JP2022543617A - Molecules with Nitrile Oxide Functionality - Google Patents

Abstract

The present invention relates to compounds of formula (I). TIFF2022543617000037.tif34164 (wherein A is one or more of the same or different aliphatic, preferably saturated, straight or branched hydrocarbon chains, optionally represents an arylene ring optionally substituted with a hydrocarbon chain substituted with one or more heteroatoms or interrupted by one or more heteroatoms, and E is optionally one or more represents a heteroatom-containing divalent hydrocarbon group, and X represents a halogen atom, preferably a chlorine atom.)

Description

TECHNICAL FIELD OF THE INVENTION The present invention comprises at least one unit capable of non-covalent bonding to each other or to a filler, and reacts with a polymer containing unsaturation to form a covalent bond with the polymer. It relates to the field of nitrogen-containing molecules containing functional groups capable of

Rather, the invention relates to molecules with nitrile oxide functionality and N-substituted imidazolidinone functionality. The present application also relates to methods for synthesizing such molecules.

PRIOR ART In industry, mixtures of polymers and fillers are often used. For such mixtures with good properties, means for improving the dispersion of fillers in the polymer have been considered. One means of achieving this result is the use of coupling agents capable of establishing an interaction between the polymer and the filler.

Agents containing nitrogen-containing dipoles for coupling polymers with fillers are described in documents published under the numbers US7186845B2 and JP2008208163.

These documents describe modified polymers containing diene units by means of nitrogen-containing dipolar compounds further containing heterocycles, said heterocycles themselves containing nitrogen atoms and oxygen and/or sulfur atoms.

More specifically, the compounds described are nitrones with oxazoline or thiazoline functional groups, such as ((2-oxazolyl)-phenyl-N-methylnitrone) and the like:

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

These rings present on the polymer can themselves react with surface functional groups of fillers, such as carbon black or silica, with which the polymer is mixed. This reaction results in the establishment of a covalent bond between the coupling agent-modified polymer and the filler through ring opening of the oxazoline or thiazoline ring. This is because, as described in document US7186845B2, the oxazoline and/or thiazoline rings can be ring-opened in the presence of nucleophiles, which can be present, for example, on the surface of the filler.

However, establishing such covalent bonds has drawbacks during the preparation of mixtures containing these polymers modified with agents for coupling with fillers. Specifically, the presence of such prematurely established covalent bonds between polymers and fillers makes these mixtures very viscous in the uncrosslinked state and causes cross-linking (vulcanization) of this rubber-based formulation. All previous manipulations, in particular the preparation of mixtures of compounds and their shaping, are made difficult. These drawbacks have a strong impact on industrial productivity.

Thus, a novel molecule that does not have the above-mentioned drawbacks, i.e. it is possible after reaction with the polymer and mixing with the filler, does not form covalent bonds with the filler, thus leading to an excessive increase in the viscosity of this mixture. It is desirable to propose molecules that do not have

Patent application WO 2012/007684 therefore relates to compounds comprising at least one group Q and at least one group A linked to each other by at least one and preferably one spacer group Sp, wherein
Q contains a dipole containing at least and preferably one nitrogen atom,
A comprises a linking group comprising at least one nitrogen atom;
Sp is the atom or group of atoms forming the bond between Q and A;

When the polymer grafted by the compounds defined above is mixed with the filler, it establishes with the filler only labile bonds, which are beneficial to the final properties of the polymer good polymer-filler interaction. without the drawback of causing overly strong polymer-filler interactions.

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

Further, in application WO2019/007881 various compounds are exemplified, including in particular 2-[2-(2-oxoimidazolidin-1-yl)ethoxy]-1-naphthonitrile oxide:

U.S. Pat. No. 7,186,845 JP 2008-208163 A WO2012/007684 WO2019/007881

It has been found that rubber compositions containing this molecule have advantageous properties in terms of hysteresis. Nonetheless, there is a constant demand for rubber compositions with improved properties.

DETAILED DESCRIPTION OF THE INVENTION In this connection, the Applicant has discovered certain halogen compounds that, once incorporated into rubber compositions, provide excellent hysteresis properties.

Accordingly, an object of the present invention are compounds of formula (I) below.

（式中、
Ａは、１以上の同じであるか又は異なっている、脂肪族の、好ましくは飽和の、直鎖状又は分枝鎖状の炭化水素鎖であって、任意選択的に１以上のヘテロ原子で置換されているかもしくは１以上のヘテロ原子によって割込まれている炭化水素鎖で任意選択的に置換されているアリーレン環を表し、
Ｅは、任意選択的に１以上のヘテロ原子を含む二価炭化水素基を表し、
Ｘは、ハロゲン原子、好ましくは塩素原子を示す。）

(In the formula,
A is one or more identical or different aliphatic, preferably saturated, straight or branched hydrocarbon chains, optionally with one or more heteroatoms represents an arylene ring optionally substituted with a hydrocarbon chain that is substituted or interrupted by one or more heteroatoms;
E represents a divalent hydrocarbon group optionally containing one or more heteroatoms;
X represents a halogen atom, preferably a chlorine atom. )

By "hydrocarbon chain" is meant within the meaning of the invention a chain containing one or more carbon atoms and one or more hydrogen atoms.

