bluuebunny/crossref_metadata_2025 huggingface dataset:
Thermolysis of 3‐azidophenalen‐1‐ones to naphtho[8,1‐ab]carbazolones and naphtho[8,1‐ab]‐8a‐azonia‐9‐λ2‐azafluoren‐7‐ones
Authors: Fischer Michaela , Stadlbauer Wolfgang
Published: April 2009

3‐Azido‐1‐phenalenones 4 with aryl‐ or hetarylsubstituents in position 2 cyclized by thermolysis to give naphtho[8,1‐ab]carbazolones 5 or naphtho[8,1‐ab]‐8a‐azonia‐9‐λ2‐azafluorenones 7. Reduction of the azides 4 gave the corresponding amino derivatives 9. The thermolysis conditions were studied by differential scanning calorimetry.
Singlet and triplet photocycloaddition reactions of 2‐pyridones with propenoate and 2,4‐pentadienotes, and the frontier molecular orbital analysis
Authors: Suishu Takaaki , Tsuru Seiichiro , Shimo Tetsuro , Somekawa Kenichi
Published: April 2009

Regioselective photocycloadditions of 2‐pyridones (1) with 2,4‐pentadienoates (3) were analysed and compared with the reactions with propenoate (2), and origins of the different regioselectivities were inferred from frontier molecular orbital properties by the use of PM3‐CI method.

Direct photoreactions of 1 with 3 being α,β,γ,δ‐unsaturated carboxylates gave four types of regio‐selective [2+2]cycloadducts, 3‐β:4‐α‐4, 5, 3‐δ:4‐γ‐6,7,5‐δ: 6‐γ‐8, 9 and 5‐δ:6‐γ‐[2+2]cycloadducts 10,11. Sensitized photoreactions of 1 with 3 did not occur, and fluorescence of 1 was weakly quenched by 3. Otherwise, main cycloadducts in the sensitized reactions of 1 with 2 have been obtained as 5‐α:6‐β‐[2+2]cycloadducts, which were different from main 3‐β:4‐α‐[2+2]cycloadducts of the direct reactions, and these site‐and regio‐selectivities were inferred from the different frontier molecular orbital coefficients at the. 3‐and 6‐positions of 1 for the triplet and singlet states. Formations of 4–7 were also interpreted by both effects of frontier orbital HSOMO‐LUMO interactions and of the electrostatic interaction between 1 and 3. The other site‐and regioselective adducts 8–11 were inferred to be formed by the electrostatic interactions similar to 2‐pyridone photodimerization.
Direct introduction of heterocyclic residues into 1,2,4‐triazin‐5(2H)ones
Authors: Rusinov Vladimir L. , Zyryanov Grigori V. , Pilicheva Tatjana L. , Chupakhin Oleg N. , Neunhoeffer Hans
Published: April 2009

3‐Aryl‐1,2,4‐triazin‐5(2H)‐ones 1a‐c react with indoles 2a‐c in trifluoroacetic acid/chloroform or in boiling butanol or acetic acid to give 3‐aryl‐6‐(indolyl‐3)‐1,6‐dihydro‐1,2,4‐triazin‐5(2H)‐ones 3a‐g. Oxidation of the dihydro‐1,2,4‐triazin‐5(2H)‐ones 3a‐e afforded 6‐(indolyl‐3)‐1,2,4‐triazin‐5(2H)‐ones 4a‐e, products of nucleophilic substitution of hydrogen in 1a‐c. Refluxing 1b with N‐methylpyrrote 5b in butanol for an extended time resulted in the formation of 3‐(4‐chlorophenyl)‐6‐(1‐meuiylpyrrolyl‐2)‐1,2,4‐triazin‐5(2H)‐one 4h. The reaction of 1a‐c with indoles 2a‐c, pyrroles 5a,b, 1,3‐dimethyl‐2‐phenylpyrazol‐4‐one (8) and aminothiazoles 9a,b in acetic anhydride affords the 1‐acetyl‐3‐aryl‐6‐hetaryl‐1,6‐dihydro‐1,2,4‐triazin‐5(2H)‐ones 6a‐s. Reaction of 1a‐c with N‐methyl‐pyrrole 5b in acetic anhydride gives beside the 1:1 addition products 6h‐k also the 2:1 addition products 7a‐c.
Synthesis, pharmacokinetics, and biological activity of a series of new pyridonecarboxylic acid antibacterial agents bearing a 5‐fluoro‐2‐pyridyl group or a 3‐fluoro‐4‐pyridyl group at N‐1
Authors: Yoon Sung June , Chung Yong Ho , Lee Chi Woo , Oh Yoon Seok , Choi Dong Rack , Kim Nam Doo , Lim Jae Kyung , Jin Yoon Ho , Lee Dug Keun , Lee Won Yong
Published: April 2009

The 1‐(5‐fluoro‐2‐pyridyl) or 1‐(3‐fluoro‐4‐pyridyl) group was introduced in the syntheses of new pyridonecarboxylic acid antibacterial agents. 1‐(5‐Fluoro‐2‐pyridyl)‐6‐fluoro‐1,4‐dihydro‐7‐(4‐methyl‐1‐piperazinyl)‐4‐oxoquinolone‐3‐carboxylic acid 7b (DW‐116) showed a moderatein vitroantibacterial activity but it was found to have very excellent pharmacokinetic profiles so that 7b (DW‐116) showed dramatic increasedin vivoefficacy.
Cyclocondensation reaction of a 1,5‐diketone with 1,2‐diamines
Authors: Márton‐Merész Magda , Zára‐Kaczián Erzsébet , Boros Sándor , Mátyus Péter
Published: April 2009

Reaction of 2‐acetonyl‐4,5‐dimethoxy‐3′‐chlorobenzophenone (1) with ethylenediamine afforded the imidazo[2,1‐a]isoquinoline 2, whereas 6‐(3‐chlorophenyl)‐8,9‐dimethoxybenzo[b]phenazine (3) and naphthol 4 were obtained with ortho‐phenylenediamine.
Stereoselective Michael addition of 6‐amino‐1,3‐dimethyl‐2,4‐pyrimidinedione to the exocyclic methylene of three sesquiterpene lactones. 1H and 13C NMR evidence of a new C‐C bond and lactam formation
Authors: Dfaz Eduardo , Barrios Hector , Nava Jose Luis , Enriquez Raul G. , Guzmán Angel , Leticia León G. , Fuentes Jose Fernando , Aidee Fuentes B. , Quintero Angelina , Solano Jose Dolores
Published: April 2009

The Stereoselective addition of the pyrimidine derivative 1 to the exocyclic methylene of the α,β unsaturated dehydrocostus lactone 2, Ivalin acetate 3 and Zaluzanin A diacetate 4, was achieved resulting in a new C‐C bond formation. In the cases of compounds 3 and 4, after the addition, the lactone was cleaved followed by reclosure into a lactam ring system.
Functionalization and cyclization reactions of various acetanilides with 4‐benzoyl‐5‐phenyl‐2,3‐furandione. Experimental and theroetical investigations
Authors: Yildirim Ismail , Ilhan I. Özer
Published: April 2009

