bluuebunny/crossref_metadata_2025 huggingface dataset:
Studies on the syntheses of analgesics. Part XXXVI. Synthesis of 1,2,3,4,5,6‐ilexahydro‐2,6‐methano‐6‐phenyl‐2 henzazocine [studies on the syntheses of heterocyclic compounds. Part D XI]
Authors: Kametani Telsuji , Aoyama Toyohiko
Published: March 2009

An attempt to obtain 2,3,4,5,6,7‐hexahydro‐lH2,7‐methano‐9‐methoxy‐3‐rnethyl‐7‐phenyl‐2,3‐benzodiazonine (II) by the Pictet‐Spengler reaction of 2,3,4,5,6,7‐hexahydro‐lH‐4‐(3‐meth‐oxyphenyl)‐l‐methyl‐4‐phenyl‐1,2‐diazepine (XI) prepared through several steps from 1‐(3‐methoxyphenyl)phenylaeetonitrile (IV) resulted instead, in the formation of 1,2,3,4,5,6‐hexa‐hydro‐2,6‐methano‐8‐methoxy‐6‐phenyl‐2‐benzazocine (XIV).
Investigations toward the total syntheses of proapoiphine and homoproaporphine alkaloids
Authors: Curran William V.
Published: March 2009

The reaction of 1,2,3,5‐telrahydro‐6‐methoxy‐1 ‐[2‐(4‐methoxy‐1,4‐eyelohexadien‐1 ‐yl)eth‐yl]‐l‐methyl‐7‐isoquinolinol (12) with hot phosphoric acid afforded (±)‐tetrahydro‐homoglazio‐vine (14) in good yield. Similar treatment of 1,2,3,4‐tetrahydro‐6‐methoxy‐l ‐[2‐(4‐methoxy‐1,4‐cyelohexadien‐l‐yl)methyl]‐2‐methyl‐7‐isoquinolinol (13) did not produce the desired (±)‐tetra‐hydroglaziovine (18) but rather a mixture of diastereomeric 4,5,6,6aϵ,7,7aϵ,8,9,11, 11aϵ‐deca‐hydro‐l‐hydroxy‐2‐metlu>xy‐6‐methyl‐10H‐dibenzo[(de,g]quinolin‐l‐ones (16 and 17) was obtained.
Snytheses of analgesics. Part XXXVII. An alternative synthesis of 1,2,3,4, 5, 6‐hexahydro‐8‐hydroxy‐2,6‐methano‐6, h‐dimethyl‐3‐phenethyl‐3‐benzazoeine [studies on the syntheses of heterocyclic compounds. Part DXXI]
Authors: Kametani Tetsuji , Kigasawa Kazuo , Hüragi Mineharu , Wagatsuma Nagatoshi , Saitoh Setsu , Sugi Hideo
Published: March 2009

Acid treatment of the alkylated products of (Va, Vb, and VIII) of piperidinols IVa and IVb, and tetrahydropyridine VII with β‐bromoethylbenzene, afforded 1,2,3,4,5,6‐hexahydro‐8‐hydroxy‐2,6‐methano‐6,1 1‐dimethyl‐3‐phenethyl‐3‐benzazocine (la) in good yield. Piperidinols Va and Vb were also obtained from the reaction of N‐(3‐methyl‐3‐pentenyl)‐β‐phenethylamine (IIb) with methyl 3‐(4‐methoxyphenyl)‐2,3‐epoxypropionate.
The synthesis of two novel pyridazines; A new ring system
Authors: Coppola Gary M. , Gimelli Salvatore P.
Published: March 2009

The Diels‐Alder reaction of 4,5‐dimethylene‐2,2‐diphenyldioxolane with diethyl azodicar‐boxylate and 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione was investigated. Reduction of the resultant adducts followed by hydrolysis provided hexahydro‐4,5‐dihydroxy‐1,2‐pyridazine dicarboxylic acid diethylester and 1,3,5,6,7,8‐hexahydro‐6,7‐dihydroxy‐2‐pheny 1‐2H‐s‐triazolo[1,2‐α ]pyrida‐zine‐1,3‐dione.
Base‐catalyzed cyclization reactions of 2‐[2‐(2,4‐dimethyl‐3‐oxopentyl)]benzimidazoles with acetic anhydride and its homologs
Authors: Linke Siegfried , Wünsche Christian
Published: March 2009

2‐[2‐(2,4‐Dimethyl‐3‐oxopentyl)]benz, imidazoles (2‐10) were obtained by allowing o‐phenyl‐enediamines to react with 2,2,4,4‐tetramethyl‐1,3‐cyclobutanedione (1). When refluxed with acetic anhydride (or sterically unhindered homologs) they cyclize in the presence of base to yield the pyrido[1,2‐α]benzimidazoles (16‐21 and 24, 25). The 2‐[2‐(2,4‐dimethyl‐3‐oxo‐pentyl) ]imidazolines (12 and 14) were obtained by reaction of 1,2‐diaminoethane and 1,2‐diaminopropane, respectively, with 1. When allowed to react with acetic anhydride/base, they gave only N‐acylated products.
1‐Methyl‐3‐piperidone and 1‐methyl‐3‐pyrrolidone derivatives from a dieckmann reaction
Authors: Nichols David E. , Barfknecht Charles F.
Published: March 2009

Attempts to prepare 1‐methyl‐5‐carbethoxy‐3‐piperidone by a Dieckmann cyclization led to formation of its diethyl ketal on workup. The five‐membered ring system, 1‐methyl‐4‐(ethoxy‐carbonylmethyl)‐3‐pyrrolidone was also formed in the cyclization.
Synthesis of 2‐aryl‐4‐phenyl‐5‐trifluoromethylimidazoles
Authors: Lombardino Joseph G.
Published: March 2009

Several 2‐aryl‐4‐phenyl‐5‐trifluoromethylimidazoles have been made from the previously unknown 1‐phenyl‐3,3,3‐trifluoro‐1,2‐propanedione monohdyrate. One analog, 4‐phenyl‐2,5‐bis(trifluoromethyl)imidazole, is quite acidic, exhibiting pKa 8.1.
The reaction of 2,2,4,4‐tetramethyl‐1,3‐cyclobutanedione with o‐aminophenols, o‐aminothiophenol and with aliphatic 2‐ and 3‐hydroxy‐ and ‐mercaptoamines
Authors: Linke Siegfried
Published: March 2009

Studies of the reaction of the dione dimer of dimethylketene (1) with a series of o‐aminophenols and with o‐aminothiophenol have been carried out. These reactions give 2‐[2‐(2,4‐dimethyl‐3‐oxopentyl)]benzoxazoles and ‐benzothiazole, respectively. Aliphatic 2‐ and 3‐hydroxy‐ and 2‐ and 3‐mercaptoamines yield 2‐substituted 2‐oxazolines, 5,6‐dihydro‐4H‐1,3‐oxazines, 2‐thiazolines and 5,6‐dihydro‐4H‐1,3‐thiazines.
Synthesis of 1‐aryl‐3,4‐dimethylenepyrrolidines by the thermal elimination of sulfur dioxide
Authors: Ottenbrite Raphael M. , Alston Peter V.
Published: March 2009

