Molecules with nitrile oxide functional groups

Abstract

The present invention relates to compounds of formula (I): wherein: -A represents an aromatic ring, which is optionally substituted by one or more identical or different aliphatic, preferably saturated, linear or branched hydrocarbon chains, and the hydrocarbon chains are optionally substituted or interrupted by one or more heteroatoms; -E represents a divalent hydrocarbon group which optionally contains one or more heteroatoms; -X is a halogen atom, preferably a chlorine atom.

Description

Technical Field

[0001] The present invention relates to the field of nitrogen-containing molecules comprising at least one unit enabling them to associate with each other or with fillers through non-covalent bonds and comprising a functional group capable of reacting with a polymer comprising unsaturation in order to form a covalent bond with said polymer.

[0002] More precisely, the present invention relates to molecules having a nitrile oxide functional group and an N-substituted imidazolinone (imidazolidinone) functional group. The application also relates to a method for the synthesis of such molecules. Background Art

[0003] In the industrial field, mixtures of polymers and fillers are often used. In order to make such mixtures have good properties, means of improving the dispersion of fillers in polymers are constantly sought. One of the means to achieve this result is the use of coupling agents that are able to establish an interaction between polymer and filler.

[0004] Reagents comprising nitrogen-containing dipoles for coupling polymers to fillers are described in the documents published under the numbers US Pat. No. 7,186,845 B2 and JP 2008208163.

[0005] These documents describe the modification of polymers comprising diene units by nitrogen-containing dipolar compounds which further comprise a heterocycle which itself comprises a nitrogen atom and oxygen and / or sulfur atoms.

[0006] More particularly, the compounds described are nitrones having an oxazoline or thiazoline functional group, for example ((2-oxazolyl)-phenyl-N-methylnitrone):

[0007]

[0008] When a diene polymer is reacted with such a compound, the resulting polymer will have an oxazoline or thiazoline ring.

[0009] These rings present on the polymer can then react with the surface functional groups of the filler (e.g. carbon black or silica) mixed with the polymer. Due to the ring opening (opening) of the oxazoline or thiazoline ring, the reaction results in the establishment of a covalent bond between the polymer and the filler modified by the coupling agent. This is because, as described in document US7186845B2, the oxazoline and / or thiazoline ring can be ring-opened in the presence of a nucleophile that may be present on the surface of the filler, for example.

[0010] However, during the preparation of mixtures containing these polymers modified by agents to couple with fillers, the establishment of such covalent bonds does have disadvantages. In particular, the presence of such prematurely established covalent bonds between polymer and filler makes these mixtures very viscous in the non-crosslinked state, which makes all operations before the crosslinking (vulcanization) of rubber-based formulations, in particular the preparation of the mixture of said compounds and its shaping difficult. These disadvantages have a strong impact on industrial productivity.

[0011] It is therefore desirable to propose novel molecules which do not have the above-mentioned disadvantages, ie molecules which, after reaction with the polymer and mixing with the filler, are able to form no covalent bonds with the filler and thus do not lead to an excessive increase in the viscosity of the mixture.

[0012] Patent application WO 2012 / 007684 thus relates to a compound comprising at least one group Q and at least one group A bonded together via at least one and preferably one spacer group Sp, wherein:

[0013] -Q comprises a dipole containing at least one and preferably one nitrogen atom;

[0014] -A comprises an associative group including at least one nitrogen atom;

[0015] -Sp is the atom or group of atoms that forms a bond between Q and A.

[0016] When a polymer grafted with a compound as defined above is mixed with a filler, it establishes only unstable bonds with the filler, which makes it possible to ensure not only good polymer-filler interactions that are beneficial to the final properties of the polymer, but also without the disadvantages that can result from too strong polymer-filler interactions.

[0017] An example of such a compound is 2-[2-(2-oxoimidazolin-1-yl)ethoxy]benzonitrile oxide as follows:

[0018]

[0019] Furthermore, in the application WO 2019 / 007881, various compounds are exemplified, in particular including the following 2-[2-(2-oxoimidazolin-1-yl)ethoxy]-1-naphthonitrile oxide:

[0020]

[0021] It was demonstrated that rubber compositions comprising this molecule have advantageous properties in terms of hysteresis. Nevertheless, there is always a constant need for rubber compositions having improved properties. Summary of the invention

[0022] In this context, the Applicant has found that specific halogen compounds, once integrated in a rubber composition, lead to excellent hysteresis properties being obtained.

[0023] The present invention therefore relates to compounds of the following formula (I):

[0024]

[0025] in:

[0026] -A represents an aromatic ring, optionally substituted by one or more identical or different aliphatic, preferably saturated, linear or branched hydrocarbon chains, said hydrocarbon chains being optionally substituted or interrupted by one or more heteroatoms;

[0027] -E represents a divalent hydrocarbon group optionally containing one or more heteroatoms;

[0028] -X represents a halogen atom, preferably a chlorine atom.

[0029] "Hydrocarbon chain" within the meaning of the present invention means a chain comprising one or more carbon atoms and one or more hydrogen atoms.

[0030] In this specification, unless otherwise expressly stated, all percentages (%) indicated are mass %. In addition, any interval value indicated by the expression "between a and b" represents a range from a value greater than (a) to a value less than b (i.e., excluding the limits a and b), while any interval value indicated by the expression "a to b" represents a range from a to a value of b (i.e., including the strict limits a and b). DETAILED DESCRIPTION

[0031] The present invention and its advantages will be readily understood from the following description and exemplary embodiments.

