WO 2006/043075 PCT/GB2005/004062
1 .
SELECTIVE OXIDATION OF ORGANIC COMPOUNDS
This invention relates to the selective oxidation of organic compounds.
The selective oxidation of organic compounds is practised widely in the chemicals
industry. The production of many large volume and high value fine chemicals
employ oxidation reactions. .
A list of industrially important chemical conversions falling within the category of
oxidations includes: the epoxidation of olefms, the conversion of alkanes to alcohols,
aldehydes, ketones and carboxylic acids, the Baeyer-Villiger oxidation of ketones to
esters and lactones, the oxidation of alcohols to aldehydes, ketones and carboxylic
acids, and the hydroxylation and oxyhalogenation of aromatics. Commercially
important compounds like phenol, ethylene oxide (and ethylene glycol), propylene
oxide (and propylene glycol), styrene oxide, caprolactone, adipic acid, catechol,
hydroquinone, cresols, terpenoids, benzaldehyde, benzoic acid and chlorotoluenes all
rely on oxidation reactions for their production.
Known chemical oxidation processes for the preparation of bulk chemicals on an
industrial scale typically suffer from drawbacks, notably because they involve multi-
step reactions, the use of expensive homogeneous catalysts that require costly
separation and recycling steps, the use of atom-inefficient processes, they produce
significant amounts of by-products or employ aggressive oxidants that in turn
produce environmentally damaging waste products and emissions. For example, the
currently practised route for producing phenol from benzene, involves a multi-step
process whereby benzene is first converted to cumene, which is in turn oxidised to
cumene hydroperoxide, and finally converted to. the desired phenol, but with acetone
as by-product. While direct routes have been proposed, such as oxidation of benzene
using solid catalysts such as titanosilicates in combination with hydrogen peroxide
and oxidation of benzene in the gas phase, these suffer from practical problems for
commercial scale production.

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Likewise, the commercial production of adipic acid from cyclohexane is a multi-step
process using a soluble cobalt catalyst to produce cyclohexanol/cyclohexanone ("KA
Oil") in a first step, and subsequently further oxidising in the presence of
concentrated nitric acid and a soluble vanadium catalyst to produce adipic acid but
also 2 moles of the greenhouse gas nitric oxide for every mole of adipic acid.
Oxidation can also naturally be employed in the production of fine chemicals. Fine
chemicals are generally prepared on a smaller scale than bulk chemicals such as
discussed above. Nevertheless acceptable levels of selectivity are important, as are
comparatively mild reaction conditions e.g. avoiding aggressive oxidation. In this
connection particular mention may be made of the oxidation of heterocyclic
aromatics such as alkyl pyridines. For example, 4-picoline, when oxidised at the
methyl group, yields 4-picolinic or isonicotinic acid, which is an important derivative
in the production of antibacterials, Pharmaceuticals e.g. for the treatment of
tuberculosis, psoriasis and arthritis (Isoniazid is isonicotinic acid hydrazide), as plant
growth regulators, herbicides, pesticides and corrosion inhibitors. Similarly 3-
picoline when oxidized at the methyl group yields nicotinic acid which is used in the
preparation of vitamins (e.g. vitamin B3). While catalytic oxidations for such
preparations have been proposed, the reactions in practice employ aggressive
conditions such as provided by nitric acid, chromic acid and hydrobromic acid. One
commercial route involves a two-step reaction via the corresponding 3-
cyanopyridine.
There have recently been various studies on the use of oxidants with
heterogeneous/solid catalysts, in particular heterogeneous transition metal catalysts,
to provide more efficient selective oxidation processes for the preparation of organic
compounds in solvent based systems. Such catalysts can be readily separated from
the reaction media and recycled. In particular, it is believed that with the
appropriate catalyst, there may be provided control of the site of oxidation of the

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starting material thus leading to good selectivity for the desired product and reducing
the production of undesired by-products.
For example US Patent 5767320 describes the oxidation of cyclohexane to a mixture
of cyclohexanone and cyclohexanol in the presence of an organic solvent with
molecular oxygen in the presence of a solid catalyst containing a phthalocyanine or
porphyrin complex of a transition metal where some or all of the hydrogen atoms of
the transition metal complex have been substituted by one or more electron
withdrawing groups. There is preferably present an alkyl hydroperoxide or dialkyl
peroxide as promoter. The porphyrin complexes, encapsulated in zeolite are further
described in Barley et al, New J Chem 1992, vol 16, page 71.
The oxidant used in such heterogeneous systems is generally molecular oxygen,
preferably in the presence of a peroxide as promoter. It is also known to use
hydrogen peroxide as an oxidant in oxidising reactions. Much work in the last two
decades has been directed towards the use of hydrogen peroxide and molecular
oxygen as oxidants in selective reactions. These are generally regarded as more
mass efficient than many other oxygen sources.
It is also been proposed to use peracids, particularly peracetic acid, as oxidants in the
oxidation of chemical compounds in solvent-based homogeneously catalysed
systems.
Despite the advances in heterogeneous catalysis, however, the yields of target
products remain relatively low in some commercially important oxidation reactions
using these catalysts and the aforementioned oxidants.
US Patent 5462692 describes solid acetyl peroxyborate compounds, which are active
oxygen containing compounds, and their preparation from acetic acid and boron-
oxygen compounds. The solid acetyl peroxyborates have a peracetic acid content
which can be liberated together with hydrogen peroxide in water. The solid acetyl

