bluuebunny/crossref_metadata_2025 huggingface dataset:
The action of organolithium compounds on phthalazine and I (2H)‐phthalazinone
Authors: Hisrch A. , Orphanos D. G.
Published: March 2009

Phthalazine and 1(2H)‐phthalazinone undergo 1,2‐addition of organolithium compounds to C = N to give, following hydrolysis, 1 ‐ substituted ‐ 1,2 ‐ dihydrophthalazines and 4‐substituted‐3,4‐dihydro‐1(2H)‐phthalazinones respectively. These dihydro‐derivatives may be easily autoxidized to the corresponding 1‐substituted phthalazines and 4‐substituted‐1(2H)‐phthalazinones.
Synthetic furocoumarins. Xanthotoxin and methylxanthotoxins
Authors: De Souza Noël J. , Nayak P. Vathsala , Secco Ella
Published: March 2009

The synthesis of 4‐methylxanthotoxin (X), 4,5′‐dimethylxanthotoxin (XXIV) and the hitherto unknown 5′‐methylxanthotoxin (XXIII) are described, using 6‐allyl‐7‐hydroxy‐8‐methoxycoumarin (XV) and its 4‐methyl derivative (XVII) as intermediates.
Synthesis of alkylaminoethanethiolsulfuric acids substituted with heterocyclic moieties
Authors: Singerman Gary M. , Kimura Ryuichi , Riebsomer J. L. , Castle Raymond N.
Published: March 2009

Several alkylaminoethanethiolsulfurie acids substituted with heterocyclic moieties have been synthesized to determine their effectiveness as radiation protection agents. These compounds are represented by the structure R(CH2)3NH(CH2)2S2O3H, where R is 8‐quinoly‐oxy (V), 8‐quinaldyloxy (IX), 5‐quinolyloxy (XII), 4‐pyridyl (XVI), and 4‐pyridylmethyl (XXIII). The diheterocyclic‐substituted compound, 2‐[bis‐(2‐phenyl‐1, 2, 3, 2H‐triazol‐4‐ylmethyl)amino]ethanethiolsulfuric acid (XIV) was also synthesized.
The thermal decomposition of 3‐azido‐4‐benzylideneamino‐s‐triazoles
Authors: Takimoto H. H. , Denault G. C. , Hotta S.
Published: March 2009

The synthesis and thermal decomposition of a series of 3‐azido‐4‐benzylideneamino‐s‐triazoles are described. The decompositions resulted in a loss of nitrogen and intra‐molecular cyclization at the carbon atom of the azomethine linkage to produce 1H‐2‐aryl‐s‐triazolo‐[3,2‐c]‐s‐triazoles.
Synthesis of vitamin B6derivatives I. Preparation of some isopyridoxamine derivatives from isopyridoxal
Authors: Brooks Houston G. , Laakso J. W. , Metzler David E.
Published: March 2009

Improved syntheses of isopyridoxal and isopyridoxamine are described. New 5‐N‐substituted isopyridoxamine derivatives resulting from condensation followed by reduction of the carbonyl group of isopropylideneisopyridoxal with aniline, 2‐aminothiazole and benzylamine are also reported.
Mass spectrometry of 10‐chloro‐5, 10‐dihydrophenarsazine (adamsite) and 10‐methyl‐5, 10‐dihydrophenarsazine
Authors: Buu‐Hoi N. P. , Mangane M. , Jacquignon P.
Published: March 2009

The mass spectrograms of 10‐chloro‐ and 10‐methyl‐5,10‐dihydrophenarsazine have been determined. These spectrograms show the following main characteristics of fragmentation behavior for these heterocycles: (a) a relative stability, in both compounds, of the arsenic atom within the heterocyclic framework; (b) an exceptionally facile splitting of the As‐Cl bond, contrasting with the behavior of the As‐CH3 bond; and (c) an easy formation of the phenarsazine species from 10‐chloro‐5,10‐dihydrophenarsazine.
A new synthesis of alkyl and aryl 2‐aminoimidazoles
Authors: Lancini Gian Carlo , Lazzari Ettore
Published: March 2009

The condensation of cyanamide with α‐aminocarbonyl compounds has been studied as a method of synthesizing alkyl and aryl 2‐aminoimidazoles. Starting fromN‐alkylamino‐aldehydes, 1,5‐dialkyl‐2‐aminoimidazoles have been prepared. Starting from suitable aminoketones a variety of monosubstituted and disubstituted derivatives were obtained.
The mass spectra of oxygen heterocycles (III) . An examination of simple lignans
Authors: Pelter Andrew , Stainton A. P. , Barber M.
Published: March 2009

The mass spectra of some simple lignans containing the tetrahydrofuran nucleus have been examined. The fragmentation patterns of various types have been defined and shown not to be sensitive to the stereochemistry of the substituents. Positional isomers however give very different mass spectra.
The synthesis of 1‐(2‐dialkylaminoethyl)‐5 (and 6)‐methoxy‐2‐methyl (and H)‐benzimidazoles
Authors: Burch Homer A. , Herbst Robert M.
Published: March 2009

The syntheses of twenty 1‐(2‐dialkylaminoethyl)‐5 (and 6)‐methoxy‐2‐methyl (and H)‐benzimidazoles in which the dialkylamino groups are dimethylamino, diethylamino, pyrrolidino, piperidino and morpholino, are presented. These compounds failed to show any significant biological activity.
Morphanthridines III. 6‐Basic substituted morphanthridines
Authors: Drukker Alexander E. , Judd Claude I. , Dusterhoft Donald D.
Published: March 2009

The reaction of hydrazines and amines with 6‐chloromorphanthridine was investigated. Grignard coupling of aminoalkyl halides with 6‐chloromorphanthridine afforded 6‐amino‐alkylmorphanthridines. Cyclization of 6‐(2‐chloroethylamino)morphanthridine yielded the new ring system 5′H‐imidazo[5, 6‐a]dibenz[b, ejazepine, which was aminoalkylated by generation of the 11‐position anion with butyllithium, followed by treatment with a tertiary aminoalkyl halide.
Electron‐bombardment and pyrolysis of meso‐ and dl‐hydrobenzoin cyclic sulfites
Authors: Pritchard J. G. , Funke Phillip T.
Published: March 2009

Only a minor yield of sulfur dioxide positive ions is eliminated from the meso‐ and dl‐hydrobenzoin cyclic sulfite molecules under electron bombardment. Among the principal fragmentation products for both sulfites are very similar yields of ions with m/e 154 and 126, which contain sulfur most probably attached to a phenyl ring. Positive ions apparently corresponding to those of diphenylacetaldehyde, desoxybenzoin, and stilbene are minor products of the positive‐ion fragmentation process of the sulfites. These three compounds along with sulfur dioxide are the products of the pyrolysis of the sulfites at 240‐250°. The principal product from the meso‐sulfite is desoxybenzoin, and from the dl‐sulfite it is diphenylacetaldehyde. Mechanistic details are discussed.
The chemistry of heterocycles. IV. 2H‐pyrido[4,3‐e]‐1,3‐oxazine‐2,4(3H)‐dione, its precursors and some 3‐substituted derivatives.
Authors: Crum J. D. , Fuchsman C. H.
Published: March 2009

