PROCESS FOR THE DECARBOXYLATIVE KETONIZATION OF FATTY ACIDS OR FATTY ACID DERIVATIVES

Abstract

The present invention is directed to a process for synthesizing an internal ketone K1 by decarboxylative ketonization reaction of a fatty acid, a fatty acid derivative or a mixture thereof in a liquid phase with a metal compound as catalyst in a reaction medium, said process being characterized in that a ketone K2 at liquid state, which is identical or similar to the ketone K1, is introduced into the reaction medium. The so-synthesized internal ketone K1 can be used for the preparation of a variety of end compounds, including surfactants having a twin-tail structure or a Gemini structure.

Claims

1. A process P for synthesizing an internal ketone K1 by decarboxylative ketonization reaction of a fatty acid, a fatty acid derivative or a mixture thereof in a liquid phase with a metal compound as catalyst in a reaction medium, wherein a ketone K2 at liquid state, which is identical or similar to the ketone K1, is introduced into the reaction medium.

2. The process according to claim 1, wherein the ketone K2 has a boiling point of at least 310 C.

3. The process according to claim 1, wherein the difference between the boiling point of the ketone K1 and the boiling point of the ketone K2 is equal to or lower than 10 C.

4. The process according to claim 1, wherein the catalysis is homogeneous catalysis, that is to say that in the reaction conditions an intermediate metal carboxylate salt is formed through the initial reaction between the fatty acid or its derivative with the metal compound and this intermediate salt is substantially soluble in the reaction medium.

5. The process according to claim 1, wherein the metal compound is an iron oxide.

6. (canceled)

7. (canceled)

8. The process according to claim 1, wherein, the molar ratio of fatty acid, fatty acid derivatives or mixtures thereof to metal is in the range of from 6:1 to 99:1.

9. The process according to claim 1, wherein the ketone K2 is identical to ketone K1 and wherein the ketone K2 introduced is originated from a previous process P for synthesizing a ketone K1 by decarboxylative ketonization reaction of a fatty acid, a fatty acid derivative or a mixture thereof.

10. (canceled)

11. The process according to claim 1, wherein a fatty acid is used as starting material and the fatty acid is at least one carboxylic acid having at least 10 carbon atoms.

12. The process according to claim 1, wherein one and only one fatty acid is used as starting material.

13. (canceled)

14. The process according to claim 1, comprising the steps of: a) introducing in any order at least part of the ketone K2 at liquid state, at least part of the metal compounds, at least part of the fatty acid, fatty acid derivative or mixture thereof into a reactor in order to synthesize the ketone K1, said reactor optionally containing before said introduction, a part of the metal compounds, and/or a part of the fatty acid, fatty acid derivative or mixture thereof and/or a part of the ketone K2 and/or a part of the ketone K1, b) recovering the ketone K1 optionally together with the ketone K2, c) optionally recycling at least part of the ketone K1 and/or ketone K2 and/or at least part of the metal compounds to step a).

15. The process according to claim 14, wherein step a) comprises the steps: a1) introducing at least part of the ketone K2 at liquid state, and at least part of the metal compounds into a reactor, said reactor optionally containing before said introduction, a part of the metal compounds, and/or a part of the ketone K2 and/or a part of the ketone K1, and said reactor being totally free of fatty acid(s) and fatty acid derivatives(s), a2) introducing the fatty acid, fatty acid derivative or mixture thereof into the reactor, optionally with: a part of the metal compounds, and/or a part of the ketone K2 and/or, a part of the intermediate metallic carboxylate salts obtained by reacting metal compounds and the fatty acids or fatty acid derivatives before decomposition to form the ketone K 1.

16. The process according to claim 15, wherein at step a2), the fatty acid, fatty acid derivative or mixture thereof is introduced sequentially or continuously into the reactor.

17. A method for the preparation of an end compound having a twin-tail structure, the method comprising using the internal ketone K1 synthesized by the process according to claim 1.

18. A method for the preparation of an end compound having a Gemini structure, the method comprising using the internal ketone K1 synthesized by the process according to claim 1.

19. (canceled)

20. A method M for the preparation of a compound from an internal ketone K1, said method M comprising: synthesizing the internal ketone K1 by the process P according to claim 1, and causing the internal ketone K1 to react in accordance with a single or multiple chemical reaction scheme involving at least one reagent other than the internal ketone K1, wherein at least one product of the chemical reaction scheme is the end compound that is not further caused to be chemically converted into another compound.

21.-25. (canceled)

26. The process according to claim 1, wherein the ketone K2 is similar to the internal ketone K1 in that the difference between the boiling point of the internal ketone K1 and the boiling point of the ketone K2 is equal to or lower than 80 C.

27. The process according to claim 1, wherein a fatty acid is used as starting material and the fatty acid is selected from the group consisting of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and mixtures thereof.

28. The process according to claim 27, wherein the fatty acid is a C.sub.8-C.sub.18 fatty acids cut.

29. A process P for synthesizing an internal ketone K1 by decarboxylative ketonization reaction of a fatty acid, a fatty acid derivative or a mixture thereof in a liquid phase with a metal compound as catalyst in a reaction medium, wherein a ketone K2 at liquid state is introduced into the reaction medium.

30. The process according to claim 29 wherein the ketone K2 has a boiling point of at least 270 C.

31. The process according to claim 30 wherein the ketone K2 has a boiling point of at least 310 C.

32. The process according to claim 31, wherein the ketone K2 is selected from the group consisting of 8-octadecanone, benzoin, 10-nonadecanone, anthraquinone, 12-tricosanone, trans,trans-dibenzylideneacetone, 13-pentacosanone, 14-heptacosanone, 16-hentriacontanone, 18-pentatriacontanone, 19-heptatriacontanone and 20-nonatriacontanone.

33. The process according to claim 29, wherein the ketone K2 is identical to internal ketone K1 and the ketone K2 introduced is originated from a previous process P for synthesizing an internal ketone K1 by decarboxylative ketonization reaction of a fatty acid, a fatty acid derivative or a mixture thereof.

34. The process according to claim 33, wherein the ketone K2 is one or more ketones of formula (I) ##STR00048## wherein R.sub.n and R.sub.m independently represent an aliphatic group, and the number of carbon atoms of R.sub.n and of R.sub.m, as herein represented by a couple (n,m), is selected from the group consisting of (9,9), (11,11), (13,13), (15,15), (17,17), (19,19), (21,21), (23,23), (25,25), (27, 27), (7,9), (7,11), (7,13), (7,15), (7,17), (7,19), (7,21), (7,23), (7,25), (7,27);(9,11), (9,13), (9,15), (9,17), (9,19), (9,21), (9,23), (9,25), (9,27), (11,13), (11,15), (11,17), (11,19), (11,21), (11,23), (11,25), (11,27), (13,15), (13,17), (13,19), (13,21), (13,23), (13,25), (13, 27), (15,17), (15,19), (15,21), (15,23), (15,25), (15,27), (17,19), (17,21), (17,23), (17,25), (17,27), (19,21), (19,23), (19,25), (19,27), (21,23), (21,25), (21,27), (23,25), (23,27) and (25,27).

35. The process according to claim 29 wherein a fatty acid is used as starting material and the fatty acid is at least one carboxylic acid having at least 10 carbon atoms or is a C.sub.8-C.sub.18 fatty acids cut.

Description

DETAILED DESCRIPTION OF THE METHOD M

[0126] 1Making Amines from Internal Ketones K1

[0127] 1.1) Reductive Amination to Afford Twin-Tail Amines

[0128] The end product can be a twin-tail amine.

[0129] Indeed, at least one internal ketone K1 (i.e. a single internal ketone or a mixture of internal ketones) that is advantageously synthesized by the process P can be reacted with at least one amine under reductive amination conditions to provide at least one twin-tail amine.

[0130] An internal ketone K1 synthesized by the process P is generally a compound of formula (I)

##STR00001##

[0131] wherein R.sub.n and R.sub.m independently represent an aliphatic group, generally a C.sub.3-C.sub.27 aliphatic group, very often a C.sub.3-C.sub.19 aliphatic group, often a aliphatic C.sub.7-C.sub.17 group.

[0132] The number of carbon atoms of R.sub.n and R.sub.m can be even or odd numbers. They are advantageously odd numbers, which happens typically when the internal ketone K1 is made from a fatty acid containing an even number of carbon atoms (e.g. a C.sub.23 internal ketone is made from a C.sub.12 fatty acid).

[0133] For the reasons above explained when detailing the process P, R.sub.n and R.sub.m may be identical to each other; alternatively, R.sub.n and R.sub.m may differ from each other.

[0134] The number of carbon atoms of R.sub.n and of R.sub.m, as herein represented by the couple (n,m), can be notably any of the following couples: [0135] (3,3), (5,5), (7,7), (9,9), (11,11), (13,13), (15,15), (17,17), (19,19), (21,21), (23,23), (25,25), (27, 27) [0136] (7,9), (7,11), (7,13), (7,15), (7,17), (7,19), (7,21), (7,23), (7,25), (7,27) [0137] (9,11), (9,13), (9,15), (9,17), (9,19), (9,21), (9,23), (9,25), (9,27) [0138] (11,13), (11,15), (11,17), (11,19), (11,21), (11,23), (11,25), (11,27) [0139] (13,15), (13,17), (13,19), (13,21), (13,23), (13,25), (13, 27) [0140] (15,17), (15,19), (15,21), (15,23), (15,25), (15,27) [0141] (17,19), (17,21), (17,23), (17,25), (17,27) [0142] (19,21), (19,23), (19,25), (19,27) [0143] (21,23), (21,25), (21,27) [0144] (23,25), (23,27) or [0145] (25,27).

[0146] The aliphatic groups R.sub.n and R.sub.m may be linear or branched.

[0147] The aliphatic groups R.sub.n and R.sub.m may be free of any double bond and of any triple bond. Alternatively, the aliphatic groups R.sub.n and R.sub.m may comprise at least one CC double bond and/or at least one CHC triple bond.

[0148] The aliphatic groups R.sub.n and R.sub.m are advantageously chosen from alkyl groups, alkenyl groups, alkanedienyl groups, alkanetrienyl groups and alkynyl groups.

[0149] Preferably, the aliphatic groups R.sub.n and R.sub.m are independently chosen from chosen from alkyl and alkenyl groups.

