HETEROCYCLIC SELENAPHOSPHITES AND PROCESS FOR PREPARATION THEREOF

Abstract

Novel heterocyclic selenaphosphites, process for preparation thereof and use thereof as ligand for employment in complexes.

Claims

1. Heterocyclic selenaphosphite compound having a general structure (I) ##STR00017## 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, N [(C.sub.1-C.sub.12)-alkyl].sub.2, where the alkyl groups are each independently 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.5-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.2O-aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, and where R.sup.1 is independently selected from O-(C.sub.6-C.sub.20-aryl, O-(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, O-(C.sub.6-C.sub.20-aryl-O-(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-O-(C.sub.6-C.sub.20)-aryl, O-(C.sub.1-C.sub.12)-alkyl, O-(C.sub.1-C.sub.12)-alkyl-O-(C.sub.1-C.sub.12)-alkyl, O-(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, O-(C.sub.3-C.sub.12)-cycloalkyl, where the alkyl groups are linear, branched or cyclic, where the alkyl and aryl groups mentioned are each independently unsubstituted or substituted, each substituted -(C.sub.6-C.sub.20)-aryl group has at least one or more than one substituent, where the substituents on each aryl group are independently selected from: O-(C.sub.1-C.sub.12)-alkyl, -(C.sub.1-C.sub.12)-alkyl-O-(C.sub.1-C.sub.12)-alkyl, -(C.sub.1-C.sub.12-alkyl, O-(C.sub.6-C.sub.20)-aryl, O-(C.sub.1-C.sub.12)-alkyl-O-(C.sub.1-C.sub.12)-alkyl, O-(C.sub.6-C.sub.20)-aryl-O-(C.sub.1-C.sub.12)-alkyl, -(C.sub.3-C.sub.12)-cycloalkyl, -(C.sub.3-C.sub.12)-heterocycloalkyl, -(C.sub.6-C.sub.20)-aryl, cyano, -halogen, OCOO-(C.sub.1-C.sub.12)-alkyl, N[(C.sub.1-C.sub.12)-alkyl].sub.2.

2. Compound according to claim 1, characterized in that in the heterocyclic selenaphosphite of the general structure (I) R.sup.1 is selected from the structures (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and (X) ##STR00018## ##STR00019## where the radicals R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14 in the structure (II), R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22 and R.sup.23 in structure (III), R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31, R.sup.32, R.sup.33 and R.sup.34 in structure (IV), R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44 and R.sup.45 in structure (V), R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50, R.sup.51, R.sup.52, R.sup.53, R.sup.54, R.sup.55, R.sup.56, R.sup.57 and R.sup.58 in structure (VI), R.sup.59, R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64 and R.sup.65 in structure (VII), and R.sup.66, R.sup.67, R.sup.68, R.sup.69, R.sup.70, R.sup.71, R.sup.72, R.sup.73 and R.sup.74 in structure (VIII), in each structure 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 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, where, in the structures (III), (IV), (V) and (VI), R.sup.23, R.sup.34, R.sup.45, R.sup.58 are each independently additionally selected from OX with X=protecting group, where the protecting group X 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-O-(C.sub.1-C.sub.12)-alkyl, COO-(C.sub.1-C.sub.12)-alkyl.

