bluuebunny/crossref_metadata_2025 huggingface dataset:
Cyelisation of arylcarboxamidouracils. Synthesis of a new 4H‐3,1‐benz‐oxazin‐4‐one. Use of mass spectrometry as a probe
Authors: Bernier Jean‐Luc , Hénichart Jean‐Pierre
Published: April 2009

The action of acetic anhydride on an anthranylcarboxamidouraeil led to a new 2‐substituted 4H‐3,1‐benzoxazin‐4‐one with potential analgesic activity. Mass spectrometry has been used as a method lor structure confirmation and several fragmentation pathways were proposed. Furthermore, an additional probe was given by opening of the lactonic ring submitted to the action of aliphatic and aromatic primary amines.
Synthesis of 8‐aza‐15‐hydroxy‐7‐oxo‐12S‐13E‐prostenoic acids
Authors: Zoretic P. A. , Sinha N. D. , Shiah T. , Maestrone T. , Branchaud B.
Published: April 2009

The synthesis of a prostaglandin E1 analog, 8‐aza‐15‐hydroxy‐7‐oxo‐12S‐13E‐prostenoic acid, is reported.
Aromatic systems with 10π electrons derived from 3a‐azapentalene. XXXV Quaternary salts of 3‐methyl‐s‐triazolo[4,3‐α]benzimidazole
Authors: de Mendoza Javier , Rull Pedro
Published: April 2009

Quaternary salts with general structures 3 and 4 are obtained by reaction of 3‐methyl‐s‐tríazolo [4,3‐α]benzimidazole and its alkyl derivatives 1 and 2 (R ≠ H) with alkyl halides. Compound 1 quaternizes at N1 and N2, whereas 2 quaternizes only at N9. Compounds 3 and 4 are useful models for the study of the sites of protonation in this series. Structures are unequivocally assigned by hydrolysis and dealkylation.
1,2,3‐Triazolo[1,5‐c]pyrimidine, a novel heterocycle in the polyazaindolizine series
Authors: Maury Georges , Paugam Jean‐Paul , Paugam Renée
Published: April 2009

The synthesis and struetural properties of the novel heterocycle 1,2,3‐triazolo[1,5‐c]pyrimidine are described. No evidence of a triazole‐diazoalkylideneazine valence tautomerism process was observed at room temperature.
The 5‐chloro‐1‐alkoxy‐1,2,3‐benzotriazole system
Authors: McGee A. W. , Serve M. P. , Seybold P. G.
Published: April 2009

The 5‐chloro‐1‐alkoxy‐1,2,3‐benzotriazole system has been synthesized and characterized via its physical and chemical properties. HMO calculations predict the most reactive sites on the molecule.
3‐Benzoyl‐2‐hydroxy‐9‐methylpyrido[1,2‐A] pyrimidin‐4‐one
Authors: Yale Harry L.
Published: April 2009

The single aberrant product of the reaction between 2‐amino‐3‐methylpyridine (2) and ethyl benzoylacetate (4) in diethylbenzene at ca. 180° was 3‐benzoyl‐2‐hydroxy‐9‐methylpyrido‐[1,2‐a]pyrimidin‐4‐one (5). When administered to naive rats, 5 induced behavioral effects strikingly similar to those manifested by morphine‐addicted rats who have been deprived of that analgetic.
Conversion of 2‐(O‐hydroxyphenyl) alkyl ketones into 2‐hydroxymethylchroman derivatives
Authors: Bravo Pierfrancesco , Ticozzi Calimero
Published: April 2009

2‐Hydroxymethylchromans are the only products arising from the oxidation by m‐chloro‐perbenzoic acid of the β‐(o‐hydroxyphenyl) olefins VI, obtained in turn form 2‐(o‐hydroxy‐phenyl) alkyl ketones (I) by the Wittig olefination with triphenylphosphonium methylide.
Structural reassignment of the condensation product of the 2‐phenylimidazole‐4,5‐dione benzamidinium salt
Authors: Braun Siegmar , Hafner Klaus
Published: April 2009

It is shown by 13C nmr spectroscopy that the thermolysis and dehydration of the 2‐phenyl‐imidazole‐4,5‐dione benzamidinium salt (1) yield 2‐cyano‐4,6‐diphenyl‐1,3,5‐triazine (7) and not as postulated previously, 2,5‐diphenylimidazo[4,5‐d]imidazole (3) as the reaction product.
Analgetika. VIII. Fluoralkylsubstituierte 2‐(äthylamino)pyrimidine
Authors: Kreutzberger Alfred , Leyke‐Röhling Swanhild
Published: April 2009

Durch Fluoralkylgruppen substituierte 2‐(Äthylamino)pyrimidine (3) können durch Umsetzung von Äthylguanidin (1) mit entsprechend substituierten β‐Diketonen (2) erhalten werden. Innerhalb der Verbindungsklasse 3 finden sich Vertreter mit analgetischer, entzündungshemmender und antimykotischer Wirksamkeit.
On the vinyl group photooxygenation of bilirubin‐like model compounds
Authors: Lightner D. A. , Park Y‐T.
Published: April 2009

The photooxygenation of z‐3‐vinyl‐4‐methyl‐5‐(phenylmethylidene)‐3‐pyrrolin‐2‐one (1) and z‐5′‐oxo‐4′‐viny1–4‐ethyl‐3′,3,5‐trimethyl‐1′,5′‐dihydro(2,2′)dipyrromethene (2) reveals no reaction at the vinyl groups; hence, none is expected at the vinyl groups of bilirubin IXα, and none has been found.
The synthesis of a 12,13‐dihydro‐5H‐dibenzo[b,g] [1,5] diazonine by a novel ring enlargement reaction
Authors: Aeberli Paul , Houlihan William
Published: April 2009

A novel method for ring expansion of a heterocycle containing a NCN system to a medium sized diaza‐heterocycle has been demonstrated for the conversion of an isoindolo[2,1‐a]‐quinazoline derivative 8 to the 5H‐dibenzo [b,g] [1,5]diazonine (13). Attempts to apply this isomerization to heterocyclic systems related to 8 were not successful.
Reaction of diethyl (phthalimidoacetyl)malonate with hydroxylamine
Authors: Bregant N. , Perina I.
Published: April 2009

The reaction of diethyl (phthalimidoacetyl)malonate with hydroxylamine was investigated. Depending upon the reaction conditions, N‐phthaloylglycinehydroxamic acid (2) and the cyclized product, 4‐ethoxycarbonyl‐5‐hydroxy‐3‐(phthalimidomethyl)isoxazole (4), were obtained.
4‐Substituted‐3‐alkyl‐3,4‐dihydro‐2H‐1,3‐benzoxazin‐2‐ones II (1,2). Solvolytic transformations of urea and thiourea derivatives into 1‐alkyldihydro‐6‐(2‐hydroxyaryl)‐1,3,5‐triazine‐2,4‐(1H,3H) diones
Authors: Bobowski George , Shavel John
Published: April 2009

