WO2018112778A1 - Procédé de préparation d'esters de lévulinate - Google Patents

Procédé de préparation d'esters de lévulinate Download PDF

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Publication number
WO2018112778A1
WO2018112778A1 PCT/CN2016/111224 CN2016111224W WO2018112778A1 WO 2018112778 A1 WO2018112778 A1 WO 2018112778A1 CN 2016111224 W CN2016111224 W CN 2016111224W WO 2018112778 A1 WO2018112778 A1 WO 2018112778A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
process according
otf
triflate
furfuryl ether
Prior art date
Application number
PCT/CN2016/111224
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English (en)
Inventor
Alban CHAPPAZ
François JEROME
Karine De Oliveira Vigier
Eric Muller
Jonathan Lai
Original Assignee
Rhodia Operations
Le Centre National De La Recherche Scientifique
Universite De Poitiers
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Application filed by Rhodia Operations, Le Centre National De La Recherche Scientifique, Universite De Poitiers filed Critical Rhodia Operations
Priority to PCT/CN2016/111224 priority Critical patent/WO2018112778A1/fr
Publication of WO2018112778A1 publication Critical patent/WO2018112778A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters

Definitions

  • the present invention relates to a process for the preparation of levulinate esters starting from furfuryl ether in the presence of specific Lewis acid catalysts.
  • Levulinate esters such as alkyl levulinates
  • the acid-catalyzed ring opening of furfuryl alcohol in alcoholic media is a reaction of high interest yielding alkyl levulinates.
  • alkyl levulinates can be produced from furfuryl alcohol through an elegant 100%atom economical process.
  • the amount of furfuryl alcohol introduced in the process of said document is relatively low.
  • homogeneous or heterogeneous catalytic processes are conducted under diluted conditions (furfuryl alcohol loading of 2-3 wt%) .
  • a first object of the invention is a process for synthesizing at least one levulinate ester, said process comprising a step of introducing furfuryl ether into a reaction medium and a step of conversion of the furfuryl ether into levulinate ester in the presence of water and at least one catalyst, said catalyst comprising at least one metal selected from bismuth, gallium, aluminum, tin and iron.
  • the catalyst further comprises at least one ligand selected from triflate, triflimidate, halogen, alkoxy, sulfate, nitrate, carboxylate, alkyl, aryl, metal, hydroxide, hydride and acetylacetonate ligands, preferably selected from triflate, triflimidate and halogen, more preferably selected from triflate.
  • at least one ligand selected from triflate, triflimidate, halogen, alkoxy, sulfate, nitrate, carboxylate, alkyl, aryl, metal, hydroxide, hydride and acetylacetonate ligands, preferably selected from triflate, triflimidate and halogen, more preferably selected from triflate.
  • the catalyst is selected from SnCl 4 , SnX 1 X 2 X 3 (OTf) . xH 2 O and MX 1 X 2 (OTf) . xH 2 O wherein:
  • M represents a metal selected from Bi, Ga and Al,
  • X 1 , X 2 , and X 3 represent independently to each other a ligand, preferably selected from triflate, halogen, alkoxy, sulfate, nitrate, carboxylate, -N (SO 2 CF 3 ) 2 , alkyl, aryl and metal ligands, more preferably from triflate and halogen ligands;
  • OTf represents a triflate
  • x ranges from 0 to 10.
  • the catalyst is selected from SnCl 4 , Bi (OTf) 3 and BiCl 2 OTf, preferably from Bi (OTf) 3 and BiCl 2 OTf.
  • the catalyst is in the form of a hydrate.
  • the reaction medium further comprises at least one solvent, preferably selected from alcohols.
  • the alcohol is selected from alcohols of formula R’ OH wherein R’ is selected from linear, branched, cyclic, saturated or unsaturated hydrocarbyl radicals.
  • R’ comprises from 1 to 30 carbon atoms, preferably from 2 to 24 carbon atoms, more preferably from 3 to 16 carbon atoms.
