Method for preparation of fluoro alkylated 1,4-dioxene by homogeneous Ni catalysis
The invention discloses a method for the preparation of fluoro alkylated 1,4-dioxene by homogeneous Ni catalyzed fluoro alkylation with fluoro alkyl halides of 1,4-dioxane in the presence of a base.
1. A method for the preparation of a fluoro alkylated 1,4-dioxene by a reaction of 1,4-dioxane with a fluoro alkyl halide FAHALIDE by homogeneous catalysis using a Ni catalyst NICAT in the presence of a base BAS;
wherein
NICAT is Ni-cat1 or Ni-cat2;
Ni-cat1 is a combination of a nickel salt NISALT with a ligand LIG
NISALT is NiCl 2 or Ni(NO 3 ) 2 ;
LIG is selected from the group consisting of compound of formula (DPEPhos), compound of formula (dppb) and Ph 3 P;
Ni-cat2 is compound of formula (Ni-cat2);
BAS is selected from the group consisting of Cs 2 CO 3 , CsHCO 3 , Na 2 CO 3 , K 3 PO 4 , NaH and NaOtBu;
FAHALIDE is a compound of formula (FAHALIDE);
X2-R3-X1 (FAHALIDE)
R3 is C 1-20 alkylen, wherein in the alkylen chain at least one of the hydrogens is substituted by F;
X1 is Br or I;
X2 is Br or H.
2. The method according to claim 1 , wherein
NISALT is NiCl 2 and LIG is compound of formula (dppb).
3. The method according to claim 1 , wherein
BAS is selected from the group consisting of Cs 2 CO 3 , Na 2 CO 3 , K 3 PO 4 , NaH and NaOtBu.
4. The method according to claim 1 , wherein
FAHALIDE is selected from the group consisting of perfluoro C 1-20 alkyl-X1, Br—(CF 2 ) n3 —Br, and F 2 HC—X1;
with n3 being an integer of 2 to 10.
5. The method according to claim 1 , wherein
n3 is 2, 3, 4, 5, 6.
6. The method according to claim 1 , wherein
FAHALIDE is selected from the group consisting of F 21 C 10 —I, F 21 C 10 —Br, F 17 C 8 —I, F 17 C 8 —Br, F 13 C 6 —I, F 13 C 6 —Br, F 9 C 4 —I, F 9 C 4 —Br, F 7 C 3 —I, F 7 C 3 —Br, F 3 C—I, F 3 C—Br, Br—(CF 2 ) 4 —Br, F 2 HC—I, and F 2 HC—Br.
7. The method according to claim 1 , wherein
FAHALIDE is selected from the group consisting of F 21 C 10 —I, F 17 C 8 —I, F 13 C 6 —I, F 9 C 4 —I, F 7 C 3 —I, and F 3 C—I.
8. The method according to claim 1 , wherein
the reaction is done neat or in a solvent SOL.
9. The method according to claim 8 , wherein SOL is selected from the group consisting of alkanes, chlorinated alkanes, ketones, ethers, esters, aliphatic nitrils, aliphatic amides, sulfoxides, C 6 F 6 , and mixtures thereof.