Process for preparing a (hetero)aromatic oxidative dye with a hydroxyalkylamino group for keratin fibers from alkylene carbonate and a (hetero)aromatic compound with an amino group

Abstract

Process for preparing (hetero)aromatic oxidation dye with hydroxyalkylamino group of keratin fibers from alkylene carbonate and (hetero)aromatic compounds with amino group The invention relates to a process for preparing one or more (hetero)aromatic compound(s) substituted by a hydroxyalkylamino group (B) from one or more aromatic compound(s) with amino group (A) in the presence i) of one or more (C2-C6)alkylene carbonate(s) possibly substituted and ii) of one or more ionic liquid(s), then iii) in alkaline medium, followed optionally iv) by one or more purification step(s), it being understood that the process is carried out "one pot" i.e. without isolating the intermediate of (hetero)aromatic compound(s) substituted by a cyclic carbamate group.

Description

Title of the invention: Process for preparing a (hetero)aromatic oxidative dye with a hydroxyalkylamino group for keratin fibers from alkylene carbonate and a (hetero)aromatic compound with an amino group

[0001] The invention relates to a process for preparing one or more (hetero)aromatic compound(s) substituted by a hydroxyalkylamino group (B) from one or more aromatic compound(s) with an amino group (A) in the presence of i) one or more (C2-C6)alkylene carbonate(s) possibly substituted and ii) one or more ionic liquid(s), then iii) in an alkaline medium, followed optionally iv) by one or more purification step(s), it being understood that the process is carried out "one pot" i.e. without isolating the intermediate of (hetero)aromatic compound(s) substituted by a cyclic carbamate group.

[0002] For a long time, many people have sought to change the color of their hair, and in particular to cover their white hair.

[0003] In the field of hair keratin fiber coloring, particularly human hair, it is already known to color hair keratin fibers by different techniques from direct dyes or pigments for non-permanent colorings or from dye precursors for permanent colorings.

[0004] There are essentially three types of hair coloring processes:

[0005] a) so-called permanent coloring which has the function of bringing about a significant change in the natural color and which uses oxidation dyes which penetrate the hair fiber and form the dye by a process of oxidative condensation;

[0006] b) non-permanent, semi-permanent or direct coloring, which does not implement the oxidative condensation process and resists 4 or 5 shampoos; consists of dyeing the keratin fibers with dyeing compositions containing direct dyes;

[0007] c) Temporary hair coloring that results in a change to the natural hair color that lasts from one shampoo to the next and serves to enhance or correct a previously achieved shade. It can also be considered a "makeup" process.

[0008] It is thus known to dye keratin fibers, in particular human keratin fibers such as hair, to obtain so-called permanent colors with dye compositions containing oxidation dye precursors, in particular oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols or heterocyclic compounds such as pyrazoles, pyrazolinones or pyrazolo-pyridines. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing agents, can give rise to colored compounds through a process of oxidative condensation.

[0009] It is also possible to vary the shades obtained with these oxidation bases by combining them with color couplers or modifiers. The variety of molecules involved in the oxidation bases and couplers allows for a rich palette of colors.

[0010] It is therefore of great interest to find new synthetic routes for oxidation dyes and in particular for couplers that can be industrially transposed.

[0011] However, the methods for producing aromatic compounds, particularly those used in oxidation staining, and especially β-hydroxyalkylanilines, possibly substituted on the phenyl ring, and more specifically β-hydroxyethylanilines, are generally carried out in several steps, potentially including steps for adding reagents, removing unwanted reaction products (byproducts), protection and deprotection, purifying intermediates, and changing solvents and temperatures. Several approaches have been described in the scientific literature or in patent applications for grafting the β-hydroxyalkyl group onto the nitrogen atom of substituted or unsubstituted anilines.One can notably cite the grafting of the β-hydroxyethyl group by reaction with 2-chloroethylchloroformate, 2-chloroethanol or methyl chlorooxoacetate and an aniline possibly substituted on the phenyl group with yields between 20% and 60% (see for example; Journal of Heterocyclic Chemistry, K. Ajay et al 47(6), 1275-1282, (2010), Cell Reports Medicine, D. Arpit et al, 5(5), 101552 (2024), Journal of Heterocyclic Chemistry, shibashi, Hiroyuki; et al, 23(4), 1163-6, (1986); CN 105753832A and WO 2024 / 015793). However, the use of 2-chloroethylchloroformate, 2-chloroethanol, methyl chlorooxoacetate and / or ethylene oxide should be avoided, particularly due to potential toxicity problems.

[0012] These "classical" methods mentioned above can also generate waste, and are generally carried out by catalysis which is rarely recyclable, not always practical from an industrial point of view and / or with yields that are not sufficiently optimized.

[0013] Moreover, these oxidation dyes are interesting because they are oxidation couplers for hair coloring.

[0014] The preparation of environmentally friendly chemical compounds, that is to say whose design and development take into account environmental issues and toxicity, is becoming a major concern to help meet planetary challenges.

[0015] It is therefore essential to propose more sustainable preparation processes to address these environmental challenges. Indeed, in a chemical compound preparation process, particularly an industrial one, it is of great interest to consider using solvents that are, if possible, renewable, inexpensive, and have low or no toxicity for humans and / or the environment, notably using a polar protic solvent such as water. Furthermore, if one or more catalysts are required, the catalysis should be chosen to be as eco-efficient as possible. Moreover, it is important that the preparation process have a synthesis yield, if possible, greater than 80%, i.e., low energy consumption, and reduced reaction times (from a few days to a few hours, and if possible, less than 24 hours). Finally, it is crucial that operators be exposed as little as possible to products known to be potentially toxic.

[0016] Thus, there is a real need to make available a process for preparing oxidation dyes and in particular those substituted by a hydroxy alkylamino group which can meet at least one of the technical problems mentioned above.

[0017] In particular, one of the aims of the present invention is to propose a method for the synthesis of at least one (hetero)aromatic amine compound substituted by a hydroxyalkylamino group, preferably hydroxyethylamino, having a better carbon footprint than the methods classically described in the prior art and which can be efficiently implemented for cosmetic applications, in particular for the cosmetic treatment of keratinous materials, in particular human keratinous fibers.

[0018] Furthermore, a direct method of chemically accessing cyclic carbamate (hetero)aromatic compounds (3-aryloxazolidin-2-ones, 3,3'-aryldioxazolidin-2-ones, and 3-aryl[l,3]oxazinan-2-ones) from cyclic carbonates and (hetero)aromatic amines has been studied, particularly in the presence of a basic ionic liquid: l-butyl-3-methylimidazolium acetate (BmimOAc) (Chem. Cat. Chem., L. Zhang et al., 3, 1359–1364, 2011 – DOI: 10.1002 / cctc.201100016; Adv. Synth. Cat. Chem., B. Wang, et al., Vol. 356, 14–15, p. 1000). 3125-3134, October 13, 2014 - DOI: 10.1002 / adsc.201400026). However, it appears from these scientific articles that the cyclic carbamates were isolated and purified (by silica gel chromatography) without proposing subsequent synthetic steps. They focus solely on the methodology and mechanistic study of the generation of said carbamates.

[0019] Thus the technical problems mentioned above have been solved by proposing a process for preparing one or more (hetero)aromatic compound(s) substituted by a hydroxyalkylamino group (B) as well as its salts of organic or inorganic acids or bases and its solvates such as hydrates, implementing in a first step the mixing of one or more compound(s) (Hetero)aromatic(s) with an amino group (A) with i) one or more alkylene carbonate(s) possibly substituted and ii) one or more ionic liquid(s) preferably chosen from the salt(s) of imidazolium, triazolium and pyridinium, then in a second step iii) the addition of one or more alkali base(s), according to Scheme 1, it being understood that the process is carried out "one pot" i.e. without isolating the intermediate of (hetero)aromatic compound(s) substituted by a cyclic carbamate group (AB):

[0020] [Chem.l] (8)

[0021] Scheme 1 in which (A), (B) and (AB):

[0022] * n represents the number of molar equivalents, preferably between 1 and 10, preferably between 2 and 8, more particularly between 3 and 6 such as 5;

[0023] * p is an integer between 1 and 5, particularly p is equal to 1 or 2, preferably p equals 1;

[0024] * X \ X 2, X 3, X 4 and X s, identical or different, represent a group or atom: CRiN, CR2 or N, CR3 or N, CR4 or N, and CR5 or N respectively with:

