Monophosphite compounds having an ether group

Abstract

Novel monophosphite compounds having an ether group, and a process for preparing these compounds, which are especially suitable for use as ligands in hydroformylation reactions.

Claims

1. Compound having one of the two general structures I and II: ##STR00029## where W is selected from: (C.sub.1-C.sub.12)-alkyl, CH.sub.2OCH.sub.3 (MOM), CH.sub.2OCH.sub.2C.sub.6H.sub.5 (BOM), CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3 (MEM), CH.sub.2OCH.sub.2CH.sub.2Si(CH.sub.3).sub.3 (SEM), CH.sub.2SCH.sub.3 (MTM), CH.sub.2SC.sub.6H.sub.5 (PTM), CH.sub.2CN, CF.sub.2CHCl.sub.2, CH.sub.2CH.sub.2Cl, CH.sub.2CH.sub.2Br, -2-tetrahydropyranyl, CH(OC.sub.2H.sub.5)CH.sub.3, CH.sub.2COC.sub.6H.sub.5, CH.sub.2COC.sub.6H.sub.4-4-Br, CH.sub.2-c-C.sub.3H.sub.5, CH.sub.2CHCH.sub.2, CH.sub.2CHC(CH.sub.3).sub.2, -c-C.sub.6H.sub.11, CH.sub.2C.sub.6H.sub.5, CH.sub.2C.sub.6H.sub.3-2,4-(CH.sub.3).sub.2, CH.sub.2C.sub.6H.sub.4-4-OCH.sub.3, CH.sub.2C.sub.6H.sub.4-o-NO.sub.2, CH.sub.2C.sub.4H.sub.6-p-NO.sub.2, CH.sub.2C.sub.6H.sub.3-2,6-Cl.sub.2, CH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2, CH.sub.2-9-anthryl, CH.sub.2-4-pyridyl, Si(CH.sub.3).sub.3, Si(CH.sub.3).sub.2C(CH.sub.3).sub.3; where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are each independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl, Cl, F, Br, I, COO(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.6-C.sub.20)-aryl, COOH, OH, SO.sub.3H, SO.sub.3Na, NO.sub.2, CN, NH.sub.2, N[(C.sub.1-C.sub.12)-alkyl].sub.2; where X and Y are each independently selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-COO(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CONH(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2, (C.sub.4-C.sub.20)-heteroaryl, (C.sub.4-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.5-C.sub.8)-cycloalkyl, (C.sub.5-C.sub.8)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl-CO(C.sub.6-C.sub.20)-aryl; where Z is selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.6-C.sub.20)-aryl, (C.sub.4-C.sub.20)-heteroaryl-, (C.sub.6-C.sub.20)-aryl-CO(C.sub.6-C.sub.20)-aryl-, (C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl-, and where the alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl groups mentioned may be substituted.

2. Compound according to claim 1, where X and Y are each independently selected from: (C.sub.1-C.sub.12)alkyl-, (C.sub.6-C.sub.20)-aryl-, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl-, (C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl-, (C.sub.4-C.sub.20)-heteroaryl and (C.sub.5-C.sub.8)-cycloalkyl.

3. Compound according to claim 1, where Z is selected from: (C.sub.1-C.sub.12)-alkyl-, (C.sub.6-C.sub.20)-aryl-, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl-, (C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl- and (C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl-.

4. Compound according to claim 1, where W is selected from: (C.sub.1-C.sub.12)-alkyl, CH.sub.2-c-C.sub.3H.sub.5, -c-C.sub.6H.sub.11, CH.sub.2C.sub.6H.sub.5, CH.sub.2C.sub.6H.sub.3-2,4-(CH.sub.3).sub.2, CH.sub.2C.sub.6H.sub.4-4-OCH.sub.3, CH.sub.2-9-anthryl, CH.sub.2-4-pyridyl.

5. Compound according to claim 1, having the general structure III: ##STR00030## where W is selected from: (C.sub.1-C.sub.12)-alkyl, CH.sub.2OCH.sub.3 (MOM), CH.sub.2OCH.sub.2C.sub.6H.sub.5 (BOM), CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3 (MEM), CH.sub.2OCH.sub.2CH.sub.2Si(CH.sub.3).sub.3 (SEM), CH.sub.2SCH.sub.3 (MTM),CH.sub.2SC.sub.6H.sub.5 (PTM), CH.sub.2CN, CF.sub.2CHCl.sub.2, CH.sub.2CH.sub.2Cl, CH.sub.2CH.sub.2Br, -2-tetrahydropyranyl, CH(OC.sub.2H.sub.5)CH.sub.3, CH.sub.2COC.sub.6H.sub.5, CH.sub.2COC.sub.6H.sub.4-4-Br, CH.sub.2-c-C.sub.3H.sub.5, CH.sub.2CHCH.sub.2, CH.sub.2CHC(CH.sub.3).sub.2, -c-C.sub.6H.sub.11, CH.sub.2C.sub.6H.sub.5, CH.sub.2C.sub.6H.sub.3-2,4-(CH.sub.3).sub.2, CH.sub.2C.sub.6H.sub.4-4-OCH.sub.3, CH.sub.2C.sub.6H.sub.4-o-NO.sub.2, CH.sub.2C.sub.4H.sub.6-p-NO.sub.2, CH.sub.2C.sub.6H.sub.3-2,6-Cl.sub.2, CH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2, CH.sub.2-9-anthryl, CH.sub.2-4-pyridyl, Si(CH.sub.3).sub.3, Si(CH.sub.3).sub.2C(CH.sub.3).sub.3; where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are each independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl, Cl, F, Br, I, COO(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.6-C.sub.20)-aryl, COOH, OH, SO.sub.3H, SO.sub.3Na, NO.sub.2, CN, NH.sub.2, N[(C.sub.1-C.sub.12)-alkyl].sub.2; and where R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16 are each independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl, Cl, F, Br, I, COO(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.6-C.sub.20)-aryl, COOH, OH, SO.sub.3H, SO.sub.3Na, NO.sub.2, CN, NH.sub.2, N[(C.sub.1-C.sub.12)-alkyl].sub.2.