4‐Benzoyl‐5‐phenyl‐2,3‐furandione (1) reacts with acetanilides 3a‐c under different conditions and gives the new open chained dibenzoylacetic acid derivatives 5a‐c, 6 and a new heterocyclic compound such as oxazole derivative 7. The electronic structures of the reactants, transitional states and final products of the reactions are investigated on the basis of AM1 method.
A two‐step synthesis of diaminofurazan and synthesis of N‐monoarylmethyl and N,N′‐diarylmethyl derivatives
Authors: Zelenin Alexander K. , Trudell Mark L.
Published: April 2009

Diaminofurazan (1) was synthesized from glyoxal (2) by an improved two‐step procedure. The N‐mono‐arylmethyl derivatives 4a‐e and N‐N'‐diarylmethyl derivatives 5a‐e of 1 were prepared in good yields by reductive alkylation with the corresponding aryl aldehydes.
Synthesis of 1‐halophenyl 4‐(2‐imidazolyl)‐1‐butanones and 5‐(2‐imidazolyl)‐1‐pentanones and their ketalization with glycerol
Authors: Huang Liang‐Fu , Bauer Ludwig
Published: April 2009

An alternate synthesis of 1‐(2,4‐dichlorophenyl)‐4‐(2‐imidazolyl)‐1‐butanones 5d is presented after 1‐[(dimethylamino)methyl‐ and 1‐methyl]‐2‐lithioimidazole failed to be substituted satisfactorily by 2‐(2,4‐dichlorophenyl)‐2‐(3‐iodopropyl)‐1,3‐dioxolane (3b). The Pinner addition of ethanol to 2‐(2,4‐dichlorophenyl)‐2‐(3‐cyanopropyl)‐1,3‐dioxolane yielded the corresponding imidate which was reacted with 1‐amino‐2,2‐dimethoxyethane to form an amidine. Hot dilute hydrochloric acid converted this ami‐dine to the 2‐imidazolyl ketone 5b. Syntheses of homologous 1‐(4‐chloro‐ and 2,4‐dichlorophenyl)‐4‐(2‐imidazolyl)‐1‐pentanones 20 are described. Ketalizations of 5 and 20 with glycerol formed imidazolyl 1,3‐dioxolanyl alcohols. Selective N‐ and O‐alkylations of some of these imidazolyl alcohols are described.
Retro‐ene reactions IV. Alkylation of 4,5‐dichloro‐1‐hydroxy‐methylpyridazin‐6‐one with α,ω‐dibromoalkanes or 4,5‐dichloro‐1 ‐(ω‐bromoalkyl)pyridazin‐6‐ones
Authors: Kim Sung‐Kyu , Cho Su‐Dong , Yoon Yong‐Jin
Published: April 2009

Alkylation of 4,5‐dichloro‐1‐hydroxymethylpyridazin‐6‐one (1) with α,ω‐dibromoalkanes 2 or ω‐bromo‐alkylpyridazin‐6‐ones 3 via a fragmentation of the retro‐ene type under the two restricted conditions was investigated.
Mass spectral studies of some 1,2,4‐oxa‐(thia)diazol‐5(4H)‐ones(thiones)
Authors: Dürüst Yasar , Faggi Cristina
Published: April 2009

Electron ionization mass spectra of some 3,4‐disubstituted 1,2,4‐oxadiazole‐5(4H)‐thiones, thiadiazol‐5(4H)‐ones and thiadiazole‐5(4H)‐thiones are reported and fragmentation pathways of their molecular ions are studied in view of metastable ion experiments and accurate mass measurements. The main fragmentation route of the compounds under investigation is retro 1,3‐dipolar cycloaddition.
Preparation of 4‐hydroxy‐3‐substituted, 2H‐1‐benzopyran‐2‐ones and 2H‐1‐benzothiopyran‐2‐ones from carboxylic esters and methyl salicylates or methyl thiosalicylate
Authors: Davis Sharon E. , Church A. Cameron , Tummons Rebecca C. , Beam Charles F.
Published: April 2009

C(α)‐Carboxylic acid esters were treated with excess lithium diisopropylamide, condensed with methyl salicylates or methyl thiosalicylate, followed by acid cyclization to either 4‐hydroxy‐3‐substituted, 2H‐1‐benzopyran‐2‐ones (coumarins), or 2H‐1‐benzothiopyran‐2‐ones (thiocoumarins).
Synthesis and spectroscopy of phosphonate derivatives of uracil and thymine. X‐ray crystal structure of diethyl 6‐uracilmethylphosphonate
Authors: Ochocki Justyn , Erxleben Andrea , Lippert Bernhard
Published: April 2009

A new class of phosphonate ligands, derived from uracil and thymine was designed, prepared and characterised. Dimethyl (4, 7) and diethyl (5, 8) uracilmethylphosphonates have been prepared by the reaction of chloromethyluracil isomers 2 and 3 with trimethyl phosphite and triethyl phosphite, respectively. The corresponding free acids, 5‐uracilmethylphosphonic acid 6 and 6‐uracilmethylphosphonic acid 9, have also been isolated. The structure of the compounds has been assigned by nmr spectroscopy and, in the case of 8, confirmed by X‐ray analysis.
A new synthesis of α‐substituted δ‐carbolines
Authors: Arzel Erwan , Rocca Patrick , Marsais Francis , Godard Alain , Quéguiner Guy
Published: April 2009

The paper describes a new general synthesis of α‐substituted δ‐carbolines based on key steps such as metalation, cross‐coupling and cyclization.
Intermediates for the synthesis of tetracyclic indole alkaloids. Synthesis of 4‐aminotetrahydrocarbazole derivatives
Authors: Patir Süleyman , Okay Görol , Gülce Ahmet , Salih Bekir , Hökelek Tuncer
Published: April 2009

An efficient method for the synthesis of 4‐aminotetrahydrocarbazole derivatives from 2,3‐dihydrospiro‐[1H‐carbazole‐1,2′‐(1,3)‐dithiolan]‐4‐(9H)‐one 1 is described. The structure of compound 6 has been confirmed by X‐ray structure analysis.
A new synthesis of 4‐phosphorylchromenes from 3‐nitrochromenes
Authors: Ono Noboru , Banshou Natsuko , Ito Satoshi , Murashima Takashi , Ogawa Takuji
Published: April 2009

3‐Nitrochromenes are readily converted into 4‐phosphorylchromenes on treatment with dialkyl phosphite in the presence of triethylamine in 60–70% yield. This method provides a general method for the preparation of alkenyl phosphonates from nitroalkenes and dialkyl phosphite.
1,2,4‐Triazoles. Improved synthesis of 5‐substituted 4‐amino‐3‐mer‐cato‐(4H)‐1,2,4‐triazoles and a facile route to 3,6‐disubstituted 1,2,4‐triazolo[3,4‐b][1,3,4]thiadiazoles
Authors: Invidiata Francesco Paolo , Furná Giancarlo , Lampronti Ilaria , Simoni Daniele
Published: April 2009

The reaction of thiocarbohydrazide with carboxylic acids at the melting temperature allows an improved preparation of the S‐substituted 4‐amino‐3‐mercapto‐1,2,4‐triazole heterocycles. The crude 4‐amino‐5‐mercapto‐1,2,4‐triazoles react easily with carboxylic acids or carboxylic acid chlorides to afford the 1,2,4‐triazolo[3,4‐fc][1,3,4]thiadiazole ring system.
Synthesis of vinca alkaloids and related compounds LXXXV. Studies with azepino[3,4‐b]indoles
Authors: Dancsó Andràs , Kajtár‐Peredy Mária , Szántay Csaba
Published: April 2009

