Title of Invention	NOVEL OXIDATION CATALYST FOR SELECTIVE OXIDATION OF ALCOHOLS
Abstract	The present invention discloses a novel heterogeneous oxidation catalyst for selective oxidation of alcohol to aldehydes in various substrates. This catalyst comprises a heteropoly acid like phosphomolybdic acid (PMA) supported on vanadium-aluminum mixed oxide. The present invention also discloses methods of producing such catalyst and method of using such catalyst for producing aldehydes or ketones from alcohols by partial oxidation.

Title of Invention

NOVEL OXIDATION CATALYST FOR SELECTIVE OXIDATION OF ALCOHOLS

Abstract

The present invention discloses a novel heterogeneous oxidation catalyst for selective oxidation of alcohol to aldehydes in various substrates. This catalyst comprises a heteropoly acid like phosphomolybdic acid (PMA) supported on vanadium-aluminum mixed oxide. The present invention also discloses methods of producing such catalyst and method of using such catalyst for producing aldehydes or ketones from alcohols by partial oxidation.

Full Text	FORM 2 THE PATENT ACT 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See section 10 and rule 13) 1. TITLE OF THE INVENTION: "NOVEL OXIDATION CATALYST FOR SELECTIVE OXIDATION OF ALCOHOLS" 2. APPLICANT (S) (a) NAME: IPCA LABORATORIES LTD. (b)NATIONALITY: Indian Company incorporated under the Indian Companies ACT, 1956 (c) ADDRESS: 48, Kandivli Industrial Estate, Mumbai-400 067, Maharashtra, India. 3. PREAMBLE TO THE DESCRIPTION The following specification particularly describes the invention and the manner in which it is to be performed. Technical field: The present invention relates to heterogeneous catalysis; particularly to a new heterogeneous catalyst for oxidation of alcohol to aldehydes and ketones. The present invention also relates to methods of producing such catalyst and method of using such catalyst for producing aldehydes from primary alcohols by partial oxidation. This invention also relates to a process of manufacture of various aldehydes such as anisic aldehyde, cinnamaldehyde, p-methyl benzaldehyde, p-chloro benzaldehyde, p-nitro benzaldehyde, benzaldehyde, o-nitro benzaldehyde, 1-Octanal and pyridine-3-methanal; and ketones such as benzophenone and cyclohexanone. This invention relates to the process of manufacture of compounds and intermediates of high industrial importance using the novel oxidation catalyst. Background of the invention Commercial oxidations constitute a major part of industrial process technologies that account for production of a wide range of commercially significant chemicals and fuels and that greatly influence world economies. However, still these processes have a number of drawbacks, which include costly feedstocks, hazardous reagents and inefficient processes involving generation of huge amounts of waste materials. Chemical processes involving partial oxidation in the liquid phase are widely used in bulk chemicals manufacture. However, the basic limitations usually encountered in oxidations arise because oxidations are consecutive reactions that lead to complete oxidation or combustion. Generally oxidation processes are highly exothermic in nature and hence even small errors / alterations in process parameters become inherently potential for run-away situations. In particular, Selective oxidation of primary alcohols is of very high industrial importance. Aldehydes are very important raw materials or intermediates, having widespread applications in perfumery, pharmaceutical, dyestuff and agrochemical industries. A wide range of oxidizing reagent has been employed in order to accomplish this reaction. In current scenario, an increasing number of chemical processes used for manufacturing monomers and chemical intermediates are seen to encounter selective oxidations using solid catalysts and there is thus wide scope and interest, for this area of the research. There is dire need for further improvements based on both better engineering of the process and better tuning of catalyst reactivity and structural properties. Generally alcohol oxidations are accompanied with corresponding acids as co-products along with aldehydes. However, there are various instances of controlled catalytic oxidation's leading to aldehyde as the only product. However, the conventional reagents used are toxic, corrosive and are used in stoichiometric amounts leading to huge amounts of inorganic waste. There are reports on aerobic oxidations using copper, palladium, ruthenium and manganese compounds. Hydrogen peroxide (H2O2) is another clean and environment friendly reagent. However, its use is limited by the fact that most valuable organic substrates and aqueous H202 are mutually insoluble. This serious limitation has been circumvented with the aid of phase transfer catalysis (PTC), a well known technique in organic synthesis. Using air/oxygen or H202, as the oxidizing agent; there are instances where heteropoly acids are used for homogeneous oxidation of benzyl alcohol [See, (1) . G. D. Yadav, C. K. Mistry, J. Mol. Catal. A.: Chemical, 172 (2001) 135], (2) sulfide [N. M. Okun, T. M. Anderson, C. L. Hill, J. Mol. Catal. A.: Chemical, 197 (2003) 283], (3) heterogeneous hydrodesulpharization of thiophene [A. A. Spojakina, N. G. Kostova, B. Sow, M. W. Stamenova, K. Jiratova, Catal. Today, 65 (2001) 315], (4) vapor phase oxidative dehydrogenation of isobutyric acid [V. Ernest, Y. Barbaux, P. Courtine, Catal. Today, 1 (1987) 167] and (5) transition metal substituted heteropoly acids as catalysts, in isobutane oxidation [M. Langpape, J. M. M. Millet, U. S. Ozkan, M. Boudeulle, J. of Catal., 181(1999)80]. Heterogeneous catalysts have the advantage, compared to their homogeneous counterparts, of facile recovering and recycling. An early example of the successful approach to the goal of clean liquid phase oxidation catalysis was the Ti(IV)/SiC»2 catalyst, commercialized by Shell in the 1970s for the production of propene oxide. Another benchmark was the development of titanium silicalite (herein after called TS-1) patented by Enichem scientists in the mid-eighties [See, (1) Taramasso, M.; Perego, G. and Notari, B.; US Pat. 4 410 501 (1983), & (2) Taramasso, M.; Manara, G.; Fattore, V.; and Notari, B.; US Pat. 4 666 692 (1987)]. The success of TS-1 as a catalyst for a variety of oxidations, including epoxidation, with 30% aqueous hydrogen peroxide led to frenetic activity worldwide on the synthesis of related heterogeneous catalysts for liquid phase oxidations. A serious shortcoming of TS-1, however, is its restriction to substrates with linetic diameters Various strategies have been employed in this area for immobilizing redox-active elements in a solid (inorganic) matrix. Metal ions have been isomorphously substituted in framework positions of molecular sieves e.g. zeolites, silicalites, aluminophosphates (APOs), silico-aluminophosphates (SAPOs), via hydrothermal synthesis or post synthesis modification. A wide variety of redox molecular sieves have been synthesized and characterized and their catalytic properties investigated. Amorphous mixed oxides have been prepared by impregnation (grafting) of metal compounds onto the surface of e.g. silica or by sol-gel method. The latter is equivalent to the hydrothermal synthesis of molecular sieve (but without the template) and can afford much higher levels of incorporation than the grafting technique. Alternatively, metal complexes can be tethered to the surface of a solid e.g. silica, via a spacer Hgand. Similarly, coordination complexes or organometallic species can be grafted or tethered to the internal surface of mesoporous molecular sieve. Another approach adopted is the so-called ship-in-a-bottle concept, which involves the entrapment of a bulky complex in a zeolites cage. This has been widely used to immobilize metal complexes of phthalocyanines, bipyridyls and Schiff s base type ligands. Finally, metal ions can be immobilized by cation exchange into zeolites or acidic clays and oxoanions such as molybdate and tungstate can be exchanged into hydrotalcite like anionic clays. A major disadvantage of cation exchange approach is the mobility of the metal ion, which manifests itself in its facile leaching into solution. ' To have real synthetic utility a heterogeneous catalyst should be stable towards leaching of the active metal into the liquid phase tinder operating conditions. This is true for all ' types of catalytic reactions, but leaching is particularly a problem in oxidation catalysts owing to the strong complexing and solvolytic properties of oxidants (H202, RC02H, etc.) and/or products (H2O, ROH, RC02H, etc.). Leaching is generally a result of solvolysis of metal-oxygen bonds, through which the catalyst is attached to the support by such polar molecules. Chromium based catalysts are notoriously known for their facile leaching that occurs and generates active homogeneous catalysts. In case of heterogeneous titanium-based epoxidation catalysts, titanium does leach but that is not an active catalyst, hence the observed catalysis is (predominantly) heterogeneous, while in case of Ti(IV)/Si02 and TS-1, the metal does not leach and the observed catalysis is truly heterogeneous. Therefore, in the final analysis the consideration in respect of activities and selectivities are not enough; stability under operating conditions is the essentiality for industrial utility. So it is of interest to develop heterogeneous oxidation catalysts that are stable under the oxidation conditions for oxidation of alcohol to aldehydes and ketones; and develop advantageous chemical processes for controlled partial oxidations using the catalyst system. Objective of the invention The object of the present invention is to provide a novel heterogenous oxidation catalyst for selective oxidation of alcohol to aldehyde and ketone. Yet another object of the present invention is to provide a catalyst which remains stable during such oxidation process. A further object of the present invention is to provide a catalyst which can be recycled. Summary of the Invention