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United States Patent [,9] [11] 4,017,550

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United States Patent [,9] [11] 4,017,550 UnitedI States Patent [,9] [11] 4,017,550 Kummer [45] Apr. 12, 1977 [54] MANUFACTURE OF 1,4-BUTANEDIOL 3,773,842 ll/l973 Schirmann et al. .......... .. 260/635 E [75] Inventor: Rudolf Kummer, Frankenthal, 3‘929'9l5 12/1975 Cumbo et a] . ............... .. 260 / 635 E Germany OTHER PUBLICATIONS [73] Assignee: BASF Aktiengesellschaft, J .F.W. McOmie, Advances in Organic Chem., Intersci Ludwigshafen (Rhine), Germany ence Publishers, vol. 3, pp. 264-265, (1963). [22] Filed: Dec. 30, 1974 . Primary Examiner-Joseph E. Evans - [21 1 Appl‘ No" 537’1l-8 . Attorney, Agent, or Firm-Johnston, Keil Thompson & [30] Foreign Application Priority Data shumeff I Jan. 14, 1974 Germany ........................ .. 2401553 [52] us. Cl. ...................... .. 260/635 E; 260/340.7; I571 ABSTRACT . 260/346-l R The manufacture of 1,4-butanediol by hydroformyla [51] lllt- cl-z ----------------- .- C07C 29/00; C07C 29/ 16 tion of cyclic acetals of acrolein in the presence of [58] Fleld of Search .............................. .. 260/635 E phosphine-modified cobalt carbonyl complexes or rho [56] References Cited dium carbonyl complexes and hydrogenation of the 3-formylpropionaldehyde-acetals which are the princi UNITED STATES PATENTS pal products ?rst formed 2,888,492 5/1959 Fischer et al. v ............... .. 260/635 E 3,239,566 3/1966 Slaugh et al. ................ .. 260/635 A ' 3,448,157 6/1969 Slaugh et al. ................ .. 260/635 A 18 Claims, N0 Drawings 4,017,550 1 2 The preferred starting materials are cyclic acrolein MANUFACTURE OF 1,4-BUTANEDIOL acetals of alkanediols of up to 4 carbon atoms, for This application discloses and claims subject matter example of ethylene glycol, l,2-propylene glycol, 1,3 described in German Patent Application P 24 01 553.0, -propylene glycol, 1,4-butylene glycol or 2-methyl-l ,3 ?led Jan. 14, 1974, which is incorporated herein by propanediol. Acrolein-acetals of 1,3-propanediol, 1,3 reference. butanediol and especially of 2-methyl-l,3-propanediol The present invention relates to a new process for the (since the latter occurs as a by-product of the synthe manufacture of 1,4-butanediol. sis) are particularly suitable. In an industrially practised process, 1,4~butanediol is The cyclic acrolein-acetals are obtained by, e.g., manufactured by reaction of acetylene with formalde treatment of acrolein with a 2M to 3M excess of the hyde in the presence of copper acetylide, to form diol at temperatures of from 30° to 50° C in the pres butynediol which is then hydrogenated to 1,4 ence of a strongly acid ion exchanger, followed by butanediol. Since acetylene is becoming increasingly distillation. , . expensive as a starting material for industrial'processes, The carbon monoxide and hydrogen are generally it is desirable to be able to manufacture, 1,4-butanediol employed in a volume ratio of from 120.25 to 1:4, espe from less expensive petrochemical feedstocks. At cially from 110.5 to 1:2. As a rule, at least the stoichio tempts have already been made (c.f. German Published metric amount of gas mixture is employed, but an ex Application 2,217,452), to manufacture 1,4 cess of up to 200 mole percent, based on the acrolein butanediol by reacting butadiene with acetic acid and acetal, is of advantage. molecular oxygen, or gases containing molecular oxy 20 The hydroformylation is carried out at temperatures gen, in the presence of noble metal catalysts, to form of from 80° to 200° C, and temperatures of from 100° 1,4-butenediol diacetate which is then hydrogenated to 160° C have proved particularly suitable. Advanta and saponi?ed. Whilst this process has the advantage of geous pressures to use are from 5 to 100, and especially using inexpensive feedstocks, it has hitherto not proved from 10 to 80, atmospheres gauge. successful in industry. 25 The hydroformylation is carried out in the presence It is an object of the present invention to provide an of cobalt carbonyl complexes or rhodium carbonyl advantageous method of obtaining 1,4-butanediol, complexes which have been modified with tertiary which is an important material for numerous organic organic phosphines. It is possible to use catalyst com syntheses. plexes which have been prepared beforehand, e.g. We have found an advantageous method of obtaining 30 Co2(CO)6L2, HCo(CO)3L, HRh(CO)L3, ClRh(CO)L2 1,4-butanediol, wherein cyclic acetals of acrolein are and L_-,RhClv (L = tert. phosphine). reacted with carbon monoxide and hydrogen in the However, it is also possible to form the catalyst com presence of cobalt carbonyl complexes or rhodium plexes under the reaction conditions in situ from the carbonyl complexes which are modi?ed with tertiary corresponding metal carbonyls and the phosphine, or a organic phosphines, at temperatures of from 80° to 35 reactive metal compound, e.g. dicobalt octocarbonyl, 200° C under superatmospheric pressure, and the re cobalt salts of fatty acids, rhodium carbonyl, rhodium sulting 3-formylpropionaldehyde-acetals