Synthesis of acridinedione derivatives as laser dyes

Synthesis of 9-alkyl, 10-alkyl, 9,10-dialkyl, and 10-aryl-3,4,6,7,9,10-hexahydro-1,8(2H,5H)acridinedione (2a–r) are described as a new class of laser dyes. Reactions of diamines with methylene bis(cyclohexane-1,3-dione) yielded the respective bisacridinediones (3a–e). These dyes lase around 478–494 nm and are compared with the standard dye coumarin-102. © 1996 John Wiley & Sons, Inc.     

A new class of laser dyes from acridinedione derivatives

Synthesis of 10-aryl-3,4,6,7,9,10-hexahydro-1,8(2H,5H)-acridinedione as a new class of laser dyes is reported. These dyes lase around 475–495 nm and are compared to the standard dye coumarin 102.     

Synthesis and antivirus activity of 1,3,5‐triazine derivatives

Reaction of 6‐phenyl‐4‐thioxo‐1,3,5‐triazine‐2‐one with alkyl halide in the presence of 1 equiv. of sodium hydroxide resulted in 4‐alkylthio‐6‐phenyl‐1,3,5‐triazine‐2‐one in good yield, whereas the above reaction provided 2‐alkoxyl‐4‐alkylthio‐6‐phenyl‐1,3,5‐triazine in the presence of 2 equiv. of sodium hydroxide. 6‐Phenyl‐4‐thioxo‐1,3,5‐triazine‐2‐one was oxidized with hydrogen peroxide to give 6‐phenyl‐1,3,5‐triazine‐2,4‐dione. Further treatment with ethyl bromoacetate or (substituted) benzyl bromides yielded 2,4‐dialkoxy‐6‐phenyl‐1,3,5‐triazines. At the same time, a small amount of 2‐dimethylamino‐4‐alkoxy‐6‐phenyl‐1,3,5‐triazines were isolated. Preliminary bioassays indicate that the title compounds possess good activities against tobacco mosaic virus. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:542–545, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10189     

Synthesis and anti‐HIV activity of substituted 1,2,4‐triazolo‐thiophene derivatives

A new series of substituted 1,2,4‐triazoles bearing thiophene molecules 8 and 10 has been synthesized from cycloaddition of thiophene 3‐and 2‐carbonitriles 5 and 9 , respectively, with the reactive cumulene intermediates 4 . The newly synthesized products have been evaluated for their anti‐HIV activity. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:443–448, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20319     

Synthesis and fungicidal activity of novel 1,3‐disubstituted 1H‐diazirine derivatives

A convenient method for synthesis of novel 1‐[pyrimidinyl], 1‐[1,3,5‐triazin‐2‐carbonyl], and 1‐[thiazol‐5‐carbonyl] derivatives of 3‐thioxo‐diaziridine 1 , 3 , 5 , and 7 from corresponding hydrazides, CS2, and KOH is elaborated. The highest reaction yield was observed when these initial reagents were taken in molar ratio of 1:1.7:2.0, respectively. By alkylation of compounds 1 , 3 , 5 , and 7 that proceeds exclusively at sulfur atom, the 3‐sulfanyl derivatives of 1‐[pyrimidinyl]‐, 1‐[1,3,5‐triazin‐2‐carbonyl]‐, and 1‐[thiazol‐5‐carbonyl]‐diazirines 2 , 4 , 6 , and 8 were formed. The structures of synthesized compounds were confirmed by proton and carbon nuclear magnetic resonance (NMR), mass spectra (MS), and elemental analysis. The fungicidal activities of S‐substituted derivatives were studied. Data of preliminary biological tests testify that these compounds can be of interest in search for new fungicides. J. Heterocyclic Chem., (2010).     

