EP0876213A1 - Peroxo group-containing metal complexes with amine oxide, phosphane oxide, arsane oxide, pyridin-n-oxide or pyridine ligands as epoxidation catalysts - Google Patents

Peroxo group-containing metal complexes with amine oxide, phosphane oxide, arsane oxide, pyridin-n-oxide or pyridine ligands as epoxidation catalysts

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Publication number
EP0876213A1
EP0876213A1 EP96931020A EP96931020A EP0876213A1 EP 0876213 A1 EP0876213 A1 EP 0876213A1 EP 96931020 A EP96931020 A EP 96931020A EP 96931020 A EP96931020 A EP 96931020A EP 0876213 A1 EP0876213 A1 EP 0876213A1
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EP
European Patent Office
Prior art keywords
oxide
groups
radicals
catalysts
mmol
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EP96931020A
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German (de)
French (fr)
Inventor
Michael Schulz
Joaquim Henrique Teles
Jörg SUNDERMEYER
Günter Wahl
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • 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
    • B01J31/18—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
    • B01J31/1845—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 phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • 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
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72—Epoxidation
    • 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
    • B01J2531/64—Molybdenum
    • 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
    • B01J2531/66—Tungsten

Definitions

  • the present invention relates to new catalysts in the form of metal complexes containing peroxo groups with amine oxide, phosphane oxide, arsenoxide, pyridine-N-oxide or pyride ligands which are suitable for the epoxidation of olefins with aqueous hydrogen peroxide.
  • the invention further relates to a process for the preparation of these catalysts and a corresponding epoxidation process.
  • hydrogen peroxide has been used industrially mainly as an unselective oxidizing agent, for example for bleaching paper, textiles and cellulose or in wastewater treatment.
  • a substantial part of the wide production of H 2 0 2 goes into the production of inorganic peroxo compounds for detergents. Only about 10% are used for the production of organic chemicals such as percarboxylic acids or N-oxides, which is due not least to the lack of suitable selective activators or catalysts.
  • EP-A 215 415 (2) relates to an oxidation process of olefins to aldehydes or ketones by means of oxodiperoxo-molybdenum or tungsten complexes with phosphoric acid triamide and others. also amine oxide or phosphine oxide ligands.
  • ammoxides are pyridm-N-oxide, 4-picomm-N-oxide, trioctylamine-N-oxide and phenylpropylpy ⁇ dm-N-oxide, and an example of phosphmoxides is called methyl methylphosphine oxide.
  • EP-A 097 551 (3) discloses the use of vanadium, niobium or tantalum complexes of the formula MO (0 2 ) 2 L 2 with phosphoric acid amide and also amine oxide or phosphine oxide ligands as epoxidation catalysts for olefins.
  • ammoxides are trimethylamine N-oxide, N-methylmorpholine-N-oxide, pyridm-N-oxide, 2-, 3- or 4-picolm-N-oxide, chromium-N-oxide and 2,2'-Bi - pyridm-N-oxide
  • examples of phosphmoxides include t ⁇ pnenylphosphmoxide, tnmethylphosphine oxide, methyldiphenylphosphmoxide, diethylphenylphosphmoxide and trimorpholmophosphine oxide.
  • L 1 is an amine oxide ligand of the formula II, a phosphine oxide or arsine oxide ligand of the formula III, a pyridm-N-oxide ligand of the formula VII or a pyridm ligand of the formula VIII
  • R 1 to R 3 are the same or different Ci to C 3 o-alkyl, C 7 to C 30 aralkyl or C b to C 30 aryl radicals which additionally contain ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups , Carboxylic acid ester groups, sulfo groups, phosphonic acid groups, nitro groups, halogen atoms and / or amino groups which are optionally substituted by C 1 -C 4 -alkyl radicals may be referred to as functional groups, where at least one of the radicals R 1 to R 3 contains at least 11 C - Must have atoms and the other two residues can be linked together to form an Rmg, and
  • R 4 to R 6 are the same or different C 4 to C 30 alkyl, C 7 to C 3 o-aralkyl or C_ .
  • _>"to C 3 o" aryl residues, which additionally ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups, carboxylic acid ester groups, sulfo groups, phosphonic acid groups, nitro groups, halogen atoms and / or optionally by Ci-bis C 4 alkyl radicals may contain substituted amino groups as functional groups, denote, and
  • R 11 to R 15 independently of one another are hydrogen or identical or different Ci to C 3 o-alkyl, C 7 to C 30 aralkyl or Cg to C 3 o aryl radicals or C 7 to C 3 o-alkoxy -, C 7 - to C 3 o-aralkoxy, C 6 to C30 aryloxy or dihydrocarbylammo groups with identical or different Ci to C 3 o "alkyl, C 7 - to C 30 aralkyl and / or C 6 to C 30 aryl radicals as hydrocarbyl radicals which additionally contain ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups, carboxylic acid ester groups, sulfo groups, phosphonic acid groups, nitro groups, halogen atoms and / or, if appropriate, through C 1 -C 4 Alkyl radicals may contain substituted amino groups as functional groups, designating where at least one of the radicals R
  • L 2 is an auxiliary ligand from the group oxo, halides, pseudo-halides, carboxylates, phenolates, alcoholates, enolates, ketones, ethers, amines, amides, urea, urea derivatives and water or another ligand L 1 or a free coordination site means
  • X represents oxo-oxygen or an imido ligand which is optionally substituted by C 1 -C 4 -alkyl
  • Z represents phosphorus or arsenic
  • n denotes the number 1 or 2
  • n the number 1, 2 or 3
  • the catalysts I according to the invention differ from those known from the prior art in that they contain long-chain or more voluminous radicals in the ligands L 1 than in the amine oxide or phosphine oxide systems described here.
  • at least one of the three radicals R 1 to R 3 must contain at least 11, preferably at least 12, in particular at least 14, carbon atoms. This is preferably a linear or branched alkyl group.
  • the lower limit for the size of linear or branched alkyl radicals R 4 to R 6 is for 4, preferably for 6, in particular for 8 C atoms, the lower limit for the size of aralkyl radicals R 4 to R 6 for 7, preferably for 9, in particular for 12 C atoms, and the lower limit for the size of aryl radicals R 4 to R 6 is 10, preferably 12, in particular 14, carbon atoms.
  • the sum of the carbon atoms of the core SuD substituents must be at least 8, preferably at least 9; in particular, one of the radicals R 11 to R 15 represents a long-chain linear or branched alkyl radical having at least 8, especially at least 9, carbon atoms.
  • Titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese and rhenium are particularly considered as transition metals for the catalyst complexes according to the invention. Molybdenum and tungsten are particularly preferred.
  • Methyl-n-dodecyl- (6-phenylhexyl) amine oxide Methyl-n-dodecyl- (6-phenylhexyl) amine oxide.
  • phosphine oxide phosphine oxide
  • arsine oxide ligands III Typical examples of phosphine oxide (phosphine oxide) and arsine oxide ligands III are:
  • Tri-n-butylphosphane and arsine oxide tri-tert. -butylphosphane and arsanoxide, tri-n-hexylphosphane and arsanoxide, tri-n-octylphosphane and arsanoxide, tri- (2-ethylhexyUphosphane and arsanoxide, tri-n-dodecylphosphane and arsanoxide, tri-n-octadecylphosphane and arsan oxide, di-n-outyl-n-octylphosphane and arsan oxide, n-butyl-di-n-octylphosphane and arsanoxide, tribenzylphosphane and arsanoxide, benzyl-di-n-octylphosphane and arsanoxide, naphthyl-di-n-octylphosphan
  • Typical examples of pyridm-N-oxide and pyridm ligands VII and VIII are:
  • radicals R 1 to R 6 and R 11 to R 15 are derived in particular from corresponding ethylene oxide, propylene oxide or butylene oxide or from tetrahydrofuran reaction products.
  • Alkoxy substituents and carboxylic acid ester substituents in R 1 to R 6 and R 11 to R 15 preferably carry C 1 -C 4 -alkyl radicals, in particular methyl or ethyl.
  • Halogen atoms in R 1 to R 6 and R u to R 15 are especially chlorine or bromine.
  • the number of functional groups listed for R 1 to R 6 and R 11 to R 15 if any, is usually from 1 to 3, and from 1 to 14 in the case of ether oxygen atoms, depending on the chain length.
  • auxiliary ligands L 2 indicated as a group are those which are usually used and are therefore familiar to the person skilled in the art.
  • Preferred catalysts according to the invention are those of the general formula I or Ib 0 0
  • the number n of the ligands L 2 preferably means 1.
  • Eme preferred embodiment is inventive catalysts I and Ia or Ib is in which L 1 is an amine oxide ligand II, which radicals R 1 to R 3 carries Ci to C 2 o _ alkyl groups, wherein at least one of R 1 to R 3 must denote a C 2 to C 20 alkyl group and the two other radicals can be linked together to form a saturated five- or six-membered ring which may also contain further heteroatoms from the group consisting of oxygen and nitrogen .
  • catalysts I or Ia or Ib according to the invention, in which L 1 is a phosphine oxide or arsine oxide ligand III which carries, as radicals R 4 to R 6, C 4 to C 2 o-alkyl groups.
  • the catalyst complexes I according to the invention are obtained in an advantageous manner by producing these catalytically active complexes from another complex of the metal M and hydrogen peroxide.
  • the complexes I are usually produced by exchanging the ligands L in the transition metal complex compounds MX (0 2 ) m (L 2 ) n + ⁇ already mentioned above, where M, X, m and n have the meanings mentioned and L in particular stands for H 2 0, DMF or HMPTA, against ammoxide II or phosphine oxide III.
  • MX (0 2 ) m (L 2 ) n + ⁇ already mentioned above, where M, X, m and n have the meanings mentioned and L in particular stands for H 2 0, DMF or HMPTA, against ammoxide II or phosphine oxide III.
  • These complex precursors themselves can usually be prepared very easily from inexpensive starting materials (metal oxide, H 2 O 2 and ligand or ligand precursor).
  • amine oxide II Phosphine or arsine oxide III
  • Pyridine-N-oxide VII or Pyridm VIII added.
  • the corresponding ames or phosphanes or arsanes can also be added directly, since they move in situ from H 2 O 2 to the desired amm-N-oxides or phosphine. phanoxides are oxidized.
  • the catalysts can be generated in situ or can also be independently represented, isolated and characterized.
  • the catalysts I according to the invention are particularly suitable for the catalytic activation of oxidation reactions, in particular for the epoxidation of olefins, especially with water-based hydrogen peroxide as the epoxidation agent.
  • the present invention thus also relates to a process for the preparation of epoxides of the general formula IV
  • R 7 to R 10 are the same or different and are hydrogen or optionally substituted alkyl, alkenyl, heteroalkyl, cycloalkyl, aryl or heteroaryl radicals, where the radicals R 7 to Rio can also be linked to one another to form rings, or substituents based on elements from the 4th to 7th main group of the Periodic Table of the Elements, from olefins of the general formula V R 8 R9
  • olefins that can be used are not subject to any restrictions with regard to the type and number of substituents.
  • Typical examples of olefins which can be epoxidized by the process according to the invention such as ethylene, propene, 1-butene, 2-butene, isobutene, 1, 3-butadiene, 1-pentene, 2-pentene, isoprene, cyclopentene, 1-hexene , Cyclohexene, C ⁇ - to C 24 - ⁇ -monoolefme, styrene, indene, norbornene, cyclopentadiene, dicyclopentadiene and alkene oligomers with reactive double bonds such as polypropene and polyisobutene.
