2,4,6-Trinitrobenzenesulfonate salts

Trinitrobenzenesulfonic Acid(called Pikryl sulfonylsaure in Ger), (O2N)3C6H2.S03H mw 293-17, N 14.33% crysts of the trihydrate, mp-sinter ca 100° and the anhyd acid melts ca 185° sol in w, ale eth diffc sol in chlf insol in benz. Can be prepd by heating an ale soln of picryl chloride with an excess of Na sulfite. Its expl props were not investigated. The Sodium salt,... 

This facile preparation is suitable for preparation of larger amounts of salt Like triethyloxonium fluoborate,2 trimethyloxonium fluoborate is a potent alkylating agent. In comparison with trimethyloxonium 2,4,6-trinitrobenzenesulfonate,5trimethyl-oxonium fluoborate is easier to make but does not keep quite as well on storage. 

Trinitrobenzenesulfonic acid (14.7 g., 0.050 mole) (Note 2), previously dried for at least 1 hour at 80-100° (1 mm.), is placed in flask B, which is then immersed to the level shown in Fig. 2 in a bath of acetone maintained at —35° to —40° by addition of small amounts of dry ice (Note 3). About 200 ml. of dimethyl ether is rapidly poured from an ampoule into flask B (Note 3). Flasks A and B are connected as shown in Fig. 2, and magnetic stirring is started in flask B. When most of the sulfonic acid has dissolved, gaseous dimethyl ether is introduced through C at such a rate that a rapid stream of individual bubbles passes through the diazomethane solution in flask A. In the course of the reaction all the acid goes into soution and is replaced by a fluffy precipitate of the oxonium salt. The introduction of dimethyl ether is discontinued as soon as the supernatant solution in flask B turns yellow (Notes 5 and 6). 

This method for the preparation of trimethyloxonium 2,4,6-trinitrobenzenesulfonate is an adaptation of that described by the submitters.7 The salt can also be prepared from trimethyloxonium fluoborate by anion exchange.7 Trimethyloxonium fluoborate and hexachloroantimonate9-11 have been prepared by other methods. 

Trimethyloxonium 2,4,6-trinitrobenzenesulfonate [1, 1232-1233, before reference]. This stable alkylating agent is prepared by the method cited1 and also by reaction of the acid with trimethyloxonium fluorohorate (71-76% yield).2 The salt can be kept... 

When supramolecular polymers are treated with bulky stopper groups, they may form poly[2]rotaxane daisy chains [45-53]. Harada et al. [31] treated 6-p-aminoCiO-a-CD (40 mM) with 2M excess 2,4,6-trinitrobenzenesulfonic acid sodium salt (TNBS) as bulky stoppers in aqueous solutions. The resulting precipitate was found to be mainly a cyclic trimer by H NMR and TOF mass spectra. After purification of the crude product, the 2D ROESY spectrum of the cyclic trimer shows cross-peaks between phenyl protons close to an amino group and secondary hydroxyl groups (0(2)H). A trinitrophenyl group is found at the secondary hydroxyl group side. A proposed structure of a cyclic trimer (cyclic daisy chain) is shown in Fig. 3.12. Kaneda et al. [38] reported the preparation of cyclic di[2]rota-xane fashion constructed tail-to-tail by azobenzene derivatives of permethylated a-CDs and showed its computer-generated supramolecular structures (Fig. 3.13). Easton et al. [39] also reported the preparation of cyclic di[2]rotaxane constructed by stilbene-appended a-CDs in tail-to-tail fashion (Fig. 3.14). Kaneda et al. [40]... 

Trialkyloxonium 2,4,6 trinitrobenzenesulfonate Thiosnlfonium salts from disulfides... 

Trinitrobenzenesulfonic acid Stereospecific formation of glycols from oxido compds. via l-hydroxy-2-(alkoxysulfonium) salts... 

A soln. of cw-9,10-epoxystearic acid in benzene added dropwise with stirring during 10 min. to a soln. of 2,4,6-trinitrobenzenesulfonic acid in anhydrous dimethyl sulfoxide, stirring continued 15 min., stirred into excess cold ether-ethyl acetate (2 1), the solvent layer decanted, and the oily lower layer stirred 12-14 hrs. with water /hreo-9,10-dihydroxystearic acid. Y 65-70%. Also erythro- from trans-isomer, and prepn. of f. l-hydroxy-2-(alkoxysulfonium) salts, s. M. A. Khud-dus and D. Swern, Tetrah. Let. 1971, 411. 

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