Syntheses,molecular structures,and antiviral activities of 1- and 2-(2′-deoxy-d-ribofuranosyl)cyclohepta[d][1,2,3]triazol-6(1H)-ones and 1-(2′-deoxy-d-ribofuranosyl)cyclohepta[b]pyrrol-8(1H)-one

The synthesis of a novel class of 2′-deoxyribonucleosides possessing tropone-fused nitrogen heterocycles as nucleobases was developed. The reaction of alkali metal salts of 1H-cyclohepta[d][1,2,3]triazol-6-one with 2-deoxy-3,5-di-O-(p-toluoyl)-α-d-ribofuranosyl chloride (α-chlorosugar) afforded an anomeric mixture of N1- and N2-coupled glycosylation products. Good stereospecificity in relation to the amount of the β-anomer was achieved in the less polar solvent DME. The reactions of the sodium salt of 1H-cyclohepta[b]pyrrol-8-one and its 3-methyl derivative with an α-chlorosugar in DME gave the β-anomer of the N1-coupled glycosylation products. The glycosylation products were treated with NaOMe in MeOH to produce the desired 2′-deoxyribonucleosides. X-ray structural analyses of the three nucleosides prepared confirmed their anomeric configuration and revealed that their sugars were puckered. The β-anomers of the nucleosides had weak antiviral activities for herpes simplex virus type 1 and herpes simplex virus type 2 in comparison with those of acyclovir (ACV). These nucleosides showed no cytotoxicity on a lung (A549) and two colon (HT-29 and HCT-116) cancer cell lines.     

Synthesis of novel spiro[indole-3,3′-pyrrolidin]-2(1H)-ones

Diastereoselective [3+2] cycloaddition of azomethine ylide to 1,3-dimethyl-6-(2-oxo-1,2-dihydro-3H-indol-3-ylidene)-3a,9a-diphenyl-3,3a,9,9a-tetrahydroimidazo[4,5-e]thiazolo[3,2-b]-[1,2,4]triazine-2,7(1H,6H)-dione yields hitherto unknown 1,1′,3-trimethyl-3a,9a-diphenyl-3,3a,9,9a-tetrahydrodispiro(imidazo[4,5-e]thiazolo[3,2-b][1,2,4]triazine-6,3′-pyrrolidine-4′,3″-indole)-2,2″,7(1H,1″H)-triones.     

Efficient one-pot synthesis of novel 6′,9′-dihydro-2H,7′H-spiro[pyrimidine-5,8′-[1,3]dioxolo[4,5-f]quinoline]-2,4,6(1H,3H)-trione derivatives under mild and “green” reaction conditions

In this paper, an efficient method is introduced for the synthesis of 7′,9′-disubstituted 6′,9′-dihydro-2H,7′H-spiro[pyrimidine-5,8′-[1,3]dioxolo[4,5-f]quinoline]-2,4,6(1H,3H)-trione derivatives under mild and “green” reaction conditions. The method is based on one-pot multicomponent reaction of an aldehyde, barbituric acid, and benzo[d][1,3]dioxol-5-amine in ethanol as a green and environmentally friendly solvent. The reaction has given the products in the highest isolated yield in the presence of acetic acid as catalyst under reflux conditions. Various aldehydes, bearing electron-donating or -withdrawing functionalities have been used under the optimized conditions and successfully gave the desired products (13 examples) in high isolated yields.     

Novel 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-2-yl)methylpyrrolidinyl[60]fullerene-hydroxyoxo(5,10,15,20-tetraphenyl-21H,23H-porphynato) molybdenum(V) dyads

Interaction between hydroxyoxo(5,10,15,20-tetraphenylporphyrinato)molybdenum(V) and 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-2-yl)methylpyrrolidinyl[60]fullerene in toluene has been studied by means of spectrophotometry. The reaction proceeds via two stages: rapidly established equilibrium between the reactants and their molecular complex 1: 1 [K = (1.97 ± 0.52) × 10⁴ L/mol] followed by slow irreversible displacement of hydroxy group into the second coordination sphere to form cationic outer sphere complex (k = 0.26 L s^?1 mol^?1). The effect of fullerene fragment on pyridine fragments coordination has been considered.     