[0032] The compounds mentioned in the description may be of fossil or biogenic origin. In the latter case, they may be derived partly or completely from biomass or obtained from renewable raw materials derived from biomass.

[0033] According to formula (I), the compounds according to the invention contain a group A representing an aromatic ring, which is optionally substituted by one or more identical or different aliphatic, preferably saturated, linear or branched hydrocarbon chains, which are optionally substituted or interrupted by one or more heteroatoms.

[0034] "Aromatic ring" within the meaning of the present invention means a monocyclic or polycyclic aromatic hydrocarbon group derived from an aromatic hydrocarbon in which two hydrogen atoms have been eliminated. Thus, the aromatic ring is a divalent group.

[0035] "Monocyclic or polycyclic aromatic hydrocarbon radical" means within the meaning of the present invention one or more aromatic rings whose backbone consists of carbon atoms. In other words, there are no heteroatoms in the backbone of the ring. The arylene ring may be monocyclic, i.e., consisting of a single ring, or polycyclic, i.e., consisting of a plurality of condensed aromatic hydrocarbon rings; such condensed rings then have at least two consecutive carbon atoms in common. These rings may be ortho-condensed or ortho- and peri-condensed.

[0036] Preferably, the arylene ring contains 6 to 14 carbon atoms.

[0037] The arylene ring may be unsubstituted, partially substituted or fully substituted. The arylene ring is partially substituted when one or two or more hydrogen atoms (but not all atoms) are replaced by one or two or more aliphatic, preferably saturated, linear or branched hydrocarbon chains (optionally substituted by one or more heteroatoms). The chain is also referred to as a substituent. If all hydrogen atoms are replaced by the chain, the arylene ring is fully substituted. The substituents of the arylene ring may be the same or different relative to each other.

[0038] Preferably, when the arylene ring is substituted by one or more identical or different aliphatic, preferably saturated, linear or branched hydrocarbon chains (optionally substituted or interrupted by one or more heteroatoms), this or these chains may be inert with respect to the N-substituted imidazolidinone functionality and the nitrile oxide.

[0039] "One or more hydrocarbon chains which are inert with respect to the N-substituted imidazolidinone functional group and the nitrile oxide" means within the meaning of the present invention a hydrocarbon chain which reacts neither with the N-substituted imidazolidinone functional group nor with the nitrile oxide. Thus, the hydrocarbon chain which is inert with respect to the N-substituted imidazolidinone functional group and the nitrile oxide is preferably an aliphatic hydrocarbon chain which has no alkenyl or alkynyl functional group which is susceptible to reaction with the functional group or the radical, i.e. an aliphatic, saturated, linear or branched hydrocarbon chain which is optionally substituted or interrupted by one or more heteroatoms and preferably comprises 1 to 24 carbon atoms.

[0040] Preferably, group A is C6-C 14 An aromatic ring, which is optionally substituted by one or more identical or different aliphatic hydrocarbon chains (preferably saturated, linear or branched), which are optionally substituted or interrupted by one or more heteroatoms. More preferably, group A is C6-C 14 The aromatic ring is optionally replaced by one or more identical or different C1-C 24 A saturated linear or branched hydrocarbon chain, which is optionally substituted or interrupted by one or more nitrogen, sulfur or oxygen heteroatoms. Still more preferably, group A is C6-C 14 The aromatic ring is optionally replaced by one or more identical or different selected from C1-C 12, preferably C1-C6, more preferably C1-C4 alkyl, OR' group, -NHR' group, -SR' group, wherein R' is C1-C 12 Alkyl, preferably C1-C6, more preferably C1-C4 alkyl.

[0041] Preferably, the compound of formula (I) according to the present invention has the following formula (Ia):

[0042]

[0043] in:

[0044] - The group selected from R1 to R7 represents a group of the following formula (II):

[0045]

[0046] Where E and X are as defined above;

[0047] - six radicals selected from R1 to R7, other than the radical representing the radical of formula (II), which are identical or different and independently of one another represent a hydrogen atom or an aliphatic, preferably saturated, linear or branched hydrocarbon chain, which is optionally substituted or interrupted by one or more heteroatoms.

[0048] Preferably, in the compound of formula (Ia), the six radicals of formula (Ia) selected from R1 to R7, except the radical representing the radical of formula (II), are identical or different and independently represent a hydrogen atom or an aliphatic, saturated, linear or branched C1-C 24 A hydrocarbon chain optionally substituted or interrupted by one or more heteroatoms.

[0049] Again more preferably, in the compound of formula (Ia), the six groups of formula (Ia) selected from R1 to R7, except for the group representing the group of formula (II), are identical or different and are selected from hydrogen atoms, C1-C 12 , preferably C1-C6, more preferably C1-C4 alkyl, -OR' group, -NHR' group and -SR' group, wherein R' is C1-C 12 , preferably C1-C6, more preferably C1-C4 alkyl.

[0050] Advantageously, in formula (Ia), R1 represents a radical of formula (II) as defined above and R2 to R7, being identical or different, represent a hydrogen atom or an aliphatic, preferably saturated, linear or branched C1-C 24 A hydrocarbon chain optionally substituted or interrupted by one or more heteroatoms.

