WO2019174221A1 - Procédé de production d'une amine dans un système de solvant contenant de l'eau - Google Patents

Procédé de production d'une amine dans un système de solvant contenant de l'eau Download PDF

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WO2019174221A1
WO2019174221A1 PCT/CN2018/109431 CN2018109431W WO2019174221A1 WO 2019174221 A1 WO2019174221 A1 WO 2019174221A1 CN 2018109431 W CN2018109431 W CN 2018109431W WO 2019174221 A1 WO2019174221 A1 WO 2019174221A1
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process according
hydrogen
group
reactant
catalyst
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PCT/CN2018/109431
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English (en)
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Peng Li
Armin T. Liebens
Hangkong Yuan
Fangzheng SU
Feng Shi
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Rhodia Operations
Lanzhou Institute of Chemical Physics, Chinese Academy of Science
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Priority to CN201880091303.5A priority Critical patent/CN112020490A/zh
Publication of WO2019174221A1 publication Critical patent/WO2019174221A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
    • C07C209/28—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with other reducing agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
    • C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention pertains to a process for producing an amine from an aldehyde or a precursor thereof, or a ketone in a solvent system containing water.
  • Amines are of significant importance to the chemical industry. Synthetic amines are used for solvents, agrochemicals, pharmaceuticals, fabric softeners, flotation agents, corrosion inhibitors, antistatic additives, lubricants, polymers and varnishes.
  • U.S. Patent No. 4598159 teaches a reductive amination reaction of furfural with ammonia by using Ni or Co based catalysts. Said reaction is conducted in the presence of dioxane or in a non-solvent system.
  • Transaminase catalyzed reaction in an aqueous solution is investigated to transfer furfurals to furfurylamines as reported by Green Chem. 2017, 19, 397-404. Nevertheless, it is difficult for large scale production in an economic way by using transaminase.
  • the amine donor, such as isopropylamine or 2- (4-nitrophenyl) ethan-1-amine in this reaction is also expensive than ammonia.
  • aminomethyl-hydroxymethylfuran derivatives are well known for their widely recognized pharmaceutical activities, including muscarinic receptor agonist, pyriculariaoryzae inhibitory, calcium antagonistic activity and cholinergic agent.
  • Those compounds are generally produced from furfural alcohol or furfural, which are accessible from biomass and can reduce fossil-fuel based energy consumption.
  • RSC Advance., 2014, 4, 59083-59087 teaches a direct reductive amination reaction of 5-hydroxymethylfurfural with primary/secondary amines via Ru-complex to produce aminomethyl-hydroxymethylfuran derivatives.
  • the bio-based ethanol is a preferable solvent for this reaction.
  • the selectivity of target product decreases heavilywhen ethanol is replaced by water.
  • Citride No. CN 105503791 discloses a method for producing 5- (aminomethyl) furan-2-yl] methanol compound in the presence of divalent ruthenium coordination compound catalyst. Nevertheless, this kind of catalyst is also sensitive to water.
  • the process according to the present invention using an effective heterogeneous catalyst system, makes it possible to perform the reaction in a solvent system containing a considerable amount of water. Thus, it is more environmentally friendly.
  • the present invention concerns a process for producing an amine, comprising reacting:
  • a first reactant being an aldehyde or a precursor thereof, or a ketone
  • R 1 and R 2 independently from each other, represent hydrogen or a hydrocarbon group, with the proviso that, when R 1 and R 2 represent a hydrocarbon group, they can further form a cyclic ring together,
  • the solvent comprises at least 20 wt%water based on total weight of the solvent
  • the catalyst being an oxide represented by the general formula (II) ,
  • -x is a number ranging from 1 to 20,
  • -y is a number ranging from 0 or 1;
  • -z is greater than zero and less than a number sufficient to satisfy the valence requirements of the other elements present when in a fully oxidized state.
  • the process does not require noble metal catalysts, especiallythose sensitive to water.
