Decomposition of organic hydroperoxides

Hydroperoxides are decomposed by contact with metal ligand catalysts of coordination complexes in which hydrogen in the ligand molecule has been substituted with electron-withdrawing elements or groups, for example halogen or nitro or cyano groups. Preferred catalysts are iron perhaloporphyrins.

BACKGROUND OF THE INVENTION 
This invention relates to the decomposition of organic hydroperoxides with 
metal catalysts which provide desirably high reaction rates, to produce 
the corresponding alcohol. The catalysts employed according to the 
invention provide very high reaction rates at relatively low temperatures 
such as room temperature, in contrast to prior art catalysts which 
catalyze decomposition of organic hydroperoxides much more slowly and 
require elevated temperatures in order to achieve satisfactory reaction 
rates. 
DESCRIPTION OF THE PRIOR ART 
Taylor et al U.S. Pat. No. 4,551,553 discloses decomposition of 
hydroperoxide by contact with a catalyst system comprising an admixture of 
Cr and Ru compounds which are soluble in the liquid hydroperoxide to be 
decomposed or in a diluent used in the process, such as a hydrocarbon, 
acid, ester or alcohol diluent, the reactiorn being conducted at 
25.degree. C. to 250.degree. C. and atmospheric to 150 atmospheres 
pressure, to maintain the reactants in liquid phase. Mixtures of Cr and Ru 
acetylacetonates are given as examples of the catalysts used. As prior 
art, Taylor et al disclose catalytic oxidation of hydrocarbons using 
organic hydroperoxide in the presence of Cr catalyst to produce alcohols 
and ketones, in U.S. Pat. No. 3,879,467; the decomposition of cycloalkyl 
hydroperoxides with catalyst comprising a soluble derivative of V, Mo or 
Ru, in U.S. Pat. No. 3,925,316; decomposition of hydroperoxides with 
binary homogeneous catalyst combinations of particular salts of Fe and Cu, 
in U.S. Pat. No. 3,401,193; cyclohexane oxidation and decomposition of 
resultant cumene hydroperoxide using nonsoluble Re compound, in U.S. Pat. 
No. 4,173,587; cumene hydroperoxide decomposition studies, employing 
certain forms of ruthenium, in "Use of the Proton NMR Relaxation Method to 
Study the Coordination of Cumene Hydroperoxide With Cobalt and Ruthenium 
Carboxylates" V. M. Nekipelov, Dokl. Akad. Nauk SSSR, V 261 (6), 1377-81 
(1981); "NMR Studies of Mu3-Oxo-triruthenium Hexacarboxylate Cumene 
Hydroperoxide Interaction", A. M. Trzeciak, Oxid. Commun., V. 1(4), p. 
295-303 (1980); and "Cumene Hydroperoxide Decomposition Reaction Catalyzed 
by Ruthenium (III) betadiketonates", A. Trzeciak et al, React. Kinet, 
Lett., V. 12(1-2), p. 121-5 (1981); and "Decomposition of Organic 
Hydroperoxides on Ruthenium-pi. - Complexes", Yu A. Aleksandrov, Ah. 
Obshsch. Khim., V 48, p. 2141 (1978). 
Worrell et al U.S. Pat. No. 4,257,852 discloses a distillation process for 
purifying t-butyl hydroperoxide from an isobutane oxidate mixture. Other 
components of the oxidate mixture are t-butyl alcohol, water, acetone, 
organic acids, esters, peroxides. 
Sanderson et al U.S. Pat. No. 4,910,349 discloses the preparation of 
t-butyl alcohol by the catalytic decomposition of t-butyl hydroperoxide, 
preferably in solution in t-butyl alcohol, in the presence of a metal 
phthalocyanine of a metal of Group IB, Group VIIB or Group VIIIB, for 
example chloroferric phthalocyanine and rhenium heptoxide-p-dioxane or 
oxotrichloro-bis-(triphenylphosphine) rhenium V; at column 7, lines 27 to 
35 this patent discloses that iron (III) phthalocyanine is more active 
than the cobalt (II) phthalocyanine and only 0.05% TBHP remains at 
60.degree. C. and 2.0 hours reaction time. At lower temperatures 
(25.degree. C., 1 hour reaction time), a 5.65% TBHP remains. Under the 
same conditions but with. an added rhenium complex, the conversion is &gt;99% 
with no loss in selectivity. Various ratios of Fe to Re and Fe+Re to TBHP 
were also studied. 
