DE2058814A1 - Process for the hydroformylation of olefins - Google Patents

Description

DR.-ING. RICHARD GLAWE DIPL-ING. KLAUS DELFS DIPL-PHYS. DR. WALTER MOLL

MUNICH HAMBURG MUNICH

2000 Hamburg 52 · Walzstrasse 12. Tel. (04Tl) 89 2255 8000 Munich 22 Liebherrstrasse 20 Tel. (0811) 22 65 48

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HAMBURG

BP CHEMICALS LIMITED,
London E ♦ C.2 / England.

Process for the hydroformylation of olefins.

The invention relates to a new process for the hydroformylation of olefins to aldehydes and a new complex catalyst.

The oxo process includes the conversion of an olefin Carbon monoxide and hydrogen using elevated temperature and pressure. The products are aldehydes and / or alcohols. Cobalt compounds, especially octacarbonyl, are the most common catalysts used, but a number of other transition metal compounds can also be used will. 109826/1912

In the registration '. .Ι & ΓΝΌΤΟ & Ό . 46 293/66 discloses that square, flat complexes of monovalent rhodium with a carboxylate ligand are active catalysts for aldehyde and / or alcohol formation by the oxo reaction

In the registration / .y.'X ΨΛ ^ ο . 43 939/68 it is disclosed that when a two-pronged (bidentate) ligand, coordinating by nitrogen and oxygen, where the oxygen in the free ligand forms part of an acidic group, was introduced instead of a carboxylate ligand, complexes are obtained which are also active catalysts for aldehyde production in the oxo process.

It has now been found that complexes of transition metals, which contain a two-pronged ligand that coordinates by means of two nitrogen atoms, also active Are hydroformylation catalysts.

The process of the invention for producing aldehydes comprises hydroformylation of an olefin with carbon monoxide and hydrogen at elevated temperatures in the presence of a complex of any one of iron, nickel, palladium or Group VIII platinum of various metal containing a two-pronged ligand formed by means of two nitrogen atoms coordinated.

The invention also includes a catalyst which is a complex of any one of iron, nickel, palladium or platinum different metal of group VIII, which is a two-pronged ligand, by means of two nitrogen atoms

109826/1912

coordinated, contains.

If ^ "*" the two-pronged ligand with the transition metal Coordinates, a complex is created that contains the Group VIII metal and the two nitrogen atoms in the Contains the shape of a ring. Examples of the type of ring formed are

ii M

M * Ji and M

where M is a Group VIII metal as defined above became.

Except for the transition metal atom and the two nitrogen atoms the remaining atoms in the ring may belong to any suitable element, including carbon, Boron and nitrogen. The ring can contain any suitable number of atoms, in particular 5 or 6 atoms; it has been found that the maximum catalytic activity is obtained with complexes in which the ring system contains 6 atoms. The substituents on the ring can also include any suitable radicals, for example the same or different alkyl, aryl or aralkyl radicals or hydrogen atoms. Catalyst complexes of the invention can, for example, by the reaction of rhodium dicarbonyl chloride dimer with a di-iminoalkane, such as substituted di-imino · pentane. So the di-o-tolyl substituted Di-iminopentane by the reaction of acetylacetone

109826/1912
- 3 -

and o-toluidine to form 4-o-tolylimino-pentan-2-one getting produced; this is then with o-toluidine hydrochloride to 2,4-di-O-tolyliminopentane hydrochloride implemented and it is the free di-iminoalkane by reaction obtained with triethylamine and crystallization from pentane. The di-imine is then mixed with rhodium dicarbonyl chloride dimer to 2-o-tolylimino-4-o-tolylaminopent-2-enatodicarbonylrhodium

CH C. CH

³ \

Il I

(o-tolyl) —N N— (o-tolyl)

CO CO

implemented.

Other catalyst complexes of the invention can be prepared by adding rhodium dicarbonyl chloride dimers with (1-pyrazolyl) borates. This creates one Complex of the following type

where M is the Group VIII metal as defined above.

The (1-pyrozolyl) borate can be prepared by the reaction of pyrozenes with borohydride salts to form ions containing 2 to k pyrazolyl groups. The pyrazole

;, 1 0 9 B 7 Π / 19 1?

can be pyrazole itself or a substituted pyrazole, such as 3 »5-t> is (trifluoromethyl) pyrazole, 3» 5-dimethylpyrazole, 3t4 »5-trimethyl-pyrazole, 3» 5-dimethyl-4-butyl-pyrazole, 4ychloropyrazole and 4-isopropylpyrazole. If that (1-pyrazolyl) borate contains more than 2 pyrazolyl groups, do not coordinate the additional groups. The preferred catalyst metals are cobalt and rhodium, especially rhodium.