The reaction of 3,4‐bis(bromomethyl)‐2,5‐dihydrothiophene 1,1‐dioxide with arylamines to produce 5‐aryl‐1,3,4,6‐tetrahydrothieno[3,4‐c]pyrrole 2,2‐dioxides was investigated. It was found that the bicyclic compound was obtained in good yields for arylamines with substituent groups with Hammett σ values of less than 0.40. These bicyclic compounds were thermally decomposed to produce the corresponding 1‐aryl‐3,4‐dimethylenepyrrolidines in good yields. Several accompanying products of both of the above reactions were isolated and characterized.
The synthesis and reactions of certain pyridazine 1‐oxides
Authors: Novinson Thomas , Robins Roland K. , O'Brien Darrell E.
Published: March 2009

Nucleophilic displacement reactions under acidic and basic conditions have been studied with 4,6‐dinitro‐3‐methoxypyridazine 1‐oxide (1) and with 6‐chloro‐3‐methoxy‐4‐nitropyridazine 1‐oxide (2). Depending on the nature of the nucleophilic reagent and the conditions of the reaction we have found that the chloro group, the nitro group, as well as the methoxy group of 1 and 2 may be displaced by the nucleophile. This type of compound possesses significant in vitro antifungal activity.
Kinetics and mechanism of the N7‐hydroxyalkylation of guanosine
Authors: Roe Robert , Paul J. S. , Montgomery P. O'B.
Published: March 2009

The kinetics of the N7‐hydroxyalkylation of guanosine by the equally substituted epoxide, trans‐2,3‐epoxybutane, and the unequally substituted epoxides, 3‐chloro‐1,2‐epoxypropane, and 1,2‐epoxypropane in glacial acetic acid, have been measured by a spectrophotomeric method over the range 20‐40°. Activation parameters have been determined. Comparative rates calculated from the ratios of second‐order rate constants indicate that 1,2‐epoxypropane reacts with guanosine about three times faster than does trans‐2,3‐epoxybutane and about two times faster than 3‐chloro‐1,2‐epoxypropane. These results coupled with the results of a previous report on the structural analysis of the products from these reactions are consistent with a “push‐pull” mechanism in which N7 of guanosine reacts preferentially at the least substituted carbon of the epoxide with simultaneous transfer of a proton from acetic acid to the oxygen of the epoxide. The lower reactivities of trans‐2,3‐epoxybutane and 3‐chloro‐1,2‐epoxypropane in comparison to that of 1,2‐epoxypropane are discussed in terms of steric factors and electronic factors which determine the stability of the requisite transition state for a “push‐pull” mechanism model.
Synthesis of 1,2‐disubstituted‐1,4,5,6‐tetrahydropyrimidines
Authors: Perillo Isabel , Lamdan Samuel
Published: March 2009

Cyclization of benzoyl derivatives of N‐substituted trimethylenediamines with polyphosphoric acid or the corresponding ethyl ester, afforded 1, 2‐disubstituted‐1, 4, 5, 6‐tetrahydropyrimidines. PPE was the more advantageous reagent. The excessive protonation of the starting material and the cleavage of the ether function produced by PPA explains the failure of this reagent to cause ring closure in some cases. Synthesis of the starting materials is described. Analytical and spectroscopic data of the new compounds are presented.
Steroidal quinoxalines
Authors: Catsoulacos Panayotis
Published: March 2009

The treatment of 3β‐hydroxy‐16α‐bromo‐5α‐androstan‐17‐one, 3β‐acetoxy‐16α‐bromo‐5‐androsten‐17‐one and 21‐bromo‐5‐pregnen‐3β‐ol‐20‐one with 4,5‐dimethyl‐o‐phenylenediamine gave substituted quinoxalines.

Hydrolysis of 3β‐acetoxy‐5‐androsteno[16,17‐b]‐6′,7′‐dimethylquinoxaline produced the corresponding 3β‐hydroxy compound. 3‐Oxo‐4‐androsteno[16,17‐b]‐6′,7′‐dimethylquinoxaline was obtained by Oppenauer oxidation of the corresponding alcohol.
Novel syntheses of thiazolo[3,2‐b]‐s‐triazoles
Authors: Tamura Yasumitsu , Hayashi Hironori , Kim Joong‐Heup , Ikeda Masazumi
Published: March 2009

The reaction of 2‐amino‐and 2‐acylaminothiazoles with O‐mesitylenesulfonylhydroxylamine resulted in the ready formation in the corresponding 3‐aminium salts, which were converted into thiazolo[3,2‐b]‐s‐triazoles in high yields.
Imidazolriazole and oxazolotriazole analogs of midafltir |4‐amino‐2,2,5,5, ‐tetrakis(trifluoromethyl)‐3‐imidazolin|
Authors: Middlelon William J. , Melzger Diana , Donald Elaine A.
Published: March 2009

Imidazotriazole (5) and oxazolotriazole (10) analogs of CNS depressant 4‐amitio‐2,2,5,5‐tetrakis(trifluoromethyl)‐3‐imidazoline (miduflur) were prepared and found to he much less active.
Benzotliiazolinc derivatives. IV. Comment on the. Mechanism of reaction of 2‐l5enzolhiazolinetliione willi ethylene oxide in acetic acid
Authors: Sohar Paul , Denny George Ii.
Published: March 2009

Treatment of 2,3‐dihydrothiazolo|2,3‐b Iben|othiazolium bromide with sodium acetate in acetic acid gave predominantly 3‐(2‐accloxyethyl)‐2‐benothiazolinelhiorie and the minor product 3‐(2‐acetyllhioelhyl)‐2‐benzothiazolinone. The mechanistic implications of this and previous results are discussed in terms of the reaction of 2‐benzothiazolitielhione and its derivatives with ethylene oxide in acetic acid.
Synthèse dc la pyrido[2,3‐f] phtalazine et des diformyl‐6,7; ‐4,6; ‐4,7; ‐2,4 quinoleines
Authors: Duballet MM. P. , Godard A. , Queguiner G. , Pastour P.
Published: March 2009

This article describes the synthesis of a new heterocycle, pyrido[2,3,f]phtalazine and three new diformylquinolincs.
Synthesis of 1‐substituted 3‐anilino‐4‐diethylaminomethyl‐5‐oxo‐3,4‐dehydropiperidines and 2‐substituted 1,2,3,5,6,11‐hexahydro‐5‐phenyl‐4H‐pyrido[3,4‐b][1,5]benzodiazepin‐4‐ones
Authors: Tamura Yasumitsu , Chen Ling Ching , Fujita Masanobu , Kita Yasuyuki
Published: March 2009

The Synthesis of novel 1‐substituted 3‐anilino‐4‐diethylaminomethyl‐5‐oxo‐3,4‐dehydro‐piperidines and 2‐substituted 1,2,3,5,6,11‐hexahydro‐5‐phenyl‐4H‐pyrido[3,4‐b][1,5]benzo diazepin‐4‐ones from the β‐arylaminovinylketones derived from N‐substituted piperidine‐3,5‐diones is described.
“Reverse chromophore” of actinomycin d. Synthesis of 2‐substituted 7‐amino‐8H‐8‐oxo‐oxazolo[4,5‐b] phenoxazine ring system
Authors: Sengupta Sisir K. , Karin Tinter S.
Published: March 2009

The synthesis and physico‐chemical properties of a new 7‐amino‐8H‐8‐oxo‐oxazolo[4,5‐b]‐phenoxazine ring system (8a and 8b) are reported. These tetracyclic heteroaromatic rings posses an extra oxazolo ring fused to the phenoxazinone chromophore observed in actinomycin D (1b). These tetracyclic compounds (8a‐8b) possess a structure in which the orientation of the A and B rings in 1b are “reversed”. Since DNA binding and the resulting specificity of the antitumor antibiotic 1b is believed to depend on the spatial orientation of P(α) and P(β) relative to the functions on the B ring of 1b, these new compounds represent a novel approach for investigating AMD‐DNA interactions.
Reaction of sulfene and dichloroketene with open‐chain N,N‐disubstituted α‐aminomethyleneketones. Synthesis of 4‐dialkylamino‐3,4‐dihydro‐5,6‐dimethyl‐1,2‐oxathiin 2,2‐dioxides and of 6,(5)(di)alkyl‐3‐chloro‐4‐methylphenylamino‐2H‐pyran‐2‐ones
Authors: Bargagna Alberto , Schenone Pietro , Bondavalli Francesco , Longobardi Mario
Published: March 2009

