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United States Patent Office Patented Jan 2,729,650 United States Patent Office Patented Jan. 3, 1956 2 1. pound having, in the molecule, at least two hydroxyl groups attached to a carbon chain with carbon monoxide 2,729,650 and hydrogen under the conditions of the Oxo reaction. PRODUCTION OF DALDEHYDES AND Preferred cyclic acetals are of the type formed by con DERVATIVES THEREOF densation of unsaturated aldehydes with aliphatic diols having, in the molecule, a carbon chain and hydroxyl JohnJohn Habeshaw, Geach, Shepperton, Clackmannshire, Middlesex, Scotland, England, and assignors Charles groups attached to adjacent carbon atoms or to carbon to The British Petroleum Company Limited atoms separated by one carbon atom, these diols being No Drawing. Application March 10, 1951, of the general formula: Serial No. 215,023 0 Ho-d-R,Rs Claims priority, application Great Britain March 31, 1950 R 10 Claims. (CI. 260-340.7) This invention relates to the production of dialdehydic 5 . organic compounds. More particularly it relates to the HO-C-Rs Synthesis of dialdehydes and derivatives thereof from acetals of olefinically unsaturated aldehydes. The term "dialdehydic organic compound” is used here and in with reference to dialdehydes and to mono- and di 20 Rs acetalsIt is thereof.now well-known that aldehydes may be produced Ho-0-R, from mono-olefines by reaction with carbon monoxide Ho-0-R, and hydrogen, in the presence of a catalyst, under suit s able conditions of temperature and pressure. The reac 25 the acetals produced therefrom being of the general tion is generally known as the Oxo reaction. As feedstock to the Oxo reaction it is possible to use, formulae, respectively: in place of a simple olefin, an unsaturated organic com R pound containing also a functional group but the yield o- -Rs of aldehydes obtained varies considerably according to 30 theIt chemical has been nature found of hitherto the feedstock. that unsaturated compounds R-CH having, in the molecule, an aldehydic group usually give poor yields of the primary product, that is, the dialdehyde formed by carbonylation at the double bond. This is 35 due in part to the occurrence of secondary reactions in the reaction zone, particularly polymerisation, and in . part to difficulties of product recovery which is complicat ed by the unstable nature of the dialdehydes. Attempts to reduce the activity of the aldehyde group present initial 40 ly, for example, by condensation of the aldehyde group with Suitable reagents and reaction of the product in the Oxo reaction, have not led to any marked improve ment in the yields of the primary carbonylation product. where R1 is an aliphatic or cycloaliphatic radical contain Thus acrolein has been converted to its dimethyl and di ing at least one carbon to carbon double bond. R2, R3, ethyl acetals but poor yields of bifunctional materials have R4, R5, Re and Ri are hydrogen or substituted or unsub been obtained by the use of these materials as feed stituted radicals selected from the group comprising ali stocks to the Oxo reaction. Acrolein has also been con phatic, cycloaliphatic and aryl radicals. '. verted to its diacetate and reasonable yields of succindi Olefinically unsaturated aldehydes which may be em aldehyde diacetate produced therefrom in the Oxo reac 50 ployed for the formation of these compounds include ali tion. The diacetate is, however, difficult to handle and phatic aldehydes such as acrolein, methacrolein, crotonal the main product of the Oxo reaction only isolated from dehyde and ethylpropylacrolein and cyclic aldehydes such by-products of the reaction with difficulty and in poor as Diolstetrahydrobenzaldehydes. which may be employed for the formation of the yields.It is an object of the invention to provide a process cyclic acetals include 1,2 glycols, for example ethylene for the production of dialdehydes and derivatives thereof. glycol and pinacol and 1,3 glycols, for example 1:3 It is a further object to provide a process for the produc butylene glycol. With acrolein, very satisfactory re tion of derivatives of dialdehydes by the Oxo reaction suits are obtained using 1:3 butylene glycol. When in good yields and in a form in which they are recoverable tetrahydrobenzaldehyde is employed the preferred diol is 60 ethylene glycol. fromIt hasthe reactionnow been product. found unexpectedly, in view of the Conditions for the condensation of aldehydes and gly Poor results obtained using simple acetals, that cyclic cols are well known in the art. Descriptions of such acetals formed by the reaction of unsaturated aldehydes processes are to be found in German specification No. and diols undergo the Oxo reaction to produce the primary 434,989 and by Lapworth and Haworth, in the Journal 65 of the Chemical Society (1922), 79. product in good yields, the product