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WO1998004538A1 - Oxygenation catalytique d'hydrocarbures par des complexes de metalloporphyrine et de metallosalen - Google Patents

Oxygenation catalytique d'hydrocarbures par des complexes de metalloporphyrine et de metallosalen Download PDF

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WO1998004538A1
WO1998004538A1 PCT/US1997/013111 US9713111W WO9804538A1 WO 1998004538 A1 WO1998004538 A1 WO 1998004538A1 US 9713111 W US9713111 W US 9713111W WO 9804538 A1 WO9804538 A1 WO 9804538A1
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complex
species
group
catalyst
ligand
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John T. Groves
Tommaso Carofiglio
Marcella Bonchio
Anthony Sauve
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Princeton University
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Princeton University
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    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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    • C07C2603/74—Adamantanes

Definitions

  • the present invention relates to catalytic oxidation of hydrocarbons using metallic porphyrin or salen complexes.
  • the metallic porphyrin or salen complexes of the present invention are designed to efficiently produce high yields of oxygenated products selectively and rapidly under conditions conducive to commercial production and scale-up. More particularly, the present invention relates to novel oxidation processes and in some cases novel oxidation compounds which can be used to oxidize olefins to their corresponding epoxides, alkanes to alcohols and subsequently to their corresponding ketones, as well as the hydroxylation of aromatics to phenols and their corresponding quinones.
  • nylon is one such product which has enormous commercial applications and which is made from starting materials, i.e. cyclohexane, which must first be oxidized into alcohol and ketone intermediate compounds during the manufacture of nylon.
  • the oxygenation of cyclohexane is extremely expensive and inefficient, having a conversion of only 3-4%.
  • Sufficient oxygenation of various saturated hydrocarbons has long been a difficult challenge which has provoked the search for efficient and cost effective oxidation catalysts and processes for use in the chemical industry.
  • transition metal catalysts have been studied for some time for their use as oxidation catalysts for saturated hydrocarbons. More recently, the use of metallic porphyrin complexes have been reported as effective oxidation catalysts using certain substrates, oxidants and process parameters.
  • U.S. Patent No. 4,822,899 to Groves et al. describes the use of metallic porphyrin complexes as catalysts in epoxidation reactions.
  • the process disclosed in this reference involves adding to a solution of metallic porphyrin catalyst an olefin or mixture of olefins to form a reaction solution.
  • the reaction solution is purged with an oxidizing agent, e.g. commercially pure oxygen or air, and the reaction is conducted at ambient conditions for 24 hours.
  • an oxidizing agent e.g. commercially pure oxygen or air
  • the results after 24 hours shows a maximum turnover rate of 45.4, as shown in Example 8, in the Table, Column 5.
  • the turnover rate is the number of molecules of oxidized product turned out per each molecule of catalyst for a given time period.
  • U.S. Patent No. 4,822,899 demonstrated the ability to use metallic porphyrin complexes as oxidation catalysts using air as the oxidant and under ambient conditions, the efficiency of such reactions even under the best of reaction conditions, e.g. under optimum temperature and pressure parameters, is comparatively low. That is, the turnover rate and yields represented an improvement over previous efforts but did not approach the level useful for commercial scale-up.
  • nitro group on a coordinated ligand has been reported in the literature. See Sheldon R.A.; Kochi J.K., Metal-Catalyzed Oxidation of Organic Compounds, p. 1 12-1 13, Academic Press (1981).
  • the nitro group is used to transfer oxygen to a substrate, i.e. to oxidize the substrate. This reference shows that the oxidation state of the metal does not change. This is in sharp contrast to the present invention where the nitrosyl group present in the porphyrin or salen ligand structure remains intact and the oxidation state of the metal center changes to the highly active M ⁇ species.
  • U.S. Patent No. 4,900, 871 to Ellis, Jr. et al. discloses iron coordination complexes containing a halogenated ligand.
