bluuebunny/crossref_metadata_2025 huggingface dataset:
5,8‐isoquinolinediones. II. Chemical and electrochemical behavior of the 5,8‐isoquinolinedione system
Authors: Joulliéa Madeleine M. , Puthenpurayil Joseph K.
Published: March 2009

We have devised two general synthetic schemes to 5,8‐isoquinolinediones and have investigated the chemical and electrochemical behavior of these compounds. The 1,4‐addition reactions of these quinones with amines was shown to occur at the 7‐position and a number of 7‐amino‐5,8‐isoquinolinediones. were synthesized. The 1,4‐addition of hydrogen bromide was also studied. The ethylenic double bond of the 5,8‐quinone system underwent Diels‐Alder additions to yield the oxidized forms of the adducts. The nucleophilic displacement of the methoxy group in 7‐methoxy‐5,8‐isoquinoline was accomplished with both potassium hydroxide and morpholine. A Polarographic study of the half‐wave potentials of substituted 5,8‐isoquinolinediones showed a linear correlation between the change in the half‐wave potential of the quinone system (ΔE° 1/2) resulting from the introduction of different substituents, and the substituent constants (σp‐x).
Synthesis of 5‐aryl‐2‐oxazolepropionic acids and analogs. Antiinflammatory agents
Authors: Short Franklin W. , Long Loren M.
Published: March 2009

Condensation of 2‐bromoacetophenones with sodium succinimide gave N‐phenacylsuccinimides (1) which were opened with sodium hydroxide to N‐phenacylsuccinamic acids (2). The latter were cyclized to 5‐aryl‐2‐oxazolepropionic acids (3) in sulfuric acid. Similar cyclization of N‐phenacylphthalamic acid (5) and succinic acid 2‐benzoylhydrazide (7) gave o‐(5‐phenyl‐2‐oxazolyl)benzoic acid (6) and 5‐phenyl‐1,3,4‐oxadiazole‐2‐propionic acid (8). The succinamic acids 2 and the phthalamic acid 5 were observed to recyclize to the corresponding imides (1 and 4) on heating, and the succinic acid hydrazide 7 was similarly cyclized to N‐benzamidosuccinimide (9) with acetic anhydride. Antiinflammatory screening data are reported for 3, 6 and 8.
Synthesis and structure of 5‐oxo‐1‐phenylpyrazoline‐3‐ and 4‐alkanoic acids. Antiinflammatory agents
Authors: Short Franklin W. , Schoeb Ernest J.
Published: March 2009

Condensation of appropriate β‐keto esters with phenylhydrazine gave 5‐oxo‐1‐phenyl‐2‐pyrazoline‐3‐and 4‐alkanoic esters 1 and 3 which were saponified to the corresponding alkanoic acids 2 and 4. Analogous condensation of the same β‐keto esters with hydrazobenzene gave 5‐oxo‐1,2‐diphenyl‐3‐pyrazoline‐3‐and 4‐alkanoic esters 5 and 7 which were similarly converted to acids 6 and 8. The structures of the oxopyrazolines as revealed by their infrared absorption are discussed, and results of their antiinflammatory screening are reported.
The chemistry of a ketene‐sulfur dioxide adduct
Authors: Gomes Ailton De Souza , Joulliéa Madeleine M.
Published: March 2009

We have demonstrated the formation of a reactive species from ketene and sulfur dioxide and have investigated some of its reactions. The 3 + 2 ← 5 cycloaddition reactions of this intermediate with benzylideneaniline and its derivatives gave the corresponding 2,3‐diphenylthiazolidin‐4‐one 1,1‐dioxides. The reduction of 2,3‐diphenylthiazolidin‐4‐one 1,1‐dioxide with lithium aluminum hydride yielded the corresponding thiazolidine. Aniline and its derivatives reacted with the ketene‐sulfur dioxide adduct to give thioaceto‐1,3‐dianilide 3‐oxide. o‐Phenylenediamine gave [2,1,5]benzothiadiazepin‐4‐one 2‐oxide, a derivative of a new ring system, [2,1,5]benzothiadiazepine. o‐Aminophenol yielded [1,2,5]benzothiazepin‐4‐one 2‐oxide.
Application of a thermal rearrangement reaction to questions of structure of condensed dihydrodiazepinones: The reaction of 2,3‐diaminopyridine with ethyl benzoylacetate
Authors: Israel Mervyn , Jones Lynne C.
Published: March 2009

The condensation of an unsymmetrical aromatic diamine with a β‐ketoester can afford two theoretically possible dihydrodiazepinone products, differentiation between which is, at best, difficult and laborious. A recently described (3) rearrangement reaction, whereby dihydrodiazepinones are thermally converted into N‐substituted imidazolones, has now been applied to the elucidation of structures of ambiguous diazepinone derivatives. By means of the thermal rearrangement method, the diazepinone derivative resulting from the reaction of 2,3‐diamino‐pyridine and ethyl benzoylacetate, for which structures 1a and 1b are equally plausible, has been definitively characterized as the 2‐phenyl‐4‐one compound, 1a.
5‐Isoxazolylhydrazines. Reduction of 5‐isoxazolones to isoxazoles
Authors: Adembri G. , Ponticelli F. , Tedeschi P.
Published: March 2009

5‐Isoxazolylhydrazines III were obtained from 5‐isoxazolones I, via the 5‐haloisoxazoles II. The decomposition of the tosyl derivatives of III results in unambigous syntheses of 3,4‐disubstituted isoxazoles.
\documentclass{article}\pagestyle{empty}\begin{document}$ \left[\!\left[ {} \right.\right. $ \end{document}[(Dialkylamino)alkyl]amino\documentclass{article}\pagestyle{empty}\begin{document}$ \left.\left. {} \right]\!\right] $ \end{document}pyrimido[1,2‐a]benzimidazoles,2,3‐dihydro‐1H‐cyclopenta[4,5]pyrimido[1,2‐a]benzimidazoles, and s‐triazolo[1,5‐a]pyrimidines as potential antimalarial agents
Authors: Werbel Leslie M. , Curry Ann , Elslager Edward F. , Hess Carolyn A. , Hutt Marland P. , Youngstrom Carl
Published: March 2009