  • the olefins V can also carry substituents on the olefinic double bond based on elements of the 4th to 7th main group, examples of which are vinyl silicones, vinylamines, vinylphosphines, vinyl ethers, vinylsulfides and halogenated alkenes such as vinyl chloride, vinylidene chloride or trichlorethylene .
  • catalyst I is normally initially introduced and the required amount of aqueous H 2 O 2 and olefin, optionally dissolved in a suitable inert organic solvent, are added.
  • concentration range of the aqueous H 2 O 2 can be 2 and 70% by weight, in particular 5 to 50% by weight.
  • Suitable inert organic solvents are, for example, chloroform, dichloromethane, ether, carboxylic acid esters or aromatics. This usually results in a two-phase reaction mixture.
  • water-miscible solvents such as methanol, acetone, dimethoxyethane or dioxane, the reaction can also be carried out homogeneously.
  • the reaction conditions of the epoxidation according to the invention are very mild, which is an advantage because of the high reactivity of the epoxides formed.
  • the reaction is typically carried out at from -20 to 160 ° C., in particular at 20 to 100 ° C., especially at 50 to 80 ° C., that is to say in a temperature range which is also favorable for the removal of the heat of reaction.
  • Increased pressure is only necessary in the case of volatile olefins such as propene or butene, normally the reaction is carried out at atmospheric pressure.
  • propene is epoxidized to propylene oxide, in particular in a two-phase system, by the process according to the invention.
  • 1,3-butadiene is epoxidized to vinyloxirane by the process according to the invention, in particular in a two-phase system.
  • M denotes a metal from the 4th to 7th subgroup of the periodic table of the elements
  • L 1 is an amine oxide ligand of the formula II, a phosphine oxide or arsine oxide ligand of the formula III, a pyridine-N-oxide ligand of the formula VII or a pyridine ligand of the formula VIII
  • R i to R 3 are the same or different C] - to C 3 o-alkyl, C 7 - to C 3 rj-aralkyl or C ⁇ - to C 3 o-aryl radicals which additionally contain ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, Carboxyl groups, cyano groups, carboxylic acid ester groups, sulfo groups, phosphonic acid groups, nitro groups, halogen atoms and / or amino groups which may be substituted by C 1 -C 4 -alkyl radicals may contain functional groups, wherein at least one of the radicals R 1 to R 3 must have at least 11 carbon atoms and the two other radicals can be linked together to form a ring, and R 4 to R 5 are the same or different C 4 to C 30 alkyl, C 7 to C 3 o-aralkyl or Cio to C 3 o-aryl radicals which additionally contain ether oxygen atoms, carbonyl groups, hydroxy
  • L 2 an auxiliary ligand from the group oxo, halides
  • Pseudohalides carboxylates, phenolates, alcoholates, enolates, ketones, ethers, amines, amides, urea, urea derivatives and water or another ligand L 1 or a free coordination point,
  • X represents oxo-oxygen or an imido ligand which is optionally substituted by C 1 -C 4 -alkyl
  • Z represents phosphorus or arsenic
  • n denotes the number 1 or 2
  • n the number 1, 2 or 3.

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

Catalysts for epoxidizing olefins have the formula (I), in which M stands for a metal of the 4th to 7th secondary group of the periodic table of elements; L1 stands for an amine oxide, phosphane oxide, arsane oxide, pyridin-N-oxide or pyridine ligand having the formulas (II), (III), (VII) or (VIII); L2 stands for a usual auxiliary ligand or another ligand L1 or a free co-ordination site; X stands for oxo-oxygen or imido ligands; m equals 1 or 2; and n equals 1, 2 or 3.

Description

Peroxogruppenhaltige Metallkomplexe mit Aminoxid- , Phosphanoxid-, Arsanoxid- , Pyridm-N-oxid- oder Pyridm-Liganden als EpoxidierungskatalysatorenMetal complexes containing peroxo groups with amine oxide, phosphine oxide, arsine oxide, pyridm-N-oxide or pyridm ligands as epoxidation catalysts
Beschreibungdescription
Die vorliegende Erfindung betrifft neue Katalysatoren in Form peroxogruppenhaltiger Metallkomplexe mit Aminoxid-, Phosphan¬ oxid-, Arsanoxid-, Pyridin-N-oxid- oder Pyridm-Liganden, welche sich zur Epoxidierung von Olefinen mit wäßrigem Wasserstoffper¬ oxid eignen. Weiterhin betrifft die Erfindung ein Verfahren zur Herstellung dieser Katalysatoren sowie ein entsprechendes Epoxi- dierungsverfahren.The present invention relates to new catalysts in the form of metal complexes containing peroxo groups with amine oxide, phosphane oxide, arsenoxide, pyridine-N-oxide or pyride ligands which are suitable for the epoxidation of olefins with aqueous hydrogen peroxide. The invention further relates to a process for the preparation of these catalysts and a corresponding epoxidation process.
Die Epoxidierung von Olefinen mit wäßrigem Wasserstoffperoxid (H202) gelingt nur in Gegenwart von organischen oder anorganischen Aktivatoren oder Katalysatoren. Die Übertragung des Sauerstoff- atoms von H202 auf das Substrat kann dabei in stöchiometrischer oder auch katalytischer Reaktion erfolgen. Der Nachteil der Not¬ wendigkeit eines Aktivators oder Katalysators wird bei Verwendung von Wasserstoffperoxid allerdings durch sein ökologisches Poten¬ tial mehr als aufgewogen. Im Gegensatz zu anderen Oxidantien ent¬ steht bei einer Oxidation mit H202 nur Wasser als Nebenprodukt. Em weiterer Vorteil ist außerdem der hohe Aktiv-Sauerstoff-Ge¬ halt von Wasserstoffperoxid, der mit 47 % den aller anderen gan¬ gigen Oxidantien (ausgenommen 02) bei weitem betrifft.The epoxidation of olefins with aqueous hydrogen peroxide (H 2 0 2 ) is only possible in the presence of organic or inorganic activators or catalysts. The transfer of the oxygen atom from H 2 0 2 to the substrate can take place in a stoichiometric or catalytic reaction. The disadvantage of the need for an activator or catalyst is more than compensated for by the use of hydrogen peroxide due to its ecological potential. In contrast to other oxidants, only water is formed as a by-product in the case of oxidation with H 2 0 2 . Another advantage is the high active oxygen content of hydrogen peroxide, which, at 47%, affects by far the other common oxidants (except 0 2 ).
Bislang wird Wasserstoffperoxid industriell hauptsächlich als un- selektives Oxidationsmittel wie z.B. zur Bleichung von Papier, Textilien und Cellulose oder in der Abwasseraufbereitung einge¬ setzt. Ein wesentlicher Teil der Weitproduktion von H202 geht in die Herstellung von anorganischen Peroxo-Verbindungen fur Wasch¬ mittel. Nur ca. 10 % werden zur Herstellung von organischen Che¬ mikalien wie Percarbonsauren oder N-Oxiden eingesetzt, was nicht zuletzt auf das Fehlen geeigneter selektiver Aktivatoren oder Katalysatoren zurückzuführen ist.So far, hydrogen peroxide has been used industrially mainly as an unselective oxidizing agent, for example for bleaching paper, textiles and cellulose or in wastewater treatment. A substantial part of the wide production of H 2 0 2 goes into the production of inorganic peroxo compounds for detergents. Only about 10% are used for the production of organic chemicals such as percarboxylic acids or N-oxides, which is due not least to the lack of suitable selective activators or catalysts.
Eine der gangigsten Methoden zur stöchiometrischen Aktivierung von Wasserstoffperoxid ist die Umsetzung mit Carbonsäuren zur Percarbonsauren, die eine Vielfalt von Olefinen epoxidieren kon nen. Problematisch hierbei ist allerdings die Saureempfindlich¬ keit vieler Epoxide, besonders in wäßrigem Medium, sowie die La¬ bilität der Percarbonsauren, die zu Ausbeuteverlusten fuhrt.One of the most common methods for stoichiometric activation of hydrogen peroxide is the reaction with carboxylic acids to form percarboxylic acids, which can epoxidize a variety of olefins. The problem here, however, is the acid sensitivity of many epoxides, particularly in an aqueous medium, and the stability of the percarboxylic acids, which leads to losses in yield.
Auch peroxogruppenhaltige Ubergangsmetall-Komplexverbindungen wie MO(02)2L2 (M = Mo oder W, L = H20, DMF (Dimethylformamid) oder HMPTA (Hexamethylphosphorsauretπamid) ) , die leicht aus H202 und dem entsprechenden Metalloxid M03 hergestellt werden können, sind in der Lage, Olefine zu epoxidieren, was einer stöchiometrischen Aktivierung von H202 entspricht. Verbindungen dieses speziellen Typs zeichnen sich besonders durch ihre leichte Zuganglichkeit aus .Also peroxo group-containing transition metal complex compounds such as MO (0 2 ) 2 L 2 (M = Mo or W, L = H 2 0, DMF (dimethylformamide) or HMPTA (hexamethylphosphoric acid amide)), which are easily made from H 2 0 2 and the corresponding metal oxide M0 3 can be produced, are able to epoxidize olefins, which corresponds to a stoichiometric activation of H 2 0 2 . Connections of this special type are particularly characterized by their easy accessibility.
Zur katalytischen Aktivierung bei der Olefmepoxidierung mit H202 werden beispielsweise von den oben genannten peroxogruppenhalti- gen Ubergangsmetall-Komplexverbmdungen MO(02)2L2 abgeleitete Katalysatoren eingesetzt. So werden in der US-A 3 953 362 (1) aus Mo03, H202 und tertiären Aminen, deren drei organische Reste je¬ weils Ci- bis Cio-Alkyl- oder C6- bis Cio-Arylgruppen darstellen, oder den N-Oxiden solcher tertiären Amme erhältliche Molybdän- komplexe als Katalysatoren fur Epoxidierungen mit H202 beschrie¬ ben.For the catalytic activation in olefin epoxidation with H 2 0 2 , for example, catalysts derived from the above-mentioned transition metal complex compounds containing peroxo groups are used MO (0 2 ) 2 L 2 . Thus, in US Pat. No. 3,953,362 (1) Mo0 3 , H 2 0 2 and tertiary amines, the three organic radicals of which each represent Ci to Cio-alkyl or C 6 - to Cio-aryl groups, or Molybdenum complexes obtainable with the N-oxides of such tertiary ames are described as catalysts for epoxidations using H 2 0 2 .
Die EP-A 215 415 (2) betrifft ein Oxidationsverfahren von Olefinen zu Aldehyden oder Ketonen mittels Oxodiperoxo-Molybdän- oder -Wolframkomplexen mit Phosphorsauretriamid- und u.a. auch Aminoxid- oder Phosphmoxid-Liganden. Als Beispiele fur Ammoxide werden Pyridm-N-oxid, 4 -Picolm-N-oxid, Trioctylamin-N-oxid und Phenylpropylpyπdm-N-oxid, als ein Beispiel fur Phosphmoxide wird Tnmethylphosphinoxid genannt.EP-A 215 415 (2) relates to an oxidation process of olefins to aldehydes or ketones by means of oxodiperoxo-molybdenum or tungsten complexes with phosphoric acid triamide and others. also amine oxide or phosphine oxide ligands. Examples of ammoxides are pyridm-N-oxide, 4-picomm-N-oxide, trioctylamine-N-oxide and phenylpropylpyπdm-N-oxide, and an example of phosphmoxides is called methyl methylphosphine oxide.