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peroxyborates are proposed for use in washing, bleaching and cleaning agents and
disinfectant applications and as oxidising agents, although there has been little
practical use of these compounds to date.
The present invention provides a process for the selective oxidation of an organic
compound which process comprises oxidising the organic compound using a peracid
or a source of peracid, a transition metal based heterogeneous catalyst and a borate or
boric acid, in the presence of water.
It has surprisingly been found that, under the conditions of the present invention,
both excellent conversion and product selectivity may be obtained. Moreover the
process achieves this using water as solvent and employing relatively mild
conditions.
The process of the present invention may be applied to industrially important
chemical conversions falling within the category of oxidations including: the
epoxidation of olefins, the conversion of alkanes to alcohols, aldehydes, ketones and
carboxylic acids, the Baeyer-Villiger oxidation of ketones to esters and lactones, the
oxidation of alcohols to aldehydes, ketones and carboxylic acids, and the
hydroxylation and oxyhalogenation of aromatics. Thus commercially important
compounds like phenol, ethylene oxide (and ethylene glycol), propylene oxide (and
propylene glycol), styrene oxide, caprolactone, adipic acid, catechol, hydroquinone,
cresols, terpenoids, benzaldehyde, benzoic acid and chlorotoluenes can be prepared
by the process of the present invention.
From the perspective of the fine chemical industry, the present invention is likely to
be considered much safer because of itsuse of water as a solvent and the fact that air
or oxygen is avoided.
Organic compounds that can be selectively oxidised using the process of this
invention include substituted and unsubstituted aromatic hydrocarbons, olefins,

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alkanes, ketones and alcohols. The aromatics include benzene, phenol and toluene.
Benzene may be oxidised to produce phenol, phenol may be oxidised to produce
catechol and hydroquinone and toluene may be oxidised to benzaldehyde, o-cresol
and p-cresol. In the presence of halide salts, for example sodium chloride, toluene
may be converted using the process according to the invention to a mixture of o-, and
p-chlorotoluene. The olefins include styrene, propylene, a-pinene, and (+)-
limonene. These may all be converted to the corresponding epoxides, with minimal
diol formation. The alkanes include cyclohexane, which may be converted to adipic
acid, rather than the intermediate mixture of cyclohexanol and cyclohexanone
produced by many existing processes. Cyclohexanone is an example of a ketone
which may be oxidised in this process to the corresponding lactone.
For example the process according to the invention may be used for the oxidation of
cyclohexane to adipic acid, the epoxidation of styrene tostyrene oxide, oxidation of
a-pinene to a-pinene-oxide, propylene to propylene oxide, oxidation of phenol to
catechol and hydroquinone, oxidation of cyclohexanone to y-caprolactone, oxidation
of benzene to phenol and oxyhalogenation/chlorination of toluene to o- and p-
chlorotoluene.
The selective oxidation of the present invention may also be used in the preparation
of fine chemicals. In this connection particular mention may be made of alkyl e.g.
methyl pyridines and heterocyclic aromatics e.g. nitrogen-containing aromatics, such
as picolines, and alkyl, e.g. methyl, derivatives of pyrimidine, pyridazine, pyrazine,
quinoline and quinoxaline. Using the process of the present invention such
compounds may be converted into the corresponding carboxylic acids. Thus for
example 4-picoline may be selectively converted into 4-picolinic acid (isonicotinic
acid), 3-picoIine to 3-picolinic acid (nicotinic acid) and alkyl quinolines to quinoline
carboxylic acids and alkyl pyridazines to pyridazine carboxylic acids.
Isonicotinic acid may be used in the preparation of antibactierals, pharmaceuticals,
plant growth regulators, herbicides, pesticides and corrosion inhibitors, Nicotinic

