FERROCENE-BASED COMPOUNDS AND PALLADIUM CATALYSTS BASED THEREON FOR THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS

Abstract

The invention relates to a compound of formula (I)

##STR00001## where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each independently selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.20)-heteroaryl; at least one of the R.sup.1, R.sup.2, R.sup.3, R.sup.4 radicals is a (C.sub.6-C.sub.20)-heteroaryl radical having at least six ring atoms; and R.sup.1, R.sup.2, R.sup.3, R.sup.4, if they are (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.20)-heteroaryl or (C.sub.6-C.sub.20)-heteroaryl, may each independently be substituted by one or more substituents selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, O(C.sub.3-C.sub.12)-cycloalkyl, S(C.sub.1-C.sub.12)-alkyl, S(C.sub.3-C.sub.12)-cycloalkyl, COO(C.sub.1-C.sub.12)-alkyl, COO(C.sub.3-C.sub.12)-cycloalkyl, CONH(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.3-C.sub.12)-cycloalkyl, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.3-C.sub.12)-cycloalkyl, N[(C.sub.1-C.sub.12)-alkyl].sub.2, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl, (C.sub.3-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl-O(C.sub.1-C.sub.12)-alkyl, COOH, OH, SO.sub.3H, NH.sub.2, halogen.

The invention further relates to precursors for preparation of the compound according to the invention, to Pd complexes comprising the compound according to the invention and to the use thereof in alkoxycarbonylation.

Claims

1. Compound of formula (I) ##STR00035## where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each independently selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.20)-heteroaryl; at least one of the R.sup.1, R.sup.2, R.sup.3, R.sup.4 radicals is a (C.sub.6-C.sub.20)-heteroaryl radical having at least six ring atoms; and R.sup.1, R.sup.2, R.sup.3, R.sup.4, if they are (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.20)-heteroaryl or (C.sub.6-C.sub.20)-heteroaryl, may each independently be substituted by one or more substituents selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, O(C.sub.3-C.sub.12)-cycloalkyl, S(C.sub.1-C.sub.12)-alkyl, S(C.sub.3-C.sub.12)-cycloalkyl, COO(C.sub.1-C.sub.12)-alkyl, COO(C.sub.3-C.sub.12)-cycloalkyl, CONH(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.3-C.sub.12)-cycloalkyl, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.3-C.sub.12)-cycloalkyl, N[(C.sub.1-C.sub.12)-alkyl].sub.2, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl, (C.sub.3-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl-O(C.sub.1-C.sub.12)-alkyl, COOH, OH, SO.sub.3H, NH.sub.2, halogen.

2. Compound according to claim 1, where at least two of the R.sup.1, R.sup.2, R.sup.3, R.sup.4 radicals are a (C.sub.6-C.sub.20)-heteroaryl radical having at least six ring atoms.

3. Compound according to claim 1, where the R.sup.1 and R.sup.3 radicals are each a (C.sub.6-C.sub.20)-heteroaryl radical having at least six ring atoms.

4. Compound according to claim 1, where the R.sup.1 and R.sup.3 radicals are each a (C.sub.6-C.sub.20)-heteroaryl radical having at least six ring atoms; R.sup.2 is (C.sub.6-C.sub.20)-heteroaryl having at least six ring atoms or is selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl; and R.sup.4 is selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl.

5. Compound according to claim 1, where the R.sup.1 and R.sup.3 radicals are each a (C.sub.6-C.sub.20)-heteroaryl radical having at least six ring atoms; and R.sup.2 and R.sup.4 are selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl.

6. Compound according to claim 1, where the R.sup.1 and R.sup.3 radicals are each a (C.sub.6-C.sub.20)-heteroaryl radical having at least six ring atoms; and R.sup.2 and R.sup.4 are (C.sub.1-C.sub.12)-alkyl.

7. Compound according to claim 1, where R.sup.1, R.sup.2, R.sup.3, R.sup.4, if they are a heteroaryl radical, are each independently selected from pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl.

8. Compound according to claim 1, of one of the formulae (8), (14) and (15) ##STR00036##

9. Compound of formula (II) as a precursor for preparation of the compounds according to claim 1, ##STR00037## where R.sup.5 is a (C.sub.6-C.sub.20)-heteroaryl radical having at least six ring atoms; R.sup.6 is selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.20)-heteroaryl; and R.sup.5 and R.sup.6, if they are (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.20)-heteroaryl or (C.sub.6-C.sub.20)-heteroaryl, may each independently be substituted by one or more substituents selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, O(C.sub.3-C.sub.12)-cycloalkyl, S(C.sub.1-C.sub.12)-alkyl, S(C.sub.3-C.sub.12)-cycloalkyl, COO(C.sub.1-C.sub.12)-alkyl, COO(C.sub.3-C.sub.12)-cycloalkyl, CONH(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.3-C.sub.12)-cycloalkyl, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.3-C.sub.12)-cycloalkyl, N[(C.sub.1-C.sub.12)-alkyl].sub.2, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl, (C.sub.3-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl-O(C.sub.1-C.sub.12)-alkyl, COOH, OH, SO.sub.3H, NH.sub.2, halogen.

10. Complex comprising Pd and a compound according to claim 1.

11. Process comprising the following process steps: a) initially charging an ethylenically unsaturated compound; b) adding a compound of formula (I) ##STR00038## where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each independently selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.20)-heteroaryl; at least one of the R.sup.1, R.sup.2, R.sup.3, R.sup.4 radicals is a (C.sub.6-C.sub.20)-heteroaryl radical having at least six ring atoms; and R.sup.1, R.sup.2, R.sup.3, R.sup.4, if they are (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.2)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.20)-heteroaryl or (C.sub.6-C.sub.20)-heteroaryl, may each independently be substituted by one or more substituents selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, O(C.sub.3-C.sub.12)-cycloalkyl, S(C.sub.1-C.sub.12)-alkyl, S(C.sub.3-C.sub.12)-cycloalkyl, COO(C.sub.1-C.sub.12)-alkyl, COO(C.sub.3-C.sub.12)-cycloalkyl, CONH(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.3-C.sub.12)-cycloalkyl, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.3-C.sub.12)-cycloalkyl, N[(C.sub.1-C.sub.12)-alkyl].sub.2, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl, (C.sub.3-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl-O(C.sub.1-C.sub.12)-alkyl, COOH, OH, SO.sub.3H, NH.sub.2, halogen and a compound comprising Pd, or adding a complex according to claim 10; c) adding an alcohol; d) feeding in CO; e) heating the reaction mixture, with conversion of the ethylenically unsaturated compound to an ester.

12. Process according to claim 11, wherein the ethylenically unsaturated compound is selected from ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, and mixtures thereof.

13. Process according to claim 11, wherein the compound comprising Pd in process step b) is selected from palladium dichloride, palladium(II) acetylacetonate, palladium(II) acetate, dichloro(1,5-cyclooctadiene)palladium(II), bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloropalladium(II), palladium(cinnamyl) dichloride.

14. Process according to claim 11, wherein the alcohol in process step c) is selected from methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tert-butanol, 3-pentanol, cyclohexanol, phenol, and mixtures thereof.

15. A process for catalysis of an alkoxycarbonylation reaction, comprising: introducing a compound of formula (I) ##STR00039## where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each independently selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.20)-heteroaryl; at least one of the R.sup.1, R.sup.2, R.sup.3, R.sup.4 radicals is a (C.sub.6-C.sub.20)-heteroaryl radical having at least six ring atoms; and R.sup.1, R.sup.2, R.sup.3, R.sup.4, if they are (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.20)-heteroaryl or (C.sub.6-C.sub.20)-heteroaryl, may each independently be substituted by one or more substituents selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, O(C.sub.3-C.sub.12)-cycloalkyl, S(C.sub.1-C.sub.12)-alkyl, S(C.sub.3-C.sub.12)-cycloalkyl, COO(C.sub.1-C.sub.12)-alkyl, COO(C.sub.3-C.sub.12)-cycloalkyl, CONH(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.3-C.sub.12)-cycloalkyl, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.3-C.sub.12)-cycloalkyl, N[(C.sub.1-C.sub.12)-alkyl].sub.2, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl, (C.sub.3-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl-O(C.sub.1-C.sub.12)-alkyl, COOH, OH, SO.sub.3H, NH.sub.2, halogen or a complex according to claim 10.

Description

DESCRIPTION OF THE FIGURES

[0163] FIG. 1 methoxycarbonylation of ethene with 3 and 8 at 80 C. and 40 bar CO

[0164] FIG. 2 methoxycarbonylation of ethene with 3 and 8 at 60 C. and 20 bar CO (constant pressure)

[0165] FIG. 3 alcohol variation in the methoxycarbonylation of ethene with ligand 8 at 80 C. and CO pressure 30 bar

[0166] FIG. 4 methoxycarbonylation experiments on propene, 1-butene and 2-butene at 100 C. and 40 bar with ligand 8.

[0167] FIG. 5 methoxycarbonylation of raffinate 1 with ligand 8 at 100 C. and CO pressure 60 bar.

[0168] FIG. 6 methoxycarbonylation of raffinate 1 at 100 C. and 50 bar with ligand 8.

[0169] FIG. 7 methoxycarbonylation of a mixture of propene, 1-butene and 2-butene at 100 C. and 60 bar with ligand 8.

[0170] FIG. 8 methoxycarbonylation of a mixture of C5 olefins at 100 C. and CO pressure 50 bar with ligand 8.

[0171] FIG. 9 methoxycarbonylation of di-n-butene with ligand 8 at 120 C. and 20 bar with constant CO pressure.

[0172] FIG. 10 methoxycarbonylation of di-n-butene with 3 and 8 at 120 C. and 40 bar CO.

[0173] FIG. 11 yield curve for the methoxycarbonylation of di-n-butene with 8 as ligand at constant total pressure 20 bar and 120 C.

[0174] FIG. 12 gas consumption curves of reactions with 3 and 8.

EXAMPLES

[0175] The invention is described in detail hereinafter by working examples.

[0176] General Procedures

[0177] 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).

[0178] Phosphorus trichloride (Aldrich) was distilled under argon before use. All preparative operations were effected in baked-out vessels. The products were characterized by means of NMR spectroscopy. Chemical shifts () 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).

[0179] The recording of nuclear resonance spectra was effected on Bruker Avance 300 or Bruker Avance 400, gas chromatography analysis on Agilent GC 7890A, elemental analysis on Leco TruSpec CHNS and Varian ICP-OES 715, and ESI-TOF mass spectrometry on Thermo Electron Finnigan MAT 95-XP and Agilent 6890 N/5973 instruments.

Preparation of Precursor E

Preparation of chloro-2-pyridyl-tert-butylphosphine

[0180] The Grignard for the synthesis of chloro-2-pyridyl-t-butylphosphine is prepared by the Knochel method with isopropylmagnesium chloride (Angew. Chem. 2004, 43, 2222-2226). The workup is effected according to the method of Budzelaar (Organometallics 1990, 9, 1222-1227).

