VCl3‐Catalyzed Selective Oxidation of Sulfides to Sulfoxides Using H2O2 as Oxidant

VCl₃ is an effective catalyst for the catalytic oxidation of sulfides to afford sulfoxides in good yields using hydrogen peroxide as an oxidant.     

Hypervalent Iodine in the Synthesis of Bridgehead Heterocycles: A Facile Route to the Synthesis of 6‐Arylimidazo[2,1‐b]thiazoles Using [Hydroxy(tosyloxy)iodo]benzene

α‐Tosyloxyketones (2), readily accessible through hypervalent iodine oxidation of enolizable ketones (1) using [hydroxy(tosyloxy)iodo]benzene (HTIB) in acetonitrile, exclusively generates the 6‐arylimidazo[2,1‐b]thiazoles (4) on treatment with commercially available 2‐aminothiazole (3).     

Synthesis of Thiazolo[2,3‐c]‐s‐triazoles Using Poly[(4‐diacetoxyiodo)styrene]

Abstract

Arenecarbaldehyde‐4‐arylthiazol‐2‐ylhydrazones underwent ring closure with poly[(4‐diacetoxyiodo)styrene] (PSDIB) to 3,5‐diarylthiazolo[2,3‐c]‐s‐triazoles in dichloromethane.     

[Hydroxy(tosyloxy)iodo]benzene in Organic Synthesis: A Facile Synthesis of Furo[3,2-c]coumarins Using α-Tosyloxyketones

Facile synthesis of furo[3,2-c]coumarins (2a–g) via cyclocondensation of 4-hydroxycoumarin and α-tosyloxyketones (1a–g) is described. A plausible mechanism involving C-C bond formation followed by 5-exo-tet cyclization is suggested.     

Synthesis of a New Polymer-supported Reagent──Poly{[4- hydroxy(tosyloxy)iodo]styrene} and Its Application to the Synthesis of 2-Amino-4-arylthiazoles

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N‐Methylpyrolidin‐2‐one Hydrotribromide (MPHT) as a New and Efficient Reagent for the Oxidation of Sulfides to Sulfoxides and Sulfones

The stable and crystalline N‐methylpyrolidin‐2‐one hydrotribromide (MPHT) effects oxidation of various sulfides to sulfoxides and sulfones.     

Selective and Efficient Oxidation of Sulfides to Sulfoxides Using Ceric Ammonium Nitrate (CAN)/Brönsted Acidic Ionic Liquid

A selective and efficient procedure for the oxidation of sulfides to the corresponding sulfoxides is reported using ceric ammonium nitrate in the presence of methylimidazolium hydrogensulfate as Brönsted acidic ionic liquid ([Hmim]HSO ₄ ) as the solvent under mild conditions. The use of nontoxic and inexpensive materials, straightforward procedure, short reaction times, and good yields of the products are the major advantages of this method.     

Poly{ [4-（hydroxyl）（tosyloxyl）iodo]styrene} Promoted Halotosyloxylation Reaction of Alkynes

Halotosyloxylation reaction of alkynes with iodine or NBS or NCS was efficiently promoted by the poly { [4-(hydroxyl)(tosoyloxyl)iodo]styrene }.     

Facile One‐Step Conversion of Ketones into α‐Azidoketones using [Hydroxy(tosyloxy)iodo]benzene and Sodium Azide in the Presence of a Phase‐Transfer Catalyst under Solvent‐Free Conditions

We have described a one‐step, solvent‐free synthesis of α‐azidoketones from the corresponding ketones that requires relatively benign [hydroxy(tosyloxy) iodo]‐benzene reagent, sodium azide, and phase‐transfer catalyst at room temperature. Generality of the protocol has been demonstrated by synthesizing various α‐azidoketones high in yield and purity within a short time.     

L‐Proline–H2O2: A New Chemoselective Approach for Oxidation of Sulfides to Sulfoxides

A facile and selective oxidation of sulfides to sulfoxides using an L‐proline–H₂O₂ system for structurally divergent sulfide substrates with excellent yields at ambient conditions is reported.     

Synthesis of Functionalized Pyrano[3,2‐c]pyridines and Their Transformations to 4‐Hydroxy‐3[(1E)‐N‐hydroxyalkanimidoyl]pyridones

Reaction of 4‐hydroxy‐6‐methyl‐2(1H)‐pyridones 1a and 4‐hydroxy‐1,6‐dimethyl‐2(1H)‐pyridones 1b with diethyl malonates 2a–e leads to the formation of pyrano[3,2‐c]pyridines 4a–j. Degradation of 4a–i affords the corresponding ketones 6a–i. Condensation of ketones 6a–i with hydroxyl amine or phenyl hydrazine hydrochloride is described.     

