Novel catalytic process for the preparation of oxalate and oxamide compounds

Abstract

The present invention relates to the use of M-NHC catalysts, comprising at least one M atom linked to at least one N-heterocyclic carbene ligand, M representing Pd or Pt and NHC representing an N-heterocyclic carbene group, in carrying out a process for the selective preparation of oxalates or oxamides from carbon monoxide, an oxidant, in particular molecular oxygen or air, and an alcohol or an amine, respectively, optionally in the presence of a cocatalyst.

Description

[Technical field]

[0001] The present invention relates to a novel process for the catalytic preparation of oxalate and oxamide compounds. [Background technology]

[0002] Oxalates and oxamides are important raw materials in the organic chemical industry, used on a large scale to produce a variety of colorants, pharmaceuticals, important solvents, extractants and various intermediates in the fine chemical industry.

[0003] For example, the hydrogenation of oxalates and oxamides can produce ethylene glycol, an important raw material in the chemical industry.

[0004] Conventional methods for the production of oxalates involve the esterification of oxalic acid with alcohols, a production technique that is costly, energy intensive, highly polluting, and involves irrational use of raw materials.

[0005] The conventional method for producing oxamide is based on the reaction of oxalic acid or its derivatives with amines. However, this method is disadvantageous because it presupposes the use of costly or highly toxic and corrosive reagents. The use of such highly reactive starting compounds easily leads to undesirable secondary reactions that reduce the selectivity and yield of the reaction.

[0006] Oxalate and oxamide compounds can be directly synthesized by oxidative carbonylation of alcohols or amines, respectively, in the presence of palladium (Pd) or platinum (Pt) catalysts.

[0007] A key step in industrial oxidation reactions catalyzed by palladium or platinum is the efficient regeneration of metal atoms in oxidation state +2 from those in oxidation state 0 that are reduced during the reaction. In general, it is quite difficult to directly reoxidize Pd(0) to Pd(II) or Pt(0) to Pt(II) with molecular oxygen, and therefore supplementary oxidants are usually used.

[0008] Pd(0) or Pt(0) can be reoxidized using metal redox couples or benzoquinone. The main disadvantages are: (1) Excessive metal is used, causing corrosive damage to equipment; (2) It is difficult to separate the reaction products from the oxidizing agent (e.g., when benzoquinone is used as the oxidizing agent, hydroquinone is formed as a by-product).

[0009] Moreover, prior art processes for the preparation of oxalates are carried out under anhydrous conditions and optionally with a drying agent, since the production of oxalates is hindered by water formed in situ when oxygen is used as the oxidizing agent or when water is present in the reagents or solvents, which deactivates the catalyst.

[0010] Another approach to the synthesis of oxalates is based on the use of alkyl nitrites (RONO), explosive compounds that act as effective reoxidants for Pd(0) and at the same time act as good nucleophiles for CO via their alkoxy functional groups (RO). However, secondary reactions occur, specifically the formation of nitric acid.

[0011] Prior art methods disclose the use of organometallic complexes of palladium or platinum as homogeneous catalysts for the oxidative carbonylation of alcohols to oxalates and amines to oxamides. In particular, Pd(II) salts such as PdCl2, PdBr2, Pd(acac)2, Pd(OAc)2, PdSO4, Pd(NO3)2, alone or in combination with phosphines or other ligands such as Ph2EtP, PhEt2P, (PhO)3P, Ph3P, or Pt(II) salts such as PtCl2 were used.

[0012] However, although the presence of ligands in palladium catalysts has been shown to improve the performance of the catalyst when working with strong oxidants such as O2 and RONO, the phosphorus donor ligand P-donor can be easily oxidized and cause the decomposition of the catalyst into toxic products that need to be removed by additional clean-up steps. Summary of the Invention [Problem to be solved by the invention]

[0013] For many years there has been a search for low cost, environmentally friendly methods for preparing oxalates and oxamides. [Means for solving the problem]

[0014] One of the objects of the present invention is the use of palladium-(N-heterocyclic carbene) or platinum-(N-heterocyclic carbene) catalysts for the preparation of oxalates or oxamides.

[0015] Another object of the invention is the use of palladium-(N-heterocyclic carbene) or platinum-(N-heterocyclic carbene) catalysts, which make it possible to work under oxidative conditions with strong oxidizing agents such as oxygen.

[0016] Another object of the present invention is the use of stable, recoverable and reusable palladium-(N-heterocyclic carbene) or platinum-(N-heterocyclic carbene) catalysts in oxidative carbonylation reactions that allow the preparation of oxalates and oxamides.

[0017] Another object of the invention is the use of palladium-(N-heterocyclic carbene) or platinum-(N-heterocyclic carbene) catalysts, advantageously immobilized on a support, to obtain recyclable and high-performance supported catalysts.

[0018] One of the objectives of the present invention in the specific case of the preparation of oxalates is to: - Harmful toxic agents such as nitric oxide (NO), - Desiccant - a transition metal co-catalyst, or - P-donor ligand, The present invention relates to the use of palladium-(N-heterocyclic carbene) or platinum-(N-heterocyclic carbene) catalysts in oxidative carbonylation processes under certain conditions, which may make it possible to avoid the use of

[0019] Another object of the present invention is the use of palladium-(N-heterocyclic carbene) or platinum-(N-heterocyclic carbene) catalysts in the process for oxidative carbonylation of alcohols or amines leading to efficient yields.

[0020] Another object of the present invention is the use of a palladium-(N-heterocyclic carbene) or platinum-(N-heterocyclic carbene) catalyst in an oxidative carbonylation process with a selectivity towards oxalate or oxamide of greater than 80%.

[0021] Another object of the present invention is a process for the preparation of oxalates or oxamides in the presence of a palladium-(N-heterocyclic carbene) or platinum-(N-heterocyclic carbene) catalyst.

[0022] [use] A first object of the present invention resides in the use of a M-NHC catalyst comprising at least one M atom bonded to at least one N-heterocyclic carbene ligand, M representing Pd or Pt and NHC representing an N-heterocyclic carbene group, in carrying out a process for the selective preparation of an oxalate or oxamide from carbon monoxide, an oxidant, in particular molecular oxygen or air, and an alcohol or an amine, respectively, optionally in the presence of a cocatalyst.

[0023] In the sense of the present invention, "oxalate" means the dialkyl oxalate corresponding to the alcohol used.

[0024] By "oxamide" is meant the 1,1'-oxalyldiamine oxamide derivative corresponding to the amine used.

[0025] M-NHC catalysts are organometallic complexes that contain at least one metal center, M, consisting of a palladium or platinum atom as a catalytic site, where said metal center is bound to at least one N-heterocyclic carbene ligand.

[0026] By "N-heterocyclic carbene" or NHC is meant a molecular species having a divalent carbon with six valence electrons enclosed within a heterocycle that contains at least one nitrogen atom.

[0027] By way of non-limiting example, the following catalysts also fall within the definition of the present invention: - complexes containing an M centre bound to one NHC ligand, - a complex comprising an M centre linked to two NHC ligands, - a complex comprising two M centres and two NHC ligands, - a complex containing two M centres and four NHC ligands, - complexes comprising n M centres and n NHC ligands, n being an integer from 1 to 1000, in particular from 1 to 10, - complexes comprising n M centres and 2n NHC ligands, where n is an integer from 1 to 1000, in particular from 1 to 10.

[0028] From the value of the integer n it is clear that the catalyst according to the invention can be polymeric.

[0029] According to a particular embodiment, the present invention relates to the use of M-NHC catalysts in a process for the selective preparation of oxalates or oxamides from carbon monoxide, an oxidant, and an alcohol or amine, respectively.

[0030] In certain embodiments, the present invention relates to the use of M-NHC catalysts in a process for the selective preparation of oxalates from carbon monoxide, an oxidant, and an alcohol.

[0031] In certain embodiments, the present invention relates to the use of M-NHC catalysts in a process for the selective preparation of oxamides from carbon monoxide, an oxidant, and an amine.

[0032] Advantageously, the present invention relates to the use of Pd-NHC palladium catalysts.

[0033] According to a particular embodiment, the present invention relates to the use of a Pd-NHC catalyst in a process for the selective preparation of oxalates or oxamides from carbon monoxide, an oxidant, and an alcohol or amine, respectively.

[0034] In certain embodiments, the present invention relates to the use of a Pd-NHC catalyst in a process for the selective preparation of oxalates from carbon monoxide, an oxidant, and an alcohol.

[0035] In certain embodiments, the present invention relates to the use of a Pd-NHC catalyst in a process for the selective preparation of oxamides from carbon monoxide, an oxidant, and an amine.

[0036] Advantageously, the present invention relates to the use of Pt-NHC platinum catalysts.

[0037] According to a particular embodiment, the present invention relates to the use of a Pt-NHC catalyst in a process for the selective preparation of oxalates or oxamides from carbon monoxide, an oxidant, and an alcohol or amine, respectively.

[0038] In certain embodiments, the present invention relates to the use of a Pt-NHC catalyst in a process for the selective preparation of oxalates from carbon monoxide, an oxidant, and an alcohol.

[0039] In certain embodiments, the present invention relates to the use of a Pt-NHC catalyst in a process for the selective preparation of oxamides from carbon monoxide, an oxidant, and an amine.

[0040] According to a particular embodiment, the invention relates to the use as defined above, in which the oxidizing agent is selected from among molecular oxygen (O2), air, diones, in particular 1,4-benzoquinone, 1,4-dichloro-2-butene and CuCl2.

[0041] For the purposes of this invention, air is defined as the oxidizing agent. Air is a gas composition containing approximately 78% nitrogen (N2), 21% oxygen O2, and approximately less than 1% carbon dioxide (CO2), methane (CH4), and other gases, including the noble gases, including argon, helium, neon, krypton, and xenon, by mole fraction. Nitrogen is an inert gas, so the oxidizing reactivity of air is dominated by the reactivity of oxygen. Dioxygen is also referred to as molecular oxygen or oxygen in this invention.

[0042] Advantageously, the invention relates to the use as defined above, in which molecular oxygen or air is used as the oxidizing agent.

[0043] According to a particular embodiment, the present invention relates to the use of M-NHC catalysts in a process for the selective preparation of oxalates or oxamides from carbon monoxide, molecular oxygen or air and alcohols or amines, respectively.

[0044] In certain embodiments, the present invention relates to the use of M-NHC catalysts in processes for the selective preparation of oxalates from carbon monoxide, molecular oxygen or air and alcohols.

[0045] In certain embodiments, the present invention relates to the use of M-NHC catalysts in processes for the selective preparation of oxamides from carbon monoxide, molecular oxygen or air and amines.

[0046] Advantageously, the invention relates to the use of a Pd-NHC catalyst as defined above, in which molecular oxygen or air is used as the oxidizing agent.

[0047] According to a particular embodiment, the present invention relates to the use of a Pd-NHC catalyst in a process for the selective preparation of oxalates or oxamides from carbon monoxide, molecular oxygen or air and alcohols or amines, respectively.

[0048] In certain embodiments, the present invention relates to the use of a Pd-NHC catalyst in a process for the selective preparation of oxalates from carbon monoxide, molecular oxygen or air and an alcohol.

[0049] In certain embodiments, the present invention relates to the use of a Pd-NHC catalyst in a process for the selective preparation of oxamides from carbon monoxide, molecular oxygen or air and amines.

[0050] Advantageously, the invention relates to the use of a Pt-NHC catalyst as defined above, in which molecular oxygen or air is used as the oxidizing agent.

[0051] According to a particular embodiment, the present invention relates to the use of a Pt-NHC catalyst in a process for the selective preparation of oxalates or oxamides from carbon monoxide, molecular oxygen or air and alcohols or amines, respectively.

[0052] In certain embodiments, the present invention relates to the use of a Pt-NHC catalyst in a process for the selective preparation of oxalates from carbon monoxide, molecular oxygen or air and an alcohol.

[0053] In certain embodiments, the present invention relates to the use of a Pt-NHC catalyst in a process for the selective preparation of oxamides from carbon monoxide, molecular oxygen or air and an amine.

[0054] Advantageously, the invention relates to the use of a Pd-NHC catalyst as defined above in the presence of a cocatalyst.

[0055] According to a particular embodiment, the present invention relates to the use of a Pd-NHC catalyst in carrying out a process for the selective preparation of oxalates or oxamides from carbon monoxide, an oxidant and an alcohol or amine, respectively, in the presence of a cocatalyst.

[0056] In certain embodiments, the present invention relates to the use of a Pd-NHC catalyst in a process for the selective preparation of oxalates from carbon monoxide, an oxidant and an alcohol in the presence of a co-catalyst.

[0057] In certain embodiments, the present invention relates to the use of a Pd-NHC catalyst in a process for the selective preparation of oxamides from carbon monoxide, an oxidant and an amine in the presence of a co-catalyst.

[0058] Advantageously, the invention relates to the use of a Pd-NHC catalyst as defined above, using molecular oxygen or air as oxidizing agent, in the presence of a cocatalyst.

[0059] In a particular embodiment, the present invention relates to the use of a Pd-NHC catalyst in a process for the selective preparation of oxalates or oxamides from carbon monoxide, molecular oxygen or air and alcohols or amines, respectively, in the presence of a co-catalyst.

[0060] In certain embodiments, the present invention relates to the use of a Pd-NHC catalyst in a process for the selective preparation of oxalates from carbon monoxide, molecular oxygen or air and an alcohol in the presence of a cocatalyst.

[0061] In certain embodiments, the present invention relates to the use of a Pd-NHC catalyst in a process for the selective preparation of oxamides from carbon monoxide, molecular oxygen or air and amines in the presence of a cocatalyst.

[0062] Advantageously, the catalyst for use in accordance with the present invention may be selected to be free of any phosphorus ligands.

[0063] According to a particular embodiment, the present invention relates to the use of M-NHC catalysts that do not have phosphorus ligands, in particular phosphine groups.

[0064] Unlike M-phosphine complexes, where the P-donor phosphine ligand oxidizes, leading to the formation of decomposition products during catalysis, the stability of the M-NHC catalysts means that they are reusable and the catalysts are stable in the oxidation reaction environment.

[0065] [Supported catalyst] Advantageously, the M-NHC catalyst can be bound to a support.

