Sulfonyl chloride resin

A-Methylimidazole (22.5 /il) was added to a mixture of Fmoc-glycinol (20.0 mg, 0.07 mmol), Fmoc-glycine (27.3 mg, 1.3 equiv.), and polystyryl-sulfonyl chloride resin (61.6 mg, 1.3 equiv., 1.49 mmol/g) in dichloro-methane (1 ml). After 2 h, aminomethylated PS-resin (138 mg, 2 equiv.) was added and the suspension shaken for 30 min. After filtration through a fritted filter, the resin was rinsed thoroughly with dichloromethane, and the combined solvents were concentrated to 3 ml. Amberlyte 15 (176 mg) was added and the suspension was shaken again for 30 min and filtered as described above. After evaporation of the solvent, the pure product was obtained as a colorless foam 93 % yield. 

In related work, solid-phase-mediated synthesis of isonitriles from formamides was achieved by using polystyrene-bound sulfonyl chloride as a suitable supported reagent [115]. The sulfonyl chloride resin could be quantitatively regenerated by treatment of the sulfonic acid resin formed with phosphorus pentachloride (PCI5) in N,N-dimethy]formamide at room temperature. 

Materials DNQ was synthesized by esterification of o-cresol formaldehyde novolac resin (Mw=900) and of l,2-diazonaphthoquinone-5-sulfonyl chloride. The esterification rate was ca. 0.4. The novolac-based resist used in EB lithography to compare with SPP was... 

These hydroxyl groups in polymers are also usually determined by acetylation [9,21] or bromination [23]. However, it should be noted that acetylation with acid anhydrides and acyl chlorides that only total hydroxyl groups in these resins can be determined [7], Aromatic sulfonyl chlorides, however, react selectively with phenolic hydroxyls [26]. 

Several resins have been used frequently in reactant sequestration. Ami-nomethylpolystyrene 1 and the more highly functionalized polyamine resins 2 and 3 have been reported to sequester excesses of solution-phase electrophiles, including isocyanates, isothiocyanates, sulfonyl chlorides, acid chlorides, anhydrides, aldehydes, and imines. Cross-site reactivity is not an issue with the more densely functionalized sequestering resins so their use in an automated laboratory environment offers a significant resin and volume economy compared to less densely functionalized resins. 

For each sulfonyl chloride, 500 MicroKans were placed into either a 2- or 3-liter three-necked round-bottom flask fitted with an overhead stirrer. The resin was swelled in anhydrous DCM (600 ml). NMM (5.5 ml, 50.0 mmol) and the sulfonyl chloride (50.0 mmol) were then added sequentially. The reaction was stirred overnight at RT. For workup, each reaction was individually drained and washed with DMF. All of the MicroKans were then combined and washed with DMF, THF, DCM, and Et20. The MicroKans were then dried overnight with a stream of nitrogen gas. 

The reaction of TFP resin with sulfonyl chlorides (3 equiv.) in the presence of diisopropylamine (DIEA 3 equiv.) provides the corresponding sulfonate-activated resins (Fig. 2). Alternatively, sulfonic acids may be loaded directly onto TFP using DIC (via the intermediate sulfonic acid anhydride) as the coupling reagent. Analogous to the carboxylate esters, the sulfonate ester resins are stable when dry and may be kept at room temperature for an extended period of time without decomposition. This is one of the clear advantages of the polymeric TFP reagents versus acid chlorides the latter decompose once exposed to air and moisture. 

Generate TFP reagents Load carboxylic acid and sulfonyl chloride building blocks to TFP resin... 

Procedure. TFP resin was added to a 100-ml polypropylene reaction vial. The resin was swelled with DMF (20 ml) for 15 min. Diisopropylamine (DIEA) was added followed by a solution of a sulfonyl chloride building block previously dissolved in DMF (10 ml). The reaction mixture was gently agitated for 3 h and filtered, and the resin was washed with DMF (3 x 30ml) and DCM (3 x 30ml), and dried in vacuo for 12h at 25°. 

Polymer-supported sulfonyl chloride 14 as a capture-release resin. 

---