Remarkable Differences in Reactivity between Benzothiazoline and Hantzsch Ester as a Hydrogen Donor in Chiral Phosphoric Acid Catalyzed Asymmetric Reductive Amination of Ketones

Described herein are differences in behavior between a Hantzsch ester and a benzothiazoline as hydrogen donors in the chiral phosphoric acid catalyzed asymmetric reductive amination of ketones with p‐anisidine. The asymmetric reductive amination of ketones with a Hantzsch ester as a hydrogen donor provided the corresponding chiral amines exclusively, regardless of the structures of the ketones, whereas a similar transformation with a benzothiazoline provided chiral amines and p‐methoxyphenyl‐protected primary amines in variable yields, depending on the structures of both the ketones and benzothiazolines. Because a benzothiazoline has an N,S‐acetal moiety that is vulnerable to p‐anisidine, the primary amine can be formed through transimination of the benzothiazoline with p‐anisidine followed by reduction of the resulting aldimine with remaining benzothiazoline.     

Rearrangement of 2-(2-thienyl)benzothiazoline in the presence of thiophilic metal ions

2-(2-thienyl)Benzothiazoline and 2-(2thienyl)benzothiazol have been synthesized and characterized by several techniques (IR, NMR, UV-VIS, MS) and elemental analysis. The reactions of a solution of 2-(2thienyl)benzothiazoline with Zn, Cd, Hg(II) and Pb(II) ions have been studied. The spectral studies of the isolated complexes showed that the arrangement of the benzothiazoline to the Schiff base, N-2-mercaptophenyl-2′-methyleneimine, had occurred. The factors influencing this arrangement are discussed. Several complexes of 2-(2-pyridyl)benzothiazoline with Cd and Pb(II) were synthesized for purposes of comparison.     

Dynamic Kinetic Resolution Approach for the Asymmetric Synthesis of Tetrahydrobenzodiazepines Using Transfer Hydrogenation by Chiral Phosphoric Acid

Asymmetric synthesis of tetrahydrobenzodiazepines was achieved by transfer hydrogenation of dihydrobenzodiazepines with benzothiazoline having a hydrogen‐bonding donor substituent by means of a newly synthesized chiral phosphoric acid. This method was applicable to various racemic dihydrobenzodiazepines to give the corresponding products in good yields with excellent diastereoselectivities and enantioselectivities taking advantage of the dynamic kinetic resolution. Furthermore, the effect of bulky substituent at 3,3′‐position on the catalyst and hydrogen‐bonding donor substituent on benzothiazoline was fully elucidated by the theoretical study.     

Palladium(II) and platinum(II) derivatives of benzothiazoline ligands: Synthesis, characterization, antimicrobial and antispermatogenic activity

A series of Pd(II) and Pt(II) complexes with two N(∩)S donor ligands, 5-chloro-3-(indolin-2-one)benzothiazoline and 6-nitro-3-(indolin-2-one)benzothiazoline, have been synthesized by the reaction of metal chlorides (PdCl2 and PtCl2) with ligands in 1:2 molar ratios. All the synthesized compounds were characterized by elemental analyses, melting point determinations and a combination of electronic, IR, 1H NMR and 13C NMR spectroscopic techniques for structure elucidation. In order to evaluate the effect of metal ions upon chelation, both the ligands and their complexes have been screened for their antimicrobial activity against the various pathogenic bacterial and fungal strains. The metal complexes have shown to be more antimicrobial against the microbial species as compared to free ligands. One of the ligands, 5-chloro-3-(indolin-2-one)benzothiazoline and its corresponding palladium and platinum complexes have been tested for their antifertility activity in male albino rats. The marked reduction in sperm motility and density resulted in infertility by 62-90%. Significant alterations were found in biochemical parameters of reproductive organs in treated animals as compared to control group. It is concluded that all these effects may finally impair the fertility of male rats.     

Chiral Phosphoric‐Acid‐Catalyzed Transfer Hydrogenation of Ethyl Ketimine Derivatives by Using Benzothiazoline

Chiral phosphoric acid catalyzed transfer hydrogenation of ketimines derived from propiophenone derivatives and reductive amination of alkyl ethyl ketone derivatives were extensively examined in the presence of two representative hydrogen donors. The excellent enantioselective transfer hydrogenation was achieved by use of benzothiazoline as a hydrogen donor. The theoretical studies elucidated that the unsymmetrical structure of benzothiazoline plays an important role in high enantioselective hydrogenation.     

Enantioselective organocatalytic reductive amination of aliphatic ketones by benzothiazoline as hydrogen donor

The chiral phosphoric acid-catalyzed enantioselective reductive amination of aliphatic ketones with aromatic amines was successfully achieved by the use of benzothiazoline as the hydrogen donor. Corresponding chiral aliphatic amines were obtained with excellent enantioselectivities.     

