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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/32—Manganese, technetium or rhenium
  • B01J23/34—Manganese
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
  • B01J23/44—Palladium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/656—Manganese, technetium or rhenium
  • B01J23/6562—Manganese
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/391—Physical properties of the active metal ingredient
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
  • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups

Definitions

• the present invention concerns a process for forming a primary or a secondary amine via a direct animation reaction comprising: reacting an alcohol with an amine in the presence of ordered porous manganese-based octahedral molecular sieves comprising a transition metal.
• Manganese octahedral molecular sieves constitute a crystalline variety of amorphous manganese oxide (Mn0 2 ) with a well-defined microporous network and different oxidation states of manganese.
• Mn0 2 amorphous manganese oxide
• Mn0 2 amorphous manganese oxide
• K-OMS-2 materials based on cryptomelane structure have proven excellent activities in the oxidation of alcohols (Y.C. Son, V.D. Makwana, A.R. Howell, S.L. Suib, Angew. Chem., Int. Ed. 9 (1999) 319.).
• the reported studies in K-OMS-2 materials point out the preferential generation of imines by N-alkylation of aromatic and aliphatic alcohols, but with no amine formation (S. Sithambaram, R. Kumar, Y-C. Son, S.L. Suib, J. Catal. 253 (2008) 269 ; S. Sithambaram, Y-C. Son, S.L. Suib, US Patent 7,355,075, 2008).
• the present invention concerns furthermore this catalyst as such, i.e. ordered porous manganese-based octahedral molecular sieves comprising a transition metal of Group 8 to 11 elements of the Periodic Table.
• the present invention also concerns a primary or a secondary amine susceptible to be obtained by the process of the present invention.
• the present invention also concerns a composition comprising at least an imine and a primary or a secondary amine, said composition is substantially free or, in some cases, completely free of tertiary amine.
• substantially free when used with reference to the absence of tertiary amine in the composition of the present invention, means that the composition comprises less than 0.1 % wt of tertiary amine, based on the total weight of the composition.
• completely free when used with reference to the absence of tertiary amine in the composition of the present invention, means that the composition comprises no tertiary amine at all.
• Reaction of the present invention may notably be represented as follows:
• x 1 or 2
• R 1 is H or a straight, branched or cyclic hydrocarbon group
• R 2 is H or a straight, branched or cyclic hydrocarbon group
• Alkyl as used herein means a straight chain or branched saturated aliphatic hydrocarbon. Preferably alkyl group comprises 1-18 carbon atoms.
• Representative saturated straight chain alkyls include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and the like; while saturated branched alkyls include isopropyl, sec-butyl, isobutyl, tert- butyl, isopentyl, and the like.
• Alkenyl refers to an aliphatic group containing at least one double bond and is intended to include both "unsubstituted alkenyls" and “substituted alkenyls”, the latter of which refers to alkenyl moieties having substituents replacing a hydrogen on one or more carbon atoms of the alkenyl group.
• Representative unsaturated straight chain alkenyls include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl and the like.
• cyclic group means a closed ring hydrocarbon group that is classified as an alicyclic group, aromatic group, or heterocyclic group.
• alicyclic group means a cyclic hydrocarbon group having properties resembling those of aliphatic groups.
• Aryl as used herein means a 6-carbons monocyclic or 10-carbons bicyclic aromatic ring system wherein 0, 1, 2, 3, or 4 atoms of each ring are substituted. Examples of aryl groups include phenyl, naphthyl and the like.
• arylalkyl or the term “aralkyl” refers to alkyl substituted with an aryl.
• arylalkoxy refers to an alkoxy substituted with aryl.
• Cycloalkyl as used herein means cycloalkyl groups containing from 3 to 8 carbon atoms, such as for example cyclohexyl.
