Phosphorous acid P,P′-[5,5′,6,6′-tetramethyl-3,3′-bis(l- methylethyl)[1,1′-biphenyl]-2,2′-diyl] P,P,P′,P'-tetrakis(2,4-dimethylphenyl) ester in hydroformylation

Abstract

The compound of the formula (1) and its complexes with metal cations are used for catalysis in hydroformylation processes. ##STR00001##

Claims

1. A symmetric bidentate metal ligand complex mixture comprising a compound represented by formula (2): ##STR00010## and a metal atom selected from the group consisting of Rh, Ru, Co and Ir, wherein the symmetric bidentate metal ligand complex mixture has a chlorine value according to Wickhold below 10,000 ppm.

2. The bidentate metal ligand complex mixture according to claim 1, wherein M is Rh.

3. A process for converting an olefin to an aldehyde comprising the process steps of: a1) initially charging an olefin having 2 to 24 carbon atoms, b1) adding the symmetric bidentate metal ligand complex mixture according to claim 1, c1) feeding in H.sub.2 and CO, d1) heating the reaction mixture, with conversion of the olefin to an aldehyde.

4. The process according to claim 3, characterized in that the metal atom is Rh.

5. The process according to claim 3, wherein the olefin having 2 to 24 carbon atoms is selected from ethene, propene butene, 1-butene or 2-butene.

6. The process according to claim 3, characterized in that, in step a1), wherein the olefin having 2 to 24 carbon atoms is selected from 1-butene or 2-butene.

7. A catalytic hydroformylation process comprising contacting an olefin with the symmetric bidentate metal ligand complex mixture according to claim 1.

8. The process according to claim 7, wherein the hydroformylation process converts the olefin to substituted or unsubstituted aldehydes having 3 to 20 carbon atoms, including substituted or unsubstituted propenals, butanals, pentanals, nonanals, tridecanals, substituted or unsubstituted propenals, butanals or pentanals.

9. The process according to claim 7, wherein the substituted or unsubstituted aldehydes having 3 to 20 carbon atoms include substituted or unsubstituted propenals, butanals or pentanals.

Description

EXAMPLES

(1) 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 (Author), Christina Chai (Author), Butterworth Heinemann (Elsevier), 6th edition, Oxford 2009). All preparative operations were effected in baked-out vessels. The products were characterized by means of NMR spectroscopy. Chemical shifts (δ) are reported in ppm. The .sup.31P NMR signals were referenced as follows: 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). Nuclear resonance spectra were recorded on a Bruker Avance 300 or Bruker Avance 400.

Example 1: Reaction of bis(2,4-dimethlphenyl) chlorophosphite with 3,3′-diisopropyl-5,5′,6,6′-tetramethyl-[1,1′-biphenyl]-2,2′-diol

(2) 8 g (0.020 mol) of bis(2,4-dimethylphenyl) chlorophosphite were dissolved at room temperature in 50 ml of toluene with addition of 3.9 ml (2.85 g, 0.028 mol) of triethylamine and equilibrated to −20° C. Added continuously to this solution within 12 minutes, while stirring, was a solution of 3.1 g (0.009 mol) of 3,3′-diisopropyl-5,5′,6,6′-tetramethyl-[1,1′-biphenyl]-2,2′-diol in 50 ml of toluene. On completion of addition, the mixture was warmed to room temperature while stirring. Subsequently, the hydrochloride formed in the reaction was separated off by means of a quartz glass filter (frit) and the filtrate was concentrated to dryness at room temperature by means of oil-pump vacuum (10.sup.−3 mbar). The resulting solids were stirred vigorously in 50 ml of acetonitrile for 1 h. After the phases had been separated, the upper phase was decanted off and the lower phase was dried at room temperature in an oil-pump vacuum (10.sup.−3 mbar). According to .sup.1H NMR, .sup.31P NMR and .sup.31P-.sup.1H HMBC NMR (dissolved in toluene-d.sub.8), the highly viscous residue contains 73.3% of compound of the formula (1). Chlorine value according to Wickbold: 58 ppm.

Example 2: Hydroformylation

(3) In a 100 ml autoclave from Parr Instruments, 5.6 g of cis-2-butene were hydroformylated at 120° C. and synthesis gas pressure 20 bar (CO/H.sub.2=1:1 (% by vol.)). As the precursor, Rh(acac)(CO).sub.2 was initially charged in 48.8 g of toluene. The ligand was used in a molar excess of 4:1 relative to rhodium. As the ligand, 0.0779 g of ligand was used in the catalyst mixture solution. Tinuvin 770DF was used as stabilizer in a molar ratio to the ligand of about 1:1. In addition, a GC standard was added. About 6 g of reactant were metered in after the reaction temperature envisaged had been attained.

(4) 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.

(5) In addition, the compound (3) was tested under corresponding conditions. Compound (3) was prepared according to EP 2 907 819 A1.

(6) ##STR00009##

(7) Table 1 shows the results of hydroformylation of cis-2-butene at synthesis gas pressure 20 bar.

(8) TABLE-US-00001 TABLE 1 Ligand = compound (X) Aldehyde yield n-Pentanal X = in [%] regioselectivity in % 1* 79 98 3  66 90 *inventive compound of the formula (1)

(9) Definition of the Selectivity:

(10) In the hydroformylation, there is the n/iso selectivity (n/iso=the ratio of linear aldehyde (=n) to branched (=iso) aldehyde)). The n-pentanol regioselectivity here means that this amount of linear product was formed. The remaining percentage then corresponds to the branched isomer. The selectivity rate was determined by means of area comparison in the GC.

(11) The results show that the compound (1) in the hydroformylation both enables a higher yield, i.e. is more reactive, and features a higher regioselectivity with regard to the n/iso ratio than the compound (3).