bluuebunny/crossref_metadata_2025 huggingface dataset:
The acid‐catalyzed rearrangement of 1‐N‐allylindolines
Authors: Izumi Taeko , Kasahara Akira
Published: March 2009

Zinc chloride‐catalyzed rearrangement of 1‐N‐allylindoline and 1‐N‐(2‐methylallyl)indoline proceeds readily in refluxing xylene to give 7‐allylindoline and 7‐(2‐methylallyl)indoline in 73% and 86% yields, respectively. The reaction of 1‐N‐2‐butenylindoline and zinc chloride give rise to the mixture of 7‐(1‐methylallyl)indoline, 7‐(cis‐ and trans‐1‐methyl‐1‐propenyl)indoline, and 7‐(trans‐2‐butenyl)indoline. On the other hand, the similar reaction of 1‐N‐(3‐methyl‐2‐butenyl)indoline with zinc chloride led to the formation of a mixture of 1,2,5,6‐tetrahydro‐4,4‐dimethyl‐4H‐pyrrolo[3,2,1‐ij]quinoline and 7‐(3‐methyl‐2‐butenyl)indoline.
Synthesis of benzimidazo‐substituted 3‐quinolinecarboxylic acids as antibacterial agents
Authors: Bran̂a Miguel F. , Castellano José M. , Yunta María J. R.
Published: March 2009

The 6‐ and 7‐(1‐ethylbenzimidazolyl)‐substituted 1‐ethyl‐1,4‐dihydro‐4‐oxoquinoline‐3‐carboxylic acids were synthesized. Antibacterial activity was tested in vitro. Only one of the new compounds prepared showed slight antibacterial activity against one of the strains tested. So, they are of no interest as antibacterial agents.
Synthesis of isochroman‐fused pyrazolone and pyrimidine derivatives
Authors: Wang Jin‐Jun , Yin Bing‐Zhu , Jiang Gui‐Ji , Imafuku Kimiaki
Published: March 2009

Unsubstituted 5, and 2‐aryl‐ 6a‐c, or 2‐(2‐benzothiazolyl)‐substituted 1,3‐dihydroisochromano[4,3‐c]pyrazol‐3(2H)‐ones 7a‐f were prepared by the reactions of 3‐ethoxyoxalyl‐ 2, or 3‐ethoxycarbonylisochroman‐4‐one 3 with hydrazine derivatives. The reactions with amidines gave 2‐substituted 4‐hydroxyisochromano[4,3‐d]‐pyrimidines 8a‐c.
Arene imine derivatives of nitrogen heterocycles: 1a,9b‐dihydrobenz[h]‐azirino[f]quinoline, 1a,9b‐dihydrobenz[f]azirino[h]quinoline and 1a,9b‐dihydroazirino[f][1,10]phenanthroline
Authors: Abu‐Shqara Elias , Blum Jochanan
Published: March 2009

The syntheses of the K‐imine derivatives of benzo[h]quinoline (1), benzo[f]quinoline (2) and 1,10‐phenanthroline (3) are described. The parent nitrogen heterocycles were oxidized with sodium hypochlorite to the corresponding K‐oxides, 4, 6 and 8, which in turn were reacted with sodium azide. The resulting azido alcohols were then cyclized with triethyl phosphite to the title compounds 5, 7 and 9. The oxirane ring cleavage in benzo[h]quinoline 5,6‐oxide (4) and in benzo[f]quinoline 5,6‐oxide (6) by sodium azide proceeded by the predicted regioselectivity: 4 gave trans‐5‐azido‐5,6‐dihydro‐6‐benzo[h]quinolinol (11) and trans‐6‐azido‐5,6‐dihydro‐5‐benzo[h]quinolinol (10) as the major and minor products respectively, and 6 yielded solely trans‐6‐azido‐5,6‐dihydro‐5‐benzo[f]quinolinol (12). The latter compound proved by X‐ray analysis to crystallize as a hydrogen bonded dimer.
Reaction of biguanides and related compounds. XVI. Synthesis of s‐triazinones and fused s‐triazinones by carbonylation of biguanides and related compounds with diethyl azodicarboxylate
Authors: Kihara Yoshito , Kabashima Shigeru , Yamasaki Tetsuo , Ohkawara Tadashi , Furukawa Mitsuru
Published: March 2009

Biguanides and the related compounds, in which a moiety of biguanide is involved in the structure as a part of the ring, were allowed to react with diethyl azodicarboxylate to afford triazinones and fused heterocycles including a triazinone ring, respectively. The mechanism of the reaction was elucidated to proceed through the initial formation of the amide intermediate, followed by cyclization to triazinone ring systems with elimination of nitrogen.
Synthesis of some novel polyoxygenated quinolines
Authors: Jaroszewski Jerzy W.
Published: March 2009

Polyfunctional quinolines were obtained via thermal cyclization of phenylaminocrotonates and malonanilides and characterized by uv, ir, and 1H and 13C nmr spectra. Dehydration of a derivative of 5‐hydroxymethyl‐4(1H)‐quinolone yielded a derivative of 5H‐furo[2,3,4‐de]quinoline, representing a novel tricyclic system.
Reaction of β‐arylidennaphthylamines with 4‐hydroxycoumarin. A correction in structural assignment of the product. III
Authors: Martínez Roberto , Cortés Eduardo , Toscano Rubén A. , Alfaro L. Josué
Published: March 2009

The reaction of 4‐hydroxycoumarin with β‐arylidennaphthylamines constitutes a convenient synthetic route to the hitherto unknown 2H‐benzo[f][1]benzopyrano[4,3‐b]quinolin‐2‐one, VI. The X‐ray crystallography data conform with the present benzopyrano[4,3‐b]quinolin‐2‐one ring system and disprove the benzopyrano[3,4‐c]quinolin‐2‐one structure previously assigned for such reaction products.
A convenient synthesis of 3‐aryl‐3,4‐dihydroisoquinolinium salts
Authors: Badía D. , Carrillo L. , Domínguez E. , Cameno A. G. , Martínez De Marigorta E. , Vicente T.
Published: March 2009

A convenient synthesis of the title compounds proceeding via direct Bischler‐Napieralski cyclization reaction of the appropriate N,N‐dialkylformamides obtained from the adequate imines is described. The reported procedure implies synthetically useful yields and mild reaction conditions.
A series of novel acyclic nucleosides. II. Synthesis of acyclic nucleosides bearing an imidazo[4,5‐d] [1,3]oxazine ring
Authors: Matsumoto Hiroatsu , Kaneko Chisato , Mori Takeo , Mizuno Yoshihisa
Published: March 2009

Novel acyclic nucleosides 3a,b,c where N‐1 of acyclovir is replaced by oxygen atom were prepared. Thus, 1‐[(2‐acetoxyethoxy)methyl]‐5‐amino‐4‐ethoxycarbonylimidazole (9) was treated with ethoxycarbonyl isothiocyanate or benzoyl isothiocyanate to give 11e,f. Methylation of the latter with methyl iodide afforded S‐methylisothiourea derivative 12f which was treated with alkali and subsequently the mixture was neutralized to give 5‐amino‐3‐[(2‐hydroxyethoxy)methyl]‐3H‐imidazo[4,5‐d][1,3]oxazin‐7‐one (3a). Compounds 3b,c were obtained by treatment of acetic anhydride or propionic anhydride with sodium 5‐amino‐1‐[(2‐hydroxyethoxy)methyl]imidazole‐4‐carboxylate (7) which was prepared via 5‐amino‐[(2‐acetoxyethoxy)methyl]‐imidazole‐4‐carboxamide (5). Evaluation of acyclic oxanosine analogs for cytotoxicity and activity against herpes simplex virus type 1 (HSV‐1) revealed that all the derivatives tested were inactive, but cytotoxicity were similar or less as compared to that of acyclovir.
Diheterocyclic compounds from dithiocarbamates and derivatives thereof. III. 3,3′‐arylenebis(2,4‐dioxo‐1,2,3,4‐tetrahydroquinazolines)
Authors: Garín Javier , Meléndez Enrique , Merchán Francisco L. , Merino Pedro , Orduna Jesús , Tejero Tomás
Published: March 2009

