WO2018087270A1 - Hydrogénation d'une composition comprenant de l'hydroxyméthylfurfural, du bishydroxyméthylfurane ou des mélanges de ceux-ci - Google Patents

Hydrogénation d'une composition comprenant de l'hydroxyméthylfurfural, du bishydroxyméthylfurane ou des mélanges de ceux-ci Download PDF

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WO2018087270A1
WO2018087270A1 PCT/EP2017/078838 EP2017078838W WO2018087270A1 WO 2018087270 A1 WO2018087270 A1 WO 2018087270A1 EP 2017078838 W EP2017078838 W EP 2017078838W WO 2018087270 A1 WO2018087270 A1 WO 2018087270A1
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alkyl
aryl
tetrahydrofuran
cycloalkyl
diyl
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PCT/EP2017/078838
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English (en)
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Dominik Ohlmann
Thomas Schaub
Jaroslaw Michael MORMUL
Alban CADU
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Basf Se
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Publication of WO2018087270A1 publication Critical patent/WO2018087270A1/fr

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    • 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
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms

Definitions

  • the invention relates to a process for the hydrogenation of a composition comprising hydroxymethylfurfural, bishydroxymethylfuran or mixtures thereof to obtain a composition comprising cis-(tetrahydrofuran-2,5-diyl)dimethanol and trans- (tetrahydrofuran-2,5-diyl)dimethanol.
  • the invention also relates to a composition comprising cis-(tetrahydrofuran-2,5-diyl)dimethanol and trans-(tetrahydrofuran-2,5- diyl)dimethanol.
  • the invention also relates to a use of transition metal complex as hydrogenation catalyst for composition comprising hydroxymethylfurfural, bishydroxymethylfuran or mixtures thereof.
  • the invention also relates to a use of the composition comprising cis-(tetrahydrofuran-2,5-diyl)dimethanol and trans- (tetrahydrofuran-2,5-diyl)dimethanol for polymerization reactions.
  • Hydroxymethylfurfural and bishydroxymethylfuran are organic compounds, which can be derived by conversion of certain sugars and carbohydrates. HMF can be converted into derivatives, which can serve, inter alia, as starting point for the synthesis of pharmaceuticals, polymers and macrocyclic compounds.
  • the derivatives can serve, inter alia, as starting point for the synthesis of pharmaceuticals, polymers and macrocyclic compounds.
  • cis-(tetrahydrofuran-2,5-diyl)dimethanol and trans-(tetrahydrofuran-2,5-diyl)dimethanol are of particular commercial interest, especially for the production of polymers.
  • THFDM Tetrahydrofuran-dimethanol
  • FDM furan dimethylol
  • the process it should be possible to provide an isomer mixture of cis/trans-2,5-bis(hydroxymethyl)-tetrahydrofuran in high yield.
  • the process should particularly allow for the production of trans-2,5-bis(hydroxymethyl)- tetrahydrofuran from hydroxymethylfurfural bishydroxymethylfuran or mixtures thereof with high regioselectivity. Very particularly, it should be possible to obtain trans-2,5- bis(hydroxymethyl)-tetrahydrofuran in the process in high yields.
  • the process should be performed economically without the need for many reaction steps. Further, the process should be performed as a homogeneously catalyzed hydrogenation of HMF.
  • the problem of the invention is solved by a process, wherein a composition comprising hydroxymethylfurfural, bishydroxymethylfuran or mixtures thereof, particularly
  • HMF 5-hydroxymethyl-2-furfural
  • BHMF 2,5-bishydroxymethylfuran
  • the transition metal catalyst complex comprises at least one ligand containing at least one phosphorus atom which is capable of coordinating to the transition metal.
  • HMF 5-hydroxymethyl-2-furfuralaldehyd
  • BHMF 2,5-bishydroxymethylfuran
  • the transition metal catalyst complex comprises at least one ligand containing at least one phosphorus atom which is capable of coordinating to the transition metal yielded in a composition comprising cis-(tetrahydrofuran-2,5-diyl)dimethanol and trans-(tetrahydrofuran-2,5- diyl)dimethanol.
  • the invention relates to a process for the hydrogenation of a composition comprising hydroxymethylfurfural, bishydroxymethylfuran or mixtures thereof to obtain a composition comprising cis-(tetrahydrofuran-2,5-diyl)dimethanol and trans- (tetrahydrofuran-2,5-diyl)dimethanol, which process comprises reacting the
  • composition comprising hydroxymethylfurfural, bishydroxymethylfuran or mixtures thereof with hydrogen in a liquid reaction medium comprising a transition metal catalyst complex in homogeneous solution, wherein the transition metal catalyst complex comprises at least one ligand containing at least one phosphorus atom which is capable of coordinating to the transition metal and wherein the transition metal is selected from metals of groups 8, 9 and 10 of the periodic table of the elements according to lUPAC.
