bluuebunny/crossref_metadata_2025 huggingface dataset:
A new synthesis of s‐triazoles from 1H‐2,3‐benzoxazine 4‐hydrazones
Authors: Pifferi G. , Consonni P.
Published: March 2009

Aliphatic and aromatic aldehydes react with 4‐hydrazino‐1H‐2,3‐benzoxazines (I) to form the corresponding 1H‐2,3‐benzoxazine hydrazones (II). Compounds II when heated in the presence of an acid catalyst rearrange to form substituted s‐triazoles (III) in high yields. In particular, the hydrazones containing one imino hydrogen undergo the same rearrangement by refluxing in xylene. Structure III, in agreement with the analytical and spectroscopic data, was confirmed by univocal syntheses. The N‐acylation and N‐alkylation of some unsymmetrically 3,5‐sub‐stituted s‐triazoles were also investigated and the mechanism of formation of III is briefly discussed.
The synthesis of 2‐azainosine and related derivatives by ring annulation of imidazole nucleosides
Authors: Panzica Raymond P. , Townsend Leroy B.
Published: March 2009

The synthesis of 7‐(β‐D‐ribofuranosyl)imidazo[4,5‐d]‐v‐triazin‐4‐one (6b, 2‐azainosine) and 5‐(β‐D‐ribofuranosyl)imidazo[4,5‐d]‐v‐triazin‐4‐one (4b) have been achieved for the first time by direct diazotization of AICA riboside (5b) and iso‐AICA riboside (3b), respectively. The conditions required for cyclization of the model methyl bases, 3a and 5a, as well as the nucleosides 3b, 5b, and 7 are described.
A reinvestigation of the structures for 5‐diazouracil, 5‐diazouridine, 5‐diazo‐2′‐deoxyuridine and certain related derivatives by proton magnetic resonance spectroscopy
Authors: Thurber T. Craig , Townsend Leroy B.
Published: March 2009

The structure of 5‐diazouracil and several closely related derivatives have been revised on the basis of pmr spectroscopy. 5‐Diazouracil, 5‐diazouracil hydrate, 5‐diazouracil methanol adduct, 5‐diazouridine and 5‐diazo‐2′‐deoxyuridine have been reassigned the structures 5‐diazopyrimidin‐2,4(3H)dione (XI), 5‐diazo‐6‐hydroxy‐1,6‐dihydropyrimidin‐2,4(1H,3H,6H)dione (XIII), 5‐diazo‐6‐methoxy‐1,6‐dihydropyrimidin‐2,4(1H,3H,6H)dione (XII), 1 ‐(β‐D‐ribofuranosyl)‐O5′ ‐6(S)cyclo‐5‐diazo‐1,6‐dihydropyrimidin‐2,4(3H,6H)dione (XVII) and 1‐(2‐deoxy‐β‐D‐ribofuranosyl)‐O5′ ‐6(S)cyclo‐5‐diazo‐1,6‐dihydropyrimidin‐2,4(3H,6H)dione (XIX), respectively. Treatment of XII with dimethylamine resulted in a coupling of the 5‐diazo group with dimethylamine and a concomitant rearomatization of the heterocyclic ring by expulsion of the 6‐methoxy group to furnish 5‐(3,3‐dimethyl‐1‐triazeno)uracil (XIV). A similar reaction of XIX and XVII with dimethylamine furnished the corresponding 5‐(3,3‐dimethyl‐1‐triazeno)derivatives. The effect which certain resonance hybrids of the diazo moiety may exert in reactions of the above hetero‐cycles and the assignment of S configuration at C‐6 for the nucleoside derivatives is also discussed.
Chemical and biological studies on dihydro‐s‐triazines. XVI. Nmr evidence for the formation of 2‐guanidino‐4‐methylquinazolines as anomalous byproducts in the three‐component synthesis
Authors: Rosowsky Andre , Modest Edward J.
Published: March 2009

The three‐component synthesis of 4,6‐diamino‐1‐aryl‐1,2‐dihydro‐2,2‐dimethyl‐s‐triazines from arylamines. cyanoguanidine, and acetone has been studied by nmr spectral analysis in trifluoro‐acetic acid solution. The presence of 2‐guanidino‐4‐methylquinazoline contaminants can be discerned clearly at concentrations as low as 1%. Arylamines most likely to give significant proportions of guanidinoquinazoline byproducts are 2‐naphthylamines and anilines containing one or more electron‐donating meta‐substituents.
Chemical and biological studies on dihydro‐s‐triazines. XVII. Modifications of the three‐component synthesis favoring the formation of 2‐guanidino‐4‐methylquinazoline byproducts
Authors: Rosowsky Andre , Nadel Marilyn K. , Modest Edward J.
Published: March 2009

A modified three‐component reaction of arylamines, cyanoguanidine, and acetone is described, wherein formation of anomalous guanidinoquinazoline byproducts is greatly enhanced at the expense of the normal dihydro‐s‐triazines. Four new guanidinoquinazolines and four new dihydro‐s‐triazines were synthesized via this modification, starting from 2,4‐, 2,5‐, 3,4‐, and 3,5‐dimethoxyaniline. The guanidinoquinazoline to dihydro‐s‐triazine ratio was much higher with 3,4‐ and 3,5‐dimethoxyaniline than with 2,4‐dimethoxyaniline. 2,5‐Dimethoxyaniline gave an unexpectedly low yield of guanidinoquinazoline, apparently because of steric hindrance. The modified three‐component synthesis was also examined in detail with 2‐naphthylamine.
Preparation of pyrylium salts from 2‐phenyl‐5H‐phenaleno [ 1,9‐bc] pyran‐5‐one
Authors: Van Allan J. A. , Reynolds G. A.
Published: March 2009

The preparation of 2‐phenyl‐5H‐phenaleno[ 1,9‐bc]pyran‐5‐one (7) is described. Compound 7 undergoes reactions typical of pyrones and was therefore a useful intermediate for the preparation of pyrylium salts. Several pyrylium dyes were prepared from 7 and the long‐wavelength absorptions of these dyes were compared with those of the corresponding flavylium dyes.
Rearrangements of 1,4‐benzodiazepine derivatives
Authors: Fryer R. Ian
Published: March 2009

The skeletal rearrangement of 1,4‐benzodiazepines to other heterocyclic systems are reviewed together with a discussion of possible mechanisms. Simple rearrangements involving migrations without skeletal changes are included for the sake of completeness.
Folate antagonists. 5. Antimalarial and antibacterial effects of 2,4‐diamino‐6‐(aryloxy and aralkoxy)quinazoline antimetabolites
Authors: Elslager Edward F. , Clarke Jane , Johnson Judith , Werbel Leslie M. , Davoll John
Published: March 2009