The title compounds 3 were synthesized from dimethyl N,N′‐arylenebisdithiocarbamates 1. An alternative synthesis for 3 and their 3,3′‐(6,6′‐dibenzothiazole‐2,2′‐diyl) analogues 7 is also described.
Synthesis, structural and conformational study of 6‐hydroxy (or acyloxy) derivatives of the 1,3‐dimethyl‐1,3‐diazoniatricyclo[3.3.1.13–7]decane system
Authors: Fernández M. J. , Gálvez E. , Lorente A. , Camuñas J. A. , Sanz J. , Fonseca I.
Published: March 2009

1,3‐Dimethyl‐1,3‐diazoniatricyclo[3.3.1.13–7]decan‐6‐ol, and his p‐chlorobenzoxy and diphenylacetoxy derivatives have been synthesized and studied by 1H and 13C nmr spectroscopy. The crystal structure of the alcohol 2a has been determined by X‐ray diffraction. Each ring of the adamantane cage system is a nearly perfect chair. From the 1H and 13C nmr data, several stereoelectronic effects have been deduced.
Metallation of diazines II. First metallation of pyridazine, metallation of 2,4‐dichloropyrimidine
Authors: Turck A. , Plé N. , Mojovic L. , Quéguiner G.
Published: March 2009

3,6‐Dichloropyridazine was ortho‐lithiated by lithium 2,2,6,6‐tetramethylpiperidide. The resulting lithio compound was reacted with carbonyl derivatives iodine and trimethylchlorosilane. An azaxanthone was synthesised. An unusual regioselectivity for the lithiation of 2,4‐dichloropyrimidine was studied.
New dehydration in the pyrrolo[1,2–6‐b]isoquinoline series. Preparation and structural identification of 3,5‐dihydrobenz[f]indolizin‐3‐one
Authors: Rigo Benoít , Tullier Etienne , Barbry Didier , Couturier Daniel , Warin Vincent , Lamiot Jocelyne , Baert François
Published: March 2009

3,5‐Dihydrobenz[f]indolizin‐3‐one was prepared by a novel dehydration reaction involving the heating of 1,2,3,5,10,10a‐hexahydro[f]indolizine‐3,10‐dione with polyphosphoric acid. The structure of this new compound was established by X‐ray crystallography, by nmr spectroscopy and by reduction to the known products 1,2,3,5‐tetrahydrobenz[f]indolizin‐3‐one and 1,2,3,5,10,10a‐hexahydrobenz[f]indolizin‐3‐one.
Stereoselective synthesis and stereochemical determination of 2,5‐dialkylpyrrolidines and 2,6‐dialkylpiperidines
Authors: Bacos D. , Célérier J. P. , Marx E. , Rosset S. , Lhommet G.
Published: March 2009

ω‐Alkyllactams 3 can be transformed into ω‐alkyl cyclic β‐enaminoesters 7 which are good precursors of insects venom alkaloids. A stereoselective synthesis of dialkylpyrrolidines and Solenopsine A is described followed by an easy stereochemical determination by 13C nmr.
Synthesis of 2‐chloro‐4,6‐di(heteroaryl)pyrimidines
Authors: Strekowski Lucjan , Harden Donald B. , Grubb William B. , Patterson Steven E. , Czarny Agnieszka , Mokrosz Maria J. , Cegla Marek T. , Wydra Roman L.
Published: March 2009

A practical method for the preparation of 2‐chloro‐4,6‐di(heteroaryl)pyrimidines and their 5‐methyl homologues from readily available 2‐chloropyrimidine and 2‐chloro‐5‐methylpyrimidine, respectively, is described. The method is based on the addition reactions of heteroaryllithium reagents with chloropyrimidines followed by dehydrogenation of the resultant substituted dihydropyrimidines. The use of 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone as the dehydrogenation agent gives the best results. Side reactions in the addition step are discussed.
Studies on quinazolinones. 2. Synthesis of 2‐(4‐benzylpiperazin‐1‐ylmethyl)‐2,3‐dihydro‐5H‐oxazolo[2,3–6]quinazolin‐5‐one and ‐2,3‐dihydro‐5H‐thiazolo[2,3‐b]quinazolin‐5‐one
Authors: Shiau Chia‐Yang , Chern Ji‐Wang , Liu Kang‐Chien , Chan Chao‐Han , Yen Mou‐Hsiung , Cheng Ming‐Chu , Wang Yu
Published: March 2009

To search for novel antihypertensive heterocycles in the condensed quinazoline series, two representative compounds were synthesized via a suitable reaction sequences. Treating anthranilonitrile with allyl isocyanate gave 2‐(allylureido)benzonitrile (10) in a quantitative yield. Compound 10 was cyclized to 3‐allylquinazoline‐2(1H, 4(3H)‐dione (11). Bromination of 11 in carbon tetrachloride converted it into the corresponding 3‐(2,3‐dibromopropyl) derivative (12) in 92% yield. Ring closure of 12 was effected by the action of alkali to afford 2‐bromomethyl‐2,3‐dihydro‐5H‐oxazolo[2,3‐b]quinazolin‐5‐one (13). The title compound, 2‐(4‐benzylpiperazin‐1‐ylmethyl)‐2,3‐dihydro‐5H‐oxazolo[2,3‐b]quinazolin‐5‐one (7) could be obtained by a reaction of either 12 or 13 with 1‐benzylpiperazine respectively. Starting from the readily available 3‐allyl‐2H‐thioxoquinazolin‐4(3H)‐one (16) via the analogous reactions gave the 2‐bromomethyl‐2,3‐dihydro‐5H‐thiazolo[2,3‐b]‐quinazolin‐5‐one (19) in good yield. However, the reaction of 19 with 1‐benzylpiperazine provided another target compound, 2‐(4‐benzylpiperazin‐1‐ylmethyl)‐2,3‐dihydro‐5H‐thiazolo[2,3‐b]quinazolin‐5‐one (8) only in poor yield (8%). As major product, the dehydrobrominated compound, 2‐methylene‐2,3‐dihydro‐5H‐thiazolo[2,3‐b]quinazolin‐5‐one (22) was isolated. A preliminary pharmacological evaluation revealed that both compounds 7 and 8 are devoid of the antihypertensive activity.
Proton‐ionizable crown compounds. 19. The synthesis of chiral dialkyl‐substituted triazolo‐18‐crown‐6 macrocycles
Authors: Bradshaw Jerald S. , Mcdaniel Christopher W. , Krakowiak Krzysztof E. , Izatt Reed M.
Published: March 2009

Four new chiral macrocyclic polyether ligands containing the proton‐ionizable triazole subcyclic unit have been prepared. The triazolo‐crowns contain two isopropyl, two isobutyl, two (S)‐sec‐butyl or two benzyl substituents on chiral macro ring carbon atoms. A racemic triazolo‐18‐crown‐6 containing two (1‐naphthoxy)methyl substituents was also prepared.
A synthetic entry to isoxazolo[5,4‐d]pyrimidine‐4(5H)thione and isothiazolo[4,3‐d]isoxazole
Authors: Vicentini C. B. , Veronese A. C. , Poli T. , Guarneri M. , Giori P. , Ferretti V.
Published: March 2009

