EP0914205A1 - Verfahren zur oxidation organischer substrate im beisein von metallkomplexe von tetra-, penta- und hexakoordinierenden liganden, und diese enthaltende oxidationskatalysatoren - Google Patents

Verfahren zur oxidation organischer substrate im beisein von metallkomplexe von tetra-, penta- und hexakoordinierenden liganden, und diese enthaltende oxidationskatalysatoren

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Publication number
EP0914205A1
EP0914205A1 EP96939124A EP96939124A EP0914205A1 EP 0914205 A1 EP0914205 A1 EP 0914205A1 EP 96939124 A EP96939124 A EP 96939124A EP 96939124 A EP96939124 A EP 96939124A EP 0914205 A1 EP0914205 A1 EP 0914205A1
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formula
oxidation
group
metal
ligand
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French (fr)
Inventor
Laurent Fraisse
Jean-Jacques Girerd
Frédéric Perie
Alain Rabion
David Tetard
Jean-Baptiste Verlhac
Alexander Nivorozhkin
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Societe National Elf Aquitaine
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Societe National Elf Aquitaine
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/16—Peroxy compounds the —O—O— group being bound between two carbon atoms not further substituted by oxygen atoms, i.e. peroxides
    • C07C409/18—Peroxy compounds the —O—O— group being bound between two carbon atoms not further substituted by oxygen atoms, i.e. peroxides at least one of the carbon atoms belonging to a ring other than a six-membered aromatic ring
    • 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
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • 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
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
    • C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
    • C07C49/453—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having three rings
    • 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
    • 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
    • B01J2531/72—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes

Definitions

  • the oxidation of these organic substrates aims either to modify their polarity and their solubility in order to facilitate their biodegradation by microorganisms, or to transform them chemically with a view to using them as such or for their reactivity in certain specific reactions such as the oxidation of cyclohexane to cyclohexanol / cyclohexanone, first step in the synthesis of adipic acid, a key monomer in the synthesis of nylon.
  • nonhemic enzymes containing iron among which are methane monooxygenase or MMO which catalyzes the conversion of methane to methanol.
  • MMO methane monooxygenase
  • This type of enzyme is particularly interesting because of the presence in its structure of oxygen bridges between two complexed iron atoms, these bridges being recognized as favorable to this oxidation.
  • the reaction is catalyzed by an iron complex pentacoordmé by bleomycme via the nitrogen atoms of the latter.
  • the present invention therefore relates to a process for the oxidation of organic substrates in the presence of active oxidants in redox reactions and to metal complexes obtained by complexation of transition metals with multicoordinating ligands with nitrogen endings.
  • This process aims to obtain smaller and more polar molecules, especially for the production of compounds with high added value, or molecules of lower molecular weight and easier to biodegrade by the techniques in use.
  • the present invention therefore relates to a process for the selective oxidation of organic substrates by bringing said substrates into contact with an oxidant chosen from hydroperoxides and / or hydrogen peroxide in the presence of a catalyst formed from at least one complex.
  • metal of at least one multidentate ligand nitrogen with at least one transition metal by operating in an aqueous diluent and / or organic, characterized in that the molar ratio metal complex / peroxide is between 1 and IO "1 ⁇ and temperature is less than 120 ° C, and in that the metal complex has a general formula (I) corresponding to:
  • M is a metal from the group consisting of manganese and iron in at least one of the possible oxidation states II, III, IV or V
  • X is a bridging species metals selected from the group consisting of water, hydroxide ions OH ⁇ , oxygen ions O 2- , 02 2 ⁇ and O2 " , sulfur ions S 2- , peroxide ions HOO", carboxyl ions RCOO " , R being an atom hydrogen, an optionally substituted alkyl or aryl group, and the sulphate, phosphate, carbonate and halide ions,
  • the organic substrates are present in solution, in suspension or in emulsion in a medium inert to oxidation, organic, aqueous or semi-aqueous such as for example a water / acetonitrile mixture or a water / dichloromethane.
  • oxidizable substrates are compounds of the group consisting of linear or branched alkanes, cyclic alkanes, linear alcohols or branched and aromatic, diaromatic and polyaromatic compounds optionally containing a heteroatom other than oxygen.
  • the preferred complexes are obtained from tetra-, penta- and hexacoordinating ligands comprising aromatic nitrogen heterocycles, these ligands containing from 4 to 6 nitrogen atoms capable of coordinating with the same metal by at least three of these nitrogen atoms.
  • Ar ⁇ and Ar 2 correspond in the ligand of formula (II) to one of the formulas (III), (IV) and (V) below:
  • R with p denoting an integer varying from 1 to 6 and R ′ and R" representing the hydrogen atom, an alkyl group comprising from 1 to 6 carbon atoms, a halogen atom or one of the nitro or methoxy groups and ethoxy.
  • the iron or manganese complexes are obtained from tetracoordinated ligands with at least one metal atom, such as in formula (II), R ⁇ and R 2 are either hydrogen or identical or different alkyl groups comprising from 1 to 6 carbon atoms and preferably 1 to 3 carbon atoms.
  • the complexes of N, N '-Bis- (2-pyridylmethyl) ethane-1,2-diamine or Bispicen of N, N' -dimethyl-N, N '-Bis- ( 2- pyridylmethyl) ethane-1,2-diamine or Bispicen (NMe) 2 and N-
  • N '-dimethyl-N, N' -Bis- (1-methylimidazol-2-yl-methyl) ethane-1,2-diamine or (1Me) Bisim (NMe) 2 with iron and / or manganese are preferred.
  • the process according to the invention is particularly effective in the presence of a complex comprising at least one metal-ligand system with tetracoordination of the metal by the ligand chosen from the group consisting of Fe-Bispicen, Mn- Bispicen, Fe-Bispicen (NMe) 2 , Mn-Bispicen (NMe) 2 , Fe- lMeBisim (NMe) 2 , Mn-lMe-Bisim (NMe) 2 , Fe-lMeBisim, Mn- lMeBisim, two coordinated metals that can be joined together by ⁇ -oxo or ⁇ bridges -carboxylato.
  • the presence of alkyl and preferably methyl groups on the nitrogen atoms of the diamine chain promotes the stabilization of the complexes obtained with these ligands.
  • the iron and manganese complexes are obtained from pentacoordinating ligands such that in formula (II), R- ⁇ is a group consisting of a hydrogen atom or a linear alkyl chain or branched containing from 1 to 3 carbon atoms, R 2 , Ari and Ar 2 are identical and correspond to one of the formulas (III), (IV) or (V) in which the heterocycle is optionally substituted benzopyridyl or benzimidazolyl counterpart.
  • the preferred metal-ligand system is obtained by complexation of iron or manganese with N, N, N '-Tris- (2-pyridylmethyl) -N' - methylethane-1, 2- diamine or TrispicMeen, also called Fe-TrispicMeen or Mn-TrispicMeen.
  • the preferred ligand is N, N, N ', N' -tetrakis- (2-pyridylmethyl) ethane-1,2-diamine or TPEN and the preferred iron and manganese complexes are the complexes of the metal-ligand systems Fe-TPEN and Mn-TPEN.
  • the oxidation reactions preferably take place in an inert oxidation, organic, aqueous or semi-aqueous medium such as, for example, water / acetonitrile and water / dichloromethane mixtures, in the presence of peroxide. hydrogen or terbutylhydroperoxide.
  • the metal complexes are used in solution or supported on inert solids with regard to the oxidation reaction, in particular on resins, silica clays, active charcoal or wool residues. They can be either impregnated or linked by a covalent chemical bond with an element of the support, in particular by grafting on the support or even by insertion into a metallic network such as silicic networks.
  • a second object of the invention is the application according to the invention to the gentle oxidation of substrates with a view to the specific production of products with high added value such as alcohols, aldehydes and ketones, characterized in that the ratio initial oxidative / substrate molar is preferably less than 0.5.
  • the present invention also relates to oxidation catalysts present in aqueous, semi-aqueous or organic solution, supported or not supported on a solid inert to oxidation, containing iron and / or manganese complexes characterized in that the said metal complex has the general formula (I) corresponding to:
  • Y is a counterion of the group consisting of halides, chlorates, borates, sulfates, phosphates, nitrates, perchlorates, sulfonates, triflates and hexafluorophospate, with x and y denoting whole numbers or equal to 1, u denoting an integer varying from 0 to 3, z denoting an integer corresponding to the charge of the metal complex and q being equal to the ratio of z to the charge of Y, and L a ligand of formula (VIII ) below:
  • Ar 2 and Ar 3 are identical or different and each consist of a linear carbon chain containing from 1 to 6 carbon atoms linked to at least one heterocycle comprising at least one nitrogen atom optionally protonated, Ri denoting a group consisting of a hydrogen atom or a linear alkyl chain or branched containing from 1 to 6 carbon atoms, optionally connected to at least one heterocycle comprising at least one nitrogen atom, optionally protonated, the ratio of the number of ligand molecules L to the number of metal atoms of the complexed ion , or x / y, being between 0.5 and 5 and preferably between