##STR00006##

[0181] 8.07 ml of a 1.3 M isopropylmagnesium chloride solution (Knochel's reagent) are introduced under argon into a 50 ml round-bottom flask with magnetic stirrer and septum, and cooled to 15 C. Thereafter, 953.5 l (10 mmol) of 2-bromopyridine are rapidly added dropwise. The solution immediately turns yellow. It is allowed to warm up to 10 C. The conversion of the reaction is determined as follows: about 100 l solution are taken and introduced into 1 ml of a saturated ammonium chloride solution. If the solution bubbles, not much Grignard has formed yet. The aqueous solution is extracted with a pipette of ether and the organic phase is dried over Na.sub.2SO.sub.4. A GC of the ethereal solution is recorded. When a large amount of pyridine has formed compared to 2-bromopyridine, conversions are high. At 10 C., there has been little conversion. After warming up to room temperature and stirring for 1-2 hours, the reaction solution turns brown-yellow. A GC test shows complete conversion. Now the Grignard solution can be slowly added dropwise with a syringe pump to a solution of 1.748 g (11 mmol) of dichloro-tert-butylphosphine in 10 ml of THF which have been cooled to 15 C. beforehand. It is important that the dichloro-tert-butylphosphine solution is cooled. At room temperature, considerable amounts of dipyridyl-tert-butylphosphine would be obtained. A clear yellow solution is initially formed, which then turns cloudy. The mixture is left to warm up to room temperature and to stir overnight. The solvent is removed under high vacuum and a whitish solid which is brown in places is obtained. The solid is suspended with 20 ml of heptane and the solid is comminuted in an ultrasound bath. After allowing the white solid to settle out, the solution is decanted. The operation is repeated twice with 10-20 ml each time of heptane. After concentration of the heptane solution under high vacuum, it is distilled under reduced pressure. At 4.6 mbar, oil bath 120 C. and distillation temperature 98 C., the product can be distilled. 1.08 g of a colourless oil are obtained. (50%).

[0182] Analytical data: .sup.1H NMR (300 MHz, C.sub.6D.sub.6): 8.36 (m, 1H, Py), 7.67 (m, 1H, Py), 7.03-6.93 (m, 1H, Py), 6.55-6.46 (m, 1H, Py), 1.07 (d, J=13.3 Hz, 9H, t-Bu)

[0183] .sup.13C NMR (75 MHz, C.sub.6D.sub.6): 162.9, 162.6, 148.8, 135.5, 125.8, 125.7, 122.8, 35.3, 34.8, 25.9 and 25.8.

[0184] .sup.31P NMR (121 MHz, C.sub.6D.sub.6) 97.9.

[0185] MS (EI) m:z (relative intensity) 201 (M.sup.+, 2), 147(32), 145 (100), 109 (17), 78 (8), 57.1 (17).

Preparation of Compound 8

Preparation of 1,1-bis(tert-butyl-2-pyridylphosphino)ferrocene

[0186] ##STR00007##

[0187] Variant A:

[0188] 474.4 mg (2.55 mmol) of sublimed ferrocene are weighed into a 50 ml round-bottom flask with magnetic stirrer and septum, and the flask was purged. After addition of 15 ml of heptane, the ferrocene has dissolved completely. Then 841 l of tetramethylethylenediamine (1.1 eq, 5.61 mmol) are added all at once and 2.04 ml of BuLi (2.5 M in hexane, 2.0 eq, 5.1 mmol) are added dropwise. After 2-3 hours, an orange solid precipitates out. The mixture is left to stir overnight, the heptane solution is decanted and the orange solid is washed twice with heptane. Then another 10 ml of heptane are added and the suspension is cooled to 70 C. 1.08 g (2.1 eq, 5.36 mmol) of chloro-2-pyridyl-tert-butylphosphine are dissolved in 7 ml of heptane. The solution is cloudy and has to be filtered through Celite. A little insoluble white solid has formed. This solution is added dropwise to the dilithioferrocene solution. While being warmed up to room temperature, the colour of the orange suspension lightens. To complete the reaction, the reaction solution is heated under reflux for about 1 hour. A clear orange solution and white precipitate have formed.

[0189] 7 ml of argon-saturated water are added to the suspension. The white precipitate dissolves. After the aqueous phase has been removed, the operation is repeated twice. This makes the heptane phase cloudy. On completion of removal of the organic phase under high vacuum, what remains is an orange oily residue. This is taken up in 10 ml of ether and dried over Na.sub.2SO.sub.4. (Crude yield 913 mg.) At 28 C., there is no formation of either a precipitate or crystals overnight. Nor does a mixture of diethyl ether and heptane lead to crystallization at 28 C. A .sup.31P NMR of the solution again shows the product peak, now at 7.39 ppm, and a signal at 40.4 ppm. The product can be purified by column chromatography. The ether solution is applied to a short column which is eluted with diethyl ether under argon. The orange product front runs off right at the front and can be collected easily. After the ether has been removed, 241 mg (16%) of an orange viscous oil are obtained in about 95% purity.

[0190] Variant B:

[0191] Batch size: 650.17 mg (3.495 mol) of ferrocene (sublimed), 2.8 ml (2 eq, 6.99 mmol) of 2.5 M BuLi (n-butyllithium), 1.1 ml (2.1 eq, 7.3 mmol) of tetramethylethylenediamine and 1.48 g (2.1 eq, 7.34 mmol) of chloro-2-pyridyl-tert-butylphosphine.

[0192] The dilithium salt of ferrocene is again prepared in 15 ml of heptane. The chloro-2-pyridyl-tert-butylphosphine is dissolved in 10 ml of THF rather than heptane, because the chlorophosphine dissolves better in THF. The workup was likewise optimized: after boiling under reflux, the reaction mixture is quenched with only 1 ml of H.sub.2O and the solvent (heptane and THF) is removed completely under high vacuum. The dark yellow/orange stringy solid is taken up in 8 ml of H.sub.2O and 15 ml of dimethyl ether and stirred for 1 minute. After phase separation, the aqueous phase is removed via a syringe and the organic phase is washed three times with H.sub.2O. The organic phase is dried over Na.sub.2SO.sub.4 and filtered. The product is washed out of the Na.sub.2SO.sub.4 3 times with 10 ml each time of diethyl ether until the solution is almost colourless. The dark orange solution is concentrated to a volume of 10 ml and sent through a column comprising silica gel 60 under argon. The eluent used is diethyl ether again. The filtrate is much brighter and more orange. After removing the solid, 1.16 g of a stringy orange solid are obtained. (64%)

Preparation of Compound 10

Comparative Compound

[0193] Proceeding from 1,1-(ferrocenediyl)phenylphosphine, the strained phosphine ring is opened with PhLi and the resulting intermediate is quenched with a chlorophosphine.

##STR00008##

##STR00009##

[0194] A 50 ml round-bottom flask with magnetic stirrer bar and nitrogen connection is initially charged with 1.13 mmol (565 l) of phenyllithium (PhLi), and a solution of 1.03 mmol (300 mg) of cyclic phosphine in 20 ml of heptane is slowly added dropwise via a syringe pump. The Li salt is washed twice with heptane and admixed with 6 ml of heptane. A heptane solution of 0.8 eq (0.824 mmol, 131 l) of ClPiPr.sub.2 in 7 ml of heptane is added dropwise to the suspension at room temperature. The red-brown suspension barely changes colour. After stirring for 20 min, the suspension is heated under reflux for 1.5 hours. The solid turns a somewhat lighter colour. Solvent is removed completely and the brown-red residue is taken up in H.sub.2O and ether. The organic phase is washed twice with H.sub.2O and dried over Na.sub.2SO.sub.4. A .sup.31P spectrum of the ether phase is recorded. The spectrum shows 2 singlets. The chlorophosphine has been fully consumed. The ether phase is dried and 300 mg (yield: 61%) of a brown-yellow oil are obtained, which dissolves in MeOH on a water bath at 65 C. The solution is put in the freezer (78 C.) overnight. 76 mg of a brown-yellow oil precipitate out, which is analysed by NMR spectroscopy.

[0195] .sup.1H NMR (300 MHz, CDCl.sub.3) 7.46-7.23 (m, 10H, Ph), 4.36 (m, 2H, Cp), 4.21 (m, 2H, Cp), 34.24 (m, 4H, Cp), 1.88 (m, 2H, iPr), 1.15-0.96 (m, 12H, iPr).

[0196] .sup.13C NMR (75 MHz, CDCl.sub.3) 139.9 (J=9.8 Hz, Ph), 133.4 (J=19.2 Hz, Ph), 128.4, 128.1, 128.0 (Ph), 77.1, 76.8, 76.2, 76.1 (Cp), 73.5 (J=14.5 Hz, Cp), 72.8 (J=2.9 Hz, Cp), 71.9 (J=10.5 Hz, Cp), 72.1 (Cp), 23.3 (J=11.0 Hz, iPr), 20.1, 20.0, 19.9, 19.8 (iPr).

[0197] .sup.31P NMR (121 MHz, C.sub.6D.sub.6) =0.88 and -16.62

Preparation of Compound 14

Preparation of bis(2-pyridyl-n-butylphosphino)ferrocene

[0198] ##STR00010##

[0199] In a 25 ml round-bottom flask with magnetic stirrer bar and tap, 1.45 ml (2.33 mmol) of 1.6 M BuLi are cooled to 78 C. (dry ice/EtOH). To this are added dropwise 208 l (2.18 mmol) of 2-bromopyridine dissolved in 2 ml of ether. The reaction solution turns yellow at first, then changes colour to orange, but remains clear. After stirring for 15 minutes, a sample (100 l) is taken and quenched with NH.sub.4Cl/H.sub.2O. According to GC, as well as pyridine, numerous other compounds have also formed. Then, at this temperature, 1,1-bis(dichlorophosphine)ferrocene dissolved in 2 ml of ether are added dropwise and the reaction mixture is allowed to warm up overnight. A pale orange suspension has formed, which is filtered through a frit (G4). A clear orange ether solution is obtained. After the solvent has been drawn off under reduced pressure, 173 mg of an orange solid are obtained, and this is chromatographed under argon. The mixture is columned first with pure diethyl ether (column parameters: diameter 4 cm, silica gel 60), and 50 mg of a stringy yellow solid are obtained. The solid is columned once again with 2:1 heptane/diethyl ether, and 31 mg of bis(2-pyridyl-n-butylphosphino)ferrocene (18%) are obtained.

[0200] .sup.1H NMR (300 MHz, C.sub.6D.sub.6): 8.54 (d, J=4.6 Hz, 2H, py), 7.43-7.32 (m, 2H, py), 6.94-6.88 (m, 2H, py), 6.58-6.49 (m, 2H, py), 4.47 (m, 1H, ferrocenyl), 4.37 (m, 1H, ferrocenyl), 4.33 (m, 1H, ferrocenyl), 4.23-4.14 (m, 5H, ferrocenyl), 2.56-2.44 (m, 2H, CH.sub.2), 2.23 (m, 2H, CH.sub.2), 1.80-1.65 (m, 4H, CH.sub.2), 1.57-1.39 (m, 4H, CH.sub.2), 0.93-0.85 (m, 6H, CH.sub.3).

