Process for double carbonylation of allyl ethers to corresponding diesters

Abstract

The invention relates to a process for doubly carbonylating allyl ethers to the corresponding diesters, wherein a linear or branched allyl ether is reacted with a linear or branched alkanol (alcohol) with supply of CO and in the presence of a catalytic system composed of a palladium complex and at least one organic phosphorus ligand and in the presence of a hydrogen halide selected from HCl, HBr and HI.

Claims

1. Process for doubly carbonylating allyl ethers to diesters, comprising: reacting, in a single step, a linear or branched allyl ether with a linear or branched alkanol with supply of CO and in the presence of a catalytic system composed of a palladium complex and at least one organic phosphorus ligand and in the presence of a hydrogen halide selected from HCl, HBr and HI, wherein both the allyl portion and the ether portion of the allyl ether are reacted with the CO.

2. Process according to claim 1, characterized in that the allyl ethers are compounds of the general formula (1): ##STR00046## where R.sup.1, R.sup.2 and R.sup.3 are independently hydrogen or a C.sub.1 to C.sub.10 alkyl radical and R is hydrogen, or a saturated or unsaturated, branched or unbranched, aliphatic, cycloaliphatic or cycloaliphatic-aliphatic hydrocarbyl radical having up to 12 carbon atoms, in which CC bonds may be interrupted by oxygen or the OCO group, or a phenyl radical, where the phenyl radical may be substituted as follows: C.sub.1- to C.sub.10-alkyl or C.sub.1- to C.sub.10-alkoxy groups, R is a saturated or unsaturated, branched or unbranched, aliphatic, cycloaliphatic, araliphatic or cycloaliphatic-aliphatic hydrocarbyl radical having up to 12 carbon atoms, in which CC bonds may be interrupted by oxygen or the OCO group.

3. Process according to claim 1, characterized in that the alkanols are compounds of the general formula ROH where R is a C.sub.1- to C.sub.10-alkyl, a C.sub.4- to C.sub.20-cycloalkyl or a C.sub.7- to C.sub.11-aralkyl group.

4. Process according to claim 1, characterized in that the reaction is conducted in the liquid phase at a temperature of 70 to 250 C.

5. Process according to claim 1, characterized in that reaction is conducted under a pressure of 2 to 100 bar.

6. Process according to claim 1, characterized in that the palladium complex is formed in situ proceeding from a pre-complex, using, as palladium source, palladium-containing salts and complexes as precursor.

7. Process according to claim 6, characterized in that the palladium complex is selected from the group comprising Pd acetates, Pd acetonates, Pd halides and Pd halide complexes, and also Pd-halogen-1,5-cyclooctadienes, Pd nitrates and Pd oxide.

8. Process according to claim 1, characterized in that the phosphine ligands have a mono- or bidentate structure, preferably selected from the group comprising L1(9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), L2(oxybis(2,1-phenylene))bis(di-tert-butylphosphine), L31,2-bis((di-tert-butylphosphinyl)methyl)benzene, L4triphenylphosphine, L5di(1-adamantyl)-n-butylphosphine.

9. Process according to claim 1, characterized in that the hydrogen halide used is hydrogen chloride.

10. Process according to claim 1, characterized in that the ratio of palladium to hydrogen halide is in the range from 1:1 to 1:20.

Description

WORKING EXAMPLES

(1) General Remarks:

(2) All commercial reagents were ordered from Alfa Aesar, Aldrich, TCI or Strem. Unless stated otherwise, commercial reagents were used without purification. The allyl ether is distilled under reduced pressure prior to use. Toluene, DMF, THF, acetonitrile and methanol are used from the PS-MD-7 solvent purification system from Innovative technology using standard Schlenk techniques. Analytical data for the compounds known from the literature were in accordance with data reported. NMR spectra were recorded on the Bruker Avance 300 (300 MHz) NMR spectrometer. Multiplets were assigned as s (singlet), d (doublet), t (triplet), dd (doublet of doublets), m (multiplet) and br s (broad singlet). All measurements were conducted at room temperature, unless stated otherwise. Electron impact (EI) mass spectra were conducted on the AMD 402 mass spectrometer (70 eV). High-resolution mass spectra (HRMS) were recorded on the Agilent 6210 time-of-flight LC/MS (Agilent) with electrospray ionization (ESI). The data are reported as mass units per charge (m/z) and intensities of signals in brackets. The products were separated from the reaction mixture by column chromatography on silica gel 60, 0.063-0.2 mm, 70-230 mesh (Merck).