2 Various4‐diamino‐6‐(phenoxy, naphthyloxy, and phenalkoxy)quinazolines (VIII, XIV) were synthesized for antimalarial and antibacterial evaluation. Treatment of the anion of the requisite phenol or naphthol with 5‐chloro‐2‐nitrobenzonitrile (V) gave the corresponding 2‐nitro‐5‐(phenoxy and naphthyloxy)benzonitriles (VI) (33–78%). Alternatively, alkylation of 5‐hydroxy‐2‐nitrobenzaldehyde (IX) with the appropriate phenalkyl halide afforded the 2‐nitro‐5‐(phenalkoxy)benzaldehydes (X) (27–62%), which were converted to the 2‐nitro‐5‐(phenalkoxy)benzonitriles (XII) via the intermediate oximes XI (62–87% overall). Reduction of the 2‐nitrobenzonitriles (VI, XII) with stannous chloride‐hydrochloric acid provided the corresponding 2‐amino‐5‐(phenoxy, naphthyloxy, and phenalkoxy)benzonitriles (VII, XIII) (30–83%), which upon cyclization with chloroformamidine hydrochloride gave the 2,4‐diaminoquinazolines VIII and XIV (12–85%). Against Plasmodium berghei in mice, eleven compounds were active orally at doses ranging from 6.3 to 174 mg./kg./day for 6 days, while seven substances displayed activity subcutaneously following single doses of 40–640 mg./kg. Fifteen compounds exhibited in vitro antibacterial activity against Streptococcus faecalis (MGH‐2), normal (UC‐76) and drug‐resistant (S18713) Staphylococcus aureus, Escherichia coli (Vogel), and Shigella sonnei (C‐10) with MIC's ranging from < 0.25 to 20 μg./ml. (gradient plate). Data on the inhibitory effects of representative compounds against Streptococcus faecalis R (S. faecium var. durans), S. faecalis A (amino‐pterin, methotrexate‐resistant), and Lactobacillus plantarum are presented, and overall structure‐activity relationships are discussed.
The direction of the dipole moments of furan, thiophen, and pyrrole: A controversial question
Authors: Marino Gianlorenzo
Published: March 2009

The report that the dipole moment in the five‐membered heterocyclic rings, furan, thiophene, and pyrrole has the positive pole on the heteroatom is contradicted with arguments based on reactivity data, theoretical calculations and moment values of substituted derivatives.

In actuality, the dipole moment in furan and thiophene is directed from the ring (positive pole) to the heteroatom (negative pole).
Pyrimidine derivatives. IV. Synthesis of N1 ‐(2‐methoxy‐4‐pyrimidyl)sulfaniiamide
Authors: Okui Kiyoshi , Ito Kiyohiko , Kametani Tetsuji
Published: March 2009

N1‐(2‐Methoxy‐4‐pyrimidyl)sulfanilamide was successfully prepared through three alternative routes. Namely, the above compound was obtained by condensation of 4‐amino‐2‐methoxy‐pyrimidine (III) with p‐acetaminobenzenesulfonyl chloride and p‐nitrobenzenesulfonyl chloride and by direct condensation with sulfanilamide.
Synthesis of 1‐(2‐ethyl‐3‐indolyl)‐1‐(3‐pyridyl)ethylene and related ellipticine analogues
Authors: Bergman Jan , Carlsson RenÉ
Published: March 2009

Indole, 2‐methylindole, and 3‐etliylindole have been condensed with acetyl‐ and propionylpyridine, respectively. When propionylpyridine was used as the reactant, the product always was a 1‐(pyridyl)‐1‐indoly[propylene. Condensation of 2‐substituted indoles with 3‐acetylpyridine gave similar products, whereas a similar condensation with 4‐acetylpyridine gave 1,2‐bis(3‐indolyl)‐1‐(4‐pyridyl)ethanes (e.g. 7a). Condensation of unsubstituted indole with 3‐or 4‐acetylpyridine respectively, gave 1,1‐bis(3‐indolyl)‐1‐(pyridyl)ethanes (e.g. 6c).
Chemistry of thienopyridines. XV. Syntheses of thieno [3,4‐b] ‐ and thieno[3,4‐c] pyridines
Authors: Klemm L. H. , Johnson W. O. , White D. V.
Published: March 2009

Thieno [3,4‐b] pyridine (5) was synthesized by means of the successive steps of (a) photochlorination of 2,3‐dimethylpyridine to the bis(chloromethyl) compound, (b) condensation with sodium sulfide, (c) oxidation to the sulfoxide, and (d) catalytic dehydration by means of alumina. Thieno[3,4‐c]pyridine (6) was obtained in an analogous manner. Spectral properties indicate that 5 and 6 have aromatic character.
A facile synthesis of 2,3‐dihydroimidazo‐ and 1,2,3,4‐tetrahydropyrirnido[1,2‐f] phenanthridines
Authors: Pan Hsi‐Lung , Fletcher T. Lloyd
Published: March 2009

When 6‐(2‐hydroxyethyl)amino‐(1), 6‐(3‐hydroxypropyl)amino‐(2),or 6‐[2‐(1‐hydroxybutyl)]‐aminophenanthridines (3), dissolved in concentrated sulfuric acid, were treated with nitrosylsulfuric acid at 0–25, then diluted with water and basified with aqueous sodium hydroxide at 65–86°, 2,3‐dihydroimidazo‐ (4a‐i), 1,2,3,4‐tetrahydropyrimido‐ (5), or 2,3‐dihydro‐2‐ethyl‐imidazo[1,2‐f]phenanthridines (4j‐p) were obtained respectively in good yields. Structures were substantiated by ir spectroscopy. The 6‐ω‐hydroxyalkylaminophenanthridines were prepared from the corresponding 6‐chlorophenanthridines. A possible mechanism for the formation of these ring systems is postulated.
Heterocycles derived from the condensation of 1,3‐propanediamine with phthalic acid derivatives
Authors: Gaozza C. H. , Grinberg H. , Lamdan S.
Published: March 2009

The condensation of phthalic anhydride with 1,3‐propanediamine afforded N‐(o‐carboxybenzoyl)‐1,3‐propanediamine (I) which by intravolecular cyclization was transformed into 2,3,4,6‐b‐tetrahydropyrimido[2,1‐a]isoindol‐6‐one (II) rather than the benzodiazonine (III). An intermediate in the condensation is proposed. The reaction of 1,3‐propanediamine with dimethyl phthalate also did not afford III, but rather a more complex product, dibenzo[c,l]‐1,6,10,15‐tetraazacyclooctadecane‐5,11,16,22‐tetraone (IX). Reaction of 1,3‐propanediamine with phthaloyl chloride gave 6,13‐propanodibenz[c,h]‐1,6‐diazecine‐5,7,12,14‐tetrone (XII). Spectroscopic data of the heterocycles obtained and chemical properties of II are given.
Preparation and mass spectra of 2,5‐diaryl‐1,4‐dithiins
Authors: Buess Charles M. , Brandt Vernon O. , Srivastava R. C. , Carper W. Robert
Published: March 2009

2 Seven5‐diaryl‐1,4‐dithiins were prepared from phenacyl halides via the corresponding Bunte salts. The mass spectra showed a number of similarities within this series of compounds. Various dipositive ions were observed in all cases while the unsubstituted and p‐methyl derivatives formed tripositive ions. Ir, nmr, and chemical analysis were also completed and reported.
Benzo‐ and indoloquinolizine derivatives. I. Synthesis of 4b,5,6,7,8,8a,10,11,16,16b‐decahydrodibenz[f,h] indolo[2,3‐a] quinolizine
Authors: Van Binst G. , Tourwe D.
Published: March 2009

Two 4b 5,6,7,8,8a,10,11,16,16b‐decahydrodibenz[f,h]indolo‐[2,3‐a]quinolizine epimers have been synthesized starting from trans‐1,2,3,4,4a,10b‐hexahydrophenanthridine. The structural assignment of both isomers is discussed by use of ir and pmr spectroscopy.
Novel polycyclic heterocycles. IX. Dibenz[b,f] [1,4]oxazocin‐11 (12H)one, 6,11‐dihydro‐12H‐dibenz[b,f] [1,4]oxazocine, and their derivatives
Authors: Yale Harry L. , Spitzmiller Ervin R.
Published: March 2009

