Dense energetic compounds of C,H, N,and O atoms. III. 5-[4-nitro-(1,2,5)oxadiazolyl]-5H-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazole

Diazidoazofurazan 8 was obtained from the bis-diazonium salt of diaminoazofurazan 7 by treatment with sodium azide and underwent thermolysis to 5-[4-azido-(1,2,5)oxadiazolyl]-5H-[1,2,3]triazolo[4,5-c][1,2,5] oxadiazole 5 . The corresponding amine 13 was obtained from the azide 5 by reduction with stannous chloride and was oxidized by ammonium persulfate to 5-[4-nitro-(1,2,5)oxadiazolyl]-5H-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazole 1 . The azide 5 was converted to a phosphinimine 9 in a reaction with triphenylphosphine.     

Synthesis of 1‐substituted [1,2,3]triazolo[4,5‐d]pyridazines as precursors for novel tetraazapentalene derivatives

A series of 1‐substituted 4,5‐diformyl‐[1,2,3]triazole derivatives were prepared by 1,3‐dipolar cyclo‐addition of aryl azides with acetylene dicarboxaldehyde mono‐diethylacetal. The triazoles were readily converted into 1‐substituted [1,2,3]triazolo[4,5‐d]pyridazines in good yields. The 1‐(2‐nitrophenyl)‐[1,2,3]triazolo[4,5‐d]pyridazine was found to be a useful intermediate for the generation of the novel 5H‐benzo[1,2,3]triazolo[1′,2′:1,2]triazolo[4,5‐d]pyridazin‐6‐ium inner salt ring system.     

Synthesis and characterization of [1,2,5]chalcogenazolo[3,4-f]benzo[1,2,3]triazole and [1,2,3]triazolo[3,4-g]quinoxaline derivatives

The synthesis and characterization is reported of low bandgap [1,2,5]chalcogenazolo[3,4-f]benzo[1,2,3]triazole and [1,2,3]triazolo[3,4-g]quinoxaline derivatives that display higher solubility and stability then their thiadiazole counterparts, [1,2,5]chalcogenazolo[3,4-f]benzo[2,1,3]thiadiazole and [1,2,5]thiadiazolo[3,4-g]quinoxaline, respectively.     

Synthesis and photovoltaic properties of new donor-acceptor benzodithiophene-containing copolymers

Four new alternating narrow band-gap copolymers containing benzodithiophene, 4,8-dithiophen-2-yl-benzo[1,2-c;4,5-c′-bis[1,2,5]thiadiazole, 4,9-bis(thiophen-2-yl)-6,7-di(2-ethylhexyl)-[1,2,5]thiadiazolo[3,4-g]quinoxaline, 5,8-dibromo-2,3-bis(5-octylthiophen-2-yl)quinoxaline, and 4,7-bis(5-bromothiophen-2-yl)benzo[1,2,5] thiadiazole units are synthesized under Stille reaction conditions. The structures, molecular masses, and physical properties of the copolymers are studied via ¹H NMR spectroscopy, GPC, cyclic voltammetry, and thermomechanical and thermogravimetric analyses. The polymers show solubility and a broad absorption region (with the band gap in the range from 0.81 to 1.53 eV). All of the polymers are photostable in air, and their levels of the highest occupied molecular orbital vary from ?4.98 to ?5.30 eV. Polymer solar cells based on these copolymers as donors and fullerene PC₆₀BM as an acceptor show open-circuit voltages in the range 0.16–0.61 V, and the efficiencies of the devices are in the range 0.02–0.49%.     

Donor-acceptor copolymers from cyclopentannulation polymerizations with dicyclopenta[cd,jk]pyrene and dicyclopenta[cd,lm] perylene acceptors

A series of donor-acceptor copolymers with dicyclopenta[cd,jk]pyrene and dicyclopenta[cd,lm]perylene acceptor units was prepared via palladium catalyzed cyclopenta-annulation reactions. The acceptor units were paired with diethynyl containing donor groups based on benzo[1,2-b:4,5-b’]dithiophene, thieno[3,2-b]thiophene, and 4-octyl-4H-dithieno[3,2-b:2′,3′-d]pyrrole to create six polymer variants. The cyclopentannulation polymerization resulted in copolymers with molecular weights (Mn) of 6–14 kDa and broad light absorption in the visible region with band gaps of 1.38–1.85 eV. The synthetic methodology, as well as optoelectronic properties, including thin-film absorption and cyclic voltammetry, of the donor-acceptor copolymers are presented.     

