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EP0342615A1
Expired / Lapsed
EP
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Process for the preparation of epoxides
Assignee: Istituto Guido Donegani SpA
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Filing: 1989-05-16
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Granted: —
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Expires: 2009-05-16
Abstract
Abstract A process for the preparation of epoxides by oxidation of the corresponding olefinic compounds is disclosed, said process being characterized in that the oxidation is carried out in a two-phase system which comprises: (a) an organic phase which contains the olefinic substrate, catalytic amounts of a porphyrinic complex of manganese and, optionally, at least one co-catalytic component selected from: (i) a nitrogen-containing, heterocyclic base; and (ii) an "onium" salt, all of said components being dissolved in an organic solvent substantially immiscible with water; (b) an aqueous phase containing a solution of an alkali or alkaline earth metal salt of an organic peracid, preferably magnesium monoperoxyphthalate hexahydrate. The resulting products may be used in the fields of foamed materials (polyurethanes), plasticizers and epoxy resins and as intermediates for fine chemistry.
Inventors
- 👤 Marco Ricci
- 👤 Cecilia Querci
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-09 04:11
CPC Classifications
C; C07; C07D; C07D303/00; C07D303/02; C07D303/04; C07D301/00; C07D301/02; C07D301/03; C07D301/14; C07D303/38; C07D303/40
Claims Analysis
Total Claims: 19
Claim 1
Independent Claim
77 words
Process for the preparation of epoxides by oxidation of the corresponding olefinic compounds, characterized in that said olefinic compounds are oxidized in a two-phase system comprising: (a) an organic phase which comprises said olefinic compound and catalytic amounts of at least one porphyrinic complex of manganese, both components being dissolved in an organic solvent substantially immiscible with water; (b) an aqueous phase comprising a solution of at least one alkali(ne) (earth) metal salt of an organic peracid.
Claim 2
Dependent Claim
42 words
Process according to claim 1, characterized in that the organic phase contains, dissolved in said organic solvent, at least one co-catalytic component selected from: (a) nitrogen-containing heterocyclic bases; and (b) "onium" salts; and, preferably, contains both types of components (a) and (b).
Claim 3
Dependent Claim
89 words
Process according to any one of claims 1 and 2, characterized in that the porphyrinic manganese complex catalyst comprises at least one meso(tetraaryl)porphyrinate of formula (II): wherein: X represents a monovalent anion stable under the reaction conditions, preferably selected from chloride and acetate, and the radicals Ar represent optionally substituted aryl groups, the same or different from each other, preferably selected from phenyl, naphthyl and anthracenyl groups, optionally substituted with at least one group selected from lower alkyl and lower alkoxy, nitro, sulfonyl, amino, amido, Cl, F and Br.
Claim 4
Dependent Claim
28 words
Process according to claim 3, characterized in that, in said porphyrinic complex of manganese of formula (II), Ar is selected from phenyl, 2-fluoro-phenyl, mesityl, perfluorophenyl and, preferably, 2,6-dichlorophenyl.
Claim 5
Dependent Claim
38 words
Process according to any one of claims 2 to 4, characterized in that said nitrogen-containing heterocyclic base is selected from the pyridines and the imidazoles and, preferably, comprises at least one of pyridine, 4-picoline, 3-phenyl-pyridine, 4-tert-butyl-pyridine and 1-hexyl-imidazole.
Claim 6
Dependent Claim
37 words
Process according to any one of claims 2 to 5, characterized in that the "onium" salt is selected from quaternary salts of formula (III): R₅R₆R₇R₈M⁺Y⁻ (III) wherein: and preferably is composed of benzyl-dimethyl-hexadecyl-ammonium chloride and/or dimethyl-[di-octadecyl(75%)+di-hexadecyl(25%)]-ammonium chloride.
