0.87 (m, 26H).

[0254] 4.3 By PAK-C 12-18 Synthesis of PAA-C 12-18

[0255] Phenyl-alkyl alcohol compound PAA-C 12-18 The corresponding phenyl-alkyl ketone fraction (PAK-C) can be prepared by catalytic hydrogenation according to the procedure described in US2020 / 0339748 A1 (see, for example, paragraphs

[0265] to

[0270] of US2020 / 0339748 A1). 12-18 ) precursors are obtained.

[0256] 4.4 By PAA-C 12-18 Synthesis of PAAS-C 12-18

[0257]

[0258] The reaction was carried out in a carefully dried vessel and under an inert argon atmosphere.

[0259] Fresh commercially available anhydrous pyridine was used as received.

[0260] In a 1 1 double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows) and baffles, a condenser and a temperature probe were added 175 ml (171.15 g, 2.16 mol, 4 eq.) pyridine.

[0261] The reaction mass was then cooled to 0°C and 39.9 ml (69.8 g, 0.593 mol, 1.1 eq.) of chlorosulfonic acid were gradually added under stirring at 300 rpm while keeping the temperature below 40°C (strong exotherm).

[0262] The mixture was then heated to 50°C and 151 g of molten phenylalkylmethanol C was added via an insulated dropping funnel maintained at 30°C. 12-18 Fraction (from Example 4.3) (0.539 mol, 1 eq., having the following side alkyl chain length distribution: C 10 : 0.8wt%, C 12 : 57.3wt%, C 14 : 21.1wt%, C16 :9.8wt% and C 18 : 10.9 wt %) was gradually added to the reaction mixture during 10 minutes under stirring at 500 rpm.

[0263] At the end of the addition, the reaction mixture was heated to 60°C and 1 H NMR analysis followed the progress of the reaction. After stirring at 60 °C for 1 hour and 00 minutes, 1 H NMR analysis showed complete and selective conversion of the starting alcohol to the desired sulfate ester.

[0264] The volatiles were then removed by distillation under vacuum (10 mbar) at 70° C. over a period of 1 hour 45 minutes. The residue containing the sulfate ester (with pyridinium as countercation) was dissolved in 1.5 L of Et2O, after which 1.5 L of aqueous NaOH solution (0.5 M) was added. The yellow aqueous phase containing the product was separated from the organic phase containing organic impurities.

[0265] 1 L of ether was then added to the aqueous phase, followed by sodium chloride until the aqueous phase was saturated. Upon addition of sodium chloride, ion exchange occurred and the desired sodium sulfate ester migrated to the organic phase, which was separated, dried over MgSO4 and filtered. The MgSO4 solid was rinsed several times with MeOH.

[0266] At this stage the sulfate ester product still contained traces of pyridinium counterions, so NaHCO 3 was introduced into solution. The mixture was stirred at room temperature during 30 minutes, the solid was filtered and the filtrate was evaporated under vacuum (10 mbar) at 40° C. until a wax was formed.

[0267] In order to remove residual trace solvent from solid, avoid product degradation simultaneously, add the solution of 100g MTBE containing 3wt% diisopropylamine to solid.The solution obtained is warmed at 40 ℃, and vacuum is gradually applied until product solidifies as white solid.Product is dried at 40 ℃ for 1 hour under vacuum (10 mbar), providing 208g white product, it has 96mol% purity, which corresponds to 96% isolated yield.

[0268] 1 H NMR (MeOD-d4, 400MHz) δ (ppm): 7.45-7.15 (m, 5H), 5.26 (t, J = 6.7Hz, 1H), 2.0 4-1.88(m,1H),1.88-1.72(m,1H),1.55-1.05(m,21H),0.90(t,J=6.9Hz,3H).

[0269] 13C NMR (MeOD-d4, 101 MHz) δ (ppm): 143.23, 129.22, 128.53, 127.75, 82.13, 38.78, 33.23, 30.91, 30.88, 30.80, 30.76, 30.65, 30.63, 26.38, 23.89, 14.59 (terminal CH3).

[0270] Example 5

[0271] 5.1 Biodegradability assessment using the 301F OECD protocol (standard protocol)

[0272] In a closed culture BOD (biological oxygen demand) flask (Oxitop TM A measured volume of inoculated mineral medium containing a known concentration of the test substance in order to reach about 50 to 100 mg ThOD / l (ThOS = theoretical oxygen demand) as nominally the only source of organic carbon is stirred in respirometry flasks at a constant temperature (20°C ± 2°C) for up to 28 days in order to evaluate the biodegradability of the test samples.

[0273] The released carbon dioxide is absorbed by the sodium hydroxide or potassium hydroxide pellets present in the head space of the flask. The amount of oxygen taken up by the microbial population during the biodegradation process (biooxidation of the test substance) (= oxygen consumption in mg / l) reduces the pressure of the head space (ΔP measured by the pressure switch) and is mathematically converted to mg consumed O2 / liter.