[0201] .sup.13C NMR (75 MHz, C.sub.6D.sub.6): 166.5, 166.2, 166.1, 150.1, 134.8 and 122.1 (py), 78.7, 78.6, 78.5, 74.9, 74.7, 74.3, 74.1, 72.8, 72.6, 72.1 and 71.7 (ferrocenyl), 29.7, 29.6, 29.5, 29.4, 28.2, 28.1, 27.9, 27.8, 24.8, 24.7, 24.6 and 14.1 (CH.sub.2), 14.1 (CH.sub.3).

[0202] .sup.31P NMR (121 MHz, C.sub.6D.sub.6) 24.7 and 24.9.

[0203] HRMS (ESI) m/z.sup.+ calculated for C.sub.28H.sub.34FeN.sub.2P.sub.2(M+H).sup.+ 517.16197. found: 517.16238.

Preparation of Compound 15

Preparation of bis(2-pyridyl-n-butylphosphino)ferrocene

[0204] ##STR00011##

[0205] In a 25 ml round-bottom flask with a magnetic stirrer, 5.3 ml (1.1 eq) of a 1.3 M isopropylmagnesium chloride solution (Knochel's reagent) are cooled to 20 C. and added all at once to 603 l (6.32 mmol) of 2-bromopyridine. The mixture is stirred at 20 C. for one hour and then at room temperature for 2 hours, in order to achieve complete conversion. In a second 50 ml round-bottom flask, 490.7 mg (1.26 mmol) of 1,1-bis(dichlorophosphino)ferrocene are weighed out in a glovebox and, after removal through the airlock, dissolved in 10 ml of THF. After cooling to 20 C., the previously prepared Grignard compound is added dropwise to the orange-yellow solution by means of a syringe pump. After dropwise addition, the solution has warmed to 00 C. and a brown/black solution has formed. To complete the reaction, the mixture is heated under reflux for another 20 minutes. The next day, 0.5 ml of water is added to the black reaction solution, and the solution lightens in colour to become a dark red/brown suspension. The solvent is drawn off under high vacuum and the residue is taken up in 15 ml of ether and 10 ml of H.sub.2O. The suspension is filtered through Celite, and an orange organic phase and a green aqueous phase are obtained. The organic phase is dried over Na.sub.2SO.sub.4 and, after the ether has been drawn off, 410 mg of a green/black solid are obtained. The dark green, almost black solid is columned in pure diethyl ether. After the ether has been removed, 112 mg of the yellow product 15 are obtained.

[0206] .sup.1H NMR (300 MHz, C.sub.6D.sub.6): 8.56 (m, 1H, py), 8.48-8.38 (m, 2H, py), 7.58 (m, 1H, py), 7.39-7.27 (m, 2H, py), 7.00-6.84 (m, 3H, py), 6.65-6.56 (m, 1H, py), 6.55-6.44 (m, 2H, py), 4.50-4.39 (m, 3H, ferrocenyl), 4.26-4.18 (m, 2H, ferrocenyl), 4.18-4.12 (m, 1H, ferrocenyl), 4.12-4.04 (m, 2H, ferrocenyl), 2.69 (oct, J=7.0 Hz, 1H ipr), 1.14-0.94 (m, 6H, ipr).

[0207] .sup.13C NMR (75 MHz, C.sub.6D.sub.6): 165.4, 163.7, 150.2, 150.0, 149.9, 134.9, 134.8, 134.7, 131.1, 130.6, 129.1, 128.8, 128.6, 122.7, 122.2, and 122.0 (py), 77.5, 77.3, 76.9, 76.5, 75.4, 75.2, 74.8, 74.6, 74.4, 72.8, 72.7, 72.5, 72.0 and 71.9 (ferrocenyl), 32.2, 28.3, 28.2, 23.0, 20.6, 20.3, 19.7, 19.5 and 14.3 (ipr).

[0208] .sup.31P NMR (121 MHz, C.sub.6D.sub.6) 6.2 and 12.9.

[0209] HRMS (ESI) m/z.sup.+ calculated for C.sub.28H.sub.27FeN.sub.3P.sub.2(M+H).sup.+ 524.11027. found: 524.11022.

Preparation of Compound 19

Comparative Compound

[0210] ##STR00012##

[0211] 0.93 g of ferrocene is dissolved in 50 ml of absolute heptane in a 100 ml three-neck flask provided with a thermometer, magnetic stirrer and reflux condenser. 1.3 g of TMEDA (1.6 ml) and 7.5 ml of 1.6 M n-BuLi/hexane are added by means of syringes at room temperature. The solution is left to stand for 5 hours. Orange/brown crystals of the dilithiated ferrocene precipitate out. The supernatant solution is removed by means of a syringe. And 20 ml of absolute heptane are added. Subsequently, the chlorophosphine dissolved in 10 ml of heptane is added dropwise. The mixture is heated under reflux for one hour. After cooling, the organic phase is washed three times with 10 ml each time of degassed water. The mixture is concentrated to dryness, and 10 ml of diethyl ether are added. The solution is filtered through 10 cm of silica gel 60 under argon with diethyl ether as solvent, concentrated to dryness and crystallized from a little hot methanol to give the target product in an about 50% non-optimized yield.

[0212] Analysis:

[0213] .sup.31P (121 MHz, CDCl.sub.3), 7.8 s, 8.15 s,

[0214] .sup.13C (75 MHz, CDCl.sub.3); 137.77, (d, J=12 Hz), 137.4 (d, J=11.3 Hz), 134.2 (d, J=20.3 Hz), 129.1 s, 128.1 (d, J=7.5 Hz), 77.4 (d, J=11.3 Hz), 75.0 (d, J=26.2 Hz), 74.0 (d, J=22.3 Hz), 72.1 bs, 71.9-71.5 m, 71.1 s, 69.0 s, 27.6 (d, J=10 Hz), 27.55 8d, J=10 Hz), 20.3-19.9 m

[0215] .sup.1H (300 MHz, CDCl.sub.3): 7.52-7.44 (m, 4H), 7.33-7.23 (m, 6H), 4.23 (sept, J=1.2 Hz, 1H), 4.1-4.0 (m, 4H), 3.93-3.9 (m, 1H), 3.87-3.84 (m, 1H), 3.58-3.54 (m, 1H), 2.1-1.9 (m, 2H), 0.99 (d, J=7 Hz, 3H), 0.94 (d, J=7 Hz, 3H), 0.83-0.7 (m, 6H)

Preparation of Palladium Complexes

Experiment 52

Preparation of Complex K4

Preparation of [Pd(Cp.SUB.2.Fe)1,1-(P(2-pyridyl)(t-butyl)).SUB.2.].SUP.2.-N-methylmaleimide] K4

[0216] ##STR00013##

[0217] 172.9 mg (0.816 mmol) of palladium precursor (see Scheme 9) and 90.64 mg (0.816 mmol) of sublimed N-methylmaleimide (see Experiment 51) are weighed out in each case into a 50 ml Schlenk vessel in a glovebox. 446.6 mg (0.866 mmol) of the viscous orange ferrocene ligand 8 are dissolved in 15 ml of heptane and added to the N-methylmaleimide. The solution is heated to 60 C. on a water bath until everything has dissolved. In order to obtain a clear orange solution, the solution is filtered through Celite. The palladium precursor is likewise dissolved in 10 ml of heptane and filtered through Celite. At room temperature, the clear orange ligand/N-methylmaleimide solution is added dropwise to the deep red palladium precursor. The dark red solution lightens in colour, and a pale yellow solid precipitates out. The mixture is left to stir overnight, and the supernatant solution is decanted after the solids have settled out. After washing with heptane twice, the solid is dried under high vacuum, and 541 mg (86%) of product are obtained.

[0218] Elemental analysis calculated for: C.sub.33H.sub.39FeN.sub.3O.sub.2P.sub.2Pd: C, 54.01; H, 5.36; N, 5.73; P, 8.44. found: C, 53.44; H, 5.48; N, 5.72; P, 8.48.

[0219] High-Pressure Experiments

[0220] Feedstocks:

[0221] Methanol (MeOH)

[0222] Ethene (also referred to as ethylene)

[0223] Crack-C4 refers to a by-product stream from what is called the steamcracking process for ethylene production and consists generally to an extent of more than 95% of a mixture of various branched and linear hydrocarbons which contain four carbon atoms and may be saturated, monounsaturated or polyunsaturated. The main components of a crack-C4 stream are n-butane, isobutane, isobutene, n-butenes, butadienes.

[0224] Raffinate 1 is obtained from crack-C4 after (generally extractive) removal of the butadienes. Raffinate 1 is composed of about 42% isobutene, 26% 1-butene, 17% cis- and trans-2-butene, and also 0.3% 1,3-butadiene and 15% n-butane and isobutane. The exact composition can vary by source and also seasonally. The values reported are therefore merely typical but nonlimiting examples.

[0225] Raffinate II is a portion of the C.sub.4 fraction which arises in naphtha cracking and consists essentially of the isomeric n-butenes, isobutane and n-butane after removal of isobutene from raffinate 1.

[0226] Raffinate III is a portion of the C.sub.4 fraction which arises in naphtha cracking and consists essentially of the isomeric n-butenes and n-butane.

[0227] 2-butene 99+%, mixture of cis and trans, Sigma Aldrich, catalogue number 36,335-9, LOT No. 14205MS

[0228] The isobutene used has a purity of min. 99.9% (m/m). The manufacturer is Evonik Industries AG, Performance Materials.

[0229] Di-n-butene was also referred to as follows: dibutene, DNB or DnB.

[0230] Di-n-butene is an isomer mixture of C8 olefins which arises from the dimerization of mixtures of 1-butene, cis-2-butene and trans-2-butene. In industry, raffinate II or raffinate III streams are generally subjected to a catalytic oligomerization, wherein the butanes present (n/iso) emerge unchanged and the olefins present are converted fully or partly. As well as dimeric di-n-butene, higher oligomers (tributene C12, tetrabutene C16) generally also form, which have to be removed by distillation after the reaction.

[0231] One process practised in industry for oligomerization of C4 olefins is called the OCTOL process.

[0232] Within the patent literature, DE102008007081A1, for example, describes an oligomerization based on the OCTOL process. EP1029839A1 is concerned with the fractionation of the C8 olefins formed in the OCTOL process.

[0233] Technical di-n-butene consists generally to an extent of 5% to 30% of n-octenes, 45% to 75% of 3-methylheptenes, and to an extent of 10% to 35% of 3,4-dimethylhexenes. Preferred streams contain 10% to 20% n-octenes, 55% to 65% 3-methylheptenes, and 15% to 25% 3,4-dimethylhexenes.

[0234] para-Toluenesulphonic acid was abbreviated as follows: pTSA, PTSA or p-TSA.

[0235] PTSA in this text always refers to para-toluenesulphonic acid monohydrate.

[0236] General Method for Performance of the High-Pressure Experiments:

[0237] General Experiment Description for Reactions in Batchwise Mode:

[0238] The appropriate amounts of substrate, palladium salt, acid and alcohol are mixed under argon in a 50 ml Schlenk vessel while stirring with a magnetic stirrer.