The synthesis of some new pyrido[1′,2′:1,2]azepino[3,4‐b]indoles starting from indole‐3‐propanamine 1 is described. Stereochemistry and observed side reactions are discussed.
Reaction of N1‐acylacetamidrazones with trifluoroacetylvinyl ethers. Synthesis of new 4‐trifluoromethyl‐ and 6‐trifluoromethylpyridines
Authors: Cocco Maria Teresa , Congiu Cenzo , Onnis Valentina , Bernard Angela Maria , Piras Pier Paolo
Published: April 2009

The reaction between N1‐acylacetamidrazones 1 and enol ether 2 is described. Depending on the reaction conditions and on the substitution pattern of amidrazones 2‐acylhydrazino‐4‐methyl‐6‐trifluoro‐methylpyridines 3 and/or 2‐acylhydrazino‐6‐methyl‐4‐trifluoromethylpyridines 4 were obtained.
Synthesis and reactions of 1‐(2‐oxopropyl)pyridazin‐6‐ones
Authors: Choi Woo‐Yong , Cho Su‐Dong , Kim Sung‐Kyu , Yoon Yong‐Jin
Published: April 2009

Oxopropylation of 4,5‐dihalopyridazin‐6‐ones with chloroacetone afforded the corresponding 1‐(2‐oxo‐propyl) derivatives. Reaction of title compound with nucleophiles such as amines, alkoxides were investigated. In addition, selective reduction of 3‐nitro‐1‐(2‐oxopropyl)pyridazin‐6‐ones with iron/ammonium chloride in two phase solutions or zinc in acetic acid gave the corresponding 3‐amino or 3‐hydroxyimino derivatives.
New epoxyisoindolines by intramolecular diels‐alder reactions of some methyl‐substituted allylaryl‐2‐furfurylamines
Authors: Mance Ana Dunja , Šindler‐Kulyk Marija , Jakopčić KreŠImir , Hergold‐Brundić Antonija , Nagl Ante
Published: April 2009

N‐Alkenyl‐N‐(5‐substituted‐2‐furfuryl)‐N‐p‐toluidines 1–10 have been selected to study the intramolecular Diels‐Alder reaction of furans. New epoxyisoindolines 11–20 were prepared and fully characterised.
Microwave synthesis and anticonvulsant activity of new 3‐benzyl‐1,2,3‐benzotriazin‐4(3H)‐ones
Authors: Komet Milton J.
Published: April 2009

Several 3‐benzyl‐1,2,3‐benzotriazin‐4(3H)‐ones 1 were prepared by alkylation of 1,2,3‐benzotriazin‐4(3H)‐one with benzyl halides in dimethylformamide in a microwave oven in moderate yields. Accompanying 1 were minor amounts of products believed to be the O‐alkylated derivatives. Support for 3‐benzylation is shown by an alternate synthesis of la from o‐amino‐N‐benzylbenzamide by nitrous acid cyclization. The title compounds were evaluated in mice and rats in maximal electroshock (MES) and pentylenetetrazole (scMet) seizure models for anticonvulsant activity, and in the rotorod test for neurotoxi‐city. They were generally non‐toxic. The 3‐benzyl analog was the most active (maximal electroshock) compound; it's maximal electroshock ED50 value was 93 mg/kg (mouse).
Biomimetic synthesis of 4‐acetylbenzoxazolin‐2(3H)‐one isolated from Zea mays
Authors: Escobar Carlos A. , Kluge Michael , Sicker Dieter
Published: April 2009

4‐Acetylbenzoxazolin‐2(3H)‐one has been prepared biomimetically during attempts to synthesize the hemiacetalic hydroxamic acid 5‐acetyl‐2,4‐dihydroxy‐2H‐1,4‐benzoxazin‐3(4H)‐one by the immediate degradation of this unstable compound generated as an intermediate. Thus, 4‐acetylbenzoxazolin‐2(3H)‐one recently isolated from Zea mays kernels, and similar to other benzoxazolin‐2(3H)‐ones known from plant sources, is assumed to have originated from the degradation of natural 5‐acetyl‐2,4‐dihydroxy‐2H‐1,4‐benzoxazin‐3(4H)‐one which in turn could have been enzymatically released by a β‐glucosidase from the corresponding 2‐β‐D‐glucoside.
Pyridazines. 84. Pyridazino[3,4‐e]pyrido[3,2‐b][1,4]diazepine, a novel tricyclic ring system
Authors: Heinisch Gottfried , Matuszczak Barbara
Published: April 2009

The preparation of pyridazino[3,4‐e]pyrido[3,2‐b][1,4]diazepin‐5‐ones 8 and 9 starting from appropriately substituted pyridazine‐4‐carboxamides is reported. The new compounds were tested for HIV‐1 reverse transcriptase inhibitory activity.
Improved synthesis of 2‐substituted 4‐chlorothiazole‐5‐carbaldehydes
Authors: Debski Norbert , Hanefeld Wolfgang , Schlitzer Martin
Published: April 2009

An improved method for the reaction of 2,4‐dichlorothiazole‐5‐carbaldehyde (2) with secondary amines was established using potassium carbonate in acetonitrile at room temperature instead of deprotonation with butyllithium in tetrahydrofuran at −78°. The method is convenient and the yields of 3 even higher. Compound 2 could also be reacted by this method with thiophenols to yield 4‐chloro‐2‐phenylthiothiazole‐5‐carbaldehydes 4.
Asymmetric synthesis of (R)‐6‐amino‐1‐methyl‐4‐(3‐methyl‐benzyl)hexahydro‐1H‐1,4‐diazepine from L‐asparagine
Authors: Kato Shiro , Harada Hiroshi , Mode Toshiya
Published: April 2009

An efficient asymmetric synthesis of (R)‐6‐amino‐1‐methyl‐4‐(3‐rnethylbenzyl)hexahydro‐1H‐1,4‐diazepine [(R)‐2] which serves as the amine part of (R)‐1, a potent and selective 5‐HT3 receptor antagonist, is described. Formation of the hexahydro‐1H‐1,4‐diazepine ring was achieved by the intramolecular ami‐dation of the optically active aminocarboxylic acid 18 or reductive cyclization of the optically active aminoaldehyde 25. Compounds 18 and 25 were prepared from L‐asparagine via the key aziridine derivatives 15 and 22, respectively, with retention of the configuration. The intramolecular aziridine ring opening reaction of 29 gave the C2N bond cleavage product of the aziridine ring, the piperazin‐5‐one 30, as the main product along with the desired 7‐membered ring, the hexahydro‐1H‐1,4‐diazepine product 19.
Intramolecular amidoalkylation cyclizations in synthesis of novel pyrrolo(or isoindolo)thieno[2]benzazepines
Authors: Mamouni Aïcha , Pigeon Pascal , Daïch Adam , Decroix Bernard
Published: April 2009

Thieno[2]benzazepines annulated to pyrrole 8a,b or isoindole 8c have been synthesized utilizing the acid‐catalyzed cyclization of hydroxylactams 7a‐c as key step.
Alkyl (E,Z)‐2‐(2‐benzoyl‐2‐ethoxycarbonyl‐1‐ethenyl)amino‐3‐dimethylaminopropenoates in the synthesis of fused pyrimidinones. A facile route to 3‐aminoazino‐4H‐pyrimidin‐4‐ones
Authors: Strah Sonja , Golobič Amalija , Golič Ljubo , Stanovnik Branko
Published: April 2009

