bluuebunny/crossref_metadata_2025 huggingface dataset:
An anomalous by‐product in the von pechmann reaction
Authors: Belletire J. L. , Donahue K. , Kellogg M.
Published: April 2009

During condensation of 4‐chloro‐2‐methylphenol with diethyloxalacetate in sulfuric acid the spirodilactone 3 was observed as well as the desired coumarin 1. Further reaction of 1 under the reaction conditions with 4‐chloro‐2‐methylphenol did not produce 3 readily. These observations imply the formation of the intermediate 10 prior to production of the novel spirodilactone 3.
New synthesis of condensed hydropyridazine derivatives. VI
Authors: Plescia Salvatore , Daidone Giuseppe , Sprio Vincenzo
Published: April 2009

The reactivity of some indole derivatives towards the semicarbazone of ω‐bromoacetophenone has been reported. Substituents at position 1 and 2 of the indole ring greatly affect the course of the reaction. 1,4,4a,9a‐Tetrahydro‐9H‐pyridazino[3,4‐b]indole derivatives or 3‐indolyl derivatives were obtained depending on the substituents. The structures were assigned on the basis of satisfactory analytical and spectroscopic data.
Synthesis and properties of alkylated imidazoles
Authors: Huang Bao Shan , Lauzon Mary Jane , Parham James C.
Published: April 2009

Alkylation of 4(5)‐nitroimidazole‐5(4)‐sulfonamide with benzyl bromide occurred on both ring nitrogens. The structures of the products could be assigned by comparison of the chemical shifts of the sulfonamide hydrogens in the nmr spectra with those of the isomeric methyl derivatives, which were prepared by differing routes. Uv and nmr spectral data are reported for a number of bromo‐, nitro‐, mercapto‐, sulfamyl‐ and amino‐ substituted imidazoles as well as for both of the isomeric methylated derivatives of the series.
Reactions of β‐heteroatom substituted α,β‐unsaturated ketones with dimethylsulfonium methylide
Authors: Nishio Takehiko , Sugawara Mitsuko , Omote Yoshimori
Published: April 2009

β‐Alkoxy‐ and β‐alkylthio α,β‐unsaturated ketones react with dimethylsulfonium methylide (DMSM) to give a furan, while β‐anilino α,β‐unsaturated ketones give the pyrrole. β,β‐Bis(alkylthio) α,β‐unsaturated ketones react with DMSM to afford the methylene inserted products, λ,λ‐bis(alkylthio) β,λ‐unsaturated ketones.
New synthesis of some 1,2,5‐benzothiadiazcpinc 1,1‐dioxide derivatives. I
Authors: Migliara Onofrio , Petruso Salvatore , Sprio Vincenzo
Published: April 2009

2‐Nitrobenzenesulfonyl chloride reacts with ω‐aminoacetophenone and 4‐amino‐3,5‐dimethyl‐isoxazole to give 3 and 7, respectively. Reduction of 3 with zinc powder and acetic acid afforded the 2,5‐dihydro‐ and 2,3,4,5‐tetrahydro‐1,2,5‐benzothiadiazepine I,1‐dioxide derivatives (4 and 5). Catalytic hydrogenolysis of 7 and successive cyclization of the intermediate 8 gave the 3‐ace‐thyl‐2,5‐dihydro‐4‐methyl‐1,2,5‐benzothiadiazepine 1,1‐dioxide (9). The structures were assigned on the basis of correct elemental data and spectroscopic evidences.
Synthesis of 1,2‐dihydroindolo [1,7‐AB] [1,5] benzodiazepines and related structures. A new heterocyclic ring system
Authors: Glamkowski Edward J. , Fortunato James M.
Published: April 2009

The synthesis of the novel 1,2‐dihydroindolo [1,7‐ab][1,5]benzodiazepine ring system 4 is described. Condensation of 2‐fluoronitrobenzene with indoline provided the starting material for the synthesis, 1‐(2‐nitrophenyl)indoline (1a) in high yield. The nitro group was reduced catalytically and the resulting amino function was acylated to afford the heterocycle percursor amide 3. Refluxing this amide in phosphorus oxychloride brought about a Bischler‐Napieralski type cyclodehydration to form the target 1,2‐dihydroindolo[1,7‐ab][1,5]benzodiazepine ring system. Dehydrogenation of the latter led to the fully aromatic indolo[1,7‐ab][1,5]benzodiazepine structure 5, while reduction with sodium borohydride provided the 1,2,6,7‐tetrahydroindolo[1,7‐ab]‐[1,5]benzodiazepine tetracycle 6.
Synthesis of substituted pyrrolo[2,3‐D]pyrimidine‐2,4‐diones
Authors: Etson Sandra Rae , Mattson Ronald J. , Sowell J. Walter
Published: April 2009

A facile route for the synthesis of substituted pyrrolo[2,3‐d]pyrimidine‐2,4‐diones from substituted 2‐amino‐3‐cyano‐4‐methylpyrroles is reported.
The mass spectra of alkyl‐ and phenyl‐4‐imidazolin‐2‐ones
Authors: Holzmann G. , Krieg B. , Lautenschläger H. , Konieczny P.
Published: April 2009

The mass spectra of a variety of alkyl‐ and aryl‐4‐imidazolin‐2‐ones have been determined and the fragmentation mechanisms have been analyzed by deuterium labelling, high resolution and metastable transitions allowing certain differentiations of positional isomers. In contrast to the benzoid systems the mass spectra of isomeric alkyl‐4‐imidazolin‐2‐ones are distinctive. The influence of the position of substituents is demonstrated by phenyl‐4‐imidazolin‐2‐ones establishing an exact prediction of fragmentation pathways. Fragment ions (e.g. [M‐HNCO].+) which are the result of rearrangement processes were excluded for structure determinations. The ion structures involved were elucidated by collisional activation comparing model ions. Alkyl‐phenyl‐4‐imidazolin‐2‐ones give almost identical mass spectra, but the positional isomers can easily be distinguished by different fragmentation patterns in both metastable and collisional activation spectra of the molecular ions.
Thallation‐iodination studies of heterocyclic systems
Authors: Hollins Richard A. , Colnago Luiz A. , Salim Vera M. , Seidl Michael C.
Published: April 2009

The thallation‐iodination of 3‐carbonylindoles (4a‐f) results in orientation control with substitution occurring at the 4‐position (6a‐f). Also described is the dithallation of N‐methylpyrrole‐2‐carboxaldehyde (2).
Reduction of cyclohexanone 2‐nitrophenylhydrazone. Formation of cyclohexane‐3‐spiro‐3,4‐dihydro‐1,2,4‐benzotriazine
Authors: Sparatore Fabio , Cerri Riccardo
Published: April 2009

The structure of compound C12H15N3, obtained by Perkin and Riley in 1923, through the reduction of cyclohexanone 2‐nitrophenylhydrazone, was reexamined. This compound, considered originally as 3,4‐cyclotetramethylene‐4,5‐dihydro‐1,2,5‐benzotriazepine (I) and later as 2‐aminophenylazocyclohexene (II), is now defined through the nmr spectrum and chemical behaviour as cyclohexane‐3‐spiro‐3,4‐dihydro‐1,2,4‐benzotriazine (V). It is formed by spontaneous oxidation of the cyclic form of cyclohexanone 2‐aminophenylhydrazone (namely, cyclohexane‐3‐spiro‐1,2,3,4‐tetrahydro‐1,2,4‐benzotriazine) obtained through amino group addition on the hydrazone double bond.
Studies in the heterocyclic series. XV. Synthesis and reactions of the first triazaphenoxazine ring system
Authors: Okafor Charles O.
Published: April 2009

