Acetals formals

Glycosides are mixed acetals formally arising by elimination of water between the hemiacetal or hemiketal hydroxy group of a sugar and a hydroxy group of a second compound. The bond between the two components is called a glycosidic bond. 

An organic sulfur compound containing an acetal function had been oxidised to the sulfone with 30% hydrogen peroxide in acetic acid. After the liquor had been concentrated by vacuum distillation at 50-60°C, the residue exploded during handling. This was attributed to formation of the peroxide of the acetal (formally a gem-diether) or of the aldehyde formed by hydrolysis, but formation and explosion of peracetic acid seems a more likely explanation. 

Bis(2,2-dinitropropyl)acetal/formal (BDNP A/F) Liquid plasticizer mixture (50% BDNPA and 50% BDNPF) used in PBX compositions... 

Probably the first reference to the polymerisation of cyclic acetals (formals) was by Hill and Carothers (143). Since then a number of groups of research workers have shown interest in these monomers, particularly in 1,3-dioxolan 12 (54, 144-147) and to a lesser extent 1,3-dioxepane 13 (148-150). 1,3-Dioxan 14 does not appear to polymerise but merely forms crystalline dimer and trimer. 

Poly(vinyl chloride) and poly(vinyl acetate) Poly(vinyl chloride), 15% glass-fiber-reinforced Poly(vinylidene chloride) Poly(vinyl formal) Chlorinated poly(vinyl chloride) Poly(vinyl butyral), flexible ... 

The observation that a system at equilibrium responds to a stress by reequilibrating in a manner that diminishes the stress, is formalized as Le Chatelier s principle. One of the most common stresses that we can apply to a reaction at equilibrium is to change the concentration of a reactant or product. We already have seen, in the case of sodium acetate and acetic acid, that adding a product to a reaction mixture at equilibrium converts a portion of the products to reactants. In this instance, we disturb the equilibrium by adding a product, and the stress is diminished by partially reacting the excess product. Adding acetic acid has the opposite effect, partially converting the excess acetic acid to acetate. 

Liquid crystal polyesters are made by a different route. Because they are phenoHc esters, they cannot be made by direct ester exchange between a diphenol and a lower dialkyl ester due to unfavorable reactivities. The usual method is the so-called reverse ester exchange or acidolysis reaction (96) where the phenoHc hydroxyl groups are acylated with a lower aHphatic acid anhydride, eg, acetic or propionic anhydride, and the acetate or propionate ester is heated with an aromatic dicarboxyHc acid, sometimes in the presence of a catalyst. The phenoHc polyester forms readily as the volatile lower acid distills from the reaction mixture. Many Hquid crystal polymers are derived formally from hydroxyacids (97,98) and thein acetates readily undergo self-condensation in the melt, stoichiometric balance being automatically obtained. 

Analogously, poly(vinyl ketals) can be prepared from ketones, but since poly(vinyl ketals) are not commercially important, they are not discussed here. The acetalization reaction strongly favors formation of the 1,3-dioxane ring, which is a characteristic feature of this class of resins. The first of this family, poly(vinyl ben2al), was prepared in 1924 by the reaction of poly(vinyl alcohol) with ben2aldehyde in concentrated hydrochloric acid (2). Although many members of this class of resins have been made since then, only poly(vinyl formal) [9003-33-2] (PVF) and poly(vinyl butyral) [63148-65-2] (PVB) continue to be made in significant commercial quantities. 

Poly(vinyl alcohol) participates in chemical reactions in a manner similar to other secondary polyhydric alcohols (82—84). Of greatest commercial importance are reactions with aldehydes to form acetals, such as poly(vinyl butyral) and poly(vinyl formal). 

A useful approach to the substitution of ring C—H positions lies in the activation of the heteroaromatic system by an A-oxide group, initiating a formal intramolecular redox reaction. 1-Methyllumazine 5-oxide reacts with acetic anhydride in a Katada rearrangement... 

The products are amorphous resins whose rigidity and softening point depend on the aldehyde used. Poly(vinyl butyral), with the larger side chain, is softer than poly(vinyl formal). Since the reaction between the aldehyde and the hydroxyl groups occurs at random, some hydroxyl groups become isolated and are incapable of reaction. A poly(vinyl acetal) molecule will thus contain ... 

