JPH09249678A - Porphyrin bearing haloalkyl side chain, its metal complex, their production and use as catalyst in chemical reaction - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel porphyrin metal complex which is a specific porphyrin metal complex bearing haloalkyl side chains and is useful as a catalyst that oxidizes a light alkane to an alcohol with high selectivity and decomposes the hydroperoxide with high efficiency.

SOLUTION: This is a novel porphyrin metal complex of formula I (M is a transition metal; R³ and R⁶ are each a hydrocarbyl containing at least one of haloalkyl of 2-8 carbon atoms between them; R¹, R², R⁴, R⁵ are each H, a hydrocarbyl, a halogen, nitro, cyano or a halocarbyl) and is useful as a catalyst for high-selective air oxidation of alkane to alcohol and for efficient decomposition of hydroperoxide. This metal complex is prepared by reaction of bis(pyrrol-2-yl)heptafluoropropylmethane with a perfluoroaldehyde of the formula: RCHO (R is C₆F₅, CF₃CF₂CF₂) to give a porphyrin of formula III, followed by reaction of the porphyrin with a transition metal salt such as ferrous chloride.

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention [Industrial applications]

The United States Government has rights in this invention pursuant to Cooperative Agreement No. DE-FC21-90MC26029 awarded by the United States Department of Energy.

This invention was filed on Dec. 29, 1993 in US application 08/1.
74,732 and 08 / 175,057, filed December 29, 1993, which is a continuation-in-part application.

[0003]

BACKGROUND OF THE INVENTION Electron-deficient metalloporphyrins are efficient catalysts for the highly selective aerial oxidation of light alkanes to alcohols (P.I.Eris and J.I. Lions, Cat. Lett., 3, 389, 1989;
Jay. A. Lions and Pee. A. Ellis, Ca
tt. Lett., 8, 45, 1991; Lions and Ellis, U.S. Pat. No. 4,900,871; 4,970,348), and an efficient catalyst for the efficient decomposition of alkylhydroperoxides (Lions and Ellis, J. Catalysis, 141). , 311, 199
3; Lions and Ellis, US Pat. No. 5,112,886). These carry out the cocondensation of pyrrole with the appropriate aldehydes (Bajager, Jones and Wrestlet, Aust. J. Chem.,
17, 1029, 1964; Lindsay and Wagner, J.Org.Che
m., 54, 828, 1989; U.S. Patents 4,970,348 and 5,120,88.
2), followed by metal insertion (Adra, Longo, Campos and Kim, J. Inorg. Nucl. Chem., 32, 2443, 1970),
And β-halogenation (US Pat. Nos. 4,892,941 and 4,
970, 348) can be created. Other patents disclosing the use of metal coordination complex catalysts in the oxidation of alkanes are described by Ellis et al., US Patents 4,895,680 and 4,895,6.
82.

Meso-tetrakis (perhaloalkyl) porphyrins, such as meso-tetra (tripolyfluoromethyl) porphyrins, are converted to the corresponding 2-hydroxy (perhalo-alkyl) pyrroles by preliminary activation of the hydroxy leaving group. Has been produced by the self-condensation of (Wigesequera, US Pat. No. 5,241,062).

T-Butyl alcohol is t-butyl hydroperoxide (TBHP), preferably in the form of a solution in t-butyl alcohol, of a metal phthalocyanine of a Group IB, VIIB or VIIIB metal such as chloroferric. It has been produced by catalytic decomposition in the presence of phthalocyanine (chloroferrous phthalocyanine) and rhenium heptoxide-p-dioxane or oxotrichloro-bis (triphenylphosphine) rhenium (Sanderson et al.,
U.S. Pat. No. 4,910,349).

T-Butyl hydroperoxide is a metalloporphyrin catalyst, eg tetraphenylporphine, optionally promoted with thiol and heterocyclic amines (Sanderson et al., US Pat. No. 4,922,034), or imidazo-. Le promoted phthalocyanine (PCY) catalysts such as Fe (I
II) PCYCl, or Mn (II) PCY, or VOPCY can be decomposed to t-butyl alcohol (Sanderson et al., U.S. Pat.
912,266).