[0239] A 100 ml steel autoclave from Parr provided with a gas inlet and a gas outlet valve, a digital pressure transducer, a temperature sensor and a ball valve, and an installed capillary for sampling, is freed of oxygen by means of vacuum and argon purging three times. Subsequently, the reaction solution from the Schlenk flask is introduced by means of a capillary into the autoclave in an argon counterflow through the ball valve. Subsequently, either the appropriate amount of CO is injected at room temperature and then the autoclave is heated up to reaction temperature (reactions that are not run under constant pressure) or the autoclave is first heated up to reaction temperature and then the CO is injected by means of a burette connected to the autoclave by means of a pressure reducer. This burette is then filled with CO to about 100 bar and, during the reaction, supplies the CO required at a constant pressure. This burette has a dead volume of about 30 ml and is provided with a digital pressure transducer. Then the reaction is conducted at the required temperature for the required time while stirring. In the course of this, by means of software (Specview from SpecView Corporation) and a Parr 4870 process controller and a 4875 power controller, data for the pressure variation in the autoclave and in the gas burette are recorded. These data are used to generate Excel tables, which are used at a later stage to create diagrams which show gas consumptions and hence conversions over time. If required, via the capillary, the GC samples are collected and analysed. For this purpose, a suitable exact amount (2-10 ml) of isooctane as internal standard is also added to the Schlenk vessel. These also give information about the course of the reaction. At the end of the reaction, the autoclave is cooled down to room temperature, the pressure is cautiously released, isooctane is added if necessary as internal standard, and a GC analysis or, in the case of new products, a GC-MS analysis is conducted as well.

[0240] General Experimental Method for Autoclave Experiments in Glass Vials:

[0241] A 300 ml Parr reactor is used. Matched to this is an aluminium block of corresponding dimensions which has been manufactured in-house and which is suitable for heating by means of a conventional magnetic stirrer, for example from Heidolph. For the inside of the autoclave, a round metal plate of thickness about 1.5 cm was manufactured, containing 6 holes corresponding to the external diameter of the glass vials. Matching these glass vials, they are equipped with small magnetic stirrers. These glass vials are provided with screw caps and suitable septa and charged, using a special apparatus manufactured by glass blowers, under argon with the appropriate reactants, solvents and catalysts and additives. For this purpose, 6 vessels are filled at the same time; this enables the performance of 6 reactions at the same temperature and the same pressure in one experiment. Then these glass vessels are closed with screw caps and septa, and a small syringe cannula of suitable size is used to puncture each of the septa. This enables gas exchange later in the reaction. These vials are then placed in the metal plate and these are transferred into the autoclave under argon. The autoclave is purged with CO and filled at room temperature with the CO pressure intended. Then, by means of the magnetic stirrer, under magnetic stirring, the autoclave is heated to reaction temperature and the reaction is conducted for the appropriate period. Subsequently, the autoclave is cooled down to room temperature and the pressure is slowly released. Subsequently, the autoclave is purged with nitrogen. The vials are taken from the autoclave, and a defined amount of a suitable standard is added. A GC analysis is effected, the results of which are used to determine yields and selectivities.

[0242] General Method for Experiments in the 12-Vial Autoclaves (600 ml Parr Autoclave):

[0243] Baked-out glass vials are each initially charged with di-n-butene (DNB) and methanol, and a solution of Pd(acac).sub.2 (0.5 mg, 0.0016 mmol) and ligand (0.0064 mmol) in 0.2 ml of methanol is added, as is H.sub.2SO.sub.4 (solution: 1 ml of H.sub.2SO.sub.4 in 50 ml MeOH). In the autoclave, the mixtures are purged twice with 10 bar of CO, CO is injected to the desired pressure, and the mixtures are stirred at the desired temperature for 20 h. After the reaction has ended, isooctane (internal standard) and 1 ml of EtOAc are added in each case. The organic phase is analysed by GC.

[0244] The yields of the reactions are determined by means of GC (isooctane as internal standard).

[0245] Analysis:

[0246] GC analysis of the products from ethene: For the GC analysis, an Agilent 7890A gas chromatograph having a 30 m HP column is used. Temperature profile: 35 C., 10 min; 10 C./min to 200 C., 16.5 min; the injection volume is 1 l with a split of 50:1. Retention time of methyl propionate: 6.158 min

[0247] GC analysis of the products from 2-butene:

[0248] For the GC analysis, an Agilent 7890A gas chromatograph having a 30 m HP column is used. Temperature profile: 35 C., 10 min; 10 C./min to 200 C., 16.5 min; the injection volume is 1 l with a split of 50:1.

[0249] Retention time for iso-C5 esters: 12.118 min

[0250] Retention time for n-C5 esters: 13.807 min

[0251] GC analysis of the products from raffinate 1: For the GC analysis, an Agilent 7890A gas chromatograph having a 30 m HP column is used. Temperature profile: 35 C., 10 min; 10 C./min to 200 C., 16.5 min; the injection volume is 1 l with a split of 50:1.

[0252] Retention time for MTBE: 5.067 min

[0253] Retention time for iso-C5 esters: 12.118 min

[0254] Retention time for n-C5 esters: 13.807 min

[0255] GC analysis of the products from crack-C4: Agilent 7890A chromatograph with a 30 m HP5 column, temperature profile: 35 C., 10 min; 10 C./min to 200 C., 16.5 min; the injection volume is 1 l with a split of 50:1.

[0256] Retention time for methyl pentanoate: 13.842 min

[0257] Retention time for methyl pent-3-enoate: 14.344 min, 14.533 min

[0258] Retention time for dimethyl adipate: 21.404 min

[0259] GC analysis of the products from isobutene:

[0260] Agilent 7890A chromatograph with a 30 m HP5 column, temperature profile: 35 C., 10 min; 10 C./min to 200 C., 16.5 min; the injection volume is 1 l with a split of 50:1.

[0261] Retention time for MTBE: 5.045 min

[0262] Retention time for C5 esters: 12.105 min

[0263] GC analysis of the products from tetramethylethene: For the GC analysis, an Agilent 7890A gas chromatograph having a 30 m HP column is used. Temperature profile: 35 C., 10 min; 10 C./min to 200 C., 16.5 min; the injection volume is 1 l with a split of 50:1.

[0264] Retention time for tetramethylethylene and products: 7.436 min

[0265] Retention time for the ether: 11.391 min

[0266] Retention time for methyl 3,4-dimethylpentanoate: 17.269 min

[0267] GC analysis of C-5 mixture and products: For the GC analysis, an Agilent 7890A gas chromatograph having a 30 m HP column is used. Temperature profile: 35 C., 10 min; 10 C./min to 200 C., 16.5 min; the injection volume is 1 l with a split of 50:1.

[0268] Retention times for the C5 olefins: 4.498, 4.437, 4.533, 4.533, 5.465, 5.793 min;

[0269] Retention times for the C6 methyl esters and their isomers: 14.547-16.362 min (main peak: 16.362 min)

[0270] GC analysis of di-n-butene: For the GC analysis, an Agilent 7890A gas chromatograph having a 30 m HP5 column is used. Temperature profile: 35 C., 10 min; 10 C./min to 200 C.; the injection volume is 1 l with a split of 50:1.

[0271] Retention times for di-n-butene and products: 10.784-13.502 min

[0272] The esters formed from di-n-butene are referred to hereinafter as MINO (methyl isononanoate).

[0273] Retention times for ether products of unknown isomer distribution: 15.312, 17.042, 17.244, 17.417 min

[0274] Retention time for iso-C9 esters 19.502-20.439 min (main peak: 19.990 min)

[0275] Retention time for n-C9 esters: 20.669, 20.730, 20.884, 21.266 min.

[0276] GC analysis of the products from 1,3-butadiene: For the GC analysis, an Agilent 7890A gas chromatograph having a 30 m HP column is used. Temperature profile: 35 C., 10 min; 10 C./min to 200 C., 16.5 min; the injection volume is 1 l with a split of 50:1. Retention time for methyl pent-3-enoate: 14.430 min, retention time for dimethyl adipate: 21.404 min.

[0277] GC analysis for methyl tert-butyl ether (MTBE) and products: Agilent 7890A chromatograph with a 30 m HP5 column, temperature profile: 35 C., 10 min; 10 C./min to 200 C., 16.5 min; the injection volume is 1 l with a split of 50:1.

[0278] Retention time of methyl 3-methylbutanoate: 12.070 min

[0279] Retention time of MTBE: 5.067 min

[0280] GC analysis for aromatic alcohols and products: Agilent 7890A chromatograph with a 30 m HP5 column, temperature profile: 35 C., 10 min; 10 C./min to 200 C., 16.5 min; the injection volume is 1 l with a split of 50:1.

[0281] Retention time: 21.197 min.

##STR00014##

[0282] Retention time: 21.988 min.

##STR00015##

[0283] GC analysis for secondary alcohols and products: Agilent 7890A chromatograph with a 30 m HP5 column, temperature profile: 35 C., 10 min; 10 C./min to 200 C., 16.5 min; the injection volume is 1 l with a split of 50:1.

[0284] Retention time for 3,3-dimethylbutan-2-ol: 10.975

[0285] Retention time for methyl 2,3,3-trimethylbutanoate: 15.312 min,

[0286] Retention time of methyl 4,4-dimethylpentanoate: 17.482 min.

[0287] GC analysis for tert-butanol and products: Agilent 7890A chromatograph with a 30 m HP5 column, temperature profile: 35 C., 10 min; 10 C./min to 200 C., 16.5 min; the injection volume is 1 l with a split of 50:1.

[0288] Retention time of tert-butanol: 4.631

[0289] Retention time of methyl 3-methylbutanoate: 12.063 min.

[0290] GC analysis for methyl oleate and products:

[0291] For the GC analysis, an Agilent 7890A gas chromatograph having a 30 m HP column is used. Temperature profile: 50 C., 0 min; 8 C./min to 260 C., 15 min; the injection volume is 1 l with a split of 50:1. Retention time for methyl oleate: 23.823 min, retention time for dimethyl nonadecane-1,19-dioate: 28.807 min, retention time for dimethyl nonadecane-1,X-dioate: 27.058 min main peak, 27.058, min, 27.206 min, 27.906 min, 28.831 min (secondary peaks). The position X is analytically undetermined.

[0292] Methanol Analysis

[0293] Methanol was pretreated in a solvent drying system: PureSolv MD Solvent Purification System, from Innovative Technology Inc. One Industrial Way, Amesbury Mass. 01013

[0294] Water Values:

[0295] Determined by Karl Fischer titration: TitraLab 580-TIM580, from Radiometer Analytical SAS (Karl Fischer titration), water content: measurement ranges, 0.1%-100% w/w, measured water content: 0.13889%

[0296] The following were used:

[0297] Technical grade methanol from Applichem: No. A2954,5000, batch number: LOT: 3L005446 water content max. 1%

[0298] Methanol from Acros Organics (over molecular sieve): water content 0.005%, code number: 364390010, batch number: LOT 1370321

[0299] TON: turnover number, defined as moles of product per mole of catalyst metal

[0300] TOF: turnover frequency, defined as TON per unit time for the attainment of a particular conversion, e.g. 50%.

[0301] The n/iso ratio indicates the ratio of olefins converted terminally to esters to olefins converted internally to esters.

[0302] The n selectivities reported hereinafter relate to the proportion of terminal methoxycarbonylation based on the overall yield of methoxycarbonylation products.