[0066] According to an advantageous embodiment, the present invention relates to the use of a M-NHC supported catalyst as defined above in carrying out a process for the selective preparation of an oxalate or an oxamide, respectively, from carbon monoxide, an oxidant and an alcohol or an amine, respectively.

[0067] According to a particular embodiment, the present invention relates to the use of a M-NHC supported catalyst as defined above in carrying out a process for the selective preparation of an oxalate from carbon monoxide, an oxidant and an alcohol.

[0068] According to a particular embodiment, the present invention relates to the use of a M-NHC supported catalyst as defined above in carrying out a process for the selective preparation of oxamides from carbon monoxide, an oxidant and an amine.

[0069] By "supported M-NHC catalyst" is meant that the M-NHC catalyst is bound to a support. The association between the organometallic complex and the support can be achieved in various ways.

[0070] The association between the catalyst and the support may be by chemical bonds, including covalent bonds, ionic bonds and / or intermolecular interactions, such as hydrogen bonds.

[0071] Preferably, the catalyst is covalently bonded to the support.

[0072] In a particular embodiment, the catalyst is bound to the support by at least one of its ligands, thus allowing access to the metal center.

[0073] In certain embodiments, the catalyst is linked to the support via an N-heterocyclic carbene group.

[0074] In one embodiment the support is an oxide, in particular silica, a polymer, a carbon material such as carbon nanotubes and graphene oxide or a magnetic nanoparticle, preferably a polymer or silica.

[0075] In one embodiment, the support is in the form of beads.

[0076] As non-limiting examples, the support may consist of polystyrene beads or silica beads, for example in the form of silica gel.

[0077] The use of supported catalysts has the advantage of facilitating separation of the catalyst from the reaction medium, facilitating recovery and reuse of the catalyst.

[0078] The use of supported catalysts also has the advantage that, when working under continuous flow, it makes it possible to fix the catalyst within the reactor in an enclosure such as a cartridge, thus obtaining a product leaving the reactor in the absence of catalyst.

[0079] M-NHC catalyst Advantageously, but not exclusively, the use according to the invention as defined above can be carried out with a M-NHC catalyst of the specific formula defined below.

[0080] M-(N-heterocyclic carbene) catalysts containing a metal center M linked to an NHC ligand According to a particular embodiment, the present invention relates to a catalyst having formula I: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L1 represents a halogen atom selected from Cl, Br and I; L2 and L3 are linked and together represent a bidentate ligand; or or L2 represents a halogen atom selected from Cl, Br and I, and L3 represents a monodentate ligand; The compound of formula I can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, For use as defined above.

[0081] According to a particular embodiment, the invention relates to the use as defined above, in which said compound of formula I is bound by at least one of the R1 or R2 groups to a support, in particular a polymer or silica.

[0082] According to a particular embodiment, the present invention relates to a catalyst having formula I, wherein: L1 represents an iodine atom; L2 and L3 are linked and together represent a bidentate ligand; or or L2 represents a halogen atom selected from Cl, Br and I, and L3 represents a monodentate ligand; For use as defined above.

[0083] Surprisingly, the inventors have discovered that the use of a catalyst carrying an iodized ligand has the advantage that a co-catalyst is not required, in particular an iodized co-catalyst such as tetrabutylammonium iodide (Bu4NI).

[0084] For the purposes of this invention, "C1-C 10 "Straight or branched alkyl" means an acyclic, saturated, linear or branched carbon chain containing from 1 to 10 carbon atoms. These groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl. The definitions propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl include all possible isomers. For example, the term butyl includes n-butyl, iso-butyl, sec-butyl and ter-butyl. One or more hydrogen atoms can be replaced in the alkyl chain.

[0085] "C3~C 10 The term "cycloalkyl" refers to a C3 cyclopropyl group, a C4 cyclobutyl group, a C5 cyclopentyl group, a C6 cyclohexyl group, a C7 cycloheptyl group, a C8 cyclooctyl group, a C9 cyclononyl group, or a C 10 It refers to cyclodecyl groups, and fused cycloalkane rings, such as adamantyl.

[0086] "C6~C 20 The term "aryl" means an aromatic group containing 6 to 20 carbon atoms in the aromatic ring, in particular 6 to 12 carbon atoms, in particular 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Aryl groups according to the invention are also in particular C1-C 10 It may be substituted with one or more substituents selected from straight chain or branched alkyl groups.

[0087] Phenyl, toluyl, anisyl and naphthyl, o-tolyl, m-tolyl, p-tolyl, o-xylyl, m-xylyl, p-xylyl are examples of aryl groups.

[0088] The term "heteroaryl" refers to an aryl group as defined above that contains an atom other than carbon atom in the aromatic ring, in particular N, O or S. Pyridyl, imidazoyl, furfuryl or furanyl are examples of heteroaryl groups according to the invention.

[0089] "C7~C 20 The term "alkyl-aryl" refers to a group of the formula -(CH) -, where m varies from 1 to 14, linked to an aryl group as defined above. 2m - means a linear alkyl chain, where the alkyl-aryl group consists of 7 to 20 carbon atoms.

[0090] "C4~C 20 The term "alkyl-heteroaryl" refers to a heteroaryl group of the formula -(CH), where m varies from 1 to 16, linked to a heteroaryl group as defined above. 2m - means a linear alkyl chain, where the alkyl-heteroaryl group consists of 4 to 20 carbon atoms.

[0091] Advantageously, the R1 and R2 radicals, independently of one another, can be chosen from among the following radicals: methyl, iso-propyl, tert-butyl, cyclohexyl, adamantyl, mesityl (2,4,6-trimethylphenyl) and diisopropylphenyl.

[0092] In one embodiment, the R1 and R2 groups are the same. In another embodiment, the R1 and R2 groups are different.

[0093] By "bidentate ligand" is meant in particular a charged or neutral molecular group which forms two bonds with the metal center M, specifically via two atoms of the molecular group.

[0094] "Monodentate ligand" means a charged or neutral molecular group that forms a bond with the metal center M, specifically via one atom of the molecular group.

[0095] In one embodiment, the ligands L1, L2 and L3 do not contain phosphorus. Advantageously, the catalyst does not contain a phosphine ligand.

[0096] The R1 or R2 groups can be used to attach the catalyst to a support to form a supported catalyst.

[0097] In certain embodiments, at least one of the R1 and R2 groups of the catalyst is attached to a support, preferably by a covalent bond. The catalyst used is a supported catalyst.

[0098] In a particular embodiment, the carrier is a polymer, in particular polystyrene (PS).

[0099] In certain embodiments, the support is silica, especially silica gel.

[0100] In certain embodiments, the R1 and R2 groups of the catalyst are not attached to a support. The catalyst used is a homogeneous catalyst.

[0101] [Palladium-(N-heterocyclic carbene) catalysts containing Pd bound to NHC ligands] In certain embodiments, the present invention provides a catalyst having formula II: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L1 represents a halogen atom selected from Cl, Br and I; L2 and L3 are linked and together represent a bidentate ligand; or or L2 represents a halogen atom selected from Cl, Br and I, and L3 represents a monodentate ligand; The compound of formula II can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, For use as defined above.

[0102] According to a particular embodiment, the invention relates to the use as defined above, in which said compound of formula II can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups.

[0103] According to a particular embodiment, the present invention relates to a catalyst which corresponds to formula II, wherein: L1 represents an iodine atom; L2 and L3 are linked and together represent a bidentate ligand; or or L2 represents a halogen atom selected from Cl, Br and I, and L3 represents a monodentate ligand; For use as defined above.

[0104] According to a particular embodiment, the present invention relates to a catalyst which corresponds to formula II, wherein: L1 and L2 each represent an iodine atom; L3 represents a monodentate ligand; For use as defined above.

[0105] According to a particular embodiment, the invention relates to the use as defined above, in which the bidentate ligand is selected from among acetylacetonate (acac), allyl, cinnamyl and acetate, in particular the bidentate ligand being acetylacetonate.

[0106] According to a particular embodiment, the present invention relates to the use as defined above, in which the monodentate ligand is selected from among pyridine, 3-chloropyridine, acetonitrile, triethylamine or a phosphine-based ligand, in particular triphenylphosphine. Preferably, the monodentate ligand is in particular 3-chloropyridine.

[0107] According to a particular embodiment, the invention relates to the use as defined above, in which the monodentate ligand is chosen from among pyridine, 3-chloropyridine, acetonitrile, triethylamine. Preferably, the monodentate ligand is 3-chloropyridine.

[0108] According to a particular embodiment, the present invention relates to a catalyst having formula II: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L1 represents a halogen atom selected from Cl, Br and I; L2 and L3 represent a bidentate ligand, in particular a bidentate ligand selected from among acetylacetonate (acac), allyl, cinnamyl and acetate, preferably acetylacetonate, or L2 represents a halogen atom selected from Cl, Br and I; L3 represents a monodentate ligand, in particular selected from pyridine, 3-chloropyridine, acetonitrile, triethylamine or a phosphine-based ligand, in particular triphenylphosphine, preferably 3-chloropyridine, The compound of formula II can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, For use as defined above.

[0109] According to a particular embodiment, the present invention relates to a catalyst having formula II: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L1 represents an iodine atom; L2 and L3 represent a bidentate ligand, in particular a bidentate ligand selected from among acetylacetonate (acac), allyl, cinnamyl and acetate, preferably acetylacetonate, or L2 represents a halogen atom selected from among Cl, Br and I and L3 represents a monodentate ligand, in particular selected from among pyridine, 3-chloropyridine, acetonitrile, triethylamine or a phosphine-based ligand, in particular triphenylphosphine, preferably 3-chloropyridine, The compound of formula II can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, For use as defined above.

[0110] According to a particular embodiment, the present invention relates to a catalyst having the formula II-4: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L2 and L3 represent a bidentate ligand, in particular a bidentate ligand selected from among acetylacetonate (acac), allyl, cinnamyl and acetate, preferably acetylacetonate, or L2 represents a halogen atom selected from among Cl, Br and I and L3 represents a monodentate ligand, in particular selected from among pyridine, 3-chloropyridine, acetonitrile, triethylamine or a phosphine-based ligand, in particular triphenylphosphine, preferably 3-chloropyridine, The compound of formula II-4 can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, For use as defined above.

[0111] According to a particular embodiment, the present invention relates to a catalyst having formula II: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L1 and L2 each represent an iodine atom; L3 represents a monodentate ligand, in particular selected from pyridine, 3-chloropyridine, acetonitrile, triethylamine or a phosphine-based ligand, in particular triphenylphosphine, preferably 3-chloropyridine, The compound of formula II can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, For use as defined above.

[0112] According to a particular embodiment, the present invention relates to a catalyst having the formula II-5: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L3 represents a monodentate ligand, in particular selected from pyridine, 3-chloropyridine, acetonitrile, triethylamine or a phosphine-based ligand, in particular triphenylphosphine, preferably 3-chloropyridine, The compound of formula II-5 can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, For use as defined above.

[0113] According to a particular embodiment, the invention relates to the use as defined above, in which said compound of formula II is bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups.

[0114] According to a particular embodiment, the invention relates to the use as defined above, in which said compound of formula II-4 is bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups.

[0115] According to a particular embodiment, the invention relates to the use as defined above, in which said compound of formula II-5 is bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups.

[0116] [Palladium-(N-heterocyclic carbene) catalysts containing bound Pd and two NHC ligands] In a particular embodiment, the invention relates to the use as defined above, wherein the catalyst comprises two palladium-bound N-heterocyclic carbene groups.

[0117] According to a particular embodiment, the present invention relates to a catalyst having formula III: [ka] Corresponding to the formula: R1, R2, R3 and R4 independently of each other; C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L1 and L2, independently of each other: - a halogen atom selected from Cl, Br and I, or - monodentate ligand, or or L1 and L2 are linked to represent a bidentate ligand; The compound of formula III may be bound to a support, in particular a polymer or silica, by at least one of the R1, R2, R3 or R4 groups, Optionally, one of the R1 or R2 groups may be linked to R3 or R4, which together represent a bidentate group containing two N-heterocyclic carbene groups. For use as defined above.

[0118] According to a particular embodiment, the invention relates to the use as defined above, in which the catalyst of formula III comprises one of the R1 or R2 groups linked to R3 or R4, which together represent a bidentate group comprising two N-heterocyclic carbene groups.

[0119] According to a particular embodiment, the invention relates to the use as defined above, in which the catalyst corresponds to formula III, in which at least one of the L1 and L2 groups represents an iodine atom.

[0120] According to a particular embodiment, the present invention relates to a catalyst having the formula III-2: [ka] Corresponding to the formula: R1, R2, R3 and R4 independently of each other; C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L1: - a halogen atom selected from Cl, Br and I, or - monodentate ligand, represents The compound of formula III-2 can be bound to a support, in particular a polymer or silica, by at least one of the R1, R2, R3 or R4 groups, Optionally, one of the R1 or R2 groups may be linked to R3 or R4, which together represent a bidentate group containing two N-heterocyclic carbene groups. For use as defined above.

[0121] According to a particular embodiment, the invention relates to the use as defined above, in which the catalyst corresponds to formula III, in which the L1 and L2 groups each represent an iodine atom.

[0122] According to a particular embodiment, the present invention relates to a catalyst having the formula III-3: [ka] Corresponding to the formula: R1, R2, R3 and R4 independently of each other; C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from The compound of formula III-3 can be bound to a support, in particular a polymer or silica, by at least one of the R1, R2, R3 or R4 groups, Optionally, one of the R1 or R2 groups may be linked to R3 or R4, which together represent a bidentate group containing two N-heterocyclic carbene groups. For use as defined above.

[0123] According to a particular embodiment, the present invention relates to the use as defined above, wherein said compound of formula III is bound to a support, in particular a polymer or silica, by at least one of the R1, R2, R3 or R4 groups.

[0124] According to a particular embodiment, the present invention relates to the use as defined above, in which said compound of formula III-2 is bound to a support, in particular a polymer or silica, by at least one of the R1, R2, R3 or R4 groups.

[0125] According to a particular embodiment, the present invention relates to the use as defined above, in which said compound of formula III-3 is bound to a support, in particular a polymer or silica, by at least one of the R1, R2, R3 or R4 groups.