Cycloaddition of sulfene to N,N‐disubstituted 4‐amino‐3‐methyl‐3‐buten‐2‐ones (III) occurred in fair to good yield only in the case of aliphatic N‐substitution to give 4‐dialkylamino‐3,4‐dihydro‐5,6‐dimethyl‐1,2‐oxathiin 2,2‐dioxides, whereas N,N‐disubstituted 1‐amino‐1‐penten‐3‐ones (II) did not react at all. Cycloaddition of dichloroketene to II, III and N,N‐disubstituted 4‐amino‐3‐buten‐2‐ones occurred only in the case of the methylphenylamino derivative, giving in good to moderate yield 6,(5)(di)alkyl‐3,3‐dichloro‐3,4‐dihydro‐4‐methylphenylamino‐2‐Hpyran‐2‐ones, which were dehydrochlorinated with DBN to 6,(5)(di)alkyl‐3‐chloro‐4‐methylphenylamino‐2H‐pyran‐2‐ones.
Photolyse stéréosélective des [α‐tétrahydropyrannyloxy] ‐2 tétrahydropyrones‐3
Authors: Descotes G. , Metras F. , Bernasconi C. , Cottier L. , Grenier M. F.
Published: March 2009

Les[α‐tétrahydropyrannyloxy]‐2 tétrahydropyrones‐3 (3)se photolysent en tétrahydropyrone‐3 (6) et δ‐valérolactone (7) avec des vitesses différentes selon leurs structures (S*, R*) ou (S*, S*) déterminées par rmn et filiation chimique avec les [α‐tétrahydropyrannyloxy]‐2 tétrahydro‐pyrannes (5) (S*, R*) et (S*, S*).
Contribution à l'étude de la réaction de Birch en séries isoquinoléique et diaza‐8,13 stéroïdique
Authors: Verchère Catherine , Viel Claude
Published: March 2009

L'étude de la réaction d'hydrogénation d'isoquinoléines selon Birch a permis de mettre au point les conditions permettant d'obtenir une dihydrogénation ou une tétrahydrogénation de Phomocycle. L'application à un dérivé de la diaza‐8,13 oestrone a permis de mettre en évidence le rôle d'une fonction amine pipéridinique lors de la tétrahydrogénation. Cette étude a conduit à la synthèse de diaza‐8,13 19‐nor androsténone‐3 et de diaza‐8,13 19‐nor androstène‐4 one‐3 possè‐dant la configuration dite “naturelle”.
Synthesis of (s)‐2‐(2‐methylbutyl)thiophene
Authors: Menicagli R. , Botteghi C. , Marchetti M.
Published: March 2009

Optically active (S)‐2‐(2‐methylbutyl)thiophene was obtained by different procedures. Among them, the cross‐coupling reaction between 2‐methylbutylmagnesium chloride and 2‐chlorothio‐phene proved to be the most efficient one. Compound 1 was thus obtained in satisfactory yield and rather high optical purity (82%).
Photolyse d'oxaziridines. 9. Structures d'oxaziridines à jonction spirannique par étude en rmn du carbone‐13
Authors: Oliveros Esther , Rivière Monique , Lattes Armand
Published: March 2009

L'Htude directe par résonance magnétique nucléaire du carbone‐13 d'une série d'oxaziridines à jonction spirannique ainsi que celle des imines utilisées pour leur synthèse, a permis l'attribution non ambigùe des configurations de ces hétérocycles.
Alkylating nucleosides. 3. The reaction of 3,5‐dimethylpyrazole nucleosides with N‐bromosuccinimide
Authors: Garcia Lópe M. Teresa , Herranz Rosario , Alonso Gregorio
Published: March 2009

Bromination of 3,5‐dimethylpyrazole nucleosides with N‐bromosuccinimide gave the corresponding 4‐bromo‐3,5‐dimethylpyrazole, 3‐methyl‐5‐(bromomethyl)pyrazole and 4‐bromo‐3‐methyl‐5‐(bromomethyl)pyrazole nucleosides. Structural assignments were made on basis of analytical and 1 H nmr spectral data. All of the bromomethylpyrazole nucleosides described showed cytostatic activity against HeLa cell sultures.
Studies on pyrazines. 6. A facile separation method for a mixture of the isomeric 2‐amino‐3,5, and 6‐methylpyrazines
Authors: Sato Nobuhiro
Published: March 2009

This paper describes a facile separation method for a mixture of the isomeric aminomethyl‐pyrazines by two‐stage processes. Thus the mixture of aminomethylpyrazines was converted into that of the aminobromomethylpyrazines, which could be separated by chromotography on silica gel. Each of the bromopyrazines was hydrogenated to regenerate the original aminopyrazine as a pure form.
Studies on chemotherapeutics III. Synthesis and cyclisation of 5‐substituted‐4‐oxo‐1,4‐dihydro‐3‐pyridinecarbonyl‐semicarbazide and‐ thiosemicarbazide
Authors: Balogh Mária , Hermecz István , Mészáros Zoltán , Pusztay Levente
Published: March 2009

1,4‐Disubstituted‐semicarbazide and thiosemicarbazide derivatives were synthetized from 5‐substituted‐4‐oxo‐1,4‐dihydro‐3‐pyridinecarbohydrazides and cyclized to 3‐mercapto‐4H‐1,2,4‐triazoles. The obtained compounds could be S‐methylated with methyl iodide in methanol. The new compounds were tested for antibacterial and antifungal activities.
Acid‐catalysed, nucleophile‐catalysed and thermal decomposition of 2‐amino‐3‐(2′,2′‐dimethylaziridino)‐1,4‐naphthoquinone
Authors: Antonini Ippolito , Claudi Francesco , Cristalli Gloria , Grifantini Mario , Martelli Sante
Published: March 2009

The course of the thermal, acid‐catalysed and iodide‐catalysed decomposition of 2‐amino‐3‐(2′,2′‐dimethylaziridino)‐1,4‐naphthoquinone (III) was investigated. Thermal and iodide‐catalysed decompositions gave mainly 2,3‐diamino‐1,4‐naphthoquinone (VI) and 2‐amino‐3‐(2′‐methylallylamino)‐1,4‐naphthoquinone (V) together with low amounts of 2,2‐dimethyl‐1,2,3,4,5,10‐hexahydrobenzo[g]quinoxaline (IV) and 2‐isopropyl‐1H‐naphthoimid‐azole‐4,9‐dione (VII). The acid catalysed isomerization of the aziridinonaphthoquinone III with halohydric acids or with acetic acid readily gave the opening of the aziridine ring; the corresponding salts of 2‐amino‐3‐(2′‐haloisobutylamino)‐1,4‐naphthoquinones (VIIIa‐c) and 2‐amino‐3‐(2′‐acetoxyisobutylamino)‐1,4‐naphthoqunone (X) were formed by cleavage of the carbon‐nitrogen bond at the substituted carbon atom. Hypotheses on the mechanism of these reactions are given.
Thiohydrazides and acetylene esters, A new route to 1,3,4‐thiadiazoles
Authors: Heindel Ned D. , Friedrich Gail , Tsai Maria C.
Published: March 2009