The structure of the product of the reaction of 2‐aminobenzimidazole with ethyl aceto‐acetate has been established by NMR spectroscopy as 2‐melhylpyrimido[1,2‐a]benzimidazol‐4‐ol (III). 7(and 8)‐Chloro‐2‐methylpyrimido[l,2‐a]benzimidazol‐4‐ol (VI and VIII, R  OH), 2‐(trifluoromethyl)pyrimido[i,2‐a]benzimidazol‐4‐ol (X), 2,7,8‐trimethylpyrimido[1,2‐a]benzimidazol‐4‐ol (XII), 2‐benzyl‐1,2,3,4‐tetrahydropyrido[4′,3′:4,5]pyrimido[1,2‐a]benzimidazol‐12‐ol (XIII), 1,2,3,4‐tetrahydrobenzimidazo[2,1‐b]quinazolin‐12‐ol (XIV), and 2,3‐dihydro‐1H‐cyclopenta[4,5]pyrimido[1,2‐a]benzimidazol‐11‐ol (XV) were prepared in a similar manner. Chlorination of III, VI and VIII, XV, and 5‐methyl‐s‐triazolo[1,5‐a]pyrimidin‐7‐ol (XXV, R  OH) with phosphorus oxychloride afforded the corresponding chloroheterocycles, which were condensed with the appropriate N,N‐dialkylalkylenediamine or Nα,Nα‐diethyl‐6‐methoxytoluene‐α,3‐diamine to give various 4‐\documentclass{article}\pagestyle{empty}\begin{document}$ \left[\!\left[ {} \right.\right. $ \end{document}[(dialkylamino)alkyl]amino\documentclass{article}\pagestyle{empty}\begin{document}$ \left[\!\left[ {} \right.\right. $ \end{document}‐2‐methylpyrimido[1,2‐a]benzimidazoles (Va‐e, VII, IX), 11‐\documentclass{article}\pagestyle{empty}\begin{document}$ \left.\left. {} \right]\!\right] $ \end{document}[(dialkylamino)alkyl]amino\documentclass{article}\pagestyle{empty}\begin{document}$ \left[\!\left[ {} \right.\right. $ \end{document}‐2,3‐dihydro‐1H‐cyclopenta[4,5]‐pyrimido[1,2‐a]benzimidazoles (XVIa and b), and 7‐\documentclass{article}\pagestyle{empty}\begin{document}$ \left[\!\left[ {} \right.\right. $ \end{document}[(dialkylamino)alkyl]amino\documentclass{article}\pagestyle{empty}\begin{document}$ \left.\left. {} \right]\!\right] $ \end{document}‐5‐methyl‐s‐triazolo[1,5‐a]pyrimidines (XXVb‐e). None of these compounds displayed significant antimalarial activity against Plasmodium berghei in the mouse.
Electronolysis of some derivatives of selenochromane
Authors: Buu‐Hoi N. P. , Mangane M. , Périn‐Roussel O. , Renson M. , Ruwet A. , Maréchal M.
Published: March 2009

The mass spectra of 4‐selenochromanone, 4‐hydroxyselenocoumarin, and 3,3′‐methylene bis(4‐hydroxyselenocoumarin) have been determined, and the fragmentation pathways of these substances under electron‐impact are discussed. A strong tendency to form the benzoselenophen ring was noted in all three cases.
A kinetic investigation of the addition of diazomethane to styrenes. Role of dipolar aprotic solvents in predicting direction of dipole orientation
Authors: Kadaba Pankaja K. , Colturi Thomas F.
Published: March 2009

The addition of diazomethane to a series of substituted styrenes has been kinetically investigated with emphasis on polar, solvent, and solvation effects. Although the reaction is generally insensitive to solvent polarity, a sizeable substituent effect (ρ = +0.90) has been observed. Also, a sizeable increase in rate was generally observed in protic solvents such as water, and a considerable rate enhancement occurred in the case of nitrostyrene in the dipolar aprotic solvent, dimethylformamide. The results are discussed in terms of a concerted mechanism involving a partially‐charged transition state II, with negative charge formation on the α‐carbon of the styrene.

The methoxystyrene offers an exception to the Hammett equation and the unexpectedly high rate constant for this compound could be discussed in terms of a possible participation of the highly nucleophilic resonance form of p‐methoxystyrene and an α‐addition via the transition state III. However, solvation effects in dimethylformamide (failure to obtain the anticipated rate increase) and the formation of a 3‐substituted pyrazoline adduct from the cycloaddition reaction indicate steric control to predominate over electronic factors and β‐addition to prevail unequivocally.

It is proposed that solvation effects in protic solvents can be utilized to advantage in cycloaddition reactions leading to 1‐pyrazolines, for which no other routes are available at the present time.
Molecular spectra and molecular structure of heterocyclic compounds. Infrared and near ultraviolet absorption spectra of pyridine N‐oxide derivatives
Authors: Ghersetti S. , Maccagnani G. , Mangini A. , Montanari F.
Published: March 2009

The infrared and ultraviolet spectra of many pyridine N‐oxide derivatives have been studied.

Ultraviolet spectra show a strong solvent effect in going from aprotic to hydroxylic solvents due to strong hydrogen bonding. Values of δ H° for several systems CH3OH/XPyNO in tetra‐chloroethylene solution were evaluated by infrared techniques and a linear correlation δ H° vs. δ v OH has been found.

Features of the infrared and ultraviolet characteristic absorption bands were also investigated.
Some methyl substituted benzo[b]naphtho[2,3‐d]thiophenes
Authors: Campaigne E. , Ashby John , Osborn S. W.
Published: March 2009

Seven benzo[b]naphtho[2,3‐d]thiophenes have been prepared with methyl groups substituted in the 6,7, and 8‐positions. These compounds are structurally related to the sulfur analogs of cholanthrene and methylcholanthrene.
The chemistry of phosphole derivatives
Authors: Hughes A. N. , Srivanavit Chit
Published: March 2009

Synthetic approaches to, and the chemistry of, phospholes, benzophospholes and dibenzophospholes are reviewed and particular attention is paid to the possible aromatic character of the phosphole ring. Systems containing the 2H‐ and 3H‐phosph(V)ole nucleus are surveyed as are phosphole derivatives containing pentacovalent and six‐coordinate phosphorus. Stereochemical considerations in the more complex phosphole derivatives are discussed.
The azomethine nitrene. I. Pyrolysis and photolysis of Δ2 1,2,4‐oxadiazoline‐5‐ones
Authors: Boyer J. H. , Frints P. J. A.
Published: March 2009

Both photolytic and pyrolytic fragmentation of the oxadiazolone ring produces carbon dioxide and a residue which may exist in part as an intermediate azomethine nitrene and may react with or without rearrangement and/or further fragmentation. Rearrangement produces carbodiimides 2 and cyanamides 6. Thermal and photo‐isornerization of carbodiimides into cyanamides provides a key step in an explanation for the formation of the latter from an oxadiazolone. A highly selective cyclization produces a benzimidazole 3 when a suitable aryl subsliluent is at nitrogen. The formation of N‐phenylbenzamidine 7a from 3‐phenyl‐4‐benzyloxadiazolone 5c requires a 1,4‐migration from carbon to nitrogen followed by hydrolysis. The same or similar migration of hydrogen and subsequent ring‐closure with dehydrogenation provides the formation of 2‐phenyl‐quinazoline 8. Products which require no rearrangement of the residue include amidines 7 and triazoles 10. A portion of each triazole corresponds to a nitrile, in turn a product along with a simple nitrene;, of more extensive fragmentation of the; oxadiazolone ring. Phenyl, benzyl, and cyclohexyl nitrenes are respectively detected by the isolation of aniline, benzaldehyde and cyclohexanone. Other recombination reactions bring about the formation of triphenyltriazine 13 and triphenylimidazole 14.
Azonia polycyclic quinones, o‐diazo‐oxides and related products
Authors: Fields D. L. , Miller J. B.
Published: March 2009

