Chain extension catalysts

The reaction is used for the chain extension of aldoses in the synthesis of new or unusual sugars In this case the starting material l arabinose is an abundant natural product and possesses the correct configurations at its three chirality centers for elaboration to the relatively rare l enantiomers of glucose and mannose After cyanohydrin formation the cyano groups are converted to aldehyde functions by hydrogenation m aqueous solution Under these conditions —C=N is reduced to —CH=NH and hydrolyzes rapidly to —CH=0 Use of a poisoned palladium on barium sulfate catalyst prevents further reduction to the alditols... 

In recent years, proprietary catalysts for advancement have been incorporated in precataly2ed Hquid resins. Thus only the addition of bisphenol A is needed to produce soHd epoxy resins. Use of the catalysts is claimed to provide resins free from branching which can occur in conventional fusion processes (10). Additionally, use of the catalysts results in rapid chain-extension reactions because of the high amount of heat generated in the processing. 

In recent years there has been some substitution of TDI by MDI derivatives. One-shot polyether processes became feasible with the advent of sufficiently powerful catalysts. For many years tertiary amines had been used with both polyesters and the newer polyethers. Examples included alkyl morpholines and triethylamine. Catalysts such as triethylenediamine ( Dabco ) and 4-dimethyla-minopyridine were rather more powerful but not satisfactory on their own. In the late 1950s organo-tin catalysts such as dibutyl tin dilaurate and stannous octoate were found to be powerful catalysts for the chain extension reactions. It was found that by use of varying combinations of a tin catayst with a tertiary amine... 

Fischer s original method for conversion of the nitrile into an aldehyde involved hydrolysis to a carboxylic acid, ring closure to a cyclic ester (lactone), and subsequent reduction. A modern improvement is to reduce the nitrile over a palladium catalyst, yielding an imine intermediate that is hydrolyzed to an aldehyde. Note that the cyanohydrin is formed as a mixture of stereoisomers at the new chirality center, so two new aldoses, differing only in their stereochemistry at C2, Tesult from Kiliani-Fischer synthesis. Chain extension of D-arabinose, for example, yields a mixture of D-glucose and o-mannose. 

For the hydrosilylation reaction various rhodium, platinum, and cobalt catalysts were employed. For the further chain extension the OH-functionalities were deprotected by KCN in methanol. The final step involved the enzymatic polymerization from the maltoheptaose-modified polystyrene using a-D-glucose-l-phosphalc dipotassium salt dihydrate in a citrate buffer (pH = 6.2) and potato phosphorylase (Scheme 59). The characterization of the block copolymers was problematic in the case of high amylose contents, due to the insolubility of the copolymers in THF. 

Next is the chain extension to get compound 214 for construction of the C-ring moiety. Again, aldol reactions are the key steps. A mild Lewis acid MgCL Et20 is the catalyst, and the desired anti, anti, anti-211 can be obtained with good selectivity. 

Many researchers have investigated the use of amines and alcohols as initiators for the ROP of lactones. As a rule, amines and alcohols are not nucleophilic enough to be efficient initiators, and it is then mandatory to use catalysts to perform the polymerization successfully. Nevertheless, highly reactive p-lactones exhibit a particular behavior because their polymerization can be initiated by nucleophilic amines in the absence of any catalyst. As far as tertiary amines are concerned, the initiation step implies the formation of a zwitterion made up of an ammonium cation and a carboxylate anion, as shown in Fig. 20. Authors coined the name zwitterionic polymerization for this process [80]. Nevertheless, this polymerization is not really new because the mechanism is mainly anionic. Interestingly, Rticheldorf and coworkers did not exclude the possibility that, at least at some stage of the polymerization, chain extension takes place by step-growth polycondensation [81]. 

For the synthesis of amino acids, the reaction of an a-haloalkyl boronic ester 4 with sodium azide and a phase-transfer catalyst in dichloromethane/water requires a large excess of azide in order to form the a-azidoalkyl boronic ester 5 with only 1-2% epimer34. With the exception of R1 = benzyl, where epimerization of 4 is relatively rapid, bromoalkyl boronic esters are preferred. Chloroalkyl boronic esters react so slowly that the azide and dichloromethane may generate hazardously explosive diazidomethane65,66. Chain extension of 5 to 6 proceeds normally. Sodium chlorite, which is known to oxidize aldehydes to carboxylic acids67-69, also oxidizes a-chloroalkyl boronic esters to carboxylic acids34. The azido acid is hydrogenated to the amino acid. 

With meso-conflgured dialdehyde precursors, the enantiotopic nature of the termini must give rise to a conflgurational terminus differentiation upon twofold chain extension because the catalyst-controlled diastereoselective aldol additions will break the inherent o symmetry. While the two enantiotopic termini cannot... 

Chain extension with PO Partially blocked hydroxypropyl lignin derivatives were reacted with propylene oxide in toluene, using KOH as catalyst, for the purpose of creating extended propyl ether chains. This has been reported elsewhere (13). 

Chain Extension of -U-Polystyrene Hiols. A two-stage chain extension of the. -kJ -polystyrene diols was accomplished by carboxylation of the diols with succinic anhydride followed by chain extension with a diepoxide. The succinic anhydride reaction was carried out 120-130°C under nitrogen. The reaction was monitored bj changes in the carbonyl bands at 1715 and 1740 cm in the infrared spectra of the reaction mixtures. The resulting dicarboxylic acid polymers were chain-extended in bulk at 130°C for 9 hours with Sow s HER diepoxide, equivalent weight =171, using bis( 3,5-diisopropylsalicylato)Cr (III) as the catalyst. 

Catalysts speed up certain reactions in the chain extension of polyurethanes. The catalysts used are those made by specialty suppliers for the polymer industry and include a range of amines and metal salts. 

In the single-step system, the entire reaction takes place when all three basic components plus catalysts and pigments are mixed together. Careful use of catalysts enables the preparation of the prepolymer and the subsequent chain extension to take place in one step. As all the reactions are exothermic, heat is liberated and must be removed otherwise, part distortion will take place. 

The polyol, the chain extender, and any catalysts are mixed and stored as a separate item. The second item, the diisocyanate prepolymer, is kept as a "B" part until the material is ready for use. When the two parts are mixed, the chain extension and cross-linking take place simultaneously. Methylene diisocyanate and a catalyst such as an organic tin or bismuth salt provide the... 

Once the prepolymer and catalyst are added together, the chain extension (curing) reactions will commence. The time taken to mix must be carefully monitored. It must be sufficient to allow complete mixing, but there must be enough pot life left to allow pouring into the mold while the material is at the lowest viscosity possible. This is to allow the polyurethane to fill the mold completely and any entrapped bubbles to reach the surface. 

The original use of hydrosilylation [117] in semi-IPN formation is attributed to Arkles [118-120]. His approach was to mix two polysiloxanes with the thermoplastic. One contained hydride functions and the other vinyl functions. The subsequent introduction of a platinum catalyst induced crosslinking. Depending on the number of hybrid and vinyl functions per chain, either chain-extension or crosslinking was observed. As pointed out by Arkles [119], according to theory, these phenomena should be obtained for a 1 1 hydride vinyl group ratio, however, in practice the hydride functions were consumed by several side reactions so that a higher hydride ratio was required. 

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