Aus der EP-A 097 551 (3) ist die Verwendung von Vanadium-, Niob- oder Tantalkomplexen der Formel MO(02)2L2 mit Phosphorsaureamid- und auch Aminoxid- oder Phosphmoxid-Liganden als Epoxidierungs- katalysatoren fur Olefine bekannt. Als Beispiele fur Ammoxide werden Trimethylamin N-oxid, N-Methylmorpholin-N-oxid, Pyridm-N- oxid, 2-, 3- oder 4 - Picolm-N-oxid, Chmolm-N-oxid und 2,2' -Bi- pyridm-N-oxid, als Beispiele fur Phosphmoxide werden Tπpnenyl- phosphmoxid, Tnmethylphosphinoxid, Methyldiphenylphosphmoxid, Diethylphenylphosphmoxid und Trimorpholmophosphinoxid genannt.EP-A 097 551 (3) discloses the use of vanadium, niobium or tantalum complexes of the formula MO (0 2 ) 2 L 2 with phosphoric acid amide and also amine oxide or phosphine oxide ligands as epoxidation catalysts for olefins. Examples of ammoxides are trimethylamine N-oxide, N-methylmorpholine-N-oxide, pyridm-N-oxide, 2-, 3- or 4-picolm-N-oxide, chromium-N-oxide and 2,2'-Bi - pyridm-N-oxide, examples of phosphmoxides include tπpnenylphosphmoxide, tnmethylphosphine oxide, methyldiphenylphosphmoxide, diethylphenylphosphmoxide and trimorpholmophosphine oxide.
Nachteile der in den Schriften (1) bis (3) beschriebenen Komplexe sind jedoch die vergleichsweise geringen Aktivitäten, Epoxid-Se- lektivitaten und Olefin Umsätze bei Olefmepoxidierungen mit wä߬ rigem H202.Disadvantages of the complexes described in the documents (1) to (3) are, however, the comparatively low activities, epoxide selectivities and olefin conversions in olefin epoxidations with aqueous H 2 O 2 .
Aufgabe der vorliegenden Erfindung war es daher, Metallkomplex- Katalysatoren insbesondere fur Olefmepoxidierungen mit wäßrigem H202 bereitzustellen, welche sich außer durch eine einfache und wirtschaftliche Herstellungsweise auch durch eine hohe Wirksam¬ keit und Effizienz auszeichnen.It was therefore an object of the present invention to provide metal complex catalysts, in particular for olefin epoxidations with aqueous H 2 O 2 , which, in addition to being simple and economical to prepare, are also notable for high effectiveness and efficiency.
Demgemäß wurden Katalysatoren der allgemeinen Formel I XAccordingly, catalysts of the general formula I X
( L2 ) n M (02 ) m ( I )(L 2 ) n M (0 2 ) m (I)
Ll L l
M em Metall aus der 4. bis 7. Nebengruppe des Periodensystems der Elemente bezeichnet,M em metal from the 4th to 7th subgroup of the Periodic Table of the Elements,
L1 einen Aminoxid-Liganden der Formel II, einen Phosphanoxid- oder Arsanoxid-Liganden der Formel III, einen Pyridm-N-oxid- Liganden der Formel VII oder einen Pyridm-Liganden der For¬ mel VIIIL 1 is an amine oxide ligand of the formula II, a phosphine oxide or arsine oxide ligand of the formula III, a pyridm-N-oxide ligand of the formula VII or a pyridm ligand of the formula VIII
(II) III ) (VII ) (VIII )(II) III) (VII) (VIII)
bedeutet, in denenmeans in which
R1 bis R3 gleiche oder verschiedene Ci- bis C3o-Alkyl-, C7- bis C30-Aralkyl- oder Cb- bis C30-Arylreste, welche zusätzlich Ethersauerstoffatome, Carbonylgruppen, Hydroxylgruppen, Alkoxygruppen, Carboxylgruppen, Cyanogruppen, Carbonsaure¬ estergruppen, Sulfogruppen, Phosphonsauregruppen, Nitrogrup¬ pen, Halogenatome und/oder gegebenenfalls durch Ci- bis C4-Alkylreste substituierte Aminogruppen als funktionelle Gruppen enthalten können, bezeichnen, wobei mindestens einer der Reste R1 bis R3 wenigstens 11 C-Atome aufweisen muß und wobei die beiden anderen Reste miteinander zu einem Rmg ver knüpft sem können, undR 1 to R 3 are the same or different Ci to C 3 o-alkyl, C 7 to C 30 aralkyl or C b to C 30 aryl radicals which additionally contain ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups , Carboxylic acid ester groups, sulfo groups, phosphonic acid groups, nitro groups, halogen atoms and / or amino groups which are optionally substituted by C 1 -C 4 -alkyl radicals may be referred to as functional groups, where at least one of the radicals R 1 to R 3 contains at least 11 C - Must have atoms and the other two residues can be linked together to form an Rmg, and
R4 bis R6 gleiche oder verschiedene C4- bis C30-Alkyl-, C7- bis C3o-Aralkyl- oder C_._>" bis C3o"Arylreste, welche zusätz¬ lich Ethersauerstoffatome, Carbonylgruppen, Hydroxylgruppen, Alkoxygruppen, Carboxylgruppen, Cyanogruppen, Carbonsaure¬ estergruppen, Sulfogruppen, Phosphonsauregruppen, Nitrogrup¬ pen, Halogenatome und/oder gegebenenfalls durch Ci- bis C4-Alkylreste substituierte Aminogruppen als funktionelle Gruppen enthalten können, bezeichnen, undR 4 to R 6 are the same or different C 4 to C 30 alkyl, C 7 to C 3 o-aralkyl or C_ . _>"to C 3 o" aryl residues, which additionally ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups, carboxylic acid ester groups, sulfo groups, phosphonic acid groups, nitro groups, halogen atoms and / or optionally by Ci-bis C 4 alkyl radicals may contain substituted amino groups as functional groups, denote, and
R11 bis R15 unabhängig voneinander Wasserstoff oder gleiche oder verschiedene Ci- bis C3o-Alkyl-, C7- bis C30-Aralkyl- oder Cg- bis C3o- Arylreste oder C7- bis C3o-Alkoxy-, C7- bis C3o-Aralkoxy- , C6 bis C30-Aryloxy- oder Dihydrocarbylammo- Gruppen mit gleichen oder verschiedenen Ci- bis C3o"Alkyl-, C7- bis C30-Aralkyl- und/oder C6 - bis C30-Arylresten als Hy- drocarbylresten, welche zusätzlich Ethersauerstoffatome, Carbonylgruppen, Hydroxylgruppen, Alkoxygruppen, Carboxyl¬ gruppen, Cyanogruppen, Carbonsaureestergruppen, Sulfogruppen, Phosphonsauregruppen, Nitrogruppen, Halogenatome und/oder ge¬ gebenenfalls durch Ci- bis C4-Alkylreste substituierte Amino¬ gruppen als funktionelle Gruppen enthalten können, bezeich¬ nen, wobei mindestens einer der Reste R11 oder Ri5 Wasserstoff sem muß, die Summe der Kohlenstoffatome in den Resten R11 bis R15 mindestens 8 betragen muß und die Reste R11 bis R15 paar¬ weise zu Ringen verknüpft sein können,R 11 to R 15 independently of one another are hydrogen or identical or different Ci to C 3 o-alkyl, C 7 to C 30 aralkyl or Cg to C 3 o aryl radicals or C 7 to C 3 o-alkoxy -, C 7 - to C 3 o-aralkoxy, C 6 to C30 aryloxy or dihydrocarbylammo groups with identical or different Ci to C 3 o "alkyl, C 7 - to C 30 aralkyl and / or C 6 to C 30 aryl radicals as hydrocarbyl radicals which additionally contain ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups, carboxylic acid ester groups, sulfo groups, phosphonic acid groups, nitro groups, halogen atoms and / or, if appropriate, through C 1 -C 4 Alkyl radicals may contain substituted amino groups as functional groups, designating where at least one of the radicals R 11 or R i5 must be hydrogen sem, the sum of the carbon atoms in the radicals R 11 to R 15 must be at least 8 and the radicals R 11 to R 15 can be linked in pairs to form rings,
L2 einen Hilfsliganden aus der Gruppe Oxo, Halogenide, Pseudo- halogenide, Carboxylate, Phenolate, Alkoholate, Enolate, Ke¬ tone, Ether, Amine, Amide, Harnstoff, Harnstoffderivate und Wasser oder einen weiteren Liganden L1 oder eine freie Koor¬ dmationsstelle bedeutet,L 2 is an auxiliary ligand from the group oxo, halides, pseudo-halides, carboxylates, phenolates, alcoholates, enolates, ketones, ethers, amines, amides, urea, urea derivatives and water or another ligand L 1 or a free coordination site means
X fur Oxo-Sauerstoff oder einen gegebenenfalls durch Ci- bis C4-Alkyl substituierten Imido-Liganden steht,X represents oxo-oxygen or an imido ligand which is optionally substituted by C 1 -C 4 -alkyl,
Z fur Phosphor oder Arsen steht,Z represents phosphorus or arsenic,
m die Zahl 1 oder 2 bezeichnet undm denotes the number 1 or 2 and
n die Zahl 1, 2 oder 3 bedeutet,n represents the number 1, 2 or 3,
gefunden.found.
Die erfindungsgemaßen Katalysatoren I unterscheiden sich von den aus dem Stand der Technik bekannten dadurch, daß sie in den Li ganden L1 langerkettige oder voluminösere Reste als bei den hier fur beschriebenen Aminoxid- oder Phosphanoxid-Systemen enthalten. Bei den Aminoxid-Liganden II muß mindestens einer der drei Reste R1 bis R3 wenigstens 11, vorzugsweise wenigstens 12, insbesondere wenigstens 14 C Atome enthalten. Vorzugsweise handelt es sich hierbei um eine lineare oder verzweigte Alkylgruppe. Bei den Phosphanoxid- bzw. Arsanoxid-Liganden III liegt die Untergrenze fur die Große von linearen oder verzweigten Alkylresten R4 bis R6 bei 4, vorzugsweise bei 6, insbesondere bei 8 C-Atomen, die Un¬ tergrenze fur die Große von Aralkylresten R4 bis R6 bei 7, vor¬ zugsweise bei 9, insbesondere bei 12 C-Atomen, und die Unter- grenze fur die Große von Arylresten R4 bis R6 bei 10, vorzugsweise bei 12, insbesondere bei 14 C-Atomen. Bei den Pyridm-N-oxid- und Pyridm-Liganden VII bzw. VIII muß die Summe der C-Atome der KernsuDStituenten mindestens 8, vorzugsweise mindestens 9, betra¬ gen; insbesondere steht einer der Reste R11 bis R15 fur einen langkettigen linearen oder verzweigten Alkylrest mit mindestens 8, vor allem mindestens 9 C-Atomen.The catalysts I according to the invention differ from those known from the prior art in that they contain long-chain or more voluminous radicals in the ligands L 1 than in the amine oxide or phosphine oxide systems described here. In the case of the amine oxide ligands II, at least one of the three radicals R 1 to R 3 must contain at least 11, preferably at least 12, in particular at least 14, carbon atoms. This is preferably a linear or branched alkyl group. In the case of the phosphine oxide or arsine oxide ligands III, the lower limit for the size of linear or branched alkyl radicals R 4 to R 6 is for 4, preferably for 6, in particular for 8 C atoms, the lower limit for the size of aralkyl radicals R 4 to R 6 for 7, preferably for 9, in particular for 12 C atoms, and the lower limit for the size of aryl radicals R 4 to R 6 is 10, preferably 12, in particular 14, carbon atoms. In the case of the pyridm-N-oxide and pyridm ligands VII and VIII, the sum of the carbon atoms of the core SuD substituents must be at least 8, preferably at least 9; in particular, one of the radicals R 11 to R 15 represents a long-chain linear or branched alkyl radical having at least 8, especially at least 9, carbon atoms.