In this description, all percentages (%) given are by weight, unless explicitly indicated otherwise. Furthermore, any interval of values denoted 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 extremes a and b), but on the other hand , any interval of values indicated by the expression "a-b" means a range of values from a to b (ie, including the strict extremities a and b).

The invention and its advantages will be readily understood in view of the following description and examples.

The compounds referred to in this description may be of fossil or biogenic origin. In the latter case, they may be partially or wholly derived from biomass or may be obtained from biomass-derived renewable raw materials.

According to formula (I), the compounds according to the invention have one or more identical or different aliphatic, preferably saturated, straight or branched hydrocarbon chains, , which represents an arylene ring optionally substituted with one or more heteroatoms or with a hydrocarbon chain that is interrupted by one or more heteroatoms.

An "arylene ring" within the meaning of the invention means a monocyclic or polycyclic aromatic hydrocarbon radical derived from an arene and having two hydrogen atoms removed. An arylene ring is therefore a divalent group.

A "monocyclic or polycyclic aromatic hydrocarbon group" means within the meaning of the invention one or more aromatic rings having a backbone consisting of carbon atoms. In other words, there are no heteroatoms in the ring backbone. Arylene rings may be monocyclic, ie, consist of one ring, or polycyclic, ie, consist of a plurality of condensed aromatic hydrocarbon rings. Such fused rings therefore share at least two consecutive carbon atoms. These rings may be ortho-fused or ortho- and peri-fused.

Preferably, the arylene ring contains 6-14 carbon atoms.

Arylene rings may be unsubstituted, partially substituted, or fully substituted. The arylene ring is a partially substituted one or more aliphatic ring in which one or more hydrogen atoms (but not all atoms) are optionally replaced by one or more heteroatoms. is replaced by a, preferably saturated, straight or branched hydrocarbon chain. The chains are also called substituents. An arylene ring is fully substituted when all hydrogen atoms are replaced with the chain. The arylene ring substituents may be the same or different from each other.

Preferably, the arylene rings are one or more identical or different aliphatic, preferably saturated, linear or branched hydrocarbon chains, optionally one or more or substituted with a hydrocarbon chain interrupted by one or more heteroatoms, this or these chains may be substituted for N-substituted imidazolidinone functional groups and nitrile oxides. can be inert.

"N-substituted imidazolidinone functional groups and hydrocarbon chains or chains that are inert to nitrile oxides" are within the meaning of the present invention, the N-substituted imidazolidinone functional groups or nitrile oxide It means a hydrocarbon chain that does not react with either. Thus, the N-substituted imidazolidinone functional group and the hydrocarbon chain that is inert to the nitrile oxide are preferably free of alkenyl or alkynyl functional groups that are reactive with the functional group or with the group. is an aliphatic hydrocarbon chain, i.e. a straight or branched saturated aliphatic hydrocarbon chain, optionally substituted or divided by one or more heteroatoms; embedded and preferably contains from 1 to 24 carbon atoms.

Preferably, the group A is one or more identical or different aliphatic, preferably saturated, straight or branched hydrocarbon chains, optionally one or more or optionally substituted with a hydrocarbon chain _interrupted by one or more _heteroatoms . More preferably, the group A is one or more of the same or different C ₁ -C ₂₄ saturated straight or branched hydrocarbon chains, optionally one or more of nitrogen, sulfur or a C ₆ -C ₁₄ arylene ring optionally substituted with an oxygen heteroatom or a hydrocarbon chain interrupted by one or more nitrogen, sulfur or oxygen heteroatoms. Even more preferably, the group A is a C ₁ -C ₁₂ , preferably a C ₁ -C ₆ , more preferably a C ₁ -C ₄ alkyl group, an OR' group, a -NHR' group, a -SR' group (R' are C ₁ -C ₁₂ alkyl groups, preferably C ₁ -C ₆ , more preferably C ₁ -C ₄ alkyl groups), which may be the same or different. A C ₆ -C ₁₄ arylene ring optionally substituted with substituents.

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

（式中、
Ｒ_１～Ｒ_７から選択される基が以下の式（ＩＩ）を示し、

(In the formula,
A group selected from R ₁ to R ₇ represents the following formula (II),

の基を示し、ここで
（式中、Ｅ及びＸは、前に記載されたとおりである）
式（ＩＩ）の基を示す１つ以外のＲ_１～Ｒ_７から選択される同じであるか又は異なっている６つの基が、互いに独立して、水素原子を表すか、又は、脂肪族の、好ましくは飽和の、直鎖状又は分枝鎖状の、炭化水素鎖であって、任意選択的に１以上のヘテロ原子で置換されているかもしくは１以上のヘテロ原子によって割込まれている炭化水素鎖を表す。

wherein E and X are as previously described.
Six identical or different groups selected from R ₁ to R ₇ other than one representing a group of formula (II) independently of each other represent a hydrogen atom or an aliphatic , preferably saturated, linear or branched, hydrocarbon chains optionally substituted or interrupted by one or more heteroatoms represents a hydrogen chain.