(3) GC Analysis:

(4) GC analysis was conducted by means of an Agilent GC 7890A gas chromatograph from Agilent Company with a 30 m HP-5 column ((polydimethylsiloxane with 5% phenyl groups, 30 m, 0.32 mm ID, 0.25 m film thickness). Temperature program: 35 C., 10 min; 10 C./min to 285 C., 5 min; injection volume 1 l with a split of 50:1.

(5) List Of Abbreviations

(6) BnOH: benzyl alcohol

(7) CyOH: cyclohexanol

(8) equiv.: equivalents

(9) HCl: hydrogen chloride

(10) THF: tetrahydrofuran

(11) T: temperature

(12) p: pressure

(13) Xantphos: 4,5-bis(diphenylphosphinyl)-9,9-dimethylxanthene

Example 1

(14) Reaction of Allyl Butyl Ether with Butanol Using Pd(OAc).sub.2 and Various Phosphine Ligands, and also Hydrogen Chloride (Table 1)

(15) ##STR00003##

(16) TABLE-US-00001 Acid T Yield Entry Pd (mol %) Ligand (mol %) Solvent (mol %) ( C.) p(bar) (n-/iso-) 1 Pd(OAc).sub.2(1.0) toluene HCl (2.0) 110 40 bar CO 90% (48:52) 2 Pd(OAc).sub.2(1.0) toluene HCl (2.0) 110 40 bar CO 2% (70:30) 3 Pd(OAc).sub.2(1.0) toluene HCl (2.0) 110 40 bar CO 50% (36:64) 4 Pd(OAc).sub.2(1.0) toluene HCl (2.0) 110 40 bar CO 4% (22:78) 5 Pd(OAc).sub.2(1.0) toluene HCl (2.0) 110 40 bar CO 4% (23:77)

Example 1.1

(17) Table 1, Entry 1

(18) A 4 ml glass vial is charged with [Pd(acac).sub.2] (2.24 mg, 1 mol %), L1 (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (137 l, 1.5 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 1.2

(19) Table 1, Entry 2

(20) A 4 ml glass vial is charged with [Pd(acac)] (2.24 mg, 1 mol %), L2 (8.1 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (137 l, 1.5 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial Is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 1.3

(21) Table 1, Entry 3

(22) A 4 ml glass vial is charged with [Pd(acac).sub.2] (2.24 mg, 1 mol %), L3 (5.9 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (137 l, 1.5 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO. CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 1.4

(23) Table 1, Entry 4

(24) A 4 ml glass vial is charged with [Pd(acac).sub.2] (2.24 mg, 1 mol %), L4 (7.9 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (137 l, 1.5 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 1.5

(25) Table 1, Entry 5

(26) A 4 ml glass vial is charged with [Pd(acac).sub.2] (2.24 mg, 1 mol %), L5 (10.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (137 l, 1.5 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 2

(27) Variation of the Amount of Acid (Table 2)

(28) ##STR00009##

(29) TABLE-US-00002 TABLE 2 Ligand T p Yield Entry Pd (mol %) (mol %) Solvent Acid (mol %) ( C.) (bar) (n-/iso-) 1 Pd(acac).sub.2 (1.0) Xantphos (1.5) toluene HCl (1.0) 110 40 25% (51:49) 2 Pd(acac).sub.2 (1.0) Xantphos (1.5) toluene HCl (1.5) 110 40 63% (49:51) 3 Pd(acac).sub.2 (1.0) Xantphos (1.5) toluene HCl (2.0) 110 40 78% (53:47) 4 Pd(acac).sub.2 (1.0) Xantphos (1.5) toluene HCl (2.5) 110 40 67% (48:52) 5 Pd(acac).sub.2 (1.0) Xantphos (1.5) toluene HCl (3.0) 110 40 22% (48:52) 6 Pd(acac).sub.2 (1.0) Xantphos (1.5) toluene HCl (4.0) 110 40 8% (46:54)

Example 2.1

(30) Table 2, Entry 1

(31) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (10 l, 1 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 2.2

(32) Table 2, Entry 2

(33) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (15 l, 1.5 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 2.3

(34) Table 2, Entry 3

(35) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 2.4

(36) Table 2, Entry 4

(37) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (25 l, 2.5 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 2.5

