New N-alkyl(trifluoromethyl)sulfonyl 1,4-benzoquinone monoimines were synthesized, and their thiocyanation gave 5-alkyl(trifluoromethyl)sulfonylamino-1,3-benzoxathiol-2-ones. An intermediate thiocyanation product, 5-trifluoromethylsulfonylamino-1,3-benzoxathiol-2-imine, was isolated for the first time. † Deceased. N-Substituted p-quinone imines were reported for the first time more than hundred years ago. Their N-aryl [1,2], N-acyl [3], N-arylsulfonyl [4][5][6][7], N-arylsulfanyl [8], N-arylsulfinyl [9], N-(N-arylsulfonylbenzimidoyl) [10], and N-arylaminocarbonyl derivatives [11] were synthesized and used for the preparation of various compounds possessing fungicidal, bactericidal [12], and anticancer activity [13], as well as of vulcanizing agents for rubber [14], corrosion inhibitors [15], and powerful dehydrating agents [16]. On the other hand, organic compounds with fluorine-containing substituents also find increasing application as medicines, pesticides, dyes, and monomers for heatresistant polymers [17].The reactivity of N-arylsulfonyl 1,4-benzoquinone monoimines was studied in sufficient detail. Their reactions with potassium thiocyanate [18-20], sodium arenesulfinates [7, 21, 22], sodium azide [7, 23], hydrogen halides [4, 24], halogens [25], aromatic amines [7, 26], phenols and naphthols [5, 27], dialkyl [7, 28, 29] and trialkyl phosphites [29, 30], aryl-and acylhydrazines [31], and alcohols [6,7,22,32] were studied. It was found that the size and electron-withdrawing power of the substituent on the nitrogen atom strongly affect the reactivity of N-substituted p-quinone imines [18][19][20][21][22].Adams and Looker [4] previously described the only representative of N-alkylsulfonyl 1,4-benzoquinone monoimines, N-methylsulfonyl-1,4-benzoquinone monoimine, whose reactivity was not studied. We previously presumed that superstrong electronwithdrawing substituents can be obtained by replacement of oxygen in various groups by an =NSO 2 CF 3 moiety [33]. With p-fluorobenzaldehyde as an example we showed that replacement of the carbonyl oxygen atom in the aldehyde group (CH=O is a mediumstrength electron-withdrawing group, σ p = 0.59) by =NSO 2 CF 3 gives CH=NSO 2 CF 3 (σ p = 1.00) which is a considerably stronger electron acceptor than nitro group (σ p = 0.78), and its strength approaches that of SO 2 CF 3 group (σ p = 1.04). Replacement of the oxygen atom in carboxylic acid azides, amides, and oximes by =NSO 2 CF 3 group made it possible to perform previously unknown rearrangements, such as aza-Curtius, aza-Hofmann, and aza-Lossen reactions [34]. We believed that replacement of oxygen atom in quinones by considerably more acceptor =NSO 2 CF 3 group, as in other cases, should give rise to unusual properties of N-trifluoromethylsulfonyl 1,4-benzoquinone monoimines.The goal of the present work was to synthesize new N-alkyl(trifluoromethyl)sulfonyl 1,4-benzoquinone monoimines, study their reactions with potassium thiocyanate, and compare the reactivities of N-arylsulfonyl, N-alkylsulfonyl, and N-trifluoromethylsu...

In reactions with sodium sulfi nates of N-substituted 1,4-benzoquinone monoimines with the quinoid ring having free positions 2 and/or 6 the fraction of products of 1,4-addition of the sulfi nate ion grows in the series ArSO 2 → MeSO 2 → CF 3 SO 2 . In the case of 2,6-dimethyl derivatives the 1,6-addition is preferable, and the amount of products of 6,1-addition decreases.

Depending on the reaction conditions N-arylsulfonyl-1,4-quinone imines with enamines led to the formation of the products of 1,4-addition, derivatives of benzo-and naphthofuran, indole, and benzindole.A multitude of publications describe the reactions of p-benzoquinone with enamines resulting in heterocyclic compounds: benzofuran (I) [1][2][3][4] or indole (II) [2, 3, 5-9] derivatives which are mostly biologically active substances [4,10,11]. The structure of the reaction products depends on the structure of initial compounds (it is the most strongly affected by the substituent at the nitrogen atom of the enamine) [2, 6, 8] and the conditions of the reaction [2,8,12].Several papers consider the reactions of N-arylsulfonyl-1,4-quinone imines with enamines, in particular, with imines of acetylacetone and ethyl 3-arylaminocrotonates [13][14][15][16]. The reaction of N-tosyl-1,4-benzoquinone imine with acetylacetone imine in methanol or acetic acid resulted in a heterocyclic derivative (I, X = TsNH, R 1 = COMe, R 2 = Me) [15,16], in acetone another structure was obtained (II, X = TsNH, R 1 = COMe, R 2 = Me, Y = 4-MeC 6 H 4 ) [16]. In reactions of N-tosyl-1,4-benzoquinone imine with esters of 3-arylaminocrotonic X O R 2 R 1 X N R 2 R 1 Y I II acid in chloroform or acetone only indole derivatives were obtained (II, X = TsNH, R 1 = COOEt, R 2 = Me, Y = 4-MeC 6 H 4 , Ph, 4-MeOC 6 H 4 ) [13, 14, 16], N-tosyl-1,4-naphthoquinone imine in acetone formed only the open-chain product of 1,4-addition [17]. The formation of indole derivatives is favored by the presence of an aryl substituent at the nitrogen atom of the enamine [13].Benzofuran derivatives were obtained at the hydrolysis of the addition products of the esters of 3-alkyl-and 3-arylaminocrotonic acids [18,19] to N-tosyl-1,4-benzoquinone monoimine. No research concerned the effect on the direction of this reaction of the substituents in the quinoid ring of the N-arylsulfonyl-1,4-quinone imines. It was formerly established that in the reactions of p-benzoquinone with enamines the substituents in the quinoid ring govern the direction of this reaction [4,6,7,9]. The goal of this study was the establishment of the effect of the reaction condition and the structure of Narylsulfonyl-1,4-quinone imines, in particular, of the position and the character of the substituent in the quinoid ring, on the direction of their reactions with the acetylacetone imine and the esters of 3-arylaminocrotonic acid .The reaction of N-arylsulfonyl-1,4-benzoquinone monoimines IIIа-IIIo with p-tolylaminopent-3-en-2-one (IVа) and esters of 3-arylaminocrotonic acid IVb, IVc was carried out in acetone, acetic acid, dichloroethane,

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Depending on the conditions and the order of addition of the reactants, reactions of N-sulfonyl-1,4benzoquinone imines with sodium azide afforded N-(3-azido-4-hydroxyphenyl)alkane(arene)sulfonamides, N-(3-azido-4-oxocyclohexa-2,5-dienylidene)alkane(arene)sulfonamides, and N-(3,5-diazido-4-hydroxyphenyl)alkanesulfonamides. Quantum chemical calculations showed that the reactions begin with addition of azide ion to the quinone imine.We previously synthesized new N-alkyl(trifluoromethyl)sulfonyl derivatives of 1,4-benzoquinone imine [1] and studied their reactivity toward potassium thiocyanate [1] and sodium arenesulfinates [2]. In the present work we examined reactions of these compounds with sodium azide.