[0051] According to a particular embodiment, in formula (Ia), R1 represents a group of formula (II) as defined above, and R2 to R7, being identical or different, are selected from a hydrogen atom, a C1-C 12 , preferably C1-C6, more preferably C1-C4 alkyl, -OR' group, -NHR' group and -SR' group, wherein R' is C1-C 12 , preferably C1-C6, more preferably C1-C4 alkyl.

[0052] Still more preferably, in this embodiment, R1 represents a group of formula (II) as defined above and R2 to R7 are identical and represent a hydrogen atom.

[0053] In the compounds of formula (I) and (Ia), the group E is a divalent hydrocarbon group which may optionally contain one or more heteroatoms.

[0054] "Divalent hydrocarbon group" means within the meaning of the present invention a spacer group (or connecting group) which forms a bridge between the group A and the imidazolidinone group, the spacer group being a saturated or unsaturated, preferably saturated, linear or branched C1-C 24 The hydrocarbon chain may optionally contain one or more heteroatoms such as N, O and S. The hydrocarbon chain may be optionally substituted provided that the substituents do not react with the nitrile oxide and imidazolidinone groups.

[0055] Preferably, in the compounds of formula (I) and (Ia), the group E is a linear or branched, preferably saturated, C1-C 24 , preferably C1-C 10 , more preferably a chain of C1-C6 hydrocarbons, which are optionally interrupted by one or more hydrogen, sulfur or oxygen atoms.

[0056] Preferably, in the compounds of formula (I) and (Ia), the group E is selected from -R-, -NH-R-, -OR- and -SR-, wherein R is a linear or branched C1-C 24 , preferably C1-C 10 , more preferably C1-C6 alkylene.

[0057] Still more preferably, in the compounds of formula (I) and (Ia), the group E is selected from -R- and -OR-, wherein R is a linear or branched C1-C 24 , preferably C1-C 10 , more preferably C1-C6 alkylene.

[0058] According to a particular embodiment, in the compounds of formula (I) and (Ia), the group E is selected from -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -O-CH2-, -O-CH2-CH2-, -O-CH2-CH2-CH2- and -O-CH2-CH2-CH2-CH2-CH2-.

[0059] According to a preferred embodiment, compounds of formula (Ia) as defined above are particularly preferred, the group E is selected from -R- and -OR-, wherein R is a linear or branched C1-C 24 , preferably C1-C 10 , more preferably C1-C6 alkylene, and group X is a chlorine atom.

[0060] According to this embodiment, more preferably, the compound of formula (I) is a compound of formula (Ia), wherein: -R1 represents a group of formula (II), wherein the group E is selected from -R- and -OR-, wherein R is a linear or branched C1-C 24 , preferably C1-C 10 , more preferably C1-C6 alkylene, and the group X is a chlorine atom; and -R2 to R7, which are the same or different, represent a hydrogen atom or an aliphatic, preferably saturated, linear or branched C1-C 24 A hydrocarbon chain optionally substituted or interrupted by one or more heteroatoms.

[0061] According to this embodiment, more preferably, the compound of formula (I) is a compound of formula (Ia), wherein: -R1 represents a group of formula (II), wherein the group E is selected from -R- and -OR-, wherein R is a linear or branched C1-C 24 , preferably C1-C 10 , more preferably C1-C6 alkylene, and the group X is a chlorine atom; and -R2 to R7 are the same or different and are selected from hydrogen atoms, C1-C 12 , preferably C1-C6, more preferably C1-C4 alkyl, -OR' group, -NHR' group and -SR' group, wherein R' is C1-C 12 , preferably C1-C6, still more preferably C1-C4 alkyl.

[0062] According to this embodiment, more preferably, the compound of formula (I) is a compound of formula (Ia), wherein: -R1 represents a group of formula (II), wherein the group E is selected from -R- and -OR-, wherein R is a linear or branched C1-C 24 , preferably C1-C 10 , more preferably C1-C6 alkylene, and the group X is a chlorine atom; and -R2 to R7 are the same and represent a hydrogen atom.

[0063] Advantageously, the compound of formula (I) has the following formula (III):

[0064]

[0065] Another object of the present invention is a process for synthesizing a compound of formula (I) according to the present invention, comprising the following successive steps:

[0066] (b1) reacting a compound of the following formula (IX) with a compound of the following formula (X) in the presence of at least one polar solvent S1 and at least one base at a temperature T1 in the range of 70 to 150° C. to form a compound of the following formula (XI):

[0067]

[0068] wherein A is as defined above and Y represents a nucleophilic group,

[0069]

[0070] wherein E is as defined above and Z represents a nucleofugal group;

[0071]

[0072] (b2) reacting the 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 the following formula (XII):

[0073]

[0074] (c) a step of recovering the oxime compound of formula (XII);

[0075] (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, wherein the proportion of the oxidizing agent is at least 6 molar equivalents relative to the molar amount of the oxime compound of formula (XII).

[0076] "Polar solvent" within the meaning of the present invention means a solvent having a dielectric constant above 2.2.

[0077] "Nucleofugal group" within the meaning of the present invention means a leaving group which takes away its bonding electron pair (doublet).

