# US 5,710,340 A · Synthesis of cycloalkyldiarylphosophines

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- Number: US 5,710,340 A
- Document ID: US5710340A
- Status: Granted
- Kind: A
- Application number: 08/639,497
- Filed: 1996-04-29
- Granted: 1998-01-20
- Earliest claimed: 1996-04-29
- Assignees: Albemarle Corporation
- Inventors: K. Pushpananda A. Senaratne
- Web page: https://patentgrep.com/patent/US5710340A

## CPC

- C07F 9/5077: {from starting materials having the structure P-Metal, including R2P-M+}
- C07F 9/5018: {Cycloaliphatic phosphines}
- 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

Phosphines having two aryl groups and one alkyl-substituted cycloalkyl group bonded to a phosphorus atom are formed by reacting an alkali metal diarylphosphide with a monoalkyl- or polyalkyl-substituted cycloalkyl mesylate or tosylate in which an alkyl group is in the 2-position, in a liquid reaction medium in which these reactants are soluble. This process avoids complications associated with prior known process technology for producing such phosphines. The phosphines are useful as ligands for making noble metal catalysts.

## Claims

### Claim 1

A process of forming a tertiary phosphine having two aryl groups and one alkyl-substituted cycloalkyl group, which process comprises reacting an alkali metal diarylphosphide with a monoalkyl- or polyalkyl-substituted cycloalkyl mesylate or tosylate in which an alkyl group is in the 2-position, in a liquid reaction medium in which these reactants are soluble, such that said phosphine is formed.

### Claim 2 (depends on 1)

A process according to claim 1 wherein the reaction medium is at least predominantely an ether reaction medium in which the ether is at least one saturated hydrocarbyl monoether, or at least one hydrocarbyl monoether having at least one aromatic group in the molecule; and wherein the alkali metal of said alkali metal diarylphosphide is sodium or potassium or a combination of sodium and potassium.

### Claim 3 (depends on 2)

A process according to claim 2 wherein said ether is a dialkyl ether, a diaryl ether, a monoalkyl monoaryl ether, or a saturated cyclic monoether.

### Claim 4 (depends on 1)

A process according to claim 1 wherein said ether is (i) tetrahydrofuran or (ii) at least one alkyl-substituted tetrahydrofuran, or a mixture of (i) and (ii).

### Claim 5 (depends on 1)

A process according to claim 1 wherein said cycloalkyl mesylate or tosylate has at least one additional alkyl group on the cycloalkyl ring.

### Claim 6 (depends on 1)

A process according to claim 1 wherein said cycloalkyl mesylate or tosylate has a 6-membered ring and one additional alkyl group on the ring in the 5-position.

### Claim 7 (depends on 1)

A process according to claim 1 wherein said diarylphosphide is reacted with a monoalkyl- or polyalkyl-substituted cycloalkyl mesylate in which an alkyl group is in the 2-position.

### Claim 8 (depends on 7)

A process according to claim 7 wherein said mesylate is menthyl mesylate.

### Claim 9 (depends on 7)

A process according to claim 7 wherein the aryl groups of the phosphide are the same aryl groups.

### Claim 10 (depends on 7)

A process according to claim 7 wherein the aryl groups of the phosphide are both phenyl groups.

### Claim 11 (depends on 1)

A process according to claim 1 wherein said diarylphosphide is reacted with a monoalkyl- or polyalkyl-substituted cycloalkyl tosylate in which an alkyl group is in the 2-position.

### Claim 12 (depends on 11)

A process according to claim 11 wherein said tosylate is menthyl tosylate.

### Claim 13 (depends on 11)

A process according to claim 11 wherein the aryl groups of the phosphide are the same aryl groups.

### Claim 14 (depends on 11)

A process according to claim 11 wherein the aryl groups of the phosphide are both phenyl groups.

### Claim 15 (depends on 1)

A process according to claim 1 wherein the alkali metal diarylphosphide is a sodium or potassium diphenylphosphide in which the phenyl group is either unsubstituted or has up to 3 alkyl substituents having up to about 4 carbon atoms each.

### Claim 16 (depends on 15)

A process according to claim 15 wherein the reaction medium is composed at least predominantly of a saturated cyclic monoether, wherein said cycloalkyl mesylate or tosylate is a dialkylcyclohexyl mesylate or tosylate in which said alkyl group in the 2-position is a secondary alkyl group having up to about 6 carbon atoms, and the other alkyl group is in the 3, 4- or 5-position.

### Claim 17 (depends on 16)

A process according to claim 16 wherein the ether is (i) tetrahydrofuran or (ii) at least one alkyl-substituted tetrahydrofuran, or a mixture of (i) and (ii).

### Claim 18 (depends on 17)

A process according to claim 17 wherein the diarylphosphide is reacted with menthyl mesylate.

### Claim 19 (depends on 18)

A process according to claim 18 wherein the alkali metal diarylphosphide is sodium diphenylphosphide or potassium diphenylphosphide, or a mixture thereof and wherein the ether is tetrahydrofuran.

