Process for catalytic preparation of aldehydes from olefins using monophosphite mixtures

Abstract

The catalytic preparation of an aldehyde from an olefin proceeds in the presence of a monophosphite mixture.

Claims

1. A mixture, which comprises a mixture of compounds 1 and 2: ##STR00013##

2. A complex mixture, comprising: are according to claim 1, and a metal atom selected from the group consisting of Rh, Ru, Co, and Ir.

3. The complex mixture according to claim 2, wherein said metal atom is Rh.

4. A process for hydroformylation of an olefin, comprising: a) initially charging an olefin, b) adding a mixture according to claim 1 c) adding a compound comprising one of the following metals: Rh, Ru, Co, or Ir, to obtain a reaction mixture, c) feeding H.sub.2 and CO into the reaction mixture, d) heating the reaction mixture, to convert the olefin to an aldehyde, wherein the additions in process steps b) and c) can also be effected in one step through the addition of a corresponding complex mixture.

5. The process according to claim 4, wherein the olefin is a mono-olefin having 2 to 24 carbon atoms, and having a terminal or an internal C≡C double bond.

6. The process according to claim 4, wherein the olefin is an α-olefin, terminally branched, internal and internally branched olefin.

7. The process according to claim 4, wherein a terminally hydroformylated olefin is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The present invention relates to a mixture comprising a compound of the structure Ia:

(2) ##STR00005##

(3) where

(4) R.sup.1 is selected from:

(5) —(C.sub.1-C.sub.12)-alkyl, —(C.sub.3-C.sub.12)-cycloalkyl, and

(6) R.sup.2, R.sup.3 are each independently selected from:

(7) —(C.sub.1-C.sub.12)-alkyl, —(C.sub.6-C.sub.20)-aryl, —(C.sub.3-C.sub.12)-cycloalkyl,

(8) the R.sup.2 and R.sup.3 radicals may also be bridged to one another, and may have a —(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl unit,

(9) where the alkyl, cycloalkyl and aryl groups mentioned may be substituted,

(10) and

(11) comprising a compound of the structure IIb:

(12) ##STR00006##

(13) where

(14) R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45, R.sup.51, R.sup.52, R.sup.53, R.sup.54, R.sup.55, R.sup.61, R.sup.62, R.sup.63, R.sup.64, R.sup.65 are each independently selected from:

(15) —H, —(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.6-C.sub.20)-aryl, —(C.sub.6-C.sub.20)-aryl, -halogen, —COO—(C.sub.1-C.sub.12)-alkyl, —CO—(C.sub.1-C.sub.12)-alkyl, —CO—(C.sub.6-C.sub.20)-aryl, —COOH, —OH.

(16) (C.sub.1-C.sub.12)-Alkyl may in each case be unsubstituted or substituted by one or more identical or different radicals selected from (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, fluorine, chlorine, cyano, formyl, acyl and alkoxycarbonyl.

(17) (C.sub.6-C.sub.20)-Aryl may in each case be unsubstituted or substituted by one or more identical or different radicals selected from —H, —(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.6-C.sub.20)-aryl, —(C.sub.6-C.sub.20)-aryl, -halogen (such as Cl, F, Br, I), —COO—(C.sub.1-C.sub.12)-alkyl, —CONH—(C.sub.1-C.sub.12)-alkyl, —(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2, —CO—(C.sub.1-C.sub.12)-alkyl, —CO—(C.sub.6-C.sub.20)-aryl, —COOH, —OH, —SO.sub.3H, —SO.sub.3Na, —NO.sub.2, —CN, —NH.sub.2, —N[(C.sub.1-C.sub.12)-alky].sub.2.

(18) (C.sub.3-C.sub.12)-Cycloalkyl may in each case be unsubstituted or substituted by one or more identical or different radicals selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkoxy, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, fluorine, chlorine, cyano, formyl, acyl and alkoxycarbonyl.

(19) All ranges described herein include al values and subvalues between the upper and lower limits of such ranges.

