Heterocyclic selenamonophosphites protected on a hydroxyl group and processes for preparation thereof

Abstract

Novel heterocyclic selenamonophosphites protected on the hydroxyl group, processes for preparation thereof and the use thereof as ligand.

Claims

1. A heterocyclic selenaphosphite compound having a general structure (I) ##STR00027## where R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, O(C.sub.6-C.sub.20)-aryl, -halogen, OCO(C.sub.1-C.sub.12)-alkyl, S-alkyl, S-aryl, COO(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.1-C.sub.12)-alkyl, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.6-C.sub.20)-aryl, COOH, SO.sub.3H, CN, or N[(C.sub.1-C.sub.12)-alkyl].sub.2, where the alkyl groups are linear, branched or cyclic, where the alkyl and aryl groups are each independently unsubstituted or substituted, where each substituted (C.sub.1-C.sub.12)-alkyl group and substituted (C.sub.6-C.sub.20)-aryl group have at least one substituent and the at least one substituent is each independently selected from (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, fluorine, chlorine, cyano, formyl, acyl, or alkoxycarbonyl, and where the R.sup.1 group is selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.6-C.sub.20)-aryl, (CO)O(C.sub.1-C.sub.12)-alkyl, -acetyl, where the alkyl groups are linear, branched or cyclic, where the alkyl and aryl groups mentioned are each independently unsubstituted or substituted, where substituted (C.sub.1-C.sub.12)-alkyl groups and substituted (C.sub.6-C.sub.20)-aryl groups have at least one substituent and the at least one substituent in each case is independently selected from (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, fluorine, chlorine, cyano, formyl, acyl, or alkoxycarbonyl, and the R.sup.1* group is an organofunctional phosphite group.

2. The compound according to claim 1, wherein in the heterocyclic selenaphosphite of the general structure (I) R.sup.1* is an organofunctional phosphite group selected from the structures (II), (III), (IV, (V), (VI) and (VII) ##STR00028## where the radicals R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22 in structure (II), R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.10*, R.sup.11*, R.sup.12*, R.sup.13*, R.sup.14* in the structure (III), R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31, and R.sup.32 in structure (IV), R.sup.43, R.sup.44, R.sup.45, R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50, R.sup.51, R.sup.52, R.sup.53 and R.sup.54 in structure (V), and R.sup.55, R.sup.56, R.sup.57, R.sup.58, R.sup.59 and R.sup.60 in structure (VII). in each case in the respective structure are independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, O(C.sub.6-C.sub.20)-aryl, or -halogen, where the alkyl groups are linear, branched or cyclic, where the alkyl and aryl groups are each independently unsubstituted or substituted, where each substituted (C.sub.1-C.sub.12)-alkyl group and each substituted (C.sub.6-C.sub.20)-aryl group has at least one substituent and the at least one substituent in each case is independently selected from (C.sub.3C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl.

3. The compound according to claim 1, wherein the R.sup.1 group in the structure (I) is selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)alkyl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-O(C.sub.6-C.sub.20)-aryl, (CO)O(C.sub.1-C.sub.12)-alkyl, where the alkyl groups are linear, branched or cyclic, where the alkyl and aryl groups mentioned are each independently unsubstituted or substituted, where substituted (C.sub.1-C.sub.12)-alkyl groups and substituted (C.sub.6-C.sub.20)-aryl groups have at least one substituent and the at least one substituent in each case is independently selected from (C.sub.3-C.sub.12)-cycloalkyl and/or (C.sub.6-C.sub.20)-aryl.

4. The compound according to claim 1, wherein the heterocyclic selenaphosphite of the general structure (I) is compound of structure (Ia) ##STR00029## where R.sup.2, R.sup.4, R.sup.7 and R.sup.9 are each independently selected from: (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, O(C.sub.6-C.sub.20)-aryl, or -halogen, where the alkyl groups are linear, branched or cyclic, where the R.sup.1 group is selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, or (C.sub.6-C.sub.20)-aryl-O(C.sub.6-C.sub.20)-aryl, where the alkyl groups are linear, branched or cyclic, and the R.sup.1* group in structure (Ia) is an organofunctional phosphite group.