Dibenz[b,f][1,4]oxazocin‐11 (12H)one, 14, was synthesized by the dicyclohexylcarbodiimide induced cyclization of α‐(o‐aminophenoxy)‐o‐toluic acid (13). Reduction of 14 by lithium aluminum hydride gave 6,11‐dihydro‐12H‐dibenz[b,f][1,4]oxazocine (16). Both 14 and 16 were converted to a series of 12‐alkylated and ‐acylated derivatives. The pmr spectra of some of these compounds are discussed.
The synthesis of some purine nucleosides from 4,6‐di‐O‐acetyl‐3‐deoxy‐3‐(ethoxycarbonylamino)‐D‐glucal
Authors: Lourens Gerhardus J. , Jordaan A.
Published: March 2009

The acid catalyzed reaction of 4,6‐di‐O‐acetyl‐3‐deoxy‐3‐(ethoxycarbonylamino)‐D‐glucal and 6‐chloropurine in nitrometliane solution gave 6‐ehloro‐9‐(4′,6′‐di‐O‐acetyl‐2′,3′‐dideoxy‐3′‐ethoxy‐carbonylamino‐α‐ and β‐D‐arafemohexopyranosyl)purine. These were converted to the corresponding deblocked 6‐dimetliylaminopurine nucleosides by treatment with ethanolic dimethylamine; acetylation of these gave the respective 4′,6′‐di‐O‐acetyl derivatives. The anomeric assignments for the nucleosides were based on their nmr spectral data.
Synthesis of 1‐alkyl‐2‐nitroimidazole‐5‐carboxaldehydes
Authors: Cavalleri Bruno , Ballotta Roberto , Lancini Gian Carlo
Published: March 2009

We report the preparation of 1‐methyl‐ and 1‐ethyl‐2‐nitroimidazole‐5‐carboxaldehydes (Ia,b). For Ia three different routes of synthesis are described, which appear of general value for preparing 1‐alkyl substituted 2‐nitroimidazole‐5‐carboxaldehydes.
Crystal and molecular structure of triphenyl 4,4,6‐Trimetliyl‐1‐oxa‐3‐azaeyeiohex‐2‐enylcarbenyl phosphonium chloride
Authors: Trefonas L. M. , Brown J. N.
Published: March 2009

The structure of the title compound has been determined by a single crystal, x‐ray diffraction study. The compound crystallizes in a monoclinic unit cell of P21/c symmetry and dimensions, a = 9.832 ± .001 Å, b = 15.398 ± .001 Å, c = 19.762 ± .002 Å, and β= 123.06 ± .01 ° with four molecules per unit cell. The 1633 statistically significant reflections (from a total of 2743 out to 20 = 100°) refined to a final value of R = 0.053. The molecule itself consists of a chloride ionically bonded to a cation containing a tetrahedral phosphorus bound to three phenyl rings and a fourth oxazine ring. It is the latter ring which displays extensive derealization as discussed in the paper.
Triazine chemistry VIII. 2,5‐dihydro‐5‐oxo‐1,2,4‐triazines
Authors: Lee Jaekeun , Paudler William W.
Published: March 2009

2,5‐Dihydro‐5‐oxo‐1,2,4‐triazine and some of its alkylated derivatives have been prepared. Nmr spectroscopic analysis has established that the 2,5‐dihydro‐5‐oxo tautomers are preferred over the 4,5‐dihydro‐5‐oxo ones. This preference, and the behavior of 1,2,4‐triazines in some other chemical reactions has been interpreted in terms of electron‐electron repulsions between the lone pairs of electrons of N1 and N2 in this ring system.
Reactions of dichloromaleimides with alcohols, phenols, and thiols
Authors: Lynch D. M. , Crovetti A. J.
Published: March 2009

Thiols react with dichloromaleimides in the presence of base to give 2,3‐bis[alkyl(aryl)‐mercapto]maleimides. Alcohols and phenols in equivalent amounts give 2‐alkyl(aryl)oxy‐3‐chloromaleimides. With two equivalents, phenols give 2,3‐bis(aryloxy)maleimides, but alcohols give 2‐chloro‐3,3‐dialkoxysuccinimides in protic solvents and dimeric compounds in aprotic solvents.
Picrylamino‐substituted heterocycles. V. pyridines
Authors: Coburn Michael D. , Singleton Jannie L.
Published: March 2009

The condensation of various aminopyridines with picryl chloride and picryl fluoride has been investigated as part of our continuing effort in the field of picrylamino‐substituted heterocycles. In addition to the expected picrylamino derivatives we obtained the 1‐picryl derivatives of the imino forms of some of the amines.
Cyclic adrenaline derivatives. Aryl‐2‐Piperidyl‐Carbinols
Authors: Sankey G. H. , Whiting K. D. E.
Published: March 2009

A synthetic route; to 3,4‐dihydroxyphenyl‐(2‐piperidyl)earbinols is described. These novel catecholamines may be regarded as derivatives of adrenaline containing a cyclic side‐chain moiety. Their biological action appears to be more selective than that of adrenaline or isoprenaline and the more active of these compounds show promise as powerful bronchodilators with minimum cardiac effect.
Studies on the syntheses of analgesics. Part XXXI. Synthesis of 1,2,3,4,5,6‐Hexahydro‐3‐methyl‐6‐phenyl‐2,6‐melhano‐2,3‐benzo[g] diazocine [studies on the syntheses of heterocyclic compounds. Part CDLXXIX]
Authors: Kamelani Tetsuji , Kigasawa Kazuo , Hiiragi Mineharu , Aoyama Toyohiko
Published: March 2009

1,2,3,4,5,6 Hexahydro‐8‐methoxy‐3‐methyl‐6‐phenyl‐2,6‐methano‐2,3‐benzo[g]diazocine (IIa) was synthesized from 1‐(3‐methoxyphenyl)phenylaeetonitrile (III), readily available by the benzyne reaction of o‐chloroanisole with phenylacetonitrile, through several steps. Treatment of IIa with 47% hydrobromic acid afforded 1,2,3,4,5,6‐hexahydro‐8‐hydroxy‐3‐methyl‐6‐phenyl‐2,6‐methano‐2,3‐benzo[g]diazocine (IIb).
Aminomereuration X ‐ Synthese D'hétérocyeliques monospiranniques par aminomereuration intramoléculaire
Authors: Hodjat H. , Lattes A. , Laval J. P. , Périé J. J. , Moulines J.
Published: March 2009

Dans Ie cours général de recherches relatives à l'hétéroeyelisation de systèmes éthyléniques par aminomercuration, nous développons ici un exemple d'extension de cette réaction: la formation d'hétérocycles monospiranniques.
Reactions of Ketones XVI. 5,5‐I)imethoxy‐Δ2‐1,2,3‐triazoline/2,2‐Dimethoxy‐2‐aminodiazoethane Mutual Conversion
Authors: Scarpati R. , Craziano M. L.
Published: March 2009