3. Compound according to claim 1, characterized in that the heterocyclic selenaphosphite has the general structure (Ia) ##STR00020## 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, and R.sup.1 in the heterocyclic selenaphosphite of the general structure (Ia) is independently selected from the structures (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and (X) ##STR00021## ##STR00022## where the radicals R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14 in the structure (II), R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21 and R.sup.22 in structure (III), R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31, R.sup.32 and R.sup.33 in structure (IV), R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41, R.sup.42, R.sup.43 and R.sup.44 in structure (V), R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50, R.sup.51, R.sup.52, R.sup.53, R.sup.54, R.sup.55, R.sup.56 and R.sup.57 in structure (VI), R.sup.59, R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64 and R.sup.65 in structure (VII), and R.sup.66, R.sup.67, R.sup.68, R.sup.69, R.sup.70, R.sup.71, R.sup.72, R.sup.73 and R.sup.74 in structure (VIII), in each structure are each independently selected from: H, -(C.sub.1-C.sub.12)-alkyl, O-(C.sub.1-C.sub.12)-alkyl, -halogen, and where, in each case independently, in addition to the aforementioned groups in the structures (III), (IV), (V) and (VI), R.sup.23, R.sup.34, R.sup.45,R.sup.58 are each independently selected from H, -(C.sub.1-C.sub.12)-alkyl, -halogen and OX with X=protecting group, where the protecting group X 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-O-(C.sub.1-C.sub.12)-alkyl, OCOO-(C.sub.1-C.sub.12)-alkyl.

4. Compound according to claim 3, characterized in that the heterocyclic selenaphosphite of the general structure (Ia) is selected from at least one compound of the structure (Ib) with R.sup.1 corresponding to the definition immediately above ##STR00023## 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, -halogen, where the alkyl groups are each independently linear, branched or cyclic.

5. Compound according to claim 1, characterized in that in the heterocyclic selenaphosphite of the general structure (I) 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, and R.sup.1 in the heterocyclic selenaphosphite of the general structure (I) is independently selected from the structures (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and (X) where the radicals R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14 in the structure (II), R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21 and R.sup.22 in structure (III), R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31, R.sup.32 and R.sup.33 in structure (IV), R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41, R.sup.42, R.sup.43 and R.sup.44 in structure (V), R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50, R.sup.51, R.sup.52, R.sup.53, R.sup.54, R.sup.55, R.sup.56 and R.sup.57 in structure (VI), R.sup.59, R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64 and R.sup.65 in structure (VII), and R.sup.66, R.sup.67, R.sup.68, R.sup.69, R.sup.70, R.sup.71, R.sup.72, R.sup.73 and R.sup.74 in structure (VIII), in each structure are each independently selected from: H, -(C.sub.1-C.sub.12)-alkyl, O-(C.sub.1-C.sub.12)-alkyl, and where in each case independently, in addition to the aforementioned groups in the structures (III), (IV), (V) and (VI), R.sup.23, R.sup.34, R.sup.45, R.sup.58 are each independently selected from H and OX with X=protecting group, where the protecting group X 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-O-(C.sub.1-C.sub.12)-alkyl, COO-(C.sub.1-C.sub.12)-alkyl.

6. Process for preparing at least one heterocyclic selenaphosphite of the general structure (I) ##STR00024## 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, N[(C.sub.1-C.sub.12)-alkyl].sub.2, where the alkyl groups are each independently 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 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, and where R.sup.1 is independently selected from O-(C.sub.6-C.sub.20)-aryl, O-(C.sub.6-C.sub.20)-aryl-(C-.sub.1-C.sub.12)-alkyl, O-(C.sub.6-C.sub.20)-aryl-O-(C.sub.1-C.sub.12)-alkyl, O-(C.sub.6-C.sub.70)-aryl-(C.sub.5-C.sub.20)-aryl, O-(C.sub.6-C.sub.20)-aryl-O-(C.sub.6-C.sub.20)-aryl, -O-(C.sub.1-C.sub.12)-alkyl, O-(C.sub.1-C.sub.12)-alkyl-O-(C.sub.1-C.sub.12)-alkyl, O-(C.sub.1-C.sub.12)-alkyl-(C.sub.6C.sub.20)-aryl, O-(C.sub.3-C.sub.12)-cycloalkyl, where alkyl in each case is independently linear, branched or cyclic, where the alkyl and aryl groups mentioned are each independently unsubstituted or substituted, each substituted (C.sub.6-C.sub.20)-aryl group has at least one or more than one substituent; where the substituents on each aryl group are independently selected from: O-(C.sub.1-C.sub.12)-alkyl, -(C.sub.1-C.sub.12)-alkyl-O-(C.sub.1-C.sub.12)-alkyl, -(C.sub.1-C.sub.12)-alkyl, O-(C.sub.6-C.sub.20)-aryl, O-(C.sub.1-C.sub.12)-alkyl-O-(C.sub.1-C.sub.12)-alkyl, O-(C.sub.6-C.sub.20)-aryl-O-(C.sub.1-C.sub.12)-alkyl, -(C.sub.3-C.sub.12)-cycloalkyl, -(C.sub.3-C.sub.12)-heterocycloalkyl, -(C.sub.6-C.sub.20)-aryl, cyano, -halogen, OCOO-(C.sub.1-C.sub.12)-alkyl, N[(C.sub.1-C.sub.12)-alkyl].sub.2, comprising at least the process step of (i) reacting a selenodiaryl of the general structure (XI) ##STR00025## 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, N[(C.sub.1-C.sub.12)-alkyl].sub.2, where the alkyl groups are each independently 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 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, (ii) with a dihalophosphite compound R.sup.1P(Hal).sub.2 of the formula (XII), where Hal is selected from fluorine, chlorine, bromine, iodine, where R.sup.1 corresponds to the above definition, (iii) and obtaining at least one seienaphosphite of the general structure (I).

