Studies on heterocyclic enamines: New syntheses of 4H-pyranes,pyranopyrazoles and pyranopyrimidines

The behaviour of several 2-amino-3-cyano-4H-pyran derivatives toward a variety of nucleophilic reagents is reported.     

Polarographic activity of the arylhydrazones of α-cyanoketones as a criterion of their acidity

The polarographic behaviour of phenylhydrazonomesoxalonitrile (2) and ethyl phenylhydrazonomesoxalonitrile (3) as well as pK′ and pK_a values are reported for a series of arylhydrazones of α-cyanoketones.     

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.     

Enaminones in heterocyclic synthesis: Synthesis and chemical reactivity of 3‐anilino‐1‐substituted‐2‐propene‐1‐ one

The 3‐anilinoenones 3a,b were prepared from the corresponding 3‐dimemyl‐aminopropenones. The reactivity of 3a,b towards a variety of carbon and nitrogen nucleophiles as well as naphthoquinones is reported.     

Studies with enaminones: The reaction of enaminones with aminoheterocycles. A route to azolopyrimidines,azolopyridines and quinolines

The enaminones 1b,d,f react with 4‐phenyl‐3‐methyl‐5‐pyrazoleamine 3a to yield the pyrazole derivatives 4a‐c that cyclised readily on reflux in pyridine solution in presence of hydrochloric acid to yield the pyrazolo[1,5‐a]pyrimidines 5a‐c. Similarly 3(5)‐amino‐1H‐triazole (3b) reacted with 1b,d,f to yield the triazolo[1,5‐a]pyrimidines 5d‐f. In contrast attempted condensation of the 5‐tetrazoloamine (3c) with 1a,d,e resulted in its trimerisation and only triaroylbenzene 8a,d,e was isolated. The reaction of 1a,b,d with anthranilonitrile 9a and the reaction of 1a‐c with the 2‐aminocyclohexene thiophene‐3‐nitrile 10a afforded the cis enaminones 11a‐c and 12a‐c. Similarly, reaction of 1a‐c with the methylanthranilate 9b and reaction of 1b,e with ethyl 2‐aminocyclohexene thiophene‐3‐carboxylate 10b afforded the cis enaminones 11d‐f and 12d,e respectively. Attempted cyclization of 11a‐c into quinoline failed. Successful cyclization of 11d into the quinolinone 13 could be affected, on heating for five minutes in a domestic microwave oven at full power. The reaction of 1a‐c,f with piperidine afforded the trans enaminones 14a‐d. Similarly, trans 14e was formed from the reaction of 1b with morpholine. The coupling reaction of 1b with excess of benzene diazonium chloride afforded the formazane 16. The enaminone 2 reacted with heterocyclic amines to yield the pyridones 17,18.     

Reactions with heterocyclic amidines. VI. Synthesis and chemistry of pyrazol-5-yl,and 1,2,4-triazol-5-ylhydrazonyl chlorides

The 4-bromo-3-phenylpyrazol-5-ylhydrazonyl chlorides (Ia,b) and 1,2,4-triazol-5-ylhydrazonyl chlorides (IIa,b) were prepared via coupling of diazotized 4-bromo-3-phenyl-5-aminopyrazole (III) and 5-amino-1,2,4-triazole (IV) with α-chloro derivatives of acetylacetone and of ethyl aceto-acetate. Compounds Ia and IIa,b were utilised for the synthesis of several new heterocyclic derivatives.     

Studies on Azolylacetonitriles: The Reactivity of Thiazole-2-yl,Thiadiazol-2-yl Acetonitriles Toward Electrophilic Reagents

5-Acetyl-2-cyanomethyl-4-methylthiazole, 2-aminothiazole, and 5-N-benzoylamino-1,3,4-thiadiazole-2-yl-acetonitrile react with acetone, and malononitrile derivatives in the presence of sulfur to yield the corresponding thiophene derivatives. Also, 4-furylmethylene-2-phenyl-2-oxazolin-5-ones react with thiophenol, and/or thionaphthol to give the thiolester derivatives in one-pot synthesis. The structures of the products were based on IR, 1 H NMR, and elemental analysis.     

Studies with arylhydrazonopyridinones: Synthesis of new arylhydrazono thieno[3,4-c]pyridinones as novel D2T2 dye class; classical verse green methodologies

A variety of arylhydrazonopyridinones were prepared via heating cyanoacetamides with ethyl acetoacetate in absence of solvent under reflux conventionally or ultrasound irradiation or in a microwave oven. The formed products 5 and 6 could be readily converted to thienopyridones. Attempted addition of the latter to electron poor olefins afforded only arylhydrazonopyridinones.     

Nitriles in organic synthesis: A novel synthesis of benzo[h]pyrimidino[1,2-c]-pyridazinone and hydrazonobut-2-enonitrile derivatives

A new synthesis of benzo[h]pyrimidino[1,2-c]pyridazinones via coupling diazotised anthranilic acid with 1-phenylethylidenemalononitrile ( 1 ) is reported. Synthesis of new 1-antipyrin-4-yl and 1-pyrazol-5-ylpyridazine derivatives utilizing 1 as starting material is also described.