Acetanilide palladacycle: an efficient catalyst for room‐temperature Suzuki–Miyaura cross‐coupling reaction

The catalytic activity of three acetanilide palladacycles derived from easily accessible and commercially available acetanilide derivatives, viz. N‐phenylacetamide ( L1 ), N‐(4‐chlorophenyl)acetamide ( L2 ) and N‐(4‐methylphenyl)acetamide ( L3 ) has been examined in Pd‐catalyzed Suzuki–Miyaura reaction of arylboronic acid with aryl bromides at room temperature. The complex 1L3 exhibited efficient activity in the Suzuki–Miyaura reaction (up to 99% isolated yield) under mild reaction conditions. Copyright © 2014 John Wiley & Sons, Ltd.     

Rhodium(I) carbonyl complexes of quinoline carboxaldehyde ligands and their catalytic carbonylation reaction

The dimeric rhodium precursor [Rh(CO)₂Cl]₂ reacts with quinoline (a) and its three isomeric carboxaldehyde ligands [quinoline-2-carboxaldehyde (b), quinoline-3-carboxaldehyde (c), and quinoline-4-carboxaldehyde (d)] in 1:2 mole ratio to afford complexes of the type cis-[Rh(CO)₂Cl(L)] (1a-1d), where L = a-d. The complexes 1a-1d have been characterised by elemental analyses, mass spectrometry, IR and NMR (¹H, ¹³C) spectroscopy together with a single crystal X-ray structure determination of 1c. The X-ray crystal structure of 1c reveals square planar geometry with a weak intermolecular pseudo dimeric structure (Rh?Rh = 3.573 Å). 1a-1d undergo oxidative addition (OA) with different electrophiles such as CH₃I, C₂H₅I and I₂ to give Rh(III) complexes of the type [Rh(CO)(COR)Cl(L)I] {R = -CH₃ (2a-2d), R = -C₂H₅ (3a-3d)} and [Rh(CO)Cl(L)I₂] (4a-4d) respectively. 1b exhibits facile reactivity with different electrophiles at room temperature (25 °C), while 1a, 1c and 1d show very slow reactivity under similar condition, however, significant reactivity was observed at a temperature ∼40 °C. The complexes 1a-1d show higher catalytic activity for carbonylation of methanol to acetic acid and methyl acetate [Turn Over Frequency (TOF) = 1551-1735 h⁻¹] compared to that of the well known Monsanto’s species [Rh(CO)₂I₂]⁻ (TOF = 1000 h⁻¹) under the reaction conditions: temperature 130 ± 2 °C, pressure 33 ± 2 bar, 450 rpm and time 1 h. The organometallic residue of 1a-1d was also isolated after the catalytic reaction and found to be active for further run without significant loss of activity.     

Synthesis and characterization of a flame retardant hyperbranched polyether

<正>A brominated hyperbranched polyether has been synthesized from cyanuric chloride and sodium salt of tetrabromobisphenol-A by an A_2+B_3 approach.The synthesized polyether was characterized by ~1H-NMR,~(13)C-NMR,UV, FTIR spectroscopy and X-ray diffraction studies,measurements of solution viscosity,molecular weight and solubility and elemental and thermogravimetric analyses.The flame retardancy of the synthesized polyether and its blends with commercially available plasticized poly(vinyl chloride)(PVC) and low density polyethylene(LDPE) was investigated by measurements of limiting oxygen index(LOI) value and thermogravimetric analysis.The properties are compared with a non-halogenated similar type of bisphenol-A based aromatic polyether after blending at different dose levels with the same base polymers.The LOI values of these blends indicated that these hyperbranched polyethers acted as flame retardant additives,and antimony trioxide had prominent synergistic effect with the bromo hyperbranched polyether for the above base polymers,and an increment of 4 to 6 units in LOI values was observed.     

Bakers’ yeast-catalyzed reductive cleavage of 3-aryl-2,1-benzisoxazoles and its quaternary salts: an efficient green synthesis of 2-aminobenzophenones

Abstract  

3-Aryl-2,1-benzisoxazoles and its salts underwent reductive cleavage of the N–O bond leading to 2-aminobenzophenones with bakers’ yeast under non-fermenting conditions in aqueous media. The procedure gives excellent yields of 2-alkylamino- and 2-aminobenzophenones.     