4α‐Azoniaanthracene‐5,6‐ and 5,8‐dione salts have been prepared by nitric acid oxidation of their respective diols, and are shown to function as either an electrophilic dienophile or a diene component in Diels‐Alder‐type reactions. Several azonia o‐quinones have been treated with tosylhydrazine in methanol saturated with hydrogen chloride to give unusually stable o‐diazo‐oxides. A four‐step dehydroxylation procedure is detailed for the conversion of .5,6‐dihydroxy‐4α‐azonia‐anthracene salts to new 5‐hydroxy‐4α‐azoniaanthracene salts.
Synthetic studies on mesoionic compounds. The mesoionic 1,3‐diazol‐4‐one system
Authors: Roche E. B. , Stansloski D. W.
Published: March 2009

The synthesis of the mesoionic 1,3‐diazol‐4‐one system is discussed. The intermediate to this system and the attempted cyclizations are described in detail. Further comments on the stability of these mesoionic compounds are also made.
Enzymic phenol oxidation of N‐methylcoclaurine. Studies on the syntheses of heterocyclic compounds. Part cccxxxii
Authors: Kametani Tetsuji , Nemoto Hideo , Kobari T. , Takano Seüchi
Published: March 2009

The enzymic phenol oxidation of N‐methylcoclaurine (111) with homogenized potato peels in the presence of hydrogen peroxide was examined and found to give a mixture of the dimer (VI) and trimer (VII) with C‐O‐C head to tail coupling. Furthermore, the same oxidation of III with homogenized rhizome of Nelumbo nucifera Gartner and hydrogen peroxide was also investigated.
The rearrangement of glycicyl N‐phenylcarbamate
Authors: Farrissey W. J. , Nashu A. Munim
Published: March 2009

The thermal rearrangement of glycicyl N‐phenylcarbamate yields 3‐phenyl‐4‐hydroxymethyl‐2‐oxazolidone and not 3‐phenyl‐5‐hydroxytetrahydro‐1,3‐oxazin‐2‐one as reported previously.
Spectrophotometric determination of the second dissociation constants of the aminoquinolines
Authors: Brown Ellis V. , Plasz Andrew C.
Published: March 2009

The second dissociation constants representing the transition from monocation to dication for all of the isomeric aminoquinolines have been determined as pKa' values. The analogous values for 2‐ and 4‐aminopyridine have been recalculated using a revised HO scale. The accurate determination of the second pKa values follows from measurement, for the first time, of the ultraviolet spectra of all the mono‐ and dications of the aminoquinolines.
Picrylamino‐substituted heterocycles. IV. Pyrazoles
Authors: Coburn Michael D.
Published: March 2009

This paper describes the synthesis of various picryl‐ and picrylamino‐substituted pyrazoles. These compounds were prepared by condensing the appropriate pyrazole or aminopyrazole with a picryl halide or picrylpyrazole. Some of these materials could be nitrated under carefully controlled conditions to the corresponding nitropyrazole derivatives. The products were identified by n.m.r. spectroscopy, and their crystal densities and thermal stabilities were determined. Drop‐weight impact sensitivities were measured for some of the more interesting compounds.
Ferrocene studies. IV. Some furan containing derivatives of ferrocene
Authors: Popp Frank D. , Moynahan E. Bradley
Published: March 2009

The condensation of ferrocenecarboxyhydrazide, ferrocenecarboxaldehyde and acetylferrocene with a number of furan derivatives is reported. The reaction of chalcones containing both the furan and the ferrocene nucleus with Phenylhydrazine and hydrazine proceeds to yield pyrazolines.
A study of some octahydroimidazo[1,5‐a] pyridines. A new example of ring‐chain tautomerism
Authors: Beim Howard J. , Day Allan R.
Published: March 2009

A series of 3‐substituted octahydroimidazo[1,5‐a]pyridines has been prepared. An nmr study at several temperatures showed that 3‐phenyloctahydroimidazo[1,5‐a] pyridine (XIII) and 3‐t‐butyloctahydroimidazo[1,5‐a] pyridine (XIV) exhibited ring‐chain tautomerism. The n‐propyl (X), isopropyl (XI) and benzyl (XII) derivatives did not show this form of isomerism. It has also been shown that Crabb and Newton's statement (3) that Freed and Day (1) had failed to obtain the parent compound, octahydroimidazo[1,5‐a]pyridine (1), is incorrect.
The total synthesis of (±)‐capaurine [studies on the syntheses of heterocyclic compounds. CCCXLVIII ]
Authors: Kametani T. , Iida H. , Kikuchi T. , Honda T. , Ihara M.
Published: March 2009

The total synthesis of (±)‐capaurine (1) confirmed the suggested structure of I.
2‐Phenyl‐5‐(trichloromethyl)‐1,3,4‐oxadiazoles, A new class of antimalarial substances
Authors: Hutt Marland P. , Elslager Edward F. , Werbel Leslie M.
Published: March 2009

An investigation of hybrids of 2,5‐dimethyl‐1,3,4‐oxadiazole (I) and α,α,α,α',α',α'‐hexachloro‐p‐xylene (Hetol®) (II) as potential antimalarial agents led to the synthesis of representative 2‐phenyI‐5‐(trichloromethyl)‐1,3,4‐oxadiazoles (VIa‐f, VIII‐X) and related trichloromethyl 1,2,4‐oxadiazole, 1,3,4‐oxadiazoles, and 1,3,4‐thiadiazole (VII, XIII‐XV). Treatment of the appropriately substituted benzoic: acid hydrazides (IVa‐f) with trichloroacetic anhydride afforded the intermediate 1‐benzoyl‐2‐(triehloroacetyl)hydrazines (Va‐f) which were cyclized to the desired 5‐(chlorophenyl, tolyl, or α,α,α‐trifluorotolyl)‐2‐(trichloromethyl)‐1,3,4‐oxadiazoles (VIa‐f) (44–66%) in situ utilizing phosphorous oxychloride. Chlorination of the 5‐tolyl‐2‐(trichloromethyl)‐1,3,4‐oxadiazoles (VId‐f) afforded 2‐(trichloromethyl)‐5‐(α,α,α‐trichloro‐m‐ and p‐tolyl)‐1,3,4‐oxadiazole (VIII and IX) and 2‐(α,α,α,α',α',α'‐hexachloro‐3,5‐xylyl)‐5‐(trichloromethyl)‐1,3,4‐oxadiazole (X) in 23–56% yield. Each of the 2‐phenyl‐5‐(trichloromethyl)‐1,3,4‐oxadiazoles (VIa‐f, VIII‐X) was active against Plasmodium berghei in mice when administered in single 160 or 640 mg./kg. subcutaneous doses or given orally by drug‐diet for 6 days at doses of 29–336 mg./kg./day. The 2‐(trichloromethyl)‐5‐(α,α,α‐trichlorotolyl)‐1,3,4‐oxadiazoles (VIII‐X) were the most active compounds prepared and exhibited activity against P. berghei comparable with Hetol®. Structure‐activity relationships are discussed.
3H‐Indol‐3‐ols by a novel ring contraction
Authors: Lednicer Daniel , Emmert D. Edward
Published: March 2009

