Synthesis of [n]Cyclo‐5,15‐porphyrinylene‐4,4′‐biphenylenes Displaying Size‐Dependent Excitation‐Energy Hopping

A set of 5,15‐biphenylene‐bridged porphyrin wheels, namely, [n]cyclo‐5,15‐porphyrinylene‐4,4′‐biphenylenes [n]CPB , have been synthesized through the platination of 5,15‐bis(4‐(pinacolboranyl)phenyl) nickel(II) porphyrin and subsequent reductive elimination of Pt^II(cod)‐bridged cyclic porphyrin intermediates. The calculated strain energies for [3]CPB , [4]CPB , [5]CPB , and [6]CPB are 49.3, 32.9, 23.5, and 16.0 kcal mol^?1, respectively. UV/Vis absorption spectra and cyclic voltammetry indicated characteristic ring‐size‐dependent absorption‐peak shifts and redox‐potential shifts, which presumably reflect the degree of strain in the π‐systems. Excitation‐energy hopping (EEH) times were determined to be 5.1, 8.0, 8.0, and 9.6 ps for [3]CPB , [4]CPB , [5]CPB , and [6]CPB , respectively, in a pump‐power‐dependent TA experiment.     

Synthesis of benzo[b]thieno‐ and benzo[b]furano‐[2,3‐a]pyrrolo[3,4‐c]carbazole‐5‐, ‐7‐ and ‐5,7‐dione

Benzo[b]thieno[2,3‐a]pyrrolo[3,4‐c]carbazoles and benzo[b]furano[2,3‐a]pyrrolo[3,4‐c]carbazoles were prepared from 2‐(2‐benzo[b]thieno)‐ (8) and 2‐(2‐benzo[b]furano)‐3‐[3‐(2,5‐dioxo‐lH‐pyrrolidinyl)]indole (9) by a palladium(II)acetate/tetrachloro‐1,4‐benzoquinone oxidative A‐E ring closure.     

Regioselectivity of cyclization of 3-allyl(propargyl)sulfanyl-5<Emphasis Type="Italic">H</Emphasis>-[1,2,4]triazino[5,6-<Emphasis Type="Italic">b</Emphasis>]indoles

The interaction of 3-allylsulfanyl-5H-[1,2,4]triazino[5,6-b]indole with iodine led to 1-iodomethyl-1,2-dihydro[1,3]thiazolo[2',3':3,4][1,2,4]triazino[5,6-b]indol-11-ium pentaiodide with an angular structure, on the basis of which 1-iodomethyl-1,2-dihydro[1,3]thiazolo-, 1-methylidene-1,2-di-hydro[1,3]thiazolo, and 1-methyl[1,3]thiazolo derivatives were obtained. The intramolecular cyclization of 3-propargyl(allyl)sulfanyl-5H-[1,2,4]triazino[5,6-b]indoles under the influence of concentrated sulfuric acid led to linear annelated products:3-methyl[1,3]thiazolo[3',2':2,3][1,2,4]tri-azino[5,6-b]indole or its 2,3-dihydro derivative.     

Synthesis of new benzo[h]‐ and benzo[f]chromeno[2,3‐b]‐pyridine‐5‐ones

A number of new benzo[h]‐ and benzo[f]chromeno[2,3‐b] pyridine‐5‐ones derivatives were synthesized from benzo[h]‐ and benzo[f]‐chromone‐carbonitriles and amino‐benzo[h]‐ and benzo[f]chromone‐carbaldehydes. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:2–7, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20152     

Synthesis of 4‐(1‐phenyl‐1H‐pyrazol‐3‐yl)‐[1,2,4]triazolo[4,3‐a]quinoxalines and their 4‐halogenopyrazolyl analogs