(38) Table 2, Entry 5

(39) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (30 l, 3 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 2.6

(40) Table 2, Entry 6

(41) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (40 l, 4 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 3

(42) Variation of the Acids (Table 3)

(43) ##STR00010##

(44) TABLE-US-00003 TABLE 3 Acid T Yield Entry Pd (mol %) Ligand (mol %) Solvent (mol %) ( C.) p (bar) (n-/iso-) 1 Pd(OAc).sub.2 (1.0) Xantphos (1.5) toluene HCl (2.0) 110 40 90% (47:53) 2 Pd(OAc).sub.2 (1.0) Xantphos (1.5) toluene H.sub.2SO.sub.4 110 40 0 () (1.0) 3 Pd(OAc).sub.2 (1.0) Xantphos (1.5) toluene HOAc 110 40 0 () (2.0) 4 Pd(OAc).sub.2 (1.0) Xantphos (1.5) toluene CF.sub.3COOH 110 40 0 () (2.0) 5 Pd(OAc).sub.2 (1.0) Xantphos (1.5) toluene CH.sub.3SO.sub.3H 110 40 0 () (2.0) 6 Pd(OAc).sub.2 (1.0) Xantphos (1.5) toluene CF.sub.3SO.sub.3H 110 40 0 () (2.0) 7 Pd(OAc).sub.2 (1.0) Xantphos (1.5) toluene PTSAH.sub.2O 110 40 0 () (2.0) 8 Pd(OAc).sub.2 (1.0) Xantphos (1.5) toluene 110 40 0 () 9 Pd(OAc).sub.2 (1.0) Xantphos (1.5) acetone HCl (aq) 110 40 55 (2.0) 10 Pd(OAc).sub.2 (1.0) Xantphos (1.5) acetone HBr (aq) 110 40 11 (2.0)

Example 3.1

(45) Table 3, Entry 1

(46) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 3.2

(47) Table 3, Entry 2

(48) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 0.5 M H.sub.2SO.sub.4 solution in diethyl ether (20 l, 1.0 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 3.3

(49) Table 3, Entry 3

(50) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %). Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and HOAc (1.1 l, 2.0 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 3.4

(51) Table 3, Entry 4

(52) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and CF.sub.3COOH (1.6 l, 2.0 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 3.5

(53) Table 3, Entry 5

(54) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and CH.sub.3SO.sub.3H (1.3 l, 2.0 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 3.6

(55) Table 3, Entry 6

(56) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and CF.sub.3SO.sub.3H (1.8 l, 2.0 mol %) are then Injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110C for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 3.7

(57) Table 3, Entry 7

(58) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %), PTSA.H.sub.2O (3.8 mg, 2.0 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 3.8

(59) Table 3, Entry 8

(60) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 3.9

(61) Table 3, Entry 9

(62) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of acetone, n-butanol (137 l, 1.5 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M HCl (aqueous solution) (20 l, 2.0 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 3.10

(63) Table 3, Entry 10

(64) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of acetone, n-butanol (137 l, 1.5 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M HBr (aqueous solution) (20 l, 2.0 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 4

(65) Variation of the Amount of Palladium and of the Butanol (Table 4)

(66) ##STR00011##

(67) TABLE-US-00004 TABLE 4 Ligand nButanol Acid P Yield Entry Pd (mol %) (mol %) (mol %) Solvent (mol %) T ( C.) (bar) (n-/iso-) 1 Pd(acac).sub.2 (1.0) Xantphos (1.5) 120 toluene HCl (2.0) 110 40 79% (45:55) 2 Pd(acac).sub.2 (1.0) Xantphos (1.5) 150 toluene HCl (2.0) 110 40 91% (46.54) 3 Pd(acac).sub.2 (1.0) Xantphos (1.5) 200 toluene HCl (2.0) 110 40 85% (48:52) 4 Pd(acac).sub.2 (0.5) Xantphos (0.75) 200 toluene HCl (1.0) 110 40 33% (50:50) 5 Pd(acac).sub.2 (0.25) Xantphos (0.375) 200 toluene HCl (0.5) 110 40 6% (51:49)

Example 4.1

(68) Table 4, Entry 1

(69) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (109 l, 1.2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 4.2

(70) Table 4, Entry 2

(71) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (137 l, 1.5 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 4.3

