Fluorovinyl-methyl

Fig. 1. SAE J200 Classification system for ASTM No. 3 oil where in volume swell nr = no requirement. EPDM is ethylene—propylene—diene monomer HR, butyl mbber SBR, styrene—butadiene mbber NR, natural mbber VMQ, methyl vinyl siUcone CR, chloroprene FKM, fluoroelastomer FVMQ, fluorovinyl methyl siUcone ACM, acryUc elastomers HSN, hydrogenated nitrile ECO, epichlorohydrin and NBR, nitrile mbber.

Silicone. SiHcone elastomers have a sdoxy backbone with methyl, vinyl, and phenyl groups attached. The elastomers are designated by their chemical composition, as foUows methyl siHcone (MQ), methyl vinyl siHcone (VMQ), methyl phenyl siHcone (PMQ), methyl phenyl vinyl siHcone (PVMQ), and fluorovinyl methyl siHcone (FVMQ). 

The intermediate carbanion may eject fluorine and thus afford an unsaturated ether (F), 2,2-dichloro-l-fluorovinyl methyl ether, sometimes obtained as the main product. 

Fluorovinyl methyl ketone, CH2=CFCOCH3. Mol. wt. 76.07, b.p. 71° polymerizes readily, but can be stabilized with hydroquinone. 

ANNELATION f-Butyl-7-iodotiglate. l-Chloro-3-pentanone. 1-Fluorovinyl methyl ketone. 1-Lithiocyclopropyl phenyl sulfide. Methyl a-trimethylsilylvinyl ketone. 

Fluorovinyl methyl ketone, 263 Fluoroxytrifluoromefhane, 263-264 Formaldehyde, 18, 264-267, 379, 590 Formaldehyde diphenyl thioacetal, 267 Formamidincsulfinic acid, 586 Formic acid, 597... 

Diastereoselective alkylation of (R)-(-F)-camphor-based glycylimine (19) with 3-bromo-2-fluoropropene gave (R)-(-F)-2-amino-4-fluoropent-4-enoic acid with 38% overall yield and 90% ee after hydrolytic deprotection, or in the case of the alanylimine, (R)-(-F)-2-amino-4-fluoro-2-methyl-pent-4-enoic acid (19% overall yield, 59% ee) [49]. Deprotection under drastic conditions was accompanied by hydrolysis of the fluorovinyl moiety to give (R)-(-)-2-amino-4-oxo-pentanoic acid hydrochloride with 28% overall yield and >95% ee (Scheme 4). 

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 direct and safe method for making a-fluorinated cyclic enones of possible therapeutic interest involves the reaction of CH2=CHFCOMe with enamines or alkali enolates. Thus, 3-fluoro-l 0-methyl-1,9-A-2-octalone was prepared regio-specifically from the fluorovinyl ketone and 2-methylcyclohexanone in Bu OH at... 

Zakharkin and co-workers have studied, in detail, the synthesis and reactions of fluorovinyl-substituted carbaboranes (Vol. 1, p. 89). In Scheme 12 are shown some of the reactions described. Apparently the ability of the o-carbaboranyl nucleus to stabilize a negative charge during nucleophilic addition-elimination reactions exceeds that of either chlorine or trifluoro-methyl, attack on the double bond occurring p to the nucleus. > 4,4-Dichloro-3,3-difluoro-l-phenylcyclobutene reacts with aryl-lithium compounds, sodium thiolates NaSAr (Ar = Ph,p-MeC,H4,orn-H2N-CeH4), or pyridine or other heterocyclic bases by substitution with rearrangement. 

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