and any 4 carbonyl chloride, rhodium carbonyl acrylate or cyclo hydroxybutyraldehyde-acetals produced at the same 1,5-octadienyl-rhodium chloride, carbon monoxide, time are then hydrogenated in the presence of water hydrogen and the phosphine. In general, the carbonyl 40 and hydrogenation catalysts, at elevated temperatures complexes are used in amounts of from 100 ppm to 2 and under superatmospheric pressure. percent by weight, in particular from 0.1 to 1.0 percent The process according to the invention has the ad— vantage of good yields and simplicity. It has the further by weight, calculated as metal and based on the starting materials. advantage that acrolein, which arises as a by-product of The preferred ligands L are tri-C1-C3o-alky1phos the oxidation of propylene t0 acrylic acid, is readily 45 obtainable. The cyclic acetals of acrolein are also easily phines such as trioctylphosphine, tridodecylphosphine, obtainable, as they can be manufactured simply by diethyldodecylphosphine or dimethyleicosylphosphine reaction of acrolein with diols. ' or arylphosphines or aralkylphosphines, especially phe The process according to the invention is noteworthy nylphosphines or alkylphenylphosphines such as tri in that it was unforeseeable that the hydroformylation 50 phenylphosphine, tritolylphosphine, dimethylphenyl of acrolein-acetals in the presence of phosphine-modi phosphine or ethylditolylphosphine. The alkyl or aryl ?ed catalysts would succeed. In fact, it is known from radicals can contain functional groups such as meth Bayer “Lehrbuch der organischen Chemie,” 1963 edi oxy, carbonyl or carbalkoxy groups, as in the case of tion, p. 124, that ole?nically unsaturated compounds p-methoxyphenyldimethylphosphine or l0-carbox containing polarized double bonds, such as acryloni 55 ydecyldimethylphosphine. The use of tri-C1-C2o-alkyl trile, acrylic esters and acrolein, polymerize in the pres phosphines and triphenylphosphines is particularly ence of phosphines. Thus, even traces of phosphine preferred. Advantageously, from 1 to 20 moles of alkyl suf?ce to initiate the polymerization of free acrolein. In phosphines are used per gram atom of cobalt. In the addition the effect of phosphine-modi?ed oxo catalysts case of rhodium, a combination with arylphosphines, in was unforeseeable since, according to Kogyo Kagaku 60 which from 5 to 50 moles'of phosphine are used per Zasshi, 74, No. 8, p. 1,640 to 1,643, dimerization oc gram atom of rhodium, has proved particularly effec curs, with degradation of the catalyst, in the case of the tive. hydroformylation of acrylic esters, i.e. of compounds The reaction can be carried out in the absence of which are chemically very closely related to the solvents. However, it is also possible to carry out the acroleinacetals. Hence, it would have been expected 65 hydroformylation in the presence of solvents such as that there would be' considerable interference with the hydrocarbons, e.g. benzene, cyclohexane orhexane, hydroformylation of acrolein-acetals in the presence of ethers, e.g. tetrahydrofuran or dibutyl ether, or alka~ phosphines. nols, e.g. butanol. 4,017,550 3 4 The hydroformylation can be carried out batchwise the total amount of gas taken up is equivalent to a 36 or by a simple continuous method in suitable equip atmospheres pressure change. Analysis of the reaction ment. The resulting reaction products consist essen product by gas chromatography indicates the following tially of 3-formylpropionaldehyde-acetals and 4 composition (ignoring solvent and catalyst): 13.9% of hydroxybutyraldehyde-acetals in addition to minor acrolein-acetal and propionaldehyde-acetal, 67.2% of amounts of the corresponding isomeric compounds, 2-formyl- and 3-formylpropionaldehyde-acetal and namely the 2-formylpropionaldehydeacetals and 2me 18.9% of 4-hydroxybutyraldehyde-acetal , and 2 tyl-3-hydroxypropionaldehyde-acetals which are hydroxyisobutyraldehyde-acetal. 81% of the hydrofor formed during the hydroformylation. mylation products are accounted for by linear isomers. After completion of the reaction, the solvents and 10 hydroformylation products in the reaction mixture are EXAMPLE 2 separated, if desired, from the catalyst residue by con Hydroformylation of ventional methods, e.g. distillation under reduced pres acrolein-( 2-methyl- 1 ,3-propanediol)-diacetal sure, and the catalyst residue can be re-used directly in the hydroformylation reaction. The procedure followed is a described in Example 1 The hydroformulation mixture thus obtained, which but the reactor is charged with 96 g of acrolein-(2 essentially consists of 3-formylpropionaldehyde-acetal methyl-l,3-propanediol)-diacetal, 4.3 g of dicobalt and 4-hydroxybutyraldehyde-acetal with minor octacarbonyl and 26 g of dimethylalkylphosphine (with amounts of isomeric compounds and, where relevant, alkyl of 20 to 26 carbon atoms). After 2 hours reaction solvents, is hydrogenated in the presence of water and 20 time the total amount of gas taken up is equivalent to a hydrogenation catalysts. The amount of water used is 38 atmospheres pressure change.
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