(72) Table 4, Entry 3

(73) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 4.4

(74) Table 4, Entry 4

(75) A 4 ml glass vial is charged with Xantphos (L1) (4.35 mg, 0.75 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. [Pd(acac).sub.2] (500 l, 0.01 M in toluene, 1.53 mg, 0.5 mol %), toluene (1.5 ml), allyl butyl ether (145 l, 1.0 mmol), n-butanol (182 l, 2.0 mmol) and 1 M HCl-diethyl ether solution (10 l, 1.0 mol %) are injected by means of a syringe. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 4.5

(76) Table 4, Entry 5

(77) A 4 ml glass vial is charged with Xantphos (L1) (2.18 mg, 0.375 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. [Pd(acac).sub.2] (250 l, 0.01 M in toluene, 0.765 mg, 0.25 mol %), toluene (1.5 ml), allyl butyl ether (145 l, 1.0 mmol), n-butanol (182 l, 2.0 mmol) and 1 M HCl-diethyl ether solution (5 l, 1.0 mol %) are injected by means of a syringe. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 5

(78) Variation of the Amount of Xantphos (Table 5)

(79) ##STR00012##

(80) TABLE-US-00005 TABLE 5 Acid Yield Entry Pd (mol %) Ligand (mol %) Solvent (mol %) T ( C.) p (bar) (n-/iso-) 1 Pd(acac).sub.2 (1.0) Xantphos (1.0) toluene HCl 110 40 7% (2.0) (48:52) 2 Pd(acac).sub.2 (1.0) Xantphos (1.5) toluene HCl 110 40 85% (2.0) (47:53) 3 Pd(acac).sub.2 (1.0) Xantphos (2.0) toluene HCl 110 40 62% (2.0) (49:51)

Example 5.1

(81) Table 5, Entry 1

(82) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1 mol %), Xantphos (L1) (5.8 mg, 1.0 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 5.2

(83) Table 5, Entry 2

(84) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is Injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 5.3

(85) Table 5, Entry 3

(86) A 4 ml glass vial is charged with [Pd(acac)] (3.07 mg, 1 mol %), Xantphos (L1) (11.6 mg, 2 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 6

(87) Variation of the Palladium Precursor (Table 6)

(88) ##STR00013##

(89) TABLE-US-00006 TABLE 6 nButanol Acid Yield Entry Pd (mol %) Ligand (mol %) (mol %) Solvent (mol %) T ( C.) p (bar) (n-/iso-) 1 Pd(acac).sub.2 (1.0) Xantphos (1.5) 200 toluene HCl (2.0) 110 40 85% (53:47) 2 Pd(OAc).sub.2 (1.0) Xantphos (1.5) 200 toluene HCl (2.0) 110 40 89% (48:52) 3 PdCl.sub.2 (1.0) Xantphos (1.5) 200 toluene HCl (2.0) 110 40 90% (45:55) 4 Pd(MeCN).sub.2Cl.sub.2 Xantphos (1.5) 200 toluene HCl (2.0) 110 40 90% (1.0) (44:56) 5 Pd(cod).sub.2Cl.sub.2 (1.0) Xantphos (1.5) 200 toluene HCl (2.0) 110 40 85% (45:55) 6 [PdCl(C.sub.3H.sub.5)].sub.2 (1.0) Xantphos (1.5) 200 toluene HCl (2.0) 110 40 87% (48:52) 7 Pd.sub.2 (dba).sub.3 (1.0) Xantphos (1.5) 200 toluene HCl (2.0) 110 40 82% (49:51) 8 Pd(TFA).sub.2 Xantphos (1.5) 200 toluene HCl (2.0) 110 40 93% (49:51) 9 Pd(acac).sub.2 (1.0) Xantphos (1.5) 150 toluene HCl (2.0) 110 40 bar 87% CO + 30 (45:55) bar N.sub.2 10 Pd(OAc).sub.2 (1.0) Xantphos (1.5) 150 toluene HCl (2.0) 110 40 bar 92% CO + 30 (45:55) bar N.sub.2 11 Pd(TFA).sub.2 (1.0) Xantphos (1.5) 150 toluene HCl (2.0) 110 40 bar 94% CO + 30 (47:53) bar N.sub.2 12 PdO (1.0) Xantphos (1.5) 200 toluene HCl (2.0) 110 40 bar CO 73% (48:52) 13 Pd(NO.sub.3).sub.2 Xantphos (1.5) 200 toluene HCl (2.0) 110 40 bar CO 74% 2H.sub.2O (1.0) (49:51)