(20) In the context of the invention, the expression “—(C.sub.1-C.sub.12-alkyl” encompasses straight-chain and branched alkyl groups. Preferably, these groups are unsubstituted straight-chain or branched —(C.sub.1-C.sub.8)-alkyl groups and most preferably —(C.sub.1-C.sub.6)-alkyl groups. Examples of (C.sub.1-C.sub.12)-alkyl groups are especially methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, nonyl, decyl.

(21) Substituted —(C.sub.1-C.sub.12)-alkyl groups may have one or more substituents, depending on their chain length. The substituents are preferably each independently selected from —(C.sub.3-C.sub.12)-cycloalkyl, —(C.sub.3-C.sub.12)-heterocycloalkyl, —(C.sub.6-C.sub.20)-aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl.

(22) The expression “—(C.sub.3-C.sub.12)-cycloalkyl”, in the context of the present invention, encompasses mono-, bi- or tricyclic hydrocarbyl radicals having 3 to 12, especially 5 to 12, carbon atoms. These include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclopentadecyl, norbonyl and adamantyl.

(23) Substituted —(C.sub.3-C.sub.12)-cycloalkyl groups may have one or more (e.g. 1, 2, 3, 4 or 5) further substituents, depending on their ring size. These substituents are preferably each independently selected from —(C.sub.1-C.sub.12)-alkyl, —(C.sub.1-C.sub.12)-alkoxy, —(C.sub.3-C.sub.12)-cycloalkyl, —(C.sub.3-C.sub.12)-heterocycloalkyl, —(C.sub.6-C.sub.20)-aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl. Substituted —(C.sub.3-C.sub.12)-cycloalkyl groups preferably bear one or more (C.sub.1-C.sub.6)-alkyl groups. Substituted —(C.sub.3-C.sub.12)-heterocycloalkyl groups preferably bear one or more —(C.sub.1-C.sub.6)-alkyl groups.

(24) In the context of the present invention, the expression “—(C.sub.6-C.sub.20)-aryl” encompasses mono- or polycyclic aromatic hydrocarbyl radicals. These have 6 to 20 ring atoms, more preferably 6 to 14 ring atoms, especially 6 to 10 ring atoms. Aryl is preferably —(C.sub.6-C.sub.10)-aryl and —(C.sub.6-C.sub.10)-aryl-(C.sub.6-C.sub.10)-aryl-. Aryl is especially phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, coronenyl. More particularly, aryl is phenyl, naphthyl and anthracenyl.

(25) Substituted —(C.sub.6-C.sub.20)-aryl groups may have one or more (e.g. 1, 2, 3, 4 or 5) substituents, depending on the ring size. These substituents are preferably each independently selected from —H, —(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl, -halogen (such as Cl, F, Br, I), —COO—(C.sub.1-C.sub.12)-alkyl, —CONH—(C.sub.1-C.sub.12)alkyl, —(C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2, —CO—(C.sub.1-C.sub.12)-alkyl, —CO—(C.sub.6-C.sub.20)-aryl, —COOH, —OH, —SO.sub.3H, —SO.sub.3Na, —NO.sub.2, —CN, —NH.sub.2, —N[(C.sub.1-C.sub.12)-alkyl].sub.2.

(26) Substituted —(C.sub.6-C.sub.20)-aryl groups are preferably substituted —(C.sub.6-C.sub.10)-aryl groups and —(C.sub.6-C.sub.10)-aryl-(C.sub.6-C.sub.10)-aryl groups, especially substituted phenyl or substituted naphthyl or substituted anthracenyl. Substituted —(C.sub.6-C.sub.20)-aryl groups preferably bear one or more, for example 1, 2, 3, 4 or 5, substituents selected from —(C.sub.1-C.sub.12)-alkyl groups, —(C.sub.1-C.sub.12)-alkoxy groups.

(27) In one embodiment, R.sup.1 is —(C.sub.1-C.sub.12)-alkyl.

(28) In one embodiment, R.sup.1 is —CH.sub.2CH.sub.3.

