Ibrahim M. A. Awad

Studies in the Vilsmeier-Haack reaction, part VII: Synthesis and reaction of 3-methyl-1-phenyl-4-acetyl hydrazono 2-pyrazoline-5-one(-5-thione)

SummaryThe keto (thio) tautomers1–4 of the hydrazono pyrazolone, thiopyrazolone derivatives underwent simultaneous diformylation, chlorination (desulphurization) and ring closure under Vilsmeier reaction conditions giving the pyrazolo[3,4-c]pyrazole aminoacroleins (5,6). Treatment of5 and/or6 with proper reagents afforded the corresponding pyrazolo[3,4-c]pyrazoles with different heterocyclic systems at the 3-position.The structures of these compounds were confirmed by elemental analysis, IR and1H-NMR spectroscopy. All synthesized compounds have been screened in vitro for their antibacterial activities against a number of Gram-positive and Gram-negative bacteria.ZusammenfassungDie Keto-(Thio)-Tautomeren1–4 der Hydrazonopyrazolon-/Thiopyrazolon-Derivate gingen unter Vilsmeier-Bedingungen zugleich Diformylierung, Chlorierung (Entschwefelung) und Ringschluß zu Pyrazolo[3,4-c]pyrazol-aminoacroleinen5 und6 ein. Aus5 und/oder6 konnten die entsprechenden Pyrazolo[3,4-c]pyrazole mit verschiedenen heterocyclischen Systemen in 3-Position erhalten werden. Die Strukturen der Verbindungen wurden mittels Elementaranalyse, IR und1H-NMR überprüft. Alle synthetisierten Verbindungen wurden in vitro bezüglich ihrer antibakteriellen Aktivität gegenüber einer Anzahl Gram-positiver und Gram-negativer Bakterien untersucht.

STUDIES IN VILSMEIER-HAAK REACTION. PART II. APPLICATION TO SOME 1-PHENYL-3-METHYL-4-AZOSULPHONAMIDO-5-PYRAZOLONE DYES

Abstract The Vilsmeier-Haak reaction on 3-methylpyrazolone azosulphonamide derivatives (1,2) has been shown to lead to chlorination of the 5-oxopyrazolone system in addition to diformylation of the 3-methyl group to give the corresponding aminoacroleins (3,4), respectively. On treatment with some reagents 3, 4 give compounds 9–20 with different heterocyclic systems in the 3-position.

HETEROCYCLO-SUBSTITUTED SULFA DRUGS: PART X. NOVEL 5-IMINO-δ2-PYRAZOLIN-4-DITHIOCARBAMYL-AZO DYES AS ANTIMICROBIAL AGENTS

Abstract Synthesis of a series of novel azo-sulfa drugs as 5-imino-3-methyl-1-phenyl-δ2-pyrazolin-4-dithiocarbamy-azo dyes (I-XV) are described via a reaction of 4-sulfamoyl and/or sulfonyl diazonium chloride with 5-imino-3-methyl 1-1-phenyl-δ2-pyrazolin-4-dithiocarbamic acid in acid medium. The corresponding iron, copper, mercury, cobalt, nickel, and lead chelates were obtained in 1:1 ligand-to-metal cation molar ratio at ice temperature as monochelate compounds (Iaf-XVaf). Furthermore, heating in 1:2 molar ratio gave di-chelate compounds (I′a-f-XV′a-f). All the synthesized azo-sulfa drugs (ligands) and their mono- and/or di-chelates were characterized by microanalysis, UV, IR and H-NMR spectroscopy and were screened in vitro for their antibacterial and antifungal activities.

SYNTHESIS AND BIOLOGICAL ACTIVITY OF SOME NEW HETEROCYCLIC QUINOLINE DERIVATIVES

Abstract Alkylation of 2-mercapto-3-cyano-4-aryl-5,6,7,8-tetrahydroquinoline (I) gave compounds II–IV. Cyclization of III and IV afforded thienoquinolines V and VI respectively. On diazotization of V and VI, the corresponding triazinone derivatives VII and VIII were obtained. Also, reaction of V with benzoyl chloride yielded the tetracyclic compound IX. Structures of the new compounds were established by their elemental analyses and spectral data. Some of these compounds were screened in vitro for their antibacterial activities.

STUDIES ON THE VILSMEIER-HAACK REACTION. PART IV. SYNTHESIS AND REACTION OF SOME 3-METHY L-l-PHENYL-4-(ACETY L; IMINOACETYL AND THIOACETYL)-2-PYRAZOLIN-5-THIONE

Abstract Three derivatives of 5-thiopyrazolone (3-5) have been synthesized. The 3-methyl group in each of these derivatives has been found to undergo diformylation by Vilsmeier reagent to give the corresponding aminoacroleins (6-8). Treatment of 6-8 with some reagents affords the related thiopyrazolone derivatives (12-29) with different heterocyclic systems at the 3-position.