The poly(vinyl acetals) may be made either from poly(vinyl alcohol) or directly from poly(vinyl acetate) without separating the alcohol. In the case of poly(vinyl formal) the direct process is normally used. 

A number of grades of poly(vinyl formal) are commercially available (Formvar, Mowital) which vary in degree of polymerisation, hydroxyl content and residual acetate content. 

The main application of poly (vinyl formal) is as a wire enamel in conjunction with a phenolic resin. For this purpose, polymers with low hydroxyl (5-6%) and acetate (9.5-13%) content are used. Similar grades are used in structural adhesive (e.g. Redux) which are also used in conjunction with phenolic resin. Poly(vinyl formal) finds some use as a can coating and with wash primers. Injection mouldings have no commercial significance since they have no features justifying their use at current commercial prices. 

Compared with the phenolics and polyesters the resins have better heat resistance, better chemical resistance, particularly to alkalis, greater hardness and better water resistance. In these respects they are similar to, and often slightly superior to, the epoxide resins. Unlike the epoxides they have a poor adhesion to wood and metal, this being somewhat improved by incorporating plasticisers such as poly(vinyl acetate) and poly(vinyl formal) but with a consequent reduction in chemical resistance. The cured resins are black in colour. 

Poly(ethylene terephtlhalate) Phenol-formaldehyde Polyimide Polyisobutylene Poly(methyl methacrylate), acrylic Poly-4-methylpentene-1 Polyoxymethylene polyformaldehyde, acetal Polypropylene Polyphenylene ether Polyphenylene oxide Poly(phenylene sulphide) Poly(phenylene sulphone) Polystyrene Polysulfone Polytetrafluoroethylene Polyurethane Poly(vinyl acetate) Poly(vinyl alcohol) Poly(vinyl butyral) Poly(vinyl chloride) Poly(vinylidene chloride) Poly(vinylidene fluoride) Poly(vinyl formal) Polyvinylcarbazole Styrene Acrylonitrile Styrene butadiene rubber Styrene-butadiene-styrene Urea-formaldehyde Unsaturated polyester... 

Benzodiazepinones also undergo rearrangement to isoindoles when treated with acetic anhydride and pyridine (Py). The diazepinone (81), for instance, gives l-phenyl-3-acetylisoindole (82) under these conditions. The structure of the product was established in this case by comparison with (82) prepared by acetylation of 1-phenyl-isoindole. The rearrangement may be formally represented by a... 

The ferrioxamines form a large group of ferric trihydroxamates composed of residues of acetic acid, succinic acid, l-amino-5-hydroxyl-aminopentane, and l-amino-4-hydroxylaminobutane. Of the.se, only ferrioxamines E (14) and D2 (15) are formally cyclic hydroxamic acids. 

Condensation of an appropriately substituted phenylacetic acid with phthalic anhydride in the presence of sodium acetate leads to aldol-like reaction of the methylene group on the acid with the carbonyl on the anhydride. Dehydration followed by decarboxylation of the intermediate affords the methylenephthal-ides (12). Treatment of the phthalides with base affords directly the indandiones, probably via an intermediate formally derived from the keto-acid anion (13). The first agent of this class to be introduced was phenindandione (14) this was followed by anisindandione (1S) and chlorindandione (16). ... 

Polyvinyl acetate and derivatives Polyvinyl acetate is used largely for coating applications, but the derivative polyvinyl alcohol, will, providing there are some residual acetate groups, dissolve in water. Reaction products of polyvinyl alcohol with aldehydes such as polyvinyl formal and polyvinyl butyral are highly specialised materials. 

McLafferty, Fred Warren, 732 McLafferty rearrangement. 416, 732 Mechanism (reaction), 139 acetal formation, 717-718 acetylide alkylation, 272 acid chloride formal ion with SOCl2, 795... 

Poly sulfide Polymers. These polymers are made up of aliphatic hydrocarbon units connected by di-, tri- or tetrasulfide links. The synthetic rubber found useful in ordn has hydrocarbon units linked by either O or formal segments. The polymers are usually prepd by the condensation of a suitable organic dihalide, usually the chloride, with aq Na polysulfide. According to Ref 8, the most practical organic dichloride is dichlorodiethylformal viz, Bis[ 2[Pg.827]

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