3-取代-(1H)-嘧啶[1, 2-a]喹啉-1-酮和2-取代嘧啶[1, 2a]苯骈 咪唑-4-(10H)- 酮的简便合成法

本文利用2-氨基喹啉和2-氨基苯骈咪唑作为亲核试剂,与5-(双甲硫基亚甲基)丙二酸亚异丙酯(1)、5-(甲硫基亚烃基)丙二酸亚异丙酯(3)反应,开发出3-取代-(1H)-嘧啶-[1,2-a]喹啉-1-酮(5)和2-取代嘧啶[1,2-a]苯骈咪唑-4-(10H)-酮(6)通用的简便合成法。     

SYNTHESIS OF SPIRO [1,3-BENZODIOXOLE-2,4′-(3′H) QUINAZOLINES]

Abstract

In the present investigation, the authors could obtain a new series of spiranes (1) through the reaction of the high potential quinone tetrachloro-o-benzoquinone with 2-aryl-3-phenyl-3H-quinazoline-4-thiones. Thus, 2,3-diphenyl- (2a), 2-p-tolyl-3-phenyl- (2b) and 2-p-anisyl-3-phenyl- (2c)-3H-quinazoline-4-thiones react readily with tetrachloro-o-benzoquinone, in boiling toluene, to give the corresponding spiro-1,3-benzodioxole-2,4′-(3′H)-quinazolines (1a-c), respectively.     

One Pot Synthesis of Some New Spiro[3H-Indol-3,5′(4′H)-[1,2,4] Oxadiazol]-2-Ones and Bis[Spiro[3H-Indol-3,5′(4′H)-[1,2,4] Oxadiazol]-2-Ones]

A facile preparation of the title compound by 1,3-dipolar cycloaddition reaction of benzonitrile oxides with isatin imines or isatin diimines, in excellent yield, are reported.     

Synthesis of 1-[6-Fluoro-(2S)-3H,4H-dihydro-2H-2-chromenyl]-(1R)-1,2- ethanediol and 1-[6-Fluoro-(2R)-3H,4H-dihydro-2H-2-chromenyl]- (1R)-1,2-ethanediol

Benzopyran compounds possess diverse pharmacological properties such as β-blockade, anticonvulsant and antimicrobial.[1,2] Our interest has been focused on the synthesis of 1-[6-Fluoro-2S]-3H,4H-dihydro-2H-2-chromenyl]-(1R)-1,2-ethanediol (6) and 1-[6-fluoro-(2R)-3H,4H-dihydro-2H-2-chromenyl]-(1R)-1,2-ethanediol (7) which are particularly convenient precursor to (S,R,R,R)-NE (8). 8 containing four asymmetrical carbon atoms was reported to be the most active isomer.[3] Chandrasekhar[4] has reported on the synthesis of 8. The key step to synthesize this compound is to obtain the chiral chromanone 6 and 7. 6 was accomplished in 8 steps by the Clasien rearrangement and a one-pot Sharpless asymmetric epoxidation, but the compound 7 was accomplished in 10 steps. Johannes[5] used Zr-catalytic kinetic resolution of allylic ethers and Mo-catalyzed chromene formation to synthesize 8 in 14 steps. However both of the methods request many synthetic steps and expensive reagents.     

Syntheses and crystal structures of oxovanadium(V) complexes derived from N′-[1-(2-hydroxynaphthyl)ethylidene]-4-nitrobenzohydrazide and 2-hydroxy-N′-[1-(2-hydroxynaphthyl)ethylidene]benzohydrazide

Reactions of bis(acetylacetonato)oxovanadium(IV) with N??-[1-(2-hydroxynaphthyl)ethylidene]-4-nitrobenzohydrazide (H₂HNB) and 2-hydroxy-N??-[1-(2-hydroxynaphthyl)ethylidene]benzohydrazide (H₂HHB), respectively, product two oxovanadium(V) species with the formulas [VO(OMe)(HNB)]₂ (I) and [VO(OMe)(HHB)] (II). The complexes I and II have been characterized by elemental analysis, IR spectra, and single crystal X-ray diffraction. The crystal of I is monoclinic: space group P2₁/n, a = 8.208(2), b = 14.528(3), c = 16.418(3) ?, ?? = 97.887(3)°, V = 1939.3(7) ?³, Z = 2. The crystal of II is triclinic: space group P $P\bar 1$ a = 8.334(2), b = 10.236(2), c = 11.337(2) ?, ?? = 80.91(3)°, ?? = 75.41(3)°, ?? = 75.63(3)°, V = 902.0(3) ?³, Z = 2. Complex I is a methoxide-bridged dimeric oxovanadium(V) complex, and complex II is a mononuclear oxovanadium(V) complex. The V atom in I is in an octahedral coordination, and that in II is in a square pyramidal coordination.     