Synthesis of {3‐[1‐(ethoxycarbonyl)‐[1,2,4]triazolo[4,3‐a]quinoxalin‐4‐yl]‐1‐phenyl‐1H‐pyrazol‐5‐yl}methyl ethyl oxalate ( 2 ), ethyl 4‐[5‐(acetoxymethyl)‐1‐phenyl‐1H‐pyrazol‐3‐yl]‐[1,2,4]triazolo[4,3‐a]quioxaline‐1‐carboxylate ( 4 ), [4‐halo‐1‐phenyl‐3‐(1‐phenyl‐[1,2,4]triazolo[4,3‐a]quioxalin‐4‐yl)‐1H‐pyrazol‐5‐yl]methyl acetate ( 11 ), {4‐halo‐3‐[1‐methyl‐[1,2,4]triazolo[4,3‐a]quinoxalin‐4‐yl]‐1‐phenyl‐1H‐pyraz‐ol‐5‐yl}methyl acetate ( 13 ), and [3‐([1,2,4]triazolo‐[4,3‐a]quinoxalin‐4‐yl)‐4‐halo‐1‐phenyl‐1H‐pyrazol‐5‐yl] methyl formate ( 15 ) was accomplished. The structural investigation of the new compounds is based on chemical and spectroscopic evidences. J. Heterocyclic Chem., (2011)     

Synthesis of Some New Fused and Polyfused [1,2,4]Triazolo-[3,4-<Emphasis Type="Italic">b</Emphasis>][1,3,4]thiadiazepines

7-[1,3-Dithiolan-2-ylidene]-3-phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo[3,4-b][1,3,4]thiadiazepine-6,8-dione and 7-[5-oxo-1,3-dithiolan-2-ylidene]-3-phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo[3,4-b][1,3,4]-thiadiazepine-6,8-diones were obtained by treating 3-phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo-[3,4-b][1,3,4]thiadiazepine-6,8-diones with CS₂ and chloroacetyl chloride, respectively. Treatment of the above compounds with mercaptoacetic acid gave 1,2-dibromoethane or the corresponding spiro polyfused heterocycles. Some other triazolothiadiazepine derivatives including spiro polyfused compounds were also synthesized. __________ Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 8, 1256–1264, August, 2005.     

Syntheses of Some 3—[1′（1′H）—Substituent—pyrazol—5′—yl] benzo [5,6] coumarins

3-[1′(1′H)-Substituent-pyrazol-5′-yl]benzo[5,6]coumarins and 3-(1′,2′-oxazol-5′-yl)benzo[5,6]coumarin were prepared via condensation of 3-(2′-formyl-1′-chlorovinyl)benzo[5,6] coumarin with hydrazine derivatives or hydroxylamine.Reaction of 3-[1′(1′H)-pyrazol-5′-yl]benzo[5,6]coumarin with alkyl halides,olefinic compunds or acid chlorides are described.     

Ligand‐Controlled Synthesis of [3]‐ and [4]Cyclo‐9,9‐dimethyl‐2,7‐fluorenes through Triangle‐ and Square‐Shaped Platinum Intermediates

The syntheses of [3]‐ and [4]cyclo‐9,9‐dimethyl‐2,7‐fluorenes ([3] and [4]CFRs), cyclic trimer, and tetramers of 9,9‐dimethyl‐2,7‐fluorene (FR), respectively, were achieved by the platinum‐mediated assembly of FR units and subsequent reductive elimination of platinum. A triangle‐shaped tris‐platinum complex and a square‐shaped tetra‐platinum complex were obtained by changing the platinum ligand. The structure of the triangle complex was unambiguously determined by X‐ray crystallographic analysis. Reductive elimination of each complex gave [3] and [4]CFRs. Two rotamers of [3]CFR were sufficiently stable at room temperature and were separated by chromatography. The physical properties of the CFRs were also investigated theoretically and experimentally.     

Synthése par deux voies différentes d'un systéme dihétérocyclique apparenté aux peltogynoides

5-Oxo-5H,7H-[2]benzopyrano[4,3-b][1]benzopyran ( 2 ) has been synthesized from 3-(o-hydroxybenzylidene)isochroman-1,4-dione ( 3 ) by reductive cyclization, and from 5H,7H[2]benzo-pyrano[4,3-b][1]benzopyran-5,7-dione ( 4 ) by selective hydro-genation. This second method affords the dihydro compound 6 or 6a,12a-dihydro-5H,7H-[2]benzopyrano[4,3-b] [1 ]benzopyran-5-one as reaction time increases.     

4,5-Diamino-1-phenyl-1,7-dihydro-6<Emphasis Type="Italic">H</Emphasis>-pyrazolo[3,4-<Emphasis Type="Italic">b</Emphasis>]pyridin-6-one in the synthesis of fused tricyclic systems

Starting from the substituted 4,5-diaminopyrazolo[3,4-b]pyridine, derivatives of a number of tricyclic systems, viz., imidazo[4,5-d]pyrazolo[3,4-b]pyridine, pyrazolo[3,4-b][1,2,5]thiadiazolo[3,4-d]pyridine, pyrazolo[3,4-b][1,2,3]triazolo[4,5-d]pyridine, and [1,3]oxazolo[5,4-b]pyrazolo[4,3-e]pyridine, were synthesized and reaction schemes for the processes were proposed.     