  • the oxidation catalysts according to the invention preferably contain complexes of iron and manganese, each ligand being coordinated with at least one metal atom in at least one of the possible oxidation states II, III, IV or V, by at least three of its nitrogen atoms, the first two coming from the diamine chain, the others, from nitrogen atoms of the nitrogen heterocyles.
  • two metal atoms are linked by a chemical bridging of the group constituted by the ligand (s), the ⁇ -oxo, ⁇ -carboxylato and hydroxo bridges.
  • the iron or manganese complexes are obtained with a ligand comprising five coordination sites, of formula (VIII) in which s is equal to 2, RI is a group consisting of a hydrogen atom or a linear or branched alkyl chain containing from 1 to 3 carbon atoms, Ari, Ar2 and Ar3 are identical or different and correspond to one of the formulas (III), (IV) or (V).
  • complexes resulting from the coordination of N, N, N '-tris- (2-pyridylmethyl) -N' -methyl-ethane-1,2-diamine or TrispicMeen with iron or manganese are preferred.
  • heterocycles Ari, Ar2 and Ar3 are identical and of formula (IV), with p preferably equal to 1.
  • the iron or manganese complexes are obtained with a ligand comprising at least six coordination sites, of formula (VIII) in which Ri corresponds as Ari, Ar 2 and Ar 3 ⁇ one of the formulas (III), (IV) and (V) in which p varies between 1 and 6.
  • Ri corresponds as Ari, Ar 2 and Ar 3 ⁇ one of the formulas (III), (IV) and (V) in which p varies between 1 and 6.
  • Ri is equal to 2
  • Ri, Ari, Ar 2 and Ar3 are identical to formula (III) and p is 1 or 2.
  • complexes resulting from the coordination of N, N, N ', N' -tetrakis- (2-pyridylmethyl) ethane-1,2-diamine or TPEN with iron and manganese are preferred.
  • s is equal to 2
  • Rj_, Ari, Ar 2 and Ar3 are identical to formula (IV) and p is equal to 1 or 2.
  • the present example aims to show the effectiveness of the process according to the invention with regard to the controlled oxidation of alkanes into products with high added value such as alcohols, aldehydes and / or ketones.
  • cyclooctane the majority oxidation product is cyclooctanone while for 0 1 adamantane, these are adamantone, and the two alcoholic forms adamantane-loi and adamantane-2ol.
  • Table 1 collates the yields obtained for each oxidation reaction after a time of reaction between 0.5 and 24 hours for each oxidation product, in ketone or aldehyde, in alcohol or in peroxide, and the total oxidation yield
  • the yields in Table I are given in molar percent: they correspond to the ratio of the number of moles of product formed to the number of moles of starting oxidizing product, this ratio being multiplied by 2 for the yields of ketone or aldehyde
  • the total yield (RDT) of oxidation product is calculated according to the formula below:
  • the metal complexes were prepared by mixing in 5 ml of acetonitrile 8 ⁇ moles of manganese perchlorate Mn (0104) 2 or of iron perchlorate Fe (0104) 3 with 8 ⁇ moles of ligand.
  • Tests from 1 to 8 were carried out by introducing into 5 ml of acetonitrile, the equivalent of 3.75 ⁇ mol of manganese complex [LMn ( ⁇ oxo) 2 MnL] 3+ , 3CIO4 " , 3.75 mmol of substrate, 75 mg of anisole (internal standard not degraded during oxidation reactions) and 0.66 mmol of ter butylhydroperoxide (TBHP) at 86% in water.
  • Test 9 was carried out as in test 2 but adding 33.4 ⁇ mol of sodium acetate to the solution.
  • cyclohexane was replaced under the conditions of test 2 by 0.15 mmol of adamantane.
  • adamantane only 20.9 mg of internal anisole standard and 0.66 mmol of TBHP are used.
  • the main oxidation products are adamantane-2-one (ketone) and two alcohols, adamantane-1- ol (in the alcohol column of table 1) and adamantane- 2- ol (yield given in the peroxide column)
  • test 16 the procedure is as for test 15 but the adamantane is replaced by 0.15 mmol of cyclooctane.
  • the manganese complex is replaced in test 1 by an iron complex of formula [LFe ( ⁇ oxo) ( ⁇ OAc) FeL] 3+ , 3CIO4 4 " , with ligand L of the substituted bispicen and unsubstituted, or alternatively substituted Bisim, the substrate to be oxidized being cyclohexane.
  • the present example aims to show the effectiveness of the process of the invention with regard to the oxidation of alcohols into products with high added value such as aldehydes and ketones.
  • Example 2 To oxidize these alcohols, the procedure is as in Example 1, in air, in acetonitrile medium in the presence of manganese or iron complexes obtained according to the procedure described in Example 1. The results of these tests are given as above in yield of oxidized products with respect to the oxidant. These results are collated in Table 2 below. Tests 22 to 24 are obtained under the same conditions as in test 2 of Example 1, but by substituting 2.5 mmol of benzyl alcohol with cyclohexane
  • Test 22 or 2.5 mmol of cyclohexanol (tests 23 and 24), the manganese complex being formed with the bispicen ligand (NMe) 2 .
  • Test 24 was carried out in the absence of oxidant but in air.
  • Tests 25 to 27 were carried out by replacing the manganese complexes with iron complexes in the procedure of test 17 of Example 1. Tests 26 and 27 were not carried out in solution in acetonitrile but in aqueous solution, to oxidize cyclohexanol (26) and 2-butanol (27) respectively, the oxidant TBHP being used at 70% in water.
  • the catalysts according to the invention are also effective in aqueous solution, which advantageously avoids the use of potentially polluting organic solvents such as than acetonitrile.
  • the present example aims to emphasize the effectiveness of the process according to the invention with regard to the oxidation of aromatics, in particular polyaromatics or PAHs which are more difficult to oxidize and therefore to biodegrade.
  • the tests are carried out on two model compounds of these polyaromatics which are phenanthrene and fluoranthrene.
  • the oxidation products of these compounds and of polyaromatic compounds in general are obtained by the opening of aromatic rings and the appearance of hydroxyl or oxidized groups in the chemical structure.
  • the disappearance of these substrates and the appearance of the oxidation products are monitored by HPLC liquid chromatography on a C18 reverse phase column (125 ⁇ 4.6) with isocratic elution with an acetonitrile / water mixture 60/40, and the pH of the reaction medium is measured at the start and end of the oxidation reaction.
  • the tests are carried out in an aqueous medium, the polyaromatics or substrates being present in emulsion in water, 50 ⁇ M of complex and 30 mM of hydrogen peroxide.
  • Table III collates the results obtained after one hour of reaction.
  • the operation is carried out at a temperature of 40 ° C. for a concentration of 112 ⁇ M of phenanthrene or of fluoranthrene.
  • the operation is carried out at 80 ° C., the phenanthrene concentration being 561 ⁇ M.
  • FeCI 3 , FeS04, Fe (CI0 4 ) 3 and MnS0 4 are controls taken alone
  • TPA tris (2-pyr ⁇ dylméthyl) amène
  • TACN 1, 4,7 bimethyl - 1, 4,7 - t ⁇ azacyclononane
  • Trispipen N, N, N '- Tris (2-Pyr ⁇ dylméthyl) -N' methylpropane - 1, 3 - diamine * complexes formed but not isolated in the solid state
  • reaction medium has an alkaline or neutral pH at the start of oxidation, it decreases very strongly during oxidation to become acid, this drop translating the appearance of acid carboxylic functions with respect to the starting substrates and therefore the opening of aromatic cycles.
  • oxidation in the presence of metal salts does not cause a change in pH, which suggests that the oxidation observed is a Fenton type oxidation without opening of the rings.