7. Process according to claim 6, characterized in that the selenodiaryl of the general structure (XI) corresponds to a compound of the structure (XIa) ##STR00026## 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, -halogen, where the alkyl groups are each independently linear, branched or cyclic.

8. Process according to claim 6, characterized in that in the dihaiophosphite compound R.sup.1P(Hal).sub.2 of the formula (XII) Hal::is selected from fluorine, chlorine, bromine, iodine, and R.sup.1 is independently selected from the structures (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and (X) ##STR00027## ##STR00028## where the radicals R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14 in the structure (II), R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21 and R.sup.22 in structure (III), R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31, R.sup.32 and R.sup.33 in structure (IV), R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41, R.sup.42, R.sup.43 and R.sup.44 in structure (V), R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50, R.sup.51, R.sup.52, R.sup.53, R.sup.54, R.sup.55, R.sup.56 and R.sup.57 in structure (VI), R.sup.59, R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64 and R.sup.65 in structure (VII), and R.sup.66, R.sup.67, R.sup.68, R.sup.69, R.sup.70, R.sup.71, R.sup.72, R.sup.73 and R.sup.74 in structure (VIII), are each independently selected from: H, -(C.sub.1-C.sub.12)-alkyl, O-(C.sub.1-C.sub.12)-alkyl, -halogen, and where, in each case independently, in addition to the aforementioned groups in the structures (III), (IV), (V) and (VI), R.sup.23, R.sup.34, R.sup.45, R.sup.58 are each independently selected from H, -(C.sub.1-C.sub.12)-alkyl, -halogen and OX with X=protecting group, where the protecting group X 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-O-(C.sub.1-C.sub.12)-alkyl, COO-(C.sub.1-C.sub.12)-alkyl.

9. Process according to claim 6, wherein (i) the reaction is effected in the presence of a base, especially of an amine or pyridine base, preferably of an alkylamine.

10. Process according to claim 6, characterized in that the selenodiaryl of the general structure (XI) is reacted with R.sup.1P(Hal).sub.2 of formula (XII) in a molar ratio of 10:1 to 1:10, preferably in a ratio of 2:1 to 1:2.

11. Process according to claim 6, characterized in that R.sup.1P(Hal).sub.2 of the formula (XII) is R.sup.1PCl.sub.2 or R.sup.1PBr.sub.2. (Currently Amended) Process according to claim 6, wherein (i) the reaction is effected in the temperature range from 45 to 80 C., especially from 15 to 30 C.

13. Use of a heterocyclic selenaphosphite according to claim 1 as a ligand.

14. Use of a heterocyclic selenaphosphite prepared according to claim 6 as a ligand.

Description

[0051] The invention is further illustrated in detail below by examples without the invention being limited to the working examples.

