Reagents and Methods for Fluorinating a Substrate

Patent metadata

Field	Value
Publication number	US-2016176901-A1
Application number	US-201414903724-A
Country	US
Kind code	A1
Filing date	Jul 8, 2014
Priority date	Jul 9, 2013
Publication date	Jun 23, 2016
Grant date	—

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

1 . A compound of Formula (I):

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

2 - 3 . (canceled)

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

5 - 6 . (canceled)

7 . The compound of claim 1 any foregoing claim, wherein L is a glyme-type solvent having the following formula: CH 3 O(CH 2 CH 2 O)CH 3 ; wherein t is an integer between 1 and 10.

8 . The compound of claim 1 any foregoing claim, wherein the glyme-type solvent comprises diethylene glycol dimethyl ether.

9 . A compound of Formula (II):
(Y)m(X) q Zn-(CF2)p-Zn(X) q (Y)m   (II)

wherein:
p is an integer between 2 and 12; and
q is an integer ranging from 1 to 2
Y comprises tetrahydrofuran; dioxane; acetonitrile; diethyl ether; N-methylmorpholine;
triethylamine; dimethoxyethane; bipyridine; N,N,N′,N′-tetramethylethylenediamine; N,N,N′,N′-tetraethylethylenediamine; a glyme-type solvent; or 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone;
m is an integer ranging from 1 to 3; and
each X is independently selected from Br; I; Cl; tosylate; mesylate; and CF3S03″.

10 . The compound of claim 9 , wherein p is 4 to 8.

11 - 14 . (canceled)

15 . The compound of claim 9 , wherein Y is a glyme-type solvent having the following formula: CH 3 O(CH 2 CH 2 O) t CH 3 ; wherein t is an integer between 1 and 10.

16 . The compound of claim 9 , wherein the glyme-type solvent comprises diethylene glycol dimethyl ether.

17 . A method for preparing a compound of Formula (I):

wherein:
n is an integer ranging from 2 to 6;
L comprises tetrahydrofuran; dioxane; acetonitrile; diethyl ether; N-methylmorpholine;
triethylamine; dimethoxyethane; bipyridine; N,N,N′,N′-tetramethylethylenediamine; N,N,N′,N′-tetraethylethylenediamine; a glyme-type solvent; 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 1 is C 1 -C 10 alkyl.

18 . The method of claim 17 , wherein the solvent comprises a C 5 -C 8 alkyl compound.

19 . The method of claim 17 , wherein the solvent comprises a hexane selected from n-hexane; 2-methylpentane; 3-methylpentane; 2,3-dimethylbutane; and 2,2-dimethylbutane.

20 . (canceled)

21 . A method for preparing a compound of claim 9 , having the structure of Formula (II):
(Y) m (X) q Zn—(CF 2 ) p —Zn(X) q (Y)m   (II)

wherein:
p is an integer ranging from 2 to 12;
q is an integer ranging from 1 to 2;
Y comprises tetrahydrofuran; dioxane; acetonitrile; diethyl ether; N-methylmorpholine;
triethylamine; dimethoxyethane; bipyridine; N,N,N′,N′-tetramethylethylenediamine; N,N,N′,N′-tetraethylethylenediamine; a glyme-type solvent; or 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone;
m is an integer ranging from 1 to 3; and
each X is independently selected from Br; I; Cl; tosylate; mesylate; and CF 3 SO 3 − ; the method comprising:
reacting a compound of Formula (III):

with a zinc metal in the presence of a solvent;

wherein:
v is an integer ranging from 2 to 12; and
each X is independently selected from Br; I; Cl; tosylate; mesylate; and CF 3 SO 3 − .

22 . The method of claim 21 , wherein the solvent comprises a glyme-type solvent having the following formula: CH 3 O(CH 2 CH 2 O) t CH 3 ; wherein t is an integer ranging from 1 and 10.

23 . The method of claim 21 , wherein the solvent comprises tetrahydrofuran;
dioxane; acetonitrile; diethyl ether; N-methylmorpholine; triethylamine; dimethoxyethane; bipyridine; N,N,N′,N′-tetramethylethylenediamine; N,N,N′,N′-tetraethylethylenediamine; or 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone.

24 . (canceled)

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

26 . The method of claim 25 , wherein the halogenated nickel compound is NiBr 2 .

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

28 . The method of claim 27 , wherein the heterocylic compound is a monocyclic or bicyclic 5-12 membered heterocyclic compound.

29 . The method of claim 27 , 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.

30 . The method of claim 27 , 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

• C07C17/263

  by condensation reactions · CPC title

• C07F3/06 Primary

  Zinc compounds · CPC title

• C07D215/18

  Halogen atoms or nitro radicals · CPC title

• C07F15/04

  Nickel compounds · CPC title