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.

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.

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.

The relative stabilities of PhE(NH-t-Bu)2 and PhE(μ-N-t-Bu)2EPh (E = As, Sb, and Bi): X-ray structures of {Li2[PhAs(N-t-Bu)2]}2 and PhE(μ-N-t-Bu)2EPh (E = Sb, Bi)

2003 ◽  
Vol 81 (2) ◽  
pp. 169-174 ◽  
Author(s):  
Glen G Briand ◽  
Tristram Chivers ◽  
Masood Parvez
Keyword(s):  
Solid State ◽  
Nmr Spectra ◽  
Phenyl Group ◽  
Synthetic Approach ◽  
Relative Stabilities ◽  
X Ray ◽  
X Ray Crystallography ◽  
In Trans ◽  
C Nmr

The reaction of PhECl2 with 2 equiv of LiHN-t-Bu has been studied for the series E = As, Sb, and Bi to determine the effect of the phenyl group on subsequent amine condensation processes. For PhAsCl2, the metathesis product PhAs(NH-t-Bu)2 4 was obtained as a colourless oil. Similar reactions involving PhECl2, where E = Sb or Bi, yielded the cyclodipnict(III)azanes PhE(μ-N-t-Bu)2EPh 5 (E = Sb) and 6 (E = Bi), respectively. Treatment of 4 with 2 equiv of n-BuLi produced the dilithium salt Li2[PhAs(N-t-Bu)2] 7a. Products 4, 5, 6, and 7a were characterized by 1H, 7Li (7a), and 13C NMR spectra, while 5, 6, and 7a were also structurally characterized by X-ray crystallography. Compound 7a is dimeric in the solid state via intermolecular Li···N and η6-Li···Ph interactions. The cyclodipnict(III)azanes 5 and 6 have similar structures, with the exocyclic phenyl groups in trans positions relative to the E2N2 ring. This synthetic approach provides a new route to the four-membered rings RE(μ-N-t-Bu)2ER (E = Sb, Bi) and the first example of a bis(organyl)cyclodibism(III)azane.Key words: arsenic, antimony, bismuth, amides, imides.

Synthetic, Infrared, 1H and 13C NMR Spectral Studies on N-(2/3/4-Substituted Phenyl)-2,4-Disubstituted Benzenesulphonamides, 2,4-(CH3)2/2-CH3-4-Cl/2,4-Cl2C6H3SO2NH(i-XC6H4) (i-X = H, 2-CH3, 3-CH3, 4-CH3, 2-Cl, 3-Cl, 4-Cl, 4-F, 4-Br)

2006 ◽  
Vol 61 (10-11) ◽  
pp. 600-606
Author(s):  
Savitha M. Basappa ◽  
Basavalinganadoddy Thimme Gowda
Keyword(s):  
Solid State ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Spectral Studies ◽  
1H And 13C Nmr ◽  
Nmr Chemical Shifts ◽  
Benzene Rings ◽  
Stretching Vibrations ◽  
Absorption Frequencies ◽  
C Nmr

Twenty six N-(2/3/4-substituted phenyl)-2,4-disubstituted benzenesulphonamides of the general formulae 2,4-(CH3)2C6H3SO2NH(i-XC6H4), 2-CH3-4-ClC6H3SO2NH(i-XC6H4) and 2,4- Cl2C6H3SO2NH(i-XC6H4), where i-X = H, 2-CH3, 3-CH3, 4-CH3, 2-Cl, 3-Cl, 4-Cl, 4-F or 4-Br, have been prepared, characterized and their infrared spectra in the solid state and 1H and 13C NMR spectra in solution studied. The infrared N-H stretching vibrational frequencies vary in the range 3298 - 3233 cm−1. Asymmetric and symmetric SO stretching vibrations appear in the ranges 1373 - 1311 cm−1 and 1177 - 1140 cm−1, respectively, while C-S, S-N and C-N stretching absorptions vary in the ranges 840 - 812 cm−1, 972 - 908 cm−1 and 1295 - 1209 cm−1, respectively. The various 1H and 13C NMR chemical shifts are assigned to the protons and carbon atoms of the two benzene rings in line with those for similar compounds. The incremental shifts due to the groups in the parent compounds have been computed by comparing the chemical shifts of the protons or carbon atoms in these compounds with those of benzene or aniline, respectively. The computed incremental shifts and other data were used to calculate the 1H and 13C NMR chemical shifts of the substituted compounds in three different ways. The calculated chemical shifts by the three methods compared well with each other and with the observed chemical shifts. It is observed that there are no particular trends in the variation of either the infrared absorption frequencies or the chemical shifts with the nature or site of substitution.