### Claim 20

A process of forming a tertiary phosphine having two aryl groups and one monoalkyl- or polyalkyl-substituted cycloalkyl group, which process comprises:
a) reacting a monoalkyl- or polyalkyl-substituted cycloalkanol in which an alkyl group is in the 2-position with a mesyl halide or tosyl halide in a liquid reaction medium in which these reactants are soluble, to form a monoalkyl- or polyalkyl-substituted cycloalkyl mesylate or tosylate; and
b) reacting at least a portion of said mesylate or tosylate with an alkali metal diarylphosphide, in a liquid reaction medium in which these reactants are soluble, such that said phosphine is formed.

### Claim 21 (depends on 20)

A process according to claim 20 wherein the reaction of b) is carried out in at least a major amount of the liquid reaction medium used in a).

### Claim 22 (depends on 20)

A process according to claim 20 wherein the liquid reaction media in a) and b) are predominantly ether reaction media, and wherein the alkali metal of said alkali metal diarylphosphide is sodium or potassium or a combination of sodium and potassium.

### Claim 23 (depends on 22)

A process according to claim 22 wherein said cycloalkanol is menthol and wherein said ether reaction media consist essentially of (i) tetrahydrofuran or (ii) at least one alkyl-substituted tetrahydrofuran, or a mixture of (i) and (ii).

### Claim 24

A process of forming a diaryl cycloalkyl tertiary phosphine having two aryl groups and one monoalkyl- or polyalkyl-substituted cycloalkyl group, which process comprises:
a) reacting an alkali metal with a triaryl phosphine in a liquid reaction medium in which the triarylphosphine is soluble, to form an alkali metal diarylphosphide;
b) reacting a monoalkyl- or polyalkyl-substituted cycloalkanol in which an alkyl group is in the 2-position with a mesyl halide or tosyl halide in a liquid reaction medium in which these reactants are soluble, to form a monoalkyl- or polyalkyl-substituted cycloalkyl mesylate or tosylate; and
c) reacting at least a portion of said mesylate or tosylate with at least a portion of said alkali metal diarylphosphide, in a liquid reaction medium in which these reactants are soluble, such that said diaryl cycloalkyl phosphine is formed.

### Claim 25 (depends on 24)

A process according to claim 24 wherein liquid reaction medium used in c) is recycled to a) or b), or to both a) and b).

### Claim 26 (depends on 24)

A process according to claim 24 wherein the liquid reaction media in a), b) and c) are at least predominantly ether reaction media, and wherein the alkali metal of said alkali metal diarylphosphide is sodium or potassium or a combination of sodium and potassium.

### Claim 27 (depends on 24)

A process according to claim 24 wherein the liquid reaction media in a), b) and c) are at least predominantly ether reaction media, wherein each of said reaction media is composed of substantially the same kind of ether or mixture of ethers as each of the other two said reaction media, and wherein the alkali metal of said alkali metal diarylphosphide is sodium or potassium or a combination of sodium and potassium.

### Claim 28 (depends on 24)

A process according to claim 24 wherein the alkali metal is sodium or potassium, wherein the triaryl phosphine is triphenyl phosphine, wherein the cycloalkanol is a polyalkyl-substituted cyclohexanol, wherein the mesyl halide or tosyl halide is mesyl chloride or tosyl chloride, respectively, and wherein the liquid reaction media in a), b) and c) are at least predominantly ether reaction media.

### Claim 29 (depends on 28)

A process according to claim 28 wherein polyalkyl-substituted cyclohexanol is menthol.

### Claim 30 (depends on 29)

A process according to claim 29 wherein the menthol is reacted with mesyl chloride in (i) tetrahydrofuran or (ii) alkyl-substituted tetrahydrofuran, or a mixture of (i) and (ii).

### Claim 31

A process of forming a diaryl cycloalkyl tertiary phosphine having two aryl groups and one monoalkyl- or polyalkyl-substituted cycloalkyl group, which process comprises:
a) reacting an alkali metal with a triaryl phosphine in a liquid reaction medium in which the triarylphosphine is soluble, to form an alkali metal diarylphosphide; and
b) reacting at least a portion of said alkali metal diarylphosphide with a monoalkyl- or polyalkyl-substituted cycloalkyl mesylate or tosylate in which an alkyl group is in the 2-position of the cycloalkyl group, in a liquid reaction medium in which these reactants are soluble, such that said diaryl cycloalkyl phosphine is formed.

### Claim 32 (depends on 31)

A process according to claim 31 wherein the reaction of b) is carried out in at least a major amount of the liquid reaction medium used in a).

### Claim 33 (depends on 31)

A process according to claim 31 wherein the liquid reaction media in a) and b) are ether reaction media, and wherein the alkali metal of said alkali metal diarylphosphide is sodium or potassium or a combination of sodium and potassium.

### Claim 34 (depends on 33)

A process according to claim 33 wherein said ether reaction media consist essentially of (i) tetrahydrofuran or (ii) at least one alkyl-substituted tetrahydrofuran, or a mixture of (i) and (ii).

### Claim 35 (depends on 34)

A process according to claim 34 wherein the triaryl phosphine is triphenyl phosphine and the mesylate or tosylate is menthyl mesylate or menthyl tosylate.