  • the invention also relates to a composition comprising cis-(tetrahydrofuran-2,5- diyl)dimethanol and trans-(tetrahydrofuran-2,5-diyl)dimethanol obtained by the process according to the invention.
  • the invention also relates to the use of a transition metal complex as hydrogenation catalyst for compositions comprising hydroxymethylfurfural, bishydroxymethylfuran or mixtures thereof.
  • the invention also relates to the use of the composition comprising
  • trans-(tetrahydrofuran-2,5-diyl)dimethanol refers to the isomers (2S,5R)-trans-tetrahydrofuran-2,5-diyldimethanol and (2S,5S)-trans- tetrahydrofuran-2,5-diyldimethanol and mixtures thereof in any mixing ratio.
  • the expressions 5-(hydroxymethyl)furan-2-carbaldehyde, 5-hydroxy-2 -furfural and HMF are used synonymously.
  • alkyl means straight and branched alkyl groups. Preferred are straight or branched Ci-C2o-alkyl groups, more preferably C1-C12- alkyl groups, even more preferably Ci-Cs-alkyl groups and in particular Ci-C6-alkyl groups. Examples of alkyl groups are particularly methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl,
  • alkyl comprises also substituted alkyl groups, which may carry 1 , 2, 3, 4 or 5 substituents, preferably 1 , 2 or 3 substituents and particularly preferably 1 substituent, selected from the groups cycloalkyl, aryl, hetaryl, halogen, NE 1 E 2 ,
  • alkyl also comprises alkyl groups which are interrupted by one or more non-adjacent oxygen atoms, preferably alkoxyalkyl.
  • alkylene in the sense of the present invention stands for straight or branched alkanediyl groups with preferably 1 to 6 carbon atoms. These are methylene (-CH2-), ethylene (-CH2-CH2-), n-propylene (-CH2-CH2-CH2-), isopropylene
  • cycloalkyi in the sense of the present invention comprises
  • cycloalkyi groups preferably C5-C7-cycloalkyl groups like cyclopentyl, cyclohexyl or cycloheptyl, which in case they are substituted may carry 1 , 2, 3, 4 or 5 substituents, preferably 1 , 2 or 3 substituents and particularly preferred 1 substituent selected from the groups alkyl, alkoxy and halogen.
  • heterocycloalkyl in the sense of the present invention comprises saturated or partially unsaturated cycloaliphatic groups with preferably 4 to 7, more preferably 5 or 6 ring atoms, in which 1 , 2, 3 or 4 ring atoms may be substituted with heteroatoms, preferably selected from the elements oxygen, nitrogen and sulfur and which are optionally substituted. In case they are substituted, these
  • heterocycloaliphatic groups examples include pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, tetrahydropyranyl and dioxanyl.
  • aryl in the sense of the present invention comprises unsubstituted and substituted aryl groups and preferably stands for phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl or naphthacenyl, more preferably phenyl or naphthyl.
  • aryl groups may carry preferably 1 , 2, 3, 4 or 5 substituents, more preferably 1 , 2 or 3 substituents and particularly preferred 1 substituent.
  • substituents are preferably selected from the groups alkyl, alkoxy, carboxyl, carboxylate, trifluoromethyl, -SO3H, sulfonate, NE 1 E 2 , alkylene- NE 1 E 2 , nitro, cyano and halogen.
  • a preferred fluorinated aryl group is
  • heterocycloaromatic groups preferably pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotriazolyl, 1 ,2,3-triazolyl, 1 ,3,4-triazolyl and carbazolyl in which in case these heterocycloaromatic groups are substituted they may carry preferably 1 , 2 or 3 substituents selected from the groups alkyl, alkoxy, carboxyl, carboxylate, -SO3H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , trifluoromethyl and halogen.
  • a preferred substituted indolyl group is 3-methylindolyl.
  • Carboxylate and sulfonate in the sense of the present invention preferably stand for a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or metal sulfonate, a carboxylic acid ester or sulfonic acid ester or a carboxylic acid amide or sulfonic acid amide.
  • esters with Ci-C4-alkanols like methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol.
  • Preferred are also the primary amides and their N-alkyl and
  • heterocycloalkyl and “hetaryl” apply accordingly to the expressions “alkoxy”,
  • acyl in the sense of the present invention stands for alkanoyl groups or aroyl groups with preferably 2 to 1 1 , more preferably 2 to 8 carbon atoms, for example acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, 2-ethylhexanoyl, 2-propylheptanoyl, benzoyl and naphthoyl.