Phenylketene dimethylacetal reacts with ethyl azidoformate to give 1‐ethoxyearbonyl‐4‐phenyl‐5,5‐dimethoxy‐Δ2‐1,2,3‐triazoline (III). The behaviour of the latter and of its isomerization product, 1‐phenyl‐2,2‐dimethoxy‐2 (N‐ethoxyearbonylamino)diazoethane (IV), have been investigated in detail. The results point out a triazoline III/diazoethane IV mutual conversion.
PMR analysis of nitroquinoline 1‐Oxides
Authors: Roe Robert , Paul J. S. , Montgomery P.O'B.
Published: March 2009

Chemical shifts and coupling values obtained from the 100 MHz pmr spectra of 12 nitrosubstituted quinoline 1‐oxide derivatives are presented. Spin‐spin decoupling, application of the paramagnetic shift reagent tris‐(1,1,1,2,2,3,3‐heptafluoro‐7,7‐dimethyl‐4,6‐octanedione) europium (III), and calculations of theoretical spectra were used in matching signals to protons in the complex portions of the pmr spectra. Precise spectral parameters were obtained by application of an iterative technique provided by a published computer program. The identification of 4‐ and 5‐nitro substituted quinoline 1‐oxides by correlation of pmr spectral parameters with chemical structure is illustrated. The preparation and structural elucidation of two potential carcinogenic compounds, 2,6‐dimethyl‐4‐nitroquinoline 1‐oxide and 2,7‐dimethyl‐4‐nitroquinoline 1‐oxide are described.
Inhibitors of platelet aggregation. 4. [1,2,5]Thiadiazolo[3,4‐c]acridines, 7,8,9,10‐Tetrahydro[1,2,5] thiadiazolo[3,4‐c]acridities, and 8,9‐Dihydro‐7H‐cyclopenta[b][1,2,5] thiadiazolo[3,4‐H]quinolines
Authors: Elslager Edward F. , Haley Neil F.
Published: March 2009

The condensation of 4‐amino‐2,1,3‐benzothiadiazole (IV) with diphenyliodonium‐2‐earboxylate gave N‐(2,1,3‐benzothiadiazoI‐4‐yl)anthranilic acid (V) (28%), which was cyclized with phosphorus oxychloride to 6‐chloro[1,2,5]thiadiazolo[3,4‐c]acridine (VI) (84%). Treatment of VI with 3‐(dimethylamino)‐1‐propanethiol hydrochloride in phenol afforded 6‐[ [3‐(dimethylamino)‐propyl]thio] [1,2,5]thiadiazolo[3,4‐c]acridine (VII) (65%). The reaction of IV with a mixture of methyl and ethyl 2‐oxocyclohexanecarboxylate gave the adduct, which was ring closed in Dowtherm to 7,9,10,1 1‐tetrahydro[1,2,5] thiadiazolo[3,4‐c]acridin‐6(8H)one (VIII) (70%). Chlorination of VIII with phosphorus oxychloride gave 6‐chloro‐7,8,9,10‐tetrahydro[1,2,5]thiadiazolo[3,4‐c]acridine (IX) (84%), which was condensed with 3‐(dimethylamino)‐1‐propanethiol hydrochloride in phenol yielding 6‐[ [3‐(dimethylamino)propyl]thio]‐7,8,9,10‐tetrahydrof 1,2,5]‐thiadiazolo[3,4‐c]acridine (X) (27%). 6‐[ [3(1)imethylamino)propyl]thio]‐8,9‐dihydro‐7H‐cyclopenta[b] [1,2,5]thiadiazolo[3,4‐h]quinoline (XIII) (25%) was prepared similarly from IV and a mixture of methyl and ethyl 2‐oxocyclopentanecarboxylate via 7,8,9,10‐tetrahydro‐6H‐cyclopenta[b][1,2,5]thiadiazolo[3,4‐h]quinolin‐6‐one (XI) (85%) and 6‐chloro‐8,9‐dihydro‐7H‐cyclopenta[b][1,2,5]thiadiazolof3,4‐h]quinoline (XII) (56%). The effects of compounds VII‐XIII as inhibitors of platelet aggregation are discussed.
Folate antagonists. 7. Antimalarial, antibacterial, and antimetabolite effects of 2,4‐Diamino‐6‐(benzyl and pyridylmethyl)‐5,6,7,8‐tetrahydropyrido[4,3‐d] pyrimidines
Authors: Elslager Edward F. , Clarke Jane , Jacob Patricia , Werbel Leslie M. , Willis J. D.
Published: March 2009

2 Various4‐diamino‐6‐(benzyl and pyridyhnethyl)‐5,6,7,8‐tetrahydropyrido(4,3‐d]pyrimidines (IX) have been synthesized for antimalarial and antibacterial evaluation. Alkylation of 4‐amino‐3‐cyano‐1,2,5,6‐tetrahydropyridine (VI) with the requisite α‐chlorotoluene or picolyl chloride in 2‐butanone afforded the corresponding 4‐amino‐3‐eyano‐1‐(benzyl and pyridvlmethyl)‐1,2,5,6‐tetraliydropyridines (VIII) (16–73%), which were cyclized to the pyrido[4,3‐d]pyrimidines (IX) utilizing guanidine carbonate in dimethylformamide. Alternatively, VI was condensed with guanidine carbonate in ethyl cellosolve to give 2,4‐diamino‐5,6,7,8‐tetrahydropyrido[4,3‐d]‐pyrimidine (VII) (52%), which upon treatment with the appropriate α‐ehlorotoluene in dimethyllormamide gave other 2,4‐diamino‐6‐benzyl‐5,6,7,8‐tetrahydropyrido[4,3‐d]pyrimidines (IX) (26–27%). Kight compounds were active orally against Plasmodium berghei in mice at doses ranging from 3.9 to 125 mg./kg./day for 6 days (0.6 to 19 times as potent as quinine hydrochloride), while three compounds displayed activity when administered in a single subcutaneous dose of 640 mg./kg. Four substances exhibited in vitro activity against Streptococcus faecalis (MGH‐2), normal (UC‐76) and drug‐resistant (S18713) Staphylococcus aureus, and Streptococcus pyogenes ((1203), with MIC's ranging from > 0.25 to 10 μg./ml. Data on the inhibitory effects of various pyrido[4,3‐d]pyrimidines against Streptococcus faecalis R (S. faecium var. durans, ATCC 8043), S. faecalis A (aminopterin, metholrexate‐resistant), and Lactobacillus plantarum (ATCC 8014) is summarized.
Quinazolincs. X. Direct formation of aminoquinazolines from hydroxyquinazolines and phenyl phosphorodiamidate
Authors: Rosowsky Andre , Papathanasopoulos Nickolas
Published: March 2009

Treatment of several types of liydroxyquinazoline ring systems with phenyl phosphorodiamidate resulted in direct formation of the corresponding aminoquinazolines. The reaction can be conducted either by fusion in the absence of solvent or with diphenyl ether added as a diluent. The main advantage of the method is that it obviates the usual requirement for chlori‐nation or thiation prior to animation.
Quinazolines. XI. Synthesis of 2,4‐diamino‐5, 10‐diliydrobenzo[g] quinazolines
Authors: Rosowsky Andre , Burrows Elizabeth P. , Huang Ping C. , Modest Edward J.
Published: March 2009