[0274] The inoculum corresponded to municipal activated sludge washed in mineral medium (ZW medium) in order to reduce the dissolved oxygen carbon (DOC) content.

[0275] Two types of control solutions were used for validation purposes: one control solution contained only the reference substance sodium acetate and the second control solution contained the reference substance and the test substance as a toxicity control. The reference substance was tested in a flask at a nominal concentration of 129 mg / l corresponding to 100 mgThOD / l in order to check the viability of the inoculum.

[0276] 5.2 Biodegradability Assessment Using Emulsion Approach

[0277] Since the compounds and mixtures of compounds of the present invention are generally poorly water soluble, the inventors have developed a specific protocol named "emulsion protocol" for biodegradability assessment. This protocol enables increasing the solubility of poorly water soluble substances in the aqueous phase containing the inoculum and thus increasing their bioavailability. In the emulsion protocol, the test substances are added to the BOD flask containing the inoculated mineral medium via a stock solution prepared in emulsion.

[0278] The emulsion used in the emulsion solution is a non-biodegradable surfactant (1g / l PE 105) in a 50 / 50 v / v mixture of a stock solution of the test substance, which is mixed with mineral silicone oil AR 20 (Sigma). In order to achieve the dissolution of the test substance in the non-biodegradable surfactant solution, a magnetic stirrer can be used for stirring, followed by ultrasonic treatment. Once the dissolution is complete, the non-biodegradable surfactant solution containing the test substance is mixed with mineral silicone oil in a 50 / 50 volume / volume ratio. This emulsion is maintained by stirring with a magnetic stirrer, and is added to a BOD flask containing an inoculated mineral culture medium until the desired test substance concentration is reached.

[0279] 5.3 Biodegradability results

[0280] The compounds of the invention have been evaluated accordingly using the standard protocol (without emulsion) or using the emulsion protocol, and the results are shown below in the following Table 1:

[0281] Table 1

[0282]

[0283] The compounds of the invention show a good biodegradability profile. It has also been observed that the PAS compounds according to the invention show a better biodegradability profile (as indicated by a shorter lag phase and a higher biodegradation rate after 28 days; the lag phase is the period during which the bacteria adapt themselves to the test substance, i.e. the period before mineralization of the test substance begins) compared to PAKS compounds ("Comp" = comparison = not according to the invention).

[0284] 5.4 Surface activity of the compounds of the present invention.

[0285] The critical micelle concentration (CMC) and the surface tension (ST) of the aqueous solution of the surfactant of the present invention are measured at room temperature using a force tensiometer (Sigma 700 / 701). The curve of surface tension relative to surfactant concentration is plotted to determine the surface tension under CMC and CMC. Using the Gibbs adsorption equation, the area occupied by the surface excess and surfactant molecules at the surface can be determined (as a reference, see, for example, "Industrial Utilization of Surfactants: principles and practice [industrial application of surfactants: principles and practice] ", MJRosen and M.Dahanayake, 2000, ISBN 1893997111), which are important parameters for characterizing surfactants. The results are summarized in the following table:

[0286]

[0287] These results show that PAKS-C 16 and PAS-C 16 have similar CMC values ​​(about 0.2 mM), but the latter shows a tighter packing at the interface characterized by a lower cross-sectional area (0.53 nm 2 0.64)), higher surface excess and thus improved surface activity (e.g. by PAS-C 16 The lower surface tension shown at the CMC (36 mN / m vs. 44) was confirmed).

Claims

1. A compound having formula I wherein Ar represents an aryl group; R1 is H or a group of formula OR, wherein R is H or SO3X, wherein X is an alkali metal, an alkaline earth metal or ammonium of the general formula R'R"R"'R""N, wherein R', R", R"' and R"" are independently selected from hydrogen or a hydrocarbon group, which hydrocarbon group may be optionally substituted and / or interrupted by one or more heteroatom-containing groups; R2 is H or SO3X, wherein X is an alkali metal, alkaline earth metal or ammonium having the general formula R'R"R"'R""N, wherein R', R", R"' and R"" are independently selected from hydrogen or a hydrocarbyl group which may be optionally substituted and / or interrupted by one or more heteroatom-containing groups; The premise is R1 and R2 are different groups When R2 is SO3X, R1 is H or OR, where R is H When R2 is H, R1 is OR, where R is SO3X R3 is C2-C 26 Aliphatic group.

2. The compound according to claim 1, wherein R3 is C2-C 18 Aliphatic group, preferably C6-C 16 Aliphatic group.

3. The compound according to claim 1 or 2, wherein R3 is an alkyl group, preferably a straight-chain alkyl group.

4. A compound according to any one of the preceding claims, wherein Ar is phenyl.

5. A compound according to any one of the preceding claims, wherein X is sodium.

6. A compound according to any one of the preceding claims, wherein R1 is OSO3X, wherein X is as defined in any one of the preceding claims, R2 is H R3 is a linear alkyl group C6 to C 16 .

