Reactions with Carbo(heterylhydrazonoyl) Halides. I. Chemistry of Carbo(3-phenylpyrazol-5-yl-hydrazonoyl) Chlorides

The Carbo(3-phenylpyrazol-5-yl-hydrazonoyl) halides 1a , b react with active methylene compounds to yield the 1-(3-phenylpyrazol-5-yl)-pyrazole derivatives 2a – k (Scheme 1). The acyclic intermediates 3a , b could be isolated from reaction of 1a , b with acetylacetone, thus establishing the substitution mechanism for these reactions. Compounds 1a , b reacted with carbon disulfide, phenyl isothiocyanate, methyl cyanide, and with p-chlorobenzaldehyde to yield the corresponding heterocyclic derivatives 5 – 8 , respectively (Scheme 2). The behaviour of compounds 2 with hydrazine hydrate is reported.     

Regiochemical aspects in the reaction of 2,3,5-tri-o-benzoyl-d-ribofuranosyl : Acetate with silyl enol ethers catalyzed by stannic chloride

In the reaction with silyl enol ethers catalyzed by stannic chloride, 2,3,5-tri-O-benzoyl-D-ribofuranosyl acetate behaves as an ambident electrophile; silyl enol ethers of ketones having α-hetero substituents afford C-1 adducts, whereas those of usual acyclic ketones give products arising from attack on C-2 benzoxyl group.     

Activated nitriles in heterocyclic synthesis. Part III. Synthesis of N-amino-2-pyridone,pyranopyrazole and thiazolopyridine derivatives

The reaction of 2-cyanoethanoic acid hydrazide and arylidenemalononitrile was studied as a new route for the synthesis of N-amino-2-pyridones. Pyrano[2,3-c]pyrazole and thiazolo[2,3-a]pyridine could be prepared from the reaction of arylideneazolones with the same reagent.     

Studies on arylhydrazonoisoxazolinethiones. Behaviour of 4-arylhydrazono-3-phenyl-2-isoxazoline-5-thiones toward hydrazines,grignard reagents and alkylating agents

The 4-arylhydrazono-3-phenyl-2-isoxazoline-5-thiones 2 react with hydrazines to yield the 5-hydrazones 3 and 5 . The reaction of 2 with Grignard reagent resulted in addition of the reagent to the thiocarbonyl group to yield 7 . Treatment of 2 with diazomethane effected S - and N -methylation beside 1,2,3-triazole derivative 11 obtained through isomerisation. The potassium salt of 2 react with alkyl halides to yield the S-alkyl derivatives 12 .     

Reactions with β-cyanoethylhydrazine,III. A new approach for the synthesis of substituted 3,5-diaminopyrazole and 1,2,4-triazoles

The reactivity of -cyanoethylhydrazine toward enaminonitrile and aroyl isothiocyanates is reported. A variety of 3,5-diaminopyrazole and ³-1,2,4-triazolin-5-thione derivatives could be prepared.

---

Reaktionen mit -Canyethylhydrazin, 3. Mitt.: Ein neuer Weg zur Synthese von substituierten 3,5-Diaminopyrazolen und 1,2,4-Triazolen

Zusammenfassung Es wird über die Reaktivität von -Cyanethylhydrazin gegenüber Enaminonitril und Aroylisothiocyanaten berichtet. Es konnte eine Reihe von 3,5-Diaminopyrazol-und ³-1,2,4-Triazolin-Derivaten hergestellt werden.

     

Reactions with cyclic amidines II. The behaviour of cyclic amidines toward ethoxycarbonyl and aroyl isothiocyanates

The behaviour of the aminopyrazole derivatives 1a-c, 2-amino-4-phenylthiazole (2) and 2-amino-5-phenyl-1,3,4-thiadiazole (3) toward the action of ethoxycarbonyl and benzoyl iso-thiocyanate is reported. The data clearly demonstrates the dependence of the nature of the products obtained from the reaction of isothiocyanates with cyclic amidines on the nature of the substituents on the heterocyclic ring.     

Transition Metal Complexes of an Antipyrine Derivative

The stepwise formation constants of N-antipyrinyl-N′-3-phenyl-2-propenoyl-thiourea (I) complexes with metal ions of the first transition series, Cu(II), Ni(II), Co(II), Mn(II) and Zn(II) have been determined in 70% (V/V) ethanol-water medium. The formation constants for the chelates follow the Irving-Williams series: Zn(II)<Cu(II)>Ni(II)>Co(II)>Mn(II) The effect of ionic radius and electronegativity on the chelate formation are discussed. Complexes of Cu(II) and Ni(II) have been synthesised and characterised by elemental analysis, electrolytic conductance, IR spectra and magnetic susceptibility measurements. The ligand forms bis-complexes with Cu(II) and Ni(II). The binding sites are oxygen and sulphur atoms.     

Pyrimidine derivatives and related compounds. A novel synthesis of pyrimidines,pyrazolo[4,3-d]pyrimidines and isoxazolo[4,3-d] pyrimidine

Benzoylacetonitrile (II) reacted with trichloroacetonitrile (III) to yield the β-amino-β-trichloromethylacrylonitrile IV. Compound IV reacted with hydrazine hydrate to yield 5-amino-4-cyano-3-phenylpyrazole (V) and with 2-aminopyridine to yield the aminopyridine derivative VIII (cf., Chart I). Compound IV reacted with III to yield 2,4-bis(trichloromethyl)-5-cyano-6-phenylpyrimidine (I) which could be converted into a variety of pyrazolo[4,3-d]pyrimidine derivatives by treatment with hydrazine hydrate under a variety of different experimental conditions (cf., Chart II).     

The reaction of malononitrile with thioglycolic acid. A novel procedure for the synthesis of thiazolone derivatives

Malononitrile (I) reacted with thioglycolic acid to yield the thiazolin-4-one derivatives II or III depending on the molar ratio of the reactants. Compound II reacted with benzaldehyde in refluxing pyridine to yield the arylidene derivative IV. On the other hand, the benzylidine bis derivative VIII was obtained when II was reacted with benzaldehyde in refluxing ethanol. The structure of IV was established via its synthesis from the reaction of benzylidenemalononitrile (VI) and thioglycolic acid in refluxing acetic acid. Similar to II, compound III condensed with benzaldehyde to yield the benzylidene derivative IX.     

The reaction of isothiocyanates with 2-cyanoethanoic acid hydrazide. A novel synthesis of 1,3,4-thiadiazoles

Benzoyl and ethoxycarbonyl isothiocyanates reacted with 2-cyanoethanoic acid hydrazide 2 to afford 1-cyanoacetyl-4-substituted thiosemicarbazide ( 5a,b ). Compound 5a afforded the pyrazolo[1,5-a]-s-triazine derivative 6 on treatment with 5% potassium hydroxide, and cyclised to 2-benzoylamino-5-cyanomethyl-1,3,4-thiadiazole ( 8 ) when boiled under reflux in glacial acetic acid. Compound 8 condensed with aromatic aldehydes to yield the corresponding arylidene derivatives 9a-c . It undergoes coupling with aromatic diazonium salts to afford the hydrazones 11a-c . Similarly, it coupled with diazotised aminopyrazole to afford the cyclic product 12 .