1,4,9‐Benzo[b]triazaphenoxazine, the first and parent compound of this new heterocyclic ring, as well as its derivatives were prepared essentially by cyclo‐condensation of 2‐amino‐3‐hydroxypyridine with the appropriate 2,3‐dichloroquinoxaline in the presence of alkaline DMF or DMAC. Nitration of the product with mixed nitric and sulfuric acids gave the corresponding 13‐nitro derivative. Structural assignments were made by chemical evidence and by a study of the ultraviolet, infrared, nmr and mass spectra.
Diazapolycyclic compounds. XVI. Nmr stereochemical studies on the acid‐catalyzed oxirane ring‐opening reactions of unsubstituted, 2‐methyland 2,3‐dimethyl‐ substituted 2,3‐epoxy‐4a,12a‐diaza‐1,2,3,4,4a,5,12,12a‐octahydronaphthacene‐5,12‐diones
Authors: Gómez Contreras F. , Navarro P.
Published: April 2009

Addition reactions in acidic media have been performed on the oxirane ring of unsubstituted, 2‐methyl‐ and 2,3‐dimethyl‐ substituted 2,3‐epoxy‐4a,12a‐diaza‐1,2,3,4,4a,5,12,12a‐octahydronaphthacene‐5,12‐diones. These reactions proceed in a stereospecific way; the Furst‐Plattner rule of 1,2‐trans‐diaxial ring‐opening is obeyed as can be deduced from the nmr stereochemical study on the terminal piperidazine‐ring moiety of the addition products. Acylation shift effects and 1,3‐syn‐diaxial interactions have been utilized to assist stereochemical assignments. The geometry of the ring corresponds in most cases to a chair slightly distorted by the sp2‐sp3 character of the nitrogens. Some of the less highly substituted among the cleavage products show certain peculiarities in their spectra, and are presumed to be in conformational equilibrium.
A convenient synthesis ofN, 5‐disubstituted‐4‐imidazoline‐2‐thiones
Authors: Doney Jeffrey J. , Altland Henry W.
Published: April 2009

The preparation ofN,5‐disubstituted‐4‐imidazoline‐2‐thiones from readily obtainable starting materials is described. These imidazolines are synthesized by refluxing in toluene the appropriate 2‐aminomethyl ketone hydrochloride with an equivalent of the desired isothiocyanate and an equivalent of triethylamine. The intermediate thiourea spontaneously eliminates water (removed from the reaction medium by a Dean‐Stark trap) to form the imidazoline thione.
A novel king closure and a new synthesis of 3‐deazaguanine
Authors: Srivastava Prem C. , Robins Roland K.
Published: April 2009

The reaction of methyl 5(4)‐cyanomethylimidazole‐4(5)‐carboxylate with hydroxylamine provided methyl 5(4)‐carboxamidoximylmethylimidazole‐4(5)‐carboxylate which cyclized on reduction Lo yield 3‐deazaguanine.
Hydrogen bonding abilities and self‐association of thiazolidin‐and imidazolidin‐2‐ones and 2‐selenones
Authors: Centric Emilie , Lauransan Jacques , Roussel Christian , Devillanova Francesco A. , Verani Gaetano
Published: April 2009

The hydrogen bonding abilities of iV‐methylimidazolidin‐2‐one and ‐2‐selone and thiazolidin‐2‐one and ‐2‐selenone have been studied by ir spectroscopy at 25° in carbon tetrachloride solutions, using dimethyl sulphoxide and 4‐chlorophenol as proton acceptor (KA) and proton donor (KB), respectively. The results are compared with those previously reported for N‐methylimidazolidine‐2‐thione and thiazolidine‐2‐thione. The KA values increase in each series in the order O < S < Se and Kg in the reverse order. The and KB values are discussed in terms of the substituent in ring. The self‐association constants (KD) are dependent on both KA and KB, although KA seems to be much more important.
Thermal decomposition of a sulfoximide in the presence of a carboxylic acid; an interesting rearrangement
Authors: Barnes Alan C. , Hairsine Peter W. , Kay David P. , Ramm Peter J. , Taylor John B.
Published: April 2009

5‐Hexyl‐7‐(S‐methylsulfonimidoyl)xanthone‐2‐carboxylic acid 1a, when heated above its melting point gives a number of products including the corresponding methyl ester 1b, which arises by a novel methyl group transfer. A similar methyl transfer reaction is observed when the sulfoximide and carboxylic acid groups are present in different molecules.
A new ring closure reaction of 2‐phenoxyphenols and 3‐(phenoxy)pyridines. Synthesis of halogenated 10‐methylphenoxazines and 10‐methyl[1,4]benzoxazino[3,2‐b]pyridines
Authors: Fuhrer H. , Sutter P. , Weis C. D.
Published: April 2009

The cyclization of 2‐(2‐chloro(bromo)phenoxy)anilines and 3‐(phenoxy)pyridines to 10‐methylphenoxazines and 10‐methyl[1,4]benzoxazino[3,2‐b]pyridines, respectively, by means of dimethyl methylphosphonate is reported. The cyclization reaction proceeded with expulsion of methyl ether. Demethylation of some 10‐methylphenoxazines was achieved with pyridine hydrobromide. Nitration was carried out with sodium nitrite, and by reduction of the nitro groups the corresponding amines were prepared.
Facile synthesis of 2,5‐diacylthiophenes
Authors: Miyahara Yuji
Published: April 2009

A base‐catalyzed condensation of diketo sulfides [(RCOCH2)2S] with glyoxal affording 2,5‐diacylthiophenes has been effected under mild conditions. Excellent results were readily obtained when R was various substituted phenyl, thienyl, or t‐butyl groups. Although the yield for R = methyl was poor, the increase in length of the aliphatic chain markedly increased the yields.
2‐(4′‐Fluorophenyl)imidazole. Nitration studies
Authors: Amato J. S. , Grenda V. J. , Liu T. M. H. , Grabowski E. J. J.
Published: April 2009

Reactions of 2‐(4′‐fluorophenyl)imidazole (1) and related compounds under various nitrating conditions are discussed. With 90% nitric acid in 20% oleum at −10°,1affords 2‐(4′fluorophenyl)‐4(5)‐nitroimidazole (2) in 80% yield. Reaction of2with the same reagents at 25° affords 2‐(4′‐fluoro‐3′‐nitrophenyl)‐4(5)‐nitroimidazole (4) in 90% yield, whereas with 90% nitric acid in acetic acid at 95°,2affords 4,5‐dinitro‐2‐(4′‐fluorophenyl)imidazole (5) in 80% yield. Reaction of1with 70% nitric acid in concentrated sulfuric acid at 25° affords 2‐(4′‐fluorophenyl)‐5‐hyroximinoimidazolin‐4‐one (6), which rearranges and hydrolyzes to 5‐(4′‐fluorophenyl)‐1,2,4‐oxadiazole‐3‐carboxylic acid. A discussion of these reactions is presented.
A new base‐induced ring transformation of pyrido[2,3‐d]pyrimidines
Authors: Matsumoto Jun‐Ichi , Mishio Shinsaku , Minami Shinsaku
Published: April 2009