Preferably, in the compounds of formula (Ia), the six same or different groups selected from R ₁ to R ₇ other than one representing a group of formula (II) are independently of each other represents a hydrogen atom or is an aliphatic, saturated, straight or branched C ₁ -C ₂₄ hydrocarbon chain, optionally substituted with one or more heteroatoms, or Represents a hydrocarbon chain interrupted by one or more heteroatoms.

Again more preferably, in the compounds of formula (Ia), the 6 same or different groups selected from R ₁ to R ₇ other than one representing a group of formula (II) are hydrogen atoms, C ₁ -C ₁₂ , preferably C ₁ -C ₆ , more preferably C ₁ -C ₄ alkyl groups, —OR′, —NHR′ and —SR′ groups (R′ is C ₁ -C ₁₂ , preferably C ₁ -C ₆ , more preferably C ₁ -C ₄ alkyl groups).

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

According to a particular embodiment, in formula (Ia), R ₁ represents a group of formula (II) as defined above and R ₂ to R ₇ which are the same or different are hydrogen atoms, C ₁ —C ₁₂ , preferably C ₁ -C ₆ , more preferably C ₁ -C ₄ alkyl groups, —OR′ groups, —NHR′ groups and —SR′ groups (R′ is C ₁ -C ₁₂ , preferably C ₁ -C ₆ , more preferably C ₁ -C ₄ alkyl groups).

Even more preferably, in this embodiment R ₁ represents a group of formula (II) as defined above and R ₂ -R ₇ are the same and represent a hydrogen atom.

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

"Divalent hydrocarbon group" means within the meaning of the invention a spacer group (or linking group) that forms a bridge between the group A and the imidazolidone group, the spacer group being saturated or An unsaturated, preferably saturated, C ₁ -C ₂₄ hydrocarbon chain, linear or branched, optionally containing one or more heteroatoms such as N, O and S may be included in The hydrocarbon chains can be optionally substituted, provided that the substituents do not react with the nitrile oxide and imidazolidone groups.

Preferably, in the compounds of formulas (I) and (Ia), the group E is a hydrocarbon, linear or branched, preferably saturated, C ₁ -C ₂₄ , preferably C ₁ -C ₁₀ , more preferably a C ₁ -C ₆ hydrocarbon chain, optionally interrupted by one or more hydrogen, sulfur or oxygen atoms.

Preferably, in the compounds of formulas (I) and (Ia) the group E is -R-, -NH-R-, -O-R- and -S-R-, where R is linear or branched linear, C ₁ -C ₂₄ , preferably C ₁ -C ₁₀ , more preferably C ₁ -C ₆ alkylene).

Even more preferably, in the compounds of formulas (I) and (Ia), the groups E are -R- and -OR-, where R is linear or branched C ₁ -C ₂₄ , preferably C ₁ -C ₁₀ , more preferably C ₁ -C ₆ alkylene).

According to a particular embodiment, in compounds of formulas (I) and (Ia), the group E is -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -O-CH ₂ -, -O-CH ₂ -CH ₂ -, -O-CH ₂ -CH ₂ -CH ₂ - and -O-CH ₂ -CH ₂ - selected from CH ₂ —CH ₂ —;

According to a preferred embodiment, compounds of formula (Ia) as defined above are particularly preferably -R- and -OR-, where R is linear or branched C ₁ -C ₂₄ , preferably C ₁ -C ₁₀ , more preferably C ₁ -C ₆ alkylene) and a group X which is a chlorine atom.

According to this embodiment, even more preferably, the compound of formula (I) is a compound of formula (Ia),
(In the formula,
R ₁ represents a group of formula (II), the group E being -R- and -OR-, where R is linear or branched C ₁ -C ₂₄ , preferably C ₁ -C ₁₀ , more preferably C ₁ -C ₆ alkylene and the group X is a chlorine atom);
R ₂ to R ₇ , which may be the same or different, represent hydrogen atoms or are aliphatic, preferably saturated, linear or branched C ₁ -C ₂₄ hydrocarbon chains. represents a hydrocarbon chain optionally substituted or interrupted by one or more heteroatoms)
is.

According to this embodiment, even more preferably, the compound of formula (I) is a compound of formula (Ia),
(In the formula,
R ₁ represents a group of formula (II), the group E being -R- and -OR-, where R is a linear or branched C ₁ -C ₂₄ , preferably C ₁ -C ₁₀ , more preferably C ₁ -C ₆ alkylene), and the group X is a chlorine atom,
R ₂ to R ₇ which are the same or different are hydrogen atoms, C ₁ -C ₁₂ , preferably C ₁ -C ₆ , more preferably C ₁ -C ₄ alkyl groups, -OR' groups, -NHR ' and -SR' groups (wherein R' is a C ₁ -C ₁₂ , preferably a C ₁ -C ₆ , even more preferably a C ₁ -C ₄ alkyl group).
is.