[0303] Methoxycarbonylation of Ethene with Ligands 3 and 8 at 80 C. and 40 Bar

[0304] The ligand 8 was tested in comparison with the DTBPMB ligand 3 at 80 C. and 40 bar of CO. The results are shown in FIG. 1 (FIG. 1: methoxycarbonylation of ethene with 3 and 8 at 80 C. and 40 bar of CO).

##STR00016##

[0305] It can be seen very clearly in FIG. 1 that the catalyst comprising ligand 8 is much more active at 80 C. than that comprising DTBPMB (ligand 3), by about a factor of 5-6. While the system comprising 8 is ready after only 10 minutes, 3 needs about 60-70 minutes. Both attain the highest possible chemoselectivity (100%) for methyl propionate. Thus, the ligand according to the invention shows a distinct improvement over the system from the prior art.

[0306] Therefore, the system comprising 8 was studied in more detail and reactions were conducted at 60 C. and 20 bar (important industrial pressure level) of CO, with the pressure of 20 bar being kept constant.

[0307] Methoxycarbonylation of Ethene with Ligands 3 and 8 at 60 C. and 20 Bar:

[0308] 3 (comparative example): A 100 ml steel autoclave is charged under argon with [Pd(acac).sub.2] (6.53 mg, 0.04 mol %), and the appropriate ligand 3 (33 mg, 0.16 mol %) and p-toluenesulphonic acid (PTSA, 61 mg, 0.6 mol %). Subsequently, MeOH (20 ml) and ethene of 3.0 purity (1.5 g, 53 mmol) are added. The autoclave is heated to 60 C. and then CO is injected up to a total pressure of 20 bar. This pressure is kept constant at 20 bar by metering in CO from a pressurized reservoir. The reaction is conducted for one hour and the gas consumption in the pressurized reservoir is measured. Subsequently, the autoclave is cooled down and the pressure is slowly released. The contents of the autoclave are transferred into a Schlenk vessel, and 5 ml of isooctane are added as internal standard. The yield was determined by means of GC analysis (100% yield). The TOF at 50% yield is 758 h.sup.1.

[0309] 8: A 100 ml steel autoclave is charged under argon with [Pd(acac).sub.2] (6.53 mg, 0.04 mol %), and the appropriate ligand 8 (44 mg, 0.16 mol %) and p-toluenesulphonic acid (PTSA, 61 mg, 0.6 mol %). Subsequently, MeOH (20 ml) and ethene of 3.0 purity (1.5 g, 53 mmol) are added. The autoclave is heated to 60 C. and then CO is injected up to a total pressure of 20 bar. This pressure is kept constant at 20 bar by metering in CO from a pressurized reservoir. The reaction is conducted for one hour and the gas consumption in the pressurized reservoir is measured. Subsequently, the autoclave is cooled down and the pressure is slowly released. The contents of the autoclave are transferred into a Schlenk vessel, and 5 ml of isooctane are added as internal standard. The yield was determined by means of GC analysis (100% yield). The TOF at 50% yield is 3213 h.sup.1.

[0310] FIG. 2 shows the gas consumption from a pressurized reservoir. The reaction was started with the injection of CO at 60 C. (FIG. 2: methoxycarbonylation of ethene with 3 and 8 at 60 C. and 20 bar of CO (constant pressure)).

[0311] Here too, it is found that 8 conducts the reaction much more quickly and without a pre-formation phase. This is therefore a much quicker and highly selective catalyst system having distinct advantages over the prior art (ligand 3).

[0312] Alkoxycarbonylation (Comparative Experiment)

##STR00017##

[0313] Ligand 59:

[0314] Ligand 59, 1,1-bis(diphenylphosphino)ferrocene, is commercially available.

[0315] A 100 ml steel autoclave is charged with Pd(acac).sub.2 (6.52 mg, 0.04 mol %) and ligand 59 (47.9 mg, 0.16 mol %) and PTSA (61.1 mg, 0.6 mol %) and methanol (20 ml) under argon. Then 1.5 g (53.6 mmol) of ethylene (3.5 from Linde AG) are transferred into the autoclave. (Monitoring the mass of the autoclave). After the autoclave has been heated up to a reaction temperature of 80 C. (pressure about 10 bar), CO (30 bar) is injected at this temperature. At this temperature, the reaction is conducted for 20 hours. Then the autoclave is cooled down to room temperature and decompressed. The contents are transferred into a 50 ml Schlenk flask, and isooctane (internal standard, 5.0 ml) is added. The yield and selectivity were determined by means of GC analysis. (Yield: 54%).

[0316] Alkoxycarbonylation of Ethene with Various Alcohols

[0317] General procedure: A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (6.52 mg, 0.04 mol %), 8 (44.3 mg, 0.16 mol %) and PTSA (61.1 mg, 0.6 mol %). 20 ml of the appropriate alcohol are added under argon. Then 1.5 g of ethene (53.6 mmol) are transferred into the autoclave (monitoring by mass). The autoclave is heated to 80 C. (the pressure is now about 10 bar). At this temperature, CO is injected to 30 bar and the reaction is conducted for 20 h while stirring. The gas consumption is measured with a pressure transducer and the Specview software from Parr Instruments and correlates to the plot of yield against time. The autoclave is cooled down to room temperature and the residual pressure is slowly released. The contents are transferred to a 50 ml Schlenk vessel, 5 ml of isooctane are added as internal standard, and the yield is determined by means of GC analysis.

[0318] GC analysis: For the GC analysis, an Agilent 7890A gas chromatograph having a 30 m HP column is used. Temperature profile: 35, 10 min; 10/min to 200, 16.5 min; the injection volume 1 l with a split of 50:1.

##STR00018##

[0319] Methanol:

[0320] A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (6.52 mg, 0.04 mol %), 8 (44.3 mg, 0.16 mol %) and PTSA (61.1 mg, 0.6 mol %). 20 ml of methanol are added under argon. Then 1.5 g of ethene (53.6 mmol) are transferred into the autoclave (monitoring by mass). The autoclave is heated to 80 C. (the pressure is now about 10 bar). At this temperature, CO is injected to 30 bar and the reaction is conducted for 20 h while stirring. The gas consumption is measured with a pressure transducer in the autoclave and the Specview software from Parr Instruments and correlates to the plot of yield against time.

[0321] The autoclave is cooled down to room temperature and the residual pressure is slowly released. The contents are transferred to a 50 ml Schlenk vessel, 5 ml of isooctane are added as internal standard, and the yield is determined by means of GC analysis. At the end of the reaction, it is 100% of methyl propionate. Retention time: 6.148 min

[0322] Ethanol:

[0323] A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (6.52 mg, 0.04 mol %), 8 (44.3 mg, 0.16 mol %) and PTSA (61.1 mg, 0.6 mol %). 20 ml of ethanol are added under argon. Then 1.5 g of ethene (53.6 mmol) are transferred into the autoclave (monitoring by mass). The autoclave is heated to 80 C. (the pressure is now about 10 bar). At this temperature, CO is injected to 30 bar and the reaction is conducted for 20 h while stirring. The gas consumption is measured with a pressure transducer and the Specview software from Parr Instruments and correlates to the plot of yield against time. The autoclave is cooled down to room temperature and the residual pressure is slowly released. The contents are transferred to a 50 ml Schlenk vessel, 5 ml of isooctane are added as internal standard, and the yield is determined by means of GC analysis. At the end of the reaction, it is 100% of ethyl propionate. Retention time: 8.896 min

[0324] 1-Propanol:

[0325] A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (6.52 mg, 0.04 mol %), 8 (44.3 mg, 0.16 mol %) and PTSA (61.1 mg, 0.6 mol %). 20 ml of 1-propanol are added under argon. Then 1.5 g of ethene (53.6 mmol) are transferred into the autoclave (monitoring by mass). The autoclave is heated to 80 C. (the pressure is now about 10 bar). At this temperature, CO is injected to 30 bar and the reaction is conducted for 20 h while stirring. The gas consumption is measured with a pressure transducer and the Specview software from Parr Instruments and correlates to the plot of yield against time. The autoclave is cooled down to room temperature and the residual pressure is slowly released. The contents are transferred to a 50 ml Schlenk vessel, 5 ml of isooctane are added as internal standard, and the yield is determined by means of GC analysis. At the end of the reaction, it is 100% of 1-propyl propionate. Retention time: 13.342 min

[0326] 1-Butanol:

[0327] A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (6.52 mg, 0.04 mol %), 8 (44.3 mg, 0.16 mol %) and PTSA (61.1 mg, 0.6 mol %). 20 ml of 1-butanol are added under argon. Then 1.5 g of ethene (53.6 mmol) are transferred into the autoclave (monitoring by mass). The autoclave is heated to 80 C. (the pressure is now about 10 bar). At this temperature, CO is injected to 30 bar and the reaction is conducted for 20 h while stirring. The gas consumption is measured with a pressure transducer and the Specview software from Parr Instruments and correlates to the plot of yield against time. The autoclave is cooled down to room temperature and the residual pressure is slowly released. The contents are transferred to a 50 ml Schlenk vessel, 5 ml of isooctane are added as internal standard, and the yield is determined by means of GC analysis. At the end of the reaction, it is 100% of 1-butyl propionate. Retention time: 16.043 min

[0328] 1-Pentanol:

[0329] A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (6.52 mg, 0.04 mol %), 8 (44.3 mg, 0.16 mol %) and PTSA (61.1 mg, 0.6 mol %). 20 ml of 1-pentanol are added under argon. Then 1.5 g of ethene (53.6 mmol) are transferred into the autoclave (monitoring by mass). The autoclave is heated to 80 C. (the pressure is now about 10 bar). At this temperature, CO is injected to 30 bar and the reaction is conducted for 20 h while stirring. The gas consumption is measured with a pressure transducer and the Specview software from Parr Instruments and correlates to the plot of yield against time. The autoclave is cooled down to room temperature and the residual pressure is slowly released. The contents are transferred to a 50 ml Schlenk vessel, 5 ml of isooctane are added as internal standard, and the yield is determined by means of GC analysis. At the end of the reaction, it is 100% of 1-pentyl propionate. Retention time: 17.949 min

[0330] 1-Hexanol:

[0331] A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (6.52 mg, 0.04 mol %), 8 (44.3 mg, 0.16 mol %) and PTSA (61.1 mg, 0.6 mol %). 20 ml of 1-hexanol are added under argon. Then 1.5 g of ethene (53.6 mmol) are transferred into the autoclave (monitoring by mass). The autoclave is heated to 80 C. (the pressure is now about 10 bar). At this temperature, CO is injected to 30 bar and the reaction is conducted for 20 h while stirring. The gas consumption is measured with a pressure transducer and the Specview software from Parr Instruments and correlates to the plot of yield against time. The autoclave is cooled down to room temperature and the residual pressure is slowly released. The contents are transferred to a 50 ml Schlenk vessel, 5 ml of isooctane are added as internal standard, and the yield is determined by means of GC analysis. At the end of the reaction, it is 100% of 1-hexyl propionate. Retention time: 19.486 min

[0332] 2-Propanol:

