Claims
- 1. A process for the preparation of n-butyraldehyde and/or n-butanol, which comprises reacting
- a) 1,3-Butadiene or a butadiene-containing hydrocarbon mixture with an alcohol of the formula I
- ROH I,
- where R is C.sub.2 -C.sub.20 -alkyl or alkenyl which is unsubstituted or substituted by 1 or 2 C.sub.1 -C.sub.10 -alkoxy or hydroxyl groups, or is C.sub.6 -C.sub.10 -aryl, C.sub.7 -C.sub.11 -aralkyl or methyl, at elevated temperatures and superatmospheric pressure in the presence of a Bronsted acid or in the presence of a complex of an element of Group Ia, VIIA or VIIIA of the Periodic Table of Elements with phosphorus- or nitrogen-containing ligands to give a mixture of the adducts of the formulae II ##STR13## and III ##STR14## b) isomerizing the adduct III to the adduct II, c) converting the adduct II into the acetal of the formula IV ##STR15## in the presence of an amount of an alcohol ROH I sufficient to form the acetal IV and of a homogeneous or heterogeneous transition metal catalyst which differs from dicobaltoctacarbonyl or hydridocobalttetracarbonyl, in the liquid phase, under essentially anhydrous conditions, and
- d) n-butyraldehyde and/or n-butanol are then produced from this acetal IV by reacting it, in the liquid phase, with hydrogen and water or water in the presence of a homogeneous or heterogeneous transition metal catalyst which differs from dicobaltoctacarbonyl or hydridocobalttetracarbonyl, and the alcohol ROH I is liberated
- and the liberated alcohol ROH I is recycled to the reaction in reaction steps a) and/or c).
- 2. A process as claimed in claim 1, wherein the reaction of 1,3-butadiene or of a butadiene-containing hydrocarbon mixture with an alcohol ROH I is carried out in the presence of an acidic ion exchanger.
- 3. A process as claimed in claim 1, wherein the reaction of 1,3-butadiene or of a butadiene-containing hydrocarbon mixture with an alcohol ROH I is carried out in the presence of a catalyst comprising an alkyl, aryl or arylalkyl-phosphine complex of a transition metal from Group IA, VIIA or VIIIA of the Periodic Table of Elements.
- 4. A process as claimed in claim 1, wherein the reaction of 1,3-butadiene or of a butadiene-containing hydrocarbon mixture with an alcohol ROH I is carried out in the presence of a catalyst comprising an alkyl, aryl or arylalkyl-phosphine complex of rhodium, of nickel, of palladium, of iridium or of platinum.
- 5. A process as claimed in claim 1, wherein the isomerization of the adduct III to give the adduct II is carried out in the presence of a catalyst as used for the catalysis of the addition reaction of the alcohol ROH I with 1,3-butadiene or a butadiene-containing hydrocarbon mixture in reaction step a).
- 6. A process as claimed in claim 1, wherein the adduct III is separated from the adduct II, and the adduct III is then recycled to reaction step a) and is isomerized there to give the adduct II.
- 7. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in succession in the liquid phase in the presence of a catalyst homogeneously soluble in the reaction medium.
- 8. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in succession in the liquid phase in the presence of a catalyst which is homogeneously soluble in the reaction medium and is a monodentate or polydentate phosphine or phosphite complex of an element of Groups VIA and/or VIIIA of the Periodic Table of Elements.
- 9. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in succession in the liquid phase in the presence of a catalyst which is homogeneously soluble in the reaction medium and comprises a phosphine or phosphite complex of an element of Group VIA and/or VIIIA of the Periodic Table of Elements and excess phosphine or phosphite ligands and reaction step d) is carried out in the presence of hydrogen and water and n-butanol is produced.
- 10. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in succession in the liquid phase in the presence of a catalyst which is homogeneously soluble in the reaction medium and comprises a phosphine or phosphite complex of an element of the platinum metal group.
- 11. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in succession in the liquid phase in the presence of a catalyst which is homogeneously soluble in the reaction medium and is a salt of an element of Group VIIIA of the Periodic Table of Elements.
- 12. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in succession in the liquid phase in the presence of a catalyst which is homogeneously soluble in the reaction medium and is an aqua, amine, halo, cyano, carbonyl, amino and/or acetylacetonato complex of an element of Group VIA and/or Group VIIIA of the Periodic Table of Elements.