Alkylation of 3-tert-Butylpyrimido[4′,5′:3,4]pyrazolo[5,1-c]-[1,2,4]triazine-4,10(1H,9H)-diones and -dithiones

Russian Journal of Organic Chemistry - The condensation of 7-amino-1-benzyl-3-tert-butyl-4-oxo-1,4-dihydropyrazolo[5,1-c][1,2,4]triazine-8-carbonitrile with formic acid afforded...     

Syntheses,structures, and properties of two new hybrid Dawson-based polyoxotungstates [Mn(2,2′-bipy)3]H2 [Mn(2,2′-bipy)2][P2W18O62] and [Co(H2biim)3)]2H2[P2W18O62] · 8H2O

Two new hybrid Dawson-based polyoxotungstates, [Mn(2,2′-bipy)₃]H₂[Mn(2,2′-bipy)₂][P₂W₁₈O₆₂] (1) and [Co(H₂biim)₃)]₂H₂[P₂W₁₈O₆₂] · 8H₂O (2) (2,2′-bipy = 2,2′-bipyridine, H₂biim = 2,2′-biimdazole), have been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric analyses (TGA), X-ray photoelectron spectroscopy (XPS), and photoluminescence spectra. Compound 1 is a 1-D zigzag chain constructed from alternate Dawson-type heteropolyanions [α-P₂W₁₈O₆₂]^6? and metal coordination cations [Mn(2,2′-bipy)₂]²⁺, in which the 1-D chains are extended into a 3-D framework through C–H ··· π and π–π stacking interactions. Compound 2 is a discrete structure consisting of [α-P₂W₁₈O₆₂]^6? and two [Co(H₂biim)₃)]²⁺ cations, forming a 3-D supramolecular framework via N–H ··· O hydrogen bonds and C–H ··· π interactions. Photoluminescence properties of 1 and 2 have been investigated at room temperature.     

Efficient and facile synthesis of 5-arylindeno[2′,1′:5,6]pyrido[2,3-d] pyrimidine-2,4(3H)-dione and 7-arylbenzo[h]pyrimido[4,5-b]quinoline-8,10(5H,9H)-dione under mild conditions

An efficient and facile method for the synthesis of 5-arylindeno[2′,1′:5,6]pyrido[2,3-d] pyrimidine-2,4(3H)-dione and 7-arylbenzo[h]pyrimido[4,5-b]quinoline-8,10(5H,9H)-dione derivatives from the reactions of 2-arylidene-2,3-dihydroinden-1-one (or 2-arylidene-3,4- dihydronaphthalen-1(2H)-one) and 6-amino-1,3-dimethylpyrimidine-2,4(1H,3H)-dione under mild conditions was described. This is a simple, efficient, and very rapid synthetic method, which is believed to provide a useful process for the synthesis of these fused heterocyclic compounds. The products were confirmed by infrared, ¹H NMR, ¹³C NMR, and high-resolution mass spectrometry.     

Design,Synthesis, and Antibacterial Evaluation of Some Novel 3′-(Phenylamino)-1′H-spiro[indoline-3,2′-quinazoline]-2,4′(3′H)-dione Derivatives

A combinatorial synthesis and evaluation of antibacterial activity against clinically isolated resistant strains of Gram-positive and Gram-negative bacteria of 3′-(phenylamino)-1′H-spiro[indoline-3,2′-quinazoline]-2,4′(3′H)-dione derivatives is described.     

Synthesis of [125I]‐, [2H]‐, and [3H]‐Labeled 3‐Iodothyronamine (T1AM)

3‐Iodothyronamine (T₁AM) is a novel metabolite of thyroid hormone. In HEK‐293 cells expressing an orphan G‐protein coupled receptor, the trace amine receptor, T₁AM, potently increased cAMP accumulation. In mice, T₁AM rapidly induced hypothermia and bradycardia within minutes of administration. These results suggest the existence of a new signaling pathway, the stimulation of which leads to rapid physiological and behavioral consequences. Isotope‐labeled T₁AM derivatives would be useful to study the biology and pharmacology of T₁AM. Herein we describe efficient syntheses of [¹²⁵I]‐, [²H]‐, and [³H]‐T₁AM.     

