Synthesis of some 4-substituted-2-(o-halogenophenyl)-1,2,3-triazoles

Mesoaldehyde 1,3-dioxime was treated with either 2,4,6-trichlorophenyl- (a), o-fluorophenyl- (b), or o-bromophenyl- (c) hydrazine to give the corresponding mesoaldehyde 1,3-dioxime-2-halogenophenylhydrazones (1a,b,c). The latter were O-acetylated with acetic anhydride, and cyclized to triazole 4-oximes (3b, c) or triazole 4-O-acetyloximes ( 6a,b,c ) with cesium carbonate, then converted to nitriles ( 7a,b,c ) by refluxing with acetic anhydride followed by pyrolysis, or to aldehydes ( 4a,b,c ) by hydrolysis. The nitriles ( 7a,b,c ) were also converted to acids ( 9a,b,c ), esters ( 10a,b,c ), amides ( 8a,c ), an alcohol (11a), and an amine ( 12a ). In addition, tetrazoles of two types were prepared. The first ( 13d,e ) were obtained from the acid chlorides by the action of 5-aminotetrazole, whereas the second ( 14f ) was produced from the respective nitrile by the action of ammonium azide.     

Thermolysis and photolysis of some 5-amino-4-methoxycarbonyl-Δ2-1,2,3-triazolines

Thermolysis of 5-amino-4-methyl-4-methoxycarbonyl-Δ²-l,2,3-triazolines leads to amidines and 1-methoxycarbonyl diazoethane. If the N₁ substituent is a tosyl or benzoyl group, the corresponding triazoline is not isolated, the azide addition to the olefin gives directly the thermolysis products at room temperature. Triazoline photolysis leads to amino aziridines which are azomethine ylids.     

Synthesis and Characterization of 2-Arylseleno-2-chloro-1,2,3-triorgano-1,3,2λ5-diazaphosphetidin-4-ones

The reactions of N,N′-dimethyl-N,N′-bis(trimethylsilyl)urea 8 and N-methyl-N′-phenyl-N,N′-bis(trimethylsilyl)urea 9 with phenylselenenyl chloride 6 and p-chlorophenylselenenyl chloride 7 furnished the N-arylseleno-N,N′-diorgano-N′-(trimethylsilyl)ureas 10–13 . The reactions of 10–13 with MePCl₂ and PhPCl₂ resulted in the formation of a new class of compounds, the 2-arylseleno-2-chloro-1,2,3-triorgano-1,3,2λ⁵-diazaphosphetidin-4-ones 14–19 . The new selenophosphoranes 20 and 21 were obtained in the reaction of 15 and 17 with p-nitrophenol in the presence of triethylamine. The identity and structure of the new compounds were established by ¹H- and ¹³C-NMR spectroscopy, elemental analysis, ³¹P- and ⁷⁷Se-NMR spectroscopy in the case of the selenophosphoranes 14–21 , and mass spectrometry in the case of 11 and 13 . A possible mechanism of the reaction leading to the selenophosphoranes is discussed. Single-crystal X-ray structure analyses of the selenophosphoranes 19 and 20 were conducted. Both display distorted trigonal bipyramidal geometry at phosphorus, the major distortions being imposed by the four-membered rings.     

Synthesis and structure elucidation of N-methyl-4-(2-benzo-γ-pyronyl)-1,2,3-triazoles

When diazomethane was reacted with 2-cyano chromones, three isomeric N-methyltriazoles were obtained. They were isolated by liquid chromatography with three different solvents for elution. Complete elucidation of the structures was performed both by pmr and cmr spectrography; X-ray analysis is in agreement with the proposed structures.     

Synthesis and some transformations of 1, 2, 3, 4-tetrahydrophenothiazine derivatives

1,2,3,4-Tetrahydrophenothiazine derivatives were obtained from cyclic monoketones and 1,3-diketones and o-nitroarenesulfenyl chlorides. The alkylation, aminomethylation, and oxidation of the compounds obtained were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1509–1513, November, 1972.     

Dass Hydrierprodukt eines β-Nitro-N-nitrosoamins ist kein 1,2,3-Triazolidin,sondern ein β-Hydroxylamino-N-nitrosoamin

The Product of Hydrogenation of a β-Nitro-N-nitrosoamine Is Not a 1,2,3-Triazolidine, but a β-Hydroxylamino-N-nitrosoamine It is shown, by spectroscopy, that the product of catalytic hydrogenation of N, 2-dimethyl-2-nitro-N-nitrosopropylamine (1) consists of a 5:1 mixture of (E)- and (Z)-2-hydroxylamino-N, 2-dimethyl-N-nitrosopropylarnine (3) and does not contain - as had been claimed - any l, 2-dihydroxy-1, 2, 3-triazolidine (2). Thus there is still no evidence for the existence of the N(OH)N(OH) functionality. The structure of intermediates on the way to 1 are also revised.     

Stereoselective Synthesis of 1,2,3‐Triazolooxazine and Fused 1,2,3‐Triazolo‐δ‐Lactone Derivatives

The stereoselective synthesis of 1,2,3‐triazolooxazine and fused 1,2,3‐triazolo‐δ‐lactone by applying chemoenzymatic methods is described. trans‐2‐Azidocyclohexanol was successfully resolved by Novozyme 435 with an ee value of 99%. Installation of the alkyne moiety on the enantiomerically enriched azidoalcohol by O‐alkylation, followed by intramolecular azide? alkyne [3+2] cycloaddition resulted in the desired 1,2,3‐triazolooxazine derivative. Enantiomerically pure azidocyclohexanol was also subjected to the Huisgen 1,3‐dipolar cycloaddition reaction with dimethylacetylene dicarboxylate, followed by intramolecular cyclization of the corresponding cycloadduct, to furnish a fused 1,2,3‐triazolo‐δ‐lactone.     

The stereochemical investigation of 3-Aryl-4-methyl-1,2,3-oxathiazolidine 2-oxides using NMR

The title compounds were prepared by the reaction of the corresponding N-2-hydroxyisopropylanilines with thionyl chloride in the presence of triethylamine, and their pmr and cmr spectra were examined. On the basis of the chemical shifts due to the γ- and δ-effects, the stereochemical structures are discussed.     

Synthesis of some 3-cyano-2-methylquinolin-4-ones

The condensation of ethyl 2-cyano-3-ethoxycrotonate with various anilines gave the corresponding anilinocrotonates which were cyclized in refluxing Dowtherm “A” to give the title quinolones.     

Synthesis of some novel annelated 1,2,3‐selena/thiadiazoles and 2h‐diazaphospholes

A number of annelated heterocyclic indene derivatives having 1,2,3‐selena/thiadiazole and 2H‐1,2,3‐diazaphosphole rings have been synthesized by exploiting the α‐ketomethylene functionality in some novel 1‐methyl‐piperidin‐4‐ones and 1‐oxo‐tetrahydrothiopyran‐4‐ones and were characterized by their physical and spectral data.     

Enantioselective separations by capillary GC on derivatized cyclodextrins. Part 2: Determination of enantiomeric excess of some racemic 2,3-isopropylidene-1,2,3-cyclohexanetriol derivatives on permethyl α-, β-, and γ-cyclodextrins

Capillary GC on permethyl α-, β-, and γ-cyclodextrins has been applied to separate and quantify the enantiomers of some 2,3-iso-propylidene-1,2,3-cyclohexanetriol derivatives. Quantitative CGC data are compared to those obtained with chiral shift ¹H NMR.