4‐Thiocarbamoyl‐5‐aminoisoxazole 4 was used as a convenient starting material for preparing both isoxazolo[5,4‐d]pyrimidine‐4(5H)thiones 5 and 4‐aminoisothiazolo[4,3‐d]isoxazole 6. The structure of the latter compound was definitively assigned by X‐ray analysis.
Unambiguous structure of the compounds in the reaction of L‐tryptophan and 5‐hydroxy‐l‐tryptophan with alkyl isocyanates in acetone
Authors: Garrido Mercedes , López Rodriguez Maria L. , José Morcillo M. , Garcia Virginia Pérez , Monge A.
Published: March 2009

On the basis of X‐ray crystallographic analysis, it is shown that the reaction of L‐tryptophan and 5‐hydroxy‐L‐tryptophan with alkyl isocyanates in acetone affords, in agreement with Claesson's work, 3‐alkylcarbamoyl‐4‐(3‐indolylmethyl)‐1,3‐oxazolidin‐5‐ones 2 and not 2‐[(3‐alkyl‐4,4‐dimethyl‐2‐oxo)‐1,3‐diazetidinyl]‐3‐(3‐indolyl)propionic acids 1 as previously proposed.
Synthesis of new polycyclic systems containing the pyrimido[2,1‐a]phthalazine skeleton
Authors: Santagati Andrea , Santagati Maria , Russo Filippo
Published: March 2009

The synthesis of new polyheterocycles containing the pyrimido[2,1‐a]phthalazine system 5, 6 and 7, obtained by condensation of phthalic anhydride with the appropriate hydrazides 2, 3 and 4, respectively, are reported. It was also synthesized the 14H‐[1]Benzothieno[3′,2′:4,5]pyrimido[2,1‐a][1,2,4]triazolo[4,3‐c]phthalazin‐14‐one (16).
Diels‐alder reactions of cyclohexadienes derived from decarboxylation of photo[4 + 2]cycloadducts between 4,6‐dimethyl‐2‐pyrone and cyclic olefins
Authors: Shimo Tetsuro , Matsuo Kenji , Somekawa Kenichi , Tsuge Otohiko
Published: March 2009

Labile photo [4 + 2] adducts between 4,6‐dimethyl‐2‐pyrone and cyclic olefins reacted with second olefins to give cross adducts, and with acetylenes to afford both bis‐adducts and benzene derivatives with the concurrent decarboxylation, respectively. The reaction mechanism of the latter was considered.
Cycloaddition of benzothiete and electron‐deficient nitriles
Authors: Schmidt Michael , Meier Herbert , Saleh Sadiq A.
Published: March 2009

The o‐quinoid 8π electron system 2, generated by thermal ring opening of benzothiete (1), enters regio‐specific [8π + 2π] cycloaddition reactions with electron‐deficient nitriles 3a‐d, yielding the 4H‐1,3‐benzothiazines 4a‐d. A competitive dimerization of 1 leads to 1,5‐dibenzo[b,f]dithiocin (5). Depending on the nitrile further competitive or subsequent reactions (2 + 3b → 7b, 2 + 3d → 4d → 8d) can occur. The cycloadducts 10e and 11e gained from 3e anticipate a primary cleavage of 3e to methylisothiocyanate 9e which reacts at the CN double bond as well as at the CS double bond.
Synthesis and structure of pyrazolo[5,1‐a]isoindol‐8‐ones from Aromatic Ortho Diesters
Authors: Chupp John P. , Leo Gregory C. , Molyneaux John M.
Published: March 2009

The title compounds 2, have now been shown to arise in certain cases from condensation of aromatic ortho‐diesters with ketone, where formerly only indeno[1,2‐c]pyrazol‐4(1H)‐ones 3 have been reported from such reaction. Heretofore 2 was obtained in a less direct fashion from phthalaldehydic acid esters. When hetero‐aromatic diesters were employed, new heterocyclic ring systems as represented by 2a,b,c were prepared for the first time. Structures of 2 have been verified from detailed 1H and 13C nmr studies, while representative intermediates 4–9 in the condensation of diesters to 2 have been isolated and identified.
Synthesis of (±)‐pantolactone and (±)‐dihydro‐4‐ethyl‐3‐hydroxy‐4‐methyl‐2(3H)‐furanone
Authors: Kinoshita Takamasa , Hirano Madoka , Miyake Hiroyuki
Published: March 2009

The title compounds were synthesized from 3‐furoic acid via the Birch reduction.
Influence of the heterocyclic side ring on orientation during nitrations of 1,2‐alkylenedioxy‐annelated benzenes and their mononitro derivatives
Authors: Takakis Ioannis M. , Hadjimihalakis Phaedon M.
Published: March 2009

Nitration of 1,2‐alkylenedioxybenzenes 1 furnished the respective nitro derivatives 3 and 4 in the relative ratios: 4a:3a/100:trace, 4b:3b/98:2.4, 4c:3c/86:14, 4e:3e/91:9 and 4f:3f/99:1.3. Nitration of 4 gave 5a:6a:8a/0:0:100, 5b:6b:8b/7.7:3.2:89, 5c:6c:8c/23:12:65, 5d:6d:8d/14:74:12, 5e:6e:8e/27:18:55 and 5f:6f:8f/23:7.0:70. Nitration of the isomeric 3 afforded the dinitro products 5, 6 and 7 in the following relative ratios: 5a:6a:7a/92:8:0, 5b:6b:7b/80:20:0, 5c:6c:7c/69:20:1 1, 5d:6d:7d/45:19:36, 5e:6e:7e/37:57:5.9 and 5f:6f:7f/64:36:0. Nitration of 3‐nitro‐1,2‐dimethoxybenzene (9) furnished: 10:11/63:37. Orientation as a function of the heterocyclic ring‐size is discussed.
Diheterocyclic compounds from dithiocarbamates and derivatives thereof. VI. unsymmetrical N1,N4‐Bis(2‐benzazolyl)sulphanilamides
Authors: Meléndez Enrique , Merchán Francisco L. , Merino Pedro , Orduna Jesús , Urchegui Raquel
Published: March 2009

The title compounds 9 are readily synthesized from dithiocarbamic acid derivative 5 by stepwise formation of the heterocyclic rings. Differences in reactivity of dithiocarbamates and dithiocarbonimidates make group protection unnecessary.
The synthesis and chemistry of 5‐carboxy‐8‐mercaptoquinoline hydrochloride monohydrate: An intermediate in the synthesis of novel H+,K+‐ATPase inhibitors
Authors: Zawistoski Michael P.
Published: March 2009

The title compound 3 was prepared in six steps from 5‐nitro‐8‐hydroxyquinoline in 14% overall yield, using a substituted pyrimidine as a protecting group for sulfur. This offers a simple entry into the synthesis of 5‐carboxy‐8‐substituted thioquinolines, useful intermediates for the synthesis of H+,K+‐ATPase inhibitors.
Synthèse de 2‐pyrimidinylphénols et de 2‐pyrazolylphénols
Authors: Sacquet Marie‐Claude , Fargeau‐Bellassoued Marie‐Claude , Graffe Bernadette
Published: March 2009

