EP0885207A1 - Procede de fabrication d'epoxydes a partir d'olefines avec des bis(triorganosilyl)peroxydes en presence d'activateurs a base de derives d'acides metalliques - Google Patents

Procede de fabrication d'epoxydes a partir d'olefines avec des bis(triorganosilyl)peroxydes en presence d'activateurs a base de derives d'acides metalliques

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Publication number
EP0885207A1
EP0885207A1 EP97907054A EP97907054A EP0885207A1 EP 0885207 A1 EP0885207 A1 EP 0885207A1 EP 97907054 A EP97907054 A EP 97907054A EP 97907054 A EP97907054 A EP 97907054A EP 0885207 A1 EP0885207 A1 EP 0885207A1
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Prior art keywords
oxides
residues
radicals
mmol
metal
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EP97907054A
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German (de)
English (en)
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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    • 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)
    • 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
    • B01J31/1895—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 arsenic or antimony
    • 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
    • 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
    • C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
    • 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
    • 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
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/74—Rhenium

Definitions

  • the present invention relates to an improved process for the preparation of epoxides from olefins with bis (triorganosilyl) peroxides in the presence of activators based on certain metal acid derivatives.
  • oxidants such as hydrogen peroxide HOOH or alkyl hydroperoxides ROOH have a firm place in organic synthesis, the synthesis potential of bis (triorganosilyl) peroxides ("BTSP”), especially that of the easily accessible bis (trimethylsilyl) peroxide ( “TMS 2 0 2 "), for a few applications.
  • BTSP bis (triorganosilyl) peroxides
  • BTSP were used as synthons for "OH + " for the stoichiometric electrophilic hydroxylation of carbanions, such as aryllithium compounds, vinyl anions, ⁇ -sulfonyl carbanions as well as lithiated carboxylic acids and their amides (cf. Taddei and Ricci in Synthesis 1986, 633 ).
  • carbanions such as aryllithium compounds, vinyl anions, ⁇ -sulfonyl carbanions as well as lithiated carboxylic acids and their amides (cf. Taddei and Ricci in Synthesis 1986, 633 ).
  • the Baeyer-Villiger oxidation of ketones by BTSP and the electrophilic hydroxylation of electron-rich aromatics in the presence of non-catalytic amounts of Lewis acids such as BF 3 , A1C1 3 or SnCl 4 are also known.
  • the object of the present invention was therefore to provide an effective activator for the epoxidation of olefins with BTSP. Accordingly, a process for the preparation of epoxides of the general formula
  • R 1 to R 4 are identical or different and are hydrogen or optionally substituted alkyl, alkenyl, heteroalkyl, cycloalkyl, aryl or heteroaryl radicals, where the radicals R 1 to R 4 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 mean from olefins of the general formula
  • R 5 to R 7 optionally denote hydrocarbon radicals substituted by functional groups, in the presence of activators based on metal acid derivatives of the general formula
  • M denotes a metal from subgroup 4 to 7 of the periodic table of the elements
  • X for anionic ligands from the group consisting of halides, alkyl residues, alkoxy residues, aryloxy residues, trialkylsilyl residues, hydroxyl groups, metal anhydride residues of the formula -OMO x , carbon acid ester residues, sulfonic acid ester residues, phosphonic acid ester residues, carbonic acid ester residues, sulfuric acid ester residues, phosphoric acid ester residues, hydroperoxy residues, peroxyalkyl residues and triorganosilylperoxy residues, where two variables X can also represent a peroxo function,
  • x for an integer from 1 to 5
  • n the number 1 or 2
  • two neutral ligands L, two anionic ligands X or one neutral ligand L and one anionic ligand X can be linked directly or through an alkylene bridge to form a chelating ligand.
  • the crucial question for catalysis is whether silyl groups, like protons, can migrate in oxo (peroxo) complexes within the O-ligand regime.
  • activators for the epoxidation system described which are latently coordinatively unsaturated metal oxo and peroxo complexes which meet this criterion of rapid silyl group migration.