(29) In one embodiment, at least one of the R.sup.1, R.sup.2, R.sup.3 radicals is not the same as the two other radicals.

(30) In one embodiment, R.sup.1 is not the same as one of the R.sup.2, R.sup.3 radicals.

(31) In one embodiment, R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45, R.sup.51, R.sup.52, R.sup.53, R.sup.54, R.sup.55, R.sup.61, R.sup.62, R.sup.63, R.sup.64, R.sup.65 are each independently selected from:

(32) —H, —(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.6-C.sub.20)-aryl, —(C.sub.6-C.sub.20)-aryl.

(33) In one embodiment, R.sup.41, R.sup.43, R.sup.51, R.sup.53, R.sup.61, R.sup.63 are each tert-butyl.

(34) In one embodiment, R.sup.45, R.sup.55, R.sup.65 are each —H.

(35) In one embodiment, the mixture is solid at 25° C.

(36) The term “solid” in this context is understood to mean the state of matter, which delimits the mixture, for example, from a liquid mixture.

(37) As well as the mixture, a complex mixture including such a mixture is also claimed.

(38) Complex mixture comprising: an above-described mixture, a metal atom selected from: Rh, Ru, Co, Ir.

(39) In this regard, see R. Franke, D. Selent, A. Börner, “Applied Hydroformylation”, Chem. Rev., 2012, DOI:10.1021/cr3001803; p. 5688, Scheme 12 “General Method for the Preparation of a P-Modified Rh precatalyst” and references cited therein, and also P. W. N. M. van Leeuwen, in Rhodium Catalyzed Hydroformylation, P. W. N. M. van Leeuwen, C. Claver (eds.), Kluwer, Dordrecht, 2000, inter alia p. 48 ff., p. 233 ff. and references cited therein, and also K. D. Wiese and D. Obst in Top. Organomet. Chem. 2006, 18, 1-13; Springer Verlag Berlin Heidelberg 2006 p. 6 ff. and references cited therein.

(40) In the complex mixture, three different cases may exist:

(41) 1) The complex has ligands either of the I or II type, and the mixture is of complex molecules having only ligands of the I type with complex molecules having only ligands of the II type.

(42) 2) A complex in itself already has ligands of the I and II type.

(43) 3) Is a mixed form of 1) and 2).

(44) As well as the mixtures/complex mixtures, also claimed is the use thereof as complex mixtures for catalysis of a hydroformylation reaction. In this case, the compounds in the mixture are the ligands in the complex. The ligands coordinate to the central metal atom. The ligand-metal complex thus obtained or the complex mixtures thus obtained then catalyze the hydroformylation reaction.

(45) Use of an Above-Described Mixture in a Complex Mixture for Catalysis of a Hydroformylation Reaction.

(46) In addition, also claimed is the hydroformylation reaction.

(47) Process comprising the process steps of:

(48) a) initially charging an olefin,

(49) b) adding a mixture comprising a compound of the structure IIIa:

(50) ##STR00007##

(51) where

(52) R.sup.10 is selected from:

(53) —(C.sub.1-C.sub.12)-alkyl, —(C.sub.6-C.sub.20)-aryl, —(C.sub.3-C.sub.12)-cycloalkyl,

(54) and

(55) R.sup.2, R.sup.3 are each independently selected from:

(56) —(C.sub.1-C.sub.12)-alkyl, —(C.sub.6-C.sub.20)-aryl, —(C.sub.3-C.sub.12)-cycloalkyl,

(57) the R.sup.2 and R.sup.3 radicals may also be bridged to one another, and may have a —(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl unit,

(58) where the alkyl, cycloalkyl and aryl groups mentioned may be substituted,

(59) and a compound of the structure IIa:

(60) ##STR00008##

(61) where

(62) R.sup.4, R.sup.5, R.sup.6 are each independently selected from:

(63) —(C.sub.1-C.sub.12)-alkyl, —(C.sub.6-C.sub.20)-aryl, —(C.sub.3-C.sub.12)-cycloalkyl,

(64) two R.sup.4 and R.sup.5 or R.sup.5 and R.sup.6 or R.sup.6 and R.sup.4 radicals may also be bridged to one another, and may have a —(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl unit,

(65) where the alkyl, cycloalkyl and aryl groups mentioned may be substituted;

(66) c) adding a compound comprising one of the following metals: Rh, Ru, Co, Ir,

(67) c) feeding in H.sub.2 and CO,

(68) d) heating the reaction mixture, with conversion of the olefin to an aldehyde,

(69) where the additions in process steps b) and c) can also be effected in one step through the addition of a corresponding complex mixture.