Oxidative ring-expansion of benzothiazolines into 1,4-benzothiazines

By treatment in boiling DMSO, benzothiazolines 1 yield 1,4-benzothiazines 4 in some cases together with benzothiazoles. Two competing pathways, namely oxidative ring-expansion and decomposition of benzothiazoline accounting for the formation of 4 and benzothiazoles, respectively, are suggested.     

Synthesis in the 2-mercaptobenzothiazole series

The reduction of some dihydrothiazolobenzothiazolium salts with sodium borohydride may take place in two directions: with the formation of thiazolidino[2, 3-b]benzathiazolines and with the cleavage of the C-S bond to give N-(Β-mercaptoethyl)benzothiazolines. The behavior of thiazolidino[2, 3-b]benzothiazoline under the conditions of acid and alkaline hydrolysis has been studied.     

Chiral phosphoric acid catalyzed enantioselective transfer deuteration of ketimines by use of benzothiazoline as a deuterium donor: synthesis of optically active deuterated amines

By use of 2-deuterated benzothiazoline as a deuterium donor in combination with a chiral phosphoric acid, the transfer deuteration of ketimine and α-iminoester took place smoothly to give α-deuterated amines in high yields with excellent enantioselectivities. The remarkable kinetic isotope effect suggests that carbon-deuterium bond cleavage is the rate-determining step.     

Efficient synthesis of benzothiazole derivatives by reaction of bis(2-aminophenyl) disulfides with aldehydes mediated by NaSH under microwave irradiation

2-Substituted benzothiazoles were synthesized through condensation of bis(2-aminophenyl) disulfides with arylaldehydes catalyzed by inexpensive NaSH in PEG-300 and assisted by low energy microwave irradiation(25 W). Various 2-substitutedbenzothiazoles were obtained in moderate to high yields after simple post-reaction processing including adding distilled water, filtrating, and drying. Moreover, it was found that the S-S bond of the disulfide was reduced by NaSH and also by the intermediate benzothiazoline.     

Synthesis and properties of derivatives of 2-mercaptobenzothiazole

2,3-Dihydro-4H-[1,3]-thlazino[2,3-b]benzothiazolium chlorides have been synthesized and their reduction with sodium borohydride has given previously-unknown derivatives of (perhydro-1,3-thiazino) [2,3-b]benzothiazoline. The stability of the compounds in acid and alkaline media has been studied.For part VII, see [1].     

UV-VIS spectroscopic study of the solvatochromism and chelating reaction of a benzothiazoline merocyanine in mixed solvents

Solvatochromism and chelating reaction of a benzothiazoline merocyanine are studied by UV-VIS spectra in DMF-H₂O, DMF-1,4-dioxane and DMSO-1,4-dioxane. The effect of solvent polarity on UV-VIS absorption maxima and on equlibrium constant K of the chelating reaction is discussed. A linear correlation is obtained between lnK and E_T.     

Sulfur-Bonded Coordination Compounds of Palladium(II) and Platinum(II) and Their Antimicrobial Activity

The synthetic, spectroscopic, and biological studies of some new palladium(II) and platinum(II) complexes derived from biologically active sulfur donor ligands 1H-indol-2,3-dione benzothiazoline (Bzt ₁ H) and 5-nitro-1H-indol-2,3-dione benzothiazoline (Bzt ₂ H) have been described. The reactions were carried out in 1:2 molar ratios. The authenticity of the benzothiazolines and their complexes has been established on the basis of elemental analyses; molecular weight determinations; and IR, ¹ H NMR, ¹³ C NMR, and UV spectral studies. Based on IR and ¹ H NMR spectral studies, a square-planar structure has been assigned to these complexes. Studies were conducted to assess the comparative growth inhibiting potential of the synthesized complexes against the benzothiazolines for a variety of fungal and bacterial strains. The studies demonstrate that the ligands and complexes possess antimicrobial properties. Further, it was noted that the growth-inhibiting potential of the complexes is greater than the parent benzothiazolines.     

Reaction of benzothiazoline with benzyne - generation of novel heterocyclic sulfur ylide,benzothiazolinium s-ylide

A novel heterocyclic sulfur ylide, 2-t-butyl-3-methyl-1-phenylbenzothiazolinium ylide ($\text{13}$) was generated as an intermediate in the reaction of 2-t-butyl-3-(nethy1benzothiazoline ($\text{2}$) with benzyne. The S-ylide $\text{13}$ underwent a novel intermolecular [1,2] shift to give 2-t-butyl-3-methyl-2-phenylbenzothiazoline ($\text{4}$).     

Synthesis and ABTS Radical,MMP‐1 Inhibitory Activity of CAPE Analogues

In the photoaging process of skin, the ultraviolet (UV)‐induced reactive oxygen species (ROS) is the key regulator of matrix metalloproteinase (MMPs) expression. In this study, a series of Caffeic acid phenethyl ester (CAPE) analogues were synthesized by conjugating the group VI elements (selenium, sulfur, oxygen)‐containing aliphatic alcohols to polyphenolic acids. Their biological activities were evaluated by in vitro testing of their radical scavenging activity the of ABTS [2,2′‐azinobis‐(3‐ethyl‐benzothiazoline‐6‐sulfonic acid)] radical and inhibitory effect against the matrix metalloproteinase‐1 (MMP‐1) activity of collagen degradation and cytotoxicity of a human dermal fibroblast skin cell. Our results suggest these compounds displayed moderate anti‐free radical, potent MMP‐1 inhibitory, and low cytotoxic activities.     