Treatment of α‐hydroxy‐α‐phenyl‐o‐toluidide with phosphorus tribromide afforded a series of 4H‐3,1‐benzoxazines. These last, when reacted with potassium amide in liquid ammonia, ring contracted to 2,3‐disubstituted 3H‐indol‐3‐ols. The scope of this rearrangement was examined. The indolols on treatment with hot base were found to rearrange to indoxyls. Several of these as well as their N‐alkylation products are described.
Bromination of 2,1,3‐benzothiadiazoles
Authors: Pilgram Kurt , Zupan Mike , Skiles Richard
Published: March 2009

The bromination of 2,1,3‐benzothiadiazoles in 47% hydrobromic acid at elevated temperature has led to a general preparative method for the synthesis in high yield of otherwise difficulty accessible brominated 2,1,3‐benzothiadiazoles. The typical addition reaction is apparently eliminated under these reaction conditions and substitution takes place exclusively. Bromination of 2,1,3‐benzothiadiazole occurs successively at positions 4 and 7. 4‐Substituted 2,1,3‐benzothia‐diazoles are selectively brominated at position 7. 5‐Bromo‐ and 5‐methyl‐2,1,3‐benzothiadiazole are brominated consecutively at positions 4 and 7.
Pyrroles and pyrazolines from the ring closure of azines
Authors: Stopfer Christian H. , D'Andrea Richard W.
Published: March 2009

Alkyl substituted pyrroles and pyrazolines are obtained in good yields by catalytic ring closure of azines, using nickel or cobalt (II) halides as catalysts. The specificity of the reaction is determined by the structure of the azines and a notable exception is discussed.
Some N‐substituted 2‐amino‐ and 2‐methylquinoline‐3,4‐dicarboximides
Authors: Campaigne E. , Hutchinson J. H.
Published: March 2009

The reaction of sodium 2‐amino‐3‐cyanoquinoline‐4‐carboxylate and 2‐methyl‐3‐cyanoquino‐line‐4‐carboxylic acid in polyphosphoric acid led to 2‐amino‐ and 2‐methylquinoline‐3,4‐dicar‐boximide, respectively. Both of these compounds undergo imide N‐alkylation reactions with methyl iodide and various chloroalkylaminodialkyl amines, while the latter also condenses with 3,4‐dichlorobenzaldehyde to form styryl derivatives. Although some of these compounds may be considered structural analogs of the antimalarial 4‐quinolinemethanols, none exhibited antimalarial activity.
The NMR spectral characteristics of some meso‐Ionic s‐triazoles
Authors: Smith Richard F. , Deutsch John L. , Almeter Patricia A. , Johnson Donald S. , Roblyer Suzanne M. , Rosenthal Thomas C.
Published: March 2009

The hetero‐ring proton of anhydro‐1,4‐diphenyl‐3‐mercapto‐s‐triazolium hydroxide (I) is more highly deshielded than its 3‐hydroxy analog (II). The chemical shifts of the hetero‐ring proton for compounds I and II were found to be solvent dependent due to hydrogen bond formation. Two series of anhydro‐1,4‐diaryl‐3‐hydroxy‐s‐triazolium hydroxides have been synthesized and their NMR spectra determined. The chemical shift of the hetero‐ring proton of these compounds was found to correlate with the Hammett sigma constants of the meta‐ and para‐ substituents in the aryl groups.
The crystal and molecular structure of 1,1,4,4‐tetraethyl‐2,5‐dimethyl‐1,4‐diphosphoniacyclohexadiene‐1,4‐dibromide
Authors: Towns R. L. R. , Majeste R. , Brown J. N. , Trefonas L. M.
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 (P21/c) with two molecules per unit cell. Least‐squared lattice parameters are: a = 7.164 ± 0.001Å, b = 14.770 ± 0.001Å, c = 10.562 ± 0.001Å, and β = 124.95 ± 0.01°. The structure parameters refined to a value of R=0.062, excluding hydrogens, for the 1475 statistically significant reflections. The structure determination confirmed that the compound is indeed a diene and not a delocalized structure. The ring is planar but the ethyl groups extend over the ring in an unusual crab‐like fashion.
Mass spectral fragmentation mechanisms of some dibenzo[c,f][1,2] diazepines
Authors: Casey Adria C. , Green James H. , Lee Agnes , Mautner Michael
Published: March 2009

The fragmentation mechanisms of 11H‐dibenzo[c,f][1,2]diazepine (I), its 3,8‐dichloro derivative (II), 3,8‐dichlorodibenzo[c,f] [1,2]diazepin‐11‐one (III) and 3,8‐dichloro‐11H‐dibenzo‐[c,f][1,2]diazepin‐N‐oxide (IV) are discussed. The initial loss of molecular nitrogen is characteristic of I, II and III. Compound IV has a strong molecular ion, that competitively eliminates cither NO or Cl‐ and N2O. The common radical ion, m/166 e present in the mass spectra of I, fluorene, 2‐methyl‐9,10‐anthraquinone and 2‐methylbenzo[c]cinnoline, appears to be formed in different states.
Cyclophosphamides from aminosugars and aminonucleosides
Authors: Fujiwara Allan N. , Acton Edward M. , Goodman Leon
Published: March 2009

Condensation of bis‐(2‐chloroethyl)phosphoramidic dichloride with 3′‐amino‐3′‐deoxy‐N,N‐dimethyladenosine afforded the 2′,3′‐cyclicphosphorodiamidate (III). By an improved synthesis, methyl 3‐amino‐3‐deoxy‐β‐D‐ribofuranoside was obtained as a model compound for conversion to the analogous 2,3‐cyclicphosphorodiamidate (XII). Existence of the latter as two diastereomers due to phosphorus asymmetry was shown by nmr analysis, using comparison with the 5‐(O‐p‐nitrobenzoate) (XIII) as a basis for assignments.
The molecular structure of 1,1‐dimethyl‐3‐phenylpyrazolium‐5‐oxide
Authors: De Camp Wilson H. , Stewart James M.
Published: March 2009

The molecular structure of 1,1‐dimethyl‐3‐phenylpyrazolium‐5‐oxide has been determined by a single crystal x‐ray diffraction study. The crystals are monoclinic, space group P21/a, with unit cell dimensions a = 12.630 (5) Å, b = 6.644 (1) Å, c = 12.486 (5) Å, β = 99.17 (2)°. The final R value was 0.049 for 2930 reflections. The bond lengths and angles suggest that a significant contribution to the structure is made by a resonance form in which one of the ring bonds does not exist. No close intermolecular approaches were found.
Intramolecular cyclization of N′‐chloroacetylsalicylhydrazide
Authors: Gaozza C. H. , Lamdan S.
Published: March 2009