Sanderson et al U.S. Pat. No. 4,912,267 discloses a similar preparation to 
that of U.S. Pat. No. 4,910,349 above, except that a base-promoted metal 
phthalocycanine catalyst is employed. 
Grane et al U.S. Pat. No. 4,296,262 discloses oxidation of isobutane with 
oxygen-containing gas, using Mo catalyst, and subsequently recovering 
t-butyl alcohol from the product mixture by distillation. 
Sanderson et al U.S. Pat. No. 4,922,035 discloses decomposition of t-butyl 
hydroperoxide with a metal phthalocyanine (PCY) catalyst, for example 
chloroferric PCY, promoted with a thiol and a free radical inhibitor. 
Sanderson et al U.S. Pat. No. 4,922,036 discloses decomposition of t-butyl 
hydroperoxide to t-butyl alcohol with a borate-promoted Group IB, VIIB or 
VIIIB metal PCY such as chloroferric PCY. 
Sanderson et al U.S. Pat. No. 4,922,034 discloses decomposition of t-butyl 
hydroperoxide to t-butyl alcohol using a metal porphine catalyst, for 
example tetraphenylporphine, optionally promoted with a thiol and a 
heterocyclic amine. 
Sanderson et al U.S. Pat. No. 4,922,033 discloses decomposition of t-butyl 
hydroperoxide to t-butyl alcohol with a soluble Ru catalyst such as Ru 
acetylacetonate, promoted with a bidentate ligand such as 2,2'-dipyridyl. 
Sanderson et al U.S. Pat. No. 4,912,266 discloses decomposition of t-butyl 
hydroperoxide with an imidazole-promoted metal PCY catalyst, for example 
Fe(III)PCYCl or Mn(II)PCY or VOPCY. 
Marquis et al U.S. Pat. No. 4,992,602 discloses a continuous method for 
converting isobutane to isobutyl alcohol including the step of decomposing 
t-butyl hydroperoxide to t-butyl alcohol, using a monocyclic aromatic 
solvent and a PCY decomposition catalyst. 
Derwent abstract (Week 8912, Other Aliphatics, page 58) of reference 
89-087492/12 (EP 308-101-A) discloses decomposition of t-butyl 
hydroperoxide to t-butyl alcohol using a metal porphine catalyst such as a 
trivalent Mn or Fe tetraphenylporphine, optionally promoted with an amine 
or thiol, or a soluble Ru catalyst promoted with a bidentate ligand such 
as Ru(acac)3 promoted with bis(salicylidene)ethylenediamine, or a promoted 
PCY catalyst such as a Mn, Fe or vanadyl PCY promoted with an amine, a Re 
compound such as NH.sub.4 ReO.sub.4, a mercaptan and a free radical 
inhibitor, a base or a metal borate. 
FURTHER BACKGROUND OF THE INVENTION 
The decomposition of hydroperoxides to give the corresponding alcohol has 
potential commercial importance. Alkyl hydroperoxides are the products of 
alkane oxidation and their alcohol decomposition products are useful fuel 
and chemical products. Specifically, t-butyl hydroperoxide is made by the 
oxidation of isobutane and can be decomposed to the high octane fuel 
additive, t-butyl alcohol, in the presence of metal complexes. Elevated 
temperature and/or high catalyst concentration is often needed, and 
product selectivity is often below 90%. 
The process of the invention provides a process for decomposing 
hydroperoxides to the corresponding alcohol which gives a desired 
decomposition at a faster rate, allowing lower temperatures and/or lower 
catalyst concentrations than those required in the prior art and a higher 
product selectivity at a given reaction temperature. The greater activity 
of the catalysts of this invention allows them to be used in much lower 
concentrations resulting in considerable savings in catalyst costs. The 
process of the invention provides the above and/or other advantages in the 
decomposition of organic hydroperoxides generally to the corresponding 
alcohols.