  • the iron porphyrin complex is disclosed as having Fe" and Fe 1 " states and the improvement in oxidation of alkanes by contact with air or oxygen is reported as being due to the introduction of halogen into the coordination complex.
  • Oxidation of propane using such complexes show a maximum turnover of 583.1 per 1.5 hours at 150 °C and a maximum turnover of 849 per 6 hours at 80°C using isobutane as the substrate.
  • This patent states in column 7, line 29.
  • halogenating the ligand of the iron coordination complex improves activity but has little or no effect on activity where the metal is other typical transition metals such as manganese or chromium.
  • these porphyrins have been reported as being free radical initiators rather than catalysts per se. See Grinstoff, M.W.; Hill, M.G.; Labinger, J.A.; Gray H.B., Science, 1994, 264, 1311-1313.
  • U.S. Patent No. 5,280,115 to Ellis, Jr. et al. discloses metal complexes of porphyrin catalysts for the oxidation of alkanes where the metal may be ruthenium.
  • the porphyrin ring has nitro groups attached thereto in the meso and/or ⁇ -pyrrolic positions.
  • U.S. Patent No. 4,895,680 to Ellis, Jr. et al. discloses nitride-activated metal coordination complexes such as M-X where M is a transition metal and X is a nitride on the oxidation of alkanes.
  • M is a transition metal
  • X is a nitride on the oxidation of alkanes.
  • This reference used a phosphine ligand and iodosylbenzene as an oxidant to achieve low oxidation product yields and low turnovers on hydrocarbon substrates such as cyclohexane, styrenc, norbornene and stilbene (see Table 1 , p. 131).
  • hydrocarbon substrates such as cyclohexane, styrenc, norbornene and stilbene
  • the present invention represents a significant improvement over the prior art oxidation processes which employ metallic porphyrin complexes as oxidative catalysts.
  • the efficiency, selectivity and speed have been significantly improved over the prior art without the use of mineral acids, and such difficult substrates as cyclohexanes and benzene have been oxygenated efficiently using the present invention.
  • the present invention addresses the long sought need of finding a means to rapidly and efficiently oxidize commercially important substrates such as olefins, alkanes, aromatics, and alcohols (aliphatic or aromatic) by carefully designing the porphyrin or salen complex and the associated ligands.
  • the coordination complexes of the present invention are designed by selecting substituents, both on the external structure and the internal ligand set, such that the maximum activity of the catalytic metal can be obtained.
  • the choice of substituents is dictated by the need to control the electronic structure of the catalyst to prevent or minimize the formation of a stabilized ligand set adjacent the metal, as well as to minimize or prevent the formation of stabilized electron configurations on the metal per se. a phenomenon known as disproportionation.
  • the present invention relates to novel oxidative processes for substrates such as olefins, alkanes, aromatics and alcohols using metallic porphyrin or salen catalytic complexes which have been specifically designed to maximize catalytic activity, thereby enhancing efficiency, selectively and speed of oxidation of these substrates.
  • substrates such as olefins, alkanes, aromatics and alcohols
  • metallic porphyrin or salen catalytic complexes which have been specifically designed to maximize catalytic activity, thereby enhancing efficiency, selectively and speed of oxidation of these substrates.
  • the choice of the substituents in the metallic complexes may be varied, but must be chosen to prevent specific ligand set arrangements known to be stable and therefore less catalytically efficient.
  • the present invention has discovered that when the metal catalyst is in the M * "-P state, or its equivalent, and the peripheral substituents on the porphyrin or salen macrocycle structure are electron-withdrawing groups, the activity of the catalyst is remarkably and synergistically improved over prior art catalysts.
  • M represents the coordination metal
  • P represents the coordination ligand attached thereto.
  • the highly active catalysts of the present invention can be formed prior to catalysis or they can be formed in situ during the catalysis steps of oxidizing hydrocarbons.
