# US 7,608,713 B2 · Tertiary phosphines and their methods of preparation

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- Number: US 7,608,713 B2
- Document ID: US7608713B2
- Status: Granted
- Kind: B2
- Application number: 10/548,777
- Filed: 2004-03-08
- Published: 2007-02-15
- Granted: 2009-10-27
- Earliest claimed: 2003-03-31
- Assignees: Cytec Canada Inc.
- Inventors: Christine J. Bradaric-Baus; Yuehui Zhou
- Web page: https://patentgrep.com/patent/US7608713B2

## CPC

- C07F 9/65683: {the ring phosphorus atom being part of a phosphine}
- C07F 9/5018: {Cycloaliphatic phosphines}
- C07F 9/5059: {by addition of phosphorus compounds to alkenes or alkynes}
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

Tertiary phosphines are prepared by reacting a phosphine (PH3 or a primary or secondary phosphine) with a cyclic alpha,beta-unsaturated carbonyl compound having no more than one C═C double bond conjugated with a carbonyl group. The inventive tertiary phosphines can have R groups that are the same or different. The inventive tertiary phosphines may be used as ligands for metal catalysts or as starting materials for preparing phosphonium salts or ylids.

## Claims

### Claim 1

A compound of formula I:
wherein:
RX is R1 or R3,
Ry is R2 or R3, and
RZ is R3;
and wherein:
(A) R1 and R2 have the following values:
(i) R1 and R2 and the phosphorus atom to which R1 and R2 are bonded form a seven-to ten-membered heterobicycle; or
(ii) each of R1 and R2 is independently: unsubstituted C1-C30 alkyl; substituted C1-C30 alkyl; unsubstituted C3-C8 cycloalkyl; substituted C3-C8 cycloalkyl; unsubstituted C2-C30 alkenyl; substituted C2-C30 alkenyl; unsubstituted C2-C30 alkynyl; substituted C2-C30 alkynyl; unsubstituted C6-C18 aryl; substituted C6-C18 aryl; unsubstituted C7-C30 aralkyl; substituted C7-C30 aralkyl; unsubstituted C2-C30 heteroalkyl containing one or two heteroatoms which are N, O or S; substituted C2-C30 heteroalkyl containing one or two heteroatoms which are N, O or S; unsubstituted C3-C8 heterocycle containing one or two heteroatoms which are N, O or S; substituted C3-C8 heterocycle containing one or two heteroatoms which are N, O or S; unsubstituted C3-C30 heteroalkenyl containing one or two heteroatoms which are N, O or S; substituted C3-C30 heteroalkenyl containing one or two heteroatoms which are N, O or S; unsubstituted C3-C30 heteroalkynyl containing one or two heteroatoms which are N, O and S; substituted C3-C30 heteroalkynyl containing one or two heteroatoms which are N, O and S; unsubstituted C6-C18 heteroaryl containing one or two heteroatoms which are N, O or S; substituted C6-C18 heteroaryl containing one or two heteroatoms which are N, O or S; unsubstituted C7-C30 heteroaralkyl containing one or two heteroatoms which are N, O or S; and substituted C7-C30 heteroaralkyl containing one or two heteroatoms which are N, O or S; and
(B) R3 is selected from:
with the proviso that when RX and RY are ethyl, R3 cannot be 3-oxo-cyclopentyl.

### Claim 2 (depends on 1)

The compound of claim 1, wherein Rx is R1 and Ry is R2.

### Claim 3 (depends on 1)

The compound of claim 1, wherein:
(i) RX is R1 and is R3;or
(ii) RX is R3 and RY is R2.

### Claim 4 (depends on 1)

The compound of claim 1, wherein RX and RY are both R3.

### Claim 5 (depends on 1)

The compound of claim 1, wherein each of R1 and R2 is independently selected from the group consisting of: unsubstituted C1-C18 alkyl, unsubstituted C3-C8cycloalkyl, and unsubstituted C6-C10 aryl.

### Claim 6 (depends on 5)

The compound of claim 5, wherein each of R1 and R2 is independently selected from the group consisting of: unsubstituted, branched C4-C18 alkyl, unsubstituted C3-C8 cycloalkyl, and unsubstituted C6-C10 aryl.