  • the present invention also relates to a composition
  • a composition comprising:
  • R 1 and R 2 independently from each other, represent hydrogen or a hydrocarbon group, with the proviso that, when R 1 and R 2 represent a hydrocarbon group, they can further form a cyclic ring together,
  • -x is a number ranging from 1 to 20,
  • -y is a number ranging from 0 or 1;
  • -z is greater than zero and less than a number sufficient to satisfy the valence requirements of the other elements present when in a fully oxidized state.
  • Fig. 1 demonstrates Ni 6 AlO z catalyst could be recycled 4 times without loss of catalytic performance in terms of 5- (aminomethyl) furan-2-yl] methanol (AMFM) yield in the reaction of reductive amination of HMF.
  • the catalytic performance could be recovered when the loss of catalyst was compensated by the addition of fresh Ni 6 AlO z catalyst.
  • Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
  • a temperature range of about 120°C to about 150°C should be interpreted to include not only the explicitly recited limits of about 120°C to about 150°C, but also to include sub-ranges, such as 125°C to 145°C, 130°C to 150°C, and so forth, as well as individual amounts, including fractional amounts, within the specified ranges, such as 122.2°C, 140.6°C, and 141.3°C, for example.
  • any particular upper concentration, weight ratio or amount can be associated with any particular lower concentration, weight ratio or amount, respectively.
  • hydrocarbon group refers to a group which contains carbon and hydrogen bonds.
  • a hydrocarbon group may be linear, branched, or cyclic, and may contain a heteroatom such as oxygen, nitrogen, sulfur, halogen, etc.
  • alkyl means a saturated hydrocarbon radical, which may be straight, branched or cyclic, such as, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, n-hexyl, cyclohexyl.
  • alkenyl as a group or part of a group denotes an aliphatic hydrocarbon group containing at least one carbon-carbon double bond and which may be straight or branched.
  • the group may contain a plurality of double bonds in the normal chain and the orientation about each is independently E or Z.
  • Exemplary alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl and nonenyl.
  • the group may be a terminal group or a bridging group.
  • aryl refers to a monovalent aromatic hydrocarbon group, including bridged ring and/or fused ring systems, containing at least one aromatic ring. 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.
  • 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.
  • cycloalkyl as used herein means cycloalkyl groups containing from 3 to 8 carbon atoms, such as for example cyclohexyl.
  • Heterocyclic may also mean a heterocyclic group fused with a benzene-ring wherein the fused rings contain carbon atoms together with 1 or 2 heteroatom’s which are selected from N, O and S.
  • heterocycloalkane is a saturated heterocycle formally derived from a cycloalkane by replacing one or more carbon atoms with a heteroatom.
  • the present invention provides a process for producing an amine, comprising reacting:
  • a first reactant being an aldehyde or a precursor thereof, or a ketone
  • R 1 and R 2 independently from each other, represent hydrogen or a hydrocarbon group, with the proviso that, when R 1 and R 2 represent a hydrocarbon group, they can further form a cyclic ring together,
  • the solvent comprises at least 20 wt%water based on total weight of the solvent
  • the catalyst being an oxide represented by the general formula (II) ,
  • -x is a number ranging from 1 to 20,
  • -y is a number ranging from 0 or 1;
  • -z is greater than zero and less than a number sufficient to satisfy the valence requirements of the other elements present when in a fully oxidized state.
  • the aldehyde as used herein is an organic compound containing at least one aldehyde functional group with the structure -CHO.
  • the aldehyde comprises only one aldehyde functional group.
  • the aldehyde comprises two aldehyde functional groups.
  • the first reactant may be an aldehyde represented by the general formula (III) :
  • R 3 may represent hydrogen, or a straight, branched or cyclic hydrocarbon group, which is optionally interrupted by one or several heteroatoms and/or which is optionally substituted by one or several functional groups.
  • Said heteroatoms can be O, S, F, or N.