DETAILED DESCRIPTION OF THE INVENTION 
The catalyst used according to the invention is a metal coordination 
complex catalyst containing a transition metal center and a ligand having 
the structure: 
##STR1## 
where M is Fe, Mn, Co, Ru or Cr, Fe being preferred, .largecircle. is a 
ligand, X is one or more electron-withdrawing substituents for hydrogen in 
the ligand molecule, for example chloride, bromide, iodide, fluoride, or 
combinations thereof, or nitro or cyano, or combinations thereof with 
halogen and A is an anion or is absent. Preferred anions are azide, 
halide, hydroxide or nitride. 
The catalyst used according to one embodiment of the invention is a metal 
coordination complex catalyst containing a transition metal center and a 
halogenated ligand, where the ligand is for example tetraphenylporphyrin, 
related porphyrinato ligands, porphycenes, porphenes, phthalocyanines, 
1,3-bis(2-pyridylimino)isoindoline ("BPI") and other 
1,3-bis(arylimino)isoindolines, acetylacetonates, acetates, hydroxides, or 
a Schiff base such as salen, saleph or the like. Preferably the transition 
metal is iron and the ligand is a perhalogenated porphyrin. Halogenation 
of the ligand itself, by replacement of hydrogen atoms therein with 
halogen atoms, and particularly perhalogenation, has been found to 
increase the activity of these catalysts for the decomposition of 
hydroperoxides according to the invention by increasing the rate of 
decomposition to the desired products. The catalyst according to this 
embodiment of the invention may have, in addition to the halogen atoms in 
the ligand, an anion, A, namely chloride, fluoride, bromide, iodide, 
azide, hydroxide or nitride. Preferred among the ligands are such 
macrocyclic groups as halogenated porphyrins, phthalocyanines, BPI, 
1,3-bis(arylamino)isoindolines, Schiff bases and the like. Examples of 
other ligands which may be employed in the catalysts of this invention are 
halogenated mono-, bi-, tri, and tetradentate ligand systems such as: 
propanates, butyrates, benzoates, naphthenates, stearates, 
acetylacetonates, and other betadiketones, 
1,3-bis(arylimino)-isoindolates, salen, saleph, porphyrinates, 
porphycenates, porphenates, phthalocyanates, and like systems. 
Bipyridines, terpyridines, phenanthrolines, dithio-carbamates, xanthates, 
salicylaldimines, cyclam, dioxy-cyclams, pyrazoylborates, and 
tetraazamacrocycles such as tetramethyltetraazadibenzocycloheptadecane, 
may also be used. The halogenated ligands are ligands in which halogen has 
been substituted for hydrogen in the ligand molecule. The halogens are 
believed to act as electron-withdrawing agents when the ligand is used as 
a catalyst for the decomposition of hydroperoxides. Other 
electron-withdrawing substituents than halogen may also be used, such as 
nitro or cyano. 
The use of cyano- and polycyanometallo porphyrins as catalysts for 
decomposition of hydroperoxides is contemplated in one embodiment of the 
invention. Cyano-substituted ligands, like halogen-substituted ligands, 
are known for their electron withdrawal capabilities. Increased electron 
withdrawal from halogenation of the porphyrin ring has been correlated to 
increased catalytic air oxidation activity. J. E. Lyons & P. E. Ellis, 
Jr., Catalysis Letters, 8, 45 (1991). Cyano groups are known for their 
large electron-withdrawing inductive effects, and cyano-containing 
metalloporphyrins with cyano groups in the beta or pyrrolic positions have 
been shown to be more easily reduced than their precursors without cyano 
substitution. R. J. Donohoe, M. Atamian and D. F. Bocian, J. Amer. Chem. 
Soc., 109, 5593 (1987). According to the present invention, such 
cyano-substituted compounds are used in the catalytic decomposition of 
hydroperoxides. 
The use of nitrated metalloporphyrins as catalysts for decomposition of 
hydroperoxides is contemplated in another embodiment of the invention. 
Successive nitration at the meso-positions of Zn(octaethylporphine), 
eventually giving Zn (meso-tetranitrooctaethyl porphine) has been found to 
lead to more easily reduced porphyrins, which is evidence for electron 
withdrawal from the rings. L. C. Gong and D. Dolphin, Can. J. Chem, 
63,401-5(1985). Other workers such as Catalano et al in J. Chem. Soc., 
1535 (1984) have been able to nitrate the beta or pyrrolic positions in 
various metal tetraphenylporphyrins. According to the present invention, 
such nitrated metalloporphyrins are used in catalytic decomposition of 
hydroperoxides. 
