EP1558385A1 - Catalyseur et procede de carbonylation d'oxiranes - Google Patents

Catalyseur et procede de carbonylation d'oxiranes

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Publication number
EP1558385A1
EP1558385A1 EP03766379A EP03766379A EP1558385A1 EP 1558385 A1 EP1558385 A1 EP 1558385A1 EP 03766379 A EP03766379 A EP 03766379A EP 03766379 A EP03766379 A EP 03766379A EP 1558385 A1 EP1558385 A1 EP 1558385A1
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EP
European Patent Office
Prior art keywords
catalyst
carbonylation
lactones
transition metal
bis
Prior art date
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EP03766379A
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German (de)
English (en)
Inventor
Gerrit Luinstra
Bernhard Rieger
Markus Allmendinger
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • 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
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0202—Polynuclearity
    • B01J2531/0208—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Definitions

  • the invention relates to the production of lactones by catalytic carbonylation of oxiranes in the presence of a catalyst system, a corresponding catalyst system and the use thereof.
  • the invention relates in particular to the production of enantiomerically enriched four-ring lactone mixtures, starting from racemic epoxides, by catalytic carbonylation. Catalysis is achieved using a two-component catalyst system.
  • the optically enriched mixture of R- and S-lactones can be converted into a biodegradable polyester.
  • Lactones are valuable compounds for the production of biodegradable polyesters, as described for example in EP-A 0 688 806. These polyesters are used in many different ways, for example as a polyol in the manufacture of polyurethane or as a material.
  • ß-alkyl hydroxyalkanoate polyesters strongly depend on stereoregularity.
  • atactic polyhydroxybutyrate (PHB) is a viscous oil and isotactic PHB is a solid with the character of a material.
  • Isotactic PHB can be obtained from enantiomerically pure butyrolactone.
  • Enantiomerically pure butyrolactone can either be prepared by a complex organic synthesis using protective groups or by biochemical means.
  • synthetic access to these compounds is very complex and costly, especially for large-scale applications.
  • the purification is also very expensive.
  • the processing of purely isotactic PHB by means of injection molding is problematic since the decomposition temperature is very close to the melting point.
  • JP-A-09 169 753 describes the carbonylation of epoxides to lactones in a continuous reactor using Co 2 CO 8 as a catalyst. The sales are only 30%. This means that a separation and recirculation device is required to achieve a high yield and purity of the lactone.
  • GB-A-1,020,575 relates to a process for the preparation of polymers of ⁇ -lactones. Carbon monoxide and a 1,2-epoxide are reacted to form a ⁇ -lactone as an intermediate. Dicobaltoctacarbonyl is used as a catalyst.
  • a promoter can be used which is selected from metal halides such as potassium iodide and quaternary ammonium halides such as
  • Tetraethylammonium Tetraethylammonium.
  • the yields of lactone are less than 10%
  • the main fractions of the products are polyhydroxypropionesters.
  • the reaction is carried out in a complicated manner with several pressure stages.
  • EP-B-0 577 206 relates to the carbonylation of epoxides on a catalyst system comprising a cobalt source and a hydroxyl-substituted pyridine compound, in particular 3-hydroxypyridine or 4-hydroxypyridine.
  • the carbonylation is preferably carried out in the presence of a hydroxy compound such as water or alcohols.
  • the activities of the catalysts used are relatively low and isolation of the lactones is not described. It was also observed that a change in the reaction mixture occurs after the carbonylation has ended. Polymerization of the lactone takes place within 24 hours. It follows from this that the lactone in the reaction mixture is not unreactive. It is also known that lactones can be polymerized under the influence of pyridines.
  • Chemistry Letters 1980, pages 1549 to 1552 relates to the reaction of epoxides with carbon monoxide on a rhodium complex as a catalyst. The yields are a maximum of 70%.
  • the object of the invention is to provide an inexpensive and efficient method for producing and isolating optically enriched ⁇ -lactones.