[0150] More preferably, the aliphatic groups R.sub.n and R.sub.m are independently chosen from alkyl and alkenyl groups, generally from C.sub.3-C.sub.27 alkyl and C.sub.3-C.sub.27 alkenyl groups, very often from C.sub.3-C.sub.19 alkyl and C.sub.3-C.sub.19 alkenyl groups and often from C.sub.6-C.sub.17 alkyl and C.sub.6-C.sub.17 alkenyl groups. More preferably, R.sub.n and R.sub.m independently represent an alkyl group, generally a C.sub.3-C.sub.27 alkyl group, very often a C.sub.3-C.sub.19 alkyl group, often a C.sub.6-C.sub.17 alkyl group.

[0151] In particular, the at least one internal ketone K1 of formula (I) can be reacted with at least one amine of formula (II) under reductive amination conditions to afford the at least one twin-tail amine of formula (III)

##STR00002##

[0152] This amination reaction is preferably performed by reacting the ketone K1 of formula (I) and the amine of formula (II) in the presence of a transition metal (e.g. Ni, Co, Cu, Fe, Rh, Ru, Ir, Pd, Pt) based catalyst (typically Pd/C), in a autoclave under hydrogen pressure (typically from 1 atm to 200 bar).

[0153] According to a possible embodiment, the reaction is carried out in a solvent. However, the presence of such a solvent is not compulsory and according to a specific embodiment, no solvent is used for this step. The exact nature of the solvent, if any, may be determined by the skilled person. Typical suitable solvents include, without limitation, methanol, ethanol, isopropanol, tert-butanol, THF, 2-methyltetrahydrofuran, 1,4-dioxane, dimethoxyethane, diglyme and mixtures thereof.

[0154] Besides, this step is usually carried out at a temperature ranging from 15 C. to 400 C. and may be conducted batchwise, semi-continuously or continuously and generally performed either in a batch mode or in a continuous mode using a fixed-bed catalyst (gas-solid or gas-liquid-solid process).

[0155] In the above amine formula (II), R.sub.1 and R.sub.2 independently represent:

[0156] hydrogen or a linear or branched hydrocarbon radical having 1 to 24 carbon atoms which can be optionally substituted and/or interrupted by one or more heteroatoms or heteroatom containing groups (for example R.sub.1 and R.sub.2 can be selected from H, CH.sub.3, CH.sub.2CH.sub.3, propyl, isopropyl, butyl, sec-butyl, isobutyl and tert-butyl),

[0157] ethylamine of formula CH.sub.2CH.sub.2NRR wherein R and R independently represent hydrogen or a short alkyl group having from 1 to 6 carbon atoms (such as for example CH.sub.3, CH.sub.2CH.sub.3, propyl, isopropyl),

[0158] [poly(ethylenimine)]ethylamine of formula (CH.sub.2CH.sub.2NH)m-CH.sub.2CH.sub.2NRR wherein R and R independently represent hydrogen or an alkyl group having from 1 to 6 carbon atoms (such as for example CH.sub.3, CH.sub.2CH.sub.3, propyl, isopropyl) and m is an integer from 1 to 20,

[0159] hydroxyethyl of formula CH.sub.2CH.sub.2OH,

[0160] [poly(ethylenimine)]ethanol of formula (CH.sub.2CH.sub.2NH)m-CH.sub.2CH.sub.2OH wherein m is an integer from 1 to 20,

[0161] a N,N-dialkylaminoalkyl radical of formula (CH.sub.2)m-NRR wherein m is an integer from 3 to 20 and R and R independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms (such as CH.sub.3, CH.sub.2CH.sub.3, propyl, isopropyl),

[0162] and wherein R.sub.1 and R.sub.2 can also form an alkanediyl radical, typically of formula (CH.sub.2)m- wherein m ranges from 3 to 8, which can be optionally interrupted or substituted by one or more heteroatoms or heteroatom containing groups; in this case, (II) is a cyclic amine such as pyrrolidine, piperidine, morpholine or piperazine.

[0163] As examples of amines (II), one can mention: ammonia, dimethylamine, monoethanolamine, diethanolamine, ethylenediamine (EN), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), aminoethylethanolamine (AEEA) and 3,3-Iminobis(N,N-dimethylpropylamine).

[0164] 1.2) Mannich Reaction Involving Condensation with an Aldehyde and an Amine to Afford Amine Gemini Compounds

[0165] The end product can be an amine Gemini compound. Typically, the amine

[0166] Gemini compound comprises a central carbonyl group which, in a two-dimensional representation of the formula of this compound, can form a symmetry axis provided some conditions are met on the nature of its substituents, as will immediately be made apparent from what follows.

[0167] Indeed, the at least one internal ketone K1 (i.e. a single internal ketone or a mixture of internal ketones) that is advantageously synthesized by the process P can be reacted with at least one aldehyde and at least one amine under Mannich reaction conditions to provide at least one ketone having one and only one of its carbonyl-adjacent carbon atoms substituted by an amine-containing group and/or at least one ketone having both of its carbonyl-adjacent carbon atoms substituted by an amine-containing group (Gemini amine).

[0168] In particular, internal ketones K1 of formula (I)

##STR00003##

[0169] as above defined, wherein methylene groups are adjacent to the carbonyl group on its both sides can be represented by formula (I)

##STR00004##

[0170] wherein R.sub.n and R.sub.m independently represent an aliphatic group, generally a C.sub.2-C.sub.26 aliphatic group, very often a C.sub.2-C.sub.18 group, often a C.sub.5-C.sub.16 group.

[0171] The at least one internal ketone K1 of formula (I) can be reacted with at least one aldehyde of formula (IV) and at least one amine of formula (II) under Mannich reaction conditions to afford at least one ketone (Va) having one and only one of its carbonyl-adjacent carbon atoms substituted by an amine-containing group and/or at least one ketone (Vb) having both of its carbonyl-adjacent carbon atoms substituted by an amine-containing group (Gemine amine).

##STR00005##

[0172] In the amine of formula (II), R.sub.1 and R.sub.2 are as previously defined in part 1.1

[0173] Regarding the aldehyde (IV), R.sub.3 can represent:

[0174] hydrogen or a linear or branched hydrocarbon radical having from 1 to 24 carbon atoms which can be optionally substituted and/or interrupted by one or more heteroatoms or heteroatom containing groups (for example, R.sub.3 can be selected from H, CH.sub.3, CH.sub.2CH.sub.3, propyl, isopropyl, butyl, sec-butyl, isobutyl and tert-butyl), or

[0175] an aromatic or a heterocyclic aromatic radical which can be optionally substituted by one or more branched or linear hydrocarbon radical which can optionally contain one or more heteroatom (for example, R.sub.3 can be phenyl, fur-2-yl, fur-3-yl, para-hydroxyphenyl, para-methoxyphenyl or 4-hydroxy-3-methoxyphenyl).

[0176] As examples of aldehydes (IV), one can mention formaldehyde, ethanal, propanal, butanal, furfural, hydroxymethylfurfural, vanillin and para-hydroxybenzaldehyde.

[0177] The amine Gemini compound (Vb) has a central carbonyl group. In a two-dimensional representation of formula (Vb), the central carbonyl group (CO) can form a symmetry axis when substituents R.sub.m and R.sub.n are identical to each other.

[0178] The Mannich reaction can be conducted under acidic conditions when the amine (II) is in its protonated form, for example as a hydrochloride salt form.

[0179] The reaction is usually carried out by contacting the ketone K1 of formula (I), the aldehyde (IV) and the amine (II) (or its protonated salt which can be generated in-situ by adding a stoichiometric amount of acid), optionally in the presence of an added solvent in a reaction zone at a temperature from 15 C. to 300 C. As examples of suitable solvents to conduct the reaction, one can mention: methanol, ethanol, isopropanol, toluene, xylenes, diglyme, dioxane, THF, methyl-THF, DMSO, etc.

[0180] The amine (II) or its protonated salt as well as the aldehyde (IV) can be used in molar excess and the excess reactants can be recovered at the end of the reaction and recycled.

[0181] The reaction can also be catalyzed by the addition of a suitable Bronsted or a Lewis acid. One can mention for example: H.sub.2SO.sub.4, HCl, triflic acid, p-toluenesulfonic acid, perchloric acid, AlCl.sub.3, BF.sub.3, metal triflate compounds such as aluminium triflate, bismuth triflate, heterogeneous solid acids such as Amberlyst resins, zeolithes, etc.

[0182] The water generated during the reaction can be optionally trapped thanks to a Dean-Stark apparatus.

[0183] If the reaction is conducted under acidic conditions, after subsequent work-up, the products (Va) and/or (Vb) are obtained in the form of their protonated salts which can be neutralized in a second stage by the reaction with an aqueous solution of a suitable base for example: NaOH, KOH, NH.sub.4OH, Na.sub.2CO.sub.3.

[0184] The desired ketones (Va) and/or (Vb) are obtained after appropriate work-up. The skilled person is aware of representative techniques so that no further details need to be given here.

[0185] 2Making Quaternary Ammoniums from Internal Ketones K1 2.1) Quatemization of Twin-Tail Tertiary Amines to Afford Twin-Tail Quaternary Ammonium Compounds

[0186] The end product can be a twin-tail quaternary ammonium compound.

[0187] Such a twin-tail quaternary ammonium compound can be obtained as end product when at least one twin-tail amine obtained from the at least one internal ketone K1 according to the reaction described in part 1.1 is a teriary amine. For example, when the twin-tail amine is of formula (III), this happens when R.sub.1 and R.sub.2 differ from a hydrogen atom.

[0188] Accordingly, at least one twin-tail tertiary amine obtained from at least one internal ketone K1 according to the reaction described in part 1.1 can be reacted with at least one alkylating agent to obtain at least one twin-tail quaternary ammonium salt.

[0189] In particular, at least one tertiary amine (III) obtained from the at least one internal ketone K1 of formula (I) according to part 1.1 can be reacted with at least one alkylating agent (VI) of formula R.sub.4-X to obtain at least one twin-tail quaternary ammonium salt (VII), as schemed below:

##STR00006##

[0190] As already pointed out, amines (III) useful for use in present part 2.1 are tertiary amines. Advantageously, the tertiary amines (III) useful for use in present part 2.1 are tertiary amines wherein R.sub.1 and R.sub.2 independently represent a linear or branched hydrocarbon radical having from 1 to 24 carbon atoms which can be optionally substituted and/or interrupted by one or more heteroatoms or heteroatom containing groups (for example R.sub.1 and R.sub.2 can be selected from CH.sub.3, CH.sub.2CH.sub.3, propyl, isopropyl, butyl, sec-butyl, isobutyl and tert-butyl) and tertiary amines wherein R.sub.1 and R.sub.2 form an alkanediyl radical, typically of formula (CH.sub.2)m- wherein m ranges from 3 to 8, which can be optionally interrupted and/or substituted by one or more heteroatoms or heteroatom containing groups.

