EP3983390A1

EP3983390A1 - Novel 1,3-dipolar compounds comprising an aromatic heterocycle and an imidazole ring

Info

Publication number: EP3983390A1
Application number: EP20732824.6A
Authority: EP
Inventors: François JEAN-BAPTISTE DIT DOMINIQUE; Sergey Ivanov; Oleg UGOLNIKOV
Original assignee: Compagnie Generale des Etablissements Michelin SCA
Current assignee: Compagnie Generale des Etablissements Michelin SCA
Priority date: 2019-06-11
Filing date: 2020-06-10
Publication date: 2022-04-20
Also published as: FR3097222A1; FR3097222B1; CN114341114B; WO2020249623A1; CN114341114A

Abstract

The invention relates to a 1,3-dipolar compound comprising a heterocycle. The invention relates to a compound of formula (I), which is useful for functionalizing a polymer by grafting and to the method for preparing same (formula (I)), in which: - Q represents a dipole comprising at least one nitrogen atom; - A represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, which may be identical or different, aliphatic, linear or branched, optionally substituted or interrupted by one or more heteroatoms; - E represents a divalent hydrocarbon linking group which may optionally contain one or more heteroatoms; - R1 represents a hydrogen atom or a C1-C20 alkyl group; and - Y and Z, which may be identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z also being able to form together a ring, in particular an aromatic ring, with the carbon atoms of the imidazole ring to which they are attached.

Description

NEW 1,3-DIPOLAR COMPOUNDS INCLUDING AN AROMATIC HETEROCYCLE AND AN IMIDAZOLE CYCLE

FIELD OF THE INVENTION:

The present invention relates to novel 1,3-dipolar compounds comprising a heteroaromatic ring, said 1,3-dipolar compounds being capable of being grafted onto a polymer. A subject of the present invention is also a process for preparing these novel compounds.

TECHNICAL BACKGROUND:

The modification of the structure of a polymer, such as the functionalization of a polymer by grafting, is particularly sought after when it is desired to bring together a polymer and a filler in a composition. This modification can make it possible to improve, for example, the dispersion of the filler in a polymer matrix and thus make it possible to obtain a more homogeneous material and, in fine, to improve the properties of the composition.

In the case of certain fillers, such as reinforcing fillers such as carbon black or silica, better dispersion of this filler will generally result in a decrease in hysteresis of the composition. Such a property is sought after, in particular in rubber compositions intended for example for applications for tires. Indeed, the decrease in hysteresis of a rubber composition is favorable to the decrease in the rolling resistance of a tire and therefore to a decrease in the fuel consumption of a vehicle running with such tires.

Now, it is known that a drop in hysteresis is often accompanied by a drop in the cured rigidity of the rubber composition, which can make, in certain cases, the composition unsuitable for the intended use. make it.

It is therefore desirable to have compounds capable, after reaction with a polymer, of promoting the dispersion of the reinforcing filler without causing an excessive drop in the cured stiffness of a rubber composition.

From WO2015059269 A1, compounds of formula Q-A-B are known in which the group Q comprises a dipole containing at least one nitrogen atom, A is a divalent group which may or may not be aromatic and B an imidazole ring. When an elastomer grafted with this compound is mixed with reinforcing fillers in a rubber composition, the compromise between curing rigidity and hysteresis of this rubber composition is improved compared to rubber compositions not comprising a grafted elastomer. These compounds are therefore particularly interesting.

The Applicant has continued his research and has sought to improve 1,3-dipolar compounds having an imidazole ring. After numerous tests, the Applicant has discovered that a family of particular 1,3-dipolar compounds exhibits an improved grafting yield compared to the 1,3-dipolar compounds of the prior art comprising an aromatic or non-aromatic ring and a imidazole cycle.

SUMMARY OF THE INVENTION

The subject of the invention is therefore a compound of formula (I)

in which :

- Q represents a dipole comprising at least one nitrogen atom;

- A represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms;

- E represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms;

- Ri represents a hydrogen atom or a C1-C20 alkyl group; and

- Y and Z, identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z can also together form a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached.

Preferably, the compound of formula (I) is chosen from the compounds of formula (Ha)

in which :

- Ri represents a hydrogen atom or a C ₁ -C ₂₀ alkyl group;

- Y and Z, identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z can also together form a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached;

- R ₂ is chosen from a hydrogen atom, a linear or branched C ₁ -C ₂₀ alkyl, a C ₃ -C ₂₀ cycloalkyl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and a C ₆ -C ₂₀ aryl optionally substituted by one or more aliphatic, preferably saturated, linear or branched hydrocarbon-based chains; and

- R ₃ is selected from the group consisting of alkyl C ₁ -C ₂₀ linear or branched, cycloalkyl C ₃ -C ₂₀ optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C ₆ -C ₂₀ optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains.

Another object of the present invention is a process for the synthesis of a compound of formula (Ha) as defined above, comprising at least one reaction of a compound of formula (III) with a compound of formula (IV) according to the following reaction scheme

with in the formulas (Ha), (III) and (IV):

A represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms; - E represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms;

- Ri represents a hydrogen atom or a C ₁ -C ₂₀ alkyl group;

Y and Z, identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z can also together form a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached;

R ₂ is chosen from a hydrogen atom, a linear or branched C ₁ -C ₂₀ alkyl, a C ₃ -C ₂₀ cycloalkyl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched, and a C ₆ -C ₂₀ aryl optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon-based chains; and R ₃ is selected from the group consisting of alkyl C ₁ -C ₂₀ linear or branched, cycloalkyl C ₃ -C ₂₀ optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C ₆ -C ₂₀ optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains.

In the present document, unless expressly indicated otherwise, all the percentages (%) indicated are percentages (%) by mass.

On the other hand, any interval of values designated by the expression “between a and b” represents the domain of values going from more than a to less than b (that is to say bounds a and b excluded) while any range of values designated by the expression “from a to b” signifies the range of values going from a to b (that is to say including the strict limits a and b). In the present document, when an interval of values is designated by the expression "from a to b", the interval represented by the expression "between a and b" is also and preferably designated.

By "heteroatom", unless stated otherwise, is meant an atom selected from the group consisting of a sulfur atom, an oxygen atom and a nitrogen atom.

The compounds comprising carbon mentioned in the description can be of fossil or biobased origin. In the latter case, they can be partially or totally derived from biomass or obtained from renewable raw materials derived from biomass. This concerns in particular polymers, plasticizers, fillers, etc.