  • the object is achieved according to the invention by a process for the preparation of lactones by catalytic carbonylation of oxiranes, a catalyst system consisting of
  • At least one carbonylation catalyst A composed of neutral or anionic transition metal complexes of metals from groups 5 to 11 of the periodic table of the elements and
  • At least one chiral Lewis acid B is used as a catalyst, with the exception of [(salph) A1 (THF) 2 ] [Co (CO) 4 ].
  • a catalyst system comprising two components, a carbonylation catalyst A and a chiral Lewis acid B, leads to lactones with an optical enrichment in the carbonylation of oxiranes.
  • the lactones obtained can advantageously be used for the production of biodegradable polyesters, it being possible for the polyesters to be used as polyol in the production of polyurethane or as a material.
  • the catalyst system used according to the invention preferably contains 0.1 to 1000 mol, particularly preferably 1 to 10 mol, of component B per mol of component A.
  • Suitable metals are, for example, vanadium, ruthenium, chromium, molybdenum, tungsten, manganese, rhenium, iron, osmium, cobalt, iridium, rhodium and nickel.
  • Such complexes could also be generated in situ, see EP-A 0 577 206.
  • the ligands are usually present as neutral ligands.
  • the number of ligands depends on the metal and depends on the coordinative saturation of the transition metal in the ground state.
  • Suitable neutral ligands are, for example, the carbon monoxide, nitro, nitroso, carbonate, ether, sulfoxide, amide, nitrile or phosphine ligand. These ligands are generally coordinated to the transition metal via a lone pair of electrons. Carbon monoxide is preferably used as the ligand.
  • Different ligands can also be present side by side in a transition metal compound (A), as in Co (CO) 6 (PMe 2 Ph) 2 .
  • Preferred transition metal complexes are (A) Co 2 (CO) 8 , Ru 3 (CO) 12 , Rh 4 (CO) ⁇ 2> Rh 6 (CO) ⁇ 6 , Co 4 (CO) 12 , Fe 2 (CO) 10 , Fe 2 (CO) 9 , Ni (CO) 4 , Mn 2 (CO) 10 , Mo (CO) 6 and W (CO) 6 or mixtures thereof.
  • Ru 3 (CO) ⁇ 2 , Co 4 (CO) 12 , Co (CO) 3 (NO), Ni (CO) 4 and Mn 2 (CO) 10 , in particular Co 2 (CO) 8 are particularly preferred.
  • Mixtures of different neutral complexes can also be used.
  • transition metal complex compounds (A) are also to be understood as those compounds in which at least one central metal or one ligand unit has a negative formal charge.
  • Suitable anionic transition metal compounds (A) have a central metal from groups 5 to 11, preferably from groups 8 to 10 of the periodic table of the elements. Examples of suitable metals are cobalt, iron, rhodium and ruthenium. Transition metals (A) based on the metals cobalt, ruthenium and rhodium are particularly preferably used. Mono- or multinuclear complexes A can be used.
  • the ligands are usually also present as neutral ligands.
  • the number of ligands depends on the metal and depends on the coordinative saturation of the transition metal in the ground state.
  • Suitable neutral ligands are, for example, the carbon monoxide, nitro, nitroso, carbonate, ether, sulfoxide, amide, nitrile or phosphine ligand. These ligands are generally coordinated to the transition metal via a lone pair of electrons. Carbon monoxide is preferably used as the ligand.
  • Different ligands can also be present side by side in an anionic transition metal compound A, for example as in [P (Ph) 3 ] Co (-l) (CO) 3 , [P (Me 2 Ph)] Co (-l) (CO) 3 , Co (-l) (CO) 3 (CNPh). These connections can also be generated in situ.
