Reaction of N-substituted 2,5-dialkyl-1,4-benzoquinone imines with arenesulfinic acids

Avdeenko, A. P.; Konovalova, S. A.; Roman’kov, D. A.; Ludchenko, O. N.; Marchenko, I. L.

doi:10.1134/s1070428009030063

Russ J Org Chem

2009

DOI: 10.1134/s1070428009030063

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Reaction of N-substituted 2,5-dialkyl-1,4-benzoquinone imines with arenesulfinic acids

A. P. Avdeenko

S. A. Konovalova

D. A. Roman’kov

et al.

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Cited by 9 publications

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“…Quinone monoimines with the quinoid ring having free positions 2 and/or 6 react with sodium arylsulfi nates as a rule regiospecifi cally providing products of 1,4-addition [6][7][8]. In reactions of N-4-(methylphenyl)sulfonyl-1,4-benzoquinone monoimine [6] and its 2,5-dimethyl- [7] and 3,5-dimethyl derivatives [8] formed up to 15% of the products of 1,6-and 6,1-addition. In the case of N-arylsulfonyl-2,6-dialkyl-1,4-benzoquinone monoimines the reaction course is mainly governed by the steric factor: the volume of the substituents in the positions 2 and 6 of the quinoid ring [8].…”

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“…The alkyl substituents in the quinoid ring notably affect the reaction course [5][6][7][8][9]. Quinone monoimines with the quinoid ring having free positions 2 and/or 6 react with sodium arylsulfi nates as a rule regiospecifi cally providing products of 1,4-addition [6][7][8]. In reactions of N-4-(methylphenyl)sulfonyl-1,4-benzoquinone monoimine [6] and its 2,5-dimethyl- [7] and 3,5-dimethyl derivatives [8] formed up to 15% of the products of 1,6-and 6,1-addition.…”

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“…This choice of conditions is due to the higher reactivity towards nucleophiles of N-trifl uoromethylsulfonyl-1,4-benzoquinone monoimines IIa-IIf: they react at room temperature and even at cooling [3], in contrast to formerly studied N-arylsulfonyl-1,4-benzoquinone monoimines whose reactions with arylsodium sulfi nates proceed only in boiling acetic acid [5][6][7][8][9].…”

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“…The reactivity of N-arylsulfonyl-1,4-benzoquinone monoimines towards sodium arylsulfi nates is suffi ciently well investigated [5][6][7][8][9]. The alkyl substituents in the quinoid ring notably affect the reaction course [5][6][7][8][9].…”

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

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

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Thiocyanation of N-arylsulfonyl-, N-aroyl-, and N-[(N-arylsulfonyl)benzimidoyl]-1,4-benzoquinone imines

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Halogenation of N-substituted p-quinone monoimines and p-quinonemonooxime ethers: XII. Halogenation of N-aroyl-2(3)-methyl-1,4-benzoquinone monoimines and their reduced forms

2010

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A strong acceptor substituent at the nitrogen atom of the N-substituted p-quinone monoimine decreases the stability of the halogen-containing cyclohexene structures formed at the addition of a halogen molecule to the C=C bond of the quinoid ring. As a result of the bromination of N-benzoyl-2-methyl-1,4-benzoquinone monoimine alongside the usual products of addition and substitution the 5-benzoyloxy-2,3,6-tribromo-6-methylcyclohex-2-ene-1,4-dione was isolated.This study is a continuation of the research on the halogenation processes of N-substituted 1,4-benzoquinone monoimines. We formerly investigated in detail the halogenation of various N-arylsulfonyl-1,4-benzoquinone monoimines and their reduced forms [2-4], 4-amino-N-aroylphenol without substituents in the ring of the aminophenol [5], and N-aroyl-1,4-benzoquinone monoimines with two alkyl substituents in the ring [6,7]. The N-aroyl-1,4-benzoquinone monoimines unsubstituted in the quinoid ring were not previously examined due to their instability [5,8].In this study N-aroyl-2(3)-methyl-1,4-benzoquinone monoimines I, II and 4-amino-N-aroyl-2(3)-methyl-phenols III, IV were chosen as the objects of the investigation. In contrast to the corresponding N-arylsulfonyl-2-methyl-1,4-benzoquinone monoimines [3] the 1 H NMR spectra of N-aroyl-2-methyl-1,4-benzoquinone monoimines Ia, Ib contain a single set of signals. It was established formerly that the N-aroyl-1,4-benzoquinone monoimines had a lower barrier to the Z,E-isomerization [9] (ΔG ≠ 298K 44-46 kJ mol -1 ), than N-arylsulfonyl derivatives [10] (ΔG ≠ 298Q 65-80 kJ mol -1 ). Therefore in the solutions of compounds Ia, Ib already at the room temperature the fast Z,E-isomerization occurs, and notwithstanding the existence of two isomeric forms the 1 H NMR spectrum contains a single set of signals, namely, the degenerate Z,E-isomerization is observed. It was earlier established that the presence of the Z,E-isomerization signifi cantly affected the halogenation course of the N-arylsulfonyl-1,4-benzoquinone monoimines [3].The difference in the chemical shifts of protons H 5 and H 6 (H 2 and H 3 ) of the quinoid ring is not so pronounced in the 1 H NMR spectra of compounds I, II as in the case of N-arylsulfonyl derivatives. This is due to the fact that the chemical shifts of the protons of the quinoid ring of N-aroyl derivatives A because of the fast Z,E-isomerization depend mainly on the position of this proton in the ring and on the character of the substituents in the neighboring positions. In N-arylsulfonyl derivatives B the chemical shifts of the protons in the quinoid ring are strongly affected by the position of the substituent at the nitrogen atom (cis-or trans-): the signal of the proton in the position 5 of the quinoid ring is shifted downfi eld and appears in the region 7. 92-8.18 [3], of the proton H 3 , in the region 6.81-6.93 ppm. In aroyl derivatives A the signal of the atom H 5 of quinone imines Ia, Ib is shifted upfi eld compared with the sulfonyl derivatives and appears in the region 7.02-7.08, and th...

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Reaction of N-substituted 2,5-dialkyl-1,4-benzoquinone imines with arenesulfinic acids

Cited by 9 publications

References 3 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

Thiocyanation of N-arylsulfonyl-, N-aroyl-, and N-[(N-arylsulfonyl)benzimidoyl]-1,4-benzoquinone imines

Halogenation of N-substituted p-quinone monoimines and p-quinonemonooxime ethers: XII. Halogenation of N-aroyl-2(3)-methyl-1,4-benzoquinone monoimines and their reduced forms

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