EP4010321A1

EP4010321A1 - Molecule having a nitrile oxide function

Info

Publication number: EP4010321A1
Application number: EP20750675.9A
Authority: EP
Inventors: Jean-Luc Couturier; Sergey Ivanov; Oleg UGOLNIKOV; François JEAN-BAPTISTE-DIT-DOMINIQUE
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2019-08-07
Filing date: 2020-08-06
Publication date: 2022-06-15
Also published as: WO2021023840A1; FR3099764A1; JP2022543617A; CA3145233A1; FR3099764B1; CN114174268A

Abstract

The invention relates to a compound of the Formula (I) where: - A represents an arylene ring optionally substituted with one or more identical or different aliphatic, preferably saturated, linear or branched hydrocarbon chains optionally substituted with or interrupted by one or more heteroatoms; - E represents a divalent hydrocarbon group optionally comprising one or more heteroatoms; - X is a halogen atom, preferably a chlorine atom.

Description

DESCRIPTION

Title: Molecule carrying a nitrile oxide function Technical field of the invention The present invention relates to the field of nitrogenous molecules comprising at least one unit making them capable of associating with one another or with a charge via non-covalent bonds, and comprising a function capable of reacting with a polymer comprising unsaturations to form a covalent bond with said polymer.

More specifically, the present invention relates to molecules carrying a nitrile oxide function and an N-substituted imidazolidinone function. The application also relates to a process for the synthesis of such molecules. State of the prior art

In the industrial field, mixtures of polymers with fillers are often used. In order for such mixtures to exhibit good properties, means are constantly sought to improve the dispersion of fillers within the polymers. One of the means to achieve this is through the use of coupling agents capable of establishing interactions between the polymer and the filler.

Agents for coupling a polymer with a filler comprising nitrogenous dipoles are described in documents published under the numbers US7186845B2 and JP2008208163. These documents describe the modification of polymers comprising diene units by nitrogenous dipolar compounds further comprising a heterocycle, said heterocycle itself comprising a nitrogen atom, and an oxygen and / or sulfur atom.

More particularly, the compounds described are nitrones carrying an oxazoline or thiazoline function such as, for example ((2- oxazolyl) -phenyl-N-methylnitrone):

O

When diene polymers are reacted with such compounds, the resulting polymers will bear the oxazoline or thiazoline rings.

These rings present on the polymer are capable of reacting in turn, with surface functions of the fillers, such as carbon black or silica, with which the polymers are mixed. This reaction leads to the establishment of covalent bonds between the polymer modified by the coupling agent and the charge due to the opening of the oxazoline or thiazoline ring. Indeed, as described in document US Pat. No. 7186845B2, the oxazoline and / or thioazoline rings are likely to open in the presence of a nucleophile which may for example be present at the surface of the filler.

The establishment of such covalent bonds nevertheless has drawbacks when preparing mixtures comprising these polymers modified by coupling agents with charges. In particular, the existence of these covalent bonds established early on, between the polymer and the fillers, makes these mixtures very viscous in the uncrosslinked state, which makes all the operations prior to the crosslinking (vulcanization) of the formulations based on rubber, in particular the preparation of mixtures of the components, and their shaping. These drawbacks have a strong impact on industrial productivity.

It is therefore desirable to provide new molecules which do not have the above drawbacks, that is to say molecules which are capable, after reaction with a polymer and mixing with a charge, of not forming covalent bonds with the polymer. load and therefore not to cause an excessively large increase in the viscosity of the mixture. Thus, patent application WO 2012/007684 relates to a compound comprising at least one group Q, and at least one group A linked together by at least and preferably one spacer group Sp in which:

- Q comprises a dipole containing at least and preferably one nitrogen atom;

- A comprises an associative group comprising at least one nitrogen atom;

- Sp is an atom or a group of atoms forming a bond between Q and

AT.

When a polymer grafted with a compound as defined above is mixed with fillers, the latter only establishes labile bonds with the fillers, which makes it possible to ensure a good polymer-filler interaction, which is beneficial for them. final properties of the polymer, but without the drawbacks that too strong a polymer-filler interaction could cause.

An example of such a compound is 2 - [2 - (2 - oxoimidazolidin-1-yl) ethoxy] benzonitrile oxide:

Furthermore, in application WO 2019/007881, various compounds are exemplified, including in particular the oxide of 2- [2- (2-oxoimidazolidin-1-yl) ethoxy] - 1 -naphtonitrile: It turns out that the rubber compositions comprising this molecule exhibit interesting properties in terms of hysteresis. Nevertheless, there is still a constant need for rubber compositions exhibiting improved properties.

Disclosure of the invention

In this context, the Applicant has discovered that a particular halogen compound, once integrated into rubber compositions, leads to the obtaining of excellent hysteresis properties.

A subject of the invention is therefore a compound of formula (I) below:

(I), in which:

- A represents an arenediyl 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 group optionally comprising one or more heteroatoms;

- X denotes a halogen atom, preferably a chlorine atom.

