Quinone Imides. IV. p-Quinone Monosulfonimides

Adams, Roger; Looker, J. H.

doi:10.1021/ja01147a078

Cited by 43 publications

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“…The choice of sodium p-toluenesulfinate and hydrogen chloride as reagents was made on the basis of the different nucleophilicity of the respective anions which results in a change of position for the addition reaction. 21,22 Intermediate quinone diimides were obtained by oxidation of the corresponding adducts with lead tetraacetate in acetic acid. 15 The structures of the addition products were determined by NMR and confirmed by CHN analysis.…”

Section: Resultsmentioning

confidence: 99%

Interaction of quinone diimides of the 10H-9-thia-10-aza-phenanthrene 9,9-dioxide series with sodium p-toluenesulfinate and hydrogen chloride

Vakulenko¹,

Burmistrov²

2005

Arkivoc

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Interaction of quinone diimides of the 10H-9-thia-10-azaphenanthrene 9,9-dioxide series with sodium p-toluenesulfinate in acetic acid and hydrogen chloride AbstractTreatment of quinone diimides of the 10H-9-thia-10-aza-phenanthrene 9,9-dioxide series with sodium p-toluenesulfinate in acetic acid and hydrogen chloride affords addition products in moderate to good yields. The chloride anion regioselectively attacks position 1 of the unsubstituted quinone diimide ring and the p-toluenesulfonyl group enters positions 1 and 4 giving a mixture of two isomers in 5 and 42% yield, respectively. The hydrochlorination of a quinone diimide, where positions 1 and 4 are blocked, proceeds at position 2 with 1,4-orientation (for designation of addition orientation see numbering in italic description at structure 2 as shown in Scheme 1). The same addition reaction using sodium p-toluenesulfinate, however, gives the benzene sulfinic acid adduct with 6,1-orientation.

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Section: Resultsmentioning

confidence: 99%

Interaction of quinone diimides of the 10H-9-thia-10-aza-phenanthrene 9,9-dioxide series with sodium p-toluenesulfinate and hydrogen chloride

Vakulenko¹,

Burmistrov²

2005

Arkivoc

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“…The reac tions were monitored and the product purity was checked on Silufol UV 254 plates in a benzene-methanol mixture, 9 : 1, and in chloroform (UV visualization). The yields, elemental analysis data, and physocochemical characteristics of the com pounds are summarized in Tables 1-5. 3 Ethoxycarbonyl 1 (4 methoxyphenyl) 2 methyl 5 tosyl aminoindole (11). Enamine 4 (0.4 g, 1.7 mmol) was added at 20 °C to a stirred solution of quinoneimine 1 (0.4 g, 1.5 mmol) 11 in acetone (7.5 mL).…”

Section: Methodsmentioning

confidence: 99%

“…The yields, elemental analysis data, and physocochemical characteristics of the com pounds are summarized in Tables 1-5. 3 Ethoxycarbonyl 1 (4 methoxyphenyl) 2 methyl 5 tosyl aminoindole (11). Enamine 4 (0.4 g, 1.7 mmol) was added at 20 °C to a stirred solution of quinoneimine 1 (0.4 g, 1.5 mmol) 11 in acetone (7.5 mL). The stirring was continued for 24 h. The reaction mixture was concentrated and the residue was recrys tallized from isopropyl alcohol to give 0.35 g of compound 11.…”

Section: Methodsmentioning

confidence: 99%

Quinoneimines in the Nenitzescu reaction

Lyubchanskaya¹,

Panisheva²,

Savina³

et al. 2005

Russ Chem Bull

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“…benzamides IVa-IVc, Va-Vc, VIa-VIc, XXXIIa, and XXXIIb were synthesized according to the procedures described in [10,11], and were recrystallized from acetic acid. Chlorination of quinone imines Ia-Ic, IIa-IIc, IIIa-IIIc, XVIa-XVIc, XVIIIa-XVIIIc, XXa-XXc, XXXIa, XXXIb, XXXVa, and XXXVb and aminophenols IVa-IVc, Va-Vc, VIa-VIc, Xa-Xc, XIIaXIIc, XIVa-XIVc, XXXIIa, XXXIIb, XXXIIIa, and XXXIIIb (general procedure).…”

Section: N-(25-dialkyl-4-oxocyclohexa-25-dien-1-ylidene)benzamides mentioning

confidence: 99%

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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Quinone Imides. IV. p-Quinone Monosulfonimides

Cited by 43 publications

References 0 publications

Interaction of quinone diimides of the 10H-9-thia-10-aza-phenanthrene 9,9-dioxide series with sodium p-toluenesulfinate and hydrogen chloride

Interaction of quinone diimides of the 10H-9-thia-10-aza-phenanthrene 9,9-dioxide series with sodium p-toluenesulfinate and hydrogen chloride

Quinoneimines in the Nenitzescu reaction

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

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