Methods for forming 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane

Patent metadata

Field	Value
Publication number	US-11111260-B2
Application number	US-201816490989-A
Country	US
Kind code	B2
Filing date	Mar 22, 2018
Priority date	Mar 23, 2017
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

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.

First claim

The invention claimed is:

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.

2. 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.

3. 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.

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

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

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.

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

8. The method according to claim 7 , wherein the boron-containing Lewis acid is BF 3 -OEt 2 and the sulfonic acid is methanesulfonic acid or p-toluenesulfonic acid.

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

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

11. 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.

12. 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.

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

14. 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.

15. 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.

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

17. 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.

18. 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.

Assignees

• Dow Global Technologies Llc

Inventors

• Klinkenberg Jessica L
• Briggs John R
• Camelio Andrew M
• Grigg Robert David
• Tu Siyu

Classifications

• C07F9/657163 Primary

  the ring phosphorus atom being bound to at least one carbon atom · CPC title