• Heterocyclic as used herein means heterocyclic groups containing up to 6 carbon atoms together with 1 or 2 heteroatoms which are usually selected from O, N and S, such as for example radicals of : oxirane, oxirene, oxetane, oxete, oxetium, oxalane (tetrahydrofurane), oxole, furane, oxane, pyrane, dioxine, pyranium, oxepane, oxepine, oxocane, oxocinc groups, aziridine, azirine, azirene, azetidine, azetine, azete, azolidine, azoline, azole, azinane, tetrahydropyridine, tetrahydrotetrazine, dihydroazine, azine, azepane, azepine, azo
• This first reactant may notably be a compound of formula (I) :
• x 1 or 2
• R 1 is H or a straight, branched or cyclic hydrocarbon group
• R 1 may represent straight, branched or cyclic hydrocarbon group that can be an alkyl, alkenyl, aryl, cycloalkyl or heterocyclic group, eventually comprising one or several heteroatoms such as O, S, F, and N.
• Preferred groups for R 1 may be for example : H, alkyl, cyclic alkane, cyclic alkene, phenyl, furanyl, and tetrahydrofuranyl.
• the first reactant may comprise additional functionalities.
• the additional functionalities may behave as electron donating or electron withdrawing groups as long as their presence does not prevent reaction with the amine to form the imine.
• Preferred first reactants of the present invention are chosen in the group consisting of: furfuryl alcohol, 2,5 furandimethanol, 2,5-tetrahydrofuranedimethanol, benzyl alcohol, 1,6-hexandiol and 1,7- heptandiol.
• Second reactant being NH 3 or a reactant having primary amine functionality
• This second reactant may notably be a compound of formula (II) : R 2 -NH 2 (II)
• R 2 is H or a straight, branched or cyclic hydrocarbon group 2 may represent straight, branched or cyclic hydrocarbon group that can be an alkyl, alkenyl, aryl, cycloalkyl or heterocyclic group, eventually comprising one or several heteroatoms such as O, S, F, and N.
• Preferred groups for R 2 may be for example : H, alkyl, phenyl, benzyl, cycloalkyl, and cycloalkene.
• the second reactant may comprise additional functionalities.
• the additional functionalities may behave as electron donating or electron withdrawing groups as long as their presence does not prevent reaction with the amine to form the imine. There is no particular limitation on the number of carbon atoms present in the reactant as long as its structure does not prevent the formation of the imine.
• Preferred second reactants of the present invention are chosen in the group consisting of: ammoniac, phenylamine, n- heptylamine, aniline and methylamine.
• This imine produced by the reaction of first and second reactant may notably be a compound of formula (III) :
• x 1 or 2
• R 1 is H or a straight, branched or cyclic hydrocarbon group
• R 2 is H or a straight, branched or cyclic hydrocarbon group
• Preferred imines of the present invention are chosen in the group consisting of: N-phenylbenzylimine, (tetrahydrofuran- 2,5-diyl)dimethanimine, (furan-2,5-diyl)dimethanimine, l, -(tetrahydrofuran- 2,5-diyl)bis(N-methyliminomethane), 1,6-hexamethylenediimine, and ⁇ , ⁇ - (tetrahydrofuran-2,5-diyl)bis(N-heptaneiminomethane).
• Primary or secondary amine N-phenylbenzylimine, (tetrahydrofuran- 2,5-diyl)dimethanimine, (furan-2,5-diyl)dimethanimine, l, -(tetrahydrofuran- 2,5-diyl)bis(N-methyliminomethane), 1,6-hexamethylenediimine, and
• the primary or secondary amine of the present invention may notably be a compound of formula (IV) :
• x 1 or 2
• R is H or a straight, branched or cyclic hydrocarbon group
• R is H or a straight, branched or cyclic hydrocarbon group
• Preferred primary or second amines of the invention are chosen in the group consisting of : N-phenylbenzylamine, (tetrahydrofuran-2,5-diyI) dimethanamine, (furan-2,5-diyl) dimethanamine, 1,6- hexamethylenediamine, 1 , 1 '-(tetrahydrofuran-2,5-diyl)bis(N- methylmethylamine), and 1 , 1 '-(tetrahydrofuran-2,5-diyl)bis(N- heptaneaminomethane) .
