Polymeric transfer reagents solution

Schrock, Gibson et al. [52d] found that styrene and 1,3-pentadiene could be used as chain transfer reagents for the living ring-opening olefin metathesis polymerization of norbornene with molybdenum based catalyst 35a. Renewed norbornene addition to a polymerization mixture containing initiator 35a and 30 equivalents of styrene resulted in the formation of polynorbomene with a low polydispersity and a molecular weight controlled by the number of norbornene equivalents in each of the individual monomer solutions, Eq. (38). This method allows a more efficient use of the catalyst. 

The commercially available 3-amino-1,2,4-dithiazole-5-one, (3), has been attached to a hydroxyl resin via a succinic acid linker, and has been used as an efficient sulfur-transfer reagent for the solution-phase synthesis of phos-phorothioates. DNA synthesis scale-up to lOOg of a 20-mer phosphorothioate has been examined " key to this was the purification of the product, which was carried out using a high efficiency polymeric anion exchange chromatographic media. 

In principle, the appearance of electron donor groups near the double bond of the monomer leads to a cationic mechanism, while positive groups that withdraw electrons mostly lead to the anionic process. An increase of temperature usually leads to a decrease in rate of reaction or length of the chain. Polymerization always occurs in solution, wherein the solvent acts as separator of the ion-pair, and quite often as a transfer reagent. As already mentioned, most monomers undergo polymerization via free radicals, mainly when conjugated double bonds are present or substitute groups that withdraw electrons. 

It has generally been accepted that aryloxy radicals are intermediates in the polymerization, largely because the effective reagents are those capable of one-electron transfer. This assumption has been confirmed recently by the identification of both monomeric and polymeric aryloxy radicals in the ESR spectra of polymerizing solutions of 2,6-xylenol (21). The first step in the reaction is the oxidation of the phenol to the aryloxy radical by Cu(II). Carbon-oxygen coupling of two aryloxy radicals yields the cyclohexadienone, which tautomerizers to the dimer (II) (Reaction 3). 

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