The preparation of 2H‐pyrido[4, 3‐e]‐1, 3‐oxazine‐2, 4(3H)‐dione (II) and the anisoyl, benzoyl, 4‐chlorobenzoyl, trans‐cinnamoyl, 3, 5‐dinitrobenzoyl, 2‐furoyl, and 2‐naphthoyl derivatives substituted at position 3 of II together with their infrared and ultraviolet spectra are described. The 3‐substituted 2 and 4‐(2‐pyridylethyl) and hydroxymethyl derivatives of quinolinimide and cinchomeronimide were also prepared and their spectra recorded.
The synthesis of substituted 8‐quinolinols
Authors: Kolobielski Marjan
Published: March 2009

2‐Isopropyl‐8‐quinolinol was prepared by alkylation of 8‐methoxyquinoline followed by demethylation. The 7‐isopropyl‐8‐quinolinol was prepared in three steps from o‐isopropylphenol. The reaction of 5‐chloromethyl‐8‐quinolinol hydrochloride with alcohols, amines, ethylene glycols and ether‐alcohols gave the corresponding 5‐substituted derivatives of 8‐quinolinol.
Nuclear magnetic resonance of benzobisheterocyclic compounds
Authors: Grandolini Giuliano , Ricci Adolfo , Martani Alfio , Delle Monache Franco
Published: March 2009

The nuclear magnetic resonance spectra of forty‐nine benzobisheterocyclic compounds, containing various heterocycles, were determined. The observed spectral data made possible the elucidation of the structure and also clarified the influences of the heterocyclic substituents and of heterocyclic rings on chemical shift values of the aromatic protons.
Aldol and claisen condensations with 1‐(3,4‐dichlorophenyl)‐2‐pyrrolidinone
Authors: Seidel Michael C. , Cook Richard S.
Published: March 2009

1‐(3,4‐Dichlorophenyl)‐2‐pyrrolidinone (I) has been condensed at the 3‐position with a series of aldehydes, ketones and esters.
Synthesis of 6‐substituted pyrimidines by the wittig reaction. III . Via 2‐amino‐4‐hydroxy‐5‐phenylbutyl‐6‐pyrimidylmethyl triphenyl phosphonium bromide
Authors: Baker B. R. , Jordaan Johannes H.
Published: March 2009

2‐Amino‐6‐bromomethyl‐5‐phenylbutyl‐4‐pyrimidinol (IV) smoothly alkylated triphenyl phosphine, resulting in a 95% yield of the phosphonium salt (V). This Wittig reagent (V) readily condensed with p‐nitrobenzaldehyde, p‐nitrocinnamaldehyde, or cinnamalde‐hyde in N,N‐dimethylformamide to give the 6‐(p‐nitrostyryl) (X), 6‐(p‐nitrophenyl‐1,3‐butadien‐1‐yl) (VIH), and 6‐(phenyl‐1,3‐butadien‐1‐yl) (IX) pyrimidinols in 72, 67 and 44% yields, respectively. Catalytic reduction of VIII and IX afforded the corresponding 6‐(p‐aminophenylethyl) (XII) and 6‐(p‐aminophenylbutyl) (XI) 4‐pyrimidinols.
Synthesis of 1,3,4‐thiadiazoles containing the trifluoromethyl group
Authors: Lalezari I. , Sharghi N.
Published: March 2009

The following compounds have been synthesized: 2‐Amino‐5‐trifluoromethyl‐1,3,4‐thiadiazole; N‐(5‐trifluoromethyl ‐ 1,3,4‐thiadizol‐2‐yl)benzenesulfonamide; N1‐(5‐trifluoromethyl‐1,3,4‐thiadiazol‐2‐yl)sulfanilamide, its N4‐acetyl, N4‐succinyl, and N4‐pathalyl derivatives; o ‐ m ‐ and p‐trifluoromethylbenzoylthiosemicarbazide, their corresponding 2‐amino‐1,3,4‐thiadiazoles, their corresponding sulfanilamides, their N4‐acetyl, N4‐succinyl and N4‐phthalyl derivatives; 3‐o‐trifluoromethylphenyl‐4H‐1,2,4‐triazole‐5‐thiol. Preliminary in‐vitro assays show that synthesized sulfanilamide derivatives have antibacterial activity against Staphylococcus aureus.
New reactions of pyrroles. I. pyridylethylpyrroles
Authors: Archibald John L.
Published: March 2009

Pyrroles with unsubstituted 2‐ and/or 5‐positions are found to react with 4‐vinyl‐pyridine, giving hitherto unreported 2‐ and 2,5‐di‐ pyridylethylpyrroles. Pyrrole‐2‐carboxylic acids can also react to give the same products by displacement of the carboxyl group. Pyridylethylation at an available 3‐ and/or 4‐position was not observed. Catalytic reductions and alkylations of the resulting piperidylethylpyrroles are also reported.
Deuterium exchange of 4‐pyrimidones and 4‐pyrimidthiones
Authors: Wright George E. , Bauer Ludwig , Bell Charles L.
Published: March 2009

The hydrogen‐deuterium exchange of H‐2 in 4‐pyrimidone, a number of 1‐ and 3‐alkyl‐4‐pyrimidones and several of their thione analogs in deuterium oxide at moderate temperatures is reported. This reaction is apparently not susceptible to acid or base catalysis. Cations of the 4‐pyrimidones were found not to exchange H‐2 at all in acid media. Catalytic amounts of bases do not alter the exchange rates whereas more concentrated alkali decompose the pyrimidone. However, 1,4(3,4)‐dihydro‐1,3‐dimethyl‐4‐oxopyrimidinium iodide (and its 6‐methyl analog) exchange H‐2 quite rapidly in neutral deuterium oxide, almost instantly when triethylamine is added as a catalyst, and very slowly in dilute solutions of deuterium chloride in deuterium oxide. Mechanisms are proposed to account for these phenomena.
4‐Amino‐2‐oxazolidinones
Authors: Strumza Jacob , Ben‐Ishai Dov
Published: March 2009

Thermal cyclization of β‐haloalkylidenebisbenzylcarbamates (III) and subsequent hydro‐genolysis of the intermediate 4‐carbobenzoxyamino‐2‐oxazolidinones (IV) afford 4‐amino‐2‐oxazolidinones (V). Some of the chemical properties of the aminooxazolidinones are also described.
Synthesis of isatin‐N‐mannich bases
Authors: Varma Rajendra S. , Nobles W. Lewis
Published: March 2009

The synthesis of a series of isatin‐N‐Mannich bases derived from isatin, 5‐methyl and 5‐bromoisatins as the active hydrogen component and dimethylamine, diethylamine, morpholine, piperidine, N‐ethylcyclohexylamine, 3‐azabicyclo[3.2.2]nonane and 3‐aza‐bicyclo[3.2.1]octane as the secondary amine moiety is described. These compounds are to be screened for their pharmacological properties.
N‐Heteroaralkyl substituted α‐amidinium thiolsulfates
Authors: Parulkar Anilkumar P. , Bauer Ludwig
Published: March 2009

