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WO1993008160A1 - Procede de preparation d'une cetoxime - Google Patents

Procede de preparation d'une cetoxime Download PDF

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Publication number
WO1993008160A1
WO1993008160A1 PCT/NL1992/000215 NL9200215W WO9308160A1 WO 1993008160 A1 WO1993008160 A1 WO 1993008160A1 NL 9200215 W NL9200215 W NL 9200215W WO 9308160 A1 WO9308160 A1 WO 9308160A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
process according
peroxo
preparation
ketoxime
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/NL1992/000215
Other languages
English (en)
Inventor
Kjell Erik Bugge
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Koninklijke DSM NV
Original Assignee
DSM NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DSM NV filed Critical DSM NV
Publication of WO1993008160A1 publication Critical patent/WO1993008160A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes

Definitions

  • the invention relates to a process for the preparation of a ketoxime by reaction of an alkanone with ammonia and a peroxide under the influence of a catalyst on the basis of a transition metal.
  • Such a process is known from JP-A-51.19743, which describes the preparation of a cycloalkanone oxime with utilization of an organic hydroperoxide.
  • the catalyst used in that process is a metal compound, the metal being chosen from the group III b -VI b , or the lanthanides or actinides o the Periodic System of the Elements.
  • the organic hydroperoxide is reduced to the corresponding alcohol. It has appeared, however, that such a process has number of drawbacks which have an adverse effect on the process operation and the selectivity.
  • thi is achieved due to the preparation of the ketoxime being effected with a catalyst containing a metal-peroxo complex.
  • Metal-peroxo complexes are known per se. Reference can be made to the publication by H. Mimoun in 'The Chemistry of Functional Groups, Peroxides', 1983, pages 464 82, issued by John Wiley & Sons, Ltd. (Edt. S. Patai). In this overview articles the properties and syntheses of suc peroxo complexes are described.
  • peroxo complexes are eminently suitable for preparation of a ketoxime starting from an alkanone and ammonia.
  • the peroxo complexes that are suitable for the invention can be described in general as:
  • M represents: a transition metal from the groups IVB, VB, VIB, VIIB, VIII and IB,
  • L one or more ligands
  • R hydrogen or an organic radical group.
  • a transition metal in the complex is started from. Vanadium, cobalt, platinum, palladium, molybdenum, chromium, titanium, zirconium, tungsten, osmium and iridium in particular have been found to be suitable transition metals for the invention. In general, it is possible to use more than one metal in such a catalyst.
  • the following radical groups can be used as ligand L at the complex (for a more detailed description, reference can be made to for instance DE-A-3.135.008, in particular pp.
  • the substituent may be either R or H (which means that the peroxo part may originate from hydrogenperoxide (H 2 0 2 ) ) or an organic radical group with 1-30 carbon atoms, such as alkyl, aralkyl, cycloalkyl and the like, which group may be either substituted or not.
  • R is preferably alkyl or cycloalkyl.
  • a catalyst is used with the peroxo part originating from the hydroperoxide which is formed in the oxidation of the alkane corresponding to the alkanone.
  • the process is in particular very suitable for application of primary, but preferably secondary hydroperoxides, because in the reaction according to the state of the art, these relatively easily cause side reactions leading to low selectivity.
  • a cycloalkylhydroperoxide is applied, such as for instance cyclohexylhydroperoxide, cyclooctylhydroperoxide or cyclododecylhydroperoxide.
  • the hydroperoxides can already be used in low concentrations. It is possible for instance to apply alkylhydroperoxide-containing mixtures which are formed in the preparation of an alkylhydroperoxide by oxidation of an alkane with oxygen.
  • the process according to the invention can be applied for the reaction between any alkanone and ammonia, giving the corresponding ketoxime.
  • substituted or non-substituted aliphatic as well as cycloaliphatic ketones, preferably with 3-30 carbon atoms, can be used.
  • Other examples are cyclooctanone oxim and cyclododecanone oxim.
  • the alkanone started from is cyclohexanone, because the reaction product, cyclohexanone oxime, is a very suitable starting material for the preparation, via a Beckmann rearrangement, of caprolactam, the starting material for nylon 6.
  • a carrier material for immobilize the metal-peroxo complex on a carrier material so that the catalyst becomes heterogeneous and, for instance, is easily separated from the reaction mixture.
  • any method for anchoring of catalysts on a carrier which is known in the art and has appeared to be suitable.
  • one of the ligands chosen for the metal-peroxo complex can be of a type that will form a bond with the carrier material applied.
  • a ligand containing an amine or amide group which reacts with a carrier with hydroxyl groups, such as ⁇ -alumina or anatase (Ti0 2 ).
  • a carrier with hydroxyl groups such as ⁇ -alumina or anatase (Ti0 2 ).
  • the alkanolate thus formed does not affect the activity and selectivity of the reaction, which is in contrast to the known state-of-the-art processes, in which alcohols appear to have a negative effect. This is the case in particular if the reaction is carried in the virtual absence of water.
  • the alkanolate probably remains bonded to the metal complex then.
  • every reaction step is carried out in the virtual absence of water.
  • water- extracting agents are added to the reaction mixture, such as for instance mol sieves.
  • the metal complex is separated out after the preparation of the ketoxime, and the complex is reacted with the desired peroxide compound so that the catalyst is oxidized to the metal-peroxo complex.
  • the alcohol thereby released can be removed.
  • the formation of the peroxo complex is carried out at a temperature of 0-50°C, in any case at a temperature which is so low that no significant thermal or catalytic decomposition of the peroxide or of the complex occurs.
  • the preparation of the ketoxime may or may not take place in a solvent.
  • suitable solvents reference can be made to JP-A-51.19743, except for alcohols which the applicant has found to have a decelerating effect on the catalytic activity of the complex or not to be chemically inert.
  • the temperature at which the preparation takes place is between 0 and 200°C, preferably between 40 and 160°C, more in particular between 60 and 120°C.
  • the pressure applied is generally between 0.1 and 10 MPa.
  • a catalyst concentration calculated as moles of transition metal in the peroxo complex per mole of alkanone, of 5:1 to 1:10 is applied.
  • a molar alkanone/ammonia ratio of 2:1 to 1:100 is applied; in this range the oxime yield is optimum. More preferably, an excess of ammonia is applied.
  • the reaction may be carried out for instance in a plug flow reactor as well as in a stirred tank reactor, depending on parameters such as type of catalyst, the natur of side reactions occurring, etc. A person skilled in the art is very well capable of making a responsible choice here.
  • the ketoxime obtained can be removed from the reaction product by processes known per se and be recovered as such or be used as starting material for a subsequent process, the cyclohexanone oxime for instance for production of caprolactam. Due to the process according to the present invention it is achieved in that case that the traditional formation of cyclohexanone oxime, i.e. from cyclohexanone and hydroxylamine, is not necessary any more.
  • the principal advantage of this lies in the option to do without a complicated hydroxylamine preparation, which in some cases will result in a substantial reduction of the amount of ammoniumsulphate obtained as side product in the preparatio of hydroxylamine.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de préparation d'une cétoxime, consistant à mettre un alcanone en réaction avec un peroxyde et de l'ammoniac en présence d'un catalyseur à base d'élément de transition, le procédé étant caractérisé en ce que le catalyseur renferme un complexe métal-peroxo. On a également prévu un procédé selon lequel on enlève le catalyseur après la préparation d'une cétoxime, et on récupère ladite cétoxime; on soumet le catalyseur à l'oxydation en présence d'un hydroperoxyde, puis on enlève le catalyseur et on le réutilise dnas la préparation d'une cétoxime.
PCT/NL1992/000215 1991-10-24 1992-10-20 Procede de preparation d'une cetoxime Ceased WO1993008160A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE9100986 1991-10-24
BE9100986A BE1005476A3 (nl) 1991-10-24 1991-10-24 Werkwijze voor de bereiding van een ketoxime.

