Application of baylis‐hillman methodology in a new synthesis of 3‐oxo‐2,3‐dihydro‐1H‐isoindoles

The Baylis‐Hillman reaction of 2‐cyanobenzaldehyde with some activated alkenes leading to the formation of 3‐oxo‐2,3‐dihydro‐1H‐isoindoles has been described.     

Potassium 3‐cyano‐4‐(dicyanomethylene)‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olate

The crystal structure of the title potassium salt, K⁺·C₈HN₄O₂⁻, of the organic anion 3‐cyano‐4‐(di­cyano­methyl­ene)‐5‐oxo‐4,5‐di­hydro‐1H‐pyrrol‐2‐olate shows that the di­cyano­methyl­ene moiety is able to accept an electron in the same way as does tetra­cyano­ethyl­ene, to yield the novel product. The organic anion is nearly planar, with deviations caused by steric crowding among the exocyclic cyano groups. The K⁺ cations lie within tricapped trigonal prisms that stack to form channels. The three‐dimensional structure is completed by the formation of hydrogen‐bonded chains by the anions.     

Synthesis,Characterization, and Anti‐inflammatory Activity of Novel Isoxazolyl‐4‐(2‐oxo‐2,3‐dihydro‐1H‐3‐indolyl)pyrrole‐3‐carboxylates

A series of novel isoxazolyl‐4‐(2‐oxo‐2,3‐dihydro‐1H‐3‐indolyl)pyrrole‐3‐carboxylates ( 17a – i) were synthesized by a three‐component reaction of 4‐amino‐3‐methyl‐5‐styrylisoxazole 14 , β‐keto ester 15 , and 3‐phenacylideneoxindole 16 , in the presence of CAN catalyst in ethanol. The structures of the synthesized compounds have been established on the basis of spectral and analytical data. The title compounds 17a – i were evaluated for their anti‐inflammatory activity. Compounds 17b and 17c exhibited potent anti‐inflammatory activity as that of standard drug.     

Synthesis and antimicrobialactivity of 2‐alkylcarbamato‐2,3‐dihydro‐5‐propylthio‐1H‐1,3,2‐benzodiazaphosphole 2‐oxides

Novel 2‐alkylcarbamato/thiocarbama‐to‐2,3‐dihydro‐5‐propylthio‐1H‐1,3,2‐benzodiazaphos‐phole 2‐oxides ( 4a–J ) were synthesized by cyclization of 4‐propylthio‐1,2‐phenylenediamine ( 3 ) with the corresponding dichlorophosphoryl carbamates/thiocarbamates ( 2a–J ) that were obtained by the addition of alcohols/thiols to isocyanatophosphoryl dichloride ( 1 ). The structures of the title compounds were confirmed by the ¹H, ¹³C, ³¹P NMR, and mass spectral studies. Some of these products were found to possess significant antimicrobial activity. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:336–340, 2000     

Synthesis of 2‐substituted‐2,3‐dihydro‐5‐benzoyl‐1H‐1,3,2‐benzodiazaphosphole 2‐oxides/sulfides

Syntheses of 2‐aryloxy/2‐chloro ethoxy‐2,3‐dihydro‐5‐benzoyl‐1H‐1,3,2‐benzodiaza‐phosphole 2‐oxides 3a–h were accomplished by reactions of equimolar quantities of 3,4‐diaminobenzophenone ( 1 ) with various aryl/chloroethoxy phosphorodichloridates 2a–g and 2h in the presence of triethylamine at 50–60°C. Compounds 3i–k were prepared by reacting 3,4‐diaminobenzophenone ( 1 ) with aryl thiophosphorodichloridates 2i–k under similar conditions. They were characterized by IR, ¹H, ¹³C, and ³¹P NMR spectral data. Some of these products possessed siginificant antimicrobial activity © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:340–345, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10044     

A Novel Conversion of 2, 4‐Diaryl‐2, 3‐dihydro‐1 H‐1, 5‐benzodiazepines into 2, 4‐Diaryl‐3 H‐1, 5‐benzodiazepines

A novel conversion of 2, 4‐diaryl‐2, 3‐dihydro‐1 H‐1, 5‐benzodiazepins into 2, 4‐diaryl‐3 H‐1, 5‐benzodiazepines by the reaction with m‐chloroperbenzoic acid (MCPBA) was reported.     

Ammonium 3‐cyano‐4‐(dicyano­methyl­ene)‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olate monohydrate

Each anion of the title salt, NH₄⁺·C₈HN₄O₂⁻·H₂O, is linked by two N—H⋯O hydrogen bonds to another anion, thus forming an essentially planar centrosymmetric dimer. The dimers are considered to be mol­ecular building blocks of an anionic wall. The building blocks form infinite ribbons via–C—N⋯N—C– dipole–dipole and π–π inter­actions. Adjacent ribbons are stacked by means of π–π inter­actions, thus forming an anionic wall. Neighbouring walls are connected by (NH₄⁺…H₂O)_n chains running along the b axis.     