• Preferred reactions of the present invention are the following :
• Ordered porous manganese-based octahedral molecular sieves constitute an exemplary class of molecular sieves. These materials have one-dimensional tunnel structures and unlike zeolites, which have tetrahedrally coordinated species serving as the basic structural unit, these materials are based on six- coordinate manganese surrounded by an octahedral array of anions (e.g., oxide).
• Manganese oxide octahedral molecular sieves possessing mono- directional tunnel structures constitute a family of molecular sieves wherein chains of Mn0 6 octahedra share edges to form tunnel structures of varying sizes. Such materials have been identified in samples of terrestrial origin and are also found in manganese nodules recovered from the ocean floor. Manganese nodules have been described as useful catalysts in the oxidation of carbon monoxide, methane and butane (U.S. Pat. No. 3,214,236), the reduction of nitric oxide with ammonia (Atmospheric Environment, Vol. 6, p.309 (1972)) and the demetallation of topped crude in the presence of hydrogen (Ind. Eng. Chem. Proc. Dev. l, Vol. 13, p.315 (1974)).
• the OMS framework topology is dictated by the type of arrangement of the MnO 3 ⁇ 4 octahedra, such as corner-sharing, edge-sharing, or face-sharing.
• the ability of manganese to adopt multiple oxidation states and of the Mn0 6 octahedra to adopt different arrangements affords the formation of a large variety of OMS materials.
• the OMS may further comprise an additional transition metal within the molecular framework as long as the incorporation of the additional transition metal does not collapse the one-dimensional tunnel structure.
• the OMS catalyst comprises todorokites.
• Todorokites include materials wherein the Mn0 6 octahedra share edges to form triple chains and the triple chains share corners with adjacent triple chains to form a 3x3 tunnel structure. The size of an average dimension of these tunnels is about 6.9 Angstroms (A).
• a counter cation, for maintaining overall charge neutrality, such as Na, Ca, Mg, and the like is present in the tunnels and is coordinated to the oxides of the triple chains.
• Todorokites are generally represented by the formula (M)Mn 3 0 7 , wherein M represents the counter cation and manganese is present in at least one oxidation state. Further, the formula may also include waters of hydration and is generally represented by (M) y Mn 3 C>7.xH 2 0, where y is about 0.3 to about 0.5 and x is about 3 to about 4.5.
• the OMS catalyst comprises hollandites.
• Hollandites include a family of materials wherein the Mn0 6 octahedra share edges to form double chains and the double chains share corners with adjacent double chains to form a 2x2 tunnel structure. The size of an average dimension of these tunnels is about 4.6 A.
• a counter cation for maintaining overall charge neutrality such as Ba, , Na, Pb, and the like, is present in the tunnels and is coordinated to the oxides of the double chains. The identity of the counter cation determines the mineral species or the structure type.
• Hollandites are generally represented by the formula (M)Mn 8 0i 6 , wherein M represents the counter cation and manganese is present in at least one oxidation state.
• the formula may also include waters of hydration and is generally represented by (M) y Mn g Oi 6 .xH 2 0, where y is about 0.8 to about 1.5 and x is about 3 to about 10.
• Suitable hollandites include hollandite (BaMn 8 0i 6 ), cryptomelane
• the OMS catalyst comprises cryptomelane-type materials.
• some or all of the counter cation is H + .
• the OMS catalyst has an average Mn oxidation state of about 3 to about 4, Within this range the average oxidation state may be greater than or equal to about 3.2, or, more specifically, greater than or equal to 3.2, or even more specifically, greater than or equal to about 3.3. Average oxidation state may be determined by potentiometric titration.
