Search results for "Adduct"
showing 10 items of 320 documents
PHOSPHORORGANISCHE VERBINDUNGEN 991VERSUCHE ZUR AUFKLÄRUNG DER O-SELEKTIVITÄT VON VERBINDUNGEN MIT DER P(O)F-GRUPPE
1982
Abstract The mechanism of the reaction of phosphoryl fluoride ( P(O)F) with alcohols in the presence of an amine is fundamentally different from the reaction of phosphoryl chlorides ( P(O)Cl) with primary or secondary amines. The following observations strongly support this proposal: 1. 1H-NMR-, 31P-NMR- and 19F-NMR-spectroscopic investigations show that methyl-phenyl-phosphinicacid-fluoride and n-butylamine form a thermolabile adduct, which yields the methyl-phenyl-phosphinicacid-amide only very slowly. 2. The rate of the reaction of methyl-phenyl-phosphinicacid-fluoride with ethanol is independent of the basicity of the amine but very sensitive to steric factors. Imidazole (which is only …
Synthesis of new cationic donor-stabilized phosphenium adducts and their unexpected P-substituent exchange reactions
2008
The reaction between two 1,3-dialkylimidazolium-2-carboxylates 1a and 1b and two different dichlorophosphines (RPCl(2), with R = Ph and NEt(2)) led to new donor-stabilized phosphenium adducts. When the reaction was performed with the 1,3-dimethylimidazolium-2-carboxylate 1a and PhPCl(2) in a 2:1 ratio, the phosphine 4a, bearing two imidazolium moieties, was obtained and led to 5a, after an anion exchange reaction with KPF(6), the latter being fully characterized by an X-ray structure analysis. In similar conditions, the bis-imidazolium phosphine or phosphene-di-ium, 4b, which is analogous to 4a, has been obtained by the addition of PhPCl(2) to the 1-dodecyl-3-methylimidazolium-2-carboxylate…
1H NMR and UV-vis spectroscopic characterization of sulfonamide complexes of nickek(II)-carbonic anhydrase. Resonance assignments based on NOE effects
1992
The binding of acetazolamide, p-fluorobenzensulfonamide, p-toluenesulfonamide, and sulfanilamide to nickel(II)-substituted carbonic anhydrase II has been studied by 1H NMR and electronic absorption spectroscopies. These inhibitors bind to the metal ion forming 1:1 complexes and their affinity constants were determined. The 1H NMR spectra of the formed complexes show a number of isotropically shifted signals corresponding to the histidine ligands. The complexes with benzene-sulfonamides gave rise to very similar 1H NMR spectra. The NMR data suggest that these aromatic sulfonamides bind to the metal ion altering its coordination sphere. In addition, from the temperature dependence of 1H NMR s…
Syntheses of Oxygenated Spongiane Diterpenes from Carvone. Synthesis of Dorisenone C.
2005
Abstract The synthesis of dorisenone C, a representative member of the spongiane-type diterpene family, is described. The synthesis follows a B→AB→ABC→ABCD approach and is based on the initial preparation of the previously known hydroxy-aldehyde 14 (AB rings) from R -(−)-carvone, followed by an intramolecular Diels–Alder reaction between an oxygenated diene moiety and an acetylenic dienophile for the construction of the C ring (compound 22 ), and adequate manipulation of the Diels–Alder adduct functionality for completion of the spongiane framework.
Synthetic studies on the preparation of oxygenated spongiane diterpenes from carvone
2003
Abstract The paper describes a new diastereoselective approach to oxygenated spongiane diterpenes functionally related to natural dorisenones. The strategy followed for the preparation of the spongiane framework, a B→AB→ABC→ABCD approach, is based on the preparation of epoxydecalone 11 (AB rings) from R-(−)-carvone, followed by an intramolecular Diels–Alder reaction for the construction of the C ring (compound 26 ). Further manipulation of the Diels–Alder adduct functionality allows the completion of the spongiane framework and the elaboration of several oxygenated spongiane-type compounds. The structures of two compounds 27 and 31 , has been established by single-crystal X-ray crystallogra…
ChemInform Abstract: Aldol Reactions with Erythrulose Derivatives: Stereoselective Synthesis of Differentially Protected syn-α,β-Dihydroxy Esters.