6. Compound according to claim 1, wherein the compound has a structure selected from L1, L2 and L3: ##STR00031##

7. Process for preparing a compound having one of the two general structures I and II: ##STR00032## where W is selected from: (C.sub.1-C.sub.12)-alkyl, CH.sub.2OCH.sub.3 (MOM), CH.sub.2OCH.sub.2C.sub.6H.sub.5 (BOM), CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3 (MEM), CH.sub.2OCH.sub.2CH.sub.2Si(CH.sub.3).sub.3 (SEM), CH.sub.2SCH.sub.3 (MTM), CH.sub.2SC.sub.6H.sub.5 (PTM), CH.sub.2CN, CF.sub.2CHCl.sub.2, CH.sub.2CH.sub.2Cl, CH.sub.2CH.sub.2Br, -2-tetrahydropyranyl, CH(OC.sub.2H.sub.5)CH.sub.3, CH.sub.2COC.sub.6H.sub.5, CH.sub.2COC.sub.6H.sub.4-4-Br, CH.sub.2-c-CH.sub.3H.sub.5, CH.sub.2CHCH.sub.2, CH.sub.2CHC(CH.sub.3).sub.2, -c-C.sub.6H.sub.11, CH.sub.2C.sub.6H.sub.5, CH.sub.2C.sub.6H.sub.3-2,4-(CH.sub.3).sub.2, CH.sub.2C.sub.6H.sub.4-4-OCH.sub.3, CH.sub.2C.sub.6H.sub.4-o-NO.sub.2, CH.sub.2C.sub.4H.sub.6-p-NO.sub.2, CH.sub.2C.sub.6H.sub.3-2,6-Cl.sub.2, CH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2, CH.sub.2-9-anthryl, CH.sub.2-4-pyridyl, Si(CH.sub.3).sub.3, Si(CH.sub.3).sub.2C(CH.sub.3).sub.3; where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are each independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.2)-aryl, Cl, F, Br, I, COO(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.6-C.sub.20)-aryl, COOH, OH, SO.sub.3H, SO.sub.3Na, NO.sub.2, CN, N[(C.sub.1-C.sub.12)-alkyl].sub.2; where X and Y are each independently selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-COO(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CONH(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2; (C.sub.4-C.sub.20)-heteroaryl, (C.sub.4-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.5-C.sub.8)-cycloalkyl, (C.sub.5-C.sub.8)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl-CO(C.sub.6-C.sub.20)-aryl; and where Z is selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.6-C.sub.20)-aryl, (C.sub.4-C.sub.20)-heteroaryl-, (C.sub.6-C.sub.20)-aryl-CO(C.sub.6-C.sub.20)-aryl-, (C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl-; where the process comprises the following steps: a) initially charging a reactant, b) adding an alkylating reagent, c) adding a compound containing phosphorus and chlorine, d) obtaining a product.

8. Process according to claim 7, wherein an intermediate having a structure of formula 40 is formed ##STR00033## where W is selected from: (C.sub.1-C.sub.12)-alkyl, CH.sub.2OCH.sub.3 (MOM), CH.sub.2OCH.sub.2C.sub.6H.sub.5 (BOM), CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3 (MEM), CH.sub.2OCH.sub.2CH.sub.2Si(CH.sub.3).sub.3 (SEM), CH.sub.2SCH.sub.3 (MTM), CH.sub.2SC.sub.6H.sub.5 (PTM), CH.sub.2CN, CF.sub.2CHCl.sub.2, CH.sub.2CH.sub.2Cl, CH.sub.2CH.sub.2Br, -2-tetrahydropyranyl, CH(OC.sub.2H.sub.5)CH.sub.3, CH.sub.2COC.sub.6H.sub.5, CH.sub.2COC.sub.6H.sub.4-4-Br, CH.sub.2-c-C.sub.3H.sub.5, CH.sub.2CHCH.sub.2, CH.sub.2CHC(CH.sub.3).sub.2, -c-C.sub.6H.sub.11, CH.sub.2C.sub.6H.sub.5, CH.sub.2C.sub.6H.sub.3-2,4-(CH.sub.3).sub.2, CH.sub.2C.sub.6H.sub.4-4-OCH.sub.3, CH.sub.2C.sub.6H.sub.4-o-NO.sub.2, CH.sub.2C.sub.4H.sub.6-p-NO.sub.2, CH.sub.2C.sub.6H.sub.3-2,6-Cl.sub.2, CH.sub.2C.sub.6H.sub.3-3,4-C.sub.2, CH.sub.2-9-anthryl, CH.sub.2-4-pyridyl, Si(CH.sub.3).sub.3, Si(CH.sub.3).sub.2C(CH.sub.3).sub.3; and where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are each independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl, Cl, F, Br, I, COO(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.6-C.sub.20)-aryl, COOH, OH, SO.sub.3H, SO.sub.3Na, NO.sub.2, CN, NH.sub.2, N[(C.sub.1-C.sub.12)-alkyl].sub.2.