Isobutane is prepared by converting t-hydroperoxide into t-butyl alcohol by using a monocyclic solvent and a PCY decomposition catalyst.
It can be continuously converted to isobutyl alcohol by a method that includes a step of degrading into alcohol (Marquis et al., US Pat. No. 4,992,602).

T-Butyl hydroperoxide is promoted with a metal porphine catalyst such as trivalent Mn or Fe tetraphenylporphine catalyst, optionally amine or thiol promoted, or with a bidentate ligand. Promoted with soluble Ru catalysts such as bis (salicylidene) ethylenediamine
PCY catalysts using Ru (AcAc) ₃ or promoted, such as amines, Re compounds such as NH ₄ ReO ₄ , mercaptans and free radical inhibitors, promoted with bases or metal borates, Mn, Fe Alternatively, vanadyl PCY can be used to decompose into t-butyl alcohol (Derwent Abstract (Week 8912, other aliphatics, 58 pages) Reference 89
-087492/12 (EP 308-101-A)).

Hydroperoxides can be decomposed with metal-ligand complexes in which the hydrogens in the ligand molecule are replaced by electron withdrawing elements or groups such as halogen or nitro or cyano groups (Lions et al., US Pat. No. 5,120,886, which is incorporated herein by reference). Include in description).

Other Publications S. di-Dimagno, A.L. Williams and M. J. Serien, “A convenient synthesis of meso-tetrakis (perfluoroalkyl) porphyrins: highly electron-deficient 5,10” , 15,20-Tetrakis- (hepta-fluoropropyl)
Spectroscopic Properties and X-ray Crystal Structure of Porphyrins ”, J.Or
g. Chem. Volume 59, No. 23, 6943-6948, 1994.

M. J. Serien et al., US Pat. No. 5,371,199 issued Dec. 6, 1994 from Aug. 14, 1992 application.
No. is a meso-haloalkylporphyrin having 1 to 20 carbon atoms in at least one haloalkyl group, β-haloalkyl having 2 to 20 carbon atoms in at least one haloalkyl group. Porphyrins,
Disclosed are β-haloalkylporphyrins having 1 to 20 carbon atoms in at least 5 haloalkyl groups, and β-haloarylporphyrins having 6 to 20 carbon atoms in at least 5 haloalkyl groups. There is.

CF to give triflorodipyrromethane
A linear array of porphyrins synthesized via a reaction involving ₃ CHO + pyrrole was obtained by the method of Al W. Wagner,
N. Shinino and J.S. Lindsey, "Synthesis of Linear Amphiphilic Porphyrin Arrays for Building Blocks," March 13-17, 1994, Organic Chemistry Meeting, San Diego, CA ( Organic Chemistry Society), American Chemical Society Division, Poster abstract.

[Means for Solving the Problems]

The present invention has the structural formula

Embedded image [Wherein M is a transition metal such as iron, manganese, cobalt,
Copper, ruthenium, chromium, etc., and R ³ and R ⁶ are 2 to
At least one haloalkyl group having 8 carbon atoms, wherein R ¹ , R ² , R ⁴ and R ⁵ are independently hydrogen, halocarbyl or electron withdrawing substituents such as halogen, nitro, cyano or halocarbyl. Is. ] Of a new substance having Anions such as azides, halides, hydroxides or nitrides can associate with the metal M. Formula I
Porphyrins having a dimer form or mu-ox dimer form (mu-ox) known in the porphyrin field.
odimer) or porphyrins, which consist of two or more of meso-halocarbylporphyrins in polymerized form.

The compounds according to the invention have at least one straight or branched chain haloalkyl group having 2 to 8 carbon atoms in the haloalkyl group, more preferably 3 to 6 carbon atoms. A haloalkylporphyrin and a metal complex thereof contained in a meso position (singular or plural). Preferred haloalkyl groups in the porphyrins according to the invention are straight or branched chain heptafluoropropyl groups.

The porphyrins according to the present invention are compounds [F
As in _{e (C 6 F 5) 2} (C 3 F 7) 2 P] 2 O in, can contain different halocarbyl groups in different meso positions, in which case P is a porphyrin, R ⁶ in formula I a C ₆ F _5, R ³ in formula I is C ₃ F _7, or, as in compound _{[Fe (C 3 F 7)} 4 P] 2 O in, in each substituted meso positions It may contain the same halocarbyl groups, where P in formula I is a porphyrin and R ³ and R ⁶ are each heptafluoropropyl.