[0025] - Ri, R2, R3, R4 and R5, whether identical or different, represent a chosen atom or group among :

[0026] a) hydrogen,

[0027] b) halogen,

[0028] c) nitro(so),

[0029] d)cyano,

[0030] e) hydroxy,

[0031] f) (Ci-C6)alkyl optionally substituted by at least one atom or group selected from: 1) halogen, 2) hydroxy, 3) (di)(Ci-C4)(alkyl)amino, and 4) (Ci-C4)alkoxy,

[0032] g) (Ci-C6)alkoxy whose alkyl portion of the alkoxy may optionally be substituted by one or more atom(s) or group(s) selected from i) to iv) as defined above,

[0033] h) amino RaRbN- with Ra and Rb, identical or different, represent a hydrogen atom, a (Ci-C6)alkyl group, or two Ra and Ra groups, together with the nitrogen atoms that bear them, form a heterocycle, saturated or unsaturated, comprising 4 to 6 links, preferably 5 or 6 links, such as morpholino, pyperazino, piperidino, optionally substituted by one or more (Cr C4)alkyl group(s), such as methyl;

[0034] i) two contiguous groups Ri and R2, and / or R2 and R3, and / or R3 and R4, and / or R4 and R5 together with the carbon atoms that bear them form a heterocycle or a carbocycle, saturated or unsaturated, non-aromatic or aromatic, comprising 4 to 6 links, preferably 5 or 6 links, optionally substituted by one or more atom(s) or group(s) chosen from: a) to g) as defined above, more particularly a 5-link heterocycle comprising preferably 1 to 3 oxygen or nitrogen atoms, preferably oxygen;

[0035] j) carboxy(late) -C(O)-O-R with R representing a hydrogen atom, a cationic counterion such as an alkali metal or alkaline earth metal, or a (Ci-C6)alkyl group;

[0036] preferably X 1 to X s, identical or different, represent a group CR1, CR2, CR3, CR4 and CR5, more particularly Ri to R5 represent a hydrogen atom or a group chosen from a) hydroxy, f) (Ci-C6)alkyl, or g) (Ci-C6)alkoxy, or k) two contiguous groups Ri and R2, or R2 and R3, or R3 and R4, or R4 and R5, preferably R2 and R3, together with the carbon atoms that bear them a 5-membered heterocycle preferably comprising 1 to 3 oxygen atoms; preferably Ri represents a hydrogen atom, R2 represents a hydrogen atom or an (CrC4)alkoxy group such as methoxy, R3 represents a hydrogen atom or an (CrC4)alkyl group, R4 represents a hydrogen atom, a hydroxy group, and R5 represents a hydrogen atom or an (CrC4)alkoxy group, or else R2 and R3 together form a methylenedioxy group, or ethylenedioxy, preferably methylenedioxy; and

[0037] * R 6 and R 7, whether identical or different, represent a hydrogen atom or a group chosen from (Ci-C6)alkyl such as methyl, (Ci-C6)alkoxy, aryloxy such as phenoxy, or aryloxy(Ci-C6)alkyl particularly phenoxy(Ci-C4)alkyl such as phenoxymethyl preferably R 6 and R 7 represent a hydrogen atom or a (CrC4)alkyl group such as methyl.

[0038] This "one pot" step is preferably followed iv) by one or more purification step(s), in particular by recrystallization or precipitation and then filtration.

[0039] The preparation process according to the invention thus makes it possible to achieve the objectives described above, namely, that it leads to a (hetero)aromatic compound substituted with a hydroxyalkylamino group (B) as defined above, with a very satisfactory degree of purity, easily handled for cosmetic applications, particularly for the treatment of keratin fibers. Furthermore, it appears after the reaction of i) + ii) + iii) that the yield of compound (B) as defined above is very satisfactory. The implementation of the reaction i) + ii) + iii) in a "one-pot" manner, without isolating the intermediate (AB), is optimized compared to conventional synthesis processes in terms of the number of steps, the number of successive purifications, and / or the solvents used.The yields are very satisfactory while minimizing the number of purification steps, in particular the number of isolation steps, compared to the chemical synthesis processes classically described in the prior art.

[0040] Moreover, the process of the invention is more virtuous, particularly from an industrial point of view, because it does not use reagents known to be potentially toxic, such as 2-chloroethylchloroformate, 2-chloroethanol or methyl chlorooxoacetate, and / or ethylene oxide.

[0041] The synthesis process according to the invention also makes it possible to significantly reduce the quantities of solvents, particularly those derived from petrochemicals. Indeed, preferably, the chemical reaction of the process of the invention takes place without a petrochemical solvent since the (C2-C6)alkylene carbonate(s), possibly substituted, and in particular ethylene carbonate, is a reagent that also acts as a solvent.

[0042] In what follows, and unless otherwise indicated, the bounds of a range of values ​​are included in that range, in particular in the expressions "between" and "ranging from ... to ...".

[0043] Furthermore, the expression "at least one" used in this description is equivalent to the expression "one or more".

[0044] Furthermore, the expression "at least" used in this description is equivalent to the expression "greater than or equal to".

[0045] In a manner known per se, a compound or group in “C„” or in “C„” is designated as a compound or group containing in its chemical structure “n” carbon atoms.

[0046] By "(Cx-C)alkyl group" is meant a linear or branched hydrocarbon chain comprising from x to z carbon atoms; for example, a (Cr) group C6)alkyl represents a hydrocarbon chain, linear or branched, comprising from 1 to 6 carbon atoms;

[0047] By "(Cx-Cv)alkylene group" we mean a (Cx-Cz)alkyl group as defined above which is divalent;

[0048] By "(C x -C , )alkenyl group" is meant a hydrocarbon chain, linear or branched comprising from x to z carbon atoms, and comprising one or more unsaturations, conjugated or not, preferably a single unsaturation; for example, a (C2-C6)alkenyl group represents a hydrocarbon chain, linear or branched comprising from 2 to 6 carbon atoms and comprising one or more unsaturations;

[0049] By group "(C x -C , )alkenylene" we mean a (Cx-Cz)alkenyl group as defined above which is divalent;

[0050] By "(Cx-Cz)alkoxy group" is meant an -O-(CX-Cz)alkyl radical, in which the (Cx-Cz)alkyl group is as defined above; for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butyloxy group, a tert-butyloxy group, a pentoxy group, a hexyloxy group, preferably a methoxy group;

[0051] By "cycloalkyl group" is meant a monocyclic or polycyclic carbocycle (cyclic hydrocarbon group), preferably between 2 and 5 rings, condensed or not, more preferably condensed, saturated or unsaturated, preferably saturated, non-aromatic, comprising from 5 to 42 carbon atoms, in particular comprising from 6 to 10 carbon atoms;

[0052] By "(di)(Cx-Cz)(alkyl)amino- group" we mean a -N((Cx-Cz)alkyl)2 radical, in which the (Cx-Cz)alkyl group is as defined above. For example, we can mention a dimethylamino- group, a diethylamino- group, a (methyl)(ethyl)amino- group, a dipropylamino- group, a diisopropylamino- group, a dibutylamino- group;

[0053] By "(hetero)aryl group", we mean an aryl or heteroaryl;

[0054] By "aryl" group is meant a monocyclic or polycyclic carbocycle, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl, preferably phenyl;

[0055] By "heteroaryl group" is meant a monocyclic or polycyclic heterocycle, condensed or not, comprising from 5 to 22 carbon atoms, and from 1 to 5 heteroatoms (particularly 1 to 3 heteroatoms, more particularly 1 heteroatom) such as oxygen, sulfur or nitrogen, preferably nitrogen, of which at least one ring is aromatic; particularly the heteroaryl radical is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenooxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl and its ammonium salt;

[0056] By "cycloalkyl group" is meant a non-aromatic carbocycle, mono- or polycyclic, condensed or non-condensed, containing from 5 to 22 carbon atoms, which may have from 1 to several unsaturations;

[0057] By "heterocycloalkyl group" is meant a non-aromatic mono- or polycyclic radical, condensed or not, containing from 5 to 22 links, comprising from 1 to 6 heteroatoms chosen from the nitrogen, oxygen, or sulfur atom;

[0058] By "polar organic solvent" is meant a solvent comprising carbon atoms, hydrogen atoms, and one or more heteroatoms preferably selected from oxygen, nitrogen, and sulfur atoms. In particular, the polar organic solvent(s) are composed of atoms with different electronegativities, the electronegativity difference being between 0.4 and 1.7, forming polarized bonds between them.