A series of 3,4‐Dihydro‐2‐oxo‐(3‐substituted‐2H‐1,3‐benzoxazin‐4‐yl)ureas (II, Table I) and 3,4‐dihydro‐2‐oxo‐(3‐substituted‐2H‐1,3‐benzoxazin‐4‐yl)thioureas (Table II) was prepared by treating 3,4‐dihydro‐4‐hydroxy‐3‐substituted‐2H‐1,3‐benzoxazin‐2‐ones with ureas and thioureas, respectively. In the presence of alcoholic alkali these compounds underwent transacylation to dihydro‐6‐(2‐hydroxyaryl)‐1,3,5‐triazine‐2,4‐(1H,2H)diones (Table III) and their 4‐thio analogues (Table IV).
The decarbonylation reaction of imidazole‐2‐carbaldehydes in ethanol
Authors: Antonini Ippolito , Cristalli Gloria , Franchetti Palmarisa , Grifantini Mario , Gulini Ugo , Martelli Sante
Published: April 2009

Imidazole‐2‐carbaldehydes in hot ethanol undergo a decarbonylation reaction involving nucleophilic attack of the alcohol on the carbonyl to form the corresponding imidazole and ethyl formate.
Intermediates in the reaction of singlet oxygen with trisubstituted oxazoles
Authors: Graziano M. L. , Iesce M. R. , Scarpati R.
Published: April 2009

Trisubstituted oxazoles I react at −15° with singlet oxygen to give dioxazoles III and iminoanhydrides V which rearrange at room temperature to triamides VI. The intermediate ratio (III/V) is sensitive to the reaction temperature. It is likely that at room temperature triamides VI are essentially formed via imino‐anhydrides V.
Synthesis of 2[(4,6‐diphenyl‐2H‐pyran‐2‐ylidene)methyl]‐4,6‐diphenylpyrylium perchlorate
Authors: Reynolds G. A. , Van Allan J. A.
Published: April 2009

The title compound was prepared by the condensation of 4,6‐diphenyl‐2H‐pyran‐2‐one and acetophenone in phosphorus oxychloride. The absorption spectrum of this 2,2‐methine dye is compared with those of the corresponding 2,4‐ and 4,4‐methine dyes.
A simple synthesis of (±)1‐Methyl benzofurocyciopentan‐3‐one
Authors: Grant Hamish G.
Published: April 2009

The synthesis of the title compound, a previously unreported tri‐cyclic benzofuran analog, and the preparation of some of its derivatives is reported
New benz[g]indole and spiroketone heterocycles from acyl thioacetamides
Authors: Marten E. Hoffmeister , Maggiulli C. A.
Published: April 2009

The acyl thioacetanilide 3 condensed with 2‐bromotetralone to give the spiroketone 5. A similar reaction of the tetralone with the acyl‐N‐ethylthioacetamide 4 afforded small amounts of the unsaturated spiroketone 6 with the isomeric dihydrobenz[g]indole 7 as the major product. Compound 7 was aromatized to the benz[g]indole 8 in high yield.
Aziridinyl ketones. XVIII. The rearrangement‐dehydrogenation of cis‐1‐cyclohexyl‐2‐phenyl‐3‐aroylaziridines
Authors: Tarburton Philip , Wall D. K. , Cromwell Norman H.
Published: April 2009

The sequential nature of the unique rearrangement‐dehydrogenation of cis‐1‐alkyl‐2‐aryl‐3‐aroylaziridines (1a‐d) into 2‐alkylamino‐3‐arylindenones (2a‐d) when treated with a lithium amide has been established. Furthermore, a competitive degradation pathway has been discovered which leads to ω‐aminoacetophenones and benzaldehyde, thereby accounting for the major product of this reaction. trans‐1‐Alkyl‐2‐aryl‐3‐aroylaziridines do not react with the lithium amides employed in these studies. Although 1‐cyclohexyl‐2‐methyl‐3‐benzoylaziridine reacts with lithium amide to produce a 3‐carbanion, neither a rearrangement‐dehydrogenation to a 2‐aminoindenone nor a more extensive degradation involving carbon‐carbon bond cleavage is observed. Mechanistic pathways for these base catalyzed reactions are discussed.
Studies on the synthesis of heterocyclic compounds. Part I. The pschorr reaction in the pyrazole series
Authors: Plescia S. , Daidone G. , Sprio V. , Aiello E. , Dattolo G. , Cirrincione G.
Published: April 2009

Preparation and structural evidence of N‐methyl‐(1,3‐R,R'‐pyrazol‐5‐yl)‐o‐nitrobenzamides (VIIIa, b) are discussed. Diazotisation of related o‐aminobenzamides XIa,b followed by the Pschorr reaction afforded a very complex mixture from which pyrazolo[3,4‐c]isoquinolin‐5‐ones XIIa.b in 7–10% yields together with N‐methyl‐(1,3‐R,R'‐pyrazol‐5‐yl)‐o‐hydroxybenzamides (XIIIa) in 15–20% yields were isolated.
Five‐Membered Heterocyclic Thiones. Part VII . 1,2,3‐ThiadiazoIe‐5‐thiolates
Authors: Demaree Patricia , Doria Marie‐Carmen , Muchowski Joseph M.
Published: April 2009

The synthesis of the stable potassium salts of the first known 1,2,3‐thiadiazole‐5‐thiols is described.
Isothiazoles XI. Diels‐alder adducts of 4‐isothiazolin‐3‐one 1‐oxides and 1,1‐dioxides
Authors: Weiler Ernest D. , Brennan John J.
Published: April 2009

4‐Isothiazolin‐3‐one 1‐oxides and 1,1‐dioxides react with a variety of cyclic and acyclic dienes to afford cycloaddition products.
Synthesis of 4,5‐dihydro‐4‐methyl‐1‐phenyl‐1,4,5‐benzotriazocine‐2,3,6(1H) triones
Authors: Daniel John K. , Peet Norton P.
Published: April 2009

The title compounds, 7a and its 9‐chloro analog 7b, were prepared in three steps from methyl N‐phenylanthranilates. Thus, methyl N‐phenylanthranilate (3a) was treated with oxalyl chloride to yield 2‐[(2‐chloro‐1, 2‐dioxoethyl) phenylamino]benzoic acid methyl ester (4a). Treatment of 4a with methylhydrazine gave 2‐([2‐(1‐methylhydrazino)‐1,2‐dioxoethyl]phenylamino) benzoic acid methyl ester (6a), which was cyclized with sodium hydride in dimethylformamide to produce 7a. Alkylation of 7a and 7b with iodomethane afforded the respective 5‐methyl derivatives 8a and 8b. A survey of the known literature benzotriazocines is presented.
Reactions of simple phospholes with dimethyl acetylenediearboxylate
Authors: Holah David G. , Hughes Alan N. , Kleemola Daniel
Published: April 2009

Reactions of the three phospholes 1‐phenylphosphole, 3‐methyl‐1‐phenylphosphole and 3,4‐dimethyl‐1‐phenylphosphole with dimethyl acetylenedicarboxylate are reported. All three phospholes react extremely readily with the acetylenic ester to give ring‐expanded bicyclic ylidic systems, although 1‐phenylphosphole appears to react by a different pathway from the other two phospholes. These reactions show that simple phospholes in general, in contrast to heavily substituted phospholes, are quite good nucleophiles in organic reactions and the results of this study are consistent with a relatively easily perturbed aromatic structure for these phospholes.
Recherches sur le benzofuranne. LXII. Orientation de la nitration de benzofurannes substitués en 2 par un groupement électro‐attracteur
Authors: Lamotte Geneviève , Demerseman Pierre , Royer René
Published: April 2009

