Phosphine oxides reduction

Patent metadata

Field	Value
Publication number	US-10815258-B2
Application number	US-201615758840-A
Country	US
Kind code	B2
Filing date	Sep 8, 2016
Priority date	Sep 9, 2015
Publication date	Oct 27, 2020
Grant date	Oct 27, 2020

Abstract

Provided is a process for the conversion of a tertiary phosphine oxide to the corresponding tertiary phosphine, comprising at least reacting said tertiary phosphine oxide with a phosphite compound, in the presence of at least a catalyst. Furthermore, provided is a composition comprising at least a tertiary phosphine oxide and a phosphite compound, and optionally a catalyst.

First claim

The invention claimed is:

1. A process for the conversion of a tertiary phosphine oxide to the corresponding tertiary phosphine, comprising at least reacting said tertiary phosphine oxide with a phosphite compound, in the presence of at least a catalyst, wherein the catalyst is selected from the group consisting of fluorine (F 2 ), chlorine (Cl 2 ), bromine (Br 2 ), iodine (I 2 ), iodine monochloride (ICl), iodine monobromide (IBr), heterocyclyl halides, haloalkanes, phosphine dihalides, and any trialkyl, cycloalkyl or aryl analogues thereof, and wherein the catalyst loading is comprised between 0.1 and 1 molar equivalents of the tertiary phosphine oxide.

2. The process according to claim 1 wherein the tertiary phosphine oxide is a compound of formula (I) as follows:

wherein R 1 , R 2 and R 3 are each independently selected from the group consisting of substituted or unsubstituted, branched or linear hydrocarbyl; and substituted or unsubstituted carbocyclyl or heterocyclyl; A is a linking moiety; m is an integer of 0 to 2.

3. The process according to claim 2 wherein each R 1 , R 2 and R 3 is independently selected from the group consisting of substituted or unsubstituted C 6 -C 20 aryl-C o -C 20 alkyl and C 5 -C 20 heteroaryl-C o -C 20 alkyl.

4. The process according to claim 2 wherein R 1 , R 2 and R 3 are all substituted or unsubstituted phenyl.

5. The process according to claim 2 wherein the linking moiety A comprises substituted or unsubstituted hydrocarbylene or substituted or unsubstituted monocyclic or polycyclic carbocyclylene or heterocyclylene, and optionally one or several functional groups.

6. The process according to claim 1 wherein the tertiary phosphine oxide is selected from the group consisting of: triphenylphosphine oxide, trioctylphosphine oxide, tris(4-methoxyphenyl)phosphine oxide, tris(4-methylphenyl)phosphine oxide, tris(4-fluorophenyl)phosphine oxide, cyclohexyldiphenylphosphine oxide, 1,2-bis(diphenylphosphinoyl)ethane dioxide, 2,2′-bis(diphenyloxyphosphino)-1,1′-binaphthyl, bis(2-(diphenyloxyphosphino) phenyl ether, 9,9-dimethyl-4,6-bis(dipheny loxyphosphino) xanthene, 1,1′-bis(diphenyloxyphosphino) ferrocene, (azanediylbis(ethane-2,1-diyl))bis(diphenylphosphine oxide), tris(4-chlorophenyl) phosphineoxide, bis(2-methylphenyl) phenylphosphineoxide, bis(2-methylphenyl) phenylphosphineoxide, (4-cyanophenyl)diphenylphosphine oxide, and any of these compounds attached to a solid and/or polymeric support.

7. The process according to claim 1 wherein the phosphorus atom of each phosphite function of phosphite compound is linked to groups selected from substituted or unsubstituted, branched or linear hydrocarbyl; and substituted or unsubstituted carbocyclyl or heterocyclyl.

8. The process according to claim 1 wherein the phosphite compound is represented by the formula (II) as follows:

wherein R 4 , R 5 and R 6 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted, branched or linear hydrocarbyl; and substituted or unsubstituted, aliphatic or aromatic carbocyclyl or heterocyclyl; B is a linking moiety; and n is an integer of from 0 to 2.

9. The process according to claim 8 wherein R 4 , R 5 and R 6 is independently selected from the group consisting of hydrogen atom, substituted or unsubstituted C 6 -C 20 aryl-C 0 -C 20 alkyl.

10. The process according to claim 1 wherein the phosphite compound is selected from the group consisting of: phosphorous acid, triphenylphosphite, diphenylphosphite, phenylphosphite, diisodecylphenylphosphite, diphenylisodecylphosphite, disooctyloctylphenylphosphite, phenyldiisodecylphosphite, tris(4-methoxyphenyl)phosphite, tri(o-tolyl)phosphite, tris (nonylphenyl)phosphite, tetraphenyl dipropyleneglycol diphosphite, and 4,4′-isopropylidenediphenol C 12 - 15 alcohol phosphite.

11. The process according to claim 1 wherein the phosphite compound is present in an amount comprised between 1 and 10 molar equivalent phosphite of the phosphite compound to the phosphine oxide of the tertiary phosphine oxide.

12. The process according to claim 1 wherein the tertiary phosphine oxide and/or the phosphite compound are attached to a solid support.

13. The process according to claim 1 wherein the process is carried out in presence of a non-polar solvent or an anhydrous aprotic polar solvent.

14. The process according to claim 1 wherein the reaction medium comprises water.

15. The process according to claim 14 wherein the reaction medium comprises water with a molar ratio of water to tertiary phosphine oxide comprised between 1/1 and 10/1.

16. The process according to claim 1 wherein the process is carried out in the presence of a base.

17. The process according to claim 16 wherein the base is present in an amount comprised between 0.1 and 2 molar equivalents of the tertiary phosphine oxide.

18. A composition comprising at least: a tertiary phosphine oxide and a phosphite compound, and a catalyst, wherein the catalyst is selected from the group consisting of fluorine (F 2 ), chlorine (Cl 2 ), bromine (Br 2 ), iodine (I 2 ), iodine monochloride (ICl), iodine monobromide (IBr), heterocyclyl halides, haloalkanes, phosphine dihalides, and any trialkyl, cycloalkyl or aryl analogues thereof, and wherein the catalyst loading is comprised between 0.1 and 1 molar equivalents of the tertiary phosphine oxide.

Assignees

• Rhodia Operations

Inventors

• Metivier Pascal
• Li Peng

Classifications

• C07F9/5325 Primary

  Aromatic phosphine oxides or thioxides (P-C aromatic linkage) · CPC title

• C07F9/509 Primary

  by reduction of pentavalent phosphorus derivatives, e.g. -P=X with X = O, S, Se or -P-Hal2 · CPC title

• C07F9/5022

  Aromatic phosphines (P-C aromatic linkage) · CPC title

• C07F9/145

  with hydroxyaryl compounds · CPC title

• C07F9/12

  with hydroxyaryl compounds · CPC title