5. The compound according to claim 4, wherein the R.sup.1* in the heterocyclic selenaphosphite of the structure (Ia) is selected from the structures (II), (III), (IV), (V), (VI) and (VII) ##STR00030## ##STR00031## where the radicals R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22 in structure (II), R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.10*, R.sup.11*, R.sup.12*, R.sup.13*, R.sup.14* in the structure (III), R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31, and R.sup.32 in structure (IV), R.sup.43, R.sup.44, R.sup.45, R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50, R.sup.51, R.sup.52, R.sup.53 and R.sup.54 in structure (V), and R.sup.55, R.sup.56, R.sup.57, R.sup.58, R.sup.59 and R.sup.60 in structure (VII), in each case for each structure are independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, O(C.sub.6-C.sub.20)-aryl, or -halogen, where the alkyl groups are linear, branched or cyclic.

6. The compound according to claim 4, wherein the R.sup.1* in the heterocyclic selenaphosphite of the structure (Ia) is selected from structure (III) and the R.sup.1 group is selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, or (C.sub.6-C.sub.20)-aryl-O(C.sub.6-C.sub.20)-aryl, where the alkyl groups are linear, branched or cyclic, ##STR00032## where R.sup.2, R.sup.4, R.sup.7 and R.sup.9 in structure (Ia) are each independently selected from (C.sub.1-C.sub.12)-alkyl, or O(C.sub.1-C.sub.12)-alkyl, where the alkyl groups are linear, branched or cyclic, and ##STR00033## with R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.10*, R.sup.11*, R.sup.12*, R.sup.13*, R.sup.14* in the structure (III) each independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, where the alkyl groups are linear, branched or cyclic.

7. A rhodium hydroformylation catalyst, comprising: the compound according to claim 1 as a ligand.

8. A process for preparing at least one heterocyclic selenephosphite of the general structure (I) ##STR00034## where R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, O(C.sub.6-C.sub.20)-aryl, -halogen, OCO(C.sub.1-C.sub.12)-alkyl, S-alkyl, S-aryl, COO(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.1-C.sub.12)-alkyl, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.6-C.sub.20)-aryl, COOH, SO.sub.3H, CN, or N[(C.sub.1-C.sub.12)-alkyl].sub.2, where the alkyl groups are linear, branched or cyclic, where the alkyl and aryl groups are each independently unsubstituted or substituted, where each substituted (C.sub.1-C.sub.12)-alkyl group and substituted (C.sub.6-C.sub.20)-aryl group have at least one substituent and the at least one substituent is each independently selected from (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, and where the R.sup.1 group is selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.6-C.sub.20)-aryl, COO(C.sub.1-C.sub.12)-alkyl, or acetyl, where the alkyl groups are linear, branched or cyclic, where the alkyl and aryl groups mentioned are each independently unsubstituted or substituted, where substituted (C.sub.1-C.sub.12)-alkyl groups and substituted (C.sub.6-C.sub.20)-aryl groups have at least one substituent and the at least one substituent in each case is independently selected from (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, and the R.sup.1* group is an organofunctional phosphite group. comprising at least the process step of (i) reacting a selenodiaryl of the general structure (IX) ##STR00035## where R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, O(C.sub.6-C.sub.20)-aryl, -halogen, OCO(C.sub.1-C.sub.12)-alkyl, S-alkyl, S-aryl, COO(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.1-C.sub.12)-alkyl, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.6-C.sub.20)-aryl, COOH, SO.sub.3H, CN, or N[(C.sub.1-C.sub.12)-alkyl].sub.2, where the alkyl groups are linear, branched or cyclic, where the alkyl and aryl groups are each independently unsubstituted or substituted, where each subtituted (C.sub.1-C.sub.12)-alkyl group and substituted (C.sub.6-C.sub.20)-aryl group have at least one substituent and the at least one substituent is each independently selected from (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, and R.sup.1 group is selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.6-C.sub.20)-aryl, COO(C.sub.1-C.sub.12)-alkyl, or acetyl, where the alkyl groups are linear, branched or cyclic, where the alkyl and aryl groups mentioned are each independently unsubstituted or substituted, where substituted (C.sub.1-C.sub.12)-alkyl groups and substituted (C.sub.6-C.sub.20)-aryl groups have at least one substituent and the at least one substituent in each case is independently selected from (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, (ii) with at least one halophosphite compound R.sup.1*Hal where Hal is selected from fluorine, chlorine, bromine, iodine, and where R.sup.1* is an organofunctional bivalent phosphite group, (iii) and obtaining at least one selenaphosphite of the general structure (I).