对叔丁基杯[10]冠醚的合成

首次合成一系列杯[10]冠醚。通过将对叔丁基杯[10]芳烃和乙二醇双对甲苯磺酸酯或多甘醇双对甲苯磺酸酯在K2CO3/甲苯或Cs2CO3/丙酮体系中反应,得到一系列杯[10]冠醚:1,2-杯[10]冠-4、1,3-杯[10]冠-2、1,2-,1,3-杯[10]冠-3、1,4-杯[10]冠-4、和1,6-杯[10]冠-4。     

Thermolysis of N‐Aryl Enaminoimine Hydrochloride Derivatives: A Short and General Method for the Synthesis of Pyranoquinolin‐3‐one and Pyranoacridin‐3‐one Derivatives

A short synthesis of 3H‐pyrano[3,2‐f]quinolin‐3‐one, 3H‐acenaphtho[1,2‐b]pyrano‐[3,2‐f]quinolin‐3‐one, and 3H‐benzo[h]pyrano[3,2‐a]acridin‐3‐one derivatives are described via thermolysis of suitable enaminoimine hydrochloride derivatives.     

Halocyclization of 3-allylthio-5H-[1,2,4]triazino[5,6-<Emphasis Type="Italic">b</Emphasis>]indole

The synthesis of 3-allylthio-5H-[1,2,4]triazino[5,6-b]indole has been carried out by the reaction of 3-mercapto-5H-[1,2,4]triazino[5,6-b]indole with allyl bromide in the NaOH–H₂O–DMSO system and in a one-pot synthesis from isatin-β-thiosemicarbazide. Halocyclization of allylthio-5H-[1,2,4]-triazino[5,6-b]indole synthesized the 3-halomethyl-3,10-dihydro-2H-[1,3]thiazolo[3',2':2,3][1,2,4]-triazino[5,6-b]indolium halides.     

Condensed isoquinolines 23. Reaction of <Emphasis Type="Italic">o</Emphasis>-bromomethylphenyl-acetonitrile with anthranilic acids: Synthesis of 6H, 12H,17H-dibenzo[3,4:6,7][1,8]-naphthyridino[1,8-<Emphasis Type="Italic">ab</Emphasis>]quinazoline-6,17-diones

The direction of the reaction of anthranilic acids with o-bromomethylphenylacetonitrile upon fusion depends on the temperature and nature of the substituent in the anthranilic acid. The reaction may lead to three types of products: Derivatives of 7,12-dihydro-5H-isoquino[2,3-a]quinazolin-5-ones below 150°C and to 6,11-dihydro-13H-isoquino[3,2-b]quinazolin-13-one or derivatives of 6H,12H,17H-dibenzo[3,4:6,7][1,8]naphthyridino[1,8-ab]quinazoline-6,17-diones above 150°C depending on the nature of the substituent in the anthranilic acid. A study was carried out on the mechanism for the formation of 6H,12H,17H-dibenzo[3,4:6,7][1,8]naphthyridino[1,8-ab]quinazoline-6,17-diones, which permitted the preparation of 6-(4-methylphenyl)-6,12-dihydro-5H-isoquino[2,3-a]quinazolin-5-one. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1059–1067, July, 2007.     

Three‐Component Reaction for Construction of Spiro[indoline‐3,7′‐thiazolo[3,2‐a]pyridines] and Spiro[benzo[4,5]thiazolo[3,2‐a]pyridine‐3,3′‐indolines]

The three‐component reaction of thiazole (benzothiazole), dialkyl but‐2‐ynedioate, and isatinylidene malononitriles in toluene at 110–120°C in a sealed tube afforded a mixture of cis/trans‐isomers of functionalized diastereoisomeric spiro[indoline‐3,7′‐thiazolo[3,2‐a]pyridines] and spiro[benzo[4,5]thiazolo[3,2‐a]pyridine‐3,3′‐indolines] in good yields. Both cis‐isomers and trans‐isomers were successfully separated out and fully characterized with spectroscopy and single crystal determination. Under similar conditions, the three‐component reaction containing 2‐(1,3‐dioxo‐1H‐inden‐2(3H)‐ylidene)malononitrile resulted in spiro[indene‐2,7′‐thiazolo[3,2‐a]pyridine] derivatives.     