Als Ubergangsmetalle für die erfindungsgemaßen Katalysatorkom¬ plexe kommen insbesondere Titan, Zirkonium, Hafnium, Vanadium, Niob, Tantal, Chrom, Molybdän, Wolfram, Mangan und Rhenium m Be¬ tracht. Besonders bevorzugt werden Molybdän und Wolfram.Titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese and rhenium are particularly considered as transition metals for the catalyst complexes according to the invention. Molybdenum and tungsten are particularly preferred.
Typische Beispiele fur Amm-N-oxid-Liganden II sind:Typical examples of Amm-N-oxide ligands II are:
Dimethyl-n-undecylaiτimoxid,Dimethyl-n-undecylimide,
Dimethyl-n-dodecy1aminoxid,Dimethyl-n-dodecylamine oxide,
Dimethyl-n-tetradecylammoxid,Dimethyl-n-tetradecylammoxide,
Dimethyl-n-hexadecylaminoxid,Dimethyl-n-hexadecylamine oxide,
Dimethyl-n-octadecylammoxid,Dimethyl-n-octadecylammoxide,
Dimethyl-n-eicosylaminoxid,Dimethyl-n-eicosylamine oxide,
Methyl-di (n-dodecyl) aminoxid,Methyl di (n-dodecyl) amine oxide,
Methyl-di (n-octadecyl) aminoxid,Methyl di (n-octadecyl) amine oxide,
Tri (n-dodecyl)aminoxid,Tri (n-dodecyl) amine oxide,
Tri (n-octadecyl)aminoxid,Tri (n-octadecyl) amine oxide,
Benzyl-di (n-dodecyl)aminoxid,Benzyl-di (n-dodecyl) amine oxide,
Diphenyl-n-octadecylammoxid,Diphenyl-n-octadecylammoxide,
N-Undecylmorpholinoxid,N-undecylmorpholine oxide,
N-Dodecylpiperidinoxid,N-dodecylpiperidine oxide,
Dimethyl- (6-phenylhexyl)aminoxid,Dimethyl- (6-phenylhexyl) amine oxide,
Dimethyl-bisphenylammoxid undDimethyl bisphenylammoxide and
Methyl-n-dodecyl- (6-phenylhexyl)aminoxid.Methyl-n-dodecyl- (6-phenylhexyl) amine oxide.
Typische Beispiel fur Phosphanoxid(Phosphmoxid) - und Arsanoxid- Liganden III sind:Typical examples of phosphine oxide (phosphine oxide) and arsine oxide ligands III are:
Tri-n-butylphosphan- und arsanoxid, Tri-tert. -butylphosphan- und arsanoxid, Tri-n-hexylphosphan- und arsanoxid, Tri-n-octylphosphan- und arsanoxid, Tri- (2-ethylhexyUphosphan- und arsanoxid, Tri-n-dodecylphosphan- und arsanoxid, Tri-n-octadecylphosphan- und arsanoxid, Di-n-outyl-n-octylphosphan- und arsanoxid, n-Butyl-di-n-octylphosphan- und arsanoxid, Tribenzylphosphan und arsanoxid, Benzyl-di-n-octylphosphan- und arsanoxid, Naphthyl-di-n-octylphosphan- und arsanoxid und Di-n-butyl-naphthylphosphan- und arsanoxid.Tri-n-butylphosphane and arsine oxide, tri-tert. -butylphosphane and arsanoxide, tri-n-hexylphosphane and arsanoxide, tri-n-octylphosphane and arsanoxide, tri- (2-ethylhexyUphosphane and arsanoxide, tri-n-dodecylphosphane and arsanoxide, tri-n-octadecylphosphane and arsan oxide, di-n-outyl-n-octylphosphane and arsan oxide, n-butyl-di-n-octylphosphane and arsanoxide, tribenzylphosphane and arsanoxide, benzyl-di-n-octylphosphane and arsanoxide, naphthyl-di-n-octylphosphane and arsanoxide and di-n-butyl-naphthylphosphane and arsanoxide.
Typische Beispiele fur Pyridm-N-oxid- und Pyridm-Liganden VII bzw. VIII sind:Typical examples of pyridm-N-oxide and pyridm ligands VII and VIII are:
4- (1-Octyl)pyridin und das entsprechende N-Oxid,4- (1-octyl) pyridine and the corresponding N-oxide,
4-[l-(2 Ethylhexyl) ]pyridm und das entsprechende N-Oxid,4- [l- (2 ethylhexyl)] pyride and the corresponding N-oxide,
4- (1-Nonyl)pyridm und das entsprechende N-Oxid,4- (1-nonyl) pyridm and the corresponding N-oxide,
4 - (5-Nonyl)pyridm und das entsprechende N-Oxid,4 - (5-nonyl) pyridm and the corresponding N-oxide,
4 - (1-Decyl)pyridm und das entsprechende N-Oxid,4 - (1-decyl) pyridm and the corresponding N-oxide,
4 - (1-Dodecyl)pyridm und das entsprechende N-Oxid,4 - (1-dodecyl) pyridm and the corresponding N-oxide,
4- (n-Octoxy)pyrιdn und das entsprechende N-Oxid,4- (n-octoxy) pyrιdn and the corresponding N-oxide,
4- (2-Ethylhexoxy)pyridin und das entsprechende N-Oxid,4- (2-ethylhexoxy) pyridine and the corresponding N-oxide,
4- (n-Nonoxy)pyridm und das entsprechende N-Oxid,4- (n-nonoxy) pyridm and the corresponding N-oxide,
4- (Dι-n-octylammo)pyrιdm und das entsprechende N-Oxid und4- (Dι-n-octylammo) pyrιdm and the corresponding N-oxide and
4- (Dι-2-ethylhexylammo)pyridm und das entsprechende N-Oxid.4- (Dι-2-ethylhexylammo) pyridm and the corresponding N-oxide.
Treten bei den Resten R1 bis R6 und R11 bis R15 zusätzliche Ether¬ sauerstoffatome auf, dann leiten sich solche Reste insbesondere von entsprechenden Ethylenoxid-, Propylenoxid- oder Butylenoxid- oder von Tetrahydrofuran-Reaktionsprodukten ab.If additional ether oxygen atoms occur in the radicals R 1 to R 6 and R 11 to R 15 , such radicals are derived in particular from corresponding ethylene oxide, propylene oxide or butylene oxide or from tetrahydrofuran reaction products.
Alkoxy-Substituenten und Carbonsaurester-Substituenten bei R1 bis R6 und R11 bis R15 tragen vorzugsweise Ci- bis C4-Alkylreste, ins¬ besondere Methyl oder Ethyl. Halogenatome bedeuten bei R1 bis R6 und Ru bis R15 vor allem Chlor oder Brom. Die Anzahl der aufge¬ zahlten funktionellen Gruppen fur R1 bis R6 und R11 bis R15 liegt, wenn solche vorhanden smd, üblicherweise bei 1 bis 3, bei Ether¬ sauerstoffatomen j e nach Kettenlange bei 1 bis 14.Alkoxy substituents and carboxylic acid ester substituents in R 1 to R 6 and R 11 to R 15 preferably carry C 1 -C 4 -alkyl radicals, in particular methyl or ethyl. Halogen atoms in R 1 to R 6 and R u to R 15 are especially chlorine or bromine. The number of functional groups listed for R 1 to R 6 and R 11 to R 15 , if any, is usually from 1 to 3, and from 1 to 14 in the case of ether oxygen atoms, depending on the chain length.
Die als Gruppe angegebenen Hilfsliganden L2 sind die üblicherweise verwenden und daher dem Fachmann geläufig.The auxiliary ligands L 2 indicated as a group are those which are usually used and are therefore familiar to the person skilled in the art.
Bevorzugte erfindungsgemaße Katalysatoren smd solche der allge¬ meinen Formel I oder Ib 0 0Preferred catalysts according to the invention are those of the general formula I or Ib 0 0
( la ) ( Ib )(la) (Ib)
in denen L2 Wasser bezeichnet und die Variablen M, L1 und n die oben genannten Bedeutungen haben.in which L 2 denotes water and the variables M, L 1 and n have the meanings given above.
Die Zahl n der Liganden L2 bedeutet im Falle von M = Chrom, Molyb¬ dän oder Wolfram vorzugsweise 1.In the case of M = chromium, molybdenum or tungsten, the number n of the ligands L 2 preferably means 1.
Eme bevorzugte Ausführungsform stellen erfindungsgemaße Katalysatoren I bzw. Ia oder Ib dar, bei denen L1 einen Aminoxid- Liganden II bedeutet, welcher als Reste R1 bis R3 Ci- bis C2o_Alkylgruppen tragt, wobei mindestens einer der Reste R1 bis R3 eine Cι2- bis C20-Alkylgruppe bezeichnen muß und wobei die beiden anderen Reste miteinander zu einem gesattigten fünf- oder sechs¬ gliedrigen Ring, der noch weitere Heteroatome aus der Gruppe Sau¬ erstoff und Stickstoff enthalten kann, verknüpft sem können.Eme preferred embodiment is inventive catalysts I and Ia or Ib is in which L 1 is an amine oxide ligand II, which radicals R 1 to R 3 carries Ci to C 2 o _ alkyl groups, wherein at least one of R 1 to R 3 must denote a C 2 to C 20 alkyl group and the two other radicals can be linked together to form a saturated five- or six-membered ring which may also contain further heteroatoms from the group consisting of oxygen and nitrogen .
Eine weitere bevorzugte Ausfuhrungsform stellen erfindungsgemaße Katalysatoren I bzw. Ia oder Ib dar, bei der L1 einen Phosphan¬ oxid- oder Arsanoxid-Liganden III bedeutet, welcher als Reste R4 bis R6 C4- bis C2o-Alkylgruppen tragt.Another preferred embodiment are catalysts I or Ia or Ib according to the invention, in which L 1 is a phosphine oxide or arsine oxide ligand III which carries, as radicals R 4 to R 6, C 4 to C 2 o-alkyl groups.
Die erfindungsgemaßen Katalysatorkomplexe I werden in vorteilhaf¬ ter Weise dadurch erhalten, daß man diese katalytisch wirksamen Komplexe aus einem anderen Komplex des Metalls M und Wasserstoff¬ peroxid herstellt.The catalyst complexes I according to the invention are obtained in an advantageous manner by producing these catalytically active complexes from another complex of the metal M and hydrogen peroxide.
