Organoaluminum compounds are weak Lewis acids, which specifically react with a number of reagents (or bases) and generate an electrophile (initiator)gegenion pair, reminiscent of classical Friedel—Crafts complexes. These complexes, under suitable reaction conditions, initiate polymerization of cationically polymerizable monomers producing useful high molecular weight polymers. In recent years a number of such organoaluminum-initiator systems have been systematically explored and their chemistry unravelled. As a consequence new insights have been gained which has led to newer applications of organoaluminum compounds in organic as well as new polymer synthesis.The present paper briefly summarizes the results in this area, especially from the point of view of initiator generation. Some recent results on the initiation of carbenium ion polymerizations using the oxyhalides of sulfur and phosphorous in conjunction with organoaluminum compounds are discussed. 相似文献
The pressure dependence of thelo-to phonons in InAs has been investigated by Raman scattering using the diamond anvil cell. Indium arsenide transforms, presumably
to the rock-salt structure at 70±1 kbar. The mode Grüneisen parameters for thelo-to phonons are γ
lo
=0.99±0.03, γ
to
=1.2±0.03 respectively. The effective charge,e*T, for InAs decreases slightly with pressure and this trend is in accordance with the behaviour of other III–V zinc blende
structured semiconductors: The structural phase transition is discussed in the light of theoretical calculations for phase
stability of III–V compounds, as well as recent high pressure x-ray diffraction studies. 相似文献
A comparative study of absorption and fluorescence maxima of 4,4′-diaminodiphenyl sulphone (4DADPS), 3,3′-diaminodiphenyl sulphone (3DADPS) and 2-aminodiphenyl sulphone (2ADPS) in different solvents reveals that (i) solvatochromic shifts are found to be mainly due to interaction of solvents with amino group, (ii) in any one solvent the net solvatochromic shifts of two amino groups are less than that of one amino group, (iii) fluorescence shift from cyclohexane to water is a maximum for 4DADPS and a minimum for 2ADPS and (iv) 4DADPS and 3DADPS possess more twisted intramolecular charge transfer character than 2ADPS. The excited-state acidity constants, determined by fluorimetric titration and Förster cycle methods, have been reported and discussed. 相似文献
The copolymerization of acrylonitrile with styrene was studied using homogeneous Ziegler-Natta initiator containing cobalt acetylacetonate and triethylaluminum in benzene at 50°C. The overall rate of polymerization shows an interesting dependence on triethylaluminum, monomer, and initiator concentrations. The overall activation energy for the polymerization was found to be 10 kcal/mol. The polymerization was susceptible to inhibition by added hydroquinone. These observations are explained based on a mechanism wherein acrylonitrile competes for complexation with both the catalyst sites and the Lewis acid. The catalyst sites appear to possess both coordinate anionic and free radical characteristics. 相似文献
In this Letter, we report a rapid one-step entry into isoindoline and Δ1-pyrrolines from chalcone. The key step in the synthesis is the addition of glycine to chalcone. In acidic medium the reaction presumably goes through aza-Michael addition, whereas in basic medium the reaction proceeds through condensation followed by cyclization. 相似文献
One-pot three-component synthesis of twelve different chromeno[2,3-b]indole derivatives were achieved by the condensation of β-naphthol, oxindole and various substituted aldehydes. Two more chromeno[2,3-b]indole derivatives were also synthesized through one-pot two-component condensation of salicylaldehyde with oxindole/chlorooxindole. Both the condensations were achieved by using Keggin-type heteropoly-11-molybdo-1-vanadophosphoric acid, H4[PVMo11O40] supported on montmorillonite K-10 clay for about 10% as catalyst under environmentally benign solvent-free reaction condition. Shorter reaction time, excellent yield of product, sustainability of catalytic material and simple workup procedure under green experimental conditions are the advantages of this protocol.