The invention and its advantages will be easily understood in the light of the description and the examples of embodiments which follow.

DETAILED DESCRIPTION OF THE INVENTION:

As explained above, the subject of the invention is therefore a compound of formula (I)

in which :

- Q represents a dipole comprising at least one nitrogen atom;

- Ri represents a hydrogen atom or a C1-C20 alkyl group; and

According to formula (I), the compound according to the invention contains a Q group designating a dipole which comprises at least one nitrogen atom.

For the purposes of the present invention, the term “dipole” is understood to mean a function capable of forming a 1,3-dipolar addition on an unsaturated carbon-carbon bond.

Preferably, the dipole comprising at least one nitrogen atom is selected from the group consisting of nitrile oxide, nitrone and nitrile imine.

For the purposes of the present invention, the term “nitrile oxide” means a dipole corresponding to the formula -CºN®0, including its mesomeric forms.

For the purposes of the present invention, the term “nitrile imine” is understood to mean a dipole corresponding to the formula —CºN®N, including its mesomeric forms.

For the purposes of the present invention, the term “nitrone” is understood to mean a dipole corresponding to the formula -C = N (- »0) -, including its mesomeric forms.

More preferably, Q is a group of formula (II), (III) or (IV) in which :

- the symbol * represents the connection of Q to A;

- R ₂ and R ₄ are chosen, independently of one another, from a hydrogen atom, a linear or branched C ₁ -C ₂₀ alkyl, a C ₃ -C ₂₀ cycloalkyl optionally substituted by one or several aliphatic hydrocarbon chains, preferably saturated, linear or branched, and a C ₆ -C ₂₀ aryl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched;

Preferably, R ₂ and R ₄ are chosen independently of one another from a hydrogen atom, a linear or branched C ₁ -C ₂₀ alkyl, a C ₃ -C ₃₀ cycloalkyl optionally by one or more C _I -C _O, linear or branched, aryl C _(- C ₂₀ optionally substituted by one or more C _I -C _O linear or branched, and R is selected from the group consisting of alkyls C ₁ -C ₂₀ linear or branched, cycloalkyl C ₃ -C ₂₀ optionally substituted by one or more C _I -C _O linear or branched and the aryl in C ₆ -C ₂₀ optionally substituted by one or more alkyl in C _I -C _Ô , linear or branched.

in which :

- Ri represents a hydrogen atom or a C ₁ -C ₂₀ alkyl group;

The compounds of the invention of formula (I) and (Ha) contain a group A which represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms.

By "divalent heteroaromatic ring" is meant a cyclic aromatic system comprising one or more heteroatoms selected from the group consisting of nitrogen, sulfur and oxygen. This system can be monocyclic or bicyclique and can be formed from 5 to 10 atoms. Preferably, this system is monocyclic and is formed from 5 to 6 atoms. This system can optionally be substituted with one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms such as, for example, O, N and S.

Preferably, when the divalent heteroaromatic ring is substituted by one or more hydrocarbon chains, identical or different, aliphatic, linear or branched, optionally substituted or interrupted by one or more heteroatoms, this chain or chains are preferably inert with respect to the imidazole ring carrying the substituents R 1, X and Y and with respect to the Q group.

For the purposes of the present invention, the term “hydrocarbon chain (s) inert with respect to the imidazole ring bearing the substituents R 1, X and Y and vis-à-vis the group Q” is understood to mean. a hydrocarbon chain which reacts neither with said imidazole heterocycle nor with said group Q. Thus, said hydrocarbon chain inert with respect to said heterocycle and to said group is, for example, a hydrocarbon chain which does not have alkenyl or alkynyl functions, capable of react with this cycle or group. Preferably, these linear or branched aliphatic hydrocarbon chains contain from 1 to 24 carbon atoms and are saturated.

Preferably, A is a divalent heteroaromatic ring formed from 5 to 10 atoms, preferably from 5 to 6 atoms, optionally substituted by one or more C1-C24 hydrocarbon chains, identical or different, aliphatic, linear or branched, optionally substituted or interrupted by one or more heteroatoms.

More preferably still, in the compounds of formula (I) and (Ha), A is a divalent heteroaromatic ring formed from 5 to 10 atoms, preferably from 5 to 6 atoms, optionally substituted by one or more substituents chosen from the group consisting of by linear or branched alkyls, in C1-C12, (more preferably in C _I -C _Ô , more preferably still in C1-C4), groups -OR ', groups -NHR', groups -SR 'where R is an alkyl C1-C12, preferably C _I -C _O, more preferably C1-C4.

More preferably, in the compounds of formulas (I) and (Ha), A is chosen from furan-diyl, thiophene-diyl, pyrrole-diyl, thiazol-diyl, imidazole-diyl, pyridine-diyl , pyrazine-diyl, pyrimidin-diyl, indole-diyl, benzofuran-diyl, risoindole-diyl, isobenzofuran-diyl and benzothiophene-diyl; these rings being optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, optionally substituted or interrupted by one or more heteroatoms such as, for example, O, N and S; more preferably these rings may be substituted by one or more C _I -C _Ô. More preferably still, these rings are not substituted.

More preferably, in the compounds of formulas (I) and (Ha), A is chosen from furan-diyl, thiophene-diyl, pyrrole-diyl, more preferably still is furan-diyl.

Among the compounds of formula (Ha), those of formula (Ilb) are particularly preferred:

in which

- X represents a heteroatom chosen from among the sulfur atom, the oxygen atom or the nitrogen atom, preferably X is an oxygen atom;

- Ri represents a hydrogen atom or a C ₁ -C ₂₀ alkyl group;

- Y and Z, identical or different, each represent a hydrogen atom or a hydrocarbon group, Y and Z can also together form a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached;

The compounds of the invention of formula (I), (Ha) and (IIb) contain a group E which represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms. For the purposes of the present invention, the term “divalent hydrocarbon bonding group” means a spacer group forming a bridge between the group A and the imidazole ring carrying the substituents R 1, X and Y, this spacer group being a hydrocarbon chain, aliphatic, preferably saturated, linear or branched, preferably C ₁ -C ₂₄ , possibly containing one or more heteroatom (s) such as for example N, O and S. Said hydrocarbon chain can optionally be substituted, provided that the substituents do not react with the group Q and the imidazole ring carrying the substituents R 1, X and Y.

