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Home , Acrolein, Phosphine

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 in the presence of [58] Fleld of Search ...... 260/635 E -modified cobalt carbonyl complexes or rho [56] References Cited dium carbonyl complexes and 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 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 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 exchanger, followed by butanediol. Since acetylene is becoming increasingly distillation. , . expensive as a starting material for industrial'processes, The and 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 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 percent, based on the acrolein butanediol by reacting butadiene with and acetal, is of advantage. molecular , 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 . 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 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 L are tri-C1-C3o-alky1phos the oxidation of propylene t0 , 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 . 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 , e.g. , 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 and catalyst): 13.9% of hydroxybutyraldehyde-acetals in addition to minor acrolein-acetal and -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. Analysis of the reac advantageously at least the stoichiometric amount but tion product by gas chromatography indicates that 82% in particular an up to 30-fold molar excess. . of linear isomers are present. The product is then dis Preferred hydrogenation catalysts are metals of tilled, benzene being removed ?rst. 13 g of the pro group 8 of the Periodic Table, especially , cobalt pionaldehyde-acetal and 108 g of acetals of the actual and noble metals of group 8, such as platinum or palla oxo products are obtained (representing 89% of the dium. 1n industrial practice, copper, nickel and cobalt amount theoretically expected), together with 36 g of catalysts have proved particularly suitable. The cata residue. lysts can also contain activators such as copper, zinc EXAMPLE 3 and chromium. Raney nickel, Raney cobalt and the so-called Adkins catalyst (copper/chromium Manufacture of 1,4-butanediol catalysts) are particularly suitable catalysts. The 108 g of the oxo product from Example 2 are The catalysts can be used unsupported or on "carriers hydrogenated with 400 ml of , 100 ml of such as silica gel, silica or aluminum oxide. In general, water and 40 g of Raney nickel (which has been care the supported catalysts contain from 5 to 40 percent by fully washed until neutral) for 5 hours at.280 atmo weight of the catalytic metals. proved spheres and a maximum temperature of 140° C. The The hydrogenation is advantageously carried out at catalyst is then ?ltered off, the solvent is stripped off temperatures of from 70° to 150° C, especially from 80° and the butanediols are distilled at from 93° to to 130° C; pressures of from 100 to 300 atmospheres 96°C/2mm. 105 g of diols are obtained, containing 60% have proved particularly suitable. 1,4-Butanediol is of 2-methyI-1,3-propanediol and 40% of 1,4 isolated from the hydrogenated material by conven butanediol, according to gas-chromatographic analysis tional methods, e.g. by distillation. The alkanediol of the diacetates. This means, taking into account the eliminated from the acetal during the hydrogenation branched isomer employed as the acetalization compo and obtained as a by-product can be re-used to manu nent, that the newly formed diol comprises 80% of facture the acrolein-acetals used as starting materials. 45 linear isomer, i.e. 1,4-butanediol and 20% of branched .l,4-Butanediol manufactured by the process of the isomer, i.e. 2-methyl-1,3-propanediol. On distillation invention can be used for the manufacture of tetrahy under reduced pressure.(l0 mm Hg) the branched drofuran, an important solvent, and for the manufac— isomer passes over at 97° C and the 1,4-butanediol at ture of polyesters and also, in particular, polyure 1 11° C. thanes. 50 EXAMPLE 4 EXAMPLE 1 Hydroformylation of Hydroformylation of acrolein-( l,3-propanediol)-diacetal acrolein-( 1,3-butanediol)-diacetal 55 450 ml of benzene, 0.51 g of HRhCO(P(C6H5)3)3 (= 2.8 g of and 12.1 g of trioctyl 0.55 milliequivalent of Rh) and 5.8 g of triphenylphos phosphine, dissolved in 120 g of benzene, are intro phine (= 22 millimoles) are introduced into a pressure duced into a pressure reactor of 2 1 capacity, which is reactor of 2 1 capacity, which is equipped with a stirrer. equipped with a stirrer. The reactor is then ?ushed The reactor is ?ushed three times with a gas mixture of twice with a gas mixture of 1 part by volume of carbon 60 1 part by volume of carbon monoxide and 1 part by monoxide and 2 parts by volume of hydrogen. After volume of hydrogen. After heating to 140° C, the pres heating the mixture to 150° C, the pressure is set to 70 sure is set to 40 atmospheres by means of the said gas atmospheres by means of the above gas mixture. A mixture. 