Sodium salt, sulfonates and carboxylates of (E)- and (Z)-3-(hydroxymethylene)-5-methyldihydro-2(3H)-furanone

1985 ◽  
Vol 50 (2) ◽  
pp. 348-356 ◽  
Author(s):  
Ctibor Mazal ◽  
Věra Rothová ◽  
Jaroslav Jonas
Keyword(s):  
Solid State ◽  
Sodium Salt ◽  
Nmr Spectra ◽  
Coupling Constants ◽  
Dihedral Angles ◽  
Acyl Chlorides ◽  
C Nmr

In the solid state, sodium salt of 3-(hydroxymethylene)-5-methyldihydro-2(3H)-furanone can be prepared in the form of the (Z)-isomer, (E)-isomer or as a mixture of both isomers; in solutions the salt exists exclusively as the (E)-isomer. Reaction of the corresponding isomers of this sodium salt with sulfonyl or acyl chlorides afforded sulfonates or carboxylates derived from (E)- or (Z)-3-(hydroxymethylene)-5-methyldihydro-2(3H)-furanone. Configurations of the obtained isomeric sulfonates and carboxylates were confirmed by their 1H and 13C NMR spectra. Dihedral angles, calculated from the observed coupling constants, were used in the discussion of preferred conformation of the prepared compounds.

Configuration of sodium salt and preparation of sulphonates and carboxylates of (E)- and (Z)-3-(hydroxymethylene)dihydro-2(3H)-furanone

1984 ◽  
Vol 49 (8) ◽  
pp. 1907-1913 ◽  
Author(s):  
Jaroslav Jonas
Keyword(s):  
Solid State ◽  
Sodium Salt ◽  
Nmr Spectra ◽  
Sulphonic Acid ◽  
Sodium Salts ◽  
Acyl Chlorides ◽  
Acid Anhydrides ◽  
High Yields ◽  
C Nmr

The sodium salt of 3-(hydroxymethylene)dihydro-2(3H)-furanone (I) can be obtained in solid state in the form of (Z)-isomer, or their mixture, whereas in solutions it only exists in the form of (E)-isomer. Reactions of these sodium salts with sulphonyl or acyl chlorides or sulphonic acid anhydrides give the respective (E)- and (Z)-sulphonates or carboxylates of 3-(hydroxymethylene)dihydro-2(3H)-furanone in high yields and purity. Configuration of the sodium salt isomers has been confirmed by their IR and 12C NMR spectra in solid state, that of the isomeric sulphonates and carboxylates has been confirmed by their 1H and 13C NMR spectra in solution.

Sulphonates and carboxylates of (E)- and (Z)-3-(hydroxymethylene)-trans-hexahydro-2(3H)-benzofuranone

1987 ◽  
Vol 52 (1) ◽  
pp. 199-206
Author(s):  
Ctibor Mazal ◽  
Jaroslav Jonas
Keyword(s):  
Solid State ◽  
Sodium Salt ◽  
Nmr Spectra ◽  
Polar Solvents ◽  
Acyl Chlorides ◽  
C Nmr

Sodium salt of 3-(hydroxymethylene)-trans-hexahydro-2(3H)-benzofuranone has been found to be formed as the (Z)-isomer in solid state and to exist as the (E)-isomer or a mixture of the both isomers in polar solvents. Some sulphonates and carboxylates of (E)-3-(hydroxymethylene)-trans-hexahydro-2(3H)-benzofuranone and (Z)-3-(hydroxymethylene)-trans-hexahydro-2(3H)-benzofuranone have been prepared by reactions of the corresponding isomers of this sodium salt with sulphonyl and acyl chlorides, respectively. The configuration of the isomeric derivatives was confirmed by 1H and 13C NMR spectra.