  • Suitable anionic transition metal complex compounds A fall, for example, under the following formula (I):
  • transition metal of the 8th to 10th group of the Periodic Table of the Elements in particular cobalt and rhodium, with the formal charge -1
  • M ⁇ metal of the 1st or 2nd group of the Periodic Table of the Elements Zn or Hg, in particular Na, K, Cs, Mg, Ca, Zn and Hg, bis (1xiarylphosphine) iminium, trityl or T (R) 4 with
  • R, R 'independently represent H, alkyl, aryl, alkaryl or aralkyl
  • the radicals R, R ' are, for example, hydrogen, straight-chain or branched Ci to Cio-alkyl such as methyl, ethyl, n- or i-propyl, n-, i- or t-butyl or n- or i-pentyl, C. 6 - to -C 4 -aryl such as phenyl or naphthyl or alkylaryl with 1 to 10 carbon atoms in the alkyl and 6 to 14 carbon atoms in the aryl part such as benzyl in question.
  • Suitable aromatic radicals also include heterocycles and are, for example, five- or six-membered monocycles such as pyridyl and phenyl, and fused systems such as anthracene.
  • non-metallic cations M tetraphenyl, tetramethyl, tetraethyl and tetra-n-butylammonium, phosphonium and arsenium and bis (triarylphosphine) imine are preferred.
  • Particularly suitable aryl radicals in the bis (triarylphosphine) iminium cation are phenyl and naphthyl, with bis (tri.phenylphospMn) iminium being preferred.
  • Possible metallic cations M ⁇ include alkali and alkaline earth metal cations. Lithium, sodium, potassium and cesium are preferred.
  • Amonic transition metal complexes A selected from the group comprising Li [Co (CO) 4 ], Na [Co (CO) 4 ], K [Co (CO) 4 ], Cs [Co (CO) 4 ], ( R 4 N) [Co (CO) 4 ], (R 4 P) [Co (CO) 4 ], (R 4 As) [Co (CO) 4 ], (PPN) [Co (CO) 4 ], Li [Rh (CO) 4 ], Na [Rh (CO) 4 ], K [Rh (CO) 4 ], Cs [Rh (CO) 4 ], (R 4 N) [Rh (CO) 4 ], (R4P ) [Rh (CO) 4 ], (R 4 As) [Rh (CO) 4 ], (PPN) [Rh (CO) 4 ] 3 Li [Ir (CO) 4 ], Na [Ir (CO)
  • anionic complexes A with cobalt in the oxidation state -1 tetraphenylphosphonium, tetraphenylarsenium, tettaphenylammonium, tetraethylphosphonium, tetraethylarsenium and tetraemylammonium tetracarbonyl cobaltate and sodium tetracarbonyl cobaltate are particularly preferred.
  • anionic transition metal complex compounds The preparation of anionic transition metal complex compounds is generally known to the person skilled in the art. Suitable manufacturing processes can be found, for example, at F.G. Stone, E.W. Abel and G. Wilkinson, "Comprehensive Organometallic Chemistry - The Synthesis, Reactions and Structures of Organometallic Compounds", Pergamon, Oxford, 1982 and F.G. Stone, E.W. Abel and G. Wilkinson, "Comprehensive Organometallic Chemistry II - A Review of the Literature 1982 - 1994", Pergamon Press, Oxford, for example in Vol. 8. Such complexes are also commercially available.
  • the molar ratio of anionic complex or neutral complex (A) in the reaction mixture is usually in the range from 0.01 to 100, preferably from 0.1 to 50, particularly preferably from 0.2 to 10 mol%, based on the amount of oxirane used.
  • Lewis acids B one or more compounds from groups 2 to 13 are generally used. These compounds have a coordinative subsaturation or can split off a ligand (reversibly) under the reaction conditions for the carbonylation, so that subsaturation can occur.
  • Lewis acids B preferentially bind ligands that do not take part in the reaction but exert a controlling effect on the carbonylation.
  • the ligand metal units are chiral and preferably not in the form of a racemic mixture, but enantiomerically pure and with an enantiomeric excess in the reaction mixture.