Alkyl (E,Z)‐2‐(2‐benzoyl‐2‐ethoxycarbonyl‐1‐ethenyl)amino‐3‐dimethylaminopropenoates 1a,b react with het‐eroarylamines 2 to give alkyl 2‐(2‐benzoyl‐2‐ethoxycarbonyl‐1‐ethenyl)amino‐3‐heteroarylaminopropenoates 3‐13. These were cyclized into fused 3‐(2‐benzoyl‐2‐ethoxycarbonyl‐1‐ethenyl)amino‐4H‐azolo‐ (or azino)‐pyrim‐idin‐4‐ones 14‐18. 2‐Benzoyl‐2‐ethoxycarbonyl‐1‐ethenyl group can be easily removed from 3‐(2‐benzoyl‐2‐ethoxycarbonyl‐1‐emenyl)amino‐8‐memyl‐4H‐pyrido[1,2‐a]pyrimidin‐4‐one (14) to give 3‐amino‐8‐methyl‐4H‐pyrido[1,2‐a]pyrimidin‐4‐one (19). The structure of 1a was confirmed by X‐ray analysis.
On triazoles. XXXIX. Synthesis and structure of some 1,2,4‐triazolo[1,5‐a]pyrimidin‐5‐one oximes
Authors: Reiter József , Reiter József
Published: April 2009

Some 1,2,4‐triazolo[1,5‐a]pyrimidin‐5‐one derivatives 1 and their alicyclic condensed ring analogues 2‐3 were converted through the corresponding “imino chlorides” 4‐6 to the oximes 7‐9. The “E” isomeric structure of the products obtained was proven with the use of cmr using the spectral data of the corresponding “benzyloximino” derivatives 10‐12 prepared as model compounds.
Enzymatic resolution of flavanone oximes
Authors: Izumi Taeko , Suenaga Kouji
Published: April 2009

The optically active (R)‐ and (S)‐flavanones were prepared by an enzymatically enantioselective hydrolysis of (±)‐flavanone oxime O‐acylates employing lipases, followed by hydrolysis with acid.
A selective synthesis of 2‐arylamino‐4H‐1,3,4‐thiadiazino[5,6‐b]‐quinoxalines and mesoionic triazolo[4,3‐a]quinoxaline
Authors: Kim Ho Sik , Kim Tong Eun , Kwag Sam Tag , Park Yong Tae , Hong Young Seuk , Okamoto Yoshihisa , Kurasawa Yoshihisa
Published: April 2009

The reaction of the 6‐chloro‐2‐(1‐methyl‐2‐thiocarbamoylhydrazino)quinoxaline 4‐oxides 3a‐d with trifluoroacetic anhydride gave the 2‐(N‐aryl)trifluoroacetamido‐8‐chloro‐4‐methyl‐4H‐1,3,4‐thiadiazino‐[5,6‐b]quinoxalines 7a‐d, respectively, while the reflux of compounds 3a‐c in N,N‐dimethylformamide afforded the mesoionic triazolo[4,3‐a]quinoxaline 4. Hydrolysis of compounds 7a‐d with triethylamine/water provided the 2‐arylamino‐8‐chloro‐4‐methyl‐4H‐1,3,4‐thiadiazino[5,6‐b)]quinoxalines 8a‐d, respectively.
Thiophene 1‐oxides. V. Comparison of the crystal structures and thiophene ring aromaticity of 2,5‐diphenylthiophene, its sulfoxide and sulfone
Authors: Pouzet Pascale , Erdelmeier Irene , Ginderow Daria , Dansette Patrick M. , Mansuy Daniel , Mornon Jean‐Paul
Published: April 2009

The detailed preparation of 2,5‐diphenylthiophene 1‐oxide (2) is reported as well as the comparative study of the crystal structures of 2,5‐diphenylthiophene, 1, its sulfoxide 2 and sulfone 3 obtained by X‐ray diffraction. This work represents the first experimental study of a complete heterocyclic series, including a thiophene derivative, and the corresponding sulfoxide and sulfone. On the basis of the geometrical parameters, the first unequivocal experimental parameters obtained for a thiophene 1‐oxide derivative, we have also examined the evolution of the aromatic character of the thiophene ring when oxidizing the sulfur atom to the sulfoxide and the sulfone. Paolini's bond orders and Julg and Francois's aromaticity indices have also been calculated for the three compounds and compared to those previously calculated for related thiophene derivatives by semi‐empirical or ab initio methods [6], [7]. All the data examined showed that, in spite of its non planarity, the thiophene ring of 2,5‐diphenylthiophene 1‐oxide 2 could still exhibit some de localization of its p electrons indicating a certain degree of aromaticity lower than in thiophene 1 but higher than in the sulfone 3.
On triazoles XXXVIII. The reaction of isomeric 5‐amino‐3‐morpholino‐1H‐1,2,4‐triazolylcarbothiohydrazides with ortho esters
Authors: Reiter József , Barkóczy József
Published: April 2009

The reaction of isomeric differently methylated 5‐amino‐3‐morpholino‐1H‐1,2,4‐triazolylcarbo‐thiohydrazides with ortho esters were studied. Except of the case of triethyl orthoacetate instead of the expected [1,2,4]triazolo[1,5‐d][1,2,4,6]tetrazepin‐5(7H)‐thione (6) derivatives different rearranged products such as 7, 8, 21, 23, 25, and 27 were obtained, derivatives 23 and 27 representing a novel ring system. Possible explanations were given for the formation of the rearranged products.
Fused pyrimidines. 7. Nucleosides of pyrimidopyrimidinediones and pteridinediones as potential chemotherapeutic agents
Authors: Nagarajan A. , Meltsner Bernard R. , Delia Thomas J.
Published: April 2009

Several nucleoside derivatives of pyrimido[4,5‐d]pyrimidine‐2,4(1H,3H)‐dione 1 and 2,4{1H,3H‐pteridinedione 2 were prepared. Treating the appropriate silylated nucleobase with 1‐O‐acetyl‐2,3,5‐tri‐O‐benzoyl‐β‐D‐ribofura‐nose 3 in the presence of trimethylsilyl Inflate gave 4 and 8 which, upon debenzoylation, gave 5 and 9, respectively. Treatment of 4 with phosphorus pentasulfide afforded the sulfur substituted compound 6. Again, deprotection gave 7. The arabinose derivatives were obtained by treating 1‐O‐acetyl‐2,3,5‐tri‐O‐benzoyl‐D‐arabinofuranose 10 with the silylated nucleobases to give 11 and 13. Debenzoylation gave the free arabinonucleosides 12 and 14 respectively. The deoxy derivative 16 was prepared by the reaction of 1 with 1‐chloro‐3,5‐di‐O‐acetyl‐2‐deoxy‐D‐ribofuranose 15. Deacetylation of 16 with methanolic ammonia gave the α‐anomer 17.
Benzofuran systems. Synthesis and biological examination of 1‐(3‐benzofuranyl)‐2‐phenylethanones
Authors: Kwiecień Halina , Baumann E.
Published: April 2009