  • R 3 can be an alkyl, alkenyl, aryl, cycloalkyl or heterocyclic group.
  • R 3 can notablybe a C 2 -C 20 alkyl, alkenyl, aryl group or heterocyclic group.
  • Preferred group forR 3 is C 3 -C 10 alkyl, alkenyl, aryl group or heterocyclic group.
  • R 3 is an alkyl goup selected from a group consisting of ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl.
  • the aldehyde represented by the general formula (III) is chosen the group consisting of propionaldehyde, butyraldehyde, valeraldehyde and caproaldehyde.
  • R 3 can also be an aromatic heterocyclic group, and may be chosen from the group consisting of benzene, pyrene, furan, thiophene, terthiophene, pyrrole, pyridine, terpyridine, pyridine oxide, pyrazine, indole, quinoline, purine, quinazoline, bipyridine, phenanthroline, naphthalene, tetralin, biphenyl, cyclohexylbenzene, indan, anthracene, phenanthrene, fluorene, and azulene.
  • R 3 is a furyl goup.
  • R 3 can notably be an aryl group or an aromatic heterocyclic group, which is optionally substituted with at least one substitutent chosen from the group consisting of C 1 -C 24 alkyl, amino, hydroxyl, hydroxyalkyl, carboxyl, ester, cyano, nitro, halogen, and oxygen.
  • Preferred substitutent is hydroxyl or hydroxyalkyl.
  • R 3 is a furyl goup which is substituted by at least one hydroxyl or at least one hydroxyalkyl group. More preferably, R 3 is a furyl goup which is substituted by at least one hydroxyalkyl group.
  • the aldehyde represented by the general formula (III) is chosen in the group consisting of furfural, hydroxymethylfurfural (HMF) , benzaldehyde, 4-methoxybenzaldehyde, 4-chlorobenzaldehyde, 4-nitrobenzaldehyde andvanillin.
  • the aldehyde precursor according to present invention refers to any chemical that is transformed into aldehyde, as in the course of the process, and therefore precedes that the aldehyde in the synthetic pathway.
  • aldehyde precursor examples include glycolaldehyde dimer, acrolein dimer and glyoxal dimer.
  • the ketone comprises only one carbonyl group.
  • the ketone comprises two carbonyl groups.
  • the ketone can be aliphatic ketone. It should be understood by the skilled person that when a compound is classified as aliphatic, it means that it's made up of only carbon and hydrogen atoms. Aliphatic compounds can be either open chains or contain a ring, and they can contain carbon-carbon single, double, or triple bonds.
  • the first reactant may be a ketone represented by the general formula (IV) :
  • R 4 andR 5 independently from each other, represent a straight, branched or cyclic hydrocarbon group, which is optionally interrupted by one or several heteroatoms and/or which is optionally substituted by one or several functional groups, andR 4 andR 5 can further form a cyclic ring together.
  • Said heteroatoms can be O, S, F, or N.
  • R 4 and R 5 represent a hydrocarbon group and form a cyclic ring together.
  • aliphatic ketone examples include cyclohexanone, butanone, cyclopentanone and 2-heptanone.
  • the ketone can also be aromatic ketone, such as acetophenone and valerophenone.
  • the second reactant is a compound represented by the general formula (I) :
  • R 1 and R 2 independently from each other, represent hydrogen or a hydrocarbon group, with the proviso that, when R 1 and R 2 represent a hydrocarbon group, they can further form a cyclic ring together.
  • R 1 and R 2 represent a hydrocarbon group and form a cyclic ring together.
  • the second reactant is a compound represented by the general formula (I’) :
  • R 1 may represent hydrogen, or a straight, branched or cyclic hydrocarbon group that can be an alkyl, alkenyl, aryl, cycloalkyl or heterocyclic group, which is interrupted by one or several heteroatoms such as O, S, F, and N.
  • Preferred groups for R 1 may be for example: H, alkyl, phenyl, benzyl, cycloalkyl.