An unequivocal synthesis of 2,4‐diamino‐5,10‐dihydrobenzo[g]quinazolines is described, starting from methyl 2‐tetralone‐3‐carboxylates. Condensation with guanidine yielded 2‐amino‐4‐hydroxy derivatives, which were thiated with phosphorus pentasulfide and S‐alkylated with dimethyl sulfate. The resultant 2‐amino‐4‐methylthio compounds were converted into 2,4‐diamino derivatives by amination at elevated temperature and pressure. Attempted synthesis from 3‐cyano‐1,4‐dihydro‐2‐methoxynaphthalene and guanidine was unsuccessful.
Novel polycyclic heterocycles. X. Synthesis of 3‐amino derivatives derived from 1,2‐dihydro‐l 1 (trifluoromethyl)‐3H,7H‐quino [8,1‐cd][ 1,5]benzoxazepin‐3‐one
Authors: Petigara Ramesh B. , Yale Harry L.
Published: March 2009

The reactions of the tetracyclic ketone, 1,2‐dihydro‐11‐(trifluoromethyl)‐3H,7H‐quino[8,1‐cd] [1,5]benzoxazepin‐3‐one (1) with pyrrolidine, piperazine, N‐methylpiperazine, and dimethyl‐amine gave the enamines 2, 13, 11, and 4. These were reduced with sodium borohydride to the corresponding 3‐amino derivatives 3, 14, 12, and 5. The 3‐(2‐hydroxyethylpiperazino) derivative (8) was obtained from the 3‐chloro compound (7); 7 was prepared from the carbinol (6). The 3‐NH2 derivative (10) was obtained by reduction of the oxime (9). In 3, 5, 6, 7, 8, 10, 12, and 14, the ‐OCH2 protons were non‐equivalent, since in the pmr spectrum of each of these compounds there was seen a symmetrical, perturbed AB quartet, with a common JAB of 12 cps, that must be attributed to geminal interproton coupling. This phenomenon had not previously been observed with 1, 9, or the enamines, since in their pmr spectra, the ‐OCH2 protons had invariably been seen as singlets.
The synthesis of pseudorutaecarpine with triethyl phosphite
Authors: Kametani Tetsuji , Yamanaka Tohru , Nyu Kiyosato
Published: March 2009

Pseudorutaecarpine was synthesized by nitrene reaction of 3‐(2‐nitrobenzal)‐1,2,3,9‐tetra‐liydropyrrolo[2,1‐b]quinazolin‐9‐one (IV).
Acid‐catalyzed rearrangement of 2‐phenyl‐2,3‐dihydro‐1,4‐benzoxazepin‐5(4H)ones
Authors: Misiti D. , Rimatori V.
Published: March 2009

2‐Phenyl‐2,3‐dihydro‐1,4‐benzoxazepin‐5(4H)ones (I) were converted into 2‐(o‐hydroxyaryl)‐5‐plienyl‐2‐oxazolines (II) and 3,4‐diliydro‐4‐plienyl‐8‐hydroxyisoearbostyrils (III) by concentrated sulfuric acid. The ratio of II and III is dependent upon substituents present in the aromatic ring of the parent benzoxazepinones.
Photo‐decarbonylation of β‐styryl isocyanates
Authors: Boyer J. H. , Mikol G. J.
Published: March 2009

β‐Styryl isocyanate (1, R  H) and its β‐methyl‐ (1, R  CH3) and β‐phenyl‐ (1, R  C6H5) derivatives underwent both extensive polymerization and the loss of the elements of carbon monoxide upon irradiation at 254 nm in cyclohexane. The formation of 2,5‐diphenylpyrazine (3) and indole 4, (R  H) from 1, (R ‐ H) and 2,3‐dimethyl‐5,6‐diphenylpyrazine (6) and 2‐methylindole (4, R  CH3) from 1, (R  CH3) provided diagnostic evidence for styryl nitrene (2a) intermediates. The formation of both phenylacetonitrile (5, R  H) and α‐phenylpropio‐nitrile (5, R  CH3) was assigned to an initial rearrangement of the residue, C8H6(R)N̈: (2), into a ketenimine concerted with the elimination of carbon monoxide from 1. Isomerization then produced a nitrile. β3‐(β‐phenyl)styryl isocyanate (1, R  C6H5) gave no product requiring the intermediacy of a nitrene and/or an azirine. The formation of 2,3,4,5‐tetraphenylpyrrole (8) was assigned to a dimerization of the isocyanate concerted with or following the elimination of the elements of carbon monoxide and isocyanic acid, and the formation of 3‐phenylisocarbo‐styril (9) was assigned to a ring‐closure of the isocyanate in an excited triplet state. Each isocyanate gave stilbene and trace amounts of oxidative fragmentation into benzaldehyde and benzonitrile. Solvent participation produced benzylcyclohexane and bicyclohexyl. Two unidentified solids, C17H14N2O and C12H14N2O, were obtained from 1, (R  CH3).
The chlorinalion of 3,5‐dimethyl‐1,2,4‐oxadiazole
Authors: Burden John A. , Heywood Donald L.
Published: March 2009

The clilorination of 3,5‐dimethyl‐1,2,4‐oxadiazole has been studied using both photo and thermal initiation. It has been found that photoinitiation allows reaction at both the 3‐ and 5‐methyl group, the former being preferred by a factor of 3‐4 at moderate (up to 75° ) temperature. The difference in reactivity is related to a difference in electron availability at the two reaction sites. The thermally initiated chlorination occurs almost exclusively at the 5‐methyl group. Overall, 3,5‐dimethyl oxadiazole is much less active than toluene or cyclo‐liexane toward chlorination.
Reaction of sulfene with heterocyclic α‐dialkylaminomethyleneketones II. Synthesis of 5N‐1,2‐oxathiino[5,6‐c] [1]benzopyran derivatives
Authors: Schenone P. , Morasso S. , Bignardi G.
Published: March 2009

The reaction of sulfene with 3‐dialkylaminomethylene‐4‐chromanone and 3‐dialkylamino‐methylene‐6‐methyl‐4‐ehromanone gave 1,4‐cycloadducts which are derivatives of a new heterocyclic system, i.e., 5H‐1,2‐oxathiino[5,6‐c][1]benzopyran. The structures of the adductswere determined by ir and nmr spectral data. Two new α‐hydroxymethyleneketones (3‐hydroxy‐methylene‐4‐chromanone and its 6‐methyl analogue) as well as some of their derived enamines were prepared. During the preparation of N,N‐diethylenamines a self‐condensation occurs, which gives the byproducts Xa‐b.
Ring closure reaction of 4‐(2‐hydroxyanilino)‐2‐phenyl‐5‐pyrimidinecarboxylic acid with acetic anhydride. Synthesis of pyrimido[5,4‐c] [1,5]benzoxazepin‐5(11H)ones
Authors: Kim Dong Han , Santilli Arthur A. , Fieber Richard A.
Published: March 2009