### Claim 7 (depends on 6)

The compound of claim 6, wherein each of R1 and R2 is independently selected from the group consisting of: iso-butyl, tert-butyl, n-pentyl, iso-pentyl, cyclopentyl, cyclohexy, phenyl, norbonyl, cyclooctyl, and (2,4,4-trimethyl)pentyl.

### Claim 8 (depends on 7)

The compound of claim 7, wherein R1 and R2 are both cyclohexyl.

### Claim 9 (depends on 7)

The compound of claim 7, wherein R1 and R2 are both iso-butyl.

### Claim 10 (depends on 1)

The compound of claim 1, wherein the heterobicycle is selected from the group consisting of:
9-phosphabicyclo[3.3.1 ]non-9-yl,
9-phosphabicyclo[4.2.1 ]non-9-yl,
9-phosphabicyclo[3.3.1 ]nonon-3-on-9-yl,
4,8-dimethyl-2-phosphabicyclo[3.1.1]non-9-yl, and
2,5-di (C1-C4 alkyl)-7-phosphabicyclo[2.2.1]hept-7-yl.

### Claim 11

A compound of formula I:
RX is R1 or R3,
RY is R2 or R3, and
RZ is R3,
and wherein:
(A) R1 and R2 have the following values:
(i) R1 and R2 and the phosphorus atom to which R1 and R2 are bonded form a seven-to ten-membered heterobicycle; or
(ii) each of R1 and R2 is independently: unsubstituted C1-C30 aklyl; substituted C1-C30 alkyl; unsubstituted C3-C8 cycloalkyl; substituted C3-C8 cycloalkyl; unsubstituted C2-C30 alkenyl; substituted C2-C30 alkenyl; unsubstituted C2-C30 alkynyl; substituted C2-C30 alkynyl; unsubstituted C6-C18 aryl; substituted C6-C18 aryl; unsubstituted C7-C30 aralkyl; substituted C7-C30 aralkyl; unsubstituted C2-C30 heteroalkyl containing one or two heteroatoms which are N, O or S; substituted C2-C30 heteroalkyl containing one or two heteroatoms which are N, O or S; unsubstituted C3-C8 heterocycle containing one or two heteroatoms which are N. O or S; substituted C3-C8 heterocycle containing one or two heteroatoms which are N, O or S; unsubstituted C3-C30 heteroalkenyl containing one or two heteroatoms which are N, O or S; substituted C3-C30 heteroalkenyl containing one or two heteroatoms which are N, O or S; unsubstituted C3-C30 heteroalkynyl containing one or two heteroatoms which are N, O and S; substituted C3-C30 heteroalkynyl containing one or two heteroatoms which are N, O and S; unsubstituted C6-C18 heteroaryl containing one or two heteroatoms which are N, O or S; substituted C6-C18 heteroaryl containing one or two heteroatoms which are N, O or S; unsubstituted C7-C30 heteroaralkyl containing one or two heteroatoms which are N, O or S; and substituted C7-C30 heteroaralkyl containing one or two heteroatoms which are N, O or S; and
(B) R3 is:

### Claim 12

A compound of formula I:
wherein:
RX is R1 or R3,
RY is R2 or R3,and
RZ is R3,
and wherein:
(A) R1 and R2 have the following values:
(i) R1 and R2 and the phosphorus atom to which R1 and R2 are bonded form a seven-to ten-membered heterobicycle; or
(ii) each of R1 and R2 is independently: unsubstituted C1-C30 aklyl; substituted C1-C30 alkyl; unsubstituted C3-C8 cycloalkyl; substituted C3-C8 cycloalkyl; unsubstituted C2-C30 alkenyl; substituted C2-C30 alkenyl; unsubstituted C2-C30 alkynyl; substituted C2 1-C30 alkynyl; unsubstituted C6-C18 aryl; substituted C6-C18 aryl; unsubstituted C7-C30 aralkyl; substituted C7-C30 aralkyl; unsubstituted C2-C30 heteroalkyl containing one or two heteroatoms which are N, O or S; substituted C2-C30 heteroalkyl containing one or two heteroatoms which are N, O or S; unsubstituted C3-C8 heterocycle containing one or two heteroatoms which are N. O or S; substituted C3-C8 heterocycle containing one or two heteroatoms which are N, O or S; unsubstituted C3-C30 heteroalkenyl containing one or two heteroatoms which are N, O or S; substituted C3-C30 heteroalkenyl containing one or two heteroatoms which are N, O or S; unsubstituted C3-C30 heteroalkynyl containing one or two heteroatoms which are N, O and S; substituted C3-C30 heteroalkynyl containing one or two heteroatoms which are N, O and S; unsubstituted C6-C18 heteroaryl containing one or two heteroatoms which are N, O or S; substituted C6-C18 heteroaryl containing one or two heteroatoms which are N, O or S; unsubstituted C7-C30 heteroaralkyl containing one or two heteroatoms which are N, O or S; and substituted C7-C30 heteroaralkyl containing one or two heteroatoms which are N, O or S; and
(B) R3 is:
with the proviso that when RX and RY are ethyl, R3 cannot be 3-oxo-cyclopentyl.