- 13. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in the liquid phase in the presence of a catalyst which is homogeneously soluble in the reaction medium and is a salt or an aqua, amine, halo, cyano, amino and/or acetylacetonato complex of an element of Group VIA and/or VIIIA of the Periodic Table of Elements and reaction step d) is carried out in the presence of water and n-butyraldehyde is produced.
- 14. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in succession in the liquid phase in the presence of a catalyst homogeneously soluble in the reaction medium and reaction step d) is carried out in the presence of hydrogen and water or water and the catalyst solution obtained after the products n-butyraldehyde and/or n-butanol have been separated off is reused for carrying out reaction steps c) and/or d).
- 15. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in succession in the liquid phase in the presence of at least one heterogeneous catalyst essentially insoluble in the reaction medium.
- 16. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in succession in the liquid phase in the presence of at least one heterogeneous catalyst which contains one or more elements of Groups IA, VIA, VIIA and/or VIIIA of the Periodic Table of Elements in the presence of absence of one or more elements of Group VA.
- 17. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in succession in the liquid phase in the presence of at least one heterogeneous catalyst which contains one or more elements of Groups IA, VIA, VIIA and/or VIIIA of the Periodic Table of Elements in the presence or absence of one or more elements of Group VA and additionally a carrier.
- 18. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in succession in the liquid phase in the presence of at least one heterogeneous catalyst which contains one or more elements of Groups IA, VIA, VIIA and/or VIIIA of the Periodic Table of Elements in the presence or absence of one or more elements of Group VA and additionally alumina, titanium dioxide, silica, zirconium dioxide, a silicate, a clay, a zeolite and/or active carbon as the carrier.
- 19. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in succession in the liquid phase in the presence of at least one heterogeneous catalyst which contains palladium.
- 20. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in succession in the liquid phase in the presence of at least one heterogeneous catalyst which is arranged in a fixed bed in each case.
- 21. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in succession in the liquid phase in the presence of at least one heterogeneous catalyst which is arranged in from 2 to 5 fixed beds in each case.
- 22. A process as claimed in claim 1, wherein the reaction steps c) and d) are carried out in the liquid phase in succession using homogeneous and/or heterogeneous catalysts in the individual process stages.
- 23. A process as claimed in claim 1, wherein the alcohol ROH I used is n-butanol.
- 24. A process for the preparation of n-butyraldehyde and/or n-butanol, which comprises converting an ether of the formula II ##STR16## where R is a C.sub.2 -C.sub.20 -alkyl or alkenyl group which is unsubstituted or substituted by 1 or 2 C.sub.1 -C.sub.10 -alkoxy or hydroxyl groups or is C.sub.6 -C.sub.10 -aryl or a C.sub.7 -C.sub.11 -aralkyl group or methyl, in the presence of an amount of an alcohol ROH I, where R has the abovementioned meanings, which is sufficient to form the acetal IV ##STR17## where R has the abovementioned meanings, and in the presence of a homogeneous or heterogeneous transition metal catalyst which differs from dicobaltoctacarbonyl or hydridocobalttetracarbonyl, in the liquid phase and under essentially anhydrous conditions, to give the acetal of the formula IV, and then producing n-butyraldehyde and/or n-butanol from this acetal IV by reacting it with hydrogen and water or water in the presence of a homogeneous or heterogeneous transition metal catalyst which differs from dicobaltoctacarbonyl or hydridocobalttetracarbonyl, in the liquid phase, and the alcohol ROH I is liberated again.
Priority Claims (1)
Number |
Date |
Country |
Kind |
197 10 994 |
Mar 1997 |
DEX |
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Parent Case Info
This is the U.S. national stage application of PCT/EP98/01324 filed Mar. 6, 1998.
PCT Information
Filing Document |
Filing Date |
Country |
Kind |
102e Date |
371c Date |
PCT/EP98/01324 |
3/6/1998 |
|
|
9/15/1999 |
9/15/1999 |
Publishing Document |
Publishing Date |
Country |
Kind |
WO98/41494 |
9/24/1998 |
|
|
US Referenced Citations (3)
Number |
Name |
Date |
Kind |
2922822 |
Beach et al. |
Jan 1960 |
|
4310709 |
Rebafka et al. |
Jan 1982 |
|
5705707 |
Kanand et al. |
Jan 1998 |
|
Non-Patent Literature Citations (1)
Entry |
Chang, Journal of Organometallic Chemistry, 492, pp. 31-34, 1995. |