According to this embodiment, even more preferably, the compound of formula (I) is a compound of formula (Ia),
(In the formula,
R ₁ represents a group of formula (II), the group E being -R- and -OR-, where R is linear or branched C ₁ -C ₂₄ , preferably C ₁ -C ₁₀ , more preferably C ₁ -C ₆ alkylene), and the group X is a chlorine atom,
R ₂ to R ₇ are the same and represent a hydrogen atom)
is.

Conveniently, the compound of formula (I) is of formula (III) below:

Another object of the invention is a process for synthesizing the compounds of formula (I) according to the invention, comprising the following sequential steps:
(b1) the following formula (IX)

（式中、Ａは、上に記載のとおりであり、Ｙは、求核試薬基を表す）化合物と、
以下の式（Ｘ）

a compound wherein A is as described above and Y represents a nucleophilic group;
Formula (X) below

（式中、Ｅは、上に記載のとおりであり、Ｚは脱離基を表す）の化合物との反応であって、
少なくとも１つの極性溶媒Ｓ１及び少なくとも１つの塩基の存在下で、７０～１５０℃の範囲の温度Ｔ１において、
以下の式（ＸＩ）

wherein E is as described above and Z represents a leaving group, wherein
in the presence of at least one polar solvent S1 and at least one base at a temperature T1 in the range from 70 to 150° C.
Formula (XI) below

の化合物を形成する反応、
（ｂ２）上記式（ＸＩ）の化合物とヒドロキシルアミンの水溶液との反応であって、３０～７０℃の範囲の温度Ｔ２において、
以下の式（ＸＩＩ）

reaction to form a compound of
(b2) the reaction of the compound of formula (XI) above with an aqueous solution of hydroxylamine, at a temperature T2 in the range from 30 to 70° C.,
Formula (XII) below

のオキシム化合物を得る反応、
（ｃ）式（ＸＩＩ）のオキシム化合物を回収する工程、
（ｄ）式（ＸＩＩ）のオキシム化合物を、少なくとも１つの有機溶媒Ｓ２の存在下で、酸化剤により酸化させる工程であって、該酸化剤の含量が、式（ＸＩＩ）のオキシム化合物のモル量に対して少なくとも６モル当量である、工程
を含む。

reaction to give the oxime compound of
(c) recovering the oxime compound of formula (XII);
(d) oxidizing the oxime compound of formula (XII) with an oxidizing agent in the presence of at least one organic solvent S2, the content of the oxidizing agent being the molar amount of the oxime compound of formula (XII) is at least 6 molar equivalents to

By "polar solvent" is meant within the meaning of the invention a solvent having a dielectric constant greater than 2.2.

By "leaving group" is meant within the meaning of the invention a leaving group that removes the double bond.

By "nucleophilic group" is meant within the meaning of the invention a compound containing at least one atom bearing a free doublet or a negatively charged atom.

As already explained, the method of synthesizing the compounds of formula (I) according to the invention specifically comprises the successive steps (b1) and (b2).

According to certain embodiments, the two steps (b1) and (b2) are separated by isolating and purifying the compound of formula (XI).

According to another embodiment, the two steps (b1) and (b2) are performed according to a monolithic synthesis, i.e. steps (b1) and (b2) are "one-pot" (single in two steps) It is a natural synthetic method), i.e. without isolation of the intermediate compound of formula (XI).

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 carrying a group Z .

Preferably, group Y is selected from hydroxyl, thiol and primary or secondary amine functionalities.

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

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

According to a particular embodiment of the invention, the polar solvent S1 is a water-miscible polar solvent, 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 solvents S1 that can be used in the process according to the invention.

Preferably, the protic solvent is alcoholic.

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

The base may be selected from alkaline alcoholates, alkaline carbonates, alkaline earth carbonates, alkaline hydroxides, alkaline earth hydroxides and mixtures thereof.

Conveniently you can add:
one or more catalysts selected from silver(I) salt catalysts, quaternary ammonium type phase transfer catalysts and mixtures thereof;
one or more ionic liquids;

Preferably, the base is selected from sodium methanolate, potassium carbonate and soda, more preferably potassium carbonate.

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

As already explained, step (b1) of the method according to the invention is carried out at a temperature T1 in the range from 70 to 150°C.

Preferably, temperature T1 is a temperature between 70 and 120°C, more preferably between 80 and 110°C.

As already explained, step (b1) of the process according to the invention comprises step (b2) of adding an aqueous solution of hydroxylamine to the reaction medium containing the compound of formula (XI) at a temperature T2 in the range from 30 to 70°C. ,Continue.