Novel 1‐(3‐benzofuranyl)‐2‐phcnylethanones 4a‐d have been prepared by acetylation of 2‐alkylbenzo‐furans 2a‐c with phenylacetyl chlorides 3a‐b. The methoxy derivatives 4b‐d have been demethylated to the corresponding phenols 5b‐d with pyridinium hydrochloride. An attempt to obtain the derivatives of 4d and 5a iodinated in the phenyl ring has been undertaken. The novel compounds have been characterized by ir and nmr spectra and their biological activity examined.
The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 19. Thieno[3′,2′:4,5]thieno[2,3‐c]‐naphtho[1,2‐f]quinoline, thieno[3′,2′:4,5]thieno[2,3‐c]naphtho‐[1,2‐f][1,2,4]triazolo[4,3‐a]quinoline and thieno[3′,2′:4,5]‐thieno[2,3‐c]naphtho[1,2‐f]tetrazolo[1,5‐a]quinoline
Authors: Luo Jiann‐Kuan , Federspiel Ronald F. , Castle Raymond N.
Published: April 2009

Photocyclization of 3‐chloro‐N‐(3‐phenanthryl)thieno[2,3‐b]thiophene‐2‐carboxamide (5) yielded only one of the two possible structural isomers, thieno[3′,2′:4,5]thieno[2,3‐c]naphtho[1,2‐f]quinolin‐6(5H)‐one (6), which was further elaborated to afford the unsubstituted ring system 10, its triazole 11 and tetrazole 12. The structural confirmation of 10 was achieved by the total assignment of its 1H and 13C nmr spectra by the concerted utilization of two‐dimensional nmr spectroscopic methods.
Synthesis, 1H‐ and 13C‐NMR spectra, crystal structure and ring openings of 1‐methyl‐6,9‐epoxy‐9‐aryl‐5,6,9,10‐tetrahydro‐1H‐imidazo [3,2‐e] [2H‐1,5] oxazocinium methanesulfonate
Authors: Upadhyaya Subhash P. , Davis Frank S. , Lee Jae Jeong , Zaw Kyaw , Bauer Ludwig , Heimer Norman E.
Published: April 2009

The methanesulfonic acid catalyzed reaction of 1‐(4‐chloro‐ and 2,4‐dichlorophenyl)‐2‐(1‐methyl‐2‐imida‐zolyl)ethanones 1a and 1b with glycerol produced cis‐ and trans‐{2‐haloaryl‐2‐[(1‐methyl‐2‐imidazolyl)methyl]‐4‐hydroxymethyl}‐1,3‐dioxolanes 2a and 2b with a 2:1 cis/trans ratio. Besides these five‐membered ketals, the reaction of 1a with glycerol afforded a small amount of trans‐{2‐(4‐chlorophenyl)‐2‐[(1‐methyl‐2‐imidazolyl)methyl]‐5‐hydroxy}‐1,3‐dioxane (3a, 7%). The reaction of methanesulfonyl chloride with cis‐1 formed the corresponding methanesulfonates, cis‐4, which rapidly cyclized to the title compounds 5. Base‐catalyzed ring opening of 5 furnished 1‐methyl‐5,6‐dihydro‐6‐hydroxymethyl‐8‐(4‐chloro‐ and 2,4‐dichlorophenyl)‐1H‐imidazo[3,2‐d][1,4]oxazepinium methanesulfonates 7. Acid‐catalyzed hydrolyses of 5 or 7 provided 1‐methyl‐2‐[(4‐chloro‐ and 2,4‐dichloro)phenacyl]‐3‐[(2,3‐dihydroxy)‐1‐propyl]imidazolium salts 12. Structure proofs were based on extensive 1H and 13C chemical shifts and coupling constants and structures of 3a and 5a were confirmed by single crystal X‐ray crystallography.
Iminium carbonic acid derivative salts. VIII. Electrophilic reactions of 2‐methylthio‐5,6‐dihydro‐1,3‐thiazinium iodides, 2‐methylthio‐5,6‐dihydrothiazolium iodides and 5‐methyl‐2‐methylthiothiazolium iodides. Part II. With active methylene compounds
Authors: Hanefeld Wolfgang , Harms Helge
Published: April 2009

The title compounds 1a‐c and 2 werre reacted with several doubly activated methylene components to yield the cyclic ketene S,N‐acetals 3‐10.
Reactions of methyl (E,Z)‐2‐(2‐benzoyl‐2‐ethoxycarbonyl‐1‐ethenyl)‐amino‐3‐dimethylaminopropenoate with heteroarylhydrazines. 2‐(2‐Benzoyl‐2‐ethoxycarbonyl‐1‐ethenyl)amino‐3‐heteroarylhydra‐zonopropanoates and 1‐heteroaryl‐4‐ethoxycarbonyl‐3‐phenylpyrazoles
Authors: Strah Sonja , Stanovnik Branko
Published: April 2009

In the reaction of methyl (E,Z)‐2‐(2‐benzoyl‐2‐ethoxycarbonyl‐1‐ethenyl)amino‐3‐dimethylaminopro‐penoate (1) with heteroarylhydrazines 2 in ethanol in the presence of catalytic amounts of hydrochloric acid two types of products were formed: methyl 2‐(2‐benzoyl‐2‐ethoxycarbonyl‐1‐ethenyl)amino‐3‐heteroaryl‐hydrazonopropanoates 4 in 73‐86% yield and 1‐heteroaryl‐4‐ethoxycarbony‐3‐phenylpyrazoles 5 in 5‐16% yield.
N,N,5‐trimethyl‐1H‐benzothiopyrano[4,3,2‐cd]‐indazole‐1‐ethanamine — A novel heterocycle
Authors: Krapcho A. Paul , Haydar Simon N.
Published: April 2009

Treatment of thioxanthenone6withN‐(2‐dimethylaminoethyl)hydrazine led to the benzothiopyranoin‐dazole3, a novel heterocycle, along with the expected compound8.
Pyrimidine synthesis ‐ A new method
Authors: Somech Iris , Shvo Youval
Published: April 2009

A new one‐step‐method for the synthesis of 2‐phenylpyrimidines of type I was developed by reacting benzotrichloride with various nitriles in the presence of aluminum chloride.
Researches on pyridodiazepines. Behavior of 7,8,9,10‐tetrahydro‐5‐methylcyclopenta[e]pyrido[3,2‐b][1,4]‐diazepin‐6(5H)‐one with chloroacetyl chloride
Authors: Boido Alessandro , Savelli Francesco , Sancassan Fernando
Published: April 2009

Following a previous experiment, an original heteropolycyclic structure 4 was obtained by a reaction of chloroacetyl chloride with compound 3 bearing a conjugated double bond system. The condensation develops with an initial NH‐chloroacetylation and ring closure by quaternarization of the pyridine nitrogen. This is achieved through an 1,4‐cycloaddition of chloroketene to make a pyranone ring.
Triazolines. XXXIII. Nonregiospecific 1,3‐cycloaddition of aryl azides to vinylpyridines: A unique route to the synthesis of 2‐pyridyl substituted aziridines via unstable 4‐pyridyltriazoline intermediates
Authors: Lin Zhaiwei , Kadaba Pankaja K.
Published: April 2009