General Methods

Solvents and Reagents

[0052] All reactions with moisture- and/or oxygen-sensitive substances were carried 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),

n-heptane (95%, Walter (Baked, 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 Solv 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.

[0053] Filtration: Filtrations for the removal of resulting solids were carried out using a G4 frit (pore width: 10-16 m).

Analysis

[0054] IR spectroscopy: IR spectra were recorded with a Nicolet 6700 FT-IR spectrometer from Thermo Electron. The substances were measured by ATR methods.

[0055] .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 Bruker, 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.

[0056] .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 (dichioromethane-d.sub.2: =54.0 ppm, toluene-d.sub.8:

=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.

[0057] .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.

[0058] Mass spectrometry: El mass spectra were recorded on a Finnigan MAT 95-XP instrument from Thermo Electron and ESI-TCF mass spectra with a model 6210 Time-of-Flight LC/MS from Agilent.

Synthesis of the Precursors

General Procedure

[0059] 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. Cyciohexane: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.

[0060] The structural formula shows the main product obtained in each reaction.

Bis(3,5-dimethyl-2-hydroxyphenyl)selenium; structure XI, 1a

[0061] ##STR00010##

[0062] 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 and heated in 1 ml of pyridine. The product is obtained as a colourless crystalline solid.

[0063] .sup.1H-NMR (400 MHz, CDCl.sub.3): (ppm)=7.12 (s,2H, 6-H), 6.91 (s, 2H, 4-H), 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-HMR (76 MHz, CDCl.sub.3): (ppm)=163.36 ppm.

Bis(3-tert-butly-5-methyl-2-hydroxyphenyl)selenium, structure XI, 1b

[0064] ##STR00011##

[0065] The reaction is conducted according to the general procedure in a screw-top test tube. For that purpose, 1.32 g (8.0 mmol, 1.0 equiv.) of

2-tert-butyl-4-methylphenol and 0.54 g (4.9 mmol, 0.6 equiv.) of selenium dioxide were dissolved and heated in 1 ml of pyridine.

[0066] .sup.1H-NMR (300 MHz, CDCl.sub.3): (ppm)=7.15 (s, 2H, 6-H), 7.05 (s, 2H, 4-H), 5.07 (s,2H, OH), 2.21 (s, 6H, 5-CH.sub.3), 2.21 (s, 18H, 3-C(CH.sub.3).sub.3: .sup.13C-NMR (75 MHz, CDCl.sub.3): (ppm)=152.1, 136.4, 133.4, 120.1, 129.5, 117.2, 35.1, 29.6, 20.8.

3,3, 5,5-Tetra-tert-butylbiphenyl-2,2-diol, structure XI, 1c

[0067] ##STR00012##

[0068] The reaction is conducted according to the general procedure in a screw-top test tube. For that purpose, 1.67 g (8.2 mmol, 1.0 equiv.) of 2,4-di-tert-butylphenol and 0.55 g (4.9 mmol, 0.6 equiv.) of selenium dioxide were dissolved and heated in 1 ml of pyridine.

[0069] .sup.1H-NMR (400 MHz, CDCl.sub.3): (ppm)=7.31 (d, J=2.4 Hz, 2H), 7.29 (d, J=2.4), 6.29 (s, 2H), 1.42 (s, 18H), 1.24 (s, 18H); .sup.13C-NMR (75 MHz, CDCl.sub.3); (ppm)=151.7, 143.5, 135.8, 129.8, 126.6, 117.2, 35,4, 34.4, 31.6, 29.7.

Biphenols

[0070] The biphenols are synthesized analogously to DE102013203865 and DE102013203867.