  • the metal acid derivatives mentioned are presented here.
  • Suitable metals M in the metal acid derivatives mentioned are, in particular, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, manganese and in particular molybdenum, tungsten and rhenium.
  • the activators used are those metal acid derivatives in which M denotes molybdenum or tungsten and at the same time n stands for the number 1 or in which M denotes rhenium and n stands for the number 1 or 2. Examples of such species are the activator structures Ib, Ilb, Illb and IVb listed below.
  • Amine oxide or phosphine oxide ligands of the formulas are particularly suitable as neutral ligands L.
  • C 3 o-alkyl, C ⁇ - to C 3 o-aralkyl or C ⁇ - to C 3 o-aryl or het-aryl radicals which additionally contain ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups, carboxylic acid ester groups, Sulpho groups, phosphonic acid groups, nitro groups, halogen atoms and / or amino groups which may be substituted by C 1 -C 4 -alkyl radicals may be referred to as functional groups.
  • Typical examples of such amine N-oxide ligands are:
  • Methyl -n-dodecyl- (6-phenylhexyl) amine oxide Typical examples of such phosphine oxide (phosphine oxide) ligands are:
  • Tri-n-butylphosphine oxide Tri-tert. -butylphosphine oxide
  • Tri- (2-ethylhexyl) phosphine oxide Tri-n-dodecylphosphine oxide
  • Tribenzylphosphine oxide benzyl-di-n-octylphosphine oxide
  • radicals R 8 to R 10 and R 11 to R 13 are derived in particular from corresponding ethylene oxide, propylene oxide or butylene oxide or from tetrahydrofuran reaction products.
  • Alkoxy substituents and carboxylic ester substituents in R 8 to R 10 and R 11 to R 13 preferably carry C 1 -C 4 -alkyl radicals, in particular methyl or ethyl.
  • Halogen atoms here primarily mean chlorine or bromine.
  • the number of functional groups listed for the radicals mentioned, if any, is usually from 1 to 3, and from 1 to 14 for ether oxygen atoms depending on the chain length.
  • Amine oxide and phosphine oxide ligands, the carboxymethyl radicals and alkoxycarbonylmethyl radicals are also of particular interest or have 2-pyridyl radicals.
  • neutral ligands L are preferably also:
  • radicals R 14 to R 16 have the meanings given above;
  • R 17 and R 18 are hydrogen or identical or mixed Ci to C 30 alkyl, C-- to C 30 aralkyl or C 6 to C_;
  • Aryl or hetaryl 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 optionally substituted amino groups substituted by Ci to C 4 alkyl radicals, as functional groups to draw;
  • a typical example of such a phosphoric acid is hexamethylphosphoric acid amide ("HMPTA");
  • R 17 and R 18 have the meanings given above;
  • typical examples of such formamides are N, N-dimethylformamide (“DMF”) and N-methyl-N-stearylformamide;
  • Py ⁇ dm-N-oxide ligands which are at one or more ring positions, preferably in the 2- and / or in the 4-position, by a Ci to C 30 alkyl, C 7 to C 30 aralkyl or Cg to C 30 aryl or hetaryl radical which additionally contains ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups, carboxylic acid ester groups,
  • Ci to C4 alkyl substituted amino groups as functional groups can contain, or by a halogen atom such as fluorine, chlorine or bromine, a hydroxy group, a C ⁇ to C 3 o alkoxy group or an optionally alkyl-substituted amino group are; typical examples of such pyridine N-oxides are ⁇ - and ⁇ picolm-N-oxide.
  • Typical examples of inorganic ligands X are:
  • Fluoride and chloride (based on: metal acid fluorides or chlorides)
  • Methyl (based on: alkyl metal oxides, e.g. methyl rhenium oxide)
  • Phenoxy (based on: phenyl metal acid)
  • Trimethylsilyloxy (based on: Metallsauretnmethyl - silylester)
  • OMO x (based on: metal acid anhydrides, e.g. Re 2 0 7 and Mo0 3 )
  • Residues of mixed metal acid anhydrides such as acetates, sulfonates, phosphonates, organocarbonates, organosulfates and organophosphates, which can be partly or perfluorinated in their organic part
  • ligands L and X linked to a chelate ligand are 2, 2 '-bipyridyl-N-oxide or N, N, N', N '-tetrabutylethylene-diamm-N, N' -oxide; in the latter case, the link between the two
  • Suitable bis (triorganosilyl) peroxides are, in particular, those of the general formula given above, in which R 5 to R 7 have the same meaning as R 8 to R 10 or R 11 to R 13 .
  • Particularly preferred are bis (tri Ci to C 4 alkylsilyl) peroxides, very particularly oevorzugt Sonders bis (trimethylsilyl) peroxide.