New cascade reaction of azides with malononitrile dimer to polyfunctional [1,2,3]triazolo[4,5-b]pyridine

A new cascade reaction of azides with malononitrile dimer yielding polyfunctional [1,2,3]triazolo[4,5-b]pyridine was found. It was established that during the reaction of aryl azides with malononitrile dimer, under base catalysis, the formed intermediate triazole underwent spontaneous cyclization leading to the pyridine ring annulation. The obtained products have provided a new entry to [1,2,3]triazolo[4,5-b]pyridine.     

Behavior of [1,2,5]oxadiazolo[3,4-<Emphasis Type="Italic">e</Emphasis>][1,2,3,4]tetrazine 4,6-dioxide in various media

A behavior of [1,2,5]oxadiazolo[3,4-e][1,2,3,4]tetrazine 4,6-dioxide (1) in organic solvents and aqueous solutions of various acidity has been studied by UV spectrophotometry. Kinetic laws for the N,N′-dioxide 1 hydrolysis have been established and decomposition process constants at various temperatures in the media with pH 6.86 have been determined. A product of the reaction with water, viz., 5H-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazole, has been isolated. 5-(tert-Butyl)-5H-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazole has been synthesized as the model compound. Decomposition of N,N′-dioxide 1 occurs in basic media. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1358–1363, July, 2008.     

Reduction of Imidazo[4,5-c]pyridine and [1,2,3]Triazolo[4,5-c]pyridine Derivatives to Spinaceamines and 2-Azaspinaceamines

Reduction of 1-substituted [1,2,3]triazolo[4,5-c]pyridines with nickel-aluminum alloy in aqueous alkali gave 2-azaspinaceamines. Reduction of imidazo[4,5-c]pyridine and [1,2,3]triazolo[4,5-c]pyridine derivatives with formic acid in the presence of triethylamine resulted in formation of 5-formylspinaceamines and 2-azaspinaceamines. The 5-formyl group in the latter can be removed by acid hydrolysis. Unsubstituted 2-azaspinaceamine, an aza analog of natural spinaceamine, was synthesized for the first time.     

The synthesis of novel polycyclic heterocyclic ring system via photocyclization. 18. Benzo[h]naphtho-[1′,2′:4,5]thieno[2,3-c]quinoline and benzo[h]naphtho-[1′,2′:4,5]thieno[2,3-c] [1,2,4]triazolo[4,3-a]quinoline

The synthesis of two previously unknown polycyclic ring systems, benzo[h]naphtho[1′2′:4,5]-thieno[2,3-c]quinoline ( 1 ) and benzo[h]naphtho[1′,2′:4,5]thieno[2,3-c][1,2,4]triazolo[4,3-a]quinoline ( 2 ), was achieved via oxidative photocyclization of 1-chloro-N-(1-naphthyl)naphtho[2,1-b]thiophene-2-carboxamide ( 5 ). The total assignment of their ¹H and ¹³C nmr spectra was determined by the concerted use of two-dimensional nmr methods.     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 4 . Benzo[f]thieno[2′,3′:4,5]thieno[2,3-c]quinoline and Benzo[h]thieno[2′,3′:4,5]thieno[2,3-c]quinoline and the total assignment of their 1H- and 13C-NMR spectra

The synthesis of two novel polycyclic heterocyclic ring systems via photocyclization are reported. These are benzo[f]thieno[2′,3′:4,5]thieno[2,3-c]quinoline and benzo[A]thieno-[2′,3′:4,5]thieno[2,3-c]quinoline. The total assignment of their ¹H- and ¹³C-nmr spectra was determined by utilizing two-dimensional nmr spectroscopic methods.     