Preferably, in the compounds of the invention of formula (I), (Ha) and (Ilb), E is chosen from hydrocarbon-based, aliphatic, saturated, linear or branched chains, in C ₁ -C ₂₄ , more preferably in C ₁ -C ₁₀ , even more preferably in C _I -C _Ô , optionally interrupted by one or more heteroatom (s), such as N, S and O.

Preferably, in the compounds of the invention of formula (I), (Ha) and (Ilb), E is chosen from the group consisting of -R-, -NH-R-, -OR- and -SR- with R a linear or branched alkylene C ₁ -C _24, preferably C ₁ -C _10, more preferably C _I -C _Ô.

More preferably still, in the compounds of the invention of formula (I), (Ha) and (Ilb), E is chosen from the group consisting of -R- and -OR- with R being a linear or branched C ₁ alkylene -C ₂₄ , preferably C ₁ -C ₁₀ , more preferably C _I -C _Ô .

More preferably still, in the compounds of the invention of formula (I), (Ha) and (Ilb), E is chosen from -CH _2- , -CH _2- CH _2- , -CH _2- CH _2- CH _2- , -CH _2- CH _2- CH _2- CH _2- , -0-CH _2- , -0-CH _2- CH _2- , -0-CH _2- CH _2- CH _2- and -0- CH _2- CH _2- CH _2- CH _2-

More preferably still, in the compounds of the invention of formula (I), (Ha) and (Ilb), E is chosen from a linear or branched C ₁ -C ₂₄ alkylene, preferably C ₁ -C ₁₀ , more preferably in C _I -C _Ô , more preferably still is chosen from -CH _2- ,

-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -.

More preferably still, in the compounds of formula (I) and (Ha), E is chosen from -CH _2- , -CH _2- CH _2- , -CH _2- CH _2- CH _2- and -CH _2- CH _2- CH _2- CH _2-

The compounds of the invention of formula (I), (Ha) and (Ilb) contain a group R 1 which represents a hydrogen atom or a C ₁ -C ₂ alkyl group. Preferably, in the compounds of the invention of formula (I), (Ha) and (Ilb), R 1 represents a hydrogen atom or a C ₁ -C 6 alkyl group _, preferably methyl. These alkyl groups can be linear or branched.

The compounds of the invention of formula (I), (Ha) and (Ilb) contain groups Y and Z, identical or different, which each represent a hydrogen atom or a hydrocarbon chain, Y and Z possibly also forming together a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached.

Preferably, in the compounds of the invention of formula (I), (Ha) and (Ilb), Y and Z, which are identical or different, each represent a hydrogen atom or an alkyl, linear or branched, in Ci-C _24, preferably C ₁ -C _10, more preferably C _I -C _O, Y and Z may also together form a ring, including aromatic, with the carbon atoms of imidazole ring to which they are attached.

According to a preferred embodiment, in the compounds of the invention of formula (I), (Ha) and (Ilb), Y and Z are a hydrogen atom. According to another preferred embodiment, in the compounds of the invention of formula (I), (Ha) and (Ilb), Y and Z together form an aromatic ring with the carbon atoms of the imidazole ring to which they are attached, from preferably Y and Z form a benzene ring with the carbon atoms of the imidazole ring to which they are attached.

Preferably, in the compounds of formula (Ha) and (Ilb), R ₂ represents a hydrogen atom or a group chosen from linear or branched C ₁ -C ₂₀ alkyls, optionally substituted C ₃ -C ₂₀ cycloalkyls. _alkyl-SO-O or C _aryl, C ₆ -C ₂₀ optionally substituted alkyl C _I -C _Ô.

Preferably, in the compounds of formula (IIa) and (IIb), R ₃ is selected from alkyl C ₁ -C ₂₀ linear or branched, cycloalkyl C ₃ -C ₂₀ optionally substituted with alkyl CI-C _O or aryl, C ₆ -C ₂₀ optionally substituted by a C _I -C _Ô.

Still more preferably, in the compounds of formula (IIa) and (IIb), R ₂ is a hydrogen atom and R ₃ is selected from alkyl C ₁ -C ₂₀ aryl and C ₆ -C _20.

More preferably still, in the compounds of formula (Ha) and (Ilb), R ₂ is a hydrogen atom and R ₃ is phenyl.

Among the compounds of formula (I), (Ha) and (Ilb), the compound of formula (VIII) is particularly preferred

A subject of the invention is also a process for preparing a compound (Ha) as defined above, said process comprising at least one reaction (c) of a compound of formula (III) with a compound of formula ( IV) according to the following reaction scheme

with in the formulas (Ha), (III) and (IV):

- Ri represents a hydrogen atom or a C ₁ -C ₂₀ alkyl group;

Preferred modes of A, E, Ri, R ₂ , R ₃ Y and Z also apply to the process for preparing a compound of formula (Ha) from a compound of formula (III) and formula ( IV).

A person skilled in the art knows how to adapt the reaction described above to obtain the compounds of formula (I) according to the invention from the compound of formula (III).

The compound of formula (IV) is commercially available from suppliers such as Sigma Aldrich, Fischer ... The process for preparing the compound for preparing a compound (Ha) as defined above, further comprises at least one reaction (b) of a compound of formula (V) with at least one compound of formula (IV ) to form the compound of formula (III)

with:

- the groups E, A, Ri, R ₂ , R ₃ , Y and Z are as defined above, including their preferred modes; and

- the T group is chosen from chlorine, bromine, iodine, fluorine, the mesylate group, the tosylate group, the acetate group, and the trifluoromethylsulfonate group.

The compound of formula (IV) is commercially available from suppliers of chemicals such as Aldrich, ABCR, ...

The process for preparing the compound for preparing a compound (Ha) as defined above further comprises at least one electrophilic activation reaction (a) of the compound of formula (VII) to form the compound of formula ( V) in the presence of an electrophilic activating agent according to the following reaction scheme

Activation agent

electrophile

(VII)

with:

- groups E, A and R ₂ as defined above, including their preferred modes, T a leaving group provided by the electrophilic activating agent; and

- the group T represents is chosen from chlorine, bromine, iodine, fluorine,

mesylate group, tosylate group, acetate group, and group

trifluoromethylsulfonate.

By “electrophilic activating agent” is meant an agent which reacts with a hydroxyl group —OH gives it an electrophilic character. These electrophilic activating agents and this electrophilic activation reaction on a hydroxyl group are well known to those skilled in the art. Mention may be made, as an electrophilic activating agent, for example, thionyl chloride, mesyl chloride, 4-toluenesulfonyl chloride, paratoluenesulfonic acid chloride, etc.