[0078] "Nucleophilic group" within the meaning of the present invention is taken to mean a compound which comprises at least one atom with a free electron pair or a negatively charged atom.

[0079] As explained previously, the process for synthesizing the compounds of formula (I) according to the invention comprises in particular the successive steps (b1) and (b2).

[0080] According to a particular embodiment, the two steps (b1) and (b2) are separated by a step of isolating and purifying the compound of formula (XI).

[0081] According to another embodiment, the two steps (b1) and (b2) are carried out according to a monotopic synthesis, i.e. steps (b1) and (b2) are "one-pot" (two-step monotopic synthesis method), i.e. without isolating the intermediate compound of formula (XI).

[0082] The process according to the invention comprises a step (b1) of reacting a compound of formula (IX) carrying a group Y as described above with a compound of formula (X) carrying a group Z as described above.

[0083] Preferably, the group Y is selected from hydroxyl, thiol and primary or secondary amine functional groups.

[0084] The group Z may be selected from chlorine, bromine, iodine, a mesylate group, a tosylate group, an acetate group and a trifluoromethylsulfonate group.

[0085] Said step (b1 ) of the process according to the invention is carried out in the presence of at least one polar solvent S1 and at least one base at a temperature T1 ranging from 70 to 150°C.

[0086] According to a particular embodiment of the present invention, the polar solvent S1 is a polar solvent miscible with water, preferably a protic solvent.

[0087] Dimethylformamide (DMF), dimethyl sulfoxide (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 solvents S1 that can be used in the process according to the invention.

[0088] Preferably, the protic solvent is alcoholic.

[0089] 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.

[0090] The base may be selected from alkali metal alkoxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydroxides, alkaline earth metal hydroxides and mixtures thereof.

[0091] Advantageously, it is possible to add:

[0092] - one or more catalysts selected from silver (I) salt catalysts, quaternary ammonium phase transfer catalysts and mixtures thereof;

[0093] - One or more ionic liquids.

[0094] Preferably, the base is selected from sodium methoxide, potassium carbonate and soda, more preferably potassium carbonate.

[0095] According to a particular embodiment of the invention, the molar amount of the base is between 1.5 and 8 molar equivalents, preferably between 2 and 6 molar equivalents, relative to the molar amount of the compound of formula (IX).

[0096] As explained previously, step (b1) of the process according to the invention is carried out at a temperature T1 ranging from 70 to 150°C.

[0097] Preferably, the temperature T1 is a temperature in the range of 70 to 120°C, more preferably 80 to 110°C.

[0098] As explained previously, step (b1) of the process according to the invention is followed by a step (b2) of adding an aqueous solution of hydroxylamine to the reaction medium containing the compound of formula (XI) at a temperature T2 ranging from 30 to 70°C.

[0099] Preferably, the aqueous solution of hydroxylamine is added when the conversion of the compound of formula (IX) is at least 70% by weight.

[0100] Advantageously, the temperature T2 varies from 40 to 60°C.

[0101] The method according to the present invention further comprises the step (c) of recovering the oxime compound of formula (XII) as described above.

[0102] Preferably, the oxime compound of formula (XII) is recovered by precipitation with water, optionally followed by washing with water.

[0103] The method according to the present invention also includes step (d): oxidizing the oxime compound of formula (XII) with an oxidant in the presence of at least one organic solvent S2 to obtain a compound of formula (I), especially a preferred compound; the amount of the oxidant is at least 6 molar equivalents, preferably 6.5 to 15 molar equivalents, relative to the molar amount of the oxime compound of formula (XII).

[0104] This amount of oxidizing agent may be added in one time or in multiple times during step (d), preferably in two times during step (d).

[0105] Preferably, the oxidant is selected from sodium hypochlorite, N-bromosuccinimide in the presence of a base and N-chlorosuccinimide in the presence of a base, preferably the oxidant is sodium hypochlorite.

[0106] Advantageously, the organic solvent S2 is an organic solvent selected from chlorinated solvents and ester, ether and alcohol type solvents, preferably selected from dichloromethane, ethyl acetate, butyl acetate, diethyl ether, isopropanol and ethanol, more preferably selected from ethyl acetate and butyl acetate.

[0107] Preferably, the oxime compound of formula (XII) accounts for 1 to 30 wt%, preferably 1 to 20 wt%, relative to the total weight of the assembly comprising the oxime compound of formula (XII), the organic solvent S2 and the oxidizing agent.

[0108] Advantageously, the process according to the invention comprises, after step (d), a step (e) of recovering the compound of formula (I).

[0109] According to a particular embodiment of the invention, the process according to the invention comprises, before step (b1), a step (a2) of manufacturing a compound of formula (X) by reacting a compound of formula (XIII) with a reagent allowing the formation of a nucleofugal group Z:

[0110]

[0111] wherein E is as defined above.

[0112] Preferably, the reagent is thionyl chloride.

[0113] Preferably, step (a2) is carried out in the absence or presence of at least one solvent S4, preferably a chlorinated solvent, more preferably dichloromethane.

[0114] Advantageously, step (a2) is immediately followed by step (a3) ​​of recovering the compound of formula (X), preferably by purification with toluene, more preferably by crystallization of the compound of formula (X) in toluene.

[0115] The invention is further illustrated by the following non-limiting examples.