Publications (1)

Publication Number Publication Date
WO1993008160A1 true WO1993008160A1 (fr) 1993-04-29

Family

ID=3885774

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1992/000215 Ceased WO1993008160A1 (fr) 1991-10-24 1992-10-20 Procede de preparation d'une cetoxime

Country Status (3)

Country Link
AU (1) AU2931092A (fr)
BE (1) BE1005476A3 (fr)
WO (1) WO1993008160A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1342714A1 (fr) * 2002-03-08 2003-09-10 Daicel Chemical Industries, Ltd. Procédé de préparation de composés azines et oximes
EP2354119A1 (fr) * 2010-02-04 2011-08-10 Universiteit van Amsterdam Procédé catalytique pour la production d'oximes de composés carbonyles
WO2011095563A1 (fr) 2010-02-04 2011-08-11 Universiteit Van Amsterdam Procédé catalytique pour l'ammoximation de composés carbonyles
US8278487B2 (en) 2010-02-04 2012-10-02 Dsm Ip Assets B.V. Catalytic process for the ammoximation of carbonyl compounds

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0384390A1 (fr) * 1989-02-21 1990-08-29 Enichem Anic S.r.l. Procédé catalytique pour la préparation d'oximes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0384390A1 (fr) * 1989-02-21 1990-08-29 Enichem Anic S.r.l. Procédé catalytique pour la préparation d'oximes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 85, no. 7, 16 August 1976, Columbus, Ohio, US; abstract no. 46056f, 'CYCLOALKANONE OXIMES' page 481 ; cited in the application *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1342714A1 (fr) * 2002-03-08 2003-09-10 Daicel Chemical Industries, Ltd. Procédé de préparation de composés azines et oximes
US7034184B2 (en) 2002-03-08 2006-04-25 Daicel Chemical Industries, Ltd. Process for producing azine compounds and oxime compounds
EP2354119A1 (fr) * 2010-02-04 2011-08-10 Universiteit van Amsterdam Procédé catalytique pour la production d'oximes de composés carbonyles
WO2011095563A1 (fr) 2010-02-04 2011-08-11 Universiteit Van Amsterdam Procédé catalytique pour l'ammoximation de composés carbonyles
US8278487B2 (en) 2010-02-04 2012-10-02 Dsm Ip Assets B.V. Catalytic process for the ammoximation of carbonyl compounds

Also Published As

Publication number Publication date
BE1005476A3 (nl) 1993-08-03
AU2931092A (en) 1993-05-21

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