9. The process according to claim 8, wherein in the halophosphite compounds R.sup.1*Hal where Hal is in each case independently selected from chlorine, chlorine, bromine, iodine, and R.sup.1* in each case is selected from the structures (II), (III), (IV), (V), (VI) and (VII) ##STR00036## ##STR00037## where the radicals R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22 in structure (II), R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.10*, R.sup.11*, R.sup.12*, R.sup.13*, R.sup.14* in the structure (III), R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31, and R.sup.32 in structure (IV), R.sup.43, R.sup.44, R.sup.45, R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50, R.sup.51, R.sup.52, R.sup.53 and R.sup.54 in structure (V), and R.sup.55, R.sup.56, R.sup.57, R.sup.58, R.sup.59 and R.sup.60 in structure (VII), in each case independently in the respective structure are selected from: H, (C.sub.1-C.sub.12),-alkyl, O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, O(C.sub.6-C.sub.20)-aryl, or -halogen, where the alkyl groups are linear, branched or cyclic, where the alkyl and aryl groups are each independently unsubstituted or substituted, where each substituted (C.sub.1-C.sub.12)-alkyl group and each substituted (C.sub.6-C.sub.20)-aryl group has at least one substituent and the at least one substituent in each case is independently selected from (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl.

10. The process according to claim 8, wherein in the halophosphite compound R.sup.1*Hal where Hal is selected from chlorine and bromine, and R.sup.1* is selected from the structures (II), (III), (IV), (V), (VI) and (VII) ##STR00038## where the radicals R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22 in structure (II), R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.10*, R.sup.11*, R.sup.12*, R.sup.13*, R.sup.14* in the structure (III), R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31, and R.sup.32 in structure (IV), R.sup.43, R.sup.44, R.sup.45, R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50, R.sup.51, R.sup.52, R.sup.53 and R.sup.54 in structure (V), and R.sup.55, R.sup.56, R.sup.57, R.sup.58, R.sup.59 and R.sup.60 in structure (VII), are each independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, O(C.sub.6-C.sub.20)-aryl, -halogen, where the alkyl groups are linear, branched or cyclic.

11. The process according to claim 8, wherein the selenodiaryl corresponds to the general structure (IXa) ##STR00039## where R.sup.2, R.sup.4, R.sup.7 and R.sup.9 are each independently selected from: (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, O(C.sub.6-C.sub.20)-aryl, or -halogen, where the alkyl groups are linear, branched or cyclic, and where the R.sup.1 group is selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, or (C.sub.6-C.sub.20)-aryl-O(C.sub.6-C.sub.20)-aryl, where the alkyl groups are linear, branched or cyclic.

12. The process according to claim 8, wherein (i) the reaction is effected in the presence of a base.

13. The process according to claim 11, wherein the selenodiaryl of the structure (IXa) is reacted with R.sup.1*Hal in a molar ratio of 10:1 to 1:10.

14. The process according to claim 8, wherein (i) the reaction is effected in a temperature range from 45 to 80 C.

15. The process according to claim 8, wherein (i) the reaction is effected in an aprotic solvent.

16. The method of claim 12, wherein (i) the reaction is effected in the presence of an amine base, an alkylamine base, or a pyridine base.

17. The method of claim 16, wherein (i) the reaction is effected in the presence of triethylamine or dimethylaminobutane.

18. The method of claim 13, wherein the selenodiaryl of the structure (IXa) is reacted with R.sup.1*Hal in a molar ratio of 4:1 to 1:4.

19. The method of claim14, wherein (i) the reaction is effected in the temperature range from 15 to 30 C.

20. The method of claim 15, wherein (i) the reaction is effected in an aprotic solvent selected from organic aromatic halogenated solvents or hydrocarbons.