Preparation of Catalysts The compounds according to the invention can be prepared, for example, from halopropyl-substituted dipyrromethanes such as bis (pyrrol-2-yl) heptafluoropropyl-methane (FIG. 7, 1) with meso-halopropyl-substituted aldehydes (FIG. 7). , 2, R = CF ₂ CF ₂ CF ₃ ) in the presence of a catalyst such as a solution of hydrobromic acid in acetic acid to give an intermediate porphyrinogen, followed by an intermediate porphyrinogen. Gen was treated with 1,2-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to give meso-tetrakis (heptafluoropropyl) porphyrin (FIG. 7,
It can be produced by producing 3b). Iron complexes of meso-tetrakis (heptafluoropropyl) porphyrins are typically prepared by reaction of meso-tetrakis (heptafluoropropyl) porphyrins with acetic acid and cuprous chloride in sodium acetate.

Acidic granular solid catalysts such as montmorillonite clay can be used as a catalyst in place of HBr-CH ₃ COOH for the reaction of dipyrromethane with an aldehyde to yield the intermediate porphyrinogen, and are substantially As a result, the yield is twice as high as that obtained with HBr—CH ₃ COOH. Other known acidic granular solid catalysts can also be used, such as other acidic clays, acidic zeolites, solid superacids such as sulfated zirconia. One of ordinary skill in the art having the benefit of this specification can adapt other known methods of preparing meso-halocarbylporphyrins for the preparation of meso-halocarbylporphyrins according to the present invention.

Oxidation Method The transition metal complex of the composition according to the invention is a very effective catalyst for the oxidation of organic compounds. Generally, such catalysts are useful for the oxidation of transition metal complexes of porphyrins, especially organic compounds for which halogen-containing porphyrin structures are useful, as is known in the art. See, for example, U.S. Pat. Nos. 4,900,871 and 4,970,348 to Lion and Ellis above.

This oxidation, which can be carried out in a generally known manner, is not critical, but is preferably carried out in the liquid phase and is inert to the conditions of the reaction, such as benzene, acetic acid, acetonitrile, methyl acetate and the like. About 15 to 1500 psig, preferably 30 to 750 psi, with an organic solvent, or as an undiluted solution of the hydrocarbon if the hydrocarbon is a liquid.
Under pressure in the range of g, about 25-250 ° C, preferably 70-180
It is carried out at a temperature of ° C. In the presence of a catalyst, for a time sufficient to produce the desired oxidation product, generally about 0.5 to 100 hours, and preferably 1 to 10 hours, is the hydrocarbon to be oxidized solid, liquid or gaseous? Depending on, the hydrocarbon is dissolved in or aerated with a solvent with oxygen or air ,.

A solvent that is not critical but is selected to be good can have an effect on the reaction rate and selectivity obtained and should be carefully selected to optimize the desired results. For example, solvents such as acetonitrile and acetic acid,
While often very effective at oxidizing alkanes to form oxygen-containing compounds, reactions carried out in solvents such as methyl acetate or benzene proceed more slowly.

The proportions of the various reactants vary widely and are not critical. For example, the amount of catalyst used can range from about ^10-6 to ^10-3 moles per mole of hydrocarbon such as alkane, and more preferably from about ^10-5 to ^10-3 moles per hydrocarbon.
^-4 mol of catalyst, although other amounts are not excluded, while the amount of oxygen relative to the hydrocarbon starting material can also vary widely, generally from 10 ^-2 to 10 per mole of hydrocarbon.
^{It is 2} moles of oxygen. Care must be taken as some ratios are within the explosion limit. Overall, the catalyst is almost always soluble unless used in high concentrations. Therefore, generally the reaction is carried out homogeneously.

Oxidation Substrates Substrates for the process for the oxidation of organic compounds using the compositions of the invention as catalysts include alkanes such as methane, ethane, propane, n-butane, isobutane, n-pentane,
It may be isopentane or the like, or an alkyl-substituted cyclic compound such as toluene, xylene, mesitylene and the like. Although not necessary, preferably the substrate is 1 to
Contains 10 carbon atoms in the molecule. Mixtures of compounds can be used.