2010
Boron enolates of 1-O-silylated erythrulose 3,4-acetonides prepared with Brown's chloro-dicyclohexylborane/tertiary amine system have been shown to react with achiral aldehydes in a highly stereoselective way to yield a 1,2-syn/1,3-syn stereoisomer. Through oxidative cleavage of the aldol adducts with periodic acid hydrate, enantiopure syn-α,β-dihydroxy esters with either hydroxyl group differently protected have been prepared. These erythrulose derivatives therefore behave as a chiral hydroxy acetate (glycolate) enolate equivalent.
Aldol Reactions with Erythrulose Derivatives: Stereoselective Synthesis of Differentially Protected syn -α,β-Dihydroxy Esters
2000
Boron enolates of 1-O-silylated erythrulose 3,4-acetonides prepared with Brown's chloro-dicyclohexylborane/tertiary amine system have been shown to react with achiral aldehydes in a highly stereoselective way to yield a 1,2-syn/1,3-syn stereoisomer. Through oxidative cleavage of the aldol adducts with periodic acid hydrate, enantiopure syn-α,β-dihydroxy esters with either hydroxyl group differently protected have been prepared. These erythrulose derivatives therefore behave as a chiral hydroxy acetate (glycolate) enolate equivalent.
Synthesis, infrared and121Sb M�ssbauer spectra of some Antimony(III) Thiocyanate Complexes
1989
The first isolation of an antimony(III) thiocyanate complex salt, [(CH3)4N][Sb(CNS)4] (I), and of two adducts of the Sb(CNS)3 formal unit with potentially tridentate nitrogen donors, Sb(CNS)3tpta (II) and [Sb(CNS)3]3(dqp)2 (III), is described. In these derivatives, infrared and Mossbauer spectral data are essentially indicating the predominant presence of N-bonded thiocyanate. For complex I, the occurrence also of groups bridging through the nitrogen atom is advanced. Synthese, IR- und 121Sb-Mosbauer-Spektren von Antimon (III)-thiocyanat-Komplexen Die erstmalige Darstellung eines Antimon(III)-thiocyanat-Komplexes, [(CH3)4N][Sb(CNS)4] (I) und von zwei Addukten der formalen Sb(CNS)3-Einheit m…
Selective labelling of melittin with a fluorescent dansylcadaverine probe using guinea-pig liver transglutaminase
1991
Abstract Melittin, a C-terminal peptide, incorporated the fluorescent probe monodansylcadaverine (DNC) when catalysed by guinea-pig liver transglutaminase and Ca2+, as determined by thin-layer chromatography (TLC) and high-performance liquid chromatography (HPLC). A 1:1 adduct DNC-melittin was identified in which a single glutamine residue out of two, i.e. Gln25, acts as acyl donor. Incubation of melittin with transglutaminase in the absence of DNC originated high molecular mass complexes indicative that the peptide lysine residue can act as an acyl acceptor. The DNC-melittin was about 3 times more active in the lysis of red cell membranes than native melittin. Fluorescence study of the lab…
1,2-Methyl shift in the reaction of 4,7-dihydro-4,5-dimethyl-7-phenyl-(1,2,4)-triazolo[1,5-a]pyrimidine with tosyl azide
2000
The reaction of the heterocyclic enamine 1 with tosyl azide (2) leads to the tosylimino derivative 4 of 1,2,4-triazolo[1,5-a]pyrimidine. The extrusion of nitrogen from the primary adduct 3 is followed by a 1,2-shift of a methyl group. The structure determination of 4 is based on 1H and 13C nmr spectra including NOE measurements.