Description

GENERAL METHODS

(1) Solvents and Reagents

(2) All reactions with moisture- and/or oxygen-sensitive substances were carded out in baked-out apparatuses under an argon atmosphere. Solvents for extraction and column chromatography were used at the following purities: dichloromethane (99,9%, Walter, Cat. No, BIE 073107033) ethyl acetate (99.5%, Walter, Cat. No. BIE 003917025) and n-hexane (95%, Walter (Baker), Cat. No. 8669),

(3) n-heptane (95%, Walter (Baker), Cat. No, 8662). Other solvents for extraction and column chromatography were of technical quality and were used without further purification unless otherwise stated. Dry solvents (abs.) were purified using a Pure Soy MD-7 System and stored under an argon atmosphere. Benzyl bromide was freshly distilled (17 mbar/82 C.) prior to use. Deuterated solvents were distilled from the drying agents specified: dichloromethane-d.sub.2 (phosphorus pentoxide), toluene-d.sub.8 (1. KOH 2. sodium). Chemicals used for the syntheses were supplied by Sigma Aldrich, Alfa Aesar, Acres Organics, Avantor Performance Materials B. V., Merck KGaA and ABCR GmbH & Co. KG. These were used without further purification unless otherwise stated.

(4) Filtration; Filtrations for the removal of resulting solids were carried out using a G4 frit (pore width: 10-16 m).

(5) Analysis

(6) IR spectroscopy: IR spectra were recorded with a Nicolet 6700 FT-IR spectrometer from Thermo Electron. The substances were measured by ATR methods.

(7) .sup.1H NMR spectroscopy: .sup.1H NMR spectra were recorded with a model AV 300 (300 MHz) and with the model Fourier 300 (300 MHz) from Broker. Chemical shifts are stated in units on the -scale. The residual proton signals of the solvent (dichloromethane-d.sub.2: =5.32 ppm, toluene-d.sub.8: =7.09; 7.00; 6.98; 2.09 ppm) served as standard.

(8) .sup.13C NMR spectroscopy: .sup.13C NMR spectra were recorded with models AV 300 (75 MHz) and Fourier 300 (75 MHz) from Bruker. The signal of the solvent (dichloromethane-d.sub.2: =54.0 ppm, toluene-d.sub.8;

(9) =137.9; 129.2; 128.3; 125.5; 20.4 ppm) served as internal standard wherein the chemical shifts were taken from the broadband .sup.1H-decoupled spectra.

(10) .sup.77Se NMR spectroscopy: .sup.77Se NMR spectra were recorded with an AV 300 (57 MHz) from Bruker. The spectra were measured in broadband .sup.1H-decoupled mode. The chemical shifts are reported in ppm.

(11) Mass spectrometry: El mass spectra were recorded on a Finnigan MAT 95-XP instrument from Thermo Electron and ESI-TOF mass spectra with a model 6210 Time-of-Flight LC/MS from Agilent.

(12) Autoclave Experiments of Rhodium-Catalysed Hydroformylation

(13) The hydroformylation was conducted in a 200 ml autoclave equipped with pressure-retaining valve, gas flow meter, sparging stirrer and pressure pipette from Premex Reactor AG, Lengau, Switzerland. The toluene used as solvent was purified using a Pure Solv MD-7 System and stored under argon. The 1-octene or n-octenes substrate (EVONIK Industries AG, octene isomer mixture of 1-octene: 3.3%; cis+trans-2-octene; 48.5%; cis+trans-3-octene: 29.2%; cis+trans-octene-4: 16.4%; structurally isomeric octenes: 2.6%) used as substrate was heated at reflux over sodium for several hours and distilled under argon.

(14) For the experiments, solutions of the catalyst precursor and the ligand were mixed in the autoclave under an argon atmosphere. [(acac)Rh(COD)] (Umicore, acac=acetylacetonate anion; COD=1,5-cyclooctadiene) was used as catalyst precursor. For experiments at a concentration of 100 ppm-m rhodium, 10 ml of a 4.31 mM solution was placed in the autoclave. Subsequently, the mass of ligand corresponding to a ratio L/Rh=5:1 (or 1:1) was dissolved and mixed in 10 ml of toluene. By adding further toluene, the starting volume of the catalyst solution was adjusted to 41.0 ml. Into a pressure-resistant pipette was filled: 1-octene or n-octanes (10.70 g). The autoclave was heated to the temperatures stated in each case at a total gas pressure (synthesis gas: Linde; H.sub.2 (99.999%): CO (99.997%)=1:1) of a) 42 bar for a final pressure of 50 bar or b) 12 bar for a final pressure of 20 bar with stirring (1500 rpm). After reaching the reaction temperature, the synthesis gas pressure was increased to a) 48.5 bar for a final pressure of 50 bar or h) 19.5 bar for a final pressure of 20 bar and the reactant was introduced under a positive pressure of about 3 bar set in the pressure pipette. The reaction was conducted at a constant pressure of 50 or 20 bar (closed-loop pressure controller from Bronkharst, the Netherlands) respectively over 4 h. After the reaction time had elapsed, the autoclave was cooled to room temperature, decompressed while stirring and purged with argon. 1.0 ml of each reaction mixture was removed immediately after the stirrer had been switched off, diluted with 5.0 ml of pentane and analysed by gas chromatography: HP 5890 Series II plus, PONA, 50 m0.2 mm0.5 m.