Hydroperoxide Decomposition Method The transition metal complexes of the compounds according to the invention are highly effective catalysts for the decomposition of organic hydroperoxides. Generally, such catalysts are useful in the decomposition of organic hydroperoxides where porphyrins, especially transition metal complexes of halogen-containing porphyrin structures, are useful catalysts, as is known in the art. See, for example, Lions and Ellis, US Pat. No. 5,112,886, supra.

The hydroperoxide decomposition process according to the invention can be carried out by any known method of hydroperoxide decomposition, but using the catalysts of the invention in place of the known catalysts of the prior art. The decomposition is preferably carried out with the hydroperoxide formed by decomposition of the hydroperoxide, dissolved in a suitable organic solvent, which may be, for example, alcohol. Any suitable temperature and pressure may be used, as is known in the art for hydroperoxide decomposition processes. The preferred temperature is in the range 25-125 ° C. Due to the rapid reaction rate of the catalysts used according to the invention, the reaction times are rather short and can be in the range 0.1-5 hours, preferably in the range 0.1-1 hour.

Substrates for Degrading Hydroperoxides Hydroperoxides that can be degraded according to the present invention include compounds having the formula ROOH. Where R is an organic group,
An aryl group, typically a linear or branched alkyl or cycloalkyl group containing from 2 to 15 carbon atoms, a monocyclic or polycyclic group, wherein the cyclic group is One or more substituents inert to the decomposition reaction, such as alkyl or alkoxy containing 1 to 7 carbon atoms, nitro, carboxyl, or carboxyl esters containing up to about 15 carbon atoms, and It is also possible that a halogen atom, for example chlorine, bromine, or an alkyl chain contains 1 to 15 carbon atoms and the aryl group is substituted with an alkali group as described above. Preferably R is 4 to
An alkyl or cycloalkyl group containing 12 carbon atoms, or a linear or branched alkyl or aromatic moiety which is phenyl and the alkyl substituent contains up to about 6 carbon atoms. It is an alkyl group which is cycloalkyl. Examples of these are t-butyl and isobutyl hydroperoxide, isoamyl hydroperoxide, 2-methylbutyl-2-hydroperoxide, cyclohexyl hydroperoxide, cyclohexylphenyl hydroperoxide, phenethyl hydroperoxide and cumyl hydroperoxide, of which The last two are converted to phenethyl alcohol and cumyl alcohol, respectively.

[0025]

【Example】

Example 1 5,15-Bis (heptafluoropropyl) -10,2
0-Bis (pentafluorophenyl) porphyrin Equimolar amounts of bis (pyrrol-2-yl) heptafluoropropylmethane 1 and pentafluorobenzaldehyde (FIG. 7, 2a; R = C ₆ F ₅ ) at 10 to reflux. Heat for 20 hours in degassed chloroform containing montmorillonite K10 clay as catalyst. The reaction mixture was treated with a solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in benzene and reflux was continued for another 20 hours. The clay catalyst was removed by filtration to give the desired porphyrin, namely 5,15-bis (heptafluoropropyl) -10,20-bis (pentafluorophenyl).
Porphyrin _{[3a; R = C 6 F} 5;; Fe (C 6 F 5) 2 (C 3 F 7) 2 PH 2 P is a porphyrin], passed through neutral alumina and dichloromethane / methanol - crystals Le It was isolated by crystallization. MS (FAB): m / z = 979 (M + 1); UV: λmax, 388
(Solet), 428 (sh), 560, 598 nm.

Example 2 Preparation of 5,10,15,20-tetrakis (heptafluoropropyl) -porphyrin. Porphyrin, 5,10,15,20-tetrakis (heptafluoropropyl) - porphyrin FIG _{7,3b; R = C 3 F 7} ; (C 3 F 7)
PH ₂ ] to pentafluorobenzaldehyde (Figure 7, 2a)
Instead of heptafluorobutyraldehyde (Fig. 7, 2
b; as an aqueous solution) was prepared as described in Example 1. MS (FAB): m / z = 984 (M + 2); UV: λmax, 404
(Solet), 508, 544, 590, 646 nm.