  • R 1 may comprise from 1 to 10 carbon atoms.
  • Preferred second reactant according to the present invention such as compounds of formula (I) , may be chosen in the group consisting of: ammonia, methylamine, n-butylamine, n-heptylamine, allylamine, benzylamine, aniline, 3-phenylprop-2-enylamine, cyclohexanamine, (tetrahydrofuran-2-yl) methanamine, ethanolamine and morpholine.
  • Preferred second reactant may notably be ammonia. It should be understood by the skilled person that ammonia or an ammonia-liberating compound or mixtures thereof should also been considered as second reactant of present invention. Examples of such ammonia-liberating compounds include urea, uric acid, ammonium salts and derivatives of a primary amide, for example, symmetrical and unsymmetrical carbamates, carbaminates, semicarbazides and semicarbazoles, or aminium salts or organic/inorganic esters thereof. Preference may be given to using ammonia itself, with aqueous ammonia being able to be used in this embodiment. Preferably, the concentration of aqueous ammonia can be from 5 wt%to 30 wt%.
  • R 4 -C ( O) -R 5 + R 1 -NH-R 2 ⁇ R 4 -CH (-NR 1 R 2 ) -R 5
  • R 1 , R 2 , R 3 , R 4 and R 5 have the same meaning as above mentioned.
  • the molar ratio of the second reactant to the first reactant may be from 0.2: 1 to 300: 1, preferably from 0.5: 1 to 150: 1 and more preferably from 1: 1 to 120: 1.
  • the catalyst is an oxide represented by the general formula (II) ,
  • -x is a number ranging from 1 to 20,
  • -y is a number ranging from0 or 1;
  • -z is greater than zero and less than a number sufficient to satisfy the valence requirements of the other elements present when in a fully oxidized state.
  • x ranges from 1 to 10
  • y is around 1
  • z is of at least 1.5 and less than a number sufficient to satisfy the valence requirements of the other elements present when in a fully oxidized state.
  • x ranges from 4 to 10
  • y is around 1
  • z is of at least 1.5 and less than a number sufficient to satisfy the valence requirements of the other elements present when in a fully oxidized state.
  • Preferred examples of the catalyst are NiO z , NiAlO z , Ni 2 AlO z , Ni 4 AlO z , Ni 6 AlO z , Ni 8 AlO z and Ni 10 AlO z , wherein z has the same meaning as above defined.
  • More preferable examples of the catalyst are Ni 4 AlO z , Ni 6 AlO z , Ni 8 AlO z and Ni 10 AlO z , wherein z has the same meaning as above defined.
  • the number sufficient to satisfy the valence requirements of the other elements present when in a fully oxidized state can be calculated based on the valence of the metal in its fully oxidized state and the number of the metal atom present.
  • the valence of Ni is +4 and the valence of Al is +3. z is less than 27.
  • the catalyst according to the present invention may be produced by a “co-precipitation” method.
  • “co-precipitation” refers to a method: Amixture containing two or more metal ions is reacted with a precipitating agent, and a precipitate containing several metal components is formed.
  • the co-precipitation method to prepare the catalyst normally comprises the following steps:
  • step (i) comprises dissolving more than one metal salts in a solvent, e.g. water.
  • step (ii) As the material used for co-precipitating agent in step (ii) , basic solutions such as sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, and aqueous ammonia can be selected.
  • the co-precipitating agent in step (ii) can be a combination of carbonate and alkali metal hydroxide.
  • Preferred carbonate can be sodium carbonate, potassium carbonate or ammonium carbonate.
  • Preferred alkali metal hydroxide can be sodium hydroxide or potassium hydroxide.
  • calcination is preferably used.
  • the calcination is typically carried out at temperatures in a range of 350°C to 750°C, and preferably from 450°C to 600°C , and under any suitable gas atmosphere, e.g. in the presence of hydrogen, nitrogen, helium, argon and/or steam or mixtures thereof.