The syntheses of a number of N‐substituted α‐amidinium thiolsulfates, CH2(S2O3−)‐C(=NH2+)NH(CH2)nR are described, where n was varied from 1 to 3 and R represents such heteroaryl groups as 2‐furyl, 2‐thienyl, 3‐indolyl and 2‐, 3‐ and 4‐pyridyl. The preparation of S‐(2‐imidazolinemethyl)thiolsulfuric acid, as an example of an N, N'‐disubstituted α‐amidinium thiolsulfate, is also reported.
Heterocyclic steroids. X. 2‐Aza‐4‐oxa‐steroid analogs
Authors: Piatak D. M. , Caspi E.
Published: March 2009

Two 2‐aza‐4‐oxa steroids have been synthesized from acid Ia. In addition the Beckmann rearrangement of the C‐1 amide Ij has been explored.
Synthesis of some N‐methylated pteridines related to 7,8‐dihydroxanthopterin
Authors: Zondler Helmut , Forrest H. S. , Lagowski J. M.
Published: March 2009

Seven methylated pteridines have been synthesized by condensation of a 4‐chloro‐5‐nitropyrimidine with a β‐ketoamine (or a blocked derivative), reduction of the nitro group, and subsequent ring closure. This scheme provides a new route to dihydroxanthopterin. Several cases are reported, however, in the uracil series where ring closure could not be effected.
Mass spectrometric fragmentation of some lignans
Authors: Duffield A. M.
Published: March 2009

Mass spectra of some lignans containing either γ‐butyrolactone, 1,2,3,4‐tetrahydro‐naphthalene or the 3,7‐dioxabicyclo[3. 3. 0]octane ring systems are reported. Probable structures are presented for the more abundant ions in the mass spectra of these lignans.
Irreversible enzyme inhibitors. LXXXI. Further observations on the mode of binding of the anilino moiety of 2‐amino‐5‐(anilinopropyl)‐6‐methyl‐4‐pyrimidinol to dihydrofolic reductase and thymidylate synthetase
Authors: Baker B. R. , Novotny Jaroslav
Published: March 2009

Replacement of phenyl group of 2‐amino‐5‐(anilinopropyl)‐6‐methyl‐4‐pyrimidinol (III) by benzyl (XI) led to a large loss in binding to both dihydrofolic reductase and thymidylate synthetase; the binding by XI returned when the protonated benzylamino group was N‐acetylated to XII, which removes the charge at pH 7.4 and changes the ground‐state conformation of the benzene ring. Replacement of the benzyl group of the acetamide, XII, with the polar 2‐, 3‐, or 4‐, picolyl groups also led to a loss in binding. Substitution of p‐fluoro or m‐trifluoromethyl on the anilino group of III, or replacement of the anilino of III by 3‐pyridylamino, gave little ‐ if any ‐ enhancement in binding to the enzymes.
Pyrimidines. XIX. Pyrimido[4,5‐e]dihydro‐1,3‐oxazines and related compounds
Authors: O'Brien Darrell E. , Weinstock Louis T. , Springer Robert H. , Cheng C. C.
Published: March 2009

A number of 2‐substituted 4,5‐dihydroxy‐6‐(substituted aminomethyl)pyrimidines (VIII) were prepared from the corresponding 2‐substituted 4,5‐dihydroxypyrimidines (VII) by a new pyrimidine Mannich reaction. The structure of VIII was proved by an independent synthesis. Further study of this reaction led to the synthesis of a new class of compounds: the pyrimido[4,5‐e]dihydro‐1,3‐oxazines (VI).
Benzologs of the thiazolo[3,2‐a]pyridinium system
Authors: Bradsher C. K. , Lohr D. F.
Published: March 2009

By use of concentrated sulfuric acid rather than hydrobromic acid as the cyclizing medium, good yields of the thiazolo[3,2‐a]quinolinium ion and its derivatives may be obtained from α‐(2‐quinolylthio) ketones or acetals. In the same way, α‐(1‐isoquinolylthio) and α‐(6‐phenanthridylthio) ketones afford thiazolo[2,3‐a]isoquinolinium and thiazolo‐[3,2‐f]phenanthridinium salts.
The chemistry of pyrazine and its derivatives. XII. The reaction of acetonylpyrazine with phenyllithium in the presence and absence of methyl benzoate
Authors: Chakrabartty Sujit K. , Levine Robert
Published: March 2009

The reaction of acetonylpyrazine with phenyllithium in the absence and presence of methyl benzoate gives (a) 2‐phenyl‐6‐acetonylpyrazine (IV) and (b) a mixture of IV and 3‐(2‐phenyl‐6‐pyrazyl)‐4‐phenylbutane‐2, 4‐dione (V, VI), respectively. Evidence in support of the structures of the products has been presented and comments on their formation are made.
Photochromism in the arylaroylaziridine system
Authors: Padwa Albert , Hamilton Lewis
Published: March 2009

Photochromism of a number of arylaroylaziridines has been observed in the solid state or in the rigid matrix. The photochromic behavior is dependent on the intensity of the incident radiation, the reaction medium, the wavelength of light used and on the relationship of the substituents on the three‐membered ring. From the visible absorption spectra it is clear that cis‐arylaroylaziridines give different colored species than do the trans isomers. These results suggest that the coloration is due to an extensive electrical interaction between the bent bonds of the aziridine ring and the π orbitals of the benzoyl and phenyl groups. Attempts to trap the colored species by co‐irradiation with substrates containing a multiple bond failed. A reaction has been found to occur upon heating various arylaroylaziridines with dimethylacetylene dicarboxylate in inert solvents.
1‐(Aziridine) carbonyl chlorides and 1‐(aziridine) carbonyl quaternary ammonium chlorides. Rearrangement to 2‐(chloroalkyl) isocyanates
Authors: Tomalia Donald A. , Paige Janet N.
Published: March 2009

Aziridine reacted with phosgene in the presence of an acid acceptor or with 1,1′‐carbonylbis(pyridinium) chloride to produce 1‐(aziridine)carbonyl chloride (XII) or 1‐(aziridine)carbonyl pyridinium chloride (XIII), respectively, as transient intermediates. Attempts to trap and observe (XII) and (XIII) at ‐10° were unsuccessful. These elusive materials underwent facile rearrangements to 2 ‐ chloroethyl isocyanate under these conditions. Aziridine reacted with 1,1′‐carbonylbis(triethylammonium)chloride (VII) at ‐20° to give 1‐(aziridine) carbonyl triethylammonium chloride (X) as a transient intermediate which proceeded to 2‐chloroethyl isocyanate. At ‐10° this reaction produced N,N‐diethyl‐1‐aziridinecarboxamide. Aziridine reacted with a large excess of phosgene in the absence of an acid acceptor to give N‐2‐(chloroethyl) carbamoyl chloride (III), 1,1′‐bis(2‐chloroethyl) urea (IV) and 2‐(β‐chloroethylamino)‐2‐oxazoline hydrochloride (V). Possible mechanisms for these reactions are discussed.
Irreversible enzyme inhibitors. XC. candidate active‐site‐directed irreversible inhibitors of thymidylate synthetase. I. 2‐amino‐5‐(benzenesulfonamidopropyl)‐6‐methyl‐4‐pyrimidinol with substituents on the benzene ring
Authors: Baker B. R. , Coward James K.
Published: March 2009