[0126] [Dimer: Palladium-(N-heterocyclic carbene) catalyst containing two Pd and two NHC ligands] According to a particular embodiment, the present invention relates to a catalyst having formula IV: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L1 and L2 represent halogen atoms selected from Cl, Br and I; For use as defined above.

[0127] Formula IV shows that the Pd---L2 bond is a coordinate bond and that the complex formed is a dimer with a symmetric structure.

[0128] [Specific formula for palladium-(N-heterocyclic carbene) catalyst containing Pd bonded to NHC ligand] According to a particular embodiment, the present invention relates to a catalyst having the formula II-1: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from The compound of formula II-1 can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, For use as defined above.

[0129] In one embodiment, the R1 and R2 groups of the catalyst of formula II-1 are the same. In another embodiment, the R1 and R2 groups of the catalyst of formula II-1 are different.

[0130] In one embodiment, the R1 and R2 groups of the Formula II-1 catalyst are not attached to a support.

[0131] In another embodiment, at least one of the R1 and R2 groups of the catalyst of formula II-1 is bound to a support, in particular a polymer or silica.

[0132] According to a particular embodiment, the present invention relates to a catalyst having the formula II-2: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from The compound of formula II-2 can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, For use as defined above.

[0133] In one embodiment, the R1 and R2 groups of the catalyst of formula II-2 are the same. In another embodiment, the R1 and R2 groups of the catalyst of formula II-2 are different.

[0134] In one embodiment, the R1 and R2 groups of the Formula II-2 catalyst are not attached to a support.

[0135] In another embodiment, at least one of the R1 and R2 groups of the catalyst of formula II-2 is bound to a support, in particular a polymer or silica.

[0136] According to a particular embodiment, the present invention relates to a catalyst having the formula II-3: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from The compound of formula II-3 can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, For use as defined above.

[0137] In one embodiment, the R1 and R2 groups of the catalyst of formula II-3 are the same. In another embodiment, the R1 and R2 groups of the catalyst of formula II-3 are different.

[0138] In one embodiment, the R1 and R2 groups of the Formula II-3 catalyst are not attached to a support.

[0139] In another embodiment, at least one of the R1 and R2 groups of the catalyst of formula II-3 is bound to a support, in particular a polymer or silica.

[0140] According to a particular embodiment, the present invention relates to the use as defined above, in which the catalyst is bound to polystyrene.

[0141] According to a particular embodiment, the present invention relates to a catalyst comprising: [ka] or Or, the catalyst bound to the support is: [ka] Selected from among For use as defined above.

[0142] According to a particular embodiment, the present invention relates to a catalyst having formula II-1 or formula II-2 or formula II-3: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from The catalyst may be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, In particular, the catalyst comprises: [ka] or or a catalyst bound to a support (PS), [ka] is selected from among For use as defined above.

[0143] According to a particular embodiment, the present invention relates to a catalyst having the formula III-1: [ka] Corresponding to the formula: R1, R2, R3 and R4 independently of each other; C1~C 10 Linear or branched alkyl, C3~C 10 cycloalkyl, and C6~C 20 Aryl or C3-C 20 Heteroaryl, C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from The compound of formula III-1 can be bound to a support, in particular a polymer or silica, by at least one of the R1, R2, R3 or R4 groups, Optionally, one of the R1 or R2 groups may be linked to R3 or R4, which together represent a bidentate group containing two N-heterocyclic carbene groups. For use as defined above.

[0144] In one embodiment, the R1, R2, R3 and R4 groups of the catalyst of formula III-1 are not attached to a support.

[0145] According to a particular embodiment, the present invention relates to the use as defined above, in which said compound of formula III-1 is bound to a support, in particular a polymer or silica, by at least one of the R1, R2, R3 or R4 groups.

[0146] According to a particular embodiment, the present invention relates to a catalyst of formula III-1 bound to a support: [ka] The use as defined above is selected from among

[0147] [Platinum-(N-heterocyclic carbene) catalysts containing Pt bound to NHC ligands] According to a particular embodiment, the present invention relates to a catalyst having formula V: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L1 represents a halogen atom selected from Cl, Br and I; L2 and L3 are linked and together represent a bidentate ligand; or or L2 represents a halogen atom selected from among Cl, Br and I and L3 represents a monodentate ligand; or L1, L2, and L3 are linked together to represent a tridentate ligand; The compound of formula V may be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, For use as defined above.

[0148] According to a particular embodiment, the invention relates to the use as defined above, wherein the bidentate ligand is ethylenediamine.

[0149] According to a particular embodiment, the invention relates to the use as defined above, in which the monodentate ligand is chosen from among pyridine, 3-chloropyridine, cyclohexylamine, morpholine and dimethylsulfide, phosphines, in particular triphenylphosphine (PPh3), ammonia (NH3) and dimethylsulfoxide (DMSO).

[0150] According to a particular embodiment, the invention relates to the use as defined above, in which the tridentate ligand is chosen from among terpyridine and diethylenetriamine.

[0151] [Platinum-(N-heterocyclic carbene) catalysts containing Pt bound to 2NHC ligands] According to a particular embodiment, the present invention relates to a catalyst having formula VI: [ka] Corresponding to the formula: R1, R2, R3 and R4 independently of each other; C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L1 and L2, independently of each other: - a halogen atom selected from Cl, Br and I, or - monodentate ligand, or or L1 and L2 are linked and represent a bidentate ligand; The compound of formula VI may be bound to a support, in particular a polymer or silica, by at least one of the R1, R2, R3 or R4 groups, Optionally, one of the R1 or R2 groups may be linked to R3 or R4, which together represent a bidentate group containing two N-heterocyclic carbene groups. For use as defined above.

[0152] [method] A second object of the present invention is a process for the preparation of oxalate or oxamide compounds from carbon monoxide (CO), an oxidant, in particular molecular oxygen or air, and an alcohol or an amine, respectively, catalyzed by an M-NHC catalyst, where M represents a palladium atom (Pd) or a platinum atom (Pt) and NHC represents an N-heterocyclic carbene ligand.

[0153] Advantageously, under certain conditions, the presence of a co-catalyst, a base, a solvent or a heating step is optional.

[0154] The reaction balance for the oxidative carbonylation of an alcohol or amine for the process for preparing an oxalate or oxamide according to the present invention is written as follows: [ka]

[0155] According to a particular embodiment, the present invention provides a method for preparing an oxalate or oxamide compound, comprising: To obtain an oxalate compound or an oxamide compound, With alcohols or amines respectively: ■ Carbon monoxide, ■ Oxidizing agents, ■ M-NHC catalysts, in which M represents Pd or Pt and NHC represents an N-heterocyclic carbene group, and which contain at least one M atom linked to at least one N-heterocyclic carbene ligand; and ■ optionally a promoter; ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating the reaction medium; The present invention relates to a method comprising the steps of:

[0156] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: To obtain the oxalate compound, Alcohol and: ■ Carbon monoxide, ■ Oxidizing agents, ■ M-NHC catalyst, and ■ optionally a promoter; ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0157] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising: To obtain the oxamide compound, · With amines respectively: ■ Carbon monoxide, ■ Oxidizing agents, ■ M-NHC catalyst, and ■ optionally a promoter; ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0158] Advantageously, the present invention relates to a process for preparing oxalate or oxamide compounds using a Pd-NHC palladium catalyst.

[0159] According to a particular embodiment, the present invention provides a method for preparing an oxalate or oxamide compound, comprising: To obtain an oxalate compound or an oxamide compound, With alcohols or amines respectively: ■ Carbon monoxide, ■ Oxidizing agents, ■ Pd-NHC catalyst, and ■ optionally a promoter; ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0160] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: To obtain the oxalate compound, Alcohol and: ■ Carbon monoxide, ■ Oxidizing agents, ■ Pd-NHC catalyst, and ■ optionally a promoter; ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0161] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising: To obtain the oxamide compound, · With amines respectively: ■ Carbon monoxide, ■ Oxidizing agents, ■ Pd-NHC catalyst, and ■ optionally a promoter; ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0162] Advantageously, the present invention relates to a method for preparing oxalate or oxamide compounds using a Pt-NHC platinum catalyst.

[0163] According to a particular embodiment, the present invention provides a method for preparing an oxalate or oxamide compound, comprising: To obtain an oxalate compound or an oxamide compound, With alcohols or amines respectively: ■ Carbon monoxide, ■ Oxidizing agents, ■ Pt-NHC catalyst, and ■ optionally a promoter; ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0164] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: To obtain the oxalate compound, Alcohol and: ■ Carbon monoxide, ■ Oxidizing agents, ■ Pt-NHC catalyst, and ■ optionally a promoter; ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating said reaction medium; The present invention relates to a method as defined above comprising:

[0165] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising: To obtain the oxamide compound, · With amines respectively: ■ Carbon monoxide, ■ Oxidizing agents, ■ Pt-NHC catalyst, and ■ optionally a promoter; ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0166] According to a particular embodiment, the present invention relates to a method for the preparation of oxalate or oxamide compounds as defined above, in which the oxidizing agent is selected from among molecular oxygen (O2), air, diones, in particular 1,4-benzoquinone, 1,4-dichloro-2-butene and CuCl2.

[0167] Advantageously, the oxidant is molecular oxygen or air.

[0168] According to a particular embodiment, the present invention provides a method for preparing an oxalate or oxamide compound, comprising: To obtain an oxalate compound or an oxamide compound, With alcohols or amines respectively: ■ Carbon monoxide, ■ Oxygen or air; ■ M-NHC catalyst, and ■ cocatalyst, ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0169] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: To obtain the oxalate compound, Alcohol and: ■ Carbon monoxide, ■ Oxygen or air; ■ M-NHC catalyst, and ■ cocatalyst, ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating the reaction medium; The present invention relates to a method as defined above, comprising:

[0170] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising: To obtain the oxamide compound, · With amines respectively: ■ Carbon monoxide, ■ Oxygen or air; ■ M-NHC catalyst, and ■ cocatalyst, ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating the reaction medium; The present invention relates to a method as defined above, comprising:

[0171] Advantageously, the present invention relates to a process for the preparation of oxalate or oxamide compounds using a Pd-NHC palladium catalyst in the presence of oxygen or air as an oxidizing agent.

[0172] According to a particular embodiment, the present invention provides a method for preparing an oxalate or oxamide compound, comprising: To obtain an oxalate compound or an oxamide compound, With alcohols or amines respectively: ■ Carbon monoxide, ■ Oxygen or air; ■ Pd-NHC catalyst, and ■ cocatalyst, ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating the reaction medium; The present invention relates to a method as defined above, comprising:

[0173] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: To obtain the oxalate compound, Alcohol and: ■ Carbon monoxide, ■ Oxygen or air; ■ Pd-NHC catalyst, and ■ cocatalyst, ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating the reaction medium; The present invention relates to a method as defined above, comprising:

[0174] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising: To obtain the oxamide compound, · With amines respectively: ■ Carbon monoxide, ■ Oxygen or air; ■ Pd-NHC catalyst, and ■ cocatalyst, ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating the reaction medium; The present invention relates to a method as defined above, comprising:

[0175] Advantageously, the present invention relates to a process for the preparation of oxalate or oxamide compounds using a Pt-NHC platinum catalyst in the presence of oxygen or air as an oxidizing agent.

[0176] According to a particular embodiment, the present invention provides a method for preparing an oxalate or oxamide compound, comprising: To obtain an oxalate compound or an oxamide compound, With alcohols or amines respectively: ■ Carbon monoxide, ■ Oxygen or air; ■ Pt-NHC catalyst, and ■ cocatalyst, ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0177] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: To obtain the oxalate compound, Alcohol and: ■ Carbon monoxide, ■ Oxygen or air; ■ Pt-NHC catalyst, and ■ cocatalyst, ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0178] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising: To obtain the oxamide compound, · With amines respectively: ■ Carbon monoxide, ■ Oxygen or air; ■ Pt-NHC catalyst, and ■ cocatalyst, ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally, a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0179] By "promoter" is meant a substance capable of improving the properties of a catalyst, such as catalytic activity, selectivity, antitoxin, stability, life, etc., or preventing deactivation of the catalyst.

[0180] According to a particular embodiment, the cocatalyst is selected from iodine derivatives and ammonium salts. The group of iodine derivatives includes I2, KI, LiI, HI, NaI and tetrabutylammonium iodide (Bu4NI). Iodine derivatives have the advantage of being soluble in the reaction medium and therefore can be advantageously used in the preparation method without excessive solid product formation. Preferably, tetrabutylammonium iodide (Bu4NI) is used as cocatalyst, which is soluble at 25°C and does not precipitate during the preparation method.

[0181] In Pd(II)-catalyzed reactions, the cocatalyst is known to be able to reoxidize the generated Pd(0) to Pa(II) in situ, thus ensuring the catalytic cycle. The cocatalyst also protects the palladium catalyst from the water present in the system, thus preventing the deactivation of the catalyst and avoiding the addition of dehydrating agents to the system.

[0182] In certain embodiments, the process according to the invention is carried out under oxidative carbonylation conditions in the presence of oxygen, with the co-catalyst acting as an additional oxidant. Thus, the co-catalyst can facilitate the oxidative carbonylation process by oxidizing M(0) to M(II) in the M-NHC catalyst during the reaction. It is quite difficult to reoxidize Pd(0) directly to Pd(II) using molecular oxygen, and therefore an additional oxidant is generally used.

[0183] The term "reaction medium" refers to all species that are brought together during a chemical reaction, including, inter alia, the reactants in liquid or gaseous form, the catalyst, and optionally any solvent, additives, or cocatalysts.

[0184] [Preparation of oxalates in the presence of Pd-NHC catalyst] [Heating stage] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: To obtain the oxalate compound, Alcohol and: ■ Carbon monoxide, ■ Oxygen or air; ■ cocatalyst, ■ Pd-NHC catalyst, and ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0185] According to a particular embodiment, the present invention relates to a process for the preparation of an oxalate compound as defined above, in which the heating step B is carried out at a temperature between 25 and 200°C, in particular between 60 and 110°C, preferably at about 90°C.

[0186] The expression "25 to 200°C" corresponds to the ranges of 25 to 40°C; 40 to 60°C; 60 to 80°C; 80 to 100°C; 100 to 120°C; 120 to 140°C; 140 to 160°C; 160 to 180°C; and 180 to 200°C.