  • furfuryl ether is present in a quantity ranging from 5 to 50%by weight, preferably from 7 to 40%by weight, more preferably from 10 to 25%by weight, based on the total weight of the alcohols.
  • the furfuryl ether responds to the following formula:
  • R represents a hydrocarbyl radical, saturated or unsaturated, linear, branched or cyclic, optionally comprising one or more heteroatoms, such as oxygen, nitrogen or sulfur.
  • ester levulinate (s) respond (s) to the following formulas (I) and/or (II) :
  • R is as defined in claim 10 and R’ is as defined above, and R and R’ may be identical or different.
  • the catalyst is present in an amount ranging from 0.05 to 20%mol, preferably ranging from 0.1 to 10%mol, more preferably ranging from 0.5 to 5%mol relative to the molar amount of furfuryl ether.
  • the molar ratio water/metal of the catalyst ranges from 0.1 to 20, preferably from 0.3 to 10, more preferably from 0.5 to 5.
  • the process comprises the following steps:
  • reaction mixture comprising all or part of the catalyst, all or part of the water, and optionally all or part of the solvents
  • the process further comprises a step of heating the reaction mixture obtained at the end of step a) to a temperature ranging from 80°C to 200°C, preferably from 100°C to 180°C, more preferably from 115°C to 165°C.
  • the process of the present invention allows obtaining a high yield of levulinate esters.
  • the process of the present invention allows reducing the amount of by-products that can be formed during the reaction.
  • the produced levulinate esters are stable and can be conveniently recovered from the reaction medium, for example by distillation, and the catalyst can be recycled for a further conversion reaction.
  • the present invention is directed to a process for synthesizing at least one levulinate ester, said process comprising a step of introducing furfuryl ether into a reaction medium and a step of conversion of the furfuryl ether into levulinate ester in the presence of water and at least one catalyst, said catalyst comprising at least one metal selected from bismuth, gallium, aluminum, tin and iron.
  • furfuryl ether refers to an ether of the furfuryl alcohol. Furfuryl ether can be commercially available or synthetized according to well-known processes for the skilled person.
  • the furfuryl ether that can be used in the present invention can be represented by the following formula:
  • R represents a hydrocarbyl radical, saturated or unsaturated, linear, branched or cyclic, optionally comprising one or more heteroatoms, such as oxygen, nitrogen or sulfur.
  • R represents a linear, branched or cyclic alkyl radical comprising from 1 to 24 carbon atoms or a linear, branched or cyclic alkenyl radical comprising from 2 to 24 carbon atoms.
  • R comprises from 1 to 16 carbon atoms, more preferably from 1 to 12 carbon atoms, even more preferably from 2 to 8 carbon atoms.
  • hydrocarbyl radical a radical comprising carbon atoms and hydrogen atoms, and optionally heteroatoms such as oxygen, nitrogen or sulfur. According to an embodiment, the hydrocarbyl radicals consist in carbon atoms and hydrogen atoms.
  • furfuryl ethers that can be used in the process of the invention, mention may be made of methyl furfuryl ether, ethyl furfuryl ether, propyl furfuryl ether, butyl furfuryl ether, or pentyl furfuryl ether.
  • the catalyst comprises at least one metal selected from bismuth, gallium, aluminum and tin, more preferably from bismuth, gallium and tin, even more preferably from bismuth and gallium or from bismuth.
  • the catalyst further comprises at least one ligand selected from triflate (OTf) , triflimidate (NTf 2 ) , halogen, alkoxy, sulfate, nitrate, carboxylate, alkyl, aryl, metal, hydroxide, hydride and acetylacetonate ligands; preferably the catalyst comprises at least one ligand selected from triflate (OTf) , triflimidate (NTf 2 ) and halogen, more preferably from triflate.
  • OTf triflate
  • NTf 2 triflimidate
  • halogen alkoxy, sulfate, nitrate, carboxylate, alkyl, aryl, metal, hydroxide, hydride and acetylacetonate ligands
  • the catalyst can be in a dimeric form, including for example a Bi-Bi or Bi-Pd bound.
