Reagents and methods for fluorinating a substrate

Patent metadata

Field	Value
Publication number	US-10144747-B2
Application number	US-201414903724-A
Country	US
Kind code	B2
Filing date	Jul 8, 2014
Priority date	Jul 9, 2013
Publication date	Dec 4, 2018
Grant date	Dec 4, 2018

Abstract

Described herein are perfluoroalkylated zinc compounds having the structure of Formula (I) or Formula (II), which can be used to perfluoroalkylate organic, inorganic and organometallic substrates. Methods of making and using these compounds by reacting zinc or a dialkylzinc compound with a perfluoroalkyl dihalide in a solvent such as tetrahydrofuran, dioxane or diglyme, are also described.

First claim

The invention claimed is:

1. A compound of formula (I):

wherein:
n is an integer ranging from 2 to 6;
L is selected from one or more of tetrahydrofuran; dioxane; acetonitrile; diethyl ether; N-methylmorpholine; triethylamine; bipyridine; N,N,N′,N′-tetramethylethylenediamine; N,N,N′,N′-tetraethylethylenediamine; a glyme; or 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidinone; and
m is an integer ranging from 1 to 3.

2. The compound of claim 1 , wherein n is 4.

3. The compound of claim 1 , wherein the glyme has the following formula: CH 3 O(CH 2 CH 2 O) t CH 3 ; wherein t is an integer between 1 and 10.

4. The compound of claim 1 , wherein the glyme is diethylene glycol dimethyl ether.

5. A method for preparing a compound of formula (I):

wherein:
n is an integer ranging from 2 to 6;
L is selected from one or more of tetrahydrofuran; dioxane; acetonitrile; diethyl ether; N-methylmorpholine; triethylamine; bipyridine; N,N,N′,N′-tetramethylethylenediamine; N,N,N′,N′-tetraethylethylenediamine; a glyme; or 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidinone; and
m is an integer ranging from 1 to 3; the method comprising:
reacting a compound of Formula (III):

wherein v is an integer ranging from 2 to 6;
with a compound of Formula (IV):
Zn(R a ) 2   (IV)

in the presence of a solvent;

wherein:
each X is independently selected from Br; I; Cl; tosylate; mesylate; and CF 3 SO 3 − ; and
R a is C 1 -C 10 alkyl.

6. The method of claim 5 , wherein the solvent comprises a C 5 -C 8 alkyl compound.

7. The method of claim 5 , wherein the solvent comprises a hexane selected from n-hexane; 2-methylpentane; 3-methylpentane; 2,3-dimethylbutane; and 2,2-dimethylbutane.

8. A method of fluorinating a substrate comprising:
reacting a compound according to claim 1 with a halogenated nickel compound.

9. The method of claim 8 , wherein the halogenated nickel compound is NiBr 2.

10. A method of fluorinating a substrate comprising:
reacting a compound according to claim 1 with a halogenated heterocylic compound.

11. The method of claim 10 , wherein the heterocylic compound is a monocyclic or bicyclic 5-12 membered heterocyclic compound.

12. The method of claim 10 , wherein the heterocylic compound is selected from a pyrrolidine, a pyrole, a piperidine, a pyridine, an azepane, an azepine, an indole, a quinoline, a benzazepine, and a carbazole.

13. The method of claim 10 , wherein the halogenated heterocyclic compound is 2,3-diiodopyridine.

Assignees

• Univ Lehigh

Inventors

• Vicic David

Classifications

• C07C2602/10

  the other ring being six-membered, e.g. tetraline · CPC title

• C07F3/06 Primary

  Zinc compounds · CPC title

• C07C17/263

  by condensation reactions · CPC title

• C07D215/18

  Halogen atoms or nitro radicals · CPC title

• C07F15/04

  Nickel compounds · CPC title