2‐Amino‐5‐[p‐ (bromoacetamidomethyl)benzenesulfonamidopropyl]‐6‐methyl‐4‐pyrimidinol (XV) was synthesized by acylation of 2‐amino‐5‐aminopropyl‐6‐methyl‐4‐pyrimidinol (III) with p‐cyanobenzenesulfonyl chloride followed by catalytic reduction and reaction of the resultant aminomethyl group with p‐nitrophenyl bromoacetate. A second irreversible inhibitor of thymidylate synthetase, namely 2‐amino‐5‐[p‐(bromoacetyl)benzene‐sulfonamidopropyl]‐6‐methyl‐4‐pyrimidinol (XVI), was synthesized by acylation of in with p‐acetylbenzenesulfonyl chloride followed by bromination. Both XV and XVI were good reversible inhibitors of thymidylate synthetase and inactivated the enzyme when the candidate compound was incubated with the enzyme. Iodoacetamide, which does not form a complex with enzyme, could inactivate thymidylate synthetase almost as well as XV; therefore it appears that XV inactivated the enzyme by a random bimolecular mechanism rather than by the desired active‐site‐directed mechanism via an enzyme‐inhibitor complex. Similar conclusions were reached with XVI since phenacyl bromide could inactivate the enzyme somewhat more rapidly than XVI.
The synthesis of 5‐ and 6‐hydroxy‐2‐methylisoquinuclidine
Authors: Degraw Joseph I. , Kennedy Jill G.
Published: March 2009

The reduction of the isomeric 5,6‐epoxy‐2‐carboethoxyisoquinuclidines with lithium aluminum hydride afforded 5‐ and 6‐hydroxy‐2‐methylisoquinuclidine. Contrary to expectation essentially single epimers were obtained for each alcohol.
Synthesis of certain tricyclic quinoline derivatives as potential antiamebal agents
Authors: Cannon Joseph G. , Lazaris Spyros A. , Wunderlich Thomas A.
Published: March 2009

Synthesis of the fused tricyclic systems, 1, 2, 3, 3a, 4, 5‐hexahydropyrrolo[1, 2a]quinoline (I) and 2, 3, 4, 4a, 5, 6‐hexahydro 1H‐benzo[c]quinolizine (II), each bearing an ethoxyl substituent on the benzene ring, has been achieved. The compounds combine certain structural features of the alkaloid emetine and of 8‐quinolinols.
The skraup syntheses and NMR spectra of some methylnaphthyridines
Authors: Paudler William W. , Kress Thomas J.
Published: March 2009

Some mono‐ and dimethylnaphthyridines were prepared by the application of the Skraup reaction to various 2‐ and 4‐aminopyridines. The proton magnetic resonance spectral data assignments are reported. The chemical shifts of the methyl protons are calculated.
Structure of the reaction product of chloral hydrate and isocyanic acid
Authors: Loev Bernard , Dudek Gerald
Published: March 2009

In a recent article describing the reactions of isocyanic acid with carbonyl compounds, Hoover, Stevenson, and Rothrock (1) observed that chloral reacted slowly with free isocyanic acid at 0° to give CCl3CH(OH)NCO, m.p. 25°. On stirring with water, this was converted to a solid, m.p. 190‐200°, assigned structure A. This latter substance was also produced by reaction of isocyanic acid directly with chloral hydrate.
The preparation and rearrangement of 2‐allylbenzimidazole
Authors: Raines Stephen , Kovacs Csaba A.
Published: March 2009

This paper reports the preparation of 2‐allylbenzimidazole (I) and the facile migration of its double bond to the known isomeric 2‐propenylbenzimidazole (II). The proposed mechanisms of reactions of this type, involving a prototropic rearrangement, have been thoroughly discussed (1,2).
Cyclic sulfoxides. I. dihydrothiophene 1‐oxides
Authors: Krug Robert C. , Boswell Donald E.
Published: March 2009

Although there have been extensive investigations on cyclic sulfones, especially the unsaturated, 5‐membered ring compounds (3), cyclic sulfoxides have received considerably less attention. In this report, we wish to present a synthesis of the previously unknown dihydrothiophene 1‐oxide isomers and, also, some preliminary results regarding their chemical reactivity (4).
Quinazolines and 1,4‐benzodiazepines XXXVI . The formation of 1,3‐dihydro and 1,5‐dihydro‐1,4‐benzodiazepines from tosyl and Mesyl ‐ substituted 1,3,4,5‐tetrahydro‐5‐phenyl‐ 1,4‐benzodiazepine derivatives
Authors: Ian Fryer R. , Winter D. , Stcrnbach L. H.
Published: March 2009

The treatment of 4‐sulfonyl derivatives of 5‐phenyl‐1,3,4,5‐tetrahydro‐1,4‐benzodiazepin‐2‐ones (I) with base was shown to result in the formation of 1,3‐dihydro or 1,5‐dihydro‐1,4‐benzodiazepin‐2‐ones (III and II respectively) depending upon the conditions used. The base treatment of 1‐sulfonyl substituted 2,3‐dihydro‐1,4‐benzodiazepines (V) was shown to give the vinylimines VI.
Chlorination of isothiocyanates. V . 5‐imino‐1,2,4‐thiadiazolidin‐3‐ones
Authors: Ottmann Gerhard , Hooks Haywood
Published: March 2009

S‐[N'‐ (Chlorocarbonyl)amino]isothiocarbamoyl chlorides (II), obtained from S‐chloroisothiocarbamoyl chlorides (I) and isocyanates, react with primary aliphatic and aromatic amines to form the unknown class of 5‐imino‐1,2,4‐thiadiazolidin‐3‐ones. The structures were confirmed by chemical means and by spectroscopic methods.
Organosilicon compounds III. Silicon‐substituted thiophene derivatives of mercaptoethylamine as possible radioprotective agents
Authors: Thames Shelby F. , Mccleskey Josef E.
Published: March 2009

The preparation of the first organosilicon containing derivatives of mercaptoethylamine as possible radioprotective agents is described. The synthesis of these compounds via the thiazolidine intermediate was chosen due to the known radioprotective action of certain thiazolidines. We have prepared seventeen previously unreported organosilicon derivatives of which eleven contain the thiazolidine moiety and six are derivatives of mercaptoethylamine. The ability of these derivatives to protect against ionizing radiation will be determined.
New synthesis routes to 2‐halopyridines. II. 2‐bromopyridine
Authors: Boudakian Max M. , Gavin David F. , Polak Roger J.
Published: March 2009

