Polystyrene azide

In addition to acyl chloride functionalized NTs, the covalent grafting to of polymers onto NTs has been carried out for other reactions. A polystyrene azide (PSt-Ns) with a designed molecular weight and a narrow molecular weight distribution was synthesized by atom transfer radical polymerization of styrene followed by end group transformation and then added to SWNTs via a cycloaddition reaction (Scheme 12.4) [45]. 

Several studies have demonstrated the successful incoriDoration of [60]fullerene into polymeric stmctures by following two general concepts (i) in-chain addition, so called pearl necklace type polymers or (ii) on-chain addition pendant polymers. Pendant copolymers emerge predominantly from the controlled mono- and multiple functionalization of the fullerene core with different amine-, azide-, ethylene propylene terjDolymer, polystyrene, poly(oxyethylene) and poly(oxypropylene) precursors [63,64,65,66,62 and 66]. On the other hand, (-CggPd-) polymers of the pearl necklace type were fonned via the periodic linkage of [60]fullerene and Pd monomer units after their initial reaction with thep-xy y ene diradical [69,70 and 71]. 

Gun Propellents. Low sensitivity gun propeUants, often referred to as LOVA (low vulnerabUity ammunition), use RDX or HMX as the principal energy components, and desensitizing binders such as ceUulose acetate butyrate or thermoplastic elastomers (TPE) including poly acetal—polyurethane block copolymers, polystyrene—polyacrjiate copolymers, and glycidyl azide polymers (GAP) to provide the required mechanical... 

A polymer bound arenesulfonyl azide can be prepared from polystyrene.138... 

There are a number of other reactions that can be used cycloaddition of an azide group allowed binding of polystyrene [43], while a radical coupling was exploited to graft polymers prepared by a nitroxide-mediated radical polymerization [121]. Other end groups could be used it was shown above how amide bonds were utilized to attach water-soluble polymers amino or hydroxyl moieties are other conventional groups. 

Sodium azide is a powerful inhibitor of HRP, but sodium azide can be used with alkaline phosphatase conjugated antibodies without harmful effects. In addition, tap water or water deionized with polystyrene resins may inactivate the enzyme conjugate. Only use distilled, deionized water Tween-20 may interfere with some antibody-antibody reactions or may wash the protein of interest off the membrane. Tween-20 may be left out of the washes, but this may result in increased background... 

Tab. 5.2 Comparative Staudinger reactions using 19 and polystyrene-PPhs with the listed azides.

Amines have been prepared on insoluble supports by Hofmann degradation of amides [222] followed by hydrolysis of the intermediate isocyanates (Figure 10.5). One reagent suitable for this purpose is [bis(trifluoroacetoxy)iodo]benzene, which can be used both on cross-linked polystyrene [223] and on more hydrophilic supports such as polyacrylamides (Figure 10.6). Support-bound carboxylic acids can also be degraded via the acyl azides (Curtius degradation [224,225]) to yield isocyanates. 

Diazocarbonyl compounds can be prepared on insoluble supports by diazo group transfer with sulfonyl azides or by diazotization of primary amines. Diazo group transfer from sulfonyl azides to 1,3-dicarbonyl compounds proceeds on cross-linked polystyrene as smoothly as in solution (Table 10.19). When 3-keto esters or amides are... 

The multicomponent Ugi-type condensation of aldehydes, secondary amines, azide, and polystyrene-bound isonitriles has been reported to yield tetrazoles in acceptable yields (Entry 9, Table 15.20). Tetrazoles have also been prepared from... 

Aube and co-workers have found that enolizable ketones react with benzyl azide in triflic acid to yield /V-(phenylamino)-methylated products [Eq. (5.354)]. The transformation is an aza-Mannich reaction interpreted with the involvement of the Mannich reagent A -phenyl iminium ion 295 formed in situ in a Schmidt rearrangement. Cyclic tertiary alcohols react with alkyl azides in triflic acid to yield N-alkylamines (296, 297)983 [Eq. (5.355)]. The Schmidt rearrangement was used to transform Merrifield resin into amino-polystyrene resin by reacting the azido derivative in excess triflic acid (CH2CI2, 0°C).984... 

Takahashi et al.45 used a 4-hydroxybenzenesulfonate linker on Syn-Phase polystyrene Crowns to prepare glucose derivatives and macrocycles (Scheme 20). Displacement of the monosaccharide-supported Crowns 70 with nucleophiles such as azide, iodide, and acetate gave the respective 6-substituted glucose derivatives 71, 72, and 73 in excellent purities and yields. The authors suggest that this methodology could be utilized for the preparation of oligosaccharide libraries. 

PS-TsNHNH2, polystyrene-bound tosylhydrazine PS-NCO, polystyrene-bound isocyanate QC, quality control RPR, Rhone-Poulenc Rorer RT, room temperature TBAF, tetrabutylammonium fluoride TFA, trifluoroacetic acid TFP, tetrafluorophenol THF, tetrahydrofuran TMSN3, trimethylsilyl azide TOF, time of flight mass spectrometry TsNHNH2, p-toluenesulfonylhydrazine UDC, Ugi/DeBoc/Cyclize Wang, 4-(hydroxy-methyl)phenoxy polystyrene. 

A dry packed column with porous material was used for the characterization according to size of the PVAc latex samples. The packing employed was CPG (Controlled Pore Glass), 2000 A, 200-400 mesh size. Deionized water with 0.8 gr/lit Aerosol O.T. (dioctyl sodium sulphosuccinate), 0.8 gr/lit sodium nitrate and 0.4 gr/lit sodium azide served as the carrier fluid under a constant flowrate. The sample loop volume was 10 pC A Beckman UV detector operating at 254 nm was connected at the column outlet to monitor particle size. A particle size-mean retention volume calibration curve was constructed from commercially available polystyrene standards. For reasons of comparison, the samples previously characterized by turbidity spectra were also characterized by SEC. A number of injections were repeated to check for the reproducibility of the method. 

Polystyrene resin-bound azide 186 reacted with disubstitutcd alkynes via l,3 dipolar cycloaddition followed by acidic cleavage to give 1,2,3-triazoles 187 <03JCO826>,... 

Green, G. M., Peet, N. P., Metz, W. A. Polystyrene-Supported Benzenesulfonyl Azide A Diazo Transfer Reagent That Is Both Efficient and Safe. J. Org. Chem. 2001, 66, 2509-2511. 

Transformation into azide groups was achieved for polystyrene, poly(MA), and poly(nBA) with the use of sodium azide (EC-18)351 353 or trimethylsilyl azide (EC-19)161-351-354 in the presence of tetrabutylammo-nium fluoride. The azide groups can be further converted into amino (— NH2) groups by treatment with PPh3/H20351 or LiAlH4.354 The reaction between the azide end group in polystyrene and Ceo was also examined.353... 

The same reaction was performed by using polystyrene-supported hydroxyproline 37.2 yhe solid catalyst 41 was prepared according to the procedure depicted in Scheme 3.12 by 1,3-dipolar cycloaddition of the azide-substituted Merrifield resin 40 with the O-propargyl hydroxyproline 38, which in turn was synthesized by a well-established method. 

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