bluuebunny/crossref_metadata_2025 huggingface dataset:
s‐Triazines. I. Linear, sulfur bridged‐s‐triazine oligomers
Authors: Loughran Gerard A. , Ehlers Gerhard F. L. , Burkett Jerald L.
Published: March 2009

A number of new thioether and disulfide oligomers of s‐triazine have been prepared and identified.

The reactions between 2,4‐diphenyl‐s‐triazine‐6‐thiol and chloro substituted‐s‐triazines are described. A suggested mechanism for the formation of 2,2′‐thiobis‐(4,6‐diphenyl‐s‐triazine) from 2,4‐diphenyl‐s‐triazine‐6‐thiol is discussed.
s‐Triazines. II. The synthesis of some new cyclopoly‐s‐triazinylene thioethers and disulfides
Authors: Loughran Gerard A. , Ehlers Gerhard F. L. , Burkett Jerald L.
Published: March 2009

A number of new cyclopoly‐s‐triazinylene thioethers and disulfides have been prepared in dilute solution. Their structures and methods of formation are discussed. A thermo‐gravimetric analysis of cyclopoly‐2‐phenyl‐s‐triazinylene‐4,6‐monosulfide is included.
The synthesis of some 4,4′‐disubstituted‐2,2′‐biquinolines
Authors: Case Francis H. , Lesser Joseph M.
Published: March 2009

2,2′‐Biquinoline dioxide and 4,4′‐dichloro‐2,2′‐biquinoline have been used for the preparation of the following 4,4′‐disubstituted‐2,2′‐biquinolines: dimethoxy, diethoxy, dihydroxy, dipiperidino, dipyrrolidino, dibromo, diphenoxy, dithiophenoxy, di(p‐chloro‐phenoxy), di(p‐bromophenoxy), di(p‐fluorophenoxy), di(β‐naphthoxy) and the dinitro dioxide. Molar extinction coefficients have been determined for several of the copper (I) complexes of these compounds.
Some novel cyclizations of propiophenones with chlorosulfonic acid
Authors: Meyer Robert F.
Published: March 2009

The reaction of chlorosulfonie acid with propiophenones was found to give the 3‐chloro‐2‐methylbenzothiophene‐1, 1‐dioxides (I) and (VIII); reaction of Mannich bases of aceto‐phenone, with chlorosulfonie acid, gave the corresponding 3‐chloro‐2‐substituted amino‐methylbenzothiophene‐1,1‐dioxides (IX) and (X). The above structures were established by reaction with various nucleophiles and by hydrogenation. o‐Hydroxypropiophenones, under the above conditions, are cyclized to the cyclic sulfones (XII) and (XIII). Ring opening with pyrrolidine gave the corresponding phenolic sulfonamides (XIV) and (XV).
Preparation and thermal decomposition of certain. Substituted bis‐(thenoyl) peroxides
Authors: Schuetz Robert D. , Gruen Fred M. , Byrne Delos R. , Brennan Richard L.
Published: March 2009

The effect of various substituents on the rates of thermal decomposition of substituted bis‐(thenoyl) peroxides has been investigated. Nine unreported peroxides were prepared, including derivatives of 2‐ and 3‐thenoic acids. The thermal decomposition rates of these peroxides were examined, in the presence of styrene as a free radical scavenger. First order kinetics were observed in all cases studied. In general it was found that electron releasing substituents increase, while electron withdrawing groups decrease, the decomposition rate; the only exception being bis‐(5‐nitro‐3‐thenoyl) peroxide. Entropies and energies of activation were determined and found to be linearly related for the peroxides studied.
A new synthesis of furo[2,3‐b]pyridine derivatives
Authors: Snyder Harry R. , Ebetino Frank F.
Published: March 2009

A new synthesis of furo[2,3‐b]pyridines starting with α‐aminofurans is described.
s‐Triazolo[4,3‐b]pyridazines and imidazo[4,5‐c]pyridazines
Authors: Kuraishi Tsukasa , Castle Raymond N.
Published: March 2009

8‐Amino‐s‐triazolo[4, 3‐b]pyridazine (I), an adenine analog has been prepared by two different routes. Likewise 8‐amino‐3‐phenyl‐s‐triazolo[4,3‐b]pyridazine (V) has been prepared. Both of these compounds have been prepared utilizing 3,4,5‐trichloropyridazine and 3,4,6‐trichloropyridazine as the starting materials thus interrelating the 3,4,5‐and the 3,4,6‐series. A variety of other transformations have been carried out.
Ten π ‐electron nitrogen heterocyclic compounds:X the syntheses and structure determinations of some 1,2,4‐triazolopyrimidines
Authors: Paudler William W. , Helmick Larry S.
Published: March 2009

It has been shown that the reaction of 2‐hydrazinopyrimidines with ethyl orthoesters yields 1,2,4 ‐triazolo[4,3 ‐a]pyrimidines as well as 1,2,4‐triazolo[1,5‐a]pyrimidines. The structures of the parent compounds and of some methyl derivatives have been established by NMR spectroscopy.
The synthesis of 1‐substituted‐2‐(β‐dimethylaminoethyl)benzimidazoles
Authors: Ganellin C. R. , Ridley H. F. , Spickett R. G. W.
Published: March 2009

2‐(β‐Dimethylaminoethyl)benzimidazoles have been prepared by the reduction of the corresponding 2‐benzimidazole‐N,N‐dimethylacetamides. Condensation of ethyl cyanoacetate with N‐benzyl or phenyl‐o‐phenylenediamines led to N‐cyanoacetyl‐N'‐substituted‐o‐phenylenediamines, the structure of which were assigned from u.v. and n.m.r. data. An improved synthesis of benzimidazole ‐ 2 ‐ acetic acid derivatives, from substituted ethyl acetimidates and o‐phenylenediamines, is described. Dimerisation of 1‐phenyl‐benzimidazole occurs in the presence of phenyllithium.
Derivatives of the thiazolo[2,3‐a]isoquinolinium system
Authors: Andrew H. F. , Bradsher C. K.
Published: March 2009

The ketosulfides (IV) formed by the reaction of α‐bromoketones with 2α‐thiohomo‐phthalimide (II) have been cyclized to form hydrogen‐bonded, dimeric hemiperchlorates (V). Alternative products from the cyclization, 2‐[2′‐(carboxymethyl)phenyl]thiazoles (VII), may be cyclized with acetic anhydride to O‐betaines (VI). The same betaines are obtained from the hemiperchlorates (V) by deprotonation. The ketosulfide hydrobromides (XIII) from α‐bromoketones and 1‐thio‐3, 4‐dihydroisocarbostyril (XII) give 5,6‐dihydro‐thiazolo[2,3‐a]isoquinolinium salts (XV) on cyclization.
Synthesis of 6‐substituted pyrimidines by the wittig reaction. II . Via 2‐acetamido‐4‐hydroxy‐5‐phenylbutylpyrimidine‐6‐carboxaldehyde
Authors: Baker B. R. , Jordaan Johannes H.
Published: March 2009