8‐Substituted 5,8‐dihydro‐5‐oxopyrido[2,3‐d]pyrimidine‐6‐carboxylates (3) rearranged to 8‐substituted 7,8‐dihydro‐5‐hydroxy‐7‐oxopyrido[2,3‐d]pyrimidine‐6‐carboxaldehydes (5) when treated with sodium ethoxide in an aprotic polar solvent at room temperature. The 6‐cyano analogue (18) also underwent ring transformation under the same mild conditions giving 7‐amino‐8‐ethyl‐5,8‐dihydro‐5‐oxopyrido[2,3‐d]pyrimidine‐6‐carboxaldehyde (21). However, the ring transformations of the pyrido[2,3‐d]pyrimidine bearing no N8‐substituent (12), ethyl 1‐ethyl‐1,4‐dihydro‐4‐oxo‐1,8‐naphthyridine‐ (14) and ‐quinoline‐3‐carboxylates (16) failed to occur. A mechanism is discussed.
Nitrogen bridgehead compounds. Part X (1). 1H and 13C nmr study of pyrido[1,2‐a]pyrimidines
Authors: Tóth Gábor , Hermecz István , Mészáros Zoltán
Published: April 2009

By 1H nmr, the predominance of the conformer with a quasi‐axial 6‐methyl group was established for the pyrido[1,2‐a]pyrimidines I‐III. The 13C nmr spectra of I‐III were completely assigned. The conjugative effect of substitution at G‐3 on 1H and 13C chemical shifts of the C‐9 methylene group parallels its effect on reactivity.
The synthesis of imidazole‐2‐thione nucleosides
Authors: Gosselin Gilles , Imbach Jean Louis , Townsend Leroy B. , Panzica Raymond P.
Published: April 2009

Ribosylation of the trimethylsilyl derivative (1b) of imidazole‐2‐thione (1a) using either stannic chloride or silver perchlorate as catalyst resulted in the formation of the acylated derivatives of 1‐(β‐D‐ribofuranosyl)imidazole‐2‐thione (3c) and 1,3‐di‐(β‐D‐ribofuranosyl)imidazole‐2‐thione (4c) with the latter predominating (4c:3c, ca. 2:1). The diribosylated nucleoside 4c was shown to be the N,N‐disubstituted product rather than the N,S‐disubstituted product by 1H nmr and 13C nmr spectroscopy. Employment of the iodine‐catalyzed fusion procedure reversed the aforementioned product ratios and provided the monoriboside 3c in excellent yield. When the trimethylsilyl derivative (5b) of 2‐methylthioimidazole (5a) was reacted with 2,3,5‐tri‐O‐benzoyl‐D‐ribofuranosyl bromide (2d) in acetonitrile, the major product was 1,3‐di‐(2,3,5‐tri‐O‐benzoyl‐β‐D‐ribofuranosyl)‐imidazole‐2‐thione (4b). The formation of 4b in this reaction is thought to arise via the Hilbert‐Johnson mechanism.
The formation of 2‐alkoxyquinolines from quinoline N‐oxides in alcoholic media
Authors: Dimsdale Michael J.
Published: April 2009

A novel transformation of certain quinoline N‐oxides which gives rise to 2‐alkoxy substituted quinolines by the action of acetic anhydride in alcoholic media is described. In the case of t‐butyl alcohol direct formation of the carbostyril is also observed. A mechanism is advanced to explain the observed phenomena.
A direct preparation of 3‐Hydroxy‐1,2‐benzisoxazoles
Authors: Friary R. , Sunday B. R.
Published: April 2009

Carbonyldiimidazole cyclizes 2‐hydroxybenzohydroxamic acids to 3‐hydroxy‐1,2‐benzisoxazoles.
Abnormal displacement reaction of 2‐(chloromethyl)‐3,4‐diphenylfuran with aqueous potassium cyanide
Authors: Yamamoto Katsumi , Tanaka Akira
Published: April 2009

2‐(Chloromethyl)‐3,4‐diphenylfuran reacted with aqueous potassium cyanide to give an α‐angelica lactone derivative (V, 3,4‐diphenyl‐5‐methyl‐2(5H)furanone), which has never been isolated in such a reaction, as the main product.
Markierungsexperimente zur fragmentierung von 1,2,3‐thiadiazolen
Authors: Timm Uwe , Meier Herbert
Published: April 2009

The generation of thiirenes in the thermal and photochemical nitrogen elimination of 1,2,3‐thiadiazoles is discussed in relation to oxirene formation. Isotope labelling experiments were performed with 4‐phenyl‐[4‐13C]‐1,2,3‐thiadiazole (7) as the substrate.
Das massenspektroskopische fragmentierungsverhalten von hydroxy‐ und methoxyphenazincarbonsäuren und ihren methylestern
Authors: Budzikiewicz H. , Stöckl D. , Römer A.
Published: April 2009

Das massenspektroskopische Fragmentierungsverhalten von isomeren Hydroxy‐ und Methoxyphenazin‐1‐carbonsäuren (bzw. deren Methylester) wird in Hinblick auf eine mögliche Strukturermiltlung polysubstituierter Verbindungen diskutiert.
Amine‐induced lossen rearrangements of 3‐hydroxy‐5,6‐dihydrouracil and N‐hydroxysuccinimide benzenesulfontes
Authors: VanVerst Mary E. , Bell Charles L. , Bauer Ludwig
Published: April 2009

The reaction of sodium succinohydroxamate with benzenesulfonyl chloride yielded 3‐benzene‐sulfonyloxy‐5,6‐dihydrouracil, 3. Treatment of 3 with ammonia, aniline, t‐butylamine or piperidine yielded a mixture of the requisite 1,2‐bis(ureido)ethane and 1‐curboxamido‐2‐imidazolidone. Acylation of N‐hydroxysuccinimide with benzenesulfonyl chloride furnished N‐benzenesulfonyl‐oxysuccinimide, 10. Aniline or t‐butylamine were used as representative amines to demonstrate their capability of inducing a Lossen degradation on 10 to afford the corresponding β‐ureido ‐propionamide.
Preparation of novel heterocyclic systems from isatoic anhydrides
Authors: Sunder Shyam , Peet Norton P.
Published: April 2009