La nitration par l'acide nitrique dans l'anhydride acétique des acétyl‐2, carbéthoxy‐2 et cyano‐2 benzofurannes s'effectue principalement en 5 et en 6, accessoirement en 4 et éventuellement en 7. Dans les deux premiers cas, il y a en outre remplacement du substituant en 2 par le groupement nitro.
Benzo[b]thiophene derivatives. XXIII. Derivatives of 5,6‐dihydroxy‐3‐benzo[b] thienylacetic acid
Authors: Campaigne E. , Homfeld E. , Mais Dale E.
Published: April 2009

A series of 5,6‐disubstituted benzo[b]thiophenes have been synthesized for biological evaluation. These include analogs of tryptamine, melatonin and harmaline types, having hydroxy, methoxy, methoxymethyloxy, or isopropylidenedioxy groups at both the 5‐ and 6‐ positions. In order to synthesize these, the appropriate mercaptoguaiacols were prepared, and condensed with chloroacetoacetic esters to the 4‐arylthioacetoacetic esters. Cyclization of these ketones was best accomplished when the free phenolic groups were masked by methoxymethyl groups. The benzo[b] thienylacetic esters were then converted to corresponding amides, reduced to tryptamine analogs, acetylated to melatonin analogs, and cyclized to harmaline analogs. N‐Acetyltryptamine and 1‐methylmelatonin were also synthesized for comparison. Preliminary bioassay results on the melatonin analogs, which showed activity, are reported.
Meso‐heterocyclic analogues of 9,10‐dihydroanthracene. XIV. Some indoles and carbazoles derived from phenoxathiin
Authors: Coïc J‐P. , Saint‐Ruf G.
Published: April 2009

2‐Aminophenoxathiin undergoes easy condensation with different ω‐bromoketones to give 2‐aroylmethylaminophenoxathiins. These compounds give pyrrolo[2,3‐b]phenoxathiins by the Möhlau‐Bischler cyclisation. Some carbazolo[2,1‐b]phenoxathiins were also synthesised from 7‐oxo‐7,8,9,10‐tetrahydrobenzo[b] phenoxathiin.
The reactivity of the A‐CH=N‐NR‐CX‐B system. 1,3,4‐Oxadiazoles and 2,3,4,5‐tetrahydro‐1,2,4‐triazin‐3‐ones through the 1–5 and 1–6 cyclization reactions of α‐thienylglyoxal monosemicarbazones
Authors: Werber Giuseppe , Buccheri Francesco , Vivona Nicolò , Gentile Manlio
Published: April 2009

The factors influencing the reactivity of α‐thienylglyoxal monosemicarbazones when treated with cyclizing reagents (bromine/sodium acetate and hydrobromic acid in acetic acid) were investigated. Depending on the experimental conditions, on the position of the substituent on the semicarbazide residue, and on the cyclizing agent, the substrates 1a‐e give the semicarbazone bromides 2a‐b, 5, the 1,3,4‐oxadiazoles 3a‐c, the 1,2,4‐triazine 11 and the 2,3,4,5‐tetrahydro‐1,2,4‐triazine‐3‐ones 6, 8 and 9. Compound 6 by thermolysis undergoes ring contraction in the Δ2‐1,3,4‐oxadiazoline 12, while treatment with base involves the conversion of 6 into 1,2,4‐triazol‐5‐one 13. Ir, nmr and mass spectra support the reported structures.
Condensed benzopyrans III. 3H,4H[1] benzopyrano [3,4‐b] pyrrol‐4‐ones
Authors: Khan Misbahul Ain , De Brito Morley Maria Lucia
Published: April 2009

The diazotization of 3‐aminocoumarin followed by its reduction gave the cournarin‐3‐yl‐hydrazine which, without isolation, reacted with various carbonyl compounds in a Fisher's indohzation reaction to give derivatives (Ib‐Ih) of the yet unreported system 3H,4H[1]benzopyrano[3,4‐b]pyrrol‐4‐one.
The synthesis and characterization of some cyclic N‐cyanoguanidines
Authors: Bristol James A.
Published: April 2009

The sodium hydroxide catalyzed synthesis of several cyclic N‐cyanoguanidines (8,10) from dimethyl cyanoimidodithioearbonate (2) and the appropriate aniline derivative (4,5) is described. Base‐induced di‐N‐alkylation to afford 9 and 11 occurs readily.
The reaction of 3‐hydroxypyridine N‐oxide with active hydrogen compounds and the synthesis of 3‐substituted 2‐aminofuro[3,2‐b] pyridines
Authors: Stein M. Luisa , Manna Fedele , Lombardi Carmine C.
Published: April 2009

3‐Hydroxypyridine N‐oxide reacts readily in acetic anhydride with ethyl cyanoacetate, cyanoacetone and malononitrile. The three reaction products (2‐substituted‐3‐acetoxypyridines) show different equilibria between tautomeric structures; in strong acids they undergo cyclization to 3‐substituted 2‐aminofuro[3,2‐b]pyridines.
Pyridylalkylthiols and derivatives
Authors: Furukawa Sunao , Wells Fred V. , Castle Raymond N.
Published: April 2009

A series of pyridylalkylthiols and their derivatives have been prepared as potential radiation‐protection agents.
Réactivité de spirochromènes et de mérocyanines azahétérocycliques vis‐à‐vis de quelques agents nucléophiles
Authors: Maguet Michel , Guglielmetti Robert
Published: April 2009

Les spirochromènes azahétérocycliques saturés réagissent avec les agents nucléophiles comme l'eau, l'hydrogène sulfuré et le borohydrure de sodium. Ils subissent alors une ouverture soit de leur partie hétérocyclique azotée, soit de leur partie chroménique, soit des deux simultanément. Quant aux mérocyanines, elles peuvent ětre soit partiellement réduites, soit décomposées par le borohydrure de sodium.
Fluoroazoles. III. Synthesis and 1H and 1–9F nmr spectra of 3‐, 4‐, and 5‐fluoro‐1‐methylpyrazole
Authors: Fabra Francesc , Vilarrasa Jaume , Coll Josep
Published: April 2009

The three monofluoro derivatives of N‐methylpyrazole have been synthesized. 3‐Fluoro‐1‐methylpyrazole and 4‐fIuoro‐1‐methylpyrazole were prepared from the appropriate amines by diazotization and photochemical irradiation of the diazonium salts in tetrafluoroboric acid. 5‐Fluoro‐1‐methylpyrazole was obtained from 1‐acetyl‐3‐fluoropyrazole and methyl fluorosulfonate, and also by direct methylation of 3(5) fluoropyrazole with dimethyl sulfate. The 1–9F chemical shifts of these N‐methylated fluoroazoles cover a great range (ca. 50 ppm) and show a good correlation with the chemical shifts of H3, H4, and H5 protons of 1‐methylpyrazole. An unexpected long‐range coupling 5J (F‐CH3) is observed in 3‐fluoro‐1‐methylpyrazole.
Selenium heterocycles XXVII . Synthesis of Thieno[2,3‐d] thiazole and Selenolo[3,4‐d]thiazole. Two novel heterocycles
Authors: Shafiee A. , Mazloumi A.
Published: April 2009