Wittig condensations of both stabilized and unstabilized ylides were successfully achieved with 2‐acetamido‐4‐hydroxy‐5‐phenylbutylpyrimidine‐6‐carboxaldehyde (XI); functionalized Wittig reagents derived from dichloroacetone, ethyl 4‐iodobutyrate, 4‐bromobutyronitrile, phenylpropyl bromide, 3‐bromopropylphthalimide, p ‐ nitrobenzyl bromide, and p‐nitrocinnamyl bromide were used. The resultant 6‐substituted pyrimidines could be further transformed by reduction of the 6‐side‐chain double bond. Successful Wittig reactions were achieved with XI where the corresponding 2‐amino‐4‐hydroxy‐5‐phenylbutylpyrimidine‐6‐carboxaldehyde (X) with its less electrophilic aldehyde group failed to give isolable yields of condensation products.
Cyclic imides III. A study of the hydroxy‐ and methoxyphthalimidoacetic acids and the methyl methoxyphthalimidoacetates
Authors: Caswell Lyman R. , Atkinson Patsey C.
Published: March 2009

The hydroxy‐ and methoxyphthalimidoacetic acids and the methyl methoxyphthalimidoacetates have been synthesized. The ultraviolet absorption spectra of these compounds in 95% ethanol, aqueous acid, and aqueous base are discussed. Structures are suggested for the hydroxy‐ and methoxyphthalamate ions which are formed in basic solution. The Gabriel‐Colman rearrangements of methyl 3‐ and 4 ‐ methoxyphthalimidoacetate give, respectively, 8‐methoxy‐4‐hydroxy‐3 ‐ carbomethoxy‐1(2H)‐isoquinolone (VII) and 6‐methoxy‐4‐hydroxy‐3‐carbomethoxy‐1(2H)‐isoquinolone (VIII).
5α‐androstano [3,2‐b]pyridines, 5α‐androstano[17,16‐b]pyridines and androst‐4 and 5‐eno[17,16‐b]pyridines
Authors: Miller Theodore C.
Published: March 2009

A new synthesis of 5α‐androstano[3,2‐b]pyridin‐17β‐ol acetate (VIa) and 17‐methyl‐5α‐androstano[3,2‐b]pyridin‐17β‐ol (VIb), first reported by Shimizu, Ohta, Ueno, and Takegoshi, was achieved. The analogous 5α ‐ androstano[17,16‐b]pyridin‐3β‐ol (XII), 5α‐androstano[17,16‐b]pyridin‐3‐one (XIVa), and androst‐4‐eno[17,16‐b]pyridin‐3‐one (XIVb) were also prepared. An illustration of the method follows. Condensation of 3β‐hydroxy‐5α‐androstan‐17‐one (VIIa) with 3‐(2‐furyl)acrolein afforded 16‐[3‐(2‐furyl)‐2‐propenylidene]‐3β‐hydroxy‐5α‐androstan‐17‐one (VIIIa), the oxime (IXa) of which was thermally cyclized to 5α‐androstano[17,16‐b]‐6′‐(2‐furyl)pyridin‐3β‐ol (Xa). 3β‐Hydroxy‐5α‐androstano[17,16‐b]pyridine‐6′‐carboxylic acid (XI) was obtained by ozonolysis of Xa. Thermal decarboxylation of XI gave XII. Cinnamaldehyde was used in place of 3‐(2‐furyl)acrolein to give the corresponding phenylpyridines.
The synthesis of some phenothiazinyl ketones and their derivatives
Authors: Kadaba Pankaja K.
Published: March 2009

The synthesis of a number of 2‐chloro‐8‐acylphenothiazines via the Friedel‐Crafts reaction has been reported. A series of dialkylaminoalkyl ketones have been derived from 2‐chloroacetyl‐ and 2‐chloro‐8‐chloroacetylphenothiazines. A number of dialkylaminoalkyl esters of 2‐phenothiazinecarboxylic acid have also been synthesized.
The formation of lactams of N‐(2‐amino)benzoylamino acids
Authors: Hoffmann Eliahu , Jagnicinski Boris
Published: March 2009

N‐(2‐Nitro)benzoylamino acids were prepared by 2‐nitrobenzoylation of amino acids via the mixed ethylcarbonic anhydride procedure. They were reduced catalytically to N‐(2‐amino)benzoylamino acids which underwent cyclization to the corresponding lactams under a variety of conditions. The use of this reaction sequence for stepwise degradation of peptides seems possible.
Synthetic experiments related to the indole alkaloids V. mercuric acetate oxidation of 2‐[2‐(3‐indolyl)ethyl]‐1,2,3,4‐tetrahydroisoquinolines and the formation of benz[a]indolo[3,2‐h]quinolizine derivatives
Authors: Potts K. T. , Roy S. K. , Liljegren D. R.
Published: March 2009

Oxidation of 2‐[2‐(3‐indolyl)ethyl]‐1,2,3,4‐tetrahydroisoquinoline (I) with mercuric acetate gave 5,6,8,9,14,14b‐hexahydrobenz[a]indolo[3,2‐h]quinolizine (IV) and 8,9‐dihydro‐14H‐benz[a]indolo[3,2‐h]quinolizin‐7‐ium iodide (VI), as well as starting material. The base (IV) was oxidized with iodine and potassium acetate to VI and on Palladium carbon ‐ maleic acid dehydrogenation yielded 5,6‐dihydro‐14H‐benz[a]indolo[3,2‐h]‐quinolizin‐7‐ium iodide (IX), and 14H‐benz[a]indolo[3,2‐h]quinolizin‐7‐ium iodide (X). Heating the iodide (VI) with Palladium‐carbon brought about an irreversible rearrangement to VII and both these salts with base yielded the red anhydro base 8, 9‐dihydrobenz[a]indolo[3,2‐h]quinolizine (VIII). This base was also obtained from IV by oxidation in air.