Aromatic thiohydrazides react with dimethyl acetylenedicarboxylate or methyl propiolate to yield carbomethoxymethyl‐substituted 1,3,4‐thiadiazoles. In a 2:1 ratio of methyl propiolate to aromatic thiohydrazide, 1,3,4‐thiadiazoles with acrylate ester side chains are formed.
Carbon‐13 nmr spectra of the tRNA “wobble” nucleosides 5‐carboxymethyl‐, 5‐carbomethoxymethyl‐, and 5‐carbamoylmethyluridine
Authors: Lipnick Robert L. , Fissekis John D.
Published: March 2009

The 13C nmr chemical shifts have been measured for 5‐carboxymethyluracil 2, 5‐carbo‐methoxymethyluracil 3, their 2‐thio derivatives 4 and 5, respectively, as well as of the three β‐D‐ribonucleosides, 5‐carboxymethyluridine 7, 5‐carbomethoxymethyluridine 8, and 5‐carbamoyl‐methyluridine 9. In addition, the 13C‐1H coupling constants for 2 and 7 have, also been obtained.
New heterocyclic ring systems. XII. Synthesis of [1,4]thiazinocarbazoles
Authors: Brunelli C. , Fravolini A. , Grandolini G. , Strappaghetti G.
Published: March 2009

Five [1,4]thiazinocarbazoles have been synthesized from 6‐, 7‐ and 8‐amino‐2H[1,4]benzo‐thiazin‐3(4H)ones by the Jaap‐Klingemann reaction with 2‐hydroxymethylenecyclohexanone followed by Fischer indolisation of the resulting hydrazones. The structures of the hitherto unknown ring systems have been confirmed by pmr spectral data.
Reactions with heterocyclic amidines. VI. Synthesis and chemistry of pyrazol‐5‐yl, and 1,2,4‐triazol‐5‐ylhydrazonyl chlorides
Authors: Elnagdi Mohamed Hilmy , Elmoghayer Mohamed Riffaat Hamza , Elfaham Hassan Attia , Sallam Mohamed Mohamed , Alnima Hikmat Hussein
Published: March 2009

The 4‐bromo‐3‐phenylpyrazol‐5‐ylhydrazonyl chlorides (Ia,b) and 1,2,4‐triazol‐5‐ylhydrazonyl chlorides (IIa,b) were prepared via coupling of diazotized 4‐bromo‐3‐phenyl‐5‐aminopyrazole (III) and 5‐amino‐1,2,4‐triazole (IV) with α‐chloro derivatives of acetylacetone and of ethyl aceto‐acetate. Compounds Ia and IIa,b were utilised for the synthesis of several new heterocyclic derivatives.
Chiroptical properties of some N‐5(6)benzofuroxanoyl‐L‐α‐amino acids and esters
Authors: El‐Abadelah Mustafa M. , Anani Ali A. , Khan Zahida H. , Hassan Ata M.
Published: March 2009

The CD spectra of a series of N‐5(6)benzofuroxanoyl‐L‐α‐amino acids and esters reveal, in ethanol and acetonitrile, cotton effect (CE) bands around 365, 320, 265 and 223 nm. It was found that the signs of the CE maxima, located at longest and shortest wavelengths, were both positive for the L ‐aliphatic series, whereas these bands display sign inversion in the CD spectra of the L ‐aromatic counterparts. This chiroptical behaviour might be attributed to conformational differences. Nmr spectral data give support to this assumption. Mass spectral fragmentations of these compounds are discussed.
cis‐ and trans‐N‐nitroso‐2,4‐diphenylazetidines
Authors: Powell Burwell F. , Reichenthal Jules , Overberger C. G. , Anselme J.‐P.
Published: March 2009

The synthesis of cis‐ and trans‐2,4‐diphenylazetidines as well as that of their N‐nitroso derivatives is described. The “abnormal” reduction of the N‐nitrosamines gives a cis‐trans mixture of the expected 1,2‐diphenylcyclopropanes. However, no stereochemical correlations could be made owing to the base‐induced isomerization of the starting N‐nitrosamines during the course of the reaction.
Synthese de nouvelles 1H,3H pyrido[2,3‐d] pyrimidinediones‐2,4
Authors: Brunel Suzanne , Montginoul Claude , Torreilles Eliane , Giral Louis
Published: March 2009

Dans cet article les auteurs décrivent la synthèse et les propriétés physico‐chimiques de nouvelles pyrido[2,3‐d]pyrimidinediones‐2,4 mono ou disubstituées.
Antibakterielle wirkstoffe. IV. Die nitrosubstitution im system der 5‐amino‐4‐cyanpyrazole
Authors: Kreutzberger Alfred , Burgwitz Klemens
Published: March 2009

Die Umsetzung von Ethoxymethylenmalononitril (1) mit Nitrophenylhydrazinen (2a‐d) führt zu 5‐Amino‐4‐cyan‐1‐(nitrophenyl)pyrazolen (4a‐d), unter denen besonders 4d durch antibakterielle Wirksamkeit auffällt.
Chemistry of sulfonyl isocyanates and sulfonyl isothiocyanates. IX. Routes to substituted oxazolidin‐2‐ones and oxazolidine‐2‐thiones
Authors: Mcfarland J. W. , Hayes C. E. , Blair E. B. , Stuhlmacher K. R.
Published: March 2009

4‐Chlorobenzenesulfonyl isocyanate (I) reacted with 2‐chloroethanol and 1‐chloro‐2‐propanol to give, respectively, 2‐chloroethyl 4‐chlorobenzenesulfonyl carbamate (III) and 1‐chloro‐2‐propyl 4‐chlorobenzenesulfonyl carbamate (VI). The carbamates III and VI cyclized under the influence of pyridine to afford, respectively, 3‐(4‐chlorobenzenesulfonyl)oxazolidin‐2‐one (IV) and 3‐(4‐chlorobenzenesulfonyl)‐5‐methyloxazolidin‐2‐one (VII). The oxazolidin‐2‐ones were stable toward hydrochloric acid but hydrolyzed in 2M sodium hydroxide solution to N‐(2‐hydroxyethyl)‐4‐chlorobenzenesulfonamide (V) and N‐(2‐hydroxy‐1‐propyl)‐4‐chlorobenzene‐sulfonamide (VIII), respectively. 4‐Toluenesulfonyl isothiocyanate (II) reacted with 2‐chloroethanol to give 2‐chloroethyl 4‐chlorobenzenesulfonyl thiocarbamate (IX), which was converted by pyridine to 3‐(4‐toluenesulfonyl)oxazolidine‐2‐thione (X).
4‐Substituted‐3,4‐dihydro‐3‐methyl‐2H‐1,3‐benzoxazin‐2‐ones. III (2,3). Solvolytic‐reductive transformation of 4‐(2‐keto)‐benzoxazin‐2‐ones into oxazin‐2‐ones
Authors: Bobowski George , Shavel John
Published: March 2009

A series of 4‐(2‐keto‐substituted)‐3,4‐dihydro‐3‐methyl‐2H‐1,3‐benzoxazin‐2‐ones 1 (Table I) was synthesized by condensation of 3‐alkyl‐3,4‐dihydro‐4‐hydroxy‐2H‐1,3‐benzoxazin‐2‐ones 4 with ketones 5 having active alpha hydrogens. In the presence of alcoholic potassium borohydride, compounds 1 underwent reductive transacylation to give 1,3‐oxazin‐2‐one derivatives 3 (Table III, a,b,c). When the other side of the ketone possessed substituents other than hydrogen, there were always also normal reduction products, i.e., secondary alcohols 2 (Table II) in addition to 3.
Studies on tertiary amine oxides. LXVII . Reactions of aromatic N‐oxides with 3‐arylrhodanines in the presence of acetic anhydride
Authors: Yousif Mohammed M. , Saeki S. , Hamana M.
Published: March 2009