(70) In this process, process steps a) to e) can be effected in any desired sequence.

(71) Preference is given to a temperature of 80° C. to 160° C. and a pressure of 1 to 300 bar.

(72) Particular preference is given to a temperature of 100° C. to 160° C. and a pressure of 15 to 250 bar.

(73) In one variant of the process, R.sup.10 is selected from: —(C.sub.1-C.sub.12)-alkyl, —(C.sub.3-C.sub.12)cycloalkyl.

(74) In one variant of the process, R.sup.10 is selected from: —(C.sub.1-C.sub.12)-alkyl.

(75) In one variant of the process, the mixture comprises a compound of the structure IIIb:

(76) ##STR00009##

(77) where

(78) R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.31, R.sup.32, R.sup.33, R.sup.34, R.sup.35 are each independently selected from:

(79) —H, —(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.6-C.sub.20)-aryl, —(C.sub.6-C.sub.20)-aryl, -halogen, —COO—(C.sub.1-C.sub.12)-alkyl, —CO—(C.sub.1-C.sub.12)-alkyl, —CO—(C.sub.6-C.sub.20)-aryl, —COOH, —OH.

(80) In one variant of the process, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.31, R.sup.32, R.sup.33, R.sup.34, R.sup.35 are each independently selected from:

(81) —H, —(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.6-C.sub.20)-aryl, —(C.sub.6-C.sub.20)-aryl.

(82) In one variant of the process, R.sup.21, R.sup.23, R.sup.31, R.sup.33 are each tert-butyl.

(83) In one variant of the process, R.sup.25, R.sup.35 are each —CH.sub.3.

(84) In one variant of the process, R.sup.10 is —(C.sub.1-C.sub.12)-alkyl.

(85) In one variant of the process, R.sup.10 is —CH.sub.2CH.sub.3.

(86) In one variant of the process, R.sup.10 is not the same as one of the R.sup.4, R.sup.5, R.sup.6 radicals.

(87) In one variant of the process, at least one of the R.sup.10, R.sup.2, R.sup.3 radicals is not the same as the two other radicals.

(88) In one variant of the process, R.sup.4, R.sup.5, R.sup.6 are each independently —(C.sub.6-C.sub.20)-aryl.

(89) In one variant of the process, the mixture comprises a compound of the structure IIb

(90) ##STR00010##

(91) where

(92) R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45, R.sup.51, R.sup.52, R.sup.53, R.sup.54, R.sup.55, R.sup.61, R.sup.62, R.sup.63, R.sup.64, R.sup.65 are each independently selected from:

(93) —H, —(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.6-C.sub.20)-aryl, —(C.sub.6-C.sub.20)-aryl, -halogen, —COO—(C.sub.1-C.sub.12)-alkyl, —CO—(C.sub.1-C.sub.12)-alkyl, —CO—(C.sub.6-C.sub.20)-aryl, —COOH, —OH.

(94) In one variant of the process, R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45, R.sup.51, R.sup.52, R.sup.53, R.sup.54, R.sup.55, R.sup.61, R.sup.62, R.sup.63, R.sup.64R.sup.65 are each independently selected from:

(95) —H, —(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.6-C.sub.20)-aryl, —(C.sub.6-C.sub.20)-aryl.

(96) In one variant of the process, R.sup.41, R.sup.43, R.sup.51, R.sup.53, R.sup.61, R.sup.63 are each tert-butyl.

(97) In one variant of the process, R.sup.45, R.sup.55, R.sup.65 are each —H.