### Claim 13

The compound 3-(dicyclohexylphosphino)cyclohexan-1-one.

### Claim 14

The compound 3-(di(iso-butyl)phosphino)cycloexan-1-one.

### Claim 15 (depends on 1)

A method of making a compound of formula I, as defined in claim 1, the method comprising contacting a compound of formula II:
wherein:
R7 is hydrogen, R1 or R3, and
R8 is a hydrogen, R2 or R3,
with a cyclic alpha, beta-unsaturated carbonyl compound selected from:
with the proviso that when R7 and R8 are ethyl, the cyclic alpha, beta-unsaturated carbonyl compound cannot be 2-cyclopenten-1-one.

### Claim 16 (depends on 15)

The method of claim 15, wherein R7 is R1 or R3 and R8 is R2 or R3.

### Claim 17 (depends on 15)

The method of claim 15, wherein:
(a) R7 is R1 or R3 and R8 is hydrogen; or
(b) R7 is hydrogen and R8 is R2or R3.

### Claim 18 (depends on 15)

The method of claim 15, wherein R7 and R8 are both hydrogen.

### Claim 19 (depends on 15)

The method of claim 15, wherein each of R1 and R2 is independently an unsubstituted C1-C18 alkyl, an unsubstituted C3-C8 cycloalkyl, or an unsubstituted C6-C10 aryl.

### Claim 20 (depends on 19)

The method of claim 19, wherein each of R1 and R2 is independently selected form the group consisting of unsubstituted, branched C4-C18 alkyl, unsubstitute C3-C8 cycloalkyl, and unsubstituted C6-C10 aryl.

### Claim 21 (depends on 20)

The method of claim 20 wherein each of R1 and R2 is independently selected from the group consisting of: iso-butyl, tert-butyl, n-pentyl, iso-pentyl, cyclopenty , cyclohexyl, phenyl, norbomyl, cyclooctyl, and (2,4,4-trimethyl)pentyl.

### Claim 22 (depends on 21)

The method of claim 21, wherein R1 and R2 are both iso-butyl.

### Claim 23 (depends on 21)

The method of claim 21, wherein R1 and R2 are both cyclohexyl.

### Claim 24 (depends on 16)

The method of claim 16, wherein R7 is R1 and R8 is R2, and R1, R2 and the phosphorus atom to which R1 and R2 are bonded form a seven-to ten-membered heterobicycle.

### Claim 25 (depends on 24)

The method of claim 24, wherein the heterobicycle is selected from the group consisting of:
9-phosphabicyclo[3.3.1]nonane,
9-phosphabicyclo[4.2.1]nonane,
9-phosphabicyclo[3.3.1]nonanone,
4,8-dimethyl-2-phosphabicyclo[3.1.1]nonane, and
2,5-di (C1-C4 alkyl)-7-phosphabicyclo[2.2.1]hept-7-yl.

### Claim 26 (depends on 1)

A method of making a compound of formula I, as defined in claim 1, the method comprising contacting a compound of formula II:
wherein:
R7 is a hydrogen, R1 or R3, and
R8 is a hydrogen, R2 or R3,
with:

### Claim 27 (depends on 1)

A method of making a compound of formula I, as defined in claim 1, the method comprising contacting a compound of formula II:
wherein:
R7 is a hydrogen, R1 or R3, and
R8 is a hydrogen, R2 or R3,
with:
with the proviso that when R7 and R8 are ethyl, the cyclic alpha, beta-unsaturated carbonyl compound cannot be 2-cyclopenten-1-one.

### Claim 28

The compound 3-(9-phosphabicyclo[3.3.1]nonan-9-yl)-cyclohexan-1-one.

### Claim 29

The compound di(cyclohexanon-3-yl)-cyclohexylphosphine.