  • halogen ligands mention may be made of chloride, bromide, fluoride or iodide ligands, and preferably chloride ligands.
  • alkoxy ligands of formula –OR’ wherein R’ represents an alkyl radical comprising from 1 to 24 carbon atoms or an alkenyl radical comprising from 2 to 24 carbon atoms, said alkyl and alkenyl radicals can be linear, branched or cyclic and can optionally comprise one or more heteroatoms, such as oxygen, sulfur or nitrogen, for example in a side chain.
  • the alkoxy ligand is selected from methoxy, ethoxy, propoxy, butoxy ligands.
  • Tf represents a triflyl group also named trifluoromethanesulfonyl (CF 3 SO 3 -) . Therefore, NTf 2 represents the triflimidate radical -N (SO 2 CF 3 ) 2 .
  • alkyl ligands mention may be made of alkyl or alkenyl radicals having from 1 to 24 carbon atoms, said alkyl and alkenyl radicals can be linear, branched or cyclic.
  • Alkyl ligands may optionally comprise one or more heteroatoms, such as oxygen, sulfur or nitrogen, for example in a side chain.
  • the alkyl ligand is selected from methyl, ethyl, propyl, butyl, pentyl, cyclopentadienyl ligands.
  • aryl radicals having from 6 to 24 carbon atoms
  • said aryl radical can be substituted by one or more substituents, such as alkyl or alkenyl having from 1 to 12 carbon atoms, said aryl radical can be bicyclic.
  • the aryl radical is selected from phenyl, benzyl, naphthenyl.
  • carboxylate ligands include carboxylate of formula -OCOR” wherein R” represents an alkyl radical comprising from 1 to 24 carbon atoms or an alkenyl radical comprising from 2 to 24 carbon atoms, said alkyl and alkenyl radicals can be linear, branched or cyclic and can optionally comprise one or more heteroatoms, such as oxygen, sulfur or nitrogen, for example in a side chain.
  • carboxylate ligands are selected from methanoate, acetate, propanoate, butanoate ligands.
  • the catalyst is selected from SnCl 4 and catalysts comprising at least one metal M and at least one ligand OTf wherein
  • -M is selected from bismuth, gallium, aluminum, tin and iron, preferably from and bismuth, gallium, aluminum and tin, more preferably from bismuth and tin, even more preferably from bismuth;
  • -OTf is a triflate, also named trifluoromethanesulfonate (CF 3 SO 3 -) .
  • the catalyst may further comprise at least one organic ligand of type “L” , i.e. a neutral ligand that donate two electrons to the metal, the bond between these ligands and the metal is a coordinate bond.
  • organic ligand of type L mention may be made of phosphine ligands, in particular diphosphine ligands, such as 1, 2-bis (diphenylphosphino) ethane (DPPE) or diamine ligands, in particular bipyridine.
  • DPPE 1, 2-bis (diphenylphosphino) ethane
  • the presence of this kind of organic ligand may improve the selectivity towards levulinate esters and may allow introducing a higher amount of furfuryl alcohol in the reaction medium.
  • Ligands may also improve the solubility of the catalyst, the stability of the catalyst or the kinetics of the reaction.
  • the catalyst is selected from SnCl 4 , Bi (OTf) 3 , Bi (NTf 2 ) 3 , Ga (OTf) 3 , Al (OTf) 3 , Sn (OTf) 4 , and BiCl 2 ( OTf) , more preferably from Bi (OTf) 3 and BiCl 2 ( OTf) .
  • Catalysts that can be used in the process of the invention are commercially available or may be synthesized by processes well known for the skilled person.
  • the catalyst used in the process of the invention may be unsupported (homogeneous catalysis) or supported (heterogeneous catalysis) .
  • a supported catalyst facilitates the process and the recovery of the catalyst at the end of the reaction and does not change the catalysis cycle or the role of the catalyst during the reaction.
  • the support may be any support well known by the skilled person in the art, such as silica, alumina, zeolites or titanium-based solids, or metal oxides such as bismuth oxides, gallium oxides, tin oxides, aluminum oxides or iron oxides.