[0187] The expression "60 to 110°C" corresponds to the ranges 60 to 70°C; 70 to 80°C; 80 to 90°C; 90 to 100°C; and 100 to 110°C.

[0188] According to a particular embodiment, the present invention relates to a method for preparing an oxalate compound according to the invention defined above, comprising: Alcohol and: ■ Carbon monoxide, ■ Oxygen or air; ■ cocatalyst, ■ Pd-NHC catalyst, and ■ Optionally, a base, ■ optionally a solvent; and a step A of contacting the reaction medium with a step B of heating said reaction medium, in particular at a temperature between 25 and 200° C., in particular between 60 and 110° C., preferably at about 90° C., to obtain an oxalate compound; The present invention relates to a method comprising the steps of:

[0189] [Base in reaction medium] The process for preparing the oxalates can be carried out with or without a base in the reaction medium.

[0190] [Presence of bases] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: Alcohol and: ■ Carbon monoxide, ■ Oxygen or air; ■ Bases, ■ cocatalyst, ■ Pd-NHC catalyst, and ■ optionally a solvent; and a step A of contacting the reaction medium with a step B of heating the reaction medium to obtain an oxalate compound; The present invention relates to a method as defined above, comprising:

[0191] According to a particular embodiment, the present invention relates to a process as defined above for preparing an oxalate compound, wherein said reaction medium comprises a base.

[0192] Advantageously, the presence of the selected base in the reaction medium increases the yield of the reaction.

[0193] According to a particular embodiment, the present invention relates to a process for the preparation of an oxalate compound as defined above, wherein the base is selected from among potassium carbonate (K2CO3), sodium carbonate (Na2CO3), potassium tert-butylate (KOtBu), potassium phosphate (K3PO4) and triethylamine (Et3N).

[0194] According to a particular embodiment, the present invention relates to a process for the preparation of an oxalate compound as defined above, wherein the base is triethylamine.

[0195] Advantageously, the use of triethylamine (Et3N) facilitates evaporation once the product is isolated, and its presence ensures that triethylamine remains in the liquid phase while not creating problems in recycling catalysts such as the solid bases K2CO3 and Na2CO3, which precipitate at room temperature.

[0196] [No base added] Advantageously, the process according to the invention for preparing oxalate compounds can be carried out without the use of a base.

[0197] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: Alcohol and: ■ Carbon monoxide, ■ Oxygen or air; ■ cocatalyst, ■ Pd-NHC catalyst, and ■ optionally a solvent; and a step A of contacting the reaction medium with a step B of heating the reaction medium to obtain an oxalate compound; The present invention relates to a method as defined above, comprising:

[0198] The absence of base in the reaction medium reduces the number of reagents to be introduced into the process and limits the formation of decomposition products.

[0199] [Solvent in the reaction medium] The process according to the invention for preparing oxalates can be carried out with or without a solvent in the reaction medium.

[0200] [Presence of solvent] According to a particular embodiment, the present invention relates to a process as defined above for preparing an oxalate compound, wherein said reaction medium comprises a solvent.

[0201] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: Alcohol and: ■ Carbon monoxide, ■ Oxygen or air; ■ Optionally, a base, ■ cocatalyst, ■ Pd-NHC catalyst, and ■ optionally a solvent; and a step A of contacting the reaction medium with a step B of heating the reaction medium to obtain an oxalate compound; The present invention relates to a method as defined above, comprising:

[0202] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: Alcohol and: ■ Carbon monoxide, ■ Oxygen or air; ■ Bases, ■ cocatalyst, ■ Pd-NHC catalyst, and ■ Solvent, and a step A of contacting the reaction medium with a step B of heating the reaction medium to obtain an oxalate compound; The present invention relates to a method as defined above, comprising:

[0203] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: Alcohol and: ■ Carbon monoxide, ■ Oxygen or air; ■ cocatalyst, ■ Pd-NHC catalyst, and ■ Solvent, and a step A of contacting the reaction medium with a step B of heating the reaction medium to obtain an oxalate compound; The present invention relates to a method as defined above, comprising:

[0204] [No solvent added to the reaction medium] According to a particular embodiment, the present invention relates to a process for the preparation of an oxalate compound as defined above, which is carried out in the absence of a solvent, the alcohol from which the oxalate is prepared acting as the solvent.

[0205] The process for preparing oxalate compounds according to the invention can be carried out without the use of solvents. This allows limiting the preparation steps and the presence of decomposition products to be handled, and limits the solvent handling steps. For example, the use of alcohols as reagents and solvents simplifies the recycling of alcohols in case of incomplete conversion. There is no need to separate the solvent, such as acetonitrile, from the alcohol.

[0206] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: Alcohol and: ■ Carbon monoxide, ■ Oxygen or air; ■ Optionally, a base, ■ Promoters, and ■ Pd-NHC catalyst, and a step A of contacting the reaction medium with a step B of heating the reaction medium to obtain an oxalate compound; The present invention relates to a method as defined above, comprising:

[0207] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: Alcohol and: ■ Carbon monoxide, ■ Oxygen or air; ■ Bases, ■ Promoters, and ■ Pd-NHC catalyst, and a step A of contacting the reaction medium with a step B of heating the reaction medium to obtain an oxalate compound; The present invention relates to a method as defined above, comprising:

[0208] According to a particular embodiment, the present invention provides a method for preparing an oxalate compound, comprising: Alcohol and: ■ Carbon monoxide, ■ Oxygen or air; ■ Promoters, and ■ Pd-NHC catalyst, and a step A of contacting the reaction medium with a step B of heating the reaction medium to obtain an oxalate compound; The present invention relates to a method as defined above, comprising:

[0209] [Presence of water] Water formed in situ or present in the reagents is detrimental and can deactivate the palladium catalyst, particularly in the oxidative carbonylation during the oxalate preparation process.

[0210] Unlike other catalysts in the prior art, such as those described in U.S. Pat. Nos. 3,393,136, 4,005,130, 4,005,129 and 4,005,128, where the presence of water during the oxalate preparation process is detrimental, the use of palladium-(N-heterocyclic carbene) catalysts under the conditions of the present invention makes it possible to eliminate the need for dehydrating agents or reactant dehydration steps in the preparation of oxalate compounds.

[0211] Advantageously, the process according to the invention, using a palladium-(N-heterocyclic carbene) catalyst in the presence of oxygen or air and a cocatalyst, makes it possible to selectively prepare oxalates in the presence of water in the reaction medium.

[0212] According to a particular embodiment, the present invention relates to the use of a palladium-(N-heterocyclic carbene) catalyst in carrying out a process for the selective preparation of oxalates from carbon monoxide, molecular oxygen or air, a cocatalyst and an alcohol, which does not require anhydrous preparation conditions.

[0213] [Alcohol as a substrate] According to a particular embodiment, the present invention provides a method for preparing a compound according to the present invention, wherein step A is a compound of formula 1: [ka] of alcohol contact, where R a but, C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, represents a group selected from The present invention relates to a process for the preparation of an oxalate compound of formula 2 as defined above.

[0214] According to a particular embodiment, the present invention relates to a process for the preparation of an oxalate compound as defined above, in which step A comprises the contacting of an alcohol selected from among methanol, ethanol and isopropanol.

[0215] Oxalates prepared using methanol, ethanol and isopropanol are: [ka] These are dimethyl oxalate, diethyl oxalate and diisopropyl oxalate, respectively.

[0216] According to a particular embodiment, the present invention provides a method for preparing a compound according to the present invention, wherein step A is a compound of formula 1: [ka] wherein R a but, C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, represents a group selected from In particular, the alcohol is selected from among methanol, ethanol and isopropanol. The present invention relates to a method for preparing an oxalate compound of formula 2 according to the present invention as defined above.

[0217] [Preparation of oxamides in the presence of Pd-NHC catalyst] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising the steps of: To obtain the oxamide compound, With amines: ■ Carbon monoxide, ■ Oxygen or air; ■ Optionally, a base, ■ optionally a promoter; ■ Pd-NHC catalyst, and ■ Solvent, and a step A of contacting the reaction medium with optionally, a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0218] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising the steps of: To obtain the oxamide compound, With amines: ■ Carbon monoxide, ■ Oxygen or air; ■ Optionally, a base, ■ cocatalyst, ■ Pd-NHC catalyst, and ■ Solvent, and a step A of contacting the reaction medium with optionally, a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0219] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising the steps of: To obtain the oxamide compound, With amines: ■ Carbon monoxide, ■ Oxygen or air; ■ Optionally, a base, ■ Pd-NHC catalyst, and ■ Solvent, and a step A of contacting the reaction medium with optionally, a step B of heating the reaction medium; The present invention relates to a method as defined above, comprising:

[0220] [Base in the reaction medium] The process for preparing the oxamide can be carried out with or without a base in the reaction medium.

[0221] [No addition of base to the reaction medium] According to a particular embodiment, the present invention relates to a process as defined above for preparing an oxamide compound, wherein the base is the amine from which said oxamide compound is prepared.

[0222] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising the steps of: To obtain the oxamide compound, With amines: ■ Carbon monoxide, ■ Oxygen or air; ■ cocatalyst, ■ Pd-NHC catalyst, and ■ Solvent, and a step A of contacting the reaction medium with optionally, a step B of heating the reaction medium; The present invention relates to a method as defined above, comprising:

[0223] [Presence of base added to the reaction medium] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising the steps of: To obtain the oxamide compound, With amines: ■ Carbon monoxide, ■ Oxygen or air; ■ Bases, ■ cocatalyst, ■ Pd-NHC catalyst, and ■ Solvent, and a step A of contacting the reaction medium with optionally, a step B of heating the reaction medium; The present invention relates to a method as defined above, comprising:

[0224] According to a particular embodiment, the present invention relates to a process for the preparation of an oxamide compound as defined above, wherein the base is selected from among potassium carbonate (K2CO3), sodium carbonate (Na2CO3), potassium tert-butylate (KOtBu), potassium phosphate (K3PO4) and triethylamine (Et3N).

[0225] According to a particular embodiment, the present invention relates to a process for the preparation of an oxamide compound as defined above, wherein said base is an inorganic base, in particular K2CO3.

[0226] According to a particular embodiment, the present invention relates to a process for the preparation of an oxamide compound as defined above, wherein said base is an organic base, in particular triethylamine.

[0227] The process for preparing the oxamide compounds of the present invention can be carried out both with the addition of inorganic bases and with the addition of organic bases. The inorganic base K2CO3 has been found to be as effective as the organic base triethylamine.

[0228] [Method involving a heating step] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising the steps of: To obtain the oxamide compound, With amines: ■ Carbon monoxide, ■ Oxygen or air; ■ Optionally, a base, ■ cocatalyst, ■ Pd-NHC catalyst, and ■ Solvent, and a step A of contacting the reaction medium with a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0229] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising the steps of: To obtain the oxamide compound, With amines: ■ Carbon monoxide, ■ Oxygen or air; ■ Bases, ■ cocatalyst, ■ Pd-NHC catalyst, and ■ Solvent, and a step A of contacting the reaction medium with a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0230] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising the steps of: To obtain the oxamide compound, With amines: ■ Carbon monoxide, ■ Oxygen or air; ■ cocatalyst, ■ Pd-NHC catalyst, and ■ Solvent, and a step A of contacting the reaction medium with a step B of heating said reaction medium; The present invention relates to a method as defined above, comprising:

[0231] According to one embodiment, the process for the preparation of an oxamide compound as defined above comprises a heating step B at a temperature between 25 and 110°C.

[0232] [Method without heating step] According to a particular embodiment, the present invention relates to a process for the preparation of an oxamide compound as defined above, in which the reaction medium is maintained at an ambient temperature between 20 and 25°C.

[0233] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising the steps of: To obtain a reaction medium containing an oxamide compound, With amines: ■ Carbon monoxide, ■ Oxygen or air; ■ Optionally, a base, ■ cocatalyst, ■ Pd-NHC catalyst, and ■ Solvent, A step A of contacting The present invention relates to a method as defined above, comprising:

[0234] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising the steps of: To obtain a reaction medium containing an oxamide compound, With amines: ■ Carbon monoxide, ■ Oxygen or air; ■ Bases, ■ cocatalyst, ■ Pd-NHC catalyst, and ■ Solvent, A step A of contacting The present invention relates to a method as defined above, comprising:

[0235] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising the steps of: To obtain a reaction medium containing an oxamide compound, With amines: ■ Carbon monoxide, ■ Oxygen or air; ■ cocatalyst, ■ Pd-NHC catalyst, and ■ Solvent, A step A of contacting The present invention relates to a method as defined above, comprising:

[0236] The process for the preparation of oxamides according to the invention by oxidative carbonylation is advantageously carried out at room temperature, between 20 and 25°C.

[0237] It has been found that the process for the preparation of oxamides according to the invention in the presence of a base and a solvent makes it possible to obtain the oxamides in the reaction medium without a heating step.

[0238] As a result, heating the reaction medium is optional, which is an industrial advantage from the standpoint of cost and safety.

[0239] According to a particular embodiment, the present invention provides a method for preparing an oxamide compound, comprising the steps of: To obtain a reaction medium containing oxamide, With amines: ■ Carbon monoxide, ■ Oxygen or air; ■ cocatalyst, ■ Pd-NHC type catalysts, and ■ Solvent, ■ optionally a base, in particular chosen from K2CO3 or EtN3, A step A of contacting The present invention relates to a method as defined above, comprising:

[0240] [Amines used as substrates] According to a particular embodiment, the present invention relates to a compound in which step A is a compound of formula 3: [ka] wherein: R b and R c but independently of each other: Hydrogen atom C1~C 20 Linear or branched alkyl groups, C2~C 20 A linear or branched alkenyl group, C1-C, where the heteroatom is in particular O or N. 20 linear or branched heteroalkyl groups, represents R b or R cat least one of the groups is other than hydrogen; R b and R c can form a ring, The present invention relates to a process for the preparation of an oxamide compound of formula 4 as defined above.

[0241] The term "linear or branched heteroalkyl" means a linear or branched alkyl group as defined above that includes atoms other than carbon atoms, specifically N, O or S, within the alkyl chain.