The catalysts used according to the invention have been previously 
disclosed for use in oxidizing alkanes to the corresponding alcohols. 
Perhalogenated metal complexes have been disclosed in Ellis et al 
copending application Ser. No. 07/568,118 filed Aug. 16, 1990, the 
disclosure of which is herein incorporated by reference. Other patents 
disclosing use of metal coordination complex catalysts in oxidation of 
alkanes are Ellis et al U.S. Pat. Nos. 4,895,680; 4,895,682 and 4,970,348. 
The term "ligand" is used herein in its conventional meaning and refers 
generically to a group or system of atoms which form one or more bonds to 
a metal ion, i.e., forms a coordination complex, and stabilizes the 
coordination complex in desirable oxidation states. Suitable ligands for 
the present purpose are the well-known phthalocyanines and porphyrins such 
as alkyl and aryl porphyrins such as tetraphenylporphyrins, 
octaethylporphyrins, tetramethylporphyrins and the like. Usually there are 
0-12 substituents, alkyl or aryl, on the basic porphyrin structure, the 
alkyls are C.sub.1 -C.sub.4 and the aryls contain 1 or 2 rings which may 
themselves have alkyl substituents. 
The electron-withdrawing component of the ligand, X, can be fluoride, 
chloride, bromide, iodide or mixtures thereof, or cyano or nitro, but 
preferably among the halogens is one of the first three mentioned, more 
preferably fluoride. The degree of ligand halogenation should be complete, 
i.e., at least 90%, preferably 100%, which is customarily referred to as 
perhalogenation for which the conventional symbols are F-, Cl-, etc. We 
have found that complete halogenation may provide substantially superior 
results. 
The catalysts of our invention can be readily prepared by simple 
modifications of procedures described in the art for preparing 
unhalogenated ligands. For example, the unhalogenated Fe(TPP)Cl complex 
(in which "TPP" is tetraphenylporphyrinato) can be prepared by a standard 
method in which (TPP)H.sub.2 and Fe(II) (or other metal) chloride are 
refluxed together in a dimethylformamide solution. Purification is 
achieved by chromatography. (See, e.g., A. D. Adler et al, J. Inorg. Nucl. 
Chem., 32, 2443 (1970).) From these metal salts the corresponding azides 
may be prepared by metathesis reactions with dissolved NaN.sub.3 or 
hydrazoic acid. 
To prepare the corresponding halogenated ligand coordination complex of 
this invention, one or more of the precursors of the ligand are 
halogenated before the ligand itself is produced by a condensation 
reaction. Thus fluorination of benzaldehyde followed by condensation with 
pyrrole yields TPPF.sub.20 in which F.sub.20 refers to twenty fluorine 
atoms on the four phenyls. Substituting this TPPF.sub.20 for TPP in the 
aforementioned method of refluxing ir a dimethylformamide solution 
containing the Fe(II) will yield the corresponding Fe(TPPF.sub.20) salt. 
By way of specific illustration the perhalogenated metal porphyrin, 
[Fe(TPPF.sub.20 Br.sub.8)]Cl, iron 
tetrakispentafluorophenyloctabromoporphyrin) chloride, is prepared as 
follows: Under N.sub.2, a flask is charged with 1.0 g of Zn(TPPF.sub.20) 
and 300 ml of CCl.sub.4. This mixture is refluxed with 150 ml of 6M 
Br.sub.2 for 5 hours and is then allowed to cool to room temperature. 
After chromatography on basic alumina, 300 mg. of pure Zn(TPPF.sub.20 
Br.sub.8) is obtained and characterized by UV/VIS, IR and elemental 
analysis. The zinc is removed by acid treatment and the iron complex 
Fe(TPPF.sub.20 Br.sub.8)Cl, is prepared by FeCl.sub.2 treatment in 
refluxing DMF. The azide, Fe(TPPF.sub.20 Br.sub.8)N.sub.3, can be prepared 
by reaction of the chloride salt with NaN.sub.3 in acetone. The ruthenium, 
chromium and manganese complexes are prepared similarly. The hydroxo salt, 
Fe(TPPF.sub.20 Br.sub.8)OH, is prepared from the chloro salt by treatment 
with dilute aqueous KOH in CH.sub.2 Cl.sub.2 /H.sub.2 O. 