Üblicherweise erzeugt man die Komplexe I durch Austausch der Li¬ ganden L in den bereits oben erwähnten peroxogruppenhaltigen Ubergangsmetall-Komplexverbmdungen MX (02)m(L2)n+ι, wobei M, X, m und n die genannten Bedeutungen haben und L insbesondere fur H20, DMF oder HMPTA steht, gegen Ammoxide II oder Phosphanoxide III. Diese Komplex-Vorstufen selbst lassen sich meist sehr einfacn aus preiswerten Edukten (Metalloxid, H202 und Ligand bzw. Ligandvor- stufe) herstellen.The complexes I are usually produced by exchanging the ligands L in the transition metal complex compounds MX (0 2 ) m (L 2 ) n + ι already mentioned above, where M, X, m and n have the meanings mentioned and L in particular stands for H 2 0, DMF or HMPTA, against ammoxide II or phosphine oxide III. These complex precursors themselves can usually be prepared very easily from inexpensive starting materials (metal oxide, H 2 O 2 and ligand or ligand precursor).
Zweckmaßigerweise werden die Katalysatoren I in situ entweder durch Auflosen von Metalloxiden in einem Überschuß an wäßrigem H202 oder aus leicht zuganglichen Vorstufen wie M02Cl2(dme) (dme = Dimethoxyethan) hergestellt und zur Aktivierung mit der notwendigen Menge an Aminoxid II, Phosphan- oder Arsanoxid III, Pyridin-N-oxid VII oder Pyridm VIII versetzt. Statt der Amm-N- oxide oder Phosphan- bzw. Arsanoxide können auch direkt die ent¬ sprechenden Amme oder Phosphane bzw. Arsane zugesetzt werden, da sie in situ von H202 zu den gewünschten Amm-N-oxiden bzw. Phos- phanoxiden oxidiert werden. Die Katalysatoren können in situ erzeugt oder auch unabhängig dargestellt, isoliert und charakte¬ risiert werden.The catalysts I are expediently prepared in situ either by dissolving metal oxides in an excess of aqueous H 2 O 2 or from easily accessible precursors such as M0 2 Cl 2 (dme) (dme = dimethoxyethane) and for activation with the necessary amount of amine oxide II , Phosphine or arsine oxide III, Pyridine-N-oxide VII or Pyridm VIII added. Instead of the amm-N-oxides or phosphane or arsane oxides, the corresponding ames or phosphanes or arsanes can also be added directly, since they move in situ from H 2 O 2 to the desired amm-N-oxides or phosphine. phanoxides are oxidized. The catalysts can be generated in situ or can also be independently represented, isolated and characterized.
Als Vorstufen fur die erfmdungsgemäßen Katalysatorkomplexe I eignen sich auch Komplexe der Formel VIComplexes of the formula VI are also suitable as precursors for the catalyst complexes I according to the invention
X γ\ IIX γ \ II
M = 0 (VI) M = 0 (VI)
\\
(L2) n Ll ( L 2) n Ll
in der Y fur Halogenid, z.B. Chlor, oder Pseudohalogenid, z.B. Rhodanid, steht und die Variablen M, X, L1, L2 und n die oben ge¬ nannten Bedeutungen haben. Die Komplexe VI wandeln sich bei Ein¬ wirkung von H202 leicht in die Komplexe I um.in which Y represents halide, for example chlorine, or pseudohalide, for example rhodanide, and the variables M, X, L 1 , L 2 and n have the meanings mentioned above. The complexes VI easily convert into the complexes I upon the action of H 2 0 2 .
Die erfindungsgemaßen Katalysatoren I eignen sich m hervorragen¬ der Weise zur katalytischen Aktivierung von Oxidationsreaktionen, insbesondere zur Epoxidierung von Olefinen, vor allem mit waßri gern Wasserstoffperoxid als Epoxidierungsagens.The catalysts I according to the invention are particularly suitable for the catalytic activation of oxidation reactions, in particular for the epoxidation of olefins, especially with water-based hydrogen peroxide as the epoxidation agent.
Gegenstand der vorliegenden Erfindung ist somit auch ein Verfah¬ ren zur Herstellung von Epoxiden der allgemeinen Formel IVThe present invention thus also relates to a process for the preparation of epoxides of the general formula IV
Rβ R9 R β R 9
in der R7 bis R10 gleich oder verschieden sind und Wasserstoff oder gegebenenfalls substituierte Alkyl-, Alkenyl-, Heteroalkyl- , Cycloalkyl-, Aryl- oder Heteroarylreste, wobei die Reste R7 bis Rio auch miteinander zu Ringen verknüpft sein können, oder Substituenten auf Basis von Elementen aus der 4. bis 7. Haupt- gruppe des Periodensystems der Elemente bedeuten, aus Olefinen der allgemeinen Formel V R8 R9in which R 7 to R 10 are the same or different and are hydrogen or optionally substituted alkyl, alkenyl, heteroalkyl, cycloalkyl, aryl or heteroaryl radicals, where the radicals R 7 to Rio can also be linked to one another to form rings, or substituents based on elements from the 4th to 7th main group of the Periodic Table of the Elements, from olefins of the general formula V R 8 R9
C = C ^ (V) C = C ^ ( V )
R7 R10R 7 R 10
mit wäßrigem Wasserstoffperoxid, welches dadurch gekennzeichnet ist, daß man die Epoxidierung der Olefine V m Gegenwart der erfindungsgemaßen Katalysatoren I durchfuhrt.with aqueous hydrogen peroxide, which is characterized in that the epoxidation of the olefins V is carried out in the presence of the catalysts I according to the invention.
Die einsetzbaren Olefine unterliegen keiner Beschrankung bezug- lieh Art und Anzahl von Substituenten. Typische Beispiele fur Olefine, welche nach dem erfmdungsgemäßen Verfahren epoxidiert werden können, smd Ethylen, Propen, 1-Buten, 2-Buten, Isobuten, 1, 3 -Butadien, 1-Penten, 2-Penten, Isopren, Cyclopenten, 1-Hexen, Cyclohexen, Cβ- bis C24-α-Monoolefme, Styrol, Inden, Norbornen, Cyclopentadien, Dicyclopentadien sowie Alkenoligomere mit reak¬ tiven Doppelbindungen wie Polypropen und Polyisobuten.The olefins that can be used are not subject to any restrictions with regard to the type and number of substituents. Typical examples of olefins which can be epoxidized by the process according to the invention, such as ethylene, propene, 1-butene, 2-butene, isobutene, 1, 3-butadiene, 1-pentene, 2-pentene, isoprene, cyclopentene, 1-hexene , Cyclohexene, Cβ- to C 24 -α-monoolefme, styrene, indene, norbornene, cyclopentadiene, dicyclopentadiene and alkene oligomers with reactive double bonds such as polypropene and polyisobutene.
Die Olefine V können auch Substituenten an der olefinischen Dop¬ pelbindung auf Basis von Elementen der 4. bis 7. Hauptgruppe tra¬ gen, Beispiele hierfür smd Vinylsilicone, Vinylamme, Vmyl¬ phosphane, Vinylether, Vinylsulfide und halogenierte Alkene wie Vmylchlorid, Vmylidenchlorid oder Trichlorethylen.The olefins V can also carry substituents on the olefinic double bond based on elements of the 4th to 7th main group, examples of which are vinyl silicones, vinylamines, vinylphosphines, vinyl ethers, vinylsulfides and halogenated alkenes such as vinyl chloride, vinylidene chloride or trichlorethylene .
Zur Durchfuhrung der erfindungsgemaßen Epoxidierung wird normalerweise der Katalysator I vorgelegt und die benotigte Menge an wäßrigem H202 und Olefin, gegebenenfalls gelost in einem geei¬ gneten inerten organischen Losungsmittel, zugegeben. Der Kon- zentrationsbereich des wäßrigen H202 kann bei 2 und 70 Gew. -%, insbesondere bei 5 bis 50 Gew.-% liegen. Als inerte organische Losungsmittel eignen sich z.B. Chloroform, Dichlormethan, Ether, Carbonsaureester oder Aromaten. Hierbei entsteht meist ein zwei- phasiges Reaktionsgemisch. Bei Verwendung von mit Wasser mischba¬ ren Losungsmitteln wie Methanol, Aceton, Dimethoxyethan oder Dioxan kann die Reaktion auch homogen durchgeführt werden.To carry out the epoxidation according to the invention, catalyst I is normally initially introduced and the required amount of aqueous H 2 O 2 and olefin, optionally dissolved in a suitable inert organic solvent, are added. The concentration range of the aqueous H 2 O 2 can be 2 and 70% by weight, in particular 5 to 50% by weight. Suitable inert organic solvents are, for example, chloroform, dichloromethane, ether, carboxylic acid esters or aromatics. This usually results in a two-phase reaction mixture. When using water-miscible solvents such as methanol, acetone, dimethoxyethane or dioxane, the reaction can also be carried out homogeneously.
Die Reaktionsbedingungen der erfindungsgemaßen Epoxidierung smd sehr mild, was einen Vorteil wegen der hohen Reaktivität der ge¬ bildeten Epoxide bedeutet. Typischerweise wird die Reaktion bei -20 bis 160°C, insbesondere bei 20 bis 100°C, vor allem bei 50 bis 80°C, durchgeführt, also in einem Temperaturbereich, der ebenso fur die Abfuhrung der Reaktionswarme gunstig ist. Erhöhter Druck ist nur im Falle von leichfluchtigen Olefinen wie z.B. Propen oder Buten notwendig, normalerweise wird die Reaktion bei At- mospharendruck durchgeführt. Durch Einsatz der Liganden II, III, VII oder VIII mit lipophilen Substituenten in Form von langkettigen oder voluminösen Resten erhalt man m der Regel grenzflächenaktive Katalysatoren, so daß die Epoxidierung auch in vorteilhafter Weise in einem zweiphasi- gen System, d.h. in zwei miteinander nicht vollständig mischbaren flussigen Phasen erfolgen kann. Diese Verfahrensweise hat zum einen den Vorteil, daß auch lipophile, wasserunlösliche Olefine oxidiert werden können, und zum anderen, daß die gebildeten Epoxide in der organischen Phase verbleiben und somit die Bildung unerwünschter Nebenprodukte unterdruckt wird. Außerdem wird die Produktabtrennung durch die zweiphasige Verfahrensweise erleich¬ tert.The reaction conditions of the epoxidation according to the invention are very mild, which is an advantage because of the high reactivity of the epoxides formed. The reaction is typically carried out at from -20 to 160 ° C., in particular at 20 to 100 ° C., especially at 50 to 80 ° C., that is to say in a temperature range which is also favorable for the removal of the heat of reaction. Increased pressure is only necessary in the case of volatile olefins such as propene or butene, normally the reaction is carried out at atmospheric pressure. By using ligands II, III, VII or VIII with lipophilic substituents in the form of long-chain or voluminous residues, surface-active catalysts are generally obtained, so that the epoxidation is also advantageously incomplete in a two-phase system, ie in two with one another miscible liquid phases can take place. This procedure has the advantage, on the one hand, that lipophilic, water-insoluble olefins can be oxidized, and, on the other hand, that the epoxides formed remain in the organic phase and the formation of undesired by-products is thus suppressed. In addition, the product separation is facilitated by the two-phase procedure.