(98) In a preferred embodiment, the metal is Rh.

(99) The reactants for the hydroformylation in the process of the invention are olefins or mixtures of olefins, especially monoolefins having 2 to 24, preferably 3 to 16 and more preferably 3 to 12 carbon atoms, having terminal or internal C≡C double bonds, for example 1-propene, 1-butene, 2-butene, 1- or 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, 1-, 2- or 3-hexene, the C.sub.6 olefin mixture obtained in the dimerization of propene (dipropene), heptenes, 2- or 3-methyl-1-hexenes, octenes, 2-methylheptenes, 3-methylheptenes, 5-methyl-2-heptene, 6-methyl-2-heptene, 2-ethyl-1-hexene, the C.sub.8 olefin mixture obtained in the dimerization of butenes (di-n-butene, diisobutene), nonenes, 2- or 3-methyloctenes, the C.sub.9 olefin mixture obtained in the trimerization of propene (tripropene), decenes, 2-ethyl-1-octene, dodecenes, the C.sub.12 olefin mixture obtained in the tetramerization of propene or the trimerization of butenes (tetrapropene or tributene), tetradecenes, hexadecenes, the C.sub.16 olefin mixture obtained in the tetramerization of butenes (tetrabutene), and olefin mixtures prepared by cooligomerization of olefins having different numbers of carbon atoms (preferably 2 to 4).

(100) The process according to the invention using the mixtures/complex mixtures according to the invention can be used to hydroformylate α-olefins, terminally branched, internal and internally branched olefins. What is remarkable is the high yield of terminally hydroformylated olefin, even when only a small proportion of olefins having a terminal double bond was present in the reactant.

(101) Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only, and are not intended to be limiting unless otherwise specified.

EXAMPLES

General Operating Procedures

(102) All the preparations which follow were carried out under protective gas using standard Schlenk techniques. The solvents were dried over suitable desiccants before use (Purification of Laboratory Chemicals, W. L. F. Armarego, Christina Chai, Butterworth Heinemann (Elsevier), 6th edition, Oxford 2009).

(103) All preparative operations were effected in baked-out vessels. The products were characterized by means of NMR spectroscopy. Chemical shifts (8) are reported in ppm. The .sup.31P NMR signals were referenced according to: SR.sub.31P=SR.sub.1H*(BF.sub.31P/BF.sub.1H)=SR.sub.1H*0.4048. (Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de Menezes, Robin Goodfellow, and Pierre Granger, Pure Appl. Chem., 2001, 73, 1795-1818; Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de Menezes, Pierre Granger, Roy E. Hoffman and Kurt W. Zilm, Pure Appl. Chem., 2008, 80, 59-84).

(104) Nuclear resonance spectra were recorded by means of a Broker Avance 300 or Bruker Avance 400; gas chromatography analysis was effected using an Agilent GC 7890A.

Preparation of bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite

(105) ##STR00011##

(106) A 250 ml Schlenk flask with magnetic stirrer, attachment, dropping funnel and reflux condenser was initially charged with 22.5 g (0.1 mol) of 2,4-di-tert-butyl-6-methylphenol (4,6-di-tert-butyl-ortho-cresol), and heated to 55° C. in order to melt the phenol. 0.13 ml (0.0015 mol) of dried degassed dimethylformamide was added to the melt. Subsequently, 5.7 ml (0.065 mol) of phosphorus trichloride were added dropwise within 2 hours. After the addition had ended, the reaction mixture was heated to 140° C. within 3 hours and stirred at this temperature for 1 hour. Then the mixture was stirred at 130° C. under reduced pressure for 1 hour. Thereafter, the clear yellow-orange melt obtained (=bis(2,4-di-tert-butyl-6-methyl)phosphochloridite) was cooled down to 80° C. overnight and diluted with 75 ml of degassed petroleum (80-110° C.). After the solution had been cooled down to −5° C., 9.1 ml (0.0665 mol) of degassed triethylamine were added within 15 minutes. Subsequently, within 2 hours, 4.4 ml (0.075 mol) of dried and degassed ethanol were added dropwise, in the course of which the temperature did not rise above 5° C. This mixture was warmed gradually to room temperature overnight while stirring.