Synthesis in the 2-mercaptobenzothiazole series

The reduction of some dihydrothiazolobenzothiazolium salts with sodium borohydride may take place in two directions: with the formation of thiazolidino[2, 3-b]benzathiazolines and with the cleavage of the C-S bond to give N-(-mercaptoethyl)benzothiazolines. The behavior of thiazolidino[2, 3-b]benzothiazoline under the conditions of acid and alkaline hydrolysis has been studied.For communication VI, see [1].     

Interactions of benzoxazolin(benzothiazolin)ones and-thiones with α-bromopropionyl chloride

At interaction of benzoxazolin(benzothiazolin)ones with -bromopropionyl chloride N-acylation takes place, while in the case of benzoxazoline(benzothiazoline)thiones, the reaction is accompanied by S-alkylation.Plant Substance Chemistry Institute, Academy of Sciences of the Uzbekistan Republic, Tashkent 700170. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 270–273, February, 1999.     

Reactions of tin tetraacetate with benzothiazolines

Tin tetraacetate with 2,2-disubstituted benzothiazolines yields mono and disubstituted derivatives, the latter being the final product even with excess of the ligand. In the products the benzothiazoline ring of the ligands is absent, but a new azomethine group is found, thus characterising the products as tin(IV)Schiff2ba se complexes. The new compounds have been characterised by elemental analysis, IR, PMR, Molecular weight determination and a conductometric study.

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Reaktionen von Zinntetraacetat mit Benzothiazolinen

Zusammenfassung Zinntetraacetat ergibt mit 2,2-disubstituierten Benzothiazolinen mono- und disubstituierte Verbindungen, wobei letztere auch mit Überschuß an Ligand die Endprodukte darstellen. In den Produkten fehlt der Benzothiazolinring, andererseits wird eine Azomethingruppe gefunden; damit sind die Produkte als Zinn(IV)-Schiff-Basen-Komplexe charakterisiert. Die neuen Verbindungen wurden mittels Elementaranalysen, IR,¹H-NMR, Molekulargewichtsbestimmungen und Leitfähigkeitsmessungen charakterisiert.

     

Concise and practical synthesis of C-glycosyl ketones from sugar benzothiazoles and their transformation into chiral tertiary alcohols

[Reaction: see text]. A collection of 13 unsymmetrical ketones, each one featuring a sugar (d-glucosyl, d-galactosyl, d-mannosyl, and l-fucosyl) and an aglycone moiety (phenyl, 2-thiazolyl, TMS-ethynyl, allyl, and 1-propenyl) was prepared by a uniform route based on the use of benzothiazole as a carbonyl group equivalent. Succinctly, C-glycosylbenzothiazoles readily prepared by addition of 2-lithiobenzothiazole to sugar lactones and deoxygenation, were subjected to a one-pot reaction sequence involving N-methylation of the heterocyclic ring by MeOTf, treatment of the N-methylbenzothiazolium salt with a Grignard reagent, and HgCl(2)-promoted hydrolysis of the benzothiazoline thus formed. The resulting ketones were isolated in yields varying from 35 to 80%. Treatment of the sugar ketones with various organometals containing the phenyl, 2-thiazolyl, TMS-ethynyl, or ethynyl group as a substituent afforded chiral tertiary alcohols. These addition reactions were highly stereoselective as observed by crude NMR analysis and isolation of a single epimer in high yield in each case examined. However, because of the complexity of the reagents involved, the stereochemical outcome of these reactions appears to be difficult to rationalize by simple classical steric models, thus, ab initio studies taking into account the role of the sugar fragment are advisable. An interesting synthetic elaboration of a propargylic alcohol containing the thiazole ring into a propargylic alcohol bearing the formyl and carboxylate groups is reported.     

Synthesis in the 2-mercaptobenzothiazole series V. Thiazolidino[2, 3-b]-benzothiazolines

Reaction of 2-mercaptobenzothiazoles substituted at position 6 by chlorine, dimethylsulfamido, benzamido, and nitro groups, with chlorobromoalkanes, is used to synthesize the corresponding 6-substituted 2-(-chloroalkylmercapto)benzothiazoles. Oxidation of these compounds with hydrogen peroxide in acetic acid converts them to sulfoxides and sulfones, while heating in nitrobenzene cyclizes them to 6 substituted 2,3-dihydrothiazolo[2,3-b]benzothiazolium chlorides. The latter and previously obtained quaternary salts are converted by sodium borohydride into derivatives of a new tricyclic system, thiazolidino[2,3-b]benzothiazoline.For Part IV see [1].