[0333] A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (6.52 mg, 0.04 mol %), 8 (44.3 mg, 0.16 mol %) and PTSA (61.1 mg, 0.6 mol %). 20 ml of 2-propanol are added under argon. Then 1.5 g of ethene (53.6 mmol) are transferred into the autoclave (monitoring by mass). The autoclave is heated to 80 C. (the pressure is now about 10 bar). At this temperature, CO is injected to 30 bar and the reaction is conducted for 20 h while stirring. The gas consumption is measured with a pressure transducer and the Specview software from Parr Instruments and correlates to the plot of yield against time. The autoclave is cooled down to room temperature and the residual pressure is slowly released. The contents are transferred to a 50 ml Schlenk vessel, 5 ml of isooctane are added as internal standard, and the yield is determined by means of GC analysis. At the end of the reaction, it is 100% of 2-propyl propionate. Retention time: 11.212 min

[0334] t-Butanol:

[0335] A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (6.52 mg, 0.04 mol %), 8 (44.3 mg, 0.16 mol %) and PTSA (61.1 mg, 0.6 mol %). 20 ml of t-butanol are added under argon. Then 1.5 g of ethene (53.6 mmol) are transferred into the autoclave (monitoring by mass). The autoclave is heated to 80 C. (the pressure is now about 10 bar). At this temperature, CO is injected to 30 bar and the reaction is conducted for 20 h while stirring. The gas consumption is measured with a pressure transducer and the Specview software from Parr Instruments and correlates to the plot of yield against time. The autoclave is cooled down to room temperature and the residual pressure is slowly released. The contents are transferred to a 50 ml Schlenk vessel, 5 ml of isooctane are added as internal standard, and the yield is determined by means of GC analysis. At the end of the reaction, it is 47% of t-butyl propionate. Retention time: 12.625 min

[0336] 3-Pentanol:

[0337] A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (6.52 mg, 0.04 mol %), 8 (44.3 mg, 0.16 mol %) and PTSA (61.1 mg, 0.6 mol %). 20 ml of 3-pentanol are added under argon. Then 1.5 g of ethene (53.6 mmol) are transferred into the autoclave (monitoring by mass). The autoclave is heated to 80 C. (the pressure is now about 10 bar). At this temperature, CO is injected to 30 bar and the reaction is conducted for 20 h while stirring. The gas consumption is measured with a pressure transducer and the Specview software from Parr Instruments and correlates to the plot of yield against time. The autoclave is cooled down to room temperature and the residual pressure is slowly released. The contents are transferred to a 50 ml Schlenk vessel, 5 ml of isooctane are added as internal standard, and the yield is determined by means of GC analysis. At the end of the reaction, it is 100% of 3-pentyl propionate. Retention time: 16.648 min

[0338] Cyclohexanol:

[0339] A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (6.52 mg, 0.04 mol %), 8 (44.3 mg, 0.16 mol %) and PTSA (61.1 mg, 0.6 mol %). 20 ml of cyclohexanol are added under argon. Then 1.5 g of ethene (53.6 mmol) are transferred into the autoclave (monitoring by mass). The autoclave is heated to 80 C. (the pressure is now about 10 bar). At this temperature, CO is injected to 30 bar and the reaction is conducted for 20 h while stirring. The gas consumption is measured with a pressure transducer and the Specview software from Parr Instruments and correlates to the plot of yield against time. The autoclave is cooled down to room temperature and the residual pressure is slowly released. The contents are transferred to a 50 ml Schlenk vessel, 5 ml of isooctane are added as internal standard, and the yield is determined by means of GC analysis. At the end of the reaction, it is 100% of cyclohexyl propionate. Retention time: 19.938 min

[0340] Phenol:

[0341] A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (6.52 mg, 0.04 mol %), 8 (44.3 mg, 0.16 mol %) and PTSA (61.1 mg, 0.6 mol %). 20 ml of phenol are added under argon. Phenol was added in solid form without solvent. The melting point of phenol is 40.5 C. All components should therefore be dissolved at 80 C. Then 1.5 g of ethene (53.6 mmol) are transferred into the autoclave (monitoring by mass). The autoclave is heated to 80 C. (the pressure is now about 10 bar). At this temperature, CO is injected to 30 bar and the reaction is conducted for 20 h while stirring. The gas consumption is measured with a pressure transducer and the Specview software from Parr Instruments and correlates to the plot of yield against time. The autoclave is cooled down to room temperature and the residual pressure is slowly released. The contents are transferred to a 50 ml Schlenk vessel, 5 ml of isooctane are added as internal standard, and the yield is determined by means of GC analysis. At the end of the reaction, it is 46% of phenyl propionate. Retention time: 20.260 min

[0342] The results are shown in FIG. 3.

[0343] FIG. 3: Alcohol variation in the methoxycarbonylation of ethene with ligand 8 at 80 C. and CO pressure 30 bar

[0344] As is clearly apparent, it is possible to use not only methanol in the alkoxylation, but it is likewise also possible to use a multitude of other alcohols. The corresponding products can be obtained in good to very good yields (in some cases quantitatively).

[0345] Conversion of 8 with Propene

##STR00019##

[0346] A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (17.5 mg, 0.04 mol %), 8 (119 mg, 0.16 mol %), MeOH (15 ml) and [98% H.sub.2SO.sub.4] (38 l, 0.5 mol %). Then the autoclave is cooled down with dry ice. Propene (6.06 g, 144 mmol) was condensed into another, separate cylinder (75 ml, monitoring by mass). This defined amount was then condensed into the autoclave. Then CO is injected into the autoclave to 40 bar at room temperature. The reaction is conducted at 100 C. for 30 minutes. After the reaction, the autoclave is cooled down to room temperature and the pressure is released. 8.5 ml of isooctane are added to the solution as an internal standard. The yield and selectivity were determined by means of GC analysis. (Yield: >99%, n/iso: 77:23).

[0347] Conversion of 1-Butene with 8

##STR00020##

[0348] A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (17.5 mg, 0.04 mol %), 8 (119 mg, 0.16 mol %), MeOH (15 ml) and [98% H.sub.2SO.sub.4] (38 l, 0.5 mol %). Then the autoclave is cooled down with dry ice. 1-Butene (8.04 g, 144 mmol) was condensed into another, separate cylinder (75 ml, monitoring by mass). This defined amount was then condensed into the autoclave. Then CO is injected into the autoclave to 40 bar at room temperature. The reaction is conducted at 100 C. for 60 minutes. After the reaction, the autoclave is cooled down to room temperature and the pressure is released. 8.5 ml of isooctane are added to the solution as an internal standard. The yield and selectivity were determined by means of GC analysis. (Yield: >99%, n/iso: 80:20).

[0349] Conversion of 2-Butene with 8

##STR00021##

[0350] A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (17.5 mg, 0.04 mol %), 8 (119 mg, 0.16 mol %), MeOH (15 ml) and [98% H.sub.2SO.sub.4] (38 l, 0.5 mol %). Then the autoclave is cooled down with dry ice. 2-Butene (8.04 g, 144 mmol) was condensed into another, separate cylinder (75 ml, monitoring by mass). This defined amount was then condensed into the autoclave. Then CO is injected into the autoclave to 40 bar at room temperature. The reaction is conducted at 100 C. for 60 minutes. After the reaction, the autoclave is cooled down to room temperature and the pressure is released. 8.5 ml of isooctane are added to the solution as an internal standard. The yield and selectivity were determined by means of GC analysis. (Yield: >99%, n/iso: 75:25).

[0351] The results are shown in FIG. 4. This figure shows the yield profile of the abovementioned reactions, which was calculated by conversion from the gas consumption curve. The curve was fitted using the yield determined by gas chromatography on completion of reaction.

[0352] FIG. 4: Methoxycarbonylation experiments on propene, 1-butene and 2-butene at 100 C. and 40 bar with ligand 8.

[0353] As can be inferred from FIG. 4, the conversion rates of the olefins fall with rising chain length. The conversion rate is higher for terminal olefins than for the olefins with an internal double bond. While propene has been fully converted within less than 10 minutes, about 40 minutes are needed for 1-butene and almost 60 minutes for 2-butene for a complete conversion (100% yield).

[0354] Conversion of Raffinate 1 with Compound 8

[0355] Technical mixtures were also tested, including what is called raffinate 1. Raffinate 1 is composed of 42% isobutene, 26% 1-butene, 17% cis- and trans-2-butene, and also 0.3% 1,3-butadiene and 15% n-butane and isobutane.

[0356] Method: A 100 ml steel autoclave was charged under an argon atmosphere with [Pd(acac).sub.2] (17.4 mg), 8 (118.9 mg) and H.sub.2SO.sub.4 (70.6 mg). Methanol (15 ml) was added under an Ar atmosphere. The autoclave was cooled with dry ice. Thereafter, 8.2 g of raffinate 1 were condensed into a separate cylinder (75 ml, monitoring by mass) and this defined amount of substrate was condensed into the cooled autoclave. Thereafter, the autoclave was pressurized with 60 bar of CO at room temperature. The reaction was conducted at 100 C. for 20 h. Thereafter, the contents were transferred into a 50 ml Schlenk flask, and isooctane was added as internal standard. Yield and selectivity were determined by means of GC analysis.

[0357] Result: C5-Ester: 9.7 g, n/iso 37/63, MTBE: 2.0 g.

##STR00022##

[0358] The results are also shown in FIG. 5.

[0359] FIG. 5: Methoxycarbonylation of raffinate 1 with ligand 8 at 100 C. and CO pressure 60 bar.

[0360] It has thus been shown that mixtures of industrial relevance too, such as raffinate 1 here, can be converted with the ligand 8 according to the invention.

[0361] Raffinate 1 with Sampling

[0362] In addition, raffinate 1 was converted with ligand 8.

##STR00023##

[0363] General procedure: A 100 ml steel autoclave is charged under argon with [Pd(acac).sub.2] (17.4 mg), 8 (118.9 mg) and H.sub.2SO.sub.4 (70.6 mg). Then 15 ml of MeOH and 10 ml of isooctane as an internal standard are added. Then the autoclave is cooled down to 78 C. with dry ice. Raffinate 1 (8.1 g) is condensed into a separate 75 ml pressure cylinder (monitoring by mass). This defined mass is then condensed into the autoclave. The autoclave is charged with 50 bar of CO at room temperature. The autoclave is heated to 100 C. and stirred at this temperature for 20 h. During this period, 16 samples are taken from the autoclave by means of an HPLC valve and an internal capillary. The yield and selectivity are determined by means of GC analysis. GC analysis: For the GC analysis, an Agilent 7890A gas chromatograph having a 30 m HP column is used. Temperature profile: 35, 10 min; 10/min to 200, 16.5 min; the injection volume is 1 l with a split of 50:1.

[0364] Retention time for MTBE: 5.067 min

[0365] Retention time for iso-C5 esters: 12.118 min

[0366] Retention time for n-C5 esters: 13.807 min

[0367] The results are shown in FIG. 6.

[0368] FIG. 6: Methoxycarbonylation of raffinate 1 at 100 C. and 50 bar with ligand 8. At the end of the reaction, 80% C5 ester and 20% methyl tert-butyl ether are present, based on the amount of olefins used.

[0369] Thus, the ligand 8 is of good suitability for the conversion of a feed of industrial relevance, raffinate 1.