The 1,3‐cycloaddition of aryl azides to the olefinic bonds of 4‐ and 2‐vinylpyridines has been found to yield pyridyl substituted aziridines as the main reaction products with only smaller amounts of the normally expected l‐aryl‐5‐pyridyl‐1,2,3‐triazolincs. Theoretical and experimental evidence are provided to explain the results: based on the fact that the olefinic bonds in 4‐ and 2‐vinylpyridines are electron‐deficient, azide addition can be expected to be not regiospecific. In the bidirectional addition reaction, the HOMOazide‐ LUMOolefin interaction predominates leading to unstable l‐aryl‐4‐pyridyl‐1,2,3‐triazolines, which, unlike the more stable 5‐pyridyl compounds, lose nitrogen under thermal conditions to yield the aziridines. At room temperature, the reactions yield the aziridine along with the l‐aryl‐4‐pyridyltriazole, providing evidence for the formation of the 4‐pyridyltriazoline intermediate. Reaction of the vinylpyridines with variously substituted phenyl azides, clearly indicates that the electron donating methyl and methoxy groups on the phenyl azide facilitate reaction, while the electron withdrawing nitro group has a retarding effect. This is consistent with an increase in the HOMOazide energy and hence in azide reactivity. According to the FMO model, the 1,3‐cycloaddition of aryl azides to vinylpyridines appears to be predominantly, but not exclusively, a HOMOazide‐LUMOolefin interaction and provides a unique route to the synthesis of 2‐pyridyl substituted aziridines.
Synthesis of 9‐amino‐, 9‐aminomethyl‐1,2,3,4‐tetrahydro‐ and 1,2,3,4,5,6,7,8‐octahydroacridine derivatives
Authors: Del Giudice Maria Rosaria , Borioni Anna , Mustazza Carlo , Gatta Franco
Published: April 2009

This paper describes the synthesis of 9‐amino‐2‐ and 4‐hydroxy‐ and 2,4‐dihydroxy‐1,2,3,4‐tetrahydro‐acridines 2 and of 9‐aminomethyl‐1,2,3,4‐tetrahydro‐ and 1,2,3,4,5,6,7,8‐octahydroacridines 3 starting from the corresponding 9‐carboxamido derivatives. A new synthetical pathway to 9‐amino‐2‐hydroxyacri‐dine 9 is also reported.
3‐Aminoacetylthiazolidine‐4‐carboxylate esters and their l‐thia‐4‐azaspiro[4.5]decane‐3‐carboxylate derivatives. Synthesis and stereochemical properties
Authors: Pellegrini N. , Refouvelet B. , Rouland J.‐C. , Robert J.‐F. , Bachet B.
Published: April 2009

Dimethyl thiazolidine‐2,4‐dicarboxylate 2 and ethyl l‐thia‐4‐azaspiro[4.5]decane‐3‐carboxylates 3‐5 were obtained as a diastereoisomeric mixture while their 3‐aminoacetyl derivatives were isolated in only one isomeric form. These reactions of N‐acylation were stereoselective, which can be explained by an interconversion of the diastereoisomers via a seco intermediate. The 1H nmr analysis of amides 6 and 11 exhibited the presence of both cis and trans amide bond conformations, whereas only one cis conformation was observed for spiro amides 8‐10 and 13‐15.
Synthesis of pyrazolo[3,4‐c][1,2]thiazin‐4(3H)‐one 2,2‐dioxides, new heterocycles
Authors: Coppo Frank T. , Fawzi Maged M.
Published: April 2009

The reaction of substituted ethyl 5‐aminopyrazole‐4‐carboxylates with two equivalents of methanesul‐fonyl chloride gave the substituted ethyl 5‐[bis(methylsufonyl)amino]‐1H.‐pyrazole‐4‐carboxylates II. Removal of one of the methanesulfonyl groups, followed by alkylation of the ethyl 5‐[(methylsulfonyl)amino]‐1H‐pyrazole‐4‐carboxylates III with methyl iodide produced the substituted ethyl 5‐[methyl(methylsulfonyl)amino]‐1H‐pyrazole‐4‐carboxylates IV. Treatment of IV with sodium hydride gave the 7‐substituted 1,7‐dihydro‐1‐methylpyrazolo[3,4‐c][1,2]thiazin‐4(3H)‐one 2,2‐dioxides V.
Synthesis of a novel heterocyclic system: 8‐Fluro‐ 1,2,3,4,4a,10a‐hexahydro‐5H‐[1]benzopyrano[2,3‐c]pyridin‐5‐ol
Authors: Löwe Werner , Witzel Sonja , Matzanke Norbert , Buddrus Joachim
Published: April 2009

The Synthesis of the title compound is described and its structure elucidated by 1H nmr spectroscopy.
The synthesis of some dialkyl 4‐(3‐substituted amino)phenyl‐1,4‐dihydro‐2,6‐dimethylpyridine‐3,5‐dicarboxylates
Authors: Simonič Igor , Stanovnik Branko
Published: April 2009

Dialkyl 4‐(3‐aminophenyl)‐1,4‐dihydro‐2,6‐dimethylpyridine‐3,5‐dicarboxylates 1 were transformed into alkyl 4‐(3‐(((2‐benzoylamino‐2‐methoxycarbonyl)ethenyl)amino)phenyl)‐1,4‐dihydro‐2,6‐dimethyl‐pyridine‐3,5‐dicarboxylates 4 and with 2,2‐disubstituted‐1‐dimethylaminoethenes 7 into dimethyl 4‐(3‐(((2,2‐diacyl‐ or 2‐acyl‐2‐alkoxycarbonyl)ethenyl)amino)phenyl)‐1,4‐dihydro‐2,6‐dimethylpyridine‐3,5‐dicarboxylates 8 and their ethyl methyl analogues 9.
One‐step furan ring formation: Synthesis of furo[3,2‐h]quinolones
Authors: Fujita Masahiro , Egawa Hiroshi , Chiba Katsumi , Matsumoto Jun‐Ichi
Published: April 2009

The one‐pot reaction of ethyl 1‐cyclopropyl‐6,7,8‐trifluoro‐1,4‐dihydro‐4‐oxoquinoline‐3‐carboxylate (6) with tert‐butyl acetoacetate gave 3‐tert‐butyl 7‐ethyl 9‐cyclopropyl‐4‐fluoro‐6,9‐dihydro‐2‐methyl‐6‐oxofuro[3,2‐h]quinoline‐3,7‐dicarboxylate (5). This regioselective cyclization was rationalized by the Hard and Soft Acids and Bases principle. By use of a similar furan‐forming reaction, we prepared 2‐(amino‐methyl)furo[3,2‐h]quinoline‐7‐carboxylic acid 4. Compound 4 showed weak antibacterial activity.
Synthesis of some N‐substituted isonicotinamides
Authors: Černigoj‐Marzi Andreja , Polanc Slovenko , Kočevar Marijan
Published: April 2009

A one‐pot transformation of some cyclic 1,3‐dicarbonyls 1 with N‐(isonicotinoyl)glycine 2 and one‐carbon synthons in acetic anhydride to the corresponding N‐substituted isonicotinamides (pyridine‐4‐carbox‐amides) 7‐9 containing a fused pyran‐2‐one ring is described. Compound 8 was further converted with some nitrogen‐containing nucleophiles either to the corresponding quinoline‐2,5‐diones 10‐11 or 5‐hydra‐zonobenzopyran‐2‐ones 14‐15. Under more severe conditions the compound 8 gave with hydrazine 5‐hydrazonoquinoline derivative 12 or even 13. Hydrazoic acid transformed compound 8 to the pyrano‐[3,2‐c]azepine system 16. Diazotization of 1‐amino derivative 10 gave deaminated product 11.
Studies on pyridonecarboxylic acids. V. A practical synthesis of ethyl 6,7‐difluoro‐ 1‐methyl‐4‐oxo‐4H‐[1,3]thiazeto[3,2‐a]quinoline‐3‐carboxylate, a key intermediate for the new tricyclic quinolone, prulifloxacin (NM441) and versatile new syntheses of the 2‐thioquinoline skeleton
Authors: Matsuoka Masato , Segawa Jun , Makita Yoshihiko , Ohmachi Sbinji , Kashima Tatsuhiko , Nakamura Ken‐Ichi , Hattori Masayuki , Kitano Masahiko , Kise Masahiro
Published: April 2009

