Structure of products of aldoses condensation with thioglycolic acid hydrazide

Еrshov, A. Yu.; Lagoda, I. V.; Yakimovich, S. I.; Zerova, I. V.; Pakal’nis, V. V.; Мокеев, М. В.; Шаманин, В. В.

doi:10.1134/s1070428009050169

Cited by 9 publications

(2 citation statements)

References 2 publications

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“…The observed doubling of the signals in the 1 H and 13 C NMR spectra of the studied compounds is possibly caused by the presence of conformational E ′, Z ′‐isomers that differ in localization of substituents relative to amide C–N bond. We did not consider appearance of E , Z ‐configurational isomerism relative to C=N bond, since aldoacylhydrazones exist predominantly or completely in E ‐configuration relative to this bond …”

Section: Resultsmentioning

confidence: 99%

Synthesis of Aldose 11‐Mercaptoundecanoyl Hydrazones as Promising Glycoligands of Noble Metal Nanoparticles

Еrshov

Martynenkov

Lagoda³

et al. 2019

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Thesynthetic method for previously unknown 11-mercaptoundecanoyl hydrazones of the aldose series (L-arabinose, D-ribose, D-xylose, L-rhamnose, L-fucose, D-mannose, D-galactose, Dglucose, N-acetyl-D-glucosamine, N-acetyl-D-mannosamine, Dlactose, D-maltose) was developed, and structures of the productes were determined. These compounds are perspective glycoligands for noble metal nanoparticles. The 1 H and 13 C NMR spectroscopy data show that most of these aldose 11mercaptoundecanoyl hydrazones in DMSO-d 6 solution exist as a tautomeric mixture of open hydrazone and cyclic pyranose forms. The linear hydrazone form is represented by a set of Z',E'-conformational isomers, differing in the arrangement of substituents relative to the amide bond C-N, in comparable amounts. In the case of 11-mercaptoundecanoyl hydrazones derived from D-glucose, D-lactoseand D-maltose, the cyclic pyranose structure represented by α,β-configurational isomers is retained.

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Section: Resultsmentioning

confidence: 99%

Synthesis of Aldose 11‐Mercaptoundecanoyl Hydrazones as Promising Glycoligands of Noble Metal Nanoparticles

Еrshov

Martynenkov

Lagoda³

et al. 2019

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“…The ability to undergo ring-chain-ring tautomeric transformation involving two different cyclic structures makes 3-sulfanylpropionylhydrazones Va-Vf similar to the condensation products of aldoses with sulfanylacetic and benzothioic acid hydrazides [11,12]. The latter were found to strongly tend to form cyclic 1,3,4-thiadiazine and dihydro-1,3,4-thiadiazole structures, respectively, via intramolecular nucleophilic addition of the SH group at the hydrazone C=N bond.…”

Section: Structure Of the Condensation Products Of 3-sulfanylpropionimentioning

confidence: 99%

Structure of the condensation products of 3-sulfanylpropionic acid hydrazide with aldehydes, ketones, and aldoses

et al. 2009

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Condensation products of aliphatic aldehydes with 3-sulfanylpropionic acid hydrazide exist in solution as mixtures of linear hydrazone and cyclic 1,3,4-thiadiazepine tautomers. Hydrazones derived from 3-sulfanylpropionic acid hydrazide and aromatic aldehydes and ketones have mostly linear structures of different stereoisomers arising from Z-E isomerism with respect to the double C=N bond and restricted rotation about the C(O)-N bond. Condensation products of 3-sulfanylpropionohydrazide with a series of aldoses give rise to ring-chain-ring tautomeric equilibrium between α,β-isomeric pyranose structures, open-chain aldose hydrazone tautomer, and two diastereoisomeric seven-membered cyclic 1,3,4-thiadiazepine forms.We previously showed that condensation products of carbonyl compounds with sulfanylacetic and 2-sulfanylbenzoic acid hydrazides in solution give rise to ring-chain tautomerism between linear acylhydrazone and cyclic 1,3,4-thiadiazine or 1,3,4-benzothiadiazepine structures, respectively [1][2][3][4][5]. In both cases, the cyclic tautomer is formed via intramolecular nucleophilic addition of the sulfanyl group at the C=N bond in the hydrazone fragment. While continuing studies in this line, we examined the ability of condensation products formed by aldehydes, ketones, and aldoses with 3-sulfanylpropionic acid hydrazide to undergo ring-chain isomerism (Schemes 1, 2).We initially studied 3-sulfanylpropanoylhydrazones IIIa-IIIj derived from aliphatic and aromatic aldehydes and ketones. These compounds were synthesized in 40-85% yield by reaction of 3-sulfanylpropionohydrazide (II) with an equimolar amount of the corresponding carbonyl compounds Ia-Ij in methanol either at room temperature or on heating under reflux for a short time.3-Sulfanylpropionylhydrazones IIIa-IIIj can exist as linear tautomer A and seven-membered cyclic 1,3,4-thiadiazepine structure B. The latter could be formed via intramolecular addition of the SH group at the C=N bond in the hydrazone fragment. Furthermore, open-chain tautomer A may be represented by four stereoisomers with different configurations with respect to the C=N bond (Z-E isomerism) and C-N bond in the amide fragment (conformational Z′-E′ isomerism) [1, 2] (Scheme 1).Let us consider condensation products of hydrazide II with acetaldehyde, propionaldehyde, and butyraldehyde (compounds IIIa-IIIc). As follows from variation of the 1 H NMR spectra with time, these compounds in the crystalline state have structure A. The 1 H NMR spectrum of acetaldehyde hydrazone IIIa in DMSO-d 6 , recorded immediately after dissolution, contained two sets of signals assignable to two stereoisomers of linear tautomer A. The major stereoisomer (its fraction was 73% in the initial moment) was characterized by a quartet signal from the CH=N proton at δ 7.29 ppm, a triplet signal from the SH proton at 2.43 ppm, and a broadened singlet from the NH proton at δ 10.91 ppm. The corresponding signals of the minor stereoisomer (27%) were located at

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ChemInform Abstract: Structure of Products of Aldoses Condensation with Thioglycolic Acid Hydrazide.

Еrshov

Lagoda²,

Yakimovich

et al. 2010

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Structure of products of aldoses condensation with thioglycolic acid hydrazide

Cited by 9 publications

References 2 publications

Synthesis of Aldose 11‐Mercaptoundecanoyl Hydrazones as Promising Glycoligands of Noble Metal Nanoparticles

Synthesis of Aldose 11‐Mercaptoundecanoyl Hydrazones as Promising Glycoligands of Noble Metal Nanoparticles

Structure of the condensation products of 3-sulfanylpropionic acid hydrazide with aldehydes, ketones, and aldoses

ChemInform Abstract: Structure of Products of Aldoses Condensation with Thioglycolic Acid Hydrazide.

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