Vinyl ether exchange

They are colourless liquids with characteristic odours, and are prepared by the condensation of ketones with alkyl orthoformates in the presence of alcohols, or by the reaction of acetylenes with alcohols in presence of HgO and BF3. In some cases trichloroethanoic acid is used as the catalyst. They lose alcohol when heated and form vinyl ethers. Exchange of alcohol groups occurs when the ketals of the lower alcohols are boiled with alcohols of greater molecular weight. See acetals. 

The procedure described illustrates a new general synthetic method for the preparation of (E)-3-allyloxyacryl ic acids and their conversion to a-unsubstituted y,5-unsaturated aldehydes by subsequent Claisen rearrangement-decarboxyl at ion. Such aldehydes are traditionally prepared by Claisen rearrangements of allyl vinyl ethers. Allyl vinyl ethers are typically prepared by either mercury-catalyzed vinyl ether exchange with allylic alcohols or acid-catalyzed vinylation of allylic alcohols with acetals. The basic conditions required for alkoxide addition to the betaine to produce carboxyvinyl allyl ethers, as described in this report, nicely complements these two methods. In addition, this Claisen rearrangement is an... 

Allyl vinyl ethers are usually obtained by either mercury salts or acid-catalyzed vinyl ether exchange with allylic alcohols, or acid-catalyzed vinylation of allylic alcohols with acetals. However, yields in these reactions are often low and care must be used when using mercury [1]. Mercuric salts of weak carboxyUc acids, for example, acetate, have been reported to be particularly effective in catalyzing the transfer of vinyl groups from vinyl ethers to alcohols (Eq. 3.1.1) [6]. 

The vinyl ether in the latter part of the equation is copolymetized with tetrafluoroethylene, and then the sulfonyl fluoride group is hydrolyzed under basic conditions in order to produce the ion-exchange membrane (44—46). 

ALKENES via HOFMANN ELIMINATION USE OF ION-EXCHANGE RESIN FOR PREPARATION OF QUATERNARY AMMONIUM HYDROXIDES DIPHENYLMETHYL VINYL ETHER... 

The reactants can be made from allylic alcohols by mercuric ion-catalyzed exchange with ethyl vinyl ether.220 The allyl vinyl ether need not be isolated and is often prepared under conditions that lead to its rearrangement. The simplest of all Claisen rearrangements, the conversion of allyl vinyl ether to 4-pentenal, typifies this process. 

Acid-catalyzed exchange can also be used to prepare the vinyl ethers. 

A recently developed application of the Ramberg-Backlund reaction is the synthesis of C-glycosides. The required thioethers can be prepared easily by exchange with a thiol. The application of the Ramberg-Backlund conditions then leads to an exocyclic vinyl ether that can be reduced to the C-nucleoside.95 Entries 3 and 4 in Scheme 10.6 are examples. The vinyl ether group can also be transformed in other ways. In the synthesis of partial structures of the antibiotic altromycin, the vinyl ether product was subjected to diastereoselective hydroboration. 

Exchange of the butyl vinyl ether for 2-hydroxyethyl vinyl ether enabled the facile transformation of vinyl triflates or bromides into protected a,/i-unsaturated methyl ketones (Eq. 11.14) [27]. One interesting aspect of this reaction is that a masked methyl ketone can easily be introduced into a structure even in the presence of other free ketone groups. 

The observation of a primary solvent deuterium isotope effect (kH/fa>) = 2-4 on the specific acid-catalyzed hydrolysis of vinyl ethers provides evidence for reaction by rate-determining protonation of the alkene.69 Values of kHikD 1 are expected if alkene hydration proceeds by rate-determining addition of solvent to an oxocarbenium ion intermediate, since there is no motion of a solvent hydron at the transition state for this step. However, in the latter case, determination of the solvent isotope effect on the reaction of the fully protonated substrate is complicated by the competing exchange of deuterium from solvent into substrate (see above). 