(15) Some abbreviations: Bn=benzyl; calc.=calculated; MOM=methylmethoxy;

Synthesis of the Precursors

(16) General ProcedureDiphenol Selenides

(17) 8.2 mmol of the particular phenol are dissolved in the appropriate solvent (8.2 m). The reaction mixture is heated, and 4.9 mmol of selenium dioxide are added while stirring. The solvent is distilled under reduced pressure (temperature <70 C.), A frit is prepared with 2.5 cm of silica gel (at the bottom) and 2.5 cm of zeolite (at the top). The distillation residue is taken up in the eluent and applied to the filtration column. Cyclohexane:ethyl acetate (95:5) is used to wash the product off the frit and collect it in fractions. The fractions containing the product are combined and freed of the eluent by distillation. The fractions obtained are recrystallized from 95:5 cyclohexane:ethyl acetate. For this purpose, the solid residue is dissolved at 50 C., and insoluble residues are filtered off using a glass frit. The reaction product crystallizes out of the saturated solution at room temperature overnight. The resulting crystals are washed once again with cold cyclohexane.

(18) The structural formula shows the main product obtained in each reaction.

Bis(3,5-dimethyl-2-hydroxyphenyl)selenium: 1a

(19) ##STR00015##

(20) The reaction is conducted according to the general procedure in a screw-top test tube. For this purpose, 1.00 g (8.2 mmol, 1.0 equiv.) of 2,4-dimethylphenol and 0.54 g (4.9 mmol, 0.6 equiv.) of selenium dioxide are dissolved in 1 ml of pyridine and heated. The product is obtained as a colourless crystalline solid.

(21) .sup.1H-NMR (400 MHz, CDCl.sub.3): (ppm)=7.12 (s,2H, 6H), 6.91 (s, 2H, 4H), 5.97 (s,2H, OH), 2.23 (s, 6H, 3-CH.sub.3) 2.23 (s, 6H, 5-CH.sub.3): .sup.13C-NMR (100 MHz, CDCl.sub.3): (ppm)=151.7 (C-2),133.2 (C-3), 133.1 (C-5), 130.4 (C-4), 124.2 (C-6), 114.9 (C-1), 20.3 (5-CH.sub.3), 16.5 (3-CH.sub.3); .sup.77Se-NMR (76 MHz, CDCl.sub.3): (ppm)=163.36 ppm.

Synthesis of the Chlorophosphites

(22) The synthesis of the rnonochlorophosphites such as 6-chlorodibenzo[d,f] [1,3,2]dioxaphosphepine is known to a person skilled in the art and is carried out in a known manner. Chlorophosphites can be prepared from the corresponding dihydroxyl compounds by addition of phosphorus trichloride in the presence of a base. For further information see also Phosphorus(III) Ligands in Homogeneous CatalysisDesign and Synthesis by Paul C. J. Kamer and Piet W. N. M. van Leeuwen; John Wiley and Sons, 2012; including p. 94 ff. and references cited therein.

Synthesis of bis(2,4-di-tert-butylphenyl)phosphorochloridite X, 2a

(23) ##STR00016##

(24) A baked-out 50 ml Schlenk flask under an argon atmosphere was initially charged with 412 mg (2.00 mmol, 2,0 eq) of 2,4-di-tert-butylphenol and 873 l (638 mg, 6.30 mmol, 6.3 eq) of triethylamine in 10 ml of abs. toluene and cooled to 0 C. Subsequently, 87.5 l (137 mg, 1.0 mmol, 1.0 eq) of phosphorus trichloride, dissolved in 2.0 ml of abs. toluene, were added dropwise to the cooled solution, in the course of which a colourless precipitate was formed. The latter was rinsed in with 5.0 ml of abs. toluene and the mixture was stirred at RT for 24 h. Subsequently, the reaction mixture was filtered for complete removal of the precipitate formed and the solids were washed with 10 ml of abs. toluene. The solvent was removed under reduced pressure and the crude product was dried under vacuum at 50 C. for three hours. 458 mg (0.962 mmol, 96%, 86% pure) of the title compound 2a were obtained as a colourless solid.