[0242] The term "linear or branched alkenyl" means a linear or branched alkyl group as defined above with a C=C double bond.

[0243] According to a particular embodiment, the present invention relates to a process for the preparation of an oxamide compound as defined above, in which step A comprises the contacting of an amine selected from among diethylamine, piperidine, pyrrolidine and morpholine.

[0244] The oxamides prepared with diethylamine, piperidine, pyrrolidine and morpholine are shown below: [ka]

[0245] According to a particular embodiment, the present invention relates to a method for producing a medicament for the treatment of osteoporosis, comprising the steps of: b and R c The present invention relates to a process for the preparation of oxamide compounds of formula 4 as defined above, in which the groups are linked to form a ring.

[0246] According to a particular embodiment, the present invention relates to a compound in which step A is a compound of formula 3: [ka] wherein: R b and R c but independently of each other: Hydrogen atom C1~C 20 Linear or branched alkyl groups, C2~C 20 A linear or branched alkenyl group, C1-C, where the heteroatom is in particular O or N. 20 linear or branched heteroalkyl groups, represents R b or R c at least one of the groups is other than hydrogen; R b and R c can form a ring, In particular, the amine is selected from diethylamine, piperidine, morpholine, pyrrolidine; The present invention relates to a process for the preparation of an oxamide compound of formula 4 as defined above.

[0247] [Common features of the methods for preparing oxalates and oxamides] [catalyst] According to a particular embodiment, the present invention relates to a catalyst having formula II-B: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L 1 represents a halogen atom selected from Cl, Br and I, L 2 and L 3represents a bidentate ligand, Or L 2 represents a halogen atom selected from Cl, Br and I; L 3 represents a monodentate ligand, The compound of formula II-B can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, It relates to a process for preparation as defined above.

[0248] According to a particular embodiment, the present invention relates to a catalyst corresponding to formula II-B, wherein: L1 represents an iodine atom; L2 and L3 are linked and together represent a bidentate ligand; or or L2 represents a halogen atom selected from Cl, Br and I, and L3 represents a monodentate ligand; It relates to a process for preparation as defined above.

[0249] According to a particular embodiment, the present invention relates to a catalyst having the formula II-4B: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, wherein L2 and L3 represent a bidentate ligand, in particular a bidentate ligand selected from among acetylacetonate (acac), allyl, cinnamyl and acetate, preferably acetylacetonate, or L2 represents a halogen atom selected from among Cl, Br and I and L3 represents a monodentate ligand, in particular selected from among pyridine, 3-chloropyridine, acetonitrile, triethylamine or a phosphine-based ligand, in particular triphenylphosphine, preferably 3-chloropyridine, The compound of formula II-4B can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, It relates to a process for preparation as defined above.

[0250] According to a particular embodiment, the present invention relates to a catalyst corresponding to formula II-B, wherein: L1 and L2 each represent an iodine atom, and L3 represents a monodentate ligand; It relates to a process for preparation as defined above.

[0251] According to a particular embodiment, the present invention relates to a catalyst having the formula II-5B: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L3 represents a monodentate ligand, in particular selected from pyridine, 3-chloropyridine, acetonitrile, triethylamine or a phosphine-based ligand, in particular triphenylphosphine, preferably 3-chloropyridine, The compound of formula II-5B can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, It relates to a process for preparation as defined above.

[0252] According to a particular embodiment, the invention relates to a process for preparation as defined above, in which the bidentate ligand is chosen among acetylacetonate (acac), allyl, cinnamyl and acetate, in which the bidentate ligand is in particular acetylacetonate.

[0253] According to a particular embodiment, the present invention relates to a process for preparation as defined above, in which the monodentate ligand is chosen among pyridine, 3-chloropyridine, acetonitrile, triethylamine or a phosphine-based ligand, in particular triphenylphosphine. Preferably, the monodentate ligand is in particular 3-chloropyridine.

[0254] According to a particular embodiment, the invention relates to a process for the preparation as defined above, in which the monodentate ligand is selected from among pyridine, 3-chloropyridine, acetonitrile, triethylamine, preferably, the monodentate ligand is in particular 3-chloropyridine.

[0255] According to a particular embodiment, the present invention relates to a process for preparation as defined above, wherein said compound of formula II-B is not bound to a carrier.

[0256] According to a particular embodiment, the invention relates to a process for preparation as defined above, in which said compound of formula II-B is bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups.

[0257] According to a particular embodiment, the invention relates to a process for the preparation as defined above, in which said compound of formula II-4B is bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups.

[0258] According to a particular embodiment, the invention relates to a process for the preparation as defined above, in which said compound of formula II-5B is bound by at least one of the R1 or R2 groups to a support, in particular a polymer or silica.

[0259] According to a particular embodiment, the present invention relates to a catalyst having the formula II-1B: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from The compound of formula II-1B can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, It relates to a process for preparation as defined above.

[0260] According to a particular embodiment, the present invention relates to a catalyst having the formula II-2B: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from The compound of formula II-2B can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, It relates to a process for preparation as defined above.

[0261] According to a particular embodiment, the present invention relates to a catalyst having the formula II-3B: [ka] Corresponding to the formula: R1 and R2 are, independently of each other: C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from The compound of formula II-3B can be bound to a support, in particular a polymer or silica, by at least one of the R1 or R2 groups, It relates to a process for preparation as defined above.

[0262] According to a particular embodiment, the invention relates to a process for preparation as defined above, in which said compound of formula II-3B is bound by at least one of the R1 or R2 groups to a support, in particular a polymer or silica.

[0263] According to a particular embodiment, the present invention relates to a preparation process as defined above, in which the support is polystyrene or silica gel and said catalyst is bound to said polystyrene or silica gel.

[0264] According to a particular embodiment, the present invention relates to a catalyst comprising [ka] or Or the supported catalyst [ka] Selected from among It relates to a process for preparation as defined above.

[0265] According to a particular embodiment, the present invention relates to a catalyst having the formula III-B: [ka] Corresponding to the formula: R1, R2, R3 and R4 independently of each other; C1~C 10 Linear or branched alkyl, C3~C 10 cycloalkyl, and C6~C 20 Aryl or C3-C 20 Heteroaryl, C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L1 and L2, independently of each other: - a halogen atom selected from Cl, Br and I, or - monodentate ligand, or or L1 and L2 are linked and represent a bidentate ligand; The compound of formula III-B may be linked to a carrier, in particular a polymer, by at least one of the R1, R2, R3 or R4 groups, Optionally, one of the R1 or R2 groups may be linked to R3 or R4, which together represent a bidentate group containing two N-heterocyclic carbene groups. It relates to a process for preparation as defined above.

[0266] According to a particular embodiment, the invention relates to a process for preparation as defined above, in which said compound of formula III-B is bound to a support, in particular a polymer or silica, by at least one of the R1, R2, R3 or R4 groups.

[0267] According to a particular embodiment, the invention relates to the use as defined above, in which the catalyst corresponds to formula III-B and at least one of the L1 and L2 groups represents an iodine atom.

[0268] According to a particular embodiment, the present invention relates to a catalyst having the formula III-1B: [ka] Corresponding to the formula: R1, R2, R3 and R4 independently of each other; C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from The compound of formula III-1B may be bound to a support, in particular a polymer or silica, by at least one of the R1, R2, R3 or R4 groups, Optionally, one of the R1 or R2 groups may be linked to R3 or R4, which together represent a bidentate group containing two N-heterocyclic carbene groups. It relates to a process for preparation as defined above.

[0269] According to a particular embodiment, the present invention relates to a catalyst of formula III-1B bound to a support: [ka] The present invention relates to a method for preparing a compound as defined above, the compound being selected from the group consisting of

[0270] According to a particular embodiment, the present invention relates to a catalyst having the formula III-2B: [ka] Corresponding to the formula: R1, R2, R3 and R4 independently of each other; C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L1: - a halogen atom selected from Cl, Br and I, or - monodentate ligand, It represents, The compound of formula III-2B can be bound to a support, in particular a polymer or silica, by at least one of the R1, R2, R3 or R4 groups, Optionally, one of the R1 or R2 groups may be linked to R3 or R4, which together represent a bidentate group containing two N-heterocyclic carbene groups. It relates to a process for preparation as defined above.

[0271] According to a particular embodiment, the present invention relates to a catalyst having the formula III-3B: [ka] Corresponding to the formula: R1, R2, R3 and R4 independently of each other; C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from The compound of formula III-3B can be bound to a support, in particular a polymer or silica, by at least one of the R1, R2, R3 or R4 groups, Optionally, one of the R1 or R2 groups may be linked to R3 or R4, which together represent a bidentate group containing two N-heterocyclic carbene groups. It relates to a process for preparation as defined above.

[0272] According to a particular embodiment, the present invention relates to a catalyst having the formula IV-B: [ka] Corresponding to the formula: R1 and R2 are independent of each other; C1~C 10 Linear or branched alkyl, C3~C 10 Cycloalkyl, C6~C 20 Aryl or C3-C 20 Heteroaryl, and C7~C 20 Alkyl-Aryl or C4-C 20 Alkyl-heteroaryl, represents a group selected from L1 and L2 represent halogen atoms selected from Cl, Br and I; It relates to a process for preparation as defined above.

[0273] [Other parameters] According to a particular embodiment, the present invention relates to a process for the preparation of a catalyst comprising the co-catalyst selected from the group consisting of tetrabutylammonium iodide (BuNI), sodium iodide (NaI) and potassium iodide (KI), The cocatalyst is in particular tetrabutylammonium iodide; It relates to a process for preparation as defined above.

[0274] According to a particular embodiment, the present invention relates to a process for the preparation of ... The solvent is in particular acetonitrile or tetrahydrofuran; It relates to a process for preparation as defined above.

[0275] According to a particular embodiment, the present invention relates to a preparation process as defined above, in which the oxidizing agent is oxygen or air, the oxygen being used at a pressure between 0.5 and 2.5 MPa (5 and 25 bar).

[0276] Advantageously, oxygen is used at 1.5 MPa for the oxalate preparation process.

[0277] Advantageously, for the oxamide preparation process oxygen is used at 1.0 MPa.

[0278] The expression MPa is 10 6 It corresponds to a pascal and is equivalent to 10 bar.

[0279] The expression "0.5-2.5 MPa" corresponds to the following ranges: 0.5-1.0 MPa; 1.0-1.5 MPa; 1.5-2.0 MPa; 2.0-2.5 MPa.

[0280] According to a particular embodiment, the present invention relates to a preparation process as defined above, in which carbon monoxide is used at 1.0-10.0 MPa (10-100 bar), in particular at 6.5 MPa (65 bar).

[0281] The expression "1.0~10.0MPa" corresponds to the following ranges: 1.0~1.5MPa; 1.5~2.0MPa; 2.0~2.5MPa; 2.5~3.0MPa; 3.0~3.5MPa; 3.5~4.0MPa; 4.0~4.5MPa; 4.5~5.0MPa; 5.0~5.5MPa; 5.5~6.0MPa; 6.0~6.5MPa; 6.5~7.0MPa; 7.0~7.5MPa; 7.5~8.0MPa; 8.0~8.5MPa; 8.5~9.0MPa; 9.0~9.5MPa; 9.5~10MPa.

[0282] According to a particular embodiment, the present invention relates to a preparation process as defined above, in which the carbon monoxide / oxygen pressure ratio used is between 3 and 10, in particular about 4.

[0283] The expression "3 to 10" corresponds to the following ranges: 3 to 4; 4 to 5; 5 to 6; 6 to 7; 7 to 8; 8 to 9; 9 to 10.

[0284] Advantageously, the CO / O2 pressure ratio for the oxalate preparation process is about 4.

[0285] Advantageously, the CO / O2 pressure ratio for the oxamide preparation process is about 6.5.

[0286] According to a particular embodiment, the present invention relates to a preparation process as defined above, in which the catalyst is used in an amount between 0.001 and 10 mol % relative to the alcohol or amine.

[0287] The expression "0.001-10%" corresponds to the following ranges: 0.001-0.005%; 0.005-0.01%; 0.01-0.05%; 0.05-0.1%; 0.1-0.15%; 0.15-0.2%; 0.2-0.5%; 0.5-1%; 1-2%; 2-3%; 3-4%; 4-5%; 5-6%; 6-7%; 7-8%; 8-9%; 9-10%.

[0288] According to a particular embodiment, the present invention relates to a preparation process as defined above, in which the cocatalyst is used in an amount between 2 and 100 molar equivalents in relation to the catalyst.

[0289] Advantageously, the cocatalyst is used in a proportion of 5 molar equivalents relative to the catalyst for the oxalate preparation process.

[0290] Advantageously, the cocatalyst is used in a proportion of 62.5 molar equivalents relative to the catalyst for the oxamide preparation process.

[0291] According to a particular embodiment, the present invention relates to a process for preparation as defined above, wherein the base is used in an amount between 2 and 150 molar equivalents in relation to the catalyst.

[0292] Advantageously, the base is used in a proportion of 5 molar equivalents relative to the catalyst for the oxalate preparation process.

[0293] Advantageously, the base is used in a proportion of 125 molar equivalents relative to the catalyst for the oxamide preparation process.

[0294] According to a particular embodiment, the present invention provides a method for preparing an oxalate or oxamide compound, comprising: To obtain an oxalate compound or an oxamide compound, With alcohols or amines respectively: ■ In detail, carbon monoxide, which is used at 1.0 to 10.0 MPa, especially 6.5 MPa. ■ An oxidizing agent, specifically oxygen or air, preferably oxygen used at 0.5 to 2.5 MPa; ■ M-NHC catalysts comprising at least one M atom linked to at least one N-heterocyclic carbene ligand, where M represents Pd or Pt and NHC represents an N-heterocyclic carbene group; and ■ Optionally, a cocatalyst, in particular selected from tetrabutylammonium iodide (Bu4NI), sodium iodide (NaI) and potassium iodide (KI), preferably tetrabutylammonium iodide. ■ optionally a base, in particular selected from potassium carbonate (K2CO3), sodium carbonate (Na2CO3), potassium tert-butylate (KOtBu), potassium phosphate (K3PO4) and triethylamine (Et3N); ■ Optionally, a solvent, in particular acetonitrile, toluene, 1,4-dioxane, tetrahydrofuran, ethanol, methanol and ethyl acetate, preferably acetonitrile and tetrahydrofuran. and a step A of contacting the reaction medium with optionally, a step B of heating the reaction medium; The present invention relates to a process for the preparation as defined above, comprising:

[0295] According to a particular embodiment, the present invention further comprises, after the heating step B, a step C of filtering the reaction medium to obtain a recovered catalyst and a catalyst-free filtrate, The catalyst is a supported catalyst as defined above; It relates to a process for preparation as defined above.

