Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D233/30—Oxygen or sulfur atoms
  • C07D233/32—One oxygen atom
  • C07D233/36—One oxygen atom with hydrocarbon radicals, substituted by nitrogen atoms, attached to ring nitrogen atoms

Definitions

• the present invention relates to the field of molecules comprising a function capable of reacting with a polymer comprising unsaturations to form a covalent bond with said polymer.
• the present invention relates to aromatic nitrones. More specifically, the application relates to a process for synthesizing such molecules.
• the compounds described are nitrones carrying oxazoline and thiazoline functional groups, for example, ((2-oxazolyl) -phenyl-N-methylnitrone):
• the resulting polymers When diene polymers are reacted with such compounds, the resulting polymers will carry the oxazolines or thiazoline. These cycles present on the polymer are likely to react in turn, with charge surface functions, such as carbon black or silica, with which the polymers are mixed. This reaction leads to the establishment of covalent bonds between the polymer modi? Ed by the coupling agent and the filler due to the opening of the oxazoline or thiazoline ring. Indeed, as described in US7 1 86845B2, the oxazoline rings and / or thioazolines are likely to open in the presence of a nucleophile may for example be present on the surface of the charge.
• the patent application WO 2012/007684 relates to a compound comprising at least one group Q and at least one group A connected to each other by mo ins and preferably a Sp spacer group in which:
• Q comprises a dipole containing at least and preferably a 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 A.
• This compound can be prepared from 4-formylbenzoic acid and 2-aminoethylimidazolidone (UDETA) according to the following synthetic scheme:
• hydroxylamine In this process, a hydroxylamine is used.
• hydroxylamines are characterized by their low commercial availability.
• the present invention aims to provide a solution to solve the problems mentioned above.
• - A is a carbon chain which may contain at least one group comprising one or more heteroatoms chosen preferentially from O, N, Si, S and P;
• Ri is a carbon group which may contain one or more heteroatoms
• - Sp represents an atom or a group of atoms
• carbon chain or “carbon group” means a chain or a group comprising one or more carbon atoms.
• step (b) is followed by a step (c) of recovering the compound of formula (I).
• A is a carbon chain containing at least one group comprising one or more heteroatoms chosen preferentially from O, N, Si, S and P, more preferably from O, N, S and combinations thereof.
• A is a carbon chain C 1 -C 20 , more preferably d -C 1 2 .
• A comprises a group selected from an associative group, an ester group, preferably a carboxylic acid ester group, and an ionomeric group.
• A is an associative group, it is meant that the groups A are capable of associating with each other by hydrogen bonds.
• each associative group capable of associating with hydrogen bonds comprises at least one donor "site” and one acceptor site with respect to the hydrogen bonding so that two identical associative groups are self-complementary and can associate with each other forming at least two hydrogen bonds.
• A is an associative group chosen from an imidazo-lidinyl, thio-imidazo-lidinyl, triazoyl, trithioazoyl, ureyl, thioureyl, bis-ureyl, bis-thioureyl, ureido-pyrimidyl and thio-ureido group.
• pyrimidyl or a group corresponding to formula (IV): - C (OR 2 ) O (IV), in which R 2 is a carbon group optionally comprising at least one heteroatom.
• said carbon group R 2 optionally comprising at least one heteroatom, comprises from 1 to 20 carbon atoms, preferably from 1 to 12, more preferably from 1 to at 6, even more preferably from 1 to 3.
• said carbon group R 2 may designate the methyl group or the ethyl group.
• A is an associative group, it corresponds to one of the following formulas (V) to (IX):
• - R denotes a hydrocarbon group optionally comprising at least one heteroatom
• X denotes an oxygen atom, sulfur atom or an NH group, preferably an oxygen or sulfur atom.
• formula (V) represents a 5- or 6-membered, preferably diazotized, di or tri-nitrogen heterocycle comprising at least one carbonyl, thio carbonyl or imine functional group.
• the group of formula (V) is the group of formula (Va):
• the group Sp is a spacer group which makes it possible to connect the aromatic ring to the group A as the formula of the compound (I) indicates, and thus can be of any type known per se.
• the group Sp is preferably a linear, branched or cyclic C1-C24 hydrocarbon-based chain which may contain one or more aromatic radicals and / or one or more heteroatoms. Said chain may optionally be substituted, provided that the substituents do not react with the group A and the nitrone function.
• the group Sp is a straight or branched alkylene chain C1-C24, preferably C1-C10, more preferably Ci-C 6, said chain being optionally interrupted by one or more nitrogen atoms or oxygen atoms, and may include one or more carbonyl groups.
• a chain may comprise one or more nitrogen or oxygen atoms in the chain or at one end chain.
• the group Sp contains a unit selected from -
• the chain of the group Sp comprises an oxygen atom or a group chosen from OC (O), NHC (O), C (O) O and C (O) NH at the end of the chain, which end is not adjacent to group A.
• the process according to the invention comprises a step (b) of reaction of a compound of formula (II), as mentioned above, with a compound of formula (III): R 1 -NO 2 (III) ), as mentioned above.
• Ri is a group selected from an alkyl group, preferably an alkyl group Ci-2, more preferably C 1 -C 6 , still more preferably C 1 -C 4; cycloalkyl, preferably cycloalkyl, C4-C12, more preferably C O -CS; and an aryl group, preferably a C 6 -C 15 aryl group, Ri may contain one or more heteroatoms.