[0191] The group X contained in the alkylating agent (VI) and that constitutes the counter anion of the salt (VII) is a leaving group, typically a halide such as Cl, Br or I, methylsulfate (SO.sub.4Me), sulfate (SO.sub.4), a sulfonate derivative such as methanesulfonate (O.sub.3SCH.sub.3), para-toluenesulfonate (O.sub.3SC.sub.7H.sub.7) or trifluoromethanesulfonate (O.sub.3SCF.sub.3).

[0192] In reactant (VI), R.sub.4 represents a linear or branched hydrocarbon radical having 1 to 10 carbon atoms which can be optionally substituted and/or interrupted by a substituted or unsubstituted aromatic group and/or a heteroatom or heteroatom containing group. For example, R4 can be: CH.sub.3, CH.sub.2CH.sub.3, benzyl, furfuryl.

[0193] As examples of alkylating agent (VI), one can mention dimethyl sulfate, methyl chloride, methyl bromide, methyl triflate, benzyl chloride and epichlorhydrin.

[0194] This reaction can be carried out by contacting both reactants in a reaction zone at a temperature from 15 C. to 400 C., optionally in the presence of an added solvent such as methanol, ethanol, isopropanol, toluene, a xylene, diglyme, dioxane, THF, methyl-THF or DMSO. The alkylating agent can be used in stoichiometric amounts or in excess and the excess reactant can be recovered after the reaction following a suitable work-up and recycled. The skilled person is aware of representative work-up techniques so that no further details need to be given here.

[0195] 2.2) Quatemization Reaction of Tertiary Amine Gemini Compounds to Afford Quaternary Ammonium salt Gemini Compounds

[0196] The end compound can be a quaternary ammonium salt Gemini compound. Typically, the quaternary ammonium salt Gemini compound comprises a central carbonyl group which, in a two-dimensional representation of the formula of this compound, can form a symmetry axis provided some conditions are met on the nature of its substituents, as will immediately be made apparent from what follows.

[0197] Such a quaternary ammonium salt Gemini compound can be obtained as end product when at least one tertiary amine Gemini compound obtained from at least one internal ketone K1 according to the reaction described in part 1.2 is a tertiary amine Gemini compound. For example, when the amine Gemini compound is of formula (Vb), this happens when R.sub.1 and R.sub.2 differ from a hydrogen atom.

[0198] At least one tertiary amine Gemini compound obtained from at least one internal ketone K1 according to the reaction described in part 1.2 can be reacted with at least one alkylating agent to obtain at least one quaternary ammonium salt Gemini compound.

[0199] For example, at least one ketone (Va) and/or at least one ketone (Vb) obtained from the at least one internal ketone K1 of formula (I) according to part 1.2 can be reacted with at least one alkylating agent (VI) of formula R.sub.4-X to obtain respectively at least one quaternary ammonium salt (VIIIa) and/or at least one quaternary ammonium salt Gemini compound (VIIIb), as schemed below:

##STR00007##

[0200] The substituents R.sub.1, R.sub.2, R.sub.4 and the group X meet the same definitions as the ones provided in part 2.1 while the substituent R.sub.3 has the same definition as in part 1.2.

[0201] This reaction can be carried out as indicated in part 2.1.

[0202] 3Making Amphoterics from Internal Ketones K1

[0203] The end compound can be a twin-tail (poly)aminocarboxylate.

[0204] 3.1) First Synthesis of Twin-Tail (poly)aminocarboxylates

[0205] At least one twin-tail tertiary amine prepared from at least one internal ketone K1 according to part 1.1 can be reacted with at least one alkylating agent to afford at least one amphoteric compound, notably when said twin-tail tertiary amine is itself substituted by at least one, possibly by two and only two, amino groups (NH.sub.2).

[0206] Certain amines of formula (III) that are suitable for undergoing this reaction comply with formula (III)

##STR00008##

[0207] wherein R.sub.n and R.sub.m have the same meaning as in formula (I) and wherein o and p are integers from 1 to 20, preferably from 2 to 20, possibly from 4 to 20.

[0208] In particular, at least twin-tail amine of formula (III) can be reacted with at least one alkylating agent (IX) to afford at least one amphoteric compound (X), as schemed hereinafter:

##STR00009##

[0209] The reaction is usually conducted by contacting both reactants in a reaction zone at temperature from 15 C. to 400 C. and optionally in the presence of an added solvent. As examples of suitable solvents, one can mention methanol, ethanol, isopropanol, DMSO, acetonitrile, water, THF, dioxane and mixtures thereof.

[0210] In a preferred embodiment, the pH of the reaction mixture is maintained during the course of the reaction from 8.5 to 9.5. This adjustment can be done by adding required amounts of concentrated NaOH and/or HCl aqueous solutions to the reaction medium.

[0211] Importantly, by adjusting the stoichiometry of the reaction (molar excess of (IX) with respect to (III), it is possible to adjust the average degree of alkylation of the starting amine (III) which means the average number of methylenecarboxylate groups (CH.sub.2CO.sub.2Na) contained in (X).

[0212] In the product (X), o, o, p and p are integers ranging from 0 to 20 provided that at least one of o and p is of at least 1. Preferably, o, o, p and p are integers ranging from 1 to 20, possibly from 2 to 20, and the following equalities must be respected:

o+o=o and p+p=p.

[0213] The substituents Y and Y can be independently a hydrogen atom or a methylenecarboxylate fragment (CH.sub.2CO.sub.2Na).

[0214] It has to be understood that the values of o, o, p and p reflect the degree of alkylation and that mixture of compounds (X) with different values for o, o, p and p and with different substituents Y and Y can be obtained. Globally, one can say that when the molar amount of the alkylating agent (IX) is increased, the value of o and p increase (and consequently o and p decrease).

[0215] The group X contained in the alkylating agent (IX) is a leaving group, and has the same meaning as in part 2.1.

[0216] As an example, one can consider the reaction between the ethylenediamine-derived amine of type (III) and 2 equivalents of sodium monochloroacetate ((IX) with X=Cl). In this case, the following mixture can be obtained:

##STR00010##

[0217] 3.2) Second Synthesis of (poly)aminocarboxylates

[0218] At least one twin-tail tertiary amine prepared from at least one internal ketone K1 according to part 1.1 can be reacted with at least one acrylate derivative (especially a hydrocarbyl acrylate of formula CH.sub.2=CHCO.sub.2A wherein A is hydrocarbyl, preferably C.sub.1-C.sub.7 hydrocarbyl, more preferably C.sub.1-C.sub.4 alkyl), to afford at least one amphoteric compound, notably when said twin-tail tertiary amine is itself substituted by at least one, possibly by two and only two, amino groups (NH.sub.2).

[0219] Certain amines of formula (III) that are suitable for undergoing this reaction comply with formula (III') as described in part 3.1.

[0220] In particular, the at least one twin-tail amine (III') obtained from the at least one internal ketone K1 (I) according to part 1.1, wherein R.sub.n and R.sub.m have the same meaning as in formula (III) and wherein o and p are integers from 1 to 20, preferably from 2 to 20, possibly from 4 to 20, is reacted in a first step with at least one acrylate derivative, such as the above described hydrocarbyl acrylate, to undergo conjugate additions affording at least one ester, such as the hydrocarbyl ester of the formula (XIa')not representedobtained by generalizing/replacing methyl (Me) by hydrocarbyl (A substituent) in below formula (XIa). The at least one obtained ester (XIa) is then saponified in a second stage using an aqueous NaOH solution to afford at least one amphoteric compound, such as the amphoteric compound of formula (XIb)not representedagain obtained by generalizing/replacing methyl (Me) by hydrocarbyl (A substituent) in below formula (XIb).

[0221] The following reaction scheme corresponds to the case when the acrylate derivative is CH.sub.2=CHCO.sub.2Me (A is methyl Me):

##STR00011##

[0222] Typically, in the intermediate (XIa) [e.g. (XIa)], the substituents Y and Y represent independently either a hydrogen atom or a hydrocarbyl ethylenecarboxylate fragment (CH.sub.2CH.sub.2CO.sub.2A), in particular a methyl ethylenecarboxylate fragment (CH.sub.2CH.sub.2CO.sub.2Me).

[0223] In the final amphoteric derivative (XIb) [e.g. (XIb)], the substituents Z and Z independently represent a hydrogen atom or an ethylenecarboxylate fragment (CH.sub.2CH.sub.2CO.sub.2Na).

[0224] o, o, p and p in the intermediate (XIa) [e.g. (XIa)], and q, q, r and r in the final product (XIb) [e.g. (XIb)] are integers ranging from 0 to 20 provided that at least one of o and p is of at least 1 and at least one of q and r is of at least 1.

[0225] Preferably, o, o, p and p in the intermediate (XIa) [e.g. (XIa)], and q, q, r and r in the final product (XIb) [e.g. (XIb)] are integers ranging from 1 to 20, possibly from 2 to 20.

[0226] In addition, the following equalities must be respected:

o+o=q+q=o

+p=r+r=p

[0227] The first step of the reaction is carried out by contacting both reactants in a reaction zone at temperature from 15 C. to 400 C. The whole amount of the reactants can be introduced directly in the reaction mixture, but in a preferred embodiment the acrylate derivative is progressively added into the reaction mixture in order to limit polymerization side reactions. The reaction can be optionally conducted in the presence of an added solvent, for example: methanol, ethanol, isopropanol, THF, dioxane, ethyl acetate, acetonitrile, etc.

[0228] The acrylate derivative can be used in excess with respect of the amine (III).

[0229] The intermediate ester (XIa) [e.g. methyl ester (XIa)] is advantageously isolated after removal of excess of acrylate derivative and optional solvents using standard techniques well known by the skilled person of the art. The second step is then carried out by contacting intermediate (XIa) with an appropriate amount of an aqueous solution of NaOH (the molar amount of NaOH is equal or higher than the molar amount of ester fragments that need to be saponified), optionally in the presence of an added solvent, such as methanol, ethanol, isopropanol, acetonitrile, DMSO or THF, and at a temperature from 15 C. to 400 C.