[0296] According to a particular embodiment, the present invention relates to a preparation process as defined above, wherein the catalyst used in the contacting step A is the catalyst recovered at the end of the filtration step C.

[0297] Advantageously, the catalyst recovered after the process of the present invention is not degraded, is stable and can be reused in another catalytic reaction process, thus allowing the process of the present invention to be repeated using the same recovered catalyst.

[0298] According to a particular embodiment, the present invention relates to a method as defined above for preparing oxalate or oxamide compounds, wherein the catalyst is stable at the end of the reaction and can be reused in another catalytic reaction method.

[0299] According to a particular embodiment, the present invention relates to a process for the preparation as defined above, wherein steps A, B and C are repeated at least five times without substantial loss of the catalytic activity of the catalyst.

[0300] According to a particular embodiment, the present invention relates to a preparation process as defined above, carried out in a continuous flow and in which the catalyst is a supported catalyst as defined above.

[0301] According to a particular embodiment, the present invention provides a method for producing a cellular membrane comprising: the catalyst is a supported catalyst installed in a column or cartridge; Alternatively, the catalyst is suspended in the reaction mixture. The present invention relates to a continuous flow process for the preparation of an oxalate or oxamide as defined above.

[0302] As non-limiting examples, continuous flow processes are carried out in the following types of reactors: - Continuous Stirred Tank Reactor (CSTR) - Flow reactor or tubular reactor - Fixed or packed bed reactors.

[0303] By way of example, the method according to the invention can be carried out in flow chemistry equipment, e.g. commercially available reactors such as "H-Cube Pro®" or "Phoenix®" manufactured by ThalesNano INC, 7 Zahony Street, Graphisoft Park, Building D, H-1031 Budapest, Hungary, or "E-Series" or "R-Series flow chemistry systems" manufactured by Vapourtec Ltd, Unit21 / Park Farm Business Center / Fornham Pk, Bury Saint Edmunds IP28 6TS, United Kingdom.

[0304] Advantageously, the continuous flow process is carried out at a temperature between 25°C and 200°C.

[0305] Advantageously, the continuous flow process is carried out at a pressure between 0.1 MPa and 4 MPa.

[0306] The expression "0.1 to 4 MPa" corresponds to the following ranges: 0.1 to 0.5 MPa; 0.5 to 1.0 MPa; 1.0 to 1.5 MPa; 1.5 to 2.0 MPa; 2.0 to 2.5 MPa; 2.5 to 3.0 MPa; 3.0 to 3.5 MPa; 3.5 to 4.0 MPa.

[0307] According to a particular embodiment, the continuous flow process is carried out in a reactor in which the gas represents 10-90% of the reactor volume.

[0308] The expression "10~90%" corresponds to the following ranges: 10~20%; 20~30%; 30~40%; 40~50%; 50~60%; 60~70%; 70~80%; 80~90%.

[0309] According to a particular embodiment, the continuous flow process is carried out by means that allows a contact time between the reagents of between 1 second and 2 hours, in particular between 1 second and 2 minutes.

[0310] The expression "1 second to 2 hours" corresponds to the following ranges: 1 second to 15 seconds; 15 seconds to 30 seconds; 30 seconds to 1 minute; 1 minute to 2 minutes; 2 minutes to 15 minutes; 15 minutes to 30 minutes; 30 minutes to 1 hour; 1 hour to 2 hours.

[0311] According to certain embodiments, the continuous flow process includes a means for introducing a CO stream into a reactor in contact with a substrate (alcohol or amine) and oxygen or air streams, either individually or as a mixture.

[0312] According to a particular embodiment, the present invention relates to a process as defined above, in which the oxalate or oxamide product is isolated in the absence of the carbonate or urea product, respectively, with an oxalate / carbonate ratio of more than 98% and an oxamide / urea ratio of more than 98%.

[0313] According to a particular embodiment, the present invention relates to a process for preparation as defined above, in which the oxalate product is isolated in the absence of the carbonate product, the oxalate / carbonate ratio being greater than 98%.

[0314] According to a particular embodiment, the present invention relates to a process for preparation as defined above, in which the oxamide product is isolated in the absence of the urea product, the oxamide / urea ratio being greater than 98%.

[0315] As non-limiting examples, the oxalate or oxamide products can be isolated by distillation, or by extraction and recrystallization.

[0316] According to a particular embodiment, the present invention relates to a process for the preparation of oxalate or oxamide compounds as defined above, in which the yield obtained is greater than 100 mmol of oxalate or oxamide compound per mmol of Pd.

[0317] According to a particular embodiment, the present invention relates to a process for preparing an oxalate compound as defined above, in which the yield obtained is greater than 100 mmol of oxalate compound per mmol of Pd.

[0318] According to a particular embodiment, the present invention relates to a process for the preparation of an oxamide compound as defined above, in which the yield obtained is greater than 200 mmol of oxamide compound per mmol of Pd.

[0319] Advantageously, the process for preparing oxamides according to the invention makes it possible to achieve a yield of more than 90%, in particular of around 97%.

[0320] The yield of the process for preparing oxalates or oxamides according to the present invention can be described in terms of the "number of catalytic cycles (NCC)".

[0321] In particular, the catalytic activity under given conditions of temperature, pressure and concentration of solute and time of the process for preparing oxalates or oxamides according to the present invention can be described in terms of NCC.

[0322] The "number of catalytic cycles (NCC)" is the number of moles of product formed (n prod ) and the number of moles of metal (Pd or Pt) in the catalyst (n cat ) is defined as the ratio between:

number

[0323] Unlike the turnover number (TON), which represents the maximum number of catalytic cycles that a catalyst can achieve before complete and irreversible degradation, the catalytic cycle number represents the total number of catalytic cycles that a catalyst has achieved under given reaction conditions. At the end of the reaction, the catalyst used is not necessarily degraded and can therefore be considered reusable. Thus, NCC is not a measure of the catalyst's lifetime, but rather a measure of the catalyst's productivity under given conditions of catalytic reaction.

[0324] According to a particular embodiment, the present invention relates to a process for the preparation of an oxalate compound as defined above, in which the NCC obtained is greater than 100.

[0325] According to a particular embodiment, the present invention relates to a process for the preparation of oxamide compounds as defined above, having an NCC of greater than 200.

[0326] According to a particular embodiment, the present invention relates to a process for the preparation of oxalate or oxamide compounds as defined above, with a selectivity towards the oxalate or oxamide product of more than 70%, in particular of about 80%.

[0327] According to a particular embodiment, the present invention relates to a process for the preparation of oxalate compounds as defined above, with a selectivity towards the oxalate product of more than 75%, in particular of about 80%.

[0328] According to a particular embodiment, the present invention relates to a process for the preparation of an oxamide compound as defined above, with a selectivity towards the oxamide product of more than 95%, in particular of about 98%.

[0329] The following examples illustrate the invention without limiting its scope. EXAMPLES

[0330] Example 1: Catalyst [ka]

[0331] PEPPSI®-IPr catalyst is commercially available from Sigma Aldrich.

[0332] The catalysts [(IPr)Pd(acac)Cl] and [(IMes)Pd(acac)Cl] were prepared according to the literature described in N. Marion et al. (Adv. Synth. Catal. 2007, 349, 2380-2384).

[0333] A polymeric support loaded with 1-(mesityl)imidazolium (PS-IMes-HCl) was prepared according to the literature described by D.-H. Lee et al. (Org. Lett. 2008, 10, 1609-1612).

[0334] The amount of imidazolium on the imidazolium-loaded polymer support (PS-IMes-HCl) was determined by evaluating the N content by elemental analysis (N 0.89%, i.e., the catalyst amount was 0.32 mmol / g).

[0335] For the preparation of the [(PS-IMes)Pd(acac)Cl] catalyst described in Example 2, the (PS-IMes-HCl) support is used.

[0336] Example 2 - Preparation of [(PS-IMes)Pd(acac)Cl] Catalyst In a flask equipped with a magnetic bar and a condenser, Pd(acac)2 (456 mg, 1.5 mmol), imidazolium-loaded polymeric support (PS-IMes-HCl) (2 g, 0.32 mmol / g) and 1,4-dioxane (30 ml) were introduced and the reaction mixture formed was heated at 100 °C for 16 h. After that, the reaction mixture was cooled to room temperature, filtered and the polymeric support was washed vigorously with distilled water (5 × 10 ml), methanol (5 × 10 ml) and dried under reduced pressure to obtain [(PS-IMes)Pd(acac)Cl] (2.1 g).

[0337] The amount of Pd loaded on the polymeric support was determined using ICP-AES analysis. Polymeric supported palladium-N-heterocyclic complex (50 mg) was treated with a mixture (25 ml) of hydrochloric and nitric acids (1:1, v / v) for 30 min at room temperature. The orange solution formed was filtered and washed with purified water. The filtrate and washings were combined and the amount of Pd was determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The amount of Pd was calculated to be 0.29 mmol per gram of support.

[0338] Example 3: Representative procedure for comparative testing with Pd-phosphine catalysts Test A: In a typical procedure, a 450 ml Parr autoclave equipped with a stir bar was charged with palladium(II) acetylacetonate (91.3 mg, 0.3 mmol), triphenylphosphine (236.1 mg, 0.9 mmol), tetrabutylammonium iodide (0.5 g, 1.5 mmol), triethylamine (0.2 ml, 1.5 mmol), acetonitrile (100 ml) and absolute ethanol (50 ml). The reactor was sealed and the mixture was purged three times with nitrogen (5 bar) and then twice with oxygen (5 bar). The autoclave was then pressurized with 15 bar oxygen and then with 65 bar carbon monoxide to obtain a total pressure of 80 bar; the reaction medium was stirred for 14 hours at 90° C. The autoclave was then cooled to room temperature before being slowly depressurized and purged three times with nitrogen (5 bar). The reactor contents were transferred to a round bottom flask, excess ethanol and solvent were removed using a rotary evaporator, and diethyl oxalate DEO (9.3 g) was recovered by vacuum distillation (bp = 120°C / 30-15 mbar).

[0339] For reactions with alcohols, results are presented in terms of the mass of oxalate product obtained and are explained in terms of the number of NCC catalytic cycles as defined above.

[0340] Test B Test B was carried out under the same process conditions as Test A, but in the absence of tetrabutylammonium iodide. Traces of diethyl oxalate were observed by quantitative analysis using gas chromatography.

[0341] Test C Test C was carried out under the same process conditions as Test A, but in the absence of triethylamine. Traces of diethyl oxalate were observed by quantitative analysis using gas chromatography.

[0342] Table 1 shows the operating conditions and results (mass and NCC of oxalate obtained) for the tests carried out with palladium-phosphine catalyst.

[0343] [Table 1]

[0344] Example 4: Representative procedure for the catalytic oxidative carbonylation of aliphatic alcohols to oxalates using homogeneous palladium catalysts In a typical procedure, a 450 ml Parr autoclave equipped with a stir bar was charged with homogeneous Pd-NHC complex (0.3 mmol), tetrabutylammonium iodide (0.5 g, 1.5 mmol), triethylamine (0.2 ml, 1.5 mmol), acetonitrile (100 ml) and aliphatic alcohol (50 ml). The reactor was sealed and the mixture was purged three times with nitrogen (5 bar) and then twice with oxygen (5 bar). The autoclave was then pressurized with 15 bar oxygen followed by 65 bar carbon monoxide to a total pressure of 80 bar and the reaction mixture was stirred at 90° C. for 14 hours. The autoclave was then cooled to room temperature before being slowly depressurized and purged three times with nitrogen (5 bar). The reactor contents were transferred to a round-bottom flask, excess aliphatic alcohol and solvent were removed using a rotary evaporator, and the dialkyl oxalate (DEO) was recovered by vacuum distillation (bp = 120 °C / 50–15 mbar). Reported dialkyl oxalate yields were calculated based on isolated mass yields and the number of catalytic cycles (NCC) was calculated as defined above.

[0345] Table 2 shows the operating conditions and results (mass and NCC of oxalate obtained) for tests carried out with the homogeneous Pd-NHC catalyst according to the invention.

[0346] [Table 2]

[0347] Example 5: Effect of promoter and base on the oxidative carbonylation reaction of alcohols Test A1 - Presence of water: Test A1 is carried out under the same operating conditions as Test 1 in Example 4, but in the presence of water (1 mol%). The reaction yield is equivalent to Test 1 in Example 4.

[0348] Test A2 - No base Et3N: Test A2 is carried out under the same operating conditions as test 1 in example 4, but in the absence of triethylamine. Diethyl oxalate was obtained in an amount of less than 1 g.

[0349] Test A3 - No nBu4NI: Test A3 was carried out under the same process conditions as Test 1 in Example 4, but in the absence of tetrabutylammonium iodide. Traces of diethyl oxalate were observed (less than 0.1 g).

[0350] Table 3 shows the operating conditions and results (mass and NCC of oxalate obtained) of the tests carried out.

[0351] [Table 3]

[0352] Example 6: Representative procedure for catalytic oxidative carbonylation of aliphatic alcohols to oxalates using heterogeneous Pd-NHC catalysts according to the present invention In a typical procedure, a 450 ml Parr autoclave equipped with a stir bar was charged with heterogeneous Pd-NHC complex (1.2 g, 0.29 mmol Pd / g, 0.35 mmol Pd), tetrabutylammonium iodide (0.5 g, 1.5 mmol), triethylamine (0.2 ml, 1.5 mmol), acetonitrile (100 ml) and aliphatic alcohol (50 ml). The reactor was sealed and the mixture was purged three times with nitrogen (5 bar) and then twice with oxygen (5 bar). The autoclave was then pressurized with 15 bar oxygen and then 65 bar carbon monoxide to a total pressure of 80 bar; the reaction mixture was stirred at 90° C. for 14 hours. The autoclave was then cooled to room temperature before slowly depressurizing and purging three times with nitrogen (5 bar). The reactor contents were filtered to recover the catalyst. The filtrate was transferred to a round-bottom flask, excess aliphatic alcohol and solvent were removed using a rotary evaporator, and the dialkyl oxalate was recovered by vacuum distillation (bp = 120 °C / 50-15 mbar).