9. Process according to claim 7, wherein the reactant used is a compound having a structure of formula 20 ##STR00034## where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are each independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.2-C.sub.12)-alkyl, O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl, Cl, F, Br, I, COO(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.6-C.sub.20)-aryl, COOH, OH, SO.sub.3H, SO.sub.3Na, NO.sub.2, CN, NH.sub.2, N[(C.sub.1-C.sub.12)-alkyl].sub.2; and wherein the compound containing phosphorus and chlorine is a chlorophosphite having a structure of formula 50 ##STR00035## where X and Y are each independently selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-COO(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CONH(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2, (C.sub.4-C.sub.20)-heteroaryl, (C.sub.4-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.5-C.sub.8)-cycloalkyl, (C.sub.5-C.sub.8)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl-CO(C.sub.6-C.sub.20)-aryl.

10. Process according to claim 7, wherein the reactant used is a compound having a structure of formula 20 ##STR00036## where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are each independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl, Cl, F, Br, I, COO(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.6-C.sub.20)-aryl, COOH, OH, SO.sub.3H, SO.sub.3Na, NO.sub.2, CN, NH.sub.2, N[(C.sub.1-C.sub.12)-alkyl].sub.2; and wherein the compound containing phosphorus and chlorine is a chlorophosphite having a structure of formula 60 ##STR00037## where Z is selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.6-C.sub.20)-aryl, (C.sub.4-C.sub.20)-heteroaryl-, (C.sub.6-C.sub.20)-aryl-CO(C.sub.6-C.sub.20)-aryl-, (C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl-.

11. Process according to claim 7, wherein an intermediate having a structure of formula 30 is formed ##STR00038## where W is selected from: (C.sub.1-C.sub.12)-alkyl, CH.sub.2OCH.sub.3 (MOM), CH.sub.2OCH.sub.2C.sub.6H.sub.5 (BOM), CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3 (MEM), CH.sub.2OCH.sub.2CH.sub.2Si(CH.sub.3).sub.3 (SEM), CH.sub.2SCH.sub.3 (MTM), CH.sub.2SC.sub.6H.sub.5 (PTM), CH.sub.2CN, CF.sub.2CHCl.sub.2, CH.sub.2CH.sub.2Cl, CH.sub.2CH.sub.2Br, -2-tetrahydropyranyl, CH(OC.sub.2H.sub.5)CH.sub.3, CH.sub.2COC.sub.6H.sub.5, CH.sub.2COC.sub.6H.sub.4-4-Br, CH.sub.2-c-C.sub.3H.sub.5, CH.sub.2CHCH.sub.2, CH.sub.2CHC(CH.sub.3).sub.2, -c-C.sub.6H.sub.11, CH.sub.2C.sub.6H.sub.5, CH.sub.2C.sub.6H.sub.3-2,4-(CH.sub.3).sub.2, CH.sub.2C.sub.6H.sub.4-4-OCH.sub.3, CH.sub.2C.sub.6H.sub.4-o-NO.sub.2, CH.sub.2C.sub.4H.sub.6-p-NO.sub.2, CH.sub.2C.sub.6H.sub.3-2,6-Cl.sub.2, CH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2, CH.sub.2-9-anthryl, CH.sub.2-4-pyridyl, Si(CH.sub.3).sub.3, Si(CH.sub.3).sub.2C(CH.sub.3).sub.3; and where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are each independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl, Cl, F, Br, I, COO(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.6-C.sub.20)-aryl, COOH, OH, SO.sub.3H, SO.sub.3Na, NO.sub.2, CN, NH.sub.2, N[(C.sub.1-C.sub.12)-alkyl].sub.2.

12. Complex comprising a metal atom or ion and at least one compound according to claim 1.

13. Complex according to claim 12, wherein the metal atom or ion is selected from the group comprising Rh, Ru, Co and Ir.