The use of bromine chloride (equilibrium mixture) in substitution reactions has been extended to heterocyclic substrates. The vapor phase bromination of pyridine (I) with bromine chloride at temperatures as low as 375° (carbon tetrachloride diluent) gave the following product distribution: 2‐bromopyridine (IV) (75%) > 2‐chloropyridine (VI) (21%) > 3‐bromopyridine (II) (2.0%) ≅ 2,6‐dibromopyridine (VI) (1.5%). In contrast, when bromine was employed in place of bromine chloride (450°; carbon tetrachloride diluent), product orientation was significantly altered to give nearly equal quantities of 3‐bromopyridine (II) (17%) and 2‐bromopyridine (IV) (22.7%).
Pyrolysis of fluorodiazirines
Authors: Mitsch Ronald A. , Neuvar Erwin W. , Ogden Paul H.
Published: March 2009

The thermal decomposition of difluorodiazirine and difluoraminofluorodiazirine results in the formation of difluorocarbene and difluoraminofluorocarbene, respectively. The isolable products of the pyrolyses include fluoro‐alkenes, ‐cyclopropanes, ‐azines, ‐aziridines and in some cases isomerization products thereof.
Synthesis of substituted pyridazino[4,5‐c]pyridazines
Authors: Singerman Gary M. , Castle Raymond N.
Published: March 2009

Several pyridazino[4,5‐c]pyridazines substituted in the 5‐ and 8‐positions with hydroxyl, mercapto and amino groups and in the 3‐position with a methyl group or a hydrogen atom have been prepared. In the course of this work five previously unreported pyridazine derivatives have also been synthesized.
Base catalyzed acylative decarboxylation. Part III. Acylation of homophthalic acid
Authors: Smith Grant Gill , Delong Carol Witte , Wetzel William H. , Muralidharan V. P.
Published: March 2009

Homophthalic acid (I) reacts with acetic anhydride in the presence of base to form the expected product, o‐carboxyphenylacetone (III). Besides III, three other new products were formed, namely, 3‐methyl‐4‐carboxyisocoumarin (II), 4‐acetyl‐3‐methylisocoumarin (IV) and 8‐acetyl‐7‐methylnaphtho[1,2‐c]isocoumarin. A mechanism for the formation of these compounds is presented. The presence of 3‐methyl‐4‐carboxyisocoumarin (II) supports an earlier suggestion (1) that acylation can occur prior to and without decarboxylation, which has been a point of concern in this reaction.
Irreversible enzyme inhibitors. CXI. Candidate active‐site‐directed irreversible inhibitors of dihydrofolic reductase derived from 4,6‐diamino‐1,2‐dihydro‐l‐phenyl‐s‐triazines. V.
Authors: Baker B. R. , Johnson Morris A.
Published: March 2009

Condensation of 5‐(p‐nitrophenyl)‐2‐pentanone with phenylbiguanide hydrochloride (V) gave a 2‐methyl‐2‐(p‐nitrophenylpropyl)‐1,2‐dihydro‐s‐triazine (IX); hydrogenation of the nitro group to amino followed by bromoacetylation afforded the candidate irreversible inhibitor of dihydrofolic reductase, namely, 2‐(p‐bromoacetamidophenylpropyl)‐4,6‐diamino‐1,2‐dihydro‐2‐methyl‐s‐triazine hydrochloride (VIII). Similarly, the o, m, and p‐isomers of 5‐nitrophenoxy‐2‐pentanone were converted to the corresponding 2‐(bromoacetamidophenoxypropyl)‐1,2‐dihydro‐s‐triazines (XI). The four candidate irreversible inhibitors were evaluated on the dihydrofolic reductases from pigeon liver, Walker‐256 rat tumor, and L‐1210/FR8 mouse leukemia. Only VIII was an irreversible inhibitor; VIII slowly inactivated the L‐121‐/FR8 mouse leukemia enzyme with a half‐life of 2–3 hours at 37°, but VIII showed no inactivation of the other two dihydrofolic reductases—a species specific inactivation.
Chlorination of isothiocyanates. VIII. Reaction of S‐chloroisothiocarbamoyl chlorides with aliphatic and cycloaliphatic ketones
Authors: Ottmann G. , Vickers G. D. , Hooks H.
Published: March 2009

Reported is the synthesis of various derivatives of 2‐imino‐5‐chloro‐1,3‐oxathiolanes, 2‐imino‐1,3‐oxathioles and 1,3‐thiazolin‐2‐ones from N‐aryl‐ and N‐alkyl‐S‐chloroisothiocarbamoyl chlorides and ketones.
The synthesis of imidazo[4,5‐c] ‐ and v‐triazolo[4,5‐c] pyridazines
Authors: Murakami Hirotaka , Castle Raymond N.
Published: March 2009

The parent imidazo[4,5‐c]pyridazine (IV) has been prepared for the first time by three different routes. 1‐Methylimidazo[4,5‐c]pyridazine (XX) and 3‐methylimidazo[4,5‐c]pyridazine (XXVII) have been prepared by unequivocal syntheses. The constitution of the methylation product of imidazo[4,5‐c]pyridazine‐2‐thiol (VIII) has been shown to be 2‐methylthioimidazo[4,5‐c]‐pyridazine (IX) by the unequivocal syntheses of 1‐methylimidazo[4,5‐c]pyridazine‐2‐thiol (XXIII) and 3‐methylimidazo[4,5‐c]pyridazine‐2‐thiol (XXXIII). Likewise, the structure of the methylation product (XIII) was shown to be S‐methylation by the unequivocal syntheses of 1‐methyl‐2‐methylthio‐6‐chloroimidazo[4,5‐c]pyridazine (XXIV) and 3‐methyl‐2‐methylthio‐6‐chloroimidazo[4,5‐c]pyridazine (XXXI), respectively. Several 7‐substituted amino‐v‐triazolo‐[4,5‐c]pyridazines (XXXVIII) have been prepared from 7‐chloro‐v‐triazolo[4,5‐c]pyridazine (XXXVII).
1‐Substituted phenothiazine derivatives
Authors: Nealey Richard H. , Driscoll John S.
Published: March 2009

An improved synthesis of phenothiazine‐1‐carboxaldehyde and several new 1‐substituted phenothiazine derivatives are reported. A 1‐substituted thionine dye is described.
4‐Thiazoline‐2‐thiones. IV. Preparation from amino acids
Authors: Lamon R. W. , Humphlett W. J.
Published: March 2009

4‐Thiazoline‐2‐thiones derived from amino acids have been obtained by an improved procedure. Depending on substitution, the type of intermediate product isolated may be a 4‐hydroxythiazolidine‐2‐thione or a dithiocarbamate.
The reaction of benzotriazoles with 3,4‐dihydro‐4H‐pyrane and 2‐acetoxymethyl‐3,4‐dihydro‐2H‐pyrane
Authors: García‐Muñoz G. , Iglesias J. , Lora‐Tamayo M. , Madroñero R. , Stud M.
Published: March 2009