De nouveaux pyrimidinylphénols 9a‐e et pyrazolylphénols 10a‐e substitués par des groupes aminométhyles sont préparés avec de bons rendements par action respective du carbonate de guanidine et de l'hydrate d'hydrazine sur les 3‐aminométhylchromones 8a‐e. Ces 3‐aminométhylchromones 8a‐e sont aisément obtenues par réaction de Mannich sur la chromone 5. Les rendements en chromone 5 et en aminométhylchromones 8a‐e ont été notablement améliorés.
Quinolone antibacterials. 1. 7‐(2‐substituted‐4‐thiazolyl and thiazolidinyl)quinolones
Authors: Zhang M. Q. , Haemers A. , Vanden Berghe D. , Pattyn S. R. , Bollaert W. , Levshin I.
Published: March 2009

A series of 7‐(2‐substituted‐4‐thiazolyl and thiazolidinyl)‐1‐ethyl‐1,4‐dihydro‐4‐oxoquinoline‐3‐carboxylic acids and their 6‐fluoro analogues were synthesized. The Hantzsch method was used for the preparation of the thiazolylquinolones. The thiazolidinylquinolones were synthesized by quaternization of the corresponding thiazolyl analogues, followed by reduction of the obtained thiazolium salts with sodium borohydride in aqueous solution. Antibacterial activity was tested in vitro. Most of the compounds were inactive against Gram‐negative bacteria but some of them showed however good activity against Gram‐positive bacteria and mycobacteria. This activity pattern is rarely found among the quinolone antibacterials.
Identification, synthesis and conformational study of a CN(R,S) synthon by‐product: (5R, 10R)‐5,10‐diphenyl‐1,6‐diaza‐3,8‐dioxabicyclo[4.4.1]undecane
Authors: Aitken David J. , Guillaume Dominique , Husson Henri‐Philippe , Chiaroni Angèle , Riche Claude
Published: March 2009

The title compound, containing a new heterocyclic skeleton, was identified by X‐ray crystallography as the product of condensation of (R)‐phenylglycinol with an excess of formaldehyde. The molecule adopts a rigid double twist‐chair conformation in both solid and solution states.
On triazoles XXIV. Synthesis of cycloalka[1,2,4]triazolo[1,5‐a]pyrimidinones
Authors: Reiter József , Berecz Gábor , Pallagi István
Published: March 2009

The uv and nmr spectral data of some 6,7,8,9,10,11‐hexahydrocyclohepta[d][1,2,4]triazolo[1,5‐a]pyrimidin‐5‐one, 5,6,7,8,9,11‐hexahydrocyclohepta[e][1,2,4]triazolo[1,5‐a]pyrimidin‐10‐one, 6,7,8,9,10,11‐hexahydrocycloocta[d][1,2,4]triazolo[1,5‐a]pyrimidin‐5(12H)‐one, 5,6,7,8,9,10‐hexahydrocycloocta[e][1,2,4]triazolo[1,5‐a]‐pyrimidin‐11(12H)‐one, 6,7,8,9,10,11,12,13,14,15‐decahydrocyclododeca[d][1,2,4]triazolo[1,5‐a]pyrimidin‐5(16H)‐one and 5,6,7,8,9,10,11,12,13,14‐decahydrocyclododeca[e][1,2,4]triazolo[1,5‐a]pyrimidin‐15(16H)‐one as well as their N‐benzylated derivatives representing six novel ring systems were compared to prove their structure. The N‐benzylation of the highly insoluble cyclic amides to yield the isomeric N‐benzyl derivatives 3/1, 3/2 and 3/3 distinguished by INAPT was performed through their readily soluble tetrabutylammonium salts.
The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 4. Benzo[f]thieno[2′,3′:4,5]thieno[2,3‐c]quinoline and Benzo[h]thieno[2′,3′:4,5]thieno[2,3‐c]quinoline and the total assignment of their 1H‐ and 13C‐NMR spectra
Authors: Luo Jiann‐Kuan , Zektzer Andrew S. , Castle Raymond N.
Published: March 2009

The synthesis of two novel polycyclic heterocyclic ring systems via photocyclization are reported. These are benzo[f]thieno[2′,3′:4,5]thieno[2,3‐c]quinoline and benzo[A]thieno‐[2′,3′:4,5]thieno[2,3‐c]quinoline. The total assignment of their 1H‐ and 13C‐nmr spectra was determined by utilizing two‐dimensional nmr spectroscopic methods.
Preparation of diastereomeric 5,8‐methanobenzoxazino[2,1–6]‐ and [2,3–6]‐1,3‐benzoxazin‐4‐ones by reaction of norbornane/ene‐condensed dihydro‐1,3‐oxazines with salicyl chloride
Authors: Stájer Géza , Frimpong‐Manso Samuel , Bernáth Gábor , Sohár Pál
Published: March 2009

Norbornane and norbornene‐condensed dihydro‐1,3‐oxazines 1–6 were converted with salicyl chloride to 5,8‐methanobenzoxazino[2,1–6]‐ and ‐[2,3‐b]‐1,3‐benzoxazin‐4‐ones 7–12. The addition takes place to the C  N bond: after acylation, the intermediate is stabilized through cyclization to the aryl‐substituted carbon by hydrogen chloride elimination. Diastereomers containing the oxazine rings in isomeric positions could be isolated in two cases. This is the first example of the isolation of diastereomers in such a salicyl chloride reaction. In contrast with earlier findings with reactions of related systems, no addition to the C  C bond could be observed. The steric structures of the compounds were elucidated by ir, 1H‐ and 13C‐nmr spectroscopy.
Synthesis of new 2‐aryl‐3,3a‐dihydro‐4‐oxo‐5H‐pyrazolo‐[1,5‐d][1,2,4]triazines and some of their derivatives
Authors: Coudert P. , Mavel S. , Couquelet J. , Tronche P. , Rubat C. , Bastide J.
Published: March 2009

The preparation of new dihydropyrazolo[1,5‐d][1,2,4]triazinones involved the formation of carboxylic acid hydrazides via the appropriate ethyl aroylacrylates, followed by condensation with an orthoester. The synthesis of some derivatives substituted on the nitrogen atom in the 5‐position of the triazine ring was reported and their anticonvulsant activity was evaluated.
Syntheses and spectral properties of β‐iodoureas and 2‐amino‐4,4‐diphenyl‐2‐oxazolines
Authors: Fernández José M. García , Mellet Carmen Ortiz , Adrián M. Angeles Pradera , Mota José Fuentes
Published: March 2009

The syntheses of N‐(trans‐2‐iodocyclohexyl)‐ 1–4, N‐(2‐iodo‐3,3‐dimethylbutyl) 5, and N‐(2‐iodo‐1,1‐diphenylethyl)ureas 6, 7 and the cyclization of 6 and 7 into 2‐amino‐2‐oxazoline derivatives 8, 9 are reported. The structures of prepared compounds are based on analytical and spectroscopic data.
Nitrogen Bridgehead Compounds. Part 81. Synthesis of 9‐(benzylidenehydrazono)‐6‐methyl‐4‐oxo‐6,7,8,9‐tetrahydro‐ and 9‐(benzylidenehydrazine)‐6‐methyl‐4‐oxo‐6,7‐dihydro‐4H‐pyrido[1,2‐a]‐pyrimidine‐3‐carboxylates
Authors: Hermecz István , Breining Tibor , Sessi John , Podányi Benjamin
Published: March 2009