[0230] During the first step, the acrylate derivative can be used in a molar excess, and generally the stoichiometric ratio between amine (III) and acrylate will dictate the average degree of alkylation of the starting amine (III), meaning the average number of hydrocarbyl ethylenecarboxylate (CH.sub.2CH.sub.2CO.sub.2A) fragments contained in the intermediate (XIa) or the like and consequently the average number of ethylenecarboxylate (CH.sub.2CH.sub.2CO.sub.2Na) fragments contained in the final amphoteric product (XIb).

[0231] It has to be understood that when the molar excess of acrylate derivative is increased during the first step, the average number of hydrocarbyl ethylenecarboxylate (CH.sub.2CH.sub.2CO.sub.2A) fragments contained in the intermediate (XIa) and the average number of ethylenecarboxylate (CH.sub.2CH.sub.2CO.sub.2Na) fragments contained in the final amphoteric product (XIb) are increased.

[0232] Usually, a mixture of intermediates (XIa) [e.g. (XIa)] with different values for o, o, p, p and different substituents Y and Y is obtained at the end of the first step.

[0233] Same applies for the final products (XIb') [e.g. (XIb)] where mixtures of derivatives with different values for q, q, r, r and different substituents Z and Z are obtained at the end of the second step.

[0234] As an example, one can consider the reaction between the ethylenediamine-derived amine of type (III) and 2.5 equivalents of methyl acrylate followed by hydrolysis.

[0235] In this case the following mixture can be obtained:

##STR00012##

[0236] 3.3) Third Synthesis of (poly)aminocarboxylates

[0237] The reaction is conducted as described in part 3.1, except that the at least one starting amine (III) made from the at least one internal ketone K1 (I) is an amine (III) which contains one or two terminal 2-hydroxyethyl fragment(s) (CH.sub.2CH.sub.2OH) based on the nature of Y.

##STR00013##

[0238] What has been said in part 3.1 regarding the degree of alkylation applies in this case as well.

[0239] In the reaction scheme above:

[0240] o and p in the reactant (III) are integers from 1 to 20, preferably from 2 to 20, possibly from 4 to 20;

[0241] o, o, p and p in the product (XII) are integers ranging from 0 to 20, provided at least one of o and p is of at least 1; preferably, o, o, p and p in the product (XII) are integers ranging from 1 to 20, possibly from 2 to 20, and

[0242] the following equalities must be respected:

o+o=o

p+p=p.

[0243] The substituent Y in the reactant (III) represents a hydrogen atom or a 2-hydroxyethyl fragment (CH.sub.2CH.sub.2OH).

[0244] The substituent Z contained in the product (XII) represents: [0245] hydrogen or methylenecarboxylate (CH.sub.2CO.sub.2Na) when Y is hydrogen, [0246] 2-hydroxyethyl (CH.sub.2CH.sub.2OH) or the ether fragment CH.sub.2CH.sub.2OCH.sub.2CO.sub.2Na when Y is 2-hydroxyethyl fragment (CH.sub.2CH.sub.2OH).

[0247] The substituent Z represents hydrogen or methylenecarboxylate fragment CH.sub.2CO.sub.2Na.

[0248] As described in part 3.1, a mixture of products (XII) containing different numbers of methylenecarboxylate fragments (CH.sub.2CO.sub.2Na), which means different values for o, o, p and p and different substituents Z and Z, can be obtained.

[0249] As an example, one can consider the reaction between the aminoethylethanolamine-derived amine of type (III) and 1.5 equivalents of sodium monochloroacetate [(IX) with X=Cl]. In this case, the following mixture can be obtained:

##STR00014##

[0250] 3.4) Fourth Synthesis of (poly)aminocarboxylates

[0251] The reaction is conducted as described in part 3.2, except that the at least one starting amine (III) made from the at least one internal ketone K1 (I) is an amine (III) which contains one or two terminal 2-hydroxyethyl fragment(s) (CH.sub.2CH.sub.2OH) based on the nature of Y.

[0252] An exemplary reaction scheme is:

##STR00015## ##STR00016##

[0253] As in part 3.2, this exemplary reaction scheme can be generalized by replacing CH.sub.2=CH-CO.sub.2Me acrylate by hydrocarbyl acrylate of formula CH.sub.2CHCO.sub.2A, wherein A is as defined in part 3.2, and more generally by whatever acrylate derivative.

[0254] The substituent Y in the reactant (III) represents a hydrogen atom or a 2-hydroxyethyl fragment (CH.sub.2CH.sub.2OH).

[0255] In the above reaction scheme:

[0256] o and p in the reactant (III) are integers from 1 to 20, preferably from 2 to 20, possibly from 4 to 20;

[0257] o, o, p and p in the intermediate (XIIIa) [or in its non-represented generalization (XIIIa) wherein Me is replaced by substituent A] and q, q, r and r in the final product (XIIIb) [or in its non-represented generalization (XIIIb) wherein Me is replaced by substituent A] are integers ranging from 0 to 20 provided that at least one of o and p is of at least 1 and at least one of q and r is of at least 1.

[0258] Preferably, o, o, p and p in the intermediate (XIIIa) or (XIIIa'), and q, q, r and r in the final product (XIIIb) or (XIIIb') are integers ranging from 1 to 20, possibly from 2 to 20.

[0259] In addition, the following equalities must be respected:

o+o=q+q=o

and

p+p=r+r=p

[0260] The substituent Z in the intermediate (XIIIa) represents:

[0261] hydrogen or hydrocarbyl ethylenecarboxylate (CH.sub.2CH.sub.2CO.sub.2A) when Y is hydrogen, [0262] 2-hydroxyethyl fragment (CH.sub.2CH.sub.2OH) or the ether fragment CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CO.sub.2A when Y is CH.sub.2CH.sub.2OH.

[0263] The substituent Z in the intermediate (XIIIa) represents either hydrogen or hydrocarbyl ethylenecarboxylate (CH.sub.2CH.sub.2CO.sub.2A). Thus, for example, when (XIIIa) is (XIIIa), Z represents either hydrogen or methyl ethylenecarboxylate (CH.sub.2CH.sub.2CO.sub.2Me)

[0264] The substituent X in the end compound (XIIIb) [e.g. in the end compound (XIIIb)] represents: [0265] hydrogen or ethylenecarboxylate (CH.sub.2CH.sub.2CO.sub.2Na) if Y is hydrogen [0266] 2-hydroxyethyl fragment (CH.sub.2CH.sub.2OH), or the ether fragment CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CO.sub.2Na if Y is CH.sub.2CH.sub.2OH, while the substituent X in the end compound (XIIIb) represents either hydrogen or ethylenecarboxylate (CH.sub.2CH.sub.2CO.sub.2Na).

[0267] What has been said in part 3.2 regarding the impact on the alkylation degree of the molar ratio between the acrylate derivative and the substrate (III) used in the first reaction step applies here as well.

[0268] As described in part 3.2, a mixture of intermediates (XIIIa') [e.g. (XIIIa)] and a mixture of end products (XIIIb) [e.g. (XIIIb)] are usually obtained.

[0269] 4Aminoxides

[0270] 4.1) Synthesis of aminoxide Twin-Tail Amines

[0271] The end compound can be an aminoxide twin-tail amine, that is to say a twin-tail amine substituted by at least one aminoxide moiety. The aminoxide twin-tail amine can be substituted by one and only one or two and only two moiety(-ies).

[0272] At least one aminoxide twin-tail amine can be obtained from at least one twin-tail tert-amino amine (that is to say an amine that is itself substituted by at least one tert-amino group), which is itself previously obtained from at least one internal ketone K1.

[0273] To this effect, a certain twin-tail amine of formula (III) obtained from at least one internal ketone K1 of formula (I) is advantageously used as reagent, namely a twin-tail tert-amino amine of formula (III.sup.3):

##STR00017##

[0274] The following reaction scheme can be followed:

##STR00018##

[0275] In the above scheme, Y is either hydrogen or 3-dimethylaminopropyl fragment (CH.sub.2CH.sub.2CH.sub.2N(CH.sub.3).sub.2); Z is hydrogen when Y is hydrogen and Z is the 3-dimethylaminoxide propyl fragment (CH.sub.2CH.sub.2CH.sub.2N(CH.sub.3).sub.2O) when Y is 3-dimethylaminopropyl fragment (CH.sub.2CH.sub.2CH.sub.2N(CH.sub.3).sub.2).

[0276] This reaction can be conducted by contacting the twin-tail tert-amino amine (III.sup.3) obtained from the internal ketone K1 (I) with H.sub.2O.sub.2 (which can be used dissolved in aqueous solution) in a reaction zone at a temperature ranging from 15 C. to 400 C. and optionally in the presence of an added solvent. As examples of suitable solvents, one can mention methanol, ethanol, isopropanol, DMSO, acetonitrile, water, THF, dioxane or a mixture thereof.

[0277] In a preferred embodiment, H.sub.2O.sub.2 solution is progressively added into the reaction medium and can be used in molar excess with respect of the twin-tail tert-amino amine (III.sup.3). The excess of H.sub.2O.sub.2 can be decomposed at the end of the reaction using appropriate techniques well known by the skilled person of the art.

[0278] 4.2) Synthesis of aminoxide Gemini Compounds

[0279] The end product can be an aminoxide Gemini compound. Typically, the aminoxide Gemini compound comprises a central hydroxyl group which, in a two-dimensional representation of the formula of this compound, can form a symmetry axis provided some conditions are met on the nature of its substituents, as will immediately be made apparent from what follows.

[0280] In particular, at least one aminoxide Gemini compound of formula (XVIb) can be obtained from at least one internal ketone K1 of formula (I) using the ketone of formula (Vb) as intermediates.

[0281] It goes without saying that at least one aminoxide derivative of formula (XVIa) can likewise be obtained from at least one internal ketone K1 of formula (I) using the ketone of formula (Va) as intermediate.

[0282] A suitable reaction scheme is described hereinafter:

##STR00019## ##STR00020##

[0283] In a first step, the ketone (Va) or (Vb) or a mixture thereof is reduced respectively to the alcohol derivative (XVa) or (XVb) or a mixture thereof.

[0284] As example of suitable reductants that can be used for this first step, one can mention H2. In this case, the reaction must be conducted in the presence of a suitable transition metal (e.g. Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu) based catalyst (for example Pd/C). The reaction can be carried out under a hydrogen pressure (typically from 1 atm to 200 bar) and at temperature ranging from 15 C. to 400 C. Optionally, the reaction is conducted in the presence of an added solvent such as methanol, ethanol, isopropanol, tert-butanol, dioxane, dimethoxyethane, diglyme or a mixture thereof.