Synthesis of the Chlorophosphites

[0071] The synthesis of the dichlorophosphites, such as dichloro((-)-menthyloxy)phosphite, is known to those skilled in the art and is effected in the manner known per se. Chlorophosphites can be prepared from the corresponding monohydroxyl 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 dichloro(2,4-di-tert-butylphenoxy)phosphite, structure XII, 2a

[0072] ##STR00013##

[0073] A baked-out 50 ml Schlenk flask under an argon atmosphere was initially charged with 629 l (989 mg, 7.20 mmol, 3.6 eq) of phosphorus trichloride in 20 ml cf abs. n-heptane and cooled to 10 C. In a separate 10 ml Schienk flask, 374 l (273 mg, 2.70 mmol, 1.35 eq) of triethylamine and 412 mg (2.00 mmol, 1.0 eq) of

2,4-di-tert-butylphenol were dissolved in 10 ml of n-heptane and added dropwise to the initial charge of PCl.sub.3 over a period of 90 minutes. The latter was rinsed in with 2.0 ml of abs. n-heptane and stirred at RT for 19 h. Subsequently, the reaction mixture was filtered for complete removal of the precipitate formed and the solids were washed with 10 ml of abs. n-heptane. The solvent of the pale yellow solution was removed under reduced pressure and the crude product was dried under vacuum at 50 C. for three hours. 569 mg (1.86 mmol, 93%, 96% pure) of the title compound 2a were obtained as colourless oil.

[0074] IR (AIR): {circumflex over (v)} (cm.sup.1)=2958; 2869; 1494; 1398; 1362; 1302; 1210; 1154; 1085; 982; 939; 887; 823; 783; 745; 699; 645; 598; 509; .sup.31P-NMR (122 MHz, Toluene-d.sub.8): (ppm)=186.0. MS (El): m/z (%)=306 (10.4) [C.sub.14H.sub.21Cl.sub.2OP]; 291 (100) [C.sub.13H.sub.18,Cl.sub.2OP]; 271 (2.06) [C.sub.14H.sub.21ClOP]; HR-MS (El): calc'd for C.sub.14H.sub.21ClOP: 306.07016, found: 306.06994; calc'd for C.sub.14H.sub.21 .sup.37ClOP: 308.06721, found: 308.06731; C.sub.14H.sub.21Cl.sub.2OP (306.07 girnol).

Reaction of tert-butyl (3,3-di-tert-butyl-2hydroxy-5,5-dimethoxy-[1,1-biphenyl]-2-yl)carbonate with phosphorus trichloride:

[0075] ##STR00014##

[0076] In a 250 ml Schlenk flask which had been repeatedly evacuated and filled with inert gas, 12 g (0.026 mol) of

tert-butyl (3,3-di-tert-butyl-2-hydroxy-5,5-dimethoxy-[1,1-biphenyl]-2-yl)carbonate were dissolved by stirring in 120 ml of dried toluene and 12.8 ml (0.091 mol) of triethylamine.
In a second 500 ml Schlenk flask, 100 ml of dried toluene were first stirred together with 8.1 ml (0.091 mol) of phosphorus trichloride. Subsequently, the phosphorus trichloride-toluene solution was added dropwise to the previously prepared carbonate-amine-toluene solution at room temperature within 30 minutes. On completion of addition, the mixture was heated to 80 C. for 30 minutes and cooled to room temperature overnight. The next morning, the mixture was filtered, the solids were washed with 50 ml of dried toluene, and the filtrate was concentrated to dryness. The target product was obtained as a solid (13.1 g, 89%). .sup.31P-NMR (202.4 MHz, toluene-d.sub.8): 203.2 and 203.3 ppm.

Preparation of biphenyl-3,3, 5,5-tetra-tert-butyl-2-hydroxy-2-dichlorophosphite

[0077] ##STR00015##

[0078] In a 250 ml Schlenk flask which had been repeatedly evacuated and filled with inert gas, 10.62 g (0.025 mol) of

3,3,5,5-tetra-tert-butyl-2-hydroxy-2-rnethoxybiphenyl were dissolved with stirring in 50 ml of dried toluene and admixed with 3.5 ml (0.025 mol) of triethylamine. Added dropwise to the resulting solution, at room temperature and with vigorous stirring, are 2.2 ml (0.025 mol) of phosphorus trichloride, and the mixture is then heated at 105 C. for 4 hours. It is worked up by filtering off the precipitated ammonium chloride and washing the filter product 2 times with 25 ml of toluene. The filtrate is concentrated to dryness. The product was obtained in 63% yield.