Reaction of ethyl 9‐hydrazono‐6‐methyl‐4‐oxo‐6,7,8,9‐tetrahydro‐4H‐pyrido[1,2‐a]pyrimidine‐3‐carboxylate and benzaldehyde and its derivatives give a tautomeric mixture of 9‐arylidenehydrazono‐6,7,8,9‐tetrahydro‐ and 9‐arylidenehydrazine‐6,7‐dihydropyrido[1,2‐a]pyrimidine derivatives. In the same case the enhydrazine and hydrazone tautomers were separated. The structure of the products were characterised by uv, ir, 1H and 13C nmr. The equilibrium of the tautomers was affected by the substituent of the phenyl ring. A fair linear correlation exists between the logarithms of the equilibrium constants and Hammett σm and σ− constants of the substituents present on the phenyl ring.
Electrochemical oxidation of substituted pyrroles. III. Anodic oxidation of 2,5‐diphenyl‐3‐acetylpyrrole
Authors: Petruso S. , Caronna S. , Gambino S. , Filardo G. , Silvestri G.
Published: March 2009

The electrochemical oxidation of 2,5‐diphenyl‐3‐acetylpyrrole (I) is described. The cyclic derivative 1,6a‐dihydro‐2,5,6a‐triphenyl‐3,4‐diacetylbenzo[g]pyrrolo[3,2‐e]indole (II) was obtained in very good yield. However, when water was present in the reaction medium, a different derivative, 4‐acetyl‐2‐hydroxy‐2,5‐diphenyl‐3‐(4′‐acetyl‐2′,5′‐diphenyl‐3′‐yl)‐2H‐pyrrole (III), was obtained as the main product. 2,2′,5,5′‐Tetraphenyl‐4,4′‐diacetyl‐3,3′‐dipyrryl (IV), a potentially useful intermediate for the synthesis of condensed pyrroles, was synthesized by zinc reduction of III.
Heterocyclization of Acetamidrazones. I. Synthesis of 1,2,4‐triazolo[4,3‐a]pyridines via ring closure of 6‐(2‐acylhydrazino)pyridine intermediates
Authors: Cocco Maria Teresa , Congiu Cenzo , Onnis Valentina , Maccioni Antonio
Published: March 2009

The reaction of N1‐acyl‐2‐ethoxycarbonylacetamidrazones with ethyl ethoxymethylenecyanoacetate (EMCA) has been examined. The acetamidrazone 1a reacts with EMCA in boiling dimethyl sulphoxide to give the 1,2,4‐triazolo[4,3‐a]pyridin‐3(2H)‐one 2 in excellent yield. Similarly from the amidrazones 1b‐h the 1,2,4‐triazolo[4,3‐a]pyridines 3b‐h were obtained. When the reaction between the amidrazones and EMCA was performed in ethanolic solution, the 6‐(2‐acylhydrazino)‐pyridines 4 were isolated. Ring closure of 4 afforded the 1,2,4‐triazolo[4,3‐a]pyridines.
Design and synthesis of the 3′‐aminocarbonylamino, aminothiocarbonylamino and N‐(Hydroxy)guanidinyl derivatives of thymidine as potential anti‐HIV agents
Authors: Morin Kevin W. , Kumar Rakesh , Knaus Edward E. , Wiebe Leonard I.
Published: March 2009

The 3′‐substituted‐3′‐deoxythymidines 3a (urea), 3b (thiourea) and 3c [N‐(hydroxy)guanidinyl)] were designed based on the known structure‐activity correlations for the active anti‐HIV agent, 3′‐azido‐3′‐deoxythymidine (AZT). Hydrolysis of 3′‐cyanamido‐3′‐deoxythymidine (2) with ammonium hydroxide in the presence of hydrogen peroxide afforded the 3′‐urea analogue 3a, whereas reaction with hydrogen sulfide in methanol gave the 3′‐thiourea derivative 3b. The 3′‐[N‐(hydroxy)guanidinyl] compound 3c was synthesized by reaction of the 3′‐cyanamide 2 with hydroxylamine.
A convenient synthesis of 2‐arylidene‐3,8‐dihydro‐2H‐cyclohepta[b]furan‐3,8‐diones
Authors: Jin Zhong‐Tian , Liu Zhong , Imafuku Kimiaki
Published: March 2009

3‐(2‐Bromoacetyl)tropolone (1) reacted with several benzaldehydes 2a‐e to afford 2‐arylidene‐3,8‐dihydro‐2H‐cyclohepta[b]furan‐3,8‐diones 3a‐e in very good yields.
Halogenation and nitration of naphtho[1,2‐c][1,2,5]thiadiazole
Authors: Smith Walter T. , Patterson John M. , Kovelesky Albert C.
Published: March 2009

Bromination of naphtho[1,2‐c][1,2,5]thiadiazole (I) gives either an addition product, 4,5‐dibromo‐4,5‐dihydronaphtho[1,2‐c][1,2,5]thiadiazole (II), or a substitution product, 5,6‐dibromonaphtho[1,2‐c][1,2,5]thiadiazole (III), depending on the reaction conditions. Dehydrobromination of II gives 5‐bromonaphtho[12‐c][1,2,5]thiadiazole (IV). Chlorination of I gives the corresponding addition product V or 5‐chloronaphtho[1,2‐c][1,2,5]thiadiazole (VI). Compound VI can also be obtained by dehydrochlorination of V. The nitration of I produces a mixture of isomeric substitution products, 9‐nitro VIII and 6‐nitronaphtho[1,2‐c][1,2,5]thiadiazoles (VII).
Trifluoromethyl substituted 4‐pyrones via self‐condensation of trifluoroacetoacetates
Authors: Babu Srinivasan , Pozzo Mark J.
Published: March 2009

When 3‐(acetoxy)‐4,4,4‐trifluoro‐2‐butenoates 7 and 8 are heated at 100°, in the presence of catalytic amounts of zinc chloride, they undergo self‐condensation to yield 2,6‐bis(trifluoromethyl)‐4‐pyrones 1 and 2 respectively. Compounds 1 and 2 were further converted to the corresponding pyridine derivatives 3 and 4 via ammoniolysis.
Preparation of 3‐(2H‐pyran‐2‐on‐6‐yl)indolizines and the diels‐alder reactions with some olefinic and acetylenic dienophiles
Authors: Shimo Tetsuro , Ohe Masayuki , Somekawa Kenichi , Tsuge Otohiko
Published: March 2009

3‐(2H‐Pyran‐2‐on‐6‐yl)indolizines 6a‐d were prepared by 1,3‐dipolar cycloaddition reactions of N‐(2H‐pyran‐2‐on‐6‐yl)methylpyridinium bromides 5a,b with dimethyl acetylenedicarboxylate (DMAD). All of the cycloaddition reactions of 6b with N‐phenylmaleimide, p‐benzoquinone, and DMAD took place at the 2‐pyrone ring to give 3‐substituted indolizines.
Synthesis of (1R,4S,5R)‐endo‐N,N‐dimethyl‐2‐azabicyclo[2.2.1]methanamine
Authors: Jordis Ulrich , Sauter Fritz , Siddiqi Suhaib M.
Published: March 2009

Starting from trans‐4‐hydroxy‐L‐proline, (1R,4S,5R)‐endo‐N,N‐dimethyl‐2‐azabicyclo[2.2.1]methanamine 1 has been synthesized. The target compound is precursor of antibacterial quinolone carboxylic acids.
Preparation of 2‐formyl‐4‐nitropyrroles
Authors: Ono Noboru , Muratani Emiko , Ogawa Takuji
Published: March 2009

The Vilsmeier reaction of 3‐nitropyrroles which are prepared by the reaction of nitroalkenes with the sodium salt of tosylmethylisocyanide gives 2‐formyl‐4‐nitropyrroles in good yields.
Photochemistry of alkenyl‐ and acetal‐substituted pyridines
Authors: Fleming Steven A. , Bachelder Vance D.
Published: March 2009