14. A process for the hydroformylation of (C.sub.2-C.sub.24) olefins, comprising: introducing a compound having one of the two general structures I and II: ##STR00039## where W is selected from: (C.sub.1-C.sub.12)-alkyl, CH.sub.2OCH.sub.3 (MOM), CH.sub.2OCH.sub.2C.sub.6H.sub.5 (BOM), CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3 (MEM), CH.sub.2OCH.sub.2CH.sub.2Si(CH.sub.3).sub.3 (SEM), CH.sub.2SCH.sub.3 (MTM), CH.sub.2SC.sub.6H.sub.5 (PTM), CH.sub.2CN, CF.sub.2CHCl.sub.2, CH.sub.2CH.sub.2Cl, CH.sub.2CH.sub.2Br, -2-tetrahydropyranyl, CH(OC.sub.2H.sub.5)CH.sub.3, CH.sub.2COC.sub.6H.sub.5, CH.sub.2COC.sub.6H.sub.4-4 Br, CH.sub.2-c-C.sub.3H.sub.5, CH.sub.2CHCH.sub.2, CH.sub.2CHC(CH.sub.3).sub.2, -c-C.sub.6H.sub.11, CH.sub.2C.sub.6H.sub.5, CH.sub.2C.sub.6H.sub.3-2,4-(CH.sub.3).sub.2, CH.sub.2C.sub.6H.sub.4-4-OCH.sub.3, CH.sub.2C.sub.6H.sub.4-o-NO.sub.2, CH.sub.2C.sub.4H.sub.6-p-NO.sub.2, CH.sub.2C.sub.6H.sub.3-2,6-Cl.sub.2, CH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2, CH.sub.2-9-anthryl, CH.sub.2-4-pyridyl, Si(CH.sub.3).sub.3, Si(CH.sub.3).sub.2C(CH.sub.3).sub.3; where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are each independently selected from: H, (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl, Cl, F, Br, I, COO(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.6-C.sub.20)-aryl, COOH, OH, SO.sub.3H, SO.sub.3Na, NO.sub.2, CN, NH.sub.2, N[(C.sub.1-C.sub.12)-alkyl].sub.2; where X and Y are each independently selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-COO(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CONH(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-CON[(C.sub.1-C.sub.12)-alkyl].sub.2, (C.sub.4-C.sub.20)-heteroaryl, (C.sub.4-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.5-C.sub.8)-cycloalkyl, (C.sub.5-C.sub.8)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl-CO(C.sub.6-C.sub.20)-aryl; where Z is selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl-O(C.sub.6-C.sub.20)-aryl, (C.sub.4-C.sub.20)-heteroaryl-, (C.sub.6-C.sub.20)-aryl-CO(C.sub.6-C.sub.20)-aryl-, (C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl-, and where the alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl groups mentioned may be substituted; or a complex according to claim 12.

15. Process according to claim 14, wherein the hydroformylation reaction comprises the following steps: a) initially charging an olefin, b) adding said complex, or said compound and a compound containing a metal atom or metal ion, c) feeding in H.sub.2 and CO, d) heating the reaction mixture, with conversion of the olefin to an aldehyde.

16. Compound according to claim 5, wherein the compound has a structure selected from L1, L2 and L3: ##STR00040##

17. Complex comprising a metal atom or ion and at least one compound according to claim 5.

18. Complex according to claim 17, wherein the metal atom or ion is selected from the group comprising Rh, Ru, Co and Ir.

19. The compound of claim 1, wherein, when W is the (C.sub.1-C.sub.12)-alkyl group, the (C.sub.1-C.sub.12)-alkyl group is selected from -Me, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, or C(CH.sub.3).sub.3.

20. The compound of claim 4, wherein, when W is the (C.sub.1-C.sub.12)-alkyl group, the (C.sub.1-C.sub.12)-alkyl group is selected from -Me, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, or C(CH.sub.3).sub.3.

21. The compound of claim 5, wherein, when W is the (C.sub.1-C.sub.12)-alkyl group, the (C.sub.1-C.sub.12)-alkyl group is selected from -Me, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, or C(CH.sub.3).sub.3.

22. The process of claim 7, wherein, when W is the (C.sub.1-C.sub.12)-alkyl group, the (C.sub.1-C.sub.12)-alkyl group is selected from -Me, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, or C(CH.sub.3).sub.3.

23. The process of claim 8, wherein, when W is the (C.sub.1-C.sub.12)-alkyl group, the (C.sub.1-C.sub.12)-alkyl group is selected from -Me, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, or C(CH.sub.3).sub.3.

24. The process of claim 11, wherein, when W is the (C.sub.1-C.sub.12)-alkyl group, the (C.sub.1-C.sub.12)-alkyl group is selected from -Me, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, or C(CH.sub.3).sub.3.

25. The process of claim 14, wherein, when W is the (C.sub.1-C.sub.12)-alkyl group, the (C.sub.1-C.sub.12)-alkyl group is selected from -Me, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, or C(CH.sub.3).sub.3.

Description

Example 1

Preparation of 3,3-di-tert-butyl-2,5,5-trimethoxy-[1,1-biphenyl]-2-ol

(1) ##STR00014##

(2) In a 1 l Schlenk flask which had been repeatedly evacuated and filled with inert gas, 37.6 g (0.104 mol) of 3,3-di-tert-butyl-5,5-dimethoxy[1,1-biphenyl]-2,2-diol and 17.3 g (0.124 mol) of potassium carbonate (anhydrous) were initially introduced and were dissolved with stirring in 10.0 ml (0.104 mol) of dimethyl sulphate and 380 ml of dried acetone. The resulting suspension was boiled under reflux for 7.5 hours and then cooled to room temperature.

