Notes - Preparation and Properties of Some Fluorohaloethyl Alkyl Ethers

Abstract

NOTES 1785 described by Mustafa el oí.1 the same product 9-phenyI-9,10-dihydro-10-oximino-9-hydroxyphenanthrene (II), is obtained according to the following scheme:The identity of the phenyllithium product and the phenylmagnesium bromide product is again verified by melting point and mixture melting point experiment, as well as by ultraviolet spectrum, X-(mju) 254, Cm«i 23990, " ( µ) 288, em" 8535, Xm»i (m^) 324, <m»i 1619.In addition, it is noticed that the addition of organolithium compounds to the ,ß-unsaturated ketones is a 1,2-addition even in cases where the organomagnesium compounds add by 1,4-addition.4-7 EXPERIMENTAL Reaction of phenanthrenequinone monoxime with phenyllithium. A solution of phenanthrenequinone monoxime (1 g.) in dry benzene (40 ml.) was treated with phenyllithium (from 16 g. bromobenzene and 1.5 g. lithium). The reaction mixture was kept overnight at room temperature in a nitrogen atmosphere and under reduced pressure. The substance dissolved completely and the color of the solution changed from orange to reddish brown. The reaction mixture was poured slowly into 100 ml. of saturated aqueous ammonium chloride solution, and shaken thoroughly. The ether-benzene layer was separated, dried over anhydrous sodium sulfate, filtered, and evaporated. The solid residue upon crystallization from benzene gave 9-phenyl-9,10-dihydro-10-oximino-9-hydroxyphenanthrene, II, as colorless needles, m.p. 162°u ndepressed on admixture with a sample of the product from the interaction between phenanthrenequinone monoxime and phenylmagnesium bromide, yield 50%. It gave a blue color with concentrated sulfuric acid and the color then turned to purple.

Claisen Rearrangement of Allyl Bromofluorovinyl Ethers

“…In the literature, only two references [4,5] report the addition of alcohols with 1 using the corresponding alkoxide as catalyst. The reaction takes place in protic medium and leads to a saturated fluorinated ether (Scheme 1).…”

“…, 1933Ϫ1937 1936 addition of Et 2 O, the reaction mixture was successively washed with saturated aqueous NaHSO 3 , NaHCO 3 and NaCl solutions. It was dried over MgSO 4…”

Polyfluorinated Ethanes as Versatile Fluorinated C2-Building Blocks for Organic Synthesis

“…Quite interesting is the chemoselectivity of the substitution. No substitution at the iodomethylene fragment but the reaction on the CF 2 Cl moiety takes place . Similarly, the reaction of CF 2 ClCHFI with ethanol gives substitution product at CF 2 Cl group 443b , subsequent hydrolysis of which permits the preparation of iodofluoroacetic acid 444b (Scheme )…”