[0079] Analogously to the preparation of the dichloro(2,4-di-tert-butylphenoxy)phosphite, it is correspondingly possible to prepare phenols, 1-naphthols, 2-naphthols, anthracene derivatives such as

9-hydroxyanthracene, and cycloalkanol compounds.

The Synthesis of the Selenium Phosphites

Synthesis of 6-(2,4-di-tert-butylphenoxy)-2,4,8, 10-tetramethyldibenzo[d,c][1,3,6,2]dioxaselenapholsphocine, structure I; 3a

[0080] ##STR00016##

[0081] A baked-out 50 ml Schlenk flask under an argon atmosphere was initially charged with 191 mg (0.624 mmol, 1.2 eq, 96% pure) of dichloro(2,4-di-tert-butylphenoxy)phosphite 2a in 5.0 ml of abs. toluene and cooled to 0 C. In a separate 10 ml Schlenk vessel, 168 mg (0.522 mmol, 1.0 eg) of selenodiphenol 1a and 159 l (116 mg, 1.14 mmol, 2.2 eq) of triethylamine were dissolved in 2.0 ml of abs, toluene. The resulting pale yellow solution was then added dropwise to the initial charge of dichlorophosphite 2a, in the course of which the formation of a colourless precipitate was recorded. The latter was rinsed in with 2.0 ml of abs. toluene and stirred at RT for 48 h. The reaction mixture was filtered for complete removal of the precipitate formed, the solids were washed with 10 ml of abs. toluene, and the solvent was removed under reduced pressure. After crystallization in 10 ml of abs. n-heptane, 191 mg (0.343 mold, 66%, 99.9% in .sup.31P NMR) of the title compound 3a were obtained as a colourless solid.

[0082] IR (ATR): {circumflex over (v)} (cm.sup.1)=3425; 2956; 2917; 2865; 1604; 1492; 1464; 1399; 1377; 1360; 1273; 1248; 1208; 1192; 1119; 1084; 1013; 958; 914; 887; 848; 810; 772; 729; 703; 680; 669; 645; 581; 527; 512; 497; 412; .sup.1H-NMR (300 MHz, Toluene-d.sub.8,): (ppm)=7.68-7.46 (m, 2H ArCH); 7.40-7.31 (m, 2H ArCH); 7.05 (dd, J=8.4 Hz, J=2.5 Hz, 1H ArCH); 6.64 (ddd, J=2.3 Hz, J=1.3 Hz, J=0.7 Hz, 2H, ArCH); 2.13 (s, 6H, CH.sub.3); 1.97-1.95 (m, 6H, CH.sub.3); 1.65 (s, 9H, C(CH.sub.3).sub.3); 1.31 (s, .sup.9H, C(CH.sub.3).sub.3); .sup.3C-NMR (75 MHz, Toluene-d.sub.8);

[0083] (ppm)=152.9 (d, J=5.4 Hz); 150.1 (d, J=4.0 Hz); 145.8; 139.6 (d, J=2.5 Hz); 134.3; 133.8; 133.1; 130.10; 124.4; 124.0; 120.3 (d, J=17.1 Hz); 120.0 (d, J=4.2 Hz); 35.41; 34.57; 31.63; 30.42; 20.16; 17.35; .sup.31P-NMR (122 MHz, Toluene-d.sub.8): (ppm)=132.6 (J.sub.PSe=62.3 Hz); .sup.77Se-NMR (57 MHz, Toluene-d.sub.8): (ppm)=323.0 P.sub.SeP=62.3 Hz); C.sub.30H.sub.37O.sub.3PSe (556.16 g/imol).