Isatoic anhydride (1a) and 5‐chloroisatoic anhydride (1b) were treated with 2‐(1‐methylhydrazino)ethanol (2) to produce 2‐aminobenzoic acid 2‐(2‐hydroxyethyl)‐2‐methylhydrazide (3a) and its 5‐chloro analog 3b, respectively. Treatment of 3a and 3b with carbon disulfide gave, respectively, 2,3‐dihydro‐3‐[(2‐hydroxyethyl)methylamino]‐2‐thioxo‐4‐(1H)quinazolinone (4a) and its 6‐chloro analog 4b. Compounds 4a and 4b afforded 5,6‐dihydro‐5‐methyl‐2‐thioxo‐4H,8H‐[1,3,5,6]oxathiadiazocino[4,5‐b]quinazolin‐8‐one (5a) and its 10‐chloro analog 5b, respectively, upon treatment with thiophosgene. Compound 5a could be produced directly from 3a and thiophosgene. Treatment of 4a and 4b with trifluoroacetic anhydride followed by potassium carbonate gave 3,4‐dihydro‐4‐methyl‐2H,6H‐[1,3,4]thiadiazino[2,3‐b]quinazolin‐6‐one (7a) and its 8‐chloro analog 7b, respectively. Treatment of 4a with thionyl chloride also gave 7a, but 4b and thionyl chloride afforded a mixture of 7b and 8‐chloro‐3,4‐dihydro‐4‐methyl‐2H,6H‐[1,3,4]oxadiazino[2,3‐b]quinazolin‐6‐one (10). The dimethyl analogs of 4a and 4b (13a and 13b) upon treatment with thiophosgene afforded 3,4‐dihydro‐2,2,4‐trimethyl‐2H,6H‐[1,3,4]oxadiazino[2,3‐b]quinazolin‐6‐one (14a) and its 8‐chloro analog 14b, respectively.
Novel heterocycles. 4. Synthesis of the pyrido[2,3‐c]‐1,2‐thiazine ring system
Authors: Coppola Gary M. , Hardtmann Goetz E.
Published: April 2009

The reaction of 2‐chloronicotinonitrile with N‐methylmethanesulfonamide and subsequent treatment with base furnished the novel pyrido[2,3‐c]‐1,2‐thiazine ring system 7. Spectrally, it was determined that the predominant tautomer in solution was the 4‐amino form 7a. Acidic hydrolysis of 7 furnished the 4‐oxo tautomer 8b, compound 8b was alkylated on oxygen with 1‐bromopentane in the presence of sodium hydride. Reaction of 8b with isocyanates occurs at the 3 position to produce carboxanilides 10. Spectral characteristics of these compounds are also discussed.
A new synthesis of 10‐arylisoalloxazines (10‐arylflavins)
Authors: Yoneda Fumio , Shinozuka Kazuo , Tsukuda Kinshiro , Koshiro Akira
Published: April 2009

The condensation of 6‐arylamino‐ and 6‐alkylaminouracils with nitrosobenzenes in a mixture of acetic anhydride and acetic acid gave the corresponding 10‐aryl‐ and 10‐alkylisoalloxazines (flavins).
Mass spectral fragmentation pattern of 2,2′‐bipyridyls. Part XII. 2,2′‐Selenodipyridine
Authors: Keats N. G. , Summers L. A.
Published: April 2009

The mass spectrum of 2,2′‐selenodipyridine obtained by electron impact is reported. The base peak in the spectrum is due to the C5H4N+ ion formed principally by rupture of the central bonds. The molecular ion gives rise to a peak of 50% of the intensity of the base peak. Other fragmentations include loss of H, Se and CSe from the molecular ion and HCN from the M‐1 ion.
The synthesis of substituted 2‐aminothiazoles
Authors: Lin Yang‐i , Seifert C. M. , Kang S. M. , Dusza J. P. , Lang S. A.
Published: April 2009

The preparation of 4‐ and 5‐acyl‐ and aroyl‐2‐substituted aminothiazoles is described. The condensation of thioureas with acyl halides leading to 4,5‐disubstituted‐2‐aminothiazoles and 7‐(4H)benzothiazolones is discussed. A discussion of the isolation of various intermediates and the mechanistic pathway is also included. A number of 2‐anilino or 2‐benzyl‐4‐ or 5‐aroylthiazoles possessed moderate oral antitubercolosis activity (2).
New derivatives of ethyl 1‐methyl‐1H‐imidazole‐2‐glyoxylate. Synthesis and properties of α‐hydroxyimino and α‐methoxyimino double‐bond stereoisomers
Authors: Elitropi Guglielmo , Tricerri Silvia
Published: April 2009

Synthetic routes for the preparation of ethyl α‐hydroxyimino and α‐methoxyimino‐1‐methyl‐1H‐imidazole‐2‐acetate are reported. Separation and characterization of the double‐bond stereoisomers are described.
An unusual synthesis of 2,3‐dihydrophosphindole 1‐oxides
Authors: Hughes Alan N. , Phisithkul Siriporn , Rukachaisirikul Thitima
Published: April 2009

A very simple route to dimeric phosphole oxides is reported as is the pyrolytic decomposition of these phosphorus‐bridged dimers. Like similar dimeric phosphole sulfides, these phosphole oxide dimers readily eliminate the bridging phosphorus grouping upon strong heating but, unlike the analogous sulfides, hydrogen transfer to give a 2,3‐dihydrophosphindole 1‐oxide rather than hydrogen elimination to give the fully unsaturated phosphindole oxide occurs. This hydrogen transfer is shown to be non‐stereospecific and some mechanistic implications of this are briefly discussed.
Mass spectral fragmentation pattern of 2,2′‐bipyridyls. Part XIII. 6‐Chloro‐ and 6‐bromo‐2,2′‐bipyridyls
Authors: Keats N. G. , Summers L. A.
Published: April 2009

The mass spectra of 6‐chloro‐ and 6‐bromo‐2,2′‐bipyridyls are reported. The principal fragmentation route from the molecular ions involves loss of the halogen group to give the M‐1 ion of 2,2′‐bipyridyl which gives rise to the base peak in the spectra. Loss of HCN before loss of Cl occurs to a small extent with 6‐chloro‐2,2′‐bipyridyl.
Comparative study on the preparation of C(3)‐hydroxy‐1,3‐dihydro‐2H‐1,4‐benzodiazepin‐2‐ones
Authors: Kovač T. , Oklobdžija M. , Šunjić V. , Kajfež F.
Published: April 2009

C(3)‐Hydroxy‐1,4‐benzodiazepin‐2‐ones 1–3 have been prepared in high yields using a new, two step approach. In the first step, the 3‐deoxy‐precursors 4–6 were acetylated at C(3) using the redox‐system lead tetraacetate and iodine, or potassium iodide, in acetic acid. The intermediary acetates 9–11 were quantitatively hydrolyzed into 1–3 in non‐aqueous conditions, i.e. in a methanol‐methylene chloride solvent mixture in the presence of sodium methoxide. Another route to the title compounds has been improved as follows. The yields of C(3)‐bromination of compounds 4–6 has been significantly augmented in relation to the known methods using the strong trifluoroacetic acid in very dilute carbon tetrachloride solutions as a catalyst for NBS mediated bromination. The intermediary C(3)‐bromo derivatives have been acetoxylated in situ, and compounds 9–11 have been isolated in over 80% yield. These compounds were solvolyzed into 1–3 as described above. The third part of this paper describes the search for feasible reaction conditions in the synthesis of 3 according to a known method (Scheme 1.); optimization of the yields in all steps was performed.
1,2,4‐Oxadiazoles. X. Aryl‐1,2,4‐oxadiazolecarbaldehydes
Authors: Palazzo G. , Baiocchi L. , Picconi G.
Published: April 2009

