Search results for "BOND"
showing 10 items of 3527 documents
A novel phosphorus–carbon bond formation by ring opening with diethyl phosphite of oxazolines derived from serine
2004
Abstract A new reaction of oxazolines derived from serine with diethyl phosphite leading to ring opening products with P–C bond formation is reported. This reaction, which proceeds under neutral conditions and without the use of any halogenated intermediate, results in a mixture of racemic α- and β-phosphono alanines in an approximate 1:2 ratio, with isolated yields up to 77%. The mechanism involves the rearrangement of the oxazoline into the corresponding α-benzamido acrylate, followed by addition of the diethyl phosphite to the double bond. Since no significant transesterification is observed, this method constitutes a simple route for α- and β-phosphono amino acids bearing suitable prote…
Synthesis of hyperbranched poly(tert-butyl acrylate) by self-condensing atom transfer radical polymerization of a macroinimer
2000
Using 2-hydroxyethyl α-bromoisobuty-rate as initiator, atom transfer radical polymerization (ATRP) of tert-butyl acrylate leads to poly(tert-butyl acrylate) (PtBA) with a hydroxyl group at one and a bromine atom at the other end. Esterification of the hydroxyl group of these heterotelechelic polymers with acryloyl chloride yields PtBA (M n = 3060) with a polymerizable double bond at one end and a bromine atom at the other end which can act as an initiator in ATRP (macroinimer). Self-condensing ATRP of such a macroinimer leads to hyperbranched or highly branched PtBA. The polymer was characterized by GPC viscosity measurements. Even at M w = 78800, a rather low polydispersity index of M w M …
Endgruppenuntersuchungen an isotaktischen Polystyrolen. VII. Mitt. über die stereospezifische Polymerisation von Styrol mit alkaliorganischen Verbind…
1963
Durch Polymerisation von Styrol mit optisch aktivem 2-Methylbutylnatrium oder -lithium konnen Polystyrole hergestellt werden, welche die Ebene des polarisierten Lichtes drehen; der gemessene Drehwert entspricht bei nicht zu hochmolekularen Polymeren einer 2-Methylbutylgruppe pro Makromolekul. Bei der Suche nach einer ungesattigten Endgruppe konnten weder mit einer infrarotspektroskopischen Kompensationsmethode noch durch eine Anlagerungsreaktion eines Siloxanmonohydrids Doppelbindungen in mit 2-Methylbutylnatrium hergestellten Polystyrolen nachgewiesen werden. Aus der Bestimmung der wachsenden Polystyrolmolekule mit Hilfe von MICHLERS Keton als Abbruchsreagenz ergibt sich, das der groste Te…
Glycidyl methacrylate derivatization of α,β-poly(N-hydroxyethyl)-dl-aspartamide and α,β-polyasparthydrazide
1997
Abstract α,β-Poly(N-hydroxyethyl)- dl -aspartamide (PHEA) and α,β-polyasparthydrazide (PAHy) are two synthetic macromolecules having many potential applications in the field of biomedical sciences. This paper describes the functionalization of PHEA and PAHy with glycidyl methacrylate (GMA), in order to introduce pendant double bonds in their chains. Derivatized PHEA and PAHy (samples PHG and PAG, respectively) at various GMA content have been obtained and characterized. It has been shown that the derivatization reaction can be controlled by varying some parameters as solvent, catalyst, pH, GMA concentration and reaction time. As expected, PAHy reacted more rapidly and more extensively than …
Gas phase charged aggregates of bis(2-ethylhexyl)sulfosuccinate (AOT) and divalent metal ions: first evidence of AOT solvated aggregates
2011
Assembling and chelating properties of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) towards divalent metal ions have been investigated in the gas phase by electrospray ionization mass spectrometry. A variety of positively charged monometallated and mixed metal aggregates are formed. Interestingly, several ions contain solvent (MeOH, H2O) molecules and constitute the most abundant AOT cationic aggregates not containing sodium. These species are the first example of solvated AOT-metal ion aggregates in the gas phase. By increasing the surfactant aggregation number, the abundance of solvated species becomes lower than that of unsolvated ones. Decompositions of ionic species have been studied…