Über das [C7H7Fe2(CO)5]--Anion (C7H7 = Cycloheptatrienyl) / About the [C7H7Fe2(CO)5]--Anion (C7H7 = Cycloheptatrienyl)

1983 ◽  
Vol 38 (11) ◽  
pp. 1446-1453 ◽  
Author(s):  
Matthias Moll ◽  
Helmut Behrens ◽  
Werner Popp ◽  
Günther Liehr ◽  
Wolf Peter Fehlhammer
Keyword(s):  
Solid State ◽  
Iron Atom ◽  
Nmr Spectra ◽  
Structural Parameters ◽  
Anionic Complex ◽  
Polar Solvents ◽  
Space Group ◽  
X Ray

AbstractThe extremely unstable anionic complex [C7H7Fe2(CO)6]- (C7H7 = cycloheptatrienyl) which decomposes in polar solvents under CO elimination to give [C7H7Fe2(CO)5]- can be prepared by deprotonation of C7H8Fe2(CO)6 (C7H8 = cycloheptatriene) with NaN(SiMe3)2 in C6H6.The NMR spectra of [C7H7Fe2(CO)5]- show the highly fluctional character of this anion in solution. The X-ray structural parameters of Ph4As[C7H7Fe2(CO)5] (space group P21/n) can be interpreted in terms of a rotation of the tub shaped C7H7 ring against the CO bridged Fe2(CO)5 fragment in the solid state. Consequently, each iron atom is alternatingly η3 -or η4-coordinated to the allyl anion and the diene part, respectively, of the anionic 8π system of the cycloheptatrienyl ring.

Triferrocenylborane – Molecular Structure in Solution and in the Solid State

1995 ◽  
Vol 50 (2) ◽  
pp. 201-204 ◽  
Author(s):  
Bernd Wrackmeyer ◽  
Udo Dörfler ◽  
Wolfgang Milius ◽  
Max Herberhold
Keyword(s):  
Molecular Structure ◽  
Solid State ◽  
Low Temperature ◽  
Single Crystal ◽  
Nmr Spectra ◽  
The Other ◽  
X Ray ◽  
Single Diastereomer ◽  
Structure In Solution ◽  
C Nmr

According to a single crystal X-ray structure determination all three ferrocenyl substituents of triferrocenylborane (1) adopt the same orientation with respect to the BC3-plane [P21/c monoclinic; Z = 4; a = 1353.5(3), b = 1695.6(3), c = 1056.4(2) pm, β = 109.27(3)°]. The simulated X-ray powder pattern of the single crystal is identical with the powder diagram of a macroscopic sample, indicating the presence of a single diastereomer (1a) in the solid state. However, at low temperature (< - 95 °C) in solution, the 13C NMR spectra suggest the presence of the second diastereomer (1b) in which one ferrocenyl group is oriented opposite to the other two with respect to the central BC3-plane.

1,4-Bis(4-acylphen-1 -yl) 1,3-cy clopentadiene und 1,2,3,4-Tetra(4-alkylphen-1-yl)-1,3-cyclopentadiene und deren Natrium-, Thallium(I)- und Eisen(II)-Komplexe / 1,4-Bis(4-acylphen-1-yl)-1,3-cyclopentadienes and 1,2,3,4-Tetra(4-alkylphen-1-yl)- 1,3-cyclopentadienes and their Sodium, Thallium (I) and Iron(II) Complexes

1997 ◽  
Vol 52 (1) ◽  
pp. 45-52
Author(s):  
Herbert Schumann ◽  
Alexander Lentz
Keyword(s):  
Nmr Spectra ◽  
Acyl Chlorides ◽  
Sodium Complexes ◽  
New Compounds ◽  
C Nmr