Example 3 Preparation of 5,15-bis (heptafluoropropyl) -10,20-bis (pentafluorophenyl) porphyrinatoiron. Porphyrins made in Example 1 Figures 7, 3a (400 mg) and sodium acetate (500 mg) were heated to neat reflux in degassed acetic acid (200 mL) and treated with ferrous chloride (500 mg). Heating was continued under argon for 30 minutes and the solution was exposed to air at room temperature and stirred overnight. Add hydrochloric acid (3M, 200mL),
The solid was filtered, washed with 1M hydrochloric acid, and dried with a desiccator. The crude iron complex was redissolved in chloroform, extracted with 2M aqueous sodium hydroxide solution, passed through neutral alumina (15% water added) and eluted with chloroform. Pure iron complex, FIG _{7,4a (R = C 6 F 5} ) was isolated by evaporation of the solvent. MS (FAB): 1032 (MX); UV: λmax, 388 (Soret), 428 (sh), 560, 598 nm.

Example 4 Preparation of 5,10,15,20-tetrakis (heptafluoropropyl) porphyrinato iron. Porphyrins prepared in Example 2, Figure 7, 3b using crude iron complex, Figure 7, 4b as described in Example 3.
Was manufactured. Purification was carried out by passing the chloroform solution through neutral alumina (15% water added) and the pure product was isolated by evaporation of the solvent. MS (FAB): 1
036 (MX); UV: λmax, 396 (Soret), 566, 600 nm.

Examples 5-11 Oxidation of isobutane with meso-perfluoropropyl-porphyrinato iron catalyst Meso-perfluoropropylporphyrinato iron catalyst,
Isobutane was oxidized to tertiary butyl alcohol using the conditions noted in the footnote to Table 1. Table 1 shows the results.

Table 1 Oxidation of isobutane using meso-perfluoropropylporphyrinato iron catalyst ^a Complex T ° C. t hour TO ^b TBA selectivity% ^c Fe (OEP) Cl 60 60 --Fe (TPP) Cl 60 60 --Fe [C ₆ F ₅ ) ₄ P] Cl 60 6 1100 90 [Fe (C ₆ F ₅ ) ₂ (C ₃ F ₇ ) ₂ P] ₂ O 60 6 ^d 90 N / A 12 710 90 [Fe (C ₃ F ₇ ) ₄ P] ₂ O 60 6 ^e 110 Not applicable 12 1110 81 a 0.013 mmol of catalyst was dissolved in 25 ml of benzene, and 7.0 g of iC ₄ H ₁₀ was added thereto. Oxygen (up to 100 psig) was added at reaction temperature and the mixture was stirred for the specified time. Product analysis is gl
pc, gas-liquid phase chromatography. After b reaction time consuming O ₂ moles / catalyst molar number c (product tertiary butyl alcohol - Rumoru number / reaction iC ₄ H ₁₀
The number of moles) × 100 d The reaction has an induction period of 5 hours. e The reaction has a provocation period of 3 hours.

[0031] Examples 12 to 14 Table 2 meso - perfluoroalkyl ribs Lupo sulfide Rinato iron complexes of tertiary butyl hydroperoxide catalyzed in the degraded ^a t Time O ₂ generation ^b complex _{T ℃ 1 2 3 4 RO 2} H Conversion rate ^c A 80 1300 N / A N / A N / A 1375 92.5% B 80 1000 N / A 1300 1390 94% C 80 1130 1260 1325 1400> 95% D 80 365 445 450 450 35% a Catalyst 0.60 mg at 80 ° C Tertiary butyl alcohol 1
To a stirred solution of 13.8 g tertiary butyl hydroperoxide in 8.1 g (dried well over activated 3A molecular sieves before use) was added directly. Oxygen evolution was measured with a manometer. Liquid products were analyzed by glpc before and after the experiment. b Oxygen evolution cc c [(RO ₂ H _init moles-RO ₂ H _final moles) / RO ₂
H _init number of moles] × 100 d A = Fe [(C ₆ F ₅ ) ₄ P] Cl B = [Fe (C ₆ F ₅ ) ₂ (C ₃ F ₇ ) ₂ P] ₂ O C = [Fe (C ₃ F ₇ ) ₄ P] ₂ O D = [Fe (CF ₃ ) P] ₂ O

[Brief description of drawings]

FIG. 1 is a function of time on the oxidation of isobutane with 32 mg of Fe [PPF ₂₈ H ₈ ] X, where X is halogen, at 80 ° C. and 35 psia O _2. Reactant isobutane (IC4) as a product, and the product tertiary butyl alcohol (TB
It is a graph which shows the mol% of A).