Synthesis and properties of new halogen‐substituted polyamides from 5‐halo‐m‐phenylenediamines and both aliphatic and aromatic dicarboxylic acids

New halogen‐substituted aromatic–aliphatic and wholly aromatic polyamides with high inherent viscosities were synthesized by the direct polycondensation of 5‐halo‐m‐phenylenediamines, where the halogens were Cl, Br, and I, with both aliphatic and aromatic dicarboxylic acids in N‐methyl‐2‐pyrrolidone with a mixture of triphenyl phosphite and pyridine as a condensing agent. The solubility of the halogen‐substituted polyamides was much higher than that of the parent polyamides derived from m‐phenylenediamine. The glass‐transition temperatures of the substituted aromatic–aliphatic polyamides increased in the order Cl < Br < I, whereas the temperatures of 10% weight loss in air decreased in the reverse order. The limiting oxygen index values, as an indication of flammability, increased for the substituted aromatic–aliphatic polyamides in the order Cl < Br < I. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3911–3918, 2000     

Synthesis,characterization, and biological activity of some aza‐uracil derivatives

Thiation of 1 by LR gave the corresponding 3,5‐dithioxo derivative 2 and the trimer 3 . Methylation of 1 afforded the S‐methyl derivative 4 . Compound 1 was fused with 6‐bromo‐2‐phenyl‐benzo[1,3‐d]oxazin‐4‐one ( 5 ) and gave 6 . Condensation of 1 with some acid derivatives 7a , 7b , 7c , 7d and/or 8a , 8b , 8c yielded thiadiazolo‐triazine derivatives 9a , 9b , 9c , 9d and 10a , 10b , 10c . Compounds 9a , 9c and 10c were hydrolyzed to furnish 11a , 11b , 11c Acetylation of 14 afforded mono‐ and diacetyl‐derivatives 15 and 16 . Benzoylation of 14 afforded mono‐ and dibezoyl‐derivatives 17 and 18 . 14 with some aromatic aldehydes yielded 9a , 9b , 9c . Reacting 14 with phenyl (iso‐ and/or isothio‐) cyanate gave the urea derivatives 20a , 20b . Thiation of 14 with P₄S₁₀ furnished 21 . The newly synthesized compounds were tested as antimicrobial agents. J. Heterocyclic Chem., (2011)     

Synthesis,characterization and biological activity of some 1,2,4‐triazine derivatives

4‐Amino‐6‐methyl‐3‐(2H)‐thioxo‐5‐(4H)‐oxo‐1,2,4‐triazine ( 1 ) was condensed with 2‐methyl (or phenyl)‐4H‐3,1‐benzoxazin‐4‐one ( 5a,b ) in boiling acetic acid to give compounds 8‐11 . Reacting 1 with chloroacetyl chloride afforded the corresponding chloroacetamido and triazinothiadiazine derivatives 12 and 13 . Condensing 2 with succinic anhydride and/or phthalic anhydride yielded compounds 14 and 15 . Benzoylation of 4‐amino‐6‐methyl‐3‐(2H)‐thioxo‐5‐(4H)‐oxo‐2‐(2,3,4,5‐tetra‐O‐acetyl‐α‐D‐glucopyra‐nosyl)‐1,2,4‐triazine ( 19 ) afforded the corresponding 4‐N,N‐dibenzoyl derivative 20 . Deblocking of the N‐2 glycoside 21 and the S‐glycoside 22 by methanolic ammonia gave compounds 23 and 24 . Acetylation of 4‐amino glycoside 25a afforded the corresponding 4‐mono‐ and 4‐diacetyl derivatives 26 and 27 . Deamination of 25a,b yielded compounds 28a,b . Methylation of compound 28b afforded the corresponding N4‐ and S‐methyl derivatives 29 and 30 .     

Synthesis and isomerization of thienotriazolopyrimidine and thienotetrazolopyrimidine derivatives with potential anti‐inflammatory activity

Several derivatives containing the thieno[2,3‐d]pyrimidine system were prepared starting from 2‐amino‐4,5‐dihydronaphtho[2,1‐b]thiophene‐1‐carbonitrile ( 1 ). In particular, the synthesis and structure characterization of 8,9‐dihydronaphtho‐ [1′,2′:4,5]thieno[3,2‐e][1,2,4]triazolo[4,3‐c]pyrimidine derivatives 13–16 and their isomerization to 8,9‐dihydronaphtho[1′,2′:4,5]thieno[3,2‐e][1,2,4]‐triazolo[1,5‐c]pyrimidine derivatives 17–20 under different suitable reaction conditions were reported and verified with X‐ray analysis. Moreover, compounds 13, 14 and 22 were tested as potential anti‐inflammatory agents and derivative 14 showed potent activity in carrageenan test. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:226–234, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20114     