The corresponding 8, 9‐dehydroanhydro base (XI), benz[a]indolo[3,2‐h]quinolizine, was readily obtained from X and alkali. The quinolizinium salts (VI), (VII), and (IX), on catalytic, zinc dust and acetic acid, or sodium borohydride reduction, regenerated the base (IV). Selenium degradation of IV gave, among other products, 1‐(2‐ethylphenyl)‐β‐carboline. An analogous series of products was obtained with the 6, 7‐dimethoxy derivative of I. Various other aspects of these and related transformations are described.
Crystal and molecular structure of 6‐(p‐iodobenzenesulfonyl)‐3‐oxa‐6‐azabicyclo[3.1.0]hexane
Authors: Trefonas L. M. , Sato Tatsuo
Published: March 2009

The crystal and molecular structure of 6‐(p‐iodobenzenesulfonyl)‐3‐oxa‐6‐azabicyclo‐[3.1.0]hexane has been determined by a three‐dimensional single‐crystal x‐ray diffraction study. The compound crystallizes in the monoclinic space group C2/c with cell dimensions, a = 19.76, b = 8.17, c = 15.72 ± 0.003 Å and β = 109.3° ± 0.2°. The aziridine ring is fused cis to the oxa‐cyclopentane ring with fusion angles of 112°. The bicyclic system is in the boat conformation with the p‐iodobenzenesulfonate group at an angle of 98.0° to it. The conformation of the ring system is discussed. A final value of R = 0.099 was obtained for the 1107 independent reflections.
The synthesis of 1,4,5‐trialkyl‐2‐pyrazolines from monoalkylhydrazines and aliphatic aldehydes
Authors: Rabjohn Norman , Havens H. R. , Rutter J. L.
Published: March 2009

It has been found that the thermal decomposition of heptanal methylhydrazone affords 5‐hexyl‐1‐methyl‐4‐pentyl‐2‐pyrazoline (I), in addition to heptanenitrile and methylamine. The formation of I suggests the synthesis of 1,4, 5‐trialkyl‐2‐pyrazolines from monoalkylhydrazines and aliphatic aldehydes. A number of these compounds have been prepared in good yields by this method, or through the related hydrazones, and some of their physical and chemical properties have been studied.
Stereochemical studies on 7‐substituted 8‐oxa‐1‐azabicyclo[4.3.0]nonanes
Authors: Crabb T. A. , Newton R. F.
Published: March 2009

A set of racemic 7‐substituted 8‐oxa‐1‐azabicyclo[4.3.0]nonanes have been prepared and configurational and conformational assignments made on the basis of the value of the geminal coupling constants for the C9 methylene protons. The limitations of the Bohlmann infrared criterion in studying the conformations of these compounds is discussed.
The bromination of isatoic anhydride
Authors: Bertelson Robert C. , Becker William J.
Published: March 2009

Bromination of isatoic anhydride in acetic acid gives N‐dibromoacetyl‐3,5‐dibromoanthranilic acid. Three new anthranils are described.
Synthesis and nucleophilic displacement reactions of fluoropyrazine and 2‐fluoroquinoxaline
Authors: Rutner Herman , Spoerri Paul E.
Published: March 2009

An improved method for the preparation of fluoropyrazine (I) by halogen exchange and a synthesis of 2‐fluoroquinoxaline (II) by a Balz‐Schiemann reaction are presented. Compound I hydrolyzes slowly in 0.01N sodium hydroxide, rapidly in 1.07N sodium hydroxide at 26.00°. Compound II hydrolyzes 240 times faster than I in 0.01N sodium hydroxide at 26.00°. Hydrolysis of I in 6N hydrochloric acid at room temperature is slow. Compound I underwent nucleophilic reactions with formation of hydroxy, amino, methylamino, piperidino, benzylamino and anilinopyrazines. Pyrazinesulfonic acid was obtained from I and sodium sulfite and tetrazolo[1, 5‐a]pyrazine (IV), a novel ring system, from I and sodium azide.
Nitroimidazoles II. synthesis and reactions of iodonitroimidazoles
Authors: Hoffer M. , Toome V. , Brossi A.
Published: March 2009

The synthesis and some chemical reactions of various iodonitroimidazoles and methods of distinguishing between the 4‐ and 5‐ nitro derivatives by UV and pK measurements are described.
8‐Arylpurines and their ultraviolet absorption spectra
Authors: Fu S.‐C. J. , Chinoporos E.
Published: March 2009

Dehydrocyclization of 4‐amino‐5‐arylamidopyrimidines in polyphosphoric acid to 8‐arylpurines was further investigated. Various other 8‐arylpurines were synthesized by this new procedure in high purity and yield. The ultraviolet absorption spectra of the arylpurines and the corresponding acylamidopyrimidines were measured at pH 1, 7, and 13 at 0.1 molar ionic strength. The spectra of the purines resemble those of the corresponding acylamidopyrimidines and, to a lesser extent, the corresponding 4,5‐diaminopyrimidines. The bathochromic shifts caused by different substituting groups in monosubstituted purines, in general, parallel the inductive effect of the substituting groups. The hyperchromicity and the inductive constant of the substituting groups assume a linear relationship, for substitution at either the 2 or 6 position. These changes in the wave length of maximum absorption and in the molar extinction coefficient caused by 2, 6 and 8 substitutions of the purines reported here are in agreement with previous studies by Mason.
5‐Amino‐5‐deoxyribose derivatives. Synthesis and use in the preparation of “Reversed” Nucleosides
Authors: Leonard Nelson J. , Carraway Kermit L.
Published: March 2009

Methyl 5‐amino‐5‐deoxy‐2,3‐O‐isopropylidene‐β‐D‐ribofuranoside (III) has been synthesized and used as an intermediate in the preparation of the kinetin analog, methyl 5‐deoxy‐5‐(purin‐6‐yl)amino‐β‐D‐ribofuranoside (X). The related 1‐substituted adenine, methyl 5‐ (6‐aminopurin‐1‐yl)‐5‐deoxy‐2,3‐O‐isopropylidene‐β‐D‐ribofuranoside (XIII), was prepared by cyclization of 1‐benzyl‐5‐cyano‐4‐ethoxymethyleneaminoimidazole (XI) with III and subsequent debenzylation with sodium in liquid ammonia. The structures and stereochemistry of these compounds were established by a combination of ultraviolet and nuclear magnetic resonance spectroscopy.
Synthetic porphyrins. I. Synthesis and spectra of some para‐substituted meso ‐ Tetraphenylporphines
Authors: Datta‐Gupta N. , Bardos T. J.
Published: March 2009

A series of derivatives of meso‐tetraphenylporphine, with neutral, acidic and basic functional groups, has been prepared. Several of these compounds were synthesized directly via the Rothemund reaction, under a variety of conditions to obtain optimal yields; others were prepared by interconversions of various functional groups. Drastic reaction conditions employed for hydrolysis, alcoholysis, or lithium aluminum hydride reduction did not affect the porphine ring system. The two amino derivatives showed anomalous spectra in the visible range.
A facile synthesis of piperazines from primary amines
Authors: Henry David W.
Published: March 2009

A general procedure is described for converting primary amines to N‐substituted piperazines. Reaction of an amine with an N‐substituted iminodiacetic acid anhydride (V) yields an iminodiacetic acid monoamide (VI) which closes to a 2,6‐piperazinedione (VII) upon treatment with acetic anhydride. The diones are reduced to piperazines with borane‐THF. Fourteen examples of this process, using twelve aliphatic or aromatic amines and three iminodiacetic acids, are presented. Yields of piperazines, based upon starting amine, ranged from 21 to 52%. The procedure is rapid and no purification problems were encountered. Alternate methods for preparing the 2,6‐piperazinedione intermediates are discussed.
The synthesis of pyrazino[2,3‐d]pyridazine and some of its derivatives
Authors: Patel Natu R. , Castle Raymond N.
Published: March 2009