Treatment of N′‐chloroacetylsalicylhydrazide (I) with sodium hydroxide in dimethylformamide produces an intramolecular cyclization. Of all theoretically possible reactions, only one proceeds to give 5,6‐dihydro‐2‐o‐hydroxyphenyl‐4H‐1,3,4‐oxadiazin‐5‐one (II). No formation of the 1,4,5‐benzoxadiazocin‐3,6‐dione (III) is detected. The structure of II, as well as of its acetylation, methylation and hydrolysis derivatives are discussed.
P.M.R. analysis of several phosphorylated aziridines
Authors: Berlin K. Darrell , Rengaraju S. , Clark Peter E.
Published: March 2009

Several new phosphorylated aziridines of related structure were prepared. P.m.r. analysis via decoupling experiments provided cis H‐H, trans H‐H, gem H‐H and PNCH coupling values. Similar to simple aziridines, the cis H‐H coupling is larger than trans H‐H coupling (on vicinal ring carbons) which in turn is larger than gem H‐H coupling. In one example operating at 100 MHz and 0° it was possible to detect the presence of two invertomers.
5H‐Thiazolo [3,2‐b]‐ and 2H‐Thiazolo [2,3‐c]‐as‐triazines
Authors: Trepanier Donald L. , Krieger Paul E.
Published: March 2009

Derivatives of the 5H‐thiazolo[3,2‐b]‐ and 2H‐thiazolo[2,3‐c]‐as‐triazine systems were synthesized via condensation of tetrahydro‐I‐methyl‐as‐triazine‐3(2H)‐thione with ethylene dibromide and ethyl bromoacetate, respectively. An hypothesis is given for the formation of the [3,2‐b] system in one of these reactions and the [2,3‐c] system in the other. Structure proof was accomplished by an unequivocal synthesis of one of the [2,3‐c] derivatives.
Syntheses of N‐(2,4‐Dinitrophenyl)nitroazoles
Authors: Khan Misbahul Ain , Lynch Brian M.
Published: March 2009

Several N‐(2,4‐dinitrophenyl)nitroazoles which cannot be obtained by direct nitration of N‐phenylazoles have been prepared by condensation of 2,4‐dinitrofluorobenzene with the appropriate nitroazoles. The structures of the products are assigned on the basis of their proton magnetic resonance spectra; in all the examples studied, condensations occur at positions remote from the nitro group of the nitroazole.
Heterocyclic N‐Glycosides. VI. The reaction of glycosyl azides with propiolic acid and methyl propiolate
Authors: Alonso G. , Garcia‐López M. T. , Garcia‐Muñoz G. , Madroñero R. , Rico M.
Published: March 2009

The synthesis of a series of N‐glycosyl‐v‐triazoles has been accomplished by the 1,3‐dipolar cycloaddition of several glycosyl azides to methyl propiolate and propiolic acid. In most of the cases the two isomeric v‐triazoles were obtained. Structural and anomeric configuration assignments for the N‐glycosides obtained were made on the basis of NMR data. None of the compounds possessed appreciable biological activity against HeLa cells in culture and mouse Sarcoma 180.
The amidoalkylation of aromatic compounds and olefins with 5‐alkoxyhydantoins
Authors: Ben‐Ishai D. , Ben‐Et G. , Warshawsky A.
Published: March 2009

5‐Butoxyhydantoin (2a), 3‐benzyl‐5‐methoxyhydantoin (2b) and 3‐p‐chlorophenyl‐5‐methoxy hydantoin (2c) were found to react, in the presence of an acid catalyst, with aromatic compounds and olefins to give 5‐arylhydantoin (3) and 5‐alkylhydantoins with an unsaturated side chain. Isomers which differ in the location of the double bond (4,5,6) as well as cis‐trans isomers were isolated and characterized.
The crystal and molecular structure of 1‐(p‐iodobenzenesulfonyl)‐1‐azaspiro[2,5] octane
Authors: Zacharis H. M. , Trefonas L. M.
Published: March 2009

The structure of 1‐(p‐iodobenzenesulfonyl)‐1‐azaspiro[2.5]octane was determined by a single‐crystal x‐ray diffraction study. The compound crystallizes in the orthorhombic space group P21 21 21 with cell dimensions: a = 11.655, b = 11.825, c = 11.068 ± 0.002 Å. The aziridine ring is spiro‐fused to the cyclohexane ring with the nitrogen atom occupying the equatorial position. The cyclohexane ring is in an undistorted chair conformation and forms a dihedral angle of 97.1° with the aziridine ring. The structure was refined to a final value of R = 0.074 for the 590 independent reflections.
The crystal and molecular structure of 9‐(p‐lodophenyl)‐9‐azatetracyclo[5.3.1.02,6 .08,10] undec‐4‐ene
Authors: Brown J. N. , Towns R. L. R. , Trefonas L. M.
Published: March 2009

The crystal and molecular structure of 9‐(p‐iodophenyl)‐9‐azatetracyclo[5.3.1.02,6 .08,10]‐undec‐4‐ene (C16H16IN) has been determined by single crystal x‐ray diffraction methods. The compound crystallizes in space group P21, (no. 4) with unit cell constants: a = 11.269 (1), b = 7.607 (1), c = 16.714 (1) Å, β = 104.73 (1)°. The structure was solved by the heavy‐atom method and refined by block‐diagonal least‐squares to a final R‐value of 0.054 for the 1546 independently measured, statistically significant reflections. The aziridine ring is fused to the norbornyl rather than to the five‐membered ring as previously assumed. The nitrogen to phenyl‐carbon distance is 1.406 Å and indicates a significant amount of double bond character.
The synthesis and PMR study of certain 3‐substituted 2‐(β‐D‐Ribofuranosyl)indazoles
Authors: Revankar Ganapathi R. , Townsend Leroy B.
Published: March 2009

The synthesis of 3‐cyano‐2‐(β‐D‐ribofuranosyl)indazole (4) has been accomplished by a condensation of N‐trimethylsilyl‐3‐cyanoindazole (1) with 2,3,5‐tri‐O‐aeetyl‐D‐ribofuranosyl bromide (2) followed by subsequent deacetylation. The reactivity of the 3‐cyano group was demonstrated by the conversion of 4 to 2‐(β‐D‐ribofuranosyl)indazole‐3‐carboxamide (5) and 2‐(β‐D‐ribofuranosyl)indazole‐3‐thiocarboxamide (6). The site of ribosylation and the assignment of anomeric configuration for 4 is discussed. The magnetic anisotropy effect of the exocyclic group at C3 on the anomeric proton as determined by pmr spectroscopy is discussed.
Condensed thiophenes from sulfur bridging. I. Phenanthro[4,5‐bcd]thiophene
Authors: Klemm L. H. , Mccoy D. R. , Olson D. R.
Published: March 2009

Treatment of phenanthrene with hydrogen sulfide and an alumina catalyst at 630° gives phenthro[4,5‐bcd]thiophene (XVII). Spectral properties of XVII, its sulfoxide, and its sulfone are presented. Other examples of the direct insertion of a sulfur bridging atom into an aromatic molecule are reviewed.
Reactions of some 4‐dicyanomethylenepyran derivatives with malononitrile and hydrazines
Authors: Vanallan J. A. , Petropoulos C. C. , Reynolds G. A. , Maier D. P.
Published: March 2009