  • step (iv) at least partial metal ions will be reduced to metal in elemental form.
  • the reduction step (iv) may be performed by contacting the catalyst precursor with hydrogen.
  • Hydrogen is normally present as a gas at low to moderate pressure in contact with the catalyst precursor. Partial pressures of hydrogen of at least one atmosphere are preferred.
  • the reduction temperature in step (iv) is suitably between 200°C and 600°C , preferably between 300°C and 500°C.
  • the co-precipitation method to prepare the catalyst comprises the following steps:
  • Specific surface of the catalyst ranges from 80 to 280 m 2 /g and pore volume of the catalyst ranges from 0.3 to 0.55 ml/g.
  • the weight ratio of the catalyst to the first reactant may be from 2: 1 to 1: 10 and preferably from 1: 1 to 1: 4.
  • the solvent according to the present invention comprises at least 20 wt%of waterbased on total weight of the solvent.
  • the solvent comprises 40 wt%to 100 wt%of water based on total weight of the solvent, more preferably, from 80 wt%to 100 wt%, even more preferably, from 90 wt%to 100 wt%.
  • the solvent according to the present invention is solely water.
  • the solvent system notably comprises between 1 to 70 weight percent of a non-water solvent that optionally contains water-soluble component (s) , and said non-water solvent may be selected from a group of:
  • -polar protic solvents such as isopropanol, methanol, ethanol, and acetic acid
  • -polar aprotic solvents such as dimethyl sulfoxide (DMSO) , acetone, and acetonitrile
  • -apolar solvents such as tetrahydrofuran, dioxane, diethylether, diisopropyl ether, cyclohexane, toluene, benzene, xylene, octane, hexane, heptane, 1, 4-dioxane, tert-butyl methyl ether (MTBE) , mesitylene, diglyme and 1, 2-dimethoxyethane.
  • MTBE tert-butyl methyl ether
  • the solvent may be used in any amount with no specific restrictions, but desirably in an amount ranging from 0.5 to 100 times the weight of the first reactant used, and more preferably in an amount of 2 to 40 times the weight of the first reactant used.
  • the reductant agent used in the process of the invention is also called reducing agent or reducer, herein refers to an organic or inorganic compound that donates a proton to another species, in a redox reaction.
  • reductant agents donate protons to the transiently formed imines.
  • Reductant agents used in the reaction may notably be hydrogen or a secondary alcohol, such as for example isopropanol, glycerol, 2-butanol, and cyclohexanol. Among them, hydrogen is preferable.
  • Molar ratio of the reductant agent to the first reactant may be from 1: 1 to 100: 1, preferably from 1: 1 to 30: 1.
  • the reactants, with a 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 an amine, in the desired quantity and yield.
  • the reaction temperature may be from 60°C to 150°C.
  • the reaction time may be from 2 to 12 hours.
  • reaction according to the present process is desirably carried out under a hydrogen partial pressure in a range of 0.1 to 25 MPa.
  • hydrogen may be added during the reaction to make up for the consumption or continuously circulated through the reaction zone.
  • the reaction may be carried out in the presence of air but preferably with an inert atmosphere such as N 2 or Ar.
  • 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.
  • At least part of the catalyst used in the process of the invention may be recycled. More preferably, all the catalyst is recycled to a fresh reaction solution.
  • the recycled catalyst may be directly reused after physical separation from reaction solution.
  • the process according to the present invention can be performed under suitable reaction conditions to obtain desired products.
  • reaction proceeding in accordance with Scheme 3 can be carried out under suitable conditions, which can be achieved by controlling reaction parameters, such as the reaction temperature, the reaction time and the hydrogen partial pressure when hydrogen is employed as the reductant agent.
  • suitable reaction temperature is from 80°C to 120°C.
  • Suitable reaction time is from 3 to 10 hours.
  • Suitable hydrogen partial pressure is from 0.5 to 20 MPa.