For the purposes of the present invention, the term "hydrocarbon chain" is understood to mean a chain comprising one or more carbon atoms and one or more hydrogen atoms.

In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by weight. 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 limits a and b excluded) while any designated range of values 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).

The invention and its advantages will be easily understood in the light of the description and the examples of embodiments which follow. The compounds mentioned in the description can be of fossil origin or biobased. In the latter case, they may be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass.

In accordance with formula (I), the compound according to the invention comprises the group A which represents an arenediyl 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. For the purposes of the present invention, the term “arenediyl ring

", A monocyclic or polycyclic aromatic hydrocarbon group, derived from an arene in which two hydrogen atoms have been deleted. An arenediyl ring is therefore a divalent group.

For the purposes of the present invention, the term "monocyclic or polycyclic aromatic hydrocarbon group" means one or more aromatic rings whose backbone consists of carbon atoms. In other words, there are no heteroatoms in the backbone of the cycle. The arenediyl ring can be monocyclic, i.e. consisting of a single ring, or polycyclic, i.e. consisting of several condensed aromatic hydrocarbon rings; such condensed rings then have at least two successive carbon atoms in common. These rings can be ortho-condensed or ortho- and peri-condensed.

Preferably, the arenediyl ring comprises from 6 to 14 carbon atoms. The arenediyl ring can be unsubstituted, partially substituted, or fully substituted. An arenediyl ring is partially substituted when one or two or more hydrogen atoms (but not all the atoms) are replaced by one or two or more hydrocarbon chains, aliphatic, preferably saturated, linear or branched, optionally substituted by one or more heteroatoms. Said chains are also called substituents. If all the hydrogen atoms are replaced by said chains, then the arenediyl ring is completely substituted. The substituents of the arenediyl ring can be the same or different from each other.

Preferably, when the arenediyl ring is substituted by one or more hydrocarbon chain (s), identical (s) or different (s), aliphatic, preferably saturated, linear or branched, optionally substituted (s) or interrupted ( s) by one or more heteroatom (s), this or these chain (s) can be inert with respect to the N-substituted imidazolidinone function and to nitrile oxide.

For the purposes of the present invention, “hydrocarbon chain (s) inert with respect to the N- substituted imidazolidinone function and to nitrile oxide” is understood to mean a hydrocarbon chain which neither reacts nor reacts. with said N-substituted imidazolidinone function or with said nitrile oxide. Thus, said inert hydrocarbon chain with respect to said N-substituted imidazolidinone function and to said nitrile oxide is preferably an aliphatic hydrocarbon chain which does not exhibit alkenyl or alkynyl functions capable of reacting with said function or said group, c ' that is to say is a saturated, linear or branched aliphatic hydrocarbon chain, optionally substituted or interrupted by one or more heteroatoms, and preferably comprising from 1 to 24 carbon atoms.

Preferably, the group A is a C 1 -C 14 arenediyl 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. More preferably, the group A is a C _Ô -C arenediyl ring, optionally substituted by one or more hydrocarbon chains, identical or different, saturated, C ₁ -C ₂₄ , linear or branched, optionally substituted or interrupted by one or more nitrogen, sulfur or oxygen heteroatoms. More preferably still, the group A is a C _Ô -C arenediyl ring, optionally substituted by one or more substituents the same or different, selected from the group consisting of alkyl C ₁ -C _12, preferably C _-C-O, more preferably C ₁ -C ₄ alkyl, a group OR ', a group - NHR' , a group -SR 'wherein R' is an alkyl group C ₁ -C _12, preferably C _-C-O, more preferably C ₁ -C _4.

Preferably, the compound of formula (I) according to the invention is of formula (Ia) below:

(la), in which:

- a group chosen from R 1 to R ₇ denotes the group of formula (II) below:

(P), in which E and X are as defined above;

- the six groups chosen from R 1 to R ₇ other than that designating the group of formula (II), which are identical or different, represent, independently of one another, a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched, optionally substituted or interrupted by or more heteroatoms. Preferably, in the compound of formula (Ia), the six groups of formula (Ia) chosen from R 1 to R 7 other than that designating the group of formula (II), which are identical or different, represent, independently of each other, an atom of hydrogen or an aliphatic, saturated, linear or branched, C ₁ -C ₂₄ hydrocarbon chain, optionally substituted or interrupted by or more heteroatoms.

More preferably still, in the compound of formula (Ia), the six groups of formula (Ia) chosen from R 1 to R ₇ other than that designating the group of formula (II), which are identical or different, are chosen from the group formed by a hydrogen atom, an alkyl group C ₁ -C _12, preferably C _-C-O, more preferably C ₁ -C ₄ alkyl, a group -OR ', -NHR' group and a group - SR ', wherein R' is an alkyl group C ₁ -C _12, preferably C _-C-O, more preferably C 1-C4.

