(Aminoethinyl)metallierimgen, IX [1] Umsetzungen von Inaminen mit Cyanketenen / (Aminoethynyl)metallations, IX [1] Reactions of Ynamines with Cyanoketenes

1981 ◽  
Vol 36 (2) ◽  
pp. 218-225 ◽  
Author(s):  
Gerhard Himbert ◽  
Lothar Henn Fachbereich
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Triple Bond ◽  
Diazo Compound ◽  
Cycloaddition Reactions ◽  
H Nmr ◽  
Derivatives Of

Ynamines 2 bearing methyl or phenyl groups at their C/C triple bond react with tert-butylcyanoketene 1a to give the cyclobutenones 3 and/or the allene carboxamides 4. 3 and 4 are the products of two different [2 + 2] cycloaddition reactions. β-Silylated, β-germylated and β-stannylated ynamines 5 add the cyanoketenes 1 under "(aminoethynyl)metallation" to furnish the new enynamines 6. These compounds were characterized by IR and 1H NMR spectroscopy and partly by mass spectrometry. The stannyl derivatives of 6 hydrolyze very easily to the corresponding acyl ynamines 7 and react with 4-nitrobenzoyl chloride to give the 1-(aminoethynyl)vinyl benzoates 8. The diazo compound 9 is formed by the interaction of tosyl azide on the enynamine 6 c, which is probably first hydrolyzed to 7a. N,N-Diethyl-N-(triphenylsilylethynyl)amine (5e) reacts with two molecules of tert-butylcyanoketene (1a) to give the allene derivative 10, probably via the corresponding enynamine 6 (R1 = R2 = Et, MR33 = SiPh3, R4 -tBu).

Carbamoyl and Thiocarbamoyl Derivatives of 3-Aminopropyl-dimethyl-phosphine Oxide

2004 ◽  
Vol 59 (2) ◽  
pp. 221-227 ◽  
Author(s):  
Victoria Lachkova ◽  
Helmut Keck ◽  
Rosario Scopelliti ◽  
Wolfgang Kläui ◽  
Sabi Varbanov ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Phosphine Oxide ◽  
Elemental Analysis ◽  
Phosphine Oxides ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Derivatives Of

A series of fourteen new 3-[N-substituted carbamoyl (or thiocarbamoyl)]-aminopropyl-dimethyl-phosphine oxides have been synthesized and characterized. The compounds were prepared via reaction of the 3-aminopropyl-dimethyl-phosphine oxide with the corresponding isocyanates or isothiocyanates. The composition of the compounds was proved by elemental analysis and the structures were confirmed by IR, 1H, 31P, 31P{1H} NMR spectroscopy and by mass spectrometry. The structures of 3[(N-phenyl-thiocarbamoyl)amino]propyl-dimethyl-phosphine oxide (5), 3[(N-4- chlorophenyl-thiocarbamoyl)amino]propyl-dimethyl-phosphine oxide (6), and 3[(N-benzyl-thiocarbamoyl) amino]propyl-dimethyl-phosphine oxide (9) have been confirmed by X-ray diffraction.

Monitoring the encapsulation of chlorin e6 derivatives into polymer carriers by NMR spectroscopy

2019 ◽  
Vol 23 (11n12) ◽  
pp. 1576-1586 ◽  
Author(s):  
Sara Pfister ◽  
Luca Sauser ◽  
Ilche Gjuroski ◽  
Julien Furrer ◽  
Martina Vermathen
Keyword(s):  
Relaxation Time ◽  
Nmr Spectroscopy ◽  
Core Region ◽  
Chlorin E6 ◽  
Polypropylene Glycol ◽  
Polymer Carriers ◽  
H Nmr ◽  
Line Shape Analysis ◽  
Dynamic Methods ◽  
Derivatives Of

The encapsulation of five derivatives of chlorin e6 with different hydrophobicity and aggregation properties into a series of five poloxamer-type triblock copolymer micelles (BCMs) with varying numbers of polyethylene and polypropylene glycol (PEG, PPG) units was monitored using 1H NMR spectroscopy. NMR chemical shift and line shape analysis, as well as dynamic methods including diffusion ordered spectroscopy (DOSY) and T1 and T2 relaxation time measurements of the chlorin and the polymer resonances, proved useful to assess the chlorin–BCM compatibility. The poloxamers had high capability to break up aggregates formed by chlorins up to intermediate hydrophobicity. Physically entrapped chlorins were always localized in the BCM core region. The loading capacity correlated with chlorin polarity for all poloxamers among which those with the lowest number of PPG units were most efficient. DOSY data revealed that relatively weakly aggregating chlorins partition between the aqueous bulk and micellar environment whereas more hydrophobic chlorins are well retained in the BCM core region, rendering these systems more stable. T1 and T2 relaxation time measurements indicated that motional freedom in the BCM core region contributes to encapsulation efficiency. The BCM corona dynamics were rather insensitive towards chlorin entrapment except for the poloxamers with short PEG chains. The presented data demonstrate that 1H NMR spectroscopy is a powerful complementary tool for probing the compatibility of porphyrinic compounds with polymeric carriers such as poloxamer BCMs, which is a prerequisite in the development of stable and highly efficient drug delivery systems suitable for medical applications like photodynamic therapy of tumors.