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acid may be used in the preparation of vitamins (e.g. vitamin B3). Quinoline
carboxylic acids have possible uses in biocides, pesticides, antibacterials, cancer
drugs, seed disinfectants, herbicides (e.g. Quinclorac, Imazaquin), plant growth
regulators, antibiotics, antifungal agents for plants, trypsin inhibitors, charge control
agents for photocopier toners, metal ion chelators for use in plating baths. Pyridazine
carboxylic acids have uses in plant growth regulators e.g. Clofencet MON21200 ex
Monsanto.
The peracid, which functions as oxidant in the process of the present invention, can
be selected from any aliphatic or aromatic, generally carboxylic, peracid, including,
but not limited to performic, peracetic, perpropidnic, percaproic, pemonanoic,
trifluoroperacetic and perbenzoic acid, and mixtures of peracids. Also included are
solid forms of peracids, notably the acetylperoxyborate compounds described in US
5462692, capable of releasing peracetic acid when dissolved in water.
Furthermore, there may be provided a source of peracid; that is the peracid can be
formed in situ, for example by the reaction of the corresponding carboxylic acid, acid
anhydride or acid chloride with hydrogen peroxide, or sources of hydrogen peroxide.
The peracid can also be formed from the autoxidation of the appropriate aldehyde
such as benzaldehyde. It is also possible to react hydrogen peroxide, or a source of
hydrogen peroxide, with acyl-donating compounds, for example tetraacetylethylene
diamine (TAED), tetraacetylglycoluril (TAGU) and sodium p-isononanoyloxy-
benzenesulphonate (iso-NOBS). Sources of hydrogen peroxide include, but are not
limited to sodium perborate monohydrate, sodium perborate tetrahydrate and sodium
percarbonate.
The peracid component and the borate component may be combined. Thus for
example when solid acetylperoxyborate compounds as described in US 5462692 are
dissolved in water they release, in addition to the peracid, peracetic acid, borate.
Also when there is provided a source of peracid and one of the components used is a

WO 2006/043075 PCT7GB2005/004062
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perborate for example as indicated above, that component can provide all or some of
the borate.
There may further be used, as peracid or source thereof and source of borate, a
mixture of compounds capable of reacting to form acetyiperoxyborate. While
acetylperoxyborate may itself not be formed in situ, the components in the
appropriate ratio to form acetylperoxyborate may be used.
There may also be used, as the borate component present in the oxidation according
to the invention, boric acid, metal borates and ammonium borates. The metal borates
and ammonium borates may be selected from sodium perborate monohydrate,
sodium perborate tetrahydrate, and borates with the general formula
M2O.xB2O3.yH2O (with xranging from 1 to 8, and y from 0 to 10), including
disodium tetraborate penta- and decahydrate and forms of disodium tetraborate with
lower levels of hydration, referred to as 'puffed' or 'expanded' borax, and sodium
metaborate di- and tetrahydrate. M is preferably sodium but it can also represent
ammonium and other alkali metals. Mixtures of borates can also be employed.
The transition metal based heterogeneous catalysts used in the process of the present
invention include;
1. Transition metal substituted aluminophosphates (MeAlPOs), where the
substituting metal Me can be for example Fe, Ru, Mn or Co and the A1PO
framework structure, includes, but is not limited to, A1PO 5, 18, II and 36.
The aluminophosphates of the present invention used according to the
invention may contain metal substitution levels in the range 0.02-0.10, and
their preparation is described in for example S. T. Wilson, et al, J. Am. Chem.
Soc. 104 (1982) 1146; A. Simmen, et al, Zeolites 11(1991) 654; J. Chen, et
al, J. Phys. Chem. 98 (1994) 10216 (AEI structure); R. Szostak, et al, in
Synthesis of Microporous Materials, M. Occelli, H. Robson, (eds.), Van
Nostrand Remhold, New York (1992), pp 240 (AEL structure); J. M. Bennett,

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et al, ACS Symp. Series 218, Am. Chem. Soc, Washington, D. C, 1983, p.
109; S. T. Wilson, et al, US Patent 4310440 (1982); S. Oju, et al, Zeolites 9
(1989) 440 (AFI structure); P.A. Wright et al, Angew. Chem. Int. Ed. Engi,
31, 1472 (1992) (ATS structure).
Preferred transition metal substituted aluminophosphates used according to
the invention have a pore size in the range 3.5 to 12 Angstroms and have
some of the aluminium atoms replaced by transition metal atoms such as Fe,
Ru, Mn, and Co, the A1PO framework structure being preferably of the form
A1PO 5, 18, 11, or 36 and the transition metal substitution level being in the
range of 2 to 10 atom percent.
Porphyrin and phthalocyanine transition metal complexes encapsulated
within the pores of zeolites, typically super-cage zeolites, Na-X. For example
the catalyst may be a solid catalyst containing a porphyrin or phthalocyanine
complex of a transition metal wherein some or all of the hydrogen atoms of
the complex have been replaced by electron withdrawing groups, the complex
being encapsulated in a zeolite matrix as described in US Patent 5767320.
Phthalocyanine-containing catalysts may for example be prepared by a
process in which neat CuCl16Pc, CoCl16Pc and FeCl16Pc are synthesized
according to the procedure first reported by Birchall et al (J. Chem. Soc. C,
2667 (1970)) and modified by Raja and Ratnasamy (Appl. Catal A., 158, L7
(1997)). The neat complexes may be encapsulated in the supercages of
Faujasites (Zeolites Na-Y or Na-X) by the "zeolite synthesis method"
reported by Balkus et al {Inorg. Chem., 33, 67 (3994)) and modified by Raja
and Ratnasamy (Appl. Catal., 143, 145 (1996); Stud. Surf. Sci. Catal., 101,
181 (1996); J. Catal., 170, 244, (1997)). The "zeolite synthesis method" has
a number of advantages (minimal amounts of free-metal or free-ligand,
enhanced complex stability and minimal adsorption of complex on surface)
over conventional "flexible-ligand" methods of encapsulation.