The perhalogenated metal porphyrin Fe(TPPF.sub.20 Cl.sub.8)Cl is prepared 
as follows: under N.sub.2, 0.5 g of Zn(TPPF.sub.20) dissolved in 500 ml of 
CCl.sub.4 is refluxed for 5 hr. while Cl.sub.2 gas is bubbled slowly 
through the solution. After cooling the mixture is filtered and 
chromatographed on alumina, yielding 0.4 g of pure Zn(TPPF.sub.20 
Cl.sub.8)Cl.sub.8. The zinc is removed by trifluoroacetic acid treatment, 
and the iron is then inserted by reaction with FeCl.sub.2 in DMF. The 
resulting Fe(TPPF.sub.20 Cl.sub.8)Cl is characterized by UV/VIS, IR, and 
elemental analysis. The ruthenium, manganese, and chromium complexes are 
prepared similarly. The azide salts are prepared from the chloride salts 
by metathesis with NaN.sub.3 in acetone. The hydroxo salt, Fe(TPPF.sub.20 
Cl.sub.8)OH, is prepared from the chloro salt by treatment with dilute 
aqueous KOH solution in CH.sub.2 Cl.sub.2. 
The perfluorinated metal porphyrin, iron perfluorotetraphenylporphyrin 
chloride, Fe(TPPF.sub.28)Cl (28 F atoms) can be prepared by the reaction 
of dilute F.sub.2 gas in N.sub.2 with Zn(TPPF.sub.20) in CCl.sub.4, with 
small added amounts of CoF.sub.3, followed by removal of zinc and 
incorporation of iron as before. This porphyrin complex is analyzed by IR, 
UV/VIS, and elemental analysis. The ruthenium, chromium, and manganese 
complexes are prepared in analagous fashion. The azide salts are prepared 
from the chloride salts by reaction with NaN.sub.3 in acetone. The hydroxo 
salt, Fe (TPPF.sub.28)OH, is prepared by the dilute aqueous KOH treatment 
of the chloro salt in CH.sub.2 Cl.sub.2. 
The preparation of the following iron complexes are examples of the 
tetraalkylporphyrins used in our invention. Freshly distilled pyrrole (0.8 
g) and triflucroacetaldehyde methyl hemiacetal (10.9 g) are refluxed for 
24 hr. in 500 ml of ethanol containing 10 ml of 48% HBr. After 
neutralization of the mixture and extraction of the crude 
tetrakis(trifluoromethyl) porphyrin into CH.sub.2 Cl.sub.2, the H.sub.2 
(TTFMP) is purified by chromatography with alumina. Iron is inserted into 
the H.sub.2 (TTFMP) by FeCl.sub.2 /DMF treatment giving Fe(TTFMP)Cl. The 
azide and hydroxide complexes are prepared by metathesis with NaN.sub.3 in 
acetone and aqueous KOH in CH.sub.2 Cl.sub.2, respectively. The pyrrolic 
hydrogens of this porphyrin can be partially or fully halogenated with Br, 
Cl, or F using the same techniques used for the tetraphenylporphyrins. As 
an example, dilute F.sub.2 gas treatment of Zn(TTFMP) in the presence of 
CoF.sub.3 in CCl.sub.4 leads to isolation of the perfluorinated zinc 
porphyrin, zinc perfluorotetramethylporphyrin Zn(FTMP). Removal of the 
zinc by strong acid treatment leads to the metal free H.sub.2 (FTMP) from 
which the iron complex Fe(FTMP)Cl can be prepared by FeCl.sub.2 /DMF 
treatment. The azide, hydroxide, and nitride complexes are prepared in 
similar fashion to those described before. The chromium, manganese, and 
ruthenium complexes can be prepared from H.sub.2 -FTMP by use of the 
appropriate metal chloride or metal acetate in DMF. 
