# US 11,111,260 B2 · Methods for forming 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 11,111,260 B2
- Document ID: US11111260B2
- Status: Granted
- Kind: B2
- Application number: 16/490,989
- Filed: 2018-03-22
- Published: 2020-01-09
- Granted: 2021-09-07
- Earliest claimed: 2017-03-23
- Assignees: Dow Global Technologies LLC
- Applicants: Dow Global Technologies LLC
- Inventors: Jessica L. Klinkenberg; John R. Briggs; Andrew M. Camelio; Robert David Grigg; Siyu Tu
- Web page: https://patentgrep.com/patent/US11111260B2

## CPC

- C07F 9/657163: {the ring phosphorus atom being bound to at least one carbon atom}
- 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

A method for forming 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane includes obtaining a solution comprising an ethereal solvent and an aluminum hydride, adding dichloro(2,4-dimethoxyphenyl)phosphine to the solution to produce 2,4-dimethoxyphenylphosphine, and reacting the 2,4-dimethoxyphenylphosphine with an acidic mixture comprising diones to produce 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane. The solution has a temperature from IN greater than −20 C. to 50 C. throughout the method. Another method for forming 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-tri-oxa-6-phosphaadamantane includes obtaining dichloro(2,4-dimethoxyphenyl)phosphine, forming 2,4-dimethoxyphenylphosphine by adding the dichloro(2,4-dimethoxyphenyl)phosphine to a solution comprising at least one solvent and an aluminum hydride, reacting the 2,4-dimethoxyphenylphosphine with a mixture to produce 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane. The mixture includes an acid selected from the group consisting of Lewis acids, sulfonic Bronsted acids, and mixtures thereof, an aromatic or non-aromatic hydrocarbons; and acetylacetone.

## Claims

### Claim 1

A method for forming 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane, comprising:
obtaining a solution comprising an ethereal solvent and an aluminum hydride;
adding dichloro(2,4-dimethoxyphenyl)phosphine to the solution to produce 2,4-dimethoxyphenylphosphine, wherein the solution has a temperature from greater than −20° C. to 50° C. throughout the method; and
reacting the 2,4-dimethoxyphenylphosphine with an acidic mixture comprising diones to produce 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantanes.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the dichloro(2,4-dimethoxyphenyl)phosphine is mixed with a non-polar hydrocarbon solvent before the dichloro(2,4-dimethoxyphenyl)phosphine is added to the solution of aluminum hydride.

### Claim 3 (depends on 2)

The method according to claim 2, wherein the non-polar hydrocarbon solvent is selected from the group consisting of hexane, cyclohexane, toluene, heptane, and mixtures thereof.

### Claim 4 (depends on 1)

The method according to claim 1, wherein the ethereal solvent is tetrahydrofuran (THF).

### Claim 5 (depends on 1)

The method according to claim 1, wherein the solution has a temperature from 0° C. to 25° C.

### Claim 6

A method for forming 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane, comprising:
obtaining dichloro(2,4-dimethoxyphenyl)phosphine;
forming 2,4-dimethoxyphenylphosphine by adding the dichloro(2,4-dimethoxyphenyl)phosphine to a solution comprising at least one solvent and an aluminum hydride;
reacting the 2,4-dimethoxyphenylphosphine with a mixture to produce 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4, 8-trioxa-6-phosphaadamantane,
wherein the mixture comprises:
an acid selected from the group consisting of Lewis acids, Bronsted acids, and mixtures thereof;
an aromatic or non-aromatic hydrocarbons; and
acetylacetone.

### Claim 7 (depends on 6)

The method according to claim 6, wherein the acid comprises at least one of a boron-containing Lewis acid and a sulfonic acid.

### Claim 8 (depends on 7)

The method according to claim 7, wherein the boron-containing Lewis acid is BF3-OEt2 and the sulfonic acid is methanesulfonic acid or p-toluenesulfonic acid.

### Claim 9 (depends on 6)

The method according to claim 6, wherein the mixture comprises from 2.5 to 4.0 equivalents of the acid.

### Claim 10 (depends on 6)

The method according to claim 6, wherein the mixture comprises toluene as an aromatic hydrocarbon.

### Claim 11 (depends on 6)

The method according to claim 6, wherein the mixture comprises one or more non-aromatic hydrocarbons selected from the group consisting of hexane, cyclohexane, and heptane.

### Claim 12 (depends on 6)

The method according to claim 6, wherein a temperature for reacting the 2,4-dimethoxyphenylphosphine with a mixture to form 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane is from greater than −20° C. to 25° C.

### Claim 13 (depends on 1)

The method according to claim 1, wherein the aluminum hydride is lithium aluminum hydride.

### Claim 14 (depends on 1)

The method of claim 1, wherein a yield of 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane is 65% or greater.

### Claim 15 (depends on 1)

The method according to claim 1, wherein the reacting the 2,4-dimethoxyphenylphosphine to produce 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane has a duration from 2 hours to 8 hours.

### Claim 16 (depends on 6)

The method according to claim 6, wherein the aluminum hydride is lithium aluminum hydride.

### Claim 17 (depends on 6)

The method of claim 6, wherein a yield of 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane is 65% or greater.

### Claim 18 (depends on 6)

The method according to claim 6, wherein the reacting the 2,4-dimethoxyphenylphosphine to produce 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane has a duration from 2 hours to 8 hours.