(3) Subsequently 100 ml of a 2-molar ammonia solution were added, followed by stirring at room temperature for 4 hours. This was followed by extraction by shaking with 200 ml of methylene chloride, and the aqueous alkaline phase was acidified using 1-molar hydrochloric acid solution (about 280 ml), and was then again extracted by shaking with 3 times 100 ml of methylene chloride. The organic phases obtained were combined and extracted by shaking with 1-molar hydrochloric acid solution (100 ml).

(4) The organic phase was washed a further 3 times with DI water (200 ml) and dried over magnesium sulphate. The solvent was removed under reduced pressure and the oil obtained was washed with 50 ml of isopropanol, filtered and then dried. The product was obtained as a white solid in 30.8 g (74.9% yield).

Example 2

Preparation of 3,3,5,5-tetra-tert-butyl-2-methoxy-[1,1-biphenyl]-2-ol

(5) ##STR00015##

(6) In a 1000 ml Schlenk flask which had been repeatedly evacuated and filled with inert gas, 43 g (0.104 mol) of 3,3,5,5-tetra-tert-butyl-[1,1-biphenyl]-2,2-diol and 21.6 g (0.154 mol) of potassium carbonate were initially introduced and were dissolved with stirring in 10.00 ml (0.104 mol) of dimethyl sulphate and 430 ml of dried acetone. The resulting suspension was boiled under reflux for 6 hours and then cooled to room temperature.

(7) Following addition of 110 ml of 2-molar ammonia solution, stirring took place for 4 hours. This was followed by extraction by shaking with 200 ml of methylene chloride, and the aqueous alkaline phase was acidified using 1-molar hydrochloric acid solution (about 280 ml), and was then again extracted by shaking with 3 times 100 ml of methylene chloride. The organic phases obtained were combined and extracted by shaking with 1-molar hydrochloric acid solution (100 ml).

(8) The organic phase was washed a further 3 times with DI water (200 ml) and dried over magnesium sulphate. The solvent was removed under reduced pressure and the oil obtained was washed with 50 ml of isopropanol, filtered and then dried. The product was obtained as a white solid in 33.5 g (75% yield).

(9) Introduction of the Benzyl Group:

(10) ##STR00016##

(11) In a 500 ml Schlenk flask which had been repeatedly evacuated and filled with inert gas, 35.8 g (100 mmol) of 3,3-di-tert-butyl-5,5-dimethoxy-[1,1-biphenyl]-2,2-diol and 1.9 g (5 mmol) of tetra-n-butylammonium iodide were suspended in 150 ml of DMF. While stirring vigorously, 3 g (75 mmol) of sodium hydride (60% in mineral oil) were added in portions. On completion of addition, the mixture was stirred at room temperature for a further 30 min and then heated to 80 C. for 30 min. In the meantime, in a 100 ml Schlenk flask, 6.5 g (50 mmol) of benzyl chloride were dissolved in 50 ml of DMF, and then this aqueous solution was added dropwise to the cooled suspension. The ice bath was removed and the mixture was stirred overnight.

(12) For purification, the mixture was washed twice with 200 ml each time of semi-concentrated ammonium chloride solution, the organic phase was dried over magnesium sulphate and the solvent was removed at 80 C. on a rotary evaporator, and the residue was slurried in 200 ml of toluene and washed twice with 200 ml of 10% sodium carbonate solution. Subsequently, the organic phase was washed once again with 200 ml of water, dried over magnesium sulphate and concentrated on a rotary evaporator. The product was obtained in 90% yield (16.4 g).

(13) Synthesis of the Chlorophosphites:

(14) 6-Chlorodibenzo[d,f][1,3,2]dioxaphosphepin was prepared according to DE 10 2008 043 584, and 2-chloro-4,4,5,5-tetraphenyl-1,3,2-dioxaphospholane according to DE 10 2006 058 682.

(15) The preparation of 2,2-bis(3,5-di-tert-butyl)phenol chlorophosphite was effected according to the following protocol:

Example 3

Preparation of 2,2-bis(3,5-di-tert-butyl)phenol chlorophosphite

(16) In a 500 ml Schlenk flask which had been repeatedly evacuated and filled with inert gas, 41 g (0.1 mol) of 2,2-bis(3,5-di-tert-butyl)phenol and 30.7 g (42.3 ml; 0.3 mol) of dried triethylamine were dissolved in 300 ml of dried toluene.

(17) In a second Schlenk flask (1000 ml) which had been repeatedly evacuated and filled with inert gas, 13.9 g (8.8 ml; 0.1 mol) of phosphorus trichloride were dissolved in 600 ml of dried toluene, and the diphenol-triethylamine-toluene solution prepared beforehand was added dropwise to this solution with vigorous stirring, slowly and steadily, at a temperature between 5 and 0 C. The solution was allowed to warm to room temperature overnight. The ammonium chloride formed was removed by filtration, and the solvent was concentrated to dryness under reduced pressure. The product was obtained in 98% yield (47 g).

(18) All other chlorophosphites can be prepared analogously, i.e. by addition of phosphorus trichloride in the presence of a base. In this regard, see also Phosphorus(III) Ligands in Homogeneous Catalysis Design 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.

Example 4

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

(19) ##STR00017##

(20) 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-methoxybiphenyl 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.