Pyrazino[2,3‐d]pyridazine (I) was synthesized by two different routes. 5, 8‐Dihydroxy‐pyrazino[2, 3‐d]pyridazine (IV) was converted to 5, 8‐dichloropyrazino[2, 3‐d]pyridazine (V) and 5, 8‐dibromopyrazino[2, 3‐d]pyridazine (Va). When V was treated with various benzyl mercaptans and alkoxides the corresponding disubstituted derivatives were obtained. Compound V when allowed to react with aromatic amines gave 5, 8‐bisamino‐pyrazino[2,3‐d]pyridazines, however, with aliphatic amines only mono substituted products were obtained substituted in the 8‐position. The reaction of pyrazine‐2, 3‐dinitrile with hydrazine gave 5, 8‐diaminopyrazino[2, 3‐d]pyridazine (X).
Oxazolo[3,2‐a]pyridinium salts
Authors: Bradsher C. K. , Zinn Mary F.
Published: March 2009

The first synthesis of the aromatic oxazolo[3,2‐a]pyridinium ring system has been accomplished by the cyclization of 1‐acetonyl‐ or 1‐phenacyl‐2‐pyridones. Through use of the analogous quinolones and 2‐(p‐bromophenacyl)‐1‐isoquinolone, benzologs of the new system have been prepared.
Heterocyclic tautomerisms. I. An investigation of the 2‐arylbenzothiazoline‐2‐(benzylideneamino)thiophenol tautomerism. Part 1
Authors: Goetz Frederick J.
Published: March 2009

A definite tautomeric relationship has been found between 2‐arylbenzothiazolines (I) and 2‐(benzylideneamino)thiophenols (II). In a reaction characteristic of the closed ring structure (I), 2‐arylbenzothiazolines were oxidized in high yield with benzoyl peroxide to the corresponding 2‐arylbenzothiazoles (III). Reactions characteristic of the open ring structure (II) include the formation of the potassium salt of the open ring structure (IV) by reaction of 2‐arylbenzothiazolines with potassium t‐butoxide in toluene and oxidation of 2‐arylbenzothiazolines to bis‐[2‐(benzylideneamino)phenyl] disulfides (V) by hydrogen peroxide in methanol.
Studies on the syntheses of heterocyclic compounds. CLXXIV. An approach to the synthesis of oxyacanthine and berbamine
Authors: Kametani Tetsuji , Lida Hideo , Kano Shinzo , Tanaka Sadao , Fukumoto Keiichiro , Shibuya Shiroshi , Yagi Haruhiko
Published: March 2009

Schotten‐Baumann reaction of the amine (X) with 4‐benzyloxy‐3,4′‐oxydiphenylacetyl chloride (XI) gave two amides, (XIIa) and (XIIb), which were cyclized to give the corresponding 3,4‐dihydroisoquinolines, respectively. Methylation of the above 3,4‐dihydro‐isoquinolines, followed by hydrolysis, afforded the compounds having the same composition as berbamine (Ia) and oxyacanthine (Ib), whose structures are under examination.
Synthesis of 6‐hydroxymethyl‐1,3‐dimethyllumazine by rearrangement of the corresponding 6‐methyllumazine 5‐oxide
Authors: Zondler Helmut , Forrest H. S. , Lagowski J. M.
Published: March 2009

Starting with a chloronitrouracil, the synthesis of 1, 3, 6‐trimethyllumazine has been achieved. Oxidation to the 5‐oxide and subsequent rearrangement gave 6‐hydroxymethyl‐1, 3‐dimethyllumazine. Because of the method of synthesis, the product is uncontaminated with the 7‐isomer.
The reaction of trans‐2‐aminocyclohexanol with formaldehyde
Authors: Crabb T. A. , Williams R. O.
Published: March 2009

From a study of the geminal coupling constants for ‐O‐CH2‐N‐ protons structure II has been assigned to the product of the reaction between trans‐2‐aminocyclohexanol and formaldehyde. The previously proposed structure I is shown to be incorrect.
Researches on the reactivity of mannich bases part VIII synthesis of N‐methyl(vinylaryl)quinolinium salts and their photosensitivity
Authors: Andreani Franco , Andrisano Renato , Tramontini Maurilio
Published: March 2009

Described in this communication is a new synthesis of N‐methyl‐4‐(vinylaryl)quinolinium salts by cyclization of the aminoketones, Ar‐CH=CH‐CO‐CH2‐CH2‐N(CH3)‐C6H4‐X. The aminoketones were obtained by replacement of the alkyiamino group of the ketoarylidene Mannich bases with various N‐methylarylamines. The U.V. spectra of the compounds were obtained. The photosensitivity characteristics in solution are reported. These data show the possibility of dimerization and probable trans → cis isomerization on exposure to visible and ultraviolet light.
Reissert compound studies. XV. preparation and reaction of the reissert anion at room temperature
Authors: Popp Frank D. , Wefer John M.
Published: March 2009

The anions (I and II) have been conveniently generated from the parent Reissert compounds in dimethylformamide using sodium hydride. Rearrangements to ketones, alkyl‐ations, and participation of I and II in other nucleophilic displacements have been investigated.
Irreversible enzyme inhibitors. XCI. candidate active‐site directed irreversible inhibitors of thymidylate synthetase. II. 2‐amino‐6‐methyl‐5‐(p‐tolylsulfonamidopropyl)‐4‐pyrimidinols with N‐substituents on the sulfonamide moiety
Authors: Baker B. R. , Coward James K.
Published: March 2009

Three derivatives of 2‐amino‐6‐methyl‐5‐(p‐tolylsulfonamidopropyl)‐4‐pyrimidinol (I) with N ‐ substituents on the sulfonamide group, namely bromoacetamidopropyl (XVI), m‐bromoacetamidobenzyl (XXIVa), and p‐bromoacetamidobenzyl (XXIVb), were synthesized as candidate active‐site‐directed irreversible inhibitors of thymidylate synthetase. The bromoacetamidopropyl derivative, (XVI), the p‐bromoacetamidobenzyl derivative (XXIVb), and iodoacetamide showed irreversible inhibition of thymidylate synthetase, but XXIVa did not. Since iodoacetamide did inactivate the enzyme, but XXIVa did not, it cannot be ascertained whether XXIVb and XVI inactivate the enzyme by a random bimolecular mechanism or by the active‐site‐directed mechanism without evaluation of additional candidate inhibitors.