4‐Dicyanomethylene‐2‐phenyl‐4H‐benzo[b]pyran, the corresponding thiapyran, and 4‐dicyanomethylene‐2,6‐diphenyl‐4H‐pyran react with malononilrile under basic conditions to give 5‐amino‐4‐cyano‐2‐phenylbenzo[b]pyrano[4,3,2‐de] [1,6]naphthyridine, the corresponding thia‐pyranonaphthyridine derivative, and 5‐amino‐6‐cyano‐2,8‐diphenylpyrano[4,3,2‐de] [1,6]naphthyridine, respectively. Certain other related reactions were studied in the course of investigating the above reactions. Hydrazine hydrate and 4‐dicyanomethylene‐2‐phenyl‐4H‐benzo[b]pyran gave 5‐(2‐hydroxyphenyl)‐3‐phenylpyrazole, and phenylhydrazine gave 5‐(2‐hydroxyphenyl)‐1,3‐diphenylpyrazole.
A new route to 2‐styrylbenzimidazoles
Authors: Balazs Marjorie K. , Furst Arthur
Published: March 2009

An attempt was made to prepare 2‐benzylquinoxalin‐3‐one by hydrolyzing the azlactone, 2‐phenyl‐4‐benzylidene‐5‐oxazolone to β‐phenylpyruvic acid and then treating this in situ with o‐phenylenediamine (OPDA). The initial hydrolysis apparantly proceeded only as far as opening the azlactone ring forming 2‐benzamidocinnamic acid which condensed with OPDA to form a substituted styrylbenzimidazole.
6‐Aryl‐1‐azabicyclo [5.4.0] undecanes
Authors: Aboul‐Enein M. Nabil , Sam J.
Published: March 2009

Some 6‐aryl‐6‐hydroxy‐l‐azabicyclo[5.4.0]undecanes and their esters were synthesized as potential cardiovascular agents and analgetics of the proheptazine type, respectively. Also, 6‐aryl‐1‐azabicyclo[5.4.0]undecanes were prepared as rigid structures related to the phenethylamine CNS stimulants.
3‐Methylpyrazolo [1,2‐a] pyridazin‐1‐one. Selenium derivatives of 5,8‐dihydropyrazolo[1,2‐a]pyridazine
Authors: Farnum Donald G. , Au Andrew T. , Rasheed Khalid
Published: March 2009

The dehydrogenation of the known 3‐methyl‐5,8‐dihydropyrazolo[1,2‐a]pyridazin‐1‐one (2) to the ten π electron heteroaromatic 3‐methylpyrazolo[1,2‐a]pyridazin‐1‐one (3) is reported. Conversions of the pyrazolone 2 to the pyrazoloselenone 6 via the chloropyrazolium chloride 7, and of pyrazolones 2 and 3 and pyrazoloselenone 6 into the corresponding O or Se ethyl pyrazolium fluoroborates 5, 4, and 8 by triethyloxonium fluoroborate are also described.
Chemical constitution and activity of bipyridylium herbicides. Part VII. 6‐Substituted derivatives of 6,7‐dihydrodipyrido[1,2‐a:2′,1′‐c] pyrazinediium dibromide (diquat) and dipyrido[1.,2‐a:2′,1′‐c] pyrazinediium dibromide
Authors: Black A. L. , Summers L. A.
Published: March 2009

6‐Methyl, 6,6‐dimethyl‐, and 6‐phenyl‐6,7‐dihydrodipyrido[1,2‐a:2, 1 ‐c]pyrazinediium dibro‐mides are reversible one electron transfer systems with similar redox potentials to diquat dibromide. They are respectively about one‐half, one‐fourteenth and one‐fiftieth as active as diquat as post‐emergent herbicides and this finding illustrates the importance of molecular size in determining whether bipyridylium salts have outstanding phytotoxic activity. This conclusion is supported by a study of 6‐methyl‐ and 6‐phenyldipyrido[1,2‐a:2′,1 ‐c]pyrazinediium dibromides.
Structural modification studies of 3‐piperonylsydnone. III. Some analogs of 3‐piperonylsydnone and 2,4‐diamino‐5‐piperonylpyrimidine
Authors: Mccaustland Daniel J. , Burton William H. , Cheng C. C.
Published: March 2009

In a continued structural modification study of the antimalarial compounds 3‐piperonylsydnone and 2,4‐diamino‐5‐piperonylpyrimidine, the related piperonyl derivatives of ψ‐1,2,3;4‐oxatriazole, ψ‐1,3,5‐oxadiazole, pyrazole, tetrazole, 1,2,4‐triazine, pyrrolidine, amino‐ and sulfamoyl‐1,2,4‐triazole, as well as some sydnones and diaminopyrimidines with side chains other than the piperonyl group have been synthesized. 3‐(3,4‐Ethylenedioxyphenyl)sydnone was found to double the survival time of Plasmodium berghei infected mice. The other compounds are not as active.
Mass spectra of pyrazine N‐oxides. Studies on pyrazine derivatives. III
Authors: Uchimaru F. , Okada S. , Kosasayama A. , Konno T.
Published: March 2009

The mass spectra of pyrazine 4‐ and 1‐oxides, their di‐N‐oxides and corresponding pyrazines have been determined. The fragmentations induced by electron impact were examined by means of deuterium labeling and high‐resolution measurements. The most pronounced feature of the spectra was the appearance of M‐16 ion peaks. In the case of the methyl and methoxy derivatives of 1‐oxides, the intensity ratio of M‐17/M‐16 was larger than in the 4‐oxides.
Base‐ and acid‐catalyzed condensation reactions of reissert compounds with vinylpyridines
Authors: Giridhar Vaidyanath , Mcewen William E.
Published: March 2009

The hydrochloric acid‐catalyzed condensation of 2‐p‐anisoyl‐1,2‐dihydroisoquinaldonitrile (3) with 2‐vinylpyridine gave 2‐(1‐isoquinolyl)‐3‐(2‐pyridyl)‐5‐p‐anisylpyrrole (4), and the corresponding reaction of 3 with 4‐vinylpyridine afforded 2‐(1‐isoquinolyl)‐3‐(4‐pyridyl)‐5‐p‐anisylpyrrole (5). The condensation of the lithium salt of 3 with 4‐vinylpyridine gave α‐(4‐pyridyl)‐β‐(1‐iso‐quinolyl)‐p‐methoxypropiophenone (10), which was cyclized to 2‐(4‐pyridyl)‐3‐p‐anisylpyrrolo‐[2,1‐a]isoquinoline (7) by the action of concentrated hydrochloric acid. 2‐(4‐Pyridyl)‐3‐phenyl‐pyrrolo[2,1‐a]isoquinoline (6) and 2‐(2‐pyridyl)‐3‐p‐anisylpyrrolo[2,1‐a]isoquinoline (8) were prepared by analogous sequences of reactions.
Geometrical isomorism of ethyl N‐(pyrimidinyl) aminomethylenceyanoacetates
Authors: Nishigaki Sadao , Ogiwara Kazuko , Yoneda Fumio
Published: March 2009

