Spontaneous resolution of new conglomerates in the series of 4-arenesulfonyliminocyclohex-2-en-1-ones

Kostyanovsky, Remir G.; Avdeenko, Anatolii P.; Konovalova, S. A.; Кадоркина, Г. К.; Prosyanik, A. V.

doi:10.1070/mc2000v010n01abeh001208

Cited by 18 publications

(12 citation statements)

References 6 publications

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“…Indeed, this approach provides the efficient resolution of the Pasteur's salt, Werner's complexes and many other conglomerates. 14(a), 20,24,32 A similar effect is reached by crystallization of conglomerates with deficiency of achiral solubilizers. 14(a), (d) The first examples of the conglomerate formation of racemic acid/racemic amine salts were found recently by G. Coquerel 33 and K. Saigo 28 groups, and in our and V. Schurig groups.…”

Section: Resolutionsmentioning

confidence: 84%

“…Using this approach, we have found 11 new conglomerates at once. 24 R. Bishop et al have found 12 conglomerates among the inclusion compounds of a bicyclic diol with various guest molecules (space group P3 1 21). 25 In 1910, I. I. Ostromisslensky proposed triboluminescence as a test for conglomerate formation (see p. 99).…”

Section: Conglomeratesmentioning

confidence: 99%

“…8(d),(i) Convenient tests are based on the identity of solid-state IR 9 or 13 C NMR spectra 8(d),26 with the latter there was revealed a striking difference between the spectra of (+)-and (±)-tartaric acid, which crystallises as a true racemate. 24 More delicate way for the search is to study isotopomeric quasi-racemates (see pp. 97-99).…”

Section: Conglomeratesmentioning

confidence: 99%

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Louis Pasteur did it for us especially

Kostyanovsky

2003

Mendeleev Communications

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Section: Resolutionsmentioning

confidence: 84%

Section: Conglomeratesmentioning

confidence: 99%

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Louis Pasteur did it for us especially

Kostyanovsky

2003

Mendeleev Communications

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“…The presence of a chiral center in isopropyl-substituted derivatives VIIIb, VIIIc, IX, XXVa-XXVc, XXVIa-XXVIc, XXVIIa, and XXVIIc, as well as in bromomethyl-substituted compound XXVIII, follows from their 1 H NMR spectra where protons in the isopropyl group give rise to two doublets (the CH 2 Br protons in XXVIII appear as a doublet of doublets). These compounds attract interest from the viewpoint of studying spontaneous enantiomer resolution, which was revealed by us previously [9].…”

Section: Hhlgmentioning

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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“…2 Discovered by Pasteur in the year 1848, 3 spontaneous resolution still remains an unpredictable phenomenon. One way to evaluate some of the empirical guidelines concerning the subject is monitoring the crystallization mode in a series of closely related chiral compounds which differ from one another by one or more substituents 4,5 or, applied to salts, by a counterion. 6,7 Far less common are examples of the (pairs of) compounds retaining the homochiral mode of crystallization after changing the chemical nature of the chiral center itself.…”

Section: Introductionmentioning

confidence: 99%

Racemic compound against racemic conglomerate formation: The crystal properties of allylbenzylmethylphenylphosphonium iodide as compared with the nitrogen analogue

et al. 2008

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Although racemic allylbenzylmethylphenylammonium iodide 1b displays spontaneous resolution crystallizing in a homochiral mode as a conglomerate, its phosphonium analogue rac-2b crystallizes in a heterochiral lattice forming racemic compound in the solid state. The more pronounced conformation freedom for 2b molecules manifests itself by multiple molecules crystallization (Z' = 3) of (S)-2b with the three independent molecules having different conformation.

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Spontaneous resolution of new conglomerates in the series of 4-arenesulfonyliminocyclohex-2-en-1-ones

Cited by 18 publications

References 6 publications

Louis Pasteur did it for us especially

Louis Pasteur did it for us especially

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

Racemic compound against racemic conglomerate formation: The crystal properties of allylbenzylmethylphenylphosphonium iodide as compared with the nitrogen analogue

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