Green One‐Pot Solvent‐Free Synthesis of Pyrazolo[1,5‐a]pyrimidines,Azolo[3,4‐d]pyridiazines,and Thieno[2,3‐b]pyridines Containing Triazole Moiety

Synthesis of pyrazolo[1,5‐a]pyrimidines, [1,2,4]triazolo[1,5‐a]pyrimidine, 8,10‐dimethyl‐2‐(5‐methyl‐1‐phenyl‐4,5‐dihydro‐1H‐1,2,3‐triazol‐4‐yl)pyrido[2′,3′:3,4]‐pyrazolo[1,5‐a]pyrimidine, benzo[4,5]imidazo[1,2‐a]pyrimidine via heterocyclic amines, and sodium 3‐hydroxy‐1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazole‐4‐yl)prop‐2‐en‐1‐one were carried out. Also, synthesis of isoxazoles, and pyrazoles from sodium 3‐hydroxy‐1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazole‐4‐yl)prop‐2‐en‐1‐one and hydroxymoyl chlorides and hydrazonoyl halides, respectively, were made. Analogously, (1,2,3‐triazol‐4‐yl)thieno[2,3‐b]pyridine derivatives were obtained from sodium 3‐hydroxy‐1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐ triazole‐4‐yl)prop‐2‐en‐1‐one and cyanothioacetamide followed by its reacting with active methylene compounds. In addition to full characterization of all synthesized compounds, they were tested to evaluate their antimicrobial activities, and some compounds showed competitive activities to those of tetracycline, the typical antibacterial drug, and clotrimazole, the typical antifungal drug.     

5-[4-amino(1,2,5)oxadiazolyl]-5H-[1,2,3]tri-azolo [4,5-c][1,2,5]oxadiazole from 4,4′-diamino-3,3′-azofurazane

4,4-Diamino-3,3-azofurazane undergoes intramolecular oxidative cyclization to give 5-[4-amino(1,2,5)oxadiazolyl]-5H-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazole upon heating with Pb(OAc)₄ in chlorobenzene oro-dichlorobenzene or with thionyl chloride.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 253–254, February, 1996.     

Synthesis of mesoionic[1,2,3]triazolo[5,1-d][1,2,5]triazepines

Intramolecular cyclization of 1-amino-3-phenacyl-4-carbohydrazido-1,2,3-triazolium-5-olates has been shown to take place via selective interaction of the carbonyl group with the terminal amino function of the hydrazido group to form a 1,2,5-triazepine ring. Minor products, resulting from the interaction of the α-nitrogen atom of the hydrazido group with the carbonyl function, having a N-amino-pyridazine structure were also detected and isolated. A general method for the synthesis of novel mesoionic 2-amino-7-aryl-4-oxo-2,4,5,8-tetrahydro[1,2,3]triazolo[5,1-d][1,2,5]triazepin-9-ium-3-olates was developed.     

Tuning the Donor–Acceptor Strength of Low‐Bandgap Platinum‐Acetylide Polymers for Near‐Infrared Photovoltaic Applications

Two near‐infrared (NIR) absorbing metallopolyynes of platinum ( P1 and P2 ) functionalized with a weakly electron‐donating fluorene unit and two strong electron acceptors (viz. benzo[1,2‐c:4,5‐c′]bis([1,2,5]thiadiazole) and [1,2,5]thiadiazolo[3,4‐i ]dibenzo[a,c]phenazine) were synthesized and applied for NIR photovoltaic applications. With these designed weak donor–strong acceptor electronic traits, these metallopolymers possess narrow bandgaps of 1.54 and 1.65 eV and a low HOMO level of about 5.50 eV, thus inducing a power conversion efficiency up to 1% for bulk heterojunction solar cells at the NIR wavelength.

     

Synthesis,Reactions, and Antimicrobial Evaluation of Some Polycondensed Thienopyrimidine Derivatives

Some novel indeno[2,1-b]thiophenes, indeno[1′,2′:4,5]thieno[2,3-d][1,2,3]triazines, indeno[1′,2′:4,5]thieno[2,3-d]pyrimidines, indeno[1′,2′:4,5]thieno[2,3-d][1,3]thiazolo[3,2-a]pyrimidines, and indeno[1′,2′:4,5]thieno[2,3-d][1,2,4]triazolo[4,3-a]pyrimidines 2–16 were prepared starting with 2-aminoindeno[2,1-b]thiophene-3-carboxylic acid amide ( 1 ). Furthermore, the antimicrobial evaluation of the prepared products showed that many of them revealed promising antimicrobial activity.     