Fluorinated polymers, especially polytetrafluoroethylene (PTFE) and copolymers of tetrafluoroethylene (TFE) with hexafluoropropylene (HFP) and perfluorinated alkyl vinyl ethers (PFAVE) as well as other fluorine-containing polymers are well known as materials with unique inertness. However, fluorinated polymers with functional groups are of much more interest because they combine the merits of pefluorinated materials and functional polymers (the terms functional monomer/ polymer will be used in this chapter to mean monomer/polymer containing functional groups, respectively). Such materials can be used, e.g., as ion exchange membranes for chlorine-alkali and fuel cells, gas separation membranes, solid polymeric superacid catalysts and polymeric reagents for various organic reactions, and chemical sensors. Of course, fully fluorinated materials are exceptionally inert, but at the same time are the most complicated to produce. 

The [3, 3] sigmatropic rearrangement of allyl vinyl ethers is known as Claisen rearrangement. Allylic alcohols can be converted to allyl vinyl ethers by mercuric acetate catalysed exchange with ethyl vinyl ether. The allyl vinyl ether need not be isolated because it undergoes rearrangement to 4-pentenal. 

A Novel Synthesis of Vinyl Ethers via an Unusual Exchange Reaction... 

Vinyl ethers are important raw materials in the production of glutaraldehyde, as well as of vinyl polymer materials which contain oxygen and are expected to degrade easily in Nature. The [IrCl(cod)]2 catalyzes an efficient exchange reaction between vinyl acetate 57 and alcohols or phenols 58, leading to the corresponding vinyl ethers 59 (Equation 10.11) [27]. Usually, the acid-catalyzed exchange reaction between alcohols and vinyl acetate results in alkyl acetates 60, and also to vinyl alcohol 61 which is readily isomerized to acetaldehyde 62. 

In view of the fact that alkyl vinyl ethers are that easily metalated, the generation of lithiated vinyl ethers by halogen-lithium or tin-lithium exchange is seldom applied. Nevertheless, 1-lithio-l-methoxyethene 56 can be generated in this way... 

Whereas carbenoid character is definitely present in metalated alkyl vinyl ethers, lithiated alkyl and aryl vinyl sulfides and thioesters, which are easily available by hydrogen-lithium exchange, do not display carbenoid-typical reactions . They rather behave like nucleophilic reagents, so that their discussion is beyond the scope of this overview despite their utility in synthesis The same appiies to various derivatives of enamines, deprotonated in the vinyiic a-nitrogen position - . 

It can be synthesized by reaction of a 1 1 molar ratio of ethyl vinyl ether and phenethyl alcohol in the presence of cation exchange resin [141]. It imparts fresh, floral, green notes and is used in fine fragrances as well as in soap, cosmetics and detergents. 

All work has been accomplished using perfluorosulfonate ion exchange membranes manufactured by E.l. duPont and sold under the trade name Nafion. Nafion is a copolymer of polytetrafluoroethy-lene (PTFE) and polysulfonylfluoride vinyl ether containing pendent sulfonic acid groups. The sulfonic acid groups are chemically bound to the perfluorocarbon backbone. 

Vinyl ethers have also been prepared by addition of alkoxides to acetylene,6 7 6 elimination from halo ethers and related precursors,6 8 and vinyl exchange reactions.6 Reaction of an electrophilic tungsten carbenoid with methylene phosphorane or diazomethane also produces vinyl ethers.9 Enol ethers have resulted from the reaction of some tantalum and niobium carbenoids with esters,10 and the reaction of phosphoranes with electrophilic esters.4... 

Dess-Martin A5-iodane 44 is an extremely useful reagent for the conversion of primary and secondary alcohols to aldehydes and ketones at 25 °C [70]. It does not oxidize aldehydes to carboxylic acids under these conditions. It selectively oxidizes alcohols in the presence of furans, sulfides, and vinyl ethers. The oxidation mechanism involves a facile ligand exchange with alcohols, followed by reductive /1-elimination. 

The aliphatic Claisen rearrangement is simpler in that there is no rearomatisation at the end but there is an ionic step first as the vinyl ether 67 has to be made and the easiest way to do that is from the allylic alcohol 65 by acetal exchange with another vinyl ether to give 66 and elimination to give 67. All these steps, including the rearrangement occur under the same conditions16 and the product is a y,S-unsaturated carbonyl compound 68. 

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