  • the groups NE 1 E 2 , NE 4 E 5 and NE 7 E 8 are preferably selected from N,N-dimethylamino, ⁇ , ⁇ -diethylamino, N,N-dipropylamino, ⁇ , ⁇ -diisopropylamino, N,N-di-n-butylamino, N,N-di-tert-butylamino, ⁇ , ⁇ -dicyclohexylamino and N,N-diphenylamino.
  • Halogen stands for fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
  • M + stands for a cation equivalent, which means a monovalent cation or the part of a polyvalent cation representing a positive single charge.
  • the cation M + is only a counter ion which neutralizes negatively charged substituents like the COO " or the sulfonate group and which can principally be selected arbitrarily.
  • Preferred are alkaline metal ions, in particular Na + , K + and Li + ions, or onium ions like ammonium ions, mono-, di-, tri-, tetraalkylammonium ions, phosphonium ions, tetraalkylphosphonium ions and tetraarylphosphonium ions.
  • anion equivalent X- which is only a counter ion for positively charged substituents like the ammonium group and which can principally be selected arbitrarily among monovalent anions and the parts of polyvalent anions which correspond to a single negative charge.
  • halogenides X " in particular chloride and bromide.
  • sulfates and sulfonates in particular S0 4 2" , tosylate, trifluoromethane sulfonate and methylsulfonate.
  • Condensed ring systems are aromatic, heteroaromatic or cyclic compounds which have fused-on rings obtained via anellation.
  • Condensed ring systems consist of two, three or more than three rings. Depending on the type of connection, one distinguishes between ortho-anellation and peri-anellation. In case of ortho-anellation each ring has two atoms in common with each adjacent ring. In case of peri-anellation a carbon atoms belongs to more than two rings.
  • Preferred among the condensed ring systems are ortho-condensed ring systems.
  • composition comprising hydroxmethylfurfural
  • bishydroxymethylfuran or mixtures thereof is a composition, wherein at least one component of the composition is 5-(hydroxmethyl)furfural (HMF),
  • the composition consists of 5-(hydroxmethyl)furfural, e.g. HMF, without further components.
  • the composition consists of 2,5-bishydroxymethylfuran, e.g. BHMF, without further components.
  • the composition consists of 5-(hydroxmethyl)furfural and 2,5-bishydroxymethylfuran without further components.
  • the composition comprising hydroxmethylfurfural, bishydroxymethylfuran or mixtures thereof, in particular 5-(hydroxmethyl)furfural (HMF), 2,5-bishydroxymethylfuran or mixtures thereof, is subjected to a hydrogenation in a liquid reaction medium in the presence of a transition metal catalyst complex.
  • HMF 5-(hydroxmethyl)furfural
  • a homogeneous transition metal catalyst complex is used. That means the transition metal catalyst complex is dissolved in the liquid reaction medium under the reaction condition. In other words, the transition metal catalyst complex is in the same phase as the reactants, in particular the composition
  • the liquid reaction medium can comprise at least one ligand in excess.
  • the liquid reaction contains free ligands that are not bound to the transition metal complex.
  • the free ligands are selected from the phosphorous containing ligands defined in the following.
  • the liquid reaction medium comprises at least one 1 , 1 '-biaryl-diol. Suitable and preferred 1 ,1 '-biaryl-diols are defined in the following.
  • the transition metal of the transition metal catalyst complex is selected from metals of groups 8, 9 and 10 of the periodic table of the elements according to lUPAC.
  • the metal of the transition metal catalyst complex is selected from ruthenium, rhenium, iridium, nickel, platinum and palladium, in particular ruthenium and nickel, especially ruthenium.
  • the transition metal catalyst complex comprises at least one ligand containing at least one phosphorus atom which is capable of coordinating to the transition metal.
  • the ligand is selected from organo phosphines, organo phosphites, organo phosphonites, organo phosphinites and organo phosphoramidites.
  • Organo phosphines are derived from phosphines (also called phosphanes), wherein one or more hydrogens are replaced by an organic substituent.
  • Organo phosphites are esters of phosphonic acid P(OH)3, having the general structure P(OR)3, wherein R is an organic substituent.
  • Organo phosphonites are esters of the phosphonous acid HP(OH)2, having the general structure P(OR)2R', wherein R and R' are the same or different organic substituents.
  • Organo phosphinites are esters of the phosphinous acid H2P(OH), having the general structure (P(OR)R'2), wherein R and R' are the same or different organic substituents.
  • Organo phosphoramidites are formally derived from organo phosphites, wherein at least one OR radical substituent is replaced by amid radical NR2, wherein R is hydrogen or an organic substituents.