Quinoline 1‐oxides 1 readily react with 3‐arylrhodanines 2 in the presence of acetic anhydride to afford 3‐aryl‐5‐(2‐quinolyl)rhodanines 3 in high yields. These products resist hydrolysis under both alkaline and acidic conditions, but is oxidized to quinaldinic acid 1‐oxide 4 with 30% hydrogen peroxide in hot acetic acid. Besides isoquinoline 2‐oxide 5, pyridine 1‐oxide 7a also reacts in the same way to give 3‐aryl‐5‐(2‐pyridyl)rhodanines 8, although the reactivity of γ‐picoline 1‐oxide 7b is considerably lower. Contrary to 3, 3‐phenyl‐5‐(2‐pyridyl)rhodanine 8a is successfully hydrolyzed with boiling 48% hydrobromic acid to 2‐pyridinemethanethiol 10 in 57% yield.
Synthesis, polarography and herbicidal activity of quaternary salts of 2‐(4‐pyridyl)‐1,3,5‐triazines, 5‐(4‐pyridyl)pyrimidine, 2‐(4‐pyridyl)pyrimidine and related compounds
Authors: Fischer Hanspeter , Summers Lindsay A.
Published: March 2009

2‐(4‐Pyridyl)‐1,3,5‐triazine, 2‐(4‐pyridyl)‐4‐methyl‐1,3,5‐triazine, 2‐(4‐pyridyl)‐4,6‐dimethyl‐1,3,5‐triazine and 2‐(4‐pyridyl)pyrimidine have been prepared by modification of established triazine and pyrimidine syntheses. These compounds and some of their relatives have been converted to quaternary pyridinium salts. The polarographic reduction potentials of the salts in aqueous solution are pH dependent. The activity of the salts as post‐emergent herbicides is reported.
Imidazo[1,2‐α]pyrimidines and 1,2,4‐triazolo[1,5‐α]pyrimidines: Two new examples of mesoionic xanthine analogs
Authors: Glennon R. A. , Rogers M. E. , El‐Said M. K.
Published: March 2009

Several derivatives of mesoionic imidazo[1,2‐α]pyrimidine‐5,7‐dione and 1,2,4‐triazolo[1,5‐α]pyrimidine‐5,7‐dione, two new examples of mesoionic xanthine ring systems, were prepared and characterized. These compounds were conveniently prepared by the condensation of bis‐(2,4,6‐trichlorophenyl) malonates with the appropriately substituted alkylaminoimiazole or 1,2,4‐triazole.
1H‐imidazo[4,5‐b] pyrazines. II. 2‐carboxylic acid derivatives
Authors: Tong Y. C.
Published: March 2009

Methods for the preparations of 1H‐imidazo[4,5‐b]pyrazine‐2‐carboxylic acid and derivatives are reported.
Synthèse d'hétérocycles en catalyse par transfert de phase
Authors: Dou Henri J.‐M. , Ludwikow Maria , Hassanaly Parina , Kister Jacky , Metzger Jacques
Published: March 2009

Dans cette note, nous décrivons brièvement quelques résultats permettant de cerner l'utilisation de la catalyse par transfert de phase dans les réactions d'hétérocyclisation. Des réactifs dihalogénés sont utilisés, les anions engagés dans la substitution provenant soit de dianions ambidents hétérocycliques, soit de l'éthanedithiol.
A novel improved synthesis of 3‐aminopyrazine‐2‐carboxylic acid
Authors: Buckland Paul R.
Published: March 2009

A three step synthesis of 3‐aminopyrazine‐2‐carboxylic acid (1) starting from pyrazine‐2,3‐dicarboxylic acid (5) is described. Diacid 5 is converted via the anhydride 6 into the ammonium salt of the half acid amide 7 which on Hofmann rearrangement gives the title compound in 55% overall yield.
Synthesis in the diazasteroid group. XII Syntheses of the 10,17‐diazasteroid and 10‐aza‐17‐thiasteroid systems
Authors: Takahata Hiroki , Hara Misao , Tomiguchi Akira , Yamazaki Takao , Castle Raymond N.
Published: March 2009

Upon desulfurization with Raney Ni, the condensed heterocycles 2a,b prepared by cyclization from β‐ketosulfoxides 1a,b gave β‐ketones 3a,b, which were condensed with 2‐carbethoxymethyl‐piperidine 4 to afford the 10,17‐diazasteroid 6 and the 10‐aza‐17‐thiasteroid 7, respectively.
Cinnoline chemistry. XIV. 3‐cyclohexylcinnolines
Authors: Maeba Isamu , Castle Raymond N.
Published: March 2009

The synthesis of 3‐cyclohexyl‐6,7‐dimethoxy‐1H‐4‐cinnolone (4), 4‐chloro‐3‐cyclohexyl‐6,7‐dimethoxycinnoline (5) and 8‐bromo‐3‐cyclohexyl‐6,7‐dimethoxy‐1H‐4‐cinnolone (6) are reported.
Syntheses and reactions of some 4,5‐dihaloimidazole‐2‐carboxylic acid derivatives
Authors: Dirlam John P. , James Richard B. , Shoop Eleanor V.
Published: March 2009

The preparation of 5H,10H‐diimidazo[1,2‐a:1′,2′‐d]pyrazine‐5,10‐dione (2a) and its 2,3,7,8‐tetrabromo‐ and 2,3,7,8‐tetrachloro‐ analogs (2b and 2c, respectively) is reported. These dimers, when allowed to react with various anilines, afford imidazole‐2‐carboxamides (3a‐c).
Synthesis of 2‐chloro‐5‐hydroxynicotinonitrile: The required intermediate in the total synthesis of a hydroxylated metabolite of (S)‐2‐(3‐t‐butylamino‐2‐hydroxypropoxy)‐3‐cyanopyridine
Authors: Ponticello Gerald S. , Engelhardt Edward L. , Freedman Mark B. , Baldwin John J.
Published: March 2009

A convenient method for the synthesis of 2‐chloro‐5‐hydroxynicotinonitrile (10) via 5‐amino‐2‐chloro‐3‐methylpyridine (3) is described. Subsequent conversions provided the basic metabolite 2 of (S)‐2‐(3‐t‐butylamino‐2‐hydroxypropoxy)‐3‐cyanopyridine (1). 13C Nmr data is also presented to characterize 2‐chloro‐5‐fluoro‐3‐methylpyridine (5), a by‐product in the Schiemann reaction having unexpected 1H and 19F nmr spectra.
Halogenation of vinyl ketoximes. Synthesis of isoxazoles and preparation and silver ion‐promoted reactions of 4‐halo‐2‐isoxazolines
Authors: Hansen John F. , Kim Yong In , Mccrotty Stephen E. , Strong Scott A. , Zimmer Douglas E.
Published: March 2009