A practical synthesis of ethyl 6,7‐difluoro‐1‐methyl‐4‐oxo‐4H‐[1,3]trüazeto[3,2‐a]quinoline‐3‐carboxylate (9), the key intermediate for 6‐fluoro‐1‐methyl‐7‐[4‐(5‐methyl‐2‐oxo‐1,3‐dioxol‐4‐yl)methyl‐1‐piperazinyl]‐4‐oxo‐4H‐[1,3]thiazeto[3,2‐a]quinoline‐3‐carboxylic acid (2), NM441, was developed. The crucial points of this synthetic route are the chlorination of ethyl 4‐acetoxy‐2‐(ethylthio)‐6,7‐difluoroquinoline‐3‐carboxylate (12) and the subsequent deacetylation of the resulting 2‐(l‐chloroethyl)thio compound 13 followed by the intramolecular cyclization reaction. Versatile new syntheses of 2‐thioquinoline skeleton were also developed. The first route includes the intramolecular cyclization of the N,S‐acetal 22 which was prepared from 2,4,5‐trifluorobenzoic acid in three steps. The second one contains the regioselective attack of lithium etiolate of ethyl acetate to the novel 2‐(methylthio)‐4H‐[3,l]benzothiazine‐4‐one 29 at the 4‐position followed by the intramolecular cyclization of the resulting β‐ketoester 30.
Synthesis and NMR characterization of 3,4′‐dibutoxy‐2,2′‐bithiophene
Authors: Goldoni Francesca , Iarossi Dario , Mucci Adele , Schenetti Luisa
Published: April 2009

3,4′‐Dibromo‐2,2′‐bithiophene was converted, in high yield, into the corresponding dibutoxy derivative. The 1H 13C and nmr data are discussed in comparison with those of 3,3′‐ and 4,4′‐dibutoxy‐2,2′‐bithiophene in relation to regiochemistry.
Synthesis and spectral properties of 2,3‐dihydro‐4‐(para‐substituted‐phenyl)‐7‐[(o‐, m‐, and p‐substituted)phenoxy]‐1H‐1,5‐benzodi‐azepine‐2‐thiones
Authors: Cortés Eduardo CortÉS , Castrejón Carlos M. Alcocer
Published: April 2009

A series of twelve new 2,3‐dihydro‐4‐(para‐substituted‐phenyl)‐7‐[(o‐, m‐, and p‐substituted)phenoxy]‐1H‐1,5‐benzodiazepine‐2‐thiones, which have potentially useful pharmacological properties, has been synthesized by condensing the 3,3‐dimercapto‐1‐(para‐substituted phenyl)‐2‐propen‐1‐one with 3,4‐diaminophenyl‐R‐phenyl ethers. The structure of all products was corroborated by ir, 1H‐nmr, 13C‐nmr and ms.
Synthesis, stereochemistry and anti‐tetrabenazine activity of bicyclo analogues of 2‐phenylmorpholines
Authors: Boswell G. Evan , Musso David L. , Davis Ann O. , Kelley James L. , Soroko Francis E. , Cooper Barret R.
Published: April 2009

A series of bicyclo analogues of several 2‐phenylmorpholines were synthesized and tested for anti‐tetrabenazine activity in mice. Most of the target compounds were prepared by reaction of 2‐bromopropio‐phenone (22) with the appropriate amino alcohol to form 2‐phenylmorpholinols. Reduction of the 2‐phenyl‐morpholinols with sodium borohydride gave amino diols, which were cyclized to morpholines with acid. Alternatively, oxazines17and18were synthesized by alkylation of phenyl‐(2‐pyrrolo)carbinol(32a)and phenyl‐(2‐piperidyl)carbinol(32b)with 2‐bromoethanol, followed by cyclization of the resulting amino diols with acid. Only the spirocyclic compounds8and9had i.p. anti‐tetrabenazine activity comparable to the non‐cyclic compounds2a‐3b, but8and9were less active by the oral route of administration.
Synthesis and spectral properties of 2‐methylthio‐3H‐4‐(para‐substituted‐phenyl)‐7‐[(o‐, and p‐substituted)‐phenylthio]‐1,5‐benzodiazepines
Authors: Cortés Eduardo Cortés , López María I. Becerra , Pichardo Yazmín M. Osornio
Published: April 2009

A series of twelve new 2‐methylthio‐3H‐4‐(p‐substituted phenyl)‐7‐[(o‐, and p‐substituted)phenylthio]‐1,5‐benzodiazepines, which have potentially useful pharmacological properties, has been synthesized by condensing the 3,3‐dimercapto‐1‐(para‐substituted‐phenyl)‐2‐propen‐1‐one with 3,4‐diamino phenyl‐R‐phenylthio ethers, and subsequently the 1H‐1,5‐benzodiazepine‐2‐thiones obtained were treated with sodium hydride and methyl iodide. The structure of all products was corroborated by ir, 1H‐nmr, 13C‐nmr and ms.
An improved synthesis of 1‐(1,2,3,6‐tetrahydro‐1‐methyl‐4‐pyridinyl)ethanone, isoarecolone
Authors: Beach J. Warren
Published: April 2009

A convenient synthesis of 1‐(1,2,3,6‐tetrahydro‐1‐methyl‐4‐pyridinyl)ethanone, isoarecolone, starting with 4‐acetylpyridine is presented. 4‐Acetylpyridine was protected as the ketal followed by reaction with iodomethane to give the quaterary salt. The quaterary salt was reduced with sodium borohydride followed by deprotection to give isoarecolone in 80% overall yield.
Treadmill running exercise results in the presence of numerous myofibroblasts in mouse patellar tendons
Authors: Szczodry Michal , Zhang Jianying , Lim Chanteak , Davitt Hongxia L. , Yeager Torin , Fu Freddie H. , Wang James H.‐C.
Published: April 2009

Mechanical loading is known to alter tendon structure, but its cellular mechanisms are unclear. This study aimed to determine the effect of mechanical loading on tendon cells in vivo. C57BL/6J female mice were used in a treadmill running study. The treadmill running protocol consisted of treadmill training for 1 week, followed by sustained moderate running at 13 m/min for 50 min/day, 5 days/week, for 3 weeks. Immunohistochemical staining of tendon sections of mice after treadmill running revealed that numerous cells in the tendon section expressed α‐SMA, whereas in the tendon sections of control mice, only a few cells exhibited weak α‐SMA signals. Furthermore, mouse patellar tendon cells (MPTCs) derived from treadmill running mice were generally larger in culture, proliferated faster, expressed a higher level of α‐SMA, and formed more abundant stress fibers compared to MPTCs from control mice. In addition, MPTCs from treadmill running mice generated larger traction forces (169 ± 66.1 Pa) than those from control mice (102 ± 34.2 Pa). Finally, cells from treadmill running mice produced higher levels of total collagen (516.4 ± 92.7 µg/10,000 cells) than their counterparts (303.9 ± 34.8 µg/10,000 cells). Thus, mechanical loading via treadmill running increased the presence of myofibroblasts in mouse patellar tendons. As myofibroblasts are activated fibroblasts, their presence in the tendon following treadmill running indicates that they actively repair and remodel tendon tissue under strenuous mechanical loading, leading to known changes in tendon structure. © 2009 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 27:1373–1378, 2009
Physicochemical and functional properties of ten cultivars of seem (Lablab purpureus L.), an underexploited bean in Bangladesh
Authors: Mortuza Md Golam , Tzen Jason TC
Published: April 2009

BACKGROUND: Increasing global protein consumption has led to the demand for new sources of food protein, particularly plant sources. Many inexpensive but protein‐rich bean cultivars have not been well evaluated and are thus underutilised. In this study the physicochemical and functional properties of seeds of ten seem cultivars were assessed.