The synthesis of 5‐aryl‐1,2,4‐oxadiazole‐3‐carbaldehydes and 3‐aryl‐1,2,4‐oxadiazole‐5‐carbaldehydes was attempted through several routes and achieved starting from both the corresponding chloromcthyl and the dichloromethyl derivatives. These aldehydes are stabilized in the hydrated form and this peculiar behavior is discussed on the basis of the relevant spectroscopic data.
Reexamination of reduced pteridine cofactors behaviour by proton nuclear magnetic resonance spectroscopy and mass spectrometry
Authors: Hénichart Jean‐Pierre , Bernier Jean‐Luc , Dhondt Jean‐Louis , Dautrevaux Michel , Biserte Gérard
Published: April 2009

In aqueous solutions, the autoxidation by air of 2‐amino‐4‐hydroxy‐6,7‐dimethyl‐5,6,7,8‐tetra‐hydropteridine, a hydroxylase cofactor, leads to the corresponding 7,8‐dihydro derivate. Oxidation by hydrogen peroxide and Horseradish peroxidase does not give a stable quinonoid form as previously claimed but affords two metabolic products. Kinetics of the two pathways and structures of the different final compounds were determined by 1H nmr and mass spectrometry.
2‐Aminothiazole derivatives. III. Mass spectra of some 5H‐thiazolo [3,2‐a] pyrimidin‐5‐ones
Authors: Saint‐Ruf G. , Silou Th.
Published: April 2009

The mass spectra of some 7‐methyl, 7‐chloro and 6‐earbethoxythiazolo[3,2‐a]pyrimidin‐5‐ones were studied (2,3,4). The electron impact fragmentation patterns of these compounds showed their relatively high stability and their similar mode of decomposition. Certain differences were observed among the three classes of compounds, due to the nature of the substituent on the pyrimidine ring.
The reaction of malononitrile with thioglycolic acid. A novel procedure for the synthesis of thiazolone derivatives
Authors: Elnagdi Mohamed Hilmy , Elmoghayar Mohamed Riffaat Hamza , Hammam Abu El‐Futooh G. , Khallaf Salah Amin
Published: April 2009

Malononitrile (I) reacted with thioglycolic acid to yield the thiazolin‐4‐one derivatives II or III depending on the molar ratio of the reactants. Compound II reacted with benzaldehyde in refluxing pyridine to yield the arylidene derivative IV. On the other hand, the benzylidine bis derivative VIII was obtained when II was reacted with benzaldehyde in refluxing ethanol. The structure of IV was established via its synthesis from the reaction of benzylidenemalononitrile (VI) and thioglycolic acid in refluxing acetic acid. Similar to II, compound III condensed with benzaldehyde to yield the benzylidene derivative IX.
Studies on 2,1 ‐benzisoxazoles and related heterocycles. Reaction of diazomethane with 6‐nitro‐2,1‐benzisoxazoles and nitrobenzofurazan oxides
Authors: Boruah Romesh Chandra , Devi Purabi , Sandhu J. S.
Published: April 2009

Some 7‐melhyl‐substituted‐2,1‐benzisoxazoles and cyclopropanobenzofurazan oxides are synthesized and characterized by their elemental and spectral analyses.
Synthesis of chloropyrimidinylmethylenephosphoranes and their wittig reactions with aldehydes
Authors: Kato Tetsuzo , Katagiri Nobuya , Takahashi Toshimitsu , Katagiri Yumiko
Published: April 2009

Methylpyrimidines were treated with phosphorus pentachloride in phosphorus oxychloride to give trichloromethylpyrimidines, which reacted with two equivalent amounts of triphenylphosphine to yield chloropyrimidinylmethylenetriphenylphosphoranes as stable ylides in one step. These phosphorus ylides were subjected to the Wittig reaction with a variety of aldehydes to afford chloropyrimidinylolefins.
The chemistry of 2H‐3,1‐benzoxazine‐2,4(1H)dione (isatoic anhydride). 7. Reactions with anions of active methylenes to form quinolines
Authors: Coppola Gary M. , Hardtmann Goetz E.
Published: April 2009

The reaction of isatoic anhydrides with carbanions of various active methylene compounds is described. The isolation of 2‐oxo or 4‐oxoquinolines is possible by varying the functional groups flanking the methylene carbon.
Préparation, configuration et réduction électrochimique d'α‐cyano β‐nitrostyrènes. Synthèse d'amino‐5 isoxazoles
Authors: Bellec Christian , Bertin Daniel , Colau Roger , Deswarte StÉPhane , Maitte Pierre , Viel Claude
Published: April 2009

Leg Z α‐cyano β‐nitrostyrènes sont préparés par nitration, à l'aide du peroxyde d'azote, des α cyanostyrènes correspondents. Les isomères E sont obtenus par photoirradiation des isomères Z. La réduction électrochimique de ces dérivés cyanonitrés engendre les oximes α‐cyanées qui conduisent, selon les conditions opératoires, par cyclisation ou hydrolyse, soit aux amino‐5 isoxazoles, soit aux β‐cétonitriles.
Synthesis of 5,8‐dihydroxynaphtho[2,3‐c][1,2,5]thiadiazole‐6,9‐dione and 6,9‐dihydroxybenzo[g]quinoxaline‐5,10‐dione
Authors: Warren James D. , Lee Ving J. , Angier Robert B.
Published: April 2009

The synthesis of 5,8‐dihydroxynaphtho[2,3‐c][1,2,5]thiadiazole‐4,9‐dione 3, 6,9‐dihydroxybenzo[g]quinoxaline‐5,10‐dione 4, and their lesser oxygenated analogs via Friedel‐Crafts and Diels‐Alder synthesis is reported.
Synthesis and conformational analysis of 7,8‐diphenyl‐1,3,4,6,9,9a‐hexahydro‐2H‐quinolizines
Authors: Trigo G. G. , Gàlvez E. , Söllhuber M. M.
Published: April 2009

New analogues of julandine with different aromatic methoxy‐ and chloro‐substituents have been synthesized. Some features of the. nmr spectra of the final products and lactams are discussed. The conformational structure of the final products was determined.
Synthesis and Properties of 10‐Benzylaminopterin
Authors: Parham James C. , Templeton Mary Agnes , Chello Paul L. , Sirotnak Francis M.
Published: April 2009

Substitution of a benzyl group for the methyl at N‐10 of Methotrexate caused only a slight decrease in the inhibitory properties of the folate analog against L1210 leukemia in cell culture.
A facile preparation of 4‐quinolinols by the condensation of dilithiobenzoylacetone or C(α),O‐dilithiooximes with methyl anthranilate or 5‐chloroisatoic anhydride
Authors: Brown Jane , Sides Kimberly L. , Fulmer Tammy D. , Beam Charles F.
Published: April 2009

Dilithiobenzoylacetone or C(α),O‐dilithiooximes were prepared in an excess of lithium düsopropylamide and condensed with methyl anthranilate or 5‐chloroisatoic anhydride to give intermediates, which after neutralization were cyclized to 4‐quinolinols.
The chemistry of polycyclic arene imines. III. N‐alkylation of phenanthrene 9,10‐imineN‐alkylation of phenanthrene 9,10‐imine
Authors: Shtelzer Sarah , Weitzberg Moshe , Jeries Juliette , Sheradsky Tuvia , Aizenshtat Zeev , Blum Jochanan
Published: April 2009

