Haloporphyrins and Their Preparation and Use as Catalysts

Electron deficient metalloporphyrins containing aromatic rings in meso positions (1; R=C.sub.6 F.sub.5, X=F,Cl,Br, M=Fe) have been shown to be efficient catalysts for the highly selective air oxidation of light alkanes to alcohols (Ellis and Lyons, Cat. Lett., 3,389, 1989; Lyons and Ellis, Cat. Lett., 8,45, 1991; U.S. Pat. Nos. 4,900,871; 4,970,348), as well as for efficient decomposition of alkyl hydroperoxide (Lyons and Ellis, J. Catalysis, 141, 311, 1993; Lyons and Ellis, U.S. Pat. No. 5,120,886). They are prepared by co-condensation of pyrrole with the appropriate aldehyde (Badger, Jones and Leslett, "Porphyrins VII. The Synthesis of Porphyrins By the Rothemund Reaction", Aust.J.Chem., 17,1028-35, 1964 Lindsey and Wagner, "Investigation of the Synthesis of Ortho-Substituted Tetraphenylporphyrins", J.Inorg. Chem., 54,828, 1989; U.S. Pat. Nos. 4,970,348; 5,120,882), followed by metal insertion (Adler, Longo, Kampas and Kim, "On the preparation of metalloporphyrins", J.Inorg. Nucl.Chem., 32,2443,1970) and .beta.-halogenation; (U.S. Pat. Nos. 4,892,941; 4,970,348). ##STR1##

U.S. Pat. No. 4,892,941 discloses halogenated tetraphenyl porphyrins disclosed to be useful for oxidation of alkanes.

U.S. Pat. Nos. 4,895,680 and 4,895,682 disclose the use of azide and nitride transition metal ligands, i.e., coordination complexes, for the air oxidation of alkanes and other hydrocarbons.

U.S. Pat. No. 4,900,871 describes the use of iron halogenated coordination complexes for similar oxidations, disclosing that halogenating the coordination complex portion of the catalyst greatly increases the activity of the catalyst.

C. Chang and F. Ebina, J.Chem. Soc. Comm., 778 (1981) disclose fluorinating iron and manganese tetraphenyl-porphyrinato chloride catalysts to improve their stability in the oxidation of alkanes and alkenes using strong oxidizers such as iodosylbenzene.

The following references disclose the preparation of partially halogenated porphines.

M. J. Billig et al, Chem. Ind. (London), 654 (1969) disclose mesomonofluorodeuteroporphyrin-dimethyl ester, a porphyrin having one fluorine atom in a meso position and having --CH.sub.3 and --CH.sub.2 CH.sub.2 COOCH.sub.3 substituents in beta positions, the remaining beta positions being unsubstituted.

Y. Naruta et al, Tetr. Lett., 33, 1069 (1992) disclose 5,10,15,20-fluorooctaethylporphines, porphyrins having fluorine atoms at 1 to 4 of the meso positions and an ethyl group at each of the beta positions.

H. Onda et al, Tetr. Lett., 26, 4221 (1985) disclose 1,3,5,7-tetrafluoro-2,4,6,8-tetramethyl porphine, a porphyrin having no meso substituents and having a fluorine atom and a --CH.sub.3 group on each of the four pyrrole groups of the porphyrin.

A. Suzuki et al, Heterocycles, 33, 87 (1992) disclose 1-fluoro-2,4-diethyl-3,5,8-trimethyl-6,7-dimethoxycarbonylethylporphine, a porphyrin unsubstituted in meso positions and containing a fluorine atom in a beta position, along with ethyl, methyl and methoxycarbonylethyl groups, also in beta positions.

R. Bonnett et al, J.Chem. Soc. 1600 (1966) disclose 5,10,15,20-chlorooctaethylporphine, 5-chlorooctaethylporphine and 5,15-dichlorooctaethylporphine, compounds which contain 1 to 4 chlorine atoms in meso positions and octaethyl groups in beta positions.