1,4-Diphenyl-1,3-cyclopentadiene reacts with acyl chlorides RC(O)Cl (R = CH3 (a), C5H11 (c )) to form the corresponding 1,4-bis(4-acylphen-1-yl)-1,3-cyclopentadienes C5 H4 (C6H4 C(O)R)2 (1a, 1c), which upon treatment with NaNH2 or with TlOC2H5 afford the corresponding sodium complexes Na[C5H3 (C6H4C(O)R)2] (2a, 2c) or thallium(I) derivatives Tl[C5H3 (C6H4C(O)R)2] (3a, 3c). The reaction of 1,1′,3,3′-tetraphenylferrocene with CH3C(O)Cl results in the formation of Fe[C5H2 {C(O)CH3} {(C6H4C(O)CH3)2}]- [C5H3 {(C6H4C(O)CH 3)2}] (5), whereas 2c and FeCl2 give Fe[C5H3(C6H4C(O)C5H11)2]2 (4c). The all-para-acylated tetraphenylcyclopentadienes C5H2 (C6H4C(O)R)4 (R = CH3 (a), C3H7 (b)) react with K[N2H4OH] to produce the ligands C5H2(C6H4CH2R)4 (6a, 6b), which undergo reactions with NaNH2 and TlOC2H5 to yield the sodium and thallium(I) salts, Na[C5H2(C6H4CH2R)4] (7a, 7b) and Tl[C5H2(C6H4CH2R)4] (8a, 8b), respectively. 7a and 7b react with FeCl2 to produce the corresponding ferrocenes Fe[C5H(C6H4CH2R)4 ]2 (9a, 9b). The 1H and 13C NMR spectra of the new compounds are reported and discussed

scholarly journals Studies of Fluxionality in Pentachlorocyclopentadienylmercurials RHgC5Cl5 by Solution and Solid State 13C NMR and by 35Cl NQR Spectroscopy

1986 ◽  
Vol 41 (1-2) ◽  
pp. 175-178
Author(s):  
Gary Wulfsberg ◽  
A. C. Buchanan ◽  
Ira Rubin ◽  
Alarich Weiss ◽  
Daniel A. Davis ◽  
...  
Keyword(s):  
Solid State ◽  
13C Nmr ◽  
Nmr Spectra ◽  
Magic Angle Spinning ◽  
Magic Angle ◽  
35Cl Nqr ◽  
Angle Spinning ◽  
C Nmr ◽  
Solid State 13C Nmr

Solution and magic-angle-spinning solid-state 13C NMR spectra are reported for η1-(pentachlorocyclopentadienyl)( pentamethylphenyl) mercury, C6Me5HgC5Cl5 (II). The latter suggests that II is fluxional in the solid state. Some expected consequences of fluxional behavior also appear in the 35Cl NQR spectra of II and several related pentachlorocyclopentadienylmercurials.

ATTEMPTS TO IMPROVE SOLID STATE 13C NMR SPECTRA OF WHOLE MINERAL SOILS

1988 ◽  
Vol 68 (3) ◽  
pp. 593-602 ◽  
Author(s):  
M. A. ARSHAD ◽  
J. A. RIPMEESTER ◽  
M. SCHNITZER
Keyword(s):  
Particle Size ◽  
Organic Matter ◽  
Solid State ◽  
Nmr Spectra ◽  
Important Indicator ◽  
Size Fractions ◽  
Particle Size Fractions ◽  
Mineral Soils ◽  
C Nmr

This study describes a number of different preparation techniques for recording solid state 13C NMR spectra of whole mineral soils. Removal of paramagnetic Fe3+ improves the quality of 13C NMR spectra of whole soils and of particle size fractions. The C:Fe ratio appears to be an important indicator for obtaining satisfactory 13C NMR spectra of whole soils and fractions separated from them. If the C:Fe ratio is >> 1, the quality of the spectrum will be good; if the ratio is > 1, a reasonable spectrum will be obtained, but if the ratio is < 1, the spectrum will be poor. Organic-matter-rich soil and particle size fractions separated by a flotation technique produce well-defined 13C NMR spectra, typical of humic materials. Reduction of C-enriched fractions with sodium dithionite and stannous chloride improves the spectral resolution. The data presented herein show that satisfactory solid state 13C NMR spectra can be run on untreated soil particle size fractions, non-magnetic portions of whole soils, and fractions enriched in soil organic matter by flotation, especially after chemical reduction. Key words: 13C NMR spectroscopy, paramagnetic mineral separation

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