Two synthetic routes were employed. The key intermediates for the bromoacetamidobenzyl sulfonamides (XXIV) were the corresponding nitrobenzyl sulfonamides (XXI); the latter were best prepared by reductive alkylation of 2‐amino‐5‐aminopropyl‐6‐methyl‐4‐pyrimidinol (XXV) with a nitrobenzaldehyde followed by tosylation. The key intermediate for XVI was a toluenesulfonamide with a carbobenzoxyaminopropyl substituent on the nitrogen (XIV); the latter was synthesized via N‐carbobenzoxy‐N'‐tosyl‐1,3‐diaminopropane (XI).
Reaction of thioxanthylium perchlorate with diazomethane
Authors: Seidl Helmut , Biemann Klaus
Published: March 2009

The reaction of thioxanthylium perchlorate with diazomethane was investigated. Depending on the reaction conditions, seven compounds (II, III, V, VI, VIII, IX, and X) are formed which were identified on the basis of spectral data (mainly mass spectra) and chemical reactions. A synthesis was worked out (reaction of compound VII with boron trifluoride) in which dibenzo[b,f]thiepine (VIII) is formed as major product (55%).
Irreversible enzyme inhibitors. XCIV. inhibition of dihydrofolic reductase with derivatives of 2,6‐diaminopurines
Authors: Baker B. R. , Santi Daniel V.
Published: March 2009

In order to gain additional information on the hydrophobic bonding region of dihydrofolic reductase, some derivatives of 2, 6‐diaminopurine with aryl or aralkyl groups at the N6, C8 and N9‐positions were investigated as inhibitors. Since none of the six compounds gave an increment in binding over the parent 2, 6‐diaminopurine, hydrophobic bonding to dihydrofolic reductase could not be detected with this ring system. Furthermore, 2, 6‐diaminopurine bridged from its 8‐position with methylene groups to the amino group of p‐aminobenzoic acid also failed to show an increment in binding.

The 8‐substituted 2, 6‐diaminopurines were synthesized by base‐catalyzed cyclodehydration of the appropriate 5‐acylamido‐2, 4, 6‐triaminopyrimidines; the latter compounds were readily prepared by selective acylation of tetraaminopyrimidine.
The mass spectra of 1,2,4‐triazine and some of its derivatives
Authors: Paudler William W. , Herbener R. E.
Published: March 2009

The mass spectra of some esters of 1,2,4‐triazine‐3‐carboxylic acid and of 1,2,4‐triazine itself are reported, and their fragmentation patterns are analyzed.

The syntheses of the methyl and of the t‐butyl esters of 1,2,4‐triazine‐3‐carboxylate are described.
Pyrrolopyrimidine nucleosides II. the total synthesis of 7‐β‐D‐ribofuranosylpyrrolo[2,3‐d]pyrimidines related to toyocamycin
Authors: Tolman Richard L. , Robins Roland K. , Townsend Leroy B.
Published: March 2009

The first synthesis of a 7‐β‐D‐ribofuranosylpyrrolo[2,3‐d]pyrimidine by direct ribosidation of a preformed pyrrolo[2,3‐d]pyrimidine has now been accomplished via the fusion procedure. Subsequent functional group transformations furnished the 6‐methyl‐thio derivative of the nucleoside antibiotic toyocamycin. Preparation of the 1‐, 3‐ and 7‐methyl isomers of 4‐amino‐5‐cyano‐6‐methylthiopyrrolo[2,3‐d]pyrimidine was accomplished and has provided an unequivocal assignment for the actual site of ribosidation by a comparison of ultraviolet absorption spectra. Factors utilized for the assignment of anomeric configuration are discussed.
Synthesis of possible metabolites of menazon
Authors: Stevens M. A. , Walker G. H.
Published: March 2009

A product of the peracetic acid oxidation of 2,4‐diamino‐6‐methylthiomethyl‐1,3,5‐triazine is identical with a major urinary metabolite of the aphicide, menazon, in the rat. This product has been shown to be the S‐oxide 2,4‐diamino‐6‐methylsulphinyl‐methyl‐1, 3, 5‐triazine and not the N‐oxide.
Synthesis and properties of trimethylsilyl derivatives of vitamin B6
Authors: Sennello Lawrence T. , Kummerow F. A. , Argoudelis C. J.
Published: March 2009

In our studies on the biosynthesis of vitamin B6 in yeast (2), we are confronted with the problem of a fairly rapid assay of the different forms (known and unknown) of this nutrient that are excreted into the culture medium. The existing assay procedures for vitamin B6 are subject to at least one of several restrictions. They are time consuming, incapable of distinguishing between the three forms of the vitamin (pyridoxol, pyridoxal, and pyridoxamine), or preclude the regeneration and reisolation of the material after analysis.
Synthesis of vitamin B6 derivatives. III. 3‐ (4‐formyl‐3‐hydroxy‐2‐methyl‐5‐pyridyl)propionic acid, an analog of pyridoxal phosphate
Authors: Iwata Chuzo , Metzler David E.
Published: March 2009

The preparation and properties of a new analog of pyridoxal phosphate, 3‐ (4‐formyl‐3‐hydroxy‐2‐methyl‐5‐pyridyl)propionic acid and of the corresponding 4‐aminomethyl compound are described. The n.m.r. spectrum of the new aldehyde is compared with those of 5‐deoxypyridoxal and pyridoxal phosphate. The broad aldehyde proton peak of 5‐deoxypyridoxal is sharpened by heating, suggesting an equilibrium between two geometrical isomers. Mass spectra of the new aldehyde and of 5‐deoxypyridoxal are analyzed. The electronic absorption spectrum is nearly the same as that of 5‐deoxypyridoxal. The new aldehyde undergoes rapid transamination with amino acids, and the corresponding aminomethyl compound can be reoxidized to the aldehyde by heating with glyoxylic acid in aqueous solution.
The mass spectra of phosphorus esters. I. Bicyclic phosphites
Authors: Hendricker David G.
Published: March 2009

The mass spectra of bicyclic phosphites of the type P(OCH2)3CR, where R = CH3, C2H5, and C3H7 and NO2, are reported, and their fragmentation patterns analyzed. Unlike trialkyl phosphites, these cyclic phosphites do not yield a large number of phosphorus‐containing fragment ions resulting from hydrogen rearrangement.
Novel halogenated imidazoles. Chloroimidazoles
Authors: Lutz Albert W. , Delorenzo Sylvio
Published: March 2009

With one exception chloroimidazoles containing an unalkylated ring nitrogen have been ignored. Procedures are described using hypochlorite solution that permit the synthesis of 4,5‐dichloroimidazole and 2,4,5‐trichloroimidazole. Various bromoimidazoles are also converted to chloroimidazoles in refluxing hydrochloric acid.
Sulfostyrils. IV. Reactions of 4‐keto‐3,4‐dihydrosulfostyril
Authors: Loev Bernard , Snader Kenneth M.
Published: March 2009