  • the at least one ligand is selected from compounds of formulae (I) or (II)
  • R A , R B , R c , R D , R E , R F and R G are independently from each other alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the alkyl radicals may carry 1 , 2, 3,
  • R A and R B and/or R c and R D and/or R E and R F together with the P atom and, if present, the groups X 1 , X 2 , X 5 and X 6 to which they are bound, are a 5- to 8-membered heterocycle which is optionally fused with one, two or three groups selected from cycloalkyl, heterocycloalkyl, aryl and heteroaryl, wherein the heterocycle and, if present, the fused-on groups independently from each other may each carry 1 , 2, 3 or 4 substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, mercapto, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, carboxyl, SO3H, sulfonate, NE 4 E 5 , NE 4 E 5 E 6+ X " , nitro, alkoxycarbonyl, formyl, acyl and
  • R x , Ry and R z are independently from each other hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl
  • Y is a divalent bridging group which contains carbon atoms
  • a, b, c, d, e and f are independently from each other 0 or 1 .
  • the transition metal catalyst complex comprises at least one ligand selected from compounds of formulae (I) or (I I), wherein
  • R A , R B , R c , R D , R E , R F and R G are independently from each other alkyl, aryl or heteroaryl, wherein the alkyl, aryl or heteroaryl radicals may carry 1 , 2, 3, 4 or 5 substituents selected from alkoxy, NE 1 E 2 , NE 1 E 2 E 3+ X " , wherein E 1 , E 2 and E 3 are the same or different and are selected from hydrogen or alkyl and X " is an anion equivalent,
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 and X 9 are O
  • Y is a divalent bridging group which contains carbon atoms
  • a, b, c, d, e, f, g, h and i are independently from each other 0 or 1 .
  • the at least one transition metal catalyst comprises at least one ligand selected from compounds of formulae (I I I) or
  • Y is a divalent bridging group which contains carbon atoms
  • Q 1 , Q 2 and Q 3 are independently from each other a divalent bridging group of the formula (V),
  • R e1 , R e2 , R e3 , R e4 , R e5 , R e6 , R e7 and R e8 are independently from each other hydrogen, in each case unsubstituted or substituted alkyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl, hetaryloxy, halogen, hydroxy, mercapto, cyano, nitro, formyl, acyl, carboxy, carboxylate, alkylcarbonyloxy, carbamoyl, SO3H, sulfonate or NE 7 E 8 wherein E 7 and E 8 are the same or different and are selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl, wherein two adjacent radicals R e1 to R e8 together with the carbon atoms
  • a 1 is a single bond, O, S, NR a31 , SiR a32 R a33 or Ci-C 4 -alkylene, which may have a double bond and/or which may be substituted with alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or which may be interrupted by O, S, NR a31 or SiR a32 R a33 , wherein R a31 , R a32 and R a33 are independently from each other hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl
  • R G is alkyl or aryl, wherein the alkyl or aryl radicals may carry 1 , 2, 3, 4 or 5 substituents selected from alkoxy, NE 1 E 2 , NE 1 E 2 E 3+ X " , wherein E 1 , E 2 and E 3 are the same or different and are selected from hydrogen or alkyl and X " is
  • B is a single bond
  • a, b, c, d, e, f, g, h and i are independently from each other 0 or 1.
  • R e1 , R e2 , R e3 , R e4 , R e5 , R e6 , R e7 and R e8 are independently from each other hydrogen, in each case unsubstituted or substituted alkyl, alkoxy, aryl, hetaryl, wherein two adjacent radicals R e1 to R e8 together with the carbon atoms of the benzene ring to which they are bound may also be a condensed ring system with 1 further ring, and
  • a 1 is a single bond, O or S,
  • R G is alkyl, which may carry 1 , 2, 3, 4 or 5 substituents selected from alkoxy, if i is 0, B is a single bond or N,
  • B is a single bond
  • a, b, c, d, e, f, g, h and i are independently from each other 0 or 1.
  • the divalent bridging group Y is a divalent bridging group which contains carbon atoms.