Other metal halogenated porphyrins or phthalocyanines are made analogously 
to the above methods. Similarly, when other porphyrin compounds are used 
similar results are obtained. The excellent catalytic activity of our 
catalyst depends on the electronic and structural nature of the porphyrin 
and phthalocyanine macro structure itself, not on any specific substituted 
group. 
From the foregoing it will be seen that the catalysts used in the process 
of the invention are comprised of the component parts: the ligand moiety, 
which has been substituted with electron-withdrawing elements or groups, 
for example having been halogenated or substituted with cyano or nitro 
groups, the metal center which is bound to (i.e., complexed with) the 
ligand, and as anion, azide, chloride, hydroxide or nitride or the like, 
which is bound to the metal. The metal-ligand portion is also frequently 
described in the art as a metal coordination complex. In some cases, 
dimetal .mu.-oxo compounds, commonly known as .mu.-oxo dimers, are 
suitable catalysts and should be regarded as the equivalent thereof. In 
these compounds, each of the two iron centers is bound to one anion 
moiety. A typical structure for such compounds is: 
##STR2## 
where M and X are as previously defined. This compound may also be 
characterized by the structure: 
##STR3## 
where M and X are as previously defined and A is: 
##STR4## 
The catalyst use the process according to the invention may also be 
prepared by the method disclosed and claimed in Ellis et al U.S. patent 
application Ser. No. 07/634,261 filed Dec. 7, 1990, the disclosure of 
which is herein incorporated by reference. As a typical reaction according 
to that application, the perhalogenation is performed by reaction of iron 
tetrakispentafluorophenyl)-porphyrinato with bromine. 
Nitro-substituted porphyrins are prepared for example by reacting iron 
tetrakispentafluorophenyl chloride with 1 to 8 equivalents of nitrogen 
dioxide in methylene dichloride or benzene, leading to various amounts of 
nitration at the beta positions on the ring according to the severity of 
the reaction conditions. Beta positions left unnitrated are subsequently 
halogenated using normal chlorination, bromination or fluorination 
techniques. The general structure for this preparation is: 
##STR5## 
where M is Fe, Cr, Mn, Ru, Co, or Cu, X is NO.sub.2, Y is NO.sub.2, Cl, Br 
or F and Z is H, Cl or F. 
Alternatively, Zn(porphine) is reacted with nitrogen dioxide in methylene 
chloride to produce Zn (mesotetranitroporphine). The zinc is removed by 
acid treatment and Fe or other transition metal, M, is inserted by the 
usual method of ferrous chloride or metal dichloride in dimethylformamide. 
The beta or pyrrolic hydrogens can be further nitrated or halogenated as 
desired. The general structure for this preparation is: 
##STR6## 
where M is Fe, Cr, Mn, Ru, Cu or Co, X is NO.sub.2, Y is NO.sub.2, Cl, F, 
Br, or any combination thereof. 
Meso-perfluorinated alkyl porphyrins as disclosed in our copending 
application Ser. No. 568,118 filed Aug. 16, 1990, the disclosure of which 
is incorporated by reference herein, can be nitrated in the beta or 
pyrrolic positions using nitrogen dioxide in methylene chloride or 
nitric/sulfuric nitrating solutions. The general structure for this 
preparation is: 
##STR7## 
where M is Fe, Cr, Mn, Ru, Cu or Co, X is 0 to 6, and Y is NO.sub.2 and 
Cl, Br or F. 
Cyano-substituted porphyrins are prepared for example by bromination of 
Zn(tetrakispentafluoroporphine) with bromine in carbon tetrachloride to 
obtain Zn(tetrakispentafluorophenyl-beta-octabromoporphine), which is then 
treated with 9 equivalents of CuCN in pyridine at reflux for several 
hours. After chromatography several of the bromines are replaced with CN 
groups giving, according to the conditions, Zn(TPPF.sub.20 
-beta-CN.sub.4-8). The zinc is removed by mild treatment with 1M HCl and 
recovered by chromatography on alumina. Metals can be inserted into the 
product, H.sub.2 (TPPF.sub.20 -beta-CN.sub.4-8) by treatment with the 
metal salt in DMF, e.g., ferrous chloride in DMF, leading to the 
production of Fe(TPPF.sub.20 beta-CN.sub.4-8)Cl. 