(25) IR (ATR): {circumflex over ()} (cm.sup.1)=2957; 2906; 2869; 1492; 1398; 1362; 1302; 1275; 1247; 1209; 1187; 1157; 1125; 1080; 1020; 941; 907; 887; 863; 819; 776; 745; 699; 645; 579; 532; 490; 464.

(26) .sup.1H-NMR (300 MHz, toluene-d8): (ppm)=7.54-7.40 (m, 4H, ArCH); 7.02 (dd, J=8.5 Hz, J=2.6 Hz, 2H, ArCH); 1.50 (s, 18H, C(CH.sub.3).sub.3); 1.24 (d, J=0.9 Hz, 18H, C(CH.sub.3).sub.3);

(27) .sup.13C-NMR (75 MHz, toluene-d.sub.8): (ppm)=149.4; 147.1; 139.8 (d, J=2.9 Hz); 124.8, 124.3; 119.9 (d, J=16.2 Hz), 35.16; 34.61; 31.50; 30.41; .sup.3P-NMR (122 MHz, toluene-d.sub.8): (ppm)=161.6 ppm;

(28) MS (El): m/z (%)=476 (16.1) [C.sub.28H.sub.42ClO.sub.2P]; 461 (100) [C.sub.27H.sub.39ClO.sub.2P]; 441 (1.69) [C.sub.28H.sub.42O.sub.2P];

(29) HR-MS (El): calc. for C.sub.28H.sub.42ClO.sub.2P: 476.25760, found: 476.26031; calc. for C.sub.28H.sub.42.sup.37ClO.sub.2P: 478.25760, found: 478.25834; C.sub.28H.sub.42ClO.sub.2P (476.26 g/mol).

Synthesis of 6-chlorodibenzo[d,f] [1,3,2]dioxaphosphepine X

(30) ##STR00017##

(31) A baked-out 100 ml three-neck flask having a reflux condenser, internal thermometer and dropping funnel was initially charged with 913 l (1.43 g, 10.4 mmol, 2.61 eq.) of phosphorus trichloride at RT, and 3.80 l of N-methyl-2-pyrrolidinone were added. The reaction mixture was heated to an internal temperature of 60 C. In a separate 10 ml Schlenk vessel, 745 mg (4.00 mmol, 1.0 eq.) of 2,2-biphenol were dissolved in 20 ml of abs. THF and added to the boiling reaction solution within 15 minutes. The latter was rinsed in with 2.0 ml of abs. THF and the mixture was heated to an internal temperature of 73 C. After a reaction time of 90 minutes, the light brown solution was cooled down to RT and the solvent was removed under reduced pressure. The brown liquid was admixed with 10 ml of abs. THF and the precipitate formed was removed by filtering. The solvent was removed again under reduced pressure and the crude product was dried under vacuum at 50 C. for three hours. 962 mg (3.85 mmol, 96%, 99% pure) of the title compound X were obtained as a dark brown liquid.

(32) IR (ATR): {circumflex over ()} (cm.sup.1)=3064; 3027; 2924; 2848; 2435; 1919; 1601; 1565; 1498; 1474; 1432; 1295; 1273; 1244; 1194; 1172; 1116; 1094; 1042; 1010; 942; 904; 855; 760; 738; 708; 614; 597; 579; 530; 514; 486; 470; 451; 428; .sup.1H-NMR (300 MHz, toluene-d8): (ppm)=7.29-6.83 (m, 8H, ArCH);

(33) .sup.13C-NMR (75 MHz, toluene-d.sub.8): (ppm)=149.3 (d, J=5.7 Hz); 137.1; 130.9 (d, J=3.5 Hz); 130.0 (d, J=1.6 Hz); 129.3; 126.0 (d, J=1.2 Hz); 122.0 (d, J=2.2 Hz); .sup.31P-NMR (122 MHz, toluene-d.sub.8): (ppm)=180.5; C.sub.12H.sub.8ClO.sub.2P (250.00 g/mol).