[0370] FIG. 5 shows the gas uptake curve for the experiment without sampling which has run for 20 hours and has led to 9.7 g of C5 ester with an n/iso ratio of 37/63 and an MTBE content of 2.0 g. The experiment conducted in FIG. 6 leads to 32% n-C5 ester and 48% iso-C5 ester. This corresponds to an n/iso ratio of 33/67. The proportion by mass of methyl tert-butyl ether is 20%. FIG. 5 shows a proportion by mass of 17%. The two experiments thus give similar results. It is apparent from FIG. 5 that most of the reaction has already ended after about 1 hour. This too is in accordance with the experiment with sampling in FIG. 6.

[0371] Methoxycarbonylation of Isobutene with Ligand 3 and 8

##STR00024##

[0372] Ligand 3 (comparative example): A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (4.9 mg), DTBPMB (25.3 mg), PTSA (45.6 mg) and MeOH (20 ml). Subsequently, the autoclave is cooled down with dry ice. In a separate pressure vessel, 2.5 g of isobutene (monitoring by mass) are condensed in. This defined mass is condensed into the autoclave. Then the autoclave is charged with CO to 40 bar at room temperature. The reaction is conducted at 120 C. for 20 hours. Subsequently, the autoclave is cooled down to room temperature and decompressed, the contents are transferred to a 50 ml Schlenk vessel, and isooctane (5 ml as internal standard) is added. A GC analysis is effected. (GC analysis (50% yield of methyl 3-methylbutanoate, 37% yield of MTBE).

[0373] Ligand 8: A 100 ml steel autoclave is charged under argon with Pd(acac).sub.2 (4.9 mg), 8 (33.1 mg), PTSA (45.6 mg) and MeOH (20 ml). Subsequently, the autoclave is cooled down with dry ice. In a separate pressure vessel, 2.5 g of isobutene (monitoring by mass) are condensed in. This defined mass is condensed into the autoclave. Then the autoclave is charged with CO to 40 bar at room temperature. The reaction is conducted at 120 C. for 20 hours. Subsequently, the autoclave is cooled down to room temperature and decompressed, the contents are transferred to a 50 ml Schlenk vessel, and isooctane (5 ml as internal standard) is added. A GC analysis is effected. (99% yield of methyl 3-methylbutanoate)

[0374] Testing of a Mixture of Propene, 1-Butene and 2-Butene

[0375] In addition, mixtures of reactants were also tested, i.e. mixtures which comprise different unsaturated compounds.

[0376] Method: A 100 ml steel autoclave was charged under an argon atmosphere with [Pd(acac).sub.2] (17.4 mg), 8 (118.9 mg) and H.sub.2SO.sub.4 (70.6 mg). Methanol (15 ml) was added under an Ar atmosphere. The autoclave was cooled with dry ice. Thereafter, 2.83 g, 2-butene 4.85 mg and propene (2.2 g) were condensed into three separate cylinders (75 ml, monitoring by mass) and these defined amounts of gas substrate were condensed into the cooled autoclave. Thereafter, the autoclave was pressurized with 60 bar of CO at room temperature. The reaction was conducted at 100 C. for 20 h. Thereafter, the contents were transferred into a 50 ml Schlenk flask, and isooctane was added as internal standard. Yield and selectivity were determined by means of GC analysis. (Yield: 100%, C4 esters: n/iso 79/21, C5 esters: n/iso: 75/25).

##STR00025##

[0377] The results are shown in FIG. 7.

[0378] FIG. 7: Methoxycarbonylation of a mixture of propene, 1-butene and 2-butene at 100 C. and 60 bar with ligand 8.

[0379] As can be inferred from FIG. 7, nearly a full yield of the methoxycarbonylation products is achieved with the mixture of propene, 1-butene and 2-butene after a reaction time of about 1 hour.

[0380] Conversion of Tetramethylethylene with Various Ligands at Various Temperatures

##STR00026##

[0381] a) Reaction temperature: 100 C.

[0382] 3 (comparative example): A 25 ml Schlenk vessel was charged with [Pd(acac).sub.2] (4.87 mg, 0.1 mol %), p-toluenesulphonic acid (PTSA) (24.32 mg, 0.8 mol %) and MeOH (8 ml). A 4 ml vial was charged with 3 (6.3 mg, 0.4 mol %), and a magnetic stirrer bar was added. Thereafter, 2 ml of the clear yellow solution and tetramethylethylene (478 l, 4 mmol) were added with a syringe. The vial was placed into a sample holder which was in turn inserted into a 300 ml Parr autoclave under an argon atmosphere. After the autoclave had been purged three times with nitrogen, the CO pressure was adjusted to 40 bar. The reaction proceeded at 100 C. for 20 hours. On conclusion of the reaction, the autoclave was cooled down to room temperature and cautiously decompressed. Isooctane (200 l) was added as internal GC standard. Yield and regioselectivity were determined by means of GC. (Conversion: 40%, no ester product yield; ether product yield 38%).

[0383] 8: A 25 ml Schlenk vessel was charged with [Pd(acac).sub.2] (4.87 mg, 0.1 mol %), p-toluenesulphonic acid (PTSA) (24.32 mg, 0.8 mol %) and MeOH (8 ml). A 4 ml vial was charged with 8 (8.3 mg, 0.4 mol %), and a magnetic stirrer bar was added. Thereafter, 2 ml of the clear yellow solution and tetramethylethylene (478 l, 4 mmol) were added with a syringe. The vial was placed into a sample holder which was in turn inserted into a 300 ml Parr autoclave under an argon atmosphere. After the autoclave had been purged three times with nitrogen, the CO pressure was adjusted to 40 bar. The reaction proceeded at 100 C. for 20 hours. On conclusion of the reaction, the autoclave was cooled down to room temperature and cautiously decompressed. Isooctane (200 l) was added as internal GC standard. Yield and regioselectivity were determined by means of GC. (Conversion: 65%, ester product yield: 37%; ether product yield 27%).

[0384] b) Reaction temperature: 120 C.

[0385] 3 (comparative example): A 25 ml Schlenk vessel was charged with [Pd(acac).sub.2] (4.87 mg, 0.1 mol %), p-toluenesulphonic acid (PTSA) (24.32 mg, 0.8 mol %) and MeOH (8 ml). A 4 ml vial was charged with 3 (6.3 mg, 0.4 mol %), and a magnetic stirrer bar was added. Thereafter, 2 ml of the clear yellow solution and tetramethylethylene (478 l, 4 mmol) were added with a syringe. The vial was placed into a sample holder which was in turn inserted into a 300 ml Parr autoclave under an argon atmosphere. After the autoclave had been purged three times with nitrogen, the CO pressure was adjusted to 40 bar. The reaction proceeded at 120 C. for 20 hours. On conclusion of the reaction, the autoclave was cooled down to room temperature and cautiously decompressed. Isooctane (200 l) was added as internal GC standard. Yield and regioselectivity were determined by means of GC. (Conversion: 54%, no ester product yield; ether product yield 52%).

[0386] 8: A 25 ml Schlenk vessel was charged with [Pd(acac).sub.2] (4.87 mg, 0.1 mol %), p-toluenesulphonic acid (PTSA) (24.32 mg, 0.8 mol %) and MeOH (8 ml). A 4 ml vial was charged with 8 (8.3 mg, 0.4 mol %), and a magnetic stirrer bar was added. Thereafter, 2 ml of the clear yellow solution and tetramethylethylene (478 l, 4 mmol) were added with a syringe. The vial was placed into a sample holder which was in turn inserted into a 300 ml Parr autoclave under an argon atmosphere. After the autoclave had been purged three times with nitrogen, the CO pressure was adjusted to 40 bar. The reaction proceeded at 120 C. for 20 hours. On conclusion of the reaction, the autoclave was cooled down to room temperature and cautiously decompressed. Isooctane (200 l) was added as internal GC standard. Yield and regioselectivity were determined by means of GC. (Conversion: 90%, ester product yield: 60%; ether product yield 28%).

[0387] Methoxycarbonylation of C5 Olefins

[0388] Procedure: A 100 ml steel autoclave is charged under argon with [Pd(acac).sub.2] (10.95 mg, 0.04 mol %), 8 (74.31 mg, 0.16 mol %) and H.sub.2SO.sub.4 (44.1 mg, 0.5 mol %). Subsequently, 10 ml of MeOH, 1-pentene (0.5 g), 2-pentene (2.21 g), 2-methyl-1-butene (1.27 g) and 2-methyl-2-butene (1.3 g) are added under argon. Then the autoclave is cooled down to 78 C. by means of dry ice. 1.1 g of 3-methyl-1-butene (1.1 g) are condensed into a separate pressure vessel (monitoring by mass) and this defined amount is condensed into the autoclave. Subsequently, the autoclave is charged with CO to 50 bar at room temperature. While stirring, the reaction is conducted at 100 C. for 20 h. Then the autoclave is cooled down to room temperature and the residual pressure is slowly released. The contents are transferred to a 50 ml Schlenk vessel, and 5 ml of isooctane are added as internal standard. The yield is determined by means of GC analysis. At the end of the reaction, it is 76% of C6 methyl esters.

[0389] GC analysis: For the GC analysis, an Agilent 7890A gas chromatograph having a 30 m HP column is used. Temperature profile: 35, 10 min; 10/min to 200, 16.5 min; the injection volume 1 l with a split of 50:1.

[0390] Retention times for the C6 methyl esters and their isomers: 14.547-16.362 min (main peak: 16.362 min)

##STR00027##

[0391] The results are shown in FIG. 8.

[0392] FIG. 8: Methoxycarbonylation of a mixture of C5 olefins at 100 C. and CO pressure 50 bar with ligand 8.

[0393] As is clearly apparent, the corresponding C6 esters can be obtained as a mixture in good yields (distinctly >50%).

[0394] Conversion of Di-n-Butene with the Ligand 8

##STR00028##

[0395] In addition, an experiment was conducted with constant pressure and gas consumption measurement with 8 at total pressure 20 bar.

[0396] Experimental example: A 100 ml steel autoclave is charged under argon with [Pd(acac).sub.2](5.85 mg, 0.04 mol %), and the appropriate ligand 8 (39.6 mg, 0.16 mol %) and p-toluenesulphonic acid (PTSA, 54.7 mg, 0.6 mol %). Subsequently, MeOH (30 ml) and di-n-butene (7.54 ml, 48 mmol) are added. The autoclave is heated to 120 C. and then CO is injected up to a total pressure of 20 bar. This pressure is kept constant at 20 bar by metering in CO from a pressurized reservoir. The reaction is conducted for 20 hours and the gas consumption in the pressurized reservoir is measured. Subsequently, the autoclave is cooled down and the pressure is slowly released. The contents of the autoclave are transferred into a Schlenk vessel, and 5 ml of isooctane are added as internal standard. The yield was determined by means of GC analysis (86% yield, n:iso=75:25).

[0397] The results are shown in FIG. 9.

[0398] FIG. 9: Methoxycarbonylation of di-n-butene with ligand 8 at 120 C. and 20 bar with constant CO pressure

[0399] After only 5 hours, with ligand 8, a yield of methyl isononanoate (MINO) of more than 80% is achieved; yield and n:iso ratio after 20 hours correspond to the experiment with ligand 8 at 120 C. and 40 bar under variable CO pressure (see above). A lower CO pressure of 20 bar during the reaction can thus be employed without loss of yield and selectivity.