Fischer et al, Chem.Ber., 46, 2460 (1913) disclose a porphyrin containing four chlorine atoms in meso positions and alkyl groups and carboxyalkyl groups in beta positions.

Fischer et al, Liebig's Ann.Chem., 494, 225 (1932) disclose 2,7,12,17-tetraethyl-5,10,15,20-tetrachloro-3,8,13,18-tetramethyl porphine, a porphyrin having four chlorine atoms in meso positions and alkyl groups in beta positions.

Gong et al, Can.J.Chem., 63, 406 (1985) disclose 5,10,15,20-tetrachlorooctaethylporphine and 5,10-dibromo-15,20-dinitrooctaethylporphine, compounds which contain four chlorine atoms and two bromine atoms, respectively, in meso positions, and eight ethyl groups in beta positions.

G. S. Marks et al, J.Am. Chem. Soc., 82, 3183 (1960) disclose 1,2,4-tribromo-3,5,8-trimethylporphin-6,7-dipropionic acid dimethyl ester, a porphyrin unsubstituted in meso positions and containing three bromine atoms in beta positions, as well as methyl groups and propionic acid dimethyl ester groups. The same authors disclose 2,4,8-tribromo-1,3,5-trimethylporphin-6,7-dipropionic acid dimethyl ester, in which the same substituents are situated at different locations on the ring.

J. S. Andrews et al, J.Am. Chem.Soc., 72, 491 (1950) disclose 1,4,5,8-tetramethyl-2,3,6,7-tetrabromoporphine, a porphyrin having four methyl groups and four bromine atoms distributed among the four pyrrole rings.

Fischer et al, Hoppe-Eysler's Z.Physiol.Chem., 191, 36 (1930) disclose 2,7-dibromo-3,8,12,13,17,18-hexamethylporphine, a porphyrin having two bromine atoms and six methyl groups in beta positions of the porphyrin ring.

L. R. Nudy et al, Tetrahedron, 40, 2359 (1984) disclose 5-bromoporphin, 5,15-dibromoporphin and 5,10,15-tribromoporphin, a beta-unsubstituted porphyrin having 1, 2 and 3 bromine atoms in meso positions.

G. F. Stephenson et al, J.Chem. Soc. 1600 (1966) disclose 5-bromooctaethylporphine, a porphyrin having one meso bromine atom, the other meso positions being unsubstituted, and eight ethyl groups in beta positions.

Fischer et al, Chem.Ber., 60, 1861 (1960) disclose 3,8-dibromodeuteroporphyrin-dimethyl ester, a meso-unsubstituted porphyrin having four methyl groups in beta positions, two bromine atoms in beta positions and two --CH.sub.2 CH.sub.2 COOCH.sub.3 groups in beta positions.

Goff et al, J.Am. Chem. Soc., 99, 3641 (1977) disclose Fe(II) (2,4-dibromodeuteroporphyrin dimethyl ester, a porphyrin having no meso eubstituents, and having two bromine atoms, three methyl groups and two CH.sub.2 CH.sub.2 COOOC.sub.3 groups in beta positions.

The present invention is directed to new compositions of matter comprising haloporphyrins containing at least one halogen atom in a meso position and/or to haloporphyrins having no aryl substituents, and two methods for making such compounds. Metal complexes of such compounds are useful as catalysts for the oxidation of hydrocarbons to hydroxy-group containing compounds and for the decomposition of hydroperoxides to hydroxy-group containing compounds. Preferably, the haloporphyrin contains halogen atoms in all four meso positions. The beta positions of such haloporphyrins may also be substituted with 1 to 8 halogen atoms. Alternatively, the beta positions may be unsubstituted, or may be substituted with electron-withdrawing groups such as nitro, cyano or halocarbyl.

The present invention comprises the following embodiments:

New compositions of matter, useful as catalysts for partially oxidizing hydrocarbons and for decomposing hydroperoxides, comprising transition metal complexes of haloporphyrins containing 1 to 12 halogen atoms in meso and/or beta positions, and (1) containing at least one halogen atom in a meso position and/or (2) containing no aryl groups in meso positions.