Chemie polyfunktioneller Liganden, 69 [1] Über drei Organo-Arsen-Käfigverbindungen mit Noradamantanstruktur / Chemistry of Polyfunctional Ligands, 69 [1] Three Organo-Arsenic Cage Compounds with Noradamantane Structure

1981 ◽  
Vol 36 (12) ◽  
pp. 1532-1537 ◽  
Author(s):  
Jochen Ellermann ◽  
Martin Lietz
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Cage Compounds ◽  
H Nmr ◽  
New Compounds

Abstract The reaction of l.l.l-tris(diiodarsinomethyl)ethane, CH3C(CH2Asl2)3 (1), with H2C(COOC2H5)2, H2C(COOCH3)2 and H2C(COC6H5)2 in presence of the auxiliary base (C2H5)3N gives the noradamantane structured compounds CH3C(CH2As)3E2 [E=C(COOC2H 5)2 (2), C(COOCH3)2 (3) and C(COC6H5)2 (4)].The new compounds have been characterized by mass spectrometry and infrared, Raman and 1H NMR spectroscopy.

Control of disaccharide conformation by π-stacking

2003 ◽  
Vol 81 (5) ◽  
pp. 364-375 ◽  
Author(s):  
Jonathan Watts ◽  
Jesús Jiménez-Barbero ◽  
Ana Poveda ◽  
T Bruce Grindley
Keyword(s):  
Nmr Spectroscopy ◽  
Molecular Modelling ◽  
Phenyl Ring ◽  
Glycosidic Linkage ◽  
Nmr Spectrum ◽  
H Nmr ◽  
Π Stacking ◽  
Nuclear Overhauser ◽  
Derivatives Of

The conformations of a series of derivatives of the disaccharide α-L-fucopyranosyl-(1[Formula: see text]3)-2-acetamido-2-deoxy-D-glucopyranoside, part of the Lex determinant, were studied by molecular modelling using the MM3* forcefield and by 1H NMR spectroscopy. Unusually shielded O-benzyl protons were observed in the 1H NMR spectrum of phenyl 2,3,4-tri-O-benzyl-α-L-fucopyranosyl-(1[Formula: see text]3)-2-deoxy-2-phthalimido-1-thio-α-D-glucopyranoside and assigned to the 2-O-benzyl group. This observation was explained by a shift in the population of the conformational mixture present about the glycosidic linkage from the positive Ψ region in the unsubstituted disaccharide to the negative Ψ region induced by π-stacking between the phthalimide and the 2-O-benzyl phenyl ring. The experimental nuclear Overhauser enhancements confirm the accuracy of the calculations.Key words: disaccharide, conformation, π-stacking, Lex determinant, NOE measurements, MM3 calculations.

Rhodium(I)–(N-heterocyclic carbene)–diphosphine complexes

2009 ◽  
Vol 87 (9) ◽  
pp. 1248-1254 ◽  
Author(s):  
Hongsui Sun ◽  
Xiao-Yan Yu ◽  
Paolo Marcazzan ◽  
Brian O. Patrick ◽  
Brian R. James
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Elemental Analysis ◽  
Benzene Solution ◽  
H Nmr ◽  
Diphosphine Dioxide

Reactions of [RhCl(COE)(IPr)]2 (1) and [RhCl(COE)(IMes)]2 (2) (COE = cyclooctene; IPr = N,N′-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene; IMes = N,N′-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) with the diphosphines Ph2P(CH2)nPPh2 and 1,2-bis(diphenylphosphino)benzene (dppbz) give the N-heterocyclic carbene (NHC) – diphosphine – rhodium(I) complexes: RhCl(NHC)[Ph2P(CH2)nPPh2] [NHC = IPr, n = 1 (3); NHC = IMes, n = 1 (4); NHC = IPr, n = 2 (5); NHC = IMes, n = 2 (6); NHC = IPr, n = 4 (7); NHC = IMes, n = 4 (8)] and RhCl(NHC)(dppbz) [NHC = IPr (9); NHC = IMes (10)]. All the complexes are characterized by 1H, 31P{1H}, and 13C{1H} NMR spectroscopy, elemental analysis, and mass spectrometry. Complexes 3, 7, and 9 are also characterized crystallographically. In benzene solution, the complexes decompose in the presence of O2 with formation of the diphosphine dioxide, whereas reaction with CO leads to replacement of the NHC ligand to give known carbonyl–diphosphine complexes.