100g of acrolein-(1,3-propanediol)-diacetal mixture of 120 g of acrolein-( l,3-butanediol)-diacetal are then introduced into the reactor. During the reac and 80 g of benzene is then introduced in four portions 65 tion, the pressure is kept at from 20 to 40 atmospheres into the reaction vessel, in the course of 2 hours. The by replenishing with the above gas mixture. The ab pressure is maintained at from 70 to 80 atmospheres by sorption of gas ceases after 45 minutes. At this stage, replenishing with the above gas mixture. After 2 hours, the analysis of the reaction product by gas chromatog 4,017,550 5 6 raphy shows traces of the starting material, and a mix phine, or one of said phosphines having one or more ture of 2-formyl- and 3-formyl-propionaldehyde-acetal methoxy, carbonyl or carbalkoxy groups. in the ratio of 32:68. Accordingly, no hydrogenated 8. A process as claimed in claim 1 wherein said ter products are obtained, in contrast to the case of the tiary organic phosphine is a tri-C, to Cao-trialkylphos cobalt catalyst. phine. The product is again distilled, and 112 g (= 89% of 9. A process as claimed in claim 1 wherein said ter theory) of formyl compounds and 10 g of residue are tiary organic phosphine is or trito obtained. lylphosphine. 10. A process as claimed in claim 1 wherein said EXAMPLE 5 hydrogenation catalyst is a nickel, cobalt or copper Manufacture of l,4-butanediol hydrogenation catalyst. 11. A process as claimed in claim 1 wherein said The 1 12 g of the formyl compounds obtained accord catalyst contains, as an activator, copper, zinc or chro ing to Example 4 are hydrogenated with 250. g of water mium. and 25 g of Raney cobalt (which have been carefully 12. A process as claimed in claim 1 wherein said washed until neutral) in an autoclave, initially for 5 hydrogenation catalyst is Raney nickel or Raney co hours at 80° C and 160 atmospheres and then for 5 balt. ' hours at 130° C and 280 atmospheres. The catalyst is 13. A process as claimed in claim 1 wherein said ?ltered off and the water is distilled off, after which l20 hydrogenation catalyst is an adkins copper/chromium g of diol mixture are obtained at from 90° to 95° C/2 oxide hydrogenation catalyst. _ mm Hg.A sample is esteri?ed with acetic anhydride 14. A process for preparing l,4-butanediol which and examined by gas chromatography; this shows the comprises hydroformylating a cyclic acetal of acrolein presence of 45% of 1,3-propanediol, l5.0% of 2-meth and an alkanediol of up to 4 carbon atoms in the pres yl-l,3-propanediol and 40.0% of l,4-butanediol. Ac ence of a cobalt carbonyl complex or a rhodium car cordingly, 72.5% of the diols newly formed are un 25 bonyl complex, said complexes being modi?ed by a branched. The diol mixture can be separated by distil tertiary organic phosphine, at temperatures of from 80° lation, as described in Example 3. to 200° C under superatmospheric pressure to produce I claim: the corresponding cyclic acetals of formylpropionalde 1. A process for the manufacture of l,4-butanediol, hydes, and hydrogenating the corresponding cyclic wherein cyclic acetals of acrolein are reacted with 30 acetals of formylpropionaldehydes at elevated temper carbon monoxide and hydrogen in the presence of atures and under superatmospheric pressure in the cobalt carbonyl complexes or rhodium carbonyl com presence of'a hydrogenation catalyst and in the pres plexes which are modi?ed with tertiary organic phos ence of water. phines, at temperatures of from 80° to 200° C under 15. A process as claimed in claim 14 wherein said superatmospheric pressure, and the resulting 3-formyl 35 cyclic acetal is the cyclic acetal of acrolein and 1,3 propionaldehyde-acetals and the 4-hydroxybutyralde propanediol, 1,3-butanediol, or 2-methyl-l,3 hyde-acetals produced are hydrogenated in the pres propanediol. ence of water at 70°-150° C and under superatmos 16. A process as claimed in claim 14 wherein the pheric pressure in the presence of a hydrogenation hydrogenation is carried out at 70-150° C and at super catalyst containing a metal of group 8 of the Periodic atmospheric pressure in the presence of a catalytic Table or copper as a catalytically active ‘metal. . amount of a hydrogenation catalyst containing a metal 2. A process as claimed in claim 1, wherein the acetal of group 8 of the Periodic Table or copper as a catalyti of acrolein with 2-methyl-l,3-propanediol is used as cally active metal. the starting material. 17. A process for preparing l,4-butanediol which 3. A process as claimed in claim 1, wherein tri-C,- to 45 comprises hydroformylating a cyclic acetal of acrolein Cm-alkylphosphines or triphenylphosphine are used as and 2-methyl-l,3-propanediol in the presence of a co modi?ers in the hydroformylation reaction. balt carbonyl complex or a rhodium carbonyl complex, 4. A process as claimed in claim 1, wherein, in the said complexes being modified by a tertiary organic case of rhodium catalysts, from 5 to 50 moles of ter phosphine, at temperatures of from 80° to 200° C and tiary organic phosphines are employed per gram atom 50 superatmospheric pressure to produce formylpro of rhodium. ' pionaldehyde acetals of Z-methyl-l ,3~propanediol, and 5. A process as claimed in claim 1, wherein, in the hydrogenating the resulting acetals at elevated temper case of cobalt catalysts, from 1 to 20 moles of tertiary atures and pressure in thepresence of water and in the organic phosphines are employed per gram atom of presence of a hydrogenation catalyst to produce a mix cobalt. 55 ture of 1,4~butanediol'and 2-methyl-1,3-propanediol. 6. A process as claimed in claim 1, wherein from 1 to 18. A process as claimed in claim ‘17 wherein said 30 moles of water are employed in the hydrogenation formylpropionaldehyde acetals of 2-methyl-l,3 reaction, per mole of the hydroformylation products propanediol are hydrogenated in the presence of from ?rst obtained. at least the stoichiometric amount up to a 30-fold 7. A process as claimed in claim 1 wherein said ter 60 molar excess of water at a temperature of 70° — 150° C. tiary organic phosphine is a tri-Cl to Cao-alkyl phos and a pressure of 100 - 300 atmospheres. phine, a triarylphosphine, a tertiary alkylphenyl phos * * * * *

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