  • the reductant agent is hydrogen;
  • X represents hydrogen or a functional group, such as hydroxyl or hydroxyalkyl.
  • the selectivity of the amine produced is of at least 30%, preferably from 35%to 100%, more preferably from 85%to 100%under such suitable reaction conditions.
  • R 1 and R 2 have the same meaning as above mentioned;
  • the reductant agent is hydrogen;
  • X represents hydrogen or a functional group, such as hydroxyl or hydroxyalkyl.
  • R 6 and R 7 independently from each other, are either identical to R 1 or R 2 respectively or represent a hydrogenated group issued from R 1 or R 2 respectively.
  • reductant agent is hydrogen
  • X represents hydrogen or a functional group, such as hydroxyl or hydroxyalkyl.
  • Said further hydrogenation can be realized by some well-known ways, such as adjusting the reaction temperature, the reaction time and the hydrogen partial pressure, separately or simultaneously.
  • Preferable reaction temperature is from 120 to 150°C.
  • Preferable reaction time is from 10 to 16 hours.
  • Preferable reaction hydrogen partial pressure is from 10 to 25 MPa.
  • R 4 -C ( O) -R 5 + R 1 -NH-R 2 ⁇ R 4’ -CH (-NR 1’ R 2’ ) -R 5’
  • R 1 , R 2 , R 3 , R 4 and R 5 have the same meaning as above andwherein R 1’ , R 2’ , R 3’ , R 4’ and R 5’ , independently from each other, are either identical to R 1 , R 2 ,R 3 , R 4 and R 5 respectively or represent a hydrogenated group issued from R 1 , R 2 ,R 3 , R 4 and R 5 respectively.
  • the present invention also relates to a composition
  • a composition comprising:
  • R 1 and R 2 independently from each other, represent hydrogen or a hydrocarbon group, with the proviso that, when R 1 and R 2 represent a hydrocarbon group, they can further form a cyclic ring together,
  • -x is a number ranging from 1 to 20,
  • -y is a number ranging from 0 or 1;
  • -z is greater than zero and less than a number sufficient to satisfy the valence requirements of the other elements present when in a fully oxidized state.
  • the compound represented by the general formula (I) is a compound represented by the general formula (I’) :
  • R 1 may represent hydrogen or a hydrocarbon group.
  • Ni (NO 3 ) 2 ⁇ 6H 2 O (4.66g, 16 mmol) and Al (NO 3 ) 3 ⁇ 9H 2 O (1 g, 2.67 mmol) were added to deionized water (30 mL) at r.t. and agitated until complete dissolution. Then, aqueous Na 2 CO 3 (20 mL, 1.25 M) was added dropwise and the mixture was stirred for 5 h. The reaction mixture was centrifuged and washed with deionized water to remove the base until the pH value of the aqueous solution was neutral.
  • the solid was dried at 100°C in air for 5 h, calcined at 450°C for 4 h, and then reduced with hydrogen at 450°C for 2 h.
  • the resulting catalyst sample was denoted as Ni 6 AlO z .
  • the reaction was performed in a stainless steel autoclave. 1 mmol HMF, 50 mg Ni 6 AlO z catalyst, 3 ml H 2 O and 1.27g of ammonia were loaded into the reactor. The autoclave was purged with hydrogen for three times, and charged with H 2 at desired pressure at room temperature. Then, the autoclave was heated under stirring to initiate the reaction.
  • the GC-yield was determined by GC-FID (Agilent 7890A) using dioxane as internal standard, and the isolated yields were obtained by flash column chromatography. The yield of 5- (aminomethyl) furan-2-yl] methanol (hereinafter AMFM) is 98%.
  • NiO z , NiAlO z , Ni 2 AlO z , Ni 4 AlO z , Ni 8 AlO z and Ni 10 AlO z are prepared by the same way as Example 1.