Syntheses of 11‐acety1‐2‐phenylpyrimido[5,4‐c][1,5]benzoxazepin‐5(11H)one (16a) and analogs (16b,c, 22) were described. The reaction of 4‐chloro‐2‐phenyl‐5‐pyrimidinecarboxylic acid ethyl ester (7) with 2‐aminophenol afforded 4‐(2‐hydroxyanilino)‐2‐phenyl‐5‐pyrimidine‐carboxylic acid ethyl ester (8a). The latter was also prepared by catalytic reduction of 4‐(2‐nitrophenoxy)‐2‐phenyl‐5‐pyrimidinecarboxylic acid ethyl ester (9), which was obtained from 7 and 2‐nitrophenol. Involvement of 4‐(2‐aminophenoxy)‐2‐phenyl‐5‐pyrimidinecarboxylic acid ethyl ester (12a) in this reduction as an intermediate was demonstrated by an independent synthesis of 12a and its subsequent rearrangement to 8a. Hydrolysis of 8a or 12a gave 4‐(2‐hydroxyanilino)‐2‐phenyl‐5‐pyrimidinecarboxylic acid (15a). Reaction of 15a with acetic anhydride afforded 16a, the first member of a novel ring system, the pyrimido[5,4‐c][1,5]‐benzoxazepin. Additional examples (16b,c) were prepared similarly. The corresponding 11‐ethyl derivative (22) was prepared in similar fashion, starting with 7 and 2‐ethylaminophenol. A possible reaction mechanism for the formation of 16a‐c from 15a‐c and acetic anhydride was discussed.
Halogenation of pyridine 1‐oxides
Authors: Abramovitch R. A. , Campbell J. , Knaus E. E. , Silhankova A.
Published: March 2009

The chlorination and bromination of α‐lithiopyridine 1‐oxides has been studied. Only dihalogenated pyridine 1‐oxides are formed. In the case of bromination dipyridyl derivatives are also formed, and, indeed, predominate. Chloromercuration of the lithiopyridine 1‐oxides gave highly insoluble, unresolvable mixtures of pyridylmercury derivatives. These could be brominated readily to give mixtures of 2‐bromo‐ and 2,6‐dibromopyridine 1‐oxides.
Maerocyelic polyether sulfide syntheses. The preparation of thia‐crown‐3,4, and 5 compounds
Authors: Bradshaw J. S. , Hui J. Y. , Haymore B. L. , Christensen J. J. , Izatt R. M.
Published: March 2009

Macrocyelic polyether sulfides have been prepared by reacting an oligoethylene glycol dichloride with a dithiol or sodium sulfide in ethanol. The trivial naming system for these compounds is an extension of the trivial crown nomenclature (5). A thia prefix is used to show that sulfur atoms have replaced ether oxygen atoms in the polyether ring. The following new compounds were prepared: 1‐thia‐(15‐crown‐5) (II) 1,4‐dithia‐(15‐crown‐5) (III) 1,7‐dithia‐(15‐crown‐5) (IV) 1,4‐dithia‐(12‐crown‐4) (VII) 1,4,7‐trithia‐(12‐crown‐4) (VIII) 1‐thia‐(9‐crown‐3) (IX) and 1,4‐dithia‐(9‐crown‐3) (X). Four other previously reported maerocyelic polyether sulfides were also prepared. The symmetry of the nmr spectra of these compounds gives added evidence for the proposed ring structures.
Azole chemistry. V. Synthesis and spectral properties of thiazolo[3,2‐d] tetrazolium salts
Authors: Alper Howard , Stout Richard W.
Published: March 2009

Thiazolo[3,2‐d] tetrazolium salts were obtained by treatment of 5‐mercapto‐1‐phenyl‐1,2,3,4‐tetrazole with α‐bromo ketones followed by cyclodehydration. The spectral properties of the salts and the β‐keto sulfide precursors were investigated.
Synthesis of pyrazoles and oxyquinoxalines from 2,4‐dioxohexenoales
Authors: El Khadem H. , El‐Shafei Zaki , Rateb Latif , Mokhtar Hassan
Published: March 2009

Condensation of ethyl 2,4‐dioxo‐6‐phenylhex‐5‐enoates (I; R = H, I; R = Me, I, R = Ph) with various hydrazines yielded ethyl 5‐styrylpyrazole‐3‐carboxylates (III), which were hydrolyzed to the acids (IV), and ozonized to 5‐keto pyrazole esters (VI) and acids (VII). Reduction of the 5‐formylpyrazoles (VI; R = II) with borohydride afforded the 5‐hydroxymethyl derivatives (VIII). The same 2,4‐dioxohexenoates (I) when treated with o‐phenylenediamine gave 2‐oxy‐quinoxalines (V; R = H, V; R = Me, V; R = Ph). The uv spectra data of these compounds are given.
Studies on the syntheses of heteroeyelie compounds. Part DV. Cyclization products of i‐substituted 2‐benzyl‐1,2,5,6‐tetrahydropyridines [syntheses of analgesics. Part XXXV]
Authors: Kametani Tetsuji , Kigasawa Kazuo , Hiiragi Mineharu , Wagatsuma Nagatoshi , Uryu Tuneo , Sugi Hideo
Published: March 2009

Treatment of 1,2,5,6‐tetrahydro‐2‐(4‐hydroxy‐ and/or 4‐methoxybenzyl)‐3,4‐dimethyl‐I‐(3‐methyl‐2‐butenyl)pyridines (IV and V) and 2‐(4‐methoxybenzyl)‐3,4‐dimethyl‐1‐(3‐methyl‐2‐butenyl)‐4‐piperidinol (X) with acid afforded 9‐(4‐hydroxy‐ and/or 4‐methoxybenzyl)‐4,4,5,6‐tetramethyl‐1‐azabicyelo[3,3,1]non‐6‐ene (XIII and XIV). In contrast, the corresponding 1‐allyl‐substituted derivatives VI, VII, and XI were converted into the expected 3‐allyl‐1,2,3,4,5,6‐hexahydro‐8‐hydroxy‐ and/or 8‐methoxy‐6,11‐dimethyl‐2,6‐methano‐3‐benzazocine (II and III).
Studies on the syntheses of heteroeyelie compounds. Part DVII. A synthesis of (±)‐N‐norgalanthamine
Authors: Kametani Tetsuji , Yamaki Kazuya , Terui Tsunekazu
Published: March 2009

(±)‐N‐Norgalanthamine (la) and (±)‐N‐norlycoramine (Ib) was synthesized through the phenolie oxidation of N‐(4‐hydroxyphenethyl)‐2‐bromo‐5‐hydroxy‐4‐methoxybenzamide (lIb).
Intramolecular nucleophilic cyclization of 3‐substituted pyridylalkylamines onto the 2‐position of the pyridine ring
Authors: Hawes Edward M. , Davis Hubert Lome
Published: March 2009

The intramolecular nucleophilic cyclization of 4‐(3‐pyridyl)butylamine (4a) to yield 6,7,8,9‐tetrahydro‐5H‐pyrido[2,3‐b]azepine (5) was investigated. Of eleven different alkali metal reagents sodium, sodium hydride, sodium amide, and potassium hydride gave good yields of 5. The sodium conditions when applied to 3‐(3‐pyridyl)propylamine (4b) afforded 1,2,3,4‐tetrahydro‐1,8‐naphthyridine (6) in good yield.
Silver and palladium complexes of some aromatic azo and azoxy compounds
Authors: Porter John J. , Murray Joel Luke , Takvorian Kenneth B.
Published: March 2009

The complexing ability of derivatives of azobenzene (I) is well known (I) and responsible for the production of a wide variety of dyestuffs and analytical chemicals. While the azo group generally participates in the coordination, the determination of the degree of its interaction is complicated by other functional groups which are also coordinated with the transition metal. In a previous publication (2), we reported the preparation of the silver and palladium complexes of benzo[c]cinnoline (II) and proposed that these results might be used to explain the electron donor properties of azobenzene. We are now reporting the preparation of some additional complexes with ligands containing the azo group.
Synthesis of 2,2′‐bipyrimidine derivatives
Authors: Feit B. A. , Teuerslein A.
Published: March 2009