Advantageously, in formula (Ia), R 1 represents a group of formula (II) as defined above and R ₂ to R ₇ , identical or different, represent a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated. , linear or branched, C ₁ -C ₂₄ , optionally substituted or interrupted by one or more heteroatoms.

According to one particular embodiment, in formula (Ia), R 1 represents the group of formula (II) as defined above, and R ₂ to R ₇ , identical or different, are chosen from the group consisting of an atom hydrogen, alkyl C ₁ -C _12, preferably C _-C-O, more preferably C ₁ -C ₄ alkyl, a group -OR ', -NHR' group and a group -SR 'wherein R 'is a C1-C12, preferably CI-C _O, more preferably C1-C4.

More preferably still, in this embodiment, R 1 represents a group of formula (II) as defined above and R ₂ to R ₇ , which are identical, represent a hydrogen atom.

In the compounds of formula (I) and (Ia), the group E is a divalent hydrocarbon group which may optionally contain one or more heteroatom (s). For the purposes of the present invention, the term “divalent hydrocarbon group” means a spacer group (or a linking group) forming a bridge between the group A and the imidazolidone group, this spacer group being a saturated or unsaturated hydrocarbon chain of preferably saturated, C ₁ -C ₂₄ , linear or branched, 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 nitrile oxide and the imidazolidone group. Preferably, in the compounds of formulas (I) and (Ia), the group E is a hydrocarbon chain, linear or branched, preferably saturated, C ₁ -C ₂₄ , preferably C ₁ -C ₁₀ , more preferably CI -C _O optionally interrupted by one or more atoms of nitrogen, sulfur or oxygen. Preferably, in the compounds of formula (I) and (Ia), the group E is chosen from the group consisting of -R-, -NH-R-, -O- R- and -SR- where R is an alkylene linear or branched C ₁ -C _24, preferably C ₁ -C _10, more preferably -C -C _Ô.

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

According to a particular embodiment, in the compounds of formula (I) and (Ia), the group E is chosen from -CH ₂ -, -CH ₂ -CH ₂ -, -CH2-CH2-CH2-, -CH2- CH2-CH2-CH2-, -O-CH2-, -O-CH2-CH2-, -O-

CH2-CH2-CH2- and -O-CH2-CH2-CH2-CH2-.

According to a preferred embodiment, the compound of formula (Ia) as defined above with the group E chosen from the group consisting of -R- and -OR- where R is an alkylene, linear or branched, is particularly preferred, C ₁ -C _24, preferably C i - C _10, more preferably -C -C _O and the group X is a chlorine atom.

According to this embodiment, more preferably still, the compound of formula (I) is the compound of formula (Ia) in which: - Ri represents a group of formula (II) in which the group E is chosen from the group consisting of -R- and -OR-, where R is a linear or branched C ₁ -C ₂₄ alkylene, preferably in C ₁ -C _10, more preferably C _-C-O and the group X is a chlorine atom; and

- R2 to R7, which are identical or different, represent a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched, C ₁ -C ₂₄ , optionally substituted or interrupted by one or more heteroatoms. According to this embodiment, more preferably still, the compound of formula (I) is the compound of formula (Ia) in which:

- Ri represents a group of formula (II) in which the group E is chosen from the group consisting of -R- and -OR-, where R is an alkylene, linear or branched, C1-C24, preferably C1- C10, more preferably C _-C-O, and the group X is a chlorine atom; and

- R ₂ to R _7, identical or different, are selected from the group consisting of hydrogen, C ₁ -C _12, preferably C -C _O, more preferably C ₁ -C ₄ alkyl, a group -OR ', -NHR' group and a group -SR 'wherein R' is alkyl C -C _12, preferably C _-C-O, more preferably C ₁ -C _4.

According to this embodiment, more preferably still, the compound of formula (I) is the compound of formula (Ia) in which:

- Ri represents a group of formula (II) in which the group E is chosen from the group consisting of -R- and -OR- where R is an alkylene, linear or branched, C ₁ -C ₂₄ , preferably C ₁ -C _10, more preferably C _-C-O and the group X is a chlorine atom; and

- R ₂ to R ₇ , identical, represent a hydrogen atom. Advantageously, the compound of formula (I) is of the following formula (III):

(III).

A subject of the invention is also a process for the synthesis of the compound of formula (I) according to the invention, comprising the following successive steps:

(b1) the reaction of a compound of formula (IX) below: x in which A is as defined above and Y represents a nucleophilic group, with a compound of the following formula (X):

(X), in which E is as defined above and Z represents a nucleofuge group; in the presence of at least one polar solvent SI, of at least one base, at a temperature T1 ranging from 70 to 150 ° C, to form a compound of the following formula (XI):

(Xi);

(b2) reacting said compound of formula (XI) with an aqueous solution of hydroxylamine at a temperature T2 ranging from 30 to 70 ° C, to obtain an oxime compound of formula (XII) below:

(c) a step of recovering said oxime compound of formula (XII);

(d) a step of oxidizing the oxime compound of formula (XII) with an oxidizing agent, in the presence of at least one organic solvent S2, the level of the oxidizing agent being at least 6 molar equivalents relative to the molar amount of oxime compound of formula (XII).