Starting from the readily available aryl 2‐substituted‐4‐methyl‐5‐thiazolyl ketones, a series of 2,6‐disubstituted‐thieno[3,4‐d]thiazoles and 2,6‐disubstituted‐selenolo[3,4‐d]thiazoles were prepared. The structures of these compounds were confirmed by analytical, spectroscopic methods and through the reaction with dimethyl acetylenedicarboxylate.
Chemistry of benzo[b] furan IV.. Chemical behaviour of furo[3,4‐b] ‐benzofuran and synthesis of 4‐Arylbenzofuro[2,3‐d] pyridazines
Authors: Shafiee A. , Behnam E.
Published: April 2009

Furo[3,2‐b]benzofuran was demonstrated to be an intermediate for the synthesis of dibenzofuran and 1,4‐epoxy‐1,4‐dihydrodibenzofuran ring systems. Starting from the readily available aryl 3‐bromomethyl‐2‐benzo[b]furyl ketones, a method was developed for the synthesis of 4‐arylbenzofuro[2,3‐d]pyridazines.
Addition reactions of heterocycles. VII. Pyrrole and C‐Acetyl‐N‐phenylnitrilimine
Authors: Ruccia Michele , Vivona Nicolò , Cusmano G. , Macaluso Gabriella
Published: April 2009

The addition reaction of C‐acetyl‐N‐phenylnitrilimine to pyrrole has been investigated. The products obtained show that the reaction proceeds via two distinct pathways. The 1,3‐addition reaction leads to the non‐cyclic‐adduct III, whereas the 1,3‐cycloaddition reaction gives a mixture of regioisomeric Δ2‐pyrroline IV and V, and Δ1 ‐pyrroline VI and VII mono‐cycloadducts. These latter compounds cannot be isolated because they undergo a further 1,3‐cycloaddition reaction leading to the N‐substituted bis‐adducts X and XI, and to the bis‐adduets XII and XIII. The stereochemical assignment for X, XI, XII and XIII is provided by nmr data which suggest also that in X and XI the rotation around the exocyclic N‐C bond is relatively slow on the instrument time scale.
The synthesis of some pyrido[1,4] benzoxazepines and a dipyrido[1,4] oxazepine
Authors: Brewster Keith , Harrison John M. , Inch Thomas D.
Published: April 2009

Synthetic routes to pyrido[2,3‐b]‐, pyrido[4,3‐b]‐, pyrido[3,2‐f] [1,4]benzoxazepines and dipyrido[2,3‐b:2,3‐f] [1,4]oxazepine are described. The applicability of one of the methods to dibenz[b,f] [1,4]oxazepine synthesis is discussed.
The reductive ring opening of some derivatives of isatin
Authors: Ashby John , Ramage E. M.
Published: April 2009

Treatment of two isatin‐3‐imines, 3‐isopropyIamino‐1‐methylindoline‐2‐one and 3‐cyclohexylamino‐1‐methylindolin‐2‐one with sodium borohydride produced the fully‐reduced anilines 2‐isopropylamino‐2‐(2‐methylaminophenyl) ethanol and 2‐cyclohexylamino‐2‐(2‐methylaminophenyl) ethanol, respectively. Reductive ring‐opening of derivatives of isatin is not observed in related examples when either catalytic or lithium aluminum hydride reduction are employed and it is concluded that the present effect is dependant upon the softness of sodium borohydride as a reducing agent.
Tetracyclic phenothiazines V. Construction of the azepino[3,2,1‐kl] ‐phenothiazine ring system by regioselective ring expansion
Authors: Kim Sun H. , Martin Arnold R.
Published: April 2009

Solvolysis of 1,2‐dihydro‐3‐hydroxy‐3‐(p‐toluenesolfonyloxymethyl) 3H‐pyrido[3,2,1‐kl]‐phenothiazine gave 1,2,3,4‐tetrahydroazepino[3,2,1‐kl]phenothiazin‐3‐one.
Synthesis of 1‐amino‐4‐chloroisoquinoline. A new approach to 1‐aminoisoquinoline
Authors: Nuvole Antonio , Pinna Gérard Aimé
Published: April 2009

The as yet unknown 1‐amino‐4‐chloroisoquinoline was synthesised from 1,4‐dichloroisoquinoline through the 1‐phenoxy‐4‐chloro derivative. This procedure was also suitable for obtaining 1‐aminoisoquinoline from 1‐chloroisoquinoline in good yields.
Synthesis and reduction of some 1H‐2,1,3‐benzothiadiazin‐4(3H) one 2,2‐dioxides
Authors: Bancroft Keith C. C. , Guindi Laila H. Morcos , Temple Arthur F.
Published: April 2009

Several 2,1,3‐benzothiadiazin‐4(3H) one 2,2‐dioxides were synthesized as possible sweetening agents by reacting sulfamoyl chloride with various anthranilic acid derivatives. The isolation of 1‐methyl‐4‐methoxy‐2,1,3‐benzothiadiazine 2,2‐dioxide and preparation of 3,4‐dihydro‐2,1,3‐benzothiadiazine 2,2‐dioxide is also reported.
An efficient synthesis of 3‐aminoisothiazolo[5,4‐b] ‐quinoline from quinoline
Authors: Iijima Ikuo , Rice Kenner C.
Published: April 2009

Treatment of readily available 3‐formylquinoline‐2‐thiol (1) with ammoniacal sodium hypochlorite directly afforded isothiazolo[5,4‐b]quinoline (3) in high yield, probably via 3‐formylquinoline‐2‐sulfenamide (2). Facile conversion of 3 to the corresponding 3‐amino derivative (7) was accomplished by the following sequence: base induced opening of the isothiazole ring to 3‐cyanoquinoline‐2‐thiol (5), oxidation of 5 to the corresponding stable sulfenamide (6) and sodium ethoxide catalysed reclosure of the isothiazole ring which provided 3‐aminoisothiazolo[5,4‐b]quinoline (7).
Preparation of ethyl 1‐hydroxy‐2‐naphthoates from 1H‐2‐benzopyran‐1‐ones: A new method
Authors: Hauser Frank M. , Pogany Stefano A.
Published: April 2009

Lithio ethyl acetate is a superior reagent for the transformation of 1H‐2‐benzopyran‐1‐ones to naphthoates.
Chemistry of the phenoxathiins VI. An examination of the 1–3C‐1H coupling constants of 1‐azaphenoxathiin by selective excitation fourier transform 1–3C‐NMR
Authors: Martin Gary E.
Published: April 2009

The complete examination of coupled 1–3C‐nmr spectra of complex heterocyclic systems is seldom attempted because of the inherrent complexity of these spectra, arising through extensive spin‐multiplet overlapping. The utilization of the selective excitation technique, in combination with gated decoupling for the specific re‐examination of the primary coupling constants of resonances at the 4‐ and 6‐positions of the 1‐azaphenoxathiin ring system is described.
Kinetic evidence for the unusual path in the hydrolysis of amides. pH‐rate profile for N‐trifluoroacetylindole
Authors: Cipiciani Antonio , Linda Paolo , Savelli Gianfranco
Published: April 2009