Ethyl 3‐(2‐pyridyl)propionate formation results from irradiation of 3‐(2‐pyridyl)propanal diethylacetal in acetonitrile. This photoreaction is unique to the heteroaromatic pyridine and only occurs in acetonitrile. A minor product, 1‐aza‐2‐methyl‐3‐(2‐ethanal diethylacetal)‐4‐ethoxycycloocta‐1,3,5,7‐tetraene, is also obtained. The irradiation of 2‐methyl‐6‐(2‐pyridyl)‐2‐pentene in the presence of various sensitizers results in addition to the alkene side‐chain to produce oxetanes.
On triazoles. XXVIII. Synthesis of isomeric 1,2,4‐triazolylcarbothiohydrazides
Authors: Barkóczy József , Reiter József
Published: March 2009

Different 3a, 3b, 9, 10 and 12 type 5‐amino‐1,2,4‐triazolylcarbothiohydrazide isomers representing all possible isomeric types derived from 5‐amino‐1,2,4‐triazoles were synthesised from the corresponding 5‐amino‐1,2,4‐triazolyldithiocarbonates and hydrazines. HPLC measurements proved that in case of mono‐substituted hydrazines the steric press in the intermediate 6 caused besides formation of the expected derivative 3a the formation of compounds 4 and 5, too, while the intermediate 7 yielded only 3b. Thermal rearrangement of derivatives 3a in acetic acid led to isomers 9 and 10, respectively.
Studies on pyrazine. 23. Homolytic acylation of 2‐amino‐3‐cyanopyrazine and the related compounds with α‐keto acids: A synthesis of 5‐acyl‐3‐aminopyrazinecarboxylic acid derivatives
Authors: Sato Nobuhiro , Kadota Hisashi
Published: March 2009

Homolytic acylation of 2‐amino‐3‐cyanopyrazine (1) with α‐keto acids led to the formation of 6‐acylated compounds in 74‐85% yields. Methyl 3‐aminopyrazinecarboxylate (2) and 3‐aminopyrazinecarboxamide (3) were also acylated under the same conditions although in lower yields. The observed reactivity of acylation is explained by comparison with the homolytic reactions of related pyrazines.
A convenient synthesis for some new pyrido[3′,2′:4,5]thieno‐[3,2‐d]pyrimidine derivatives with potential biological activity
Authors: Peinador Carlos , Ojea Vicente , Quintela José Ma.
Published: March 2009

Ready, convenient synthesis for 8‐cyano‐7‐ethoxy‐4‐oxo‐9‐phenyl‐2‐substituted‐1,2,3,‐4‐tetrahydropyrido‐[3′,2′:,4,5]thieno[3,2‐d]pyrimidines 5, 8‐cyano‐7‐ethoxy‐4‐oxo‐9‐phenyl‐2‐substituted‐3,4‐dihydropyrido[3′,2‐: 4,5]thieno[3,2‐d]pyrimidines 6, 4‐chloro‐8‐cyano‐7‐ethoxy‐9‐phenyl‐2‐substitutedpyrido[3′,2′:4,5]thieno[3,2‐4 ‐pyrimidines 7 and 8‐cyano‐7‐ethoxy‐2‐(2′‐nitrophenyl)‐9‐phenyl‐4‐substitutedpyrido[3′,2′:4,5]thieno[3,2‐d]pyrimidines 8‐18 from 2‐chloro‐3,5‐dicyano‐6‐ethoxy‐4‐phenylpyridine 1 via 3,5‐dicyano‐6‐ethoxy‐2‐mercapto‐4‐phenylpyridine 2 and aminocarboxamide 4 are reported. In addition, the reaction of hydrazino derivative 12 with reagents such as formic acid and triethyl orthoformate yielded the fused tetraheterocyclic 8‐cyano‐9‐ ethoxy‐5‐(2′‐nitrophenyl)‐ 7‐phenylpyrido[3′,2′:4,5]thieno[2,3‐e]‐1, 2,4‐triazolo[4,3‐c]pyrimidine system 19.
Synthesis of 4,5‐dihydroisoxazole and isoxazolin‐5‐ones
Authors: Barluenga Joseé , Gotor Vicente , Iglesias María José
Published: March 2009

The synthesis of 5‐hydrazono‐4,5‐dihydroisoxazoles 3, from N'‐(3‐imino‐3‐aryl‐1‐methyl‐1‐alquenyl) hydrazones 1 and hydroxylamine hydrochloride, is described. These 4,5‐dihydroisoxazoles can be transformed into oximes 5 and isoxazolones 6 by treatment with reducing agents and ethyl chloroformate, respectively.
1,2,3‐Thiadiazole derivatives with a nearly linear N‐S…O grouping. X‐ray crystal structure analysis of four methylated products of 4‐phenyl‐1,2,3‐thiadiazole‐5‐carbaldoxime
Authors: L'Abbé Gerrit , Bastin Lieve , Dehaen Wim , Van Meervelt Luc , Feneau‐Dupont J. , Declercq J. P.
Published: March 2009

The title oxime 6 was methylated under different conditions and yielded four monomethylated products 7‐10 and two bismethylated products 11 and 12 which were easily distinguished by their 13C nmr spectra. In view of the potential thiapentalene character of 8, 9, 10 and 11, their X‐ray crystal structures were determined. The structural properties of the nitroso compound 9 are in accordance with a thiapentalene structure, whereas those of the other compounds deviate in the order 10 < 11 < < 8.
Influence of the coordination number of nitrogen on the structure of 6aλ4‐thia‐1,3,4,6‐tetraazapentalenic systems. Crystal structure analyses of 3‐(2‐pyridylimino)‐3H‐[1,2,4]thiadiazolo[4,3‐a]pyridine and its 1‐methylated salt
Authors: L'Abbé Gerrit , Van Meervelt Luc , Emmers Sabine , Dehaen Wim , Toppet Suzanne
Published: March 2009

Structural data were obtained by X‐ray crystallography for the title compounds which show that they are essentially planar and exhibit an approximately linear N2‐S1‐N8 arrangement. In compound 3 the separation between the sulfur atom and the pyridine nitrogen atom (2.61 Å) is larger than the Huggins constant energy distance (2.58 Å), suggesting that there is little or no bonding between them. The methylated salt 4, on the contrary, has a closer S…N(pyridine) distance (2.19 Å) with an estimated bond dissociation energy of 6 kcal/mole.
Synthesis and spectral analysis of (±)‐cis‐N‐[1‐(2‐hydroxy‐2‐phenyl‐ethyl)‐3‐methyl‐4‐piperidyl]‐N‐phenylpropanamide and (±)‐cis‐N‐[1‐(2‐hydroxy‐1‐phenylethyl)‐3‐methyl‐4‐piperidyl]‐N‐phenylpropanamide
Authors: Brine G. A. , Sawyer D. K. , Huang P.‐T. , Stark P. A. , Gaetano K. D. , Carroll F. I.
Published: March 2009