In einer bevorzugten Ausfuhrungsform epoxidiert man nach dem erfindungsgemaßen Verfahren Propen zu Propylenoxid, insbesondere im zweiphasigen System.In a preferred embodiment, propene is epoxidized to propylene oxide, in particular in a two-phase system, by the process according to the invention.
In einer weiteren bevorzugten Ausfuhrungsform epoxidiert man nach dem erfindungsgemaßen Verfahren 1,3-Butadien zu Vinyloxiran, ins¬ besondere im zweiphasigen System.In a further preferred embodiment, 1,3-butadiene is epoxidized to vinyloxirane by the process according to the invention, in particular in a two-phase system.
Mit den erfindungsgemaßen hochaktiven Katalysatoren I erhalt man in einfacher und wirtschaftlicher Verfahrensweise unter milden und schonenden Bedingungen aus Olefinen mittels wäßrigem Wasser¬ stoffperoxid Epoxide mit hohen Selektivitäten und hohen Umsatzra¬ ten.With the highly active catalysts I according to the invention, epoxides with high selectivities and high conversion rates are obtained from olefins by means of aqueous hydrogen peroxide in a simple and economical procedure under mild and gentle conditions.
BeispieleExamples
Beispiel 1:Example 1:
Herstellung der Katalysator-StammlosungenPreparation of the catalyst stock solutions
a) Herstellung einer wäßrigen Stammlosung von [Mo(0) (02) (H20) 2]a) Preparation of an aqueous stock solution of [Mo (0) (0 2 ) (H 2 0) 2 ]
In 24,0 g (212 mmol) 30 gew. -%ιger H202-Losung wurden unter kraftigem Ruhren 6,00 g (41,7 mmol) [M0O3] suspendiert. Die farblose Suspension wurde 4 h bei 40°C gerührt, wobei sich eine klare, hellgelbe Losung bildet, die bei 4°C aufbewahrt wurde. - Gehalt [Mo (O) (02) (H20) 2] : 1,39 mmol/g.In 24.0 g (212 mmol) 30 wt. % H 2 0 2 solution were suspended with vigorous stirring 6.00 g (41.7 mmol) [M0O 3 ]. The colorless suspension was stirred at 40 ° C. for 4 hours, a clear, light yellow solution being formed which was stored at 4 ° C. - Content [Mo (O) (0 2 ) (H 2 0) 2 ]: 1.39 mmol / g.
a) Herstellung einer wäßrigen Stammlosung von [W(O) (02) (H20) 2]a) Preparation of an aqueous stock solution of [W (O) (0 2 ) (H 2 0) 2 ]
In 24,0 g (212 mmol) 30 gew. -%ιger H202-Losung wurden unter kraftigem Ruhren 8,00 g (32,0 mmol) [W03 H20] suspendiert. Die gelbe Suspension wurde 6 h bei 40°C gerührt, wobei sich eine milchig trübe Losung bildete. Nach Abtrennung des unlöslichen Rückstands (25 mg) durch Zentrifugieren wurde die klare, far¬ blose Losung bei 4°C aufbewahrt. - Gehalt [W(O) (02) (H20)2] : 1,01 mmol/g.In 24.0 g (212 mmol) 30 wt. % H 2 0 2 solution were suspended with vigorous stirring 8.00 g (32.0 mmol) [W0 3 H 2 0]. The yellow suspension was stirred at 40 ° C. for 6 hours, a milky, cloudy solution being formed. After separating the insoluble Residue (25 mg) by centrifugation, the clear, colorless solution was stored at 4 ° C. - Content [W (O) (0 2 ) (H 2 0) 2 ]: 1.01 mmol / g.
Beispiel 2:Example 2:
Darstellung der Katalysatoren [M(0) (02)2Li]Representation of the catalysts [M (0) (0 2 ) 2 L i ]
a) Darstellung von [Mo(0) (02) 2{0P(n-Oct) 3}]a) Representation of [Mo (0) (0 2 ) 2 {0P (n-Oct) 3 }]
Zu 1,86 g (2,58 mmol) Mo-Stammlόsung (Beispiel la) wurden zu¬ nächst 4 ml Tetrahydrofuran (THF) zugegeben. Unter Rühren wurden bei 25°C 500 mg (1,29 mmol) Tri-n-octylphosphanoxid4 ml of tetrahydrofuran (THF) were first added to 1.86 g (2.58 mmol) of Mo stock solution (Example Ia). 500 mg (1.29 mmol) of tri-n-octylphosphine oxide were stirred at 25 ° C.
[OP(n-Oct)3] zugegeben. Nach 2 h kraftigem Rühren wurde die gelbe Losung im Vakuum auf ca. 3 ml eingeengt, wobei sich em gelbes 01 abschied. Die Reaktionsmischung wurde mit CH2C12 [OP (n-Oct) 3 ] added. After stirring vigorously for 2 h, the yellow solution was concentrated in vacuo to about 3 ml, a yellow 01 separating. The reaction mixture was treated with CH 2 C1 2
(3 mal je 5 ml) extrahiert. Die vereinigten Extrakte wurden im Vakuum vollständig eingedampft. Der hellgelbe, wachsartige Rückstand wurde mit Wasser (2 mal mit j e 2 ml) gewaschen und 6 h bei 25°C/10 5 mbar getrocknet.(3 times 5 ml each) extracted. The combined extracts were completely evaporated in vacuo. The light yellow, waxy residue was washed with water (2 times with 2 ml each) and dried for 6 h at 25 ° C./10 5 mbar.
Ausbeute: 675 mg (93 %) hellgelbes Wachs DTA: 81°C (exotherme Zersetzung) CHN-Analyse: C24H5ιP06Mo (562,6) ber. C 51,24 H 9,14 gef. C 51,68 H 9,45Yield: 675 mg (93%) light yellow wax DTA: 81 ° C (exothermic decomposition) CHN analysis: C 24 H 5 ιP0 6 Mo (562.6) calcd. C 51.24 H 9.14 found. C 51.68 H 9.45
b) Darstellung von [W(O) (02) 2{0P(n-Oct) 3}]b) Representation of [W (O) (0 2 ) 2 {0P (n-Oct) 3 }]
Zu 6,00 g (6,06 mmol) W-Stammlosung (Beispiel lb) wurden zu¬ nächst 12 ml THF zugegeben. Unter Ruhren wurden bei 25°C zur Losung 1,50 g (3,87 mmol) [0P(n-0ct)3] gegeben. Nach 4 h kraftigem Rühren wurde die farblose Losung im Vakuum auf ca. 5 ml eingeengt, wobei sich ein farbloses 01 abschied. Die Re¬ aktionsmischung wurde mit CH2C12 (3 mal je 10 ml) extrahiert. Die vereinigten Extrakte wurden im Vakuum vollständig einge¬ dampft. Der farblose, olige Rückstand wurde mit Wasser (3 mal mit je 15 ml) gewaschen und 6 h bei 25°C/10"5 mbar getrocknet.12 ml of THF were first added to 6.00 g (6.06 mmol) of W stock solution (Example 1b). 1.50 g (3.87 mmol) [0P (n-0ct) 3 ] were added to the solution with stirring at 25 ° C. After 4 h of vigorous stirring, the colorless solution was concentrated in vacuo to about 5 ml, a colorless oil separating. The reaction mixture was extracted with CH 2 C1 2 (3 times 10 ml each). The combined extracts were completely evaporated in vacuo. The colorless, oily residue was washed with water (3 times with 15 ml each) and dried for 6 hours at 25 ° C./10 5 mbar.
Ausbeute: 2,40 g (95 %) farbloses 01 DTA: 98°C (exotherme Zersetzung) CHN-Analyse: C24H5ιP06W (650,0) ber. C 44,35 H 7,91 gef. C 45, 14 H 8,53 c) Darstellung von [Mo(0) (02) 2{0NMe2 (n-Cι8H37) }]Yield: 2.40 g (95%) colorless 01 DTA: 98 ° C (exothermic decomposition) CHN analysis: C 24 H 5 ιP0 6 W (650.0) calcd. C 44.35 H 7.91 found. C 45, 14 H 8.53 c) Representation of [Mo (0) (0 2 ) 2 {0NMe 2 (n-Cι 8 H 37 )}]
Zu 5,00 g (6,95 mmol) Mo-Stammlösung (Beispiel la) wurden bei 25°C unter Rühren 6,00 g (5,74 mmol) Dimethyl-n-octadecyl - aminoxid [0NMe2 (n-CιβH37) ] (30 Gew. -% in Wasser) gegeben, wo¬ bei sich spontan ein blaßgelber Niederschlag bildete. Nach 2 h kräftigem Rühren wurde der Niederschlag abfiltriert, mit Wasser (3 mal mit je 50 ml) gewaschen und im Vakuum 6 h bei 25°C/10"5 mbar getrocknet.6.00 g (5.74 mmol) of dimethyl-n-octadecylamine oxide [0NMe 2 (n-CιβH 37 )] (30% by weight in water), whereby a pale yellow precipitate formed spontaneously. After vigorous stirring for 2 h, the precipitate was filtered off, washed with water (3 times with 50 ml each) and dried in vacuo for 6 h at 25 ° C./10 5 mbar.
Ausbeute: 2,00 g (71 %) blaßgelbe, amorphe Festsubstanz DTA: 78°C (exotherme Zersetzung)Yield: 2.00 g (71%) pale yellow, amorphous solid substance DTA: 78 ° C (exothermic decomposition)
CHN-Analyse: C20H43MoN06 (489,5) ber. C 49,07 H 8,85 N 2,86 gef. C 49,07 H 8,88 N 2,82CHN analysis: C 20 H 43 MoN0 6 (489.5) calcd. C 49.07 H 8.85 N 2.86 found C 49.07 H 8.88 N 2.82
d) Darstellung von [Mo (O) (02) 2{0N(dodec) 3}]d) Representation of [Mo (O) (0 2 ) 2 {0N (dodec) 3 }]
Zu 2,00 g (2,87 mmol) Mo-Stammiösung (Beispiel la) wurden bei 25°C unter Rühren 1,20 g (2,23 mmol) Tri-n-dodecylaminoxid [ON(dodec)3] gelöst in 5 ml CH2C12 gegeben. Nach 5 h kräftigem Rühren bei 25°C wurde die organische Phase abgetrennt, mit Wasser (3 mal mit je 5 ml) gewaschen und im Vakuum vollstän¬ dig eingedampft. Der blaßgelbe, amorphe Rückstand wurde 6 h bei 25°C/10'5 mbar getrocknet.1.20 g (2.23 mmol) of tri-n-dodecylamine oxide [ON (dodec) 3 ] were dissolved in 5 at 2.00 [deg.] (2.97 mmol) of Mo stock solution (Example la) at 25 ° C. while stirring ml of CH 2 C1 2 are given. After 5 h of vigorous stirring at 25 ° C., the organic phase was separated off, washed with water (3 times with 5 ml each) and evaporated completely in vacuo. The pale yellow, amorphous residue was dried at 25 ° C./10 5 mbar for 6 h.