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

Advantageously, the temperature T2 varies between 40 and 60°C.

The process according to the invention also comprises a step (c) of recovering the oxime compound of formula (XII) as mentioned above.

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

The process according to the invention also comprises step (d), in the presence of at least one organic solvent S2, by oxidation of the oxime compound of formula (XII) with an oxidizing agent to obtain the compound of formula (I), particularly the preferred compound. the amount of oxidizing agent 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).

This amount of oxidizing agent may be added once or multiple times during step (d), preferably twice during step (d).

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

Advantageously, the organic solvent S2 is an organic solvent selected from chlorinated solvents and ester, ether and alcoholic solvents, preferably selected from dichloromethane, ethyl acetate, butyl acetate, diethyl ether, isopropanol and ethanol, It is more preferably selected from ethyl acetate and butyl acetate.

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

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 the following formula (XIII)

（式中、Ｅは上で規定されたとおりである）の化合物を、脱離基Ｚの形成を可能にする薬剤と反応させることによって式（Ｘ）の化合物を製造する工程（ａ２）を、工程（ｂ１）の前に含む。

A step (a2) of preparing a compound of formula (X) by reacting a compound of (wherein E is as defined above) with an agent that allows formation of a leaving group Z, Included before step (b1).

Preferably, the agent is thionyl chloride.

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

Conveniently, 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, is immediately followed by step (a2). followed by.

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

Molecules Structural analysis and determination of molar purity of synthesized molecules are performed by NMR analysis. Spectra are required on a Bruker Avance 3 400-MHz spectrophotometer equipped with a BBFOz gradient 5 mm wide probe. Quantitative ¹ H NMR experiments use a simple 30° pulse sequence a and a 3 second iteration delay between each 64 acquisitions. Unless otherwise indicated, samples are solubilized in the deuterated solvent deuterated dimethylsulfoxide (DMSO). Deuterated solvents are also used for locking signals. For example, calibration is performed at the DMSO deuteration proton signal at 2.44 ppm relative to the TMS reference at 0 ppm. ¹ H NMR spectra combined with 2D HSQC ¹ H/ ¹³ C and HMBC ¹ H/ ¹³ C experiments allow structural determination of the molecule (see tables of attributes 1, 2 and 3 below). Molar quantification is performed using quantitative ¹ H 1D NMR spectra.

Analysis by mass spectrometry is performed by direct injection with electrospray ionization mode (ID/ESI). Analysis was performed on a Bruker HCT spectrophotometer (flow rate 600 μL/min, nebulizer gas pressure 10 psi, nebulizer gas flow rate 4 L/min).

Molecules grafted onto SBR or IR 2-[2-(3-chloro-2-oxoimidazolidin-1-yl)ethoxy]-1 grafted onto SBR (styrene butadiene rubber) or IR (isoprene rubber) - The molar fraction of naphthonitrile oxide is determined by NMR analysis. Spectra are acquired on a Bruker 500 MHz spectrophotometer equipped with a 'BBFO z-gradient 5 mm CryoProbe'. Quantitative ¹ H NMR experiments use a simple 30° pulse sequence and a 5 second repeat delay between each acquisition. For the purpose of obtaining lock signals, samples are solubilized in deuterated chloroform (CDCl ₃ ). 2D NMR experiments can confirm the nature of the grafted units by the chemical motions of carbon atoms and protons.

Dynamic Properties Dynamic properties tan(δ)max are measured with a viscometer (Metravib VA4000) according to ASTM D 5992-96. The response of a sample of vulcanized composition (4 mm thick cylindrical specimen and 400 mm ² cross-sectional area) subjected to sinusoidal stress in simple alternating shear at a frequency of 10 Hz was measured according to ASTM D 1349-99 under normal conditions of temperature. Recorded below (23°C). Modified amplitude scans were performed from 0.1% to 100% (outward cycle) and from 100% to 0.1% (regression cycle). The result used is the loss factor tan(δ). The maximum value of tan(δ) observed for the regression period is indicated and denoted as tan(δ)max.

I. Synthesis of (2-(2-(3-chloro-2-oxoimidazolidin-1-yl)ethoxy)-1-naphthonitrile oxide

（２－（２－（３－クロロ－２－オキソイミダゾリジン－１－イル）エトキシ）－１－ナフトニトリルオキシドを、工程ａ１、工程ａ２、工程ｂ１、工程ｂ２、工程ｃ及び工程ｄと呼ぶ６つの工程で合成する。

(2-(2-(3-chloro-2-oxoimidazolidin-1-yl)ethoxy)-1-naphthonitrile oxide is referred to as step a1, step a2, step b1, step b2, step c and step d It is synthesized in six steps.

Step a1 is carried out according to protocol 1, step a2 according to protocol 2, and step b1 according to protocol 3. Steps b2 and c are performed according to protocol 4. Step d is performed according to protocol 5.

