Arylsulfonyl

Fluorosulfuric acid may be used to prepare diazonium fluorosulfates, ArN SO.F (44), which decompose on heating to give aryl (Ar) fluorosulfates (36,45). Aryl fluorosulfates are also obtained from arylsulfonyl chlorides and fluorosulfuric acid (35). Alkyl and other organofluorosulfates form during electrolysis of fluorosulfuric acid in the presence of organic species (46,47). 

Oligomers of phosgene, such as diphosgene [503-38-8] (COCl2)2, have found use in the laboratory preparation of isocyanates. Carbamoyl chlorides, A[,A/-disubstituted ureas, dimethyl- and diphenylcarbonates, and arylsulfonyl isocyanates have also been used to convert amines into urea intermediates, which are subsequendy pyroly2ed to yield isocyanates. These methods have found appHcations for preparation of low boiling point aUphatic isocyanates (2,9,17). 

Tetrazolin-5-one, l-arylsulfonyl-4-butyl-polymerization, 5, 838 Tetrazolin-5-one, 1-methyl-methylation, 5, 819 Tetrazolin-5-ones 1,4-disubs tituted synthesis, 5, 831 1-substituted alkylation, 5, 794 tautomerism, 5, 794 Tetrazolinyl radicals, 5, 801 1,2,3,4-Tetrazolium-5-aminide nomenclature, 1, 35... 

Cycloaddition reactions where bis(trifluoromethyl)-substituted hetero-1,3-dienes act as dienophiles have been descnbed for open-chain and cyclic dienes [115, 126, 127] The balance of the diene -dienophile activity of bis(tnfluoro-methyl)-substituted hetero-l,3-dienes can be influenced strongly by the substituents bonded to the inuno nitrogen atom For instance, A/-(arylsulfonyl) denvatives of tnfluoroacetaldimine and hexafluoroacetone imine do not act as dienes but exhibit only the dienophile reactivity of electron deficient imines [5 229, 234,235, 236 237] (equation 52)... 

Arylsulfonyl chlorides and enamines reacted to give sulfonated enamines (452,453,474). The latter could be hydrolyzed to the corresponding sulfonyl ketones. 

The accelerative effect of London forces of attraction between a nucleophile and nearby substituents has been investigated in quinoline and benzene derivatives by Bunnett and co-workers, ii7b, 307 In 2-, 4-, and 6-arylsulfonyl-3-nitrochlorobenzene, Loudon and Shulman found that arylmercaptide ion, presumably through this effect, displaced the arylsulfonyl group while methoxide or ammonia displaced the nitro or chloro group. 

In contrast to alkoxides, thiolates react with 3,4-bis(arylsulfonyl)furoxans to give both isomeric products 283 and 284 (Scheme 185) (96JHC327, 97JMC463). 

Treatment of l-arylsulfonyl-2-(l-iodoalkyl)piperidines 48 (R = H) with 2.7 equiv. of BusSnH in the presence of azobisisobutyronitrile (ABIN) furnished a mixture of 7,8,9,10,10u,ll-hexahydropyrido[l,2-ft][l,2]ben-zothiazine 5,5-dioxides 50, 2-benzylpiperidines 51 and l-arylsulfonyl-2-alkylpiperidines 52 in a radical process (Scheme 6) (77TL631,78JCS(CC)166, 80JCS(CC)142). The yield of 7,8,9,10,10u,ll-hexahydropyrido[l,2-6][l,2]... 

Acetyl-3-(perhydropyrido[l, 2-u]pyrazin-2-yl)-1 //-indole was deacety-lated in boiling MeOH in the presence of NaOH, and the product, 3-(perhydropyrido[l,2-u]pyrazin-2-yl)-l//-indole was N-acylated with different arylsulfonyl chloride in THF at 0°C in the presence of (Me3Si)2NNa (99MIP12, 01USP6251893)). 

Mass spectral data on l-(arylsulfonyl)-l//-azepines have been amassed,73 and the fragmentation patterns of several 1-acyl-1//-azepines elucidated.61 For the latter systems, the base peaks correspond to the azatropylium cation (m/z 92). Loss of hydrogen cyanide to yield the cyclo-pentadienyl cation (m/z 65) has also been noted. 

A comparison of the electron impact (El) and chemical ionization (Cl-methane) mass spectra of 1//-azepine-1-carboxylates and l-(arylsulfonyl)-l//-azepines reveals that in the El spectra at low temperature the azepines retain their 8 -electron ring structure prior to fragmentation, whereas the Cl spectra are complicated by high temperature thermal decompositions.90 It has been concluded that Cl mass spectrometry is not an efficient technique for studying azepines, and that there is no apparent correlation between the thermal and photo-induced rearrangements of 1//-azepines and their mass spectral behavior. 

The nitrene can be generated by a variety of methods, the most popular being the thermal or photolytic decomposition of azidoformates. Other methods, particularly the base-catalyzed a-elimination of arylsulfonate ion from 7V-[(arylsulfonyl)oxy]urethanes, are useful as they avoid the use of the potentially explosive azido esters. 

Early attempts to induce the thermal ring expansion of arenes with (arylsulfonyl)nitrenes were disappointing in that primary sulfonamides, formed by hydrogen abstraction by the singlet nitrene, and A-phenylsulfonamides, were the major products.157 l-(Arylsulfonyl)-l//-azepines were produced in low yields and were isolated only as their [4 + 2] eycloadducts with ethene-... 

Far superior yields of l-(arylsulfonyl)-l//-azepines 16 are now available by a one-pot synthesis involving the action of sodium azide on an arylsulfonyl chloride under solid-liquid phase-transfer conditions which prevents the formation of acidic sulfonamides and, hence, the ring-contraction process.75 This procedure also has the advantage of avoiding the use of high pressures and the isolation and handling of the potentially explosive sulfonyl azides. 

Arylsulfonyl)-l//-azepines 16 Using Solid-Liquid Phase-Transfer Conditions General Procedure 75... 

A mixture of the arylsulfonyl chloride (5 mmol), benzene (2.56 mol), NaN3 (5 mmol), NaHCO, (20 mmol), and methyltrioctylammonium chloride (0.5 mmol), under N2 in an autoclave, was stirred al 40 C for 3 h. The mixture was then heated slowly to 125 C and maintained at this temperature for another 3 h, during which time the pressure in the vessel rose to 31 -54 atm. The mixture was allowed to cool and the autoclave was depressurized. The residual mass was filtered, and the residue washed thoroughly with cold H20. The benzene solution was separated from the aqueous filtrate, dried, and evaporated to give the crude product as a reddish yellow mass which was purified by column chromatography (neutral alumina, hexane/ benzene 3 2). The 1-(arylsulfonyl)-l//-azepines 16 were crystallized from light petroleum ether (bp 60-80 LC). 

The use of neutral alumina rather than silica gel for the chromatographic separation of l-(arylsulfonyl)-l//-azepines is recommended as silica gel promotes rearrangement of the azepines to yV-(arylsulfonyl)anilines.62... 

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