Protecting phenol groups

Patent metadata

Field	Value
Publication number	US-9604893-B2
Application number	US-201414895792-A
Country	US
Kind code	B2
Filing date	May 12, 2014
Priority date	Jun 5, 2013
Publication date	Mar 28, 2017
Grant date	Mar 28, 2017

Abstract

A method for protecting a phenol group on a precursor compound is provided. The method includes reacting the phenol group with dihydropyran in an acid catalyzed protection reaction and quenching the protection reaction with a strong base within less than about 60 seconds to form a protected precursor compound.

First claim

What is claimed is:

1. A method for protecting a phenol group on a precursor compound, comprising:
reacting the phenol group with dihydropyran in an acid catalyzed protection reaction; and
quenching the protection reaction with a strong base within about 60 seconds to form a protected precursor compound.

2. The method of claim 1 , comprising:
performing an additional reaction with the protected precursor compound and a reagent, wherein the reagent would attack an unprotected phenol group; and
deprotecting the phenol group to form a product compound.

3. The method of claim 1 , comprising quenching the reaction within about 10 seconds.

4. The method of claim 1 , comprising quenching the reaction immediately after a first color change.

5. The method of claim 2 , comprising using the product compound in further reactions to form a final product compound.

6. The method of claim 2 , wherein the product compound is a pharmaceutical.

7. The method of claim 2 , wherein the product compound is a catalyst.

8. The method of claim 2 , wherein the product compound is a polymerization catalyst.

9. A method for forming a polymerization catalyst, comprising:
reacting a phenol group on a precursor compound with dihydropyran to form a protected phenol precursor;
quenching the reaction with a strong base within about 60 seconds;
performing an additional reaction with the protected phenol precursor and a reagent to form a ligand precursor compound, wherein the reagent would attack an unprotected phenol group; and
deprotecting the phenol on the ligand precursor compound.

10. The method of claim 9 , comprising quenching the reaction within about 10 seconds.

11. The method of claim 9 , comprising forming a ligand from the ligand precursor compound.

12. The method of claim 11 , comprising forming a catalyst compound with the ligand.

13. The method of claim 12 , comprising forming a spray dried catalyst.

14. The method of claim 12 , comprising combining the catalyst compound with a metallocene catalyst to form a commonly supported catalyst system.

15. The method of claim 12 , comprising combining the catalyst compound with a catalyst of the formula:
Cp A Cp B MX n or Cp A (A)Cp B MX n ,
wherein M is a Group 4, 5, or 6 atom; Cp A and Cp B are each bound to M and are independently selected from the group consisting of cyclopentadienyl ligands, substituted cyclopentadienyl ligands, ligands isolobal to cyclopentadienyl and substituted ligands isolobal to cyclopentadienyl; (A) is a divalent bridging group bound to both Cp A and Cp B selected from the group consisting of divalent C 1 to C 20 hydrocarbyls and C 1 to C 20 heteroatom containing hydrocarbonyls, wherein the heteroatom containing hydrocarbonyls comprise from one to three heteroatoms; X is a leaving group selected from the group consisting of chloride ions, bromide ions, C 1 to C 10 alkyls, and C 2 to C 12 alkenyls, carboxylates, acetylacetonates, and alkoxides; and n is an integer from 1 to 3.

16. The method of claim 12 , comprising combining the catalyst compound with a catalyst of the formula:

wherein M is a Group 3 to 12 transition metal or a Group 13 or 14 main group metal; each X is independently an anionic leaving group; y is 0 or 1; n is the oxidation state of M; m is the formal charge of the ligand represented by YZL or YZL′; L is a Group 15 or 16 element; L′ is a group 15 or 16 element or Group 14 containing group; Y is a Group 15 element; Z is a Group 15 element; R 1 and R 2 are independently a C 1 to C 20 hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus; R 1 and R 2 may be interconnected to each other; R 3 is absent, a hydrocarbon group, hydrogen, a halogen, or a heteroatom containing group; R 4 and R 5 are independently an alky group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group, or a multiple ring system; R 4 and R 5 may be interconnected to each other; R 6 and R 7 are independently absent, hydrogen, an alkyl group, a halogen, a heteroatom, or a hydrocarbyl group; and R* is absent, hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group.

17. The method of claim 12 , comprising forming a catalyst that includes a non-metallocene comprising a ligand complexed to a metal through an oxygen atom.

18. The method of claim 12 , comprising:
supporting a non-metallocene on a catalyst support to form a supported catalyst; and
adding a metallocene catalyst to the supported catalyst to form a commonly supported catalyst system.

19. A method for generating a polyethylene polymer, comprising reacting at least ethylene with a catalyst system comprising a catalyst formed by reacting a metal compound with a ligand, wherein the ligand is formed by:
reacting a phenol group on a precursor compound with dihydropyran to form a protected phenol precursor;
quenching the reaction with a strong base within about 60 seconds;
performing an additional reaction with the protected phenol precursor and a reagent to form a ligand precursor compound, wherein the reagent would attack an unprotected phenol group; and
deprotecting the phenol on the ligand precursor compound to form the ligand.

20. The method of claim 19 , comprising adding a comonomer to the reaction of the ethylene with the catalyst system, wherein the comonomer comprises an alphaolefin having 4 to 8 carbon atoms.

Assignees

• Univation Tech Llc

Inventors

• Harlan C Jeff
• Brown Steven D

Classifications

• C07B51/00

  Introduction of protecting groups or activating groups, not provided for in the preceding groups · CPC title

• C07D309/30 Primary

  Oxygen atoms, e.g. delta-lactones · CPC title

• C07C41/01

  Preparation of ethers · CPC title

• C07D309/12 Primary

  only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers · CPC title

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title