[0285] Another example of a suitable reductant for this first step is a secondary alcohol, preferably isopropanol which acts as a sacrificial reagent. In this case, the reaction requires the need of a metal based (e.g. Ni, Al, In, Ru, Zr) catalyst (e.g. aluminum isopropoxide Al(O-i-Pr).sub.3) and acetone is formed as by-product. Importantly acetone can be removed during the reaction thanks to distillation in order to displace equilibrium toward the formation of (XVa) and (XVb).

[0286] The second step consists in the oxidation using H.sub.2O.sub.2 of the tertiary amine group of the compound of formula (XVa) and/or the compound of formula (XVb) to form respectively the aminoxide derivative of formula (XVIa) and/or the aminoxide Gemini compound of formula (XVIb).

[0287] This second step can be carried out as described in part 4.1.

[0288] R.sub.1, R.sub.2 and R.sub.3 have the same definitions as in part 2.2.

[0289] 5Making betaines and sultaines from Internal Ketones K1

[0290] 5.1) Synthesis of dibetaine Twin-Tail amines and disultaine Twin-Tail amines

[0291] The end compound can be a dibetaine twin-tail amine, that is to say a twin-tail amine substituted by two betaine moieties.

[0292] The end compound can also be a disultaine twin-tail amine, that is to say a twin-tail amine comprising two sultaine moieties.

[0293] At least one dibetaine twin-tail amine can be obtained from at least one twin-tail di-tert-amino amine (that is to say a twin-tail amine that is itself substituted by two tert-amino groups) -which twin-tail di-tert-amino amine is itself previously obtained from at least one internal ketone K1 that is advantageously synthesized by the process P- by reacting said twin-tail di-tert-amino amine with a compound of formula

X-Alk-R.sub.0

[0294] wherein:

[0295] X is a leaving group,

[0296] Alk is an alkylene group, and

[0297] R.sub.0 is CO.sub.2M with M being an alkaline metal.

[0298] Methylene is preferred as the alkylene group Alk.

[0299] Na is preferred as the alkaline metal M.

[0300] The leaving group X is typically a halide such as Cl, Br or I, methylsulfate (SO.sub.4Me), sulfate (SO.sub.4.sup.), a sulfonate derivative such as methanesulfonate (O.sub.3SCH.sub.3), para-toluenesulfonate (O.sub.3SC.sub.7H.sub.7) or trifluoromethanesulfonate (O.sub.3SCF.sub.3).

[0301] At least one disultaine twin-tail amine can similarly be obtained from at least one twin-tail di-tert-amino amine which twin-tail di-tert-amino amine is itself previously obtained from at least one internal ketone K1 advantageously synthesized by the process P, by reacting said twin-tail di-tert-amino amine with a compound of formula

X-Alk-R.sub.0

[0302] wherein:

[0303] X is a leaving group,

[0304] Alk is an alkylene group, and

[0305] R.sub.0 is CH(OH)CH.sub.2SO.sub.3M with M being an alkaline metal.

[0306] Preferred X, Alk and M to make the disultaine twin-tail amine are the same as the ones preferred to make the dibetaine twin-tail amine.

[0307] To make the dibetaine and/or the disultaine, at least one certain twin-tail amine of formula (III) is advantageously used as reactant, namely a twin-tail amine of formula (III.sup.4):

##STR00021##

wherein R.sub.n and R.sub.m have the same meaning as R.sub.n and R.sub.m of the internal ketone K1 of formula (I).

[0308] Then, at least one dibetaine of formula (XVIIa) and/or at least one disultaine of formula (XVIIb) can be prepared from at least one twin-tail amine of formula (III.sup.4) according to the following scheme:

##STR00022##

[0309] In the above reaction scheme, X is as previously defined.

[0310] The twin-tail amine (III.sup.4) obtained according to part 1.1 from the internal ketone K1 (I) is reacted with the alkylating compound (IX) to afford the betaine (XVIIa) or the sultane (XVIIb) depending on the nature of (IX).

[0311] Betaine (XVIIa) is obtained when R.sub.0is CO.sub.2Na and sultaine (XVIIb) is obtained when R.sub.0=CH(OH)CH.sub.2SO.sub.3Na. A mixture of betaine and sultaine is obtained when using a mixture of reagents (IX) including at least one reagent wherein R.sub.0 is CO.sub.2Na and at least one reagent wherein R.sub.0=CH(OH)-CH.sub.2SO.sub.3Na.

[0312] The reaction is usually conducted by contacting the reactants in a reaction zone at temperature from 15 C. to 400 C. and optionally in the presence of an added solvent. As examples of suitable solvents, one can mention methanol, ethanol, isopropanol, DMSO, acetonitrile, water, THF, dioxane and mixtures thereof.

[0313] In a preferred embodiment, the pH of the reaction mixture is maintained during the course of the reaction from 8.5 and 9.5. This adjustment can be done by adding required amounts of concentrated NaOH and/or HCl aqueous solutions to the reaction medium during the course of the reaction.

[0314] 5.2) Synthesis of betaine Derivatives and sultaine Derivatives, Especially of betaine Gemini Derivatives and sultaine Gemini Derivatives

[0315] The end product can be a betaine Gemini compound or a sultaine Gemini compound. Typically, the betaine or sultaine Gemini compound comprises a central hydroxyl group which, in a two-dimensional representation of the formula of this compound, can form a symmetry axis provided some conditions are met on the nature of its substituents, as will immediately be made apparent from what follows.

[0316] At least one dibetaine and/or at least one disultaine can be obtained from at least one ketone having one or both of its carbonyl-adjacent carbon atoms substituted by an amine-containing group, in particular from at least one ketone of formula (Va) and/or at least one ketone of formula (Vb), the preparation of which from the internal ketone K1 of formula (I) has been described in part 1.2.

[0317] At least one dibetaine and/or at least one disultaine can be obtained from at least one ketone having both of its carbonyl-adjacent carbon atoms substituted by a tert-amino-containing group, in particular from at least one ketone of formula (Vb), the preparation of which from the internal ketone K1 of formula (I) has already been described in part 1.2.

[0318] At least one monobetaine and/or at least one monosultaine can be obtained from at least one ketone having one (and only one) of its carbonyl-adjacent carbon atoms substituted by a tert-amino-containing group, in particular from at least one ketone of formula (Va), the preparation of which from the internal ketone K1 of formula (I) has already been described in pad 1.2.

[0319] To this effect, the following reaction scheme can be followed:

##STR00023## ##STR00024##

[0320] The first step is identical as in part 4.2.

[0321] The second step is carried out as in part 5.1.

[0322] Betaine (XVIII) or sultaine (XIX) is obtained depending on the nature of R.sub.0 in the alkylating agent (IX).

[0323] R.sub.1, R.sub.2 and R.sub.3 have the same definition as in part 2.2.

[0324] 6Making anionic Surfactants from Internal Ketones K1

[0325] Synthesis of dicarboxylate Salt Derivatives

[0326] The end compound can be an anionic surfactant.

[0327] For example, it can be a dicarboxylate salt derivative of formula

##STR00025##

[0328] wherein X is Li, Na, K, Cs, Fr, NH.sub.4, triethanolamine or other monovalent or polyvalent metal or group able to form the cationic counterion of the salt.

[0329] In particular, X is Li, Na or K.

[0330] The following reaction scheme can be followed:

##STR00026##

[0331] In a first step, at least one ketone K1 of formula (I) as previously defined is condensed with at least one diester (XX) derived from tartaric acid in which R denotes a linear or branched alkyl radical containing from 1 to 6 carbon atoms.

[0332] The reaction is realized by contacting the ketone and the diester in a reaction zone at a temperature ranging from 15 C. to 400 C. The reaction can be optionally carried out in the presence of an added solvent such as toluene, xylene, dioxane, diglyme, hexanes, petroleum ether, DMSO or a mixture thereof.

[0333] In a preferred embodiment, an acid catalyst (either Bronsted or Lewis acid) is employed to accelerate the reaction. One can mention for example H.sub.2SO.sub.4, HCl, triflic acid, p-toluenesulfonic acid, AlCl.sub.3, metal triflate compounds such as aluminium triflate, bismuth triflate, heterogeneous solid acids such as Amberlyst resins and zeolites.

[0334] The water generated during the reaction can be trapped thanks to a Dean-Stark apparatus in order to displace the reaction equilibrium toward the formation of intermediate product (XXI).

[0335] At the end of the reaction, this intermediate (XXI) can be isolated after solvent and catalyst removal using standard work-up techniques well known by the skilled person of the art so that no further detail needs to be given here.

[0336] In a second step, the ketal diester (XXI) is hydrolysed by conducting the reaction in a basic aqueous XOH or X(OH).sub.2 solution (X as above defined, in particular X=Li, Na, K, Cs, Mg, Ca) at temperature ranging from 15 C. to 400 C. to afford the final ketal carboxylate product (XXII) along with R-OH as by-product.

[0337] 7Making Non-Ionic Surfactants from Internal Ketones K1

[0338] The end compound can be a non-ionic surfactant.

[0339] 7.1) First Synthesis of Non-Ionic Surfactants

[0340] The end compound can be a compound of formula (XXV)

##STR00027##

[0341] wherein: [0342] m, m, n and n are integers ranging from 0 to 40 with the proviso that at least one of m, m, n and n is of at least 1, and m+m+n+n ranges preferably from 2 to 40, possibly from 4 to 20, [0343] R.sub.m and R.sub.n are as defined in part 1.1, [0344] R is nil (meaning that there is no substituent on the benzene rings) or R is at least one C.sub.1-C.sub.24 alkoxy or a linear or branched C.sub.1-C.sub.24 hydrocarbon group, which alkoxy or hydrocarbon group can be optionally interrupted and/or substituted by one or more heteroatoms or heteroatom containing groups.

[0345] By specifying that R can be at least one linear or branched hydrocarbon group, it is intended to denote that the benzene rings of compound (XXV) can be substituted not only by one substituent but also by several one linear or branched hydrocarbon substituents.

[0346] Two examples of possible R substituents are methyl and methoxy.

[0347] The following reaction scheme can be followed:

##STR00028##

[0348] Accordingly, in a first step, at least one ketone K1 of formula (I) is first condensed with 2 equivalents of a substituted or unsubstituted phenolic compound (XXII) (e.g. when R is nil, (XXII) is phenol, while when R is methyl or methoxy, (XXII) is respectively cresol or guaiacol) in order to afford the bi-phenolic derivative (XXIV).