Treatment of (±)‐cis‐N‐(3‐methyl‐4‐piperidyl)‐N‐phenylpropanamide(2)with styrene oxide(1)yielded a mixture of (±)‐cis‐N‐[1‐(2‐hydroxy‐2‐phenylethyl)‐3‐methyl‐4‐piperidyl]‐N‐phenylpropanamide(3)and (±)‐cis‐N‐[1‐(2‐hydroxy‐1‐phenylethyl)‐3‐methyl‐4‐piperidyl]‐N‐phenylpropanamide(4). The structure of compound3was confirmed by an unambiguous synthesisvia(±)‐cis‐N‐[1‐(2‐oxo‐2‐phenylethyl)‐3‐methyl‐4‐piperidyl]‐N‐phenylpropanamide(6). The proton and carbon‐13 resonances of compounds3and4were assigned with the aid of two‐dimensional heteronuclear correlation experiments.
Synthesis, structural, and biochemical study of a series of methyl 2,6‐diaryl‐1‐methyl‐4‐oxopiperidine‐3,5‐dicarboxylates and a series of methyl 2,4‐diaryl‐3,7‐dimethyl‐9‐oxo‐3,7‐diazabicyclo[3.3.1]nonane‐1,5‐dicarboxylates
Authors: Fernandez M. J. , Casares J. M. , Galvez E. , Gómez‐Sal P. , Torres R. , Ruiz P.
Published: March 2009

A series of methyl‐2,6‐diaryl‐1‐methyl‐4‐oxopiperidine‐3,5‐dicarboxylates Ia‐c and 2,4‐diaryl‐3,7‐dimethyl‐1,5‐dimethoxycarbonyl‐9‐bispidinones IIa‐c have been synthesized and studied by ir, 1H and 13C nmr spectroscopy and the crystal structure of methyl 2,4‐diphenyl‐3,7‐dimethyl‐9‐oxo‐3,7‐diazabicyclo[3,3.1]nonane‐1,5‐dicarboxylate (IIa) has been determined by X‐ray diffraction. The enolic form of compound Ia (I'a) was also studied.
Assignments of the 1H and 13C NMR spectra of pseudo‐symmetric heterocyles using the HMQC‐TOCSY experiment to differentiate overlapping spin systems
Authors: Castle Lyle W. , Johnston Milton D. , Camoutsis Charalampos L. , Castle Raymond N.
Published: March 2009

The 1H nmr spectra of phenanthro[9′,10′:4,5]thieno[2,3‐c]quinoline, benzo[f]phenanthro‐[9′,10′:4,5]thieno[2,3‐c]quinoline and benzo[h]phenanthro[9′,10′:4,5]thieno[2,3‐c]quinoline are highly congested. For each compound, all protons abide in an aromatic environment complicated by pseudo‐symmetric regions which result in multiple overlap of the different spin systems these molecules contain. We illustrate here the utility of the HMQC‐TOCSY experiment to identify spin systems when the proton spectrum is highly congested. To complete the assignment of the 1H and 13C nmr spectra of each compound the HMBC experiment is used to assign the quaternary carbons.
Synthesis of N‐substituted α‐aminoacids from 4‐hydroxycoumarin
Authors: Hamdi Maǎmar , Sakellariou Reine , Spéziale Vincent
Published: March 2009

A new series, the N‐(methylene‐4‐oxocoumarinyl)aminoacids were synthesized by condensation of 4‐hydroxycoumarin with α‐aminoacids in the presence of excess ethyl orthoformate.
Acetylene chemistry. Part 23. N‐vinylation on acridinones
Authors: Reisch Johannes , Dittmann Stefan
Published: March 2009

The vinylation of 9(10H)‐acridinones 1a‐1d with propiolic acid ethylester resulting in acridinonyl‐N‐acrylic esters is reported.
The chemistry of 2H‐3,1‐benzoxazine‐2,4(1H)‐dione (isatoic anhydride). 22 . An efficient synthesis of leiokinine B
Authors: Coppola Gary M.
Published: March 2009

The alkaloid leiokinine B has been synthesized in one step from the reaction of N‐methylisatoic anhydride and the enolate derived from 3‐ethyl‐2‐pentanone.
On the formation of homo‐aza‐steroids and derivatives by beckmann rearrangement. Antitumor activity of stereoisomers homo‐aza‐steroidal esters
Authors: Catsoulacos P. , Catsoulacos D.
Published: March 2009

The Beckmann rearrangement of steroidal oximes is reported. Different methods of esterification of homo‐aza‐steroids with carboxylic derivatives of N,N‐bis(2‐chloroethyl)aniline are reported.

The lipophilic nature of the steroidal hormones is the reason for searching compounds containing as the biological platform the steroid molecule and as the active moiety the alkylating agent, such as nitrogen mustards linked to the steroid with a stable bond or with an easily cleaved ester or ether molecule and different other active species, hopefully to transport and deliver the alkylating agent to the specific target tissue. The concept to design hybrid compounds containing as the biological platform steroidal lactams and as the alkylating congener carboxylic derivatives of N,N‐bis(2‐chloroethyl)aniline might form compounds with synergistic activity.

The findings suggest that the conformation of the alkylating agent influences the anticancer activity, while the amide group of the lactam molecule is important for activity in L1210 leukemia.

These hybrid compounds with a modified steroid as the biological platform furnish derivatives with advantages compared to the unmodified steroids with alkylating agents.

Different methods of esterification of homo‐aza‐steroids with carboxylic derivatives of N,N‐bis(2‐chloro‐ethyl)aniline are reported.
Ring‐cleavage of isoxazoles with heterocyclic amines. Synthesis of fused pyrimidines
Authors: Bossio Ricardo , Marcaccini Stefano , Pepino Roberto , Paoli Paola
Published: March 2009

The reaction between 2‐substituted ethyl 2,5‐dihydro‐5‐oxoisoxazole‐4‐carboxylates (2a,b) and heterocyclic amines 1, 4, and 6, having the amino group in position 2 with respect to the nuclear nitrogen afforded fused pyrimidines 3, 5, and 7.
Synthesis and structure of 2,3,3a,4,9,9a‐hexahydro‐3,9a‐epoxy‐1H‐cyclopenta[b]quinoline and 5,7‐dibromo‐2,3,3a,4,9,9a‐hexahydro‐3,9a‐epoxy‐1H‐cyclopenta[b]quinoline
Authors: Jedrzejas Marek J. , Baker Ronald J. , Sheibley Fred A. , Oplinger Fred K. , Towns Robert L. R.
Published: March 2009

A novel fused oxonorbornyl ring system synthesized by reaction of substituted aniline and methacrolein dimer in acidic media has been characterized by single crystal X‐ray diffraction. Two such structures are reported herein. These compounds represent the first reported structures of fused oxonorbornyl derivatives.
The structure of new cis and trans 3′‐phenyl‐3′,3a′,4′,5′,6′,7a′‐hexahydro‐2,1‐benzisoxazole‐7a′‐spiro‐2‐(3‐phenylaziridine)
Authors: Diaz Eduardo , Barrios Héctor , Yuste Francisco , Aguilera José Luis , Reynolds William F. , Van Calsteren Marie Rose , Jankowski Christopher
Published: March 2009

The reaction of dibenzalcyclohexanone with hydroxylamine hydrochloride afforded three compounds 1–3 including the aziridine 3 showing a 3′,3a′‐trans configuration. Now we report on the isolation of a new aziridine 4, possessing a 3′,3a′‐cis configuration. Its structure was deduced by 2D nmr and single crystal X‐ray diffraction studies.
Synthesis of 2‐substituted 5‐(1,3‐dithiolan‐2‐ylidene)‐1,3‐dioxane‐4,6‐dione derivatives
Authors: Jung Ji Hun , Kim Jae Nyoung , Ryu Eung K.
Published: March 2009

Some 2‐substituted 5‐(1,3‐dithiolan‐2‐ylidene)‐1,3‐dioxane‐4,6‐dione derivatives 3 were prepared from the condensation reaction of 1,3‐dithiolan‐2‐ylidenemalonic acid (2) with carbonyl compounds in 40–93% yields.
Synthesis of dibenzocrown ethers with pendent amide groups
Authors: Kasprzyk Stanislaw P. , Bartsch Richard A.
Published: March 2009