(34) According to the above experimental methods, it is possible to prepare the following monochlorophosphites of the structure X according to Table 1:

(35) TABLE-US-00001 TABLE 1 Monochlorophosphites X 0

Synthesis of 2-((2-(benzyloxy)-3,5-dimethylphenyl)sefanyl)-4,6-dimethylphenol IXA, 3a

(36) ##STR00024##

(37) In a baked-out 25 ml Schlenk flask under an argon atmosphere, 40.2 mg (1.01 mmol, 1.0 eq, 60% in paraffin oil) of sodium hydride were suspended in 3.0 ml of abs. THF and cooled to 0 C. Subsequently, 324 rug (1.01 mmol, 1.0 eq) of selenodiphenol, dissolved in 2.0 ml of abs. THF, were added dropwise. The yellowish solution was stirred at 0 C. for 15 minutes and at RT for two hours. Subsequently, at 0 C., 119 l (172 mg, 1.01 mmol, 1.0 eq) of benzyl bromide were added and the mixture was stirred at 0 C. for 30 minutes. After a further 16 hours at RT, the solvent was removed under reduced pressure. 391 mg of the reaction mixture of 2-((2-(benzyloxy)-3,5-dimethylphenyl)selanyl)-4,6-dimethylphenol 3a (314 mg, 0.762 mmol, 76%) and bis(2-(benzyloxy)-3,5-dimethylphenyl)selane 3b (Bn: benzyl) (76.6 mg, 0.152 mmol, 15%) in a ratio of 4.96:1 (determined from crude .sup.1H NMR spectrum) were obtained. It was not possible to separate the reaction mixture completely by column chromatography purification (100% H.fwdarw.100:1.fwdarw.50:1.fwdarw.20:1.fwdarw.10:1 H/DCM). 51.0 mg of 3a were prepared in pure form (analytical evaluation below).

(38) IR (ATR): {circumflex over ()} (cm.sup.1)=3409; 3030; 3011; 2919; 2854; 2730; 1567; 1497; 1467; 1372; 1328; 1284; 1268; 1251; 1231; 1208; 1123; 1078; 1010; 976; 912; 858; 814; 763; 749; 725; 695; 602; 570; 516; 491; 461; .sup.1H-NMR (300 MHz, toluene-d.sub.8): (ppm)=7.62-7.43 (m, 2H, ArCH); 7.36-7.29 (m, 1H, ArCH); 7.28-7.08 (m, 2H, ArCH); 6.86-6.66 (m, 3H, ArCH); 6.58 (d, J=2.1 Hz, 1H, ArCH); 4.82 (s, 2H, OCH.sub.2Ph); 2,27 (s, 3H, CH.sub.3); 2.12 (d, J=2.4 Hz. 3H, CH.sub.3); 2.07 (s, 3H, CH.sub.3); 1.86 (s, 3H, CH.sub.3); .sup.13C-NMR (75 MHz, toluene-d.sub.8): (ppm) 154.2; 153.2; 137.7; 136.0; 135.1; 134.6; 131.3; 131.2; 129.7; 129.0; 128.6; 128.3; 128.2; 128,1; 74.94; 30.30; 20.53; 20.18; 16.93; 16.31;

(39) .sup.77Se-NMR (57 MHz, toluene-d.sub.8): (ppm)=207.3; HR-MS (ESI-TOF): calc. for C.sub.23H.sub.25O.sub.2Se ([M+H].sup.+): 413.10155, found: 413.10109; calc. for C.sub.23H.sub.24O.sub.2SeNa ([M+Na].sup.+): 435.0835, found: 435.08378; C.sub.23H.sub.24O.sub.2Se (412.09 g/mol).

(40) In an analogous manner, 3,3,5,5-tetra-tert-butylbiphenyl-2,2-diol, 1c, and bis(3-tert-butyl-5-methyl-2-hydroxyphenyl)selenium, 1b, were reacted with benzyl bromide to give the hydroxyl-protected structures IX, IXa.