[0059] By “practical solvent” we mean that the polar solvents according to a second criterion, proticity, that is to say the capacity of the solvent to release acidic H+ ions or to create hydrogen bonds i.e. generally including hydroxyl or amino groups.

[0060] By "polar aprotic organic solvent" one can cite di(Ci-C6)alkylketones such as acetone, methylethylketone, di(Ci-C6)alkylsulfoxide such as DiMethylSulfOxide (DMSO), (Ci-C6)alkylnitrile, heterocycloalkyl and cycloalkyl(Ci-C6)alkoxy such as pyridine, THF, or cyclopentylmethyl ether (CPME), or (Ci-C6)alkylcarbonyl(Ci-C6)alkoxy such as tert-butylacetate TBA.

[0061] By "protic polar organic solvent" one can cite the (C2-C10)alkan(poly)ols preferably the (C2-C8)alkanols such as ethanol, 2-Methyl-2-Butanol (2M2B).

[0062] For the purposes of this invention, "geometric isomer" means any molecule with the same constitution as the formula in question but with a different spatial arrangement of atoms. In particular, this may refer to conformational stereoisomers, i.e., compounds differing by rotation around a single bond, or configurational stereoisomers, in particular enantiomers or diastereomers.

[0063] By "acid" is meant an organic or inorganic substance which, when dissolved in water, releases proton ions (H+). The acid(s) may be a Brønsted or Lewis acid. The acid(s) of the invention may be organic or mineral. In particular, the acid(s) is / are chosen from among inorganic or mineral acids, including i) acid halides such as hydrochloric acid; ii) organic acids, including sulfonic acids such as Alk-S(O)2OH; iii) Ar-S(O)2OH acids such as benzenesulfonic acid and toluenesulfonic acid; iv) (poly)(hydroxy) (Ci-C6)alkyl(poly)carboxylic acids such as succinic acid, tartaric acid, lactic acid, and acetic acid; v) Alk-OS(O)OH acids; vi) Ar-OS(O)OH acids; vii) Alk-OS(O)2OH acids, viii) Ar-OS(O)2OH acids, ix) Phosphoric acids O=P(OH)3, HO-[P(O)(OH)]wP(O)(OH)2 with w being an integer; x) triflic acid; and xi) tetrahalogenoboric acids, xii) hexahalogeno Hal6PH acids such as HPF6.

[0064] By "anionic counter-ion" is meant an anion or anionic group derived from a salt of an organic or mineral acid counterbalancing the cationic charge of the ionic liquid LI; more particularly, the anionic counter-ion is chosen from i) halides such as chloride, bromide; ii) nitrates NO3; iii) sulfonates including Ci-C6 alkylsulfonates: Alk-S(O)2O such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S(O)2O such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-OS(O)O such as methysulfate and ethylsulfate; x) arylsulfates: Ar-OS(O)O such as benzene sulfate and toluene sulfate; xi) alkoxysulfates: Alk-OS(O)2O such as methoxy sulfate and ethoxysulfate;xii) aryloxysulfates: Ar-OS(O)2O, xiii) phosphates O=P(OH)2-O, O=P(O)2-OH, O=P(O)3, HO-[P(O)(O)]WP(O)(O)2 with w being an integer; xiv) Ci-C6 alkylcarboxylates Alk-C(O)-O such as acetate; xv) triflate; and xvi) borates such as tetrafluoroborate, xvii) hexahalogen phosphates such as PF6, xviii) tetrahalogenborates such as BF4, xix) disulfate (O=)2S(O)2 or SO42 and monosulfate HSO4; the anionic counter ion, derived from the salt of an organic or mineral acid, ensures the electroneutrality of the LI molecule; particularly the anionic counter-ion is an organic counter-ion, more particularly of molecular molar mass MM greater than or equal to 45, and preferably greater than or equal to 55 g / mol;

[0065] Furthermore, the addition salts usable within the framework of the invention are in particular chosen from among the addition salts with a cosmetically acceptable base such as alkalizing agents as defined below as alkali metal hydroxides such as soda, potash, ammonia, amines or alkanolamines.

[0066] For the purposes of this invention, "organic or mineral acid or base salt" means a salt obtained by combining an ionic form of the compound in question with a corresponding counterion. In particular, such a salt is obtained by adding an organic or mineral base or acid, especially one that is cosmetically acceptable, to the compound in question. Examples of mineral bases or mineral alkali bases include hydroxides or carbonates of alkali or alkaline earth metals, such as sodium, potassium, calcium, ammonium, magnesium, lithium, or sodium. Examples of organic bases or organic alkali bases include amines or alkanolamines.Examples of acids include hydrochloric acid, hydrobromic acid, sulfuric acid, alkylsulfonic acids, arylsulfonic acids, citric acid, succinic acid, tartaric acid, lactic acid, alkoxysulfinic acids, aryloxysulfinic acids, phosphoric acid, and acetic acid.

[0067] For the purposes of this invention, "solvated" means the form of the compound in question when the latter is associated with a solvent. Solvates include conventional solvates formed during the preparation process of the compound in question. Examples of solvates are those obtained in the presence of water or a linear or branched alcohol, in particular ethanol or isopropanol.

[0068] By "ionic liquid" or "L1" is meant an organic salt comprising at least one cationic part and at least one other anionic part, it being understood that the salt comprises as many cationic group(s) as anionic group(s) to achieve the electroneutrality of the molecule, preferably the ionic liquid is distinguished from all molten salts by a melting point below 100 °C at atmospheric pressure, particularly the LI is liquid at room temperature or above i.e. greater than or equal to 25 °C at atmospheric pressure. Preparation process

[0069] The process of the invention relates to a process for preparing (hetero)aromatic compound(s) substituted with a hydroxy alkylamino group, preferably hydroxy ethylamino (B) as described above, involving in a first step the mixing of one or more (hetero)aromatic compound(s) with an amino group (A) as described above with i) one or more alkylene carbonate(s), possibly substituted as defined above, and ii) one or more ionic liquid(s), preferably selected from imidazolium, triazolium, and pyridinium salt(s), and then in a second step iii) the addition of one or more alkali base(s), according to Scheme 1, it being understood that the process is carried out without isolating the intermediate of (hetero)aromatic compound(s). substituted(s) by a cyclic carbamate group (AB) as defined above.

[0070]

[0071]

[0072] Preferably the process of the invention does not use 2-chloroethylchloroformate, 2-chloroethanol, methyl chlorooxoacetate, or ethylene oxide. According to another particular embodiment, the process is a process for preparing aromatic compound(s) substituted with a hydroxy alkylamino group (Bl) as well as its salts of organic or inorganic acids or bases and its solvates such as hydrates, as described below, carrying out in a first step the mixing of one or more aromatic compound(s) with an amino group (Al) as described below with i) one or more alkylene carbonate(s), possibly substituted, as defined above, and ii) one or more ionic liquid(s), preferably selected from imidazolium, triazolium, and pyridinium salts, and then in a second step iii) the addition of one or more alkali bases, according to Scheme 2, it being understood that the process is carried out to isolate the intermediate of compound(s) aromatic(s) substituted by a cyclic carbamate group (AB1); [Chem. 2]

[0073]

[0074] Scheme 2 in which n, p, Ri to R7 are as defined previously. More specifically, the process for preparing aromatic compound(s) substituted with a hydroxyethylamino group (B'1), as well as its salts of organic or inorganic acids or bases and its solvates such as hydrates, as described below, involving in a first step the mixing of one or more aromatic compound(s) with an amino group (Al) as described above with i) one or more ethylene carbonates, possibly substituted as defined above, and ii) one or more preferably ionic liquid(s) chosen from the imidazolium, triazolium and pyridinium salt(s), then in a second step iii) the addition of one or more alkali base(s), according to Scheme 3, it being understood that the process is carried out without isolating the intermediate of aromatic compound(s) substituted by a cyclic carbamate group (AB'l):

[0075] [Chem.3]

[0076] Scheme 3 in which n, Ri to R7 are as defined previously.