  • the reaction was performed in a stainless steel autoclave. 1 mmol HMF, 50 mg catalyst (NiO z , NiAlO z , Ni 2 AlO z , Ni 4 AlO z , Ni 6 AlO z , Ni 8 AlO z and Ni 10 AlO z ) and 3 ml aqueous ammonia (28 wt%) were loaded into the reactor.
  • the autoclave was purged with hydrogen for three times, and charged with H 2 at 1 bar pressure at room temperature. Then, the autoclave was heated to 100°C and kept for 6 hours.
  • the GC-yield was determined by GC-FID (Agilent 7890A) using dioxane as internal standard, and the isolated yields were obtained by flash column chromatography. The yields of AMFM are shown in Table 1.
  • the reaction was performed in a stainless steel autoclave. 1 mmol HMF, different amount of Ni 6 AlO z catalyst and 3 ml aqueous ammonia (28 wt%) were loaded into the reactor. The autoclave was purged with hydrogen for three times, and charged with H 2 at 1 bar pressure at room temperature. Then, the autoclave was heated to 100°C and kept for 6 hours. The GC-yield was determined by GC-FID (Agilent 7890A) using dioxane as internal standard, and the isolated yields were obtained by flash column chromatography. The yields ofAMFM are shown in Table 2.
  • the reaction was performed in a stainless steel autoclave. 2 mmol first reactant (aldehydes or ketones) , 50 mg Ni 6 AlO z catalyst and 3 ml aqueous ammonia (28 wt%) were loaded into the reactor. The autoclave was purged with hydrogen for three times, and charged with H 2 at 1 bar pressure at room temperature. Then, the autoclave was heated to desired temperature and kept for several hours. The GC-yield was determined by GC-FID (Agilent 7890A) using dioxane as internal standard, and the isolated yields were obtained by flash column chromatography. The yields of amines obtained are shown in Table 3.
  • the reaction was performed in a stainless steel autoclave. 1 mmol HMF, 1.2 mmol second reactant (amines) , 40 mg Ni 6 AlO z catalyst and 3 ml H 2 O were loaded into the reactor. The autoclave was purged with hydrogen for three times, and charged with H 2 at 3 bar pressure at room temperature. Then, the autoclave was heated to 90°C and kept for 6 hours. The GC-yield was determined by GC-FID (Agilent 7890A) using dioxane as internal standard, and the isolated yields were obtained by flash column chromatography. The yields of amines obtained are shown in Table 4.
  • Ni 6 AlO z catalyst could be recycled 4 times without loss of catalytic performance in terms of AMFM yield.
  • there was a drop of HMF conversion which was ascribed to catalyst loss in repetitive recovery process. Specifically, 15 mg fresh Ni 6 AlO z catalyst was added to compensate the loss of catalyst and to maintain 50 mg catalyst in the reaction medium. Fortunately, the catalytic performance could be recovered whenthe loss of catalyst was compensated by the addition of fresh Ni 6 AlO z catalyst.
  • the reaction was performed in a stainless steel autoclave. 1 mmol HMF, 50 mg Ni 6 AlO z catalyst, 3 ml H 2 O and 1.3g of ammonia were loaded into the reactor. The autoclave was purged with hydrogen for three times, and charged with H 2 at 10 barpressure at room temperature. Then, the autoclave was heated to 150°C and kept for 16hours. The GC-yield was determined by GC-FID (Agilent 7890A) using dioxane as internal standard, and the isolated yields were obtained by flash column chromatography. The yield of 5- (aminomethyl) tetrahydrofuran-2-yl] methanol is 95%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de production d'une amine à partir d'un aldéhyde ou d'un précurseur de celui-ci, ou d'une cétone dans un système de solvant contenant de l'eau. Le procédé est plus respectueux de l'environnement et permet d'obtenir un composé amine dans des conditions de réaction modérées.
PCT/CN2018/109431 2018-03-15 2018-10-09 Procédé de production d'une amine dans un système de solvant contenant de l'eau WO2019174221A1 (fr)

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