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EP96939124A 1995-11-16 1996-11-15 Verfahren zur oxidation organischer substrate im beisein von metallkomplexe von tetra-, penta- und hexakoordinierenden liganden, und diese enthaltende oxidationskatalysatoren Withdrawn EP0914205A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9513580 1995-11-16
FR9513580A FR2741340B1 (fr) 1995-11-16 1995-11-16 Procede d'oxydation de substrats organiques en presence de complexes metalliques de ligands tetra-, penta- et hexacoordinants et catalyseurs d'oxydation les contenant
PCT/FR1996/001804 WO1997018035A1 (fr) 1995-11-16 1996-11-15 Procede d'oxydation de substrats organiques en presence de complexes metalliques de ligands tetra-, penta- et hexacoordinants et catalyseurs d'oxydation les contenant

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EP (1) EP0914205A1 (de)
JP (1) JP2000500151A (de)
AU (1) AU7628996A (de)
CA (1) CA2235764A1 (de)
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NO (1) NO982240L (de)
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DE19605688A1 (de) * 1996-02-16 1997-08-21 Henkel Kgaa Übergangsmetallkomplexe als Aktivatoren für Persauerstoffverbindungen
ES2206853T3 (es) * 1998-11-10 2004-05-16 Unilever N.V. Catalizadores de blanqueo y oxidacion.
EP1008645B1 (de) * 1998-11-10 2004-07-21 Unilever Plc Wasch- und Bleichzusammensetzungen
US6573409B1 (en) 1999-07-02 2003-06-03 The Nutrasweet Company Process for the preparation of 3,3-dimethylbutanal
JP2005194244A (ja) * 2004-01-09 2005-07-21 Shigenobu Yano 亜鉛イオン蛍光センサー
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FR2741340B1 (fr) 1997-12-26
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FR2741340A1 (fr) 1997-05-23
AU7628996A (en) 1997-06-05
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NO982240D0 (no) 1998-05-15

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