Example 5

Preparation of dichloro((3,3-di-tert-butyl-2,5,5-trimethoxy-[1,1-biphenyl]-2-yl)oxy)phosphine

(21) ##STR00018##

(22) In a 250 ml Schlenk flask which had been repeatedly evacuated and filled with inert gas, 28.4 g (0.072 mol) of 3,3-di-tert-butyl-2,5,5-trimethoxy[1,1-biphenyl]-2-ol were dissolved with stirring in 200 ml of dried toluene and 40.0 ml (0.282 mol) of degassed triethylamine.

(23) A second 500 ml Schlenk flask is initially charged with 200 ml of dried toluene and then 25 ml (0.281 mol) of phosphorus trichloride are added. Then, with vigorous stirring, the phenol/amine/toluene solution prepared beforehand is added dropwise at room temperature over the course of 1 hour to the phosphorus trichloride/toluene solution. Following complete addition, heating takes place at 80 C. for 4 hours, followed by cooling to room temperature overnight.

(24) The reaction mixture is filtered, washed with three times 50 ml of dried toluene, and the filtrate is concentrated to dryness. The product was obtained in 83% yield (35.3 g).

Synthesis of the Monophosphites

Example 6

Preparation of 6-((3,3,5,5-tetra-tert-butyl-2-methoxy-[1,1-biphenyl]-2-yl)oxy)dibenzo[d,f][1,3,2]dioxaphosphepin

(25) ##STR00019##

(26) In a 250 ml Schlenk flask which had been repeatedly evacuated and filled with inert gas, 5 g (0.012 mol) of 3,3,5,5-tetra-tert-butyl-2-hydroxy-2-methoxybiphenyl were dissolved in 50 ml of dried THF. Then 7.5 ml of butyllithium (1.6-molar solution, 0.012 mol) were added dropwise with vigorous stirring at 20 C. to the tetrahydrofuran/phenol mixture. Following complete addition, the mixture was stirred at 0 C. for an hour. In a second Schlenk flask (100 ml) which had been repeatedly evacuated and filled with inert gas, 3 g (0.012 mol) of 6-chlorodibenzo[d,f][1,3,2]dioxaphosphepin were dissolved with stirring in 50 ml of dried THF. The chlorophosphite solution was then added dropwise to the pre-prepared phenol solution at 0 C. with vigorous stirring. The reaction mixture was heated at 60 C. for 2 hours. After the mixture had cooled to room temperature, the solvent was removed under reduced pressure.

(27) The residue obtained was taken up in 50 ml of methylene chloride, filtered to remove the lithium chloride, then concentrated to dryness again and washed with isopropanol. The product was obtained in 5.5 g (72.8%).

Example 7

Preparation of 2,4,8,10-tetra-tert-butyl-6-((3,3,5,5-tetra-tert-butyl-2-methoxy-[1,1-biphenyl]-2-yl)oxy)dibenzo[d,f][1,3,2]dioxaphosphepin

(28) ##STR00020##

(29) In a 250 ml Schlenk flask which had been repeatedly evacuated and filled with inert gas, 5 g (0.012 mol) of 3,3,5,5-tetra-tert-butyl-2-hydroxy-2-methoxybiphenyl were dissolved in 50 ml of dried THF and admixed at 20 C. with 7.5 ml of butyllithium (1.6-molar solution, 0.012 mol). Following complete addition, stirring took place at 0 C. for a further hour. In a second Schlenk flask (100 ml) which had been repeatedly evacuated and filled with inert gas, 5.7 g (0.012 mol) of 2,2-bis(3,5-di-tert-butyl)phenol chlorophosphite were dissolved with stirring in 50 ml of dried THF. The chlorophosphite solution was then added dropwise with vigorous stirring to the pre-prepared phenol solution at 0 C. Following complete addition, the reaction mixture was warmed slowly to room temperature overnight. The reaction mixture was then heated at 60 C. for 20 hours. For working up, the solvent was removed under reduced pressure at room temperature. The residue obtained was taken up in 50 ml of methylene chloride, and the lithium chloride which remained was removed by filtration. The resulting filtrate was washed with about 40 ml of dried acetonitrile, followed by further filtration. The residue was washed with about 50 ml of isopropanol and about 50 ml of pentane. The product was obtained in 35% yield.

Example 8

Preparation of bis(2,4-di-tert-butylphenyl)-(3,3,5,5-tetra-tert-butyl-2-methoxyl-[1,1-biphenyl]-2-yl) phosphite

(30) ##STR00021##

(31) In a 250 ml Schlenk flask which had been repeatedly evacuated and filled with inert gas, 2.6 g (0.012 mol) of 2,4-di-tert-butylphenol were dissolved with stirring in 100 ml of dried toluene and admixed with 3.5 ml (0.025 mol) of dried triethylamine.

(32) In a second Schlenk flask (100 ml) which had been repeatedly evacuated and filled with inert gas, 3.3 g (0.006 mol) of biphenyl-3,3,5,5-tetra-tert-butyl-2-methoxy-2-dichlorophosphite were dissolved with stirring in 100 ml of dried toluene. The chlorophosphite/toluene solution was subsequently added dropwise with vigorous stirring at 0 (4) C. to the phenol/amine/toluene solution, and the solution was allowed to warm to room temperature overnight.

