1,2-Naphthoquinone-4-sulfonic acid salts in organic synthesis

Several low molecular weight naphthoquinones are very useful in organic synthesis. These compounds have given rise to thousands of other naphthoquinones that have been tested against various microorganisms and pharmacological targets, including being used in the preparation of several drugs that are on the pharmaceutical market. Among these naphthoquinones, the series of compounds prepared from 1,2-naphthoquinone-4-sulfonic acid salts (β-NQS) stands out. In addition to being used in organic synthesis, they are excellent analytical derivatization reagents to spectrophotometrically determine drugs containing primary and secondary amino groups. This review summarizes the literature involving β-NQS.

Glycation of N-ε-carboxymethyllysine

The Maillard reaction is traditionally subdivided into three stages that start consecutively and run in parallel. Here, we show that N-ε-carboxymethyllysine (CML), a compound formed in the late stage of the reaction, can undergo a second glycation event at its secondary amino group leading to a new class of Amadori rearrangement products. When N-α-hippuryl-CML was incubated in the presence of reducing sugars such as glucose, galactose, ribose, xylose, maltose, or lactose in solution for 1 h at 75 °C, the compound was degraded by 6–21%, and N-ε-carboxymethyl-N-ε-deoxyketosyl lysine derivatives were formed. Under the same conditions, lysine was 5–10 times more reactive than CML. N-α-hippuryl-N-ε-carboxymethyl-N-ε-(1-deoxyfructosyl)-l-lysine (hippuryl-CMFL) and N-ε-carboxymethyl-N-ε-(1-deoxyfructosyl)-l-lysine (CMFL) were synthesized, isolated and characterized by MS/MS and NMR experiments. Depending on the reaction conditions, up to 21% of CMFL can be converted to the furosine analogue N-ε-carboxymethyl-N-ε-furoylmethyl-l-lysine (CM-Fur) during standard acid protein hydrolysis with hydrochloric acid. Incubation of bovine serum albumin (BSA) with glucose for up to 9 weeks at 37 °C revealed the formation of CMFL in the protein as assessed by HPLC–MS/MS in the MRM mode. Under these conditions, ca. 13% of lysine residues had been converted to fructosyllysine, and 0.03% had been converted to CMFL. The detection of glycation products of glycated amino acids (heterogeneous multiple glycation) reveals a novel pathway in the Maillard reaction.

New 4-iminohydantoin sulfamide derivatives with antiviral and anticancer activity

A number of sulfamides were obtained by reaction of (5-(dichloromethylene)-2-oxoimidazolidin-4-ylidene)sulfamoyl chloride with anilines, benzylamines, Boc-protected piperazine, methylalylamine, and amino acids methyl esters with primary and secondary amino group. The antiviral and anticancer activity of new derivatives was evaluated. The most effective compounds against Human cytomegalovirus were sulfamides based on anisidine (1b), N-Boc-piperazine (1h), and the derivatives 1n,o with fragments of nipecotic and azetidine-3-carboxylic acids, respectively. Anticancer activity was most significant for sulfamides based on p-methoxybenzylamine (compound 1d), benzylmethylamine (compound 1f), and allylmethylamine (compound 1g).

Evaluation of factors affecting the sorption of sulfur dioxide by FIBAN fibrous anion exchangers

The sorption of sulfur dioxide from the air by the fibrous anion exchangers containing amino groups of different structure and basicity has been comparatively investigated. The most effective sorbents of sulfur dioxide are the anion exchangers with ternary amino groups, which have a high exchange capacity (more than 5 meq/g) and additionally contain secondary amino groups. The anion exchangers with high-base amino groups absorb sulfur dioxide at low relative humidity (30 %) but have low dynamic sorption capicity (up to 1.3 meq/g). The anion exchangers with primary and secondary amino groups absorb sulfur dioxide at high relative humidity (more than 54 %) if their cation exchange capacity is several times less than the anion exchange capacity.

Polymeric proton exchange media with ionic bonds in the main chain of the polymer

This paper proposes a method of obtaining the first representative of a polymeric proton-conducting medium with protic ionic groups in the main chain of a polymer by the mutual neutralization of linear telechelic oligomers with end groups of the basic and acidic nature. Oligoethylene oxide containing 1-(3-aminopropyl) imidazole fragments with two types of basic centers (aliphatic secondary amine groups and imidazole fragments) at the ends of the chain was used as the oligomer with basic properties. Sulfonic acid-terminated oligoethylene oxide was used as the acid oligomer. Protonation of aliphatic secondary amino groups in the composition of the oligomer of the basic type with the formation of an ion-elongated polymer chain is more probable at the equimolar ratio of the starting compounds according to the analysis of ΔKa values. It is shown that the synthesized polymer contains two types of crystalline formations with melting points of 37.6 °C and 46.2 °C and turns into a liquid state, when heated to higher temperature values. The proton conductivity of the polymer under anhydrous conditions is close to the conductivity of the initial sulfonic acid-terminated oligomer in the temperature inter val of 40-100 °C and reaches 2.3 · 10–4 S/cm at 100 °C, despite a much lower content of proton charge carriers.

Ni-catalyzed asymmetric hydrogenation of N-aryl imino esters for the efficient synthesis of chiral α-aryl glycines

Chiral α-aryl glycines play a key role in the preparation of some bioactive products, however, their catalytic asymmetric synthesis is far from being satisfactory. Herein, we report an efficient nickel-catalyzed asymmetric hydrogenation of N-aryl imino esters, affording chiral α-aryl glycines in high yields and enantioselectivities (up to 98% ee). The hydrogenation can be conducted on a gram scale with a substrate/catalyst ratio of up to 2000. The obtained chiral N-p-methoxyphenyl α-aryl glycine derivatives are not only directly useful chiral secondary amino acid esters but can also be easily deprotected by treatment with cerium ammonium nitrate for further transformations to several widely used molecules including drug intermediates and chiral ligands. Formation of a chiral Ni-H species in hydrogenation is detected by 1H NMR. Computational results indicate that the stereo selection is determined during the approach of the substrate to the catalyst.

A solid solution of ethyl and d 3-methyl 2-[(4-methylpyridin-2-yl)amino]-4-(pyridin-2-yl)thiazole-5-carboxylate

The synthesis of ethyl 2-[(4-methylpyridin-2-yl)amino)-4-(pyridin-2-yl)thiazole- 5-carboxylate via the Hantzsch reaction and partial in situ transesterification during recrystallization from methanol-d 4 to the d 3-methyl ester, resulting in the title solid solution, ethyl 2-[(4-methylpyridin-2-yl)amino)-4-(pyridin-2-yl)thiazole-5-carboxylate–d 3-methyl 2-[(4-methylpyridin-2-yl)amino)-4-(pyridin-2-yl)thiazole-5-carboxylate (0.88/0.12), 0.88C17H16N4O2S·0.12C16D3H11N4O2S, is reported. The refined ratio of ethyl to d 3-methyl ester in the crystal is 0.880 (6):0.120 (6). The pyridine ring is significantly twisted out of the plane of the approximately planar picoline thiazole ester moiety. N—H...N hydrogen bonds between the secondary amino group and the pyridine nitrogen atom of an adjacent symmetry-related molecule link the molecules into polymeric hydrogen-bonded zigzag tapes extending by glide symmetry in the [001] direction. There is structural evidence for intramolecular N...S chalcogen bonding and intermolecular weak C—H...O hydrogen bonds between adjacent zigzag tapes.