Example 6.1

(90) Table 6, Entry 1

(91) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 6.2

(92) Table 6, Entry 2

(93) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 6.3

(94) Table 6, Entry 3

(95) A 4 ml glass vial is charged with [PdCl.sub.2] (1.76 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 6.4

(96) Table 6, Entry 4

(97) A 4 ml glass vial is charged with [Pd(MeCN).sub.2Cl.sub.2] (2.58 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 6.5

(98) Table 6, Entry 5

(99) A 4 ml glass vial is charged with [Pd(cod).sub.2Cl.sub.2] (2.85 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 6.6

(100) Table 6, Entry 6

(101) A 4 ml glass vial is charged with [PdCl(C.sub.3H.sub.5)].sub.2 (1.83 mg, 0.5 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 6.7

(102) Table 6, Entry 7

(103) A 4 ml glass vial is charged with [Pd.sub.2(dba).sub.3] (4.58 mg, 0.5 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 6.8

(104) Table 6, Entry 8

(105) A 4 ml glass vial is charged with [Pd(TFA).sub.2] (3.32 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula. 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 6.9

(106) Table 6, Entry 9

(107) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (136 l, 1.5 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar and nitrogen (5.0 purity) to 30 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 6.10

(108) Table 6, Entry 10

(109) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (136 l, 1.5 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar and nitrogen (5.0 purity) to 30 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 6.11

(110) Table 6, Entry 11

(111) A 4 ml glass vial is charged with [Pd(TFA).sub.2] (3.32 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (136 l, 1.5 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar and nitrogen (5.0 purity) to 30 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 6.12

(112) Table 6, Entry 12

(113) A 4 ml glass vial is charged with PdO (1.2 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 6.13

(114) Table 6, Entry 13

(115) A 4 ml glass vial is charged with [Pd(NO.sub.3).sub.2.2H.sub.2O] (2.65 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 7

(116) Variation of the Solvent, Table 7

(117) ##STR00014##

(118) TABLE-US-00007 TABLE 7 Ligand Acid Temp Yield Entry Pd (mol %) (mol %) Solvent (mol %) ( C.) pbar) (n-/iso-) 1 Pd(acac).sub.2 (1.0) Xantphos (1.5) toluene HCl 110 40 85% (2.0) (47:53) 2 Pd(acac).sub.2 (1.0) Xantphos (1.5) THF HCl 110 40 27% (2.0) (45:55) 3 Pd(acac).sub.2 (1.0) Xantphos (1.5) MeCN HCl 110 40 6% (2.0) (66:34) 4 Pd(acac).sub.2 (1.0) Xantphos (1.5) heptane HCl 110 40 18% (2.0) (57:43) 5 Pd(acac).sub.2 (1.0) Xantphos (1.5) acetone HCl 110 40 60% (2.0) (54:46) 6 Pd(acac).sub.2 (1.0) Xantphos (1.5) dioxane HCl 110 40 20% (2.0) (48:52) 7 Pd(acac).sub.2 (1.0) Xantphos (1.5) n-butanol HCl 110 40 6% (2.0) (76:24)
Table 7, Entry 1

(119) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 7.2

(120) Table 7, Entry 2

(121) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of THF, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 7.3

(122) Table 7, Entry 3

(123) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of MeCN, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO. CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 7.4

(124) Table 7, Entry 4

(125) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of heptane, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as Internal standard. The yield and selectivity are determined by means of GC analysis.

Example 7.5

(126) Table 7, Entry 5

(127) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of acetone, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then Injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 7.6

(128) Table 7, Entry 6

(129) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of dioxane, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 7.7

(130) Table 7, Entry 7

(131) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of n-butanol, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 8

(132) Variation of Substrate (Table 8)

(133) ##STR00015##

(134) TABLE-US-00008 TABLE 8 Entry Substrate Alcohol Main products Yield (n-/iso-) 1.sup. MeOH (1.5 equiv.) 81% (50:50) 2.sup. EtOH (1.5 equiv.) 0 83% (46:54) 3.sup. .sup.nBuOH (1.5 equiv.) 90% (48:52) 4.sup. BnOH (1.5 equiv.) 70% (70%.sup.b) (48:52) 5.sup. 0 61% (53:47) 6.sup. .sup.nBuOH (6.0 equiv.) 93% (54:46) 7.sup. BnOH (1.5 equiv.) 61% (6:94) 8.sup. BnOH (1.5 equiv.) 0 44% (7:93) 9.sup.a MeOH (1.5 equiv.) 35%.sup.b (69:31) .sup.a4.0 mol % HCl, 48 h .sup.bIsolated yield