Ausbeute: 2,81 g (95 %) blaßgelbe, amorphe Festsubstanz DTA: 75°C (exotherme Zersetzung)Yield: 2.81 g (95%) pale yellow, amorphous solid substance DTA: 75 ° C (exothermic decomposition)
CHN-Analyse: C36H75MoN06 (713,9) ber. C 60,57 H 10,59 N 1,96 gef. C 60,62 H 10,72 N 1,95CHN analysis: C 36 H 75 MoN0 6 (713.9) calc. C 60.57 H 10.59 N 1.96 found C 60.62 H 10.72 N 1.95
d) Darstellung von [W(O) (02) 2{0N(dodec) 3}]d) Representation of [W (O) (0 2 ) 2 {0N (dodec) 3 }]
Zu 3,00 g (3,03 mmol) W-Stammlösung (Beispiel lb) wurden bei 25°C unter Rühren 1,30 g (2,42 mmol) [ON(dodec)3] gelöst in 5 ml CH2CH2 gegeben. Nach 5 h kräftigem Rühren bei 25°C wurde die organische Phase abgetrennt, mit Wasser (3 mal mit je 5 ml) gewaschen und im Vakuum vollständig eingedampft. Der farblose, klebrige Rückstand wurde 6 h bei 25°C/10"5 mbar ge¬ trocknet.1.30 g (2.42 mmol) [ON (dodec) 3 ] dissolved in 5 ml of CH 2 CH 2 were added to 3.00 g (3.03 mmol) of W stock solution (Example 1b) at 25 ° C. while stirring given. After 5 h of vigorous stirring at 25 ° C., the organic phase was separated off, washed with water (3 times with 5 ml each) and completely evaporated in vacuo. The colorless, sticky residue was dried for 6 hours at 25 ° C./10 5 mbar.
Ausbeute: 1,84 g (95 %) farbloses, klebriges Wachs DTA: 68°C (exotherme Zersetzung)Yield: 1.84 g (95%) colorless, sticky wax DTA: 68 ° C (exothermic decomposition)
CHN-Analyse: C36H75WN06 (801,8) ber. C 53,93 H 9,43 N 1,75 gef. C 53,88 H 9,29 N 1, 67 Beispiel 3CHN analysis: C 36 H 75 WN0 6 (801.8) calc. C 53.93 H 9.43 N 1.75 found C 53.88 H 9.29 N 1.67 Example 3
Katalytische Oxidation von Cycloocten und l-Octen durch 30 Gew. -% H202 mit in situ erzeugten Katalysatoren des Typs MO(02) 2LX (H20)Catalytic oxidation of cyclooctene and l-octene by 30% by weight of H 2 0 2 with catalysts of the type MO (0 2 ) 2 L X (H 2 0) generated in situ
Zu einem aliquoten Teil (0,36 mmol = 4 Mol-%) der m Beispiel 1 beschriebenen Katalysator-Stammlosung wurden bei 25°C 36 mmol 30 Gew. -% H202 und 9 mmol Olefm zugegeben. Anschließend wurde die Reaktionslösung mit 0,36 mmol an Phosphanoxid- bzw. Amm-N-Oxid- Ligand gelost in 4 ml CHC13 versetzt und 24 h bei 60°C gerührt. Die Bestimmung von Olefm-Umsatz und Epoxid-Selektivitat erfolgte durch Gaschromatographie.36 mmol of 30% by weight of H 2 O 2 and 9 mmol of olefin were added to an aliquot (0.36 mmol = 4 mol%) of the catalyst stock solution described in Example 1 at 25 ° C. Then the reaction solution was mixed with 0.36 mmol of phosphine oxide or amm-N-oxide ligand in 4 ml of CHC1 3 and stirred at 60 ° C. for 24 h. Olefm conversion and epoxide selectivity were determined by gas chromatography.
Die Ergebnisse der Versuche smd zusammengefaßt in Tabelle 1 dar¬ gestellt.The results of the experiments are summarized in Table 1.
Die gleichen Ergebnisse erhalt man im Prinzip auch mit den analo¬ gen unter Beispiel 2 beschriebenen unabhängig dargestellten Katalysatoren (jeweils mit 0,36 mmol gelost in 4 ml CHC13) .In principle, the same results are also obtained with the analogous catalysts described independently in Example 2 (in each case with 0.36 mmol dissolved in 4 ml of CHCl 3 ).
Beispiele 4 und 5Examples 4 and 5
Epoxidation mit Lx = Tri (n-dodecyl) -arsanoxidEpoxidation with L x = tri (n-dodecyl) arsenic oxide
In einem Glasautoklav legte man l-Octen (500 mg, 4,45 mmol), M03 (0,17 mmol, 4,0 mol% bzgl. l-Octen, als 0,5 M Losung in 30 gew. -%ιgem H202) und Tri- (n-dodecyl) -arsanoxid (0,17 mmol in 3 ml Chloroform gelost) vor. Danach gab man H202 (17,8 mmol, als 30 gew. %ιge wäßrige Losung) hinzu und rührte bei 60°C. Octenep- oxid war das einzige nachgewiesene Produkt. Die Octenoxidausbeu- ten bei verschiedenen Reaktionszeiten smd in Tabelle 2 zusammen¬ gefaßt.In a glass autoclave, 1-octene (500 mg, 4.45 mmol), M0 3 (0.17 mmol, 4.0 mol% with respect to l-octene) was placed as a 0.5 M solution in 30% by weight H 2 0 2 ) and tri- (n-dodecyl) arsenic oxide (0.17 mmol dissolved in 3 ml chloroform). Then H 2 0 2 (17.8 mmol, as 30% by weight aqueous solution) was added and the mixture was stirred at 60.degree. Octenep oxide was the only product identified. The octene oxide yields at different reaction times are summarized in Table 2.
Tabelle 2Table 2
Beispiele 6 und 7 Examples 6 and 7
Epoxidation mit L1 = 4 - (5 -Nonyl) -pyridinEpoxidation with L 1 = 4 - (5 -nonyl) pyridine
In einem Glasautoklav legte man l-Octen (500 mg, 4,45 mmol) , M03 (0,17 mmol, 4,0 mol% bzgl. l-Octen, als 0,5 M Lösung in 30 gew. -%igem H202) und 4 - (5 -Nonyl) -pyridin (0,17 mmol in 3 ml Chloroform gelöst) vor. Danach gab man H202 (17,8 mmol, als 30 gew. -%ige wäßrige Lösung) hinzu und rührte bei 60°C. Octenep- oxid war das einzige nachgewiesene Produkt. Die Octenoxidausbeu- ten bei verschiedenen Reaktionszeiten sind in Tabelle 3 zusammen¬ gefaßt.In a glass autoclave, 1-octene (500 mg, 4.45 mmol), M0 3 (0.17 mmol, 4.0 mol% with respect to l-octene) was placed as a 0.5 M solution in 30% by weight H 2 0 2 ) and 4 - (5-nonyl) pyridine (0.17 mmol dissolved in 3 ml chloroform). Then H 2 0 2 (17.8 mmol, as a 30% strength by weight aqueous solution) was added and the mixture was stirred at 60.degree. Octenep oxide was the only product identified. The octene oxide yields at different reaction times are summarized in Table 3.
Tabelle 3Table 3
Beispiele 8 und 9Examples 8 and 9
Epoxidation mit L1 = 4 - (5 -Nonyl) -pyridin-N-oxidEpoxidation with L 1 = 4 - (5-nonyl) pyridine-N-oxide
In einem Glasautoklav legte man l-Octen (500 mg, 4,45 mmol) , M03 (0,17 mmol, 4,0 mol% bzgl. l-Octen, als 0,5 M Lösung in 30 gew. -%igem H202) und 4 - (5-Nonyl) -pyridin-N-oxid (0,17 mmol in 3 ml Chloroform gelöst) vor. Danach gab man H202 (17,8 mmol, als 30 gew. -%ige wäßrige Lösung) hinzu und rührte bei 60°C. Octenep- oxid war das einzige nachgewiesene Produkt. Die Octenoxidausbeu- ten bei verschiedenen Reaktionszeiten sind in Tabelle 4 zusammen¬ gefaßt.In a glass autoclave, 1-octene (500 mg, 4.45 mmol), M0 3 (0.17 mmol, 4.0 mol% with respect to l-octene) was placed as a 0.5 M solution in 30% by weight H 2 0 2 ) and 4 - (5-nonyl) pyridine-N-oxide (0.17 mmol dissolved in 3 ml chloroform). Then H 2 0 2 (17.8 mmol, as a 30% strength by weight aqueous solution) was added and the mixture was stirred at 60.degree. Octenep oxide was the only product identified. The octene oxide yields at different reaction times are summarized in Table 4.
Tabelle 4Table 4
Beispiele 10 und 11Examples 10 and 11
Epoxidation mit L1 = 4 - (Dioctylamino) -pyridinEpoxidation with L 1 = 4 - (dioctylamino) pyridine
In einem Glasautoklav legte man l-Octen (500 mg, 4,45 mmol) , M03 1-Octene (500 mg, 4.45 mmol), M0 3 was placed in a glass autoclave
(0,17 mmol, 4,0 mol% bzgl. l-Octen, als 0,5 M Lösung in(0.17 mmol, 4.0 mol% with respect to l-octene, as a 0.5 M solution in
30 gew. -%igem H202) und 4 - (Dioctylamino) -pyridin (0,17 mmol in 3 ml Chloroform gelost) vor. Danach gab man H202 (17,8 mmol, als 30 gew. -%ιge wäßrige Losung) hinzu und rührte bei 60°C. Octenep- oxid war das einzige nachgewiesene Produkt. Die Octenoxidausbeu- ten bei verschiedenen Reaktionszeiten sind in Tabelle 5 zusammen¬ gefaßt.30 wt. -% H 2 0 2 ) and 4 - (dioctylamino) pyridine (0.17 mmol in 3 ml of chloroform dissolved). Then H 2 0 2 (17.8 mmol, as 30% by weight aqueous solution) was added and the mixture was stirred at 60.degree. Octenep oxide was the only product identified. The octene oxide yields at different reaction times are summarized in Table 5.