The first complete pH‐rate profile (HO‐4 ÷ pH 12) for an amide is reported. Hydration of carbonyl moiety is suggested to be the first step of the reaction between HO‐4 ÷ pH 6.
Synthesis and spectroscopic studies of some heterocyclic compounds. Reaction of 3‐aryl‐1‐phenyl‐2‐propen‐1‐ones with ethyl phenylacetate
Authors: Al‐Farkh Yousuf A. , Al‐Hajjar Farouk H. , Hamoud Hayat S.
Published: April 2009

3‐Aryl‐1‐phenyl‐2‐propen‐1‐one I reacted with ethyl phenylacetate (II) in the presence sodium ethoxide at room temperature to give the corresponding ethyl β‐aryl‐γ‐benzoyl‐α‐phenyl‐butyrate III. However,' when the same ketones were refluxed with ethyl phenylacetate, they gave the corresponding 4‐aryI‐3,6‐diphenyl‐3,4‐dihydro‐2H‐pyran‐2‐ones IV. The reactions of III and IV with hydrazine hydrate afforded the corresponding hydrazones VI and 2‐pyridones VIII, respectively. The structure and configuration of the products are based on chemical and spectroscopic evidence.
Nouvelle voie de synthèse des dérivés de l'ellipticine et analogues alcaloïdes à activité antitumorale
Authors: Gilbert Jacques , Rousselle Dominique , Gansser Charles , Viel Claude
Published: April 2009

Les auteurs rapportent une voie originate d'accès aux 6H‐pyrido[4,3‐b]carbazoles, qui est aisément mise en oeuvre à partir de cyclohexanones convenablement substituées. Elle réalise la fusion des synthèses de Borsche d'obtention des carbazoles et de Cranwell et Saxton de preparation de l'ellipticine, et présente le double avantage de la commodité d'accès des matières premières et d'une aromatisation effectuée dès la seconde étape. Les 7H‐pyrido[3,4‐c]‐carbazoles ne sont obtenus que lore de la preparation des desméthyl‐11 ellipticines.
New heterocyclic ring systems. IX. Polyazadithiasteroid analogues
Authors: Fravolini A. , Schiaffella F. , Strappaghetti G.
Published: April 2009

The synthesis of the novel tricyclic ring 5‐rnethyl‐4‐oxo‐2,3,4,5‐tetrahydrothiopyrano[3,2‐c]‐[1,2]benzothiazine 6,6‐dioxide (III) is described.

By the reaction of hydrazine and hydroxylamine with the glyoxylate (IV) and ester (V) obtained from III, several polyazadithiasteriod analogues have been synthesized.
Réactions induites par ies halogénures de pyridinium. XXVII. Sur la formation d'ethers cycliques par action du chlorure ou du bromure de pyridinium sur l'hexanediol‐2,5
Authors: Dauzonne Daniel , Demerseman Pierre , Royer René , Lang Catherine , Ratzer Nicole
Published: April 2009

Il est montré que la cyclodéshydratation des hexanediols‐2,5 en diméthyl‐2,5 tétrahydrofurannes peut ětre effectuée au moyen du chlorure ou du bromure de pyridinium, aussi bien qu'avec n'importe quel autre réactif précédemment utilise' pour cela. On détermine les diverses réactions secondares qui accompagnent alors cette cyclodéshydratation et on précise par quels mécanismes elle s'effectue.
Organische photochemie XXI. 9H‐cyclopenta[b] [1]benzoselenin ‐ein neues heterocydisches ringsystem
Authors: Praefcke Klaus , Schmidt Dietmar
Published: April 2009

By way of a photo‐induced selenolester‐seleninone rearrangement, the derivative 5 of a new heterocyclic ring system, 9H‐cyclopenta[b][1]benzoselenin, has been formed. This rearrangement occurs via a new photosubstitution reaction of S‐aryl‐ in competition with Se‐aryl‐groups, followed by photocyclization using 2‐p ‐tolythiocyclopentene ‐1 ‐ selenocarbonic acid Se‐p‐tolylester (1a) as starting materials. As a competing product in this photo‐rearrangement, a second heterocycle, 7‐methylcyclopenta[b] [1]benzothiopyrone (4) (9) has been formed via an intramolecular photochemical Friedel Crafts reaction.
13C Nmr study of 1,2,4‐triazino[4,5‐b]indazole derivatives
Authors: Rabaron Alain , Lancelot Jean‐Charles , Maurne Daniel , Robba Max
Published: April 2009

The main nmr parameters of 1,2,4‐triazino[4,5‐b]indazole derivatives were measured on the basis of their 13C nmr spectral analysis compared to indazole models. 1J C‐H coupling constants were studied and the correct structure of 1,2,4‐triazino[4,5‐b]indazoles was elucidated.
Comparative chromatographic adsorbabilities of some azines, thioles and thienopyridines, their heteroatom oxides and other derivatives on silica gel
Authors: Klemm L. H. , Lee F. H. W. , Lawrence Ross F.
Published: April 2009

Thin layer chromatographic Rf data on silica gel are reported for 64 compounds containing either a thiole sulfur atom, one or more azine nitrogen atoms, or both. Thiole adsorbates are compared with 28 aromatic hydrocarbons and non‐heterocyclic sulfur compounds. In general the orders of Rf values found are thioles > sulfides > sulfones > sulfoxides > azine N‐oxides and azines > azine‐N‐oxides. Results are interpreted in terms of hydrogen bonding from the silica gel to the adsorbate. The different orders of adsorbability found amongst four series of condensed thiophenes and their arene analogs for chromatography on silica gel and on alumina are rationalized in terms of planarity and acid‐base interactions. Correlations of the tlc data with separations on columns are presented.
Synthesis of a novel 8‐thia‐1,4‐diazacycl[3.3.2] azine
Authors: Campaigne E. , Selby T. P.
Published: April 2009

A unique covalently hydrated cyclazine adduct, 2‐imino‐6a‐hydroxy‐4,5,6,6a‐tetrahydro‐7H‐8‐thia‐J, 4‐diazacycl[3.3.2]azin‐5‐one hydrochloride was prepared by reacting ethyl 4‐chloro‐acetoacetate with 4,6‐diamino‐2‐thiopyrimidine in neutral alcohol. Neutralization gave 2‐imino‐5,6a‐dihydroxy‐6,6a‐dihydro‐7H‐8‐thia‐1,4‐diazacycl[3.3.2]azine which decomposed to 4,6‐diamino‐2‐acetonylthiopyrimidine upon heating in water. Warming the hydrated hydrochloride in concentrated hydrochloric acid caused dehydration to yield 2‐imino‐5‐hydroxy‐6H‐8‐thia‐1,4‐diazacycl[3.3.2]azine hydrochloride. Partial isomerization (20%) to 2‐imino‐5‐hydroxy‐7H‐8‐thia‐1,4‐diazacycl[3.3.2]azine hydrochloride occurred during recrystallization from aqueous acidic methanol. The free base, 2‐imino‐5‐hydroxy‐7H‐8‐thia‐1,4‐diazacycl[3.3.2]azine was obtained after neutralizing either of the tautomeric hydrochlorides. Treating the free base with trifluoroacetic acid produced a mixture of the trifluoroacetate salts of the two tautomeric bases. Isomerization of one trifluoroacetate salt into the other in trifluoroacetic acid was observed by pmr at room temperature. Both 2‐amino‐5‐hydroxy‐7‐nitroso‐8‐thia‐1,4‐diazacycl[3.3.2]azine and 2‐amino‐5‐hydroxy‐6‐nitroso‐8‐thia‐1,4‐diazacycl[3.3.2]azine were isolated after nitrosation of the hydrochloride mixture.
Antimykotische wirkstoffe. VIII. Aufbau von dehydro‐N‐mannich‐basen durch piperidin‐ und piperazinring
Authors: Kreutzberger Alfred , Kreutzberger Elfriede
Published: April 2009