[0077] More preferably, the process of the invention is a process for preparing aromatic compound(s) substituted with a hydroxy alkylamino group (B2), as well as its salts of organic or inorganic acids or bases and its solvates such as hydrates, as described below, involving, in a first step, the mixing of one or more aromatic compound(s) with an amino group (A2) as described below with i) one or more alkylene carbonate(s), possibly substituted, as defined above, and ii) one or more ionic liquid(s), preferably selected from imidazolium, triazolium, and pyridinium salt(s), and then, in a second step, iii) the addition of one or more alkali base(s), according to Scheme 4, it being understood that the process is carried out without isolating 1' intermediate of aromatic compound(s) substituted by a cyclic carbamate group (AB2);

[0078] [Chem.4] IBS?

[0079] Scheme 4 in which n, p, R2, R? and R5 are as defined previously.

[0080] More preferably, the process of the invention is a process for preparing aromatic compound(s) substituted with a hydroxyethylamino group (B'2) as well as its salts of organic or inorganic acids or bases and its solvates such as hydrates, as described below, involving, in a first step, the mixing of one or more aromatic compound(s) with an amino group (A2) as described above with i) one or more ethylene carbonate(s), possibly substituted as defined above, and ii) one or more ionic liquid(s), preferably selected from imidazolium, triazolium, and pyridinium salt(s), and then, in a second step, iii) the addition of one or more alkali base(s), according to Scheme 5, it being understood that the process is carried out without isolating the intermediate. of aromatic compound(s) substituted by a cyclic carbamate group (AB'2);

[0081] [Chem.5]

[0082] Scheme 5 in which n, R2, Ri and R5 are as defined previously.

[0083] The alkylene carbonate(s):

[0084] According to one embodiment, the process uses i) alkylene carbonate following formula

[0085] [Chem.6]

[0086] in which p is 1, 2 or 3, preferably 1 or 2, R6 and R7 are as defined above, preferably R6 and R7 represent a hydrogen atom or R6 and R7 represent a (Ci-C4)alkyl group such as methyl, or else R6 represents a hydrogen atom and R7 represents a (Ci-C4)alkyl group, or else R7 represents a hydrogen atom and R6, identical or different if p is greater than or equal to 2, represents a hydrogen atom or a (Ci-C4)alkyl group.

[0087] In particular, the process uses i) ethylene carbonate, i.e., p equals 1, of the following formula (i-1):

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095] in which R6 and R7, identical or different, are as defined previously, preferably R6 and R7 represent a hydrogen atom ie of the following formula i'-D: [Chem. 8] vS According to another advantageous variant the process uses i) substituted ethylene carbonate ie p is 1, and at least one of the two radicals R6 and / or R7 are such as defined above represent a group other than a hydrogen atom, preferably R6 represents a hydrogen atom and R7 represents a (Ci-C4)alkyl group such as methyl of the following formula i”-l): [Chem.9] in which R7 as defined previously. According to another variant of the invention, the process uses i) propylene carbonate, i.e., p equals 2, with the following formula (i-2): [Chem. 10]

[0096] wherein R6 and R7, identical or different, are as defined above, preferably R6 and R7 represent a hydrogen atom or R6 and R7 represent a (Ci-C4)alkyl group such as methyl, or else R6 represents a hydrogen atom and R7 represents a (Ci-C4)alkyl group, or else R7 represents a hydrogen atom and R6, identical or different, represents a hydrogen atom or a (Cr C4)alkyl group, preferably R6 and R7 represent a hydrogen atom.

[0097] Preferably the process implements i), i-1), i'-1), i”-1) and i-2) of the alkylene carbonate as defined above in molar excess with respect to the molar amount of aromatic compound(s) with amino group (A), (Al), or (A2) as defined above, i is greater than 1, preferably is between 1 excluded and 10 inclusive, preferably between 2 and 8, more particularly between 3 and 6 such that 5.

[0098] The ionic liquid(s) ii)

[0099] According to one embodiment of the invention, the ionic liquid(s) is / are solid at a temperature greater than or equal to 40 °C, or even solid at a temperature greater than or equal to 60 °C, more particularly solid at a temperature greater than or equal to 80 °C, in which case the ionic liquid(s) is / are soluble in the alkylene carbonate(s) i), i-1), i'-l), i”-l) and i-2) as defined, preferably at a temperature greater than or equal to 40 °C.

[0100] According to another advantageous embodiment of the invention, the ionic liquid(s) is / are liquid(s) at a temperature less than or equal to 100 °C, or even liquid at a temperature less than or equal to 60 °C, more particularly liquid at a temperature less than or equal to 40 °C.

[0101] During the first step of the process of preparing the (hetero)aromatic compound(s) substituted by a hydroxyalkylamino group (B), (Bl), (Bl'), (B2), or (B2') as defined above, a mixture of one or more (hetero)aromatic compound(s) with an amino group (A), (Al) or (A2) as defined above is implemented with i) one or more alkylene carbonate(s) possibly substituted as defined above and ii) one or more ionic liquid(s).

[0102] Particularly, the LI(s) is / are chosen from organic salts of formula Q+X, where Q+ represents the cationic part of the molecule and X is the anionic counter ion of the molecule. In particular, the cationic part comprises at least one ammonium and / or phosphonium group, and there are as many anionic counter ions as there are cationic parts to achieve electroneutrality of said salt. Preferably, the salt is asymmetric.

[0103] More particularly, the IL(s) is / are chosen from a) ammonium salt(s), b) phosphonium salt(s), c) pyrrolidinium salt(s), possibly substituted by one or more (CrC8)alkyl groups, d) imidazolium possibly substituted by one or more (Ci-C8)alkyl groups, e) triazolium possibly substituted by one or more (CrC8)alkyl groups and f) pyridinium possibly substituted by one or more (CrC8)alkyl groups.

[0104] Preferably the IL(s) is / are chosen from the following salts of formulas ii)-1 to ii)-6, as well as their optical isomers, and their tautomers,

[0105] [Tables 1]

[0106] Formulas ii)-1 to ii)-6 wherein:

[0107] * Rio representing a (Ci-Cio)alkyl group, particularly (CrC8)alkyl, more particularly (Ci-C6)alkyl, such as n-butyl;

[0108] * Ru to R19, identical or different, represent a hydrogen atom or a (Ci-Cio)alkyl group, particularly (CrC8)alkyl, more particularly (CrC6)alkyl, such as methyl;

[0109] * X represents an anionic counter ion, organic or inorganic, preferably organic, such as (Ci-C6)alkylcarboxylate RC(0)-0 with R representing a (Ci-C6)alkyl group, more particularly (Ci-C4)alkyl, such as methyl.

[0110] More particularly, the LI(s) used in the process of the invention is / are chosen from among the salts of formulas ii)-4 and ii)-5 as defined above, more preferably ii)-4, in which, in particular, Rio represents a (CrC6)alkyl group, more particularly (Ci-C4)alkyl, such as n-butyl, Ru represents a (Ci-C6)alkyl group, more particularly (CrC4)alkyl, such as methyl, Rn, Ri4 and Rb, identical or different, are as defined above, preferably identical, particularly represent a hydrogen atom; and X is an anionic counterion as defined above, preferably is an organic counterion, such as (Ci-C6)alkylcarboxylate RC(0)-0 with R representing a (Cr C6)alkyl group, more particularly (Ci-C4)alkyl, such as methyl.

[0111] More preferably, the LI(s) is / are chosen from those of the following formula: ii)-4':

[0112] [Chem. 11]

[0113] in which R10, Ru and Rn are as defined previously.

[0114] In particular, the LI(s) of the invention is / are chosen from among those whose cationic part is such that:

[0115] [Tables2] Name of the cationic part of ii)-4 or ii)-4' Acronym Rio Ru R12 l-ethyl-3-methyllimidazolium EMIM ch3 H c2h5 1-buty 1-3-methyllimidazolium BMIM ch3 H c4h9 1-hexy 1-3-methyllimidazolium HMIM ch3 H c6h13 l-octyl-3-methyllimidazolium OMIM ch3 H c8h17 l-decyl-3-methylimidazolium DMIM ch3 H C10H21 1,3-dibutylimidazolium BBIM c4h9 H c4h9 l-butyl-2,3-dimethylimidazolium BMMIM ch3 ch3 c4h9

[0116] Preferably their anionic counter ion is organic, and more particularly chosen from (Ci-C6)alkylcarboxylates such as CH3-C(0)-0 acetate. More preferably the cation of ii)-4 or ii)-4' is BMIM.