The geometrical isomers of ethyl N‐(Pyrimidinyl)a minomethylenecy anoacetates were isolated and their structures and interconversions are discussed.
Mass spectra of some 2‐, 3‐, and 4‐pyridinecarboxylic acids. Further evidence of a N‐H interaction for loss of carbon dioxide
Authors: Brown Ellis V. , Moser Russell J.
Published: March 2009

Mass spectra of 3‐acetamido‐, 3‐methoxy‐, and 4‐methoxy‐2‐pyridinecarboxylic acids, 2,6‐pyridinedicarboxylic acid, 4‐nitro‐2‐pyridinecarboxylic acid N‐oxide, 2‐chloro‐ and 2‐nitro‐x‐pyridinecarboxylic acids (X = 3 and 5), 2‐chloro‐ and 2‐nitro‐4‐pyridinecarboxylic acids, and 4‐pyridinecarboxylic acid are reported. The 2‐pyridinecarboxylic acids lost carbon dioxide (M‐44) as has been reported. The 3‐pyridinecarboxylic acids showed no definite trend in fragmentation; however, the 4‐pyridinecarboxylic acids lost OH (M‐17) first. This change in fragmentation pat‐tern is due to an interaction of the ring nitrogen and carboxyl group in the 2‐pyridinecarboxylic acids which is not present in the 4‐pyridinecarboxylic acids.
Mass spectra of bithiophthalide and related compounds
Authors: Koch Charks W. , Markgraf I. Hodge
Published: March 2009

High resolution mass spectra of biphlhalidu (1), bithiophthalide (2), and thioindigo (3) were investigated and the major fragmentation patterns were elucidated. The simultaneous loss of two sulfur atoms from the molecular ion of 2 was particularly noteworthy.
1,2,3,5‐Tetrahydro‐4H‐1,5‐benzodiazepin‐4‐ones and 1,2,3,4‐tetrahydro‐5H‐1,4‐benzodiazepin‐5‐ones from the reaction of hydrazoic acid on 1,2,3,4‐tetrahydroquinolin‐4‐ones
Authors: Misiti D. , Gatta F. , Landi‐Vittory R.
Published: March 2009

The Schmidt reaction on 1,2,3,4‐telrahydroquinolin‐4‐ones (1) gave 1,2,3,5‐telrahydro‐l,5‐benzodiazepin‐4‐ones (II) and 1,2,3,4‐tetrahydro‐1,4‐benzodiazepin‐5)‐ones(III). The ratio of II and III is dependent upon substituents present on the nitrogen ring atom of the quinolinones.
Preparation of 3,4‐dihydro‐2H‐1,3‐benzoxazines
Authors: Gaines Jack R. , Swanson Alan W.
Published: March 2009

N,N‐Di(butoxymethyl)alkylamines react with phenols under mild conditions to yield substituted 3,4‐dihydro‐2H‐l,3‐benzoxazines.
Azetidinyl ketones. Synthesis of 1‐Alkyl‐2,4‐diphenyl‐3‐benzoylazetidines
Authors: Stevens Michael Fred , Cromwell Norman H.
Published: March 2009

α‐(α'‐Bromobenzyl)chalcone (3) reacts with primary amines (t‐butyl, isopropyl,cyclohexyl) to give α‐(α'‐alkylaminobenzyl)chalcones (4, 5 and 6). When these allylic amines are treated with hydrogen bromide followed by reaction with base, they produce l‐alkyl‐2,4‐diphenyl‐3‐benzoyl‐azetidines (7,8 and 9). These azetidines were readily converted to their 3‐deuterio derivatives (10, 11 and 12) by treatment with sodium methoxide in deuteriomethanol. The configurations were assigned primarily by pmr spectra and mass spectra in reference to analogous compounds.
Reactions of 4‐dicyanomethylenepyrans with hindered primary amines
Authors: Vanallan J. A. , Reynolds G. A.
Published: March 2009

The reaction of 2,6‐dimethyl‐ and 2,6‐diphenyl‐4‐dicyanomethylene‐4H‐pyran with hindered primary amines such as isopropylamine and cyclohexylamine gave 1‐alkyl‐2‐amino‐3‐cyano‐6‐rnethyl(or phenyl)‐4‐acetonylidene (or phenacylidene)‐1,4‐dihydropyridine derivatives. The 6‐methyl‐4‐acetonylidene examples underwent a facile thermal rearrangement to give 1‐alkyl‐2,6‐dimethyl‐4‐dicy anomethy lene‐1,4‐dihydropy ridines. Several reactions of the acylidene derivatives are described.
On the reaction between coumarins and hydroxylamine
Authors: Giannella Mario , Gualtieri Fulvio , Stein Maria Luisa
Published: March 2009

The Posner reaction between coumarin and hydroxylamine was studied and extended to several substituted coumarins. Isolation of some significant reaction intermediates permitted rationalization of a possible reaction pathway.
Reactions of aziridines. Preparation and properties of 2‐thiazolinium salts
Authors: Westland Roger D. , Lin May H. , Vandenbelt J. M.
Published: March 2009

Reaction of 1‐substituted aziridines with thioamides in the presence of perchloric acid has provided a facile route to 2‐thiazolinium salts. Thioformamide was used in this reaction to give the 2‐unsubstituted 2‐thiazolinium salts 3‐[4‐(2,6‐xylyloxy)butyl]‐2‐thiazolinium perchlorate (11a) and 3‐(2‐cyelohexylbutyl)‐2‐thiazolinium perchlorate (IIc). A study of the rates of hydro‐lytic breakdown of IIc and 3‐(2‐cyelohexylbutyl)‐2‐methyl‐2‐thiazolinium perchlorate (IId) showed that the 2‐unsubstituted compound (IIc) was considerably less stable than the 2‐methyl analog (IId) over the entire pH range. Use of 1‐substituted aziridines in ring‐opening reactions, previously applied only to 1‐unsubstituted aziridines, has given expected products when thio‐cyanate ion or thiourea was the nucleophile.
The synthesis of 1,2,5‐thiadiazolo[3,4‐d] pyridazines
Authors: Pichler Don , Castle Raymond N.
Published: March 2009

A number of previously unreported 1,2,5‐thiadiazolo[3,4‐d]pyridazines in this relatively unexplored ring system have been reported, charaeterized and screened for antibacterial and antifungal activity.
Studies on the syntheses of azole derivatives. Part VII. Syntheses of 1 ‐phenyl‐Δ2‐1,2,4‐triazolin‐5‐one derivatives [studies on the syntheses of heteroeyclic compounds. CD XI]
Authors: Kamatani Tetsuji , Shibuya Shiroshi , Shio Mamhisa
Published: March 2009