Preparation of the Hydroxyl-Protected Monophosphites

Synthesis of 2-((2-(benzyloxy)-3,5-dimethylphenyl)sefanyl)-4,6-dimethylphenyl-bis(2,4-di-tert-butylphenyl)phosphite 1a, 4

(41) ##STR00025##

(42) In a baked-out 50 ml Schlenk flask under an argon atmosphere, 547 mg (1.15 mmol, 1.5 eq, 86% pure) of dichloro(2,4-di-tert-butylphenyl)phosphorochloridite 2a were dissolved in 10 ml of abs. toluene and cooled to 0 C. In a separate 10 ml Schlenk vessel, 314 mg (0.762 mmol, 1.0 eq, mixture with compound bis(2-(benzyloxy)-3,5-dimethylphenyl)selane 3b, 3a/3b ratio 4.96:1) of 2-((2-(benzyloxy)-3,5-dimethylphenyl)selanyl)-4,6-dimethylphenol 3 and 230 l (170 mg, 1.68 mmol, 2.2 eq) of triethyiamine were dissolved in 10 ml of abs. toluene and added dropwise to the initially charged phosphorochloridite 2a. In the course of this, a yellow colour of the solution was observed with simultaneous formation of precipitate. Subsequently, a further 5.0 ml of abs. toluene were added and the mixture was stirred at 0 C. for 30 minutes and at RT for 16 hours. The reaction mixture was filtered for complete removal of the precipitate formed and the solids were washed with 10 ml of abs. toluene. The solvent was removed under reduced pressure and the crude product was purified by column chromatography (100% H.fwdarw.100:1.fwdarw.50:1.fwdarw.20:1 H/DCM.fwdarw.100% DCM). After the product had been dried under reduced pressure at 50 C. for three hours, 296 mg (0.347 mmol, 45%) of the title compound 4 were obtained as a colourless oil.

(43) IR (ATR): {circumflex over ()} (cm.sup.1)=2955; 2922; 2864; 1491; 1462; 1399; 1361; 1271; 1246: 1191; 1157; 1125; 1082; 1015: 924; 906; 886; 843; 816; 770; 748; 726; 687; 748; 726; 687; 663; 644; 600; 573; 494;

(44) .sup.1H-NMR (300 MHz, toluene-d.sub.8): (ppm)=7.45 (d, J=2.5 Hz, 2H, ArCH); 7.43-7.38 (m, 1H, ArCH); 7.34 (dd, J=8.4 Hz, J=2.1 Hz, 2H, ArCH); 7.26 (d, J=2.5 Hz, 1H, ArCH); 7.09 (dt, J=2.2 Hz, J=1.1 Hz, 2H, ArCH); 7.03-6.95 (m, 2H, ArCH); 6,89-6.81 (m, 3H, ArCH); 6,72 (dd, J=1.3 Hz, J=0.7 Hz, 1H, ArCH): 6.62-6.57 (m, 1H, ArCH); 4.63 (s, 2H, CH.sub.2Ph); 2.20 (d, J 0.9 Hz, 3H, 5-CH.sub.3); 1.92 (d, J=0.7 Hz, 3H, 5-CH.sub.3); 1.77-1.75 (m, 3H, 3-CH.sub.3):1.74 (d, J=0.7 Hz, 3H, 3-CH.sub.3); 1.29 (s, 18H, C(CH.sub.3).sub.3), 1.00 (s, 18H, C(CH.sub.3).sub.3); .sup.77Se-NMR (57 MHz, toluene-d.sub.8): (ppm)=317.3 ppm (d, J.sub.Se-P=78.6 Hz); .sup.31P-NMR (122 MHz, toluene-d.sub.8): (ppm)=137.0 (J.sub.P-Se=78.8 Hz);

(45) HR-MS (ESI-TOF): calc. for C.sub.51H.sub.68O.sub.4PSe ([M+H].sup.+): 853.38646, found: 853.38638; calc. for C.sub.51H.sub.65O.sub.4PSeNa ([M+Na].sup.+): 876.37140, found: 876.37119; calc. for C.sub.51H.sub.65O.sub.4PSeK ([M+K].sup.+): 891.34232, found: 891.34248; C.sub.51H.sub.65O.sub.4PSe (852.38 g/mol).

(46) Hydroformylation

(47) ##STR00026##

(48) TABLE-US-00002 TABLE 2 Illustration of the catalysis experiments using organoselenium compounds. Olefin/ Ratio of p T t Entry Ligand solvent Rh/ligand/olefin [bar] [ C.] [h] S [%] 1 4* n-octene/ 1:5:2230 50 120 4 20.2 toluene (100 ppm Rh) Elucidations for Table 1: p = pressure, T = temperature, t = time, Y = yield; S = n-regioselectivity. *inventive

(49) When the inventive ligand 4 is used, it was possible to achieve good selectivity in the hydroformylation of n-octenes.

(50) Thus, the hydroxyl group-protected selenamonophosphites are usable as ligands in hydroforrnylation.