[0117] In particular, the molar quantity added of the LI(s) i) as defined above in the first step of the process of the invention is a catalytic quantity, namely less than 1 molar equivalent (i.e., less than 100%), particularly between 0.01% and 80% molar, more particularly between 0.1% and 60% molar, better between 1% and 40%, even better between 2% and 20%, preferably between 3% and 7%, such as 5% molar in relation to the molar quantity of the (hetero)aromatic compound(s) substituted by an amino group (A), (Al) or (A2) as defined above.

[0118] According to a particular embodiment of the invention, the first step is carried out at a temperature between 40°C and 200°C, more particularly between 45°C and 180°C, preferably between 50°C and 170°C, more preferably between 60°C and 160°C, more preferably between 70°C and 160°C, even more preferably between 80°C and 150°C such as 135°C ± 5°C. In particular, the mixture is left to heat during the first step for a period of between 5 minutes and 24 hours, preferably between 30 minutes and 18 hours, more preferably between 1 hour and 12 hours, more preferably between 4 hours and 8 hours such as 6 hours ± 60 minutes.

[0119] Preferably the first step is carried out under agitation.

[0120] According to one embodiment, the first step is carried out under an inert atmosphere under argon or nitrogen.

[0121] During the second step of the process of the invention, iii) one or more alkaline base(s) are added, which may be chosen from mineral or organic or hybrid alkaline agents or mixtures thereof.

[0122] The mineral alkali base(s) are preferably chosen from ammonia, alkali carbonates or bicarbonates such as sodium or potassium carbonates and sodium or potassium bicarbonates, alkali or alkaline earth metal hydroxides such as sodium (soda) or potassium (potash) hydroxides or mixtures thereof.

[0123] According to one embodiment of the invention, the alkali base(s) used in step iii) of the process are organic, particularly organic amines, i.e., those containing at least one substituted or unsubstituted amino group. The organic alkali base(s) are most preferably chosen from among organic amines whose pKb at 25 °C is less than 12, and preferably less than 10, even more advantageously less than 6. It should be noted that this is the pKb corresponding to the highest basicity function. Examples of hybrid compounds include salts of the aforementioned amines with acids such as carbonic acid and hydrochloric acid.

[0124] The organic alkaline base(s) used in step iii) are, for example, chosen from alkanolamines, oxyethylenated and / or oxypropylenated ethylenediamines, amino acids and compounds of the following formula (C):

[0125] [Chem. 12] R\ , R* Ry R'

[0126] Formula (C) wherein:

[0127] * W is a divalent alkylene radical in the Ci-C6 group, possibly substituted by a hydroxyl group or an alkyl radical in Ci-C6, and / or possibly interrupted by one or more heteroatoms such as oxygen or NRU;

[0128] *RX,R\R!R' and R u, identical or different, represent a hydrogen atom, an alkyl radical in CrC6 or hydroxyalkyl in Ci-C6, aminoalkyl in Cr C6.

[0129] The term "alkanolamine" refers to an organic amine comprising a primary, secondary, or tertiary amine function and one or more linear or branched CrC8 alkyl groups bearing one or more hydroxyl radicals. Alkanolamines such as mono-, di-, or tri-alkanolamines, comprising one to three identical or different Ci-C4 hydroxyalkyl radicals, are particularly suitable for the implementation of the invention.

[0130] Preferably, in the second step iii) one or more hydroxides of alkali metals such as soda and / or potash, more preferably potash, are added as alkali base(s).

[0131] Particularly the alkali base(s) is / are added in diluted form in water, more particularly at a mass concentration of between 10% and 80% of alkali base(s) in water.

[0132] Particularly the amount added of alkali base(s) is in molar excess with respect to the number of moles of starting (hetero)aromatic(s) substituted by an amino group (A), (Al) or (A2), preferably the amount of alkali base(s) in equivalent number of moles is between 2 and 10, particularly between 5 and 8 such that 7 equivalents of alkali base(s) with respect to the number of moles of (A), (Al) or (A2).

[0133] Particularly the addition of the alkaline base(s) is carried out at a temperature between 5 °C and 100 °C, particularly between 20 °C and 80 °C such as 50 °C + / -5 °C.

[0134] According to one embodiment, the mixture in the second step is kept under stirring, and / or for a period of between 5 minutes and 6 hours, more particularly for a period of between 20 minutes and 5 hours, more particularly between 30 minutes and 4 hours, better between 1 hour and 3 hours, such as 2 h + / - 60 minutes.

[0135] According to one embodiment, the two aqueous and organic phases are allowed to settle, followed optionally by dilution of the organic phase by the addition of water, preferably distilled. In particular, the dilution is carried out at a temperature between 20 °C and 60 °C, such as 50 °C + / - 5 °C.

[0136] According to a particular embodiment of the invention, the mixture is then cooled to a temperature between 1 °C and 15 °C, such as 10 °C + / -1 °C, followed preferably by filtration and one or more wash(s) of the precipitate (cake), preferably with a polar protic solvent such as water, particularly distilled, and drying preferably under vacuum to lead to the (hetero)aromatic compound(s) substituted by a hydroxyalkylamino group (B), (Bl), (Bl'), (B2) or (B2') as defined above.

[0137] According to one embodiment of the process of the invention, step iii) is followed by one or more purification step(s) iv) in particular by recrystallization or precipitation and then filtration of the substituted (hetero)aromatic compound(s) hydroxyalkylamino (B), (Bl), (Bl'), (B2) or (B2') as defined above.

[0138] According to one embodiment of the process of the invention, the purification step iv) comprises at least one step of pooling the substituted (hetero)aromatic compound(s) hydroxyalkylamino (B), (Bl), (Bl'), (B2) or (B2') from step iii) with an activated carbon, in one or more organic solvent(s) of which at least one is a polar aprotic organic solvent, preferably of the ketone type such as acetone.

[0139] According to a particular embodiment of the invention, the solvent used in the purification step iv) of the process is chosen from among polar aprotic organic solvents.

[0140] More particularly of the ester type preferably of formula (D): R7-C(O)-O-R8 in which: R7 and R8, identical or different, represent a hydrocarbon chain comprising from 1 to 10 carbon atoms, acyclic, linear or branched, or cyclic, saturated or unsaturated, aromatic or non-aromatic, optionally interrupted by one or more heteroatom(s) such as oxygen, more preferably R7 and R8, identical or different, represent an acyclic, saturated, linear or branched hydrocarbon chain comprising between 1 and 8 carbon atoms, even more preferably R7 and R8 represent a (Ci-C6)alkyl group, more particularly R7-C(O)-O-R8 is selected from methyl acetate, propyl acetate, isopropyl acetate, butyl acetate and mixtures thereof.

[0141] According to a particular embodiment of the invention, the solvent used in the purification step iv) of the process is a polar aprotic organic solvent of the ketone type preferably of formula (E): R7-C(O)-R8 in which R7 and R8 are as defined previously in formula (D), more particularly R7-C(O)-R8 is chosen from acetone, methyl ethyl ketone (MEC) and their mixtures.

[0142] According to a particular embodiment of the invention, the solvent used in the purification step iv) of the process is a polar aprotic organic solvent of the ether type, preferably of formula (F): R'7-O-R'8, in which R'7 and R'8 are such as defined for R7 and R8 previously in formula (D). R'7 and / or R'8 may also represent a cycloalkyl group comprising from 3 to 10 carbon atoms, preferably 5 carbon atoms, or alternatively, R'7 and R'8 together form with the oxygen atom a saturated or unsaturated heterocycle comprising from 3 to 10 members, preferably comprising from 5 to 7 members, optionally substituted by one or more (Ci-C4)alkyl groups such as methyl. More particularly, R'7-O-R'8 is chosen from diethyl ether, (di)glyme, tetrahydrofuran, (THF), the (Ci-C4)alkyl-THF such as methyl-THF, CycloPentylMethylEther (CPME) and their mixtures.

[0143] According to a particular embodiment of the invention, the solvent used in the purification step iv) of the process is a polar aprotic organic solvent of the amide type, preferably of formula (G): R'7R'8N-C(O)-R9 in which R'7 and R'8 are as defined in formula (F), preferably represent a (Cr C4)alkyl group such as methyl, and R9 represents a hydrogen atom or an R7 group as defined previously in formula (D), preferably a hydrogen atom, R'7R'8N-C(O)-R9 represent DiMethylFormamide (DMF).

[0144] Preferably in the purification step iv) of the process the solvent used is a polar aprotic organic solvent of ketone type preferably of formula (E) as defined above more particularly chosen from acetone.