[0116] Example

[0117] molecular

[0118] Structural analysis and determination of molar purity of the synthesized molecules were performed by NMR analysis. Spectra were collected on a Bruker Avance 3 400-MHz spectrometer equipped with a BBFO z-gradient 5 mm broadband probe (required). Quantification 1 H NMR experiments used a simple 30° pulse sequence and a 3 second repetition delay between each of the 64 acquisitions. Unless otherwise stated, the samples were dissolved in the deuterated solvent deuterated dimethyl sulfoxide (DMSO). The deuterated solvent was also used to lock the signal. For example, calibration was performed on the signal of the protons of deuterated DMSO at 2.44 ppm relative to the TMS reference at 0 ppm. 1 H NMR spectroscopy and 2DHSQC 1 H / 13 C and HMBC 1 H / 13 The combination of C experiments allowed the structural determination of the molecule (see assignment tables 1, 2 and 3 below). 1 H 1D NMR spectra were used for molar quantification.

[0119] Mass spectrometry analysis was performed by direct injection via electrospray ionization mode (ID / ESI). The analysis was performed on a Bruker HCT spectrometer (flow rate 600 μL / min, nebulizer gas pressure 10 psi, nebulizer gas flow rate 4 L / min).

[0120] Molecules grafted onto SBR or IR

[0121] The molar fraction of 2-[2-(3-chloro-2-oxoimidazolin-1-yl)ethoxy]-1-naphthonitrile oxide grafted on SBR (styrene-butadiene rubber) or IR (isoprene rubber) was determined by NMR analysis. The spectra were collected on a Bruker 500 MHz spectrometer equipped with a "BBFO z-gradient 5 mm CryoProbe". Quantification 1 The H NMR experiments used a simple 30° pulse sequence and a 5 second repetition delay between each acquisition. For the purpose of obtaining a locking signal, the samples were dissolved in deuterated chloroform (CDCl3). The 2D NMR experiments allowed the nature of the grafted units to be verified by the chemical shifts of carbon atoms and protons.

[0122] Dynamic properties

[0123] According to ASTM D 5992-96, the dynamic property tan (δ) maximum value is measured on a viscosity analyzer (Metravib VA4000). According to ASTM D 1349-99, the sample (cylindrical test piece, 4mm thick and 400mm2 cross section) of the composition of vulcanization is recorded under normal temperature conditions (23°C) and experiences the response of sinusoidal stress in the simple alternating shearing under a frequency of 10Hz. The deformation amplitude sweep is implemented from 0.1% to 100% (outward circulation) and then from 100% to 0.1% (return circulation). The result used is the loss factor tan (δ). For the return circulation, the maximum value of tan (δ) observed is marked, which is recorded as tan (δ) maximum value.

[0124] I. Synthesis of (2-(2-(3-chloro-2-oxoimidazolin-1-yl)ethoxy)-1-naphthonitrile oxide

[0125]

[0126] (2-(2-(3-Chloro-2-oxoimidazolin-1-yl)ethoxy)-1-naphthocarbonitrile oxide is synthesized in six steps, which are referred to as step a1, step a2, step b1, step b2, step c and step d.

[0127] Step a1 is carried out according to Scheme 1, step a2 is carried out according to Scheme 2, and step b1 is carried out according to Scheme 3. Steps b2 and c are carried out according to Scheme 4. Step d is carried out according to Scheme 5.

[0128] Step a1: Preparation of 2-hydroxy-1-naphthaldehyde

[0129]

[0130] Scenario 1:

[0131] This compound can be obtained from naphthol by formylation reaction according to the so-called Reimer-Tiemann protocol described in Russell, Alfred and Lockhart, Luther B., Organic Syntheses, 22, 63-4; 1942 or in Wynberg, Hans and Meijer, Egbert W., Organic Reactions (Hoboken, NJ, United States), 28, 1982, 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 by the Vilsmeier reaction described by Jones, Gurnos and Stanforth, Stephen P. in Organic Reactions (Hoboken, NJ, United States), 49, 1997.

[0132] 2-Hydroxy-1-naphthaldehyde is commercially available. For example, it can be obtained from Aldrich (CAS 708-06-5). Step a2: Preparation of 1-(2-chloroethyl)imidazolin-2-one

[0133]

[0134] Scenario 2:

[0135] This compound can be obtained according to the protocol described in patent application WO 2012 / 007684. Step b1: Preparation of 2-(2-(2-oxoimidazolin-1-yl)ethoxy)-1-naphthaldehyde

[0136]

[0137] Scenario 3:

[0138] A mixture of 2-hydroxy-1-naphthaldehyde (20.0 g; 0.116 mol), potassium carbonate (24.08 g; 0.174 mol) and 1-(2-chloroethyl)imidazolin-2-one (25.9 g; 0.174 mol) in DMF (20 mL) is heated at 75° C. (bath temperature) for 3.0-3.5 hours. A second portion of 1-(2-chloroethyl)imidazolin-2-one (17.26 g; 0.116 mol) is then added and the reaction medium is stirred at 75° C. (bath temperature) for 9 to 10 hours. After returning to 40-45° C., the reaction medium is poured into a solution of sodium hydroxide (10 g; 0.25 mol) in water (700 mL). The mixture is stirred for 10 to 15 minutes. The precipitate is filtered and washed on the filter with distilled water (3 times, 400 mL).