Glycosylation of 4‐Aryl‐1‐thioxo[1,2,4] triazolo[4,3‐a] quinazolin‐5(4H)‐one

Reaction of 4‐aryl‐1‐thioxo [1,2,4] triazolo [4,3‐a] quinazolin‐5 (4H)‐ones (2a,b) with acetylated glycosyl bromides 3a–c under alkaline conditions afforded the corresponding S‐glycoside derivatives 4, 5 and N‐glycoside derivatives 6, 7. Oxidation of S‐glycosyl derivatives 4, 5 with m‐chloroperbenzoic acid yielded the corresponding sulphones 8, 9, whereas the N‐glycosyl derivatives 6, 7 yielded 1‐oxo derivatives 10, 11. However their O‐deacetylation with sodium methoxide in methanol caused cleavage of the S‐glycosyl residue and gave N ²‐glycosylated analogues 12, 13, 14 and 15.     

Synthesis of Poly[2‐decyloxy‐5‐(4′‐tert‐butylphenyl)‐1,4‐phenylenevinylene] as a Light Emitting Material

In this study, a new electroluminescent poly(2‐decyloxy‐5‐(4′‐tert‐butylphenyl)‐1,4‐phenylene‐vinylene) (designated as DBP‐PPV) with no tolane‐bis–benzyl (TBB) structure defect was prepared by dehydrohalogenation of 1,4‐bisbromomethyl‐2‐decyloxy‐5‐(4′‐tert‐butyl‐phenyl) benzene (as monomer). The monomer bearing decyloxy and 4′‐tert‐butylphenyl substituents was synthesized via alkylation, bromination and Suzuki coupling reactions. The two asymmetric substituents of the monomer can suppress the formation of TBB defect during polymerization process and make the resultant polymer be soluble in common organic solvents. The structure and properties of DBP‐PPV were examined by ¹H‐NMR, FT‐IR, UV/Vis, TGA and photoluminescence (PL) analyses. Moreover, with the DBP‐PPV acting as a light‐emitting polymer, a device with sequential lamination of ITO/PEDOT/DBP‐PPV/Ca/Ag was fabricated. The electroluminescence (EL) spectrum of the device showed a maximum emission at around 546 nm, corresponding to a yellowish‐green light. The device showed a turn‐on voltage of about 8.4 V and a maximum luminescence efficiency of 0.11 cd/A at an applied voltage of 12 V.     

Synthesis,Characterization, Thermal and Antimicrobial Activity of Poly[(2‐Hydroxy‐4‐methoxy benzophenone)propylene] and its Polychelates with Lanthanides(III)

The polymeric ligand (resin) was prepared from 2‐hydroxy‐4‐methoxy‐benzophenone with propylene glycol in the presence of polyphosphoric acid as a catalyst at 160°C for 13 h. The poly[(2‐hydroxy‐4‐methoxybenzophe‐none) propylene] H(HMBP‐PG) form 1:2 metal:ligand chelates with La(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III) and Dy(III). The polymeric ligand and its polychelates were characterized on the basis of elemental analyses, electronic spectra, magnetic susceptibilities, IR‐spectroscopy, NMR, and thermogravimetric analyses. The molecular weight was determined using Number Average Molecular Weight (Mn) by a Vapor Pressure Osmometry (VPO) method. All the polychelates are paramagnetic in nature. The resin and their polychelates were tested for antimicrobial activity against E. coli, B. substilis, S. aureus (bacteria) and S. cerevisiae (yeast). It is found that the synthesized polychelates can be used as antibacterial agents.     

(PhCH2PPh3)+Br3 −: A Versatile Reagent for the Chemoselective Oxidation of Sulfides to Sulfoxides

Benzyltriphenylphosphonium tribromide (BTPTB), as a stable solid reagent, is easily prepared by the reaction of benzyltriphenylphosphonium bromide with Br₂. This reagent can be used as an efficient reagent for the chemoselective oxidation of dialkyl and aryl-alkyl sulfides to their corresponding sulfoxides in the presence of diaryl sulfides and primary alcohols. All reactions were performed in a refluxing mixture of methanol and water in very short reaction times.     

Synthesis of Star‐Shaped Poly(ϵ‐caprolactone)‐b‐Poly(styrene) Block Copolymer by Combining Ring‐Opening Polymerization and Atom Transfer Radical Polymerization

Newly designed star‐shaped block copolymers made of poly(?‐caprolactone) (PCL) and polystyrene (PS) were synthesized by combining ring‐opening polymerization (ROP) of ?‐caprolactone (CL) and atom transfer radical polymerization (ATRP) of styrene (St). The switch from the first to the second mechanism was obtained by selective transformation of “living” radical sites. First, tri‐ and tetrafunctional initiators were used as an initiator for the “living” ring opening polymerization (ROP) of ?‐caprolactone producing a hydroxyl terminated three or four arm star‐shaped polymer. Next, the OH end groups of PCL star branches were derivatized into 2‐bromoisobutyrate groups which gave rise to the corresponding tri‐ and tetrabromoester ended‐PCL stars; the latter served as macroinitiators for the ATRP of styrene at 110°C in the presence of CuBr/2,2‐bipyridine (Bipy) catalyst system affording star‐shaped block copolymers PCL_n‐b‐PS_n (n=3 or 4). The samples obtained were characterizated by ¹H‐NMR spectroscopy and GPC (gel permeation chromatograph). These copolymers exhibited the expected structure. The crystallization of star‐shaped block copolymers was studied by DSC (differential scanning calorimetry). The results show that when the content of the PS block increased, the T_m of the star‐shaped block copolymer decreased.     