Aus einer die Umsetzung von Cyanamid (1) und s‐Triazin (2) mit einem sekundàren Amin (5) beinhaltenden Dreikomponcntenreaktion gehen die Dehydro‐N‐Mannich‐Basen (6), unter denen 6a, b und c antimykotische Wirksamkeit aufweisen, hervor.
Reaction of sulfene with heterocyclic N,N‐disubstituted α‐aminomethvlene ketones V. Synthesis of 1,2‐oxatliiino[5.6‐c] pyridine and 1,2‐oxathiino[5,6‐c] quinoline derivatives
Authors: Mosti Luisa , Menozzi Giulia , Schenone Pietro
Published: April 2009

Reaction of sulfene with N,N‐disubstituted 3‐aminomethylene‐1‐(methyl, methylphenyl, phenyl)‐4‐piprridones and 3‐aminomethylene‐2,3‐dihydro‐1‐plumy 1–4(1H) quinolones gave N,N‐disubstituted 4‐amino‐3,4,5,6,7.8‐hexahydro‐6‐(methyl, methylphenyl, phenyl)‐1,2‐oxathiino‐[5,6‐c] pyridine 2,2‐dioxides and 4‐amino‐6‐phenyl‐3,4,5,6‐tetrahydro‐1,2‐oxathiino[5,6‐c]quinoline 2,2‐dioxides, respectively, whereas N,N‐disubstituted 3‐aminomethylene‐2,3‐dihydro‐1‐methyl‐4(1H) quinolones did not react. Slow air oxidation in the cold of intermediates 2,3‐dihydro‐3‐hydroymethyIene‐1‐(methyl, phenyl)‐4(1H) quinolones gave the corresponding 1‐substituted 1,4‐dihydro‐4‐oxo‐3‐quinolinecarboxyaldehydes.
The synthesis of some benzo[d1]furo[3,2‐e] [1,4] diazepin‐2‐ones
Authors: Ashby John , Ramage E. M.
Published: April 2009

Reaction of 3‐amino‐2‐benzoylbenzo[b]furan with bromoacetyl bromide followed by cyclization in methanolic ammonia gave 5‐phenyl‐1,3‐dihydrobenzo[d′] furo[3,2‐e] [1,4]diazepin‐2‐one, a representative of a new ring‐system. The corresponding chloro substituted diazepin‐2‐one was similarly prepared from 3‐amino‐2‐(4‐chlorobenzoyl) benzo[b] furan. Some alkylation and thionation reactions of these diazepines have been investigated.
Structural reassignment of the alleged 6‐hydroxy‐1,2,4‐triazine‐3,5‐(2H,4H)dione
Authors: Schuan Thomas J. , Sanford Timothy J. , White It. L. , Miles Nelson J.
Published: April 2009

The reaction of 6‐amino‐1,2,4‐triazine‐3,5‐(2H,4H)clione with sodium hydroxide or nitrous acid has been shown to give 5‐hydroxy‐1,2,4‐triazole‐3‐carboxylic acid instead of 6‐hydroxy‐1,2,4‐triazine‐3,5‐(2H,4H)dione as reported in the literature. The triazolecarboxylic acid was also obtained from the aminotriazine and hydrochloric acid.
Addition des azidosulfatcs d'arylr sur le norborncne
Authors: Hedayatullah Mir , Guy Alain
Published: April 2009

La cycloaddition des azidosulfatcs d'aryle sur le norhornène dans l'acétonitrile à 25°, conduit, après perte d'azote, à des aziridines N‐substituées par des restes aryloxysulfonyles. Par rmn et svnthèse indépendante on montre que l'addition est stére'ospécifique avec formation exclusive d'aziridines exo.
Synthesis of I‐Hydroxy‐2,4‐diphenylpyrrolo[2,3‐d] pyridazin‐7(6H)one
Authors: Migliara Onofrio , Petruso Salvatore
Published: April 2009

The synthesis of 1‐hydroxy‐2,4‐diphenylpyrrolo[2,3‐d]pyridazin‐7(6H)one is described.
Cyclic imides. XII(i). Absorption and fluorescence spectra of 3‐benzamidophthalimides
Authors: Caswell Lyman R. , Campbell Jo‐Anne B. , Cecil Rosemary
Published: April 2009

The ultraviolet absorption, fluorescence, and infrared absorption spectra of fifteen 3‐benz‐amidophthalimides are described. In general, the nature or position of the substituents on the benzamide moiety has little effect on the ultraviolet absorption and fluorescence spectra of these, compounds. The absorption baud at 271 nm is more sensitive to substituent variations than the other two bands (at 227 nm and 341 nm), indicating this band is a composite of bands observed in the spectra of 3‐aminophthalimide and the substituted benzamide. The fluorescence of 3‐amino‐phthalirnide and the 3‐benzamidophthalimides is due to the same transitions. The infrared absorption wavenumbers for the amide and imide vibrations of the 3‐benzamidophthalimides are characterized.
Benzo[B]thiophene derivatives XXIV. Oxidation of o‐dihydroxybenzo[b]thiophene methyl ethers
Authors: Campaigne K. , Homfeld E.
Published: April 2009

The attempted oxidative demethylation of a series of o‐dihydroxybenzo[b]thiophene methyl ethers with cerium (IV), argentic oxide, periodale and thallate usually led to intractable mixtures. However, in one ease, use of ceric ammonium nitrate resulted in nitration of the benzo[b]‐thiophene ring. In another example, treatment with aqueous periodate or thallate resulted in oxidative hydroxylation of benzo[b]thiophene.
A novel synthesis of the benzo[F]quinazoline ring system
Authors: Delia Thomas J. , Munslow William D.
Published: April 2009

An approach to the synthesis of the benzo[f]quinazoline ring system using a preformed pyrimidine is described. A facile cyclization of a ketone function into the 5‐position of uracil is the key step in this sequence.
Synthesis of 5,6‐dihydro‐4H‐pyrrolo[1, 2‐a] [1,4]benzodiazepines
Authors: Cheeseman G. W. H. , Greenberg S. G.
Published: April 2009

The title compounds are. Prepared by the reaction of carbonyl compounds with 1‐(2′‐amino‐methylphenyl)pyrrole hydrochloride.
Condensed Pyridazines. Part I. Synthesis of 2‐Oxo‐2H‐pyrano[2,3‐D]‐pyridazine and 2‐Oxo‐2H‐pyrano[2,3‐c] pyridazine
Authors: Maeba Isamu , Ando Masahiko , Yoshina Shigetaka , Castle Raymond N.
Published: April 2009