[0139] A grey solid was obtained (31.51 g; 95% yield).

[0140] Molar purity greater than 85% ( 1 1H NMR).

[0141]

[0142] [Table 1]

[0143] N° <![CDATA[δ 1 H(ppm)]]> <![CDATA[δ 13 C(ppm)]]> 1 10.86 191.6 2 / 116.7 3 / 131.5 4 9.19 124.9 5 7.56 130 6 7.37 124.9 7 7.71 128.3 8 / 128.6 9 7.99 137.7 10 7.2 113.1 11 / 162.9 12 4.31 68.7 13 3.63 13.4 14 3.59 16.8 15 3.72 38.3 16 / 162.6

[0144] Solvent: CDCl3

[0145] Steps b2 and c: Preparation of 2-(2-(2-oxoimidazolin-1-yl)ethoxy)-1-naphthaldehyde

[0146]

[0147] The product isolated at the end of Scheme 3 was used in Scheme 4 below.

[0148] Solution 4:

[0149] A solution of hydroxylamine (2.05 g; 31.0 mmol, 50% in water, Aldrich) in ethanol (5 mL) is added to a solution of 2-(2-(2-oxoimidazolin-1-yl)ethoxy)-1-naphthaldehyde (6.3 g; 22.2 mmol) in ethanol (30 mL) at 45° C. (bath temperature). The reaction medium is stirred at 55° C. (bath temperature) for 4 hours. After returning to 40° C., ethyl acetate (30 mL) is added dropwise for 15 minutes. The precipitate is filtered and washed on the filter with an ethanol / ethyl acetate mixture.

[0150] A white solid was obtained (4.00 g; 60% yield).

[0151] pass 1 The molar purity estimated by H NMR was greater than 95%.

[0152]

[0153] [Table 2]

[0154] N° <![CDATA[δ 1 H(ppm)]]> <![CDATA[δ 13 C(ppm)]]> 1 8.75 147.5 2 / 115.9 3 / 133 4 8.78 127 5 7.46 128.5 6 7.35 125.2 7 7.88 132.8 8 / 130.9 9 7.79 129.4 10 7.36 115.2 11 / 157.1 12 4.28 69.3 13 3.59 44.4 14 3.64 47.6 15 3.40 39.3 16 / 165.3

[0155] Solvent: MeOH

[0156] Step d: Preparation of (2-(2-(3-chloro-2-oxoimidazolin-1-yl)ethoxy)-1-naphthonitrile oxide

[0157]

[0158] Solution 5:

[0159] An aqueous solution of NaOCl (74.44 g / L; 98 mL; 4.0 eq. (eq. = molar equivalent)) was added dropwise over 10 minutes to a suspension of the above 2-(2-(2-oxoimidazolin-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.). The reaction medium was stirred at 0-2° C. (bath temperature = 0° C.) for 8.5 hours.

[0160] A second portion of an aqueous solution of NaOCl (74.44 g / L; 98 ml; 4.0 eq.) is added over 5 minutes. The reaction medium is stirred at 0-2° C. (bath temperature = 0° C.) for 10-11 hours. The precipitate is filtered and washed on the filter with water (twice, 25 ml) and then with ethyl acetate (twice, 10 mL).

[0161] A white solid (6.24 g; 18.7 mmol, 77% yield) with a melting point of 127.0-127.5° C. was then obtained.

[0162] (2-(2-(3-chloro-2-oxoimidazolin-1-yl)ethoxy)-1-naphthonitrile oxide having a molar purity of greater than 92% ( 1 H NMR) and less than 6 mol % of 2-(2-(2-oxoimidazolin-1-yl)ethoxy)-1-naphthonitrile oxide and 2 mol % of residual solvent impurities.

[0163]

[0164] [Table 3]

[0165] N° <![CDATA[δ 1 H(ppm)]]> <![CDATA[δ 13 C(ppm)]]> 1 / / 2 / 96.9 3 / 134.0 4 7.93 124.1 5 7.57 129.1 6 7.40 125.3 7 7.78 128.7 8 / 128.7 9 7.90 133.1 10 7.16 112.6 11 / 160.2 12 4.33 68.8 13 3.71 44.8 14 3.75 45.2 15 3.58 52.1 16 / 161.3

[0166] Solvent CDCl3

[0167] II. Production of SBR grafted with (2-(2-(3-chloro-2-oxoimidazolin-1-yl)ethoxy)-1-naphthonitrile oxide

[0168] The previously obtained (2-(2-(3-chloro-2-oxoimidazolin-1-yl)ethoxy]-1-naphthonitrile oxide was used (at the end of Scheme 5). It will be referred to as compound A below.

[0169] 2-[2-(3-chloro-2-oxoimidazolin-1-yl)ethoxy]-1-naphthonitrile oxide (0.27 g; 0.81 mmol) compound A was introduced into 20 g of a nonfunctionalized styrene-butadiene copolymer (containing 26.5% by weight of styrene relative to the total weight of the polymer and 25% by weight of butadiene-1,2 units relative to the total weight of the butadiene part; Mn=150000 g / mol and Ip=1.84) on a cylindrical tool (external mixer at 23° C.). The mixture was homogenized in 15 portfolio passes. This mixing stage was followed by a heat treatment at 120° C. for 10 minutes in a press at a pressure of 10 bar.