Absorption and Rayleigh scattering and resonance Rayleigh scattering spectra of [HgX<Subscript>2</Subscript>]<Subscript>n</Subscript> nanoparticles

The composition and existing species ot the reaction production ot Hg ana X (X= Cl, Br and I) under different conditions, and their absorption, Rayleigh scattering (RS) and resonance Rayleigh scattering (RRS) spectra have been studied. The results show that the products exist in the form of nanoparticles as [HgX2]n aggregates under suitable conditions, and their average diameters increase with the increase of X- diameters. The diameters of [HgCI2]n, [HgBr2]n and [Hgl2]n are less than 4 nm, equal to 9 nm and 70 nm respectively. There are bathchromic shifts gradually with the increase of X- diameters in their absorption spectra. The absorption bands of [HgCI2]n and [HgBr2]n locate at ultraviolet region. However, the absorption band of [Hgl2]n is obvious in visible light region. Among three particles, only [Hgl2]n exhibits a strong RRS and its scattering peak is at 580 nm. The main reasons leading to the enhancement of resonance scattering are the large size of nanoparticle, the formation of the interface     

Synthesis,Characterization and Reactions of 4‐Hydrazino‐2‐methylpyrimidino[4′5′:4,5]thiazolo[3,2‐a]benzimidazole

4‐Hydrazino‐2‐methylpyrimidino[4′,5′:4,5]thiazolo[3,2‐a]benzimidazole ( 4 ) was obtained from hydrazinolysis of the 4‐chloro derivative 3 with hydrazine hydrate. The hydrazino derivative 4 was further cyclized to the corresponding pyrazole 5 , pyrazolone 6 and 5‐methyl‐1,2,4‐triazolo[1″,5″:3′,4′]pyrimidino[5′,6′:5,4]‐thiazolo[3,2‐a]benzimidazole ( 9 ) and 5‐methy‐1,2,4‐triazolo[4″,3″:3′,4′]pyrimidino[5′,6′:5,4]thiazolo‐[3,2‐a]benzimidazole ( 10 ), respectively. The triazolo derivative 10 was isomerized to the triazolo derivative 9 under a variety of reaction conditions.     

RhII‐Catalyzed [3+2] Cycloaddition of 2 H‐Azirines with N‐Sulfonyl‐1,2,3‐Triazoles

Rh^II‐catalyzed intermolecular [3+2] cycloaddition of 2 H‐azirines with N‐sulfonyl‐1,2,3‐triazoles is disclosed, in which a series of fully functionalized pyrroles is produced via rhodium azavinyl carbene intermediates. A distinct feature of this reaction is that the azavinyl carbene serves as a [2 C] equivalent, instead of as [1 C] or aza‐[3 C] synthons, which have been reported previously in cyclopropanations and [3+n] cycloadditions. Moreover, this methodology has also been successfully applied in the total synthesis of URB447 as well as the formal synthesis of Atorvastatin (Lipitor).     

Pyridyl-substituted [1,3]Dithiolo-[4,5-<Emphasis Type="Italic">b</Emphasis>][1,4]dithiine-2-thiones

We have obtained 5-(2-pyridyl)[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione for the first time by cycloaddition of 2-ethynylpyridine to 4,5-dihydro-1,3-dithioltrithione (isotrithionedithiol). We have studied this thione, 5-(2-pyridyl)- and 5-(4-pyridyl)-5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiine-2-thiones by mass spectroscopy and also IR, UV, ¹H and ¹³C NMR spectra. We have determined the crystal and molecular structure of 5-(2-pyridyl)-5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 429–434, March, 2005.     

Spectrométrie de Masse D'hétérocycles Séléniés. III—Etude de la Fragmentation de Quelques Selenolo [2, 3-b] Pyridines

The mass spectra of thirteen selenolo[2,3-b]pyridine derivatives have been measured and compared with those of benzo[b]selenophene, quinoline and thieno[2,3-c]pyridine. The influence of diheteroatomic structure of the nucleus on the mechanism of fragmentation of the oxygenated substituents is discussed.