The reaction of 4,7‐diehlorofuro[2,3‐d]pyridazine (1) with potassium cyanide in DMSO gave two products, (E)‐3,6‐diehloro‐5‐(2‐cyanovinyl)‐4‐hydroxypyridazine (II) and 5,8‐dichloro‐2‐oxo‐2H‐pyrano[2,3‐d]pyridazine (III) as a result of ring opening or ring expansion. A new ring system, 2‐oxo‐2H‐pyrano[2,3‐c]pyridazines (IX, XII, XIII) was obtained from 5,8‐dichloro‐3‐methyl‐2‐oxo‐2H‐pyrano[2,3‐d]pyridazine (VI).
Condensed pyridazines. Part II. Synthesis of pyrido[2,3‐C] pyridazines
Authors: Maeba Isamu , Castle Raymond N.
Published: April 2009

The synthesis of some pyrido[2,3‐c]pyridazines from 5,8‐diehloro‐3‐methyl‐2‐oxo‐2H‐pyrano‐[2,3‐d]pyridazine (I) is described. Attempted oxidation of 8‐amino‐3‐chloro‐1,6‐dimethyl‐4,7‐dioxo‐1,4,7,8‐tetrahydropyrido[2,3‐c]pyridazine (VI) with LTA led only to the deaminated compound VII. Treatment of VI with LTA A in the presence of cyclohexene gave the nitrene adduct XI.
On the photooxygenation and autoxidation of dipyrrylmethenes and dipyrrylmethanes
Authors: Norris R. D. , Lightner D. A.
Published: April 2009

The dye‐sensitized photooxygenations of 4,4′‐diethyl‐3,5,3′5′‐tetramethyldipyrrylmethene and 4,4 ‐diethyl‐3,5,3′5‐tetramethyldipyrrylmethane have been investigated in neutral, basic and acidic methanol solution. Several photoproducts are common to the photooxygenation of both substrates. The dipyrrylmethene was detected as an intermediate in the photooxygenation of the dipyrrylmethane; however, it was determined not to be an important precursor to monopyrrole products. Autoxidations of the two dipyrrole compounds were also investigated and were found to be slower than the corresponding photooxygenation. Autoxidation and photooxygenation were both found to be faster in basic than in acidic methanol with the dipyrrylmethane faster than with the dipyrrylmethene in the same solvent.
Synthesis of heterocyclic compounds. XIII. 2‐amino‐3‐benzyl‐3,5‐dieyano‐6‐methoxy‐4‐phenyl‐3,4‐dihydropyridines
Authors: Fuentes L. , Lorente A. , Soto J. L.
Published: April 2009

A synthesis of 2‐amino‐3‐benzyl‐3,5‐dicyano‐6‐methoxy‐4‐phenyl‐3,4‐dihydropyridines from benzylmalononitriles and benzylidenemalononitrile is described. The structures of the new compounds have been elucidated on the basis of spectral data (ir, nmr, ms), and in two cases (Vb and Ve) by chemical degradation.
Heterocyclic. Compounds. X. Bis(2‐chloroethyl)amino substituted β‐lactams as potential antineoplastic agents
Authors: Manilas M. S. , Min S. G. A. , Glazer R. D.
Published: April 2009

The synthesis of variously substituted β‐lactams carrying a bis(2‐chloroethyl) amino group is described. Some of these compounds show mild antitumor activity and low toxicity.
Reactions of nitrogen compounds with ruthenium tetroxide. Determination of the absolute configuration of 3‐ethylpiperidine
Authors: Morlacchi Flaviano , Losacco Vincenzo , Tortorella Vincenzo
Published: April 2009

(‐)‐3‐Kthylpiperidine and (R)‐(‐)‐2‐ethylglutarie acid have been chemically correlated through N‐subslituted α‐ethylglutarimides obtained from the oxidation of optically active N‐ethyl‐ and N‐benzyl‐3‐ethylpiperidine with ruthenium tetroxide. The (R)‐(‐) configuration of (‐)‐3‐ethylpiperidine was confirmed by CD measurements. The selective oxidation of endocyclic methylenes linked to the nitrogen atom was explained in term of different conformational freedom of endo‐ and exocyclic methylene groups.
On the mechanism of the conversion of 6‐chloropyrido[2,3‐B]pyrazine into 1h‐lmidazo[4,5‐b] pyridine by potassium amide in liquid ammonia
Authors: Nagel A. , Van Der Plas H. C. , Geurtsen G. , Van Der Kuilen A.
Published: April 2009

The synthesis of a number of 2‐R1, 3‐R2‐6‐X‐pyrido[2,3‐b]pyrazines (1) is reported and their reaction with potassium amide in liquid ammonia investigated. Ring contraction into a 2‐R‐1H‐imidazo[4,5‐b]pyridine was found to occur with X = Cl, R1 = H, R2 = C6H5 (1b); X = Cl, R1 = R2 = C6H5 (1c); X = Cl, R1 = H, R2 = t‐C4H9 (1d). Besides ring contraction, an increasing amount of dechlorination of 1 was found: 1a, 20%; 1b, 30%; 1d, 40%; 1c, 60%; 1g, 95%. 1e (X = Cl, R1 = t‐C4H9, R2 = H) yields the unreactive anionic σ‐adduct at C‐3 i.e., 3‐amino‐2‐t‐butyl‐6‐chloro‐3,4‐dihydropyrido[2,3‐b]pyrazine. The ring contraction only proceeds with X = Cl. 1b (X = F) gives an amino‐defluorination, 1b (X = Br) exclusively undergoes reductive debromination. The ring contraction of 1a (X = Cl, R1 = R2 = H) is investigated by 15N‐ and 13C‐labelling. It is concluded that the conversion into 1H‐imidazo[4,5‐b]pyridine proceeds via the reactive anionic σ‐adduct at C‐2, under exclusive elimination of C‐2.
Competition entre les réactivités dipolarophiles et nucléophiles des pyrazolines‐2 dans l'action de l'oxyde de benzonitrile. Synthèse, identification, comportement chimique des tétrahydropyrazolo‐[4,5‐b] oxadiazoles‐1,2,4
Authors: Giberl J.‐P. , Petrus C. , Petrus F.
Published: April 2009

L'action de l'oxyde de benzonitrile sur une série de pyrazolines‐2 permet de montrer la réaetivité dipolarophile de la liaison C=N et la présence de deux sites nucléophiles; l'azote en 1, ou le carbone en 3 pour les pyrazolines‐2 non substituées en 1 ou 3. La régiospécificité de la cycloaddition est démontrée. Cette dernière conduit à une nouvelle série d'hétérocycles condenses que nous décrivons.
Synthesis of heterocyclic analogs of α‐methyldopa
Authors: Tilley Jefferson W. , Levitan Paul , Kierstead Richard W.
Published: April 2009

The condensation of various halomethyl heterocycles with the potassium salt of the alanine derivative 3, followed by hydrolysis, gave a series of novel 3‐heterocyclic‐2‐methylalanines.
2‐(Aminomethyl)phthalimide. A new reagent for the synthesis of 2,4‐benzodiazepines
Authors: Lauer Rudolph F. , Zenchoff Gladys
Published: April 2009

2,4‐Benzodiazepines can be prepared by condensation of an activated 2‐benzoylbenzoic acid with 2‐(aminomelhyl)phthalimide. A synthesis of this reagent is described.
4‐Thiazolidinones and 2,4‐thiazolidinediones from α‐mercaptopropionic acid and carbodiimides
Authors: Monforte P. , Fenech G. , Basile M. , Ficarra P. , Silvestro A.
Published: April 2009