  • the divalent bridging group Y has preferably the formulae (VIII) or (IX)
  • # denotes the remaining binding sites to the molecule, R', R 1' , R", R" ' , R 111 , R 111' , R IV , R IV' , R v , R v' , R VI , R VI' , R v ", R VI " ' , R vm , R IX , R x , R XI and
  • R XM are each, independently from each other, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, polyalkylenimine, alkoxy, halogen, SO3H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , nitro, alkoxycarbonyl, carboxyl, acyl or cyano, wherein E 1 and E 2 are identical or different and are selected from hydrogen, alkyl, cycloalkyl and aryl, wherein two adjacent radicals R r , R" ' , R'" ' , R IV' , R v' , R vr , R vm' together with the carbon atoms of the benzene ring to which they are bound may also be a condensed ring system with 1 , 2 or 3 further rings, wherein the ring atoms selected from carbon, oxygen and sulfur
  • R XM are each, independently from each other, hydrogen, alkyl, aryl, hetaryl, wherein two adjacent radicals R 1' , R" ' , R 111' , R IV' , R v' , R vr , R vm' together with the carbon atoms of the benzene ring to which they are bound may also be a condensed ring system with 1 further, wherein the ring atoms selected from carbon, oxygen and sulfur and wherein the condensed ring system may carry 1 , 2 or 3 substituents selected from halogen. ⁇
  • the hydrogenation is performed in a liquid reaction medium comprising at least ligand of the formula P, wherein the reaction medium additionally comprises at least on 1 ,1 '-biaryl-diol.
  • the reaction medium additionally comprises at least on 1 ,1 '-biaryl-diol.
  • Preferred 1 ,1 '-biaryl-diols are unsubstituted or substituted 1 ,1 '-biphenyl-2,2'-diols or unsubstituted or substituted 1 ,1 '-binaphthyl-2,2'-diols.
  • 1 '-biaryl-diol is 3,3',5,5'-tetra-tert-butyl- [1 ,1 '-biphenyl]-2,2'-diol.
  • the ligand has at least one phosphorus atom that is bonded via an oxygen atom to the oxgygen-organyl moiety.
  • the transition metal catalyst of the process of the invention can be employed in the form of a preformed metal complex which comprises the metal compound and one or more ligands.
  • the transition metal catalyst is formed in situ in the reaction medium by combining a metal compound, herein also termed pre-catalyst, with one or more suitable ligands to form a catalytically active metal complex in the reaction medium.
  • the transition metal catalyst is formed in situ in the presence of an auxiliary ligand by combining a metal compound, herein also termed pre-catalyst, with one or more auxiliary ligands to form a catalytically active metal complex in the reaction medium.
  • Suitable pre-catalysts are selected from neutral metal complexes, oxides and salts of metals of groups 8, 9 and 10 of the periodic table of the elements.
  • Preferred pre- catalysts are selected from metal complexes, oxides and salts of ruthenium, rhenium, iridium, nickel, platinum or palladium.
  • Ruthenium compounds that are useful as pre-catalyst are, for example,
  • Iridium compounds that are useful as pre-catalyst are, for example, [lrCI 3 -H 2 0], KlrCI 4 , K 3 lrCI 6 , [lr(COD)CI] 2 , [lr(cyclooctene) 2 CI] 2 , [lr(ethene) 2 CI] 2 , [lr(Cp)CI 2 ] 2 , [lr(Cp * )CI 2 ] 2 ,
  • Nickel compounds that are useful as pre-catalyst are, for example [Ni(COD) 2 ], Ni(CO) 4 , NiCI 2 , NiBr 2 , Nil 2 , Ni(OAc) 2 [Ni(AcAc) 2 ], [Ni(CI) 2 (TMEDA)], [Ni(CI) 2 (DME)],
  • nickel(ll)hexafluroacetlyacetonate bis(N,N'-di-t-butylacetamidinato)nickel(ll), nickel(ll)oxalate, Ni(N0 3 ) 2 , nickel(ll)stearate, Ni(S0 4 ), nickel(ll)tetrafluoroborate hexahydrate, nickel(ll)trifluoroaceylacetonate dehydrate,
  • Rhenium compounds that are useful as pre-catalyst are, for example
  • ammoniumperrhenate chlorotricarbonyl(2,2'-bipyridine)rhenium(l),
  • Platinum compounds that are useful as pre-catalyst are, for example ammonium tetrachloroplatinate(ll), bis(tri-t-butylphosphine)platinum (0),
  • Palladium compounds that are useful as pre-catalyst are, for example allyl(cyclopentadienyl)palladium(ll), bis[(trimethylsilyl)methyl](1 ,5- cyclooctadiene)palladium(ll), allylpalladium chloride dimer, ammonium
  • tetrachloropalladate(ll) bis[1 ,2-bis(diphenylphosphino)ethane]palladium(0), bis(dibenzylideneacetone)palladium(0), trans- bis(dicyclohexylamine)bis(acetato)palladium(ll), bis(2-methylallyl)palladium chloride dimer, bis(tri-t-butylphosphine)palladium(0), bis(tricyclohexylphosphine)palladium(0), bis(tri-o-tolylphosphine)palladium(0), chloromethyl(1 ,5-cyclooctadiene)palladium(ll), diacetato[1 ,3-bis(diphenylphosphino)propane]palladium(ll),
  • palladium(ll) bromide palladium(ll) chloride, palladium(ll) hexafluoroacetylacetonate, palladium(ll) iodide, palladium(ll) sulfate, palladium(ll) trifluoroacetate, palladium(ll) trimethylacetate, tetrakis(triphenylphosphine)palladium(0),
  • COD denotes 1 ,5-cyclooctadiene
  • Cp denotes cyclopentadienyl
  • Cp * denotes pentamethylcyclopentadienyl
  • binap denotes 2,2'-bis(diphenylphosphino)-1 ,1 '-binaphthyl.