(33) The ammonium chloride was allowed to settle and a sample was taken, for conversion testing, from the supernatant solution, for the GC/MS. Thereafter the ammonium chloride formed was removed by filtration and the solvent was concentrated to dryness under reduced pressure. The resulting oil was recrystallized from dried acetonitrile and dried. The product was obtained in 52% yield.

Example 9

Preparation of 6-((3,3-di-tert-butyl-2,5,5-trimethoxy-[1,1-biphenyl]-2-yl)oxy)-2,4,8,10-tetramethyldibenzo[d,f][1,3,2]dioxaphosphepin

(34) ##STR00022##

(35) In a 500 ml Schlenk flask which had been repeatedly evacuated and filled with inert gas, 4.1 g (0.008 mol) of dichloro((3,3-di-tert-butyl-2,5,5-trimethoxy[1,1-biphenyl]-2-yl)oxy)phosphine were dissolved in 100 ml of degassed acetonitrile.

(36) In a second Schlenk flask (500 ml) which had been repeatedly evacuated and filled with inert gas, 1.89 g (0.008 mol) of 3,3,5,5-tetramethyl(1,1-biphenyl)-2,2-diol were dissolved in 100 ml of degassed acetonitrile and 2.3 ml (0.016 mol) of N,N-dimethylaminobutane. The chlorophosphite solution was subsequently added dropwise, slowly and steadily, at room temperature to the biphenol-amine solution, and the combined solutions were stirred at room temperature for 2.5 hours.

(37) The solvent was removed under reduced pressure at 40 C. and the residue obtained was taken up in toluene, the hydrochloride was removed by filtration, and the solvent was again removed under reduced pressure. The product was obtained in 72% yield (4.1 g).

Example 10

Preparation of 2,4,8,10-tetramethyl-6-((3,3,5,5-tetra-tert-butyl-2-methoxy-[1,1-biphenyl]-2-yl)oxy)dibenzo[d,f][1,3,2]dioxaphosphepin

(38) ##STR00023##

(39) In a 250 ml Schlenk flask which had been repeatedly evacuated and filled with inert gas, 10 g (0.017 mol) of biphenyl 3,3,5,5-tetra-tert-butyl-2-methoxy-2-dichlorophosphite were dissolved in 50 ml of degassed toluene. In a second Schlenk flask (100 ml), 5 g (0.019 mol) of 3,3,5,5-tetramethyl[1,1-biphenyl]-2,2-diol were dissolved in 50 ml of degassed toluene and 4 ml (0.029 mol) of degassed triethylamine. The phenol/amine/toluene solution was then added dropwise with vigorous stirring at room temperature to the chlorophosphite/toluene solution.

(40) On completion of addition, the reaction mixture was heated at 80 C. for one hour and cooled back down to room temperature in an oil bath overnight.

(41) For workup, the amine hydrochloride formed was filtered off and the mother liquor obtained was concentrated to dryness under reduced pressure. The solids (8.7 g) were then dissolved once again in 30 ml of toluene. Another Schlenk flask was charged with 260 ml of methanol, 13 ml of degassed water and 13 ml of degassed dimethylaminobutane. Then, with stirring, the monophosphite/toluene solution was added slowly at room temperature to the methanol solution, followed by stirring at room temperature for an hour, then by cooling to 0 C. with an ice bath, and then by stirring for two hours more. The resulting suspension was filtered. The product was obtained as a solid (6.4 g).

(42) Procedure for the Catalysis Experiments:

(43) In order to test the catalysis properties of the compounds or complexes of the invention, they were used in the hydroformylation of various olefins in accordance with the general experimental description which follows.

General Experimental Description

(44) In a 100 ml autoclave from Parr Instruments, various olefins were hydroformylated at various temperatures and at synthesis gas pressure 20 and 50 bar in each case (CO/H.sub.2=1:1 (% by vol.)). As precursor, 0,005 g of Rh(acac)(CO).sub.2 was initially charged for a catalyst concentration of 40 ppm of Rh based on the overall reaction mixture, and correspondingly 0.0123 g of Rh(acac)(CO).sub.2 for a concentration of 100 ppm of Rh. The solvent used was 40 to 46 g of toluene in each case.

(45) The compounds to be tested were used in different molar excesses relative to rhodium. In addition, as GC standard, about 0.5 g of tetraisopropylbenzene (TIPB) was added. About 6 g of reactant were metered in after the reaction temperature envisaged had been attained.

(46) During the reaction, the pressure was kept constant via metered addition of synthesis gas with a mass flow meter and pressure regulator. The stirrer speed was 1200 min.sup.1. After 3 hours and after 12 hours, samples were taken from the reaction mixture.

Example 11

Catalysis Experiments with Compounds L1, L2 and L3

(47) Compounds L1, L2 and L3, the structures of which are given below, were tested for their suitability for catalysis of hydroformylation reactions according to the general experimental description above.

(48) ##STR00024##

(49) Comparative compounds used were the noninventive compounds L4 and L5, the synthesis of which is elucidated hereinafter.

(50) The compounds L4 and L5 are likewise monophosphite compounds, except that they bear a BOC group (tert-butyloxycarbonyl=BOC) rather than the Me group.