A new total synthesis of 2,2′ ‐bipyrimidine derivatives by the direct condensation of 2‐amidinopyrimidinebenzenesulfonate with dicarbonyl compounds is described. The following 2,2′‐bipyrimidines have been prepared: 5‐ethyl‐4,6‐dihydroxy‐2,2′‐bipyrimidine; 5‐ethyl‐4,6‐dichloro‐2,2 ‐bipyrimidine; 4,6‐dihydroxy‐2,2′ ‐bipyrimidine; 5‐ethyl‐4,6‐dimethoxy‐2,2′ ‐bipyrimidine.
Studies on the hydrolysis of cyclophosphamide II. Isolation and characterization of intermediate hydrolytic products
Authors: Chakrabarli Jiban K. , Friedman Orrie M.
Published: March 2009

Two new products of hydrolysis of cyclophosphamide in water at 100°,N‐(2‐chloroethyl)‐N' ‐(3‐phosphatopropy l)ethylenediamine andN‐(2‐hydroxyethyl)‐N‐(3‐phosphatopropyl)ethylene‐diamine, have been isolated after 30 minutes, and 6 hours of reaction times, respectively. These products have been shown to be intermediates leading to the formation ofN‐(2‐hydroxyethyl)‐N'‐(3‐hydroxypropyl)ethylenediamine, the principal ultimate product of cyclophosphamide hydrolysis. The nature of these new products supports the previously postulated mechanism involving an intramolecular alkylation as the initial step in the hydrolytic process although the pathway appears to be an unlikely model for the metabolic transformations of cyclophosphamidein vivo.
3‐Amino‐1‐[2‐(2‐ethoxyethoxy)ethoxy ] benzo[∫]quinazoline
Authors: Sengupta Sisir K. , Protopapa Heljo Kangur , Modest Edward J. , Das Bhupesh C.
Published: March 2009

The structure of an anomalous product, isolated as a companion substance during the catalytic dehydrogenation of 1,3‐diamino‐5,6‐dihydrobenzo[ƒ] quinazoline, has been elucidated with the aid of chemical and spectral evidence, including mass spectrometric data. The mass spectrometric fragmentation pattern of the compound is in good agreement with the assigned structure.
Reaction of 2‐aminobenzimidazole with bifunetional carboxylie acid derivatives. Formation of pyrimido[1,2‐a] benzimidazolones
Authors: Chow A. W. , Jakas D. R. , Trotter B. P. , Hall N. M. , Hoover J. R. E.
Published: March 2009

2‐Aminobenzimidazole reacts with α,β‐unsaturated carboxylic acid chlorides or esters to give only pyrimido [1,2‐a] benzimidazol‐2‐(1H) ones. β‐Ethoxymethylenemalonie acid derivatives or β‐ketocarboxylic acid derivatives give only pyrimido [1,2‐a] benzimidazol‐4‐(1H)ones. Structural assignments based on nmr and chemical manipulations are discussed.
Synthesis of a potential camptothecin intermediate
Authors: Kametani Tetsuji , Takeda Hiromitsu , Satoh Fumio , Takano Seiichi
Published: March 2009

Condensation of dimethyl 1,2‐dihydro‐2‐oxopyridine‐4,6‐dicarboxylate (IIIb) with methyl acrylate yielded 1,2,3,5‐tetrahydro‐2,7‐dimethoxycarbonyl‐1,5‐dioxoindolizine (IV), which on hydrolysis and decarboxylation gave 1,2,3,5‐tetrahydro‐1,5‐dioxoindolizine‐7‐carboxylic acid (VI). Friedländer condensation of VI with 2‐aminobenzaldehyde, followed by esterification of the resulting oxoindolizino[1,2‐b]quinoline‐7‐carboxylic acid (VIIa), yielded a potential camptothecin intermediate 9,10‐dihydro‐7‐methoxycarbonyl‐9‐oxoindolizino[1,2‐b]quinoline (VIIb).
Aziridines. V. Etude par rmn de l'inversion de l'azote dans les aziridines symétriques à fonetion amine secondaire
Authors: Martina R. , Abeba Mile J. , Lattes Et A.
Published: March 2009

This article describes the nitrogen inversion in two symétrie secondary aziridines. It was possible, by nmr, in avoiding the exchange of NH proton with water, to record spectra at different temperatures and to determine the temperature of coalescence. Persistance of coupling HCNH after coalescence demonstrates the attribution of signals multiplicity to both invertomers.
A study of some quinolizone derivatives
Authors: Al‐Jallo Hikmat N. , Al‐Azawi Fatin W.
Published: March 2009

The condensation of methyl 2‐pyridylacetate and ethyl phenylpropiolate has been found to be a simple and convenient method for the preparation of 4‐quinolizone derivatives. Upon hydrolysis and decarboxylation, the initial condensation product, l‐carbethoxy‐2‐phenyl‐4H‐quinolizin‐4‐one (V) was converted to 2‐phenyl‐4H‐quinolizin‐4‐one (VII). Nitration and bromination of these quinolizones were affected under mild conditions. Nitration of V displaced the carbethoxy group, while bromination did not and 1,3‐dinitro‐4H‐quinolizin‐4‐one and 1‐carbeth‐oxy‐2‐phenyl‐3‐bromo‐4H‐quinolizin‐4‐one were obtained, respectively.
Nitration of trans‐2‐styrylthiophene
Authors: Arcoria Antonino , Maccarone Emanuele , Tomaselli Gaetano A.
Published: March 2009

The nitration of trans‐2‐styrylthiophene in carbon tetrachloride, nitroethane and acetic anhydride has been investigated.

The nitration products were: β‐nitro‐2‐styrylthiophene as the main product with 3‐nitro‐2‐styrylthiophene and the 5‐nitro isomer in smaller amounts. They were identified by the chromato‐graphic and spectroscopic (uv and nmr) comparison with the reference compounds.

The isomer percentages, determined by glc, were unchanged under different nitration conditions (time, temperature and molar ratio), but were dependent on the solvent used.
Synthese d'lsosélénazoles et de benzisosélénazoles‐1,2
Authors: Weber R. , Reason M.
Published: March 2009

A general preparation of the isoselenazole ring by addition of bromine followed by ammonia on cis‐β–methylseleno‐2‐propenal is described. This reaction was successfully applied to 1,2‐benz‐isoselenazole, a new heterocyclic system.
Selective ring opening reactions of 3,7‐diarylsulfonyl‐1,3,5,7‐tetrazabicyclo[3.3.1] nonaries
Authors: Yoshida H. , Sen C. , Thyagarajan B. S.
Published: March 2009

The selective formation of 1,3,5,7‐tetrazacyelooctanes from the title compounds is described. Exclusive cleavage of the IN‐CH2‐N bonds at the bridge methylene is shown to be a facile process, thus providing a convenient route to tetrazacyclooctane derivatives.
1,2,4‐Triazines X: Dimerizations of 1,2,4‐triazmes
Authors: Krass Dennis K. , Chen Teh‐Kuei , Paudler William W.
Published: March 2009

5,5′‐Bi‐1,2,4‐triazinyl compounds are obtained by the treatment of 5‐unsubstiluted 1,2,4‐triazines with either sodium methoxide or with aqueous potassium cyanide.