The catalysts of the invention can also contain at least one neutral complex-forming ligand which contains an atom of a group Vb or VIb element which has a single pair of electrons available for donation, for example nitrogen, oxygen, phosphorus, arsenic, antimony and sulfur. Suitable nitrogen donor ligands of this type are, for example, monoalkyl and monoarylamines, for example methylamine, ethylamine, n-propylamine and similar dialkyl, trialkyl and triarylamines, for example dimethylamine, diphenylamine, trimethylamine and triphenylamine; Diamines and triamines, e.g., ethylenediamine, diethylenetriamine, ammonia, hydroxylamine, and other neutral molecules of the formula NX ", where X is any suitable group, are acceptable ligands. Suitable oxygen donors are of the form OX ₂ , for example ether. Other suitable ligands of this type include phosphines, arsines and stibines of the general formula (R) (β «) (ROD! Phosphites (RO) (R ¹ O) (R" o) Dj mercaptans RR ¹ Sj sulfoxides RR ¹ SOj pyridine and substituted Pyridines, for example OC- picoline, 2,2 · -dipyridyl, 1,10-phenanthene.

If ¹ ^

109 826/1912

The preferred neutral complexing ligands are tertiary phosphines. Ligands are particularly suitable Triethylphosphine, tri-n-propylphosphine or tri-n-butylphosphine.

In addition, a carbonyl ligand is usually present, at least under reaction conditions.

In the hydroformylation process of the invention, the olefin feed can contain olefins having between 2 and 20 carbon atoms have per molecule, contain, and in particular ethylene, propylene, hexenes, heptenes and octenes. The double bond is preferably terminal, but can also be inside.

The ratio of hydrogen to carbon monoxide in the feed can be between 4: 1 and 1: 4.

The catalyst is suitably present in amounts between 1:20 and 1:25,000,000 moles per mole of olefin feed and preferably between 1: 360 and 1: 5,000,000 moles per mole Feed. The catalyst can be dissolved in a solvent or in the feed or in the recycled product to be introduced. The solvent can be a saturated or aromatic hydrocarbon. Normal paraffins, such as η-hexane, n-heptane and n-octane are suitable. The hydroformylation is expediently carried out at a pressure between 0 and 281 atmospheres (θ and 4000 psig), preferably between 0 and 14 liters (O and 2000 psig). the The temperature is expediently between 20 and 25O C, and preferably between 60 and 180 C.

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example 1

Solid 2-0 - ^^ 1x111 ^ 0-4-0-tolylaminopent-2-enatodicarbonylrhodium (O.IOO5 g) was treated with tri-n-butylphosphine (O.O6 ml) under toluene to produce the phosphine derivative, and the resulting solution, together with more toluene, to make a total volume of 20 ml, placed in a stainless steel pressure vessel. Propene (approximately 100 ml) was added and the autoclave cleaned and pressurized to 63 atmospheres (900 psig) with premixed hydrogen and carbon monoxide in a 1: 1 molar ratio. The olefin to catalyst molar ratio was about 5000: 1. The temperature was raised to 84 ° Q while shaking the lid and held at 84Hh2C. The pressure was maintained in the 79 to 65.4 atmospheres (II25-93O psig) range by applying additional pressure as necessary. After the autoclave had been at reaction temperature for 5-5 hours, it was allowed to cool and the excess gases vented and the product collected and analyzed. The product was found to be Λ59 (83.5 sec) & isobutyraldehyde, 55 $ n-butyraldehyde.

Example 2

Dihydrobis- (1-pyrazolyl) -borato-dicarbonylrhodium (0.1457 g) was with tri-n-butylphosphine (0.12 ml) in the presence treated by n-heptane. The resulting solution was made up to 10 ml with n-heptane, and this became 5 ml diluted solution together with another 15 ml of n-heptane filled in a stainless steel vessel. It became propene

_ ₇ _ 109826/1912

(about 100 ml) added. The olefin * catalyst molar ratio was about 5000: 1. The vessel was placed in a heating / shaking arrangement, cleaned and pressurized to 63 atmospheres (900 spig) with premixed hydrogen and carbon monoxide in a molar ratio of lsi. Shaking was started and the vessel was heated to 80.degree. During a reaction time of 10 hours, the temperature was held at 80 ^ 2 ⁰ C and the pressure at 89.6-63.6 atmospheres (1275-905 psig). After the jar was allowed to cool, the excess gases were vented and the products (91 »4 g) collected and analyzed. (Found: isobutyraldehyde $ 49, n-butyraldehyde 51%).