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As indicated above there may be used transition metal complexes encaged in
the super cage of zeolites Na-X, These include the phthalocyanine and
porphyrin complexes described in US 5767320 . The transition metal in the
complex may be selected from iron, cobalt, copper, chromium, manganese
and mixtures thereof.
Preferred such catalysts are solid catalysts containing a phthalocyanine or
porphyrin complex of a transition metal wherein some or all of the hydrogen
atoms of the transition metal complex have been substituted by one or more
electron withdrawing groups; the complex being encapsulated in a zeolite
matrix.
3. Porous titanium-containing crystalline silicas comprising silicon and titanium
oxides and known as titanium silicalites (e.g. TS-1). The products are
synthesised by methods as described for example in U.S. Patent 4410501.
The oxidation process of the present invention may be carried out with excellent
selectivity. While it is not wished to be bound by theory, it is considered that the
excellent selectivity is attributable in part to the 3-dimensional network form of the
preferred catalysts used according to the invention. In particular it is believed the
pore size of network controls the access and orientation of molecules to be oxidised
and thus the selectivity of the reaction.
The catalysts used according to the invention generally have matrixes with pore sizes
in the range 3.5 to 12 Angstroms.
The molar ratio of peracid, or peracid liberating component, or components
employed, to the compound to be oxidised, is typically in the range 0.05:1 to 5:1,
generally 0.05:1 to 3:1, e.g. 0.05:1 to 1:1, preferably 0.1:1 to 3:1, more preferably
0.1:1 to 0.4:1.

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The amount of catalyst employed is typically in the range 1 to 20 % by weight,
preferentially in the range 2 to 15 % by weight and further preferentially in the range
2 to 10% by weight, based on the weight of the compound being oxidised.
The weight ratio of borate, or borates to peracid employed is typically in the range
0.1:1 to 4:1.
The process according to the invention is carried out in the presence of water. This
contrasts and is preferred to prior art processes carried out in organic solvents. The
water present according to the invention may assist to liberate peracetic acid. Of
course, there may also be present according to the invention an organic phase
comprising e.g. substrate, products and optionally an inert water-immiscible organic
solvent for solubilising the same, and the solid catalyst phase.
The temperature employed in the process varies according to the compound being
oxidised, but is generally in the range from 25 to 120°C.
The reaction times employed also vary with the compound to be oxidised, but are
generally within the range 0.2 to 20, e.g. 0.5 to 16, suitably 0.5 to 30, hours.
The reactions are generally carried out in a nitrogen purged atmosphere, and can be
carried out under atmospheric pressure, providing that the temperature of the reaction
does not exceed 100°C.
The invention is further illustrated with reference to the following Examples. The
catalytic reactions were carried out in a stainless-steel catalytic reactor (100 ml, Parr)
lined with Poly Ether Ether Ketone (PEEK). The substrates, a suitable internal
standard (mesitylene) and catalyst were then introduced into the reactor and the
reactor was sealed. The reactor and the inlet and outlet ports were purged with dry
nitrogen prior to reaction. The contents of the reactor were stirred at 800 rpm and the
reactor was heated to the desired temperature under autogeneous pressure (N2).

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The sources of peracid and borate (if separate from the source of the peracid) were
dissolved in double distilled water and the resulting solution was fed slowly, over the
course of the reaction, employing a syringe pump (Harvard "33") to the stirred
contents of the reactor.
Conversion (Conv) and selectivity (Sel) for each product were determined as
defined by the following equations:
Conv % = [(moles of initial reactant - moles, of residual reactant)/(moles of initial
reactant)]x 100
In most of the Examples, a ratio of compound being oxidised (substrate) to oxidant
of 3:1 is employed. Thus the theoretical maximum conversion is 33.3%.
Sel % = [(moles of individual product)/(moles of total products)] x 100.
Example 1
Oxidation of cvclohexane to adipic acid

cyclohexane cyclohexanol cyclohexanone adipic acid
Two runs (each with different reaction times) were carried out as follows.
Solid acetylperoxyborate (3.49g) prepared according to US 5462692 and capable of
liberating peracetic acid (0.701g) and hydrogen peroxide (0.045g) when dissolved in
water, was mixed with double-distilled water (20ml). The resulting solution was fed