Preferably, the group T leaving provided by the electrophilic agent is chosen from the group consisting of chlorine, bromine, iodine, the mesylate group, the tosylate group.

The compounds of formulas (VII) and (VI) are commercially available from suppliers of chemical products such as Aldrich, ABCR, etc.

According to a preferred embodiment, the process for preparing a compound of formula (Ha) comprises at least the following successive reactions: reaction (b) followed by reaction (c) as they have been defined above.

According to another preferred embodiment, the process for preparing a compound of formula (Ha) comprises at least the following successive reactions: reaction (a), followed by reaction (b), followed by reaction (c) as defined above. Preferably in this embodiment, the compound of formula (VII) is obtained by dehydration of fructose or glucose; more preferably still, the compound of formula (VII) is obtained by dehydration of bio-based fructose or bio-based glucose. By “biobased fructose” and “biobased glucose” is meant within the meaning of the present invention fructose and glucose obtained from biomass which can be differentiated respectively from fructose and glucose synthesized from fossil raw materials by the methods described in ASTM D6866-12 standard.

As explained previously, the compounds of formula (I), in particular those of formula (Ha) or (Ilb), are used as grafting agent. They can be grafted onto one or more polymers, said polymers comprising at least one unsaturated carbon-carbon bond. In particular, this polymer can be an elastomer and more particularly a diene elastomer. The compounds of formula (I), in particular those of formula (Ha) and (Ilb) advantageously exhibit an improved grafting yield on polymers having at least one unsaturation compared to the compounds of the prior art.

By diene elastomer (or rubber without distinction), whether natural or synthetic, should be understood in a known manner an elastomer consisting at least in part (ie a homopolymer or a copolymer) of diene monomer units (monomers bearing two double bonds carbon-carbon, conjugated or not).

The grafting of the polymer comprising at least one unsaturated carbon-carbon bond is carried out by reaction of the polymer with the compound of formula (I), in particular the compound of formula (Ha) or of formula (IIb). The grafting of these compounds is carried out by cycloaddition [3 + 2] of the group Q of the compound of formula (I) (respectively of the nitrone of the compound of formula (Ha) or of formula (IIb) on an unsaturated carbon-carbon bond of the polymer chain. The mechanism of this cycloaddition is illustrated in particular in document WO2012 / 007441. During this reaction, said compound of formula (I), in in particular that of formula (Ha) or of formula (Ilb), forms covalent bonds with the polymer chain.

The grafting of the compound of formula (I), in particular of the compound of formula (Ha) or of formula (Ilb) can be carried out in bulk, for example in an extruder, in an internal mixer or in an external mixer such as a roller mixer, or in solution. The grafting process can be carried out in solution continuously or batchwise. The polymer thus obtained by grafting can be separated from its solution by any type of means known to those skilled in the art and in particular by a steam stripping operation.

In addition to the objects described above, the invention relates to at least one of the objects described in the following embodiments:

in which :

Q represents a dipole comprising at least one nitrogen atom;

A represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, linear or branched, optionally substituted or interrupted by one or more heteroatoms;

- Ri represents a hydrogen atom or a C1-C20 alkyl group; and

Y and Z, identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z can also together form a ring, in particular an aromatic ring, with the carbon atoms of the imidazole ring to which they are attached.

2 Compound according to embodiment 1, in which Q is a group of formula (II), (III) or (IV) in which :

- the symbol * represents the connection of Q to A;

- R- ₂ and R ₄ are chosen, independently of one another, from a hydrogen atom, a linear or branched C ₁ -C ₂₀ alkyl, a C ₃ -C ₂₀ cycloalkyl optionally substituted by a or several aliphatic hydrocarbon chains, preferably saturated, linear or branched, and a C ₆ -C ₂₀ aryl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched; and

3. Compound according to embodiment 2 in which the compound of formula (I) is chosen from the compounds of formula (Ha)

(Ha)

in which :

- A represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, linear or branched, optionally substituted or interrupted by one or more heteroatoms;

- Ri represents a hydrogen atom or a C ₁ -C ₂₀ alkyl group; - Y and Z, identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z also being able to form together a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached;

- R- ₂ is chosen from a hydrogen atom, a linear or branched C ₁ -C ₂₀ alkyl, a C ₃ -C ₂₀ cycloalkyl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and a C ₆ -C ₂₀ aryl optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon-based chains; and

Compound according to any one of embodiments 1 to 3, in which A is a divalent heteroaromatic ring formed from 5 to 10 atoms, preferably from 5 to 6 atoms, optionally substituted by one or more C ₁ -C ₂₄ hydrocarbon chains, identical or different, aliphatic, linear or branched, optionally substituted or interrupted by one or more heteroatoms.

Compound according to any one of embodiments 1 to 4, in which A is a divalent heteroaromatic ring formed from 5 to 10 atoms, preferably from 5 to 6 atoms, optionally substituted by one or more substituents chosen from the group consisting of alkyls linear or branched, in C ₁ -C ₁₂ , (more preferably in C _I -C _Ô , more preferably still in C ₁ -C ₄ ), the groups -OR ', the groups -NHR', the groups -SR 'where R 'is an alkyl group C ₁ -C _12, preferably C _I -C _O, more preferably C ₁ -C _4.

Compound according to any one of embodiments 1 to 5, in which A is chosen from furan-diyl, thiophene-diyl, pyrrole-diyl, thiazol-diyl, imidazol-diyl, pyridin-diyl, pyrazine-diyl, pyrimidin-diyl, indole-diyl, benzofuran-diyl, isoindole-diyl, isobenzofuran-diyl and benzothiophene-diyl; these rings being optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, optionally substituted or interrupted by one or more heteroatoms such as, for example, O, N and S; more preferably these rings may be substituted by one or more C _I -C _Ô.

Compound according to embodiment 6, in which A is chosen from furan-diyl, thiophene-diyl, pyrrole-diyl, more preferably still is furan-diyl. Compound according to any one of embodiments 1 to 7, in which A as defined in embodiments 1 to 6 is not substituted.