  • connection B is to be understood to mean connections L n MX m with
  • M Mg, Ca, Sc, Y, rare earth element, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, AI, Ga, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Hf Ta, W, Re, Os, Ir, Pt, Au, Hg, TI, Pb.
  • Preferred M are Ti, Zr, Hf, Cr, Mo, W 5 Co, Rh, Ir, Ni, Pd, Cu, Cd, Al, Mg, Zn, Fe.
  • Particularly preferred M are Cr, Co, Ti, Fe, Ni, Pd.
  • X anion, for example halide, sulfate, sulfite, nitrate, nitrite, carboxylate, sulfide, phosphate, sulfonate, borate.
  • X Cl, sulfonate or carboxylate.
  • L (n) phosphine, cyclopentadienyl or ansa ligands, spearlen, Irnine, oxazoline, alkoxide, phenoxide, carboxylate, where different L can also be connected to one another, and L is chiral.
  • Preferred ligands are columns (1,2-cyclohexanediamino-N, N-bis-3,5-di-t-butylsalicylidene), diphosphines - (such as (2S, 4S) - (-) - (diphenylphosphino) -2- (Diphenylphosphinomethyl) pyrrolidine, (R) - (+) - 2,2'-bis (Diphenylphosphino) - 1,1'-binaphthyl (Binap), R - (+) - 1, 2-bis (diphenylphosphino) propane, ( 4R, 5R) - (-) - o-isopropylidene-2,3-dihydroxy-l, 4-bis (diphenylphosphino) butane (Diop), (lS, 2S) - (+) - l, 2-bis ( diphenylphosphinomethyl) cyclohexane
  • Ethylene bis (4,5,6,7-tetrahydro-l-indenyl), binaphthol, amino acids Possible further ligands are known to the person skilled in the art from asymmetric catalysis with homogeneous organometallic compounds.
  • Preferred compound B is Cr (1,2-cyclohexanediamino-N, N-bis-3,5-di-t-butylsalicylidene) chloride or acetate.
  • oxirane compounds are ethylene oxide as . substituted epoxides suitable. 'These are usually compounds that fall under the following general formula (II):
  • the radicals R 2 here are independently hydrogen, halogen, nitro group - NO 2 , cyano group -CN, ester group -COOR 3 or a hydrocarbon group with 1 to 32 C atoms, which can be substituted.
  • the radicals R 2 can correspond completely or partially or can also represent four different radicals.
  • R 3 may be C ⁇ -12 alkyl, aryl.
  • Geminally substituted epoxides are preferably used, particularly preferably only epoxides substituted in the 1-position.
  • Suitable hydrocarbon groups are, for example, C 1-32 -alkyl such as methyl, ethyl, i- or n-propyl, i-, n- or t-butyl, n-pentyl or n-hexyl, C 2-2 o-alkenyl such as propenyl or Butenyl, C 3-20 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, C 6- 18 aryl such as phenyl or naphthyl, and C -2 o-arylalkyl, for example benzyl.
  • Two R 2 radicals if they are on different C atoms of the epoxy group, can be bridged to form a C 3-2 o-cycloalkylene group.
  • the following groups are particularly suitable as substituents with which the C 1-32 -hydrocarbon group, as also R above, can be substituted: halogen, cyano, nitro, thioalkyl, tert-amino, alkoxy, aryloxy, arylalkyloxy, carbonyldioxyalkyl, carbonyldioxyaryl, Carbonyldioxyarylalkyl, alkoxycarbonyl, aryloxycarbonyl, arylalkyloxyca bonyl, alkylcarbonyl, arylca bonyl, arylalkylcarbonyl, alkylsulfinyl, arylsulfinyl, arylalkylsulfinyl, alkylsulfonyl, arylsulfonyl and arylalkylsulfonyl.
