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United States Patent 0 3,532,740 United States Patent 0 " IC€ Patented Oct. 6, 1970 1 2 5 3,532,740 CH2 0 0 OXIDATIVE DEHYDROGENATION PROCESS Charles W. Hargis, Johnson City, and Howard S. Young, Kingsport, Tenn., assignors to Eastman Kodak Com CH3 pany, Rochester, N.Y., a corporation of New Jersey 2 N 0 Drawing. Continuation-impart of application Ser. N 0. and 152,630, Nov. 15, 1961. This application May 18, 1966, Ser. No. 550,931 Int. Cl. C07c 45/12 US. Cl. 260-486 24 Claims 10 are oxidized to the corresponding alpha,beta-unsaturated derivatives This application is a continuation-in-part of our co pending application Ser. No. 152,630, ?led Nov. 15, 1961, now abandoned, which was copending with and a con tinuation-in-part of our application Ser. No. 10,107, ?led Feb. 23, 1960, now abandoned. This invention relates to selective oxidation of un 1 2 saturated aliphatic hydrocarbon derivatives. More par and ' ticularly the invention relates to selective oxidation of B a an alkyl derivative having a functional group in which functional unsaturation occurs, to produce a correspond ing ole?nic derivative. We have found that selective oxidation of the alpha, The principal object of the invention is to provide a beta-carbon atoms of the alkyl radical is accomplished method for selective oxidation of a compound consisting by action of an oxidizing agent consisting of one of, or of a lower alkyl radical attached to a functional group 25 a mixture of, the oxides of arsenic, antimony, and bis in which functional unsaturation occurs, and by such muth. When contacted with the “functionally unsatur oxidation to produce the corresponding alpha-beta un ated” organic compound at elevated temperatures, the saturated compound. Another object of the invention is metal oxide is reduced and yields oxygen which combines to provide a method for reacting an aliphatic derivative with hydrogen from the alpha and beta carbon atoms of with an oxide of antimony, arsenic bismuth to produce the oxidized compound. An alpha,beta-unsaturated com such alpha-beta unsaturated ole?nic derivatives. pound is produced. The invention provides a method for selective oxida Therefore, according to the invention, vapor of a com tion at the alpha and beta carbon atoms of the alkyl pound having the formula: radical in compounds consisting of a lower alkyl radical R1—CH—CH—X attached to a functional group in which functional un IIW Ila saturation occurs between the ?rst carbon atom and an wherein X is a functional group in which functional un— adjacent atom. saturation occurs between the ?rst carbon atom and an By “functional unsaturation” as the term is used in adjacent atom, is contacted at a temperature above 100° this speci?cation we mean an unsaturated linkage, either 40 C. with at least one memben selected from the group con a double bond or a triple bond, between two atoms of a sisting of oxides of arsenic, antimony, and bismuth. functional group (between the ?rst carbon atom and an In the foregoing formulae for the functionally unsatur adjacent atom of the functional group in the instance of ated compounds useful in the process of our invention the invention). To illustrate, in the functional group of the substituent X is typically of the formula: ketone 0 H C (10) functional unsaturation as we use the term occurs at the double bond between C and 0. or Functional unsaturation occurs between the ?rst car (c) bon atom and an adjacent atom in the following func tional groups for instance: ’ in 'which R4, when taken singly, is typically hydrogen, alkyl, hydroxy, or alkoxy. The substituents R1, R2, and R3, when taken singly are hydrogen or alkyl. The sub stituents R1 and R3, when taken collectively, represent joined alkylene groups completing a saturated carbo cyclic ring having 5 to 6, preferably 6, carbon atoms in the ring; and the substituents R1 and R4, when taken collectively, represent joined alkylene groups complet ing a saturated carbocyclic ring having 5 to 6, preferably 6, carbon atoms in the ring. The substituents R1, R2, R3 and R4, when alkyl, are typically alkyl of 1 to about 8 carbon atoms and are preferably lower alkyl, e.g., alkyl of 1 to about 4 carbon 65 atoms. When R4 is alkoxy, it typically contains an alkyl moiety of 1 to about 8 carbon atoms. The alkyl moiety of the alkoxy group represented by R4 is preferably lower alkyl, e.g., alkyl of 1 to about 4 carbon atoms. Typical of the alkyl groups represented by R1, R2, R3, 70 and R4 are methyl, ethyl, propyl, isopropyl, butyl, iso Thus, alkyl derivatives such as butyl, sec-butyl, tert-butyl, etc.'The substituent R4, when 3,532,740 4 alkoxy, is typically methoxy, ethoxy, propoxy, isopro the ratio of bulk contact mass volume (for instance in poxy butoxy, isobutoxy, sec-butoxy, tert-butoxy, etc. cubic feet) to reactant vapor feed rate (for instance in When R1 and R3 collectively