13C NMR Analysis of some 4-hydroxy-2H-1,2-benzothiazine 1,1-dioxides

The ¹³C nmr spectra of some 4-hydroxy-2H-1,2-benzothiazine 1,1-dioxides I have been recorded and analyzed. Spectroscopic assignments were made on the basis of chemical shift theory, APT and fully coupled ¹³C nmr spectra. Spectral data support the enolic structure of these compounds.     

New approach to the synthesis of 3-amino-1,2-benzothiazine 1,1-dioxides

The possibility of obtaining 3-amino-1,2-benzothiazine 1,1-dioxides by nucleophilic substitution of the chlorine atom in 5-nitro-2-chlorobenzenesulfonamides by carbanions generated from substituted acetonitriles was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 264–266, February, 1992.     

Mass spectra of heterocyclic compounds VI. 3,4-dihydro-1H-2,3-benzothiazine 2,2-dioxides

The mass fragmentation behaviour of 3,4-dihydro-1H-2,3-benzothiazine 2,2-dioxides was studied. The rationalizations suggested are supported by accurate mass measurements, metastable evidence and deuterium labelling.     

Studies on the reaction of 3-substituted-4-hydroxy-2H-1,2-benzothiazine 1,1-dioxides with aryl isocyanates and the synthesis of corresponding derivatives

The reaction of 3-substituted-4-hydroxy-2H-1,2-benzothiazine 1,1-dioxides with aryl isocyanate under different equivalents of strong base NaH was studied.Seventeen of new derivatives were obtained whose structures were characterized by 1H NMR,IR,MS,elementary analysis and FeCl3 test.     

Spiro[(2,3-dihydro-2-oxo-imidazo[1,2-a]pyridine)-3,3-(3,4-dihydro-2-methyl-4-oxo-2H-1,2-benzothiazine 1,1-dioxide)]-A novel product derived from piroxicam

A novel compound, spiro[(2,3-dihydro-2-oxo-imidazo[1,2-a]pyridine)-3,3-(3,4-dihydro-2-methyl-4-oxo-2H-1,2-benzothiazine 1,1-dioxide)] (3) , was isolated during an attempt to convert 4-hydroxy-2-methyl-N-(2-pyridinyl)-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide ( 1 ) (Piroxicam) to an O-trifluoromethanesulfonyl ester. A possible mechanism is offered to explain this unusual transformation.     

Synthesis of 2-(2-imidazolinyl) substituted 2,3-dihydro-4H-1,4-benzothiazine and 3,4-dihydro-2H-1,4-benzoxazines

An investigation into the synthesis of benzoxazine, benzoxathiane and benzothiazine derivatives of 2-(2-imidazolinyl)-1,4-benzodioxane has been carried out.     

Synthesis of 2H-1,2-benzothiazine 1,1-dioxides via heteroannulation reactions of 2-iodobenzenesulfonamide with ketone enolates under S(RN)1 conditions

[Reaction: see text]. 2-iodobenzenesulfonamide (1a) underwent photostimulated S(RN)1 reactions in liquid NH3 with the potassium enolates derived from acetone, pinacolone, butanone, and 3-methyl-2-butanone to give fair to good yields of 2H-1,2-benzothiazine 1,1-dioxides 2. Reductive dehalogenation of 1a was found to predominate in photoinduced reactions of 1a with 3-pentanone, 2-methyl-3-pentanone, and 2,4-dimethyl-3-pentanone, the extent of reduction being proportional to the number of beta-hydrogen atoms present in the ketone enolate. Isotopic labeling studies with 2,4-dimethyl-3-pentanone-d14 (24) confirmed the major role of the beta-hydrogens in the reduction process. Reactions of 1a with cyclopentanone, cyclohexanone, and cyclooctanone enolates afforded new tricyclic benzothiazine derivatives 26-29. Attempts to extend the heteroannulation reaction to the preparation of 2H-1,2-benzothiazin-3(4H)-one 1,1-dioxides 3 (R = H, Ph) through reactions of 1a with tert-butyl acetate and ethyl phenylacetate enolates resulted only in hydrodehalogenation of 1a. However, oxazoline anion 30, a synthetic equivalent of ethyl phenylacetate, was successfully employed in an alternative S(RN)1-based synthesis of benzothiazine 3 (R = Ph).     

New synthetic approaches to 3-carhoxamides of 4-hydroxy-2H-1,2-benzothiazine 1,1-dioxide

Two new synthetic approaches to the title compounds are reported. In the first of these, starting with N-carbobenzyloxysarcosine, four synthetic steps are employed to finally assemble the C³? C⁴ bond of the 1,2-benzothiazine ring. In the second approach, an enol ether is employed as a protecting group to allow formation of the 3-carboxamide function, which is followed by cleavage of the ether function to yield the desired 4-hydroxy-1,2-benzothiazine-3-carboxamide 1,1-dioxide.     