From the reaction of benzotriazoles with 2,3‐dihydro‐4H‐pyrane and 2‐acetoxymethyl‐3,4‐dihydro‐2H‐pyrane the corresponding 1‐(2‐tetrahydropyranyl)benzotriazole and cis‐and trans‐1‐(6‐acetoxymethyl‐2‐tetrahydropyranyl)benzotriazole derivatives were obtained. The structures and conformations of these compounds were confirmed by UV and NMR spectra.
Diazepines. V. The reaction of homophthalic anhydride with hydrazines
Authors: Rosen Gerald , Popp Frank D.
Published: March 2009

The reaction of homophthalic anhydride with hydrazine and a number of substituted hydrazines has been investigated. Only in the case of the reaction of homophthalic anhydride and 1,2‐dimethylhydrazine has a diazepine been isolated. The previously reported (2) diazepine from homophthalic anhydride and hydrazine appears to be a product resulting from the reaction of twomolec of homophthalic anhydride with one mole of hydrazine.
Acylation of purine‐8‐thione and benzimidazole‐2‐thione: A reinvestigation of the site of acylation
Authors: Dyer Elizabeth , Minnier Carl E.
Published: March 2009

Purine‐8‐thione (1) is acylated on nitrogen, not on sulfur as was previously reported. Thus, the reactions of 1 with ethyl chloroformate and with acetic anhydride yield, respectively, ethyl purine‐8‐thione‐9(7)‐carboxylate (3) and 9(7)acetylpurine‐8‐thione (7) as shown by independent synthesis and spectra. In like manner, benzimidazole‐2‐thione (10) reacts with acetic anhydride, ethyl chloroformate, benzoyl chloride, and cyclohexyl isocyanate to yield the corresponding N‐acylated derivatives. In addition, 10yields 1,3‐dibenzoylbenzimidazole‐2‐thione on treatment with 2 equivalents of benzoyl chloride.
The reactions of 2,2‐difluoro‐4‐methylnaphtho[l,2‐e] ‐1,3,2‐dioxaborin and Its [2,1‐e] Isomer with Carbonyl compounds and with Aniline
Authors: Vanallan J. A. , Reynolds G. A.
Published: March 2009

2,2‐Difluoro‐4‐methylnaphtho[l,2‐e]‐l,3,2‐dioxaborin (1) and its [2,1‐e]isomer (2) react with equimolecular quantities of carbonyl compounds, giving colored ethylenic derivatives. With aniline, 1 and 2 give the corresponding oxazaborins 21 and 22. The structures of 1 and 2 are discussed.
Syntheses of benzomorphan and related compounds. Part 1. Synthesis ofN‐substituted‐l,2,3,4,5,6‐hexahydro‐8‐hydroxy‐2,6‐methano‐6,11‐dimethyl‐3‐benzazocine [studies on the syntheses of heterocyclic compounds. Part CCLXXXII ]
Authors: Kametani T. , Kigasawa K. , Hüragi M. , Hayasaka T. , Wagatsuma N. , Wakisaka K.
Published: March 2009

A modified synthesis of pentazocine, l,2,3,4,5,6‐hexahydro‐8‐hydroxy‐2,6‐methano‐6, H‐dimethyl‐3‐(3‐methyl‐2‐butenyl)‐3‐benzazocine (III), has been achieved and catalytic hydro‐genation has been found to be effective for the debenzylation of quaternary ammonium salts.
Ochotensine and related compounds. II. A synthesis of iso‐ochotensine. (Studies on the syntheses of heterocyclic compounds. CCLXXV )
Authors: Kametani T. , Takano S. , Hibino S. , Terui T.
Published: March 2009

In order to examine the total syntheses of ochotensine (1) and ochotensimine (II), one of the isomers, iso‐ochotensine (III), was synthesized as a preliminary experiment. Namely, Wittig reaction of VI, followed by treatment with sodium bicarbonate solution, gave the expected compound, 7‐ethoxycarbonyl‐3‐ethoxycarbonyloxy‐2‐methoxy‐13‐methyIene‐10,11‐methyIene‐dioxyochotensinan (VII) which was reduced with lithium aluminum hydride to give III. This was also obtained by methylation of 3‐hydroxy‐2‐methoxy‐13‐methylene‐10,11‐methyIenedioxy‐ochotensinan (VIII).
Chemistry of thienopyridines. VI. Reaction of hydrogen sulfide with pyridines bearing C2‐groups in the 3‐position
Authors: Klemm L. H. , Mccoy D. R.
Published: March 2009

3‐Substituted pyridines (bearing vinyl, ethyl, α‐hydroxyethyl, and acetyl substituents) react with hydrogen sulfide at 630° to give low yields of thieno[2,3‐b]pyridine and thieno[3,2‐c]‐pyridine. For 3‐vinylpyridine as substrate, it is proposed that a free‐radical process is involved in this synthesis.
Enamine formation from anilines and methyl propiolate. The synthesis of 4(1h)‐quinolones
Authors: Heindel Ned D. , Kennewell Peter D. , Fish Velmer B.
Published: March 2009

The addition of substituted anilines to methyl propiolate produces labile cis‐trans mixtures of enamines which can be isomerized by acid, solvent variation, and thermal techniques. Thermal cyclization of these enamines provides a synthesis of 4( lH)‐quinolones.
The synthesis of lmidazo[4,5‐d] pyridazines. VI. v‐Triazolo[4,5‐d] pyridazines, pyrazino[ 2,3‐d ] pyridazines and 7H‐Imidazo [4,5‐d] tetrazolo[ 1,5‐b] pyridazine
Authors: Martin Stephen F. , Castle Raymond N.
Published: March 2009

Several pyridazines have been prepared as intermediates in the synthesis of monosubstituted imidazo[4,5‐d]pyridazines, monosubstituted v‐triazoIo[4,5‐d]pyridazines and monosubstituted pyrazino [2,3d] pyridazines. The new ring system, 7H‐imidazo[4,5‐d]tetrazolo[l,5‐b] pyridazine (XIV) has been prepared unsubstituted. Furthermore, unsubstituted imidazo[4,5‐d]pyridazine (XI) has been prepared. Calculations for XI and XIV were made by approximate SCF LCAO‐MO with CNSO II theory.
2‐Aminothiophene. Heterocyclization of benzylthionitriles
Authors: Eck David L. , Stacy Gardner W.
Published: March 2009

Synthesis of unstable 2‐aminothiophene by way of its hydrochloride salt has been achieved in excellent yield. The key reaction in the scheme involves a novel heterocyclization of benzylthionitriles, which would appear to have general utility. Spectral and physical properties are tabulated and a possible mechanism is proposed.
Azetidinyl ketone chemistry. C‐Methylation reactions and stereostructure ‐ spectra relationships
Authors: Doomes Earl , Cromwell Norman H.
Published: March 2009