Synthetic routes to twenty six crown ether compounds with pendent amide, N‐alkylamide, or N,N‐dialkyl‐amide groups are reported. The new crown ether compounds are based on sym‐dibenzo‐16‐crown‐5‐oxyacetamide and sym‐(propyl)‐dibenzo‐16‐crown‐5‐oxyacetamide and are obtained in high yields.
Synthesis of 1,3‐disubstituted‐2‐amino‐5‐hydroxyindoles by reductive aromatization
Authors: Player Mark R. , Sowell J. Walter
Published: March 2009

Reductive aromatization and demethylation of 1,3‐disubstituted‐2‐amino‐5‐oxo‐7a‐methyl‐5,7a‐dihydroindoles with zinc, pyridine and a trace of water yields 1,3‐disubstituted‐2‐amino‐5‐hydroxyindoles. Simple derivatives of the 5‐hydroxy substituent are described.
Substituted γ‐lactones. Some observations on the synthesis and reactivity of 4‐aroyl‐3‐hydroxy‐2(5H)‐furanones
Authors: Zimmer Hans , Palmer‐Sungail R. , Ho Douglas , Amer Adel
Published: March 2009

The reaction pathway towards formation of 4‐aroyl‐3‐hydroxy‐2(5H)‐furanones 1 from the base catalyzed reaction between an acetophenone, diethyl oxalate and formaldehyde was investigated. If methoxide was used as base, a transesterification was found to occur in the first step, while a side reaction, namely the retro Claisen reaction, was in competition with the desired lactone formation in the second step. The nature of the solvent and the acidic character of 1 as well as the basicity of the aminoarylene were found to have a profound influence on the course of the reaction of 1 with aminoarylenes.
Pyrrolo[2,1‐c][1,4]benzoxazepines. 2. Synthesis of 5‐phenyl derivatives
Authors: Kapples Kevin J. , Effland Richard C.
Published: March 2009

A series of 5‐phenylpyrrolo[2,1‐c][1,4]benzoxazepines with basic substituents at the 11‐position has been synthesized utilizing a nucleophilic aromatic fluoride displacement‐cyclization. Piperidinyl derivatives were prepared by Vilsmeier formylation of the key 1‐[(2‐fluorophenyl)phenylmethyl]pyrrole (4) followed by addition of a piperidinyl Grignard reagent and cyclization of the resulting carbinol. A (dimethylamino)methyl derivative was prepared via an analogous cyclization of α‐(dimethylamino)methyl‐1‐[(2‐fluorophenyl)phenyl‐methyl]‐1H‐pyrrole‐2‐methanol (10), obtained by the Hoeben‐Hoesch acylation of 4 with chloroacetonitrile, addition of dimethylamine to the resulting α‐chloroketone 8, and reduction of the α‐(dimethylamino)ketone 9 with sodium borohydride to give 10.
Diels‐alder reactions of 3‐(2‐nitrovinyl)indoles: Formation of carbazoles and bridged carbazoles
Authors: Noland Wayland E. , Konkel Michael J. , Tempesta Michael S. , Cink Russell D. , Powers Dawn M. , Schlemper Elmer O. , Barnes Charles L.
Published: March 2009

The Diels‐Alder reactions of 1‐substituted‐3‐(2‐nitrovinyl)indoles 3 with quinones and acetylenes give aromatized 1:1 adducts (‐ nitrous acid) (1) or (‐ nitrous acid, ‐2 hydrogens) 2,5. Likewise, dimerization (‐2 nitrous acids) of 3 gives aromatized 2‐(3‐indolyl)carbazoles 4. In contrast, 3 reacts with maleimides 6 to give 1:2 adducts (‐ nitrous acid or ‐2 hydrogens) 10 and 11, respectively, along with smaller amounts of 1:1 adducts (‐ nitrous acid, ‐2 hydrogens; or ‐4 hydrogens) 12 and 13, respectively. A mechanism for formation of the nitro products 11 and 13 is discussed. A 1:2 adduct (‐2 hydrogens) 19 was also obtained from a Diels‐Alder reaction between maleimide and the vinylindole produced in situ by condensing 1‐methylindole with acetone. The stereochemisty of this 1:2 adduct has been determined by X‐ray crystallography.
Studies on quinones. Part 25. Synthetic approaches to 6,9‐dioxygenated‐benzazepinones
Authors: Valderrama J. A. , Pessoa‐Mahana H. , Tapia R.
Published: March 2009

The Schmidt and Beckmann rearrangement of 3,4‐dihydro‐4,4‐dimethyl‐1(2H)‐naphthalenones bearing oxygenated groups at the 5,8‐positions, and some of their oximes are reported. Depending upon the structure of the substrates and the reaction conditions 4,5‐dihydro‐3H‐naphth[1,8‐cd]isoxazol, benzazepin‐2‐one and 5,6‐dihydro‐7H‐tetrazolo[1,5‐a][2]benzazepine derivatives were generated.
Manganese(III)‐mediated free‐radical cyclization of acitve methylene compounds, alkenes and molecular oxygen. Syntheses of sulfur‐ and phosphorus‐containing 1,2‐dioxan‐3‐ols
Authors: Qian Chang‐Yi , Nishino Hiroshi , Kurosawa Kazu
Published: March 2009

The reactions of β‐keto sulfoxide, β‐keto sulfones, or β‐keto phosphinate with 1,1‐disubstituted ethenes in the presence of manganese(III) acetate and molecular oxygen yielded 4‐phenylsulfinyl‐, 4‐phenylsulfonyl‐, or 4‐phosphinoyl‐1,2‐dioxan‐3‐ols 3 in moderate‐to‐good yields. m‐Chloroperbenzoic acid oxidation of 4‐phenylsulfinyl‐1,2‐dioxan‐3‐ols gave the corresponding 4‐phenylsulfonyl derivatives. The temperature dependence of the reactions was observed and the stereochemistry of the 1,2‐dioxan‐3‐ols are discussed.
Synthetic studies on indoles and related compounds. XXXI. Chemical confirmation of the synthetic route for the benz[f]indole skeleton and its application
Authors: Watanabe Toshiko , Miyagi Chiemi , Murakami Yasuoki
Published: March 2009

To confirm the structure of ethyl 9‐methoxybenz[f]indole (8a) prepared from ethyl pyrrole‐2‐carboxylate (4) via a new synthetic route, the following chemical correlation work was performed. Ethyl 9‐methoxybenz[f]in‐dole (8a) was converted to 1‐benzyl‐3‐methyl‐5,6,7,8‐tetrahydrobenz[f]indole (25), which was alternatively and authentically synthesized from ethyl 3‐methylpyrrole‐2‐carboxylate (11). On the basis of the established route to the benz[f]indole nucleus, two representative benz[f]indoles, benz[f]indole (1) and 4,9‐dioxobenz[f]indole (26) were synthesized.
Synthesis of novel isoquinoline derivatives as potential CNS‐agents
Authors: Bonnaud B. , Carlessi A. , Bigg D. C. H.
Published: March 2009

A series of 4‐aminomethyl‐1,2,3,4‐tetrahydroisoquinoline derivatives were prepared as potential CNS‐agents acting via amino‐acid neurotransmitter systems. The compounds were synthesized from 1,2,3,4‐tetra‐hydro‐1‐oxoisoquinoline‐4‐carboxylic acids obtained by dipolar cycloaddition reactions of imines with homo‐phthalic anhydride. Among the compounds tested 5c and 5m showed sub‐micromolar affinity for the NMDA receptor and represent a structurally novel class of ligand for this site.