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slowly by a syringe pumpto a stirred reactor containing cyclohexane (2.5g) and
FeAlPO-31 catalyst (0.25g), while the temperature was maintained at 110°C. This
corresponds to a cyclohexane to peracetic acid molar ratio of 3:1.
The reaction products were analysed by gas chromatography (GC, Varian Model
3400 CX) employing a HP Innovax Column (30m x 0.53 mm x 0.1 um) and flame
ionisation detector using a variable ramp temperature program from 65°C to 220°C.
The identity of each product was first confirmed using authenticated standards and
their individual response factors were determined using a suitable internal standard
(calibration method).
The identity of the products was also confirmed by liquid crystal mass spectrometry
using an LCMS-QP8000 (Shimadzu).
The reaction pH was 5.2.
One run was conducted for 16 hours. In this case the results were as follows:
Conversion of cyclohexane to oxidised products was calculated to be 29.5% .
Product selectivity was as follows:
Product Selectivity (%)
Adipic acid 81.2
Cyclohexanone 11.3
Other acids* 7.5
* Other acids (here and below) = succinic, glutaric and valeric acids.
One run was conducted for 8 hours. In this case the results were as follows:

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Conversion of cyclohexane to oxidised products was calculated to be 24.7%.
Product selectivity was as follows:
Product Selectivity (%)
Adipic acid 67.0
Cyclohexanone 27.2 .
Other acids 5.8

Example 2
Two runs (each with a reaction time of 16 hours) were carried out a follows.
A liquid comprising borax pentahydrate (1.9g) (Neobor ex Borax Europe Limited),
sodium perborate monohydrate (0.4g), 25% peracetic acid solution in acetic acid
(4.2g) and double-distilled water (20.5g) was fed slowly by a syringe pump to a
stirred reactor containing cyclohexane (2.5g) and FeAlPO-31 catalyst (0.25g), while
the temperature was maintained at 110°C.
The results were as follows:
Conversion of cyclohexane to oxidised products was calculated to be 25.0% (Run 1)
and 26.5% (Run 2).
Product selectivity was as follows:
Product Run 1 (%) Run 2 (%)
Adipic acid 61.4 63.3
Cyclohexanone 21.5 19.3


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Cyclohexanol 3.4 4.5
Other acids 12.0 11.0
Carbon dioxide 1.5 1.7
Example 3 (comparative)
Two runs (each with a reaction time of 16 hours) were carried out a follows.
A solution containing 25% peracetic acid solution in acetic acid (4.2g) and double-
distilled water (20.5g), was fed slowly by a syringe pump to a stirred reactor
containing cyclohexane (2.5g) and FeAlPO-31 catalyst (0.25g), while the
temperature was maintained at 110°C.
The reaction pH was 1.65.
The results were as follows:
Conversion of cyclohexane to oxidised products was calculated to be 32.5% (Runl)
and 32.3% (Run 2)
Product selectivity was as follows:
Product Run 1 (%) Run2(%)
Adipic acid 30.5 33.1
Cyclohexanone - -
Cyclohexanol - -
Other acids 59.0 56.0
Carbon dioxide 10.3 10.5
Example 4 (comparative)

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The procedure of Example 1 was repeated but air was used as oxidant and the
reaction was conducted for 24 hours. Full experimental details are given in M
Dugal, G Sankar, R Raja & J M Thomas, Angew Chem Ed Engl, 39, 2310-2313
(2000).
Conversion of cyclohexane to oxidised products was only 6.6%.
Product selectivity was as follows:
Product Selectivity (%)
Adipic acid 65
Cyclohexanone 15.3
Example 5
The procedure of Example 1 was repeated but using, as oxidant-containing solution,
(a) peracetic acid solution containing borax pentahydrate or (b) peracetic acid
solution containing sodium acetate.
The oxidant solution (a) was obtained from 25% peracetic acid solution in acetic acid
(4.2g), Neobor (1 g), NaOH (1 g) and double-distilled water (20.5g)
The oxidant solution (b) was obtained from 25% peracetic acid solution in acetic acid
(4.2g), sodium acetate trihydrate (0.934g), NaOH (lg) and double-distilled water
(20.5g).
Each run was conducted for 16 hours and the pH was, in each case, 5.1,
Product selectivity was as follows:

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Product Oxidant a (%) Oxidant b (%)
Adipic acid 72.5 51.2
Cyclohexanone 17.7 16.8
Cyclohexanol 3.3 3.5
Other acids 6.5 24.3
Conversion 27.5 29.9
Conclusion
While Examples 1 and 2 according to the invention lead to acceptably high rates of
both conversion and selectivity for the desired adipic acid, this was not the case with
comparative Examples 3 and 4.
Example 5 demonstrates the contribution of the borate component to selectivity.
Example 6
Epoxidation of stvrene to stvrene oxide

This example was carried analagously to the procedure of Example 1.
Solid acetylperoxyborate (3.49g), capable of liberating peracetic acid (0.701 g) and
hydrogen peroxide (0.045g) when dissolved in water, was mixed with double-
distilled water (20ml). The resulting solution was fed slowly by a syringe pump to a
stirred reactor containing styrene (2.8g) and MnAlPO-5 catalyst (0.25g), while the
temperature was maintained at 65°C, and the reaction time was 1 hour.