RESULTS: In agreement with their sizes, seeds of Airet had the highest 1000‐seed weight and volume, while those of Bari had the lowest. In terms of proximate composition (g kg−1), protein content ranged from 240.08 (Ashina) to 292.63 (Puti), fat content from 31.47 (Goalgadda) to 38.40 (Puti), ash content from 32.80 (Puli) to 45.53 (Goalgadda) and fibre content from 21.90 (Tatulia) to 28.90 (Noldog). Hydration (g kg−1) and swelling (mL L−1) capacities ranged from 1688.60 and 1850.43 (Goalgadda) to 1999.40 and 2208.66 (Rupbhan) respectively. Similarly, cooking time (min) varied from 114 (Rupbhan) to 179 (Goalgadda). Lowest gelation concentration was in the range 80–100 g kg−1. Water and fat absorption capacities (g kg−1) ranged from 941.00 and 644.44 (Ashina) to 1043.33 and 749.26 (Puti) respectively. Foaming capacity and stability (mL L−1) ranged from 443 (Puli) to 635 (Puti) and from 314 (Ashina) to 643 (Rupbhan) respectively.

CONCLUSION: Seeds of seem cultivars appear to be a promising food in terms of their protein content and functionality. Copyright © 2009 Society of Chemical Industry
HPLC‐DAD and HPLC‐ESI‐MS separation, determination and identification of the spin‐labeled diastereoisomers of podophyllotoxin
Authors: Zhao Lei , Liu Zhen‐Ling , Fan Peng‐Cheng , Zhang Zhi‐Wei , Liu Xiong , Zhan Yun‐Jing , Tian Xuan
Published: April 2009

Spin‐labeled nitroxide derivatives of podophyllotoxin had better antitumor activity and less toxicity than that of the parent compounds. However, the 2‐H configurations of these spin‐labeled derivatives cannot be determined by nuclear magnetic resonance (NMR) methods. In the present paper, a high‐performance liquid chromatography‐diode array detection (HPLC‐DAD) and a high‐performance liquid chromatography‐electrospray ionization tandem mass spectrometry (HPLC‐ESI/MS/MS) method were developed and validated for the separation, identification of four pairs of diastereoisomers of spin‐labeled derivatives of podophyllotoxin at C‐2 position. In the HPLC‐ESI/MS spectra, each pair of diastereoisomers of the spin‐labeled derivatives in the mixture was directly confirmed and identified by [M+H]+ ions and ion ratios of relative abundance of [M‐ROH+H]+ (ion 397) to [M+H]+. When the [M‐ROH+H]+ ions (at m/z 397) were selected as the precursor ions to perform the MS/MS product ion scan. The product ions at m/z 313, 282, and 229 were the common diagnostic ions. The ion ratios of relative abundance of the [M‐ROH+H]+ (ion 397) to [M+H]+, [A+H]+ (ion 313) to [M‐ROH+H]+, [A+H‐OCH3]+ (ion 282) to [M‐ROH+H]+ and [M‐ROH‐ArH+H]+ (ion 229) to [M‐ROH+H]+ of each pair of diastereoisomers of the derivatives specifically exhibited a stereochemical effect. Thus, by using identical chromatographic conditions, the combination of DAD and MS/MS data permitted the separation and identification of the four pairs of diastereoisomers of spin‐labeled derivatives of podophyllotoxin at C‐2 in the mixture.
Optimum extraction Process of polyphenols from the bark of Phyllanthus emblica L. based on the response surface methodology
Authors: Yang Li , Jiang Jian‐Guo , Li Wei‐Feng , Chen Jian , Wang Ding‐Yong , Zhu Liang
Published: April 2009

Phyllanthus emblica L. is an economic plant used in Chinese medicine for the treatment of various diseases. The bark of P. emblica is rich in polyphenols and its extractions have shown strong antioxidative and radical scavenging activity. Response surface methodology (RSM) was used to assess the optimal extraction of polyphenols from P. emblica bark. Various extraction parameters including ethanol concentration, extraction time, temperature, solid–liquid ratio, and extraction times were chosen to identify their effects on polyphenols extraction. Among these parameters, extraction times and solvent concentration were found to have significant effect on polyphenols extraction. RSM was applied to obtain the optimal combination of solvent concentration, extraction time, temperature, and extraction time for maximum rate of extraction. The most suitable condition for the extraction of polyphenols was at ethanol concentration 75%, extraction time 25 min, extraction temperature 45°C, and extraction times 3. At these optimal extraction parameters, the maximum extraction of polyphenols obtained experimentally was found to be very close to its predicted value. The extraction rate of polyphenols was 19.78% at the optimum conditions. The mathematical model developed was found to fit with the experimental data of polyphenols extraction.
The shrine of remembrance Melbourne: a short study of visitors' experiences
Authors: Winter Caroline
Published: April 2009

The Shrine of Remembrance in Melbourne, Australia opened in 1934 to articulate the social memory of the Great War of 1914–1918. The site has developed to incorporate other memorials and a Visitor Centre. An exploratory study of visitors indicated that the traditional and new memorials continue to evoke a number of responses to war. People expressed a sense of sadness and gratitude for sacrifices made by all those who have fought in war. Many people had poor knowledge of the battles which had initiated the creation of the Shrine. The study indicates the Shrine's complexity which now commemorates multiple conflicts. Copyright © 2009 John Wiley & Sons, Ltd.
Contact size effect on fretting wear behaviour: application to an AISI 52100/AISI 52100 interface
Authors: Merhej R. , Fouvry S.
Published: April 2009

Fretting situations are becoming increasingly important for industrial applications. Fretting wear is defined as a small oscillatory displacement between two contacting bodies. The interface is damaged by debris generation and its ejection from the contact area. In this work, investigations on AISI 52100 steel self‐mated contacts with a ball on flat configuration under dry conditions have been carried out. Fretting tests at a constant maximum Hertzian pressure of 1.1 GPa for different ball diameters have been performed to cover a huge range of contact sizes. A specific experimental procedure is considered to discriminate between the relative impact of the sliding amplitude and the contact size effect. It is shown that a single parameter cannot capture the total interface behaviour. Indeed, an asymptotic decrease in the friction coefficient and wear rate versus the contact size is observed. The increase in the contact area accentuates the implication of third body in the interface. The larger the contact size, the more difficult the debris ejection, the higher the third‐body accommodation, and the lower the coefficient of friction and wear rates. A simple power function is introduced to formalise friction and wear behaviours. Copyright © 2009 John Wiley & Sons, Ltd.