The C‐methylation of the potassium salt of 1‐t‐butyl‐2‐phenyl‐3‐(p‐phenylbenzoyl)azetidine (1a) with methyl iodide was studied in three solvents, and the stereochemical outcome of the reaction was shown to be dependent upon the solvent used. These results are rationalized in terms of the probable relative rates of the reaction in the various solvents and/or the effect of solvent on the structure of the anionic intermediate. Similar treatment of the potassium salt of 1‐t‐butyl‐2‐phenyl‐3‐benzoylazetidine (3a) in ethyl ether gave a comparable result. The configurations of the epimeric C‐methyl products (2a and 2b, and 4a) were assigned on the basis of their spectral properties. With the aid of spectral data for a model compound, l‐t‐butyl‐3‐benzoyl‐azetidine (5), several stereostructure‐spectra relationships for 3‐azetidinyl ketones are presented.
Synthesis of substituted 2‐amino‐3‐cyanodihydrofurans from styrene oxides and malononitrile
Authors: Campaigne E. , Ellis R. L. , Bradford Mary
Published: March 2009

The reaction of styrene oxides with the malononitrile anion leads to the formation of 2‐amino‐3‐eyano‐5‐aryl‐4,5‐dihydrofurans (III), while a similar reaction with β,β‐dimethylstyrene oxides leads to 2‐amino‐3‐cyano‐4‐aryl‐5,5‐dimethyI‐4,5‐dihydrofurans (V). Therefore steric factors may play a significant role in the site of attack of the malononitrile anion on the oxide. Compounds of type V are more conveniently obtained from the cyanolaetones (VI) by rearrangement and dehydration.
Electron bombardment induced fragmentation of substituted oxathiolanes
Authors: Pasto Daniel J.
Published: March 2009

The mass spectral fragmentation patterns of 1,3‐oxathiolane and 2‐, 4‐, and 5‐substituted oxathiolanes have been recorded. The various fragments have been identified by high‐resolution mass spectrometry when appropriate. Of the five possible modes of ring cleavage to produce two‐ and three‐atom fragments only two modes are actually observed. The mode of fragmentation of the 1,3‐oxathiolane ring differs from that proposed for 1,3‐dioxalane and in all probability occurs in multistep processes.
Benzodifurans. I. The synthesis of benzo[1,2‐b:5,4‐b]difuran and some methyl analogs
Authors: Worden Leonard R. , Burgstahler Albert W. , Kaufman Kurt D. , Weis James A. , Schaaf Thomas K.
Published: March 2009

The first parent benzodifuran (XVI) and three di‐ and trimethylated derivatives have been synthesized and screened for erythemal activity (negative response). Two benzodifurans were prepared from resorcinol and 2‐methylresorcinol by acetylation, Fries rearrangement, alkylation of the resulting 4,6‐diacetylresorcinols with ethyl bromoacetate, saponification, and then cyclization of the (4,6‐diacetyl‐1,3‐phenylenedioxy)diacetic acids. Another was prepared from the Claisen rearrangement product of 1,3‐bis(allyloxy)‐2‐methylbenzene by acetylation, bromina‐tion, and cyclization. Ozonolysis of the Claisen rearrangement product gave additional support to the formulation of o‐hydroxyphenylaeetaldehydes as cyclic hemiacetals. The parent benzodifuran was synthesized from 5‐formyI‐6‐hydroxybenzofuran, which was prepared in two steps from 5‐bromo‐6‐methoxybenzofuran. Alkylation of the former with ethyl bromoacetate, saponification, and cyclization furnished benzo[1,2‐b.5,4‐b ]difuran. The ultraviolet and nuclear magnetic resonance spectra of the four benzodifurans are compared.
On 1,2‐benzisoxazole‐3‐acetic acid and 3‐methyl‐1,2‐benzisoxazole: a restatement
Authors: Casini Giovanni , Guallieri Fulvio , Stein Maria L.
Published: March 2009

A compound formulated in the literature as 4‐hydroxylaminocoumarin is now recognized to be the isomeric 1,2‐benzisoxazole‐3‐acetic acid. Therefore, a preceding paper by the authors describing this acid is proved incorrect due to inexact data in the previous literature on the preparation of 3‐methyl‐1,2‐benzisoxazole.
Diazepines. VI. The chemistry of 3,8‐dihalo‐11H‐dibenzo[c,f] [1,2]diazepin‐11‐ones
Authors: Popp Frank D. , Dubois Ronald J. , Casey Adria Catala
Published: March 2009

The carbonyl group in the title compounds undergoes a number of reactions typical of ketones but in general is less reactive than a typical ketone. Reaction with hydrazine leads to reduction of the 5,6‐bond rather than reaction at the carbonyl group. Reduction of the carbonyl group gives rise to a rather inert carbinol. The carbonyl group appears to exert little influence on typical reactions at the 5,6‐position.
Proton magnetic resonance studies of compounds with bridgehead nitrogen atoms. IX Configurational and conformational studies with methyl‐substituted 8‐phenyl‐l,8‐diazabicyclo[4.3.0]nonanes
Authors: Crabb T. A. , Newton R. F.
Published: March 2009

The synthesis of a series of methyl‐substituted 8‐phenyl‐1,8‐diazabicyclo[4.3.0]nonanes is described. The preferred conformations of these compounds have been assigned on the basis of the 2850‐2500 cm−1 region of their infrared spectra and of the geminal coupling constant of the C‐9 methylene group.
Chemical and nuclear magnetic resonance studies of 3,3‐diphenyltetrahydrofuran derivatives
Authors: Portoghese P. S. , Williams D. A.
Published: March 2009

Pyrolytic cyclization of a‐ and β‐methadol methiodides afforded cis and trans isomers of 2‐ethyl‐3,3‐diphenyl‐5‐methyltetrahydrofuran, respectively. Catalytic hydrogenation of 2‐ethyli‐dene‐3,3‐diphenyl‐5‐methyltetrahydrofuran yielded the cis and trans isomers in a 2:1 ratio. The nmr spectra of these and structurally related compounds have been analyzed in terms of a half‐chair conformation for 2‐ethyl‐5‐methyl, 2‐ethyl, and 5‐methyl derivatives. An envelope conformation has been suggested for the compounds containing a double bond at C‐2.
N‐Oxides and S‐oxides of ellipticine analogs
Authors: Fujiwara Allan N. , Acton Edward M. , Goodman Leon
Published: March 2009

Oxidation with perbenzoic acid derivatives in neutral organic solvents of 11‐desmethylellipticine (at the pyrido‐N) and oxa‐ellipticine afforded the corresponding N‐Oxides. Thia‐ellipticine afforded the sulfone N‐oxide, which underwent N‐deoxygenation with triphenylphosphine to yield thia‐ellipticine sulfone.
Electrophilic substitution reactions in 4H‐benzo[d,e,f]carbazole
Authors: Hoellinger H. , Buu‐Hoï N. P. , Mabille Ph.
Published: March 2009

The behavior of 4H‐benzo[d,e,f]earbazole and its N‐aeetyl derivative in various electrophilic substitution reactions (e.g. nitration, nitrosation, bromination, Friedel‐Crafts acylations) has been investigated, and a number of new derivatives of this heterocycle (some of which are to be tested as potential carcinogens and enzyme‐inducers) have been synthesized.
Studies on the syntheses of heterocyclic compounds. Part CCCXV erythrinan and related compounds. II . An alternative synthesis of cis‐16‐hydroxy‐15‐methoxyerythrinan‐8‐one and its mass spectrum
Authors: Kametani T. , Agui H. , Saito K. , Fukumoto K.
Published: March 2009