  • a substoichiometric amount of catalyst is generally used, with the amount of catalyst typically being not more than 50 mol%, frequently not more than 20 mol% and in particular not more than 10 mol% or not more than 5 mol%, based on the amount of hydrogenable composition selected from
  • a substoichiometric amount of catalyst is generally used, with the amount of catalyst typically being not more than 50 mol%, frequently not more than 20 mol% and in particular not more than 10 mol% or not more than 5 mol%, based on the amount of HMF or BHMF in the composition comprising
  • a substoichiometric amount of catalyst is generally used, with the amount of catalyst typically being not more than 50 mol%, frequently not more than 20 mol% and in particular not more than 10 mol% or not more than 5 mol%, based on the amount of HMF and BHMF in the composition comprising
  • the process of the invention is generally carried out at temperatures in the range from -20°C to 300°C, preferably in the range from 50°C to 200°C and particularly preferably in the range from 80°C to 180°C. Temperatures below 150°C have surprisingly been found to be particularly advantageous.
  • Suitable solvents are selected from aliphatic hydrocarbons, aromatic hydrocarbons, amides, ureas, nitriles, sulfoxides, sulfones, alcohols, esters, carbonates, ethers, water and mixtures thereof.
  • Preferred solvents are aliphatic hydrocarbons such as pentane, hexane, heptane, octane or
  • aromatic hydrocarbons such as benzene, toluene, xylenes, ethylbenzene, mesitylene or benzotrifluoride;
  • amides such as dimethylformamide, diethylformamide, /V-methylpyrrolidone, N-ethylpyrrolidone or dimethylacetamide;
  • ureas such as tetramethylurea, ⁇ , ⁇ -dimethylimidazolinone (DMI) and
  • DMPU ⁇ , ⁇ -dimethylpropyleneurea
  • - nitriles such as acetonitrile or propionitrile
  • sulfoxides such as dimethyl sulfoxide
  • sulfones such as sulfolane
  • alcohols such as methanol, ethanol, propanol or isopropanol
  • esters such as methyl acetate, ethyl acetate, /-butyl acetate;
  • ethers such as dioxane, tetrahydrofuran, diethyl ether, dibutyl ether, methyl /-butyl ether, diisopropyl ether or diethylene glycol dimethyl ether;
  • mixtures of two or more of the aforementioned solvents can also be used.
  • the hydrogenation can principally be performed according to all processes known to a person skilled in the art which are suitable for the hydrogenation of a HMF-comprising composition.
  • the hydrogen used for the hydrogenation can be used in pure form or, if desired, also in the form of mixtures with other, preferably inert gases, such as nitrogen or argon. Preference is given to using hydrogen in undiluted form.
  • the hydrogenation is typically carried at a hydrogen pressure in the range from 0.1 to 100 bar, preferably in the range from 1 to 50 bar, more preferably in the range from 1 to 5 bar.
  • the hydrogenation can principally be performed continuously, semicontinuously or discontinuously. Preference is given to a continuous process.
  • the hydrogenation can principally be performed in all reactors known by a person in the art for this type of reaction and therefore, will select the reactors accordingly.
  • Suitable pressure-resistant reactors are also known to a person skilled in the art and are described for example in "Ullmanns Enzyklopadie der ischen Chemie", Vol. 1 , 3rd edition, 1951 , page 769 ff.
  • an autoclave is employed which may have an internal stirrer and an internal lining.
  • composition obtained in the hydrogenation process of the invention comprises cis- (tetrahydrofuran-2,5-diyl)dimethanol and trans-(tetrahydrofuran-2,5-diyl)dimethanol.
  • the obtained composition comprises cis-(tetrahydrofuran-2,5-diyl)dimethanol and trans-(tetrahydrofuran-2,5- diyl)dimethanol, wherein the ratio of cis-(tetrahydrofuran-2,5-diyl)dimethanol to trans- (tetrahydrofuran-2,5-diyl)dimethanol is in the range of 7:1 to 1 :1 , preferably in the range of 5:1 to 1 :1 .
