Allylmalonic acid

However, upon terminating chains with thiols, sulphur centered low-molecular weight radicals are formed that are able to start a polymerization of the remaining monomer B. Therefore, formation of homopolymer consisting of B is inevitable if thiols are used. A suitable alternative to the classical transfer additives are degra-dative chain transfer agents, such as allylmalonic acid... 

Olefinic halides may be used as alkylating agents in the malonic ester synthesis. The olefinic malonic acids are decatboxylated to olefinic acids at lower temperatures (140-160°) than those employed for alkylmalonic acids. Examples include the conversion of 4-pentenylmalonic acid to 6-heptenoic acid (67%), allylmalonic acid to allylacetic acid (70%), and 2-cyclopentenylmalonic acid to 2-cyclopentenylacetic acid (99%)- ... 

Similarly, Ishizu and Tahara [86] used allylmalonic acid diethylester as a transfer agent in the polymerization of MMA. 

Heterocyclization. Allylmalonic acids ncorporating iodine, giving y-butyrolactones a hey are treated with Ij in dichloromethane at t The stereoselectivity of pyrrolidine form creatly affected by a base. ... 

Heterocyclization. Allylmalonic acids and o-allylphenols cyclize without incorporating iodine, giving y-butyrolactones and dihydrobenzofuranes, respectively, when they are treated with in dichloromethane at room temperature. 

Ester and ester derivative polymers are biodegradable polymers, and there are a large number of biodegradable hydrogels made of ester prepolymers by cross-linking with monomers such as AM and VP. The ester prepolymers are prepared via condensation reactions between an unsaturated diacid like fumaric acid, itaconic acid, or allylmalonic acid and a diol such as low molecular weight PEG. 

As stated in section I, the termination mode of the particular monomer determines the number of functionalities per macromolecular chain. Most monomers undergo both unimolecular and bimolecular termination reactions. It is often observed that both respective monofunctional and bifunctional polymers are formed and well-defined functional polymers cannot be prepared. The use of allylmalonic acid diethylester in free-radical polymerization has been proposed to overcome the problems associated with the aforementioned functionality. In the presence of the allyl compound, the free-radical polymerization of monomers, regardless of their termination mode, proceeds entirely with the unimolecular termination mechanism, as shown in Scheme 9. Because allyl compounds lead to degradative chain transfer, the resulting allyl radical is quite stable due to the allyl resonance. Monofunctional polystyrene, polyvinylacetate, and poly(t-butyl methacrylate) were prepared by using this approach [33]. Subsequently, various macromonomers were derived from these polymers. 

Diethyl 2-allylmalonate 3. heat 4-Pentenoic acid 4-Penten-l-ol... 

A broad variety of acids can be applied ranging from aromatic and heteroaromatic acids, simple aliphatic acids to a,p-unsaturated acids. The configuration of stereogenic centers in a-position is fully retained. Acyliron complexes are proposed as intermediates. A (trichloro)[bis(imidazolonyl)pyridine]iron complex catalyzes the alkylative cyclization of 2-chloro-1,6-dienes and the deallylation of allyl malonates in the presence of triethylaluminum (Scheme 4-356). The yields, however, vary and depend very much on the substrate. 2-Substituted 2-allylmalonates can be demetalated under the same reaction conditions. 

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