Structural organization of surfactant aggregates in vacuo: a molecular dynamics and well-tempered metadynamics study
2015
Experimental investigations using mass spectrometry have established that surfactant molecules are able to form aggregates in the gas phase. However, there is no general consensus on the organization of these aggregates and how it depends on the aggregation number and surfactant molecular structure. In the present paper we investigate the structural organization of some surfactants in vacuo by molecular dynamics and well-tempered metadynamics simulations to widely explore the space of their possible conformations in vacuo. To study how the specific molecular features of such compounds affect their organization, we have considered as paradigmatic surfactants, the anionic single-chain sodium …
C2-Symmetric Ferrocene-Bis(ureido)peptides : Synthesis, Conformation and Solid-State Structure
2009
The extension of peptide derivatives of ferrocene-1,1'-dicarboxylic acid by formal insertion of NH units between ferrocene and peptide strands results in ferrocene-bis(ureido)-peptides. Experimentally, alanine and dialanine methyl esters were attached to the 1- and 1'-position of 1,1'-diiso-cyanoferrocene to give the corresponding bis(ureido)peptide derivatives 3 and 4. The conformation of 3 has been determined in the solid state by X-ray crystallography. In solution the preferred conformation of 3 and 4 has been elucidated by NMR, IR and CD spectroscopy in concert with DFT calculations. The secondary structure of ferrocene―bis(ureido)peptides 3 and 4 is determined by double bifurcated intr…
Palladium-Catalyzed C—C Coupling Reactions in the Enantioselective Synthesis of 2,4-Disubstituted 4,5-Dehydropiperidines Using Galactosylamine as a S…
2005
Abstract Stereoselective synthesis of enantiomerically pure 2,4-disubstituted piperidine derivatives, which are considered interesting pharmacophoric structures, was achieved starting with a tandem Mannich–Michael reaction sequence on O -pivaloylated N -galactosyl aldimines. Subsequent conversion of the thus formed 2-substituted dehydropiperidinones into the corresponding enol triflates was carried out by conjugate hydride addition and trapping the enolate with N , N -bis(trifluoromethanesulfonyl)aniline. Their Suzuki–Miyaura coupling with aryl and heteroaryl boronic acids was performed under conditions compatible with the carbohydrate structure, in particular, with the sensitive N -glycosi…
Crystal structure analysis of supramolecular arrangements in bis(1-isoquinolinecarboxamide)alkanes and their Ag(i) complexes
2017
A homologous series of bis(1-isoquinolinecarboxamide)alkane derivatives (3a–f) with two to seven carbon atoms in the alkyl bridge and their Ag(I) complexes (4a–f) have been synthesized. Four ligand and five Ag(I) complex crystal structures were obtained by single crystal X-ray diffraction and analyzed in terms of: a) their structural patterns based on intra- and intermolecular hydrogen bonds which were compared to those of bis(2-quinolinecarboxamide)alkanes (1n) and bis(6-quinolinecarboxamide)alkanes (2n) attending to specific geometrical parameters and b) the Ag(I) coordinate bond effect on these patterns and the amide-to-amide hydrogen bonds. The crystal structures of the ligands 3a, 3c, …
Photochemical Functionalization of Allyl Benzoates by C-H Insertion
2013
The photoreactivity of allyl benzoates, containing an electron-rich double bond, has been explored by irradiation at 305 nm in different solvents. Solvent addition products arising from an insertion of the alpha H–C bonds of THF, dioxane, and i-PrOH to the allylic double bond was realized. The observed reactivity depended on reaction conditions and substitution pattern of the substrate. A DFT study on this unusual reaction was performed allowing the formulation of two mechanistic pathways.