A compound according to any one of embodiments 3 to 8, in which the compound of formula (Ha) is selected from those of formula (Ilb)

in which

- X represents a heteroatom group selected from the sulfur atom, the oxygen atom or the nitrogen atom, preferably X is an oxygen atom;

- Ri represents a hydrogen atom or a C ₁ -C ₂₀ alkyl group;

A compound according to any of the embodiments 2-9, wherein R ₂ is a hydrogen atom and R ₃ is selected from alkyl C ₁ -C ₂₀ aryl and C ₆ -C _20. 11. Compound according to any one of the preceding embodiments, in which E is chosen from aliphatic, linear or branched hydrocarbon chains, saturated with C ₁ -C ₂₄ , preferably with C ₁ -C ₁₀ , more preferably with C _I -C _Ô optionally interrupted by one or more nitrogen, sulfur or oxygen atoms.

12. A compound according to any one of the preceding embodiments, in which E is chosen from the groups -R-, -NHR-, -OR- and -SR- where R is an alkylene, linear or branched, C ₁ -C. ₂₄ , preferably C ₁ -C ₁₀ , more preferably C ₁ -C _6.

13. Compound according to embodiment 12, in which E is chosen from the group consisting of -R- and -OR- with R being a linear or branched C ₁ -C ₂₄ , preferably C ₁ -C ₁₀ , more preferably alkylene. in C _I -C _Ô .

14. Compound according to embodiment 13 in which, E is chosen from -CEE-,

-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -O-CH ₂ -,

-O-CH2-CH2-, -0-CH _2- CH _2- CH _2- and -0-CH _2- CH _2- CH _2- CH _2-

15. A compound according to embodiment 12, wherein E is a linear or branched alkylene Ci-C _24, preferably C1-C10, more preferably C _I -C _O, even more preferably selected from -CH ₂ - CH _2- CH _2- , -CH _2- CH _2- CH _2- , - CH _2- CH _2- CH _2- CH _2-.

16. Compound according to any one of the preceding embodiments, in which Y and Z, which are identical or different, each represent a hydrogen atom or an alkyl, linear or branched, in Ci-C ₂₄ , preferably in C1-C10, more preferably C _I -C _O, Y and Z may also together form a ring, including aromatic, with the carbon atoms of imidazole ring to which they are attached.

17. A compound according to any one of the preceding embodiments, wherein Y and Z are hydrogen.

18. A compound according to any one of embodiments 1 to 16, in which Y and Z together form an aromatic ring with the carbon atoms of the imidazole ring to which they are attached, preferably Y and Z form a benzene ring with the atoms of carbon of the imidazole ring to which they are attached.

19. A compound according to any one of the preceding embodiments, wherein Ri is a hydrogen atom or a C _I -C _O, preferably methyl.

0. Compound according to any one of the preceding embodiments, characterized in that it is the compound of formula (VIII)

21. Process for the synthesis of a compound of formula (Ha) as defined in any one of embodiments 3 to 14, comprising at least one reaction of a compound of formula (III) with a compound of formula (IV) according to the diagram

with in the formulas (Ha), (III) and (IV):

- Ri represents a hydrogen atom or a C ₁ -C ₂₀ alkyl group;

- Y and Z, identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z can also together form a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached; and

- R ₃ is selected from the group consisting of alkyl C ₁ -C ₂₀ linear or branched, cycloalkyl C ₃ -C ₂₀ optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C ₆ -C ₂₀ optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains. EXAMPLES

1. Characterizations of molecules

The structural analysis as well as the determination of the molar purities of the synthetic molecules are carried out by an NMR analysis. The spectra are acquired on an Avance 3400 MHz BRUKER spectrometer equipped with a “broadband BBFO-zgrad 5 mm” probe. The quantitative 1 H NMR experiment uses a 30 ° single pulse sequence and a 3 second repetition delay between each of the 64 acquisitions. The samples are solubilized in a deuterated solvent, deuterated dimethyl sulfoxide (DMSO) unless otherwise indicated. The deuterated solvent is also used for the "lock" signal. For example, the calibration is performed on the proton signal of deuterated DMSO at 2.44 ppm relative to a TMS reference at 0 ppm. The ¾ NMR spectrum coupled to the 2D HSQC and HMBC ′ H / ^l ′ C experiments allow the structural determination of the molecules (see allocation tables). The molar quantifications are carried out from the quantitative 1 D ′ H NMR spectrum.

2. Characterization of molecules grafted onto a diene elastomer

The determination of the molar content of the grafted compound tested on a diene elastomer is carried out by an NMR analysis. The spectra are acquired on a 500 MHz BRUKER spectrometer equipped with a "CryoSonde BBFO-zgrad-5 mm" probe. The quantitative 1 H NMR experiment uses a 30 ° single pulse sequence and a 5 second repetition delay between each acquisition. The samples are solubilized in a deuterated solvent, deuterated chloroform (CDCf) unless otherwise indicated in order to obtain a "lock" signal. 2D NMR experiments made it possible to verify the nature of the grafted motif thanks to the chemical shifts of the carbon and proton atoms.

3. Measurement of the number-average molar masses (Mnb by weight (Mw) and of the polydispersity index of diene elastomers.

Unless expressly indicated to the contrary, the average molar masses in number and in weight of the diene elastomers used are measured by the technique of size exclusion chromatography or SEC (Size Exclusion Chromatography). SEC makes it possible to separate macromolecules in solution according to their size through columns filled with a porous gel. Macromolecules are separated according to their hydrodynamic volume, the larger ones being eluted first.

Without being an absolute method, SEC makes it possible to understand the distribution of the molar masses of an elastomer. From commercial standard products, the different average molar masses in number (Mn) and in weight (Mw) can be determined and the polymolecularity index (Ip = Mw / Mn) calculated via a so-called MOORE calibration. There is no particular treatment of the elastomer sample before analysis. This is simply dissolved at a concentration of approximately 1 g / l, in chloroform or in the following mixture: tetrahydrofuran + 1% vol. of diisopropylamine + 1% vol. of triethylamine + 1% vol. of distilled water (% vol. =% volume). Then, the solution is filtered through a filter with a porosity of 0.45 μm before injection.

The apparatus used is a “WATERS alliance” chromatograph. The elution solvent is the following mixture: tetrahydrofuran + 1% vol. of diisopropylamine + 1% vol. triethylamine or chloroform depending on the solvent used for dissolving the relastomer. The flow rate is 0.7 ml / min, the system temperature is 35 ° C and the analysis time is 90 min. A set of four WATERS columns in series, with the trade names “STYRAGEL HMW7”, “STYRAGEL HMW6E” and two “STYRAGEL HT6E” is used.

The injected volume of the Telastomer sample solution is 100 pL. The detector is a "WATERS 2410" differential refractometer with a wavelength of 810 nm. The chromatographic data processing software is the system

"WATERS EM POWER".