If the CuCN treatment is conducted under milder conditions some of the 
bromine groups can be reatined leading to mixed bromo/dyano 
metalloporphyrins. Pyrrolic positions without cyano or bromo substitution 
can also be brominated, chlorinated or fluorinated leading to complexes of 
the general structure; 
##STR8## 
where M is Fe, Cr, Mn, Ru, Co or Cu, X is CN, Y is CN, Cl, Br or F and Z 
is H, Cl or F. 
Meso-perfluorinated alkyl porphyrins can also be converted to cyano 
derivatives as shown in the previous examples. The general structure is: 
##STR9## 
where M is Fe, Cr, Mn, Ru, Cu or Co, X is 0 to 6, and Y is CN and Cl, Br 
or F. 
The decomposition of hydroperoxide according to the invention 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 is formed by decomposition of the hydroperoxide, for 
example, t-butanol formed by decomposition of t-butylhydroperoxide. A 
suitable solvent can be selected by a person skilled in the art. Any 
suitable temperature and pressure may be used. Preferably the temperature 
is in the range from 25.degree. to 100.degree. C. 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. 
In the process of the invention, the hydroperoxide dissolved in a solvent 
is introduced into a reaction zone wherein it is contacted with catalyst, 
in the substantial absence of added oxidizing agent, to convert the 
hydroperoxide, ROOH, where R is an organic radical, to the corresponding 
alcohol, ROH. 
Hydroperoxides which may be decomposed 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 chloride, bromide, or an alkaryl 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 alkaryl group in which the aromatic moiety is phenyl 
and the alkyl substitutent is straight or branched chain alkyl or 
cycloalkyl containing up to about 6 carbon atoms. Examples are t-butyl and 
isobutyl hydroproxide, isoaml hydroperoxide, 
2-methylbutyl-2-hydroperoxide, cyclohexyl hydroperoxide, alpha- and 
beta-ethylbenzene hydroperoxide, cumyl hydroperoxide, phenethyl 
hydroperoxide and cyclohexylphenyl hydroperoxide. Phenethyl hydroperoxide 
and cumyl hydroperoxide are each converted to phenethyl alcohol. 
The invention will be further described below in connection with Example 2, 
with reference to the drawing, in which FIG. 1 is a plot of t-butyl 
alcohol produced in examples according to the invention and comparison 
examples, against reaction time. 
The following examples illustrate the invention: 
EXAMPLE 1 
Tertiary butyl hydroperoxide (90%), 10 ml. was added dropwise over a 6-13 
minute period to a stirred solution of 2.times.10.sup.-4 mmole of the 
catalyst complex in 50 ml of benzene. Aliquots (ml) were withdrawn at 25 
min. intervals and analyzed by glpc. The complex was an iron porphyrin 
complex as shown in Table I. The results for four different complexes were 
as shown in Table I. The first and second complexes were perhalogenated 
complexes, the third a partially halogenated complex and the fourth 
contained an unhalogenated triphenylporphyrin complex. 
TABLE I 
__________________________________________________________________________ 
t-BUTYLHYDROPEROXIDE DECOMPOSITION CATALYZED BY IRON 
PORPHYRIN COMPLEXES AS A FUNCTION OF THE EXTENT OF 
PORPHYRIN RING HALOGENATION 
Reaction 
Reaction Products, 
mmoles 
.sub.- tBu.sub.2 OH 
.sub.- tBuOH 
Time. Hrs. 
tBuOH 
Acetone 
(tBuO).sub.2 
Conv. % 
Sel. % 
__________________________________________________________________________ 
Fe(TPPF.sub.20 .beta.-Br.sub.8)Cl 
1.9 91.3 2.1 4.2 99 94 
Fe(TPPF.sub.20 .beta.-Cl.sub.8)Cl 
1.9 89.0 2.1 3.9 98 94 
Fe(TPPF.sub.20)Cl 
2.0 44.2 2.9 na 62 &lt;94 
Fe(TPP)Cl 1.9 19.1 3.3 na 29 &lt;85 
__________________________________________________________________________ 
EXAMPLE 2 
Further data on the process of the invention are shown in FIG. 1, which is 
a plot of weight percent t-butyl alcohol formed against reaction time in 
the reactions carried out a described in Example 1, using different 
complexes in each of six runs. Complexes A and B as shown in FIG. 1 were 
perhalogenated iron porphyrin complexes, complex C a partially halogenated 
complex, complex D contained an unhalogenated porphyrin complex, complex E 
was Fe(II)acetylacetonate and complex F was Cr(TPPF)OH where TPPF is 
perfluorinated porphyrin. 