Tabelle 5Table 5
VOVO
Tabelle 1 o ©Table 1 o ©
σiσi
"0 n H"0 n H
-β-β
o e O e
Patentansprücheclaims
1. Katalysatoren der allgemeinen Formel I1. Catalysts of the general formula I
XX
[L2)n M(02) ;D[L 2 ) n M (0 2 ); D
Ll L l
in derin the
M ein Metall aus der 4. bis 7. Nebengruppe des Periodensy¬ stems der Elemente bezeichnet,M denotes a metal from the 4th to 7th subgroup of the periodic table of the elements,
L1 einen Aminoxid-Liganden der Formel II, einen Phosphanoxid- oder Arsanoxid-Liganden der Formel III, einen Pyridin-N-oxid- Liganden der Formel VII oder einen Pyridin-Liganden der For¬ mel VIIIL 1 is an amine oxide ligand of the formula II, a phosphine oxide or arsine oxide ligand of the formula III, a pyridine-N-oxide ligand of the formula VII or a pyridine ligand of the formula VIII
°Θ ( I I ) ( I I I ) ( VI I ) ( VI I I )° Θ (I I) (I I I) (VI I) (VI I I)
bedeutet, in denenmeans in which
Ri bis R3 gleiche oder verschiedene C].- bis C3o-Alkyl-, C7- bis C3rj-Aralkyl- oder Cξ - bis C3o-Arylreste, welche zusätzlich Ethersauerstoffatome, Carbonylgruppen, Hydroxylgruppen, Alkoxygruppen, Carboxylgruppen, Cyano¬ gruppen, Carbonsaureestergruppen, Sulfogruppen, Phosphon¬ sauregruppen, Nitrogruppen, Halogenatome und/oder gegebe- nenfalls durch Ci- bis C4-Alkylreste substituierte Amino¬ gruppen als funktionelle Gruppen enthalten können, be¬ zeichnen, wobei mindestens einer der Reste R1 bis R3 we¬ nigstens 11 C-Atome aufweisen muß und wobei die beiden anderen Reste miteinander zu einem Ring verknüpft sein können, und R4 bis R5 gleiche oder verschiedene C4- bis C30-Alkyl-, C7- bis C3o-Aralkyl- oder Cio- bis C3o-Arylreste, welche zusätzlich Ethersauerstoffatome, Carbonylgruppen, Hydroxylgruppen, Alkoxygruppen, Carboxylgruppen, Cyano- gruppen, Carbonsaureestergruppen, Sulfogruppen, Phosphon¬ sauregruppen, Nitrogruppen, Halogenatome und/oder gegebe¬ nenfalls durch Ci- bis C4-Alkylreste substituierte Amino¬ gruppen als funktionelle Gruppen enthalten können, be¬ zeichnen, undR i to R 3 are the same or different C] - to C 3 o-alkyl, C 7 - to C 3 rj-aralkyl or Cξ - to C 3 o-aryl radicals which additionally contain ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, Carboxyl groups, cyano groups, carboxylic acid ester groups, sulfo groups, phosphonic acid groups, nitro groups, halogen atoms and / or amino groups which may be substituted by C 1 -C 4 -alkyl radicals may contain functional groups, wherein at least one of the radicals R 1 to R 3 must have at least 11 carbon atoms and the two other radicals can be linked together to form a ring, and R 4 to R 5 are the same or different C 4 to C 30 alkyl, C 7 to C 3 o-aralkyl or Cio to C 3 o-aryl radicals which additionally contain ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, Cyano groups, carboxylic acid ester groups, sulfo groups, phosphonic acid groups, nitro groups, halogen atoms and / or amino groups which may be substituted by C 1 -C 4 -alkyl radicals as functional groups, denote, and
und Rü bis Rι s unabhängig voneinander Wasserstoff oder gleiche oder verschiedene Ci- bis C30-Alkyl-, C7- bis C3o"Aralkyl- oder Ce- bis C30- Arylreste oder Ci- bis C30-Alkoxy-, C7- bis C30-Aralkoxy- , C6- bis C3o-Aryloxy- oder Dihydrocarbylammo-Gruppen mit gleichen oder ver¬ schiedenen Ci- bis C3o-Alkyl-, C7- bis C3o-Aralkyl- und/ oder Cβ - bis C3o-Arylresten als Hydrocarbylresten, welche zusatzlich Ethersauerstoffatome, Carbonylgruppen, Hydro¬ xylgruppen, Alkoxygruppen, Carboxylgruppen, Cyanogruppen, Carbonsaureestergruppen, Sulfogruppen, Phosphonsaure¬ gruppen, Nitrogruppen, Halogenatome und/oder gegebenen¬ falls durch Ci- bis C4-Alkylreste substituierte Amino¬ gruppen als funktionelle Gruppen enthalten können, be¬ zeichnen, wobei mindestens einer der Reste R11 oder Ri5 Wasserstoff sem muß, die Summe der Kohlenstoffatome in den Resten Ru bis R15 mindestens 8 betragen muß und die Reste RU bis R1S paarweise zu Ringen verknüpft sein kön¬ nen,and Rü to R ι s independently of one another hydrogen or identical or different Ci to C 30 alkyl, C 7 to C 3 o "aralkyl or Ce to C 30 aryl radicals or Ci to C 30 alkoxy, C 7 - to C 30 -aralkoxy, C 6 - to C 3 o-aryloxy or dihydrocarbylammo groups with identical or different C 1 to C 3 o-alkyl, C 7 - to C 3 o-aralkyl groups and / or Cβ - to C 3 o-aryl radicals as hydrocarbyl radicals which additionally contain ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups, carboxylic acid ester groups, sulfo groups, phosphonic acid groups, nitro groups, halogen atoms and / or, if appropriate, by ci- to C 4 -alkyl radicals may contain substituted amino groups as functional groups, denote wherein at least one of the radicals R 11 or Ri 5 must be hydrogen sem, the sum of the carbon atoms in the radicals R u to R 15 must be at least 8 and the residues RU to R 1S can be linked in pairs to form rings no,
L2 emen Hilfsliganden aus der Gruppe Oxo, Halogenide,L 2 an auxiliary ligand from the group oxo, halides,
Pseudohalogenide, Carboxylate, Phenolate, Alkoholate, Enolate, Ketone, Ether, Amine, Amide, Harnstoff, Harn¬ stoffderivate und Wasser oder einen weiteren Liganden L1 oder eine freie Koordinationsstelle bedeutet,Pseudohalides, carboxylates, phenolates, alcoholates, enolates, ketones, ethers, amines, amides, urea, urea derivatives and water or another ligand L 1 or a free coordination point,
X für Oxo-Sauerstoff oder einen gegebenenfalls durch Ci- bis C4-Alkyl substituierten Imido-Liganden steht,X represents oxo-oxygen or an imido ligand which is optionally substituted by C 1 -C 4 -alkyl,
Z fur Phosphor oder Arsen steht,Z represents phosphorus or arsenic,
m die Zahl 1 oder 2 bezeichnet undm denotes the number 1 or 2 and
n die Zahl 1, 2 oder 3 bedeutet.n represents the number 1, 2 or 3.
2. Katalysatoren I nach Anspruch 1, bei denen M Molybdän oder Wolfram bezeichnet. 3. Katalysator der allgemeinen Formel Ia oder Ib nach Anspruch 1 oder 22. Catalysts I according to claim 1, in which M denotes molybdenum or tungsten. 3. Catalyst of the general formula Ia or Ib according to claim 1 or 2
(Ia) (Ib) (Ia) (Ib)
in denen L2 Wasser bezeichnet und die Variablen M, Ll und n die oben genannten Bedeutungen haben.in which L 2 denotes water and the variables M, L l and n have the meanings given above.
4. Katalysatoren I nach den Ansprüchen 1 bis 3, bei denen L1 einen Ammoxid-Liganden II bedeutet, welcher als Reste R1 bis R3 Ci- bis C2rj-Alkylgruppen tragt, wobei mindestens einer der Reste Ri bis R3 eine Cι2- bis C2o-Alkylgruppe bezeichnen muß und wobei die beiden anderen Reste miteinander zu einem ge- sattigten fünf- oder sechsgliedrigen Ring, der noch weitere Heteroatome aus der Gruppe Sauerstoff und Stickstoff enthal¬ ten kann, verknüpft sem können.4. Catalysts I according to claims 1 to 3, in which L 1 is an ammoxide ligand II, which carries as residues R 1 to R 3 Ci to C 2 rj-alkyl groups, at least one of the radicals R i to R 3 has to denote a C 2 to C 2 o-alkyl group and the two other radicals can be linked together to form a saturated five- or six-membered ring which can also contain further heteroatoms from the group consisting of oxygen and nitrogen.
5. Katalysatoren I nach den Ansprüchen 1 bis 3, bei denen hl einen Phosphanoxid- oder Arsanoxid-Liganden III bedeutet, welcher als Reste R4 bis R6 C4- bis C20-Alkylgruppen tragt.5. Catalysts I according to claims 1 to 3, in which h l is a phosphine oxide or arsine oxide ligand III, which carries as radicals R 4 to R 6 C 4 - to C 20 -alkyl groups.
6. Verfahren zur Herstellung der Katalysatoren I gemäß den An¬ sprüchen 1 bis 5, dadurch gekennzeichnet, daß man die kataly- tisch aktiven Komplexe der allgemeinen Formel I aus einem an¬ deren Komplex des Metalls M und Wasserstoffperoxid herstellt.6. Process for the preparation of the catalysts I according to claims 1 to 5, characterized in that the catalytically active complexes of the general formula I are prepared from another complex of the metal M and hydrogen peroxide.
7. Verwendung der Katalysatoren I gemäß den Ansprüchen 1 bis 5 zur Epoxidierung von Olefinen.7. Use of the catalysts I according to claims 1 to 5 for the epoxidation of olefins.
8. Verfahren zur Herstellung von Epoxiden der allgemeinen For¬ mel IV8. Process for the preparation of epoxides of the general formula IV
RS R9 RS R 9
R7- C Rl° :ιv) in der R7 bis Ri0 gleich oder verschieden sind und Wasserstoff oder gegebenenfalls substituierte Alkyl-, Alkenyl-, Heteroal- kyl- , Cycloalkyl-, Aryl- oder Heteroarylreste, wobei die Re¬ ste R7 bis Ri° auch miteinander zu Ringen verknüpft sem kon- nen, oder Substituenten auf Basis von Elementen aus der 4. bis 7. Hauptgruppe des Periodensystems der Elemente bedeuten, aus Olefinen der allgemeinen Formel VR 7 - CR l °: ιv) in which R 7 to R i0 are the same or different and are hydrogen or optionally substituted alkyl, alkenyl, heteroalkyl, cycloalkyl, aryl or heteroaryl radicals, the radicals R 7 to R i ° also being rings with one another linked sem, or mean substituents based on elements from the 4th to 7th main group of the Periodic Table of the Elements, from olefins of the general formula V
Rβ R β
's, R9's, R9
(V)(V)
R7" R10R 7 " R 10
mit wäßrigem Wasserstoffperoxid, dadurch gekennzeichnet, daß man die Epoxidierung der Olefine V in Gegenwart derwith aqueous hydrogen peroxide, characterized in that the epoxidation of the olefins V in the presence of
Katalysatoren I gemäß den Ansprüchen 1 bis 5 durchfuhrt.Performs catalysts I according to claims 1 to 5.
9. Verfahren zur Herstellung von Epoxiden IV nach Anspruch 8, dadurch gekennzeichnet, daß man die Epoxidierung der Olefine V mit wäßrigem Wasserstoffperoxid in zwei miteinander nicht vollständig mischbaren flüssigen Phasen durchführt.9. A process for the preparation of epoxides IV according to claim 8, characterized in that one carries out the epoxidation of the olefins V with aqueous hydrogen peroxide in two liquid phases which are not completely miscible with one another.
10. Verfahren zur Herstellung von Propylenoxid aus Propen nach Anspruch 8 oder 9.10. A process for the preparation of propylene oxide from propene according to claim 8 or 9.
11 . Verfahren zur Herstellung von Vmyloxiran aus 1 , 3 -Butadien nach Anspruch 8 oder 9 . 11. A process for the preparation of Vmyloxiran from 1, 3-butadiene according to claim 8 or 9.
EP96931020A 1995-09-11 1996-09-04 Peroxo group-containing metal complexes with amine oxide, phosphane oxide, arsane oxide, pyridin-n-oxide or pyridine ligands as epoxidation catalysts Withdrawn EP0876213A1 (en)

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DE19533331A DE19533331A1 (en) 1995-09-11 1995-09-11 Metal complexes containing peroxo groups with amine oxide or phosphine oxide ligands as epoxidation catalysts
DE19533331 1995-09-11
PCT/EP1996/003888 WO1997010054A1 (en) 1995-09-11 1996-09-04 Peroxo group-containing metal complexes with amine oxide, phosphane oxide, arsane oxide, pyridin-n-oxide or pyridine ligands as epoxidation catalysts

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