[0400] Methoxycarbonylation of Di-n-Butene with Ligands 3 and 8

[0401] In order to have a good comparison of the ligands in the methoxycarbonylation of di-n-butene, experiments with gas consumption measurements were conducted.

##STR00029##

[0402] 3 (comparative example): A 100 ml steel autoclave is charged under argon with [Pd(acac).sub.2](5.85 mg, 0.04 mol %) and 3 (30.3 mg, 0.16 mol %). Subsequently, MeOH (30 ml) and di-n-butene (7.54 ml, 48 mmol) and PTSA (54.7 mg, 0.6 mol %) are added. The autoclave is charged at room temperature with CO of purity 4.7 to 40 bar and the reaction is conducted at 120 C. for 20 hours. Subsequently, the autoclave is cooled down and the pressure is slowly released. The contents of the autoclave are transferred to a Schlenk flask. 5 ml of isooctane are added as internal standard and the yield and selectivity are determined by means of GC analysis (60% yield of MINO, n/iso: 93/7).

[0403] 8: A 100 ml steel autoclave is charged under argon with [Pd(acac).sub.2] (5.85 mg, 0.04 mol %) and 8 (39.6 mg, 0.16 mol %). Subsequently, MeOH (30 ml) and di-n-butene (7.54 ml, 48 mmol) and PTSA (54.7 mg, 0.6 mol %) are added. The autoclave is charged at room temperature with CO of purity 4.7 to 40 bar and the reaction is conducted at 120 C. for 20 hours. Subsequently, the autoclave is cooled down and the pressure is slowly released. The contents of the autoclave are transferred to a Schlenk flask. 5 ml of isooctane are added as internal standard and the yield and selectivity are determined by means of GC analysis (86% yield of MINO, n/iso: 75/25).

[0404] FIG. 10 shows the gas consumption curves (or plot of yield against time) for the systems tested.

[0405] FIG. 10: Methoxycarbonylation of di-n-butene with 3 and 8 at 120 C. and 40 bar CO.

[0406] It is clearly apparent from the gas consumption measurements and the experimental examples that 8 is quicker than 3. Even though the n selectivity at 75% is lower than in the reactions with 3 as ligand, preference is given to ligand 8 with regard to possible industrial implementation and the very high space-time yield.

[0407] In addition, an experiment was conducted with constant pressure and gas consumption measurement with 8 at total pressure 20 bar.

[0408] Experimental example: A 100 ml steel autoclave is charged under argon with [Pd(acac).sub.2] (5.85 mg, 0.04 mol %), and the appropriate ligand 8 (39.6 mg, 0.16 mol %) and p-toluenesulphonic acid (PTSA, 54.7 mg, 0.6 mol %). Subsequently, MeOH (30 ml) and di-n-butene (7.54 ml, 48 mmol) are added. The autoclave is heated to 120 C. and then CO is injected up to a total pressure of 20 bar. This pressure is kept constant at 20 bar by metering in CO from a pressurized reservoir. The reaction is conducted for one hour and the gas consumption in the pressurized reservoir is measured. Subsequently, the autoclave is cooled down and the pressure is slowly released. The contents of the autoclave are transferred into a Schlenk vessel, and 5 ml of isooctane are added as internal standard. The yield was determined by means of GC analysis (86% yield, n:iso=75:25).

[0409] The results are shown in FIG. 11.

[0410] FIG. 11: Yield curve for the methoxycarbonylation of di-n-butene with 8 as ligand at constant total pressure 20 bar and 120 C.

[0411] An equal performance to that in the non-constant 40 bar CO experiment is found. This means that the methoxycarbonylation of di-n-butene with 8 as ligand is independent of the CO pressure over a certain CO pressure range, and industrially favourable lower pressures below 20 bar are achievable.

[0412] Conversion of Di-n-Butene with Further Ligands (Comparative Experiments in a 12-Well Autoclave)

[0413] The conversion of di-n-butene with the aid of various ligands was effected by the following method:

[0414] Method: A 50 ml Schlenk vessel was charged with [Pd(acac).sub.2] (3.9 mg, 0.04 mol %), MeSO.sub.3H (methanesulphonic acid) (13 l, 0.6 mol %) and MeOH (20 ml). A 4 ml vial was charged with ligand X (0.16 mol %), and a magnetic stirrer bar was added. Thereafter, 1.25 ml of the clear yellow stock solution and di-n-butene (315 l, 2 mmol) were added with a syringe. The vial was placed into a sample holder which was in turn inserted into a 600 ml Parr autoclave under an argon atmosphere. After the autoclave had been purged three times with nitrogen, the CO pressure was adjusted to 40 bar. The reaction proceeded at 120 C. for 20 hours. On conclusion of the reaction, the autoclave was cooled down to room temperature and cautiously decompressed. Isooctane was added as internal GC standard. Yield and regioselectivity were determined by means of GC.

[0415] The results are summarized in Scheme 22 below:

##STR00030##

[0416] Determination of Space-Time Yield STY

[0417] The space-time yield (STY) is understood to mean the specific product output (amount of product formed in a reactor) of a reaction vessel (reactor) per unit space and time, for example t (tonnes) of product per cubic metre and unit time or kg per litre and second.

[0418] Method: A baked-out Schlenk flask is initially charged in each case with 1.6 mol % of PTSA (180 mg), 0.04 mol % of Pd(acac).sub.2 (7.5 mg) and 0.16 mol % of ligand 3 or 8. Then 6.26 ml (150 mmol) of methanol (technical grade) and 9.39 ml (60 mmol) of di-n-butene are added and the mixture is transferred to a 100 ml autoclave. The autoclave is then purged twice with CO at 10 bar, charged with CO to 6 bar and heated to 100 C. Then the autoclave is charged with CO to 12 bar by means of a gas burette and stirred at 100 C. under constant CO pressure (12 bar) for 20 h. After the reaction has ended, isooctane (internal standard) and 10 ml of EtOAc are added. The organic phase was analysed by GC.

##STR00031##

[0419] The results are shown in FIG. 12.

[0420] FIG. 12: Gas consumption curves of reactions with 3 and 8.

[0421] C-18 Olefins

[0422] Methyl oleate (Alfa Aesar, H311358, LOT:10164632)

[0423] Conversion of Methyl Oleate with Ligands 3 and 8

##STR00032##

[0424] 3 (comparative example): A 25 ml Schlenk vessel was charged with [Pd(acac).sub.2] (4.57 mg, 0.05 mol %), H.sub.2SO.sub.4 (22.05 mg, 7.5 mol %) and MeOH (6 ml). A 4 ml vial was charged with 3 (7.9 mg, 2.0 mol %), and a magnetic stirrer bar was added. Thereafter, 2 ml of the clear yellow solution and methyl oleate (339 l, 1 mmol) were added with a syringe. The vial was placed into a sample holder which was in turn inserted into a 300 ml Parr autoclave under an argon atmosphere. After the autoclave had been purged three times with nitrogen, the CO pressure was adjusted to 40 bar. The reaction proceeded at 100 C. for 20 hours. On conclusion of the reaction, the autoclave was cooled down to room temperature and cautiously decompressed. Isooctane (100 l) was added as internal GC standard. Yield and regioselectivity were determined by means of GC. Yield of linear ester: 54%, no branched ester.

[0425] 8: A 25 ml Schlenk vessel was charged with [Pd(acac).sub.2] (4.57 mg, 0.05 mol %), H.sub.2SO.sub.4 (22.05 mg, 7.5 mol %) and MeOH (6 ml). A 4 ml vial was charged with 8 (10.3 mg, 2.0 mol %), and a magnetic stirrer bar was added. Thereafter, 2 ml of the clear yellow solution and methyl oleate (339 l, 1 mmol) were added with a syringe. The vial was placed into a sample holder which was in turn inserted into a 300 ml Parr autoclave under an argon atmosphere. After the autoclave had been purged three times with nitrogen, the CO pressure was adjusted to 40 bar. The reaction proceeded at 100 C. for 20 hours. On conclusion of the reaction, the autoclave was cooled down to room temperature and cautiously decompressed. Isooctane (100 l) was added as internal GC standard. Yield and regioselectivity were determined by means of GC. Yield of linear ester: 98%, no branched ester.

[0426] It is apparent from the results that the inventive ligand 8 is better suited to conversion of methyl oleate than ligand 3 from the prior art.

[0427] Conversion of Various Olefins Under Optimized Conditions

[0428] The conditions of the methoxycarbonylation of di-n-butene were optimized as follows:

##STR00033##

[0429] The optimized conditions were applied to a series of alkenes (Table 1).

##STR00034##

[0430] Method: Baked-out glass vials were each initially charged with 1 mg (0.04 mol %) of Pd(acac).sub.2 and 7.2 mg (0.16 mol %) of ligand 8, and 812 l (20 mmol) of methanol (technical grade) and 8 mmol of alkene in each case were added. Then 2 l (0.5 mol %) of H.sub.2SO.sub.4 (98%) (100 l of a sulphuric acid solution in methanol contain 2 l of sulphuric acid) are added.

[0431] The reactions in the autoclave are purged twice with CO at 10 bar, charged with CO to 15 bar and stirred at 100 C. for 20 h. After the reaction has ended, isooctane (internal standard) and 1 ml of EtOAc are added in each case. The organic phase is analysed by GC.

[0432] The results are compiled in Table 1.

TABLE-US-00001 TABLE 1 Substrate testing with various alkenes Alkene Ester n-Selectivity Alkene [%] [%] [%] Di-n-butene 16 82 79 1-Octene 0 100 72 1-Decene 0 100 72 1-Hexene 0 100 78 2-Octene 2 98 72 Limonene 27 14 Vinylcyclohexene 13 52 95 1,7-Octadiene 27 26 65 Methyl 10- 13 86 75 undecanoate Methyl oleate 23 75 not attributable Methyl 3-pentenoate 23 74 82

[0433] The n selectivity in Table 1 is defined as the proportion of terminal methoxycarbonylation based on the overall yield of the methoxycarbonylation products.

[0434] It is found that linear terminal olefins such as 1-octene, 1-decene, 1-hexene and 2-octene give quantitative ester yields. Good yields are likewise afforded by methyl 3-pentenoate, methyl oleate and methyl undecenoate. In the case of vinylcyclohexene, there is 52% monomethoxycarbonylation and also partial methoxycarbonylation of the internal double bond (35%). Octadiene is singly methoxycarbonylated to an extent of 55% and doubly methoxycarbonylated to an extent of 26%.

[0435] The experiments described show that the compounds according to the invention are suitable as catalyst ligands for the alkoxycarbonylation of a multitude of ethylenically unsaturated compounds. More particularly, with the compounds according to the invention, better yields are achieved than with the bidentate phosphine ligands known from the prior art, such as 1,2-bis(di-tert-butylphosphinomethyl)benzene (DTBPMB, ligand 3), 1,1-bis(diphenylphosphino)ferrocene (ligand 59), 1-(diphenylphosphino)-1-(diisopropylphosphino)ferrocene (ligand 10) and 1,1-bis(isopropylphenylphosphino)ferrocene (ligand 19). In addition, the compounds according to the invention also enable the alkoxycarbonylation of long-chain olefins of industrial importance, such as di-n-butene and 2-octene, and also of olefin mixtures such as the raffinate 1 described.