EXAMPLE 3 
Table II shows in Runs 1-6 and 11, the results after one hour reaction time 
for the seven catalysts shown in FIG. 1. Table II also shows the results 
after one hour reaction time for the other catalysts identified in Table 
II. The reactions were carried out in the same manner as described in 
Example 1. In Table II, "AA" is acetylacetonate, "PcF" is 
perfluorophthalocyanine, "N.sub.3 " is azide, "BPI" is 
1,3-bis-(2-pyridylimino)isoindoline, "OAc" is acetate, "OO-t-C.sub.4 " is 
tertiarybutyl-peroxy, "Pc" is phthalocyanine, "F.sub.3 AAF.sub.3 is 
perfluoroacetylacetonate. The values given for "Wt. % C.sub.4 OH" include 
0.6 (plus or minus 0.2) wt. % C.sub.4 OH(t-butyl alcohol) in the starting 
material. 
TABLE II 
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CATALYTIC HYDROPEROXIDE DECOMPOSITION 
CATALYST t-C.sub.4 H.sub.9 OH 
t-C.sub.4 H.sub.9 OOH 
(CH.sub.3).sub.2 CO 
RUN .0033 mM./L. G.C.Wt. % 
G.C.Wt. % 
G.C.Wt. % 
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1 Fe(III) [TPPF.sub.20 ]Br.sub.8 Cl 
11.2 2.3 0.2 
2 Fe(III) [TPPF.sub.20 Cl.sub.8 ]Cl 
9.8 2.9 0.3 
3 Fe(III) [TPPF.sub.20 ]Cl 
4.7 9.7 0.4 
4 Fe(III)[TPPF.sub.20 ]Cl 
6.6 11.9 0.1 
5 Fe(III) [TPP]Cl 
2.3 13.2 0.4 
6 Fe(II) [AA].sub.2 
1.0 15.0 0.4 
7 Fe(III) [PcF]N.sub.3 
0.8 15.0 0.2 
8 Fe(II) [PcF] 0.9 15.5 0.2 
9 Co(II) [PBI] [OAc] [OO-t-C.sub.4 ] 
0.6 15.9 0.2 
10 Fe(III) [AA].sub.3 
0.5 15.9 0.2 
11 Cr(III) [TPPF.sub.20 ]OH 
1.0 16.0 0.3 
12 Co(II) [TPPF.sub.20 ]Cl.sub.8 
0.7 16.0 0.2 
13 Mn(III) [TPPF.sub.20 ]N.sub.3 
0.6 16.0 0.2 
14 Fe(II) [Pc] 0.6 16.0 0.2 
15 Fe(III) [F.sub.3 AAF.sub.3 ].sub.3 
0.5 16.0 0.2 
16 Co(II) [TPP] 0.4 16.0 0.2 
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Runs 1, 2, 3, 4, 7, 8, 11, 12, 13 and 17 in Table II were performed with 
catalysts according to the invention. The best results were obtained with 
catalysts containing Fe and porphyrin (Runs 1-4). Runs with Fe and 
halogenated phathalocyanine (Runs 7 and 8), Cr and halogenated porphyrin 
(Run 11), Co and halogenated porphyrin (Run 12), Mn and halogenated 
porphyrin (Run 13), Fe and halogenated acetylacetonate (Run 15) gave poore 
results. Satisfactory reaction rates for the catalysts of Runs 7, 8, 11, 
12, 13 and 15 may be obtained by using higher catalyst concentrations 
and/or by raising the temperature; however, raising the temperature may 
result in loss of selectivity, and the results obtained with the 
halogenated ligands of Runs 7, 8, 11, 12, 13 and 15 may not be improved 
over the corresponding unhalogenated ligand. In any event, the ligands of 
Runs 1-4 are clearly much superior to those of Runs 7, 8, 11, 12, 13 and 
15.