  • 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 are 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 also alkene oligomers with reactive double bonds such as polypropene and polyisobutene.
  • the olefins 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, vinylammes, vinylphosphines, vinyl ethers, vinyl sulfides and halogenated alkenes such as vinyl chloride, vinylidene chloride or t ⁇ chlorethylene.
  • the epoxidation process according to the invention is expediently carried out in such a way that the olefin to be epoxidized is initially introduced together with the bis (triorganosilyl) peroxides and then the activator based on metal acid derivatives or a precursor for this, which passes under the reaction conditions into the activator, is added.
  • the bis (triorganosilyl) peroxide is normally mixed with the olefin to be epoxidized in a molar ratio of 1: 1 (preferably with a slight excess of olefin). There is usually no reaction between these components in the long term either. Then the activator, for example Ib-IVb
  • the ligand L has the task of increasing the activity of the activator precursor, which is in principle present even without the presence of L, while at the same time increasing the selectivity of the epoxidation reaction which proceeds rapidly after addition of the activator.
  • Catalytically active compounds such as Ib-IVb can usually be isolated and characterized from the corresponding precursors such as Ia-IVa.
  • Amine oxides, phosphine oxides, arsane oxides, stiban oxides and - somewhat slower - also pyridine-N-oxides as ligands L usually form under the catalytic conditions from the corresponding tertiary amines, phosphines, arsanes, stibans or pyridines and BTSP.
  • the epoxidation according to the invention is preferably carried out in an inert organic solvent and at temperatures from 0 to 120 ° C., in particular 10 to 100 ° C., above all 20 to 80 ° C. You usually work at normal pressure.
  • Suitable inert organic solvents are in particular those from the class of the alkanes, aromatics, haloalkanes,
  • Halogen aromatics, ethers, ketones, esters and tertiary alcohols such as tert-butanol.
  • the can also serve the reaction from the silyl peroxide resulting siloxane R 3 S1O S1R 3 , R definition-appropriate organic residue), so that it is possible to work entirely on another solvent.
  • residues R the activator is homogeneously soluble in these media.
  • the activator described can be used on the basis of metal acid derivatives in a bound form on an inorganic or organic carrier material which is insoluble in the reaction medium.
  • Suitable carrier materials for this purpose are, in particular, those from the group consisting of silicon dioxide, silica gels, silica, aluminum oxides, kaolins, aluminum silicates and poly-tert. -amin- N-oxide, Polyvmylpy ⁇ dm-N-oxide and chemically fixed Hexamethylphosphorsauretriamid on a polystyrene matrix into consideration.
  • Silica gels Silica gels are colloidal shaped or unshaped silicas of elastic to firm consistency with loose to dense pore structure and high adsorption capacity. Kieseigel surfaces have acidity properties. Silica gel is usually made from water glass by reaction with mercury acids.
  • the thermally obtained ie publicly produced by flame hydrolysis of SiCl 4
  • highly disperse "pyrogenic" Si0 2 qualities for example Aerosile or Sipernate ®
  • silica with an average (agglomerate) particle size of 100 nm to 30 ⁇ m, in particular 1 ⁇ m to 20 ⁇ m, and an SiO 2 content of 95 to 100, preferably 98 to 100% by weight used.
  • Aluminum oxides occur in nature, for example, as alumina or as corundum.
  • the aluminum oxide is present in the ⁇ modification.
  • ⁇ -Al 2 0 3 is obtained from bauxite using the Bayer process.
  • "Active" aluminum oxides with a high specific surface area, which are particularly suitable as adsorbents, are produced by precipitation processes from aluminum salt solutions or by calculation from ⁇ -aluminum hydroxide.
  • Kaolins are naturally occurring hydrated aluminum silicates (clays), which are also called china clays because of their previous main use.
  • the main constituents are the tapered kaolimte and the monoclimate dickite and nacrite together with montmorillonite and gel-like alumina silicates (allophanes).
  • Aluminum silicates are compounds with different proportions Al 2 0 3 and Si0 2 , which occur in nature as andalusite, sisthen, mullite, sillimanite, etc.
  • Aluminum silicate minerals, in which Al takes up lattice positions in the crystal lattice instead of Si, are the aluminosilicates (eg ultramarine, zeolites, feldspars). Freshly precipitated aluminum silicates are finely dispersed and have a large surface area and high adsorption capacity.