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The reaction pH was 5.2.
The reaction products were analysed by gas chromatography (GC, Varian Model
3400 CX) employing a HP-1 capillary column (25 m x 0.32 mm) and flame
ionisation detector.
The conversion of styrene was 31.7% and the selectivity for styrene oxide was 100%.
Example 7
This example was carried out analagously to the procedure of Example 2.
Two runs (each with a reaction time of 1 hour) were carried out a follows.
A liquid comprising borax pentahydrate (1.9g) (Neobor ex Borax Europe Limited),
sodium perborate monohydrate (0.4g), 25% peracetic acid solution in acetic acid
(4.2g) and double-distilled water (20.5g) was fed slowly by a syringe pump to a
■stirred reactor containing styrene (2.8g) and MnAlPO-5 catalyst (0.25g), while the
temperature was maintained at 65°C.
The results were as follows:
Conversion of styrene was calculated to be 26.5% (Run 1) and 27.1% (Run 2).
Product selectivity was as follows:
Product Run 1 (%) Run 2.(%)
Styrene oxide 88.7 89.0
Diol 11.3 . 11.0

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Example 8 (comparative)
This example was carried out analagously to the procedure of Example 3.
Two runs (each with a reaction time of 1 hour) were carried out a follows.
A solution containing 25% peracetic acid solution in acetic acid (4.2g) and double-
distilled water (20.5g), was fed slowly by a syringe pump to a stirred reactor
containing styrene (2.8g) and MnAlPO-5 catalyst (0.25g), while the temperature was
maintained at 65 °C.
The reaction pH was 1.65.
The results were as follows:
Conversion of styrene was calculated to be 32.5% (Run 1) and 32.3% (Run 2).
Product selectivity was as follows:
Product Run 1 (%) Run 2 (%)
Styrene oxide 15.5 17.0
Diol 35.2 32.5
Benzaldehyde 39.7 41.2
Polymers 9.5 9.3
Example 9
The procedure of Example 6 was repeated but using, as oxidant containing solutions
(a) peracetic acid solution containing borax pentahydrate as described in Example 5
or (b) peracetic acid solution containing sodium acetate as described in Example 5.

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Each run was conducted for ] hour and the pH was, in each case, 5.1.
Product selectivity was as follows:
Product Oxidant a (%) Oxidant b (%)
Styrene oxide 87.3 63.3
Diol 12.5 27.5
Benzaldehyde - 9.2
Conversion 24.3 26.0
Example 10
This example relates to the epoxidation of styrene to styrene oxide using air and
benzaldehyde where the benzaldehyde is used as a sacrificial oxidant to produce
perbenzoic acid in situ.
A liquid comprising borax pentahydrate (1.9g) (Neobor ex Borax Europe Limited),
sodium perborate monohydrate (0.4g), benzaldehyde and double-distilled water
(20g) was fed slowly by a syringe pump to a stirred reactor containing styrene (35g)
and MnAlPO-5 catalyst (0.25g) under air (dry; 30 bar). The styrene: benzaldehyde
molar ratio was 1:3. The temperature was maintained at 50°C and the reaction time
was 4 hours.
The results were as follows:
Conversion of styrene was calculated to be 45.3%. (Theoretical maximum 100% as
an excess of air and benzaldehyde was used).
Product selectivity was as follows:

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Product Selectivity (%)
Styrene oxide 71.3
Dial 20.5
Polymers 8.1
Example 11 (comparative)
Example 10 was repeated but omitting the borax pentahydrate, sodium perborate
monohydrate and the distilled water.
The results were as follows:
Conversion of styrene was calculated to be 32.0%.
Product selectivity was as follows:
Product Selectivity (%)
Styrene oxide 49
Diol 50
Polymers 1
Conclusion
While Examples 6, 7 and 10 according to the invention lead to acceptably high
conversion and selectivity for the desired styrene oxide, this was not the case with
comparative Examples 8 and 11.
Example 9 demonstrates the contribution of the borate component to selectivity.
Example 12

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Oxidation of a-pinene

The procedure of Example 6 was repeated but using a-pinene (3.7g), instead of the
styrene, and using MnAlPO-5 (0.25g) as catalyst. The reaction temperature
employed was 65°C and the reaction time was 1 hour.
Conversion was 25.9% and the selectivity for a-pinene-oxide was 100%.
Example 13
Oxidation of phenol

The procedure of Example 1 was repeated but using phenol (2.5g), instead of the
cyclohexane, and using iron hexa deca chloro phthalocyanine encapsulated in zeolite
Na-X (0.25g) as catalyst. The reaction temperature employed was 90°C and the
reaction time was 6 hours.
The reaction products were analysed by gas chromatography (GC, Varian Model
3400 CX) employing a HP-1 capillary column (25 m x 0.32 mm) and flame
ionisation detector.