[0349] The reaction can be carried out by contacted both reactants in a reaction zone at a temperature ranging from 15 C. to 400 C. optionally in the presence of an added solvent. An excess of the phenolic derivative (XXIII) can be used for this reaction and the reactant in excess can be removed later during the subsequent work-up and recycled.

[0350] An acid catalyst (either Bronsted or Lewis acid) can be employed to accelerate the reaction. One can mention for example H.sub.2SO.sub.4, HCl, triflic acid, p-toluenesulfonic acid, AlCl.sub.3, metal triflate compounds such as aluminium triflate and bismuth triflate, heterogeneous solid acids (such as Amberlyst resins, zeolites, etc.

[0351] Water generated during this step can be trapped thanks to a Dean-Stark apparatus is order to drive the reaction equilibrium toward the desired product (XXIV).

[0352] The intermediate product (XXIV) can be isolated using standard work-up techniques well known by the skilled person of the art so that no further detail needs to be given here.

[0353] In a second step, the di-phenolic derivative (XXIV) is condensed with m+m equivalents of propylene oxide and/or by, possibly followed by, n+n equivalents of ethylene oxide using standard conditions for alkoxylation of di-phenolic derivatives in order to afford the non-ionic surfactant (XXV).

[0354] Other non-ionic surfactants than (XXV) can be prepared according to the same reaction scheme but using another aromatic alcohol than (XXIII) as reagent.

[0355] As examples of other aromatic alcohols, one can mention naphthols and aromatic diols such as catechol and resorcinol.

[0356] 7.2) Second Synthesis of Non-Ionic Surfactants

[0357] The end compound can be a non-ionic surfactant of formula (XXVIIa)

##STR00029##

[0358] or a non-ionic surfactant of formula (XXVIIb)

##STR00030##

[0359] wherein:

[0360] R.sub.m and R.sub.n represent an aliphatic group, generally a C.sub.2-C.sub.26aliphatic group, very often a C.sub.2-C.sub.18 group, often a C.sub.5-C.sub.16 group,

[0361] o, o, o, p, p and p are as defined hereinafter.

##STR00031##

[0362] In the above scheme, 1) m propylene oxide | 2) n ethylene oxide should be broadly understood, not implying that both propoxylation and ethoxylation must take place (otherwise said, m or n can be equal to 0), a fortiori not implying that propoxylation must take place before ethoxylation, although this is an embodiment that may be preferred.

[0363] In a first step, at least one ketone K1 of formula (I) is condensed with formaldehyde (CH.sub.2O). The condensation takes advantageously place in a reaction zone at a temperature ranging from 20 C. to 400 C. The reaction can be carried out in the presence of a basic catalyst, such as for example NaOH, KOH, MgO, Na.sub.2CO.sub.3, NaOMe, NaOEt, tBuOK or NEt.sub.3 wherein Me is methyl, Et is ethyl and Bu is butyl. The reaction can optionally be carried out in a solvent such as methanol, ethanol, isopropanol, DMSO, THF, methyltetrahydrofuran, toluene, a xylene, water, dioxane or a mixture thereof.

[0364] For this first reaction step, formaldehyde can be used in excess and the reactant in excess can be recovered and recycled.

[0365] The aldol products (XXVIa), (XXVIb) or their mixture can be isolated using standard work-up techniques well known by the skilled person of the art.

[0366] In the second step, at least one product (XXVIa) and/or (XXVIb) is/are condensed with m+n equivalents of alkylene oxide (m equivalents of propylene oxide and/or n equivalents of ethylene oxide, e.g. m equivalents of propylene oxide followed by n equivalents of ethylene oxide) using standard conditions for alkoxylation of alcohols in order to afford the non-ionic surfactants (XXVIIa) and/or (XXVIIb).

[0367] In the above equation scheme, m and n are integers ranging from 0 to 40 but m and n cannot be both equal to 0.

[0368] o, p, o, p, o and p are integers ranging from 0 to 40 and the following equalities must be respected:

o+o+o=m

p+p+p=n

[0369] 7.3) Third Synthesis of Non-Ionic Surfactants

[0370] The end compound can be a compound of formula (XXIX)

##STR00032##

[0371] wherein:

[0372] R.sub.n and R.sub.m are as defined in part 1.1,

[0373] m, m, n and n are as defined hereinafter.

[0374] To this end, in a first step, at least one internal ketone K1 of formula (I) is condensed with pentaerythritol to afford at least one intermediate (XXVIII).

##STR00033##

[0375] This reaction is advantageously carried out by contacted both reactants in a reaction zone at a temperature ranging from 15 C. to 400 C. The reaction can be optionally carried out in the presence of an added solvent such as toluene, xylene, dioxane, diglyme, hexane, petroleum ether, DMSO or a mixture thereof.

[0376] In a preferred embodiment, an acid catalyst (either Bronsted or Lewis acid) is employed to accelerate the reaction. One can mention for example: H.sub.2SO.sub.4, HCl, triflic acid, p-toluenesulfonic acid, AlCl.sub.3, metal triflate compounds such as aluminium triflate, bismuth triflate, heterogeneous solid acids such as Amberlyst resins, zeolites, etc.

[0377] The water generated during the reaction can be trapped thanks to a Dean-Stark apparatus in order to displace the reaction equilibrium toward the formation of the at least one intermediate (XXVIII).

[0378] At the end of the reaction, this intermediate (XXVIII) can be isolated after solvent and catalyst removal using standard work-up techniques well known by the skilled person of the art so that no further detail needs to be given here.

[0379] In the second step, the at least one intermediate (XXVIII) is condensed with m+n equivalents of alkylene oxide (m equivalents of propylene oxide and/or n equivalents of ethylene oxide, e.g. m equivalents of propylene oxide followed by n equivalents of ethylene oxide) using standard conditions for alkoxylation of alcohols in order to afford the non-ionic surfactant (XXIX)

[0380] The reaction taking place in the second step can be represented as follows:

##STR00034##

[0381] In the above reaction scheme, 1) m propylene oxide | 2) n ethylene oxide should be broadly understood, not implying that both propoxylation and ethoxylation must take place (otherwise said, m or n can be equal to 0), a fortiori not implying that propoxylation must take place before ethoxylation, although this is an embodiment that may be preferred.

[0382] As a matter of fact, in the above reaction scheme, m and n are integers ranging from 0 to 40 provided at least one of m and n is of at least 1.

[0383] m, m, n and n are integers ranging from 0 to 40 and the following equalities must be respected:

m+m=m

n+n=n

[0384] 8Making Intermediates and Monomers from Internal Ketones K1

[0385] 8.1) Synthesis of Beta Diketones

[0386] The at least one end compound can be a beta diketone of formula (XXXIa) and/or a beta diketone of formula (XXXIb), such as the reaction products of the following reaction involving at least one internal ketone K1 of formula (I):

##STR00035##

[0387] Accordingly, at least one ketone K1 of formula (I) with R.sub.m and R.sub.n as previously defined is reacted with at least one acrylate derivative (XXX) to obtain at least one diketone (XXXIa) and/or at least one diketone (XXXIb).

[0388] In the above reaction scheme, the substituent R is selected from a linear or branched hydrocarbon radical having from 1 to 24 carbon atoms which can be optionally substituted and/or interrupted by one or more heteroatoms or heteroatom containing groups. For example, R can be selected from CH.sub.3, CH.sub.2CH.sub.3, propyl, isopropyl, butyl, sec-butyl, isobutyl and tert-butyl.

[0389] The substituent R.sub.1 is selected from hydrogen and a linear or branched hydrocarbon radical having from 1 to 24 carbon atoms which can be optionally substituted and/or interrupted by one or more heteroatoms or heteroatom containing groups. For example, R.sub.1 can be H, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl or tert-butyl.

[0390] The reaction zone takes advantageously place at a temperature ranging from 15 C. to 400 C.

[0391] At least one equivalent relative to the ketone K1 of formula (I) of a base may be required for the reaction to occur. As example of suitable bases to carry out the reaction, one can mention NaOMe, tert-BuOK, NaOEt, KOH or NaOH.

[0392] During the course of the reaction an alcohol R-OH is generated which can optionally be distilled off from the reaction mixture.

[0393] In addition, a suitable solvent can be used for the reaction such as for example methanol, ethanol, isopropanol, THF, DMSO, methyltetrahydrofuran, dioxane or diglyme.

[0394] At the end of the reaction, the at least one diketone compound (XXXIa) and/or the at least one diketone compound (XXXIb) are possibly obtained in their deprotonated form so that an acidic quench is needed to recover the neutral derivatives (XXXIa) and/or (XXXIb).

[0395] 8.2) Synthesis of a First Monomer

[0396] The at least one end compound can be a compound of formula (XXXIII). Such a compound, which contains an ethylenic carbon-carbon double bond, is suitable to undergo a radical polymerization.

##STR00036##

[0397] R.sub.m and R.sub.n are as defined in part 1.1, and m and n are integers ranging from 0 to 40 but m and n cannot be both equal to 0.

[0398] R and R.sub.1 have the same meaning as in part 8.1.

[0399] According to the above reaction scheme, at least one ketone K1 of formula (I) is hydrogenated using standard hydrogenation conditions, then condensed with m equivalents of propylene oxide and/or n equivalents or ethylene oxide (e.g. with m equivalents of propylene oxide followed by n equivalents of ethylene oxide).

[0400] Standard conditions for secondary alcohols alkoxylations are generally used in order to afford the at least one intermediate (XXXII).

[0401] The intermediate (XXXII) is then reacted with at least one acrylate derivative (XXX) according to a transesterification reaction in order to afford at least one other acrylate derivative (XXXIII).

[0402] This last reaction is advantageously carried out by contacting both reactants in a reaction zone at a temperature ranging from 15 C. to 400 C.

[0403] The reaction can be catalysed either by acids or by bases. As example of suitable acids, one can mention H.sub.2SO.sub.4, HCl, triflic acid, p-toluenesulfonic acid, AllC.sub.3, metal triflate compounds such as aluminium triflate, bismuth triflate, heterogeneous solid acids such as Amberlyst resins, zeolites etc.

[0404] As examples of suitable bases, one can mention NaOH, KOH, MgO, Na.sub.2CO.sub.3, NaOMe, NaOEt, tBuOK or NEt.sub.3wherein Me is methyl, Et is ethyl and tBu is tert-butyl.