Bromination of 3‐methyl‐1‐phenyl‐Δ2‐1,2,3‐lriazolin‐5‐one (II) and its 4‐phenyl derivative III afforded the corresponding I‐(p‐Bromophenyl) derivatives IV and V, respectively. (Chlorination of the 4‐phenyl derivative III gave I‐(P‐chlorophenyl) derivative VI. In addition, 3‐N‐subsuituted‐carhamoyl‐1,2,4‐triazolin‐5‐ones(XII, XIII, and XIV) were synthesized by the Schotten‐Baumann reaction of 3‐carboxy‐1‐phenyl‐Δ2‐1,2,4‐triazolin‐5‐one (XI) with various amines.
Carbenes in sulfur and nitrogen heterocycles: A π‐electron‐scf‐mo study
Authors: Sorensen Herbert C. , Ingraham Lloyd L.
Published: March 2009

The properties of a lone pair carbon orbital have been assessed in the context of self consistent field molecular orbital theory. An improved parameter for sulfur is presented as well as a derivation of “carbene” type parameters. The relative effects of adjacent nitrogen and/or sulfur on a carbene have been predicted and compared to experiment. Special reference has been made to the biological systems of thiamine and anhydroleucovorin.
Ring closures from eneearbamoyl azides. Syntheses of tetrahydro‐3‐indazolinones and 4‐imidazolin‐2‐ones
Authors: Chupp John P.
Published: March 2009

Reaction of phosgene with cyclohexylidene amines gives good yields of (1‐eyclohexen‐l‐yl)‐carbamoyl chlorides (1). Compound 1 can be converted to the corresponding eneearbamoyl azide (2), which on pyrolysis gives an improved synthesis of 1‐substituted‐4,5,6,7‐tetrahydro‐3‐indazolinones (7). When 1 is substituted by an allylic rather than alkyl or aryl group, the major products are 4‐imidazolin‐2‐ones (8) accompanied by only minor amounts of 7. The thermolysis reaction has been extended to N‐allylcarbamoyl azides in general, thus providing a new and facile synthesis for 1,4‐disubstituted 4‐imidazolin‐2‐ones (9). A tentative mechanism is advanced, involving intermediate azide addition to the allylic double bond.
Isothiazoles II: 5‐chloro‐4‐isothiazolin‐3‐ones
Authors: Miller G. A. , Weiler E. D. , Hausman M.
Published: March 2009

Quantitative gas chromatographic analysis of the 3‐hydroxyisothiazole product distributions formed in the chlorine induced cyclization of 3,3′ ‐dithiodipropionamide and 3‐mercaptopropion‐arnide has led to reaction conditions which yield respectively 3‐hydroxyisothiazole, 5‐chloro‐3‐hydroxyisothiazole, or 4,5‐dichloro‐3‐hydroxyisothiazole as the predominant product. The 4‐chloro analog was found in only small quantity. Similar glc analysis of the cyclization of N,N′‐dimethyl‐3,3′‐dilhiodipropionamide showed 5‐ehloro‐2‐methyl‐4‐isothiazolin‐3‐one to he the major 4‐isothiazolin‐3‐one product under varied conditions. Also, a representative series of 5‐chloro‐2‐subtiuted‐4‐isohiazolin‐3‐oncs were prepared under extrapolated reaction conditions.
Isothiazoles IV: 4‐isothiazolin‐3‐one i‐oxide and 1,1‐dioxides
Authors: Lewis S. N. , Miller G. A. , Hausman M. , Szamborski E. C.
Published: March 2009

Representative 4‐isothiazolin‐3‐one I‐oxides and I, I‐dioxides have been prepared by the reaction of m‐chloroperbenzoic acid with the respective 4‐isothiazolin‐3‐ones. Chromic acid, dinitrogen tetroxide, and nitric acid have also been successfully employed in the oxidation of several 3‐hydroxyisothiazoles to their respective I‐oxides.
Reactions of tetrahydro‐as‐triazine‐3(2H)‐thiories with α, β‐difunctional compounds
Authors: Trepanier Donald L. , Krieger Paul E.
Published: March 2009

The results of allowing tetrahydro‐as‐triazine‐3(2H)‐thiones to react with various α,β‐diiunctional compounds, such as, α‐bromoethyl p‐toluenesulfonate, chloroacetaldehyde, α‐bromophenylacet‐uldehyde, phenaeyl bromide, chloroacetonitrile, α‐bromophenylaeelonitrile, and α‐cyanobenzyl p‐toluenesulfonate are discussed. These condensations give either a 5H‐thiazolo[3,2‐b]‐as‐triazine or a 2H‐thiazolo[2,3‐c]‐as‐triazine.
An investigation of the minimal structural conditions lor the dirnroth‐type rearrangement in the polyazaindolizine series
Authors: Guerret Patrick , Jacquier Robert , Maury Georges
Published: March 2009

In the imidazo[1,2]diazine series, only the imidazo[1,2‐a]‐ and [1,2‐c] pyrimidine systems were found to undergo a Dimroth‐type rearrangement under basic aqueous conditions. The electronic and steric factors influencing the rearrangement rates of methyl substituted imidazo‐[1,2‐a] pyrimidines are discussed.
Purine N‐oxides: XXXVII. Derivatives from 6‐chloropurine 3‐oxide
Authors: Giner‐Sorolla Alfredo
Published: March 2009

Interaction of 6‐chloropurine 3‐oxide with several amines led to 6‐substituted purine 3‐oxides. 6‐Chloropurine 3‐oxide and selenourea gave 6‐selenopurine 3‐oxide. 6‐Mereaptopurine 3‐oxide, prepared from the 6‐chloro derivative and ammonium dithioearbonate, was transformed with chlorine and hydrogen fluoride into 6‐purinesulfonyl fluoride 3‐oxide which upon ammonolysis afforded purine‐6‐sulfonamide 3‐oxide. Methanelhiol and 6‐ehloropurint: 3‐oxide yielded the known 6‐methylthiopurine 3‐oxide, which by treatment with chlorine was oxidized to 6‐methyl‐sulfonylpurine 3‐oxide. Reaction of the latter with hydroxylamine led to an improved synthesis of 6‐hydroxylaminopurine 3‐oxide, which by interaction with manganese dioxide was transformed into 6‐nitrosopurine 3‐oxide.
2‐Aryl‐4(3H)quinazolinones
Authors: Pater Richard
Published: March 2009

Reaction of isatoic anhydride with benzamides is shown to produce 2‐aryl‐4(3H)quinazolinones. The quinazolinones carrying a 2‐(o‐hydroxyphenyl) group are obtained in high yields.
Studies of polyazapentalenes. I. The preparation of 6‐dehydroindazolo[1,2‐a]benzotriazole
Authors: Tsuge Otohiko , Samura Hideo
Published: March 2009

The photolysis of 1‐(o‐azidophenyl)‐1H‐indazole (IV) has been found to give a mix ture of 6‐dehydroindazolo[1,2‐a]benzolriazole (VI) and 2,2′‐di(1‐indazolyl)azobenzene (VII). On the other hand, 1‐(o‐nilrophenyl)‐1H‐indazole (1) was reduced with triethyl phosphite, affording VI and dibenzo[a,i] indazolo[1,2,′3‐cd] indazolo[3,2,1‐fg]‐3,3a,5a,6,8a,8b‐hexaaza‐as‐indacene (XIa).