• the OMS catalyst can be prepared by combining an aqueous solution of KMnO 4 (0.2 to 0.6 molar), an aqueous solution of MnSO 4 .3 ⁇ 40 (1.0 to 2.5 molar) and a concentrate acid such as HN0 3 .
• the aqueous solution is refluxed at 100°C for 18-36 hours.
• the product is filtered, washed and dried, typically at a temperature of 100 to 140°C.
• Similar procedures are known in the literature, for example, DeGuzman et ah, Chem. Mater. 1994, 6, 815-821.
• the OMS may be used in any form that is convenient, such as particulate, aggregate, film or combination thereof.
• the OMS may be affixed to a substrate to facilitate separation of the catalyst from the product.
• the hydrothermal method of producing OMS-2 involves autoclaving an aqueous solution of manganese cation and permanganate anion under acidic conditions, i.e., pH ⁇ 3, at temperatures ranging from about 80 to about 140°C in the presence of counter cations having ionic diameters of between about 2.3 and about 4.6 A.
• the counter cations serve as templates for the formation of OMS-2 product and can be retained in the tunnel structures thereof.
• OMS-2 produced via this method is thermally stable up to about 600°C.
• OMS-2 can be produced by the method disclosed in R. Giovanili and B. Balmer, Chimia, 35 (1981) 53.
• a layered manganese oxide precursor is produced.
• This precursor is ion exchanged to form another layered manganese oxide which is then calcined at high temperatures, i.e., temperatures generally exceeding about 600°C, to form OMS-2 product.
• temperatures to produce OMS may be reached either thermically or via microwave irradiation.
• the transition metal is preferably chosen from the group consisting of Pd, Pt, Ru, Os, Ir, Ag, Au or a mixture thereof. More preferably the metal transition is a metal from the platinum group metals (PGMs), that are Pd, Pt, Rh, Ru, Ir and Os.
• PGMs platinum group metals
• the preferable method to prepare ordered porous manganese-based octahedral molecular sieves comprising a transition metal of Group 8 to 11 elements of the Periodic Table is the successive wet impregnation, or the co-precipitation, notably with the potassium permanganate and the magnesium sulfate under acidic conditions.
• the activation or re-activation of the modified OMS catalysts may involve a calcination step and/or a reduction step under hydrogen.
• the activation of the modified OMS catalysts may involve a calcination step under air 0 2 at 300-500°C for 1-24 hours and a reduction step under hydrogen at the same temperature for 1 -6 hours according to M.
• the concentration of transition metal on the OMS carrier may be comprised between 0.1 and 20% by weight, preferably from 1 to 10% by weight.
• the weight ratio of ordered porous manganese-based octahedral molecular sieves comprising a transition metal of Group 8 to 11 elements of the Periodic Table to the second reactant may be comprised between 0.05 and 2, preferably from 0.1 to 0.5.
• the reaction temperature may be comprised between 80 and 250°C.
• the reaction may be carried out in liquid or gas phase. In liquid phase, the reaction may be performed in the absence or presence of a solvent.
• the solvent is typically chosen based on its ability to dissolve the reactants.
• the solvent may be protic, aprotic or a combination of protic and aprotic solvents. Exemplary solvents include toluene, octane, xylene, benzene, n- butanol, and acetonitrile.
• the solvent is a non-polar, aprotic solvent such as toluene. Solvents comprising hydroxyl functionalities or amine functionalities may be used as long as the solvent does not participate in the reaction in place of the reactant.
• the reactants, with an optional solvent, and the catalyst are typically combined in a reaction vessel and stirred to constitute the reaction mixture.
• the reaction mixture is typically maintained at the desired reaction temperature under stirring for a time sufficient to form the primary or the secondary amine in the desired quantity and yield.
• the reaction may be carried out in the presence of air but preferably with an inert atmosphere such as N 2 , Ar, C0 2 or even NH 3 .