[0145] If the mixture includes activated carbon, it is then removed, preferably by filtration.

[0146] According to one embodiment of the process of the invention, in the purification step iv) the mixture comprising the substituted (hetero)aromatic compound(s) hydroxyalkylamino (B), (Bl), (Bl'), (B2) or (B2'), optionally activated carbon and the solvent(s), is stirred for 1 minute to 4 hours, preferably 30 minutes to 2 hours, more preferably 1 hour. In particular, said mixture is heated to a temperature above 30 °C, more particularly until the solvent refluxes.

[0147] In particular, the process of the invention comprises at least one purification step iv) in which one or more inorganic or organic acids, preferably inorganic, are added to the mixture comprising the substituted hydroxyalkylamino (B), (Bl), (Bl'), (B2) or (B2') (hetero)aromatic compound(s) as defined above. halogenated acids such as hydrochloric acid. The acid(s) is / are diluted in preferably distilled water.

[0148] Preferably the addition of the acid(s) as defined above to the mixture comprising the substituted (hetero)aromatic compound(s) hydroxyalkylamino (B), (Bl), (Bl'), (B2) or (B2'), and the organic solvent(s) as defined above, is carried out at a temperature less than or equal to 80 °C, particularly less than or equal to 60 °C, more particularly less than or equal to 50 °C, preferably at a temperature between 20 °C and 50 °C such as 35 °C + / - 5 °C.

[0149] After adding the acid(s) as defined above, the mixture comprising the substituted (hetero)aromatic compound(s) hydroxyalkylamino (B), (Bl), (Bl'), (B2) or (B2'), the organic solvent(s) as defined above and the inorganic or organic acid(s), is cooled to a temperature below 20 °C, preferably less than or equal to 10 °C, more preferably less than or equal to 5 °C, such as 0 °C + / - 2 °C until a solid appears which is preferably collected by filtration, said solid is preferably washed with a polar aprotic organic solvent, followed by drying preferably under vacuum to produce the hydrated salt of acid as defined above.

[0150] Preferably, the reagent (A) is an aniline i.e. in which X, X2, X3, X4, and Xs, identical or different, represent a group: CR1, CR2, CR3, CR4, or CR5, or an aniline selected from (A1), (A'1), (A2), and (A'2) in which:

[0151] * Rb R2, R3, R4 and R5 represent a hydrogen atom, or

[0152] * Rb R4 and R5 represent a hydrogen atom, R2 represents a hydroxy group and R3 represents a (CrC4)alkyl group such as methyl; or

[0153] * Rb R3 and R4 represent a hydrogen atom, R2 and R5 represent, identical or different, represent a (Ci-C4)alkoxy group, such as methoxy; or

[0154] * Rb R4, R5 represent a hydrogen atom and R2 and R3 together form with the carbon atoms which bear them a fused, monocyclic heterocycle comprising 5 to 6 links, one or more heteroatoms chosen from O and N, preferably one or two O, preferably R2 and R3 together form a methylenedioxy or ethylenedioxy group, more preferably methylenedioxy.

[0155] More preferably, reagent (A), (A'1), (Al), (A2) or (A'2) is chosen from:

[0156] [Tables3]

[0157] To produce, according to the process of the invention, the following preferred reaction products (B), (Bl), (B'1), (B2), or (B2'):

[0158] [Tables4]

[0160] The following examples serve to illustrate the invention without, however, being limiting in nature. Examples

[0161] Example 1: Synthesis of compound B-(4) A-2-hydroxyethyl-3,4-methylenedioxyaniline:

[0162] [Chem. 13]

[0163] In a reactor preheated to 50 °C, ethylene carbonate (321 g, 3.65 mol, 5 equiv.) is introduced. The mixture is heated to 135 °C. 1-Butyl-3-methylimidazolium acetate (7.2 g, 0.04 mol, 0.05 equiv.) and then 3,4-(methylenedioxy)aniline (100 g, 0.73 mol, 1 equiv.) are introduced into the reaction mixture at 135 °C. After 6 h of stirring, the mixture is cooled to 60 °C. Water (200 mL) and then 50% aqueous potassium hydroxide solution (573 g, 5.1 mol, 7 equiv.) are added at 60 °C. After 2 h of stirring, the two phases are separated. The organic phase is diluted in 300 mL of water while maintaining a temperature of 50 °C. After cooling to 10 °C followed by filtration, washing the cake with water, and drying under vacuum, 2-(1,3-benzodioxol-5-ylamino)ethanol is isolated with a yield of 85%. 2-(1,3-benzodioxol-5-ylamino)ethanol (100 g, 0.55 mol, 1 equiv.) and 2 g of activated carbon are stirred in acetone (300 mL) for 1 h at 45 °C.After filtration, the juices are acidified at 35 °C by adding 50 mL of a 37% aqueous hydrochloric acid solution. After cooling to 0 °C, the solid is filtered, washed with acetone, and dried under vacuum to yield 2-(l,3-benzodioxol-5-ylamino)ethanol hydrochloride in 80% yield. The 2-(l,3-benzodioxol-5-ylamino)ethanol hydrochloride (100 g, 0.46 mol, 1 equiv.) is stirred at 60 °C in 80 mL of water for 30 min. After filtration, the juices are acidified at 40 °C by adding 100 mL of a 37% aqueous hydrochloric acid solution. After cooling to 0 °C, the solid is filtered, washed with acetone and dried under vacuum to yield 2-(l,3-benzodioxol-5-ylamino)ethanol hydrochloride with a yield of 80% and with an HPLC purity greater than 99%.

[0164] It is possible to synthesize the compounds B-(l), B-(2), B-(3), by replacing the 3,4-methylenedioxyaniline A-(4), with the anilines A-(l), A-(2) and A-(3) respectively, of the experimental protocol of Example 1.

[0165] [Tables5] B-(l) B-(2) I B-(3) H “ XV ■ A-(l) A-(2) A-(3) iV-2-hydroxyethylanilin Af-2-hydroxyethyl-3-hydrox A42-hydroxyethyl-3,6-dimeth e : y-4-methylaniline oxyaniline

Claims

Demands

1. A process for preparing one or more (hetero)aromatic compound(s) substituted with a hydroxyalkylamino group (B), as well as its salts of organic or inorganic acids or bases and its solvates such as hydrates, involving, in a first step, the mixing of one or more (hetero)aromatic compound(s) with an amino group (A) with: (i) one or more alkylene carbonate(s), possibly substituted; and ii) one or more ionic liquid(s); then iii) in a second step iii) the addition of one or more alkali base(s), according to Scheme 1; it being understood that the process is carried out without isolating the intermediate of (hetero)aromatic compound(s) substituted by a cyclic carbamate group (AB): R Diagram 1 in which (A), (B) and (AB): * n represents the number of molar equivalents, preferably between 1 and 10, preferably between 2 and 8, more particularly between 3 and 6 such that 5; * p is an integer between 1 and 5, particularly p is 1 or 2, preferably p is 1; * X \ X 2, X 3, X 4 and X s, identical or different, represent a group or atom: CR1N, CR2 or N, CR3 or N, CR4 or N, and CR5 or N respectively with: Ri, R2, R3, R and R5, whether identical or different, represent an atom or group chosen from: a) hydrogen, b) halogen, c) nitro(SO), d) cyano, e) hydroxy, f) (Ci-C6)alkyl possibly substituted by at least one atom or group selected from: 1) halogen, 2) hydroxy, 3) (di)(CrC4) (alkyl)amino, and 4) (CrC4)alkoxy, g) (Ci-C6)alkoxy of which the alkyl part of the alkoxy may optionally be substituted by one or more atom(s) or group(s) chosen from i) to iv) as defined above, h) amino RaRbN- with Ra and Rb, identical or different, represent a hydrogen atom, a (Ci-C6)alkyl group, or two Ra and Ra groups, together with the nitrogen atoms bearing them form a heterocycle, saturated or unsaturated, comprising 4 to 6 links, preferably 5 or 6 links, such as morpholino, pyperazino, piperidino, optionally substituted by one or more (CrC4)alkyl group(s), such as methyl; (i) two contiguous groups Ri and R2, and / or R2 and R3, and / or R3 and Ri, and / or Ri and R5 together with the carbon atoms that bear them form a heterocycle or a carbocycle, saturated or unsaturated, non-aromatic or aromatic, comprising 4 to 6 links, preferably 5 or 6 links, optionally substituted by one or more atom(s) or group(s) chosen from: (a) to (g) as defined above, more particularly a 5-linked heterocycle preferably comprising 1 to 3 oxygen or nitrogen atoms, preferably oxygen; j) carboxy(late) -C(O)-O-R with R representing a hydrogen atom, a cationic counterion such as an alkali metal or alkaline earth metal, or a (Ci-C6)alkyl group; preferably X 1 to X s, identical or different, represent a group CR1, CR2, CR3, CR and CR5, more particularly Ri to R5

2.