[0405] The reaction can be carried out in a suitable solvent such as methanol, ethanol, isopropanol, DMSO, THF, methyltetrahydrofuran, toluene, xylenes, water, dioxane or a mixture thereof.

[0406] The acrylate derivative (XXX) can be added progressively in the reaction medium in order to avoid side-polymerization to occur.

[0407] 8.3) Synthesis of a Second Monomer

[0408] The at least one end compound can be a compound of formula (XXXIV)

##STR00037##

[0409] Such a compound, which also contains an ethylenic carbon-carbon double bond, is likewise suitable to undergo a radical polymerization.

[0410] It can be prepared from a certain twin-tail amine of formula (III), namely an a primary of secondary twin-tail amine of formula (III.sup.5)

##STR00038##

[0411] wherein:

[0412] R.sub.m and R.sub.n are as defined in part 1.1;

[0413] R.sub.2 is selected from hydrogen or a linear or branched hydrocarbon radical having 1 to 24 carbon atoms which can be optionally substituted and/or interrupted by one or more heteroatoms or hereroatom containing groups; for example, R.sub.2 can be selected from H, CH.sub.3, CH.sub.2CH.sub.3, propyl, isopropyl, butyl, sec-butyl, isobutyl and tert-butyl.

[0414] At least one amine (III.sup.5) prepared according to part 1.1 is reacted with at least one acrylate derivative (XXX) under suitable conditions that prevent conjugate addition to occur in order to afford at least one acrylamide (XXXIV).

[0415] The reaction scheme is as follows:

##STR00039##

[0416] In compounds (XXX) and (XXXIV), R and R.sub.1 have the same meaning as in part 8.1.

[0417] The reaction is advantageously carried out by contacting both reactants in a reaction zone at a temperature ranging from 15 C. to 400 C.

[0418] The reaction can be catalysed by acids or bases. As example of suitable acids one can mention H.sub.2SO.sub.4, HCl, triflic acid, p-toluenesulfonic acid, AlCl.sub.3, metal triflate compounds (such as aluminium triflate, bismuth triflate), heterogeneous solid acids such as Amberlyst resins, zeolites, etc. As examples of suitable bases, one can mention NaOH, KOH, MgO, Na.sub.2CO.sub.3, NaOMe, NaOEt, tBuOK, NEt.sub.3 etc.

[0419] The reaction can be carried out in a suitable solvent such as methanol, ethanol, isopropanol, DMSO, THF, methyltetrahydrofuran, toluene, xylenes, water, dioxane or a mixture thereof.

[0420] As an alcohol ROH is generated during the reaction as a side product, it can be removed thanks to distillation in order to drive the reaction toward the desired product (XXXIV).

[0421] The acrylate derivative (XXX) can be added progressively in the reaction medium in order to avoid side-polymerization to occur.

[0422] 8.4) Synthesis of a Branched Fatty Acid

[0423] The end compound can be a branched fatty acid of formula (XXXV), as obtainable by the following reaction:

##STR00040##

[0424] In a first stage, at least one ketone K1 of formula (I) with R.sub.m and R.sub.n being defined as in part 1.1 is hydrogenated to afford the corresponding secondary alcohol. Standard hydrogenation conditions can be used.

[0425] This alcohol is then engaged in a carbonylation reaction to afford at least one end product (XXXV).

[0426] The carbonylation reaction is advantageously carried out by reacting the secondary alcohol under a CO pressure (typically from 1 atm to 200 bar), in a reaction zone at a temperature usually ranging from 15 C. to 400 C.

[0427] The reaction can be optionally carried out in the presence of a suitable solvent and the skilled person of the art will choose the most suitable solvent. Importantly, the reaction can be catalysed by transition metal based catalysts (for example Co, Rh, Ir and Pd based homogeneous catalyst).

[0428] Usually, a halide based promoter is necessary for the reaction to occur. Preferably, the promoter is an iodide, such as HI.

[0429] Importantly, during the reaction significant isomerization may occur and mixture of isomeric products (XXXV) may be obtained having their alkyl substituents R.sub.m and R.sub.n different from the initial alkyl substituents R.sub.m and R.sub.n present in the starting ketone K1 of formula (I). Thus, in formula (XXXV) specifically, R.sub.m and R.sub.n fall under the same general definition of R.sub.m and R.sub.n although being possibly specifically different from initial R.sub.m and R.sub.n of starting ketone K1 of formula (I).

[0430] 8.5) Synthesis of Polyamines

[0431] The end compound can be a polyamine, especially a polyamine of formula (XXXVII):

##STR00041##

[0432] Such a polyamine can be prepared using at least one internal ketone K1 of formula (I) as starting material, with R.sub.m and R.sub.n being defined as in part 1.2, according to the following reaction scheme:

##STR00042##

[0433] X.sub.1, X.sub.2, X.sub.3 and X.sub.4 independently represent a hydrogen atom or CH.sub.2CH.sub.2CN but all cannot be hydrogen, meaning that at least one of X1, X.sub.2, X.sub.3 and X.sub.4 is CH.sub.2CH.sub.2CN.

[0434] Y.sub.1, Y.sub.2, Y.sub.3 and Y.sub.4 independently represent a hydrogen atom or CH.sub.2CH.sub.2CH.sub.2NH.sub.2 but all cannot be hydrogen, meaning that at least one of Y.sub.1, Y.sub.2, Y.sub.3 and Y.sub.4 is CH.sub.2CH.sub.2CH.sub.2NH.sub.2.

[0435] Z can be either a carbonyl group (CO) or a carbinol (CHOH) group or a mixture thereof.

[0436] Thus, at least one ketone K1 of formula (I) is first condensed with acrylonitrile to afford at least one intermediate of formula (XXXVI).

[0437] The reaction is advantageously carried out by contacting both reactants in a reaction zone at a temperature ranging generally from 15 C. to 400 C. and in the presence of an optional solvent such as methanol, ethanol, isopropanol, DMSO, THF, methyltetrahydrofuran, toluene, a xylene, water, dioxane or a mixture thereof.

[0438] The reaction can be catalysed by a suitable base such as for example NaOH, KOH, MgO, Na.sub.2CO.sub.3, NaOMe, NaOEt, tBuOK or NEt.sub.3.

[0439] Optionally and possibly preferably, the reaction is carried out by adding acrylonitrile progressively in the reaction medium in order to avoid side polymerizations, and acrylonitrile can be used in stoichiometric excess. The acrylonitrile in excess can be recovered and recycled.

[0440] Mixture of products (XXXVI) with different substituents X.sub.n (n=1 to 4) can be obtained.

[0441] In a second step, at least one (poly)nitrile derivative (XXXVI) is hydrogenated to afford the at least one corresponding (poly)amine (XXXVII). Usually, standard conditions for nitrile hydrogenation are used, for example under hydrogen pressure ranging from 1 atm to 200 bar, at a temperature ranging from 15 C. to 400 C., in the presence of an optional solvent and using advantageously a transition metal based catalyst (e.g. Nickel Raney).

[0442] A mixture of products (XXXVII) with different Yn (n=1 to 4) and Z groups can be obtained.

[0443] Special Embodiments of the Method M

[0444] In certain special embodiments of the invented method M:

[0445] when the internal ketone K1 is caused to react by being subjected to a hydrogenation reaction to obtain a secondary alcohol, the so-obtained secondary alcohol may be an intermediate that is in turn caused to react in accordance with a single or multiple reaction scheme that does not include a dehydration reaction that would convert said internal secondary alcohol into an internal olefin as an other intermediate or as the end compound;

[0446] the end compound may differ from an a-sulfocarbonyl compound C1* of of formula (1)

##STR00043##

from an -sulfocarbonyl compound C2* of formula (2)

##STR00044##

[0447] and from a mixture thereof,

[0448] wherein in above formulae (1) and (2) [0449] R.sub.1, R.sub.3 and R.sub.5, which may be the same or different at each occurrence, are hydrogen or a linear or branched alkyl chain having 1 to 20 carbon atoms, [0450] R.sub.2 and R.sub.4, which may be the same or different at each occurrence, are a linear or branched alkyl group having 4 to 24 carbon atoms and in which the alkyl chain may comprise one or more cycloaliphatic groups, and X is H or a cation forming a salt with the sulfonate group; [0451] the end compound may differ from a surfactant C3* of formula (3)

##STR00045##

from a diamine C4* of formula (4)

##STR00046##

[0452] and from a mixture thereof,

[0453] wherein in above formulae (3) and (4)

[0454] each of R.sup.a and R.sup.b, which are identical or different, is a linear or branched, saturated or unsaturated, hydrocarbon chain that may be interrupted and/or substituted by at least a monocyclic or polycyclic group

[0455] each of R.sup.c and R.sup.d, which are identical or different, is a linear or branched, alkyl chain having 1 to 10 carbon atoms

[0456] each of (E.sup.1) and (E.sup.2) is a divalent hydrocarbon radical linear or branched, not substituted or substituted,

[0457] A is: a carboxylate group COO.sup., optionally in all or part in its protonated form COOH; or a sulfonate group SO.sub.3, optionally in all or part in its protonated form SO.sub.3H;

[0458] the end compound may differ from a secondary alcohol C5; it may notably differ from a secondary alcohol C5* comprising as sole functional group(s) an internal alcohol group and, optionally in addition, one or more alkene and/or alkyne groups

##STR00047##

[0459] the end compound may differ from an internal olefin C6*;

[0460] the end compound may also differ from an a-sulfocarbonyl compound C7*

[0461] The method M differs advantageously from the methods that are disclosed in International application PCT/EP2016/060106 filed on May 4, 2016, in International application PCT/EP2016/060070 filed on May 4, 2016, in European patent application 16305409.1 filed on Apr. 8, 2016, in European patent application 16305410.9 filed on Apr. 8, 2016 and in European patent application 16306069.2 filed on Aug. 19, 2016. The whole content of all these applications is herein incorporated for all purposes, especially for disclaiming purposes, if useful.

[0462] Valuable Compounds Preparable by the Method M

[0463] It is a last object of the present invention to provide new valuable compounds, with a particular interest for surfactants.

[0464] This last object of the present invention is achieved by a variety of compounds, notably surfactants, susceptible of being prepared by the method M as above described.

[0465] Many of these compounds can be characterized by their twin-tail or Gemini structure.