Conformational structure of ethylene glycol dibenzoate. Vibrational and NMR spectra

1981 ◽  
Vol 46 (8) ◽  
pp. 1913-1929 ◽  
Author(s):  
Bohdan Schneider ◽  
Pavel Sedláček ◽  
Jan Štokr ◽  
Danica Doskočilová ◽  
Jan Lövy
Keyword(s):  
Ethylene Glycol ◽  
Vibrational Spectra ◽  
Nmr Spectra ◽  
Coupling Constants ◽  
Conformational Structure ◽  
Infrared And Raman Spectra ◽  
H Nmr ◽  
Liquid States ◽  
Crystalline Forms ◽  
C Nmr

It was found that three crystalline forms of ethylene glycol dibenzoate can be prepared. Infrared and Raman spectra of these three forms, as well as of the glassy and liquid states, were measured. From 3JHH coupling constants obtained by analysis of the 13C satellite band of the -CH2- group in 1H NMR spectra, and from the 3JCH coupling constants of the -CO.O.CH2- fragment obtained by analysis of the carbonyl band in 13C NMR spectra it was found that in the liquid state the -CH2-CH2- group exists predominantly in the gauche conformational structure, and the bonds C-O-C-C assume predominantly a trans orientation. The results of the analysis of NMR and vibrational spectra were used for the structural interpretation of conformationally sensitive bands in vibrational spectra of ethylene glycol dibenzoate.

Carbon-13 and nitrogen-14 NMR spectra of 1-(substituted phenyl)pyridinium salts

1980 ◽  
Vol 45 (10) ◽  
pp. 2766-2771 ◽  
Author(s):  
Antonín Lyčka
Keyword(s):  
Heavy Water ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Pyridinium Salts ◽  
Nmr Signals ◽  
C Nmr

The 13C and 14N NMR spectra of 1M solutions of 1-(substituted phenyl)pyridinium salts (4-CH3, 4-OCH3, H, 4-Cl, 4-Br, 4-I, 3-NO2, 4-NO2, 2,4-(NO2)2 (the 13C NMR only)) have been measured in heavy water at 30 °C. The 13C and 14N chemical shifts, the 1J(CH) coupling constants, some 3J(CH) coupling constants, and values of half-widths Δ 1/2 of the 14N NMR signals are given. The 13C chemical shifts of C(4) correlate with the σ0 constants (δC(4) = (1.79 ± 0.097) σ0 + (147.67 ± 0.041)), whereas no correlation of the nitrogen chemical shifts with the σ constants has been found. The half-widths Δ 1/2 correlate with the σ0 constants (Δ 1/2 = (76.2 ± 4.9) σ0 + (106.4 ± 2.2)) except for 1-phenylpyridinium chloride.

E-Homolupane Derivatives Substituted in Position 17 and 22a. 1H NMR, 13C NMR and IR Spectra

1995 ◽  
Vol 60 (4) ◽  
pp. 619-635 ◽  
Author(s):  
Václav Křeček ◽  
Stanislav Hilgard ◽  
Miloš Buděšínský ◽  
Alois Vystrčil
Keyword(s):  
Nmr Spectra ◽  
2D Nmr ◽  
Coupling Constants ◽  
Side Chain ◽  
Oxidation Reactions ◽  
H Nmr ◽  
Complete Assignment ◽  
Nmr Techniques ◽  
Intramolecular Association ◽  
C Nmr

A series of derivatives with various oxygen functionalities in positions 17,22a or 19,20 was prepared from diene I and olefin XVI by addition and oxidation reactions. The structure of the obtained compounds was confirmed by 1H NMR, 13C NMR and IR spectroscopy. The kind of intramolecular association of the 17α-hydroxy group was studied in connection with modification of the side chain and substitution in position 22a. Complete assignment of the hydrogen signals and most of the coupling constants was accomplished using a combination of 1D and 2D NMR techniques. The 1H and 13C NMR spectra are discussed.

Structural studies of digitoxin and related cardenolides by two-dimensional NMR

1990 ◽  
Vol 68 (2) ◽  
pp. 272-277 ◽  
Author(s):  
Torbjörn Drakenberg ◽  
Peter Brodelius ◽  
Deane D. McIntyre ◽  
Hans J Vogel
Keyword(s):  
Nmr Spectroscopy ◽  
Nmr Spectra ◽  
Chair Conformation ◽  
Coupling Constants ◽  
Two Dimensional ◽  
Structural Studies ◽  
Solution Conformation ◽  
Phase Sensitive ◽  
Multiple Relay ◽  
C Nmr

The 1H and 13C NMR spectra of the cardenolides digitoxigenin, digoxigenin, digitoxin, and mono- and bis-digitoxigenin digitoxosides have been completely assigned by two-dimensional NMR spectroscopy. The techniques used include phase-sensitive COSY, multiple relay COSY, and carbon–proton correlation (HETCOR and HMQC) spectra. Various aspects of the solution conformation of the steroid moiety of digitoxin and digoxigenin could be determined from coupling constants and NOE difference experiments and they are indicative of an all-chair conformation. The carbohydrate rings in digitoxin and the mono- and bis-digitoxigenin digitoxosides are also in the chair conformation. Keywords: cardenolides, digitoxigenin, digitoxin, 2-dimensional NMR, conformational analysis.