Functionalized 5,6-dihydro-2H-1,2,6-thiadiazine 1,1-dioxides. Synthesis,structure and chemistry

Treatment of sulfamide 4a and aryl-substituted sulfamides 4b-e with ethyl 3,3-diethoxypropionate ( 13 ) provided a convenient procedure for the synthesis of functionalized 5,6-dihydro-2H-1,2,6-thiadiazine 1,1-dioxides 14 . Key spectral properties of this novel class of heterocycles are reported. The generality and utility of this transformation is briefly explored.     

Multigram scale synthesis of 3,4- and 3,6-dihydro-2H-thiopyran 1,1-dioxides and features of their NMR spectral behavior

A new four-step synthesis of 3,4- and 3,6-dihydro-2H-thiopran-1,1-dioxides from dihydro-2H-thiopyran-3(4H)-one is reported. The title compounds are synthesized starting with oxidation of the ketone with a 30% aqueous solution of hydrogen peroxide in a mixture of AcOH-Ac₂O. The keto group is then reduced by sodium borohydride followed by mesylation and elimination of methanesulfonic acid under basic conditions (pyridine for 3,4-isomer and aqueous NaOH for 3,6-isomer). This sequence is simpler, than previously known methods, uses cheaper and more readily available reagents, and leads to 2H-thiopran-1,1-dioxides on multigram scale with 64% and 74% total yields, respectively. The structure and purity of the compounds were confirmed by 2D NMR and GCMS methods. The proposed method expands the means to access functionalized cyclic sulfones as building blocks in the synthesis of combinatorial libraries of new biologically active compounds.     

Synthesis of 3-substituted 4,1,2-benzothiadiazine 4,4-dioxides and 2 or 3-substituted 1,4-benzothiazine 1,1-dioxides

The title compounds were prepared starting from the synthones 6 using two different synthetic approaches: 3-substituted 1,4-benzothiazine 1,1-dioxides were synthesised by cyclisation with phosphorus oxychloride as the Vilsmeier reagent, while 4,1,2-benzothiadiazine 4,4-dioxides and 3-substituted 1,4-benzothiazine 1,1-dioxides were obtained by direct diazotisation or by cyclisation with triethyl orthoformate.     

Novel boron heterocycles. II. 2,3-dihydro-1,3,5,2-oxadiazaboroles, 1,2-dihydro-1,3,2-benzodiazaborine 3-oxide,and 3,4-dihydro-2H-1,2,4,3-benzothiadiazaborine 1,1-dioxide

A number of arylamidoximes, an o-aminobenzaloxime, and an o-aminobenzenesulfonamide have been reacted with boronic acids to give three novel boron containing heterocycles. Evidence, based on mass spectroscopy, that the product from o-aminobenzaloxime is a 1,2-dihydro-l,3,2-benzodiazaborine 3-oxide, is presented.     

New 2-substituted 4-hydroxy-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxides: Spectral and pharmacological properties

A series of 4-hydroxy-2H-1,2-benzothiazme-3-carboxamide 1,1-dioxides substituted on the sulfonamide nitrogen with ethoxycarbonylalkyl, cyanoalkyl and dialkylaminoalkyl groups was synthesized. Spectroscopic properties of the obtained products were analyzed. Findings from the pharmacological study of some of the compounds as antiinflammatory and analgesic agents are reported.     

Reactivity of 2-methyl-4-(1-pyrrolidinyl)-2H-1,2-benzothiazine 1,1-dioxide towards p-toluenesulphonyl azide

The 2-methyl-2H-1,2-benzothiazin-4-(3H)-one 1,1 dioxide ( 2 ), obtained according to a new, one-pot method, is transformed into the pyrrolidino enamine 3 . Reaction of p-toluenesulphonyl azide with 3 gives, via an unstable triazoline adduct which loses nitrogen, the two isomeric tosylamino derivatives 4 and 5 . The structures have been assigned by exhaustive nmr analysis and some aspects on their formation and chemical behaviour are discussed.     

Synthesis of 3,4-dihydro-2H-1,3,5-thiadiazines

3,4-Dihydro-2H-1,3,5-thiadiazines substituted at the 3 and 6 positions were synthesized by treatment of N-substituted N,N-bis(1H-1,2,3-benzotriazol-1-ylmethyl)-amines with thioamides and zinc bromide in dry CH(2)Cl(2) at room temperature for 48-60 h in 48-80% yields.