  • a further aspect of the invention relates to a composition
  • a composition comprising
  • the invention relates also to the composition obtained by the process according to the invention and described above comprising cis-(tetrahydrofuran-2,5-diyl)dimethanol and trans-(tetrahydrofuran-2,5-diyl)dimethanol, wherein the ratio of cis-(tetrahydrofuran-2,5- diyl)dimethanol to trans-(tetrahydrofuran-2,5-diyl)dimethanol is in the range of 7:1 to 1 :1 , preferably in the range of 5:1 to 1 :1.
  • a further aspect of the invention is the use of a transition metal complex according to the process as described above as hydrogenation catalyst for compositions comprising hydroxymethylfurfural, bishydroxymethylfuran or mixtures thereof.
  • a further aspect of the invention is the use of the composition comprising
  • cis-(tetrahydrofuran-2,5-diyl)dimethanol and trans-(tetrahydrofuran-2,5-diyl)dimethanol obtained by the process of according to the invention and described above for polymerizing reactions.
  • the work-up of the reaction mixture obtained in the hydrogenation of the inventive process and the isolation of cis-(tetrahydrofuran-2,5-diyl)dimethanol and trans- (tetrahydrofuran-2,5-diyl)dimethanol are effected in a customary manner, for example by filtration, an aqueous extractive work-up or by a distillative separation, for example under reduced pressure.
  • the cis-(tetrahydrofuran-2,5-diyl)dimethanol and trans- (tetrahydrofuran-2,5-diyl)dimethanol may be obtained in sufficient purity by applying such measures or a combination thereof, obviating additional purification steps.
  • trans-THF-glycol trans-(tetrahydrofuran-2,5-diyl)dimethanol
  • BINAP 2,2'-bis(diphenylphosphanyl)-1 ,1 '-binaphthalene
  • A DM-BINAP: 2,2'-bis(bis(3,5-dimethylphenyl)phosphanyl)-1 ,1 '- binaphthalene
  • B 2,2'-bis(bis(3,5-dimethylphenyl)phosphanyl)-1 ,1 '- binaphthalene
  • DtBM-SEGPHOS 5,5'-bis(bis(3,5-di-tert-butyl-4-methoxyphenyl)phos- phanyl)-4,4'-bibenzo[o][1 ,3]dioxole (D)
  • DtBM-MeOBIPHEP (6,6'-dimethoxy-[1 ,1 '-biphenyl]-2,2'-diyl)bis(bis(3,5-di-tert- butyl-4-methoxyphenyl)phosphane) (E)
  • Kelliphite 2,2'-bis((4,8-di-te/f-butyl-1 ,2,10,1 1 -tetramethyldibenzo[o',/f
  • L2 2,2'-bis((bis(3-methyl-1 indol-1 -yl)phosphanyl)oxy)-1 ,1 '- biphenyl (H)
  • L3 1 ,1 ',1 ",1 "'-(((3,3',5,5'-tetramethyl-[1 , 1 '-biphenyl]-2,2'- diyl)bis(oxy))bis(phosphanetriyl))tetrakis(3-methyl-1 ⁇ indole) (I)
  • BiPhePOS 6,6'-((3,3'-di- fert-butyl-5,5kjimethoxy-[1 ,1 '-biphenyl]-2,2'- diyl)bis(oxy))didibenzo[ d, f[[ ⁇ ,3,2]dioxaphosphepine
  • MonoPHOS I N, Ndimethyldinaphtho[2,1 - d.V,2'- /][1 ,3,2]dioxa- phosphepin-4-amine (L)
  • MonoPHOS 2 N, NBis(( S)-1 -phenylethyl)dibenzo[ ,/[[1 ,3,2]dioxa- phosphepin-6-amine (M)
  • MonoPHOS 3 N, Nd i m et hy I-8 , 9 , 10 , 1 1 , 12 , 13 , 14 , 15-octa hyd ro- dinaphtho[2,1 - ⁇ 1 ',2'- /[[1 ,3,2]dioxaphosphepin-4-amine
  • DIOL 1 3,3',5,5'-tetra- fert-butyl-[1 ,1 ⁇ )iphenyl]-2,2'-diol
  • reaction was performed under argon atmosphere.
  • a schlenk tube was charged with phosphorus trichloride (15.5 g; 1 12.9 mmol) in dry THF (200 ml).
  • a mixture of 3-methylindol (29.6 g; 225.8 mmol), triethylamine (29.6 g; 295 mmol) in THF (100 ml) was added dropwise at room temperature.
  • the obtained mixture was heated under reflux for 16 hours.
  • the reaction mixture was allowed to cool down to room
  • reaction was performed under argon atmosphere.
  • a schlenk tube was charged with phosphorus trichloride (34.4 g; 0.25 mol) in dry THF (200 ml).