The average molar masses calculated relate to a calibration curve produced from commercial standard polystyrenes “PSS READY CAL-KIT”.

4. Synthesis of oxid methyl-1H-imidazole-1-v0methylfuran-2-vQ-N-phenylmethanimine l

1- (5 - ((2-Methyl-1H-imidazol-1-yl) methylfuran-2-yl) -N-phenylmethanimine oxide can be synthesized according to the following reaction scheme

The 1 - (5 - ((2-methyl- 1H-imidazol-1 -yl) methylfuran-2-yl) -N-phenylmethanimine oxide is synthesized in 2 steps which are described below. All the chemical compounds used in of this synthesis come from "Sigma Aldrich" or "Fischer Scientific"

5- (hydroxymethyl) furan-2-carbaldehyde (compound A, CAS 67-47-0) is commercial or can be synthesized biochemically or chemically from fructose.

The product N-phenylhydroxylamine (compound D, CAS 100-65-2) is commercial or perhaps synthesized from nitrobenzene according to the procedure described in Organic Syntheses, Coll. Flight. 1. p. 445 (1941); Flight. 4.p. 57 (1925).

5- (Chloromethyl) furan-2-carbaldehyde (compound B) can be synthesized from fructose or 5- (hydroxymethyl) furan-2-carbaldehyde according to the procedure described in Sanda, Komla et al, Synthesis of 5- (bromomethyl) - and of 5- (chloromethyl) -2-furancarboxaldehyde, Carbohydrate Research, 187 (1), 15-23; 1989

4.1 Step 1: Synthesis of 5 - ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-carhaldehyde (product C)

A mixture of 2-methylimidazole (4.83 g; 58.80 mmol; 2.5 Eq.) And

5- (chloromethyl) furan-2-carbaldehyde (3.40 g; 23.52 mmol) in DMF (4 ml) is heated to a bath temperature of 70 C. After 2-3 hours of stirring at this temperature and 2 hours at a bath temperature of 80 ° C., the reaction medium is diluted with water (50 ml) then the organic phase is separated. The aqueous phase is extracted 4 times with dichloromethane (4 times 20 ml). The organic phase fractions are combined and then washed with water (4 times 5 ml) then concentrated under reduced pressure (2-3 mbar; 32 ° C) to yield a black oil (2.44 g; 12). , 8 mmol) with a yield of 55%. This product is used in the next step without further purification.

4.2 Step 2: Synthesis of l- (5 - ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-yl) -N-phenylmethanimine oxide (product E)

Has a solution of 5 - ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-carbaldehyde (compound

C) (5.00 g; 26.3 mmol) in ethanol (5 ml) at a bath temperature of 35-40 C, is added N-phenylhydroxylamine (2.87 g; 26.3 mmol; lEq .) in portions for 5 minutes. The reaction medium is heated to a bath temperature of 60 C. After

Stirring for 1.5 hours at this temperature and then returning to a temperature of 30-35 C, tert-butyl methyl ether (15 ml) is added dropwise. After stirring for one hour at room temperature (23 ° C.), the precipitate obtained is filtered off and washed on a filter with a mixture of ethanol and tert-butyl methyl ether (1 ml and 5 ml), then with tert- butyl methyl ether (8 mL). A clear solid of brown color and of melting point 147-150 C is obtained with a yield of 68.4% (5.06 g; 17.99 mmol) and with a molar purity greater than 98% (1 H NMR). [Table 1]

5. Polymer grafting with compound E

5.1 Manufacture of a styrene-butadiene copolymer grafted with 1- (5 - ((2-methyl- 1H-imidazol-1-yl) methyl) furan-2-yl) -N-phenylmethanimine oxide (compound E)

1- (5 - ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-yl) -N-phenylmethanimine oxide (0.31; 1.14 mmol) is added to 15 g of a styrene-butadiene SBR copolymer (containing 26.5% by weight of styrene relative to the total weight of the copolymer and 24% by weight of 1,2-butadiene units relative to the weight of the butadiene part, 28% in weight of 1,4-cis-butadienic units relative to the weight of the butadiene part and 48% by weight of trans-1,4-butadiene units relative to the weight of the butadiene part, Mn = 120,000 g / mol and Ip = l, 84 measured according to the method described in paragraph 3) on a roller tool at 23 ° C. The mixture is homogenized in 15 wallet passes. This mixing phase is followed by heat treatment at 160 ° C. for 60 minutes in a press at 10 bar pressure.

The results of the grafting according to the 1 H NMR analysis are shown in Table 2.

5.2 Manufacture of a polybutadiene polymer grafted with 1- (5 - ((2-methyl-1H- imidazol-1-yl) methyl) furan-2-yl) -N-phenylmethanimine oxide (compound E)

0.5 g of polybutadiene (75.4 mol% of 1,2-butadiene units and 24.6 mol% of 1,4-butadiene units; of Mn = 7800 g / mol and Ip = 1.02 measured according to the method described in paragraph 3) were swept with nitrogen for 15 minutes. Then, 2 ml of dichloromethane, previously bubbled with nitrogen for 5 minutes, was added to dissolve this polymer.

Once this polymer has dissolved, 0.265 g of 1- (5 - ((2-methyl-1H-imidazol-l-yl) methyl) furan-2-yl) -N-phenylmethanimine oxide (compound E) (0, 94 mmol) dissolved beforehand in 2 ml of dichloromethane were added to the reaction medium with stirring. After 15 minutes of stirring, the reaction medium was left under a nitrogen purge for 15 minutes to evaporate the dichloromethane. Once all of the solvent has evaporated, the reaction medium was heated to 150 ° C. (bath temperature), under a constant flow of nitrogen. After 10h30 of reaction, the reaction medium is allowed to return to room temperature (23 ° C.).

5.3 Manufacture of an ethylene butadiene copolymer grafted with 1- (5 - ((2-methyl- 1H-imidazol-1-yl) methyl) furan-2-yl) -N-phenylmethanimine (compound E)

1- (5 - ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-yl) -N-phenylmethanimine oxide (0.57; 2 mmol) is incorporated into 15 g of ' an EBR ethylene-butadiene copolymer (containing 16.8 mole% butadiene, 7.7 mole% butadiene / ethylene ring and 75.5 mole% ethylene) on a roll tool at 23 ° C. The mixture is homogenized in 15 wallet passes. This mixing phase is followed by a heat treatment at 160 ° C for 60 minutes in a press at 10 bar pressure.