The ketone group in 4‐keto‐3,4‐dihydrosulfostyril (I) displays anomalous properties. Its reactions are described; in some reactions it behaved normally, in others it proved quite inert. Attempted oximination of I led to extrusion of the sulfone group with formation of isatin derivatives. Compound I was converted to a tetracyclic indole derivative.
Syntheses of some analogs of a possible intermediate formed in the thymidylate synthetase reaction
Authors: Santi Daniel V.
Published: March 2009

The syntheses of a number of analogs of a possible intermediate formed in the thymidylate synthetase reaction are described. These consist of a number of 5‐arylaminomethyluracils (X) and N‐methyl‐N‐[1,‐(2′‐deoxy‐β‐D‐ribofuranosyl)thyminyl]‐p‐aminobenzoyl glutamic acid (XXb).
The preparation of triazines and benzimidazoles from 1‐ and 3‐cyanoisoquinolines
Authors: Case Francis H. , Kennon Lloyd
Published: March 2009

The preparation from 1‐ and 3‐cyanoisoquinolines of certain benzimidazoles and symmetrical triazines containing the ferroin group is described; also that of certain unsymmetrical triazines from 3‐cyanoisoquinoline.
The synthesis of seneciphyllic acid
Authors: Edwards J. D. , Hase Tsunao , Ichikawa Nobutaka
Published: March 2009

A total synthesis of seneciphyllic acid, the necic acid of the Senecio alkaloid seneciphylline, is reported.
Ion radicals. XIII. Spectroscopic and cryoscopic characterization of ions and ion radicals from phenothiazine and N‐methylphenothiazine in sulfuric acid solutions
Authors: Shine H. J. , Thompson D. R. , Veneziani C.
Published: March 2009

The formation and interconversion of the N‐methylphenothiazine cation radical and the N‐methylphenothiazine dication from both N‐methylphenothiazine and N‐methylphenothiazine S‐oxide in sulfuric acid solutions have been demonstrated with e.s.r. and absorption spectroscopy. Cryoscopic measurements have shown that in slightly aqueous sulfuric acid N‐methylphenothiazine S‐oxide is converted to the N‐methylphenothiazine dication and, analogously, phenothiazine 5‐oxide is converted to the protonated phenazathionium ion (the phenothiazine dication).
The preparation, structure and reactions of some “malonyl‐α‐aminopyridines”
Authors: Ingalls Elizabeth A. , Popp Frank D.
Published: March 2009

The reaction of several substituted 2‐aminopyridines with diethyl malonate was studied. The “methylmalonyl‐α‐aminopyridines” were shown to exist in the same tautomeric form as “malonyl‐α‐aminopyridine”. Formylation of these compounds takes place in the 3‐position and has led to the formation of a new tricyclic compound.
Friedländer syntheses with o‐aminoaryl ketones. III. Acid‐catalyzed condensations of o‐aminobenzophenone with polyfunctional carbonyl compounds
Authors: Fehnel Edward A.
Published: March 2009

The acid‐catalyzed condensations of o‐aminobenzophenone with a variety of diketones, ketoesters, ketoacids, and representatives of several other classes of polyfunctional carbonyl compounds containing the ‐COCH2 ‐ moiety have been investigated. Under the conditions used, normal Friedländer‐type ring‐closure was found to occur in all cases, giving good yields of substituted quinolines which have been identified as the 4‐phenyl analogs of the products obtained in classical base‐catalyzed Friedländer condensations with o‐aminobenzaldehyde. The method appears to be quite general and should provide a convenient synthetic route to a previously inaccessible series of 4‐arylquinolines.
Linear free energy relations and the hammett equation for substituted pyridine 1‐oxides
Authors: Nelson John H. , Garvey Roy G. , Ragsdale Ronald O.
Published: March 2009

It is recommended that a self‐consistent set of sigma constants be used to obtain linear free energy relations with pyridine 1‐oxides rather than using adjusted benzoic acid sigma constants. These recommended constants are derived from the literature values of the acid dissociated constants of the protonated substituted pyridine 1‐oxides. A survey and discussion of linear free energy relations using these new constants (σPyNO) is given. Comparisons of correlations using adjusted benzoic acid sigma constants and (σPyNO) are presented.
Some hydroxylated derivatives of chlorpromazine
Authors: Grotta H. M. , Page T. F. , Riggle C. J. , Manian A. A.
Published: March 2009

As part of a program to determine the metabolic fate of chlorpromazine [2‐chloro‐10‐(3‐dimethylaminopropyl)phenothiazine] (I), the synthesis of several hydroxylated derivatives of I was undertaken. This paper reports the preparation and structural verification of the 1‐ and 6‐hydroxy and the desdimethyl 3‐hydroxy derivative, and summarizes unsuccessful attempts to prepare the 4‐hydroxy derivative of I.
A study of the acylation of 4‐hydroxy‐6‐methyl‐2‐pyrone and 4 hy(lroxy‐6‐phenyl‐2‐pyrone
Authors: Marcus E. , Stephen J. F. , Chan J. K.
Published: March 2009

The acylation of 4‐hydroxy‐6‐melhyl‐2‐pyrone (1) and 4‐hydroxy‐6‐phenyl‐2‐pyrone (XXII) with aliphatic acid anhydrides, or with aliphatic acid chlorides in trifluoroacetic acid, has been found to product; first the corresponding ester, which then rearranges, partially or wholly, depending on the conditions and on the nature of the acyl moiety, to form the corresponding 3‐acylpyrone. With aromatic acid chlorides in pyridine or in trichloroacetic acid only the corresponding ester was obtained. These esters, however, could be rearranged to the corresponding 3‐acylpyrones with aluminum chloride. Acetoaeetylation of 1 and 4‐hydroxycoumarin (XXIX) with diketene gave, in both cases, the C‐acetoacetylated product.
Nucleophilic substitutions in some derivatives of 4‐ and 5‐nitroimidazoles
Authors: Sunjić V. , Fajdiga T. , Japelj M. , Rems P.
Published: March 2009

Hydrogen, as well as the halogen atom, at the 4 or 5 position in some 5‐ and 4‐nitroimidazoles were displaced by various nucleophiles such as the amino, cyano, hydroxy, and alkoxy groups. The greater reactivity of the departing group in the 4 position, which was regularly observed, is ascribed to the double activating effect of the azo and nitro groups. Cyanide ion in alcoholic solution reacted peculiarly with both 4‐ and 5‐nitroimidazoles giving o‐cyanoazoxyimidazoles as the only products. In some of the nucleophilic displacements at the 4 position of 5‐nitroimidazoles the formation of intermediate S̀‐complexes was observed.
Polyazanaphthylene nucleosides II. Synthesis of β‐D‐ribofuranosyl derivatives of 4‐quinazolone
Authors: Stout Mason G. , Robins Roland K.
Published: March 2009

