United States Patent (19) 11, 3,989,755 McCoy et al. (45) Nov. 2, 1976 54 PRODUCTION OF OXIMES BY THE (56) References Cited REACTION OF CARBON MONOXDE WITH UNITED STATES PATENTS NTROCOMPOUNDS 2,945,065 7/1960 Donaruma...................... 260/566 A 75) Inventors: John J. McCoy, Media; John G. 3,480,672 11/1969 Kober et al..................... 260/566 A Zajacek, Strafford, both of Pa.; Karl 3,734,964 5/1973 Knifton........................... 260/566. A E. Fuger, Therwil, Switzerland (73) Assignee: Atlantic Richfield Company, Los Primary Examiner-Gerald A. Schwartz Angeles, Calif. Attorney, Agent, or Firm-Delbert E. McCaslin 22 Filed: Feb. 20, 1975 (21) Appl. No.: 551,487 57) ABSTRACT Related U.S. Application Data Production of oximes (and ketones) by contacting at 63) Continuation-in-part of Ser. No. 372,457, June 21, elevated temperatures and pressures, a primary or sec 1973, abandoned. ondary saturated aliphatic nitrocompound with carbon monoxide in the presence of a catalyst comprising me 52 U.S. C. ........................ 260/566 A; 260/586 C; tallic selenium or inorganic selenium compounds and 260/586 R; 260/593 R a base. (51 int. Cl”........................................ C07C 131/04 58) Field of Search........ 260/566 A, 586 A, 586 R, 20 Claims, No Drawings 260/593 R 3,989,755 2 cycloaliphatic nitrocompound is contacted with carbon PRODUCTION OF OXIMES BY THE REACTION OF monoxide at temperatures in the range of from 50° to 200 C. under pressures in the range of from 10 atmo CARBON MONOXIDE WITH NITROCOMPOUNDS spheres to 200 atmospheres in the presence of a sele nium catalyst and a base. RELATED APPLICATION It is an object of the present invention, therefore, to This application is a continuation-in-part of applica provide an improved process for the production of tion Ser. No. 372,457 filed June 21, 1973, entitled oximes. PRODUCTION OF OXIMES BY THE REACTION It is another object of this invention to provide a OF CARBON MONOXIDE WITH NITROCOM 0 process for the production of oximes and ketones. POUNDS now abandoned. It is another object of this invention to provide an efficient process for the production of oximes that FIELD OF INVENTION minimizes the formation of undesirable by-products. The present invention relates to a process for the It is another object of this invention to provide an manufacture of oximes (and ketones) by the reaction 15 efficient, high yield process for the production of an of carbon monoxide with a primary or secondary satu efficient, high yield process for the production of ox rated aliphatic nitrocompound, or a saturated cycloali imes from the reaction of primary or secondary satu phatic nitrocompound under elevated temperature and rated aliphatic nitrocompounds, or a saturated cycloal pressure conditions in the presence of a catalyst and a iphatic nitrocompound by using metallic selenium, or base. inorganic compounds of selenium or combinations Oximes are an important class of organic compounds thereof as a catalyst in conjunction with a base. and are of significant importance in industrial chemis It is another object of this invention to provide a try. Cyclohexanone oxime, for example is used as an process for the production of oximes which uses readily intermediate in the manufacture of caprolactam, an available, low cost starting materials. important fiber precursor, by the Beckmann rearrange 25. These and other objects of the invention will become ment. Other oximes, such as acetoxime, can be used as apparent from the following description of the process a source of the oxime moiety, instead of using hydrox and from the claims. ylamine itself. This can overcome the many disadvan tages in handling hydroxylamine solutions, and in the DESCRIPTION OF THE PROCESS subsequent workup of its reaction mixtures. Other 30 In the instant process the nitrocompound is, in gen open chain oximes such as methyl ethyl ketoxime, eral, largely converted to the oxime. In some cases, butyraldoxime, etc. are used commercially as anti-skin however, depending on the starting nitrocompound ning agents in paints. and the particular reaction conditions employed, the Although methods are available for the reduction of corresponding ketone can be formed. For example, aliphatic nitrocompounds to oximes, they have a num 35 when nitrocyclohexane is reacted under the conditions ber of disadvantages not found in the instant process. of this process to prepare cyclohexanone oxime, cyclo For example, in U.S. Pat. No. 3,480,672 there is de hexanone can be formed as a by-product. This ketone scribed a process for the reduction of aliphatic nitro can be easily converted to the oxime by reaction with compounds using carbonyl sulfide as a reducing agent. hydroxylamine or, if desired, simply separated from the This process requires the use of a large molar excess of 40 cyclohexanone oxime by any number of suitable sepa toxic carbonyl sulfide as compared to the starting nitro ration techniques. compound, gives