[Table 2]

6. Synthesis of the compound 1,3 dipolar oxide of N- (4 - ((2-methyl-1H-imidazol-l- vl) methvl) benzvlidene) aniline (Compound El)

This compound can be prepared in 5 steps according to the following reaction scheme:

A1

To 150 ml of methanol cooled to a temperature of -8 ° C (bath temperature) is added thionyl chloride SOCI2 (2.4 ml; 32.2 mmol) dropwise for 10 minutes at a temperature of -8 ° C (Bath temperature). After 5 min of stirring at -8 ° C (bath temperature), 4- (chloromethyl) benzoic acid (5.0 g; 29.3 mmol) is added in small portions for 10 minutes at -8 ° C. (Bath temperature). After 20 minutes of stirring at -8 ° C (bath temperature), the reaction medium is heated to 14 ° C (bath temperature) for 20 minutes. Then, the reaction medium is heated to 50 ° C. (bath temperature) for one hour and is stirred at this temperature for 2 hours. The product solution is concentrated under reduced pressure (28 mbar, 40 ° C., bath temperature) to yield an oil which crystallizes at room temperature. A white solid (5.16 g; 27.9 mmol; molar yield of 95%) of melting point 38 -40 ° C is obtained.

The molar purity is greater than 95 mol%. (1 H NMR)

[Table 3]

Solvent: CDCI3

6.2 Step 2: Synthesis of 4-methyl - ((2-methyl-1H-imidazol-1-yl)) methyl) henzoate:

A mixture of methyl 4- (chloromethyl) benzoate (5.15 g; 28 mmol), and 2-methyl-1H-imidazole (2.52 g; 31 mmol) and K2CO3 (2.89 g; 21 mmol) in DMF (4 ml) is heated to 60 ° C (bath temperature) for 1 to 1.5 hours; then for 5 hours at 80 ° C. After cooling, the reaction medium is diluted with water at 0 ° C. (50 ml) and ethyl acetate (25 ml). The aqueous phase is separated and extracted with ethyl acetate (3 times 10 ml). The combined organic phases are washed with water (3 times 5 ml). The product solution is concentrated under reduced pressure (7 mbar, 40 ° C., bath temperature) to yield a yellow oil (4.266 g; 18.5 mmol, molar yield 66%).

[Table 4]

Solvent: CDCI3

6.3 Step 3: Synthesis of 4 - ((2-methyl-1H-imidazol-1-yl)) methyl) phenylmethanol: A solution of L1AIH ₄ (1.50 g, 0.039 mol) in anhydrous THF (230 ml) is cooled to -60 ° C. A solution of ethyl 4 - ((2-methyl-1H-imidazol-1-yl) methyl) benzoate (7.80 g, 0.028 mol, 81% mol) in anhydrous THF (100 ml) is added under argon for 15 minutes. The reaction medium is stirred for 1 hour at -60 ° C., then 10-12 hours at room temperature. Water (20 ml) is added dropwise (an exothermic reaction). The precipitate formed is filtered off. The filtrate is concentrated under reduced pressure. The crude product obtained is solubilized in CH ₂ Cl ₂ (100 ml) to precipitate insolubles. After filtration and concentration under reduced pressure, a yellow oil (4.96 g, 93% molar yield) is obtained. The molar purity is greater than 85% ( ¹ H NMR).

[Table 5]

Solvent: CDCI3

6.4 Step 4: Synthesis of 4 - ((2-methyl-1H-imidazol-1-yl)) methyl) benzaldehyde:

A mixture of MnCL (6.88 g; 0.079 mol) and 4 - ((2-methyl-1H-imidazol-1-yl) methyl) phenylmethanol (4.57 g; 0.021 mol, 85 mol% by ¾ NMR ) in CHCl ₃ (180 ml) is stirred for 4 hours at reflux temperature. The reaction medium is cooled to ambient temperature and is kept under stirring at this temperature for 10-12 hours. The insoluble products are filtered off, the filtrate is concentrated under reduced pressure. A yellow oil (3.78 g, molar yield of 98%) is obtained after concentration under reduced pressure. The molar purity is greater than 81% ( ¹ H NMR).

[Table 6]

Solvent: CDCI3

6.5 Synthesis of phenylhydroxylamine:

Phenylhydroxylamine was synthesized according to the procedure described in Org. Syntheses, Coll. Flight. 1, p. 445, 1941; Org. Syntheses, Coll. Flight. 3, p. 668, 1955

6.5 Step 5: Synthesis of N-4 - ((2-methyl-1H-imidazol-1-yl)) methyl) benzyldiene) aniline oxide:

A solution of 4 - ((2-methyl-1H-imidazol-1-yl)) methyl) benzaldehyde (3.48 g; 0.015 mol, 81 mol% by ¾ NMR) and phenylhydroxylamine (2.86 g; 0.026 mol) in anhydrous ethanol (20 ml) is stirred for 2 hours at 60 ° C (bath temperature) and then for 12 hours at room temperature. The yellow precipitate (0.249 g containing the expected product) is filtered. To the filtrate is added water (30 ml) with vigorous stirring. The yellow precipitate thus formed is filtered off after 20 minutes of stirring and washed with a mixture of EtOH (10 ml) and water (20 ml), then with water (50 ml). The two portions of solid are combined and dried for 10-12 hours under atmospheric pressure at room temperature. A yellow solid (3.71 g, 89% molar yield) with a molar purity greater than 82% ( ¹ H NMR) is obtained. Additional purification is applied by stirring for 1.5 hours at room temperature, filtration, washing on the filter with 50 ml of ethyl ether, drying for 2 days at room temperature.

A yellow solid (3.04 g, 78% molar yield) with a melting point of 115-116 ° C is obtained. The molar purity is greater than 88% ( ¹ H NMR). [Table 7]

Solvent: CDCb

7. Study of the grafting yield of compound E as a function of time.

In this test, we compare, on a styrene / butadiene SBR copolymer, the grafting yield as a function of time of a 1,3-dipolar compound according to the invention (compound E) relative to that of a 1,3 compound. dipolar of the prior art (Compound El).

A styrene-butadiene copolymer used is an SBR containing 26.5% by weight of styrene relative to the total weight of the copolymer and in its butadienic part, relative to the weight of the butadiene part, 24% by weight of butadiene-1 units. , 2.28% by weight of 1,4-cis-butadienic units and 48% by weight of trans-1,4-butadiene units relative to the weight of the butadienic part. Its Mn is equal to 120,000 g / mol and its Ip is equal to 1.84, they are measured according to the method described in paragraph 3.