  • the present invention relates to a method of catalyzing the oxidation of hydrocarbons including contacting in the presence of an oxidant under reaction conditions said hydrocarbon with a metallo macrocyclic catalyst complex selected from the group consisting of porphyrins, salens and mixtures thereof, said catalyst complex having electron withdrawing substituents on its periphery and a highly reactive M 111 species or its equivalent contained within which catalytically effectuates rapid formation of oxidized hydrocarbon product.
  • a coordination ligand transition metal complex having a nitrosyl axial liquid on the metal is described.
  • the coordination ligand is preferably a porphyrin or salen structure which may optionally have various substitutions on its periphery.
  • the transition metal is ruthenium and the peripheral substitutions on the coordination ligand are electron- withdrawing groups.
  • the present invention relates to a method of catalyzing the oxidation of hydrocarbons using high activity porphyrin metal complexes which includes the steps of (i) providing a coordination ligand "P" having electron- withdrawing substituent groups on its periphery and containing within it a low activity metallic species selected from the group consisting of dioxo-M v ', XY-M IV and Z-M";
  • M is Ru, Os, Rh, Ir, Nb, Re or Tc
  • X and Y may be the same or different and are oxygen or a halogen
  • Z is CO or a weakly coordinating ligand such as an alcohol, ether or acetonitrile.
  • the coordination ligand is a porphyrin or salen, but other ligands which coordinate with the metal center to form a complex and stabilize the complex in the desired oxidation state are contemplated.
  • the present invention further includes novel metalloporphyrin complexes used in the process which generate M" 1 centers and have electron-withdrawing substituents on the ligand peripheral structure.
  • novel complexes particularly include those with halogen peripheral substituents on a porphyrin ligand having Ru" at its center. These complexes generate Ru 1 " as the highly active species in the presence of oxidants.
  • the catalysts and catalytic processes of the present invention greatly enhance the efficiency, selectivity and yield of oxidized substrate products.
  • the turnover rate i.e. the number of molecules of oxidized products per molecule of catalyst as measured over a given time period is exponentially increased over those processes of the prior art, and in particular, the aforementioned processes reported by Ohtake et al.
  • the present invention includes oxidation of a wide variety of compound types, including olefins, alkanes, aromatics, alcohols and the like.
  • the catalysts of the present invention are used to convert olefins to epoxides.
  • the catalysts are used to convert alkanes to alcohols and subsequently to their corresponding ketones.
  • the catalysts are used in the hydroxylation of aromatics to phenols and further oxidized to their corresponding quinones.
  • M +3 and M" 1 will be used interchangeably and will designate the same highly active species.
  • the use of equal Roman and Arabic numbers designating other chemical species will also be intended to refer to the same species.
  • the catalyst precursors of the present invention are soluble in organic media. They can be converted to insoluble, heterogeneous forms by contacting them with solids support structures such as silica, alumina, aminopropylsilane derivatives of these solids, and the like.
  • solids support structures such as silica, alumina, aminopropylsilane derivatives of these solids, and the like.
  • insoluble molecular sieve support structures can be used to form the heterogeneous catalyst complex with the precursors of the present invention. Examples of such molecular sieves include zeolites.
  • Other forms of solid support structures and various types of materials used therefor can be combined effectively with the catalysts of the present invention without loss of catalytic conversion speeds as would normally be expected when heterogeneous catalyst systems are used.
  • Figure 1 is a schematic of the mechanistic pathways of obtaining the highly active M 111 porphyrin species using ruthenium as the metal center.
  • Figure 2 is a schematic of the mechanistic pathway of obtaining the highly active M" 1 species using ruthenium porphyrin containing nitrosyl (NO) as an axial ligand.
  • Figure 3 is a schematic of catalytic oxidation of various hydrocarbons which were performed using a ruthenium salen complex containing an axial nitrosyl ligand.
  • Figure 4 is a graph of percent reaction vs. time for hydroxylation of adamantine by a catalyst of the present invention.
  • Figure 5 shows the UV spectra of the M" 1 highly active catalyst species of the present invention.