  • polystyrene resins acid oxides, such as niobium oxides, zeolites or sulfonated charcoals.
  • the catalyst may also be immobilized in a liquid phase.
  • one or more other catalysts different from the (Lewis acid) catalysts defined above may be also present in the reaction medium.
  • said other catalysts are selected from Bronsted acids, in particular strong Bronsted acids, such as triflic acid, perfluorosulfonic acid or Nafion is well known by the skilled person and can be defined as a sulfonated tetrafluoroethylene based fluoropolymer-copolymer.
  • the catalyst (s) is (are) present in an amount ranging from 0.05 to 5%mol, preferably ranging from 0.1 to 3%mol, more preferably ranging from 0.5 to 2%mol based on the molar amount of furfuryl ether.
  • the reaction takes place in the presence of a catalytic amount of water.
  • the reaction takes place with a molar ratio water/metal M (metal of the catalyst) ranging from 0.1 to 20, preferably from 0.3 to 10, more preferably from 0.5 to 5.
  • Water may for example be introduced into the reaction medium by an addition of (external) water or through the use of a catalyst in the form of a hydrate.
  • a SnCl 4 catalyst may be in the form of SnCl 4 .5H 2 O or a AlCl 3 catalyst may be in the form of AlCl 3 .6H 2 O.
  • the catalyst can also be in an anhydrous form.
  • the catalyst comprises triflate ligands
  • the catalyst will be preferably in an anhydrous form.
  • reaction medium By “reaction medium” , it is to be understood the medium wherein the reaction takes place.
  • the reaction medium comprises the furfuryl ether, the catalyst (s) , water, and optionally at least one solvent (different from furfuryl ether) .
  • the reaction medium is substantially free, or even totally free, of organic solvents different from alcohol solvents and the catalyst of the conversion reaction.
  • the main levulinate ester obtained may be:
  • the furfuryl ether may be purified before introduction into the reaction medium, by purification methods well known for the skilled person.
  • the furfuryl ether is present in a quantity of at least 5%by weight, preferably in an amount ranging from 5 to 50%by weight, more preferably from 7 to 40%by weight, even more preferably from 10 to 25%by weight, based on the total weight of the reaction medium.
  • the alcohol which can be used in the reaction medium for the conversion of furfuryl ether may be selected from aliphatic alcohols or aromatic alcohols, preferably from aliphatic alcohols.
  • An aliphatic alcohol is a non-aromatic alcohol.
  • An aromatic alcohol comprises a OH function directly linked to an aryl ring.
  • An example of an aromatic alcohol is a phenol.
  • the alcohol may be a monol or a polyol comprising for example from 2 to 5 OH functions or from 2 to 4 OH functions or from 2 to 3 OH functions, preferably the alcohol is a monol, i.e. an alcohol comprising only one OH function.
  • the alcohol is introduced through an alcoholic solution that may comprise one or several different alcohols, preferably the alcoholic solution comprises only one alcohol.
  • the alcoholic solution comprises a mixture of different alcohols
  • the levulinate esters obtained at the end of the reaction may be a mixture of different levulinate esters.
  • the alcohol is selected from primary alcohols, i.e. compounds comprising at least the following radical: -CH 2 -OH.
  • the alcohol is of formula R’ OH wherein R’ is selected from linear, branched, cyclic, saturated or unsaturated hydrocarbyl radicals.
  • the alcohol comprises from 1 to 30 carbon atoms, preferably from 2 to 24 carbon atoms, more preferably from 3 to 16 carbon atoms.
  • the alcohol is selected from methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, dodecanol.
  • the reaction is performed at a temperature ranging from 80°C to 200°C, preferably from 100°C to 180°C, more preferably from 115°C to 165°C.
  • the reaction is generally performed at a pressure such that the reactants remain in a liquid state.
  • the reaction is performed at a pressure ranging from 0.5 to 5 bars, preferably from 1 to 3 bars, more preferably at atmospheric pressure.