2,3‐Substituted 5‐methyl‐4‐thiazolidinones (1) and 3‐substituted 5‐methyl‐2,4‐thiazolidine‐diones (II) were prepared by reacting some carbodiimides with α‐mercaptopropionic acid, with the purpose of obtaining potentially chemotherapeutic agents. It is noteworthy that 3‐cyclohexyl‐5‐methyl‐2,4‐thiazolidinedione (IId) was obtained in three different crystalline structures. Some secondary compounds were also obtained: the N,N‐disubstituted ureas (III) and thioureas (IV) in all cases, the dianilides (V) and the tri‐substituted guanidines (VI) from the arylcarbodiimides, and the dithiolactide (VII) from the isopropyl‐ and cyclohexylcarbodiimides.
Reaction of 1‐formyladamantane with heterocyclic compounds. Mass spectra, antibacterial and antifungal activity
Authors: Fenech G. , Monforte P. , Chimirri A. , Grasso S.
Published: April 2009

1‐Formyladamantane reacts with some amino derivatives to give I, II, III and IV. 3‐Substiluted 2‐adamantyl‐4‐thiazolidinones (V), (VI) and (VII) were obtained by reacting the above compounds with mercaptoacetic acid. Their structure was established by ir, pmr and mass spectroscopy. All compounds synthesized inhibit the growth of gram‐negative and gram‐positive bacteria and fungi.
arabinonucleosides
Authors: Montgomery John A. , Jeanette Thomas H.
Published: April 2009

The α‐D‐arabinonucleosides of cytosine (6) and 5‐fluorouracil (9) were prepared from the 2,3,‐5‐tri‐O‐benzoyl‐D‐arabinofuranosyl halides, in keeping with thetransrule. The 2′‐O‐methyl‐)3‐D‐arabinonucleosides of 5‐fluorouraeil (β‐14) and adenine (β‐21a) were prepared from 3,5‐di‐O‐(4‐ehlorobenzoyl)‐2‐O‐methyl‐α‐D‐arabinofuranosyl chloride, although in both cases a lesser amount of the α‐anomer was also found. Reaction of 3,5‐di‐O‐(4‐chlorobenzoyl)‐2‐deoxy‐2‐(methylthio)‐α‐D‐arabinofuranosyl chloride, prepared in four steps from methyl 2,3‐anhydro‐α‐D‐ribofurano‐side (15), withN‐benzoyladenine gave slightly more of the β‐ than the α‐arabinonucleoside20b. The β‐anomer was converted to 9‐[2‐deoxy‐2‐(methylthio)‐β‐D‐arabinofuranosyl]adenine. Only 1‐α‐D‐arabinofuranosylcytosine (6) proved to be cytotoxic.
Mononuclear heterocyclic rearrangements. Part III. Rearrangement of the P‐methoxyphenylhydrazone and the m‐nitrophenylhydrazone of 3‐benzoyl‐5‐phenyl‐1,2,4‐oxadiazole in dioxane/water in the pS+ range 3.8–11.5
Authors: Spinelli Domenico , Corrao Antonino , Frenna Vincenzo , Vivona Nicolò , Ruccia Michele
Published: April 2009

The rates of the mononuclear heterocyclic rearrangement of the p‐methoxyphenylhydrazone (Ib) and the m‐nitrophenylhydrazone (1c) of 3‐benzoyl‐5‐phenyl‐1,2,4‐oxadiazole have been measured in the range of pS+ 3.8–11.5 (solvent: dioxane/water 1:1, v:v) and compared with those of the unsubstituted phenylhydrazone (Ia). The obtained results show that in the base‐catalyzed range, electron‐repelling as well as electron‐withdrawing substituents accelerate the rearrangement rates.
Synthesis of chromones
Authors: Reynolds G. A. , Van Allan J. A. , Seidel A. K.
Published: April 2009

A general procedure for the preparation of chromones from the boron difluoride complex of o‐hydroxyaryl methyl ketones is described. One of the best methods used for the preparation of chromones and benzochromones is the treatment of o‐hydroxyaryl methyl ketones with the dimethylacetal of dimethylformamide followed by treatment with sulfuric acid (1). We previously had shown (2) that benzochromone 4 was prepared in reasonable yield by the following reaction sequence.
Azobilirubin and azomesobilirubin isomers. A carbon‐13 nmr analysis
Authors: Salmón Manuel , Legoff I. , Joseph‐Nathan P.
Published: April 2009

The 13C nmr chemical shifts of azobilirubin and azomesobilirubin isomers are reported. The signals are assigned on the basis of substituent effects and comparison with structurally related compounds.
A reinvestigation of the bamberger‐ham phenazine. Synthesis: A limitation
Authors: Sawhney Shanti N. , Boykin David W.
Published: April 2009

The Bamberger‐Ham condensation of 4‐substituted nitrosobenzenes in concentrated sulfuric acid reported as a method of synthesis for phenazine N‐oxides has been found to be limited to electron donating substituents. Methyl 4‐nitrosobenzoale has been found to react under these conditions to give dimethyl 2‐nitrodiphenylamine‐4, 5‐diearboxylate (2). Compounds of unknown structure previously reported to arise from acid treatment of 4‐bromo‐ and 4‐chloronilrosobenzene have been shown to be 4, 5‐dibromo‐2‐nitrosophenylamine (10) and the analogous dichloro compound. Treatment under stronger acidic conditions (oleum) converted 10 but not 2 into the corresponding phenazine N‐oxide. Mechanistic implications are discussed.
Some reactions of 1,2‐dihydropyridines with cyanogen azide. Synthesis of üiazabieyclo[4.1.0]hept‐4‐enes
Authors: Ondrus T. A. , Knaus E. E. , Ciam C. S.
Published: April 2009

The regiospecific 1,3‐dipolarcycloaddition reaction of 1,2‐dihydropyridines 1 with cyanogen azide 2 afford 2,7‐diazabieyelo[4.1.0]hept‐4‐enes 3 in quantitative yield. Catalytic hydrogenation of 3 gives rise to a tautomeric mixture of piperidylidene‐2‐cyanamides 5 in quantitative yield. Alternatively treatment of 3 with a suspension of alumina oxide in chloroform yields 1,2,5,6‐tetrahydropyridylidenes 4 which are also quantitatively reduced to 5.
Electrochemical behaviour of heterocyclic amidines I. Anodic oxidation of 2‐amino‐5‐ethoxycarbonyl‐4‐methylthiazole
Authors: Cauquis G. , Pierre G. , Elnagdi M. H. , Fahmy H. M.
Published: April 2009

The behaviour of 2‐amino‐5‐ethoxycrbonyl‐4‐methylthiazole on oxidation at a rotating platinum disc electrode is reported. The mechanism of the formation of the azo and hydraazo dimeric compounds as main oxidation products is discussed.
Substituent effects in chemical carcinogenesis: Methyl derivatives of the benzacridines
Authors: Smith Idea A. , Seybold Paul G.
Published: April 2009

An explanation for the different carcinogenic potencies observed among methyl derivatives of the angular benzacridines is given in terms of the tendencies of these compounds to undergo specific metabolic activating reactions analogous to those of polycyclic aromatic hydrocarbons. Theoretical reactivity indices representing these reactions correlate with the carcinogenic activities of these compounds.