Unexpected synthesis of a novel heterocyclic system – (7E,10aE)-2,7-Dimethylfuro[3′,4′:6,7]cycloocta[1,2,3-cd]indole-8,10(2H,6H)-dione

The first derivative of a novel heterocyclic system, (7E,10aE)-2,7-dimethylfuro[3′,4′:6,7]-cycloocta[1,2,3-cd]indole-8,10(2H,6H)-dione, was synthesized based on the Stobbe condensation of 3-chloro-1-methylindole-2-carbaldehyde with diethyl isopropylidenesuccinate. Cyclization of the 2-indolyl-containing diacid, formed by subsequent hydrolysis of the condensation product, did not lead to the expected fulgide, but rather to an unprecedented tetracyclic compound, the structure of which was established by ¹H, ¹³C NMR, IR spectroscopy, mass-spectrometry and single crystal X-ray diffraction.     

2-{(4a′S,6a′S,10a′R,10b′R)-Octahydrospiro[1,3-dioxolane-2,2′-pyrano[2,3-c]chromen]-6a′(1′H)-yloxy}ethanol in the Synthesis of (2S)- and (2R)-Dodecane-1,2-diols

Russian Journal of Organic Chemistry - Michael adduct of levoglucosenone and cyclohexanone, 1,6-anhydro-3,4-dideoxy-4-C-(2-oxocyclohexan-1-yl)-β-D-erythrohexo-2-ulose, was treated with...     

[2,3′-联-1H-吲哚]-3(2H)-酮类化合物的单重态氧反应

[2,3’-联-1H-吲哚]-3(2H)-酮衍生物(1a～1c)在甲醇中的单重态氧反应给出溶剂捕捉产物4,后者在分离过程中脱去甲醇分子生成5。考察了标题化合物分子中二氢吲哚酮结构单元以及吲哚结构单元在单重态氧反应中的作用。并探讨了反应机理。     

Synthesis,crystal structure and magnetic properties of [1-(4′-bromobenzyl)-4-methylquinolinium] [Ni(mnt)2] complex (mnt2 − =maleonitriledithiolate)

A new ion-pair complex, [BrBzMeQl][Ni(mnt)₂] (1) ([BrBzMeQl]⁺?=?1-(4′-bromobenzyl)-2-methylquinolinium; mnt^2??=?maleonitriledithiolate), has been prepared and characterized. X-ray diffraction analysis shows that the Ni(mnt)₂ anion and [BrBzMeQl]⁺ cations of 1 form completely segregated stacking columns, with the Ni?···?Ni distances alternating between 3.717 and 4.466?Å?in the Ni(mnt)₂ stacking column. The variable-temperature magnetic susceptibilities of 1 have been measured over the range 75–300?K and the results reveal that the complex exhibits antiferromagnetic behavior.     

Spiro[1,3-benzoxathiepin-4(5H),1′-cyclohexa[2,4]dien]-2,2′-dione,a Novel Heterocyclic Ring System

Abstract

Besides the common cyclisation reactions between divalent electrophiles such as Soc1₂, SC1₂, etc. and 2,2′-alkylidene-bisphenols 1 with selective attack by the two oxygens yielding dibenzo[d,g][1,3,2]dioxathiocines [1] we observed previously an unusual cyclisation of 1 with S₂CI₂ with a nucleophilic attack by the ortho- and para-carbon atoms (C(2) and C(4)) of bisphenol 1 [2]. We now report a new type of cyclocondensation reaction of 4,4′,6,6′-tetrasubstituted 2,2′-alkylidene-bisphenols 1 with ClSCOCl affording spiro[1,3-benzoxathiepin-4(5H),1′-cyclohexa[2,4]dien]-2,2′-diones 2 together with the cyclic carbonates 3. The structures of the products were elucidated mainly by ^l3C-NMR- and ¹H-NMR-spectroscopy. The mode of formation of the novel spiro thiocarbonates 2 resp. the known carbonates 3 [3] is discussed.