(51) Synthesis Method for the Comparative Compounds:

(52) Precursors:

(53) Introduction of the BOC Group:

(54) ##STR00025##

(55) In a 2 l Schlenk flask, 400 mmol (143.8 g) of 3,3-di-tert-butyl-5,5-dimethoxy-[1,1-biphenyl]-2,2-diol and 40 mmol (4.8 g) of N,N-dimethylaminopyridine (DMAP) were dissolved in 900 ml of CH.sub.2Cl.sub.2. Subsequently, at room temperature, 400 mmol (88 g) of di-tert-butyl dicarbonate were dissolved in 280 ml of CH.sub.2Cl.sub.2, transferred to a 500 ml dropping funnel and added dropwise to the biphenol/DMAP solution at 32 C. within one hour. The solution was stirred at room temperature overnight. The next morning, the solvent was removed under reduced pressure. The slightly waxy, reddish residue was admixed with 800 ml of n-heptane and stirred overnight. This gave a white residue which was filtered off, washed twice with 50 ml of n-heptane and then dried. The target product was obtained as a white solid (161.6 g, 84%). .sup.1H-NMR (toluene-d.sub.8): 95% and further impurities.

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

(56) ##STR00026##

(57) 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.

(58) 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 RT overnight.

(59) 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 (100%).

Synthesis of L4

Reaction of tert-butyl (3,3-di-tert-butyl-2-((dichlorophosphino)oxy)-5,5-dimethoxy-[1,1-biphenyl]-2-yl)carbonate with 3,3,5,5-tetra-tert-butylbiphenol

(60) ##STR00027##

(61) In a 250 ml Schlenk flask which had been repeatedly evacuated and filled with inert gas, 7.0 g (0.0125 mol) of tert-butyl (3,3-di-tert-butyl-2-((dichlorophosphino)oxy)-5,5-dimethoxy-[1,1-biphenyl]-2-yl)carbonate were dissolved in 100 ml of dried acetonitrile.

(62) In a second Schlenk flask (100 ml) which had been repeatedly evacuated and filled with inert gas, 5.1 g (0.0125 mol) of 3,3,5,5-tetra-tert-butylbiphenol were dissolved in 60 ml of dried acetonitrile and 4.2 ml (0.03 mol) of dried triethylamine while stirring. Subsequently, the biphenol-triethylamine solution was slowly added dropwise at room temperature to the chlorophosphite solution and the mixture was stirred overnight. A portion of the solvent was removed under reduced pressure. The precipitated solids were filtered off and dried. The target product was obtained as a white solid (10.2 g, 91%). 31P NMR (202.4 MHz, toluene-d.sub.8): 142.7 ppm (100%).

Synthesis of L5

Reaction of tert-butyl (3,3-di-tert-butyl-2-((dichlorophosphino)oxy)-5,5-dimethoxy-[1,1-biphenyl]-2-yl)carbonate with 2,2-biphenol

(63) ##STR00028##

(64) In a 250 ml Schlenk flask which had been repeatedly evacuated and filled with inert gas, 10.5 g (0.019 mol) of tert-butyl (3,3-di-tert-butyl-2-((dichlorophosphino)oxy)-5,5-dimethoxy-[1,1-biphenyl]-2-yl)carbonate were dissolved in 50 ml of degassed acetonitrile while stirring.

(65) In a second Schlenk flask (250 ml) which had been repeatedly evacuated and filled with inert gas, 3.6 g (0.019 mol) of 2,2-biphenol were dissolved in 40 ml of degassed acetonitrile and 6.3 ml (0.045 mol) of dried triethylamine while stirring. Subsequently, the chlorophosphite mixture was slowly added dropwise at room temperature to the biphenol/triethylamine solution, and the mixture was stirred at room temperature overnight. The resultant solids were filtered and dried. The target product was obtained as a white solid (11.5 g, 90%). .sup.31P NMR (202.4 MHz, toluene-d.sub.8): 146.2 ppm (100%).

(66) The inventive monophosphite compounds L1 to L3 and the comparative compounds L4 and L5 were each used for catalysis of hydroformylation reactions. The olefin used in each case was di-n-butene (a mixture of isomers of n-octenes (about 16%), 3-methylheptenes (about 65%) and 3,4-dimethylhexenes (about 19%)).

(67) The reaction parameters and the yields achieved in each case are summarized in Table 1 below:

(68) TABLE-US-00001 TABLE 1 Overview of the reaction parameters Synthesis T c(Rh) gas pressure in in Yield Compound in [bar] [ C.] ppm P:Rh in % L1* 50 130 100 20 92 L1* 50 140 100 20 84 L2* 50 130 100 20 79 L3* 50 120 100 20 90 L3* 50 130 100 20 89 L4 50 140 100 20 38 L5 50 140 100 10 74 *inventive compound

(69) As can be inferred from Table 1, the inventive compounds L1, L2 and L3 and the comparative compounds L4 and L5 were used for catalysis in hydroformylation reactions at a constant temperature in each case within the range from 120 C. to 140 C.

(70) With all the compounds of the invention used, a good to very good yield was achieved, in each case above the yield achieved with the comparative compound L5 and well above the yield achieved with the comparative compound L4.

(71) The compounds of the invention are therefore notable for very good suitability for catalysis and are thus of very good suitability as catalysts for the hydroformylation reaction of technical olefin mixtures.