3. represent a hydrogen atom or a group chosen from a) hydroxy, f) (Ci-C6)alkyl, or g) (Ci-C6)alkoxy, or k) two contiguous groups Ri and R2, or R2 and R3, or R3 and R4, or R4 and R5, preferably R2 and R3, together with the carbon atoms that bear them form a 5-membered heterocycle preferably comprising 1 to 3 oxygen atoms; preferably Ri represents a hydrogen atom, R2 represents a hydrogen atom or an (Cr C4)alkoxy group such as methoxy, R3 represents a hydrogen atom or an (Ci-C4)alkyl group, R4 represents a hydrogen atom, a hydroxy group, and R5 represents a hydrogen atom or an (Ci-C4)alkoxy group, or else R2 and R3 together form a methylenedioxy group, or ethylenedioxy, preferably methylenedioxy; and * R 6 and R 7, identical or different, represent a hydrogen atom or a group chosen from (Ci-C6)alkyl such as methyl, (Ci-C6)alkoxy, aryloxy such as phenoxy, or aryloxy(Ci-C6)alkyl particularly phenoxy(Ci-C4)alkyl such as phenoxymethyl preferably R 6 and R 7 represent a hydrogen atom or a (CrC4)alkyl group such as methyl. A method according to the preceding claim in which X \ X 2, X 3, X 4 and X s, identical or different, represent a group or an atom: CR1 N, CR2 or N, CR3 or N, CR4 or N, and CR5 or N respectively, it being understood that at least one of the X \ X 2, X 3, X 4 and X 5 represents a nitrogen atom N, preferably one, two or at most three of X \ X 2, X 3, X 4 and X 5 represents 1, 2 or 3 nitrogen atom(s), preferably 1 nitrogen atom. A method according to the preceding claim, wherein one or more aromatic compound(s) substituted with a hydroxyalkylamino group (Bl) and its salts of organic or inorganic acids or bases and its solvates such as hydrates, carrying out in a first step the mixing of one or more aromatic compound(s) with an amino group (Al) as described below with i) one or more alkylene carbonate(s), optionally substituted as defined above, and ii) one or more ionic liquid(s), preferably selected from imidazolium, triazolium, and pyridinium salts, and then in a second step iii) the addition of one or several alkali base(s), according to Scheme 2, it being understood that the process is carried out to isolate the intermediate of aromatic compound(s) substituted by a cyclic carbamate group (AB1); Scheme 2 in which n, p, Ri to R7 are as defined in claim 1

4. A process according to claim 1 or 3 for preparing aromatic compound(s) substituted by a hydroxyethylamino group (B'1) as well as its salts of organic or inorganic acids or bases and its solvates such as hydrates, as described below, carrying out in a first step the mixing of one or more aromatic compound(s) with an amino group (Al) as described in the preceding claim with i) one or more ethylene carbonate(s) possibly substituted; and ii) one or more ionic liquid(s), then iii) in a second step the addition of one or more alkali base(s), according to Scheme 3, it being understood that the process is carried out without isolating the intermediate of aromatic compound(s) substituted by a cyclic carbamate group (AB'l): Scheme 3 in which n, Ri to R7 are as defined in claim 1 or 3;

5. A process according to claim 1, 3 or 4 for preparing aromatic compound(s) substituted with a hydroxy alkylamino group (B2) as well as its salts of organic or inorganic acids or bases and its solvates such as hydrates, as described below, comprising in a first step the mixing of one or more aromatic compound(s) with an amino group (A2) as described below with i) one or more alkylene carbonate(s), optionally substituted, and ii) one or more ionic liquid(s), preferably selected from imidazolium, triazolium and pyridinium salt(s), and then in a second step iii) the addition of one or more alkali base(s), according to Scheme 4, it being understood that the process is carried out without isolating the intermediate of aromatic compound(s). substituted(s) by a cyclic carbamate group (AB2); Scheme 4 in which n, p, R2, R3 and R5 are as defined previously; More preferably, the process for preparing aromatic compound(s) substituted with a hydroxyethylamino group (B'2), as well as its salts of organic or inorganic acids or bases and its solvates such as hydrates, as described below, involving, in a first step, the mixing of one or more aromatic compound(s) with an amino group (A2) as described above with i) one or more ethylene carbonates, possibly substituted, and ii) one or more ionic liquid(s), preferably selected from imidazolium, triazolium, and pyridinium salts, and then, in a second step, iii) the addition of one or more alkali bases, according to Scheme 5, it being understood that the process is carried out without isolating the intermediate of aromatic compound(s) substituted with a cyclic carbamate group. (AB'2); Scheme 5 in which n, R2, R3 and R5 are as defined previously

6. A process according to any one of the preceding claims that employs i) alkylene carbonate of the following formula: in which p is 1, 2 or 3, preferably 1 or 2. R6 and R7 are as defined previously; preferably R6 and R7 represent a hydrogen atom, or R6 and R7 represent a (Ci-C4)alkyl group such as methyl, or else R6 represents a

7. hydrogen atom and R7 represents a (Ci-C4)alkyl group, or R7 represents a hydrogen atom and R6, identical or different if p is greater than or equal to 2, represents a hydrogen atom or a (Ci-C4)alkyl group. A process according to any one of the preceding claims that implements i) ethylene carbonate, i.e., p equals 1, of formula next i-1): in which R6 and R7 are identical or different, are as defined previously, preferably R6 and R7 represent a hydrogen atom i.e. of the following formula i'-D: ; preferably i) ethylene carbonate is substituted i.e. p equals 1, and at least one of the two radicals R6 and / or R7 are such as defined previously represent a group other than a hydrogen atom, preferably R6 represents a hydrogen atom and R7 represents a (Ci-C4)alkyl group such as methyl of the following formula i”-l): in which R7 such that R- defined previously.

8. A method according to any one of the preceding claims that implements i) propylene carbonate, i.e., p equals 2, of formula next i-2): in which R6 and R7 are identical

9. or different, are as defined above, preferably R6 and R7 represent a hydrogen atom or R6 and R7 represent a (Ci-C4)alkyl group such as methyl, or R6 represents a hydrogen atom and R7 represents a (CrC4)alkyl group, or R7 represents a hydrogen atom and R6, identical or different, represents a hydrogen atom or a (CrC4)alkyl group, preferably R6 and R7 represent a hydrogen atom. A process according to any one of the preceding claims which employs alkylene carbonate (i), i-1), i'-1), i”-1) and i-2) as defined above in molar excess with respect to the molar amount of aromatic compound(s) with amino group (A), (Al), or (A2) as defined in any one of the preceding claims, i.e. n is greater than 1, preferably is between 1 excluded and 10 inclusive, preferably between 2 and 8, more particularly between 3 and 6 such that 5.

10.