[0170] 1 H NMR analysis showed that the grafting mole fraction was 0.29% and the grafting yield was 96%.

[0171] III. Preparation of IR grafted with (2-(2-(3-chloro-2-oxoimidazolin-1-yl)ethoxy)-1-naphthonitrile oxide

[0172] The previously obtained (2-(2-(3-chloro-2-oxoimidazolin-1-yl)ethoxy]-1-naphthonitrile oxide was used (at the end of Scheme 5).

[0173] 2-[2-(3-Chloro-2-oxoimidazolin-1-yl)ethoxy]-1-naphthonitrile oxide (0.29 g; 0.88 mmol) compound A was introduced into 20 g of synthetic polyisoprene (containing 99.35% by weight of cis-1,4-isoprene units and 0.65% by weight of 3,4-isoprene units; Mn=375000 g / mol and Ip=3.6) on a cylindrical tool (external mixer at 23° C.). The mixture was homogenized in 15 combined passes. This mixing stage was followed by a heat treatment at 120° C. for 10 minutes in a press at a pressure of 10 bar.

[0174] 1 H NMR analysis showed that the grafting mole fraction was 0.2% and the grafting yield was 66%.

[0175] IV. Rubber Composition

[0176] 1) Preparation of rubber composition

[0177] Three rubber compositions, hereinafter referred to as compositions C1, C2 and C3, were prepared and are defined as follows.

[0178] Composition C1 is a “conventional” rubber composition for use as tire tread, comprising in particular a non-grafted synthetic polyisoprene, silica and a silane polysulfide coupling agent.

[0179] Composition C2 is identical to composition C1 except that it also comprises compound B grafted onto synthetic polyisoprene. This is a composition comprising comparative compound B.

[0180] Composition C3 is the same composition as composition C1 except that it also comprises compound A grafted onto synthetic polyisoprene. This is a composition comprising compound A according to the invention.

[0181] The amounts of the various ingredients of these compositions, expressed as percentages (parts by weight per hundred parts by weight of elastomer), are listed in Table 4:

[0182] [Table 4]

[0183] Composition C1 C2 C3 Diene Elastomers(1) 100 100 100 Compound B(2) - 1.31 - Compound A(3) - - 1.46 Reinforcement fillers(4) 60 60 60 Coupling agent (5) 6 6 6 Carbon Black(6) 3 3 3 Antioxidants (7) 1.5 1.5 1.5 TMQ(8) 1 1 1 paraffin 1 1 1 ZnO(9) 2.7 2.7 2.7 Stearic acid (10) 2.5 2.5 2.5 CBS(11) 1.6 1.6 1.6 sulfur 1.3 1.3 1.3

[0184] Compositions C2 and C3 comprise the same molar amount of grafted compound A or B, namely 0.2 mol %.

[0185] (1) polyisoprene containing 99.35 wt% of cis-1,4-isoprene units and 0.65 wt% of 3,4-isoprene units; Mn=375000 g / mol and Ip=3.6;

[0186] (2) Compound B: (2-(2-(2-oxoimidazolin-1-yl)ethoxy)-1-naphthonitrile oxide;

[0187] (3) Compound A: (2-(2-(3-chloro-2-oxoimidazolin-1-yl)ethoxy)-1-naphthonitrile oxide;

[0188] (4) "Zeosil 1165MP" silica sold by Solvay;

[0189] (5) TESPT (sold by Evonik under the name "S169";

[0190] (6) Carbon black grade N234 sold by Cabot Corporation;

[0191] (7) N-1,3-dimethylbutyl-N-phenyl-p-phenylenediamine sold under the name "Santoflex 6-PPD" by Flexys;

[0192] (8) 2,2,4-trimethyl-1,2-dihydroquinoline sold by Flexys;

[0193] (9) Zinc oxide (technical grade) sold by Umicore;

[0194] (10) "Pristerene 4031" stearin sold by Uniquema;

[0195] (11) N-Cyclohexyl-2-benzothiazolyl-sulfenamide sold under the name “Santocure CBS” by the company Flexys.

[0196] The composition was prepared in the following manner: the diene elastomer was introduced into 85 cm 3 The mixture was filled to 70% in a "Polylab" internal mixture, with the initial temperature of the container being about 110° C. Compound A or compound B was introduced simultaneously with the diene elastomer, for the compositions relating to the compound A or compound B. Thermomechanical processing was then carried out at a temperature of 120° C. for one and a half minutes.

[0197] Next, for each of the three compositions, any reinforcing filler or fillers are introduced, as well as the coupling agent for the filler and the diene elastomer, and then, after one or two minutes of mixing, the various other ingredients, except the vulcanization system, are introduced. Thermomechanical processing (non-productive phase) is then carried out in one step (total mixing duration equal to about 5 minutes), until a maximum "descent" temperature of 160° C. is reached.

[0198] The mixture thus obtained is taken up and cooled, then the vulcanization system (sulphur and accelerator of sulphenamide type) is added at 25° C. on an external mixer (homofinisher), and the whole is mixed (productive phase) for approximately 5 to 6 minutes.

[0199] The composition thus obtained is then calendered in the form of a rubber plate (thickness ranging from 2 to 3 mm) or sheet in order to measure its physical and mechanical properties.