represent joined alkylene cubic feet per second). This is to be distinguished from groups completing a carbocyclic ring, the carbocyclic exposure time for the metal oxide which is the total rings so represented are typically cyclopentyl or cyclo time a sample of solid metal oxide is exposed to reactants hexyl. When R1 and R4 collectively represent joined in the reaction zone. alkylene groups completing a carbocyclic ring, the carbo To the extent found necessary, temperature in the re cyclic rings so represented are typically cyclopentyl or action zone may be regulated by controlling feed tem cyclohexyl. _ perature and, when a diluent is used, by controlling the The alpha,beta-unsaturated compounds formed in the 10 ratio of diluent to reactant in the feed stream. The reac process of our invention can be represented by the for tion proceeds at a temperature above about 100° C. and mula: reactions conducted at temperatures between about 325° C. and 475° ‘C. give good product yields. Good yields are obtained at atmospheric pressure which is pre ferred for economic reasons, but the pressure in the re in which R1, R21, R3 and X are as de?ned hereinbefore, action zone may be varied. when the functionally unsaturated compound employed The oxide or mixture of oxides selected for a particular has only one alpha-beta position capable of being 0x1 reaction and the valence state of the oxide or mixture datively dehydrogenated. of oxides must be considered as factors having marked When the functionally unsaturated compound has two 20 in?uence on the choice of operating conditions. An oxide or more alpha-beta positions capable of being oxidatrvely in which the metallic element is present in a higher val dehydrogenated, dehydrogenation can occur at both POSI ence state, a valence of 5 for example, is more vigorous tions. Thus, diethyl ketone can react with antimony in oxidative action than one in a lower valence state. tetroxide to form divinyl ketone. In a particularly in Less severe operating conditions such as lower reaction teresting embodiment of this aspect of our invention, temperature and decreased contact time can therefore be cyclohexanone reacts with an inorganic oxide apparently employed when an oxide of the higher valence state is to form 2,5-cyclohexadiene-1-one or 2,4-cyclohexadiene used. Also, oxidation activity of the metal oxides in a l-one which immediately rearranges to phenol. given valence state tends to increase as oxides of metal Typical of the functionally unsaturated compounds in descending order in the periodic series are selected. which are useful in the process of our invention are com 30 For example, arsenic pentoxide requires higher operating pounds such as propionaldehyde, methyl ethyl ketone, temperatures and/or more prolonged contact times for propionic acid, methyl propionate, cyclohexanone, ethyl a comparable production of unsaturates than does anti benzene, l-butene, cyclohexanecarboxaldehyde, methyl mony pentoxide. The ?exibility in operating conditions cyclohexanecarboxylate, cyclohexanecarboxylic ac1d, made possible by varying degrees of oxidation activity cyclohexyl benzene, etc. 03 Gr of the oxides or mixtures thereof can be of considerable The process of our invention involves a reaction be importance in selection of a suitable oxide and suitable tween the functionally unsaturated compound and the operating conditions, since the heat stability and reac selected metal oxide or oxy-acid thereof. For example, tion stability of the various organic compounds which isobutyraldehyde, reacts with arsenic pentoxide to form may be oxidized will differ. methacrolein, water, and a reduced form of the arsenic 40 Some of the organic compounds which may be oxidized pentoxide, e.g., arsenic trioxide or elemental arsenic. according to the invention possess suf?cient stability to The mechanics of the process consist simply of con allow feeding of some air into the reaction zone with tacting the organic compound to be oxidized with a the organic compound. The advantage of introducing metal oxide in a reaction zone at a temperature between air with the feed stream is that the exposure time for the 100° C. and 600° C., preferably between 150° C. and oxidizing agent is extended because some of the reduced 500° C. This is conveniently done by passing a stream metal oxide in the reaction zone is reoxidized by the air of vapor of the organic compound through a reaction introduced with the feed stream. But in some-cases pres vessel packed with particles of the selected metal oxide. ence of air will cause excessive side reactions which will Fine particles of the metal oxide are preferred because reduce the product yield substantially. Ethylbenzene is more surface area per unit of volume will be available ' an example of a compound with which air may be intro for contact with the organic vapor.
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