  • metal porphyrins and salen complexes can be made to function as exceptionally fast or "hot" catalysts for the oxidation of hydrocarbons provided certain conditions and structures of the complexes are present. While these conditions and structures can be organized into at least two main categories, they all serve to function to control the electronic configuration of the catalyst complex and thereby promote the formation of a highly active metal ion species for efficient transfer of oxygen to a hydrocarbon substrate.
  • One category of catalysts and processes of the present invention concerns the use of metallic and salen porphyrin complexes having an axial nitrosyl coordinating ligand which remains present and intact throughout the catalysis reaction.
  • the peripheral substituents on the porphyrin may be selected from a wide variety of moieties, depending on the substrate and oxidant chosen.
  • the present invention seeks to prevent the hydrocarbon oxidation from occurring in the presence of metal oxidation states which are relatively stable and therefore relatively slow in their ability to catalyze oxygenation of hydrocarbons. For example, the formation of a dioxo-metal, as discussed in the aforementioned U.S. Patent No.
  • nitrosyl axial ligand a very strong coordinating ligand which renders the metal center more positively (electrophilically) charged. Due to the strong electron withdrawing effect of the nitrosyl on the metal center, the metal becomes highly activated.
  • the combination of the nitrosyl axial ligand which remains intact and electron withdrawing groups on the periphery of the coordination ligand are unique to the present invention.
  • the present invention has discovered through experimentation that the nitrosyl imparts activity to the metal cation but does not itself get oxidized to
  • Another category of catalysts and processes of the present invention which also involves providing an electronic configuration to the metal coordination complex which favors a highly reactive metal center are those having (i) a macrocyclic coordination metal complex having a porphyrin or salen ligand or mixtures thereof and having electron withdrawing substituent groups on the periphery of said ligand and (ii) containing within the complex a highly reactive M 1 " species such as Ru 1 ", or its equivalent. It has been determined that a coordination complex having the M" 1 ion species or its equivalent, e.g. Ru" 1 renders the catalyst exceptionally active in its ability to catalyze the oxidation of hydrocarbons.
  • FIG. 1 where the proposed mechanisms are illustrated using by way of example a ruthenium porphyrin.
  • complex 1 shows as a starting material a ruthenium" porphyrin complex (Ru"-P) having ligand axial "L".
  • Axial ligand L can be a carbonyl group (CO), or a weakly coordinating ligand known in the art and/or commercially available, such as an alcohol, ether or acetonitrile.
  • Ru with the attainment of the highly active complex 3, Ru"'-P, there are at least three basic pathways which can be employed, each being useful in their own right depending upon the choice of oxidant and electron withdrawing substituent groups on the macrocyclic periphery. As stated previously, the presence of the peripheral electron withdrawing groups on the macrocycle serve to enhance the formation of the highly active species M 1 ".
  • complex 2 is formed by adding an electron-removing oxidant A to complex 1.
  • Complex 2 shows axial ligand L still present but the net charge on the porphyrin complex is now +1.
  • This complex is an intermediate precursor to the highly active complex 3, Ru 111 porphyrin, and is in effect equivalent thereto since it quickly and autogenously loses axial ligand L under oxidation conditions in the presence of oxidant B to form complex 3 having the highly active Ru" 1 species at its center.
  • the weakly coordinating axial ligand L is lost and is replaced by an appropriate counterion X which serves to coordinate the Ru" 1 porphyrin complex.
  • Counterion X may be any suitable counterion and may be present and part of the oxidant A solution or may be separately added thereto.
  • Oxidant A may be selected from classes of organic and inorganic oxidants. Examples include N-oxides, peroxidic compounds, oxygen, air, periodates, Fe" 1 perchlorate, triphenylamine cation radical, among others.
  • Oxidant B is an oxygen transfer oxidant and therefore differs in functions from oxidant A and must contain an oxygen.
  • oxidant B materials include N- oxides, peroxidic compounds, oxygen, air and periodates, among others.