Phenanthrene 9,10‐imine (1) was shown to undergo N‐alkylation without aziridine ring cleavage by (a) metallation with sodium methylsulfinylmethide followed by addition of an alkyl halide at −20° (b) reaction of 1, sodium hydride and the halide in dimethylformamide at 40° (c) treatment of a dichloromethane solution of 1, the halide and triethylbenzylammonium chloride with aqueous sodium hydroxide under phase transfer conditions. The syntheses of N‐isopropyl‐, N‐butyl‐, N‐pentyl‐, N‐allyl‐ and N‐benzylphenanthrene 9,10‐imine (2–6) are described.
Synthesis of 3‐alkenyl‐4‐oxo‐6,7‐dihydro‐1H‐pyrano[4,3‐c]pyrazole derivatives
Authors: Chantegrel Bernard , Nadi Abdel‐Ilah , Gelin Suzanne
Published: April 2009

A series of 1‐substituted 3‐alkenyl‐4‐oxo‐6,7‐dihydro‐1H‐pyrano[4,3‐c]pyrazoles was prepared by reaction of arylhydrazines or benzylhydrazine with 4,5‐dioxo‐2,3,7,8‐tetrahydro‐4H,5H‐pyrano[4,3‐b]pyran derivatives.
Polyazaphénanthrenes. Synthèse de pyridazino[4,5‐c]quinoléines
Authors: Godard Alain , Quéguiner Guy
Published: April 2009

Une nombre important de pyridazino[4,5‐c]quinoléines a été synthétisé à partir de quinoléines disubstituées en 3 et 4. Ces synthèses ont permis de mettre en évidence l'importance de contraintes stériques lors des réactions de cyclisation. Certains hétérocycles ont été testés pour leur propriétés antitumorales.
Antimalarials. 15. Side‐chain analogues of 8‐(4‐amino‐1‐methylbutylamino)‐6‐methoxy‐4‐methyl‐5‐(3‐trifluoromethylphenoxy)quinoline
Authors: Lamontagne Maurice P. , Blumbergs Peter
Published: April 2009

Six side chain analogs of the highly active antimalarial agent 8‐(4‐amino‐1‐methylbutylamino)‐6‐methoxy‐4‐methyl‐5‐(3‐trifluoromethylphenoxy)quinoline (I) were prepared and evaluated for blood and tissue schizonticidal activity. Although most examples were markedly superior to primaquine none was superior to the parent compound I.
Synthèses de la benzo[b][1,4]diazocino[7,6‐f]indole, de pyrrolo[f]phtalazines et réactions de cycloadditions
Authors: Duflos Jack , Quéguiner Guy
Published: April 2009

A partir du méthyl‐1 dibenzoyl‐5,6 1H indole nous avons obtenu deux nouveaux systèmes hétérocycliques les benzo[b][1,4]diazocino[7,6‐f]indole et pyrrolo[2,3‐f]phtalazine. Avec le méthyl‐2 dibenzoyl‐5,6 2H isoindole, nous avons synthétisé la pyrrolo[3,4‐f]phtalazine et étudié sur cette dernière des réactions de cycloadditions avec des diénophiles pauvres en électrons.
Carbon‐13 nuclear magnetic resonance spectra of phencyclidine analogs substituted in the piperidine and aromatic rings
Authors: Brine G. A. , Boldt K. G. , Coleman M. L. , Carroll F. I.
Published: April 2009

Natural abundance carbon‐13 chemical shifts are reported for the hydrochloride salts of phencyclidine (1a) and twelve analogs substituted in the piperidine and aromatic rings. The signals are assigned on the basis of chemical shift theory, SFORD multiplicities, signal intensities, and comparisons with related compounds.
Synthesis of mannich bases of bioactive benzylphenols
Authors: Jurd Leonard
Published: April 2009

2,4‐Bis(1,1‐dimethyl)‐6‐[(4‐methoxyphenyl)methoxymethyl]phenol (4), prepared by oxidation of 2,4‐bis(1,1‐dimethylethyl)‐6‐[(4‐methoxyphenyl)methyl]phenol (1) with silver oxide in methanol, reacts with secondary amines in boiling toluene to give Mannich bases (6) related to the biologically active o‐benzylphenol. Mannich basis of the isomeric p‐benzylphenol (7) were prepared by reaction of amines with the p‐quinone methide formed by oxidation of 7.
Étude des conditions d'accès au tétrazolo‐1,2,3,4‐[5′,1′:6,1] triazino‐1,2,4‐[4,5‐b]indazole et au thioxo‐3 triazolo‐1,2,4‐[2′,1′:6,1] triazino‐1,2,4‐[4,5‐b]indazole
Authors: Robba Max , Lancelot Jean‐Charles
Published: April 2009

Les triazinoindazolones 8 et 9 sont accessibles, soit par transposition des oxadiazoles 5 et 6, soit par cyclisation des éthoxyméthylidènehydrazides indazoliques 2 et 3. Les triazinoindazolethiones 17 et 18 obtenues par thionation des triazinoindazolones 8 et 9 constituent des intermédiaires permettant d'accéder aux hydrazinoindazoles 19 et 20. Le tétrazolotriazinoindazole 21 est obtenu par l'intermédiaire de l'hydrazinoindazole 19. L'indazolyldithiocarbazate de potassium 12 permet l'acccès à la thioxo‐4 triazinoindazolone 10 et à l'amino‐4 thioxo‐3 triazolylindazole 15. Ce dernier permet, après cyclisation, d'obtenir le thioxo‐3 triazolotriazinoindazole 16. Les spectres de rmn confirment la structure des derives obtenus.
A novel synthesis of cis‐dihydro‐rose oxide and related stereochemistry
Authors: Liu Chu‐tsin , Chang Chi‐hsien , Chou Tsu‐liang
Published: April 2009

A new synthesis of cis‐dihydro‐rose oxide from elsholtzia oil is presented. The stereochemistry of catalytic hydrogenation of elsholtziol is discussed, and configurations of the diastereoisomers of the resulting tetrahydroelsholtziol have been deduced with the aid of gas chromatography, infrared spectroscopic analysis and conformational analysis. Stereochemical study of catalytic dehydration of tetrahydroelsholtziols indicates that the dehydration‐rearrangement reactions follow a (trans‐elimination process.
Mass spectral study of N‐1,2,3‐triazol‐1‐yl)‐N′‐arylureas
Authors: Adamopoulos S. , Alexandrou N. E.
Published: April 2009

The fragmentation pattern upon electron impact at 70 eV of several N‐(1,2,3‐triazol‐1‐yl)ureas as well as of the corresponding N′‐aryl substituted is studied. The spectra examined contain the molecular ion peak in very low intensity and in some cases is absent, whereas the ion ArNCO is the base peak or one of the most prominent. The principal fragmentation pathway takes place via the [M‐‐‐28]+ ion.
Derivatives of benzo[4,5]cyclohepta[1,2‐b]thiophene. 1. Synthesis and cyclization of N‐(9,10‐dihydro‐4H‐benzo[4,5]cyclohepta‐[1,2‐‐6]thiophene‐4‐ylmethyl)amides
Authors: Arribas Enrique , Vega Salvador
Published: April 2009