The preparation of N1 (2,3‐O‐isopropylidene‐β‐D‐ribofuranosyl)‐4‐quinazolone (6) and N3‐β‐D‐ribofuranosyI‐4‐quinazolone (3b) are reported. The N3 derivative was prepared by the direct condensation of 4‐trimethylsilyloxyquinazoline (2) and 2,3,5‐tri‐O‐benzoyl‐D‐ ribofuranosyl bromide. The N1 derivative was prepared from the previously reported N1 ‐β‐D‐ribofuranosyl‐2,4‐quinazolinedione via the cyclonucleoside 4.
A study of some pyridopyrazines and pyridopyrimidines
Authors: Peck Robert L. , Day Allan R.
Published: March 2009

The d‐ and l‐forms of 2H‐octahydropyrido[1,2‐a]pyrazine (I) have been prepared and their absolute configurations established. These configurations were confirmed by an optical rotary dispersion study. The infrared spectra of 2H‐octahydropyrido[1,2‐a]pyrazine (I), lH‐octahydropyrido[ 1,2‐a]pyrimidine (11) and 2H‐octahydropyrido[ 1,2‐c]pyrimidine (111) were compared with the infrared spectrum of quinolizidine. All of these spectra showed the Bohlmann bands characteristic of a trans ring structure. A few derivatives of these ring systems have been prepared.
The kinetics of hydrogen‐deuterium exchange of methylisothiazoles
Authors: White James A. , Anderson Richard C.
Published: March 2009

The rates of hydrogen‐deuterium exchange of 3‐methyl, 4‐methyl, 5‐methyI and 3,5‐dimethyl‐isothiazole were determined and compared with the rate of exchange of 2‐methylpyridine. The rates were measured in dimethylsulfoxide‐d6 ‐deuterium oxide (90:10), using sodium deuteroxide as catalyst. The relative rates for exchange of both ring protons and methyl protons were 5 > 3 > 4. For exchange of methyl hydrogens, the approximate ratio of rate constants is 100:1:< 10−4 for positions 5,3, and 4, respectively. Activation parameters are reported for 5‐methylisothiazole.
Synthesis of (R)‐5‐(2′‐pentyl)barbituric acid derivatives of high optical purity
Authors: Cook C. E. , Tallent C. Ray
Published: March 2009

Natural (R)‐(+)‐pulegone (1) was converted to 3‐methylhexanoic acid (4) by a sequence which precluded racemization. Conversion of this to malonic esters8, 5, and 11 permitted the synthesis of pentobarbital (6) secobarbital (12), thiopental (9),thiamylal(10), and 5‐(2′‐pentyl)barbituric acid (7), all having the (R)‐configuration in the side chain.
A study of electrophilic substitution in the pyrrolo[2,3‐d]pyrimidine ring
Authors: Gerster John F. , Hinshaw Barbara C. , Robins Roland K. , Townsend Leroy B.
Published: March 2009

Several 4,5‐disubstituted pyrrolo[2,3‐d ]pyrimidines were prepared for the first time via electrophilic substitution, e.g. halogenation, nitration and sulfonation. PMR data for certain pyrrolo[2,3‐d]pyrimidines are included which has furnished conclusive evidence that electrophilic substitution occurred at position 5. These pyrrolo[2,3‐d]pyrimidines, with electron ‐withdrawing substituents at position 5, are of considerable interest as bases for the preparation of nucleoside derivatives related to tubercidin, toyocamcin and sangivamycin.
Reactions of 2,2,4,4‐tetramethyl‐1,3‐cyclobutanedione with amines and other nucleophiles. II
Authors: Hansen Gary R. , Demarco Ronald A.
Published: March 2009

The reaction of 2,2,4,4‐tetramethyl‐1,3‐cyclobutanedione with various nucleophiles has been demonstrated to be dependent on the reaction conditions, steric factors and the nucleophilicity of the attacking species. In the reaction with primary amines the intermediate has been established as the N‐substituted imine which is hydrolyzed to the corresponding amide in the presence of water. The reaction of diamines with the dione has been shown to be a method of synthesizing 2‐substituted imidazolines and 1 H‐4,5‐dihydropyrimidines.
4‐phenyl‐4H‐pyrazolo[3,4‐c] furazans. The reactions of 3,4‐dacylfuroxans with phenylhydrazine and with aniline
Authors: Bertelson Robert C. , Glanz Kenneth D. , Mcquain David B.
Published: March 2009

Three different 3,4‐diaeylfuroxans (1) are shown to give 3‐substituted‐l‐phenyl‐4,5‐dioximino‐2‐pyrazolines (2) upon reaction with phenylhydrazine. The compounds 2 were dehydrated to 6‐sul)stituted‐4‐phenyl‐4H‐pyrazolo[3,4‐c]furazans. (3) and thermally converted to 3‐substituted 5‐imino‐4‐oximino‐1‐phenyl‐2‐pyrazolines (6). The compounds 1 react with aniline to give 3‐anilino‐4‐acylfurazans (10).
Reactions of 1,2‐dialkyl‐3‐pyrazolidinones
Authors: Kornet Milton J. , le Tan Sip
Published: March 2009

The condensation of 1,2‐dialkyl‐3‐pyrazoIidinones (1) with a series of aldehydes, ketones and esters in the presence of sodium hydride is described. Alkylation of I with several alkyl bromides gave 4‐alkyl substitution products in modest yield and reaction of 1,2,4‐trimethyl‐3‐pyrazolidinone with n‐butyl bromide gave a 4,4‐dialkylation product. Compound 1 reacted with aryl Grignard reagents to form 3‐aryl‐3‐pyrazoIines whereas the corresponding products were not realized in the case of alkyl Grignards. The reduction of a single example of 1 as well as the reduction of two 3‐pyrazolines to pyrazolidines is also reported.
Cinnolines. X. The oxidative‐rearrangement of 1‐aminooxindoles to 3‐cinnolinols
Authors: Baumgarten Henry E. , Wittman William F. , Lehmann Gerhard J.
Published: March 2009

An improved route for the oxidative‐rearrangement of 1 ‐aminooxindoles, treatment with equimolar amounts of t‐butyl hypochlorite, produces nearly quantitative yields of 3‐cinnolinols of excellent purity. The syntheses of the previously inaccessible 4‐ and 6‐ehloro‐1‐armnooxin‐doles has shown that this method, first applied to 1‐aminooxindole, may be reasonably general. The mechanism of this reaction is discussed in terms of nitrene and nitrenoid intermediates.
A new synthesis of anthyridine derivatives
Authors: Carboni S. , Da Settimo A. , Segnini D.
Published: March 2009

An Ullmann reaction between 2‐bromonicotinic acid and 2,6‐diaminopyridine gave 6 ‐amino‐2,2 ‐dipyridylamino‐3‐carboxylic acid (V). The latter was converted into 7‐amino‐5H‐dipyrido‐[1,2‐a:2,3 ‐d]pyrimidin‐5‐one (VII) by heating with polyphosphoric acid and into 2‐amino‐5,10 H‐anthyridin‐5‐one (VIII) by heating with concentrated sulfuric acid. Structure proofs of VII and VIII are given and some derivatives of VIII are described.
The reactions of 2,2‐difluoro‐4‐methylnaphtho[l,2‐e]‐1,3,2‐dioxaborin and its [2,1‐e]isomer with N,N‐dimethylformamide
Authors: Reynolds G. A. , Van Allan J. A.
Published: March 2009

The title compounds react with dimethylformamide in acetic anhydride to give dimethylamino‐vinyl derivatives which, on treatment with base, yield benzochroman‐4‐ones. The [1,2‐e] isomer reacts with the Vilsmeier complex to give 3‐formylbenzo[f]chrom‐4‐one and 9‐hydroxy‐1‐phenalenone, and the [2,1‐e]isomer gives 3‐formylbenzo[h]chrom‐4‐one.
The synthesis of benzo[c]cinnoline 5,6‐dioxides and related compounds
Authors: Kempter Fritz E. , Castle Raymond N.
Published: March 2009

The preparation of a variety of benzo[c]cinnolines as well as benzo[c]cinnoline monoxides and dioxides by reduction of the corresponding 2,2‐dinitrobiphenyls with hydrogen and Raney nickel of low activity is described. The detailed procedures developed produce superior yields of benzo[c]cinnoline monoxides and dioxides. The structure of some intensely‐colored red‐violet amino, alkylamino, and hydroxybenzo[c]cinnoline monoxides and dioxides is discussed and these are compared with the essentially colorless alkoxyl and acetylamino derivatives. The long wave length band in the U. V. spectrum of the colored compounds is compared.
Substitution reactions of 4‐methyldibenzothiophene
Authors: Campaigne E. , Hewitt L. , Ashby John
Published: March 2009

Succinoylation, acetylation and nitration of 4‐methyldibenzothiophene yields 2‐substituted products. Bromination however, gave 3‐bromo‐4‐methyldibenzothiophene as the major product along with a small amount of the 2‐isomer. The bromo‐compounds were used to prepare related derivatives via lithium exchange. 4‐Methyldibenzothiophene 5,5‐dioxide was also shown to nitrate in the 3‐position. The structures of the derivatives were determined by NMR analyses. An alternative synthesis of 4‐methyldibenzothiophene is described.
Syntheses in the pyridazine series. XXX. Protonation and quaternization studies on imidazo[1,2‐b] pyridazines and s‐triazolo[4,3‐b] pyridazines
Authors: Japelj M. , Stanovnik B. , Tišler M.
Published: March 2009

Sterically unhindered s‐triazolo[4,3‐b] pyridazines form N1‐methiodides, whereas 3‐ and/or 8‐substituted analogs form a mixture of N1‐ and N2‐methiodides. In some cases thermal rearrangement occurred. Imidazo[1,2‐b]pyridazines form N1‐methiodides and here also steric interactions were observed as evidenced by the NMR spectra.
Mass spectra of some phenylazopyridines and quinolines
Authors: Brown Ellis V.
Published: March 2009

All of the isomeric phenylazoquinolines and phenylazopyridines have been prepared and subjected to electron impact in the mass spectrometer. Fragmentation patterns of these compounds are discussed along with some of their para‐bromo derivatives.
1,2,3‐benzotriazines. IV. The chemical reactivity of benzimidazo[1,2‐c] [1,2,3]benzotriazine
Authors: Spector Richard H. , Joulliéa Madeleine M.
Published: March 2009

The reactions of benzimidazo[1,2‐c][1,2,3]benzotriazine (1) with fluoroboric acid, potassium iodide and phenyl isothiocyanate are described. The structure of the phenyl isothiocyanate product is elucidated by chemical and spectroscopic techniques. The reaction of 1 with alcoholic potassium hydroxide is shown to proceed by a free radical mechanism. The structure of the compound formed from 1 and sodium diethyl malonate is investigated by spectroscopic methods. The reduction and photochemical reactivity of 1 are also discussed.
Dithioheterocycles from ethane‐1,2‐disulfenyl chloride
Authors: Mueller Wolfgang H. , Dines Martin
Published: March 2009

A convenient route to 1,4‐dithianes from ethane‐1,2‐disulfenyl chloride and acetylenes is presented. The reaction of this new sulfenyl halide with primary and secondary amines is also discussed.
Heterocyclic N‐glycosides. III. Synthesis of N‐glycosyl‐v‐triazoles from glycosyl azides and phenylacetylene
Authors: Garcíaa‐Lóapez M. T. , Garcíaa‐Mun̈toz G. , Iglesias J. , Madroïtero R.
Published: March 2009

A number of v‐triazoles were prepared by the 1,3‐dipolar cycloaddition of glycosyl azides on phenylacetylene. In all the cases studied, except when 2‐O‐trichloroacetyI‐3,4,6‐tri‐O‐acetyl‐α‐D‐glucopyranosyl azide was used, the two possible v‐triazoles were obtained. The assignment of structure and anomeric configuration for all N‐glycosides obtained is discussed.
Base catalyzed isomerization of epoxides. I. The isomerization of β‐chloroepoxides
Authors: Sheng M. N.
Published: March 2009

The base catalyzed isomerizations of epichlorohydrin, 1‐chloro‐2,3‐epoxy‐2‐methylpropane, 1‐chloro‐2,3‐epoxybutane, and 3‐chloro‐1,2‐epoxybutane have been studied, using lithium ortho‐phosphate as the basic catalyst. Chloroketones and dichloro‐alcohols are the major products. This is the first example of a compound with an electron withdrawing group attached to the carbon atom adjacent to the oxirane ring which undergoes the α‐elimination pathway. A bidirectional mechanism is proposed to explain the experimental results. The stereochemistry of the hydrochlorination of 1‐chloro‐2,3‐epoxybutane and 3‐chloro‐1,2‐epoxybutane has also been studied.
A study of some 1‐alkyl‐2,3‐dihydroimidazo[1,2‐a]benzimidazoles
Authors: North Robert J. , Day Allan R.
Published: March 2009

A series of 1‐alkyl‐7‐nitro (and 7‐amino)‐2,3‐dihydroimidazo[1,2‐α]benzimidazoles has been prepared. Similarly, a series of 1‐alkyl‐2,3‐dihydroimidazo[1,2‐α]benzimidazoles has been prepared. The prototropic tautomerism of this system has been studied. The site of electrophilic attack (alkylation) has been examined. 1‐Alkylation takes place under strongly basic conditions and 9‐alkylation occurs under neutral conditions.