5,5′‐Bi‐1,2,4‐triazinyl is also obtained by the reaction of 1,2,4‐triazine with potassium cyanide.

It is proposed that the sodium methoxide catalyzed dimerizations occur via a carbanionic intermediate; the aqueous potassium cyanide catalyzed reactions via a cyanide addition product and the potassium in liquid ammonia reaction via a free radical dimerization process.
The synthesis and ultraviolet spectra of some N‐aryl‐2,3‐dihydro‐3‐oxo‐4H‐1,4‐oxazine derivatives
Authors: Abdulla Riaz F.
Published: March 2009

Two new derivatives of the 1,4‐oxazine ring system (3a and 3b) derived from p‐aminobenz‐amides have been synthesized. The uv absorption spectra of sixteen representative 1,4‐oxazines all show two high intensity bands (ϵ ∼ 105) between 220‐400 ran. The positions and intensities of the absorption maxima have been correlated with the steric and electronic effects of the oxazine ring substituents.
The preparation of substituted 1,2,4‐triazolines and substituted picolinic acid methylene hydrazides by the action of certain carboxamide hydrazones with ketones
Authors: Case Francis H.
Published: March 2009

The action of certain ketones with carboxamide hydrazones, yielding, depending on conditions, 1,2,4‐triazolines or substituted picolinic acid methylene hydrazides, has been investigated. Also the preparation of 3‐subsliluted‐5‐phenyl‐1,2,4‐triazines from the action of phenyl glyoxal and certain carboxamide hydrazones is described.
Synthesis of 4(5)‐substituted 2‐amino‐5(4)‐hydroxyimino‐5(4)H‐imidazoles and their transformation into the corresponding 3‐substituted 5‐amino‐1,2,4‐oxadiazoles
Authors: Cavalleri Bruno , Bellani Piero , Lancini Giancarlo
Published: March 2009

Treatment of 4(5)‐phenyl(or alkyl)‐2‐aminoimidazoles with isoamyl nitrite in acetic acid afforded the corresponding 4(5)‐substituted 2‐amino‐5(4)‐hydroxyimino‐5(4)H‐imidazoles which by heating in water were transformed into 3‐benzoyl(or acyl)‐5‐amino‐1,2,4‐oxadiazoles.
Synthesis and antimalarial effects of 5,6‐dichloro‐2‐[(4‐||4‐(diethylamino)‐i‐methylbutyl] amino||‐6‐methyl‐2‐pyrirnidinyl)amino] benzimidazole and related benzimidazoles and lH‐imidazo[4,5‐b] pyridines
Authors: Werbel Leslie M. , Curry Ann , Elslager Edward F. , Hess Carolyn
Published: March 2009

A group of fifty‐five 2‐[(4‐11[(dialkylamino)alkyI]amino11‐6‐methyl‐2‐pyrimidinyl)amino]‐benzimidazoles (VII) was synthesized in 3‐88% yield by the condensation of the requisite 2‐[(2‐benzimidazolyl)amino]‐4‐chloro‐6‐methylpyrimidine (VI) with the appropriate polyamine in ethanol‐hydrochloric acid or neat with excess amine containing potassium iodide. The 2‐[(2‐benzimidazolyl)amino]‐6‐methyl‐4‐pyrirnidinol precursors (V), obtained in 11‐51% yield by cyclization of 2‐(cyanoamino)‐4‐hydroxy‐6‐methylpyrimidine with a suitably substituted o‐phenylenediamine, were chlorinated with phosphorus oxychloride to give the intermediate 2‐[(2‐benzimidazolyl)amino]‐4‐chloro‐6‐rnethylpyrimidines (VI) (27‐99%). Oxidation of 5,6‐dichloro‐2‐[(4‐11[4‐(diethylamino)‐l‐methylbutyl] amino 11‐6‐methyl‐2‐pyrimidinyl) amino ]benzimidazole (29) with m‐chloroperbenzoic acid gave the distal N4'‐oxide (31) (19%). Fusion of 2,3‐uiaminopyridine with 2‐(cyanoamino)‐4‐hydroxy‐6‐methylpyrimidine provided 2‐[(4‐hydroxy‐6‐tnethyl‐2‐pyrimidinyl)amino]‐lH‐imitlazo[4,5‐b]pyrimidine (VIII) (30%), which upon chlori‐nation with phosphorus oxychloride (63%) followed by amination with i N, N‐diethylethylene‐diamine afforded 2‐(4‐11[2‐(diethylamino)ethyl] amino 11‐6‐methyl‐2‐pyrimidinyl)‐lH‐imidazo [4,5‐b]pyridine (X) (8%). Thirty‐eight of the novel 2‐[(4‐amino‐6‐methyl‐2‐pyrimidinyl)amino]‐benzimidazoles possessed “curative” activity against Plasmodium berghei at single subcutaneous doses ranging from 20.640 mg./kg. Orally, thirty‐one compounds exhibited suppressive activity against P. berghei comparable with or superior to the reference drugs 1‐(p‐chlorophenyl)‐3‐(4‐11[2‐(diethylarnino)ethyl]amino 11‐6‐methyl‐2‐pyrimidinyl)guanidine (I) and quinine hydrochloride, while twelve of them were 5 to 28 times as potent as I and quinine hydrochloride. Eight compounds also displayed strong suppressive activity against P. gallinaceum in chicks. 5,6‐Dichloro‐2‐[(4‐112‐(diethylamino)ethyl]amino11‐6‐methyl‐2‐pyrimidinyl] benzimidazole (18) showed marked activity against a cycloguanil‐resistant line of P. berghei, and the most promising member of the series, namely 5,6‐dichloro‐2‐[(4‐11[4‐(diethylamino)‐l‐methylbutyl]amino11‐6‐methyl‐2‐pyrimidinyl)amino]benzimidazole (29) (Q = 28), was designated for preclinical toxico‐logical studies and clinical trial. Structure‐activity relationships are discussed.
The formation of a stable o‐semidine rearrangement intermediate
Authors: Paudler William W. , Zeiler Andrew C. , Goodman Mark M.
Published: March 2009

Treatment of 5,6,11,12‐tetrahydrodibenzo‐[b, f][1,2] diazocine with dilute acids affords a spiro‐1,2,3,4‐tetrahydroquinoline derivative which represents the first isolated stable o‐semidine rearrangement intermediate.
The schmidt reaction with oxa‐ and azabenzocycloalkenones
Authors: Misiti D. , Rimatori V. , Gatta F.
Published: March 2009

Five, seven and eight membered ring oxa‐ and azabenzocycloalkenones were submitted to the Schmidt reaction and the ratio of the respective isomeric rearrangement products have been determined and compared with that of six membered ring oxa‐ and azabenzocycloalkenones.
Heterocyclic derivatives of naphthalene‐1,8‐dicarboxylic anhydride. Part II. Colour and dyeing properties on synthetic fibres of some substituted 7H‐benzimidazo[2,1‐a]benz[de]isoquinolin‐7‐ones
Authors: Grayshan P. H. , Peters Arnold T.
Published: March 2009

The effect on colour resulting from substitution in the phenyl and naphthyl rings of 7H‐benzimidazo [2,1‐a]benz[de]isoquinolin‐7‐one (I) is discussed; dycing and fastness properties of these dyes on synthetic fibres are described and the synthesis of some new 1,8‐naphthalimides and derivatives of I recorded.