Reaction of several α,β‐unsaturated ketoximes with N‐bromosuccinimide (NBS) gave isoxazoles, but yields were lower and the reaction less general than a similar transformation using iodine under basic conditions. With β,β‐disubstituted oximes, 4‐halo‐5,5‐disubstituted‐2‐isoxazolines were obtained using NBS, iodine, or N‐chlorosuccinimide. Treatment of the 4‐bromoisoxazo‐lines with silver acetate or silver nitrate caused either elimination with rearrangement to give isoxazoles or substitution at C‐4, depending upon the nature of the substituents at C‐5.
The specificity of reductive dechlorination in the polychloropyridine series. Synthesis of 2,3,5‐trichloro‐ and of 2,3,5,6‐tetrachloropyridine
Authors: Sutter P. , Weis C. D.
Published: March 2009

The high specificity of the reduction system zinc and ammonium salts in dimethyl methylphosphonate as solvent is demonstrated in several reductive dechlorination reactions of polychloropyridines. The reduction of pentachloropyridine with zinc/ammonium chloride system in dimethyl methylphosphonate yielded solely 2,3,5,6‐tetrachloropyridine. Similarly, the reduction of 2,3,4,5‐tetrachloropyridine with zinc and the tetramethylammonium salt of methyl methylphosphonate furnished exclusively 2,3,5‐trichloropyridine. A synthetic procedure for the preparation of the new ammonium salts of methyl methylphosphonate is given.
Reactions of ethyl 2‐benzoyl‐3‐phenylcyclopropanecarboxylate with hydrazines and hydroxylamine
Authors: El‐Kholy Ibrahim El‐Sayed , Fuid‐Alla Hassan Mostafa , Mishrikey Marcos Michael
Published: March 2009

While the reaction of the cyclopropane ester 1 with hydrazine hydrate or phenylhydrazine led to the formation of diazabicycloheptenones, its reaction with several para‐substituted phenyl‐hydrazines gave the corresponding hydrazones. With hydroxylamine, either oxime or 1,2‐oxazinone is formed.
Nuclear magnetic resonance spectra of psychotherapeutic agents. III.. Stereochemistry of 1‐methyl‐5‐phenyl‐2,3,4,5‐tetrahydro‐1H‐1,5‐benzodiazepine‐2,4‐diones
Authors: Aversa Maria C. , Giannetto Placido , Romeo Giovanni , Ficarra Paola , Vigorita Maria G.
Published: March 2009

The stereochemistry of some 1‐methyl‐5‐phenyl‐2,3,4,5‐tetrahydro‐1H‐1,5‐benzodiazepine‐2,4‐diones was determined by proton magnetic resonance using the paramagnetic shift reagent tris(6,6,7,7,8,8,8‐heptafluoro‐2,2‐dimethyl‐3,5‐octanedionato)europium [Eu(fod)3] two of these compounds, clobazam and triflubazam, are clinically used as psychotherapeutic agents. Several model structures, with intermediate stereochemistry in the range of the possible limit situations of benzocycloheptene, ‐cycloheptadiene or ‐cycloheptatriene type, are considered; LIS (3) are computer simulated on the basis of proton geometric parameters. It was found that at room temperature, these derivatives exist in only one pseudo‐boat cycloheptadiene‐like conformation, showing the 5‐phenyl group directed pseudo‐axially. This conformational preference is interpreted in terms of a balance between the steric requirements of the bulky substituent and electronic repulsion in the ring π‐system.
Neue synthese von 1‐acetyl‐3‐methoxycarbonyl‐β‐carbolin
Authors: Razmilića Iváan , Castillo Mariano , Lóapez Joséa Tomáas
Published: March 2009

A new synthetic method to obtain 1‐acetyl‐3‐methoxycarbonyl‐β‐carboline using dl‐tryptophan and acetaldehyde as starting materials is described.
Intramolecular 1,3‐dipolar cycloadditions of aliphatic nitrile oxides
Authors: Garanti Luisa , Zecchi Gaetano
Published: March 2009

Treatment of functionalized 1‐chloro‐oximes (3c and 4a,b) with triethylamine originates nitrile oxides (1c and 2a,b) which undergo an intramolecular cycloaddition providing fused‐ring isoxazole derivatives (7c and 8a,b). The latter reaction was not observed for one substrate (2c).
Heterocycles from carbohydrate precursors. Part XIX. The X‐ray crystal structure determination of the reaction product of 4‐(2‐acetoxyethylidene)‐4‐hydroxy‐2,3‐dioxobutyro‐1,4‐lactone‐2‐(p‐bromophenylhydrazone) with methylhydrazine
Authors: Stam C. H. , El Ashry El Sayed , El Kilany Yeldez , Van DerPlas H. C.
Published: March 2009

X‐ray crystallographic data show that the product obtained in the reaction of 4‐(2‐acetoxy‐ethylidene)‐4‐hydroxy‐2,3‐dioxobutyro‐1,4‐lactone‐2‐(p‐bromophenylhydrazone) with methyl‐hydrazine is the bicyclic compound 2,6‐dimethyl‐3,4‐dioxo‐2,3,4,6,7,8‐hexahydropyridazino‐[4,3‐c]pyridazine 4‐(p‐bromophenylhydrazone) (10) and not as originally suggested 1‐methyl‐3‐(1‐methylpyrazolin‐3‐yl)‐4,5‐pyrazoledione 4‐(p‐bromophenylhydrazone) (8).
Pyrrolo[1,2‐d]triazines‐1,2,4. II. Etude des pyrrolo[1,2‐d]triazinones‐1 et ‐4
Authors: Lancelot Jean‐Charles , Maume Daniel , Robba Max
Published: March 2009

La synthèse des dihydro‐1,2 oxo‐1 pyrrolo[1,2‐d]triazines‐1,2,4 2 est effectuée soit par transposition en milieu alcalin de pyrrolyl‐2 oxadiazoles, soit par cyclisation de N‐éthoxyméthylidène‐hydrazides pyrroliques. La dihydro‐3,4 oxo‐4 pyrrolo[1,2‐d]triazine‐1,2,4 5a est accessible par cyclisation en milieu alcalin de la N‐carbéthoxyhydrazone du formyl‐2 pyrrole. Les réactions de substitution électrophile des pyrrolotriazinones‐1 et ‐4 sont réalisables soit au niveau de l'azote lactamique avec des agents électrophiles tels que le sulfate diméthylique, le chlorure de benzyle ou l'acide monochloracétique, soit au niveau du cycle pyrrolique avec le brome ou l'acide nitrique. Les structures des dérivés obtenus sont établies par rmn 1H.
Two anomalous cyclizations in the dibenz[b,f][1,4]oxazepine series
Authors: Mckenzie Thomas C.
Published: March 2009

The cyclization of 3,5′‐dichloro‐2′‐phenoxypropionanilide (2) to a trimeric cyclohexane 4 and of 4‐bromo‐5′‐chloro‐2′‐phenoxybutyranilide (1) to a tetracyclic pyrrolooxazepine 5 is reported.
Quinazolinone derivatives. Kinetics of the reaction of 2‐chloromethyl‐3‐hydroxy‐4‐(3H)quinazolinone with nucleophiles
Authors: Fernandez Beatriz M. , Schapira Celia B. , Lamdan Samuel
Published: March 2009

Reaction of 2‐Chloromethyl‐3‐hydroxy‐4(3H)quinazolinone (1) with aliphatic amines and hydroxide follows two different routes affording substituted methyl quinazolinones and a dimer 2 derived from 1. The former were formed by SN2 reactions while the latter was formed by an inter‐molecular nucleophilic displacement. Second‐order and third‐order rate constants, respectively, were determined, and the kinetic factors influencing both parallel reactions were analysed.
Action des isocyanates sur les benzisothiazol‐2,1 ones‐3 (1H) et sur les thiadiazol‐1,2,4 ones‐5: Un nouveau réarrangement avec extrusion de l'atome de soufre
Authors: Perronnet Jacques , Taliani Laurent
Published: March 2009