  • a mixture of 3-methyl-1 H-indole (70 g; 0.502 mol) and triethylamine (70 g; 0.7 mol) in THF (200 ml) was added at a temperature of 25 °C within two hours. The obtained mixture was stirred for 30 minutes at room temperature and heated under reflux for 16 hours.
  • the reaction mixture was stirred for one hour at a temperature of -20°C to -40°C and heated under reflux for two hours.
  • the reaction mixture was again cooled down to -40°C and a mixture of 2-tert-butyl-6-(3-tert-butyl-2- hydroxy-5-methoxy-phenyl)-4-methoxy-phenol (UCC-II Biphenol) (17.9 g; 50 mmol) and triethylamine (25 g; 250 mmol) in dry toluene (200 ml) was added within two hours at a temperature of -20°C to -40°C.
  • the reaction mixture was stirred for one hour at a temperature of -20°C to -40°C and heated under reflux for two hours.
  • HMF typically 100 mg, 1 molar equivalent
  • the catalyst 4.5 mol% placed in a microwave vial, along with the solvent (10 ml. toluene) and sealed.
  • the solution was sonicated to allow full dissolution of the substrate and catalyst (ca. 5-15 min).
  • the solution was transferred to an IS -purged glass autoclave under a flow of N2.
  • the autoclave was tightly closed, purged with N2, then H2 (typically, 3 times each, 5 bar), and finally pressurized with H2 to the desired pressure (typically 10 bar).
  • An oil bath was used to bring the autoclave to the desired temperature
  • HMF typically 100 mg, 1 molar equivalent
  • HMF:BHMF:THF-glycol was determined by H 1 NMR, and the ratio of cis. trans THF- glycol was determined by integration of the relevant carbon peaks by 13 C-NMR, as per literature (G. Bottari, A. J. Kumalaputri, K. K. Krawczyk, B. L. Feringa,H. J. Heeres, K. Barta, ChemSusChem 2015, 8, 1323 - 1327).
  • General procedure 3 Auxiliary guided catalyst
  • HMF typically 100 mg, 1 molar equivalent
  • the auxiliary ligand typically 10 mol%
  • the metal pre catalyst Ru(methylallyl)2(COD)
  • 1 1 mg, 4.5 mol% placed in a microwave vial, along with the solvent (10 ml_, typically toluene) and sealed.
  • the solution was shaken (ca. 250-300 rpm) for 1 -4 h to allow full dissolution of the substrate, the binding of the auxiliary to the substrate and
  • the solution was transferred to an IS -purged glass autoclave under a flow of N2.
  • the autoclave was tightly closed, purged with N2, then H2 (typically, 3 times each, 5 bar), and finally pressurized with H2 to 10 bar.
  • An oil bath was used to bring the autoclave to the desired temperature (typically 120°C), and was stirred for the specified duration (typically overnight).
  • a sample was collected (while the autoclave was still at the indicated temperature), the solvent was removed in vacuo, the resulting oil was dissolved in afe-DMSO and analysed by NMR.
  • the ratio of HMF:BHMF:THF-glycol was determined by 1 H-NMR, and the ratio of cis.
  • the result of the hydrogenation is reported as a ratio of the starting material (HMF), the intermediate (BHMF) and the desired product (THF-glycol).
  • the amount of BHMF is normalised to 1 to facilitate comparison of the results.

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Abstract

L'invention concerne un procédé d'hydrogénation d'une composition comprenant de l'hydroxyméthylfurfural, du bishydroxyméthylfurane ou des mélanges de ceux-ci pour obtenir une composition comprenant du cis- (tétrahydrofurane -2,5-diyle) diméthanol et trans- (tétrahydrofurane -2,5-diyl) diméthanol. L'invention concerne également une composition comprenant du cis- (tétrahydrofuran -2,5-diyl) diméthanol et du trans- (tétrahydrofurane -2,5-diyl) diméthanol. En outre, l'invention concerne également l'utilisation d'un complexe de métal de transition en tant que catalyseur d'hydrogénation pour une composition comprenant de l'hydroxyméthylfurfural, du bishydroxyméthylfurane ou des mélanges de ceux-ci. L'invention concerne également l'utilisation de la composition comprenant du cis- (tétrahydrofuran -2,5-diyl) diméthanol et du trans- (tétrahydrofurane -2,5-diyl) diméthanol pour des réactions de polymérisation.
PCT/EP2017/078838 2016-11-11 2017-11-10 Hydrogénation d'une composition comprenant de l'hydroxyméthylfurfural, du bishydroxyméthylfurane ou des mélanges de ceux-ci WO2018087270A1 (fr)

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