FIG. 2 is a graph showing ln (C, mol%) of isobutane as a function of time in the same oxidation experiment.

FIG. 3 shows the reactants and formation as a function of time in the oxidation of isobutane in the second experiment under the same conditions and the same catalyst as in the experiments of FIGS. 1 and 2. It is a graph which shows the mol% of the thing.

FIG. 4 is a graph showing ln (C, mol%) of isobutane as a function of time in the second experiment.

FIG. 5: Reactants, products and isobutane in a third experiment at 40 ° C. and O ₂ at 35 psia using 40 mg of the same catalyst in the first and second experiments. The graph which shows the mol% of ln (C, mol%) of.

FIG. 6 shows the same 40 in the first and second experiments.
Figure 3 is a graph showing the mol% ln (C, mol%) of reactants and products and isobutane in a third experiment at 80 ° C and 35 psia O ₂ with mg catalyst.

FIG. 7 is a schematic diagram depicting reaction pathways for the preparation of exemplary compounds according to the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 31/10 9155-4H C07C 31/10 31/133 9155-4H 31/133 45/33 9049- 4H 45/33 45/53 9049-4H 45/53 49/08 9049-4H 49/08 A 49/403 9049-4H 49/403 A // C07B 61/00 300 C07B 61/00 300 (72) Inventor James E. Lions United States 19086 Wallingford Cooper Drive, Pennsylvania 211 (72) Inventor Paul Y. Ellis Jr. United States 19335 Downington, PA Glenside Avenue 1179 (72) Inventor Manoji Buoy. Binde United States 19061 Boothwin Spring Meadow Lane, Pennsylvania 1578

Claims (39)