  • the oxirane compound used is preferably ethylene oxide, propylene oxide, butylene oxide (1-butene oxide, BuO), cyclopentene oxide, cyclohexene oxide (CHO), cycloheptene oxide, 2,3-
  • Ethylene oxide (EO), propylene oxide (PO), butylene oxide or i-butene oxide are particularly preferably used, very particularly preferably ethylene oxide and propylene oxide or mixtures thereof.
  • a solvent is also present, usually in small amounts, the main purpose of which is to introduce the catalyst compounds into the polymerization vessel or to keep the oxirane or lactone in solution.
  • catalyst components (A) and (B) By applying the catalyst components (A) and (B) to a particulate support material, for example silica or aluminum oxide, a solvent-free reaction in the sense of a gas phase polymerization is also possible.
  • a particulate support material for example silica or aluminum oxide
  • Suitable solvents include, in particular, polar solvents such as ether compounds, for example tefrahydrofuran, diethyl ether, dioxane, 2,5,8-trioxanone, anisole, dimethoxyethane (DME) and diethylene glycol dimethyl ether (diglyme), tetraglyme and dimethylformamide or dimethyl sulfoxide.
  • polar solvents such as ether compounds, for example tefrahydrofuran, diethyl ether, dioxane, 2,5,8-trioxanone, anisole, dimethoxyethane (DME) and diethylene glycol dimethyl ether (diglyme), tetraglyme and dimethylformamide or dimethyl sulfoxide.
  • the carbonylation is usually carried out under elevated carbon monoxide pressure.
  • the carbon monoxide pressure is preferably carried out in a range from 2 to 250 bar, in particular in a range from 10 to 80 bar.
  • Suitable reaction temperatures are in the range of room temperature, i.e. about 25 ° C to 150 ° C and are preferably set to values in the range of 35 to 90 ° C.
  • the polymerization according to the process of the invention can be carried out batchwise or continuously.
  • the reaction is carried out by first adding the transition metal complexes (A) and the Lewis acid (B) individually, simultaneously or premixed, optionally with cooling, to the reaction vessel.
  • the oxirane compound can also be added to the solution / suspension of the catalyst components before it is transferred to the reaction vessel.
  • the oxirane compound can also be introduced directly into the reaction vessel.
  • the order of addition is generally not critical to the process.
  • the carbonylation is preferably carried out under inert conditions, ie in the absence of moisture and air. Termination of the carbonylation, separation and purification of the lactones can be carried out by generally known methods. For example, the lactone can be isolated in a simple manner by distillation or crystallization.
  • corresponding 3-hydroxypropionic acid lactones can be obtained starting from oxirane compounds.
  • lactones are obtained, the degree of optical purity corresponding directly to the efficiency of the Lewis acid and the percentage conversion of the oxirane.
  • the thermoplastic property profile of the biodegradable polymer class can be controlled, the properties of which can be set very easily and specifically for desired applications.
  • the lactones are preferably a mixture of S- and R-lactones with an excess of one enantiomer.
  • the invention also relates to a process for producing the catalyst used according to the invention by mixing components A and B. Furthermore, the invention relates to the use of the catalyst in carbonylation reactions.
  • the invention opens up the possibility of producing biodegradable materials in the form of polyhydroxyalkanoates using lactones as an intermediate stage on the basis of chemicals which are available on an industrial scale.
  • Polymers of this type have a material character if there is reliable stereoregularity. This can be achieved with the catalyst system via the optical purity, the enantiomers (mixtures). For example, these are present in organically produced material.
  • Cr-salen complex (2) 1,2-benzenediamino-N, N'-bis (3,5-di-t-butylsalicylidene)] chromium (III) chloride was synthesized according to literature [Paddock, R.L .; Nguyen, S.T. J Am. Chem. Soc. 2001, 123, 11498-11499].
  • the carbonylation reactions were carried out in a 100 mL Parr steel autoclave or in a 250 mL Büchi autoclave equipped with a ReactLR TM SiComp TM dipping system from Mettler Toledo. This enables the online analysis of the reaction mixture.