[0466] Thus, the present invention concerns also:

[0467] a compound of formula (III) as previously described, in particular a compound of formula (III), a compound of formula (III), a compound of formula (III.sup.3), a compound of formula (III.sup.4) ora compound of formula (III.sup.5) as previously described;

[0468] a compound of formula (Va) as previously described, a compound of formula (Vb) as previously described or a mixture thereof;

[0469] a compound of formula (VII) as previously described;

[0470] a compound of formula (VIIIa) as previously described, a compound of formula (VIIIb) as previously described or a mixture thereof;

[0471] a compound of formula (X) as previously described;

[0472] a compound or a mixture of compounds of general formula (XIa) as previously described;

[0473] a compound or a mixture of compounds of general formula (XIb) as previously described;

[0474] a compound of a mixture of compounds of general formula (XII) as previously described;

[0475] a compound of a mixture of compounds of general formula (XIIIa) as previously described;

[0476] a compound of a mixture of compounds of general formula (XIIIb) as previously described;

[0477] a compound of formula (XIV) as previously described;

[0478] a compound of formula (XVa) as previously described, a compound of formula (XVb) as previously described or a mixture thereof;

[0479] a compound of formula (XVIa) as previously described, a compound of formula (XVIb) as previously described or a mixture thereof;

[0480] a compound of formula (XVIIa) as previously described;

[0481] a compound of formula (XVIIb) as previously described;

[0482] a compound of formula (XVIIIa) as previously described, a compound of formula (XVIIIb) as previously described or a mixture thereof;

[0483] a compound of formula (XIXa) as previously described, a compound of formula (XIXb) as previously described or a mixture thereof;

[0484] a compound of formula (XXI) as previously described;

[0485] a compound of formula (XXII) as previously described;

[0486] a compound of formula (XXIV) as previously described;

[0487] a compound of formula (XXV) as previously described;

[0488] a compound of formula (XXVIa) as previously described, a compound of formula (XXVIb) as previously described or a mixture thereof;

[0489] a compound of formula (XXVIIa) as previously described, a compound of formula (XXVIIb) as previously described or a mixture thereof;

[0490] a compound of formula (XXVIII) as previously described;

[0491] a compound of formula (XXIX) as previously described;

[0492] a compound of formula (XXXIa) as previously described, a compound of formula (XXXIb) as previously described or a mixture thereof;

[0493] a compound of formula (XXXII) as previously described;

[0494] a compound of formula (XXXIII) as previously described;

[0495] a compound of formula (XXXIV) as previously described;

[0496] a compound or a mixture of compounds of general formula (XXXV) as previously described;

[0497] a compound or or a mixture of compounds of general formula (XXXVI) as previously described; and

[0498] a compound or or a mixture of compounds of general formula (XXXVII) as previously described.

[0499] Summary of the Advantages of the Present Invention

[0500] The process P of the present invention thus offers an easy access to internal ketones K1. The process P yields the desired ketones in high yield with only minor amounts (if at all) of undesired by-products being obtained and which can be easily separated from the reaction mixture.

[0501] The internal ketones K1 may be separated from the reaction mixture by convenient and economic processes and the catalytic material can be used for several catalytic cycles without significant deterioration of catalytic activity.

[0502] As thoroughly shown, the internal ketones K1 are versatile starting materials that can be easily converted into a variety of valuable end compounds through the method M.

[0503] The method M of the present invention, since it is based on the process P, thus likewise offers an easier access to these compounds.

[0504] Many end compounds obtainable by the method M are useful as surfactants.

[0505] Many other compounds obtainable by the method M are useful as intermediates that can in turn be converted into valuable end compounds like surfactants.

[0506] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

[0507] The following examples further explain the present invention.

EXAMPLES

Example 1

Ketonization of C.SUB.8.-C.SUB.18 .Fatty Acids Cut Using Magnetite Fe3O4 as the Catalyst

[0508] The reaction is carried out under an inert atmosphere of argon.

[0509] In a 750 mL reactor equipped with a mechanical stirrer, a Dean-Stark apparatus to trap water generated during the reaction and an addition funnel, are dispensed 40 g of product C15-C35 ketones (made through a preliminary ketonization of the starting C8-C18 fatty acids) and 9.3 g (0.040 mole) of magnetite Fe3O4.

[0510] The addition funnel of the reactor is filled with 200 g (0.970 mole) of melted fatty acids (C8: 7 wt %, C10: 8 wt %, C12: 48 wt %, C14: 17 wt %, C16: 10 wt %, C18: 10 wt %).

[0511] The reaction mixture is then heated at 330 C. under stirring (500 rpm) and 200 g (0.970 mole) of the melted fatty acids is slowly introduced into the reactor such that the temperature of the reaction medium doesn't fall down below 320 C. (for example with an addition flow rate of around 25 g fatty acids/hour).

[0512] Practically this can be done also through the successive slow additions (1 hour per addition) of 4 portions of 50 g (60 mL) of melted fatty acids followed by 1 hour of stirring at 330 C. after each addition.

[0513] At the end of the last addition, the crude medium is stirred at 330 C. during an additional hour and the reaction progress is monitored through FTIR.

[0514] At the end of the reaction when the intermediate iron complex is not detected anymore through FTIR (absorption bands at 1550 cm-1 and 1408 cm-1), the mixture is allowed to cool down at room temperature and dissolved in 400 mL of CHCl3.

[0515] The obtained solution is filtered through a path of 400 g of silica gel followed by elution with 5 liters of CHCI3 in order to remove iron oxide.

[0516] The chloroform is evaporated under vacuum and the crude product is dried overnight under 10 mbar at 50 C. to obtain 207 g of ketone (which contains 167 g (0.475 mole) of product generated through ketonization of the 200 g of fatty acids in addition to the 40 g of fatty ketones that have been dispensed initially in the reactor) as a light brown wax corresponding to a crude yield of 98%.

[0517] Analysis of the crude shows a GC purity of 96% (impurities being mainly hydrocarbons) with the following composition for the ketones cut:

[0518] C15: 0.5 wt %, C17: 1.3 wt %, C19: 8.4 wt %, C21: 11.4 wt %, C23: 28.4 wt %, C25: 19.0 wt %, C27: 13.0 wt %, C29: 11.7 wt %, C31: 3.7 wt %, C33: 1.6 wt %, C35: 0.9 wt %.

Example 2

Ketonization of C8-C18 Fatty Acids Cut Using Fe(III) Oxide Fe2O3 as the Catalyst

[0519] The reaction is carried out under an inert atmosphere of argon.

[0520] In a 750 mL reactor equipped with a mechanical stirrer, a Dean-Stark apparatus to trap water generated during the reaction and an addition funnel, are dispensed 40 g of product C15-C35 ketones (made through a previous ketonization of the starting C8-C18 fatty acids) and 9.74 g (0.060 mole) of Fe2O3.

[0521] The addition funnel is filled with 200 g (0.970 mole) of melted fatty acids (C8: 7 wt %, C10: 8 wt %, C12: 48 wt %, C14: 17 wt %, C16: 10 wt %, C18: 10 wt %).

[0522] The reaction mixture is then heated at 330 C. under stirring (500 rpm) and 200 g (0.970 mole) of the melted fatty acids is slowly introduced into the reactor such that the temperature of the reaction medium doesn't fall down below 320 C. (for example with an addition flow rate of around 25 g fatty acids/hour).

[0523] Practically this can be done through the successive slow additions (1 hour per addition) of 4 portions of 50 g (60 mL) of melted fatty acids with 1 hour of stirring at 330 C. between each addition.

[0524] At the end of the last addition, the crude medium is stirred at 330 C. during 0.5 hour and the reaction progress is monitored through FTIR.

[0525] At the end of the reaction when the intermediate iron complex is not detected anymore through FTIR (absorption bands at 1550 cm-1 and 1408 cm-1), the mixture is allowed to cool down at room temperature and dissolved in 300 mL of CHCl3.

[0526] The obtained solution is filtered through a path of 400 g of silica gel followed by elution with 3 liters of CHCl3 in order to remove iron oxide.

[0527] The chloroform is evaporated under vacuum and the crude product dried overnight under 10 mbar at 50 C. to obtain 204 g of ketone (164 g (0.475 mole) of product generated through ketonization of the 200 g of fatty acids in addition to the 40 g of fatty ketones that have been dispensed initially in the reactor) as a light brown wax corresponding to a crude yield of 96%.

[0528] Analysis of the crude shows a GC purity of 97% (impurities being mainly alkanes) with the following composition for the ketones cut:

[0529] C15: 0.5 wt %, C17: 1.2 wt %, C19: 8.4 wt %, C21: 11.2 wt %, C23: 28.6 wt %, C25: 19.1 wt %, C27: 13.2 wt %, C29: 11.4 wt %, C31: 3.5 wt %, C33: 1.5 wt %, C35: 0.7 wt %.

Example 3 (comparative)

Ketonization of C8-C18 Fatty Acids Cut Using Magnetite Fe3O4 as the Catalyst with Direct Introduction of Entire Amount of Fatty Acids to be Converted and Without Initial Introduction of Ketone

[0530] The reaction is carried out under an inert atmosphere of argon.

[0531] In a 500 mL round bottom flask equipped with a mechanical stirrer and a Dean-Stark apparatus to trap water generated during the reaction, 100 g (0.480 mole) of melted fatty acids (C8: 7 wt %, C10: 8 wt %, C12: 48 wt %, C14: 17 wt %, C16: 10 wt %, C18: 10 wt %) and 4.7 g (0.020 mole) of magnetite Fe3O4 are dispensed.

[0532] The mixture is then allowed to stir under reflux (330 C. ordered) during 8 hours. The reaction media temperature increases progressively over the course of the reaction from 250 C. (beginning) to 303 C. after 8 hours of stirring. Importantly generation of water is observed and at the end of the reaction GC analysis (normalization) shows approximately that the conversion of fatty acids is around 40% (significant amounts of fatty acids remaining), the selectivity of ketone formation is about 55% and the approximate yield of ketones is only 23%.

Example 4 (comparative)

Ketonization of Lauric Acid Using Fe as the Pre-Catalyst with Direct Introduction of Entire Amount of Fatty Acids to be Converted and Without Initial Introduction of Ketone

[0533] Lauric acid was mixed with 12.5 mol % of iron powder and heated to 298 C. (boiling point of lauric acid) and kept at this temperature for 5 hours. Formation of complex is observed through FTIR analysis.

[0534] Thereafter the composition of the reaction product was determined. The yield of 12-tricosanone was only 18% and a significant amount of undecane was formed (8%). Furthermore, substantial amounts of unreacted lauric acid were still present (total conversion of lauric acid is 46%).