Methods for synthesizing metallohaloporphyrins by reacting a transition metal complex of a porphyrin with halogen to obtain a metallohaloporphyrin containing 1 to 12 halogen atoms in meso and/or beta positions.

Each of the above embodiments comprises, in addition to the metalporphyrin complexes per se and their preparation: azide derivatives thereof, hydroxide derivatives thereof where obtainable with the porphyrin configuration, and oxo-dimer derivatives thereof, and the preparation of such derivatives.

In one embodiment, the present invention involves new compositions of matter containing at least one halogen atom and comprising a compound having the formula: ##STR2## where at least one of the R atoms or groups is chlorine, bromine or fluorine, and the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 atoms or groups are independently hydrogen, chlorine, bromine or fluorine atoms or nitro, cyano or halocarbyl groups, and M comprises transition metal, for example Fe(II) or Fe(III)X where X is halogen. Preferred compositions are those containing no unsubstituted hydrogen atoms; that is, the preferred compositions are compounds in which each of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 is halogen, nitro, cyano or halocarbyl. More preferred compounds are those in which each of the above R.sup.1 to R.sup.6 is halogen.

Thus, in a preferred embodiment, the compositions according to the invention are perhaloporphyrins; that is, the meso-tetrahalo-beta-octahaloporphyrins (2; R.sup.1 =R.sup.2 =R.sup.3 =R.sup.4 =R.sup.5 =R.sup.6 =halogen). Examples of such compounds are meso-tetrachloro-beta-octachloroporphyrin, meso tetrachloro-beta-octabromoporphyrin, meso-tetrafluoro-beta-octachloroporphyrin, and the like. "Perhaloporphyrin" as used herein means porphyrins in which halogen atoms are fully substituted for hydrogen atoms, or as fully substituted therefor as reasonably attainable under the circumstances.

All of the halogen atoms in the haloporphyrin may be the same halogen, for example chlorine. Alternatively, the haloporphyrin may contain more than one halogen, for example chlorine and bromine, or chlorine and fluorine, etc.

The methods of making haloporphyrins according to the present invention involve at least one step involving halogenation of a metal complex of a porphyrin. Such step typically involves the following procedure. A porphyrin metal complex such as copper porphine (2;R.sup.1 =R.sup.2 =R.sup.3 =R.sup.4 =R.sup.5 =R.sup.6 =H, M=Cu), preferably dissolved in a solvent, for example carbon tetrachloride, is contacted with a halogenating agent, such as chlorine or bromine, at elevated temperature, for example reflux temperature. Chlorine may for example be bubbled through the solution intermittently for a prolonged period of time, for example two to five minutes every hour for twelve hours. A solution of bromine in carbon tetrachloride may alternatively be used as the halogenating agent. The product contains metal porphine complex in various degrees of halogenation, including the perhalogenated complex in which all four meso hydrogens and all eight beta hydrogens have been replaced with halogen atoms. Since the activity of transition metal, for example iron porphyrin complexes for oxidation of hydrocarbons to alcohols, and for decomposition of hydroperoxides to alcohols, generally increases with increasing degrees of halogen substitution, it is preferred to separate perhalogenated metal complex from the reaction product, and convert the perhalogenated copper complex, for example, which is relatively inactive as catalyst for hydrocarbon oxidation or hydroperoxide decomposition, to a perhalogenated complex with a metal such as iron which is highly active for such oxidation and decomposition. The conversion may be accomplished for example by cooling and removing solvent from the reaction products, separating the perhaloporphyrin complex, redissolving the separated product in CH.sub.2 Cl.sub.2, acidifying to remove copper, and inserting iron by refluxing the perhaloporphyrin with FeCl.sub.2.H.sub.2 O.

Where compounds containing more than one halogen are desired, this may be accomplished by reacting a metal porphyrin in stages with one halogen in the one stage and another halogen in a subsequent stage. Where compounds containing both halogen and another electron-withdrawing substituent are desired, this may be accomplished by reacting a metalporphyrin in stages with halogen in one stage and another reactant such as nitrating agent in another stage.