Accordingly, in one aspect, the present invention provides a heterogeneous oxidation catalyst for selective oxidation of alcohol to aldehydes in various substrates. This catalyst comprises phosphomolybdic acid (PMA) supported on vanadium-aluminum mixed oxide. In a preferred embodiment the catalyst comprises at least one heteropoly acid supported on a mixed metal oxide support which comprises an inorganic, porous material, which exhibits after calcination, a BET surface area in between 100 - 600 m2/gm, average pore dimensions in the range of 25 - 50 °A, pore volume in preferably in the range of 0.1 - 0.5 cm /gm and a powder X-ray diffraction pattern having at least one d-spacing in between 3 - 10 °A, with a relative intensity of 100 %. The heteropoly acid used in the present invention comprises at least one hetero element selected from the group consisting of P, V, Al and Mn, as a central element and a second metal element selected from Mo or W as a co-ordinating element. The weight ratio of heteropoly acid to support material is from about 1:50 to 1:1. In another aspect, the present invention provides process for producing the heterogeneous solid catalyst comprising heteropoly keggin ion supported on vanadium-aluminum mixed oxide. In yet another aspect present invention provides process for manufacture of various aldehydes such as, not limited to, anisic aldehyde, cinnamaldehyde, p-methyl benzaldehyde, p-chloro benzaldehyde, p-nitro benzaldehyde, benzaldehyde, o-nitro benzaldehyde, 1-Octanal and pyridine-3-methanal; and ketones such as benzophenone and cyclohexanone from corresponding precursors using the catalyst of the present invention. In particular, this invention relates into the synthesis of compounds and intermediates of high industrial importance. In yet another aspect, present invention provides semi-batch or batch or continuous liquid phase slurry type process for oxidation of anisic alcohol, cinnamyl alcohol, p-methyl benzyl alcohol, p-chloro benzyl alcohol, p-nitro benzyl alcohol, o-nitro benzyl alcohol, 1-Octanol, pyridine-3 -methanol, cyclohexanol and diphenyl methane. Brief Description of Drawings Figure 1 represents scheme of degradation of phosphomolybdate anion /vanadium-aluminum mixed oxide Figure 2 represents X-ray diffraction patterns of PMA(l), PMA/Vanadium-aluminum oxide(2), vanadium/aluminum oxide (3)and pure vanadia (4) Figure 3 represents IR spectra of PMA (5)_, PMA/vanadium-aluminum oxide (6), vanadium-aluminum oxide (7) and pure vanadia (8). Figure 4 represents IR spectra of used Catalyst ( PMA/ vanadium-aluminum mixed oxide) Figure 5 represents H2 Temperature Programmed Reduction (TPR) profiles of PMA (10), PMA/aluminum oxide (11), PMA/Vanadium-aluminum oxide (12). Figure 6 represents evaluation of PMA stability on vanadium-aluminum oxide Figure 7 represents Progress of selective oxidation of various alcohols wherein ♦ 1-octanol ■ o-nitro BnOH A BnOH x p-nitro BnOH x p-methoxyBnOH • Cinnamyl alcohol + p-chloro BnOH -3-pyridine methanol ♦ p-m ethyl BnOH -BnOH* A cyclohexanol o diphenyl methane Figure 8 represents a plot of reusability of PMA/ Vanadium-aluminum oxide wherein ♦ Fresh ■ 1 st Reuse A 2nd Reuse Detailed Description As used herein, heteropoly acids belong to a large class of nano-sized metal-oxygen clusters and are polyoxometalates represented by the general formula [XxMmOy]q" (x As used herein heteropoly keggin anion means a polyanionic structure containing 12 M06 (M is metal atom) octahedra linked by edge and corner sharing, with the hetero atom occupying a tetrahedral hole in the center. In present invention a heterogeneous catalyst was designed by supporting a heteropoly acid on open inorganic framework, which was a mixed metal oxide. Amongst heteropoly acids, PMA (H3PM012O40) (phosphomolybdic acid) was supported on the surface of a mixed metal oxide, which forms the novel catalyst. The new high surface area vanadium-aluminum mixed oxide was synthesized and used for its robustness and strength. The vanadium-aluminum oxide seems to have vanadium oxide species in the matrix framework, as seen from the enhanced surface area of the material in comparison to pure aluminum oxide used. PMA is present on the surface of vanadium-aluminum mixed oxide in the form of a heteropoly keggin anion, which is phosphomolybdate anion, {PM0 12O40]3". The characteristic feature of the material is the interaction between keggin anion and surface vanadium oxide species. Supported phosphomolybdate keggin anion was characterized to undergo degradation to form Polyperoxomolybdate/Vanadium-aluminum mixed oxide, in presence of peroxides during the course of oxidation reaction. A scheme of degradation of phosphomolybdate anion is shown in figure 1. The PMA has the role of providing surface bound polyoxomolybdate species. Surface bound polyoxomolybdate ions adsorb oxygen from the oxidizing agent and form polyperoxomolybdate ions, which then transfer oxygen to the substrate to be oxidized. PMA/Vanadium-aluminum mixed oxide, was synthesized by impregnating phosphomolybdate keggin anion in a bonded form by treating a PMA solution in a suitable solvent to a preformed vanadium -aluminum mixed oxide, subsequently followed by calcination to impart surface bonding. PMA was impregnated in a weight / weight ratio of at least 5%, preferably 15 %, more preferably 20%, yet more preferably 50% of the support material. The PMA solution is in a solvent that includes but not limited to, methanol, water, acetone, ethanol, propanol, butanol and combinations thereof. The support material is preferably Vanadium-aluminum mixed oxide. Calcination of the impregnated keggin anion is performed in the temperature range of 100° C to 450° C with a care so that supported keggin anion is intact and does not undergo degradation due to thermal treatment. This produces the catalyst material with BET surface area ranging from 100 - 600 m2/gm, an average pore dimensions in the range of 25 - 50° A, pore volume in the range of 0.1 - 0.5 cm3/gm. PMA/Vanadium-aluminum mixed oxide, is a true heterogeneous catalyst that belongs to category I. Generally, there are three different categories for heterogeneous catalysts, (i) The active species does not leach and the observed catalysis is truly heterogeneous, (ii) The active species does leach but is not an active catalyst; the observed catalysis is (predominantly) heterogeneous, (iii) The active species leaches to form a highly active homogeneous catalyst; the observed catalysis is homogeneous in nature. Being specific, for liquid phase oxidations, more number of heterogeneous catalysts belong to the 2nd or 3rd category. The invention is now described hereunder in greater detail by way of examples given below which are provided by way of illustration only of some preferred embodiments and should not be constructed to limit the scope of the present invention. Synthesis of PMA supported on vanadium-aluminum mixed oxide is disclosed in this invention by way of examples 2-4. Example 1: Synthesis of support, vanadium-aluminum mixed oxide. A mixed vanadium-aluminum oxide support was prepared by first dispersing fine crystallites of vanadia on to the surface of alumina by employing Wet-impregnation method, which subsequently formed a mixed vanadium-aluminum oxide material. The vanadium oxide precursor was 29 gm of ammonium metavanadate dissolved in 2000 ml of 2M oxalic acid solution. The vanadium precursor solution was adsorbed onto the surface of neutral alumina gel (255 gm), followed by subsequent calcination at 450 ° C in the flow of air for 5 hours. Example 2: Synthesis of phosphomolybdic acid supported on vanadium-aluminum mixed oxide (Incipient Wetness Technique). 36 gm of PMA dissolved in 200 ml of methanol was used to anchor keggin ion onto the surface of 204 gm of mixed vanadium-aluminum oxide (synthesized in example 1) via incipient wetness method. It was followed by drying at 120 ° C for 8 hours and calcination at 285 °C for 4 hours in flow of air. Example 3: Synthesis of phosphomolybdic acid supported on vanadium-aluminum mixed oxide (Wet Impregnation method). 36 gm of PMA dissolved in 200 ml of methanol was used to anchor keggin ion onto the surface of mixed vanadium-aluminum oxide (synthesized in example 1) via wet impregnation method followed by drying at 120 °C for 8 hours and calcination at 285 °C for 4 hours in flow of air. Example 4: Direct Synthesis of supported phosphomolybdic acid on vanadium-aluminum mixed oxide Vanadium oxide crystallites and PMA were supported directly in one step on the surface of aluminum oxide via wet impregnation method. A solution of 29 gm of ammonium metavanadate in to the 2M oxalic acid (200 ml) was mixed with a solution of 36 gm PMA in 200 ml methanol. The mixture was used as a precursor for simultaneous impregnation of vanadium and PMA keggin anion. The material obtained was dried at 120 °C for 8 hours and calcined at 285 °C for 4 hours in flow of air. Structural Characterization of supported heteropoly acid catalyst. The novel oxidation catalyst as synthesized under examples 1-4, was characterized by X-ray diffraction, framework IR analysis and H2 temperature programmed reduction (TPR) analysis (examples 5-7). Example 5: X-ray Diffraction Analysis of PMA, PMA/ Vanadium-aluminum oxide catalyst, Vanadium/aluminum oxide and pure vanadia The X-ray scattering measurements of phosphomolybdic acid(PMA), PMA/ Vanadium-aluminum oxide catalyst, Vanadium/aluminum oxide and pure vanadia were made with CUKQ (alpha) radiation on a SIEMENS D 500 diffractometer equipped with reflection geometry, a Nal scintillation counter, a curved graphite crystal monochromator and a nickel filter. The scattered intensities were collected from 2° to 40° (20) by scanning at 0.030° (20) steps with a counting time of 0.5 s at each step. In figure 2, X-ray powder diffraction patterns of phosphomolybdic acid 1), 20% w/w PMA/ vanadium-aluminum mixed oxide (2), vanadium-aluminum mixed oxide ( 3) and pure vanadia ( 4), are as shown , wherein, X-axis exemplifies 2θ values while Y-axis exemplifies intensity in terms of Lin (counts) . While referring to figure 2, the XRD pattern of pure vanadia (4) contains very sharp peaks at d = 4.4, 3.4, 2.9, 5.7,4.1, 2.8 and 2.6 °A. Vanadium-aluminum oxide (3) sample with V2O5 content of 15 wt% and calcined at 450 °C show small XRD peaks at d = 6.2 and 3.2 °A. The results show that XRD peaks of individual V2O5 are absent. This is a clear indication that vanadia is in a highly dispersed form or in amorphous state or it has formed a mixed oxide with aluminum oxide. Diffractogram of pure phosphomolybdic acid (1) shows XRD peaks at d = 3.3, 8.1, 2.9, 4.1, 2.5, 5.8, 2.3, 3.7, 4.7, 2.6, 3.1, 6.6 °A. X-ray diffractogram of phosphomolybdic acid supported on vanadium-aluminum mixed oxide (2) was similar to that of phosphomolybdic acid. Identical sharp XRD peaks indicate that in supported form heteropoly keggin anion is intact and is present in crystalline form. No XRD peaks were observed for orthorhombic α-MoO3 or monocinic β- M0O3 species or any other anhydrous form, which generally appears on thermal destruction of heteropoly keggin anion. Example 6: Nitrogen Sorption Analysis of Vanadium-aluminum oxide supported phosphomolybdic acid catalyst and aluminium oxide. Surface area, Pore volume and pore diameter measurements were performed, by using nitrogen sorption technique on Micromeritics ASAP 2010 instrument. Catalyst samples were pretreated under vacuum at 200 ° C, and then subjected to analysis at the temperature of liquid nitrogen. The catalyst is essentially mesoporous. The textural characteristics of the catalyst are given in Table 1 Sample Single Point Surface area m2/g BET Surface area m2/g Langmuir Surface area m2/g BJH Adsorption cumulative pore volume cm3/g Average Pore Diameter (4V/A) °A PMA/Vanadiu m-aluminum oxide (Example 2) 178.2 177.8 239.2 0.145 32.6 aluminum oxide 247.7 245.3 328.4 0.28 45.5 Example 7: Framework IR Analysis of PMA, PMA/ Vanadium-aluminum oxide catalyst, Vanadium/aluminum oxide, pure vanadia and used Vanadium-aluminum oxide catalyst. Framework IR spectra were recorded on Perkin-Elmer Spectrum one spectrometer equipped with DRS system. The homogeneous powdered mixture was made by co-grinding 3 mg of catalyst with 100 mg of potassium bromide and was subjected to IR radiation. IR spectra of phosphomolybdic acid as such and in its supported form on vanadium-aluminum mixed oxide are shown in figure 3, wherein X-axis exemplifies wavenumber in cm"1 and Y-axis exemplifies % Reflectance. While referring to figure 3, Phosphomolybdic acid (5) shows characteristic absorption bands at 3217, 2425, 1935, 1621,1403,1063, 864, 800, and 597 cm-1. In supported form ( 6), characteristic bands of heteropoly keggin anion are shifted to lower frequencies, which is attributed to the interaction of phosphomolybdic acid with vanadium oxide species present on thesupport surface. Within the range of 1100-600 cm"1, the bands corresponding to the stretching of Mo-0 bonds in the Keggin unit were observed with shift. The band at 1002 cm-1, has been attributed to the usMo=Ot vibration. Generally, pure V2O5 ( 8)shows a characteristic sharp band at 1020 cm'1, which is due to the V=0 stretching vibration. A weak absorption band is observed at 1020 cm"1 in case of vanadium-aluminum mixed oxide ( 7), which is associated with amorphous vanadia species dispersed on the surface, indicating absence of any crystalline form of V2O5. When heteropoly keggin anion is supported on the surface of vanadium-aluminum mixed oxide, this weak absorption band at 1020 cm-1 disappears indicating probable interaction of keggin anion with the surface bound vanadia species. In agreement to this argument, significant reduction in absorption intensity of P-0 stretching vibration band is noticed, when peak at 1063 cm-1 is compared for keggin anion supported on vanadium-aluminum mixed oxide against unsupported keggin anion and also keggin anion supported on aluminum oxide. Figure 4 (9) shows the IR spectra of used catalyst, 20 % w/w PMA/ vanadium-aluminum mixed oxide (obtained in example 2) recovered after performing alcohol oxidation. (Here also, X-axis exemplifies wavenumber in cm'1 and Y-axis exemplifies % Reflectance.) It was lacking all four absorption bands that are typical features of heteropoly keggin anion that was attributed to degradation of polyoxometalate anion into polyperoxometalate anions. This provided direct understanding of mechanistic aspects of alcohol oxidation, which seems to be similar to the mechanism of epoxidation of olefins or olefinic compounds under Ishii-Venturello chemistry conditions. Example 8 H2 Temperature Programmed Reduction Analysis of PMA, PMA/aluminum oxide, PMA/ Vanadium-aluminum oxide catalyst. H2 temperature programmed reduction experiments were carried out on a Thermoquest TPDRO 1100. Samples were tested by increasing the temperature from 50 to 800 °C, at a heating ramp of 10 °C min-1. The reducing gas, a mixture of 5 vol% H2 in Ar, at a flow rate of 30 ml min-1 was used to reduce the catalyst samples with continuous temperature ramp. The temperature was then kept constant at 800 °C until the signal of hydrogen consumption returned to the initial values. H2 Temperature programmed reduction (TPR) was used to investigate the oxidative activity of heteropoly phosphomolybdate anion under the influence of its subsequent interaction with surface bound vanadia species. Figure 5 shows the TPR profiles of PMA/ vanadium-aluminum mixed oxide (12), PMA/aluminum oxide (11) and pure PMA (10) wherein X-axis exemplifies the temperature and Y-axis exemplifies the TCD signal in mV. The reduction of heteropoly phosphomolybdate anion anchored on aluminum oxide was also performed. H2 TPR data for pure phosphomolybdic acid showed one peak at 614 °C with a distinctive shoulder at 582 °C resulting from the release of oxygen upon the reaction with hydrogen under high temperature. H2 TPR profile of phosphomolybdate keggin ion anchored on aluminum oxide showed only one peak with maxima at 556 °C. Generally, vanadia (20% w/w) dispersed on the surface of aluminum oxide shows three distinctive peaks with maxima in the range of 481-486°C, 570-575°C and 600-610°C [E. P. Reddy, R. S. Varma, J. of Catal., 221, (2004) 93]. The authors, have attributed the first peak to the presence of vanadium in oxidation state between V+5 and V+4 and the second and third peak to the subsequent reduction of vanadium oxide to V+4 and V+3 oxidation states respectively. In present study, H2 TPR profile of phosphomolybdate keggin ion supported on vanadium-aluminum oxide revealed a peak with maxima at 525 °C associated with shoulder at 486 °C. We do not observe small peaks associated with reduction of vanadium oxide to V+4 and V+3 oxidation states, which in accordance to IR studies, indicates there is a strong interaction between heteropoly keggin anion and surface vanadium oxide species. Evaluation of catalyst stability 20% w/w PMA/vanadium-aluminum oxide is highly active in alcohol oxidation and the activity shown by 20% w/w PMA/vanadium-aluminum oxide is attributed to the interaction of supported keggin ion with peroxides. Hence, to ascertain that the catalyst was truly heterogeneous, it was important to establish the exact nature of interaction between PMA and vanadium-aluminum oxide surface. If PMA was physically adsorbed on vanadium-aluminum oxide surface, then the catalyst would not be reused because of leaching out of PMA into the reaction mixture. It was observed that the 20% w/w PMA/vanadium-aluminum oxide showed a consistent activity up to a minimum of three runs, which suggested that PMA was chemically bonded to the support. Example 9: Heteropoly blue colour test The stability was evaluated by the characteristic, heteropoly blue colour test [G.D. Yadav, H. G. Manyar, Microporous and Mesoporous Materials, 63 (2003) 85]. PMA solutions develop blue colour when reacted with a mild reducing agent like ascorbic acid. This property was used for quantitative determination of leaching, if any. Two grams of 20% w/w PMA/vanadium-aluminum oxide was refluxed in 25 ml of methanol with vigorous stirring for 1 h. Five millilitre aliquot of the refluxing solution was drawn to which 2 ml of 10% ascorbic acid solution was added. The solution remained clear and colourless and there was no development of the blue colour which otherwise is an instantaneous phenomenon in authentic PMA solutions. The above test was repeated to confirm absence of leaching. Example 10: Experimental evidence A further proof of PMA stability on vanadium-aluminum oxide was obtained. A typical experiment was carried out, wherein the reaction mixture consisted of 0.02 mol benzyl alcohol, 0.5 gm CTABr in 40 ml toluene and aqueous H2O2 (50% w/v), was added with peristaltic pump, at the addition rate of 0.5 mmol/min. Keeping standard catalyst loading of 0.025 g/cm3, the reaction was carried out at 65 °C, for 60 min. A conversion of 15% of benzyl alcohol was obtained. The reaction mixture was hot filtered and all catalyst particles were separated. The reaction was further continued at the same temperature for next 30 min without any catalyst. The sample was again analysed to find 15.5% of benzyl alochol conversion, which is the same within experimental error. Continuation of the reaction showed no further conversion (refer Figure 6, wherein X-axis exemplifies time. in minutes and Y-axis exemplifies % conversion). Thus, it is concluded, that the PMA was chemically adsorbed on the vanadium-aluminum oxide surface and the catalyst is stable. Oxidation of alcohols by supported heteropoly acid catalyst Chemicals The substrates are obtained from commercial sources. 50% w/v aqueous hydrogen peroxide (sourced from Merck India Ltd.), was stored under refrigeration and there was no significant change in its concentration during the period when the reactions were performed. The exact concentration of Hydrogen peroxide solution was determined by iodometry. Reaction Methodology The liquid phase oxidation of alcohols was carried out with PMA/Vanadium-aluminum mixed oxide as the catalyst and oxidizing agent selected from peroxidic oxidants like tert-butyl hydroperoxide or aqueous solution (30-60% w/v) of hydrogen peroxide, or perbenzoic acids or the like under Liquid-Liquid-Solid phase transfer condition. The reactions were studied in a mechanically agitated contactor made of glass and a reflux condenser. The organic phase containing the required amount of alcohol, catalyst, cetyl trimethyl ammonium bromide (CTABr) as phase-transfer catalysts (PTC) in toluene as solvent was stirred. Required amount of H2O2 was added with the help of a peristaltic pump, at the addition rate of 0.5 mmol/min. The reaction was performed in a water bath assembly where the desired temperatures were properly maintained Phase transfer catalysts are used to impart solubility of peroxide in the organic solvent. Where R group is OCH3, CH3, CI, N02. Reaction Scheme Method of Analysis The samples (organic phase) were withdrawn periodically from the reaction mixture and were filtered before being analyzed by HP 6890N gas chromatograph equipped with autosampler 7683 series injector' and HP chemstation. A (30 m x 0.32 mm ID x 0.25 u) column packed with DB-5 (5.% polyphenyl + 95% polymethyl siloxane) was used for analysis (injector/detector temperature 250°C, oven 60°C-2 min- 10°C/min-250°C-5 min). 3-pyridyI methanol was analyzed by Water's Aliance HPLC system equipped with 2695 sample handling unit and 2487 UV detector. Purosphere star (250 x 4.6 mm x 5 u) column was used with 0.02 mol Na2HP04 (pH 7) buffer : acetonitrile (90:10) mobile phase. Synthetic mixtures were prepared and used for calibration and quantification. GC-MS and LC-MS confirmed the products. Chemical processes catalyzed with said catalyst produce no inorganic salts and offer different process configurations of semi batch as well as batch process. This methodology can replace advantageously conventional hazardous stoichiometric catalysts. Chemical processes mentioned in this invention are environmentally clean and fit well into the domain of green chemistry. General Example -Reaction Conditions Alcohol: 0.005 - 0.2 mol, solvent: 40 cm3, Catalyst loading: 0.005 - 0.25 g/cm3, CTABr: 0.5 - 10 mmol, H202 addition rate: 0.1-2 mmol/min, Temperature: Ambient - Reflux, Time: 1 - 5 h., Agitation speed: 200 -1000 rpm. Example 11 Liquid phase oxidation of Anise alcohol, under solid-liquid-liquid phase transfer conditions; was performed in £ mechanically agitated contactor made of glass and a reflux condenser. The organic phase contained 0.02 mol Anise alcohol and 40 cm toluene. 1 gm of the catalyst (example 2), 20% w/w PMA/Vanadium-aluminum oxide with a specific catalyst loading of 0.025 g/cm3 was added. 1.4 mmol of CTABr was added as a phase transfer agent and stirring maintained at 700 rpm. Temperature of the reaction mixture was maintuened at 800 C and aqueouls doluition of H2O2(50 %w/V)was. added at the constant rate of 0.5 mmol/min in a semi-batch mode. Reaction was completed in 2 hours with very high selectivity towards anisaldehyde and no traces of anisic acid were observed due to over oxidation. This is a very interesting example of controlled partial oxidations. Analogously the following alcohol substrates are oxidized to aldehydes. Examples 12-22. The scope of supported heteropoly acid as a catalyst was tested in a wide array of primary alcohols that includes benzylic, heterocyclic and aliphatic alcohols. The progress of oxidation of following alcoholic substrates is shown in figure 8, wherein X-axis exemplifies time in minutes and Y-axis exemplifies % conversion of alcohol. 20% w/w PMA/vanadium-aluminum oxide (Example 2), a very interesting catalyst for controlled partial oxidation reactions. As depicted in Table 2, various alcohols were converted into corresponding aldehydes in excellent yield with 100% selectivity and no over oxidation to carboxylic acids was observed. Using 20% w/w PMA/vanadium-aluminum oxide as a catalyst, the oxidation protocol showed high reactivity towards benzylic alcohols, than aliphatic alcohols. Substituted benzylic alcohols, with both activating and deactivating group substitutions showed higher reaction rate constants than aliphatic octan-1-ol. The above design of partial oxidation was further extended to heterocyclic, pyridine-3-methanol, however due to poor solubility of substrate in toluene; acetonitrile was used as a reaction solvent (Example 22). The rate constant for this oxidation was further enhanced due to additional effect of solvent polarity. To compare with this solvent effect, benzyl alcohol was also oxidized in acetonitrile, resulting in high reaction rate constant (Example 21). The reaction rate constant of p-nitro benzyl alcohol oxidation was observed to be slightly higher than that of benzyl alcohol, under otherwise identical experimental conditions (Example 17,18). Such anomalous reactivity is already observed in past and is mentioned in literature [C. Zondervan, R. Hage and B. L. Feringa, J. Chem. Soc, Chem. Commun, (1997) 419]. Table 2. Oxidation of Alcohols using 20% w/w PMA/Vanadium-aluminum mixed oxide catalyst Reaction conditions: Alcohol: 0.02 mol, toluene: 40 cm3, Catalyst loading: 0.025 g/cm3, CTABr. 1.4 mmol, H202 addition Tate: 0.5 mmoi/rnin, Temperature: 65 °C, Time: 2 h., Agitation speed: 700 rpm, * Acetonitrile was used as solvent instead of toluene. Reusability of 20% w/w PMA/vanadium-aluminum oxide Example 23-25 The catalyst reusability was studied three times including the use of fresh catalyst (refer figure 8, wherein, X-axis exemplifies time in minutes and Y-axis exemplifies % conversion of alcohol); Oxidation of anise alcohol was arbitrarily selected for this evaluation, without any technical reason. The catalyst was filtered, washed with methanol and subsequently heated at 250 °C for two hours, before being reused in subsequent batches. In the presence of the fresh catalyst, the conversion of anise alcohol was 87%. During the third run, the conversion decreased to 83%, while the selectivity towards anisaldehyde remained 100%. This decrease in conversion is because of the observed losses due to attrition, during filtration of the catalyst particles and no make up quantity of catalyst was added. It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples and that the present invention may be embodied in other specific forms without departing from the essential attributes thereof, and it is therefore desired that the present embodiments and examples be considered in all respects as illustrative and not restrictive, reference being made to the appended claims, rather than to the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. We claim, 1. A heterogeneous oxidation catalyst for selective oxidation of alcohol to aldehydes or ketones in various substrates comprising at least one heteropoly acid supported on vanadium-aluminum mixed oxide support. 2. The catalyst as claimed in claim 1, wherein the catalyst material after calcination shows a BET surface area ranging from 100 - 600 m2/gm, an average pore dimensions in the range of 25 - 50°A, pore volume in the range of 0.1 - 0.5 cm /gm and a powder X-ray diffraction pattern having at least one d-spacing in between 3 - 10 °A with a relative intensity of 100 %. 3. The catalyst as claimed in claim 1 or 2, wherein said heteropoly acid comprises at least one hetero atom selected from the group consisting of P, V, Al and Mn as a central atom and a second metal atom selected from Mo or W as a co-ordinating or addenda metal atom. 4. The catalyst as claimed in any one of the preceding claim, wherein said mixed oxide support material consists of 10 to 20% w/w of vanadium oxide and 80 to 90% w/w of aluminum oxide. 5. The catalyst as claimed in any one of the preceding claim, wherein the weight ratio of heteropoly acid to support material is from about 1: 50 to 1:1. 6. The catalyst as claimed in any one of the preceding claim, wherein the catalyst is phosphomolybdic acid supported on a vanadium-aluminum mixed oxide. 7. A method for preparing heterogeneous oxidation catalyst as claimed in claim 1 comprising the step of impregnating a heteropolyacid solution in one or more solvent to preformed porous vanadium -aluminum mixed oxide support, followed by calcination to form said catalyst. 8. A method for preparing heterogeneous oxidation catalyst as claimed in claim 1 comprising the step of mixing a heteropoly acid and a vanadium precursor in one or more solvent, impregnating said solution to porous aluminum oxide, and followed by calcination to form said catalyst. 9. The method as claimed in claim 8, wherein the vanadium precursor is ammonium meta vanadate. 10. The method as claimed in claim 7 or 8, wherein the suitable solvent is methanol, water, acetone, ethanol, propanol, butanol and combinations thereof. 11. The method as claimed in claim 7 or 8, wherein said calcination is performed in the temperature range of about 100 °C to 450 °C. 12. A heterogenous oxidation catalyst as claimed in any of the preceding claim for oxidation of an active methylene group in diphenyl methane to diphenyl ketone. 13. A method for oxidation of alcohol functional group in any substrate to an aldehyde or ketone by using the catalyst as claimed in any one of the preceding claims comprising treating a solution of alcohol in an organic solvent with a peroxide agent and said catalyst optionally in presence of a phase transfer catalyst. 14. The method as claimed in claim 14 wherein said alcohol is benzylic, heterocyclic aliphatic or aHcyclic alcohols. 15. The method as claimed in claim 14, wherein the peroxide agent is selected from hydrogen peroxide or organic peroxides like tertiary butyl hydroperoxide, perbenzoic acid etc. 16. The method as claimed in claim 14, wherein said catalyst is reusable in said method. 17. Heterogeneous oxidation catalyst for selective oxidation of alcohol to aldehydes or ketones in various substrates and their oxidation process as substantially described herein with reference to foregoing examples 2 to 4 and 11 to 22. Dated this the 17th day of October 2008 Dr. Gopakumar G. Nair Agent for the applicant

Full Text

FORM 2
THE PATENT ACT 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10 and rule 13)
1. TITLE OF THE INVENTION:
"NOVEL OXIDATION CATALYST FOR SELECTIVE OXIDATION OF
ALCOHOLS"
2. APPLICANT (S)
(a) NAME: IPCA LABORATORIES LTD.
(b)NATIONALITY: Indian Company incorporated under the Indian Companies ACT, 1956
(c) ADDRESS: 48, Kandivli Industrial Estate, Mumbai-400 067, Maharashtra, India.
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed.

Technical field:
The present invention relates to heterogeneous catalysis; particularly to a new heterogeneous catalyst for oxidation of alcohol to aldehydes and ketones. The present invention also relates to methods of producing such catalyst and method of using such catalyst for producing aldehydes from primary alcohols by partial oxidation.
This invention also relates to a process of manufacture of various aldehydes such as anisic aldehyde, cinnamaldehyde, p-methyl benzaldehyde, p-chloro benzaldehyde, p-nitro benzaldehyde, benzaldehyde, o-nitro benzaldehyde, 1-Octanal and pyridine-3-methanal; and ketones such as benzophenone and cyclohexanone. This invention relates to the process of manufacture of compounds and intermediates of high industrial importance using the novel oxidation catalyst.
Background of the invention
Commercial oxidations constitute a major part of industrial process technologies that account for production of a wide range of commercially significant chemicals and fuels and that greatly influence world economies. However, still these processes have a number of drawbacks, which include costly feedstocks, hazardous reagents and inefficient processes involving generation of huge amounts of waste materials. Chemical processes involving partial oxidation in the liquid phase are widely used in bulk chemicals manufacture. However, the basic limitations usually encountered in oxidations arise because oxidations are consecutive reactions that lead to complete oxidation or combustion. Generally oxidation processes are highly exothermic in nature and hence even small errors / alterations in process parameters become inherently potential for run-away situations.
In particular, Selective oxidation of primary alcohols is of very high industrial importance. Aldehydes are very important raw materials or intermediates, having widespread applications in perfumery, pharmaceutical, dyestuff and agrochemical industries. A wide range of oxidizing reagent has been employed in order to accomplish

this reaction. In current scenario, an increasing number of chemical processes used for manufacturing monomers and chemical intermediates are seen to encounter selective oxidations using solid catalysts and there is thus wide scope and interest, for this area of the research. There is dire need for further improvements based on both better engineering of the process and better tuning of catalyst reactivity and structural properties.
Generally alcohol oxidations are accompanied with corresponding acids as co-products along with aldehydes. However, there are various instances of controlled catalytic oxidation's leading to aldehyde as the only product. However, the conventional reagents used are toxic, corrosive and are used in stoichiometric amounts leading to huge amounts of inorganic waste. There are reports on aerobic oxidations using copper, palladium, ruthenium and manganese compounds. Hydrogen peroxide (H2O2) is another clean and environment friendly reagent. However, its use is limited by the fact that most valuable organic substrates and aqueous H202 are mutually insoluble. This serious limitation has been circumvented with the aid of phase transfer catalysis (PTC), a well known technique in organic synthesis. Using air/oxygen or H202, as the oxidizing agent; there are instances where heteropoly acids are used for homogeneous oxidation of benzyl alcohol [See, (1) . G. D. Yadav, C. K. Mistry, J. Mol. Catal. A.: Chemical, 172 (2001) 135], (2) sulfide [N. M. Okun, T. M. Anderson, C. L. Hill, J. Mol. Catal. A.: Chemical, 197 (2003) 283], (3) heterogeneous hydrodesulpharization of thiophene [A. A. Spojakina, N. G. Kostova, B. Sow, M. W. Stamenova, K. Jiratova, Catal. Today, 65 (2001) 315], (4) vapor phase oxidative dehydrogenation of isobutyric acid [V. Ernest, Y. Barbaux, P. Courtine, Catal. Today, 1 (1987) 167] and (5) transition metal substituted heteropoly acids as catalysts, in isobutane oxidation [M. Langpape, J. M. M. Millet, U. S. Ozkan, M. Boudeulle, J. of Catal., 181(1999)80].
Heterogeneous catalysts have the advantage, compared to their homogeneous counterparts, of facile recovering and recycling. An early example of the successful approach to the goal of clean liquid phase oxidation catalysis was the Ti(IV)/SiC»2 catalyst, commercialized by Shell in the 1970s for the production of propene oxide. Another benchmark was the development of titanium silicalite (herein after called TS-1)

patented by Enichem scientists in the mid-eighties [See, (1) Taramasso, M.; Perego, G. and Notari, B.; US Pat. 4 410 501 (1983), & (2) Taramasso, M.; Manara, G.; Fattore, V.; and Notari, B.; US Pat. 4 666 692 (1987)]. The success of TS-1 as a catalyst for a variety of oxidations, including epoxidation, with 30% aqueous hydrogen peroxide led to frenetic activity worldwide on the synthesis of related heterogeneous catalysts for liquid phase oxidations. A serious shortcoming of TS-1, however, is its restriction to substrates with linetic diameters Various strategies have been employed in this area for immobilizing redox-active elements in a solid (inorganic) matrix. Metal ions have been isomorphously substituted in framework positions of molecular sieves e.g. zeolites, silicalites, aluminophosphates (APOs), silico-aluminophosphates (SAPOs), via hydrothermal synthesis or post synthesis modification. A wide variety of redox molecular sieves have been synthesized and characterized and their catalytic properties investigated. Amorphous mixed oxides have been prepared by impregnation (grafting) of metal compounds onto the surface of e.g. silica or by sol-gel method. The latter is equivalent to the hydrothermal synthesis of molecular sieve (but without the template) and can afford much higher levels of incorporation than the grafting technique. Alternatively, metal complexes can be tethered to the surface of a solid e.g. silica, via a spacer Hgand. Similarly, coordination complexes or organometallic species can be grafted or tethered to the internal surface of mesoporous molecular sieve. Another approach adopted is the so-called ship-in-a-bottle concept, which involves the entrapment of a bulky complex in a zeolites cage. This has been widely used to immobilize metal complexes of phthalocyanines, bipyridyls and Schiff s base type ligands. Finally, metal ions can be immobilized by cation exchange into zeolites or acidic clays and oxoanions such as molybdate and tungstate can be exchanged into hydrotalcite like anionic clays. A major disadvantage of cation exchange approach is the mobility of the metal ion, which manifests itself in its facile leaching into solution.
' To have real synthetic utility a heterogeneous catalyst should be stable towards leaching
of the active metal into the liquid phase tinder operating conditions. This is true for all
' types of catalytic reactions, but leaching is particularly a problem in oxidation catalysts

owing to the strong complexing and solvolytic properties of oxidants (H202, RC02H, etc.) and/or products (H2O, ROH, RC02H, etc.). Leaching is generally a result of solvolysis of metal-oxygen bonds, through which the catalyst is attached to the support by such polar molecules. Chromium based catalysts are notoriously known for their facile leaching that occurs and generates active homogeneous catalysts. In case of heterogeneous titanium-based epoxidation catalysts, titanium does leach but that is not an active catalyst, hence the observed catalysis is (predominantly) heterogeneous, while in case of Ti(IV)/Si02 and TS-1, the metal does not leach and the observed catalysis is truly heterogeneous. Therefore, in the final analysis the consideration in respect of activities and selectivities are not enough; stability under operating conditions is the essentiality for industrial utility.
So it is of interest to develop heterogeneous oxidation catalysts that are stable under the oxidation conditions for oxidation of alcohol to aldehydes and ketones; and develop advantageous chemical processes for controlled partial oxidations using the catalyst system.
Objective of the invention
The object of the present invention is to provide a novel heterogenous oxidation catalyst for selective oxidation of alcohol to aldehyde and ketone.
Yet another object of the present invention is to provide a catalyst which remains stable during such oxidation process.
A further object of the present invention is to provide a catalyst which can be recycled.

Summary of the Invention
Accordingly, in one aspect, the present invention provides a heterogeneous oxidation catalyst for selective oxidation of alcohol to aldehydes in various substrates. This catalyst comprises phosphomolybdic acid (PMA) supported on vanadium-aluminum mixed oxide. In a preferred embodiment the catalyst comprises at least one heteropoly acid supported on a mixed metal oxide support which comprises an inorganic, porous material, which exhibits after calcination, a BET surface area in between 100 - 600 m2/gm, average pore dimensions in the range of 25 - 50 °A, pore volume in preferably in the range of 0.1 - 0.5 cm /gm and a powder X-ray diffraction pattern having at least one d-spacing in between 3 - 10 °A, with a relative intensity of 100 %. The heteropoly acid used in the present invention comprises at least one hetero element selected from the group consisting of P, V, Al and Mn, as a central element and a second metal element selected from Mo or W as a co-ordinating element. The weight ratio of heteropoly acid to support material is from about 1:50 to 1:1.
In another aspect, the present invention provides process for producing the heterogeneous solid catalyst comprising heteropoly keggin ion supported on vanadium-aluminum mixed oxide.
In yet another aspect present invention provides process for manufacture of various aldehydes such as, not limited to, anisic aldehyde, cinnamaldehyde, p-methyl benzaldehyde, p-chloro benzaldehyde, p-nitro benzaldehyde, benzaldehyde, o-nitro benzaldehyde, 1-Octanal and pyridine-3-methanal; and ketones such as benzophenone and cyclohexanone from corresponding precursors using the catalyst of the present invention. In particular, this invention relates into the synthesis of compounds and intermediates of high industrial importance.
In yet another aspect, present invention provides semi-batch or batch or continuous liquid phase slurry type process for oxidation of anisic alcohol, cinnamyl alcohol, p-methyl

benzyl alcohol, p-chloro benzyl alcohol, p-nitro benzyl alcohol, o-nitro benzyl alcohol, 1-Octanol, pyridine-3 -methanol, cyclohexanol and diphenyl methane.
Brief Description of Drawings
Figure 1 represents scheme of degradation of phosphomolybdate anion /vanadium-aluminum mixed oxide
Figure 2 represents X-ray diffraction patterns of PMA(l), PMA/Vanadium-aluminum oxide(2), vanadium/aluminum oxide (3)and pure vanadia (4)
Figure 3 represents IR spectra of PMA (5)_, PMA/vanadium-aluminum oxide (6), vanadium-aluminum oxide (7) and pure vanadia (8).
Figure 4 represents IR spectra of used Catalyst ( PMA/ vanadium-aluminum mixed oxide)
Figure 5 represents H2 Temperature Programmed Reduction (TPR) profiles of PMA (10), PMA/aluminum oxide (11), PMA/Vanadium-aluminum oxide (12).
Figure 6 represents evaluation of PMA stability on vanadium-aluminum oxide
Figure 7 represents Progress of selective oxidation of various alcohols wherein
♦ 1-octanol ■ o-nitro BnOH
A BnOH x p-nitro BnOH
x p-methoxyBnOH • Cinnamyl alcohol
+ p-chloro BnOH -3-pyridine methanol
♦ p-m ethyl BnOH -BnOH*
A cyclohexanol o diphenyl methane
Figure 8 represents a plot of reusability of PMA/ Vanadium-aluminum oxide wherein ♦ Fresh ■ 1 st Reuse A 2nd Reuse

Detailed Description
As used herein, heteropoly acids belong to a large class of nano-sized metal-oxygen clusters and are polyoxometalates represented by the general formula [XxMmOy]q" (x As used herein heteropoly keggin anion means a polyanionic structure containing 12 M06 (M is metal atom) octahedra linked by edge and corner sharing, with the hetero atom occupying a tetrahedral hole in the center.
In present invention a heterogeneous catalyst was designed by supporting a heteropoly acid on open inorganic framework, which was a mixed metal oxide. Amongst heteropoly acids, PMA (H3PM012O40) (phosphomolybdic acid) was supported on the surface of a mixed metal oxide, which forms the novel catalyst. The new high surface area vanadium-aluminum mixed oxide was synthesized and used for its robustness and strength. The vanadium-aluminum oxide seems to have vanadium oxide species in the matrix framework, as seen from the enhanced surface area of the material in comparison to pure aluminum oxide used. PMA is present on the surface of vanadium-aluminum mixed oxide in the form of a heteropoly keggin anion, which is phosphomolybdate anion, {PM0 12O40]3". The characteristic feature of the material is the interaction between keggin anion and surface vanadium oxide species. Supported phosphomolybdate keggin anion was characterized to undergo degradation to form Polyperoxomolybdate/Vanadium-aluminum mixed oxide, in presence of peroxides during the course of oxidation reaction. A scheme of degradation of phosphomolybdate anion is shown in figure 1. The PMA has the role of providing surface bound polyoxomolybdate species. Surface bound polyoxomolybdate ions adsorb oxygen from the oxidizing agent and form polyperoxomolybdate ions, which then transfer oxygen to the substrate to be oxidized.
PMA/Vanadium-aluminum mixed oxide, was synthesized by impregnating phosphomolybdate keggin anion in a bonded form by treating a PMA solution in a

suitable solvent to a preformed vanadium -aluminum mixed oxide, subsequently followed by calcination to impart surface bonding. PMA was impregnated in a weight / weight ratio of at least 5%, preferably 15 %, more preferably 20%, yet more preferably 50% of the support material. The PMA solution is in a solvent that includes but not limited to, methanol, water, acetone, ethanol, propanol, butanol and combinations thereof. The support material is preferably Vanadium-aluminum mixed oxide. Calcination of the impregnated keggin anion is performed in the temperature range of 100° C to 450° C with a care so that supported keggin anion is intact and does not undergo degradation due to thermal treatment. This produces the catalyst material with BET surface area ranging from 100 - 600 m2/gm, an average pore dimensions in the range of 25 - 50° A, pore volume in the range of 0.1 - 0.5 cm3/gm.
PMA/Vanadium-aluminum mixed oxide, is a true heterogeneous catalyst that belongs to category I. Generally, there are three different categories for heterogeneous catalysts, (i) The active species does not leach and the observed catalysis is truly heterogeneous, (ii) The active species does leach but is not an active catalyst; the observed catalysis is (predominantly) heterogeneous, (iii) The active species leaches to form a highly active homogeneous catalyst; the observed catalysis is homogeneous in nature. Being specific, for liquid phase oxidations, more number of heterogeneous catalysts belong to the 2nd or 3rd category.
The invention is now described hereunder in greater detail by way of examples given below which are provided by way of illustration only of some preferred embodiments and should not be constructed to limit the scope of the present invention.
Synthesis of PMA supported on vanadium-aluminum mixed oxide is disclosed in this invention by way of examples 2-4.
Example 1: Synthesis of support, vanadium-aluminum mixed oxide.
A mixed vanadium-aluminum oxide support was prepared by first dispersing fine
crystallites of vanadia on to the surface of alumina by employing Wet-impregnation

method, which subsequently formed a mixed vanadium-aluminum oxide material. The vanadium oxide precursor was 29 gm of ammonium metavanadate dissolved in 2000 ml of 2M oxalic acid solution. The vanadium precursor solution was adsorbed onto the surface of neutral alumina gel (255 gm), followed by subsequent calcination at 450 ° C in the flow of air for 5 hours.
Example 2: Synthesis of phosphomolybdic acid supported on vanadium-aluminum mixed oxide (Incipient Wetness Technique).
36 gm of PMA dissolved in 200 ml of methanol was used to anchor keggin ion onto the surface of 204 gm of mixed vanadium-aluminum oxide (synthesized in example 1) via incipient wetness method. It was followed by drying at 120 ° C for 8 hours and calcination at 285 °C for 4 hours in flow of air.
Example 3: Synthesis of phosphomolybdic acid supported on vanadium-aluminum mixed oxide (Wet Impregnation method).
36 gm of PMA dissolved in 200 ml of methanol was used to anchor keggin ion onto the surface of mixed vanadium-aluminum oxide (synthesized in example 1) via wet impregnation method followed by drying at 120 °C for 8 hours and calcination at 285 °C for 4 hours in flow of air.
Example 4: Direct Synthesis of supported phosphomolybdic acid on vanadium-aluminum mixed oxide
Vanadium oxide crystallites and PMA were supported directly in one step on the surface of aluminum oxide via wet impregnation method. A solution of 29 gm of ammonium metavanadate in to the 2M oxalic acid (200 ml) was mixed with a solution of 36 gm PMA in 200 ml methanol. The mixture was used as a precursor for simultaneous impregnation of vanadium and PMA keggin anion. The material obtained was dried at 120 °C for 8 hours and calcined at 285 °C for 4 hours in flow of air.

Structural Characterization of supported heteropoly acid catalyst.
The novel oxidation catalyst as synthesized under examples 1-4, was characterized by X-ray diffraction, framework IR analysis and H2 temperature programmed reduction (TPR) analysis (examples 5-7).
Example 5: X-ray Diffraction Analysis of PMA, PMA/ Vanadium-aluminum oxide catalyst, Vanadium/aluminum oxide and pure vanadia
The X-ray scattering measurements of phosphomolybdic acid(PMA), PMA/ Vanadium-aluminum oxide catalyst, Vanadium/aluminum oxide and pure vanadia were made with CUKQ (alpha) radiation on a SIEMENS D 500 diffractometer equipped with reflection geometry, a Nal scintillation counter, a curved graphite crystal monochromator and a nickel filter. The scattered intensities were collected from 2° to 40° (20) by scanning at 0.030° (20) steps with a counting time of 0.5 s at each step.
In figure 2, X-ray powder diffraction patterns of phosphomolybdic acid 1), 20% w/w PMA/ vanadium-aluminum mixed oxide (2), vanadium-aluminum mixed oxide ( 3) and pure vanadia ( 4), are as shown , wherein, X-axis exemplifies 2θ values while Y-axis exemplifies intensity in terms of Lin (counts) . While referring to figure 2, the XRD pattern of pure vanadia (4) contains very sharp peaks at d = 4.4, 3.4, 2.9, 5.7,4.1, 2.8 and 2.6 °A. Vanadium-aluminum oxide (3) sample with V2O5 content of 15 wt% and calcined at 450 °C show small XRD peaks at d = 6.2 and 3.2 °A. The results show that XRD peaks of individual V2O5 are absent. This is a clear indication that vanadia is in a highly dispersed form or in amorphous state or it has formed a mixed oxide with aluminum oxide. Diffractogram of pure phosphomolybdic acid (1) shows XRD peaks at d = 3.3, 8.1, 2.9, 4.1, 2.5, 5.8, 2.3, 3.7, 4.7, 2.6, 3.1, 6.6 °A. X-ray diffractogram of phosphomolybdic acid supported on vanadium-aluminum mixed oxide (2) was similar to that of phosphomolybdic acid. Identical sharp XRD peaks indicate that in supported form heteropoly keggin anion is intact and is present in crystalline form. No XRD peaks were observed for orthorhombic α-MoO3 or monocinic β- M0O3 species or any other anhydrous form, which generally appears on thermal destruction of heteropoly keggin anion.

Example 6: Nitrogen Sorption Analysis of Vanadium-aluminum oxide supported phosphomolybdic acid catalyst and aluminium oxide.
Surface area, Pore volume and pore diameter measurements were performed, by using nitrogen sorption technique on Micromeritics ASAP 2010 instrument. Catalyst samples were pretreated under vacuum at 200 ° C, and then subjected to analysis at the temperature of liquid nitrogen. The catalyst is essentially mesoporous. The textural characteristics of the catalyst are given in Table 1

Sample Single Point
Surface area
m2/g BET
Surface area
m2/g Langmuir
Surface area
m2/g BJH
Adsorption
cumulative
pore volume
cm3/g Average Pore Diameter
(4V/A) °A
PMA/Vanadiu m-aluminum oxide (Example 2) 178.2 177.8 239.2 0.145 32.6
aluminum oxide 247.7 245.3 328.4 0.28 45.5
Example 7: Framework IR Analysis of PMA, PMA/ Vanadium-aluminum oxide catalyst, Vanadium/aluminum oxide, pure vanadia and used Vanadium-aluminum oxide catalyst.
Framework IR spectra were recorded on Perkin-Elmer Spectrum one spectrometer equipped with DRS system. The homogeneous powdered mixture was made by co-grinding 3 mg of catalyst with 100 mg of potassium bromide and was subjected to IR radiation.
IR spectra of phosphomolybdic acid as such and in its supported form on vanadium-aluminum mixed oxide are shown in figure 3, wherein X-axis exemplifies wavenumber in cm"1 and Y-axis exemplifies % Reflectance. While referring to figure 3, Phosphomolybdic acid (5) shows characteristic absorption bands at 3217, 2425, 1935, 1621,1403,1063, 864, 800, and 597 cm-1. In supported form ( 6), characteristic bands of

heteropoly keggin anion are shifted to lower frequencies, which is attributed to the interaction of phosphomolybdic acid with vanadium oxide species present on thesupport surface. Within the range of 1100-600 cm"1, the bands corresponding to the stretching of Mo-0 bonds in the Keggin unit were observed with shift. The band at 1002 cm-1, has been attributed to the usMo=Ot vibration. Generally, pure V2O5 ( 8)shows a characteristic sharp band at 1020 cm'1, which is due to the V=0 stretching vibration. A weak absorption band is observed at 1020 cm"1 in case of vanadium-aluminum mixed oxide ( 7), which is associated with amorphous vanadia species dispersed on the surface, indicating absence of any crystalline form of V2O5. When heteropoly keggin anion is supported on the surface of vanadium-aluminum mixed oxide, this weak absorption band at 1020 cm-1 disappears indicating probable interaction of keggin anion with the surface bound vanadia species. In agreement to this argument, significant reduction in absorption intensity of P-0 stretching vibration band is noticed, when peak at 1063 cm-1 is compared for keggin anion supported on vanadium-aluminum mixed oxide against unsupported keggin anion and also keggin anion supported on aluminum oxide.
Figure 4 (9) shows the IR spectra of used catalyst, 20 % w/w PMA/ vanadium-aluminum mixed oxide (obtained in example 2) recovered after performing alcohol oxidation. (Here also, X-axis exemplifies wavenumber in cm'1 and Y-axis exemplifies % Reflectance.) It was lacking all four absorption bands that are typical features of heteropoly keggin anion that was attributed to degradation of polyoxometalate anion into polyperoxometalate anions. This provided direct understanding of mechanistic aspects of alcohol oxidation, which seems to be similar to the mechanism of epoxidation of olefins or olefinic compounds under Ishii-Venturello chemistry conditions.
Example 8 H2 Temperature Programmed Reduction Analysis of PMA, PMA/aluminum oxide, PMA/ Vanadium-aluminum oxide catalyst.
H2 temperature programmed reduction experiments were carried out on a Thermoquest TPDRO 1100. Samples were tested by increasing the temperature from 50 to 800 °C, at a heating ramp of 10 °C min-1. The reducing gas, a mixture of 5 vol% H2 in Ar, at a flow rate of 30 ml min-1 was used to reduce the catalyst samples with continuous temperature

ramp. The temperature was then kept constant at 800 °C until the signal of hydrogen consumption returned to the initial values.
H2 Temperature programmed reduction (TPR) was used to investigate the oxidative activity of heteropoly phosphomolybdate anion under the influence of its subsequent interaction with surface bound vanadia species. Figure 5 shows the TPR profiles of PMA/ vanadium-aluminum mixed oxide (12), PMA/aluminum oxide (11) and pure PMA (10) wherein X-axis exemplifies the temperature and Y-axis exemplifies the TCD signal in mV. The reduction of heteropoly phosphomolybdate anion anchored on aluminum oxide was also performed. H2 TPR data for pure phosphomolybdic acid showed one peak at 614 °C with a distinctive shoulder at 582 °C resulting from the release of oxygen upon the reaction with hydrogen under high temperature. H2 TPR profile of phosphomolybdate keggin ion anchored on aluminum oxide showed only one peak with maxima at 556 °C. Generally, vanadia (20% w/w) dispersed on the surface of aluminum oxide shows three distinctive peaks with maxima in the range of 481-486°C, 570-575°C and 600-610°C [E. P. Reddy, R. S. Varma, J. of Catal., 221, (2004) 93]. The authors, have attributed the first peak to the presence of vanadium in oxidation state between V+5 and V+4 and the second and third peak to the subsequent reduction of vanadium oxide to V+4 and V+3 oxidation states respectively. In present study, H2 TPR profile of phosphomolybdate keggin ion supported on vanadium-aluminum oxide revealed a peak with maxima at 525 °C associated with shoulder at 486 °C. We do not observe small peaks associated with reduction of vanadium oxide to V+4 and V+3 oxidation states, which in accordance to IR studies, indicates there is a strong interaction between heteropoly keggin anion and surface vanadium oxide species.
Evaluation of catalyst stability
20% w/w PMA/vanadium-aluminum oxide is highly active in alcohol oxidation and the activity shown by 20% w/w PMA/vanadium-aluminum oxide is attributed to the interaction of supported keggin ion with peroxides. Hence, to ascertain that the catalyst was truly heterogeneous, it was important to establish the exact nature of interaction between PMA and vanadium-aluminum oxide surface. If PMA was physically adsorbed

on vanadium-aluminum oxide surface, then the catalyst would not be reused because of leaching out of PMA into the reaction mixture. It was observed that the 20% w/w PMA/vanadium-aluminum oxide showed a consistent activity up to a minimum of three runs, which suggested that PMA was chemically bonded to the support.
Example 9: Heteropoly blue colour test
The stability was evaluated by the characteristic, heteropoly blue colour test [G.D. Yadav, H. G. Manyar, Microporous and Mesoporous Materials, 63 (2003) 85]. PMA solutions develop blue colour when reacted with a mild reducing agent like ascorbic acid. This property was used for quantitative determination of leaching, if any. Two grams of 20% w/w PMA/vanadium-aluminum oxide was refluxed in 25 ml of methanol with vigorous stirring for 1 h. Five millilitre aliquot of the refluxing solution was drawn to which 2 ml of 10% ascorbic acid solution was added. The solution remained clear and colourless and there was no development of the blue colour which otherwise is an instantaneous phenomenon in authentic PMA solutions. The above test was repeated to confirm absence of leaching.
Example 10: Experimental evidence
A further proof of PMA stability on vanadium-aluminum oxide was obtained. A typical experiment was carried out, wherein the reaction mixture consisted of 0.02 mol benzyl alcohol, 0.5 gm CTABr in 40 ml toluene and aqueous H2O2 (50% w/v), was added with peristaltic pump, at the addition rate of 0.5 mmol/min. Keeping standard catalyst loading of 0.025 g/cm3, the reaction was carried out at 65 °C, for 60 min. A conversion of 15% of benzyl alcohol was obtained. The reaction mixture was hot filtered and all catalyst particles were separated. The reaction was further continued at the same temperature for next 30 min without any catalyst. The sample was again analysed to find 15.5% of benzyl alochol conversion, which is the same within experimental error. Continuation of the reaction showed no further conversion (refer Figure 6, wherein X-axis exemplifies time. in minutes and Y-axis exemplifies % conversion). Thus, it is concluded, that the PMA was chemically adsorbed on the vanadium-aluminum oxide surface and the catalyst is stable.

Oxidation of alcohols by supported heteropoly acid catalyst
Chemicals
The substrates are obtained from commercial sources. 50% w/v aqueous hydrogen
peroxide (sourced from Merck India Ltd.), was stored under refrigeration and there was
no significant change in its concentration during the period when the reactions were
performed. The exact concentration of Hydrogen peroxide solution was determined by
iodometry.
Reaction Methodology
The liquid phase oxidation of alcohols was carried out with PMA/Vanadium-aluminum mixed oxide as the catalyst and oxidizing agent selected from peroxidic oxidants like tert-butyl hydroperoxide or aqueous solution (30-60% w/v) of hydrogen peroxide, or perbenzoic acids or the like under Liquid-Liquid-Solid phase transfer condition. The reactions were studied in a mechanically agitated contactor made of glass and a reflux condenser. The organic phase containing the required amount of alcohol, catalyst, cetyl trimethyl ammonium bromide (CTABr) as phase-transfer catalysts (PTC) in toluene as solvent was stirred. Required amount of H2O2 was added with the help of a peristaltic pump, at the addition rate of 0.5 mmol/min. The reaction was performed in a water bath assembly where the desired temperatures were properly maintained Phase transfer catalysts are used to impart solubility of peroxide in the organic solvent.
Where R group is OCH3, CH3, CI, N02.
Reaction Scheme

Method of Analysis
The samples (organic phase) were withdrawn periodically from the reaction mixture and were filtered before being analyzed by HP 6890N gas chromatograph equipped with autosampler 7683 series injector' and HP chemstation. A (30 m x 0.32 mm ID x 0.25 u) column packed with DB-5 (5.% polyphenyl + 95% polymethyl siloxane) was used for analysis (injector/detector temperature 250°C, oven 60°C-2 min- 10°C/min-250°C-5 min). 3-pyridyI methanol was analyzed by Water's Aliance HPLC system equipped with 2695 sample handling unit and 2487 UV detector. Purosphere star (250 x 4.6 mm x 5 u) column was used with 0.02 mol Na2HP04 (pH 7) buffer : acetonitrile (90:10) mobile phase. Synthetic mixtures were prepared and used for calibration and quantification. GC-MS and LC-MS confirmed the products.
Chemical processes catalyzed with said catalyst produce no inorganic salts and offer different process configurations of semi batch as well as batch process. This methodology can replace advantageously conventional hazardous stoichiometric catalysts. Chemical processes mentioned in this invention are environmentally clean and fit well into the domain of green chemistry.
General Example -Reaction Conditions Alcohol: 0.005 - 0.2 mol, solvent: 40 cm3, Catalyst loading: 0.005 - 0.25 g/cm3, CTABr: 0.5 - 10 mmol, H202 addition rate: 0.1-2 mmol/min, Temperature: Ambient - Reflux, Time: 1 - 5 h., Agitation speed: 200 -1000 rpm.
Example 11
Liquid phase oxidation of Anise alcohol, under solid-liquid-liquid phase transfer conditions; was performed in £ mechanically agitated contactor made of glass and a reflux condenser. The organic phase contained 0.02 mol Anise alcohol and 40 cm toluene. 1 gm of the catalyst (example 2), 20% w/w PMA/Vanadium-aluminum oxide with a specific catalyst loading of 0.025 g/cm3 was added. 1.4 mmol of CTABr was added as a phase transfer agent and stirring maintained at 700 rpm. Temperature of the reaction mixture was maintuened at 800 C and aqueouls doluition of H2O2(50 %w/V)was.

added at the constant rate of 0.5 mmol/min in a semi-batch mode. Reaction was completed in 2 hours with very high selectivity towards anisaldehyde and no traces of anisic acid were observed due to over oxidation. This is a very interesting example of controlled partial oxidations. Analogously the following alcohol substrates are oxidized to aldehydes.
Examples 12-22.
The scope of supported heteropoly acid as a catalyst was tested in a wide array of primary alcohols that includes benzylic, heterocyclic and aliphatic alcohols. The progress of oxidation of following alcoholic substrates is shown in figure 8, wherein X-axis exemplifies time in minutes and Y-axis exemplifies % conversion of alcohol. 20% w/w PMA/vanadium-aluminum oxide (Example 2), a very interesting catalyst for controlled partial oxidation reactions. As depicted in Table 2, various alcohols were converted into corresponding aldehydes in excellent yield with 100% selectivity and no over oxidation to carboxylic acids was observed. Using 20% w/w PMA/vanadium-aluminum oxide as a catalyst, the oxidation protocol showed high reactivity towards benzylic alcohols, than aliphatic alcohols. Substituted benzylic alcohols, with both activating and deactivating group substitutions showed higher reaction rate constants than aliphatic octan-1-ol. The above design of partial oxidation was further extended to heterocyclic, pyridine-3-methanol, however due to poor solubility of substrate in toluene; acetonitrile was used as a reaction solvent (Example 22). The rate constant for this oxidation was further enhanced due to additional effect of solvent polarity. To compare with this solvent effect, benzyl alcohol was also oxidized in acetonitrile, resulting in high reaction rate constant (Example 21). The reaction rate constant of p-nitro benzyl alcohol oxidation was observed to be slightly higher than that of benzyl alcohol, under otherwise identical experimental conditions (Example 17,18). Such anomalous reactivity is already observed in past and is mentioned in literature [C. Zondervan, R. Hage and B. L. Feringa, J. Chem. Soc, Chem. Commun, (1997) 419].

Table 2. Oxidation of Alcohols using 20% w/w PMA/Vanadium-aluminum mixed oxide catalyst

Reaction conditions: Alcohol: 0.02 mol, toluene: 40 cm3, Catalyst loading: 0.025 g/cm3, CTABr. 1.4 mmol, H202 addition Tate: 0.5 mmoi/rnin, Temperature: 65 °C, Time: 2 h., Agitation speed: 700 rpm, * Acetonitrile was used as solvent instead of toluene. Reusability of 20% w/w PMA/vanadium-aluminum oxide
Example 23-25
The catalyst reusability was studied three times including the use of fresh catalyst (refer figure 8, wherein, X-axis exemplifies time in minutes and Y-axis exemplifies % conversion of alcohol); Oxidation of anise alcohol was arbitrarily selected for this evaluation, without any technical reason. The catalyst was filtered, washed with methanol and subsequently heated at 250 °C for two hours, before being reused in subsequent batches. In the presence of the fresh catalyst, the conversion of anise alcohol was 87%. During the third run, the conversion decreased to 83%, while the selectivity towards anisaldehyde remained 100%. This decrease in conversion is because of the observed losses due to attrition, during filtration of the catalyst particles and no make up quantity of catalyst was added.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples and that the present invention may be embodied in other specific forms without departing from the essential attributes thereof, and it is therefore desired that the present embodiments and examples be considered in all respects as illustrative and not restrictive, reference being made to the appended claims, rather than to the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

We claim,
1. A heterogeneous oxidation catalyst for selective oxidation of alcohol to aldehydes or ketones in various substrates comprising at least one heteropoly acid supported on vanadium-aluminum mixed oxide support.
2. The catalyst as claimed in claim 1, wherein the catalyst material after calcination shows a BET surface area ranging from 100 - 600 m2/gm, an average pore dimensions in the range of 25 - 50°A, pore volume in the range of 0.1 - 0.5 cm /gm and a powder X-ray diffraction pattern having at least one d-spacing in between 3 - 10 °A with a relative intensity of 100 %.
3. The catalyst as claimed in claim 1 or 2, wherein said heteropoly acid comprises at least one hetero atom selected from the group consisting of P, V, Al and Mn as a central atom and a second metal atom selected from Mo or W as a co-ordinating or addenda metal atom.
4. The catalyst as claimed in any one of the preceding claim, wherein said mixed oxide support material consists of 10 to 20% w/w of vanadium oxide and 80 to 90% w/w of aluminum oxide.
5. The catalyst as claimed in any one of the preceding claim, wherein the weight ratio of heteropoly acid to support material is from about 1: 50 to 1:1.
6. The catalyst as claimed in any one of the preceding claim, wherein the catalyst is phosphomolybdic acid supported on a vanadium-aluminum mixed oxide.
7. A method for preparing heterogeneous oxidation catalyst as claimed in claim 1 comprising the step of impregnating a heteropolyacid solution in one or more solvent to preformed porous vanadium -aluminum mixed oxide support, followed by calcination to form said catalyst.
8. A method for preparing heterogeneous oxidation catalyst as claimed in claim 1 comprising the step of mixing a heteropoly acid and a vanadium precursor in one or more solvent, impregnating said solution to porous aluminum oxide, and followed by calcination to form said catalyst.
9. The method as claimed in claim 8, wherein the vanadium precursor is ammonium meta vanadate.

10. The method as claimed in claim 7 or 8, wherein the suitable solvent is methanol, water, acetone, ethanol, propanol, butanol and combinations thereof.
11. The method as claimed in claim 7 or 8, wherein said calcination is performed in the temperature range of about 100 °C to 450 °C.
12. A heterogenous oxidation catalyst as claimed in any of the preceding claim for oxidation of an active methylene group in diphenyl methane to diphenyl ketone.
13. A method for oxidation of alcohol functional group in any substrate to an aldehyde or ketone by using the catalyst as claimed in any one of the preceding claims comprising treating a solution of alcohol in an organic solvent with a peroxide agent and said catalyst optionally in presence of a phase transfer catalyst.
14. The method as claimed in claim 14 wherein said alcohol is benzylic, heterocyclic aliphatic or aHcyclic alcohols.
15. The method as claimed in claim 14, wherein the peroxide agent is selected from hydrogen peroxide or organic peroxides like tertiary butyl hydroperoxide, perbenzoic acid etc.
16. The method as claimed in claim 14, wherein said catalyst is reusable in said method.
17. Heterogeneous oxidation catalyst for selective oxidation of alcohol to aldehydes or ketones in various substrates and their oxidation process as substantially described herein with reference to foregoing examples 2 to 4 and 11 to 22.
Dated this the 17th day of October 2008

Dr. Gopakumar G. Nair Agent for the applicant

Documents:

207-mum-2005-abstract(17-10-2008).pdf.doc

207-MUM-2005-ABSTRACT(24-2-2005).pdf

207-mum-2005-abstract(granted)-(28-11-2008).pdf

207-mum-2005-abstract.doc

207-mum-2005-abstract.pdf

207-MUM-2005-CANCELLED PAGES(17-10-2008).pdf

207-MUM-2005-CLAIMS(17-10-2008).pdf

207-MUM-2005-CLAIMS(24-2-2005).pdf

207-MUM-2005-CLAIMS(AMENDED)-(17-10-2008).pdf

207-mum-2005-claims(granted)-(17-10-2008).pdf.doc

207-mum-2005-claims(granted)-(28-11-2008).pdf

207-mum-2005-claims.doc

207-mum-2005-claims.pdf

207-mum-2005-correspondance-received-ver-240205.pdf

207-mum-2005-correspondance-received.pdf

207-MUM-2005-CORRESPONDENCE(17-10-2008).pdf

207-MUM-2005-CORRESPONDENCE(2-11-2006).pdf

207-MUM-2005-CORRESPONDENCE(IPO)-(8-12-2008).pdf

207-mum-2005-description (complete).pdf

207-MUM-2005-DESCRIPTION(COMPLETE)-(24-2-2005).pdf

207-mum-2005-description(granted)-(28-11-2008).pdf

207-MUM-2005-DRAWING(23-5-2008).pdf

207-MUM-2005-DRAWING(24-2-2005).pdf

207-mum-2005-drawing(granted)-(28-11-2008).pdf

207-mum-2005-drawings.pdf

207-MUM-2005-FORM 1(10-3-2005).pdf

207-MUM-2005-FORM 1(24-2-2005).pdf

207-MUM-2005-FORM 1(26-7-2007).pdf

207-MUM-2005-FORM 18(2-11-2006).pdf

207-mum-2005-form 2(24-2-2005).pdf

207-mum-2005-form 2(granted)-(17-10-2008).pdf.doc

207-mum-2005-form 2(granted)-(28-11-2008).pdf

207-MUM-2005-FORM 2(TITLE PAGE)-(24-2-2005).pdf

207-mum-2005-form 2(title page)-(granted)-(28-11-2008).pdf

207-mum-2005-form-1.pdf

207-mum-2005-form-2.doc

207-mum-2005-form-2.pdf

207-mum-2005-form-26.pdf

207-mum-2005-form-3.pdf

207-MUM-2005-REPLY TO FIRST EXAMINATION REPORT(23-5-2008).pdf

207-MUM-2005-SPECIFICATION(AMENDED)-(17-10-2008).pdf

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Patent Number

225765

Indian Patent Application Number

207/MUM/2005

PG Journal Number

07/2009

Publication Date

13-Feb-2009

Grant Date

28-Nov-2008

Date of Filing

24-Feb-2005

Name of Patentee

IPCA LABORATORIES LTD.

Applicant Address

48, KANDIVLI INDUSTRIAL ESTATE, MUMBAI 400 067, MAHARASHTRA, INDIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	KUMAR, ASHOK	A4/203-4, STERLING CHS, SUNDERAVAN COMPLEX, ANDHERI (WEST) MUMBAI-400 053 MAHARASHTRA, INDIA.
2	MANYAR, HARESH GOPALDAS	201, KRISHNA KUNJ, OPP.SANT KANWAR RAM CHOWK, STATION ROAD, ULHASNAGER, THANE-421 003, MAHARASHTRA, INDIA.
3	CHAURE, GANESH SHANKAR	A/P: KUKANA TALUKA: NEWASA, DIST; AHMEDNAGER PIN: 414 606, MAHARASHTRA, INDIA.

PCT International Classification Number

C07C 5/333

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA