Patent GB-1101229-A (GB)
Title: Molecular rearrangement of oximes
IPC: C07D201/04
Filed: 1965-10-25
Abstract: A crystalline aluminosilicate containing active cation sites within an ordered internal structure having a pore size, preferably of at least 6<\>rA, is suitable for use as a catalyst in Beckmann rearrangements of oximes to amides (see Division C2). The silicon to aluminium ratio is preferably at least 1.8.  The active cation sites may be produced from cations of exchangeable metals, ammonium, hydrogen or mixtures thereof.  The catalyst may contain cations of the rare earth metals, cobalt, nickel, zinc, alkali metals or alkaline earth metals.  Suitable aluminosilicates are fanjasite or homologues thereof, dadriardite or mordenite. Hydrogen exchanged catalysts may be prepared by base exchange of the aluminosilicate with a fluid medium containing hydrogen ions. In the case of some aluminosilicates it is necessary to incorporate metal cations as well as hydrogen ions in order to achieve stability.  Polyvalent metal cations particularly those of the rare earth metals, are especially effective.  The incorporation of these ions also increases the hydrogen ion concentration without subsequent base exchange of hydrogen ions. The concentration of hydrogen ion sites may be further increased by incorporation of cations capable of being converted into hydrogen ions, e.g. NH4+.  The rare earth cations may be provided from the salt of a single metal or preferably mixtures, e.g. didynium chloride.  In examples, rare earth exchanged fanjasites, zinc, nickel and cobalt exchanged fanjasites, a hydrogen exchanged fanjasite and hydrogen exchanged mordenite are employed.ALSO:Amides including lactams are prepared by a Beckmann rearrangement of the corresponding oximes in the presence of a catalyst comprising a crystalline aluminosilicate containing active cation sites within an ordered internal structure, the ordered internal structure having a pore size sufficient to admit the oxime.  The oxime may be an acylic, alicyclic, aliphatic-aromatic or heterocyclic compound containing 3 to 20 carbon atoms and at least one oxime group. The oxime may have substituents of alkyl, aryl, nitro, bromo, chloro, iodo, carbonyl, hydroxy, amino and/or cyano.  The process is preferably carried out at from 100 DEG  to 450 DEG  C. and from atmospheric to superatmospheric pressures. The process may be carried out in an organic solvent or under sufficient pressure to maintain a liquid phase.  A carrier gas of hydrogen, nitrogen, helium, carbon dioxide, carbon monoxide, sulphur dioxide or mixtures thereof may be used. Examples describe the preparation of caprolactam, acetanilide and N-methylacetamide. 5-Cyano-pentene-1 is produced as a by-product of the caprolactam production. Other products which may be prepared are N-ethyl - p - chloroacetanilide, 3 - methyl- and 5-methyl-6-caprolactam, valerolactam and 2-acetamidothiophene.ALSO:A catalyst, useful in Beckmann rearrangement of oximes to amides (see Division C2), comprises a crystalline aluminosilicate containing active cation sites within an order internal structure having a pore size sufficient to admit the oxime.  The pore size should preferably be at least 6  and the silicon to aluminium ratio at least 1.8. Suitable alumino-silicates are fanjasite or its homologues, dachiardite and mordenite.  The active cation sites may be produced from cations of exchangeable metals, ammonium, hydrogen or mixtures thereof.  The catalyst may contain cations of rare earth metals, cobalt, nickel, zinc, alkali metals or alkaline earth metals.  The catalyst may be combined with suitable supports or binders, e.g. dried inorganic oxide gels, gelatinous precipitates of alumina, silica, zinconia, magnesia, thoria, titania, to boria or combinations of these, activated charcoal, mullite, Kieselguhr, bauxite, silicon carbide, sintered alumina and various clays.  They may be prepared by growing crystals of aluminosilicate in the pores of the support.  The catalyst may also be intimately composited with a suitable binder such as an inorganic oxide hydrogel or clay for example by ball milling the two materials together over an extended period of time preferably in the presence of water.  The catalyst may be distributed throughout a gel matrix by dispersing it in powdered form in an inorganic oxide hydrosol.  The inorganic oxide gel may be a gel of any hydrous inorganic oxide, e.g. aluminous or siliceous.  Preferably a cogel of silica and an oxide of metals of Groups IIA, IIIB or IVA is employed.  Certain carrier gases such as hydrogen and sulphur dioxide are found to extend the catalyst life and improve yields. The catalyst may be regenerated in a cyclic process or subsequent to its use in a batch operation by burning the contaminants off in an air stream at 550 DEG C for one to three hours.