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Conversion was 31.5% and the selectivity was catechol 73.7% and hydroquinone
26.5%.
Example 14
The procedure of Example 13 was repeated but using FeAlPO-5 as catalyst.
Conversion was 27.6% and the selectivity was catechol 49.5% and hydroquinone
50.3%.
Example 15
Oxidation of cvclohexanone

The procedure of Example 6 was repeated but using cyclohexanone (2.65g), instead
of the styrene, and using MnAlPO-5 (0.25g) as catalyst. The reaction temperature
employed was 50°C and the reaction time was 2 hours.
Conversion was 31.5% and the selectivity for y-caprolactone was 99.8%.
Example 16
Oxidation of benzene

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The procedure of Example 1 was repeated but using benzene (2.15g), instead of the
cyclohexane, and using copper hexa deca chloro phthalocyanine encapsulated in
zeolite Na-X (0.25g) as catalyst. The reaction temperature employed was 80°C and
the reaction time was 6 hours.
The reaction products were analysed by gas chromatography (GC, Varian Model
3400 CX) employing a HP-1 capillary column (25 m x 0.32 mm) and flame
ionisation detector.
Conversion was 11.5% and the selectivity for phenol was 95.2%.
Example 17
Oxvhalogenation (chlorination) of toluene

The procedure of Example 1 was repeated but using toluene (2.5g), instead of the
cyclohexane, and using iron hexa deca chloro phthalocyanine encapsulated in zeolite
Na-X (0.25g) as catalyst. NaCl (4.73g dissolved in 10ml water) was used as the
source of halogen (toluene:NaCl molar ratio 1:3). The reaction temperature
employed was 90°C and the reaction time was 10 hours.

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The reaction products were extracted with diethyl ether at the end of the reaction and
were analysed by gas chromatography (GC, Varian Model 3400 CX) employing a
HP-1 capillary column (25 m x 0.32 mm) and flame ionisation detector.
Conversion was 32.5% and the selectivity was o-chlorotoluene 21.5% and p-
chlorotoluene 78.4%.
Example 18
Oxidation of 4-picoline to 4-picolinic acid (isonicotinic acid")
COOH
6
CH3 ^v 4-picolinic acid
1 ;/ (Isonicotinic acid)
\^^ ?H3 COOH
4-picoline ^K A. I
o- 0- ■ .
4-picoline N-oxide |sonicotinjc ac|d N.oxide
. (3) (4) ..
Solid acetylperoxyborate (3.49g) as described in Example 1 was dissolved in double
distilled water (20.5g). The resulting solution was fed slowly by a syringe pump to a
stirred reactor containing 4-picoline (2.8g) and MnALPO-5 catalyst (0.30g). This
corresponds to a 4-picoline to peracetic acid molar ratio of 3:1.
Six runs (each of 4 hours) were carried out with different temperatures being
maintained.

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The results obtained were.as follows:
Temp°C Conversion(%) 2 Product Sel3 ectivity (%)4 Others
65 13.8 100 - - -
75 16.7 100 - - -
85 20.5 92.5 2.2 - 5.0
95 24.3 91.0 3.5 - 5.3
105 28.3 87.0 11.2 - 1.7
115 32.2 71.1 11.9 16.9 -
It can be seen that at 65° and 75°C very good selectivity for the desired oxidation of
the methyl group to a carboxylic acid was obtained.
At higher temperatures, while there is increased conversion, selectivity is decreased
as in particular, increased oxidation of the ring nitrogen atom was observed.
Example 19
The procedure of Example 18 was followed with the exception that there were used
as qxidant-containing liquid:
(i) borax pentahydrate (1.9g) (Neobor), sodium perborate monohydrate
(0.4g), 25% peracetic acid solution in acetic acid (4.2g) and double-
distilled water (20.5g);
(ii) peracetic acid solution as described in Example 3;
(iii) peracetic acid solution containing borax pentahydrate as described in
Example 5;
(iv) peracetic acid solution containing sodium acetate as described in
Example 5;

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(v) hydrogen peroxide such that the 4-picoline to oxidant molar ratio was
3:1;
(vi) t-butyl hydroperoxide such that the 4-picoline to oxidant molar ratio
was 3:1
Each run was carried out at 95°C for 4 hours.
The results obtained were as follows:

* See Example 18
The best selectivity of isonicotinic acid is obtained in the Examples where boron is
present.
Example 20
The procedure of Example 18 was followed with the exception that the mole ratio of
substrate to oxidant was varied. Each run was carried out at 95°C for 4 hours.
Substrate:
Oxidant Conversion % Product Selectivity (%)
(mole ratio) (Theoretical max) 2* 3* 4* Others