  • a methylene chloride solution of complex 1 is oxidized with solid Fe (ClO 4 ) 3 at room temperature under ambient conditions over 5-10 minutes to form a solution of complex 2 where x is ClO 4 -.
  • Conversion of complex 2 to the highly active complex 3 (Ru 111 ) can be accomplished by adding 1-5 equivalents of a pyridine-N-oxide. This transformation was complete in a few seconds and could be observed by a color change from green to orange.
  • cylohexanol to cyclohexanone products were produced as indicated in Table 1.
  • the active complex 3 can be generated in situ from complex 1 in a catalytic reaction mixture containing substrate S and oxidant B.
  • L-Ru" porphyrin L-Ru"-P
  • oxidant B differs in function from oxidant A in that oxidant B serves as an oxygen transfer agent and consequently must contain an oxygen atom available for such purpose.
  • Complexes 4 and 6 are thus obtained by reacting complex 1 with oxidant B as shown. At this point continued oxidation forms the dioxo-Ru v '-P which is known from U.S.
  • Patent 4,822,899 as being useful as a catalyst for hydrocarbons.
  • the oxidation of hydrocarbon substrate S to form oxidation product SO using this complex is slow.
  • the present invention improves on the process described in the aforementioned '899 patent by taking complexes 4 and 6 and further reducing or oxidizing (third pathway) them respectively to ultimately generate the highly reactive metal species shown as Ru * "-P, (complex 3).
  • complexes 4 and 6 ethanol will reduce complexes 4 and 6 to the highly active complex III species.
  • the removal of an electron via further oxidation with an electron removing oxidant such as oxidant A yields intermediate precursor complex 7 which readily converts to complex 5 and ultimately to the highly active species Ru 1 " (complex 3).
  • ruthenium As the metal, other metals such as those disclosed herein are also useful and can be substituted therefor.
  • porphyrins and salens are the preferred coordination ligand, other ligands capable of generating the highly active species are contemplated.
  • the periphery substituents may be various combinations of electron withdrawing groups which impede the formation or reformation of the dioxo- or oxo-ruthenium species.
  • Halogen groups and nitro groups (NO 2 ) are examples of the preferred electron withdrawing groups.
  • the precatalyst complexes of the present invention from which the activated M" 1 species is generated include the use of known complexes as well as novel porphyrin and salen complexes.
  • a catalyst precursor complex 1 useful in the first pathway (described in Figure 1) to obtaining the M" 1 species the following precatalyst porphyrin structure has been employed:
  • axial ligand L is CO or a weakly coordinating ligand, such as an alcohol, ether or acetonitrile
  • the preferred starting material i.e. catalyst precursor complex capable of generating the highly active species are [Ru"(O 2 )TPFPP] and [Ru"TFPPX 8 (CO)], where x is Cl or Br.
  • catalyst precursor complex capable of generating the highly active species are [Ru"(O 2 )TPFPP] and [Ru"TFPPX 8 (CO)], where x is Cl or Br.
  • Examples of highly active Ru , ⁇ -P catalysts obtained via the first pathway of Figure 1 include:
  • X is ClO 4 , SbF 6 ' or other suitable coordinating anion.
  • the metallosalen catalysts of the present invention are generally represented by the formula:
  • R 1 , R 2 , R 3 , R 4 may be the same or different and are selected from the group consisting of haloalkyl, haloaryl, alkaryl, aryalkyl, haloalkyaryl, haloaryalkyl where the alkyl portion has C,. 0 and the aryl portion has C 6 . l4 ; Z may be R 1 4 , H, halogen or -NO 2 ; and X and Y may be the same or different and are CO, or a weakly coordinating ligand such as an alcohol, ether, acetonitrile and the like.
  • complex 6 complex 4 or the equivalent Ru IV -P, and a reducing agent such a ethanol to produce the active Ru" 1 species 100.
  • oxidation of complex 6 with oxidant A affords complex 7 which under the oxidative catalytic conditions described above forms complex 3 via complex 5.