  • the present invention also relates to the activator complexes themselves, which are generally suitable for the catalytic activation of a whole series of chemical reactions, in particular oxidation reactions, especially for the catalytic epoxidation of olefins, and which ones
  • M denotes a metal from subgroup 4 to 7 of the periodic table of the elements
  • X for anionic ligands from the group consisting of halides, alkyl residues, alkoxy residues, aryloxy residues, trialkylsilyl residues, hydroxyl groups, metallic acid anhydride residues of the formula OMO x , carboxylic acid ester residues, sulfonic acid ester residues, phosphonic acid ester residues, carbonic acid ester residues, sulfuric acid ester residues, phosphate residues, phosphate residues Peroxyalkyl radicals and
  • n the number 1 or 2
  • two neutral ligands L, two anionic ligands X or one neutral ligand L and one anionic ligand X can be linked directly or through an alkylene bridge to form a chelate ligand
  • inorganic or organic carrier materials which are insoluble in the reaction medium and are selected from the group consisting of silicon dioxide, silica gels, silica, aluminum oxides, kaolins, aluminum silicates and poly tert . amm-N oxide, Polyvmylpy ⁇ dm-N oxi ⁇ e and chemically fixed Hexamethylphosphorsauret ⁇ amid on a polystyrene matrix
  • the epoxidation process according to the invention has a number of special advantages. These are to be discussed below using the example of bis (trimethylsilyl) peroxide TMS 2 0 2 compared to conventional hydroperoxides or hydrogen peroxide:
  • TMS 2 0 2 and other BTSP are comparatively unproblematic peroxides that meet the highest demands on plant, warehouse and laboratory safety.
  • TMS 2 0 2 only decomposes at 200 ° C and in a controlled manner.
  • TMS 2 0 2 and other BTSP are only activated when the special catalyst, namely the described activators based on metal acid derivatives, is added, which promotes the heterolytic 0-0 cleavage. This class of substances does not have a particular tendency towards autocatalytic (radical) decay, initiated, for example, by heavy metal traces.
  • TMS 2 0 2 can also be produced in large quantities from largely recyclable raw materials (eg urea, TMSC1, H 2 0 2 , base) and can be stored virtually indefinitely and safely.
  • largely recyclable raw materials eg urea, TMSC1, H 2 0 2 , base
  • Bis (triorganosilyl) peroxides are aprotic substitutes for anhydrous 100% H 2 0 2 . In the presence of a catalyst, these eme a comparable oxidation power, the Oxidation reactions, however, generally proceed more selectively than with H 2 0 2 .
  • bis (triorganosilyl) peroxides can also be used for the oxidation of hydrolysis-sensitive olefins (e.g. enolates, unsaturated carboxylic acid chlorides, etc.).
  • hydrolysis-sensitive olefins e.g. enolates, unsaturated carboxylic acid chlorides, etc.
  • the siloxanes R 3 S ⁇ OSiR 3 formed in the redox reaction of bis (triorganosilyl) peroxides are hardly basic, sterically demanding, ie poor ligands, which are characterized by only a low coordination ability.
  • Competitive inhibition of the Lewis acidic metal center known from H 2 0 or tert-BuOH (the reduction products of H 2 0 2 or tert--BuOOH), is thus virtually impossible.
  • silyl peroxides and siloxanes can be used for oxidation purposes. With a correspondingly high proportion of the siloxanes, they can take on the role of the solvent.
  • the reaction mixture is stirred in an oil bath at 60 ° C.
  • IR (film): v 2960 vs and 2869 vs v (C-H), 2729 s and 2432 s v (N-C-H), 1772 s v (Mo-O-N), 1467 vs, 1381 s, 1261,
  • Catalytic converter type II active species
  • a reaction control with analogous reaction control in CDC1 3 shows a decrease in the TMS signal when the solvent is evaporated.
  • the colorless oily residue is h in vacuo at 25 6 ° C / 10 ⁇ 5 mbar freed of volatile constituents, wherein a far ⁇ Bloser, waxy solid remains.
  • Variant B [Re 2 0 7 ] as starting material 202 mg (1.00 mmol) of ON n Bu 3 dissolved in 2 ml of CHC1 3 are added dropwise to a suspension of 243 mg (0.50 mmol) of [Re 2 0 7 ] in 3 ml of CHCI 3 at 25 ° C Forms a colorless, clear solution for 10 minutes. After stirring at 25 ° C. for 2 h, the solvent is completely removed in vacuo. The colorless, oily residue is freed from volatile constituents in vacuo for 6 hours at 25 ° C./10 -5 mbar, leaving a colorless, waxy solid.
  • IR (film): v 3085 s, 2961 s, 1886 w, 1469 s, 1383 m, 1345 m, 1118 m, 1062 m, 1026 m, 965 vs, 922 vs, 735 s, 502 w cm -1 .