Synthesis,crystal structure and cytotoxic activity of novel 5‐methyl‐4‐thiopyrimidine derivatives

This article presents the synthesis of three new 4‐thiopyrimidine derivatives obtained from ethyl 4‐methyl‐2‐phenyl‐6‐sulfanylpyrimidine‐5‐carboxylate as the starting material, namely, ethyl 4‐[(4‐chlorobenzyl)sulfanyl]‐6‐methyl‐2‐phenylpyrimidine‐5‐carboxylate, C₂₁H₁₉ClN₂O₂S, ( 2 ), {4‐[(4‐chlorobenzyl)sulfanyl]‐6‐methyl‐2‐phenylpyrimidin‐5‐yl}methanol, C₁₉H₁₇ClN₂OS, ( 3 ), and 4‐[(4‐chlorobenzyl)sulfanyl]‐5,6‐dimethyl‐2‐phenylpyrimidine, C₁₉H₁₇ClN₂S, ( 4 ), which vary in the substituent at the 5‐position of the pyrimidine ring. The compounds were characterized by ¹H NMR, ¹³C NMR, IR and mass spectroscopies, and also elemental analysis. The molecular structures were further studied by single‐crystal X‐ray diffraction. Compound ( 2 ) crystallizes in the space group P with one molecule in the asymmetric unit, whereas compounds ( 3 ) and ( 4 ) crystallize in the space group P2₁/c with two and one molecule, respectively, in their asymmetric units. The conformation of each molecule is best defined by the dihedral angles formed between the pyrimidine ring and the planes of the two aryl substituents attached at the 2‐ and 4‐positions. The only structural difference between the three compounds is the substituent at the 5‐position of the pyrimidine ring, but they present significantly different features in the hydrogen‐bond interactions. Compound ( 2 ) displays a one‐dimensional chain formed by hydrogen bonds and the chains are further extended into a two‐dimensional network. Molecules of ( 3 ) and ( 4 ) generate one‐dimensional chains formed through intermolecular interactions. The study examines the cytotoxicity of compounds ( 3 ) and ( 4 ) against Human umbilical vein endothelial cells (HUVEC) and HeLa, K562 and CFPAC cancer cell lines. The presence of the hydroxymethyl and methyl groups in ( 3 ) and ( 4 ), respectively, offers an interesting new insight into the structures and behaviour of these derivatives. Compound ( 4 ) was found to be nontoxic against CFPAC and HUVEC; however, it shows weak activity against the HeLa and K563 cell lines. The presence of a hydroxy group in ( 3 ) significantly increases its cytotoxicity towards both, i.e. the cancer (HeLa, K562 and CFPAC) and normal (HUVEC) cell lines.     

Synthesis,characterization and in vitro antitumour activity of di‐ and tri‐organotin derivatives of fenbufen

The di‐ and tri‐organotin derivatives of fenbufen (4‐(4‐biphenyl)‐4‐oxobutyric acid), [{(n‐C₄H₉)₂Sn(OCOCH₂CH₂COC₆H₄C₆H₅‐4)}₂O]₂ ( 1 ) and R₃SnOCOCH₂CH₂COC₆H₄C₆H₅‐4 (R?C₆H₅, 2 ; c‐C₆H₁₁, 3 ; C₆H₅C(CH₃)₂CH₂, 4 ), have been prepared and characterized by means of elemental analysis, IR and NMR (¹H, ¹³C and ¹¹⁹Sn) spectroscopies. The crystal structure of 1 , bis[4‐(4‐biphenyl)‐4‐oxobutyrato]tetra‐n‐butyldistannoxane, has been determined and it is a centrosymmetric dimer with two distinct types of carboxylate moieties and tin atoms with distorted trigonal bipyramidal geometries. The in vitro antitumour activity of 1 and 2 against two human tumour cell lines was found to be higher than that for cis‐platin used clinically. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis of norcantharidin‐dimer derivatives

We use one molecule of ethylene diamine as a connecting arm to combine two molecules of 5,6‐dehydronorcantharidin. Then, ten novel norcantharidin derivatives were synthesized in a single step by the [3 + 2] 1,3‐dipolar cycloaddition reaction with oxime or hydrazone in the presence of chloramine‐T, which is simpler than the conventional method. J. Heterocyclic Chem., 2011.     