[0200] 2) Characterization Tests – Results

[0201] The rubber properties of these compositions were measured after curing for 60 minutes at 150°C. The results obtained are reported in Table 5.

[0202] [Table 5]

[0203] Composition C1 C2 C3 Maximum value of Tanδ at 23℃ 100 80 70

[0204] According to Table 5, it is found as expected that the composition C2 comprising the comparative compound (which comprises an elastomer modified with a compound comprising an unsubstituted imidazolidinone functional group) exhibits a reduction in hysteresis (tan(δ) maximum at 23° C.) compared to the composition C1 comprising no modified elastomer.

[0205] Surprisingly, composition C3 comprising a compound according to the invention, which comprises an elastomer modified with a compound comprising an N-substituted imidazolidinone functional group, has a significant reduction in hysteresis compared to comparative composition C1 and a significant reduction in hysteresis compared to comparative composition C2, which already had good hysteresis properties compared to composition C1.

[0206] The elastomer modified by the compounds according to the invention thus makes it possible to improve the hysteresis and therefore the anti-rolling properties of the compositions containing them.

Claims

1. A compound of the following formula (I): in: -A for C6-C 14 The arylene ring is optionally substituted with one or more C1-C 24 the same or different aliphatic, linear or branched hydrocarbon chains, which are optionally substituted or interrupted by one or more heteroatoms; -E stands for C1-C 24 A linear or branched hydrocarbon chain of , which is optionally interrupted by one or more nitrogen, sulfur or oxygen atoms; -X represents a halogen atom.

2. The compound according to claim 1, characterized in that It has the following formula (Ia): in: - The group selected from R1 to R7 represents a group of the following formula (II): in: - E and X are as defined in claim 1; - six groups selected from R1 to R7, other than the group representing the group of formula (II), which are identical or different and independently represent a hydrogen atom or an aliphatic C1-C 24 A linear or branched hydrocarbon chain, which is optionally substituted or interrupted by one or more heteroatoms.

3. The compound according to claim 2, characterized in that R1 represents a group of formula (II) as defined in claim 2 and R2 to R7, being identical or different, represent a hydrogen atom, or an aliphatic C1-C24, linear or branched hydrocarbon chain, which is optionally substituted or interrupted by one or more heteroatoms.

4. The compound according to claim 1 or 2, characterized in that It has the following formula (III):

5. A process for the synthesis of a compound of formula (I) as defined in any one of the preceding claims, comprising the following sequential steps: (b1) reacting a compound of the following formula (IX) with a compound of the following formula (X) in the presence of at least one polar solvent S1 and at least one base at a temperature T1 in the range of 70 to 150° C. to form a compound of the following formula (XI): wherein A is as defined in claim 1 or 2 and Y represents a nucleophilic group, wherein E is as defined in claim 1 and Z represents a nucleofugal group, (b2) reacting the 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 the following formula (XII): (c) a step of recovering the 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, wherein the content of the oxidizing agent is at least 6 molar equivalents relative to the molar amount of the oxime compound of formula (XII).

6. The process according to claim 5, wherein the two steps (b1) and (b2) are separated by a step of isolating and purifying the compound of formula (XI).

7. The method according to claim 5, wherein the two steps (b1) and (b2) are performed according to a single-zone synthesis.

8. The method according to any one of claims 5 to 7, wherein the group Y is selected from hydroxyl, thiol and primary or secondary amine functional groups.

9. The method according to any one of claims 5 to 7, wherein the group Z is selected from chlorine, bromine, iodine, a mesylate group, a tosylate group, an acetate group and a trifluoromethylsulfonate group.

10. The method according to any one of claims 5 to 7, wherein the polar solvent S1 is a polar solvent miscible with water.

11. The process according to any one of claims 5 to 7, wherein the compound of formula (IX) represents 5 to 40% by weight, relative to the weight of the solvent.

12. The process according to any one of claims 5 to 7, wherein the base is selected from alkali metal alkoxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydroxides, alkaline earth metal hydroxides and mixtures thereof.

13. The process according to any one of claims 5 to 7, wherein the base is selected from sodium methoxide, potassium carbonate and soda.

14. The process according to any one of claims 5 to 7, wherein the molar amount of the base is 1.5 to 8 molar equivalents relative to the molar amount of the compound of formula (IX).

15. The process according to any one of claims 5 to 7, wherein an aqueous solution of hydroxylamine is added when the conversion of the compound of formula (IX) is at least 70% by weight.

16. The method according to any one of claims 5 to 7, wherein the oxidizing agent is selected from sodium hypochlorite, N-bromosuccinimide in the presence of a base and N-chlorosuccinimide in the presence of a base.

17. The method according to any one of claims 5 to 7, wherein the organic solvent S2 is an organic solvent selected from chlorinated solvents and ester, ether and alcohol type solvents.

18. A process according to any one of claims 5 to 7, comprising a step (a2) of manufacturing a compound of formula (X) by reacting a compound of formula (XIII) with a reagent allowing the formation of a nucleofugal group Z before step (b1): Wherein E is as defined in claim 1 or 5.

19. The method of claim 18, wherein the reagent is thionyl chloride.

20. The process according to claim 18, wherein step (a2) is performed in the absence or presence of at least one solvent S4.

21. The method according to claim 18, wherein step (a3) ​​of recovering the compound of formula (X) is performed immediately after step (a2).

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