7. A compound according to any one of the preceding claims, wherein R1 is OH R2 is SO3X, wherein X is as defined in any one of the preceding claims, R3 is a linear alkyl group C6 to C 16 .

8. A compound according to any one of the preceding claims, wherein R1 is H R2 is SO3X, wherein X is as defined in any one of the preceding claims, R3 is a linear alkyl group C6 to C 16 .

9. A composition comprising a mixture of two or more compounds of formula I according to any one of the preceding claims.

10. The composition according to claim 9, comprising a mixture of a first compound having formula I and a second compound having formula I, wherein R1 is OH R2 is SO3X, wherein X is as defined in any one of the preceding claims, R3 is a linear alkyl group C6 to C 16 , In the second compound R1 is H R2 is SO3X, wherein X is as defined in any one of the preceding claims, R3 is a linear alkyl group C6 to C 16 .

11. A composition comprising at least one compound having formula I and at least one additional surfactant, wherein the at least one additional surfactant is not a compound having formula I.

12. A method for preparing a compound of formula I according to any one of claims 1 to 8, wherein The method starts from a mixture of Ar-COOH (II) and R3-CH2-COOH (III) to produce an aromatic aliphatic ketone having formula IV: Ar-C(=O)-CH2-R3 (IV), wherein Ar and R3 are as defined in any of the preceding claims, and further comprises derivatizing the aromatic aliphatic ketone having formula IV: Ar-C(=O)-CH2-R3 (IV) by a hydrogenation-sulfation sequence or a sulfonation-hydrogenation sequence to produce the compound having formula I.

13. The method according to claim 12, wherein: The method comprises the following steps: a. a decarboxylative cross-ketonization between Ar-COOH (II) and R3-CH2-COOH (III) in the presence of a metal-based catalyst, wherein Ar and R3 are as defined in any one of the preceding claims, thereby obtaining an arylaliphatic ketone having the formula IV: Ar-C(=O)-CH2-R3 (IV), wherein Ar and R3 are as defined above, b. hydrogenating the aromatic aliphatic ketone of formula IV obtained in step a. in the presence of H2 and a catalyst to obtain a secondary alcohol of formula V: Ar-CH(OH)-CH2-R3(V), wherein Ar and R3 are as defined above, c. The secondary alcohol having formula V obtained in step b. is sulfated with a sulfating agent, and then neutralized with XOH or X(OH)2, thereby obtaining the compound having formula I, wherein R1 is OSO3X, wherein X is as defined in any one of the preceding claims R2 is H R3 is C2-C 26 Aliphatic group.

14. The method according to claim 12, wherein: The method comprises the following steps: a. a decarboxylative cross-ketonization between Ar-COOH (II) and R3-CH2-COOH (III) in the presence of a metal-based catalyst, wherein Ar and R3 are as defined in any one of the preceding claims, thereby obtaining an arylaliphatic ketone having the formula IV: Ar-C(=O)-CH2-R3 (IV), wherein Ar and R3 are as defined above, b. sulfonating the aryl aliphatic ketone of formula IV obtained in step a. with a sulfonating agent, followed by neutralization with XOH or X(OH)2, thereby obtaining an aryl aliphatic ketone sulfonate of formula VI: Ar-C(=O)-CH(SO3X)-R3(VI), wherein Ar, X and R3 are as defined above, c. hydrogenating the arylaliphatic ketone sulfonate of formula VI obtained in step b. in the presence of H2 and a catalyst, thereby obtaining a first compound of formula I, wherein R1 is OH R2 is SO3X, wherein X is as defined in any one of the preceding claims R3 is C2-C 26 aliphatic groups; or a second compound having formula I, wherein R1 is H R2 is SO3X, wherein X is as defined in any one of the preceding claims R3 is C2-C 26 aliphatic groups; Or a mixture of the first compound having formula I and the second compound.

15. The method according to claim 13, wherein: The sulfating agent is selected from the group consisting of SO 3 , chlorosulfonic acid (ClSO 3 H), oleum and sulfamic acid (H 3 NSO 3 ), and is preferably selected from the group consisting of SO 3 and chlorosulfonic acid (ClSO 3 H).

16. The method according to claim 14, wherein: The sulfonating agent is selected from the group consisting of SO 3 , chlorosulfonic acid (ClSO 3 H), oleum and aminosulfonic acid (H 3 NSO 3 ), and is preferably selected from the group consisting of SO 3 and chlorosulfonic acid (ClSO 3 H).

17. Use of a compound of formula I according to any one of claims 1 to 8 as a surfactant or use of a composition according to claims 9 to 11 as a surfactant.

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