  • NMR spectra were recorded with a Brucker (AMX 400) device.
  • the Cr-salen complex 1 242 mg (0.39 mmol) was added to Na (CoCO 4 ) (0.39 mmol) in rac-propylene oxide (8 mL, 320 eq.) Under ice cooling and under an argon atmosphere.
  • the steel autoclave 100 mL was first evacuated and charged under counter-argon flow. After the solution had been transferred, a carbon monoxide pressure of 60-65 bar was set and the carbonylation was carried out at 25.degree. C. over a period of 1/2 hour (initially the reaction mixture warms up significantly). The reaction was stopped by ice cooling and depressurization to ambient pressure, and the reaction solution obtained was analyzed.
  • Al-salen complex (4) (IR, 2R) - (-) - [1,2-Cyclohexanediamino-N, N'-bis (3,5-di-t-butylsalicylidene)] aluminum (111) chloride was made from the corresponding salen ligand and (Et) 2 AlCl according to the literature-known synthesis of similar compounds [Atwood, DA; Jeiger, LA .; Rutherford, D. Inorg. Chem. 1996, 35, 63-70].
  • the Al-salen complex 4,234 mg (0.39 mmol) was added to Na (CoCO) (0.39 mmol) in rac-propylene oxide (16 mL, 640 eq.) With ice cooling and under an argon atmosphere.
  • the steel autoclave (100 ml) was first evacuated and charged under counter-argon flow. After the solution had been transferred, a carbon monoxide pressure of 60-65 bar was set and the carbonylation was carried out at 50 ° C. over a period of 3 hours.
  • the reaction was stopped by ice cooling and reducing the pressure to ambient pressure, and the reaction solution obtained was analyzed.
  • An NMR of the reaction solution showed a conversion of about 11% of the epoxide to ß-butyrolactone.
  • the reaction mixture of carbonylation 2 is introduced into a distillation device. PO is distilled off at atmospheric pressure. The volatile part of the residue was first recondensed in a high vacuum (lO ⁇ -lO "4 Torr). The recondensed was then finely distilled in a vacuum of 15 mmHg at 60-63 ° C: yield butyrolactone 2.4 g.
  • 1H NMR (CDC1 3 ): ⁇ 1.53 (d, 3H), 3.08 and 3, 57 (dd, 1H)), 4.7 (m, 1H).

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Abstract

La présente invention concerne la préparation de lactones par carbonylation catalytique d'oxiranes, faisant intervenir en tant que catalyseur, à l'exception de [(salph)Al(THF)2][Co(CO)4], un système de catalyseur qui comprend a) au moins un catalyseur de carbonylation A constitué de complexes neutres ou anioniques de métaux de transition des groupes 5 à 11 du tableau périodique des éléments, et b) au moins un acide de Lewis chiral B.
EP03766379A 2002-08-01 2003-07-31 Catalyseur et procede de carbonylation d'oxiranes Ceased EP1558385A1 (fr)

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DE10235316A DE10235316A1 (de) 2002-08-01 2002-08-01 Katalysator und Verfahren zur Carbonylierung von Oxiranen
DE10235316 2002-08-01
PCT/EP2003/008478 WO2004012861A1 (fr) 2002-08-01 2003-07-31 Catalyseur et procede de carbonylation d'oxiranes

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EP (1) EP1558385A1 (fr)
JP (1) JP4634797B2 (fr)
DE (1) DE10235316A1 (fr)
WO (1) WO2004012861A1 (fr)

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US7145022B2 (en) 2006-12-05
WO2004012861A1 (fr) 2004-02-12
JP2006500338A (ja) 2006-01-05
JP4634797B2 (ja) 2011-02-16
DE10235316A1 (de) 2004-02-12
US20050240032A1 (en) 2005-10-27

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