L'action des isocyanates sur les benzisothiaxol‐2,1 ones‐3 (1H) et sur les thiadiazol‐1,2,4 ones‐5 a été étudiée. En présence de quantité stoechiométrique de base organique elle conduit, dans les deux cas, à l'incorporation de deux atomes de l'isocyanate dans l'hétérocycle, avec extrusion simultanée de l'atome de soufre.
Synthesis and spectroscopic studies of some quinolylmethylphosphonates
Authors: Jagodić V. , Tušek‐Božić L. J. , Božić B. , Herak M. J.
Published: March 2009

Monoethyl esters of 2‐quinolylmethylphosphonic acid (3) and 8‐quinolylmethylphosphonic acid (6) have been prepared. The corresponding diethyl esters 1 and 4, and sodium salts of monoesters 2 and 5, respectively, have also been isolated. The properties of the monoethyl esters of 8‐ and 2‐quinolylmethylphosphonic acid are very different. While the former was isolated as the hydrochloride, the latter did not form such a salt. Molecular weight determination indicated a dimeric structure of the monoester 3, and spectroscopic measurements confirmed the association presumably owing to the hydrogen bonding between the PO and P‐OH groups.
Polycondensed nitrogen heterocycles. IX. 5,6‐dihydro‐7H‐pyrrolo[1,2‐d][1,4]benzodiazepin‐6‐one
Authors: Dattolo Gaetano , Cirrincione Girolamo , Aiello Enrico
Published: March 2009

The reaction of amino derivative I with bromoacetyl bromide led to the formation of a complex mixture from which, in addition to the title compound, which was formed in low yield, compounds III, IV and VI were separated. Pyrrolo[1,2‐d][1,4]benzodiazepine V was obtained in 85% yield when the bromoamide III was treated with an equimolar amount of potassium t‐butoxide.
Isothiazolo[5,4‐b]pyridine analogs of nalidixic acid
Authors: Gilis P. M. , Haemers A. , Bollaert W.
Published: March 2009

The synthesis and antibacterial evaluation of a number of isothiazolo[5,4‐b]pyridine isosteres of nalidixic acid are described.
The syntheses of ethoxycarbonyl‐1,3‐dioxoles and oxazoles from the copper catalyzed thermolysis of ethyl diazopyruvate in the presence of ketones, aldehydes and nitriles
Authors: Alonso Miguel E. , Jano Patricia
Published: March 2009

The copper salt‐catalyzed interaction of ethyl diazopyruvate with ketones, aldehydes and nitriles was examined. A variety of 1,3‐dioxoles and oxazoles was obtained in moderate yield. The formation of enol ethers, epoxides, carbon‐carbon insertion products, aziridines, and azetidines, typical products of carbene reactions with carbon‐heteroatom multiple bonds, was not observed. Evidence for the operation of a 1,3‐dipolar cycloaddition reaction is presented.
Heterocycles from ylides. Part VIII Reactivity of 2‐arylmethylenebenzofuran‐3‐ones with stabilized sulphur ylides
Authors: Dalla Croce Piero , De Michele Anna
Published: March 2009

2‐Arylmethylenebenzofuran‐3‐ones react with carbonyl stabilized sulphur ylides yielding spiro‐[cyclopropane‐1,2′‐benzofuran‐3′‐ones], whose structure and stereochemistry were assigned on the basis of spectroscopic data and chemical behaviour.
Studies on pyridazine derivatives. IV Mesylation reaction of pyridazinylpyrazoles
Authors: Mátyus Péter , Szilágyi Géza , Kasztreiner Endre , Sohár PÁL
Published: March 2009

On mesylation, 1‐pyridazinylpyrazoles (1), give, depending on the substituents and reaction conditions, O‐mesylpyrazoles (2) and O‐mesyl‐4‐N‐mesyl‐1,4‐dihydro‐4‐pyridyl‐pyrazole derivatives (3). The structures of these compounds were confirmed by ir and 1H nmr spectral data.
Investigation of the reaction products of 5‐amino‐1,3‐disubstituted‐pyrazoles with aromatic aldehydes. synthesis of new fluorinated 1,3,4‐trisubstituted‐4H‐pyrazolo[3,4‐e][1,4]thiazepin‐7‐ones
Authors: Joshi Krishna C. , Pathak Vijai N. , Garg Urmila
Published: March 2009

The condensation products of 5‐amino‐1,3‐disubstituted‐pyrazoles with aromatic aldehydes were identified as 2,4‐dihydro‐2,5‐diphenyl‐4‐(phenylmethylene)‐3H‐pyrazol‐5‐imine derivatives Treatment of these products with mercaptoacetic acid gave new fluorine containing 1H‐pyrazolo[3,4‐e][1,4]thiazepin‐7‐ones.
Adducts of 2‐aminothiophenol with acetylenic nitriles or esters and their conversion into benzothiazoles and/or 1,4‐benzothiazines
Authors: Liso Gaetano , Trapani Giuseppe , Berardi Vincenza , Latrofa Andrea , Marchini Paolo
Published: March 2009

The reaction between 2‐aminothiophenol 1 and acetylenic nitriles or esters 2a‐d leads to the vinyl thio‐ethers 3a‐d. The conversion of 3 into benzothiazoles 8 and/or 1,4‐benzothiazines 9, in boiling dimethyl sulfoxide, has been achieved. A possible pathway involving benzothiazolines 5 as key intermediates is suggested.
Electron impact mass spectrometry of 3‐methyl‐4‐benzylideneamine‐5‐styrylisoxazoles. II
Authors: Martinez R. , Cortés E.
Published: March 2009

The mass spectra of a series of substituted 3‐methyl‐4‐benzylideneamine‐5‐styrylisoxazoles are reported and discussed. The spectra of these isoxazoles show a characteristic fragmentation pattern different from the 5‐styryl‐4‐nitroisoxazoles. Perhaps this is due to the presence of the Schiff base at position 4.
Synthesis and spectroscopic studies of some new substituted 6H‐indolo[2,3‐b]quinoxalines
Authors: Sarkis George Y. , Al‐Badri Hashim T.
Published: March 2009

Six substituted 6H‐indolo[2,3‐b]quinoxalines were synthesized by the interaction o‐phenyl‐enediamine with substituted isatins. The uv, ir and nmr spectral data for the compounds synthesized are presented and discussed.
1,2,4‐Triazines. 3. halogen‐sulfur exchange in the preparation of 5,6‐disubstituted‐1,2,4‐triazines
Authors: Neumann R. E. , Lovelette Charles A.
Published: March 2009

The preparation and displacement reactions of 3‐amino‐5,6‐bismethylthio‐1,2,4‐triazine (3) are described.
Improvement in the synthesis of α‐Methyl‐L‐tryptophan
Authors: Brana Miguel F. , Garrido Mercedes , López Maria L. , Sanz Antonio M.
Published: March 2009

A new synthesis of α‐methyl‐L‐tryptophan as the methyl ester derivative is described. This method is an improvement over previous methods.
Synthesis of 9‐substituted‐1,4,5,8‐tetraazaphenanthrenes
Authors: Nasielski‐Hinkens Raymonde , Benedek‐Vamos Marie , Maetens Daniel
Published: March 2009

