ChemInform Abstract: Reaction of N‐(p‐Tolyl)‐1,4‐benzoquinonemonoimine with Thiocyanic Acid.

Burmistrov, K. S.; Toropin, N. V.; Burmistrov, S. I.; Nichvoloda, V. M.

doi:10.1002/chin.199342146

Cited by 9 publications

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“…In this case the content of the products of the 1,6-and 6,1-addition reached 44 (IXc), 59 (IXd) and 56 (VIIc), 41% (VIId). The same products ratios were previously observed for N-arylsulfonyl analogs [49-52 (1,6-) and 48-51% (6,1-)] [10,11]. With N-trifl uoromethylsulfonyl derivative IIh complex mixtures of compounds were obtained whose composition we failed to determine.…”

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confidence: 64%

“…The characteristics of compounds Iа-Ig, IIа-IIg are in agreement with those published in [3], of compound Ih, in [10]. Sodium sulfi nates IIIа-IIIe were obtained by procedure [24], reagent IIIf, by method [25].…”

Section: Methodsmentioning

confidence: 95%

“…N-Methyl(trifl uoromethyl)sulfonyl-1,4-benzoquinone monoimines Ia-Ii, IIa-IIi were synthesized by procedures described in [3,10]. The results of reactions between benzoquinone monoimines Ia-If, IIa-IIf and sodium sulfi nates IIIa-IIIf are presented in Scheme 1.…”

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confidence: 99%

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Reactions of N-aryl(methyl, trifluoromethyl)sulfonyl-1,4-benzoquinone monoimines with sodium sulfinates

et al. 2012

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confidence: 64%

Section: Methodsmentioning

confidence: 95%

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Reactions of N-aryl(methyl, trifluoromethyl)sulfonyl-1,4-benzoquinone monoimines with sodium sulfinates

et al. 2012

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“…N-arylsulfonyl analogs [5]; no reduction of the latter was observed previously [2]. By contrast, the bromination of N,N′-bis(arylsulfonyl)-1,4-benzoquinone diimines was accompanied by reduction process [6], for their redox potentials are considerably higher than those of the corresponding quinone monoimines [7].…”

Section: The Bromination Of Quinone Imines I-iii Afforded N-(3-bromo-mentioning

confidence: 97%

Halogenation of N-substituted p-quinone monoimines and p-quinone monooxime esters: X. Halogenation of N-aroyl-2,5(2,3)-dialkyl-1,4-benzoquinone monoimines and their reduction products

2009

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Introduction of a strong electron-withdrawing substituent to the nitrogen atom of 2,5(2,3)-dialkyl-1,4-benzoquinone imines makes their halogenation products, the corresponding cyclohexene derivatives, very unstable and favors halogenation of methyl groups in the quinoid ring. Bromination of 4-amino-N-aroyl-2,5-dialkyl-6-bromophenols gave 2,5-dialkyl-6-benzoyloxy-3,5-dibromocyclohex-2-ene-1,4-diones. * For communication IX, see [1].We previously examined halogenation of N-arylsulfonyl-2,5-dialkyl-1,4-benzoquinone imines [2] and found that the main factors determining the direction of addition of halogen molecule are the size of substituents in the quinoid ring and the size of the halogen atom. The presence of a strong electron-withdrawing substituent on the nitrogen atom, in particular aroyl group, also considerably affects the halogenation process [1, 3,4]. Halogenation of N-aroyl-2,5(2,3)-dialkylsubstituted 1,4-benzoquinone imines and their reduction products, N-aroyl-2,5(2,3)-dialkyl-4-aminophenols was not reported previously.The goal of the present work was to study halogenation of N-aroyl-2,5(2,3)-dialkyl-1,4-benzoquinone imines, elucidate specific features of the halogenation process, and compare these reactions with halogenation of the corresponding N-arylsulfonyl derivatives. As substrates we used N-aroyl-1,4-benzoquinone imines which, like N-arylsulfonyl derivatives studied previously [2], contained different alkyl substituents (i-Pr, Me) in positions 2 and 5 of the quinoid ring: N-aroyl-2,5-dimethyl-, -2-isopropyl-5-methyl-, and -5-isopropyl-2-methyl-1,4-benzoquinone imines Ia-Ic, IIa-IIc, and IIIa-IIIc, and their reduction products, 4-amino-N-aroyl-2,5-dimethyl-, 2-isopropyl-5-methyl-, and -5-isopropyl-2-methylphenols IVa-IVc, Va-Vc, and VIa-VIc.Due to the presence of a methyl or isopropyl group in the ortho position with respect to the imino nitrogen atom, quinone imines I-III in solution exist as a single isomer, which is confirmed by the 1 H NMR data. In the 1 H NMR spectra of N-aroyl-2,5-dialkyl-1,4-benzoquinone imines, differences in the chemical shifts of protons in the quinoid ring were considerably smaller than those observed for analogous N-arylsulfonyl derivatives; therefore, assignment of signals in the spectra of compounds I-III was more difficult. The 3-H proton in I-III resonated in the 1 H NMR spectra in the region δ 6.58-6.66 ppm, while the 6-H signal was located at δ 6.44-6.59 ppm; the corresponding signals of N-arylsulfonyl derivatives appeared in the regions δ 7.89-7.96 and 6.50-6.64 ppm, respectively [2]. N-Aroyl-2,5-dialkyl-1,4-benzoquinone imines I-IIIwere synthesized by oxidation of the corresponding aminophenols IV-VI with lead tetraacetate in acetic acid. The chlorination of quinone imines I-III and aminophenols IV-VI was performed using gaseous chlorine, and the bromination was carried out with molecular bromine in CHCl 3 , AcOH, DMF, or DMFAcOH (1 : 5) at different substrate-to-reagent ratios under different temperature conditions. The results are given in Scheme 1. Unlike N-a...