Each of the individual reactions of the preparation according to the invention usually produces a mixture of products, from which a desired single product or range of products can be separated by selective adsorption-elution processes or other methods as known to the person skilled in the art.

The new compositions of matter according to the invention are useful for partially oxidizing a hydrocarbon to a hydroxy-group containing compound by contacting the hydrocarbon with oxygen and as catalyst a composition of matter as described above. The oxidation, which may be carried out in a generally known manner, is desirably conducted in the liquid phase, although this is not critical, using such organic solvents as benzene, acetic acid, acetonitrile, methyl acetate, or like solvents which are inert to the conditions of the reactions, or in a neat solution of the hydrocarbon if it is liquid, and under pressures ranging from about 15 to 1500 psig, preferably 30 to 750 psig, at temperature of from about 25.degree. to 250.degree. C., more preferably 30.degree. to 180.degree. C. Depending upon whether the hydrocarbon to be oxidized is a solid, liquid or gas, it is dissolved in or bubbled through the solvent, together with air or oxygen, in the presence of the catalyst for periods of time sufficient to yield the desired oxidation product, generally from about 0.5 to 100 hours, and more preferably from 1 to 10 hours.

The choice of solvent, while not critical, can have an effect on the rates and selectivities obtained and should be selected carefully in order to optimize the desired results. For example, it has been found that solvents such as acetonitrile and acetic acid are often very effective for the oxidation of hydrocarbons to form hydroxy-group containing compounds, whereas reactions carried out in solvents such as methyl acetate or benzene may occur more slowly. Thus, by routine experimentation the optimum solvent for the particular process can be readily determined.

The ratios of the various reactants may vary widely, and are not critical. For example, the amount of catalyst employed can range from about 10.sup.-6 to 10.sup.-3 mole per mole of hydrocarbon such as alkane, and more preferably from about 10.sup.-5 to 10.sup.-4 mole of catalyst per mole of hydrocarbon, although other amounts are not precluded; while the amount of oxygen relative to the hydrocarbon starting material may also vary widely, generally the ratio will be from 10.sup.-2 to 10.sup.2 moles of oxygen per mole of hydrocarbon. Care should be taken since some of the ratios fall within explosive limits. As a group, the catalysts are almost always soluble unless used in large excess. Thus, as a rule the reactions are generally carried out homogeneously.

The starting materials for the partial oxidation method in which the compositions according to the invention are useful include alkanes and alkenes including cycloalkanes, substituted alkanes and alkenes and the like. The starting materials thus include straight and branched-chain compounds having from about 1 to 20 carbon atoms, such as methane, ethane, propane, n-butane, isobutane, n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, heptane, 2-methylheptane, 3-methylheptane, the corresponding alkene forms and the like, as well as cycloalkanes and alkenes having from about 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms, such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, the corresponding alkene forms, and the like. These compounds, if desired, may be substituted with various moieties, although care should be taken to exclude substituents which will adversely affect the activity of the catalyst.

The new compositions according to the present invention are also useful as catalysts for decomposing a hydroperoxide to a hydroxy-group containing compound by contacting the hydroperoxide with a catalyst comprising a composition of matter as above described.

The decomposition of hydroperoxide is preferably carried out in a solution of the hydroperoxide, preferably a solution containing from about 5 to about 50 wt. % of hydroperoxide. Suitable solvents include benzene, chlorobenzene, o-dichlorobenzene, acetonitrile, benzonitrile, alcohols, ketones and the like. A useful solvent is the alcohol which corresponds to that formed by decomposition of the hydroperoxide, for example t-butanol formed by decomposition of t-butyl hydroperoxide.

