Preparation of fluoro sulfides

Fuchigami and co-workers utilized the regioselective anodic fluorination of aryl propargyl sulfides 301 for the preparation of fluorinated alkyne intermediates, which were subsequently isomerized by sodium ethoxide to furnish 1-fluoro-l-arylthioallenes 302 (Scheme 8.80) [166]. 

Addition of a sulfenyl chloride to an alkene in the presence of silver fluoride affords (3-fluoro sulfides, as shown in equation (2).18 The same trans adducts can also be prepared from the sulfenyl chloride adducts and silver fluoride. An alternative procedure for the formal addition of methanesulfenyl fluoride to alkenes involves the use of dimethyl(methylthio)sulfonium tetrafluoroborate and triethylamine tris(hy-drofluoride) as in equation (3).19... 

The ultrasonic irradiation of aqueous sulfide solutions was conducted with a Branson 200 sonifier operating at 20 kHz by Kotronarou et al. (1992). Reactions were performed in a 50-mL water-jacketed, stainless-steel cell from Sonics Materials. The temperature inside the reaction vessel was kept constant at 25°C. All irradiations were carried out in air-saturated solutions at t = 0. A Haake A80 water circulating and temperature-controlling system was used for temperature control. Hydrogen peroxide was analyzed fluoro-metrically. Deionized water was used to prepare all the solutions. 

Photochemical [2+2] cycloaddition reactions and [2+2] cycloaddition reactions of ketenes have been widely used for the preparation of cyclobutane derivatives. The thermal [2+2] cycloaddition reaction is known to proceed between highly electrophilic and nucleophilic alkenes alkenes having cyano, fluoro, and trif-luoromethyl groups react with electron-rich alkenes such as alkenyl ethers and sulfides [8]. As for the catalyst-mediated [2+2] cycloaddition reactions, Lewis acids are known to promote [2+2] cycloadditions [9,10,11,12,13,14,15,16,17,... 

The a- and /3-cyclodextrins have been found to accelerate the Smiles rearrangement of 4-nitrophenyl salicylate. The reaction of 2,4-dinitrobenzenesulfonamide with acyl chlorides in the presence of excess triethylamine has been found to produce the corresponding nitrile in good yield. Mechanistic studies have indicated that the reaction proceeds via a Smiles rearrangement of the initially formed iV-(2,4-dinitrobenzenesulfonyl)amide to form the nitrile, 2,4-dinitrophenol, and sulfur dioxide (see Scheme 12). l-Chloro-3-fluorophenothiazines have been prepared by Smiles rearrangement of 3-chloro-5-fluoro-2-formamido-2 -nitrophenyl sulfides in alcoholic... 

Treatment of methyl phenyl sulfoxide with diethylaminosulfur trifluoride (DAST), in the presence of antimony trichloride provides 159 in quantitative yield (66). The reaction proceeds in good yield with dialkyl sulfoxides and alkyl aryl sulfoxides (163). Reoxidation of the a-fluorosulfide (165) to the corresponding sulfoxide (161), followed by pyrolysis, provides a direct synthesis of fluoroolefins (65). The reaction is believed to proceed by a Pummerer-type mechanism (l.e., a fluoro-Pummerer reaction, Scheme 48). Similarly, Umemoto (67) reported that N-fluorocollidine (167) converted sulfides to ot-fluorosulfides (170) presumably via an S-fluorosulfonium cation species 168 (Scheme 49). The synthetically challenging fluorovinyl ether nucleosides (175) and (176) were prepared using the fluoro-Pummerer reaction (Scheme 50) (60) the (E)-isomer (175) could be isomerized to 176 under photolytic conditions. Finch and co-workers (69) converted 160 to the sulfoximine 178 and demonstrated the utility of this compound as a mild fluoromethylene synthon (Scheme 51). Base-catalyzed condensation 178 with a carbonyl compound gave 179 which afforded... 

A series of high molecular weight poly(thioether ketone)s (M = 55,000-100,000), eg, (24) and (25), have successfully been prepared from bis(4-mercaptophenyl) ether (4,4 -dimercaptodiphenyl ether) or bis(4-mercaptophenyl) sulfide (4,4 -dimercaptodiphenyl sulfide) by reaction with a series of ketone-activated aromatic fluoro-compoimds in the presence of anhydrous K2CO3. The polymers are amorphous and soluble in common organic solvents. They show TgS from 154 to 251°C and excellent thermal stability [temperatures of 5% weight loss (Tds) even above 500°C] (65). 

---