[0353] The reported dialkyl oxalate yields were calculated based on the isolated mass yield and the catalytic cycle number NCC was calculated as defined above.

[0354] Table 4 shows the operating conditions and results (mass and NCC of oxalate obtained) for the tests carried out with the heterogeneous Pd-NHC catalyst according to the invention.

[0355] [Table 4]

[0356] Example 7: Representative procedure for studying the recyclability of the [(PS-IMes)Pd(acac)Cl] complex In a typical experimental procedure, the reaction was carried out as described in Example 6 above. However, once the reaction was completed, vented, and purged with nitrogen, the catalyst was filtered and washed vigorously with distilled water (5×10 ml) and methanol (5×10 ml) to remove any traces of product or reagents present. The filtered catalyst was then dried under reduced pressure before being further recycled. The dried catalyst was then used in catalyst recyclability experiments, and it was found that the recovered catalyst could be reused for at least five consecutive cycles to obtain the desired product in good to fair yield.

[0357] Recyclability studies have shown that heterogeneous catalysts can be used in continuous flow reactors.

[0358] Table 5 shows the conditions and results of the recyclability test for the [(PS-IMes)Pd(acac)Cl] complex.

[0359] [Table 5]

[0360] The results of these manual recycling experiments show that the Pd-NHC catalyst is stable. The recovered catalyst shows little or no sensitivity to water and oxygen. Furthermore, there is no efficiency loss from the NHC point of view during the recycling of the catalyst as part of a series of multiple catalytic reactions.

[0361] By switching to "flow mode", manual recycle is no longer necessary, catalyst loss during washing is prevented, and thus reaction conditions are stable, which should maintain efficiency during the reaction.

[0362] [Oxamide] Example 8: Representative procedure for catalytic oxidative carbonylation of amines to oxamides In a 450 ml Parr autoclave equipped with a stir bar, PEPPSI®-IPr, tetrabutylammonium iodide, base, solvent and piperidine were introduced. The reactor was sealed and the mixture was purged three times with nitrogen (5 bar) and then twice with oxygen (5 bar). The autoclave was then pressurized with 10 bar of oxygen followed by 65 bar of carbon monoxide to obtain a total pressure of 75 bar and the reaction medium was stirred for 18 hours at room temperature. The pressure was then carefully released and the autoclave was purged three times with nitrogen (5 bar). The contents of the reactor were transferred to a round-bottom flask and the volatile substances were removed under reduced pressure. The residue was then extracted in toluene, filtered on silica gel (2-3 cm) and the solution was evaporated to dryness to obtain 1,1'-oxalyldipiperidine in the form of an off-white powder.

[0363] The oxamide yields were given by mass of isolated product and the catalytic cycle numbers (CCN) were calculated as defined above.

[0364] Example 9: Effect of solvent on the catalytic oxidative carbonylation of amines to oxamides M1-THF study In a 450 ml Parr autoclave equipped with a stir bar, PEPPSI®-IPr catalyst (62.5 mg, 0.092 mmol), tetrabutylammonium iodide (2.12 g, 5.75 mmol), potassium carbonate (1.59 g, 11.5 mmol), THF (200 ml) and piperidine (22.7 ml, 230 mmol) were introduced. The reactor was sealed and the mixture was purged three times with nitrogen (5 bar) and then twice with oxygen (5 bar). The autoclave was then pressurized with 10 bar of oxygen and then with 65 bar of carbon monoxide to obtain a total pressure of 75 bar and the reaction medium was stirred for 18 hours at room temperature. After this time, the pressure was carefully released and the autoclave was purged three times with nitrogen (5 bar). The contents of the reactor were transferred to a round-bottom flask and the volatiles were removed under reduced pressure. The residue was then extracted in toluene, filtered onto silica gel (2-3 cm), and the solution was evaporated to dryness to give 1,1'-oxalyldipiperidine as an off-white powder (9.5 g; 42 mmol).

[0365] Test M2 - Acetonitrile Test M2 was carried out under the same conditions as test M1, except that 200 mL of acetonitrile was used instead of THF. Results: 9.5 g of oxamide 2 was isolated.

[0366] Test M3 - No Solvent Test M3 was carried out under the same conditions as test M1, in the absence of solvent. Results: 4.2 g of oxamide 2 was isolated.

[0367] Table 6 shows the conditions regarding the nature and presence of the solvent as well as the results of the catalytic oxidative carbonylation of amines to oxamides tests using the homogeneous Pd-NHC catalyst according to the invention.

[0368] [Table 6]

[0369] As demonstrated in experiments M1 and M2, the reaction occurs with equal efficiency in the presence of both THF and CH3CN.

[0370] As demonstrated by test M3, the reaction occurs in the absence of solvent.

[0371] Example 10: Effect of base on the catalytic oxidative carbonylation of amines to oxamides M4 Exam Test M4 was carried out under the same conditions as test M1, except that the base used was triethylamine (5 mol %).

[0372] M5 Exam Test M5 was carried out under the same conditions as test M1, but without any added base.

[0373] Table 7 reports the conditions for the nature and presence of added base and the results of the catalytic oxidative carbonylation of amines to oxamides tests using homogeneous Pd-NHC catalysts according to the invention.

[0374] [Table 7]

[0375] As demonstrated by the results for M1 and M4, organic and inorganic bases have comparable effects on the reaction.

[0376] The reaction is more efficient when no base is added to the reaction mixture, as demonstrated in test M5.

[0377] Example 11: Use of [(PS-IMes)Pd(acac)Cl] catalyst for catalytic oxidative carbonylation of amines to oxamides using heterogeneous Pd-NHC catalyst; Test M6 In a 450 ml Parr autoclave equipped with a stir bar, the catalyst [(PS-Imes)Pd(acac)CI] (317 mg, 0.29 mmol Pd / g, 0.092 mmol Pd), tetrabutylammonium iodide (2.12 g, 5.75 mmol), THF (200 ml) and piperidine (22.7 ml, 230 mmol) were introduced. The reactor was sealed and the mixture was purged three times with nitrogen (5 bar) and then twice with oxygen (5 bar). The autoclave was then pressurized with 10 bar oxygen followed by 65 bar carbon monoxide to obtain a total pressure of 75 bar and the reaction medium was stirred for 18 hours at room temperature. The pressure was then carefully released and the autoclave was purged three times with nitrogen (5 bar). The contents of the reactor were filtered to recover the catalyst. The filtrate was transferred to a round-bottom flask and the volatiles were removed under reduced pressure. The residue was then extracted in toluene, filtered over silica gel (2-3 cm) and the solution was evaporated to dryness to give 1,1'-oxalyldipiperidine in the form of an off-white powder.

[0378] Table 8 shows the operating conditions and yield results for homogeneous and supported catalyst tests for the catalytic oxidative carbonylation of amine piperidines to oxamide 1,1'-oxalyldipiperidine.

[0379] [Table 8]

[0380] Example 12: Effects of CO and O2 Introduction M7 Exam Test M7 was carried out under the same conditions as test M5, except that after 18 hours of stirring at room temperature, the reactor was purged and pressurized a second time with 10 bar of oxygen and 65 bar of CO; the reaction medium was stirred at room temperature for a further 18 hours.

[0381] Table 9 shows the operating conditions.

[0382] [Table 9]

[0383] Test M7 shows that repressurizing the reactor with additional CO and O2 during the reaction allows for maximum yield to be achieved.

[0384] Example 13: Representative procedure for catalytic oxidative carbonylation of aliphatic alcohols to oxalates using Pt-NHC catalysts In a typical procedure, a 450 ml Parr autoclave equipped with a stir bar is charged with homogeneous Pt-NHC complex (0.6 mmol), tetrabutylammonium iodide (1.1 g, 3.0 mmol), triethylamine (0.4 ml, 3.0 mmol), acetonitrile (100 ml) and aliphatic alcohol (50 ml). The reactor is sealed and the mixture is purged three times with nitrogen (5 bar) and then twice with oxygen (5 bar). The autoclave is then pressurized with 15 bar oxygen and then 65 bar carbon monoxide to a total pressure of 80 bar and the reaction medium is stirred for 14 hours at 90° C. The autoclave is then cooled to room temperature before being slowly depressurized and purged three times with nitrogen (5 bar). The contents of the reactor are transferred to a round-bottom flask and the excess aliphatic alcohol and solvent are removed using a rotary evaporator. Dialkyl oxalates (DEO) were recovered by vacuum distillation (boiling point = 120 °C / 50–15 mbar). The reported yields of dialkyl oxalates were calculated based on the isolated mass yield and the number of catalytic cycles (NCC) calculated as defined above.

[0385] Example 14: Representative procedure for catalytic oxidative carbonylation of amines to oxamides using Pt-NHC catalyst In a 450 ml Parr autoclave equipped with a stir bar, Pt-NHC catalyst (1.0 mmol), tetrabutylammonium iodide (2.12 g, 5.75 mmol), THF (200 ml) and piperidine (22.7 ml, 230 mmol) were added. The reactor was sealed and the mixture was purged three times with nitrogen (5 bar) and then twice with oxygen (5 bar). The autoclave was then pressurized with 10 bar oxygen followed by 65 bar carbon monoxide to obtain a total pressure of 75 bar and the reaction medium was stirred at 90 °C for 14 h. The autoclave was then cooled to room temperature before slowly depressurizing and purging three times with nitrogen (5 bar). The contents of the reactor were transferred to a round-bottom flask and the volatiles were removed under reduced pressure. The residue was then extracted in toluene, filtered over silica gel (2-3 cm) and the solution was evaporated to dryness to obtain 1,1'-oxalyldipiperidine.

[0386] Example 15: A compound of the formula: [ka] Synthesis of Pd-NHC catalyst supported on silica gel (PdCl NHC / Si2)

[0387] The catalyst was prepared by the following steps: A) Synthesis of 1-methyl-3-(trimethoxysilylpropyl)-imidazolium chloride according to the following reaction scheme: [ka]

[0388] In a flask equipped with a magnetic bar and a condenser, a mixture of (freshly distilled) N-methylimidazole (10.3160 ​​g, 0.1258 mol) and 3-chloropropyltrimethoxysilane (25 g, 0.1258 mol) was refluxed for 24 hours at 95° C. After cooling to room temperature, the reaction mixture was washed with diethyl ether and dried under vacuum to give the desired product.

[0389] B) The reaction scheme below: [ka] Immobilization of 1-methyl-3-(trimethoxysilylpropyl)-imidazolium chloride on the surface of silica gel according to

[0390] To a solution of 1-methyl-3-(trimethoxysilylpropyl)-imidazolium chloride (0.70 g, 2.2 mmol) in toluene was added silica gel. The mixture was stirred at 105 °C for 12 h. After cooling, the reaction mixture was filtered, washed with CHCl (3 × 10 mL), and dried under vacuum at 60 °C to give silica-supported ionic liquid (2.39 g). Elemental analysis showed the presence of 0.89 mmol of ligand on 1.0 g of support.

[0391] C) The reaction scheme below: [ka] Preparation of NHC-Pd complexes supported on silica gel according to

[0392] To a solution of the ligand supported on silica (1.0 g, 0.89 mmol) in THF (5 mL) was added Pd(OAc)2 (101 mg, 0.45 mmol). The mixture was stirred at 60° C. for 4 h and then at 100° C. for an additional 30 min. The NHC-Pd complex supported on silica was filtered through a sinter and washed with water and then with CHCl2 (3×10 mL). Once washed, the catalyst was dried. ICP analysis showed the presence of 0.35 mmol of Pd on 1 g of support.

[0393] With a Pd load of 0.35 mmol on 1 g of support, better complexation of palladium is observed on this supported ligand compared to the [(PS-IMes)Pd(acac)Cl] catalyst of Example 2, which contains a load of 0.29 mmol / g.

[0394] Example 16: Recyclability study of PdCl-catalyzed NHC / Si2 protocol In a typical procedure, a 450 ml Parr autoclave equipped with a stir bar was charged with heterogeneous Pd-NHC complex (1.0 g, 0.35 mmol Pd / g), tetrabutylammonium iodide (0.5 g, 1.5 mmol), triethylamine (0.2 ml, 1.5 mmol), acetonitrile (100 ml) and aliphatic alcohol (50 ml). The reactor was sealed and the reaction mixture was purged three times with nitrogen (5 bar) and then twice with oxygen (5 bar). The autoclave was then pressurized with 15 bar oxygen followed by 65 bar carbon monoxide to a total pressure of 80 bar and the reaction mixture was stirred at 90° C. for 14 h. The autoclave was then cooled to room temperature before being slowly depressurized and purged three times with nitrogen (5 bar). The reactor contents were filtered to recover the catalyst. The filtrate was transferred to a round-bottom flask, excess aliphatic alcohol and solvent were removed using a rotary evaporator, and the dialkyl oxalate was recovered by vacuum distillation (bp = 120 °C / 50–15 mbar). Reported dialkyl oxalate yields were calculated based on the isolated mass yield and the number of catalytic cycles (NCC) was calculated as defined above.

[0395] Table 10 shows the conditions and results of the recyclability test using the PdCl2NHC / Si catalyst.

[0396] [Table 10]

[0397] Example 17: A compound of the formula: [ka] Preparation of palladium catalyst with NHC group supported on iodized ligand of PdI2NHC / PS

[0398] In a flask equipped with a magnetic bar and a condenser, PdCl2 (266 mg, 1.5 mmol), imidazolium supported polymeric support (PS-IMes-HCl) (1 g, 1.6 mmol / g), potassium iodide (1.2 g, 7.5 mmol), potassium carbonate (1.03 g, 7.5 mmol) and pyridine (7 ml) were introduced and the reaction mixture formed was heated at 80° C. for 16 hours. After that, the reaction mixture was cooled to room temperature, filtered and the polymeric support was washed vigorously with distilled water (5×10 ml), methanol (5×10 ml) and dried under reduced pressure to obtain the desired product (1.6 g).