Phenolic cyclization of 2‐ethoxycarbonylmethylidenecyclohexanone (IV) with 3‐hydroxy‐4‐methoxyphenethylamine (V) were performed in the process of finding a synthetic approach to dihydroerysolidine (I). Thus, 16‐hydroxy‐15‐methoxyerythrinan‐6‐ene‐8‐one (VI) and 16‐hydroxy‐15‐methoxyerythrinan‐7‐ene‐8‐one (VII) were synthesized, both of which were hydrogenated in the presence of Adams platinum to give the same product (XI). Furthermore, on the basis of the mass spectra of XI and XII, these compounds were assumed to be stereoisomeric at the C5‐ and C6‐positions.
Synthesis of phthalimidines. Acid‐catalyzed cyclodehydration versus cyclodeamination of γ‐hydroxyamides obtained from dilithio‐N‐substituted benzamides and ketones
Authors: Mao Chung‐Ling , Barnish I. T. , Hauser Charles R.
Published: March 2009

An earlier method of preparation of γ‐hydroxyamides from N‐substituted benzamides and ketones or aldehydes by means of n‐butyllithium was improved and extended. The γ‐hydroxyamides were found to undergo cyclodehydration to form γ‐lactams with relatively strong acids, but cyclodeamination formed γ‐lactones with relatively weak acids; the γ‐lactams are substituted phthalimidines. The predominant course of cyclization was dependent also on the structure of the γ‐hydroxyamide. Certain γ‐hydroxyamides afforded phthalimidines with cold, concentrated sulfuric acid whereas certain others yielded γ‐lactones with this acid. The latter γ‐hydroxyamides, however, produced phthalimidines with the stronger acid, perchloric acid. The cyclodehydration reaction furnished a convenient and, apparently, quite general method for the synthesis of 2,3,3‐trisubstituted or 2,3‐disubstituted phthalimidines. Mechanisms are considered.
Photo‐elimination of nitrogen from fused‐ring triazoles
Authors: Boyer J. H. , Selvarajan R.
Published: March 2009

By irradiation in methanol at 3000Å, aniline and o‐anisidine were produced from benzo‐triazole and N‐methylaniline and N‐methyl‐o‐anisidine were produced from N‐methylbenzotriazole. Carbazole was the only product detected from similar treatment of N‐phenylbenzotriazole. Linear naphthotriazole was photolytically transformed into β‐naphthylamine but a methoxy derivative could not be found. Angular naphthotriazole gave no identifiable photolytic product. u‐Triazolo[1,5‐α]pyridine underwent photolysis in methanol to give α‐picoline, α‐picolylmethyl ether and α‐picolylmethanol in low yield. A similar photolysis in acetic acid afforded α‐pyridylmethyl acetate. The mechanisms for the formations of products are discussed.
Synthesis of 2,7‐disubstituted‐4,5,9,10‐tetraazapyrenes
Authors: Castle Raymond N. , Guither William D. , Hilbert Peter , Kempter Fritz E. , Patel Natu R.
Published: March 2009

2,7‐Dimethyl‐4,5,9,10‐tetraazapyrene (VI) was synthesized by the catalytic hydrogenation of 4,4′‐dimethyl‐2,2′,6,6′‐tetranitrobiphenyl (IIa) with W‐2 Raney nickel in the presence of alkali. 4,4′‐Dicarbomethoxy‐2,2′,6,6′‐tetranitrobiphenyl (IIc) under similar conditions in neutral medium gave 4,4′‐dicarbomethoxy‐2,2′,6,6′‐tetraaminobiphenyl (IV) which on oxidation gave 2,7‐dicarbomethoxy‐4,5,9,10‐tetraazapyrene (V). 2,7‐Dimethyl‐, 2,7‐dimethoxy‐, and 2,7‐diacetamido‐4,5,9,10‐tetraazapyrene di‐N‐oxides (III a,b,c) were obtained by catalytic reduction of the corresponding 4,4′‐disubstituted‐2,2′,6,6′‐tetranitrobiphenyls with W‐7 Raney nickel in the presence of alkali. Compound VI on oxidation with hydrogen peroxide gave the di‐N‐oxide (IIIa).
Pinacol rearrangement of quinoline analogs of benzopinacol and evidence for rearrangement under the conditions of electron impact
Authors: Brown Ellis V. , Frazer Marshall G.
Published: March 2009

The pinacols, 1,2‐di(2‐quinolyl)‐1,2‐diphenylethane‐1,2‐diol and 1,2‐di(8‐quinolyl)‐1,2‐diphenylethane‐1,2‐diol, were prepared and rearranged. The mass spectrum of the phenyl‐2‐quinolylpinacolone showed fragment peaks corresponding to the pinacolone resulting from 2‐quinolyl migration. The mass spectrum of the phenyl‐8‐quinolylpinacolone showed fragment peaks corresponding to the pinacolone resulting from phenyl migration. Evidence for the rearrangement by electron impact was observed in the mass spectrum of each pinacol.
Ring closure reactions with nitriles. III. Formation of 2‐amino‐ and 2‐oxo‐3‐hydroxyindoles from the reaction of 2′‐aroylacylanilides with cyanide
Authors: Bell Stanley C. , Wei Peter H. L.
Published: March 2009

Treatment of 2′‐aroylhaloacylanilides with potassium cyanide produced quinazolines, carbostyrils, and 3‐hydroxyindoles. From the reaction of 2′‐aroyl‐2,2‐dichloroacetanilides with cyanide, good yields of 2‐amino‐3‐hydroxyindoles were obtained and their reactions were studied.
Synthesis of 2,4‐diamino‐9H‐indeno[2,1‐d]pyrimidines
Authors: Rosowsky Andre , Dey Adrienne S. , Battaglia Josephine , Modest Edward J.
Published: March 2009

As part of a search for new antifolic, antimalarial, and antitumor agents, a series of 2,4‐diamino‐9H‐indeno[2,1‐d]pyrimidines was prepared by condensation of guanidine with substituted 2‐alkoxy‐3‐cyano‐1H‐indenes. Base‐catalyzed cyclization of 1,2‐bis(cyanomethyl)benzenes afforded 2‐amino‐3‐cyano‐1H‐indenes, which were converted into 3‐cyano‐2‐methoxy‐1H‐indenes by acid hydrolysis and treatment of the resultant 1‐cyano‐2‐indanones with diazomethane. Alternatively, 2‐amino‐3‐cyano‐1H‐indenes could be transformed directly into 2‐ethoxy‐3‐eyano‐1H‐indenes by reaction with ethanol and sulfuric acid. The 2,4‐diamino‐9H‐indeno[2,1‐d]‐pyrimidines represent a new type of planar, tricyclic pyrimethamine analog, in which free rotation of the phenyl and pyrimidine rings is prevented by means of a methylene bridge.