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“…We have found only one early publication on the synthesis of N-formylarenesulfonamides ArSO 2 NHCHO by reaction of arenesulfonamide sodium salts ArSO 2 NHNa with formic acid esters HCOOR [7]. Diformyl derivatives of sulfonamides were not reported previously.…”

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confidence: 94%

N,N-diformyltrifluoromethanesulfonamide

Shainyan

Meshcheryakov

2011

Russ J Org Chem

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SHORT COMMUNICATIONSIn continuation of our studies on trifluoromethylsulfonyl derivatives of azoles [1][2][3] we made an attempt to perform cross coupling of trifluoromethanesulfonamide with 4,5-dibromo-1,2,3-triazole by analogy with copper(I) iodide-catalyzed amidation of aryl bromides with 2,2,2-trifluoroacetamide [4]. However, targeted N,N′-bis(trifluoromethylsulfonyl)-2H-1,2,3-triazole-4,5-diamine was not formed, but the reaction in formamide unexpectedly produced 4,5-dibromo-1-methyl-1H-1,2,3-triazole (I) and N,N-diformyltrifluoromethanesulfonamide (II) (Scheme 1). of the aldehyde group in intermediate III with formamide on heating (Scheme 2), by analogy with the reduction with formamide of a nitro group [6]. dicyclohexano-18-crown-6 110-120°C, 5-6 h N N N Br Br + CF 3 SO 2 Me N CHO CHO I I I NH N N Br Br + CF 3 SO 2 NH 2 Scheme 1.Compound I displayed in the 1 H NMR spectrum only one singlet at δ 4.06 ppm, whereas its 13 C NMR spectrum contained signals assignable to methyl (δ C 37 ppm) and two nonequivalent olefinic carbon atoms (C 4 , δ C 122 ppm, and C 5 , δ C 114 ppm); these findings indicated that the methyl group in molecule I is linked to the N 1 atom. The IR and UV spectra of I coincided with those reported in [5] where methylation of 4,5-dibromo-1,2,3-triazole with dimethyl sulfate was shown to give a 1 : 1 mixture of compound I and isomeric 4,5-dibromo-2-methyl-2H-1,2,3-triazole, which differed by spectral parameters. Obviously, the only source of methyl group in I may be formamide molecule, and the process is likely to involve reduction Scheme 2. N N N Br Br + HCONH 2 H K 2 CO 3 -NH 3 N N N Br Br CHO III 2 HCONH 2 , H 2 O -2 CO 2 , -2 NH 3 IThe formation of 1-methyl rather than 2-methyl isomer may be rationalized in terms of charge-controlled reaction of 4,5-dibromo-1,2,3-triazolate anion with formamide. This follows from the fact that the negative charge in 4,5-dibromo-1,2,3-triazolate anion is localized mainly on the N 1 and N 3 atoms (-0.88 e; cf. -0.19 e on N 2 ), whereas the contribution of N 2 to the highest occupied molecular orbital of the anion exceeds by an order of magnitude the overall contribution of the N 1 and N 3 atoms.The 1 H NMR spectrum of N,N-diformyltrifluoromethanesulfonamide (II) contained a singlet at δ 8.7 ppm as the only signal, and the CF 3 and C=O carbon nuclei resonated in the 13 C NMR spectrum at δ C 120 and 170 ppm, respectively. Due to the presence of two carbonyl groups, absorptions bands due to their symmetric and antisymmetric stretching vibrations were observed in the IR spectrum of II in the region 1610-1640 cm -1 .N,N-Diformyltrifluoromethanesulfonamide (II) is the first representative of N-formyl-substituted trifluoromethanesulfonamide and is one of a few representatives of N-formyl amides. We have found only

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ChemInform Abstract: Reaction of N‐(p‐Tolyl)‐1,4‐benzoquinonemonoimine with Thiocyanic Acid.

Cited by 9 publications

References 0 publications

Reactions of N-aryl(methyl, trifluoromethyl)sulfonyl-1,4-benzoquinone monoimines with sodium sulfinates

Reactions of N-aryl(methyl, trifluoromethyl)sulfonyl-1,4-benzoquinone monoimines with sodium sulfinates

Halogenation of N-substituted p-quinone monoimines and p-quinone monooxime esters: X. Halogenation of N-aroyl-2,5(2,3)-dialkyl-1,4-benzoquinone monoimines and their reduction products

N,N-diformyltrifluoromethanesulfonamide

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