Starting from ketone III several acyl derivatives of 4‐aminomethyl‐9,10‐dihydro‐4H‐benzo[4,5]cyclohepta‐[1,2‐‐6]thiophene (VII) have been synthesized. The intramolecular cyclization of some of these new amides through the Bischler‐Napieralski reaction is described.
Derivatives of benzo[4,5]cyclohepta[1,2‐è]thiophene. 2. Synthesis of (±)‐6,t‐8b,9,10,11,12,13,t‐13a‐Octahydro‐5H‐7‐thia‐12a‐azabenzo[f]‐naphth[1,2,3‐cd]azulene (QM‐7184)
Authors: Arribas Enrique , Vega Salvador
Published: April 2009

The synthesis of (±)‐6,t‐8,9,10,11,12,13,t‐13a‐octahydro‐5H‐7‐thia‐12a‐azabenzo[f]naphth[1,2,3‐cd]azulene (III) (QM‐7184) by two independent pathways is described. Configurational assignments have been made on the basis of nmr spectral interpretations.
Sur l'orientation de l'acétylation des nitriles et amides coumariliques Bz‐méthoxylés
Authors: Bachelet Jean‐Pierre , Clavel Jean‐Marc , Demerseman Pierre , Royer René
Published: April 2009

L'acétylation des amides et nitriles coumariliques s'effectue lentement en donnant respectivement l'acétyl‐5 coumarilamide et un mélange d'acide acétyl‐5 coumarilique, d'acétyl‐4 cyano‐2 benzofuranne et d'acétyl‐5 cyano‐2 benzofuranne. Dans les měmes conditions, les acétylations des dérivés Bz‐méthoxylés de ces amides et nitriles coumariliques ont lieu rapidement, avec d'excellents rendements, en ortho ou en para du méthoxyle, avec ou sans déméthylation selon les cas.
Nitrogen bridgehead compounds. Part 35. Structures of α‐formyl‐2,3‐polymethylene‐3,4‐dihydroquinazolin‐4‐ones
Authors: Horváth ágnes , Hermecz István , Pongor‐Csákvári Marianna , Mészáros Zoltán , Kökösi József , Tóth Gábor , Szöllósy áron
Published: April 2009

The structures of the title compounds bearing a five‐, six‐ or seven‐membered A ring have been investigated by uv and 1H and 13C nmr spectroscopy. The imine‐enol‐enamine (I‐II‐III) tautomerism of these compounds depends greatly on the ring size. A significant solvent‐dependence is observed only for the five‐membered‐ring compounds 1 and 2, which in ethanolic solution exist predominantly in the imine form I, and in chloroform solution in the enol form II. The compounds with a six‐membered A ring, 3 and 4, are mainly in the enamine form III. On protonation, 3 and 4 change into the E and Z isomeric mixture of the enol tautomer II. The seven‐membered‐ring compound 5 is a mixture of the imine I and the enamine III tautomers.
Efficient synthesis of 1,2,4‐dithiazolidine‐3,5‐diones (dithiasuccinoyl‐amines) and observations on formation of 1,2,4‐thiadiazolidine‐3,5‐diones by related chemistry
Authors: Slomczyńska Urszula , Barany George
Published: April 2009

An efficient synthesis of 1,2,4‐dithiazolidine‐3,5‐diones (1) from chlorocarbonylsulfenyl chloride (3) plus O‐dimethylaminoethyl‐N‐alkyl or aryl thiocarbamates (4) has been worked out. In this synthesis, 1,2,4‐thiadiazolidine‐3,5‐diones (5) have been shown to arise as low‐level by‐products, and experiments were conducted to elucidate the mechanism of the side reaction. N,N′‐Dimethyl‐1,2,4‐thiadiazolidine‐3,5‐dione (5a) was prepared in one step from N,N′‐dimethylurea plus 3, or from 4a plus one equivalent of sulfuryl chloride. A general route to 5 involved reaction of equimolar amounts of isocyanates (6), isothiocyanates (7) and sulfuryl chloride followed by hydrolysis of intermediate 9. Heterocycles reported have been characterized by nmr, ir, uv, ms, and hplc.
Synthesis and physical properties of N‐2‐phenylethyl‐ and N‐2‐(3‐indolyl)ethyl‐5′‐deoxy‐5′‐adenosineacetamides
Authors: Kurihara Takushi , Ota Atsutoshi , Hayashi Hirofumi , Inoue Masatoshi , Ishida Toshimasa
Published: April 2009

The synthesis and physical properties of N‐2‐phenylethyl‐ and N‐2‐(3‐indolyl)ethyl‐5′‐deoxy‐5′‐adenosineacetamides (2 and 3), which are stable compounds of phenylalanyl‐ and tryptophanyl‐AMPs, are described.
Synthesis of 9,10,11,12,12a,13‐hexahydro‐2,3‐dimethoxy‐7H‐naphtho[l, 2‐b]quinolizine hydrobromide. A cell growth inhibitor related to cryptopleurine
Authors: Bargar T. M. , Dulworth J. K. , Graham M. C.
Published: April 2009

9,10,11,12,12a,13‐Hexahydro‐2,3‐dimethoxy‐7H‐naphtho[1,2‐‐6]quinolizine hydrobromide (4), which has structural similarity to cell growth inhibitory alkaloid cryptopleurine (1), was found to inhibit the growth of HeLa cells by 50% versus control at a concentration of 0.6 μg/ml. An expeditious synthesis of the title compound was based on hydrogenation of quinolizinium salt 10, available through Friedel‐Crafts cyclization of aldoxime 9.
Pyrimidine analogues. Reaction of 1,3‐dimethyl‐6‐hydroxylaminopyrimidine‐2,4‐dione with nitrophenyl isothiocyanates
Authors: Prasad A. Siva , Sandhu J. S. , Baruah J. N.
Published: April 2009

Reaction between 6‐hydroxylaminouracil and nitrophenylisothiocyanates gave new purines which could be of biological interest.
Aromaticity in bridged heteroannulenes
Authors: Jurić A. , Sabljić A. , Trinajstić N.
Published: April 2009

The aromatic stabilities of bridged hetero[n]annulenes (n = even, odd) and the parent structures of hetero‐[n]annulenes and hetero[n]polycycles have been predicted by the topological resonance energy, TRE, approach. The TRE criterion places bridged structures in all cases studied between the hetero[n]annulenes and hetero[n]polycyclic systems. The extra aromatic stability of the bridged heteroannulenes compared to heteroannulenes is attributed to homoaromatic interaction across the ring at the bridge sites. Available experimental evidence supports the theoretical results.
Indole esters as heterocyclic synthons. II. Preparation of 1,3‐oxazino[5,6‐b]indoles and 3‐substituted‐pyrano[3,2‐b]indoles
Authors: Unangst Paul C. , Brown Richard E.
Published: April 2009

A number of novel 1,3‐oxazino[5,6‐b]indoles and 2‐oxo‐ or 4‐oxopyrano[3,2‐b]indoles containing #3‐position substituents were prepared. Starting materials were 3‐hydroxy‐indole‐2‐carboxylic acid esters in which the #2‐position ester function is converted to carboxamide, β‐ketoester, or β‐ketosulfone.
Potential anticonvulsants. VII. Synthesis of 5′‐methylspiro[3H‐indole‐3,2′‐thiazolidine]‐2,4′(1H)‐diones
Authors: Rajopadhye Milind , Popp Frank D.
Published: April 2009