Diversity‐oriented One‐pot Synthesis of Novel Imidazo[4′,5′:4,5]benzo[e][1,4]thiazepinones and Benzo[d]imidazolyl Thiazolidinones through pTSA Promoted Cyclization and Evaluation of Antimicrobial and Anti‐inflammatory Activities

In contrast to target‐oriented synthesis that aims to access precise regions of chemistry, diversity‐oriented synthesis via multicomponent synthesis populates chemical space broadly with small molecules having diverse structures. This study has achieved the diversity‐oriented synthesis of novel imidazo[4′,5′:4,5]benzo[e][1,4]thiazepinones ( 4 ) and benzo[d]imidazolyl thiazolidinones ( 5 ) controlled by the nature of substitution effect of the reaction component. The one‐pot reaction of benzimidazole 1 , aromatic aldehyde 2 , and mercaptoacetic acid 3 leads to the formation of imidazo[4′,5′:4,5]benzo[e][1,4]thiazepinones ( 4 ) with electron‐donating groups as substitution on aromatic aldehyde while electron‐withdrawing substitutions produced benzo[d]imidazolyl thiazolidinones ( 5 ). The title compounds ( 4 ) and ( 5 ) were evaluated for their antimicrobial and anti‐inflammatory activities.     

Synthesis and reactions of 3-thioxo[1,2,4]-triazino[3,2-b]quinazolin-10-ones

Thiation of [1,2,4]triazino[3,2-b]quinazoline-3,10-dione 1 proceeds selectively to give the 3-thioxo-analog 3 . The latter was converted to the corresponding 3-methylthio derivative 4 which was reacted with aniline and hydrazine to give the corresponding anilino- and hydrazino derivatives 5 and 7 . Compound 7 was converted to the hydrazones 8a,b and into the novel heterocyclic ring systems [1,2,4]triazolo[4′,3′:4,5][1,2,4]triazino-[3,2-b]quinazolin-7-ones 9, 10a,b and tetrazolo[1′,5′:4,5][1,2,4]triazino[3,2-b]quinazolin-7-one 11 .     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 9. Phenanthro[9′,10′:4,5]thieno[2,3-c]quinoline,benzo[f]phenanthro[9′,10′:4,5]thieno[2,3-c]quinoline,and benzo[h]-phenanthro[9′,10′:4,5]thieno[2,3-c]quinoline

The synthesis of three novel polycyclic heterocyclic ring systems are reported via photocyclization. The specific final products in these ring systems are: phenanthro[9′,10′:4,5]thieno[2,3-c]quinoline ( 13 ), benzo[h]-phenanthro[9′,10′:4,5]thieno[2,3-c]quinoline ( 14 ), and benzo[f]phenanthro[9′,10′:4,5]thieno[2,3-c]quinoline ( 15 ).     

Synthesis of 2-(6-nitrobenzofuroxan-4-yl)-2H-[1,2,3]triazolo-[4,5-e][1,2,3,4]tetrazine 4,6-dioxide

Russian Chemical Bulletin - At heating of 2-(2-azido-3,5-dinitrophenyl)-2H-[1,2,3]triazolo[4,5-e][1,2,3,4]tetrazine 4,6-dioxide in toluene at 110 °C, the azido group interacts mainly with the...     

Syntheses of Examples of the 5,6-dihydro-4H-[1,2,3]triazolo[4,5,1-ij]quinoline, 4,5,6,7-tetrahydro[1,2,3]triazolo[4,5,1-jk][1,4]benzodiazepine,and 5,6,7,8-tetrahydro-4H-[1,2,3]triazolo[4,5,1-kl][1]benzazocine ring systems

Lithiation of 1-vinylbenzotriazole 9 with n-BuLi (2 equiv) generates dianion 10, which upon subsequent reaction with 1,2- and 1,4-diketones affords 14 and 13, representatives of the 5,6-dihydro-4H-[1,2,3]triazolo[4,5,1-ij]quinoline 1 and 5,6,7,8-tetrahydro-4H-[1,2,3]triazolo[4,5,1-kl][1]benzazocine 2 ring systems, respectively. Reactions of dianion 10 with isocyanates give 15a,b, which contain the 4,5,6,7-tetrahydro[1,2,3]triazolo[4,5,1-jk][1,4]benzodiazepine 3 ring system.