14N Quadrupole Interactions in Nitrogen-Containing Ceramics. Effects on 29Si NMR Line Shapes and Structural Implications

1992 ◽  
Vol 47 (1-2) ◽  
pp. 39-44 ◽  
Author(s):  
Alejandro Olivieri
Keyword(s):  
Solid State ◽  
Nmr Spectra ◽  
Dipolar Coupling ◽  
Coupling Constants ◽  
Simple Equation ◽  
29Si Nmr ◽  
Experimental Conditions ◽  
Line Shapes ◽  
Quadrupole Interactions ◽  
Quadrupole Coupling

AbstractSimulations of solid-state 29Si NMR spectra in nitrogen-containing silicon ceramics and glasses are described. The range of SiNxO4-x tetrahedra is covered, with emphasis on the experimental conditions needed to observe the effect of the incompletely averaged 29Si, 14N dipolar coupling. A simple equation is discussed concerning its use in the interpretation of these 29Si spectra, including the computation of 14N quadrupole coupling constants with its absolute sign.

Notizen: 13C-NMR an paramagnetischen Phenylmetallocenen1: Analogie zum Benzylradikal.

1976 ◽  
Vol 31 (8) ◽  
pp. 1153-1154 ◽  
Author(s):  
Frank H. Köhler ◽  
G. Matsubayashi
Keyword(s):  
Density Distribution ◽  
Spin Density ◽  
13C Nmr ◽  
Nmr Spectra ◽  
Hyperfine Coupling ◽  
Spin Density Distribution ◽  
Coupling Constants ◽  
Methyl Radicals ◽  
Benzyl Radical ◽  
C Nmr

The 13C NMR spectra of seven phenylated paramagnetic metallocenes have been recorded. From the spectra the 13C hyperfine coupling constants A(13C) have been extracted and compared with corresponding A(1H). It is found that the phenyl A′s in nickelocenes and cobaltocenes behave as in benzyl radical being reduced by a factor of 27. This offers a new route to informations about spin density distribution in substituted methyl radicals.

Phosphinsubstituierte Chelatliganden, XXIII [1] Darstellung und NMR-Spektren von Alkyl-arylphosphinothioformamiden, R(Ph)PC(S)NHMe / Phosphine-Substituted Chelate Ligands, XXIII [1] Synthesis and NMR Spectra of Alkyl-arylphosphinothioformamides, R(Ph)PC(S)NHMe

1987 ◽  
Vol 42 (1) ◽  
pp. 77-83 ◽  
Author(s):  
Udo Kunze ◽  
Rolf Tittmann
Keyword(s):  
Chemical Shift ◽  
Linear Correlation ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Cone Angle ◽  
Coupling Constants ◽  
Methyl Isothiocyanate ◽  
Signal Sets ◽  
The Asymmetry ◽  
C Nmr

Abstract A series of alkyl-arylsubstituted N-methyl phosphinothioformamides, R(Ph)PC(S)NHMe (2 a-g), with varying bulkiness of the alkyl rest was synthesized from the racemic secondary phosphines 1a-g and methyl isothiocyanate. 1H and 13C NMR spectra of 2a−g reveal signal sets of diastereotopic nuclei due to the asymmetry of the molecule. The chemical shift and coupling constants were confirmed by simulation in case of 2b, c. The vicinal 31P−13C couplings of the menthyl and neomenthyl compounds 2f, g show an "anti-Karplus" behaviour (3J(gauche) > 3J(trans)) and allow the conformational assignment of the alicyclic group. The 31P chemical shifts of 2a−d give a linear correlation with the cone angle of the alkyl substituents quoted from literature.

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