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1:1 78.2(100) 80.3 6.2 10.4 3.2
2:1 35.5 (50) 86.1 4.1 7.1 2.7
3:1. 24.3 (33.3) 91.2 3.6 0 5.2
4:1 18.7(25) 91.4 4.0 0 4.5
5:1 15.3(20) 90.6 4.2 0 5.1
It can be seen that at low substrate to oxidant ratios (e.g. 1:1), good conversions and
selectivities are obtained.
Example 21
The procedure of Example 18 was followed with the exception that there was used as
catalyst TS-1 (titanium silicalite ex National Chemical Laboratory, Pune, India)
(0.3g).
Four runs (each of 4 hours) were carried out with different temperatures being
maintained.
The results obtained were as follows:

* See Example 18.
Example 22

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The phases from the product of Example 6 were separated and the catalyst phase was
calcined at 550°C in air for 16 hours. The recovered catalyst was used in the
procedure according to Example 6. Conversion of styrene was 30.0%. The catalyst
was separated and re-calcined as described above. The recovered catalyst was again
used in the procedure according to Example 6. Conversion of styrene was 29.9%. In
both cases, selectivity was 100% for styrene oxide. This demonstrated that the
catalyst was recyclable and maintained its activity.

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CLAIMS
1. A process for the selective oxidation of an organic compound which process
comprises oxidising the organic compound using a peracid or a source of peracid, a
transition metal based heterogeneous catalyst and a borate or boric acid, in the
presence of water.
2. A process according to claim 1 wherein there is used, a peracid or source
thereof and source of borate, acetylperoxyborate.
3. A process according to claim 1 wherein there is used, a peracid or source
thereof and source of borate, a mixture of compounds capable of reacting together to
form acetylperoxyborate.
4. A process according to claim 3 wherein the mixture of compounds comprises
borax pentahydrate, sodium perborate monohydrate and peracetic acid.
5. A process according to claim 1 wherein there are used, a peracid or source
thereof and source of borate, benzaldehyde, borax pentahydrate and sodium
perborate in the presence of air.
6. A process according to any one of the preceding claims wherein the molar
ratio of peracid or source thereof to the compound to be oxidised, is 0.05:1 to 3:1.
7. A process according to any one of the preceding claims wherein the weight
ratio of borate or boric acid to peracid employed is in the range 0.1:1 to 4:1.
8. A process according to any one of the preceding claims wherein the transition
metal based heterogeneous catalyst comprises a matrix having a pore size in the
range 3.5 to 12 Angstroms.

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9. A process according to any one of the preceding claims wherein the transition
metal based heterogeneous catalyst used is a transition metal substituted
aluminophosphate having a pore size in the range 3.5 to 12 Angstroms and having
some of the aluminium atoms replaced by transition metal atoms, the transition metal
substitution level being in the range 2 to 10 atom percent.
10. A process according to any one of claims 1 to 8 wherein the transition metal
based heterogeneous catalyst used comprises a phthalocyanine or porphyrin complex
of a transition metal wherein some or all of the hydrogen atoms of the transition
metal complex have been substituted by one or more electron withdrawing groups;
the complex being encapsulated in a zeolite matrix.
11. A process according to any one of claims 1 to 8 wherein the transition metal
based heterogeneous catalyst used is titanium silicalite.
12. A process according to any one of the preceding claims wherein the amount
of catalyst employed is in the range 1 to 20% by weight based on the weight of the
compound being oxidised.
13. A process according to any one of the preceding claims for the selective
oxidation of substituted and unsubstituted aromatic hydrocarbons, olefins, alkanes,
ketones and alcohols.
14. A process according to any one of claims 1 to 12 for the oxidation of
cyclohexane to adipic acid, the epoxidation of styrene to styrene oxide, oxidation of
a-pinene to a-pinene-oxide, oxidation of propylene to propylene oxide, oxidation of
phenol to catechol and hydroquinone, oxidation of cyclohexanone to 7-caprolactone,
oxidation of benzene to phenol and oxyhalogenation/chlorination of toluene to 0- and
p- chlorotoluene.

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15. A process according to any one of claims 1 to 12 for the selective oxidation
of heterocyclic aromatics to yield corresponding carboxylic acids.
16. A process according to any one of claims 1. to 12 for the selective oxidation
of alkyl pyridines to yield corresponding carboxylic acids.
17. A process according to any one of claims 1 to 12 for the selective oxidation
of 4-picoline to 4-picolinic acid (isonicotinic acid).
18. A process according to claim 1 substantially as hereinbefore described.

This invention relates to the selective oxidation of organic compounds. According to the invention organic compounds are selectively oxidized using a peracid or a source of peracid, a transition metal based heterogeneous catalysts and a borate
or boric acid in the presence of water. Using the process of the present invention, both excellent conversion and product selectivity
maybe obtained.