Synthesis of Some Novel 2,3,4,8,9‐Pentahydro‐7‐(4‐haloaryl)‐pyrazolo[5,1‐e]benzo[1,5]oxazocines and 2,3(erythro), 7,8‐Tetrahydro‐2‐aryl‐3‐(4‐fluoro‐3‐methylbenzoyl)‐6‐(4‐haloaryl)pyrazolo[5,1‐d] Benzo[1,4]oxazepines via Solid–Liquid PTC

In this communication, a simple and straightforward procedure for the heterocyclization of 1H‐4,5‐dihydro‐3‐(4‐haloaryl)‐5‐substituted phenylpyrazoles (4) with 1‐bromo‐3‐chloropropane and 2,3‐dibromo‐1‐(4‐fluoro‐3‐methylphenyl)‐3‐phe‐ nylpropanone affording 2,3,4,8,9‐pentahydro‐7‐(4‐haloaryl)pyrazolo[5,1‐e]benzo[1,5] oxazocines 5 and regioselective synthesis of 2,3(erythro),7,8‐tetrahydro‐2‐ aryl‐3‐(4‐fluoro‐3‐methylbenzoyl)‐6‐(4‐halophenyl)pyrazolo[5,1‐d]benzo[1,4]oxa‐ zepines 6, respectively, via solid–liquid PTC is reported. All the synthesized compounds have been characterized on the basis of their spectral studies (IR, PMR, and MS) and analytical data.     

Poly(acrylate‐b‐styrene‐b‐isobutylene‐b‐styrene‐b‐acrylate) Block Copolymers via Carbocationic and Atom Transfer Radical Polymerizations

A series of polyacrylate‐polystyrene‐polyisobutylene‐polystyrene‐polyacrylate (X‐PS‐PIB‐PS‐X) pentablock terpolymers (X=poly(methyl acrylate) (PMA), poly(butyl acrylate) (PBA), or poly(methyl methacrylate) (PMMA)) was prepared from poly (styrene‐b‐isobutylene‐b‐styrene) (PS‐PIB‐PS) block copolymers (BCPs) using either a Cu(I)Cl/1,1,4,7,7‐pentamethyldiethylenetriamine (PMDETA) or Cu(I)Cl/tris[2‐(dimethylamino)ethyl]amine (Me₆TREN) catalyst system. The PS‐PIB‐PS BCPs were prepared by quasiliving carbocationic polymerization of isobutylene using a difunctional initiator, followed by the sequential addition of styrene, and were used as macroinitiators for the atom transfer radical polymerization (ATRP) of methyl acrylate (MA), n‐butyl acrylate (BA), or methyl methacrylate (MMA). The ATRP of MA and BA proceeded in a controlled fashion using either a Cu(I)Cl/PMDETA or Cu(I)Cl/Me₆TREN catalyst system, as evidenced by a linear increase in molecular weight with conversion and low PDIs. The polymerization of MMA was less controlled. ¹H‐NMR spectroscopy was used to elucidate pentablock copolymer structure and composition. The thermal stabilities of the pentablock copolymers were slightly less than the PS‐PIB‐PS macroinitiators due to the presence of polyacrylate or polymethacrylate outer block segments. DSC analysis of the pentablock copolymers showed a plurality of glass transition temperatures, indicating a phase separated material.     

Solid State Oxidative Aromatization of Hantzsch 1,4-Dihydropyridines to Pyridines Using Iodobenzene Diacetate or Hydroxy(tosyloxy)iodobenzene

An easy, safe, solvent-free and effective method for oxidative aromatization of Hantzsch 1,4-dihydropyridines catalyzed by hypervalent iodine (IBD and HTIB) to corresponding pyridine derivatives in high yields within short span of time. All reactions were carried out just by grinding the two reactants.     

Improved Syntheses of 5‐Hydroxy‐2‐Pyridones (2,5‐Dihydroxypyridines)

Improved syntheses of 5-hydroxy-2-pyridone, 6-chloro-5-hydroxy-2-pyridone, 2,5-dihydroxynicotinic acid, and three methyl-substituted 5-hydroxy-2-pyridones are reported.