Step a1: Preparation of 2-hydroxy-1-naphthaldehyde

Protocol 1:
This compound is prepared according to Russell, Alfred and Lockhart, Luther B.; Organic Syntheses, 22, 63-4; 1942 or Wynberg, Hans and Meijer, Egbert W.; Organic Reactions (Hoboken, NJ, United States), 28, 1982, or according to the so-called Reimer-Tiemann protocol described in Casiraghi, Giovanni et al. in Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), (9), 1862-5, 1980; in Organic Reactions (Hoboken, NJ, United States), 49, 1997, from naphthol by a formylation reaction according to the Vilsmeier reaction.

2-hydroxy-1-naphthaldehyde is commercially available. It can be obtained, for example, from Aldrich (CAS 708-06-5).

Step a2: Preparation of 1-(2-chloroethyl)imidazolidin-2-one

Protocol 2:
This compound can be obtained according to the protocol described in patent application WO2012/007684.

Step b1: Preparation of 2-(2-(2-oxoimidazolidin-1-yl)ethoxy)-1-naphthaldehyde

Protocol 3:
2-hydroxy-1-naphthaldehyde (20.0 g; 0.116 mol), potassium carbonate (24.08 g; 0.174 mol), and 1-(2-chloroethyl)imidazolidin-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)imidazolidin-2-one (17.26 g; 0.116 mol) is then added and the reaction medium is stirred at 75° C. (bath temperature) for 9-10 hours. do. After returning to 40-45° C., the reaction medium is introduced into a solution of sodium hydroxide (10 g; 0.25 mol) in water (700 mL). The mixture is stirred for 10-15 minutes. The precipitate is filtered and washed on the filter paper with distilled water (3 times 400 mL).

A gray solid (31.51 g; 95% yield) is obtained.
Molar purity exceeds 85% ( ¹ H NMR).

Steps b2 and c: Preparation of 2-(2-(2-oxoimidazolidin-1-yl)ethoxy)-1-naphthaldehyde

The product isolated at the end of Protocol 3 is used in Protocol 4 below.

Protocol 4:
A solution of hydroxylamine (2.05 g; 31.0 mmol, 50% in water, Aldrich) in ethanol (5 mL) was added to 2-(2-(2-oxoimidazolidin-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 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 and washed on the filter with an ethanol/ethyl acetate mixture.

A white solid (4.00 g; 60% yield) is obtained.
Molar purity estimated by ¹ H NMR is >95%.

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

Protocol 5:
An aqueous solution of NaOCl (74.44 g/L; 98 mL; 4.0 eq. (eq. = molar equivalents)) in ethyl acetate (230 ml) cooled to 1°C (bath temperature = 0°C) over 10 min. Add dropwise to the above 2-(2-(2-oxoimidazolidin-1-yl)ethoxy)-1-naphthaldehyde oxime (7.30 g; 24.4 mmol). The reaction medium is stirred at 0-2° C. (bath temperature=0° C.) for 8.5 hours.

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 paper with water (2×25 ml) and then with ethyl acetate (2×10 mL).

A white solid is obtained (6.24 g; 18.7 mmol, 77% yield), mp 127.0-127.5°C.

(2-(2-(3-Chloro-2-oxoimidazolidin-1-yl)ethoxy)-1-naphthonitrile oxide was obtained with a molar purity greater than 92% ( ¹ H NMR), which is 6% Contains less than molar 2-(2-(2-oxoimidazolidin-1-yl)ethoxy)-1-naphthonitrile oxide and 2% molar residual solvent impurities.

II. Preparation of SBR grafted with 2-(2-(3-chloro-2-oxoimidazolidin-1-yl)ethoxy)-1-naphthonitrile oxide The 2-( 2-(3-Chloro-2-oxoimidazolidin-1-yl)ethoxy]-1-naphthonitrile oxide is used, hereafter referred to as Compound A.

20 g of functionalized compound A, 2-[2-(3-chloro-2-oxoimidazolidin-1-yl)ethoxy]-1-naphthonitrile oxide (0.27 g; 0.81 mmol). styrene-butadiene copolymer containing 26.5 wt. 1.84) on a cylindrical tool (external mixer at 23°C). The mixture is homogenized for 15 portfolio passes. This mixing step is followed by a heat treatment at 120° C. for 10 minutes while applying a pressure of 10 bar.

Analysis by ¹ H NMR demonstrated grafting of a mole fraction of 0.29% with a grafting yield of 96%.

III. Preparation of IR grafted with 2-(2-(3-chloro-2-oxoimidazolidin-1-yl)ethoxy)-1-naphthonitrile oxide 2-(2 obtained above (at the end of protocol 5) -(3-Chloro-2-oxoimidazolidin-1-yl)ethoxy]-1-naphthonitrile oxide is used.