[0399] The amount of Pd supported on the polymer support was determined using ICP-AES analysis. The polymer supported palladium-N-heterocyclic complex (50 mg) was treated with a mixture (25 ml) of hydrochloric acid and nitric acid (1:1, v / v) for 30 min at room temperature. The orange solution formed was filtered and washed with distilled water. The filtrate and washings were combined and the amount of Pd was determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). The amount of Pd was calculated to be 0.9 mmol per gram of support.

[0400] Example 18: Carbonylation procedure without the addition of iodine salt The inventors have been able to dispense with the addition of iodine salts: iodine can be directly incorporated into catalysts such as PdI2NHC / PS prepared in Example 17, allowing efficient catalytic reoxidation to be maintained while avoiding the need to add additional iodine salts.

[0401] protocol A 450 ml Parr autoclave equipped with a stir bar was charged with heterogeneous Pd-NHC complex (1.0 g, 0.35 mmol Pd / g), triethylamine (0.2 ml, 1.5 mmol), acetonitrile (100 ml) and ethanol (50 ml). The reactor was sealed and the reaction mixture was purged three times with nitrogen (5 bar) and then twice with oxygen (5 bar). The autoclave was then pressurized with 15 bar oxygen followed by 65 bar carbon monoxide to a total pressure of 80 bar and the reaction mixture was stirred at 90° C. for 14 h. The autoclave was cooled to room temperature and then slowly depressurized and purged three times with nitrogen (5 bar). The reactor contents were filtered to recover the catalyst. The filtrate was transferred to a round bottom flask and the residual ethanol and acetonitrile were removed using a rotary evaporator. The purified dialkyl oxalate was recovered by vacuum distillation (bp = 120 °C / 50-15 mbar). The reported dialkyl oxalate yields were calculated based on the isolated mass yield and the number of catalytic cycles (NCC) was calculated as defined above.

[0402] Table 11 shows the operating conditions and the results obtained.

[0403] [Table 11]

[0404] Example 19: Representative procedure for catalytic oxidative carbonylation of amines to oxamides without the addition of iodine salts

[0405] A 450 ml Parr autoclave equipped with a stir bar was charged with PdI2NHC / PS complex (1.0 g, 0.9 mmol Pd / g) prepared according to Example 17, THF (200 ml) and piperidine (22.7 ml, 230 mmol). The reactor was sealed and the mixture was purged three times with nitrogen (5 bar) and then twice with oxygen (5 bar). The autoclave was then pressurized with 10 bar oxygen followed by 65 bar carbon monoxide to obtain a total pressure of 75 bar and the reaction medium was stirred for 18 hours at room temperature. The pressure was then carefully released and the autoclave was purged three times with nitrogen (5 bar). The contents of the reactor were filtered to recover the catalyst. The filtrate was transferred to a round-bottom flask and the volatiles were removed under reduced pressure. The residue was then extracted in toluene, filtered over silica gel (2-3 cm) and the solution was evaporated to dryness to give 1,1'-oxalyldipiperidine in the form of an off-white powder.

Claims

1. 1. Use of an M-NHC catalyst comprising at least one M atom linked to at least one N-heterocyclic carbene ligand, wherein M represents Pd or Pt and NHC represents the N-heterocyclic carbene group, in carrying out a process for the selective preparation of an oxalate or an oxamide from carbon monoxide, an oxidant, particularly molecular oxygen or air, and an alcohol or an amine, respectively, optionally in the presence of a co-catalyst.

2. 1. The catalyst of formula II: 【Chemical 1】 Corresponding to the formula: R １ and R ２ are independent of each other, ・C １ ~C １０ linear or branched alkyl, ・C ３ ~C １０ cycloalkyl, ・C ６ ~C ２０ Aryl or C ３ ~C ２０ heteroaryl, and ・C ７ ~C ２０ Alkyl-aryl or C ４ ~C ２０ alkyl-heteroaryl, represents a group selected from L １ represents a halogen atom selected from Cl, Br and I, ・ L ２ and L ３ represents a bidentate ligand, in particular a bidentate ligand selected from among acetylacetonate (acac), allyl, cinnamyl and acetate, preferably acetylacetonate, or ・ Or L ２ represents a halogen atom selected from Cl, Br and I; L ３ represents a monodentate ligand, in particular selected from pyridine, 3-chloropyridine, acetonitrile, triethylamine or phosphine-based ligands, in particular triphenylphosphine, preferably 3-chloropyridine, The compound of formula II is R １ or R ２ can be bound to a support, in particular a polymer or silica, by at least one of the groups 2. The use according to claim 1.

3. 1. The catalyst of formula II: 【Chemistry 2】 Corresponding to the formula: R 1 and R 2 are, independently of each other, C 1 -C 10 linear or branched alkyl; C3-C10 cycloalkyl, - C6-C20 aryl or C3-C20 heteroaryl, and - C7-C20 alkyl-aryl or C4-C20 alkyl-heteroaryl; represents a group selected from L １ represents an iodine atom, ・ L ２ and L ３ are linked together and together represent a bidentate ligand, or ・ Or L ２ represents a halogen atom selected from Cl, Br and I; L ３ represents a monodentate ligand, The compound of formula II can be bound to a support, in particular a polymer or silica, by at least one of the R 1 or R 2 groups; 2. The use according to claim 1.

4. 1. The catalyst of formula II: 【Chemistry 3】 Corresponding to the formula: R 1 and R 2 are, independently of each other, C 1 -C 10 linear or branched alkyl; C3-C10 cycloalkyl, - C6-C20 aryl or C3-C20 heteroaryl, and - C7-C20 alkyl-aryl or C4-C20 alkyl-heteroaryl; represents a group selected from L １ and L ２ each represents an iodine atom, L ３ represents a monodentate ligand, The compound of formula II can be bound to a support, in particular a polymer or silica, by at least one of the R 1 or R 2 groups; 2. The use according to claim 1.

5. 1. The catalyst has the formula III: 【Chemistry 4】 Corresponding to the formula: R １ , R ２ , R ３ and R ４ are independent of each other, ・C １ ~C １０ linear or branched alkyl, ・C ３ ~C １０ cycloalkyl, ・C ６ ~C ２０ Aryl or C ３ ~C ２０ heteroaryl, and ・C ７ ~C ２０ Alkyl-aryl or C ４ ~C ２０ alkyl-heteroaryl, represents a group selected from L １ and L ２ But independently of each other, a halogen atom selected from Cl, Br and I, or - monodentate ligands, or Or, L １ and L ２ are linked and represent a bidentate ligand, The compound of formula III is R １ , R ２ , R ３ or R ４ can be bound to a support, in particular a polymer or silica, by at least one of the groups, Optionally, R １ or R ２ One of the groups is R ３ or R ４ which together represent a bidentate group comprising two N-heterocyclic carbene groups.

2. The use according to claim 1.

6. 1. The catalyst has the formula III: 【Chemistry 5】 Corresponding to the formula: R 1 , R 2 , R 3 and R 4 are each independently C 1 -C 10 linear or branched alkyl; C3-C10 cycloalkyl, - C6-C20 aryl or C3-C20 heteroaryl, and - C7-C20 alkyl-aryl or C4-C20 alkyl-heteroaryl; represents a group selected from L １ and L ２ at least one of the groups represents an iodine atom; The compound of formula III may be bound to a support, in particular a polymer or silica, by at least one of the R 1 , R 2 , R 3 or R 4 groups; Optionally, one of the R 1 or R 2 groups may be linked to R 3 or R 4 , together representing a bidentate group comprising two N-heterocyclic carbene groups; 2. The use according to claim 1.

7. 1. The catalyst has the formula III: 【Chemistry 6】 Corresponding to the formula: R 1 , R 2 , R 3 and R 4 are each independently C 1 -C 10 linear or branched alkyl; C3-C10 cycloalkyl, - C6-C20 aryl or C3-C20 heteroaryl, and - C7-C20 alkyl-aryl or C4-C20 alkyl-heteroaryl; represents a group selected from L １ and L ２ each group represents an iodine atom, The compound of formula III may be bound to a support, in particular a polymer or silica, by at least one of the R 1 , R 2 , R 3 or R 4 groups; Optionally, one of the R 1 or R 2 groups may be linked to R 3 or R 4 , together representing a bidentate group comprising two N-heterocyclic carbene groups; 2. The use according to claim 1.

8. 1. The catalyst according to claim 1, wherein the catalyst is of formula IV: 【Chemistry 7】 Corresponding to the formula: R １ and R ２ are independent of each other, ・C １ ~C １０ linear or branched alkyl, ・C ３ ~C １０ cycloalkyl, ・C ６ ~C ２０ Aryl or C ３ ~C ２０ heteroaryl, and ・C ７ ~C ２０ Alkyl-aryl or C ４ ~C ２０ alkyl-heteroaryl, represents a group selected from L １ and L ２ represents a halogen atom selected from Cl, Br and I, 2. The use according to claim 1.

9. The catalyst is of formula II-1 or II-2 or II-3: 【Chemistry 8】 Corresponding to the formula: R １ and R ２ are independent of each other, ・C １ ~C １０ linear or branched alkyl, ・C ３ ~C １０ cycloalkyl, ・C ６ ~C ２０ Aryl or C ３ ~C ２０ heteroaryl, and ・C ７ ~C ２０ Alkyl-aryl or C ４ ~C ２０ alkyl-heteroaryl, represents a group selected from The catalyst is R １ or R ２ can be bound to a support, in particular a polymer or silica, by at least one of the groups, In particular, the catalyst is 【Chemistry 9】 or a catalyst bound to a support (PS) selected from 【Chemistry 10】 Selected from among 2. The use according to claim 1.

10. The catalyst has the formula III-1: 【Chemistry 11】 Corresponding to the formula: R １ , R ２ , R ３ and R ４ are independent of each other, ・C １ ~C １０ linear or branched alkyl, ・C ３ ~C １０ cycloalkyl, ・C ６ ~C ２０ Aryl or C ３ ~C ２０ heteroaryl, and ・C ７ ~C ２０ Alkyl-aryl or C ４ ~C ２０ alkyl-heteroaryl, represents a group selected from The compound of formula III-1 is R １ , R ２ , R ３ or R ４ can be bound to a support, in particular a polymer or silica, by at least one of the groups, Optionally, R １ or R ２ One of the groups is R ３ or R ４ which together represent a bidentate group containing two N-heterocyclic carbene groups; In particular, the supported catalyst of formula III-1 is 【Chemistry 12】 Selected from:

2. The use according to claim 1.

11. 2. Use of a Pt-NHC catalyst according to claim 1 in a process for the selective preparation of oxalates or oxamides from carbon monoxide, an oxidant, in particular molecular oxygen or air, and an alcohol or amine, respectively.

12. 1. A method for preparing an oxalate or oxamide compound, comprising: To obtain an oxalate compound or an oxamide compound, - with an alcohol or an amine, respectively ■ Carbon monoxide, specifically used at 1.0 to 10.0 MPa, especially 6.5 MPa; ■ an oxidizing agent, in particular oxygen or air, preferably oxygen used at 0.5 to 2.5 MPa; ■ M-NHC catalysts comprising at least one M atom linked to at least one N-heterocyclic carbene ligand, where M represents Pd or Pt and NHC represents an N-heterocyclic carbene group; and Optionally, specifically tetrabutylammonium iodide (Bu ４ a co-catalyst selected from among sodium iodide (NI), sodium iodide (NaI) and potassium iodide (KI), preferably tetrabutylammonium iodide; Optionally, in particular potassium carbonate (K ２ CO ３ ), sodium carbonate (Na ２ CO ３ ), potassium tert-butylate (KotBu), potassium phosphate (K ３ P.O. ４ ) and triethylamine (Et ３ N), ■ Optionally, a solvent, in particular acetonitrile, toluene, 1,4-dioxane, tetrahydrofuran, ethanol, methanol and ethyl acetate, preferably acetonitrile and tetrahydrofuran and a step A of contacting the reaction medium with optionally a step B of heating the reaction medium; A preparation method comprising:

13. To obtain an oxalate compound or an oxamide compound, - with an alcohol or an amine, respectively ■ Carbon monoxide, ■ Oxygen or air; ■ Pd-NHC catalyst, ■ optionally a promoter; ■ optionally a base, ■ optionally a solvent; and a step A of contacting the reaction medium with optionally a step B of heating the reaction medium; 13. The method of claim 12 for preparing an oxalate or oxamide compound, comprising:

14. Alcohol and ■ Carbon monoxide, ■ Oxygen or air; ■ Pd-NHC catalyst, and ■ optionally a promoter; ■ optionally a base, ■ optionally a solvent; and a step A of contacting the reaction medium with a step B in which the reaction medium is heated, in particular at a temperature between 25 and 200°C, in particular between 60 and 110°C, preferably at about 90°C, to obtain an oxalate compound; 13. The method of claim 12 for preparing an oxalate compound, comprising:

15. Step A comprises reacting the compound of Formula 1: 【Chemistry 13】 where R ａ teeth, ・C １ ~C １０ linear or branched alkyl, ・C ３ ~C １０ cycloalkyl, represents a group selected from In particular, the alcohol is chosen from among methanol, ethanol and isopropanol.

13. The process for preparing an oxalate compound of formula 2 according to claim 12.

16. amines, ■ Carbon monoxide, ■ Oxygen or air; ■ optionally a promoter; ■ Pd-NHC type catalyst, ■ Solvents, and ■ Optionally, in detail, K ２ CO ３ or Et ３ N, Step A, in which a reaction medium containing oxamide is obtained by contacting 13. The method of claim 12 for preparing an oxamide compound, comprising:

17. Step A is a reaction of Equation 3: 【Chemistry 14】 wherein R ｂ and R ｃ are independent of each other, hydrogen atoms, ・C １ ~C ２０ linear or branched alkyl groups, ・C ２ ~C ２０ a straight-chain or branched alkenyl group, C, in which the heteroatom is in particular O or N １ ~C ２０ represents a linear or branched heteroalkyl group, R ｂ or R ｃ at least one of the groups is different from hydrogen, R ｂ and R ｃ can form one ring, In particular, the amine is chosen from diethylamine, piperidine, pyrrolidine and morpholine.

13. A process for preparing an oxamide compound of formula 4 according to claim 12.

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