11. A method according to any one of the preceding claims which employs one or more ionic liquid(s) LI selected from organic salts of formula Q+X in which Q+ represents the cationic part of the molecule and X is the anionic counter ion of the molecule, particularly the cationic part comprises at least one ammonium and / or phosphonium group and comprising as many anionic counter ions as cationic part(s) to achieve electroneutrality of said salt; preferably the salt is asymmetric; more particularly the LI(s) is / are chosen from a) ammonium salt(s), b) phosphonium salt(s), c) pyrrolidinium possibly substituted by one or more (CrC8)alkyl groups, d) imidazolium possibly substituted by one or more (Ci-C8)alkyl groups, e) triazolium possibly substituted by one or more (Ci-C8)alkyl groups and f) pyridinium possibly substituted by one or more (Cr C8)alkyl groups. A method according to any one of the preceding claims that employs one or more ionic liquid(s) LI selected from the salts of formulas ii)-1 to ii)-6 below, as well as their optical isomers and their tautomers, Formulas ii)-1 to ii)-6 in which: * Rio representing a (Ci-Cio)alkyl group, particularly (Cr C8)alkyl, more particularly (Ci-C6)alkyl, such as n-butyl; * Rn to R19, identical or different, represent a hydrogen atom or a (Ci-Cio)alkyl group, particularly (Cr C8)alkyl, more particularly (Ci-C6)alkyl, such as methyl; * X represents an anionic counterion, organic or inorganic, preferably organic, such as (Ci-C6)alkylcarboxylate RC(0)-0 with R representing a (Ci-C6)alkyl group, more particularly (Ci-C4)alkyl, such as methyl; particularly the ionic liquid(s) LI is / are chosen from the salts of formulas ii)-4 and ii)-5 as defined above, more preferably ii)-4, in which in particular Rio represents a (Ci-C6)alkyl group, more particularly (Ci-C4)alkyl, such as n-butyl, Ru represents a (Ci-C6)alkyl group, more particularly (CrC4)alkyl, such as methyl, R[2, Ri4 and Ri5, identical or different, are as defined above, preferably identical, more particularly represent a hydrogen atom;and X is an anionic counterion as defined above, preferably is an organic counterion, such as (Ci-C6)alkylcarboxylate RC(0)-0 with R representing a (Ci-C6)alkyl group, more particularly (Ci-C4)alkyl, such as methyl; preferably the LI(s) is / are chosen from those of the following formula: ii)-4': in which R10, Rn and Rn are such that; defined previously; more preferably the LI(s) is / are chosen from among those whose cationic part is such that: Name of the cationic part of ii)-4 or ii)-4' Acronym Rio Ru R12 1-ethyl-3-methylimidazolium EMIM ch3 H c2h5 1-butyl-3-methylimidazolium BMIM ch3 H c4h9 1-hexyl-3-methylimidazolium HMIM ch3 H c6h13 1-octyl-3-methylimidazolium OMIM ch3 H c8h17 1-decyl-3-methylimidazolium DMIM ch3 H CioH2i 1,3-dibutylimidazolium BBIM c4h9 H c4h9 1-butyl-2,3-dimethylimidazolium BMMIM ch3 ch3 c4h9

12.

13.

14. preferentially their anionic counter ion is organic, and more preferentially chosen from (Ci-C6)alkylcarboxylates such as CH3-C(0)-0 acetate; better the cation of ii)-4 or ii)-4' is the BMIM. A process according to any one of the preceding claims which employs one or more ionic liquid(s) i) in an amount less than 1 molar equivalent, particularly between 0.01% and 80% molar, more particularly between 0.1% and 60% molar, better between 1% and 40%, even better between 2% and 20%, preferably between 3% and 7% such that 5% molar relative to the molar amount of the (hetero)aromatic compound(s) substituted by an amino group (A), (Al) or (A2). A process according to any one of the preceding claims, the first step of which is carried out at a temperature between 40°C and 200°C, more particularly between 45°C and 180°C, better between 50°C and 170°C, preferably between 60°C and 160°C, more preferably between 70°C and 160°C, even better between 80°C and 150°C such as 135°C + 1 / 5°C; particularly the mixture is allowed to be heated during the first step for a period of between 5 minutes and 24 hours, preferably between 30 minutes and 18 hours, more preferably between 1 hour and 12 hours, better between 4 hours and 8 hours such as 6 hours + / - 60 minutes. A method according to any one of the preceding claims, wherein in the second step iii) one or more alkali base(s) selected from mineral alkali agents are added organic or hybrid or mixtures thereof, preferably selected from ammonia, alkali carbonates or bicarbonates such as sodium or potassium carbonates and sodium or potassium bicarbonates, alkali or alkaline earth metal hydroxides such as sodium (soda) or potassium (potash) hydroxides or mixtures thereof; preferably, in the second step iii, one or more alkali metal hydroxides such as soda and / or potash, more preferably potash, more preferably the alkali base(s) is / are added in dilute form in water, more particularly at a mass concentration of between 10% and 80% of alkali base(s) in water.

15. A method according to any one of the preceding claims wherein the amount added of alkali base(s) is in molar excess with respect to the starting number of moles of (hetero)aromatic(s) substituted by an amino group (A), (Al) or (A2), preferably the amount of alkali base(s) in equivalent number of moles is between 2 and 10, particularly between 5 and 8 such that 7 equivalents of alkali base(s) with respect to the number of moles of (A), (Al) or (A2).

16. A process according to any one of the preceding claims wherein the addition of the alkali base(s) is carried out at a temperature between 5 °C and 100 °C, particularly between 20 °C and 80 °C such as 50 °C + / - 5 °C and / or the second step is maintained under stirring, for a period of between 5 minutes and 6 hours, more particularly for a period of between 20 minutes and 5 hours, more particularly between 30 minutes and 4 hours, better between 1 hour and 3 hours, such as 2 h + / -60 minutes.

17. A process according to any one of claims 14 to 16, wherein the two aqueous and organic phases are allowed to settle, optionally followed by dilution of the organic phase by the addition of preferably distilled water. In particular, the dilution is carried out at a temperature between 20 °C and 60 °C, such that 50 °C ± 5 °C.

18. V-. A method according to the preceding claim, wherein the mixture is then cooled to a temperature between 1 °C and 15 °C, such as 10 °C + / -1 °C, preferably followed by filtration and a or several wash(s) of the precipitate (cake) preferably with a polar protic solvent such as water, particularly distilled, and drying preferably under vacuum to lead to the (hetero)aromatic compound(s) substituted by a hydroxyalkylamino group (B), (Bl), (Bl'), (B2) or (B2') as defined in any of the preceding claims.

19. A process according to any one of the preceding claims wherein step iii) is followed by one or more purification step(s) iv) in particular by recrystallization or precipitation and then filtration of the substituted (hetero)aromatic compound(s) hydroxyalkylamino (B), (Bl), (Bl'), (B2) or (B2') as defined in any one of the preceding claims; preferably the purification step iv) comprises at least one step of pooling the substituted (hetero)aromatic compound(s) hydroxyalkylamino (B), (Bl), (Bl'), (B2) or (B2') from step iii) with optionally an "activated" carbon, in one or more organic solvent(s) of which at least one of the solvents is a polar aprotic organic solvent, preferably of the ketone type such as acetone; If the mixture includes activated carbon, it is then removed, preferably by filtration.

20. A process according to the preceding claim comprising at least one purification step iv) in which one or more inorganic or organic acids, preferably inorganic, in particular halogenated acids such as hydrochloric acid, are added to the mixture comprising the substituted hydroxyalkylamino (B), (Bl), (Bl'), (B2) or (B2') (hetero)aromatic compound(s) as defined above; the acid(s) is / are diluted in water, preferably distilled;more preferably after the addition of the acid(s) as defined above, the mixture comprising the substituted (hetero)aromatic compound(s) hydroxyalkylamino (B), (Bl), (Bl'), (B2) or (B2'), the organic solvent(s) as defined above and the inorganic or organic acid(s), is cooled to a temperature below 20 °C, preferably less than or equal to 10 °C, more preferably less than or equal to 5 °C, such as 0 °C + / - 2 °C until the appearance of a solid which is taken from; preferably by filtration, said solid is preferably washed with a polar aprotic organic solvent, followed by drying preferably under vacuum to lead to the hydrated or unhydrated salt of organic or inorganic acid as defined above.

21. A process according to any one of the preceding claims wherein the reagent (A) is an aniline i.e. in which X, X2, X3, X4 and Xs, identical or different, represent a group: CR1, CR2, CR3, CR4, or CR5, or an aniline selected from (Al), (A'1), (A2) and (A'2) in which: * Rb R2, R3, R4 and R5 represent a hydrogen atom, or * Rb R4 and R5 represent a hydrogen atom, R2 represents a hydroxy group and R3 represents a (Ci-C4)alkyl group such as methyl; or * Rb R3, and R4 represent a hydrogen atom, R2 and R5 represent, identical or different, a (Cr C4)alkoxy group, such as methoxy; or * Rb R4.R5 represents a hydrogen atom and R2 and R3 together with the carbon atoms that bear them form a fused, monocyclic heterocycle comprising 5 to 6 links, one or more heteroatoms chosen from O and N, preferably one or two O, preferably R2 and R3 together form a methylenedioxy or ethylenedioxy group, more preferably methylenedioxy; more preferably the reagent (A), (A'1), (Al), (A2) or (A'2) is chosen from:. to produce, according to the process of the invention, the following preferred reaction products (B), (Bl), (B'1), (B2), or (B2'): More preferably B-(4).