The synthesis of 9‐substituted‐1,4,5,8‐tetraazaphenanthrenes was undertaken in the course of a study aimed at the preparation of organometallic complexing agents.
The selective preparation of 1,4‐diaryl‐6‐methyl‐ and 1,6‐diaryl‐4‐methyl‐2‐(1H)pyrimidinones
Authors: Kashima Choji , Katoh Akira
Published: March 2009

N‐Phenylurea reacted with benzoylacetone derivatives (I) to give 1,4‐diaryl‐6‐methyl‐2‐(1H)pyrimidinones (II) in addition to low yields of 1,6‐diaryl‐4‐methyl‐2‐(1H)pyrimidinones (IV), while N‐phenylthiourea afforded only 1,6‐diaryl‐4‐methyl‐2‐(1H)pyrimidinethiones (III) in good yields. Further 1,6‐diaryl‐4‐methyl‐2‐(1H)‐ pyrimidinethiones (III) were successfully converted in satisfactory yields into the corresponding 2‐(1H)‐pyrimidinones (IV) by the treatment with methyl iodide in the presence of sodium methoxide in methanol at room temperature.
A convenient synthesis of substituted piperazines via aminomercuration‐demercuration of diallylamines
Authors: Barluenga J. , Nájera C. , Yus M.
Published: March 2009

cis and trans‐2,6‐Bis[bromomercuriomethyl]piperazines II which bear equal or different substituents at each nitrogen are obtained in the reaction of N‐substituted diallylamines with mercury(II) acetate and aryl‐amines followed by a double decomposition process with potassium bromide. Their reduction with sodium borohydride lead to the corresponding 1,4‐disubstituted cis‐ and trans‐2,6‐dimethylpiperazines III. Steric factors account for the remarkable stereoselectivity observed in the preparation of compounds IIIi‐IIIn in which a 3:1 cis to trans isomer ratio is found.
Analogs of propranolol. Synthesis of 3‐alkylamino‐1‐(3‐benzo[b]thienyloxy)‐2‐propanols
Authors: Conde Santiago , Corral Carlos , Lissavetzky Jaime
Published: March 2009

The synthesis by two alternative routes of 1‐(3‐benzo[b]thienyloxy)‐3‐isopropylamino‐2‐propanol hydrochloride (1a HCl), a thiophenic isoster of Propranolol, and related compounds, is reported. The protecting and enolizing properties of the 2‐methoxycarbonyl group on benzo[b]thiophene‐3‐one, along with its facile removal, are utilized in the first route. In the second one, conversion of 3‐bromobenzo[b]thiophene in 1‐(3‐benzo[b]thienyloxy)‐2,3‐o‐isopropylidenepropane is the key step. On the other hand, hydrolysis of 1‐(3‐benzo[b]furanyloxy)‐2,3‐o‐isopropylidenepropane to the corresponding diol, in order to obtain a furanic isoster of Propranolol (17a), was unsuccessful.
Synthesis and spectral data of some heterocyclic compounds. The reaction of arylpropiolic esters with tetralones and acetylcyclopropane
Authors: Al‐Jobour Nazar H. , Shandala Mowafaq Y.
Published: March 2009

Reaction of phenylpropiolic ester (I) with α‐ and β‐tetralones in the presence of sodium ethoxide yielded 5,6‐dihydro‐7,8‐benzflavones and ethyl β‐(2‐tetralon‐1‐yl)cinnamates, as a result of Claisen and Michael reactions, respectively. The reaction of I with 3‐ethoxy‐2‐cyclohexen‐l‐one and acetylcyclopropane in the presence of sodium ethoxide yielded acetylenic β‐diketones and 2‐aryl‐6‐cyclopropylpyran‐4‐ones, respectively. These products were identified on the basis of spectral and analytical data.
Synthesis of phenylurethans of a pyrazolidinylcarbinol as anticonvulsant agents
Authors: Kornet Milton J.
Published: March 2009

Eleven phenylurethans were prepared from 1,2‐dimethyl‐3‐hydroxymethylpyrazolidine and various phenyl isocyanates. Anticonvulsant screening revealed that two of the phenylurethans exhibited moderate activity in the maximal electroshock seizure (MES) test in mice.
Derivatives of 2‐sulfonamido‐4,5‐dimethoxyphenylacetic acid and of 2‐carboxamido(2‐chloroethyl)methylbenzenesulfonamides
Authors: Catsoulacos P. , Camoutsis Ch.
Published: March 2009

Series of variously sustituted amides of 2‐sulfonamido‐4,5‐dimethoxyphenylacetic acid have been prepared. The reaction of diethylamine, piperidine, morpholine and bis(2‐chloroethyl)amine with carbo‐methoxymethyl‐3,4‐dimethoxybenzenesulfonyl chloride produced the corresponding sulfonamido derivatives. Acid hydrolysis of the latter and action of thionyl chloride gave the chlorocarboxymethyl‐benzenesulfonamides. The acid chlorides of the sulfonamides were transformed to the 2‐carboxamido‐bis(2‐chloroethyl)methylbenzenesulfonamides with bis(2‐chloroethyl)amine. These agents were tested in L‐1210 and P‐388 leukemias and were found not to possess antitumor activity in these two transplantable tumor lines.
β‐Dicéto énamines hétérocycliques: 2. (Pyridyl‐4)‐2 indanediones‐1,3 C‐et N‐substituées
Authors: Ploquin J. , Sparfel L. , Le Baut G. , Floc'h Et R.
Published: March 2009

La substitution des (pyridyl‐4)‐2 indanediones‐1,3 conduit généralement à des composés N‐substitués. Ceux‐ci peuvent être obtenus également par condensation des pyridines mono‐ ou pluriméthylées sur les phtalates symétriques, mixtes ou acides et par condensation oxydative de bromures de N‐alkyl pyridinium sur l'indanedione‐1,3. La solvatochromie négative, observée dans les spectres electroniques de ces derives N‐substitués, traduit la prédominance d'une forme limite bétainique dans ces composés.
Photolyse d'oxaziridines. 10. Photolyse et thermolyse d'oxaziridines N‐arylées
Authors: Oliveros Esther , Rivière Monique , Lattes Armand
Published: March 2009

La régiosélectivité de la formation de lactameg par photolyse ou thermolyse des spirooxaziridines est indépendante de la nature du substituant sur l'azote. La thermolyse des oxaziridines N‐arylées constitue une méthode de synthèse de choix d'hétérocycles N‐aromatiques.
Steroidal thiadiazines
Authors: Kallias Dimitrios , Stassinopoulou C. I. , Catsoulacos Panayotis
Published: March 2009

The reaction of 16α‐bromoketosteroids, 2α‐bromoketosteroids and 21‐bromoketosteroids with thiosemi‐carbazide in 2‐propanol produces the corresponding 2′‐amino‐1′,3′,4′‐thidiazinosteroids. Acetylation of the 2′‐aminothiadiazino‐compounds led to the diacetamidothiadiazinosteroids. The title compounds prepared were substantiated by examination of infrared and nuclear magnetic resonance spectra.
Synthesis of 4H‐3,1‐benzoxazin‐4‐ones and 4‐(3H)quinazolinones from anthranilic acids and their derivatives by the use of triphenyl phosphite and pyridine
Authors: Rabilloud Guy , Sillion Bernard
Published: March 2009

A series of 2‐substituted 4H‐3,1‐benzoxazinones and 2,3‐disubstituted 4‐(3H)quinazolinones have been synthesized in mild conditions by the use of triphenyl phosphite and pyridine as cyclising medium. Benzox‐azinones are produced either by ring closure of 2‐(acylamino)benzoic acids or in the reaction of benzoic acid with anthranilic acids. In the presence of aniline, the reaction leads to quinazolinones.