Vinyl esters halides

Monomers that copolymerize with thiocarbonyl fluoride include olefins, vinyl halides, vinyl esters, ally esters, acrylates, vinyl ethers, and vinyltrichloro-silane. Nonconjugated diolefins lead to crosslinked products. Conjugated dienes inhibit polymerization. 

The methine protons in secondary esters and halides that resemble active species in the polymerization of styrene and vinyl esters absorb in the range of 5 to 6 ppm, usually as quartets coupled to the neighboring methyl group, whereas those in the corresponding carbenium ions absorb at much lower field, 9-10 ppm [105,123,254,255] ... 

Several related cross-couplings that involve both catalytic levels of Pd and Cu have also been reported, such as Hecklike reactions see Heck Reaction) of vinyl esters with arylstannanes (equation 6), aryl selenenylations between BusSnSeAr and aryl halides (equation 7), and thioarene or thioester couplings to aryl, vinyl, or alkyl stannanes (equation 8). ... 

Recent literature describes the synthesis of vinyl esters in the presence of platinum metal complexes. Complexes which have proven particularly suitable in this context are those of ruthenium (eq. (15)), such as, for example, cyclooc-tadienylruthenium halides [36], ruthenium carbonyl complexes, and ruthenium acetate complexes [37]. A characteristic feature of these is their high selectivity with regard to acetylene, so that the production of acetylene polymers is reduced. 

As can be seen from equations 2-5, the formation of A -acylenamines proceeds from derivatives of carboxylic acids (having an oxidation level equal to three ), namely anhydrides or add halides RCOX or amides RCONH2, on the one hand, and from carbonyl compounds or their derivatives (oxidation level equal to two ), namely enamines 3, acetylenes 5, or vinyl ethers 6, on the other. Indeed, the acetylenes 5, being the dehydration products of enols, may be regarded as having a masked carbonyl functionwhile the enamines 3 rank with vinyl ethers, vinyl esters and enols, as the heteroanalogs of these carbonyl derivatives (see Section IV). 

Vinyl monomers such as styrene, vinyl halides, and vinyl esters react with sulfur dioxide to give polysulfones. 

Ziegler-Natta type polymerizations of vinyl esters with trialkyl aluminum and metal halides have been discussed [189-193]. 

This section deals with paints based on vinyl resins (including vinyl copolymers) which are synthesized by polymerization of monomers containing terminal CH2 = CH groups. Polyolefins, poly(vinyl halides) and vinyl halide copolymers, poly(vinyl esters), poly(vinyl alcohol), poly(vinyl acetals), poly(vinyl ethers), and polystyrene are discussed. Polyacrylates (acrylic resins) are treated in Section 2.5. 

Ethers, acetals with a hydrogens Alkenes, alkylacetylenes with aUyUc hydrogens nyl halides, vinyl esters, vinyl ethers Dienes, vinylacetylenes... 

Similarly, Fischer carbene complexes are formed when Grubbs systems react with vinyl esters, vinyl carbonates, and vinyl halides. However, these Fischer car-benes are known to decompose to give terminal ruthenium carbide species by elimination of HX (X = OjCR, OjCOR, halide) [83-86]. Notably, the formation of the carbide complexes is less favorable in phosphine-free systems, which enables the Hoveyda [56] and Piers [87] catalysts to promote the cross metathesis of vinyl hahdes and terminal or internal olefins [88]. 

Polyolefins Polystyrenes Polyacrylates Polymethacrylates Polyacrylonitriles Polyacrylamides Poly(vinyl halides) Poly(vinylidene halides) Poly(vinyl ethers) Poly(vinyl ketones) Poly(vinyl esters) Poly(vinyl pyridines) Polydienes Polyethers Polyesters, aliphatic Polyesters, aromatic Polyamides Polysiloxanes Polyphosphazenes Polysulfones... 

Benzoic acid and substituted benzoic acids are readily thallated by thallium(III) trifluoroacetate. Subsequent reaction with palladium chloride and simple alkenes, allylic or vinyl halides, or vinyl esters result in the formation of isocoumarins eg ... 

Styrene, a-methyl styrene Vinyl halides Vinyl esters Vinyl ethers... 

Isobutene Vinyl ethers Ethylene Vinyl esters Vinyl halides Acrylic esters Acrylonitrile Vinylidene halides 1-Nitro-l-alkenes Vinylidene cyanide Styrene... 

It has been reported [1] that vinyl esters are obtained by the reaction of aliphatic and aromatic acid halides with acetaldehyde in the presence of pyridine. It was postulated that acetaldehyde enolizes to vinyl alcohol in the presence of pyridine, which subsequently reacts with the acid halide. 

TABLE 6. FUMARIC DERIVATIVES Fumaric Derivatives, Vinyl Halides, and Vinyl Esters 11/87... 

Poly(vinyl halides) Vll-I 7 alcohol), Poly(vinyl esters). ... 

POLY(VINYL ETHERS), POLY(VINYL ALCOHOL), POLY(VINYL ESTERS), POLY(VINYL HALIDES)... 

Acid chlorides and bromides, allyl halides, a-halo-ketones, esters, amides and nitriles react at 25° within 3 minutes. Vinyl and aryl halides are inert. 

In the reaction of Q,/3-unsaturated ketones and esters, sometimes simple Michael-type addition (insertion and hydrogenolysis, or hydroarylation, and hydroalkenylation) of alkenes is observed[53,54]. For example, a simple addition product 56 to methyl vinyl ketone was obtained by the reaction of the heteroaromatic iodide 55[S5]. The corresponding bromide affords the usual insertion-elimination product. Saturated ketones are obtained cleanly by hydroarylation of o,/3l-unsaturated ketones with aryl halides in the presence of sodium formate, which hydrogenolyses the R—Pd—I intermediate to R— Pd—H[56]. Intramolecular hydroarylation is a useful reaction. The diiodide 57 reacts smoothly with sodium formate to give a model compound for the afla-toxin 58. (see Section 1.1.6)[57]. Use of triethylammonium formate and BU4NCI gives better results. 

---