Example 8.1

(135) Table 8, Entry 1

(136) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, methyl allyl ether (72 mg, 1.0 mmol), methanol (48 mg, 1.5 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 8.2

(137) Table 8, Entry 2

(138) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, ethyl allyl ether (86 mg, 2 mmol), ethanol (69 mg, 1.5 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 1.0 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 8.3

(139) Table 8, Entry 3

(140) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, n-butyl allyl ether (114 mg, 1.0 mmol), n-butanol (111 mg, 1.5 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is Injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 8.4

(141) Table 8, Entry 4

(142) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, benzyl allyl ether (148 mg, 1.0 mmol), BnOH (162 mg, 1.5 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 8.5

(143) Table 8, Entry 5

(144) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, cyclohexyl allyl ether (140 mg, 1.0 mmol), CyOH (150 mg, 1.5 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 8.6

(145) Table 8, Entry 6

(146) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, diallyl ether (98 mg, 1.0 mmol), n-butanol (444 mg, 6.0 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 8.7

(147) Table 8, Entry 7

(148) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, ((but-3-en-2-yloxy)methyl)benzene (162 mg, 1.0 mmol), BnOH (162 mg, 1.5 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 8.8

(149) Table 8, Entry 8

(150) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, ((but-2-en-1-yloxy)methyl)benzene (162 mg, 1.0 mmol), BnOH (162 mg, 1.5 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 8.9

(151) Table 8 Entry 9

(152) A 4 ml glass vial is charged with [Pd(OAc).sub.2] (2.24 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of toluene, (3-methoxyprop-1-en-1-yl)benzene (148 mg, 1.0 mmol), MeOH (48 mg, 1.5 mmol) and 2 M HCl solution in diethyl ether (20 l, 4.0 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO Is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 9

(153) Variation of Temperature (Table 9)

(154) TABLE-US-00009 Acid Temp Yield Entry Pd (mol %) Ligand (mol %) Solvent (mol %) ( C.) p(bar) (n-/iso-) 1 Pd(acac).sub.2 (1.0) Xantphos (1.5) toluene HCl 100 40 64% (2.0) (48:52) 2 Pd(acac).sub.2 (1.0) Xantphos (1.5) toluene HCl 110 40 85% (2.0) (53:47) 3 Pd(acac).sub.2 (1.0) Xantphos (1.5) toluene HCl 120 40 77% (2.0) (48:52) 4 Pd(acac).sub.2 (1.0) Xantphos (1.5) toluene HCl 140 40 75% (2.0) (48:52)

Example 9.1

(155) Table 9, Entry 1

(156) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of propylene carbonate, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 100 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 9.2

(157) Table 9, Entry 2

(158) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of propylene carbonate, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 110 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 9.3

(159) Table 9, Entry 3

(160) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of propylene carbonate, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 120 C. for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.

Example 9.4

(161) Table 9, Entry 4

(162) A 4 ml glass vial is charged with [Pd(acac).sub.2] (3.07 mg, 1.0 mol %), Xantphos (L1) (8.7 mg, 1.5 mol %) and a magnetic stirrer. This vial is closed with a phenolic resin cap consisting of a septum made from Teflon-coated styrene-butadiene rubber. This septum is pierced with a cannula, and the atmosphere in the vial is replaced by an argon atmosphere through this cannula by three cycles of application of reduced pressure and purging with argon. Through this cannula, 2 ml of propylene carbonate, n-butanol (182 l, 2 mmol), allyl butyl ether (145 l, 1 mmol) and 1 M hydrochloric acid solution in diethyl ether (20 l, 2 mol %) are then injected by means of syringes. This vial is then placed in a metal plate which is then transferred into a 300 ml steel autoclave from Parr Instruments under an argon atmosphere. After the autoclave has been purged three times with CO, CO is injected to 40 bar at room temperature. The reaction is conducted while stirring with a magnetic stirrer at 140C for 24 hours. After the end of the reaction, the autoclave is cooled down and the pressure is released gradually. The autoclave is purged three times with nitrogen. Subsequently, dodecane (100 l) is added as internal standard. The yield and selectivity are determined by means of GC analysis.