For the purposes of the present invention, the term “polar solvent” is understood to mean a solvent having a dielectric constant greater than 2.2.

For the purposes of the present invention, “nucleofuge group” is understood to mean a leaving group which carries its binding doublet.

For the purposes of the present invention, “nucleophilic group” is understood to mean a compound comprising at least one atom carrying a free doublet or a negatively charged atom.

As explained above, the process for synthesizing the compound of formula (I) according to the invention comprises in particular the successive steps (b l) and (b2).

According to a particular embodiment, the two steps (b l) and (b2) are separated by a step of isolation and purification of the compound of formula (XI).

According to another embodiment, the two steps (b1) and (b2) are carried out according to a one-pot synthesis, that is to say that the steps (b1) and (b2) are “one pot” (one-pot synthesis process in two stages), ie without isolation of the compound of formula (XI) intermediate.

The process according to the invention comprises a step (b1) of reacting a compound of formula (IX), as mentioned above, carrying a group Y, with a compound of formula (X), as mentioned above. above, carrying a group Z.

Preferably, the Y group is chosen from hydroxyl, thiol and primary or secondary amine functions.

The Z group can be selected from chlorine, bromine, iodine, mesylate group, tosylate group, acetate group and trifluoromethylsulfonate group.

Said step (b l) of the process according to the invention is carried out in the presence of at least one polar solvent S I, and of at least one base, at a temperature Tl ranging from 70 to 150 ° C. According to a particular embodiment of the invention, the polar solvent S I is a polar solvent miscible in water, preferably a protic solvent.

Dimethylformamide (DMF), Dimethylsulfoxide (DMSO), 1,3-Dimethyl-2-imidazolidinone (DMI), 1,3-Dimethyl-3, 4,5,6-tetrahydro-2 (1H) -pyrimidinone ( DMPU), isopropanol, acetonitrile, ethanol, n-butanol and n-propanol are examples of SI solvents which can be used in the process according to the invention.

Preferably, the protic solvent is alcoholic.

Advantageously, the compound of formula (IX) represents from 5 to 40% by weight, preferably from 10 to 30% by weight, relative to the weight of the solvent.

The base can be chosen from alkaline alcoholates, alkaline carbonates, alkaline earth carbonates, alkali metal hydroxides, alkaline earth hydroxides and mixtures thereof. Advantageously, it is possible to add:

- One or more catalysts chosen from a catalyst of silver (I) salt type, a phase transfer catalyst of quaternary ammonium type, and mixtures thereof;

- one or more ionic liquids. Preferably, the base is chosen from sodium methanolate, potassium carbonate and sodium hydroxide, more preferably potassium carbonate.

According to a particular embodiment of the invention, the molar amount of base is 1.5 to 8 molar equivalents, preferably 2 to 6 molar equivalents, relative to the molar amount of compound of formula (IX).

As explained above, step (b l) of the process according to the invention is carried out at a temperature T l ranging from 70 to 150 ° C. Preferably, the temperature T l is a temperature ranging from

70 to 120 ° C, more preferably 80 to 110 ° C.

As explained previously, step (b1) of the process according to the invention is followed by step (b2) of the addition to the reaction medium containing the compound of formula (XI) of an aqueous solution of hydroxylamine to a temperature T2 ranging from 30 to 70 ° C.

Preferably, the addition of the aqueous solution of hydroxylamine is carried out when the conversion of the compound of formula (IX) is at least 70% by weight.

Advantageously, the temperature T2 varies from 40 to 60 ° C. The process according to the invention also comprises a step (c) of recovering, as mentioned above, the oxime compound of formula (XII).

Preferably, the oxime compound of formula (XII) is recovered by precipitation with water, optionally followed by washing with water.

The process according to the invention also comprises a step (d) of oxidizing the oxime compound of formula (XII) with an oxidizing agent to give the compound of formula (I), in particular the preferred compounds, in the presence of at least an organic solvent S2; the amount of oxidizing agent is at least 6 molar equivalents, preferably from 6.5 to 15 molar equivalents, relative to the molar amount of oxime compound of formula (XII). This amount of oxidizing agent can be added all at once or in several times during step (d), preferably added twice during step (d).

Preferably, said oxidizing agent is chosen from sodium hypochlorite, N-bromosuccinimide in the presence of a base and N-chlorosuccinimide in the presence of a base, preferably said oxidizing agent is sodium hypochlorite.

Advantageously, the organic solvent S2 is an organic solvent chosen from chlorinated solvents of ester, ether and alcohol type, preferably chosen from dichloromethane, ethyl acetate, butyl acetate, diethyl ether, isopropanol and ethanol, more preferably chosen from ethyl acetate and butyl acetate.