• Suitable oxygen containing gases include air, oxygen gas, and mixtures of oxygen gas with other gases such as nitrogen or argon.
• the oxygen containing gas is a flowing oxygen containing gas.
• the reaction vessel is charged with the oxygen containing gas.
• reaction times are 1 to 24 hours, preferably 1 to 8 hours.
• the catalyst is typically removed from the reaction mixture using any solid/liquid separation technique such as filtration, centrifugation, and the like or a combination of separation methods.
• the product may be isolated using standard isolation techniques, such as distillation.
• the OMS catalyst can be reused. If desired, the catalyst can be regenerated by washing with methanol, water or a combination of water and methanol and subjecting the washed catalyst to a temperature of about 150°C to about 300°C for about 6 to 24 hours in the presence of oxygen.
• the preparation of the OMS catalyst used in the examples is as follows. 680 milliliters (ml) of potassium permanganate solution (40g) was added to a mixture of 173 ml manganese sulfate hydrate solution (54.4g) and 6.8 ml of concentrated nitric acid in a 1000 ml of round bottom flask with a condenser. The dark brown slurry was refluxed for 24 hours at 1 10°C, then filtered and washed with de-ionized water several times. The catalyst was dried at 120°C overnight before use. The composition of the K-OMS-2 catalyst was KMn 8 0i 6 .nH 2 0 and the runnels had dimensions of 4.6x4.6 angstroms.
• the average oxidation state of the manganese was approximately 3.8.
• the H-K- OMS-2 catalyst was generated by stirring the K-OMS-2 catalyst in a 1 Molar solution of nitric acid for 6 hours at 60-70°C for 6 hours.
• the morphological and textural characteristics of the K-OMS-2 catalyst were inspected, respectively, by X-ray diffraction analysis and N 2 isotherm adsorption at 77.4 K.
• the XRD patterns for the fresh K-OMS-2 sample reveals the presence of a pure cryptomelane phase (KMn8016, JCPDS 29, 1020).
• the K-OMS-2 catalyst show a high surface area (143 m /g).
• the N 2 adsorption/desorption isotherm plots for the -OMS-2 catalyst reveal the presence of mesopores in the structure.
• the mesopore size range is between 17 and 62 nm, indicating a large amount of slit-shaped mesopores with uniform form sizes or shapes.
• a sharp increase of the sorption loading is observed at low P/Po values, pointing out the presence of micropores with a pore size of 0.36 nm.
• the thermal stability of the K-OMS-2 material was studied by thermo- gravimetric analysis (TGA) under N 2 atmosphere in the range of 50-100°C with a ramp of 10°C/min.
• TGA thermo- gravimetric analysis
• Four characteristic weight loss temperature ranges are observed: (i) 50-200°C (1.2 %wt), which is attributed to physisorbed 0 2 and water; (ii) 350-550°C (3%), which is most likely attributed to chemisorbed oxygen and water; (iii) 550-700°C, involving the release of lattice oxygen from the manganese oxide; and (iv) 700-750°C, which is ascribed to the conversion of manganese Mn(IV) to lower oxidation states.
• the palladium/K-OMS-2 catalyst was prepared by dry impregnation of lg of K- OMS-2. 7.03 mL of Pd(NH 3 ) 4 (N0 3 ) 2 [Pd: 1.42 g/L] was added drop wise to the support. The mixture was stirred for 2 hours at 80°C. The slurry was dried in a rota-evaporator first at 80°C for 2 hours and at 120°C overnight. Finally the solid was calcined at 350°C for 2 hours under oxygen.
• Benzylalcohol and aniline are used to produce the N-phenyl benzylimine (a) and N-phenyl benzylamine (b) and eventually N-phenyl dibenzylamine (c).
• the catalyst of the present invention permits to produce secondary amine with a very high selectivity and a very good conversion of aniline without generating tertiary amine.

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• 2012
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