Compound A, 2-[2-(3-chloro-2-oxoimidazolidin-1-yl)ethoxy]-1-naphthonitrile oxide (0.29 g; 0.88 mmol) was added to 20 g of synthetic isoprene (99. containing 35 wt% cis-1,4-isoprene units and 0.65 wt% 3,4-isoprene units; ) above. The mixture is homogenized for 15 portfolio passes. This mixing step is followed by a heat treatment at 120° C. for 10 minutes while applying a pressure of 10 bar.

Analysis by ¹ H NMR demonstrated grafting of a mole fraction of 0.2% with a grafting yield of 66%.

IV. Rubber Compositions 1) Preparation of Rubber Compositions Three rubber compositions (hereinafter referred to as compositions C1, C2 and C3, defined below) are prepared.

Composition C1 is a "conventional" rubber composition used as a tire tread, specifically comprising ungrafted synthetic polyisoprene, silica and a silane polysulfide coupling agent.

Composition C2 is the same as composition C1 except that it contains compound B grafted onto synthetic polyisoprene. This is the composition containing comparative compound B.

Composition C3 is the same as composition C1 except that it contains Compound A grafted onto synthetic polyisoprene. This is a composition comprising compound A according to the invention.

The amounts of the various constituents of these compositions in terms of percentage of elastomer, parts by weight, and hundred parts by weight are shown in Table 4:

Compositions C2 and C3 contain the same number of moles as grafted compound A or B, ie 0.2% molar.
(1) 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,
(2) Compound B: (2-(2-(2-oxoimidazolidin-1-yl)ethoxy)-1-naphthonitrile oxide,
(3) Compound A: (2-(2-(3-chloro-2-oxoimidazolidin-1-yl)ethoxy)-1-naphthonitrile oxide,
(4) "Zeosil 1165MP" silica marketed by Solvay;
(5) TESPT (marketed by Evonik under the name 'S169');
(6) Carbon black, N234 grade, marketed by Cabot Corporation;
(7) N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine marketed by Flexys under the name "Santoflex 6-PPD";
(8) 2,2,4-trimethyl-1,2-dihydroquinoline marketed by Flexys;
(9) zinc oxide marketed by Umicore (industrial grade);
(10) Pristerene 4031 stearin marketed by Uniquema;
(11) N-Cyclohexyl-2-benzothiazyl-sulfenamide marketed by Flexys under the name "Santocure CBS".

The composition is prepared in the following manner: the diene elastomer is introduced into the mixture inside a 70% filled 85 cm ³ Polylab, where the initial temperature of the vessel is approximately 110°C. For compositions involving compound A or compound B, compound A or compound B is introduced at the same time as the diene elastomer. Thermomechanical processing for 1.5 minutes is then performed at a temperature of 120°C.

Next, for each of the three compositions, the optional reinforcing filler(s) and the coupling agent between the filler and the diene elastomer are introduced and after 1 or 2 minutes of mixing, the vulcanization system is cured. Except for introducing various other ingredients. Thermomechanical processing (non-productive stage) is then carried out in one step until a maximum "drop" temperature of 160° C. is reached (the total length of mixing is approximately equal to 5 minutes).

The mixture thus obtained is collected and cooled, then the vulcanization system (sulphur and sulfenamide type accelerator) is added in the external mixture (homofinisher) at 25° C. and the whole is mixed for approximately 5-6 minutes. (generation stage).

The mixture thus obtained is then calendered in the form of plates (2-3 mm thick) or thin sheets of rubber, whose physical and mechanical properties are measured.

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.

In view of Table 5, as expected, composition C2, which contains the comparative compound, contains an elastomer modified with a compound containing an unsubstituted imidazolidinone functional group, compared to composition C1, which contains no modified elastomer. In comparison, it shows a decrease in hysteresis (tan(δ)max at 23°C).

Composition C3, which contains a compound according to the invention, comprises an elastomer modified with a compound containing N-substituted imidazolidinone functional groups, which surprisingly compared to Comparative Composition C1: and also has a significant reduction in hysteresis compared to comparative composition C2 (which already had better hysteresis properties compared to composition C1).

Elastomers modified with compounds according to the present invention can thus improve the hysteresis of compositions containing them and thus improve the rolling resistance performance of compositions containing them.

Claims (23)

Compounds of formula (I) below.

(In the formula,
A is one or more identical or different aliphatic, preferably saturated, straight or branched hydrocarbon chains, optionally with one or more heteroatoms represents an arylene ring optionally substituted with a hydrocarbon chain that is substituted or interrupted by one or more heteroatoms;
E represents a divalent hydrocarbon group optionally containing one or more heteroatoms;
X represents a halogen atom, preferably a chlorine atom. ) 2. The compound of claim ₁ , wherein said arylene ring is C6 _- C14. Formula (Ia) below

A compound according to claim 1 or 2 of
A group selected from R ₁ to R ₇ represents the following formula (II),