Claim 7
Dependent Claim
56 words
Process according to any one of claims 1 to 6, characterized in that said alkali(ne) (earth) metal salt of the organic peracid is selected from the Na, K and Mg salts of mono-peroxy-phthalic acid, the Mg salts of monoperoxy-hexahydro-phthalic acid, monoperoxy-maleic acid and monoperoxy-citraconic acid and mixtures of said salts, and preferably is magnesium monoperoxyphthalate hexahydrate.
Claim 8
Dependent Claim
125 words
Process according to any one of claims 1 to 7, characterized in that the olefinic compound is selected from compounds having the formula (I): wherein R₁, R₂, R₃ and R₄, which optionally may contain functional groups inert under the reaction conditions, are the same or different from each other and represent hydrogen or linear or branched hydrocarbyl groups selected from alkyl groups and alkenyl groups containing up to 30 carbon atoms, cycloalkyl groups and cycloalkenyl groups containing from 3 to 12 carbon atoms, aryl, alkylaryl or alkenylaryl groups containing up to 12 carbon atoms; and any two of the above groups R₁, R₂, R₃ and R₄ may be combined to form a ring containing up to 12 carbon atoms and having one or more unsaturations.
Claim 9
Dependent Claim
37 words
Process according to claim 8, characterized in that the olefinic compound is a compound of formula (I) which contains at least one group selected from nitro, hydroxy, alkoxy, carbonyl, carboxy, ester, amide, nitrile and the halogen atoms.
Claim 10
Dependent Claim
58 words
Process according to any one of claims 1 to 9, characterized in that the olefinic compound is selected from propylene, the butenes, the pentenes, 1-dodecene, cyclohexene, cyclooctene, limonene, styrene, α-methyl-styrene, the stilbenes, the allyl halides and the methallyl halides, 3-butenoic acid or oleic acid and their esters or is a polyunsaturated olefin preferably selected from dienes and trienes.
Claim 11
Dependent Claim
36 words
Process according to any one of the preceding claims, characterized in that it is carried out at temperatures ranging from the freezing point of the aqueous phase to +40°C and, preferably, from 0°C to about +25°C.
Claim 12
Dependent Claim
27 words
Process according to any one of the preceding claims, characterized in that it is carried out under a pressure ranging from atmospheric pressure to about 50 atm.
Claim 13
Dependent Claim
36 words
Process according to any one of the preceding claims, characterized in that the porphyrinic complex is used in amounts of from 0.0001 to 0.01 mole, preferably from 0.0005 to 0.005 mole, per mole of olefinic substrate.
Claim 14
Dependent Claim
42 words
Process according to any one of the preceding claims, characterized in that said alkali(ne) (earth) metal salt of the organic peracid is used in amounts of from 0.1 to 10 moles, preferably from 2 to 5 moles per mole of olefinic substrate.
Claim 15
Dependent Claim
38 words
Process according to any one of claims 2 to 14, characterized in that said nitrogen-containing heterocyclic base is used in amounts of from 0.0001 to 1 mole, preferably from 0.0001 to 0.5 mole per mole of olefinic substrate.
Claim 16
Dependent Claim
36 words
Process according to any one of claims 2 to 15, characterized in that said "onium" salt is used in amounts of from 0.001 to 0.02 mole, preferably from to 0.01 mole per mole of olefinic substrate.
Claim 17
Dependent Claim
40 words
Process according to any one of the preceding claims, characterized in that the inert organic solvent substantially immiscible with water is selected from chlorinated hydrocarbons, preferably dichloromethane, dichloroethane, trichloroethane and mixtures thereof, and the olefinic compound used as starting material.
Claim 18
Dependent Claim
30 words
Process according to any one of the preceding claims, characterized in that the concentration of the olefinic substrate in the organic phase ranges from 10% to about 95% by weight.
Claim 19
Dependent Claim
49 words
Process according to any one of the preceding claims, characterized in that the concentration of the alkali(ne) (earth) metal salt of the organic peracid in the aqueous phase is at least 1% by weight and, preferably, corresponds substantially to the saturation concentration of the salt in the aqueous phase.
References Cited (Backward Citations)
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