Effect of Sn-doping at Mo-site on the conductivity of La2Mo2O9 series of compounds

Taking oxygen ion conductor La₂Mo₂O₉, as a base compound, a series of Sn-doped La₂Mo_2−x Sn _x O_9−δ, x = 0, 0.01, 0.02, 0.03, 0.05, 0.1, 0.15, 0.2 specimens were prepared and characterized by XRD for phase and crystal structure determination and ac impedance spectroscopy for ac and dc conductivity measurement. We have found that there is slight improvement in overall conductivity of the specimen with x = 0.03 at 800°C compared to the undoped compound at the same temperature. The value of conductivity when extrapolated to 800°C is found to be 0.055 S cm-1 for the specimen with x = 0.03, whereas conductivity of undoped specimen at the same temperature is found to be 0.033 Scm⁻¹.     

Palladium complexes of P,P and P,S type bidentate ligands: Implication in Suzuki–Miyaura cross-coupling reaction

New palladium complexes of the type [PdCl₂(η²–P∩P)] (1a,1b) and [PdCl₂(η²–P∩S)] (1c,1d) have been synthesised by the reaction of PdCl₂ with P,P and P,S type bidentate ligands in 1:1 mol ratio, where, P∩P = 9,9–dimethyl-4,5-bis(diphenylphosphanyl) xanthene {Xantphos}(a) or bis(2-diphenylphosphanylphenyl)ether{DPEphos}(b); P∩S = 9,9-dimethyl-4,5-bis(diphenyl -phosphanyl) xanthenemonosulfide {Xantphos(S)}(c) or bis(2-diphenylphosphanyl phenyl) ether monosulfide {DPEphos(S)}(d). The complexes are characterized by elemental analyses, mass spectrometry, ¹H, ¹³C and ³¹P NMR spectroscopy together with the single crystal X-ray structure determination of 1a and 1d. The palladium atom in all the complexes occupies the centre of a slightly distorted square planar environment formed by a P atom, a P/S atom and two Cl atoms. The catalytic activities of 1a–1d investigated for Suzuki–Miyaura cross-coupling reactions at room temperature exhibit higher yield of the coupling products than catalysed by PdCl₂ itself. Among 1a–1d, the palladium complexes of bidentate phosphine (1a, 1b) show higher efficacy than their monosulfide analogues (1c, 1d). However, the recycling experiments with the catalysts for a selected coupling reaction between 4-bromobenzonitrile and phenylboronic acid exhibit that 1c and 1d are more efficient than 1a and 1b, which may be due to the donor effect of the P,S ligands during catalytic reaction.     

An efficient,regiospecific synthesis of (±)-Daunomycinone

The development of a general strategy for the control ofregiochemistry in the Diels-Alder reactions of substituted naphthazarins is described. Application of this strategy to the synthesis of(±)-daunomycinone (2) employs two successive regiochemically controlled Diels-Alder reactions and leads to a ten-step, regiospecific synthesis of(±)-2 in 36% overall yield (Scheme 4).     

Stereoselective intramolecular hetero Diels-Alder reactions of 1-oxa-1,3-butadienes: synthesis of novel annelated pyrrolo[1,2-a]indoles

Novel classes of pyrano-1,3-dioxane-, pyranopyrimidine- and pyranopyrazole-fused pyrrolo[1,2-a]indoles are synthesised via stereoselective intramolecular 1-oxa-1,3-butadiene hetero Diels-Alder reactions.     

Physical, thermal, dielectric and chemical properties of a hyperbranched polyether and its linear analog

The hyperbranched and the linear polyethers were prepared by one-pot nucleophilic displacement polymerization technique using cyanuric chloride and aromatic diol as reported earlier. The physical, thermal, dielectric and chemical properties of the hyperbranched polyether and its linear analog have been studied. The amorphous character of both the polyethers was observed in XRD study. The solubility studies showed that the hyperbranched polyether has relatively higher solubility in different solvents compared to its linear analog. The thermal properties of both polymers have been studied by thermogravimetric (TG) and differential scanning calorimetric (DSC) analyses. The chemical resistance tests indicated that both polyethers are very good chemical resistances except in dilute aqueous alkali solution. The dielectric properties such as dielectric constant and loss factor for both polyethers have also been studied with respect to changes of frequency (50-500 kHz) and temperature (303-343 K).