The title compounds have been prepared, by the cyclocondensation of thiolactic acid with isatin‐3‐imines. 5′‐Methyl‐3′‐phenyl‐spiro[3H‐indole‐3,2′‐thiazolidine]‐2,4′(1H)‐dione has been subjected to the Mannich condensation to give 1‐substituted derivatives. With one exception, all of the products were inactive in an anticonvulsant screen.
Synthesis of α‐Oxo and α‐hydroxy‐1‐benzyl‐1,4‐dihydro‐3(2H)‐isoquinolinones
Authors: Sanna Paolo , Savelli Francesco
Published: April 2009

The reaction of some primary amines with the methyl 2‐[(α‐oxobenzyl)‐(α‐bromo)methyl]phenylacetate (5) afforded the isoquinolinones 7a‐d, which in turn were hydrogenated to 10a‐d. The synthesis of these compounds was designed on the basis of a potential depressant and antiinflammatory activity found in other structurally related compounds.
Stereoselective epoxidation of 3‐trans‐benzylideneisoborneol
Authors: Sanghvi Y. S. , Rao A. S.
Published: April 2009

2‐Benzylidenecyclopentanol (2) can be epoxidized stereoselectively to furnish 2‐trans‐benzylidene‐1β‐hydroxycyclopentane β‐oxide (4) with either t‐butyl hydroperoxide in the presence of vanadium catalyst or m‐chloroperoxybenzoic acid. Epoxidation of 3‐trans‐benzylideneisoborneol (10) with t‐butyl hydroperoxidevanadium catalyst furnishes stereoselectively 3‐trans‐benzylideneisoborneol exo‐oxide (11) whereas epoxidation of alcohol 10 with m‐chloroperoxybenzoic acid furnishes stereoselectively 3‐trans‐benzylideneisoborneol endo‐oxide (14).
Angular polycyclic thiophenes containing two thiophene rings. Part II
Authors: Tedjamulia Marvin L. , Kudo Hirotaka , Castle Raymond N. , Lee Milton L.
Published: April 2009

The syntheses of naphtho[1,2–6:7,6‐b′]bisbenzo[b]thiophene (4), naphtho[1,2–6:7,8‐b′]bisbenzo[b]thiophene (5), naphtho[2,1‐b:7,6‐b′]bisbenzo[b]thiophene (8), naphtho[2,1‐b:7,8‐b′]bisbenzo[b]thiophene (9), naphtho‐[1,2–6:5,6‐b′]bisbenzo[b]thiophene (14), naphtho[1,2–6:6,5‐b]bisbenzo[b]thiophene (17) and naphtho[2,1–6:‐6,5‐b′]bisbenzo[b]thiophene (23) are reported.
Reactivities of 3‐(1‐Azolyl)‐2‐alken‐1‐ones and the related compounds with pyrrolidine
Authors: Kashima Choji , Tajima Tadakuni , Higuchi Chihiro , Omote Yoshimori
Published: April 2009

From the rate constants of the reaction with pyrrolidine, the reactivities of 3‐(1‐azolyl)‐2‐alken‐1‐ones with nucleophiles were evaluated to be rather high. Especially the reactivities of the quaternary salts of 3‐(1‐imidazolyl)‐2‐alken‐1‐ones were nearly equal to those of 3‐chloro‐2‐alken‐1‐ones. In conclusion, 3‐(1‐imidazolyl)‐2‐alken‐1‐ones satisfied the practical requirements for the starting materials of the synthesis of 3‐hetero‐substituted 2‐alken‐1‐ones.
Identification of quinoline nitration products by NOE
Authors: Hutt Marland P. , Mackellar Forrest A.
Published: April 2009

The structures of the products from the nitration of 2‐ and 4‐oxodihydroquinolines were assigned based on Nuclear Overhauser Effects of their nmr spectra and confirmed by unambiguous synthesis.
Synthesis of 3H[1,2]diazepino[5,6‐b]indole and 3H[1,2]diazepino[4,5‐b]indole derivatives
Authors: Monge A. , Palop J. A. , Goñi T. , Martinez A. , Fernández‐Alvarez E.
Published: April 2009

The synthesis of two new derivatives of 3H[1,2]diazepino[5,6‐b]indole, 5 and 11, and one new derivative of 3H[1,2]diazepino[4,5‐b]indole, 16, are described. Compound 5 was obtained by the reaction of methyl 2‐(3‐methoxycarbonyl‐1‐methylindole)acetate 2, with hydrazine. Compound 11 was obtained in two ways from ethyl 2‐(1‐methylindole)acetate (8) by formylation and reaction with hydrazine. Compound 16 was obtained treating 3‐(2‐ethoxycarbonylindole)acetonitrile (14) with hydrazine.
The reaction of 2‐indolecarbohydrazones with ethoxycarbonyl chloride. New synthesis of 2,3‐dihydro‐2‐oxo‐1,3,4‐oxadiazoles and 1,2,3,4‐tetrahydro‐4‐oxo‐5H‐pyridazino[4,5‐b]indoles
Authors: Monge A. , Palop J. A. , Tabar P. , Fernández‐Alvarez E.
Published: April 2009

The synthesis of 2,3‐dihydro‐2‐oxo‐1,3,4‐oxadiazole (4) and 5H‐pyridazino[4,5‐b]indole (7), are described. Compounds 4 were obtained by reduction of O‐ethoxycarbonylcarbohydrazones 3 with sodium borohydride. Compounds 7 were obtained by cyclization of compounds with ethanol/hydrochloric acid and removing the ethoxycarbonyl group with hydrazine. Compounds 3 were obtained by reaction of 2‐indolecarbohydrazones 1 with ethoxycarbonyl chloride.
Thiazolopyridine analogs of naldixic acid. 1. Thiazolo[5,4‐b]pyridines
Authors: Leysen D. C. , Haemers A. , Bollaert W.
Published: April 2009

A series of 2‐substituted‐7‐alkyl‐4,7‐dihydro‐4‐oxothiazolo[5,4‐b]pyridine‐5‐carboxylic acids were synthesized. Antibacterial activity was tested in vitro. None of the new compounds prepared showed any antibacterial activity in vitro against the strains tested.
Studies on ketene and its derivatives. Part 119. Reactions of haloketenes with 2‐arylideneaminopyridines
Authors: Katagiri Nobuya , Kato Tetsuzo , Niwa Ryuji
Published: April 2009

Reactions of haloketenes with 2‐arylideneaminopyridines were examined. Reaction of dichloroketene with 2‐benzylideneaminopyridines gave 2,2‐dichloro‐3‐phenyl‐3‐(2‐pyridylamino)propanoic acids and 3‐chloro‐2‐phenylpyrido[1,2‐a]pyrimidin‐4(4H)‐ones. Similar reaction of dichloroketene with 2‐(2‐furfurylideneamino)‐pyridines gave 3‐chloro‐2‐(2‐furyl)pyrido[1,2‐a]pyrimidin‐4‐(4H)‐ones. Chloroketene and chlorophenylketene also reacted with 2‐arylideneaminopyridines to give pyrido[1,2‐a]pyrimidin‐4(4H)‐ones. Ring transformations of pyrido[1,2‐a]pyrimidin‐4‐(4H)‐ones were carried out to give 1,8‐naphthyridin‐4(1H)‐ones and imidazo[1,2‐a]‐pyridines.