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Abstract

Fabrication d'époxydes à partir d'oléfines avec des bis(triorganosilyl)peroxydes en présence d'activateurs à base de dérivés d'acides métalliques de formule générale (1), où M représente un métal des groupes secondaires 4 à 7, notamment molybdène, tungstène ou rhénium; L représente un ligand neutre sélectionné dans le groupe comprenant amino-oxyde, phosphanoxyde, arsanoxyde, triamide d'acide phosphorique, formamide et N-oxyde de pyridine; X représente un ligand inorganique; x est compris entre 1 et 5; y est 0, 1 ou 2; Z est 1 ou 2; n est 1 ou 2.
EP97907054A 1996-03-04 1997-02-28 Procede de fabrication d'epoxydes a partir d'olefines avec des bis(triorganosilyl)peroxydes en presence d'activateurs a base de derives d'acides metalliques Withdrawn EP0885207A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19608004 1996-03-04
DE19608004A DE19608004A1 (de) 1996-03-04 1996-03-04 Verfahren zur Herstellung von Epoxiden aus Olefinen mit Bis(trisorganosilyl)peroxiden in Gegenwart von Aktivatoren auf Basis von Metallsäurederivaten
PCT/EP1997/000982 WO1997032867A1 (fr) 1996-03-04 1997-02-28 Procede de fabrication d'epoxydes a partir d'olefines avec des bis(triorganosilyl)peroxydes en presence d'activateurs a base de derives d'acides metalliques

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EP0885207A1 true EP0885207A1 (fr) 1998-12-23

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US (1) US6090956A (fr)
EP (1) EP0885207A1 (fr)
JP (1) JP2000507924A (fr)
DE (1) DE19608004A1 (fr)
WO (1) WO1997032867A1 (fr)

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US6271400B2 (en) * 1997-10-23 2001-08-07 The Scripps Research Institute Epoxidation of olefins
DE19938609C2 (de) * 1999-08-14 2002-11-14 Erhard Weber Kugelgel-Flächenlager
JP5138147B2 (ja) * 2003-04-18 2013-02-06 住友化学株式会社 エポキシドの製造方法
US7880038B2 (en) * 2003-04-18 2011-02-01 Sumitomo Chemical Company, Limited Metal catalyst and its use
JP5801727B2 (ja) * 2012-01-16 2015-10-28 株式会社日本触媒 ペルオキソ錯体
US12084464B2 (en) * 2019-11-22 2024-09-10 Applied Materials, Inc. Rhenium complexes and methods of use

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US6090956A (en) 2000-07-18
WO1997032867A1 (fr) 1997-09-12
DE19608004A1 (de) 1997-11-13

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