Search results for "SOLVENT"

One-Pot Three-Component Solvent-Free Syntheses of n-Alkyl-Bridged N,N,N,N-tetra(2-hydroxybenzyl)diamines and N,N-bis(2-hydroxybenzyl) amines

2010

A simple solvent-free method to prepare four N,N,N’,N’-tetra(2-hydroxy-3,5dimethylbenzyl)diaminoalkanes and four N,N,N’,N’-tetra(2-hydroxy-5-t-butyl-3-methylbenzyl)-diaminoalkanes containing a long n-alkyl-bridge (58 CH2 groups between N-atoms) is described. In addition, preparations of four dihydrochlorides of prepared n-alkyl-bridged N,N,N’,N’-tetra(2-hydroxybenzyl)diamines are described. This method was also tested in the preparation of eight previously reported N,N-bis(2-hydroxybenzyl)amine derivatives.

1985

Proposition d'une methode qui utilise l'information contenue dans la relation entre la vitesse de cisaillement et la viscosite. Solutions de polystyrene dans la trans-decaline

Lateral versus perpendicular segregation in mixed polymer brushes.

2002

Grafting of incompatible polymers on a substrate prevents macrophase separation and the chains self-assemble laterally. Mixed brushes are exposed to different solvents and the morphology is observed via atomic force and x-ray photoemission microscopy. In a nonselective solvent the different species segregate into parallel cylinders ("ripple structure"). Upon exposure to a selective solvent, we encounter a transition to a "dimple" structure, in which the unfavored component forms clusters. Simultaneously, we observe an enhanced perpendicular segregation. The experimental observations are compared to self-consistent field calculations, where qualitative agreement is found.

Microphase separation in bottlebrush polymers under poor-solvent conditions

2009

Molecular-dynamics simulations are used to study the structure of bottlebrush polymers with rigid backbones, for various grafting densities, side chain lengths, and varying solvent quality. While we confirm different states of the bottlebrush proposed by Sheiko et al. (Eur. Phys. J. E, 13 (2004) 125) we find that the transition between stretched and collapsed brushes occurs in a rather gradual manner. The pearl-necklace structure occurring at intermediate grafting densities and rather low temperatures has a pronounced medium-range order along the backbone.

1986

The variation of the Huggins coefficient KH with the relative molecular mass M of the polymers was measured for solutions of polystyrene and of polyisobutylene and found to be most pronounced in the case of thermodynamically good solvents but vanishing at the theta-temperature, where the individual curves kH (T; M) intersect with each other. The experimental results are interpreted as a consequence of the rheological inequality of inter- and intra-molecular contacts between polymer segments. A model is presented according to which kH should be a linear function of M−(a−0,5), where a is the exponent of the intrinsic viscosity-relative molecular mass relationship (Kuhn-Mark-Houwink). The eval…

ChemInform Abstract: Highly Enantioselective Protonation of the 3,4-Dihydro-2-methylnaphthalen-1(2H)-one Li-Enolate by TADDOLs.

2001

A series of nine TADDOLs (=α,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanols) 1a – 1i, have been tested as proton sources for the enantioselective protonation of the Li-enolate of 2-methyl-1-tetralone (=3,4-dihydro-2-methylnaphthalen-1(2H)-one). The enolate was generated directly from the ketone (with LiN(i-Pr)2 (LDA)/MeLi) or from the enol acetate (with 2 MeLi) or from the silyl enol ether (with MeLi) in CH2Cl2 or Et2O as the solvent (Scheme). The Li-enolate (associated with LiBr/LDA, or LiBr alone) was combined with 1.5 – 3.0 equiv. of the TADDOL at −78° by addition of the latter or by inverse addition. 2-Methyl-1-tetralone of (S)-configuration is formed (≤80% yield) with up to 99.5% sele…

1971

The anionic polymerization of β-propiolactone at 25°C in ethanol initiated by the betain was investigated. Macrozwitterions of the structure were produced, n being intentionally as low as ca. 11. The structure of the product was proven by the nitrogen content of the reprecipiated polymer, by IR and NMR spectroscopy and by titration of the carboxylate endgroups. Some carboxylic acid endgroups were formed by chain transfer with the solvent ethanol. The positive charge at the polymer chain was proven by electrophoresis of polymer after esterification of the carboxylate chain end. Furthermore the dielectric constant of dilute solutions of the polymer in CHCl3 was determined and is discussed. Th…

Mesoporous Materials Incorporating Metal Triflates

2016

Metal triflates attracted a large interest as catalysts in the past three decades especially due to the Lewis acid properties exhibited by these compounds and the variety of the functional group transformations. This chapter proposes an overview presenting the catalytic performances of triflates both as molecular compounds and as triflates dispersed in different solid matrices. In the first part the performances of molecular triflates in organic reactions carried out in the presence of water or water as solvent considering both water-sensitive and -insensitive metals are discussed. Then, the importance of materials incorporating triflates is demonstrated for catalysts obtained via immobiliz…

On the determination of underivatised fatty alcohol ethoxylates by electrospray ionisation–mass spectrometry

2006

Abstract The oligomers of fatty alcohol ethoxylates (FAEs) exhibit large sensitivity differences in mass spectrometry with electrospray ionisation (ESI–MS) and atmospheric pressure chemical ionization (APCI). Standards of the oligomers from m = 1 to 7 ethylene oxide units (EOs) and linear alkyl chains from n = 10 to 18 carbon atoms were infused to examine the relative sensitivities or response factors in several media. The response factors of the [M + H]+ and [M + Na]+ peaks in 9:1 acetonitrile/water and methanol/water media containing acid buffers increased following irregular patterns when n and m increased. In methanol/water the response factors depended on the parity of m, being larger …

Internal rotation of 1,2-dichloroethane in haloalkane dehalogenase. A test case for analyzing electrostatic effects in enzymes

2003

1,2-Dichoroethane (DCE) is a prototypical molecule for studying electrostatic solvent effects on molecular conformation as far as rotation around the carbon−carbon bond notably changes the electric...