Tosyl perchlorate

Tosylhydrazones, 1051 l-0-Tosyl-(— >inositol, 67, 68 Tosyl perchlorate, 1187-1188 Transacetalation, 1118 Transnitrosatian, 741 Trdialose, 664... 

Tosyl perchlorate. P CH CfHqSOi ClOq, Mol. wt. 254.60. The reagent is prepared in nilromethane aolullon by reaction of tosyl bromide with silver perchlorate at 0. II Is a powerful sulfonatlon reagent which reads with even the relatively inert halofaencenes to il vt lulfonos. ... 

Excess phenetol added at 0° to tosyl perchlorate in nitromethane, and allowed to stand 2 hrs. at room temp. 4-methyl-4 -ethoxydiphenyl sulfone. Y 85.5%. — Tosyl perchlorate is the strongest sulfonation agent yet known. F. e. s. F.Klages and F.E.Malecki, A. 691, 15 (1966). 

Reactions with tosyl perchlorate, the strongest sulfonation agent yet known, have been reported. It easily converts even less susceptible benzene derivatives, such as monohalogenobenzenes, into sulfones... 

In the reaction with enamino ketones derived from dimedone (e.g., 49) p-toluenesulfonyl chloride gives the chloroiminium cation (138) isolated as the perchlorate. This indicates that initial O sulfonation is followed by addition of chloride ion and subsequent expulsion of tosylate (42) in a manner similar to the trichloroacetyl chloride reaction with 49 (Section IV.A). 

Use of the perchlorate salt gives a cleaner product than the tosylate, but is more hazardous. 

Treatment of 2-benzoylpyridine 81 with p-toluene-sulfonamide gave 1-amino-2-benzoylpyridinium tosylate 82 (X = OTs), which was cyclized with formamide in the presence of triethylamine hydrobromide to give 83 (82FRP2486942). The reaction of the perchlorate 82 (X = C104) with urea in polyphosphoric acid afforded 3-hydroxy-l-phenylpyrido[2,l-/][l,2,4]triazinium perchlorate 84. Treatment of this salt with base led to the zwitterionic l-phenylpyrido[2,l-/][l,2,4]triazin-5-ium-3-olate 85 (86JHC375). Pharmaceutical compositions contain 83 (82FRP2486942). 

Interestingly, the acetoxyl group in the product comes not from acetic acid (a solvent) but from acetate ion (a conducting electrolyte)—salts with tosylate or perchlorate anions stop acetoxylation in the solution of acetic acid. 

Amino-3,5-dimethylisoxazole (372, R = H) gave an iV-tosyl derivative (372, R = tosyl), which by treatment with methyl fluorosulfonate followed by perchloric acid gave the salt 371, R = R = R = Me, R = tosyl, X = C104. Attempts to isolate the meso-ionic sul-fonamidate (370, R = R = R = Me, R = tosyl) by treatment of the salt with potassium hydroxide or triethylamine were unsuccessful, but spectroscopic evidence for its formation in solution has been offered. 

The model polypeptide acetyltetraglycine ethyl ester (ATGEE) behaves in this manner. Citrates, sulfates, phosphates, acetates, and chlorides salt out ATGEE whereas phenol, perchlorates, tosylates, trichloroacetates, thiocyanates, iodides, and bromides salt in (8). The heat denaturation of ribonuclease also fits this cTass. 

Even more scrambling was found in trifluoroacetolysis of l-propyl-l-14C-mercuric perchlorate.25 However, protonated cyclopropane intermediates accounted for less than 1% of the products from diazotization of labeled isobutylamine26 and from formolysis of labeled 1-propyl tosylate.27... 

Another method of preparing azobisindolizines is by reaction with tosyl or picryl azide.191-193 2-Methylindolizine is converted into the 3,3 -bisazo compound after 2 minutes. The product yields the radical ion 130 (detected by EPR) when treated with 1 mole of silver perchlorate.194,195 The redox characteristics of such compounds have been studied by Hiinig and co-workers.196,197 In view of the instability of aminoindolizines, they have not been used to prepare diazonium salts. 1-Nitrosoindolizines, however, yield diazonium nitrates in good yield when treated with dry nitric oxide.182,198 The products are stable both in... 

The anode acetoxylation of aromatic compounds in solutions of acetic acid carrying alkali or tetraalkylammonium acetates takes the same route. As shown (Eberson 1967 Eberson Jonsson 1981), the process starts with one-electron oxidation at the anode and then passes through the same stages as on oxidation with cobalt trifluoroacetate. The reaction takes place at potentials sufficient to oxidize the substrate but not sufficient to convert the acetate ion into the acetoxy radical. Interestingly, the acetoxyl group comes to the product not from acetic acid (a solvent) but from the acetate ion (a conducting electrolyte) Salts with the tosylate or perchlorate anions stop the acetoxylation in the solution of acetic acid. 

The reagent is prepared in 67.7% yield by the reaction of N-methylpyrrolidinc with tosyl chloride in Ihc presence of silver perchlorate in the dark. ... 

In bmim BF4 and CIO4 l-butyl-3-methylimidazolium tetrafluoroborate and perchlorate Fischer, T. Sethi, A. Welton, T. Woolf, J. Tetrahedron Lett. 1999, 40, 793. In chloroaluminates Lee, C.W. Tetrahedron Lett 1999, 40, 2461. In phosphonium tosylates Ludley, P Karodia, N. Tetrahedron Lett. 2001, 42, 2011. In pyridinium salts Xiao, Y MaUiotra, S.V. Tetrahedron Lett. 2004, 45, 8339. In HBuIm, hydrogenbutylimidazolium tetrafluoroborate and DiBuIm, 1,3-dibutylimidazolium, tetrafluoroborate Jaegar, D. A. Tucker, C. E. Tetrahedron Lett. 1989, 30, 1785. 

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