[Claims] (1) Structural formula (1) [Wherein M is a transition metal, and R ³ and R ⁶ are 2 to
Containing between them at least one haloalkyl group having 8 carbon atoms, and R ¹ , R ² , R
⁴ and R ⁵ are independently hydrogen, hydrocarbyl, halogen, nitro, cyano or halocarbyl. ] The new compound having. 2. A compound as claimed in claim 1, wherein the first-mentioned haloalkyl group has 3 to 6 carbon atoms. 3. The compound according to claim 2, wherein the first mentioned haloalkyl group is a heptahalopropyl group. 4. A compound according to claim 3, wherein the first mentioned haloalkyl group is a heptafluoropropyl group. 5. A compound according to claim 1, wherein the first mentioned haloalkyl group is a straight chain haloalkyl group. 6. A compound according to claim 1, wherein the first mentioned haloalkyl group is a branched chain haloalkyl group having 3 to 8 carbon atoms. 7. The first mentioned haloalkyl group is straight-chain heptafluoropropyl, M is iron, R ¹ , R ² , R ² .
The compound of claim 1, wherein ⁴ and R ⁵ are hydrogen. 8. Having the formula [Fe (C ₆ F ₅ ) ₂ (C ₃ F ₇ ) ₂ P] ₂ O, where P is porphyrin, R ⁶ is C ₆ F ₅ , and R ³ Is C ₃ F ₇
The compound of claim 1, wherein 9. A compound according to claim 1 having the formula [Fe (C ₃ F ₇ ) ₄ P] ₂ O, where P is porphyrin and R ³ and R ⁶ are each heptafluoropropyl. 10. A method for producing meso-halocarbyl-porphyrin, which comprises contacting halocarbyl dipyrromethane with a halocarbyl-substituted aldehyde in the presence of an acidic granular solid catalyst. 11. The halocarbyl-porphyrin is meso-tetrakis (pa-haloalkyl) -porphyrin and the halocarbyl dipyrromethane is bis (pyrrole-2-).
Yl) perhaloalkane, and the aldehyde is
11. The method of claim 10, which is a haloalkane-substituted aldehyde. 12. The halocarbylporphyrin is bis.
(Pyrrol-2-yl) trifluoromethyl-methane,
The method of claim 11 wherein the halocarbyl dipyrromethane is bis (pyrrol-2-yl) trifluoromethylmethane and the aldehyde is trifluoroacetaldehyde methyl hemiacetate. 13. The halocarbylporphyrin is bis.
(Pyrrol-2-yl) heptafluoropropylmethane, wherein the halocarbyl dipyrromethane is bis (pyrrol-2-yl).
13. The method of claim 12, wherein the aldehyde is heptafluorobutyraldehyde. 14. The method of claim 12, wherein the catalyst is montmorillonite. 15. A structural formula: [Wherein M is a transition metal, R ³ and R ⁶ are at least one haloalkyl group having 2 to 8 carbon atoms, and R ¹ , R ² , R ⁴ and R ⁵ are Independently hydrogen, hydrocarbyl, halogen, nitro, cyano or halocarbyl. ] The method for partial oxidation of alkanes, which comprises contacting an alkane with a catalyst composed of a compound having the above formula and oxygen to form a partial oxidation product under partial oxidation conditions. 16. The method according to claim 15, wherein the first mentioned haloalkyl group contains from 3 to 6 carbon atoms. 17. The method according to claim 16, wherein the first mentioned haloalkyl group is a heptahalopropyl group. 18. The method according to claim 17, wherein the first mentioned haloalkyl group is a heptafluoropropyl group. 19. The method according to claim 15, wherein the first mentioned haloalkyl group is a straight chain haloalkyl group. 20. The method according to claim 15, wherein the first mentioned haloalkyl group is a branched chain haloalkyl group containing from 3 to 8 carbon atoms. 21. The first mentioned haloalkyl group is straight-chain heptafluoropropyl, M is iron, R ¹ , R ² ,
R ⁴ and R ⁵ are hydrogen, A method according to claim 15. 22. A formula has a _{[Fe (C 6 F 5)} 2 (C 3 F 7) 2 P] 2 O, where P is a porphyrin, a method according to claim 15. 23. The method of claim 15, having the formula [Fe (C ₃ F ₇ ) ₄ P] ₂ O, where P is a porphyrin. 24. The alkane is isobutane and the partial oxidation product is t-butyl alcohol.
5. The method according to 5. 25. The alkane is cyclohexane,
The method according to claim 15, wherein the partial oxidation product is a mixture of cyclohexanol and cyclohexanone. 26. The method of claim 15 wherein the alkane is isopentane and the partial oxidation product is a t-amyl alcohol rich mixture. 27. The method of claim 15, wherein the alkane is propane and the partial oxidation product is a mixture of acetone and isopropyl alcohol. 28. A structural formula: [Wherein M is a transition metal and R ³ and R ⁶ include at least one haloalkyl group having 2 to 8 carbon atoms between them, and R ¹ , R ² , R ⁴ and R ⁵ are independently hydrogen, hydrocarbyl, halogen, nitro, cyano or halocarbyl. ] And a catalyst consisting of a compound having the
A method of partially decomposing into a mixture of alcohol or alcohol and a ketone. 29. The method according to claim 28, wherein the first mentioned haloalkyl group contains from 3 to 6 carbon atoms. 30. The method according to claim 29, wherein the first mentioned halocarbyl group is a heptahalopropyl group. 31. The method according to claim 30, wherein the first mentioned haloalkyl group is a heptafluoropropyl group. 32. The method of claim 28, wherein the first mentioned haloalkyl group is a straight chain haloalkyl group. 33. The method according to claim 28, wherein the first mentioned haloalkyl group is a branched chain haloalkyl group containing from 3 to 8 carbon atoms. 34. The first mentioned haloalkyl group is straight-chain heptafluoropropyl, M is iron, R ¹ , R ² ,
R ⁴ and R ⁵ are hydrogen, A method according to claim 28. 35. The method of claim 28 having the formula [Fe (C ₆ F ₅ ) ₂ (C ₃ F ₇ ) ₂ P] ₂ O, where P is a porphyrin. 36. The method of claim 28 having the formula [Fe (C ₃ F ₇ ) ₄ P] ₂ O, wherein P is a porphyrin. 37. The method of claim 28, wherein the hydroperoxide is t-butyl hydroperoxide and the decomposition product is t-butyl alcohol. 38. The method of claim 28, wherein the hydroperoxide is t-amyl hydroperoxide and the decomposition product is a t-amyl alcohol-rich mixture. 39. The method of claim 28, wherein the hydroperoxide is cyclohexyl hydroperoxide and the decomposition product is a mixture of cyclohexanol and cyclohexanone.