Imidazole Nucleosides, V. Synthesis of 3′-Fluoro-3′-deoxy-ribofuranosides of 4(5)-Amino-imidazoIe-5(4)carboxamide

1999 ◽  
Vol 54 (8) ◽  
pp. 1055-1060 ◽  
Author(s):  
Hans Guglielmi ◽  
Markus Dachtler ◽  
Klaus Albert
Keyword(s):  
Nmr Spectroscopy ◽  
Elemental Analysis ◽  
H Nmr ◽  
Anti Cancer ◽  
Derivatives Of ◽  
Fluoro Derivatives

The synthesis of the 3′-fluoro-derivatives of 5-amino-1-(β-D-ribofuranosyl)imidazole-4- carboxamide (AICA-riboside) and the isomeric 4-amino-1(β-D-ribofuranosyl)imidazole-5- carboxamide (iso-AICA-riboside) are described. Structures were confirmed by elemental analysis, UV and 1H NMR spectroscopy. The anti-viral and anti-cancer activities of these imidazole nucleosides were tested.

Nine-Vertex Polyhedral Monoazaborane Chemistry: Synthesis and NMR Characterization of exo-6-Ligand-arachno-4-azanonaboranes(11), 6-L-4-NB8H11

1994 ◽  
Vol 59 (10) ◽  
pp. 2244-2252 ◽  
Author(s):  
Tomáš Jelínek ◽  
Bohumil Štíbr ◽  
John D. Kennedy
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Lewis Bases ◽  
H Nmr ◽  
Nmr Characterization ◽  
Complete Assignment

Reactions between arachno-4-NB8H13 and Lewis bases L in dichloromethane or without solvent generate the previously unreported series of arachno compounds exo-6-L-arachno-4-NB8H11, where L = pyridine (py), quinoline (quin), isoquinoline (i-quin), urotropine (uro), and MeCN. These are characterized by mass spectrometry together with 11B and 1H NMR spectroscopy. The NMR results permit complete assignment of all resonances and thence permit comparison with the structurally similar compounds exo-6-L-arachno-4-EB8H10 (for E = CH2 or S).

scholarly journals Fluorinated maleimide-substituted porphyrins and chlorins: synthesis and characterization

2019 ◽  
Vol 15 ◽  
pp. 2704-2709
Author(s):  
Valentina A Ol’shevskaya ◽  
Elena G Kononova ◽  
Andrei V Zaitsev
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Maleic Anhydride ◽  
Click Reaction ◽  
Synthesis And Characterization ◽  
H Nmr

Maleimide-containing fluorinated porphyrins and chlorins were prepared based on the reaction of Zn(II) or Ni(II) complexes of 5,10,15,20-tetrakis(4-amino-2,3,5,6-tetrafluorophenyl)porphyrin and chlorin with maleic anhydride. Porphyrin maleimide derivatives were also prepared by the reaction of 5,10,15,20-tetrakis(4-azido-2,3,5,6-tetrafluorophenyl)porphyrinato Zn(II) or Ni(II) with N-propargylmaleimide via the CuAAC click reaction to afford fluorinated porphyrin–triazole–maleimide conjugates. New maleimide derivatives were isolated in reasonable yields and identified by UV–vis, 1H NMR, 19F NMR spectroscopy and mass-spectrometry.

A combined 1H-NMR spectroscopy- and mass spectrometry-based metabolomic study of the PPAR-α null mutant mouse defines profound systemic changes in metabolism linked to the metabolic syndrome

2006 ◽  
Vol 27 (2) ◽  
pp. 178-186 ◽  
Author(s):  
Helen J. Atherton ◽  
Nigel J. Bailey ◽  
Wen Zhang ◽  
John Taylor ◽  
Hilary Major ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Metabolic Syndrome ◽  
Adipose Tissue ◽  
Nmr Spectroscopy ◽  
Magic Angle Spinning ◽  
Magic Angle ◽  
H Nmr ◽  
The Metabolic Syndrome ◽  
Chromatography Mass Spectrometry ◽  
Metabolic Role

The mobilization of triacylglycerides from storage in adipocytes to the liver is a vital response to the fasting state in mammalian metabolism. This is accompanied by a rapid translational activation of genes encoding mitochondrial, microsomal, and peroxisomal β-oxidation in the liver, in part under the regulation of peroxisome proliferator-activated receptor-α (PPAR-α). A failure to express PPAR-α results in profound metabolic perturbations in muscle tissue as well as the liver. These changes represent a number of deficits that accompany diabetes, dyslipidemia, and the metabolic syndrome. In this study, the metabolic role of PPAR-α has been investigated in heart, skeletal muscle, liver, and adipose tissue of PPAR-α null mice at 1 mo of age using metabolomics. To maximize the coverage of the metabolome in these tissues, 1H-NMR spectroscopy, magic angle spinning 1H-NMR spectroscopy, gas chromatography-mass spectrometry, and liquid chromatography-mass spectrometry were used to examine metabolites in aqueous tissue extracts and intact tissue. The data were analyzed by the multivariate approaches of principal components analysis and partial least squares. Across all tissues, there was a profound decrease in glucose and a number of amino acids, including glutamine and alanine, and an increase in lactate, demonstrating that a failure to express PPAR-α results in perturbations in glycolysis, the citric acid cycle, and gluconeogenesis. Furthermore, despite PPAR-α being weakly expressed in adipose tissue, a profound metabolic perturbation was detected in this tissue.

Sign in / Sign up

Export Citation Format

Share Document