Any suitable temperature and pressure may be used. Preferably the temperature is in the range from 0.degree. to 200.degree. more preferably 25.degree. to 125.degree. C. The pressure may be adjusted as necessary to accomplish decomposition; preferably 15 to 1000 psig, more preferably 15 to 100 psig. The time of reaction may be relatively short, in view of the rapid reaction rate with the catalysts employed according to the invention, but will typically be in the range from 0.1 to 5 hours, preferably 0.1 to 1 hour.

Typically, the hydroperoxide dissolved in a solvent is introduced into a reaction zone wherein it is contacted with catalyst, in the substantial absence of oxidizing agent, to convert the hydroperoxide, ROOH, where R is an organic radical, to the corresponding hydroxy-containing compound, ROH.

Hydroperoxides which may be decomposed using the catalysts according to the invention include compounds having the formula ROOH, where R is an organic radical, typically a straight or branched chain alkyl or cycloalkyl group containing 2 to 15 carbon atoms, an aryl group such as a monocyclic or polycyclic group in which the cyclic groups may optionally be substituted with one or more substituents inert to the decomposition reaction, such as alkyl or alkoxy, containing 1 to 7 carbon atoms, nitro, carboxyl or carboxyl ester containing up to about 15 carbon atoms and a halogen atom such as chlorine, bromine, or an aralkyl group in which the alkyl chain contains from 1 to 15 carbon atoms and the aryl group is as above described. Preferably R is an alkyl or cycloalkyl group containing 4 to 12 carbon atoms or an alkylaryl group in which the aromatic moiety is phenyl and the alkyl substituent is straight or branched chain alkyl or cycloalkyl containing up to about carbon atoms. Examples are t-butyl and isobutyl hydroperoxide, isoamyl hydroperoxide, 2-methylbutyl-2-hydroperoxide, cyclohexyl hydroperoxide, cumyl hydroperoxide, phenethyl hydroperoxide and cyclohexylphenyl hydroperoxide. Phenethyl hydroperoxide and cumyl hydroperoxide are converted to phenethyl alcohol and cumyl alcohol, respectively.

The following examples illustrate the invention:

Cu porphine is dissolved in CCl.sub.4 and heated to reflux. Cl.sub.2 is bubbled into the very dry CCl.sub.4 solution for 2-5 minutes every hour for 12 hours. After this time, the solution is cooled and washed with water then evaporated to dryness. Many porphyrin products with varying amounts of chlorine incorporation are produced. Chromatography on alumina is used to recover the first band off the column eluting with CH.sub.2 Cl.sub.2. This material is the perchlorinated copper porphyrin, Cu(PCl.sub.12), copper complex of meso-tetrachloro .beta.-octachloroporphyrin. The Cu can be removed by dissolving 100 mg of Cu(PCl.sub.12) in 150 ml of CH.sub.2 Cl.sub.2 then adding 2.5 ml of H.sub.2 SO.sub.4 in 10 ml of trifluoroacetic acid. After 10 minutes of stirring the H.sub.2 PCl.sub.12, meso-tetrachloro-.beta.-octachloroporphine, is recovered by extraction with CH.sub.2 Cl.sub.2 and sodium bicarbonate wash. Iron is inserted into the H.sub.2 PCl.sub.12 by refluxing the porphyrin in tetrahydrofuran with an excess of FeCl.sub.2.4H.sub.2 O. After chromatography and treatment with HCl, Fe(PCl.sub.12)Cl, an iron complex of meso-tetrachloro-.beta.-octachloroporphyrin is obtained.

The catalyst prepared in Example 1 is dissolved in benzene (25 mL) and isobutane (7 g) added. Oxygen (5 bars) is pressed on the stirred solution at 60.degree. C. for six hours. After this time, the solution is cooled and brought to atmospheric pressure. The main product is tert-butyl alcohol, acetone and di-tert-butylperoxide being minor products.

The complex prepared in Example 1 is directly added to a stirring solution of tert-butylhydroperoxide (TBHP, 13.8 g) in tert-butyl alcohol (TDA, 18.1 g) at 80.degree. C. Oxygen is rapidly evolved and the TBHP converted largely to TBA, acetone and di-tert-butylperoxide being minor products.