  • oxidation of complex 6 with Fe (ClO 4 ) 3 would ultimately produce species 101 as the active catalyst, where x is a coordinating anion such as ClO 4 ⁇ SbF 6 " and the like.
  • a coordination ligand/ transition metal complex having the structure [ ] +
  • M represents a transition metal selected from the group consisting of Ru, Os, Rh, Ir, Nb, Re, Tc and the standard Group VIB, VIIB and VIIIB metals of the periodic table
  • X is a coordinating ligand
  • the present invention also includes novel metalloporphyrin and metallosalen catalysts having a nitrosyl (N ⁇ O) axial ligand which remains intact on the metal center, i.e. does not donate oxygen, during catalysis. These novel compounds also generate the highly activated species M"'-P as shown in Figure 2.
  • Figure 2 shows the oxidation of Ru"-P starting material having a nitrosyl axial ligand, with oxidant OX to generate the highly active species Ru'"-P.
  • the oxidant used in this mechanism may be chosen from the same materials as oxidant A in Figure 1.
  • the highly active metal center species [M-NO] +3 is maintained.
  • the peripheral substituents on the porphyrin or salen are electron withdrawing groups are also present, such a complex further enhances the activity of the [M-NO] +3 species.
  • the metal loporphyrin catalysts having an axial nitrosyl ligand have the general structure: i r
  • R', R 2 , R 3 , R 4 may be the same or different and are haloalkyl C, .20 , haloaryl C 6 . 14 , alkyaryl having a C,. 20 alkyl portion and a C 6 . ]4 aryl portion; aryalkyl having a C 6 . 14 aryl portion and a C,. 20 alkyl portion; and haloalkylary and haloarylakyl having the alkyl and aryl species containing C,_ 20 and C 6 . 14 respectively; and R 5 through R 12 may be the same or different and may be H, Halo, -NO 2 or R 1 , R 2 , R 3 or R 4 as defined above.
  • the preferred nitrosyl-containing metalloporphyrin catalyst is [Ru(TPFPP)(NO)(H 2 O)](SbF 6 ). This structure is shown below: [ Y
  • nitrosyl-containing metallosalen catalysts of the present invention are generally represented by the formula:
  • R 1 , R 2 , R ⁇ R 4 may be the same or different and are selected from the group consisting of haloalkyl, haloaryl, alkaryl, aryalkyl, haloalkyaryl, haloaryalkyl where the alkyl portion has C,. 20 and the aryl portion has C 6 . l4 ; and Z may be R , H, halogen or -NO 2 .
  • the catalyst is employed in a catalytic amount.
  • the catalyst is present in molar ratios of catalyst to oxidizable substrate of about 1 :100 to about 1 :100,000, and preferably about 1 : 1000 to about 1 :30,000. These ratios may vary depending on the specific catalyst and oxidizable substrate employed.
  • the catalyst can be employed with or without a support.
  • catalyst complexes are useful.
  • certain catalyst complexes which are very slow to become activated can be mixed with those which are more easily oxidized, with the result being that activation of slower catalyst complex is triggered by the catalyst complex more easily oxidized.
  • alkanes which can be oxidized to alcohols and further to their corresponding ketones include cyclohexane, n-hexane, decalin, among others.
  • aromatics which can be hydroxylated to alcohols and further to their corresponding quinones include benzene, naphthalene, chlorobenzene, among others. Mixtures of aromatics are contemplated.
  • the above classes of substrates can be employed in mixtures in the present invention.
  • the oxidizing agent can be chosen from oxidants A and B as discussed above, depending on the starting material, the pathway chosen to obtain the highly active species and the reaction conditions.
  • the oxidant is supplied in an amount sufficient to allow the reaction to proceed. Typically, about 0.1 to about 40 moles and preferably about 0.5 to about 15 moles of oxygen is employed per mole of olefine double bond. These ratios also apply with respect to oxidation of alkanes and aromatics. Gaseous diluents such as carbon dioxide, nitrogen, noble gases and mixtures thereof may also be incorporated into the oxidants.