Preferably, the oxime compound of formula (XII) represents from 1 to 30% by weight, preferably from 1 to 20% by weight, relative to the total weight of the assembly comprising said oxime compound of formula (XII), said organic solvent S2 and said oxidizing agent.

Advantageously, the process according to the invention comprises, after step (d), a step (e) of recovering the compound of formula (I).

According to a particular embodiment of the invention, the method according to the invention comprises a step (a2) of manufacturing the compound of formula (X), prior to step (b1), by reacting a compound of formula (XIII) below:

(XIII), in which E is as defined above, with an agent allowing the formation of the nucleofuge group Z.

Preferably, said agent is thionyl chloride. Preferably, step (a2) is carried out in the absence or in the presence of at least one solvent S4, preferably a chlorinated solvent, more preferably dichloromethane.

Advantageously, step (a2) is immediately followed by a step (a3) of recovering the compound of formula (X), preferably by purification with toluene, more preferably by crystallization of the compound of formula (X) from toluene.

The present invention is further illustrated by the following non-limiting examples.

EXAMPLES

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 5 mm BBFO-zgrad "broadband" probe. The quantitative ³ 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 dimethylsulfoxide (DMSO), unless otherwise indicated. The deuterated solvent is also used for the lock signal. For example, the calibration is carried out on the proton signal of deuterated DMSO at 2.44 ppm compared to a TMS reference at 0 ppm. The NMR spectrum ^3H coupled to 2D HSQC experiments H / ¹³ 0 HMBC and H / ¹³ 0 allow structural determination molecules (cf. Tables of attributions 1, 2 and 3 below). The molar quantifications are carried out from the 1D ³ H quantitative NMR spectrum.

The mass spectrometry analysis is performed by direct injection by an electrospray ionization mode (ID / ESI). The analyzes were performed on a Bruker HCT spectrometer (flow rate 600 qL / min, nebulizer gas pressure 10 psi, nebulizer gas flow rate 4 L / min).

Molecule grafted on SBR or IR The determination of the molar content of the oxide of 2- [2- (3-chloro-2-oxoimidazolidin-1 -yl) ethoxy] - 1 -naphtonitrile grafted on SBR (styrene-butadiene rubber) or IR (isoprene rubber) is performed by NMR analysis. The spectra are acquired on a 500 MHz BRUKER spectrometer equipped with a “BBFO-zgrad-5 mm CryoSonde”. Experience NMR quantitative ^X H, uses a simple pulse sequence 30 ° and a repeating time of 5 seconds between each acquisition. The samples are solubilized in deuterated chloroform (CDCl3) 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 carbon and proton atoms.

Dynamic property

The dynamic property tan (ô) max is measured on a viscoanalyst (Metravib VA4000), according to standard ASTM D 5992-96. The response of a sample of vulcanized composition (cylindrical test piece 4 mm thick and 400 mm ² in section), subjected to a sinusoidal stress in alternating simple shear, at a frequency of 10 Hz, under normal conditions is recorded. temperature (23 ° C) according to ASTM D 1349-99. A strain amplitude sweep is carried out from 0.1% to 100% (outward cycle), then from 100% to 0.1% (return cycle). The result used is the loss factor tan (ô). For the return cycle, we indicate the maximum value of tan (ô) observed, denoted tan (ô) max.

I. Synthesis of (2- (2- (3-chloro-2-oxoimidazolidin-1-yl) ethoxy) -l-naphthonitrile oxide The oxide of (2- (2- (3-chloro-2-oxoimidazolidin-l -yl) ethoxy) - l-naphthonitrile is synthesized in six steps, called step a1, step a2, step b1, step b2, step c and step d.

Step al is carried out according to protocol 1, step a2 according to protocol 2, step b1 according to protocol 3. Steps b2 and c are carried out according to protocol 4. Step d is carried out according to protocol 5.

Protocol 1:

This compound can be obtained from napthol by a formylation reaction according to the so-called Reimer-Tiemann protocol described in Organic Synthesis, 22, 63-4; 1942 by Russell, Alfred and Lockhart, Luther B. or in Organic Réactions (Hoboken, NJ, United States), 28, 1982 by Wynberg, Hans and Meijer, Egbert W., or according to the procedure described by Casiraghi, Giovanni et al. in Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972- 1999), (9), 1862-5, 1980 or even by a Vilsmeier reaction described by Jones, Gurnos and Stanforth, Stephen P. in Organic Reactions (Hoboken, NJ, United States), 49, 1997.

2-hydroxy-1-napthaldehyde is commercial. It can for example be obtained from Aldrich (CAS 708-06-5).