Synthesis and properties of m‐ferrocenylbenzoylthiadiazole derivatives

A series of m‐ferrocenylbenzoylthiadiazole compounds, namely FcL₁–FcL₇, were synthesized using 3‐ferrocenylbenzoic acid and 2‐amino‐5‐aryl‐1,3,4‐thiadiazole as raw materials. These compounds were characterized using infrared and NMR spectroscopies and elemental analysis. The crystal structure of FcL₇ was determined using X‐ray diffraction. The electrochemical behaviors of FcL₁–FcL₇ revealed that the redox reactions on the surface of electrodes were reversible with a single‐electron mechanism. Also, FcL₁–FcL₇ demonstrated certain redox responses to Pb²⁺ and Zn²⁺. Moreover, FcL₅–FcL₇ exhibited good inhibition against human esophageal cancer cells in anticancer activity tests.     

Synthesis and antifungal activity of spiro[cyclopropane‐1,4′‐pyrazol‐3‐one] derivatives

A series of new spiro[cyclopropane‐1,4′‐pyrazol‐3‐one] derivatives 3a‐h were synthesized by the reaction of 4‐arylidene‐3H‐pyrazol‐3‐one 1 with secondary and tertiary carbanions derived from a methylene and methine group bearing both a leaving group and electron‐withdrawing group, e.g. methyl chloroacetate, ethyl chloroacetate, isopropyl chloroacetate, tert‐butyl chloroacetate, chloroacetonitrile, 2‐chloro‐N,N‐diethylacetamide, methyl 2‐chloropropionate and 2‐chloropropionitrile, in the presence of sodium hydride. All the synthesized compounds 3a‐h were active against Candida albicans with MIC ≤ 25 μg/mL in vitro.     

Synthesis and growth regulatory activity of pyrazolesulfanyl‐ and isoxazolesulfanyl‐1H‐[1,2,4]triazoles and their azinyl derivatives

By cyclocondensation of 3‐(1H‐[1,2,4]triazol‐3‐ylsulfanyl)‐pentane‐2,4‐dion with hydroxylamine, hydrazine, methylhidrazine, and arylsulfonyl‐hydrazides, the 3‐(3,5‐dimethyl‐isoxazol‐4‐ylsulfanyl)‐1H‐[1,2,4]triazole ( 2 ) and 3‐(3,5‐dimethyl‐1‐R‐pyrazol‐4‐ylsulfanyl)‐1H‐[1,2,4]triazoles ( 3a , 3b , 3c , 3d ) are synthesized. Under the action of quaternary ammonium salts of azines with limited heating in acetone they form a series of compounds ( 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h ), which molecules simultaneously contain three different heterocyclic rings. Structures of compounds were confirmed by ¹H and ¹³C NMR, MS, and elemental analysis. The plants growth regulatory activities of compounds 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h were investigated. Data of biological tests testify that these compounds can be of interest to search for new growth stimulators. J. Heterocyclic Chem., (2010).     

Synthesis,anti‐inflammatory,and anticancer activity evaluation of some heterocyclic amidine and bis‐amidine derivatives

Heterocyclic amidine derivatives of benzothiazole ( 6a , 6b , 6c ), benzimidazole ( 6d , 6e , 6f ), benzoxazole ( 6g , 6h , 6i ), and bis‐amidine derivatives of pyrimidine, ( 7a , 7b ) & triazole ( 7c , 7d , 7e ) ring system have been synthesized by nucleophilic addition reaction. All these compounds were screened for anti‐inflammatory and anticancer activities. At a dose of 50 mg/kg p.o., compounds 6c (39%), 6e (39%), and 6f (39%) exhibited anti‐inflammatory activity comparable to standard drug ibuprofen, which showed 39% activity and compounds 6b , 6e , 7a , and 7c exhibited moderate anticancer activity against cervix (HELA); neuroblastoma (IMR‐32); breast (MCF‐7), leukemia (THP‐1); and cervix (HELA) human cancer cell lines, respectively. J. Heterocyclic Chem., (2011).