(107) The next morning, the precipitated triethylamine hydrochloride was filtered off and the filtrate was concentrated under reduced pressure. This gave a white residue which was recrystallized in 60 ml of degassed ethanol. The product was thus obtained in a yield of 73.9% (19.03 g) as a white solid in 98% purity by LC-MS.

(108) Procedure for the Catalysis Experiments

(109) Experiment Description—General

(110) In a 100 ml autoclave from Parr Instruments, n-octenes were hydroformylated at 120° C. and synthesis gas pressure 50 bar (CO/H.sub.2=1:1 (% by vol.)). As precursor, 0.123 g of Rh(acac)(CO).sub.2 was initially charged for a catalyst concentration of 100 ppm of Rh based on the overall reaction mixture. The solvent used was 40 to 46 g of toluene in each case. Ligand 1 or ligand 2 or the ligand mixture consisting of ligands 1 and 2 was used in different molar excesses relative to rhodium. In addition, as GC standard, about 0.5 g of tetraisopropylbenzene (TIPB) was added. About 6 g of reactant were metered in after the reaction temperature envisaged had been attained.

(111) During the reaction, the pressure was kept constant via synthesis gas regulation with a mass flow meter. The stirrer speed was 1200 min.sup.−1. Samples were taken from the reaction mixture after 12 hours. The results of the experiments are summarized in Table 1.

(112) (acac=acetylacetonate)

(113) Ligands Used in the Catalysis Experiments:

(114) ##STR00012##

(115) The preparation of ligand 1 is described in the above experimental section. Ligand 2 (TDTBPP or Alkanox 240) is commercially available.

(116) Table 1 gives the results for the hydroformylation of di-n-butene. Di-n-butene is a mixture of isomers of n-octenes (about 16%), 3-methylheptenes (about 65%) and 3,4-dimethylhexenes (about 19%).

(117) (Yield=total aldehyde and alcohol yield; S=n/iso selectivity of the octenes present in the mixture for the linear product)

(118) TABLE-US-00001 TABLE 1 Ligand A Ligand B in Y S Entry Ligand A Ligand B in [mmol] [mmol] in % in % 1 — 2 — 20** 96.9 21.8 2* 1 2 0.62  0.32 95.9 36.4 3* 1 2 0.47  0.47 95.7 24.6 4* 1 2 0.31  0.62 95.5 23.4 Reaction conditions: synthesis gas pressure 50 bar, T = 140° C., substrate: di-n-butene, P:Rh = 20:1; 100 ppm [Rh], 12 hours *inventive mixture or complex mixtures **ratio of ligand to Rh 20:1

(119) Table 1 contains experiments for hydroformylation of di-n-butene with various mixtures/complex mixtures. Entry 1 contains a comparative experiment which was conducted with ligand 2 only. A good yield was achieved here, but the selectivity leaves something to be desired.

(120) Through the use of the inventive mixtures/complex mixtures, it was possible to increase the selectivity in all cases. Selectivity for the desired linear aldehydes is noticeably greater here than in the case of the commercially available ligand 2. No significant deterioration is apparent in the yields.

(121) Through the use of the inventive mixtures/complex mixtures, it is possible to selectively control and increase the proportion of terminally hydroformylated product.

(122) The process according to the invention using the mixtures/complex mixtures according to the invention can be used to hydroformylate α-olefins, terminally branched, internal and internally branched olefins. What is remarkable is the high yield of terminally hydroformylated olefin, even when only a small proportion of olefins having a terminal double bond was present in the reactant.

(123) It was thus possible to show, with the aid of the above examples, that the stated problems have been solved through the use of the inventive mixtures/complex mixtures.

(124) German patent application no. DE102014209535.2 filed May 20, 2014, and German patent application no. DE102015202722.8 filed Feb. 16, 2015, are incorporated herein by reference.

(125) Numerous modifications and variations on the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.