Example 3

Hydridotis-1- (3 »5- di.me thylpyrazolyl) -boratodicarbonylrhodium (0.109 g) was treated with tri-n-butylphosphine (0.06 ml) in the presence of toluene. The solution was made up to 10 ml

together
filled up and 1 ml of it / filled with toluene (19 ml) and propene (about 100 ml) in an autoclave. The autoclave was cleaned and pressurized to 63 atmospheres (900 psig) with carbon monoxide-hydrogen in a ratio of 1: 1 and heated to 83-90 ° C. for 3 hours 15 minutes. After cooling and releasing the excess gases, the product ( 79.9 g) was analyzed and found that it contained k9% isobutyraldehyde and 51% n-butyraldehyde.

example k

- ^ - O- tolylaminoi) ent-2-eiiatodicarbony! Rhodium

10 9 3 2 6/1912

(θ, 1005 g) was used together with toluene (20 ml) and hexene-1 (147 ml) was placed in a stainless steel vessel in order to an olefin: catalyst molar ratio of 5000: 1 result. The vessel was cleaned three times with hydrogen / carbon monoxide in a molar ratio of 1: 1 and then with the same gas under a pressure of 42 atmospheres (600 psig) set. The temperature v-urde increased to about 85 C during the jar was shaken and the pressure was at 53f4 to 35.8 atmospheres (76Ο to 50 psig) and the temperature at 84 - 87 ° C held. After the autoclave had been at the reaction temperature for 2 1/3 hours, it was allowed to cool, the excess Gas was vented and the product removed and analyzed. It was found that there was an olefin reaction from 64% to 59% branched aldehyde and 41% normal aldehyde has revealed.

Example 5

Hydrido-tris- (1- (3 »5-dinethyl) -pyrazolyl) -boratodicarbonylrhodium (0.0545 g) was added together with toluene (20 ml) and Hexen-1 (74 nil) filled in a stainless steel vessel, to give an olefin to catalyst ratio of 5000-1. The vessel was cleaned as in Example 4 and pressurized and the temperature for 8 hours at 110-5 ° C under 54.8-42 atmospheres (780-600 psig) hydrogen / Carbon monoxide held. After cooling, the product was analyzed} 98% olefin conversion, branched aldehyde normal aldehyde 34%.

109826/1912

Example 6

Dihydrobis- (1-pyrazolyl) -boratodicarbonylrhodium (0.0364 g) was placed in a stainless steel vessel along with toluene (20 ml) and hexene-1 (74 ml) to give an olefin / catalyst ratio of 5000: 1 result. The vessel was cleaned and pressurized as in Example 4 and then heated to 103-1 C with shaking. It was held at this temperature for 7 1/4 hours while the pressure was maintained in the range 53.4-39.5 atmospheres (760-560 psig). The products were removed and analyzed. Olefin conversion $ 98, branched aldehyde 66%, normal aldehyde $ 34.

-10-

109826/1912

Claims (10)

2058014 H. Claims { Process for the preparation of aldehydes, characterized in that an olefin is hydroformylated with carbon monoxide and hydrogen at elevated temperature in the presence of a complex of a group VIII metal other than iron, nickel, palladium or platinum which contains a two-pronged ligand which by means of two nitrogen atoms coordinated. 2. The method according to claim 1, characterized in that the complex containing the Group VIII metal and the two nitrogen atoms in the form of one containing 6 atoms Ring's goal is. 3. The method according to any one of the preceding claims, characterized characterized in that the transition metal is cobalt or rhodium. h . Process according to one of the preceding claims, characterized in that the catalyst contains at least one neutral complex-forming ligand which contains an atom of an element from group Vb or VIb which contains a single pair of electrons available for donation. 5. The method according to claim k, characterized in that the catalyst contains an alkylphosphine ligand. 6. Catalyst, characterized in that it is a complex is a Group VIII metal other than iron, nickel, palladium or platinum which has a two-pronged ligand, which coordinates by means of two nitrogen atoms contains. 7. Catalyst according to claim 6, characterized in that he by the reaction of Rhodiumdioarbonylcliloriddimeren with a di-iminoalkane is made. 109826/1912 - ii - 8. 2-o-Tolylxmino-4-o-tolylaminopent-2-o-enatodicarbonylrhodium. 9 · Catalyst according to claim 6, characterized in that it is made by reacting rhodium dicarbonyl chloride dimer with a (1-pyrazolyl) borate. 10. Dihydrobis- (1-pyrazolylj-borato-dxcarbonylrhodium. 109826/1912