Protocol 2:

This compound can be obtained according to a protocol described in patent application WO 2012/007684. Step b1: preparation of 2- (2- (2-oxoimidazolidin-l -yl) ethoxy) -l - naphthaldehyde

Protocol 3:

A mixture of 2-hydroxy-1-naphthaldehyde (20.0 g; 0.16 mol), potassium carbonate (24.08 g; 0.14 mol), and 1- (2-chloroethyl) imidazolidin-2 -one (25.9 g; 0.14 mol) in DMF (20 mL) is heated to 75 ° C (bath temperature) for 3.0-3.5 hours. Then, a second portion of 1- (2-chloroethyl) imidazolidin-2-one (17.26 g; 0.116 mol) is added and the reaction medium is stirred for 9 to 10 hours at 75 ° C (bath temperature ). After returning to 40-45 ° C, the reaction medium is poured into a solution of sodium hydroxide (10g; 0.25 mol) in water (700 mL). The mixture is stirred for 10 to 15 minutes. The precipitate is filtered off and washed on the filter with distilled water (3 times 400 mL).

A gray solid (31.51g; yield 95%) is obtained.

The molar purity is greater than 85% (NMR ^).

[Table 1]

Solvent: CDCL

The product isolated at the end of protocol 3 is used in the following protocol 4.

Protocol 4:

To a solution of 2- (2- (2-oxoimidazolidin- l -yl) ethoxy) - 1 - naphthaldehyde (6.3 g; 22.2 mmol) in ethanol (30 mL) at 45 ° C (room temperature bath), a hydroxylamine solution (2.05 g; 31.0 mmol, 50% in water, Aldrich) in ethanol (5 mL). The reaction medium is stirred for 4 hours at 55 ° C. (bath temperature). After returning to 40 ° C., ethyl acetate (30 mL) is added dropwise over 15 minutes. The precipitate is filtered off, washed on the filter with an ethanol / ethyl acetate mixture.

A white solid (4.00 g; yield of 60%) is obtained.

The molar purity estimated by ^ NMR is greater than 95%.

[Table 2]

MeOH solvent

Step d: preparation of the oxide of (2- (2- (3-chloro-2-oxoimidazolidin- 1 -yl) ethoxy) -1 - naphthonitrile

Protocol 5:

To a suspension of the above 2- (2- (2-oxoimidazolidin-1-yl) ethoxy) - 1-naphthaldehyde oxime (7.30 g; 24.4 mmol) in ethyl acetate (230 ml ) cooled to 1 ° C (bath temperature = 0 ° C), is added dropwise an aqueous solution of NaOCl (74.44 g / L; 98 ml; 4.0 eq. (eq = molar equivalent)) for 10 minutes. The reaction medium is stirred for 8.5 hours at 0-2 ° C (bath temperature = 0 ° C). A second portion of aqueous NaOCl solution (74.44 g / L; 98 ml; 4.0 eq.) Is added over 5 minutes. The reaction medium is stirred for 10-11 hours at 0-2 ° C (bath temperature = 0 ° C).

The precipitate is filtered off and washed on a filter with water (twice 25 ml) and then with ethyl acetate (twice 10 ml). A white solid with a melting point of 127.0-127.5 ° C. is then obtained (6.24 g; 18.7 mmol, yield of 77%). (2- (2- (3-chloro-2-oxoimidazolidin-l-yl) ethoxy) - l-naphthonitrile oxide is obtained with a molar purity greater than 92% (NMR ^), and less than 6 mol% 2- (2- (2-oxoimidazolidin-1-yl) ethoxy) -1-naphthonitrile oxide and 2 mol% of residual solvent impurity.

[Table 3] Solvent CDCh

II. Manufacture of an SBR grafted with 2- (2- (3-chloro-2-oxoimidazolidin-1-yl) ethoxy) -l-naphthonitrile oxide

The 2- (2- (3-chloro-2-oxoimidazolidin-l -yl) ethoxy] - 1 - naphtonitrile oxide obtained previously (at the end of protocol 5) is used. In the following, it is called compound. AT.

2- [2- (3-Chloro-2-oxoimidazolidin-1-yl) ethoxy] - 1 -naphtonitrile oxide (0.27 g; 0.81 mmol), compound A, is added to 20 g of copolymer non-functionalized styrene-butadiene (containing 26.5% by weight of styrene relative to the total weight of the polymer and 25% by weight of butadiene-1, 2 unit, relative to the weight of the butadienic part; Mn = 150,000 g / mol and Ip = l, 84) on a roller tool (external mixer at 23 ° C). The mixture is homogenized in 15 wallet passes. This mixing phase is followed by a heat treatment at 120 ° C for 10 minutes in a press at 10 bar pressure.

The NMR analysis showed a molar grafting rate of 0.29% with a grafting yield of 96%.

III. Manufacture of an IR grafted with 2- (2- (3-chloro-2-oxoimidazolidin-1-yl) ethoxy) -l-naphthonitrile oxide

The 2- (2- (3-Chloro-2-oxoimidazolidin-1 -yl) ethoxy] - 1 - naphtonitrile oxide obtained previously (at the end of protocol 5) is used.