FeCI3‐promoted [3+3] cycloaddition: Efficient preparation of 1,2‐dihydro‐2‐oxo‐3‐pyridinecarboxylate and 1,2‐dihydro‐2‐oxo‐3‐pyridinecarboxamide derivatives

A facile approach was developed on assembly of the 2‐pyridone nucleus by ferric chloride promoted [3+3] cycloaddition in propionic acid. The tandem process involves cyclization of Michael adduct followed by aromatization. Thus, different substituted 1,2‐dihydro‐2‐oxo‐3‐pyridinecarboxylate and 1,2‐dihydro‐2‐oxo‐3‐pyridinecarboxamide derivatives were prepared in good yields from various enones with malonamic ester and malonamide, respectively     

Synthesis and antimicrobial activity of 2‐substituted‐2,3‐dihydro‐5‐propoxy‐1H‐1,3,2‐benzodiazaphosphole 2‐Oxides

Several 2‐alkylcarbamato/thiocarbamato/aryloxy/trichloromethyl‐2,3‐dihydro‐5‐propoxy‐1H‐1,3,2‐benzodiazaphosphole 2‐oxides ( 4 and 6 ) were synthesised by reacting 4‐propoxy‐o‐phenylenediamine ( 1 ) with various N‐dichlorophosphinyl carbamates ( 3 ), aryl phosphorodichloridates ( 5a‐f ) and trichloromethyl phosphonic dichloride ( 5g ) in the presence of triethylamine at 45‐65 °C. Their ir, ¹H, ¹³C, ³¹P nmr and mass spectral data are discussed. The compounds were screened for antifungal activity against Curvularia lunata and Aspergillus niger and for antibacterial activity against Bacillus subtilis and Escherichia coli. Most of these compounds exhibited moderate activity in the assays.     

Poly[[[diaqua­zinc(II)]‐bis(μ2‐3‐cyano‐4‐dicyano­methyl­ene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olato‐κ2N3:N3′)] dihydrate]

The coordination of the 3‐cyano‐4‐dicyano­methyl­ene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olate anion to Zn^II, the apical sites of which are occupied by two water mol­ecules, results in the formation of two‐dimensional layers of the title coordination polymer, {[Zn(C₈HN₄O₂)₂(H₂O)₂]·2H₂O}_n, in which the Zn^II cations lie on inversion centres in space group C2/c, with water ligands in the apical sites of octa­hedral geometry. Hydrogen bonds between coordinated and lattice water mol­ecules, and π–π stacking inter­actions between the anions link adjacent layers into a continuous framework.     

Luminescent properties of three structures built from 3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olate and cadmium

Yellow–orange tetraaquabis(3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olato‐κN³)cadmium(II) dihydrate, [Cd(C₈HN₄O₂)₂(H₂O)₄]·2H₂O, (I), and yellow tetraaquabis(3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olato‐κN³)cadmium(II) 1,4‐dioxane solvate, [Cd(C₈HN₄O₂)₂(H₂O)₄]·C₄H₈O₂, (II), contain centrosymmetric mononuclear Cd²⁺ coordination complex molecules in different conformations. Dark‐red poly[[decaaquabis(μ₂‐3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olato‐κ²N:N′)bis(μ₂‐3‐cyano‐4‐dicyanomethylene‐1H‐pyrrole‐2,5‐diolato‐κ²N:N′)tricadmium] hemihydrate], [Cd₃(C₈HN₄O₂)₂(C₈N₄O₂)₂(H₂O)₁₀]·0.5H₂O, (III), has a polymeric two‐dimensional structure, the building block of which includes two cadmium cations (one of them located on an inversion centre), and both singly and doubly charged anions. The cathodoluminescence spectra of the crystals are different and cover the wavelength range from UV to red, with emission peaks at 377 and 620 nm for (III), and at 583 and 580 nm for (I) and (II), respectively.     

A new synthesis of 4‐cyano‐1,3‐dihydro‐2‐oxo‐2H‐imidazole‐5‐(N1‐tosy1)carboxamide : reactive precursor for thiopurine analogues

N‐[(5‐Cyano‐2‐oxoimidazolidin‐4‐yl)‐iminomethyl]‐p‐toluensulfonamide 3 was prepared in fairly good yield by the base catalyzed cyclisation of N‐[(Z)‐2‐amino‐1,2‐dicycanovinylcarbamoyl]‐p‐toluenesulfon‐amide 2 . The N‐[(Z)‐2‐amino‐1,2‐dicycanovinyl carbamoyl]‐p‐toluenesulfonamide 2 was reacted readily with two molar amount of p‐nitrobenzaldehyde at room temperature in the presence of base to give 7,8‐dihy‐dro‐2‐(4‐nitrophenyl)‐8‐oxo‐9‐tosylpurine‐6‐carboxamide 8 . Thiation of compounds 3 and 8 using Lawesson's reagent in tetrahydrofuran gave novel thioimidazoles 4, 5 , and 6 and thiopurines 9, 10 , and 11 , which have been characterized spectroscopically.     

Regiospecific synthesis of 5‐(1H‐indol‐2‐yl)‐1‐ and 2‐methyl‐6,7‐dihydro‐2H‐indazole isomers

A regiospecific approach to each N‐methyl‐5‐(1H‐indol‐2‐yl)‐6,7‐dihydro‐2H‐indazole isomer is reported. The 1‐methyl isomer 1 was prepared from 5‐bromo‐1‐methyl‐6,7‐dihydro‐1H‐indazole 3 and indole‐2‐boronate 5 by palladium catalyzed Suzuki coupling. The 2‐methyl regioisomer 2 was synthesized via addition of lithium (1‐carboxylato‐1H‐indole‐2‐yl)lithium 6 with 2‐methyl‐2,4,6,7‐tetrahydro‐indazol‐5‐one 8 followed by acid catalyzed dehydration.