  • the process of the invention comprises the following steps:
  • reaction mixture comprising all or part of the catalyst, all or part of the water, and optionally all or part of the solvent
  • the reaction mixture obtained in step a) comprises all of the catalyst used in the reaction and/or all the water used in the reaction.
  • the reaction mixture, before step b) is heating to a temperature ranging from 80°C to 200°C, preferably from 100°C to 180°C, more preferably from 115°C to 165°C. This heating step may help for the preparation of the catalyst.
  • water is added into the reaction mixture before step b) and before the heating of said reaction mixture if any.
  • all the furfuryl ether is introduced during step b) .
  • furfuryl ether is mixed with the remaining part of the solvents before its introduction into the reaction mixture obtained in step a) .
  • the process of the reaction may be a batch process or a continuous process.
  • furfuryl ether may be sequentially or continuously introduced into the reaction mixture obtained at step a) .
  • the sequentially or continuously addition allows improving the selectivity towards levulinate esters and allows loading a higher amount of furfuryl ether into the reaction medium.
  • levulinate esters and other products can be recovered and isolated, for example by distillation.
  • the catalyst may be recycled for performing another reaction and another process.
  • the reaction can be followed by gas chromatography or by HPLC (high performance liquid chromatography) or also by 1 H or 13 C NMR (Nuclear magnetic resonance) , according to well-known methods for the skilled person; and the reaction is preferably stopped when all the furfuryl ether has been converted in situ.
  • the process of the invention generally leads to a yield in levulinate ester of at least 40%mol, preferably at least 45%mol, more preferably at least 50%mol, based on moles of furfuryl ether in the reaction medium.
  • Samples (0.1 g) were taken from the reaction mixture after different times and quenched with 1.1 g of isopropanol. An aliquot of the sample was filtered on Nylon Acrodisc 0.2 ⁇ m and analysed by GC without any further treatments.
  • the catalyst is present in an amount of 1%mol.
  • the main levulinate ester obtained at the end of the reaction is the butyl levulinate.
  • the yield (or selectivity) in levulinate esters corresponds to the amount of levulinate esters expressed in molar percentage based on the molar amount of furfuryl ether introduced into the reaction medium.
  • the Lewis acid catalyst based on Bi allows the production of alkyl levulinates with a yield improved as compared to acid catalysts based on In or Sc and also with an improved yield as compared to triflic acid catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de synthèse d'au moins un ester de lévulinate, ledit procédé comprenant une étape d'introduction d'éther furfurylique dans un milieu réactionnel et une étape de conversion d'éther furfurylique en ester de lévulinate en présence d'eau et d'au moins un catalyseur, ledit catalyseur comprenant au moins un métal choisi parmi le bismuth, le gallium, l'aluminium, l'étain et le fer.
PCT/CN2016/111224 2016-12-21 2016-12-21 Procédé de préparation d'esters de lévulinate WO2018112778A1 (fr)

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PCT/CN2016/111224 WO2018112778A1 (fr) 2016-12-21 2016-12-21 Procédé de préparation d'esters de lévulinate

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4236021A (en) * 1979-05-07 1980-11-25 The B. F. Goodrich Company Process for the manufacture of levulinic acid and esters
CN104959154A (zh) * 2015-07-09 2015-10-07 南京林业大学 一种用于制备乙酰丙酸酯的催化剂及用它制备乙酰丙酸酯的方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4236021A (en) * 1979-05-07 1980-11-25 The B. F. Goodrich Company Process for the manufacture of levulinic acid and esters
CN104959154A (zh) * 2015-07-09 2015-10-07 南京林业大学 一种用于制备乙酰丙酸酯的催化剂及用它制备乙酰丙酸酯的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HUANG, YAOBING ET AL.: "Microwave-assisted alcoholysis of furfural alcohol into alkyl levulinates catalyzed by metal salts", GREEN CHEMISTRY, vol. 18, no. 6, 22 October 2015 (2015-10-22), pages 1516 - 1523, XP055496509, ISSN: 1463-9262 *

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