(Wherein, E and X are as described in claim 1)
Six identical or different groups selected from R ₁ to R ₇ other than one representing a group of formula (II) independently of each other represent a hydrogen atom or an aliphatic , preferably saturated, straight or branched hydrocarbon chains optionally substituted or interrupted by one or more heteroatoms representing a chain,
Compound. R ₁ represents a group of formula (II) as defined in claim 3 and R ₂ to R ₇ which are the same or different represent a hydrogen atom or aliphatic C1-C24 straight or branched hydrocarbon chain, preferably saturated, optionally substituted or interrupted by one or more heteroatoms represents a hydrogen chain, preferably R ₁ represents a group of formula (II) as defined in claim 3, and the same or different R ₂ to R ₇ represent a hydrogen atom, C ₁ - C ₁₂ , preferably C ₁ -C ₆ , more preferably C ₁ -C ₄ alkyl groups, -OR', -NHR' and -SR' groups (R' is C ₁ -C ₁₂ , preferably C _{1 - C.sub.6} , more preferably C.sub.1 _- C.sub.4 alkyl groups);
4. A compound according to claim 3. The group E is a C ₁ -C ₂₄ , preferably C ₁ -C ₁₀ , more preferably C ₁ -C ₆ , straight or branched, preferably saturated, hydrocarbon chain, optionally A compound according to any one of claims 1 to 4, which is optionally a hydrocarbon chain interrupted by one or more nitrogen, sulfur or oxygen atoms. Formula (III) below

A compound according to any one of claims 1 to 5, which is A process for synthesizing a compound of formula (I) as defined in any one of claims 1-6, comprising the following sequential steps:
(b1) the following formula (IX)

(wherein A is as defined in claim 1 or 2 and Y represents a nucleophilic group); and
Formula (X) below

wherein E is as defined in claim 1 or 5 and Z represents a leaving group,
in the presence of at least one polar solvent S1 and at least one base at a temperature T1 in the range from 70 to 150° C.
Formula (XI) below

reaction to form a compound of
(b2) the reaction of the compound of formula (XI) with an aqueous solution of hydroxylamine, at a temperature T2 in the range of 30-70° C.,
Formula (XII) below

reaction to give the oxime compound of
(c) recovering said oxime compound of formula (XII);
(d) oxidizing said oxime compound of formula (XII) with an oxidizing agent in the presence of at least one organic solvent S2, the content of said oxidizing agent being in moles of the oxime compound of formula (XII) is at least 6 molar equivalents to the amount. 8. The process of claim 7, wherein the two steps (b1) and (b2) are separated by isolating and purifying the compound of formula (XI). 8. A method according to claim 7, wherein the two steps (b1) and (b2) are performed by monolithic synthesis. A method according to any one of claims 7 to 9, wherein the group Y is selected from hydroxyl, thiol and primary or secondary amine functions. A process according to any one of claims 7 to 10, wherein the group Z is selected from chlorine, bromine, iodine, mesylate groups, tosylate groups, acetate groups and trifluoromethylsulfonate groups. A process according to any one of claims 7 to 11, wherein said polar solvent S1 is a water-miscible polar solvent, preferably a protic solvent, more preferably an alcohol protic solvent. A process according to any one of claims 7 to 12, wherein the compound of formula (IX) constitutes 5-40% by weight, preferably 10-30% by weight, relative to the weight of the solvent. Process according to any one of claims 7 to 13, wherein the base is selected from alkaline alcoholates, alkaline carbonates, alkaline earth carbonates, alkaline hydroxides, alkaline earth hydroxides and mixtures thereof. Process according to any one of claims 7 to 14, wherein the base is selected from sodium methanolate, potassium carbonate and soda, preferably potassium carbonate. 16. Any one of claims 7 to 15, wherein the molar amount of the base is 1.5 to 8 molar equivalents, preferably 2 to 6 molar equivalents relative to the molar amount of the compound of formula (IX). Method. A process according to any one of claims 7 to 16, wherein the aqueous solution of hydroxylamine is added when the conversion of the compound of formula (IX) is at least 70% by weight. wherein said oxidizing agent is selected from sodium hypochlorite, N-chlorosuccinimide in the presence of a base, and N-bromosuccinimide in the presence of a base, preferably sodium hypochlorite; Item 18. The method according to any one of Items 7 to 17. The organic solvent S2 is an organic solvent selected from chlorinated solvents and ester, ether and alcohol solvents, preferably selected from dichloromethane, ethyl acetate, butyl acetate, diethyl ether, isopropanol and ethanol, more preferably A method according to any one of claims 7 to 18, selected from ethyl acetate and butyl acetate. Formula (XIII) below

Preparing a compound of formula (X) by reacting a compound of (wherein E is as defined in claim 1 or 5) with an agent that allows the formation of a leaving group Z ( A method according to any one of claims 7 to 19, comprising a2) before step (b1). 21. The method of claim 20, wherein said drug is thionyl chloride. 22. A process according to claim 20 or 21, wherein step (a2) is performed in the absence or presence of at least one solvent S4, preferably a chlorinated solvent, more preferably dichloromethane. 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. Item 23. The method according to any one of Items 20 to 22.