  • reaction temperatures are generally from about room temperature to about 100°C, although temperatures outside of these ranges are operable.
  • the preferred temperature range for practical purposes is about 65-70°C.
  • Reaction pressure conditions can also vary and be selected based on the reactants. Ambient pressure is generally suitable although slight pressure will assist the speed of reaction when oxidants such as air, pure oxygen or nitrous oxide are employed. In such cases, pressures of about 0.5 to about 4.0 atmospheres are employed.
  • the catalysts of the present invention although generated and soluble in organic media, can be converted to insoluble, heterogeneous forms by contacting them with solid support materials and/or structures such as silica, alumina, aminopropylsilane derivatives of silica or alumina and the like.
  • solid support materials and/or structures such as silica, alumina, aminopropylsilane derivatives of silica or alumina and the like.
  • zeolites may be produced with various silica: alumina ratios to produce specified pore sizes, shapes and Constraint Indexes, as known in the art. These materials can serve as the support structures for the catalysts of the present invention.
  • specific intermediate pore zeolites include ZSM-5, ZSM-11, ZSM-5/ZSM-11 and the like.
  • soluble ruthenium porphyrin catalyst precursors such as carbonylruthenium(II)pentafluorophenyl porphyrin have been converted to an insoluble heterogeneous form by contacting it with one or more of the above- mentioned solid support materials.
  • the ruthenium content of the resulting solid was confirmed by elemental analysis and the porphyrin content was assayed by visible spectroscopy of the diagnostic Soret band near 400 nm.
  • the heterogeneous solid forms of the catalysts of the present invention showed catalytic activity comparable to the soluble versions described herein.
  • 10 micromoles of the heterogeneous carbonylruthenium(II)pentafluorophenyl porphyrin catalyst precursor oxidized cyclohexane to cyclohexanol and cyclohexanone with 1700 turnovers under conditions which produced 2500 turnovers with the same amount of ruthenium in homogeneous solution.
  • the present invention can be made into heterogeneous forms while retaining a large percentage of its activity as compared to its homogeneous form.
  • the unusually high activity of the ruthenium catalyst system of the present invention is clearly retained in the heterogeneous version. It is contemplated that the catalysts of the present invention can therefore be used in many applications requiring solid support media for catalytic conversions. The chemical and petroleum industries have many uses for such a product.
  • a preferred catalyst precursor species used to form the M 1 " active species of the present invention is carbonyl (5,10,15,20-tetrapentafluorophenylporphyrinato) ruthenium (II), hereinafter abbreviated as [Ru"(TPFPP)(CO)].
  • Catalyst precursor complex 1 ( Figure 1) was prepared by metallation of the free base with Ru 3 (CO) !2 in refluxing o-diclorobenzene. A 55% yield of the catalyst was obtained. For similar preparation details see Murashashi, S.I., et al., Tetrahedron Lett., 1995, 35, 8059-8062.
  • Catalyst precursor complex 1 was then used for the catalytic oxygentation of a number of hydrocarbon substrates.
  • the chosen substrates and the oxygenated product yields and turnover rates are shown in Table I, below.
  • Catalyst precursor complex 1 was reacted with 2,6-dichloropyridine-N-oxide, hereinafter [pyCl 2 NO], as the oxygen donor.
  • pyCl 2 NO 2,6-dichloropyridine-N-oxide
  • the hydoxylations of adamantane and cis-decalin were achieved with high selectivity, complete stereoretention, high rate, i.e., up to 800 turnovers/minute, and high efficiency (see Experiment #'s 1-3).
  • Oxygenation of less reactive substrates also proceeded with significant turnover numbers.
  • Ruthenium porphyrin radical cations are known to be formed from the corresponding carbonyl compounds by chemical or electrochemical oxidation. See Barley, M.; Becker, J.Y.; Domazetis, G.; Dolphin, D.; James, B.R. Can. J. Chem. 1983, 61, 2389-2396. Further, these species show a characteristic absorption band in the 600-700 nm region. See Dolphin D.; James, B R.; Leung, T. Inorg. Chim. Ada.
