Search results for "Reaction"

Living and Controlled Anionic Polymerization of Methacrylates and Acrylates in the Presence of Tetraalkylammonium Halide-Alkylaluminum Complexes in T…

1997

The size of both the cation and the anion of added NR4 X influences the rate of living polymerization of acrylates and methacrylates with alkylaluminum compounds. This controlled reaction, which occurs near to room temperature, provides unimodal polymers with narrow molecular-weight distributions. The complex shown to the right is suggested as a possible active species. R=Me, Et, nBu; R'=Me, Et; X=Cl, Br, I.

Formation of Bridging Alkene and Conjugated Dialkenes Exclusively Generated from Alkynes on the [3,3‘-Co(1,2-C2B9H11)2]- Platform. The Unique Hydrobo…

2003

The unprecedented metal-mediated transformation of an alkyne into a B,B' bridging alkene is reported. Also, the unprecedented synthesis of a conjugated dialkene derivative of [3,3'-Co(1,2-C2B9H11)2]- generated only from an alkyne, contrary to the usual case where an alkyne and an alkene are needed, is described. This has been possible through the singular capacity of a B-H to produce hydroboration.

Telechele des methylpropens durch kationische polymerisation

1986

Amorcage par des hydrocarbures aromatiques et aliphatiques contenant des groupes terminaux chlorure d'isopropyle, associes a du trichlorure de bore. Mecanisme. Recyclage du coamorceur et du solvant

Experimental and DFT study of the conversion of ephedrine derivatives into oxazolidinones. Double SN2 mechanism against SN1 mechanism

2010

Sulfonation of the N-Boc derivatives of 1,2-aminoalcohols, such as ephedrine, pseudoephedrine, norephedrine, norpseudoephedrine, thiomicamine, and chloramphenicol yields a mixture of the corresponding oxazolidinones with inversion (erythro derivatives) and/or retention of configuration (threo derivatives)at C5. We suggest a competition between two mechanisms: an intramolecular SN2 process initiated by attack of the carbonyl oxygen of the Boc group to the benzylic carbon and the other one through a double SN2 process. In the erythro derivatives the first mechanism is predominant, while in the threo derivatives both mechanisms have similar energy. This hypothesis is supported by theoretical c…

Electrocarboxylation of aromatic ketones: Influence of operative parameters on the competition between ketyl and ring carboxylation

2007

Abstract The purpose of this work is to investigate the effect of operational parameters on the competition between the formation of the target 2-hydroxy-2-arylpropanoic acid and ring carboxylation in the electrocarboxylation of aromatic ketones. For the investigated ketones, this competition has been found to be dramatically influenced by different parameters such as the water content and the ratio between the carbon dioxide and the ketone concentrations (q = [CO2]/[ketone]). In particular, the target carboxylic acid formation can be favoured with respect to ring carboxylation by operating at high q ratios or by addition of small amounts of H2O to the reaction medium. An increase of the wa…

Mechanism of anionic polymerization of (meth)acrylates in the presence of aluminium alkyls

1995

Summary Methyl methacrylate was polymerized with tert-butyl lithium in the presence of triethylaluminum or triisobutylaluminium at -78~ in toluene. As indicated by GPC and MALDI-TOF mass spectrometry, the polymerization is accompanied by side reactions. The lower oligomers were fractionated by distillation and characterised by NMR, FT-IR, UV and electron impact (EI) mass spectrometry. All these data show that part of the polymer chains are carrying exactly one tert-butyl isoprenyl ketone unit. In order to avoid the formation of tert-butyl isoprenyl ketone a molar ratio of A1/Li > 2 is necessary.

Oxidation of N,N-Benzylalkylamines to Nitrones by Mo(VI) and W(VI) Polyperoxo Complexes

1996

Abstract Oxidation of N,N-benzylalkylamines in chloroform by Mo(VI) and W(VI) polyperoxo complexes (PPC) of general formula Q+3{PO4[MO(O2)2]4}3− (Q+ = onium ion) yield the corresponding nitrones as oxidized products quantitatively. Only in the case of N,N-benzylmethylamine the formation of nitrone is accompanied by 25% of benzaldoxime. Oxidation of N,N-benzyltertbutylamine and N,N-benzylisopropylamine follows second order kinetics. This finding does not disqualify the hypothesis that the reaction might occur by a rate determining nucleophilic attack of the amine onto the peroxide oxygens leading, through a Bartlett-type transition state, to the probable formation of the corresponding hydrox…

γ-radiation-initiated polymerization of vinylidene fluoride in dense carbon dioxide

2002

The γ-ray-initiated batch polymerization of vinylidene fluoride (VF2) has been investigated in dense carbon dioxide under relatively mild operative conditions (T ≤ 40 °C and P < 25 MPa). When the initial VF2 molar concentration was increased from 3.4 to 6.4 mol/L, monomer conversion increased from 20 to 73%; a similar trend was observed for the number-average molecular weight and the molecular complexity of synthesized poly(vinylidene fluoride) (PVDF) as determined from rheological measurements. Under all adopted experimental conditions, a synthesized PVDF polymer was collected in the form of a white powder. Despite the inherent heterogeneous character of the polymerization process, a homog…

On the Dichotomic Behavior of the Z-2,4-Dinitrophenylhydrazone of 5-Amino-3-benzoyl-1,2,4-oxadiazole with Acids in Toluene and in Dioxane/Water:  Rea…

2004

The mononuclear rearrangement (MRH) of the Z-2,4-dinitrophenylhydrazone (4a) and of the Z-phenylhydrazone (4b) of 5-amino-3-benzoyl-1,2,4-oxadiazole into the relevant triazoles 5a and 5b in toluene has been quantitatively investigated in the presence of trichloroacetic acid (TCA) and of piperidine at 313.1 K. While the behavior in the presence of piperidine recalls the one previously evidenced for some Z-hydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazole, the study of the reactivity in the presence of TCA has most interestingly evidenced a general-acid-catalyzed rearrangement for “both” 4a and 4b. Thus, 4a offers the first example of a solvent-dependent dichotomic behavior in MRH processes o…

1987