With cyclic anhydrides

Lustoh, J. and Vass, F. Anionic Copolymerization of Cyclic Ethers with Cyclic Anhydrides. Vol. 56, pp. 91 —133. 

Friedel-Crafts acylation can be carried out with cyclic anhydrides, in which case the product contains a carboxyl group in the side chain. When succinic... 

The reactivity of hydrido(ethoxo) complex 4 was examined (Scheme 6-15) [8]. Metatheses similar to those postulated for alcohol exchange (Eq. 6.5) occurred between HCl, LiCl, phenyl acetate or primary amines and yielded complexes 94. The reaction of 4 with cyclic anhydrides proceeded similarly to give iridium-assisted ring opening products 95. Heterocumulenes afforded the inserhon products 96 into the Ir-O bond. 

The double bond of maleic anhydride may undergo free radical polymerization with the proper initiator. Polymers of maleic anhydride (or copolymers made with another monomer) are commercially available (Polysciences). They consist of a linear hydrocarbon backbone (formed from the polymerization of the vinyl groups) with cyclic anhydrides repeating along the chain. Such polymers are highly reactive toward amine-containing molecules. 

Quinazolines, the benzo derivatives of pyrimidines, were prepared in a variety of ways, from methods analogous to those for synthesizing pyrimidines to vastly different condensation schemes. In analogous fashion to many pyrimidine preparations, Yang and coworkers reported the condensation of polymer-tethered amidines 109 with cyclic anhydrides 110 to yield a library of 2-amino-4(3//)-quinazoIinones 111 after cleavage from the resin <00TL7005>. 

Reactions of wood with cyclic anhydrides do not yield a by-product, leaving the modified wood polymers with a covalently bonded carboxylic group an example is reaction with succinic anhydride (SA) (Figure4.1a). With reactions above 100°C there is some formation of diester observed (Figure 4.1b), resulting in cross-linking within the cell wall matrix (Matsuda, 1987). 

Halo-lactonization of ketophosphoranes has been achieved via reaction with cyclic anhydrides and subsequent halogenation. " The products, halo enol lactones (75), are synthetically useful compounds, and an alternative synthesis via incorporation of the halogen at the ylid stage is also described. Mechanistic investigation of the Wittig reactions involved reveals subtle variations in pathway, allowing optimum experimental conditions to be selected to allow for the variation in reactivity of different anhydrides and halides. 

This reaction, similar in scope and mechanism8S2 to 0-52, can be carried out with ammonia or primary or secondary amines.853 However, ammonia and primary amines can also give imides, in which two acyl groups are attached to the nitrogen. This is especially easy with cyclic anhydrides, which produce cyclic imides.854... 

Friedel-Crafts acylation can be carried out with cyclic anhydrides,272 in which case the product contains a carboxyl group in the side chain. When succinic anhydride is used, the product is ArCOCH2CH2COOH. This can be reduced (9-37) to A1CH2CH2CFLCOOH, which can then be cyclized by an internal Friedel-Crafts acylation. The total process is called the Haworth reaction 173... 

LiAlH4 usually reduces open-chain anhydrides to give 2 moles of alcohol, With cyclic anhydrides the reaction with LiAIH4 can be controlled to give either diols or lactones572 (see 9-41). NaBH4 in THF, with dropwise addition of methanol, reduces open-chain anhydrides to one mole of primary alcohol and one mole of carboxylic acid.573 OS VI, 482. 

Anionic Copoiymerization of Cyclic Ethers with Cyclic Anhydrides... 

This article summarizes and analyzes the results obtained for the anionic copolymerization of cyclic ethers with cyclic anhydrides. This reaction is of great practical importance, especially as curing reaction of epoxy resins and is also used for the preparation of linear polyesters with special functional pendant groups. 

Several publications dealing with problems of the copolymerization of cyclic ethers with cyclic anhydrides have recently appeared I4 I8), but they are not concerned with all aspects of the problems involved. 

In this paper, we try to review results obtained from anionic copolymerization of cyclic ethers with cyclic anhydrides. For a better understanding data and theoretical views on non-catalyzed copolymerizations are also included. We concentrate mainly on the kinetics and mechanism of copolymerization and the effect of the type and character of the initiator used. The influence of the epoxide and anhydride structure on copolymerization, of proton donors on the rate and course of copolymerization, and on the molecular weight of the resulting polyesters are also discussed. 

Hilt et al. 42,541 found by conductivity measurements that the copolymerization of epoxides with cyclic anhydrides initiated by alkali salts is of ionic character. Luston and Manasek 36,57), who used ammonium salts, came to the same conclusion. The rate of copolymerization increases linearly with rising initiator concentration (Fig. 1, the slope of the curve log k vs log c,n is unity) but only up to a limit which depends on the solubility of the initiator in the reaction system54). A rise in the copolymerization rate is accompanied by an increase in the conductivity of the reaction... 

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