2- [2- (3-Chloro-2-oxoimidazolidin-1-yl) ethoxy] - 1 -naphtonitrile oxide (0.29 g; 0.88 mmol), compound A, is added to 20 g of a synthetic polyisoprene (containing 99.35% by weight of isoprene-1,4 cis unit and 0.65% by weight of isoprene unit 3,4; Mn = 375,000 g / mol and Ip = 3.6) on a tool with cylinders (external mixer at 23 ° C). The mixture is homogenized in 15 wallet passes. This mixing phase is followed by a heat treatment at 120 ° C. for 10 minutes in a press at 10 bar pressure. Analysis by ^C H NMR made it possible to demonstrate a molar grafting rate of 0.2% with a grafting yield of 66%.

IV. Rubber compositions) Preparation of rubber compositions

Three rubber compositions are prepared, referred to hereinafter as compositions C1, C2 and C3, and are defined as follows. Composition C1 is a “conventional” rubber composition used as a tire tread, including in particular an ungrafted synthetic polyisoprene, silica and a polysulphide silane coupling agent.

Composition C2 is identical to composition C 1 except that it additionally comprises compound B which is grafted onto synthetic polyisoprene. It is a composition comprising the comparative compound B.

Composition C3 is a composition identical to composition C1 except that it additionally comprises compound A which is grafted onto synthetic polyisoprene. It is a composition comprising the compound A according to the invention.

The rate of the various constituents of these compositions expressed in phr, part by weight per hundred parts by weight of elastomer, are presented in Table 4: [Table 4]

Compositions C2 and C3 comprise the same number of moles of grafted compounds A or B, namely 0.2 mole%.

(1) Polyisoprene containing 99.35% by weight of isoprene- 1.4 cis unit and 0.65% by weight of 3.4 isoprene unit; Mn = 375000 g / mol and Ip = 3.6;

(2) Compound B: (2- (2- (2-oxoimidazolidin-1-yl) ethoxy) - 1 -naphtonitrile oxide;

(3) Compound A: (2- (2- (3-chloro-2-oxoimidazolidin-1-yl) ethoxy) - 1-naphthonitrile oxide;

(4) “Zeosil 1165MP” silica sold by Solvay;

(5) TESPT (marketed by Evonik under the reference “S 169”;

(6) N234 grade carbon black marketed by Cabot Corporation;

(7) N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine sold by Flexys under the reference “Santoflex 6-PPD”;

(8) 2,2,4-trimethyl-1, 2-dihydroquinoline sold by the company Flexys;

(9) Zinc oxide (industrial grade) marketed by the company Umicore;

(10) “Pristerene 4031” stearin marketed by the company Uniquema;

(11) N-cyclohexyl-2-benzothiazyl-sulfenamide sold by the company Flexys under the reference “Santocure CBS”.

Fes compositions are prepared as follows: one introduced into an internal mixer “Polylab” of 85 cm3, filled to 70% and of which the initial temperature of the tank is approximately 1 10 ° C, the diene elastomer. For the compositions relating to compound A or compound B, compound A or compound B is introduced at the same time as the diene elastomer. Then a thermomechanical work of a minute and a half is carried out at a temperature of 120 ° C. Then, for each of the three compositions, one or more reinforcing fillers are introduced, the agent for coupling the filler with the diene elastomer and then, after one to two minutes of mixing, the various other ingredients with the exception of the system. vulcanization. Thermomechanical work is then carried out (non-productive phase) in one step (total mixing time equal to approximately 5 minutes), until a maximum “fall” temperature of 160 ° C. is reached.

The mixture thus obtained is recovered, it is cooled and then the vulcanization system (sulfur and sulfenamide type accelerator) is added on an external mixer (homo-finisher) at 25 ° C, while mixing everything (productive phase) for approximately 5 to 6 minutes.

The compositions thus obtained are then calendered in the form of plates (thickness of 2 to 3 mm) or of thin rubber sheets for the measurement of their physical or mechanical properties. 2) Characterization tests - Results

The rubber properties of these compositions are measured after curing at 150 ° C for 60 minutes. The results obtained are shown in Table 5.

[Table 5]

It can be seen from Table 5, as expected, that composition C2 comprising the comparative compound, which comprises an elastomer modified with a compound comprising an unsubstituted imidazolidinone function, exhibits a decrease in hysteresis (tan (ô) max at 23 ° C), relative to composition C1 which does not include a modified elastomer. Surprisingly, composition C3 comprising the compound according to the invention, which comprises an elastomer modified with a compound comprising an N-substituted imidazolidinone function, exhibits a significant decrease in hysteresis compared with comparative composition C 1 as well as a significant decrease in hysteresis compared to comparative composition C2, which already exhibited good hysteretic properties compared to composition C1.

The elastomer modified by the compound according to the invention therefore makes it possible to improve the hysteresis of the compositions containing it, and therefore to improve the rolling resistance performance of the compositions containing it.

Claims

1. Compound of formula (I) below:

(I), in which:

- X denotes a halogen atom, preferably a chlorine atom.