  • Figure 4 shows superimposed UV spectra (CH 2 C1 2 25°C) of catalyst species la (not shown), and complexes 2 and 3.
  • the inset shows x-band EPR of complex 2
  • Figure 5 shows % reaction vs. time plot for adamantane hydroxylation by catalyst precursor complex 1 in the presence of pyCl 2 NO in CH 2 C1 2 at 65 °C.
  • Adamantane (0.02 mmoles), pyCl 2 NO (0.02 mmole), catalyst precursor complex 1 (50 ⁇ mole).
  • Curve C Complex 3 was recycled and used as the catalyst. In view of the high number of turnovers, it was totally unexpected that recycling of the catalyst would be possible.
  • the active catalyst species is generated from [Ru(TFPP)(NO)(H 2 O) 1 f as described below.
  • Adamantane was oxidized at a rate of at least 50 turnovers per minute as determined by H NMR spectroscopy. Up to 6000 turnovers of adamantane oxidation were obtained in three hours in d6-benzene, with a mixture of 1 -adamantanol (85%), 2-adamantanol (1%), 1 ,3-adamantanediol (5%) and 2-adamantanone (0.5%) produced. No obvious deterioration of catalyst occurred over time.
  • Olefin substrates were also readily epoxidized by the high temperature [Ru(TPFPP)(NO)(H 2 0)](SbF 6 ) /N-oxide oxidation system. An excess of 4800 turnovers was obtained in the epoxidation of methylene cyclohexene over a 12 hour period in a 92% yield versus consumed oxidant. Unreactive olefinic substrate methyl acrylate was slowly epoxidized by the catalyst system in 70 turnovers and 35% yield in a 12 hour period. In the absence of catalyst the ⁇ *-, ⁇ epoxy-methylacrylate could not be obtained nor was oxidant decomposed. Hence, uncatalyzed ⁇ -conjugate addition of the N-oxide to the olefin was not responsible for the observed epoxide yield.
  • Cyclohexene was an interesting substrate at high temperature. In contrast to the high selectivity of the room temperature oxidation (95% cyclohexene oxide, 5% cyclohexenol) the high temperature oxidation was relatively non-selective (59% cyclohexene oxide and 39% cyclohexenol, 98% overall). Indeed, the reaction of cyclohexane proceeded to give predominantly ketone (4: 1) whereas in this case, the reaction of alcohol to ketone was not observed. Adamantane oxidation also provides a small amount of the 2-ketone with respect to the 2-alcohol (.5% versus 1%).

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Abstract

La présente invention se rapporte à de nouveaux processus oxydants conçus pour des substrats du type oléfines, alcanes, composés aromatiques et alcools et utilisant des complexes catalytiques métalliques de porphyrine ou de salen qui ont été conçus spécifiquement pour maximiser l'activité catalytique, ce qui permet d'accroître l'efficacité, la sélectivité et la rapidité d'oxydation de ces substrats. On peut choisir diversement les substituants présents dans les complexes métalliques mais les substituants choisis doivent empêcher des agencements fixes de ligands spécifiques réputés stables et, par conséquent, moins efficaces d'un point de vue catalytique. Les complexes préférés sont des complexes de coordination, notamment des porphyrines ou des salens ayant des ligands axiaux de nitrosyle et des substituants périphériques extracteurs d'électrons. Les métaux de coordination à base de ruthénium constituent le centre métallique préféré, l'espèce catalytique à forte réactivité étant déterminée comme étant le RuIII. Il est possible d'incorporer les catalyseurs de la présente invention à des formes hétérogènes en les mettant en contact, par exemple, avec des structures de support solides, telles que des tamis moléculaires.
PCT/US1997/013111 1996-07-26 1997-07-25 Oxygenation catalytique d'hydrocarbures par des complexes de metalloporphyrine et de metallosalen Ceased WO1998004538A1 (fr)

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