NAPHTHALENESULFONYL CHLORIDE

Numerous aryl bromides, iodides [203], borates [204] and triflates [205, 206] have been successfully carbonylated. Triflates could serve as a route for the synthesis of arenecarboxylic acid derivatives from phenols. This carbonylation using dppf in a catalytic mixture generally shows higher efficiency than PPhj or P(o-Tol)3 [207]. Poor performance is also noted for PPhj in a Pd-catalyzed vinyl substitution of aryl bromides [208]. Side-reactions involving the formation of [PPhjAr]Br and ArH are responsible. A system which is catalyzed effectively by PdCljfdppf) under 10 atm CO is the desulfonylation of 1-naphthalenesulfonyl chloride 58 in the presence of Ti(OiPr)4. Formation of isopropyl 1-naphthoate 59 can be explained in a sequence of oxidative addition, SOj extrusion, carbonylation and reductive elimination (Fig. 1-27) [209]. A notable side-product is di-l-naphthyl disulfide. 

Mono-altro-/ -CyD was selectively sulfonylated by 2-naphthalenesulfonyl chloride at the 2A-0H of the altrose residue. By using 1-naphthalenesulfonyl chloride as reactant, the 3G-OH of the neighboring glucose became available for selective sul-fonylation [95]. Secondary imidazole-appended fi-CyD, with a nondistorted cavity built of glucoside units synthesized from the novel intermediate 3-amino-) -CyD, exhibits much greater catalytic activity in ester hydrolysis than its isomer with the distorted cavity obtained from altroside units [96]. 

A mixture of 1-naphthalenesulfonyl chloride, /i-butyl acrylate, K2CO3, and catalytic amounts of bis(benzonitrile)dichloropalladium(II) and benzyltrioctylammonium chloride in m-xylene stirred at 140° for 4 h under N2 butyl 3-(l-naphthyl)-2-prope-noate. Y 90%. F.e.s. M. Miura et al.. Tetrahedron Letters 30, 975-6 (1989). 

Zinc iodide catalysts are also known. Desulfonylative iodination of naphthalenesulfonyl chlorides has been carried out by treatment with zinc iodide in the presence of a palladium(II) catalyst.642... 

Reagents. NaCl (Spectrum Chemical Co.) was fired 4 h at 550 °C in a muffle furnace to remove trace organic contaminants. Acetonitrile (HPLC grade J. T. Baker), dichloromethane (Burdick and Jackson), 5-dimethylamino-l-naphthalenesulfonyl chloride (dansyl chloride Aldrich), O-p-nitrobenzyl-N,N -diisopropylisourea (PNBDI Regis), and N-succinimidyl-p-nitrophenyl acetate (SNPA Regis) were used as purchased. 

Tosyl chloride 2-Naphthalenesulfonyl chloride Penta 6 9 Hexa 6 78 Hexa 6 32 321 321... 

Examples of other AB monomers have been polymerized to yield polysul-fones are the following a-naphthalenesulfonyl chloride, p-thiophenoxy-benzenesulfonyl chloride, p-phenylbenzenesulfonyl chloride, and 2-di-benzofuransulfonyl chloride [131]. 

SYNS 1 -CHLOROSULFONYL-5-DIMETHYL-AMINONAPHTHALENE DANSYL DANSYL CHLORIDE DIMETHYLAMINONAPHTHALENE-SULFONYL CHLORIDE 1-DIMETHYLAAIINO-NAPHTHALENE-5-SULFONYL CHLORIDE 1-piMETHYXAMINO)-5-NAPHTHALENESULFONYL-CHLORIDE 5-DIMETHYLAMINONAPHTHYL-5-SL LFONYL CHLORIDE... 

Naphthalenesulfonyl chloride, m.p. 76°, is prepared in similar manner and 73% yield from 2 kg. of sodium )3-naphthalenesulfonate. 

A mixture of 80 g. (0.35 mole) of )8-naphthalenesulfonyl chloride (p. 208), 400 ml. of ethanol, and 2 ml. of concentrated hydrochloric acid is stirred while 70 g. (1.07 gram atoms) of zinc dust is added in small portions. The temperature of the mixture is held at 40 or below. The mixture is stirred for 30-45 minutes, with the same temperature control, after completion of the addition. The resulting mixture is warmed slowly while a second portion of 70 g. (1.07 gram atoms) of zinc dust is added this is followed by 100 ml. of concen-... 

Sample preparation Dissolve 20 mg neomycin sulfate powder in 100 mL 100 mM pH 8.0 sodium phosphate buffer. Remove a 10 mL aliquot and add it to 10 mL 40 mg/mL 2-naphthalenesulfonyl chloride in MeCN (prepare fresh daily), shake briefly, heat at 100-105° for 10 min, cool to room temperature, add 15 mL IS solution, shake vigorously for 10 min, centrifuge at <300 g for 3-5 min, inject a 50 p,L aliquot of the lower organic layer. (Prepare IS solution by dissolving 2 mg prednisolone in a small amount of THF, make up to 100 mL with chloroform.)... 

Fluorescence was to study the reaction of 5-dimethyl-amino-l-naphthalenesulfonyl chloride (dansyl chloride) with butylamine in ethyl acetate and chloroform at 60° and 40 °C, respectively. This study was conducted in the presence of polystyrene and polyoxyethylene (POE) as cosolvents as well as their respective low-molecular weight analogues, namely toluene and diethyloxyethane, respectively [180]. 

Tsuji, K. Jenkins, K.M. Derivatization of primary amines by 2-naphthalenesulfonyl chloride for high-performance liquid chromatographic assay of neomycin sulfate. J.Chromatogr, 1986, 369, 105-115... 

We found that 2-naphthalenesulfonyl chloride is better than p-toluene-sulfonyl chloride in respect of lowering the amounts of di- and tri-substituted by-products. Purification of the crude products was performed by recrystallization from water or a mixed solvent of n-butanol, ethanol and water and/or chromatography with Sephadex G-15. 

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