2. Compound according to claim 1, characterized in that the arenediyl ring is C _Ô -CH.

3. Compound according to claim 1 or 2, characterized in that it is of the following formula (la):

(la), in which: - a group chosen from R 1 to R 7 denotes the group of formula (II) below:

(P), in which:

- E and X are as defined in claim 1;

- the six groups chosen from R 1 to R 7 other than that designating the group of formula (II), which are identical or different, represent, independently of one another, a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched , optionally substituted or interrupted by one or more heteroatoms.

4. Compound according to claim 3, characterized in that R i represents the group of formula (II) as defined in claim 3 and R2 to R7, identical or different, represent a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched, C 1 -C24, optionally substituted or interrupted by one or more heteroatoms, preferably R i represents the group of formula (II) as defined in claim 3 and R2 to R7, identical or different, are selected from the group consisting of hydrogen, alkyl C ₁ -C _12, preferably C CI _O, more preferably C ₁ -C ₄ alkyl, a group -OR ', a group -NHR 'and a group -SR' wherein R 'is an alkyl group C ₁ -C _12, preferably C CI _O, more preferably C 1 -C 4.

5. Compound according to any one of the preceding claims, characterized in that the group E is a hydrocarbon chain, linear or branched, preferably saturated, C ₁ -C ₂₄ , preferably C ₁ -C ₁₀ , more preferably -C -C _O optionally interrupted by one or more atoms of nitrogen, sulfur or oxygen.

6. Compound according to any one of the preceding claims, characterized in that it is of the following formula (III):

(III).

7. Synthesis process of the compound of formula (I) as defined in any one of the preceding claims, comprising the following successive steps:

(b1) the reaction of a compound of formula (IX) below: x in which A is as defined in claim 1 or 2 and Y represents a nucleophilic group, with a compound of the following formula (X):

(X), wherein E is as defined in claim 1 or 5 and Z represents a nucleofuge group; in the presence of at least one polar solvent SI, of at least one base, at a temperature T1 ranging from 70 to 150 ° C, to form a compound of the following formula (XI): x

(XII);

(c) a step of recovering said oxime compound of formula (XII);

8. The method of claim 7, wherein the two steps (b l) and (b2) are separated by a step of isolation and purification of the compound of formula (XI).

9. The method of claim 7, wherein the two steps (b l) and (b2) are carried out according to a one-pot synthesis.

10. A method according to any one of claims 7 to 9, wherein the Y group is selected from hydroxyl, thiol and primary or secondary amine functions.

11. A method according to any one of claims 7 to 10, wherein the Z group is selected from chlorine, bromine, iodine, mesylate group, tosylate group, acetate group and trifluoromethylsulfonate group.

12. A method according to any one of claims 7-1 1, wherein the polar solvent SI is a polar solvent miscible in water, preferably a protic solvent, more preferably an alcoholic protic solvent.

13. Method according to any one of claims 7 to 12, wherein the compound of formula (IX) represents 5 to 40% by weight, preferably 10 to 30% by weight, relative to the weight of the solvent.

14. A method according to any one of claims 7 to 13, wherein the base is selected from alkali alcoholates, alkali carbonates, alkaline earth carbonates, alkali hydroxides, alkaline earth hydroxides and mixtures thereof.

15. Process according to any one of claims 7 to 14, in which the base is chosen from sodium methanolate, potassium carbonate and sodium hydroxide, preferably potassium carbonate.

16. A method according to any one of claims 7 to 15, wherein the molar amount of base is 1.5 to 8 molar equivalents, preferably 2 to 6 molar equivalents, relative to the molar amount of compound of formula (IX).

17. The method of any of claims 7 to 16, wherein the addition of the aqueous hydroxylamine solution is carried out when the conversion of the compound of formula (IX) is at least 70% by weight.

18. Process according to any one of claims 7 to 17, in which the oxidizing agent is chosen from sodium hypochlorite, N-bromosuccinimide in the presence of a base and N-chlorosuccinimide in the presence of a base. , preferably sodium hypochlorite.

19. Process according to any one of claims 7 to 18, in which the organic solvent S2 is an organic solvent chosen from chlorinated solvents of ester, ether and alcohol type, preferably chosen from dichloromethane, acetate. ethyl, butyl acetate, diethyl ether, isopropanol and ethanol, more preferably chosen from ethyl acetate and butyl acetate.

20. A method according to any one of claims 7 to 19, comprising a step (a2) of manufacturing the compound of formula (X), prior to step (b1), by reacting a compound of the following formula (XIII):

(XIII), in which E is as defined in claim 1 or 5, with an agent allowing the formation of the nucleofuge group Z.

21. The method of claim 20, wherein said agent is thionyl chloride.

22. The method of claim 20 or 21, wherein step (a2) is carried out in the absence or in the presence of at least one solvent S4, preferably a chlorinated solvent, more preferably dichloromethane.

23. A method according to any one of claims 20 to 22, wherein step (a2) is immediately followed by step (a3) of recovering the compound of formula (X), preferably by purification with toluene, plus preferably by crystallization of the compound of formula (X) in toluene.