We proceed as follows: 1- (5 - ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-yl) -N-phenylmethanimine oxide (0.27g, 0.97 mmol) (compound E according to the invention) or N- (4 - ((2-methyl-1H-imidazol-1-yl) methyl) benzylidene) aniline oxide (Compound El not in conformity) (0.28 g, 0.97 mmol) to 15 g of SBR as described above on a roller tool at 23 ° C. The mixture is homogenized in 15 wallet passes. This mixing phase is followed by a heat treatment at 160 ° C. for 15 minutes in a press at 10 bar pressure.

The same experiment is carried out for grafting times of 30 min and 60 min.

At the end of each experiment, the molar grafting rate of the compound E, in accordance with the invention, or of the compound El, not in accordance with the invention, is analyzed, is determined by 1 H NMR in accordance with the method described in paragraph 2. The results are reported in Table 8.

[Table 8]

Surprisingly, it can be seen from Table 8 that the grafting yield of compound E in accordance with the invention is always significantly improved compared with compound El that does not conform. In addition, the grafting yield of compound E in accordance with the invention continues to increase beyond the 30 min of reaction, whereas a plateau is reached from 15 min for compound El not in accordance with the invention.

Claims

1. Compound of formula (I)

in which :

Q represents a dipole comprising at least one nitrogen atom;

- Ri represents a hydrogen atom or a C1-C20 alkyl group; and

2. A compound according to claim 1, wherein Q is a group of formula (II), (III) or (IV)

in which :

- the symbol * represents the connection of Q to A;

- IC and R4 are chosen, independently of one another, from a hydrogen atom, a linear or branched C ₁ -C ₂₀ alkyl, a C ₃ -C ₂₀ cycloalkyl optionally substituted by one or more chains aliphatic, preferably saturated, linear or branched hydrocarbons and a C6-C20 aryl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched; and

3. Compound according to claim 2 wherein the compound of formula (I) is chosen from the compounds of formula (Ha)

(lia)

in which :

- Ri represents a hydrogen atom or a C ₁ -C ₂₀ alkyl group;

- R ₂ is chosen from a hydrogen atom, a linear or branched C ₁ -C ₂₀ alkyl, a C ₃ -C ₂₀ cycloalkyl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and a C ₆ -C ₂₀ aryl optionally substituted by one or more aliphatic, preferably saturated, linear or branched hydrocarbon-based chains; and - R ₃ is selected from the group consisting of alkyl C ₁ -C ₂₀ linear or branched, cycloalkyl C ₃ -C ₂₀ optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C ₆ -C ₂₀ optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains.

4. Compound according to any one of claims 1 to 3, in which A is a divalent heteroaromatic ring formed from 5 to 10 atoms, preferably from 5 to 6 atoms, optionally substituted by one or more C ₁ - hydrocarbon chains. C ₂₄ , identical or different, aliphatic, linear or branched, optionally substituted or interrupted by one or more heteroatoms.

5. A compound according to claim 3, in which the compound of formula (Ha) is chosen from those of formula (Ilb)

in which

- Ri represents a hydrogen atom or a C ₁ -C ₂₀ alkyl group;

- R ₂ is chosen from a hydrogen atom, a linear or branched C ₁ -C ₂₀ alkyl, a C ₃ -C ₂₀ cycloalkyl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and a C ₆ -C ₂₀ aryl optionally substituted by one or more aliphatic, preferably saturated, linear or branched hydrocarbon-based chains; and - R-3 is chosen from the group consisting of linear or branched C1-C20 alkyls, C3-C20 cycloalkyls optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched, and C6- aryls. C20 optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched.

6. A compound according to any one of claims 2 to 5, wherein R2 is a hydrogen atom and R3 is selected from C1-C20 alkyls and C6-C20 aryls.

7. Compound according to any one of the preceding claims, in which E is chosen from aliphatic, linear or branched, saturated C ₁ -C ₂₄ , preferably C ₁ -C ₁₀ , more preferably C _I -C hydrocarbon-based chains. _Ô optionally interrupted by one or more nitrogen, sulfur or oxygen atoms.

8. A compound according to any one of the preceding claims, in which E is chosen from the groups -R-, -NHR-, -OR- and -SR- where R is an alkylene, linear or branched, C ₁ -C. _24, preferably C ₁ -C _10, more preferably C _I -C _Ô.

9. A compound according to any preceding claim, wherein E is a linear or branched alkylene C ₁ -C _24, preferably C ₁ -C _10, more preferably C _I -C _O, more preferably selected among -CH _2- , -CEE-CEE-, -CEE-CEE- CH _2- , -CH _2- CH _2- CH _2- CH _2- .

10. A compound according to any one of the preceding claims, in which Y and Z, identical or different, each represent a hydrogen atom or an alkyl, linear or branched, C ₁ -C ₂₄ , preferably C ₁ - C _10, more preferably a C -C _O, Y and Z may also together form a ring, including aromatic, with the carbon atoms of imidazole ring to which they are attached.

11. A compound according to any preceding claim, wherein Y and Z are a hydrogen atom.

12. A compound according to any one of claims 1 to 10, wherein Y and Z together form an aromatic ring with the carbon atoms of the imidazole ring to which they are attached, preferably Y and Z form a benzene ring with the atoms of carbon of the imidazole ring to which they are attached.

13. A compound according to any preceding claim, wherein Ri is a hydrogen atom or a C _I -C _O, preferably methyl.

14. Compound according to any one of the preceding claims, characterized in that it is the compound of formula (VIII)

15. Process for the synthesis of a compound of formula (Ha) as defined in any one of claims 3 to 14, comprising at least one reaction of a compound of formula (III) with a compound of formula (IV) according to the following reaction scheme

with in the formulas (Ha), (III) and (IV):

- Ri represents a hydrogen atom or a C1-C20 alkyl group;

- R ₂ is chosen from a hydrogen atom, a linear or branched C ₁ -C ₂₀ alkyl, a C ₃ -C ₂₀ cycloalkyl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and a C6-C20 aryl optionally substituted by one or more aliphatic, preferably saturated, linear or branched hydrocarbon-based chains; and - R ₃ is selected from the group consisting of alkyl C ₁ -C ₂₀ linear or branched, cycloalkyl C ₃ -C ₂₀ optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C ₆ -C ₂₀ optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains.