Title of Invention

"A PROCESS FOR THE MANUFACTURE OF CYCLOHEXANONEOXIME"

Abstract

A process for the manufacture of cyclohexanoneoxime by reacting ammonia with cyclohexanone in a ratio of 1 to 2 and an oxidant in a ratio of 1 to 1.5 with respect to cyclohexanone in the presence of a solid catalyst containing an organotransition metal complex wherein some or all of the hydrogen atoms of the said organotransition metal complex have been substituted by one or more electron withdrawing groups encapsulated in solid matrix 0.1 to 10.0 parts by wt of solid catalyst for 100 parts by wt of cyclohexanone at a temperature in the range of 200C to 900C, at a pressure in the range of 15 to 1000 psi optionally in presence of solvent or promoter and isolating the cyclohexanoneoxime formed by extraction with ether.

Full Text

This invention relates to a process for the manufacture of cyclohexanoneoxime. More particularly, the present invention relates to a process for the manufacture of cyclohexanoneoxime by the ammoxidation of cyclohexanone using ammonia, an oxidant and using a solid organotransition metal complex as a catalyst. Cyclohexanoneoxime is the major intermediate in the manufacture of caprolactam, nylon 6, etc. In the current commercial art, cyclohexanoneoxime manufacture consists of the following steps : (1). ammonia oxidation followed by nitric oxide or nitrite and nitrate reduction in the hydroxylamine synthesis; (2). formation of hydroxylamine sulphate by reaction of hydroxylamine with sulphuric acid and (3). cyclohexanone oximation with hydroxylamine sulphate. Some of the drawbacks of this above mentioned current technology are : (1). the high complexity of the process necessary to produce hydroxylamine from ammonia through two opposite reaction steps, first involving the oxidation of nitrogen of ammonia to a higher than required oxidation state to produce the nitrogen oxides or nitrates followed by a second controlled reduction step in reducing the nitrogen oxides to hydroxylamine; (2). the second major disadvantage of the current process is the heavy by-production of ammmonium and sodium sulphates during the process. These sulphates are produced as by-products when the sulphuric acid is neutralised by an alkali in the final recovery of the oxime. It is therefore an object of the present invention to provide a process for the manufacture of cyclohexanone oxime which will introduce nitrogen into the cyclohexanone molecule starting from ammonia but without its unnecessary oxidation to a so high level as that of nitric oxide or nitrite or nitrate. It is an additional object of the present invention to use an inexpensive source of oxidant, like air or aqueous hydrogen peroxide, to perform the two electron oxidation of the ammonia. It is an additional object of the present invention to avoid the production of sulphate byproducts. Various processes had been proposed in the prior art to overcome some of the drawbacks of the conventional process mentioned hereein above. One such process developed by Toagosei uses phosphotungstic acid catalyst for the anunoxidation of cyclohexanone with NH3 and H202. Substantial loss of H2O2 due to oxygen formation and rapid catalyst decomposition are some of the disadvantages of the Toagosei process. An alternate process, developed by Allied, concerns the gas phase ammoxidation by oxygen on a silica gel catalyst. Rapid fouling and low yield of the catalyst as well as the low selctivity based on cyclohexanone precluded the adoption of this process in commercial practice. U.S. Patent 4,745,221 assigned to Montedipe, describes a process for preparing cyclohexanoneoxime with NH3 and H202 in the liquid phase using a titanosilicate zeolite as a catalyst. A major drawback of ta i.s process, however, is the deactivation of the titanosilicate catalyst during the process. Researchers from Montedipe in their article titled "Deactivation phenomena on Ti-silicalite" published in the book Catalyst Deactivation, 1991 (Editors : C.H. Bartholmew and J.B. Butt, Elsevier Science Publishers, Amsterdam, 1991) have identified three main deactivation processes : (1). slow dissolution of the zeolite framework with accumulation of Ti on the external surface of the remaining solid (2). direct removal of Ti from the zeolite framework and (3). pore-filling of the byproducts. It is therefore an additional object of the present invention, to develop a solid catalyst which will not dissolve or deactivate during the ammoxidation reaction. In its wide form, the present invention concerns a catalytic process for the manufacture of cyclohexanoneoxime by reacting cyclohexanone with NH3 and either H2O2 or 02 characterised in that the catalyst is a solid organotransition metal complex. Pthalocyanines consist of large, planar, conjugated, ring systems which serve as tetradentate ligands. Metalic cations can be easily accommodated at the center of these systems with the four nitrogens as the ligating atoms. Metal containing pthalo-cyanine compounds are known to be useful as chemical reagents of a catalytic nature, more particularly in directing certain oxida-tive processes. Many known pthalocyanines have been judged to suffer certain drawbacks by being deficient in the combination of properties desired for many candidate uses, such as in ammoxida-tion. One major drawback of homogeneous pthalocyanine catalysts in industrial oxidation processes is the formation of aggregates in solution which significantly deactivates these catalysts. Due to our continued research in this area we observed that the organotransition metal complexes used as catalysts are solids insoluble in ketones or the reaction products arising from ammox-idation of ketones. Hence they do not undergo aggregation or change of phase during the ammoxidation wherein such changes are known to lead to catalyst deactivation problems. Another drawback of pthalocyanines used in the prior art as catalysts for ammoxidation is their low oxidative stability which is due to the easy oxidisability of the hydrogen atoms attached to the nucleus of the pthalocyanines. We have found that the oxidative stability as well as the catalytic activity of the metal pthalocyanines used as catalysts in the ammoxidation of cyclohexanone are enhanced by replacing the hydrogens from the pthalocyanines by electron withdrawing groups like the halogens, nitro or cyano groups thereby rendering the metal ions easier to reduce leading to an improved oxidation activity and stability of the catalysts during the reaction. There are a total of 16 hydrogen atom positions on such pthalocyanine molecules which can in principle, be substituted by other substituents. We have observed that when some or all of the hydrogen atoms of the said pthalocyanines are substituted by one or more electron withdrawing groups such as halogen, nitro or cyano groups or mixtures of such groups there is substantial improvement in selectivity and conversion to cyclohexanoneoxime. Accordingly, the present invention provides a process for the manufacture of cyclohexanoneoxime which comprises reacting ammonia with cyclohexanone in a ratio of 1 to 2 and an oxidant in a ratio of 1 to 1.5 with respect to cyclohexanone in the presence of a solid catalyst containing an organotransition metal complex wherein some or all of the hydrogen atoms of the said organotransition metal complex have been substituted by one or more electron withdrawing groups encapsulated in solid matrix at a temperature in the range of 200C to 900C, at a pressure in the range of 15 to 1000 psi optionally in presence of solvent or promoter and isolating the cyclohexanoneoxime formed by extraction with ether. In an embodiment of the present invention the organotransition metal complex is selected from pthalocyanines and porphyrins. In another embodiment of the present invention, the transition metal is selected from iron, cobalt, copper, chromium , manganese or mixtures thereof. Some nonlimiting examples of such organo transition metal complexes used as catalysts in the ammoxidation of cyclohexanone to cyclohexanoneoxime are iron halopthalocyanines, copper, halo pthalocyanines, cobalt halo pthalocyanines, chromium halo pthalocyanines, manganese halo pthalocyanines, iron nitro pthalocyanines, copper nitro pthalocyanines, chromium nitro pthalocyanines, cobalt nitro pthalocyanines, manganese nitro pthalocyanines, manganese cyano pthalocyanines, copper cyano pthalocyanines and chromium cyano pthalocyanines. In yet another embodiment of present invention the electron withdrawing groups attached to the organotransition metal complex is selected from the halogens, fluorine, chlorine or bromine or the nitro or cyano groups. In a preferred embodiment of the present invention, the ammoxidation of cyclohexanone by molecular oxygen or H2O2 is catalysed by the halogen, cyano or nitro pthalocyanines of the metals iron, cobalt, copper, chromium or manganese. In yet another embodiment of the present invention, the source of molecular oxygen can be pure oxygen gas, air or a mixture of oxygen and an inert gas diluent like nitrogen. In yet