SYNTHESIS OF SOME NEW HETEROCYCLIC COMPOUNDS CONTAINING THIENO[2,3-b]QUINOLINE MOIETY

Abstract 2-Cyano-3-amino-4-aryl-5, 6, 7, 8-tetrahydro-thieno[2,3-b]quinoline (1) reacted with carbon disulfide to give compound 2. Alkylation of 2 with different reagents gave the corresponding thioethers 3–7. Diazotisation of 1 furnished chloro derivative 8 which reacted with thiourea to give mercaptotriazine 9. Methylation of 9 yielded 10. On treatment of 8 with hydrazone hydrate, the expected hydrazinocompound 11 was obtained. Reaction of 11 with aromatic aldehydes, acetylacetone, acetic acid, acetic anhydride, carbon disulfide and nitrous acid gave compounds 12–17, respectively. The structures of all synthesized compounds were confirmed by elemental and spectral analysis.

DIPHOSPHINE COMPOUNDS: PART I. NOVEL BIOLOGICALLY ACTIVE 1,1′bis-AND/OR 1,2-cis-(DIPHENYLPHOSPHINO-)ETHENE AND THEIR COMPLEXES [M(CO)n{Ph2P(CHn)nPPh2}] & [Cu(Cl)2{Ph2P(CHn)nPPh2}], (M = W, Mo, Crn = 1,2….n)

Interaction of [Ph2PC(═CH2)PPh2] (A)1–3 and/or [Ph2P (CH═CH) PPh2](B) ligands in different molar ratio with hexacarbonyl metals M(CO)6 gives [M(CO) n Ph2PC(═CH2)PPh2] and/or [M(CO) n Ph2P (CH═CH)PPh2 where M═ Cr, Mo or W, n = 2 and/or 4]. The carbon diphosphine complexes of type (A) which form four heteromemebered rings and/or type (B) form five heteromembered rings which reacts (addition reaction) with some different amines (methyl amine, dimethyl amine), phenyl hydrazine and/or some of amino acids (glycine, alanine, aspartic acid, serene). The structures of A and/or B complexes and their amino derivatives have been characterized by using elemental analysis, IR spectra, 1HNMR,1H-31P-NMR, and mass spectra. Ligands and their complexes were screened in vitro to investigate the biological activities (antibacterial and antifungi). Interestingly, complexes are having strong and remarkable activities increases than the free ligands.

STUDIES ON THE VILSMEIER-HAACK REACTION. PART III-REACTION OF 3-METHYL-1-PHENYL-4-ARYLIDENE-2-PYRAZOLIN-5-THIONE

Abstract The 3-methyl group in 3-methyl pyrazolthione derivatives (2,3) has been found to undergo diformylation by Vilsmeier reagent to give the aminoacroleins 4.5 with some reagents affords the related l-phenyl-4-arylidene-5-pyrazolthione derivatives (8–21) with different heterocyclic systems at the 3-position.

HETEROCYCLO-SUBSTITUTED SULFA DRUGS: PART XI. NOVEL BIOLOGICALLY ACTIVE N-(PIPERIDINO-, MORPHOLINO-, PIPERAZINO-) DITHIOCARBAMYL-AZO DYES AND THEIR CHELATES

Abstract A Series of novel azo-sulfa drugs of piperidino-, morpholino-, mono-, and bis-piperazino-N-dithiocarbamyl-azo dyes (Ia-h - IV a-h) are synthesiezed via a reaction of 4-[(4′-heterocyclo- substituted) suflamoy I and/or sulfonyl] benzenediazonium salts with N-piperidino-, N-morpholino-, mono-, and bis- N-piperazino- dithiocarbamate sodium salts in acid medium to afford the corresponding azo dye legands. Interaction of these ligands with metal salts: iron(III). copper(II) and mercuric(II) chlorides in ethanolic solution afforded the corresponding metal chelates (I′a-h - ′IVa-h), (I″a-h - ″IVa-h) and (I′″a-h - ″IVa-h). Ligands and their metal chelates are characterized by microanalysis, IR, UV-Vis H-NMR spectroscopy and are screened in vitro for their antimicrobial activities. Chelation of ligands induces a remarkable increase in their antimicrobial activity.

SYNTHESIS AND APPLICATION OF SOME NEW 5-SULPHONYL-N-HETEROCYCLO-8-HYDROXYQUINOLINE DERIVATIVES AS POTENTIAL DRUGS

Abstract Some new sulphonyl-N-heterocyclo-8-hydroxy quinolines have been synthesised by the reaction of 8-hydroxyquinoline-5-sulphonyl hydrazide with different active methylene compounds. The pyrazole, pyrazoline, pyrazolidine and pyridazine derivatives were reacted with some metal cations to give the corresponding chelates. All synthesized compounds have been screened in vitro for their biological activities.