• the compound of formula (III) is chosen from nitromethane, nitrobenzene and 2-methyl-2-nitropropane.
• Said step (b) of the process according to the invention is carried out in the presence of at least one solvent, and at least one reducing agent, at a temperature T ranging from -15 to 100 ° C.
• the solvent is chosen from water, an alcohol solvent, an ether solvent, a nitrile solvent and their mixture.
• the solvent is chosen from an alcohol solvent such as methanol, ethanol, propanol and isopropanol, water and their mixture.
• the compound of formula (II) represents from 5 to 50% by weight, preferably from 10 to 30% by weight, relative to the weight of the solvent.
• the reducing agent is chosen from zinc and hydrogen in the presence of a metal catalyst, preferably zinc.
• the amount of reducing agent is from 1.5 to 6 equivalents, preferably from 2 to 5 equivalents, relative to the amount of compound of formula (II).
• step (b) is carried out, when the reducing agent is zinc, in the presence of an acid chosen from an organic acid and a weak acid salt.
• step (b) is carried out, when the reducing agent is zinc, in the presence of ammonium chloride.
• step (b) is carried out, when the reducing agent is zinc, both in the presence of an acid selected from an organic acid and a weak acid salt and ammonium chloride .
• step (b) takes place at a temperature T ranging from 0 to 25 ° C.
• the process according to the invention comprises a step (c) of recovery, as mentioned above, of the compound of formula (I).
• the process according to the invention comprises a step (a) of manufacturing the compound of formula (II), prior to step (b), by reacting a compound of formula (X):
• Z 1 is selected from OH, COOH, NH 2 , COOR 3 , wherein R 3 is C 1 -C 4 alkyl, and COY, Y is halogen,
• Z 1 denotes OH
• Z 2 is chosen from OH, COOH and Cl
• Z 2 is chosen from OH and NH 2 ;
• Z 2 is chosen from OH and NH 2 ;
• step (a) is an etherification reaction (Z 2 denotes OH or Cl) or esterification reaction (Z 2 denotes COOH).
• step (a) is an esterification reaction (Z 2 denotes OH) or amidification reaction (Z 2 denotes NH 2 ).
• step (a) is an amidification reaction.
• step (a) is a transesterification reaction (Z 2 denotes OH) or amidification reaction (Z 2 denotes NH 2 ).
• step (a) is an esterification reaction (Z 2 denotes OH) or amidification reaction (Z 2 denotes NH 2 ).
• the group Sp ' is a spacer group which makes it possible to connect the group Z 2 to the group A as the formula of the compound (XI) indicates, and thus can be of any type known per se.
• the group Sp ' is preferably a linear, branched or cyclic C1-C24 hydrocarbon-based chain which may contain one or more aromatic radicals and / or one or more heteroatoms. Said chain may optionally be substituted, provided that the substituents do not react with the group A and the nitrone function.
• the group Sp is a straight or branched alkylene chain C1-C24, preferably C1-C10, more preferably Ci-C 6, said chain being optionally interrupted by one or more nitrogen atoms or oxygen atoms, and may include one or more carbonyl groups.
• the present application also relates to the use of the compound of formula (I) obtained by the process according to the invention.
• the structural analysis as well as the determination of the molar purities of the synthesis molecules are carried out by NMR analysis.
• the spectra are acquired on a BRUKER 500 MHz Avance spectrometer equipped with a BBIz-grad 5 mm wideband probe.
• the quantitative 1H NMR experiment uses a 30 ° single pulse sequence and a 3 second repetition time between each of the 64 acquisitions.
• the samples are solubilized in the deuterated dimethylsulfoxide (DMSO). This solvent is also used for the lock signal.
• Calibration is performed on the proton signal of DMSO deuterated at 2.44 ppm with respect to a TMS reference at 0 ppm.
• the 1 H NMR spectrum coupled to the 2D HSQC 'H / 13 C and HMBC' H / 13 C experiments allows the structural determination of the molecules.
• the molar quantifications are made from the quantitative 1H 1H NMR spectrum.
• the mass spectrometry analysis is carried out by direct injection by an electrospray ionization mode (ID / ESI).
• ID / ESI electrospray ionization mode
• the analyzes were performed on a Bruker HCT spectrometer (600 ⁇ / ⁇ flow rate, 10 psi nebulizer gas pressure, 4 l / min nebulizer gas flow).
• the intermediate compound (Ia) can be obtained according to the protocol described in Example 4 of the patent application WO 2012/007684. This synthesis step corresponds to step (a) as described above.
• the nitrone (1) is then obtained according to step (b) of the process according to the invention.
• the 1- (2-chloroethyl) imidazolidin-2-one (compound (2a)) can be obtained according to the protocol described in Example 1 of the patent application WO 2012/007684.
• the derivative (2b) (39.3 g), in the form of a light yellow solid, is obtained with a mass yield of 82%.
• said derivative (2b) is obtained according to step (a) as described above.
• nitrone (2) is then obtained according to step (b) of the process according to the invention.
• the derivative (3a) (39.3 g) is obtained with a mass yield of 88%.
• said derivative (3a) is obtained according to step (a) as described above.
• nitrone (3) is then obtained according to step (b) of the process according to the invention.
• the 1- (2-aminoethyl) imidazolidine-2-thione (compound 4a) can be obtained according to the protocol described in Example 4 of the patent application WO 2012/007684.
• nitrone (4) is then obtained according to step (b) of the process according to the invention.

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• 2015
  • 2015-10-14 FR FR1559758A patent/FR3042499B1/fr not_active Expired - Fee Related
• 2016
  • 2016-10-14 WO PCT/EP2016/074797 patent/WO2017064296A1/fr not_active Ceased
  • 2016-10-14 EP EP16782219.6A patent/EP3362437A1/de not_active Withdrawn

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