a relatively low conversion for the Suitable nitrocompounds for the process of this in quantity of carbonylsulfide used and, apparently, is not vention are primary or secondary saturated aliphatic a catalytic reaction. In U.S. Pat. No. 2,945,065 there is mononitrocompounds and saturated cycloaliphatic described a method by which nitrocyclohexane is re 45 mono-nitrocompounds. The term "saturated' herein duced to the oxime by reaction with carbon monoxide refers to compounds which contain no olefinic or acet at an elevated temperature and pressure. However, this ylinic bonds but does not exclude the arylalkyl nitro process requires that the nitrocyclohexane be con compounds. Substituted or unsubstituted nitroalkanes verted to an alkaline nitronate salt in a previous and which are suitable include nitromethane, nitroethane, separate step. Further, this process requires the use of 50 1-nitropropane, 2-nitropropane, l-nitrobutane, 2 anhydrous conditions, an alkanol as a solvent (some of nitrobutane, 1-nitropentane, 1-nitro-1-methylpropane, which is also consumed as a reactant), and a higher 1-nitro-3-methylpropane, 2-nitro-3-ethylbutane, 1 temperature to achieve a convenient reaction rate than nitro-2,2-dimethylbutane, 1-nitro-3-methylbutane, 2 is required by the instant process. In U.S. Pat. No. nitro-4-methylpentane, 1-nitrohexane, 3-nitro-4,5- 3,734,964 there is described a method for partial re 55 dimethylhexane, 3-nitrododecane, nitrooctadecane, duction of a nitroparaffin to the corresponding oxime 5-nitro-7,8-dimethyloctadecane, and the like. Also using critical ratios of a copper salt catalyst, nitroge suitable are the nitrocycloalkanes such as nitrocyclobu nous base and water. This process requires that a base tane, nitrocyclopentane, nitrocyclohexane, nitrocy copper catalyst complex be formed and then passing cloheptane, nitrocyclooctane, nitrocyclododecane and carbon monoxide into a reaction mixture of the formed 60 the like including the alkyl substituted or halo substi complex and nitroparaffin. Other methods, well known tuted compounds. Likewise the aryl nitroalkyl com in the art, employing hydrogen as a reducing agent are pounds such as phenyl nitromethane, p-bromo-phenyl complicated by the undesirable reduction of the oxime nitromethand, p-toluyl nitromethane and the like are to an amine. suitable. These are merely representative of the com 65 pounds suitable, since in general any nitrocompound of SUMMARY OF THE INVENTION the types described containing up to 20 carbon atoms In accordance with this invention a primary or secon can be employed including mixtures of such nitrocom dary saturated aliphatic nitrocompound or saturated pounds. 3,989,755 3 4 Catalysts for use in this invention include selenium. It will be understood from the foregoing disclosure In addition, various compounds containing selenium that all of the disclosed catalysts, solvents and bases are can be used alone or in combination with selenium operable with all of the nitrocompounds disclosed for metal. One of the simpletstand least expensive forms of the production of the oximes. It will be distinctly under Selenium is the metal itself which can be as good, if not 5 stood, however, by those skilled in this art that every better, than most selenium compounds. Nevertheless, combination is not equally effective in maximizing good yields can be obtained with such compounds as Oxime production from a particular nitrocompound Selenium dioxide, titanium diselenide, sodium selenite, starting material since these vary widely in their reac Zinc selenite, zinc selenide, tungsten selenide, selenium tivity. sulfide and selenium disulfide. 10 The catalyst of this invention is preferably used in The catalyst material, as indicated above, can be molar ratios of 2:1 to 1000:1 of the nitrocompound to self-supported or the catalyst material can be deposited catalyst. Preferably, the molar amounts of the nitro on a support or carrier for dispersing the catalyst to compound to catalyst is in the range of from 5:1 to increase its effective surface. Alumina, silica, carbon, 100:1. It will be understood, however, that larger or asbestos, bentonite, diatomaceous earth, fuller's earth, 15 smaller amounts of catalyst can be used. The ratio of and analogous materials are useful as carriers for this base to nitrocompound can range from 0.01:1 to 10:1, purpose. Preferably, the carrier selected is one which is however, larger or smaller amounts can be used, for inert in the described process. example, when an amine is used as both solvent and A base must also be added to the reaction. Organic base the quantity of base is of necessity far in excess of bases, metal salts of carboxylic acids and metal hydrox 20 the molar quantity of the catalyst or of nitrocompound ides have been found to be effective. Organic bases since it must be and is sufficient to dissolve the nitro suitable for the reaction are tertiary amines such as compound.