being, in general, re The Oxo reaction is preferably carried out in the pres coverable from the reaction product without substantial ence of a cobalt catalyst, at a temperature in the range loss.According to the invention, the above objects are ac 120 C-200 C. and at a pressure of 50-300 atmospheres complished by a process which comprises reacting a cyclic 70 or Theeven reaction higher. may be carried out in solvents inert under acetal, of the type formed by condensation of an ole finically unsaturated aldehyde with an aliphatic com the conditions used. Lower aromatic hydrocarbons (e.g. 3. benzene, toluen xylene) naphthenes (e. g. cyclohexane, 4 methylcyclohexane) or paraffins (e.g. pentanes, hexanes, and under milder and more economical conditions than etc.) are suitable and readily available materials for this have hitherto been considered feasible. purpose. It is, in general, advantageous to employ a The fluid catalyst may be prepared in the form of a feedstock free of organic acids since these acids depress solution by the use of any solvent which is inert to the the reaction rate. 5 said catalyst and which will not prevent the subsequent The preferred cobalt catalysts for use in the synthesis use of the catalyst in the Oxo synthesis reaction. reaction are cobalt carbonyls, introduced into the synthe According to one method, the solvent and carbon sis reactors in the liquid or gaseous phase. The term monoxide-containing gas may be pumped concurrently or "cobalt carbonyl' is used herein with reference to true countercurrently, over a fixed bed of the cobalt-contain carbonyls having molecules consisting of cobalt atoms O ing material. and the group -CO, such as Co2(CO)8 and to carbonyl Suitable solvents have been found to be hydrocarbons hydrides, having molecules consisting of cobalt atoms, such as xylene, paraffins or cycloparaffins, ethers, esters, hydrogen atoms and the group -CO, such as Co(CO)4H. alkanols, such as octyl alcohol, and high-boiling prod The cobalt carbonyl catalyst may be produced by con ucts obtained in the Oxo synthesis reaction. If desired tacting carbon monoxide, alone or in the presence of other the high-boiling products may be hydrogenated before gases such as hydrogen or nitrogen, with a solid cobalt being used as solvents for the purpose described. containing material in a catalyst-generating zone at a According to one method of operation, for the produc temperature within the range 30° C.-250 C. and at a par tion of a gaseous catalyst a vessel is packed with a cobalt tial pressure of carbon monoxide of 20-300 atmospheres compound and maintained at a temperature of between to form a fluid cobalt containing compound. 20 30 C, and 250 C. A carbon monoxide-containing gas It is preferred that the fluid product of the catalyst (advantageously water gas) is passed through the vessel generating Zone be removed either as a solution in a suit to maintain the partial pressure of carbon monoxide with able solvent or in admixture with a carrier gas. in a range of about 30-300 atmospheres. The catalyst generating zone may be operated in the To produce a liquid catalyst, the above procedure is presence of carbon monoxide alone, or if desired, there 25 modified by simultaneously pumping a solvent through may be used mixtures of hydrogen and carbon monoxide. the vessel, when the catalyst is obtained as a solution in Thus, instead of carbon monoxide alone, there may be the solvent. used mixtures of hydrogen and carbon monoxide, such as When the fluid cobalt compound is to be employed as water gas, which are in general cheaper and more readily catalyst in the Oxo synthesis reaction in the gaseous state, available. So called "blue water gas' is a particularly 30 the carbon monoxide-containing gas is preferably a mix suitable gaseous mixture for use in the process of the ture of carbon monoxide and hydrogen having a molar invention. The preferred pressure range when using a ratio at least 1:2. Under these conditions carbon mon carbon monoxide/hydrogen mixture is 30-250 atmos oxide and hydrogen are usually present in the effluent gas pheres. Mixtures of carbon monoxide and hydrogen from the catalyst-generating zone in suitable proportions having a molar ratio in the range 1:5 to 1:0.5 are pre for direct use in the subsequent synthesis. ferred, and particularly mixtures containing less hydrogen It is not, however, essential to employ these molar than corresponds to a CO:H2 ratio of 1:2. ratios of carbon monoxide and hydrogen in the catalyst The solution or gaseous mixture obtained from the generating zone since the proportions of CO:He may be catalyst generating Zone is suitable for direct use as a adjusted after catalyst generation by blending-in further catalyst in the Oxo synthesis reaction. By operating ac 40 carbon monoxide/hydrogen mixtures.
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