another embodiment of the present invention, the above mentioned ammoxidation reaction can be carried out in the presence or absence of solvents. It may be an advantageous option to carry out the said ammoxidation reaction in the presence of a suitable solvent which would have a high solubility for 02 and, in addition, maintain the ammoxidation product, cyclohexanoneoxime in the dissolved state during the course of the reaction, thereby facilitating the separation of the said cyclohexanoneoxime from the solid catalysts. Suitable solvents for such use include acetonitrile, methanol, water, butanol and cyclohexanol. Examples of such solvents which can be used in the process of the present invention include acetonitrile, acetone, benzene or any other organic solvent which is inert under the oxidation reaction conditions. In another advantageous embodiment of the present invention, the rates of the ammoxidation may be significantly enhanced by addition of very small catalytic quantities of a promoter. Examples of such promoters include alkyl hydroperoxide, dialkylp-eroxides and such compounds. Cyclohexyl hydroperoxide, cunxyl peroxide, tertiary butyl hydroperoxide are some of the examples of such promoters which may be present in concentrations not exceeding 1% by weight of cyclohexanone and more preferably 0.1% by weight of the ketone. In yet another advantageous embodiment of the present invention, the organotransition metal complex may be encapsulated in a solid matrix. Due to the greater dispersion of the organotransition metal complex catalyst in solid matrices and the consequent enhanced stability of the structural integrity of the catalyst significant process advantages like greater activity, stability and easy recovery and recyclability of the catalyst are observed. Examples of such solid matrices include inorganic oxide like silica, alumina, molecular sieves, zeolites and the like as well as organic polymeric material. It is an advantageous feature of the process of the present invention that due to the high activity the catalysts used herein, the ammoxidation reaction can be carried out at temperatures much below those used in the prior art and preferably below 100°C, thereby leading to much lower yields of undesired side products like peroxy dicyclohexylamine, 2-cyclohexylidene cyclo-hexanone and 2-(1-cyclohex-l-en-l-yl)-cyclohexanone. The ammoxidation reaction can be carried out in either bateh or continuous reactors. When the reaction is carried out in a batch reactor it is preferable to use from 0.1 to 10.0 parts by weight of the solid catalyst (binder excluded) for 100 parts by weight of cyclohexanone. If the reaction is performed in a continuous reactor, it is advisable to employ a space velocity from 0.1 to 10.0 kg/hr of cyclohexanone per kg of solid catalyst. The oxidant : cyclohexanone mole ratio shall generally range from 1.0 to 1.5. The molar ratio of NH3 : cyclohexanone may preferably range from 1.0 to 2.0. At the end of the ammoxidation reaction the product cyclo-hexanoneoxime can be isolated from the reaction products by conventional methods well known to those skilled in the art, such as extraction with a solvent immiscible with H2O, for example, diethyl ether. The ether extract contains cyclohexanoneoxime and unreacted cyclohexanone from which the cyclohexanoneoxime may be obtained by fractional distillation. The details of the present invention is described in the examples given below which are provided by way of illustration only and therefore should not be construed to limit the scope of the invention. Example-1 In a three-necked glass flask (200 ml capacity) fitted with a mechanical stirrer, a glass condenser and a rubber septum through which aqueous H202 could be injected using a feed pump (Sage instruments, USA), 10 g of cyclohexanone, 12 g (22 wt%) of ammonia solution, and 1 g of solid iron tetra deca bromo pthalocya-nine were stirred at 60°C. An aqueous solution of H2O2 (26 wt %, 13.3 g) was injected dropwise by a feed pump over a period of 4 hr. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography (Hewlett Packard 5880 A) using a capillary column (HPl, cross-linked methyl silicone gum, 50 m x 0.5 mm) and flame ionization detector (FID). The identity of the products was confirmed by GC mass spectroscopy (Shimadzu GCMS-QP 2000A) using standard compounds. In view of the large differences in the response factors for the different components of the products, standard calibration mixtures were used to estimate their response factors accurately. The conversion of cyclohexanone was 25% wt and the yield of cyclohexanoneoxime was 24% wt. Example-2 In a three-necked glass flask (200 ml capacity) fitted with a mechanical stirrer, a glass condenser and a rubber septum through which aqueous H202 could be injected using a feed pump (Sage instruments, USA), 10 g of cyclohexanone, 12 g (22 wt%) of ammonia solution, and 1 g of solid copper tetra deca chloro pthalo-cyanine were stirred at 60°C. An aqueous solution of H202 {26 wt %, 13.3 g) was injected dropwise by a feed pump over a period of 4 hr. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography (Hewlett Packard 5880 A) using a capillary column (HP1, cross-linked methyl silicone gum, 50 m x 0.5 mm) and flame ionization detector (FID). The identity of the products was confirmed by GC mass spectroscopy (Shimadzu GCMS-QP 2000A) using standard compounds. In view of the large differences in the response factors for the different components of the products, standard calibration mixtures were used to estimate their response factors accurately. The results are given in Table 1. Example-3 In a three-necked glass flask (200 ml capacity) fitted with a mechanical stirrer, a glass condenser and a rubber septum through which aqueous H202 could be injected using a feed pump (Sage instruments, USA), 10 g of cyclohexanone, 12 g (22 wt%) of ammonia solution, and 1 g of solid cobalt tetra deca fluoro pthalo-cyanine were stirred at 60°C. An aqueous solution of #2^2 (^ wt %, 13.3 g) was injected dropwise by a feed pump over a period of 4 hr. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The results are given in Table 1. Example-4 In a three-necked glass flask (200 ml capacity) fitted with a mechanical stirrer, a glass condenser and a rubber septum through which aqueous H202 could be injected using a feed pump (Sage instruments, USA), 10 g of cyclohexanone, 12 g (22 wt%) of ammonia solution, and 1 g of solid chromium tetra deca bromo pthalo-cyanine were stirred at 60 °C. An aqueous solution of H202 (26 wt %, 13.3 g) was injected dropwise by a feed pump over a period of 4 hr. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The results are given in Table 1. Example-5 In a three-necked glass flask (200 ml capacity) fitted with a mechanical stirrer, a glass condenser and a rubber septum through which aqueous H202 could be injected using a feed pump (Sage instruments, USA), 10 g of cyclohexanone, 12 g (22 wt%) of ammonia solution, and 1 g of solid manganese tetra deca chloro pthalocyanine were stirred at 60°C. An aqueous solution of H2O2 (26 wt %, 13.3 g) was injected dropwise by a feed pump over a period of 4 hr. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The results are given in Table 1. Table 1 indicates the wt % conversion of cyclohexanone and wt % yield of cyclohexanoneoxime when using different organotransition metal complexes as catalysts and using the conditions mentioned herein above (Examples 2-5) Table 1 (Table Removed) Example-6 In a three-necked glass flask (200 ml capacity) fitted with a mechanical stirrer, a glass condenser and a rubber septum through which aqueous H202 could be injected using a feed pump (Sage instruments, USA), 10 g of cyclohexanone, 12 g {22 wt%) of ammonia solution, and 1 g of solid copper tetra nitro pthalocyanine were stirred at 60°C. An aqueous solution of H2O2 (26 wt %, 13.3 g) was injected dropwise by a feed pump over a period of 4 hr. f At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The conversion of cyclohexanone was 31 % wt and the yield of cyclohexanoneoxime was 24% wt. The yield of peroxy dicylcohexy-lamine was 7 % wt. Example-7 In a three-necked glass flask (200 ml capacity) fitted with a mechanical stirrer, a glass condenser and a rubber septum through which aqueous H202 could be injected using a feed pump (Sage instruments, USA), 10 g of cyclohexanone, 12 g (22 wt%) of ammonia solution, and 1 g of solid iron tricyano pthalocyanine were stirred at 60°C. An aqueous solution of H202 (26 wt %, 13.3 g) was injected dropwise by a feed pump over a period of 4 hr. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The conversion of cyclohexanone was 32% wt and the yield of cyclohexanoneoxime was 31% wt. The yield of peroxy dicyclohexy-lamine was 1 % wt. Example-8 In a three-necked glass flask (200 ml capacity) fitted with a mechanical stirrer, a glass condenser and a rubber septum through which aqueous H202 could be injected using a feed pump (Sage instruments, USA), 10 g of cyclohexanone, 12 g (22 wt%) of ammonia solution, 15 g of acetonitrile solvent and 1 g of solid copper tricyano pthalocyanine were stirred at 60°C. An aqueous solution of H202 (26 wt %, 13.3 g) was injected dropwise by a feed pump over a period of 4 hr. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The conversion of cyclohexanone was 12% wt and the yield of cyclohexanoneoxime was 11% wt. The yield of peroxy dicyclohexy-lamine was 1 % wt. Example-9 In a three-necked glass flask (200 ml capacity) fitted with a mechanical stirrer, a glass condenser and a rubber septum through which aqueous H202 could be injected using a feed pump (Sage instruments, USA), 10 g of cyclohexanone, 12 g (22 wt%) of ammonia solution, 15 g of acetonitrile solvent and 1 g of solid cobalt tetra deca chloro phthalocyanine encapsulated in the aluminosilicate molecular sieve-X were stirred at 60°C. An aqueous solution of H2O2 (26 wt %, 13.3 g) was injected dropwise by a feed pump over a period of 4 hr. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The conversion of cyclohexanone was 45% wt and the yield of cyclohexanoneoxime was 44% wt. The yield of peroxy dicyclohexy-lamine was 1 % wt. Example-10 In a three-necked glass flask (200 ml capacity) fitted with a mechanical stirrer, a glass condenser and a rubber septum through which aqueous H202 could be injected using a feed pump (Sage instruments, USA), 10 g of cyclohexanone, 12 g (22 wt%) of ammonia solution, 15 g of acetonitrile solvent and 1 g of solid copper tetra deca chloro pthalocyanine encapsulated in the aluminosilicate molecular sieve-Y were stirred at 60°C. An aqueous .solution of H202 (26 wt %, 13.3 g) was injected dropwise by a feed pump over a period of 4 hr. At the end of the redaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The conversion of cyclohexanone was 53% wt and the yield of cyclohexanoneoxime was 51% wt. The yield of peroxy dicyclohexy-lamine was 2 % wt. Example-11 In a three-necked glass flask (200 ml capacity) fitted with a mechanical stirrer, a glass condenser and a rubber septum through which aqueous H202 could be injected using a feed pump (Sage instruments, USA), 10 g of cyclohexanone, 12 g (22 wt%) of ammonia solution, 15 g of methanol solvent and 1 g of solid copper tetra deca chloro pthalocyanine encapsulated in polystyrene were stirred at 60°C. An aqueous solution of H202 (26 wt %, 13.3 g) was injected dropwise by a feed pump over a period of 4 hr. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The conversion of cyclohexanone was 14% wt and the yield of cyclohexanoneoxime was 11% wt. The yield of peroxy dicyclohexy-lamine was 3 % wt. Example-12 In an autoclave, 10 g of cyclohexanone, 12 g (22 % wt) ammonia solution 1 g of solid copper tetra deca bromo pthalocyanine, 15 g of acetonitrile solvent, and 0.08 g of tert. butyl hydroperoxide promoter were stirred at 60°C with a continuous bubbling of air for 6 hrs. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The conversion of cyclohexanone was 9.4% wt and the yield of cyclohexanoneoxime was 9.1% wt. The yield of peroxy dicyclohexy-lamine was 0.3 % wt. Example-13 In an autoclave, 10 g of cyclohexanone, 12 g (22 % wt) ammonia solution 1 g of solid manganese tetra nitro pthalocyanine encapsulated in the aluminosilicate molecular sieve-X, 15 g of acetonitrile solvent, and 0.08 g of tert. butyl hydroperoxide promoter were stirred at 60°C with a continuous bubbling of air for 6 hrs. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The conversion of cyclohexanone was 11.9% wt and the yield of cyclohexanoneoxime was 11.9. Example-14 In an autoclave, 10 g of cyclohexanone, 12 g (22 % wt) ammonia solution 1 g of solid cobalt tricyano pthalocyanine encapsulated in polystyrene, 15 g of acetonitrile solvent, and 0.08 g of tert. butyl hydroperoxide promoter were stirred at 60°C with a continuous bubbling of air for 6 hrs. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The conversion of cyclohexanone was 19.4 % wt and the yield of cyclohexanoneoxime was 12.1% wt. The yield of peroxy dicyclo-hexylamine was 7.3 % wt. Example-15 In an autoclave, 10 g of cyclohexanone, 12 g (22 % wt) ammonia solution 1 g of solid iron tetra phenyl porphyrin, 15 g of acetonitrile solvent, and 0.08 g of tert. butyl hydroperoxide promoter were stirred at 60°C with a continuous bubbling of air for 6 hrs. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The conversion of cyclohexanone was 29.7% wt and the yield of cyclohexanoneoxime was 29.1% wt. The yield of peroxy dicyclo-hexylamine was 0.6 % wt. Example-16 In an autoclave, 10 g of cyclohexanone, 12 g (22 % wt) ammonia solution 1 g of solid manganese hexa chloro tetraphenyl porphyrin encapsulated in the aluminosilicate molecular sieve-Y, 15 g of methanol solvent, and 0.08 g of tert. butyl hydroperoxide promoter were stirred at 60°C with a continuous bubbling of air for 6 hrs. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The conversion of cyclohexanone was 34.4% wt and the yield of cyclohexanoneoxime was 29.1% wt. The yield of peroxy dicyclo-hexylamine was 5.1 % wt. Example-17 In a three-necked glass flask (200 ml capacity) fitted with a mechanical stirrer, a glass condenser and a rubber septum through which aqueous H202 could be injected using a feed pump (Sage instruments, USA), 10 g of cyclohexanone, 12 g (22 wt%) of ammonia solution, and 1 g of solid chromium tetra phenyl porphyrin encapsulated in polystyrene were stirred at 60°C. An aqueous solution of H202 (26 wt %, 13.3 g) was injected dropwise by a feed pump over a period of 4 hr. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography. The conversion of cyclohexanone was 32% wt and the yield of cyclohexanoneoxime was 29% wt. The yield of peroxy dicyclohexy-lamine was 3 % wt. Example-18 In a three-necked glass flask (200 ml capacity) fitted with a mechanical stirrer, a glass condenser and a rubber septum through which aqueous H2O2 could be injected using a feed pump (Sage instruments, USA), 10 g of cyclohexanone, 12 g (22 wt%) of ammonia solution, 15 g of methanol and 1 g of solid manganese hexa chloro tetra phenyt porphyrin encapsulated in the aluminosilicate molecular sieve-Y were stirred at 60°C. An aqueous solution of H,0 (26 wt %, 13.3 g) was injected dropwise by a feed pump over a period of 4 hr. At the end of the reaction (6 hr), the reaction mixture was separated from the solid catalyst by centrifugation, extracted with diethyl ether and analysed by gas chromatography . The conversion of cyclohexanone was 51.5% wt and the yield of eyelohexanoneoxime was 51% wt. The yield of peroxy dicyclohexy-lamine was 0.4 % wt. We claim : 1. A process for the manufacture of cyclohexanoneox- ime which comprises reacting ammonia with cyclohexa- none in a ratio of 1 to 2 and an oxidant in a ratio of 1 to 1.5 with respect to cyclohexanone in the presence of a solid catalyst containing an organotran- sition metal complex wherein some or all of the hydro gen atoms of the said organotransition metal complex have been substituted by one or more electron withdraw ing groups encapsulated in solid matrix at a tempera- o o ture in the range of 20 C to 90 C, at a pressure in the range of 15 to 1000 psi optionally in presence of solvent or promoter and isolating the cyclohexanoneox-ime formed by extraction with ether. 2. A process as claimed in claim 1, wherein the oxidant is hydrogen peroxide or molecular oxygen. 3. A process as claimed in claim 1, wherein the molar ratio of ammonia to cyclohexanone 1.2. 4. A process as claimed in claim 1, wherein the molar ratio of oxidant to cyclohexanone is preferably 1.3. 5. A process as claimed in claim 1 wherein the orga notransition metal complex solid catalysts are phthalo- cyanines or porphyrins. 6. A process as claimed in claim I and 5 wherein the transition metal used in organotranisition metal com plex is selected from iron, cobalt, copper, chromium, manganese or mixtures thereof. 7. A process as claimed in claim 1 wherein the said electron withdrawing group in organotranisition metal complex is selected from the halogens, the nitro group, the cyano group or mixtures thereof. 8. A process as claimed in claim 1 wherein the ammox- idation reaction is carried out in the presence of solvents sselected from acetonitrile and methanol. 9. A process as claimed in claim 1 wherein a promot er used is alkyl hydroperoxide, dialkyl peroxide or mixtures thereof. 10. A process as claimed in claim 9 wherein the con centration of the promoter in the reaction mixture does not exceed 1% by weight of cyclohexanone. 11. A process as claimed in claim 10 wherein the encapsulated solid matrix used is an inorganic oxide selected from silica, alumina, aluminosilicates or molecular sieves selected from zeolites or an organic polymer selected from polystyrene. 12. A process for the manufacture of cyclohexanoneox-ime substantially as herein above with reference to the examples.

Documents:

696-del-1996-abstract.pdf

696-del-1996-claims.pdf

696-del-1996-correspondence-others.pdf

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696-del-1996-description (complete).pdf

696-del-1996-form-1.pdf

696-del-1996-form-2.pdf

696-del-1996-form-4.pdf